• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    CHEMICALLY FUNCTIONALIZED RUBBER COMPOSITION. Currently, reclaimed rubber material exhibits excellent processability but compromises compound properties, while alternative recycled material options are either uneconomical, degrade compound performance, or lead to unacceptable processing behavior. The renewed rubber of the present invention can be processed much more easily than conventional recycled rubber compositions. It also consistently exhibits a structure of better overall properties than cured rubber with only minimal variations in characteristics, by using raw materials produced by various crushing methods. In a chemical functionalization of the renewed rubber compositions of the present invention, the sulfur-sulfur bonds in micronized rubber powder are broken to partially devulcanize the rubber, with only a minimal number of carbon-carbon double bonds in the polymer structure being broken. This allows the renewed rubber of the present invention to be used in rubber formulations that are used in manufacturing the large structure of rubber products, including tires, power transmission belts, conveyor belts, hoses, and the large structure of other products. The present invention more specifically describes a method for manufacturing a composition (...).
    公开号:BR102015009848B1
    申请号:R102015009848-0
    申请日:2015-04-30
    公开日:2021-06-01
    发明作者:Chad Aaron Jasiunas；Frank P. Papp；Charles T. Rosenmayer；Adel Farhan Halasa
    申请人:Lehigh Technologies, Inc；
    IPC主号:
    专利说明:

    Field of Invention
    [001] The present invention relates in general to methods of using recovered crosslinked elastomeric material (heat setting polymers) and in particular to methods of chemical functionalization of recovered elastomeric materials such as micronized rubber powder and composites of elastomer and compositions comprising chemically functionalized elastomeric materials. Background of the present invention
    [002]Millions of used tires, hoses, belts and other rubber products are discarded each year after they have been used during their limited life. Said used rubber products are typically transported to a landfill or burned as fuel in that there is very little use for them after they have served their original intended purpose. A limited number of used tires are used in building retaining walls, as protection for boats and similar things where weather resistance is desirable. Some tires are crushed into powder form to be used in various applications such as tire compounds, asphalt binding agents, roofing applications and on sports fields, just to name a few. However, many more tires, hoses and belts are simply discarded or burned.
    [003] Recycling cured rubber products proved to be an extensively challenging problem. Said problem associated with the recycling of cured rubber products (such as tires, hoses and belts) arises from the fact that, in the vulcanization process, the rubber becomes crosslinked with sulfur. Sulfur crosslinks are very stable and the vulcanization process is extremely difficult to reverse. After vulcanization, the crosslinked rubber becomes heat-set and cannot be easily reformed into other products. In other words, cured rubber cannot be fused and reformed into other products such as metals or thermoplastic materials. Thus, cured rubber products cannot simply be melted and easily recycled into new products.
    [004] 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 rubber cured from tires and other rubber products is chopped or crushed to a small particle size and incorporated into various products as a type of filler. For example, crushed rubber can be incorporated into asphalt for road paving or parking lots. Small cured rubber particles can also be included in rubber formulations for new tires and other rubber products. However, it should be understood that recycled rubber serves only load capacity in that it has previously been cured and does not bind to an appreciable extent of virgin rubber in a rubber formulation. Therefore, recycled rubber is typically limited to lower loads because of poor compound processing (compounds become more viscous with higher loads) as well as higher loads that lead to unacceptable curing properties.
    [005] Several techniques to devulcanize cured rubber have been developed. Devulcanization offers the advantage of making the rubber suitable to be reformulated and re-cured into new rubber articles if it can be done without rubber degradation. In other words, the eraser can once again be used for its original intended purpose. However, none of the previously developed devulcanization techniques have proven to be commercially viable at high loads. For example, some devulcanized materials can be used at 3-5% loads. However, above this level the properties of the new rubber article are diminished. This is unsuitable for high performance applications such as rubber compounds for vehicle tyres. In other cases, devulcanized materials are unsuitable for processing at high loads in rubber compounds. Said processing challenges can include short cure times (dries out), too little tack, too high viscosity, and poor crush handling and extrusion quality. A renewable material that can be used in high performance applications at loads of 5% and higher is required.
    [006] US Patent 4,104,205 describes a technique for devulcanizing polar groups containing elastomer vulcanized to sulfur 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 of the carbon-sulfur and sulfur-sulfur bonds and insufficient to sever significant amounts of carbon-carbon bonds.
    [007] US Patent 5,284,625 describes a continuous ultrasonic method for breaking carbon-sulfur bonds, sulfur-sulfur and, if desired, carbon-carbon bonds in a vulcanized elastomer. By applying certain levels of ultrasonic amplitudes in the presence of pressure and optionally heat, it is reported that the cured rubber can be broken. Using this process, the rubber becomes soft, thereby allowing it to be reprocessed and resized in a manner similar to that employed with previously uncured elastomers.
    [008] US Patent 5,602,186 describes a process for devulcanizing rubber cured by desulfurization, which comprises the steps of: contacting a piece of rubber vulcanizate with a solvent and an alkali metal to form a reaction mixture, heating the reaction mixture in the absence of oxygen and with mixing at a temperature sufficient to cause the alkali metal to react with sulfur in a rubber vulcanizate and maintain the temperature below that at which thermal breakage of the rubber occurs, thereby devulcanizing the vulcanized rubber. U.S. Patent 5,602,186 indicates that it is preferred to control the temperature below about 300°C, or where thermal breakage of the rubber is initiated. Toluene, naphtha, terpenes, benzene, cyclohexane, diethyl carbonate, ethyl acetate, ethylbenzene, isophorone, isopropyl acetate, methyl ethyl ketone and derivatives thereof are identified as solvents that can be used in the process described by said patent.
    [009] US Patent 6,548,560 is based on the discovery that cured rubber can be devulcanized by heating it to a temperature of at least about 150°C under a pressure of at least about 3.4 x 106 Pascals in the presence of a solvent selected from the group consisting of alcohols and ketones having a critical temperature within the range of about 200°C to about 350°C. The molecular weight of rubber can be maintained at a relatively high level if devulcanization is carried out at a temperature of no more than about 300°C. Said devulcanization technique is reported to not significantly disrupt the polymeric structure of rubber or change its microstructure. In other words, devulcanized rubber can be recomposed and re-cured into useful articles in substantially the same way as the original (virgin) rubber was. Said patent more specifically discloses a process for devulcanizing cured rubber to devulcanized rubber which is capable of being recomposed and re-cured into useful rubber products, said process comprising (1) heating the cured rubber to a temperature that is within the range of about 150°C to about 300°C under a pressure of at least about 3.4 x 106 Pascals in the presence of a solvent selected from the group consisting of alcohols and ketones, wherein said solvent has a temperature critique that is within the range of about 200°C to about 350°C, to devulcanize the cured rubber to a devulcanized rubber thereby producing a slurry of a devulcanized rubber in the solvent; and (2) separating the devulcanized rubber from the solve.
    [010] US Patent 5,770,632 describes a process for recovering elastomeric material from elemental sulfur cured elastomeric material having a vulcanized network without using hexamethylene tetramine, by treating the sulfur cured elastomeric material having a vulcanized network with a or more rubber dissociation accelerators selected from the group of zinc salts of thiocarbamates and zinc salts of dialkyl dithiophosphates, 2-mercaptobenzothiazole or derivatives thereof, thiourames, guanidines, 4,4'-dithiomorpholine and sulfenamides, and an activator of zinc oxide in an amount sufficient to act as an activator for the accelerator(s) to disassociate the elastomeric material at a temperature below 70°C, whereby the vulcanized network is opened or dissociated to provide a curable reclaimed elastomeric material capable of being vulcanized without adding chemicals to vulcanize rubber. The technique described in said patent also includes compositions capable of dissociating the vulcanized networks of sulfur-cured elastomeric material including the accelerators and activator described above. The recycled or reclaimed elastomeric material obtained has the desired physical and dynamic characteristics that make it suitable for use in molded goods or for blending with fresh compounds in tires and related products.
    [011] US Patent 6,831,109 describes a modifier for the devulcanization of cured elastomers, and especially vulcanized rubber, said modifier containing a first chemical substance, which is disposed towards the formation of an organic cation and amine, and additionally containing a second chemical substance as a promoter element for dissociation from the first chemical substance, said promoter element containing a functional group constituting a receiving agent for said amine.
    [012] US Patent 6,541,526 describes a mechanical/chemical method composition for rubber devulcanization that is reported to keep the macromolecules in the composition and to make the sulfur in it passive for further revulcanization. This process is also reported to be economical, environmentally friendly and to produce high quality devulcanized rubber to replace virgin rubber. According to the method of U.S. Patent 6,541,526 the rubber scrap is crushed, crushed and the metal removed. Then the modifying composition is added as the crushed rubber scrap particles are poured between two rollers which further crush the particles. The modifying composition is a mixture of ingredients that includes, by weight, the following components: (1) between approximately 76% and approximately 94% of a proton donor that breaks sulfur to sulfur bonds in the waste rubber ; (2) between approximately 1% and approximately 5% of a metal oxide, (3) between approximately 1% and approximately 5% of an organic acid having between 16 and 24 carbon atoms per molecule, (4) between approximately 2% and approximately 10% of a vulcanization inhibitor and (5) between approximately 2% and approximately 10% of a friction agent.
    [013] US Patent Application Publication No. 2010/0317752 describes a method that is reported to be effective in recycling vulcanized elastomeric materials via an economical devulcanization process that opens or "disassociates" the crosslinks of a mesh structure vulcanized to used vulcanized elastomers without unduly degrading the rubber polymer structure. Said patent more specifically describes a dissociation composition in the form of a combined solid dose comprising: (i) one or more elastomer dissociation accelerators selected from the group consisting of zinc salts of thiocarbamates and zinc salts of dialkyl dithiophosphates; and (ii) one or more elastomer dissociation accelerators selected from the group consisting of 2-mercaptobenzothiazole or derivatives thereof, thiourames, guanidines, 4,4'-dithiomorpholine and sulfenamides; and (iii) at least one elastomer dissociation activator. However, said patent absolutely requires as essential ingredients zinc salt, an elastomer dissociation accelerator and a dissociation activator.
    [014] Therefore, the aforementioned aforementioned patents have not proven to be commercially viable and the recycled rubber produced by said processes has not proven to be possible for use in high load demand applications, such as certain rubber compounds for vehicle tires. To date very little characterization data has been presented to substantiate determinations concerning the selectivity of sulfur-sulfur or sulfur-carbon bonds being broken rather than carbon-carbon bonds within the vulcanized rubber composite network.
    [015]Cured rubber articles can also be crushed to form a powder and used in the manufacture of a wide variety of products. Reclaimed elastomeric materials, such as reclaimed elastomers, ground tire rubber (GTR), and micronized rubber powders (MRP), which include vulcanized elastomeric materials, are used in a variety of products. For example, micronized rubber powders are commonly used as fillers in rubber, asphalt, and plastic items. More specifically, micronized rubber powders are currently being used as fillers in tires, industrial rubber products (hoses, power transmission belts, conveyor belts, floor pads), asphalt products (paving and tile formulations) and a wide variety of other products. The use of reclaimed elastomers in said rubber products is typically significantly less costly than the use of virgin materials and leads to an overall reduction in manufacturing costs. The use of reclaimed material is also environmentally advantageous in that it prevents cured rubber reclaimed from post-consumer and industrial sources from going to landfills or simply being burned. Finally, the use of recycled shredded tire rubber and micronized rubber powders provides a strategic supply chain barrier against the supply chain price of petroleum-based products and supply volatility.
    [016]The devulcanized rubber material currently known as reclaimed exhibits excellent processability but poor curing properties in compounds at loads above 3-5%. Micronized rubber powder (MRP) shows acceptable curing properties, and even higher loads (above 5%) than the processability of the compound can suffer.
    [017] In general, crushed tire rubber (GTR) consists of particle size distributions ranging from a diameter of about 0.5 mm to about 5 mm that can be produced by a variety of techniques including methods room temperature grinding and cryogenic grinding. Micronized rubber powders (MRP) typically contain a significant fraction of rubber particles having a particle size of less than 100 microns. In any case, crushed tire rubber and micronized rubber powders are commonly referred to as mesh size. For example, powders in the 10-30 mesh size range are usually considered to be crushed tire rubber while powders having a smaller particle size that is within the 40-300 mesh range are generally considered to be rubber powder. micronized. Micronized rubber powder is typically more uneconomical to produce because it requires more processing and/or more demanding processing conditions to meet the smaller particle size. For this reason, crushed tire rubber is typically used in low-performance applications, such as tread pads, with micronized rubber powder only being used in more demanding applications, such as in tires, where the additional cost can be justified. .
    [018]Recovered elastomeric polymers that are used as the raw material for the production of crushed tire rubber and micronized rubber powder, such as scraped tire rubber, are cured (formerly vulcanized) rubbers. They are thus being relatively inert particles that are essentially unreactive with virgin elastomers, resulting in compromised processing and high loading properties.
    [019] There is a long perceived but still unresolved need for renewed elastomer compositions that are derived from reclaimed rubber that retain cured and uncured chemical and mechanical characteristics that are virtually the same as virgin rubber. In other words, it would be highly desirable for such an elastomer to be able to be processed in essentially the same way as virgin rubber and to be able to be replaced in whole or at least in part by virgin rubber in useful manufacturing products. Said renewed rubber can optimally exhibit physical and dynamic properties which are in fact identical to the properties of virgin rubber. It will also be great if it has curing characteristics and viscosity process that are similar to virgin rubber. Renewed rubber can be used in more demanding applications as an elastomeric component rather than filler, as its properties more closely resemble the properties of virgin rubber. Therefore, renewed rubber will have greater value from a technical and economic standpoint as it more closely mimics the curing characteristics and physical properties of virgin rubber. Summary of the present invention
    [020] The present invention provides a method for chemically functionalizing micronized rubber powder that is recovered from rubber products to provide a renewed rubber composition with properties that mimic virgin rubber and that can be used as a rubber for the manufacture of new rubber items. In other words, said renewed rubber can be used as a constituent rubber or the part of the rubber formulation employed in the manufacture of rubber products, such as tires, hoses, power transmission belts, conveyor belts, and numerous other articles of rubber. The renewed rubber of the present invention performs the role of an uncured elastomer rather than merely serving the filler function.
    [021] The renewed rubber of the present invention can be processed much more easily than conventional recycled rubber compositions. It also consistently exhibits a structure of better overall properties of cured rubber with only minimal variations in characteristics by using raw materials produced by various grinding methods. In the functionalization of the renewed rubber compositions of the present invention the sulfur-sulfur bonds in micronized rubber powder are disrupted to devulcanize the rubber with only a minimal number of carbon-carbon double bonds in the polymer structure being disrupted. This allows the renewed rubber of the present invention to be used at least in part, or combined with other materials such as virgin polymers, reclaimed rubber, or rubber chemicals to name a few, such as the rubber component of rubber formulations ( rubber compounds) which are used in manufacturing a large structure of rubber products, including tires, power transmission belts, conveyor belts, hoses, and the large structure of other products.
    [022] The present invention more specifically describes a method for manufacturing a renewed, chemically functionalized, environmentally friendly rubber composition having a highly desirable combination of physical properties and exhibiting excellent processability comprising the steps of (1) blaend a micronized rubber powder with a processing aid and functionalizing agent(s) to produce a blended blend; (2) processing the blend blend under conditions of high shear and low temperature to produce a reacted blend; (3) add a stabilizer to the reacted mixture to produce the renewed rubber.
    [023] The present invention further discloses a chemically functionalized renewed rubber composition, which is comprised of an elastomeric polymer and a stabilizer; wherein the rubber composition has a crosslink density that is within the range of 0.05 to 2.0 x 10-5 mol/g, preferably in a range of 0.1 to 1.8 x 10-5 mol/ g, and wherein the rubber composition has a solubility fraction of less than 90%, preferably less than 50%, and more preferably less than 30%.
    [024] The present invention also describes a rubber composition that is typically in the form of a board that is comprised of a micronized rubber powder having a maximum particle size of 400 µm, preferably less than 200 µm, and even more preferably a maximum particle size of less than 100 µm, where the micronized rubber powder is comprised of polymer chains containing multiple double bonds in their structures, where the polymer chains within the micronized rubber powder are cross-linked together with sulfur, and in which the polymer chains within the micronized rubber powder are functionalized with fractions of the structural formula:

    [025]where n represents an integer from 1 to 10, where x represents an integer from 1 to 10, and where y represents an integer from 1 to 10. Said compositions also typically they will contain a soluble moiety of a rubber having a soluble processing aid and polymer chains containing multiple double bonds in their structures that are functionalized with moieties having the structure illustrated above. The plates of said functionalized rubber composition are easily processed in internal mixers and extruders and incorporated in a rubber matrix alone or with other polymeric materials and composition ingredients and fillers.
    [026] The present invention also discloses a renewed functionalized rubber composition which is typically in the form of a board which is comprised of a micronized rubber powder having a maximum particle size of 400 µm, preferably less than 200 µm, and even more preferably a maximum particle size of less than 100 µm, wherein the micronized rubber powder is comprised of polymeric chains containing multiple double bonds in their structures, wherein the polymeric chains within the micronized rubber powder are cross-linked together with sulfur, and where the polymer chains within the micronized rubber powder are functionalized with fractions of the structural formula:

    [027]where n represents an integer from 1 to 10. Said compositions will also typically contain the soluble fraction of a rubber having soluble processing aid and polymer chains containing multiple double bonds in their structures that are functionalized with fractions having the structure illustrated above. Plates of said functionalized rubber composition are easily processed in internal mixers and extruders and incorporated in a rubber matrix alone or with other polymeric materials and composition ingredients and fillers.
    [028] The renewed functionalized rubber composition of the present invention can be processed from being in the form of a powder and in the form of a board. Therefore, the present invention also describes a renewed functionalized rubber composition which is in the form of a board which is comprised of a micronized rubber powder having a maximum particle size of 400 µm, preferably less than 200 µm, and even more preferably a maximum particle size of less than 100 µm, wherein the micronized rubber powder is comprised of polymer chains containing multiple double bonds in their structures, wherein the polymer chains within the micronized rubber powder are cross-linked sulfur joints, and in which the polymer chains within the micronized rubber powder are functionalized with fractions of the structural formula:

    [029] Where n represents an integer from 1 to 10. Said compositions will also typically contain a soluble fraction of a rubber having soluble processing aid and polymer chains containing multiple double bonds in their structures that are functionalized with fractions having the structure illustrated above. In some cases it is desirable for the functionalized fresh rubber compositions of the present invention to be further processed into slabs. This is because functionalized rubber composite boards can be easily processed in internal mixers and extruders and incorporated into a rubber matrix alone or with other polymeric materials, compounding ingredients and/or fillers. Brief Description of Drawings
    [030] Figure 1 illustrates the functionalization of a polyisoprene rubber cured according to the present invention using tetrabenzylthiourama disulfide as the functionalizing agent.
    [031] Figure 2 illustrates the Horikx graph for examples 2-4.Detailed Description of the Present Invention
    [032] The micronized rubber powder used in the process of the present invention can be produced using in fact any technique that results in the powder having a small particle size that is typically 10 mesh or less. The micronized rubber powder will most typically have a particle size of no more than 30 mesh. In some applications it may be advantageous to employ a micronized rubber powder having a particle size of 80 mesh, 140 mesh, or even smaller.
    [033] In a specific embodiment of the present invention micronized rubber powder can be produced using the cryogenic grinding system described in US Patent 7,445,170 and an impact crusher as described in US Patent 7,861,958. The teachings of North American Patent 7,445,170 and North American Patent 7,861,958 are incorporated herein for the purpose of describing useful techniques and equipment that can be employed in the production of micronized rubber powder that can be employed in the production of chemically functionalized rubber renewed compositions of according to the present invention.
    [034] Micronized rubber powder can also be produced in many other ways than described above, such as but not limited to a wet grinding process, room temperature grinding process, and other cryogenic processes. Using micronized rubber powder of the same compounding material manufactured by any process in the present invention will result in similar chemically functionalized materials that exhibit excellent processability as well as curing properties.
    [035] The rubber used in the production of micronized rubber powder can in fact be any type of sulfur-cured rubber compound and can come from a wide variety of sources. For example, a rubber compound can be comprised of natural rubber, synthetic polyisoprene rubber, higher cis-1,4-polybutadiene rubber, medium polybutadiene vinyl rubber, higher polybutadiene vinyl rubber, styrene-butadiene rubber emulsion, styrene-butadiene rubber solution, styrene-isoprene-butadiene rubber, styrene-isoprene rubber, butyl rubber, chlorobutyl rubber, bromobutyl rubber, polynorbornene rubber, ethylene-propylene rubber (EPR), rubber of ethylene-propylene-diene (EPDM), nitrile rubber, carboxylated nitrile rubber, polychloroprene rubber (neoprene rubber), polysulfide rubbers, polyacrylic rubbers, silicone rubbers, chlorosulfonated polyethylene rubbers, and the like as well as various blends the same.
    [036] A rubber compound recovered from vehicle tire treads in retreading procedures is an example of a source of a rubber compound for use in the production of micronized rubber powder. However, a rubber compound can come from a wide variety of sources including total tire rubber, tire sidewalls, tire inner liners, tire casings, power transmission belts, conveyor belts, hoses, and a wide variety of other rubber products. In any case, the "rubber grinds" from tire treads are comprised of a rubber compound, which is ground from the vehicle tire tread in preparing the old tire casing to be recapped. In the retreading procedure a new tread is applied to the old tire carcass and cured over it to produce the retreaded tire. In any case, said vehicle tire retread grinding is predominantly comprised of natural rubber, synthetic polyisoprene rubber, polybutadiene rubber, and styrene-butadiene rubber. Said retread grindings are typically the blend of natural rubber and various synthetic rubbers. Therefore, the micronized rubber powder used in accordance with the present invention is typically a powder of a mixture of natural rubber, synthetic polyisoprene rubber, polybutadiene rubber, and styrene-butadiene rubber. However, micronized rubber powder can be a blend of any two or more of said rubbers or it can be comprised of only one type of rubber. For example, the micronized rubber powder may consist solely of natural rubber, synthetic polyisoprene rubber, styrene-butadiene rubber, a blend of natural rubber and polybutadiene rubber, or a blend of natural rubber and styrene-butadiene rubber.
    [037]More specifically optimal properties in tire applications, especially wear, can be obtained when the feed material (starting raw material) used to produce the micronized rubber powder matches the final rubber compound composition. For example, using truck tread scraping based predominantly on natural rubber as the starting material to produce micronized rubber powder. So using said specific micronized rubber powder back to truck tire applications will exhibit excellent compound properties. In passenger car tire applications, predominantly use styrene-butadiene rubber compounds as the starting material for micronized rubber powder and then use said specific micronized rubber powder back in styrene rubber tread applications butadiene in passenger car tires will exhibit excellent compound properties.
    [038] In the first step of the process of the present invention, the micronized rubber powder is blended with a processing aid and a functionalizing agent to produce the blend. The processing aid will typically be added at a level that is within the range of about 1 phr (parts by weight per 100 parts by weight of MRP) to about 20 phr. The processing aid will most typically be added at a level that is within the range of about 4 phr to about 15 phr, and preferably will be included at a level that is within the range of 6 phr to 12 phr. The purpose of adding the processing aid is to penetrate a rubber compound and make it swell (surface wetting is not sufficient). Therefore, the processing aid is typically a low-viscosity processing oil, such as a naphthenic oil, a pinecone oil, an orange oil, or a vegetable oil, which will swell the rubber rather than simply act as a lubricant.
    [039]The functionalizing agent is typically added at a level that is within the range of 0.25 phr to about 8 phr and is more typically added at a level that is within the range of 0.5 phr to 6 phr. The functionalizing agent is preferably added at a level that is within the range of about 1 phr to about 4 phr. The functionalizing agent is typically a compound that acts to devulcanize the micronized rubber powder. Some representative examples of functionalizing agents that can be used include thiourama monosulfide, thiourama disulfide, thiourama multisulfide, tetrabenzylthiourama disulfide, cyclohexyl sulfonamide, t-butyl sulfonamide, tetraalkylthiourama disulfide, tetramethylthiourama disulfide, disulfide tetraethylthiouram, dipentamethylthiouram monosulfide, and tetramethylthiouram disulfide.
    [040] Additionally protocols for optimizing the process of the present invention to meet the needs of specific applications will be apparent to those skilled in the art. For example, in some cases to reduce material costs it will be possible to use a lower level of processing aid while still achieving the desired material objectives. Additionally, to increase productivity, some powders can be introduced into a processing aid and added to the process as a solution or paste which can result in faster processing times. Optimization is also necessary in compound development. For example, micronized rubber powder is currently used in typical rubber compounds over batch weight. Functionalized renewed rubber can also be used to replace raw material such as polymer or filler.
    [041] The functionalizing agent can be a compound that includes the xanthate group, such as di-alkyl xanthate, sodium ethyl xanthate, potassium ethyl xanthate, sodium isopropyl xanthate, sodium isobutyl xanthate, potassium amyl xanthate , It is similar. Said xanthate group containing compounds are typically of the structural formula:
    wherein R and R' represent hydrocarbyl groups containing from 1 to 12 carbon atoms.
    [042]Thioxantates can also be used as the functionalizing agent. They can be synthesized by reacting carbon disulfide (CS2) with thiolate salts. For example, sodium ethylthioxanthate (C2H5SCS2Na) can be used as the functionalizing agent in an embodiment of the present invention. Dithiocarbamates are also useful as functionalizing agents in the practice of the present invention. Dithiocarbamates are produced by reacting carbon disulfide with an amine. Sodium diethyldithiocarbamate (C2H5)2NCS2Na) is a representative example of the preferred dithiocarbamate that can be used in the practice of the present invention.
    [043] Some additional representative examples of functionalizing agents that can be used in the practice of the present invention include tetramethyl-2-phenylguanidine, N,N,N',N'-trimethylguanidine, 1,1,1trimethylguanidine, p-acid (1,3-dimethyl-3-phenylguanidino)benzoic acid, (diaminomethyleneamino)acetic acid, and 1,1,3-triethylguanidinium chloride.
    [044] After the processing aid and functionalizing agent are added to the micronized rubber powder it is typically advantageous to age the blend mixture for at least 2 hours before further processing. The blend blend will most typically be aged for at least 4 hours and in many cases for at least 6 hours before further processing. The blend blend will preferably be aged for at least 8 hours and in many cases for 12 hours to 24 hours before further processing. It is also typically advantageous to mix N,N'-diphenyl guanidine in the blend mixture.
    [045]The blend mixture is then processed under conditions of high shear and low temperature to produce the reacted mixture. During said step the reacted mixture will typically be maintained at a temperature of 70°C or less and preferably 50°C or less. In some cases it is advantageous to keep the reacted mixture at a temperature of 30°C or even as low as 0°C. For example, a temperature that is within the range of -20°C to 30°C will be highly suitable. In one embodiment of the present invention, this is accomplished by passing the blend mixture through a crusher having counter-rotating rollers that rotate at different speeds. In accordance with some embodiments of the present invention the rolls are maintained at a temperature of 70°C or less, preferably 50°C or less and even more preferably 30°C or less while the recovered elastomer is subjected to shear. In accordance with some embodiments of the present invention, the rollers are spaced apart a distance of 0.4 mm or less, typically 0.2 mm or less, and preferably 0.1 mm or less. According to some embodiments of the present invention, the rubber blend is passed through the crusher rollers multiple times.
    [046]A stabilizer is then added to the reacted mixture to produce the renewed, chemically functionalized rubber composition. The stabilizer can be mixed into a reacted mixture using a crusher mixer or an internal mixer such as a Banbury mixer. The stabilizer will typically be added at a level that is within the range of about 0.25 phr to about 5 phr and more typically will be added at a level that is within the range of about 0.5 phr to about 3 phr . The stabilizer will preferably be added at a level that is within the range of about 1 phr to about 2 phr. The stabilizer is typically a vulcanization retarding agent, such as N-cyclohexyl(thio)phthalimide (CAS No. 17796-82-6).
    [047] The renewed functionalized rubber composition produced by the process of the present invention typically has a Mooney ML1+4 viscosity that is within the range of about 50 to 140 and which is preferably within the range of 70 to 120. Said composition of renewed functionalized rubber is comprised of an elastomeric polymer and a stabilizer; wherein the rubber composition has a crosslink density which is within the range of 0.05 to 2.0 x 10-5 mol/g, preferably within the range of 0.1 to 1.8 x 10-5 mol/ g, and wherein the rubber composition has a solubility fraction of less than 90%. The renewed rubber functionalized compositions of the present invention are typically chemically functionalized in a manner in which the functional group is attached to the rubber by covalent bonds, ionic bonds, hydrogen bonds, and/or van der Waals forces. The elastomeric polymer is typically a polydiene rubber, such as natural rubber, polybutadiene rubber, synthetic polyisoprene rubber, styrene-butadiene rubber, or a blend of any or all of said rubbers. The chemically functionalized renewed rubber compositions of the present invention typically have a solubility fraction of less than 50% and more typically of less than less than 30. Said compositions also typically contain aniline.
    [048] In one embodiment of the present invention the renewed functionalized rubber composition is comprised of a micronized rubber powder having a maximum particle size of 75 µm, wherein the micronized rubber powder is comprised of polymer chains containing multiple double bonds in their structures, in which the polymer chains within the micronized rubber powder are cross-linked together with sulfur, and in which the polymer chains within the micronized rubber powder are functionalized with fractions of the structural formula:
    where n represents an integer from 1 to 10, where x represents an integer from 1 to 10, and where y represents an integer from 1 to 10. In many cases n, x, and y will represent an integer from 1 to 6 and will often represent an integer from 1 to 4. In one embodiment of the present invention x and y will represent the integer 1. Said cases the polymeric chains within the powder of micronized rubber will be functionalized with fractions of the structural formula:

    [049]where n represents an integer from 1 to 10 and typically represents an integer from 1 to 4.
    [050] In an embodiment of the present invention the micronized rubber powder is additionally functionalized with fractions of the structural formula:
    where n represents an integer from 1 to 10 and represents an integer from 1 to 6. It is often preferred that n represents an integer from 1 to 4, just as integer 1. n represents 1. Said functionalized renewed rubbers are typically additionally comprised of a stabilizer such as N-cyclohexyl(thio)phthalimide.
    [051] In another embodiment of the present invention the functionalized renewed rubber is comprised of a micronized rubber powder having a maximum particle size of 75 µm, wherein the micronized rubber powder is comprised of polymer chains containing multiple double bonds in their structures, in which the polymer chains within the micronized rubber powder are cross-linked together with sulfur, and in which the polymer chains within the micronized rubber powder are functionalized with fractions of the structural formula:
    where n represents an integer from 1 to 10.
    [052] In a further embodiment of the present invention the functionalized renewed rubber is comprised of a micronized rubber powder having a maximum particle size of 75 µm, wherein the micronized rubber powder is comprised of polymer chains containing multiple double bonds in their structures, in which the polymer chains within the micronized rubber powder are cross-linked together with sulfur, and in which the polymer chains within the micronized rubber powder are functionalized with fractions of the structural formula:
    where n represents an integer from 1 to 10 and more typically represents an integer from 1 to 6. It is generally preferred that n represents an integer from 1 to 4, such as integer 1 .
    [053] The functionalized renewed rubber formulations of the present invention can be in a wide variety of physical forms. For example, in typically used grinding procedures, the renewed rubber formulations will generally be in the form of a slab or sheet. Said sheets or sheets are convenient for use by manufacturers of rubber products in view of the fact that said sheets can be conveniently blended with other rubbers and compounding ingredients such as antidegradants, accelerators, curatives, and the like. However, the renewed rubber composition of the present invention can also be processed into other geometric shapes that are useful for incorporation into rubber and plastic products or articles. For example, in rubber applications it is typically convenient to reuse the rubber formulation in the form of plates, sheets, cubes, or hexahedra. In the plastics industry, it is typically preferred that renewed rubber formulations be presented in the form of pellets, or a powder. In either case, the functionalized rubber refurbishment formulations of the present invention can be processed into a geometric shape of any desired size or shape. For example, the boards of renewed rubber formulations can be cut into cubes, granulated, or ground into a powder. In either case, the renewed rubber formulations will contain the functionalized micronized rubber powder that is formed into the desired size and shape.Examples 1-4
    [054] In this series of experiments, a micronized rubber powder was functionalized according to the present invention to produce the renewed, chemically functionalized rubber composition. In the procedure used, 200 grams of micronized rubber powder having a particle size of 30 mesh was treated in a first stage with the chemicals outlined in Tables 1 and 2. Said composition was allowed to rest overnight. The mixture was then passed through a 2-roll crusher to a gap of 100 microns. The 2-roll crusher cooling system was set to 35°C. The composition was passed through the grinder in several passes until the mixture became homogeneous. Once the composition became homogeneous, CTP was then added in the amounts determined in Tables 1 and 2.
    Table 1. Amounts of functional agent, processing aids, and stabilizer added to Examples 1-3.TBzTDT = Tetrabenzylthiourama disulfide DPG = N,N'-diphenyl guanidine CTP = N-cyclohexyl(thio)phthalimideOil = Cross C-100
    [055] In Example 4, an industrial reference chemistry was investigated. In the procedures used, 200 grams of micronized rubber powder which had a particle size of 30 mesh was added to the chemical mixture just before grinding. The composition of the chemicals added to the MRP is outlined in Table 2. The mixture was then passed through a 2-roll crusher at a gap of 100 microns. The 2-roll crusher cooling system was set at 55°C. The composition was passed through the grinder in several passes until the mixture became homogeneous.
    Table 2. Composition of chemicals added to Example 4.
    [056] Rheology, cure characteristics, and hardness measurements were then taken for each of the samples. The MDR 2000 Rheometer and Mooney viscosity results are shown in Table 3. Sample 1 was a fully cured baseline material; therefore, rheometer results were not obtained. From the results below, those skilled in the art will note that samples 2 and 3 have viscosities that are acceptable compared to sample 4.
    Table 3. Cure & Hardness Rheology Results (A) for Examples 24.
    [057]A crosslink density analysis was also performed on said samples. Table 4 shows the general crosslinking densities as well as the poly-, di-, and mono-sulfide densities for each material. It also reports the combined soluble fraction of each sample extract performed not only in acetone but also in THF.
    Table 4. Analysis of crosslink density and soluble fraction for examples 1-4.
    [058] By plotting the reduction in crosslink density in, relative to the soluble fraction, one can investigate whether carbon-carbon bonds, sulfur-carbon bonds, or sulfur-sulfur bonds are broken during functionali- - ration. The crosslinking split line in the Horikx plot is indicative of more S-C and S-S bonds that are broken while not disturbing the C-C bonds in the polymer structure. The main-chain cleavage line on the Horikx plot is more indicative of the C-C bonds being broken in the polymer structure. See Figure 2 for the Horikx plot in Samples 2-4.
    [059] Said samples were then blended into a control compound comprised of a 70%/30% blend of styrene rubber-butadiene rubber emulsion and polybutadiene rubber that included carbon black as the filler using an internal mixer at one level 20% loading by weight. The processability and compound cure characteristics of these rubber blends were then determined after being cured with a standard sulfur cure pack. The curing rheology and compound properties of said rubber blends are shown in Table 5. From the data below it can be seen that the renewed rubber composition has better processing and properties than MRP alone.
    Table 5. Compound characteristics at 20% loading in control compound for example 2 compared to MRP alone and control compound.Examples 5-23
    [060] In said series of experiments, a micronized rubber powder was functionalized according to the present invention to produce the renewed, chemically functionalized rubber composition. In the procedure used, 200 grams of micronized rubber powder which had a particle size of 80 mesh (except in example 22 which was 40 mesh) were treated in a first stage with the chemicals outlined in Table 6. Said composition was allowed to rest overnight. The mixture was then passed through a 2-roll shredder at a gap of 100 microns. The 2-roll crusher cooling system was set to 35°C. The composition was passed through the grinder in several passes until the mixture became homogeneous. Once the composition became homogeneous, CTP was then added in the amounts determined in Table 6.
    Table 6. Chemical Compositions of Examples 5-23.
    [061] A 2000 MDR was then used to investigate rheology and healing characteristics for each treated sample outlined above. Results for all examples are shown in Table 7.

    Table 7. Rheology & cure data for examples 5-23.
    [062] Said samples were then blended into a control compound comprised of a 70%/30% blend of styrene rubber-butadiene rubber emulsion and polybutadiene rubber that included carbon black as the filler using a non-styrene two-roll mill. only 10% by weight but also 20% by weight of the curing rheology fillers are shown in Table 8. The processability and curing rheology characteristics of said blends were then determined after being cured with a standard curing pack. sulfur and are reported in Table 9.
    [063] Cure rheology for the control compound used in examples 515 is shown in Table 9.
    Table 8. Curing rheology for the control compound used in Examples 5-15

    Table 9. Characteristics of curing rheology at 10 & 20% by weight fillers in control compound for examples 5-15.
    [064]Example 11 was investigated in addition to 10% loading in a 70/30 eSBR/PBR carbon black control compound. Tables 10 & 11 illustrate the cured physical properties obtained for not only the control compound but also the compound containing 10% material after being cured with a standard sulfur cure pack.

    [065]Table 10. Physical properties of the control compound and MRP alone with respect to 10% loading of Example 11.
    Table 11. Continued physical properties of eMRP control compound alone versus 10 wt% filler from Example 11.
    [066]Examples 16-23 were ground mixed at 10 wt% filler in a 70/30 eSBR/PBR carbon black control compound. After being cured with a standard sulfur cure pack, the curing rheology and properties are shown in Table 12.
    Table 12. Cure rheology characteristics and properties for 10% by weight filler of Examples 16-23. Example 24
    [067] In said experiment a micronized rubber powder was functionalized according to the present invention to constitute the renewed rubber composition, chemically functionalized. 200 grams of micronized rubber powder which had a particle size of 80 mesh was treated with 3 phr of MBT and 9.1 phr of oil and allowed to rest overnight. The mixture was then passed through a 2-roll shredder at a gap of 100 microns. The 2-roll crusher cooling system was set to 35°C. The composition was passed through the grinder in several passes until the mixture became homogeneous. The results of rheology and cure are shown in Table 13.

    Table 13. Rheology & cure data for example 24.
    [068] Example 24 was also ground mixed at 10% by weight filler level in a carbon black control compound comprised of a 70%/30% blend of styrene-butadiene rubber and polybutadiene rubber emulsion. at the. After being cured with a standard sulfur cure pack the curing rheology characteristics of said rubber formulation were determined and are reported in Table 14.
    Table 14. Characteristics of Cure Rheology for 10 wt% filler of Example 24 in Control Compound. Examples 25-29
    [069] In said series of experiments, a micronized rubber powder was functionalized according to the present invention to produce the renewed, chemically functionalized rubber composition. In the procedure used, 200 grams of micronized rubber powder having a particle size of 80 mesh was treated in a first stage with the chemical composition outlined in Table 15. Said composition was allowed to rest overnight. The mixture was then passed through the 2-roll shredder at a gap of 100 microns. The 2-roll crusher cooling system was set to 35°C. The composition was passed through the grinder in several passes until the mixture became homogeneous. Once the composition became homogeneous, a stabilizer was then added in the amounts determined in Table 15.

    Table 15. Chemical Compositions of Examples 25-29.
    [070] A 2000 MDR was then used to test the characteristics of the curing rheology for each of these samples. Table 16 illustrates the results.
    Table 16. Characteristics of curing rheology for examples 25-29.
    [071] When reviewing and comparing the information provided in Tables 15 and 16 it is apparent that the use of stearic acid and zinc oxide does not provide a beneficial result. Therefore, the method of the present invention and the compositions so produced can be prepared without using stearic acid or zinc oxide with excellent results still being obtained. The renewed and functionalized rubber compositions of the present invention therefore will normally not contain zinc oxide or long chain fatty acids such as stearic acid.
    [072] The renewed rubber composition of the present invention can be blended with a wide variety of other elastomers and elastomeric compounds to make useful rubber formulations that can be used in numerous applications in rubber products. Said products include all types of tires including luxury car tyres, all season car tyres, high performance car tyres, racing car tyres, winter tyres, off-road tyres, agricultural tyres, tires for mining, light truck tires, medium weight truck tires, heavy duty truck tires, earth removal equipment tires, aircraft tires, bicycle tires, motorcycle tires, forklift tires, solid application tires domestic and industrial. The renewed rubber compositions of the present invention can also be used in a retread formulation to actually retread any type of tire such as truck tires, aircraft tires, earth removal equipment tires and automobile tires. The renewed rubber compositions of the present invention can also be used in the production of power transmission belts, conveyor belts, hoses, O-rings, rings, gaskets, military bands, industrial, agricultural and recreational vehicles, including commercial vehicles. snow, windshield wiper blades, air springs, industrial vibration dampers. The renewed rubber compositions of the present invention can also be used in the modification of plastics and as a processing aid for fillers including but not limited to clay, silica, carbon black, graphene, graphite and nanostructures (including carbon nanotubes) , concrete and asphalt modification for high performance asphalt applications. They can also be used in the fabrication of a large structure of building materials such as roofing, insulation, waterproof materials, and pond linings.
    [073] With the use of the renewed rubber formulations of the present invention in the production of useful rubber products, it is typically blended with one or more other elastomeric materials at a level ranging from 1 phr to 99 phr. It will typically be incorporated in such products in a range of 3 phr to 50 phr and more typically it will be incorporated in a range of 5 phr to 40 phr. For example, the renewed rubber formulations of the present invention can be incorporated into a rubber polymer at a level that is within the range of 10 phr to 30 phr.
    [074] The renewed rubber formulations of the present invention can be included in blends with natural rubber, synthetic polyisoprene rubber, styrene butadiene rubber emulsion, styrene butadiene rubber solution, polybutadiene cis 1.4-top rubber having a cis isomer content greater than 96%, medium polybutadiene vinyl rubber, lower polybutadiene vinyl rubber, upper polybutadiene vinyl rubber, upper trans polybutadiene rubber, upper trans styrene butadiene rubber, and α-methylstyrene butadiene rubber styrene isoprene rubber, styrene isoprene butadiene rubber, nitrile rubber, butyl rubber, carboxylated nitrile rubber, halobutyl rubber, ethylene propylene diene monomer rubber (EPDM), ethylene propylene rubber (EPR), hydrogenated nitrile rubber, and various blends thereof. Said blends may contain from 1 to 100 phr of the renewed rubber formulations of the present invention. Said blends can additionally be comprised of conventional reclaimed rubber and also ground tire rubber. The level of conventional reclaimed rubber and crushed tire rubber will typically be in the range of 1.0 phr to 25 phr.
    [075] In tire tread formulations the renewed rubber formulations of the present invention are typically blended with virgin natural rubber, styrene butadiene rubber emulsion, styrene butadiene rubber solution and/or polybutadiene rubber at one level which is within the range of 5 to 50 phr. For example, truck tire tread rubber used in steering tires and guide tires can be a blend of 5 phr to 50 phr of the renewed rubber formulations of the present invention with 5 to 80 phr virgin natural rubber and 5 phr to 80 phr styrene butadiene rubber emulsion. Truck tire tread rubber used in tow truck tires can be comprised of a simple blend of 5 phr to 50 phr of the renewed rubber formulations of the present invention and 50 phr to 95 phr of virgin natural rubber.
    [076] Rubber formulations containing the renewed rubber of the present invention can be compounded with reinforced silica to improve the processability and to improve the rolling resistance of tires produced with them. However, the renewed rubber of the present invention can be reinforced with conventional fillers of carbon black, starch, clay, lignin, modified lignin, graphene, modified graphene, carbon nanotubes, silica beads, talc, crosslinked gel and the like.
    [077] The renewed rubber formulations of the present invention can be used in fact in any component of a tire, including the tread, the side, the belt, the tarpaulin, the apex, the bead, the monofil nylon fabric - ment, the inner lining cloth, the surface coating, the under-tread, the base, the shoulder edge, the belt edge, the tread padding, the tread fins, the tread portion skirt of the shoulder member, the padding of the layer, the lashing rubber, the edge strap, and the like. In rubber tread formulations for automotive and light truck applications, the renewed rubber will typically be blended with superior cis PBD, SBR solution, and/or SBR emulsion. Said tread rubber compounds will typically contain from 5 to 50 phr of renewed rubber, 40 to 80 phr of SBR emulsion or solution, and 5 to 50 phr of cis-higher polybutadiene rubber. In tire side formulations the renewed rubber will typically be blended with natural rubber and polybutadiene rubber. In liner formulations the renewed rubber will typically be blended with natural rubber, butyl rubber or halobutyl rubber.
    [078] A tire tread compound produced with the renewed rubber formulations of the present invention may include, as a specific example, 40 phr of styrene butadiene rubber emulsion having a bound styrene content of 19%, a viscosity of Mooney of 50-65 and a glass transition temperature of -55°C, 67.50 phr of carbon black masterbatch, 30 phr of superior cis polybutadiene rubber, 22.73 phr of the renewed rubber formulations of the present invention, 5 phr process oil, 1 phr 40MS plasticizer, 3 phr adhesion promoting phenolic resin, 42.50 phr N339 carbon black, 2.24 phr N-(1,3-dimethylbutyl) antidegradant -N'-phenyl-p-phenylenediamine, 1.12 phr of 2,2,4-trimethyl-1,2-dihydroquinoline, 2.24 phr of microcrystalline wax/paraffin wax blend, 3.53 phr of oxide dispersion zinc (85% ZnO), 2 phr stearic acid, 1 phr N-tert-butyl-2-benzothioazolasulfenamide pellets, 0.10 phr diphenyl gu pellets anidine, 2.75 phr of sulfur dispersion (80% sulfur), and 0.10 phr of N-cyclohexylthio phthalimide retardant.
    [079] A specific example of an undertread tire base or formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 70 phr of natural rubber, 30 phr of superior cis polybutadiene rubber , 17.46 phr of the renewed rubber formulations of the present invention, 2 phr process oil (PAH < 3%), 45 phr N660 carbon black, 2 phr 2,2,4-trimethyl-1.2 antidegradant -dihydroquinoline, 3 phr of zinc oxide, 1.50 phr of stearic acid, 1.50 phr of N-tert-butyl-2-benzothioazolesulfenamide accelerator pellets, 2 phr of sulfur, and 0.20 phr of N-retardant (cyclohexylthio)phthalimide.
    [080] A specific example of a steel belt coating formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 60 phr of natural rubber, 40 phr of superior cis polybutadiene rubber, 23, 24 phr of the renewed rubber formulations of the present invention, 8 phr of process oil, 2 phr of adhesion promoting resin alkyl phenol formaldehyde novalak, 75 phr of N326 carbon black, 2 phr of 2,2,4-trimethyl-antidegradant 1,2-dihydroquinoline, 3 phr hexamethyloxymethyl melamine resin, 8 phr reinforcing resin, 3 phr zinc oxide, 1.50 phr stearic acid, 1.50 phr N-tert accelerator pellets -butyl-2-benzothioazolesulfenamide, 5 phr of sulfur, and 0.20 phr of N-(cyclohexylthio)phthalimide retardant.
    [081] A specific example of a shoulder edge or padding formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 100 phr of natural rubber, 19.13 phr of the renewed rubber formulations of present invention, 5 phr process oil, 55 phr N660 carbon black, 1 phr 2,2,4-trimethyl-1,2-dihydroquinoline antidegradant, 5 phr zinc oxide, 2.50 phr stearic acid, 0.75 phr of N-cyclohexyl-2-benzothiazole sulfenamide accelerator (CBS), and 3 phr of sulfur.
    [082] A specific example of a belt edge formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 100 phr of natural rubber, 21.06 phr of the renewed rubber formulations of the present invention, 2 phr process oil (PAH < 3%), 62 phr N326 carbon black, 2 phr 2,2,4-trimethyl-1,2-dihydroquinoline antidegradant, 6.70 phr hexamethyloxymethyl-melamine resin, 2.50 phr of B-20-M booster resin, 7 phr of zinc oxide, 1 phr of stearic acid, 0.75 phr of benzothiazil-2-dicyclohexyl sulfonamide accelerator (DCBS), and 5.60 phr of OT20 oil ( PAH < 3%).
    [083] A specific example of a tread padding formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 100 phr of natural rubber, 21.19 phr of the renewed rubber formulations of the present invention, 8 phr of process oil (PAH < 3%), 4 phr of novalak alkyl phenol formaldehyde adhesion promoter resin, 60 phr of N326 carbon black, 1 phr of 2,2,4-trimethyl-1 antidegradant ,2-dihydroquinoline, 2.50 phr hexamethyloxymethyl melamine resin, 1.25 phr B-20-M booster resin, 7 phr zinc oxide, 1 phr stearic acid, 0.50 phr benzothiazil-2-dicyclohexyl accelerator sulfonamide, and 5.50 phr of OT20 oil (PAH < 3%).
    [084] A specific example of a tread fin formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 50 phr of natural rubber, 50 phr of superior cis polybutadiene rubber, 22, 17 phr of the renewed rubber formulations of the present invention, 16 phr of process oil, 2 phr of low molecular weight polyethylene wax, 5 phr of adhesion promoting resin alkyl phenol formaldehyde novalak, 60 phr of N660 carbon black, 4 .50 phr of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) antidegradant, 2 phr of 2,2,4-trimethyl-1,2-dihydroquinoline antidegradant, 2.50 phr of a blend of microcrystalline wax and paraffin wax, 3 phr of zinc oxide, 2 phr of stearic acid, 0.50 phr of N-tert-butyl-2-benzothioazolesulfenamide accelerator pellets, and 2 phr of sulfur.
    [085] A specific example of a shell formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 50 phr of natural rubber, 50 phr of superior cis polybutadiene rubber, 20.43 phr of the formulations of renewed rubber of the present invention, 15 phr process oil, 3 phr of novalak alkyl phenol formaldehyde adhesion promoter resin, 50 phr of N660 carbon black, 4 phr of N-(1,3-dimethylbutyl)-antidegradant N'-phenyl-p-phenylenediamine (6PPD), 2 phr of 2,2,4-trimethyl-1,2-dihydroquinoline antidegradant, 2.50 phr of microcrystalline wax and paraffin wax blend, 3 phr of zinc oxide, 2 phr of stearic acid, 0.50 phr of N-tert-butyl-2-benzothioazolesulfenamide accelerator pellets, and 2 phr of sulfur.
    [086] A specific example of a canvas quilting formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 60 phr natural rubber, 40 phr styrene-butadiene rubber emulsion, 19.60 phr das renewed rubber formulations of the present invention, 10 phr process oil, 3 phr alkyl phenol formaldehyde novalak adhesion promoting resin, 55 phr N660 carbon black, 1 phr 2,2,4-trimethyl-1 antidegradant ,2-dihydroquinoline, 3 phr zinc oxide, 1 phr stearic acid, 0.80 phr 2,2'-dibenzothiazil disulfide, 0.10 phr diphenyl guanadine accelerator, and 2.50 phr sulfur.
    [087] A specific example of a rim support formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 40 phr of natural rubber, 15 phr of styrene-butadiene rubber emulsion, 45 phr of high cis polybutadiene rubber, 22.21 phr of the renewed rubber formulations of the present invention, 15 phr of process oil, 2 phr of dark hydrocarbon resins, 3 phr of novalak alkyl phenol formaldehyde adhesion promoting resin, 85 phr of N351 carbon black, 3 phr of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) antidegradant, 1 phr of 2,2,4-trimethyl-1,2-dihydroquinoline antidegradant, 2 phr microcrystalline wax blend and paraffin wax blend, 3 phr zinc oxide, 2 phr stearic acid, 0.50 phr N-tert-butyl-2-benzothioazolesulfenamide accelerator pellets, 1 phr of benzothiazil-2-dicyclohexyl sulfenamide accelerator, 2.25 phr of sulfur and 0.25 phr of N-(cycloh) retardant exylthio) phthalimide.
    [088] A specific example of a monofilament nylon fabric rubber formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 50 phr natural rubber, 25 phr styrene-butadiene rubber emulsion , 25 phr of high cis polybutadiene rubber, 23.49 phr of the renewed rubber formulations of the present invention, 10 phr of process oil, 2 phr of dark hydrocarbon resins, 2 phr of adhesion promoting resin alkyl phenol formaldehyde novalak, 85 phr N326 carbon black, 2 phr 2,2,4-trimethyl-1,2-dihydroquinoline antidegradant, 1 phr microcrystalline wax blend and paraffin wax blend, 3 phr zinc oxide, 2 phr of stearic acid, 1.25 phr of N-tert-butyl-2-benzothioazolesulfenamide accelerator pellets, 3 phr of sulfur and 0.2 phr of N-(cyclohexylthio)phthalimide retarder.
    [089] A specific example of a formulation for the filler produced with the renewed rubber formulations of the present invention may include, as a specific example, 65 phr natural rubber, 35 phr high cis polybutadiene rubber, 24.99 phr das renew rubber formulations of the present invention, 10 phr process oil, 4 phr alkyl phenol formaldehyde novalak adhesion promoting resin, 80 phr N326 carbon black, 2 phr 2,2,4-trimethyl-1,2 antidegradant -dihydroquinoline, 3.5 phr hexamethyl oxymethyl melamine resin, 10 phr reinforcing resin, 5 phr zinc oxide, 2.50 phr stearic acid, 1.50 phr N-tert-butyl-2-accelerator pellets benzothioazolesulfenamide, 6.25 phr of OT20 oil, and 0.25 phr of N-(cyclohexylthio)phthalimide retardant.
    [090] A specific example of a liner formulation produced with the renewed rubber formulations of the present invention may include, as a specific example, 100 phr of chlorobutyl rubber, 24.13 phr of the renewed rubber formulations of the present invention, 8 phr process oil, 10 phr dark hydrocarbon resins, 4 phr alkyl phenol formaldehyde novalak adhesion promoter resin, 60 phr N660 carbon black, 30 phr clay, .15 phr magnesium oxide, 1 phr of zinc oxide, 2 phr of stearic acid, 1.50 phr of 2,2'-debenzothiazile disulfide, and 3 phr of sulfur.
    [091] In this series of experiments a conventional compound rubber for tire tread (Example 30) was prepared using 10% natural micronized rubber powder of 80 mesh. In the production of said conventional tread rubber formulation, the micronized natural rubber was blended with 75 phr of styrene-butadiene rubber solution and 25 phr of 1,4-superior cis polybutadiene rubber and cured with a conventional sulfur cure pack. In this series of experiments another tire tread rubber formulation (Example 31) was produced by replacing the chemically functionalized renewed natural rubber composition at 10% load level. Both cured rubber formulations produced in the above experiment were tested for abrasion loss using a Zwick Rotary Drum Abrader (Din Abrasion) Method A ASTM D 5963. The rubber formulation produced using conventional micronized natural rubber showed an abrasion loss of 105 mm3 (compared to a conventional standard according to the procedure). However, the second rubber formulation produced using the chemically functionalized renewed natural rubber composition showed a much better abrasion loss of only 62 mm3.Examples 32-33
    [092] In this series of experiments a tire tread rubber compound (Example 32) was prepared using 10% styrene-butadiene rubber emulsion (ESBR). In this series of experiments another tire tread rubber formulation (Example 33) was produced by replacing the renewed chemically functionalized ESBR composition at 10% load level. Both rubber formulations produced in the above experiment were tested for abrasion loss using the Zwick Rotary Drum Abrader (Din Abrasion) Method A ASTM D 5963. The rubber formulation produced using 10% ESBR solution showed an abrasion loss of 87 mm3 (compared to a conventional standard according to the procedure). However, the second rubber formulation produced using the chemically functionalized renewed ESBR composition showed a much better abrasion loss of only 69 mm3.
    [093] Although certain representative embodiments and details have been shown for the purpose of illustrating the subject of the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made to it without departing from the spirit and scope of the present invention .
    权利要求:
    Claims (14)
    [0001]
    1. Renewed functionalized rubber composition CHARACTERIZED by the fact that it is comprised of an elastomeric polymer and a stabilizer; wherein the rubber composition has a crosslink density that is within the range of 0.05 x 10-5 mol/g to 2.0 x 10-5 mol/g, and wherein the rubber composition has a solubility fraction less than 90%, and where the stabilizer is a vulcanization retarding agent.
    [0002]
    2. Renewed functionalized rubber composition according to claim 1, CHARACTERIZED by the fact that the elastomeric polymer is a diene rubber, wherein the rubber composition includes a soluble rubber fraction, wherein the elastomeric polymer has a fraction of solubility of less than 30%, and wherein the soluble rubber is functionalized with functional groups which are covalently linked to the rubber polymer chain by one or more sulfur atoms.
    [0003]
    3. Renewed functionalized rubber composition, according to claim 1 or 2, CHARACTERIZED by the fact that said composition further comprises aniline.
    [0004]
    4. Renewed functionalized rubber composition according to any one of claims 1 to 3, CHARACTERIZED by the fact that the elastomeric polymer is recycled tire rubber which is derived from tire sidewalls, inner tire linings or tire treads. tires.
    [0005]
    5. Renewed functionalized rubber composition, according to any one of claims 1 to 4, CHARACTERIZED by the fact that the stabilizer is N-cyclohexyl(thio)phthalimide.
    [0006]
    6. Renewed functionalized rubber composition according to any one of claims 1 to 5, CHARACTERIZED by the fact that the renewed functionalized rubber composition is in the form of a sheet, a plate, a hexahedron, a pellet or powder.
    [0007]
    7. Renewed functionalized rubber composition according to any one of claims 1 to 6, CHARACTERIZED by the fact that the rubber composition has a crosslink density that is within the range of 0.1 x 10-5 mol/g 1 .8 x 10-5 mol/g.
    [0008]
    8. Renewed functionalized rubber composition according to any one of claims 1 to 7, CHARACTERIZED by the fact that the renewed rubber composition is predominantly styrene-butadiene rubber.
    [0009]
    9. Renewed functionalized rubber composition according to any one of claims 1 to 8, CHARACTERIZED by the fact that the renewed rubber composition is derived from tire treads that are comprised of a cis-1 rubber blend, Higher 4-polybutadiene and one or more additional rubbers, wherein the higher cis-1,4-polybutadiene rubber has a cis microstructure content of at least 95%.
    [0010]
    10. Method for manufacturing the renewed functionalized rubber composition, as defined in claim 1, CHARACTERIZED by the fact that said method is defined by the steps of (1) blending a micronized rubber powder with a processing aid and an agent functionalization to produce a blended blend; (2) processing the blend mixture under conditions of high shear and low temperature to produce the reacted mixture; (3) adding the stabilizer to the reacted mixture to produce the renewed rubber, wherein the stabilizer is a vulcanization retarding agent.
    [0011]
    11. Method according to claim 10, CHARACTERIZED by the fact that processing under high shear conditions is generated in step (2) in a 2-roll mill.
    [0012]
    12. Method according to claim 10 or 11, CHARACTERIZED by the fact that the functionalizing agent is a compound selected from the group consisting of alkyl thiourama sulfides, aryl thiourama sulfides, heterocyclic thiourama sulfides, thiourama disulfides , thiouram polysulfides, thiouram disulfides, thiouram multisulfides, tetrabenzylthiouram disulfides, cyclohexyl sulfonamides, t-butyl sulfonamides, tetraalkylthiourama disulfides, tetramethylthiouram disulfides, tetramethylthiouram disulfides, tetramethylthiouram disulfides, and tetramethylthiouram disulfides .
    [0013]
    13. Method according to any one of claims 10 to 12, CHARACTERIZED by the fact that a guanidine compound is blended into the micronized rubber powder in step (1) and in which the guanidine compound is selected from the group that consists of alkyl guanidines, aryl guanidines and heterocyclic guanidines.
    [0014]
    14. Method, according to any one of claims 10 to 13, CHARACTERIZED by the fact that N,N'-diphenyl guanidine is blended into the micronized rubber powder in step (1).
    类似技术:
    公开号 | 公开日 | 专利标题
    BR102015009848B1|2021-06-01|RENEWED FUNCTIONALIZED RUBBER COMPOSITIONS AND METHOD FOR MANUFACTURING IT
    US9598564B2|2017-03-21|Chemically functionalized renewed rubber composition
    Adhikari et al.2000|Reclamation and recycling of waste rubber
    US9815974B2|2017-11-14|Recycled micronized rubber formulation having improved abrasion resistance
    TWI564322B|2017-01-01|Improvements in and relating to the recycling of natural and synthetic rubbers
    US6265454B1|2001-07-24|Rubber compositions containing ground tire rubber
    De et al.2011|Processing and material characteristics of a reclaimed ground rubber tire reinforced styrene butadiene rubber
    EP1434817A1|2004-07-07|Recycled rubber processing and performance enhancement
    CA2307973A1|2000-12-09|Surface devulcanization of cured rubber crumb
    US9714325B2|2017-07-25|Method for producing rubber wet masterbatch, rubber wet masterbatch, and rubber composition including rubber wet masterbatch
    CN101323679A|2008-12-17|Rubber composition for carcass ply or band and pneumatic tire using the same
    JP6800869B2|2020-12-16|Rubber composition and tires
    JP4338365B2|2009-10-07|Rubber composition for tire
    NL2024936B1|2021-09-16|A rubber formulation
    Dierkes et al.2021|Regeneration and devulcanization
    Hong2001|The application of powerful ultrasound to devulcanization of rubbers and compatibilization of polymer blends
    Jacob et al.2005|Powdered rubber waste in rubber compounds
    Rakhman2021|Improvement of Workability and Integrity for Ambient Ground Rubber as Elastomer Alternative: Direct Incorporation and Functionalization
    JPH10310662A|1998-11-24|Method for reclaiming composite vulcanized rubber
    CN108473725A|2018-08-31|Rubber composition, crawler belt rubber composition, decorative pattern block portion rubber and rubber belt track
    CN101326227A|2008-12-17|Improved and related recovery natural and synthetic rubber
    Isayev et al.2005|Tire Materials: Recovery and Re-use
    Kamau2013|Recycling of rubber chips into composite elastomers
    JP2006213787A|2006-08-17|Rubber composition using reclaimed rubber
    Budinski-Simendić et al.0|THE VULCANIZATION PROPERTIES OF HYBRID ELASTOMERIC MATERIALS BASED ON WASTE RUBBER POWDER
    同族专利:
    公开号 | 公开日
    BR102015009848A2|2015-10-27|
    US9574069B2|2017-02-21|
    KR20150125603A|2015-11-09|
    JP2015212377A|2015-11-26|
    US10227421B2|2019-03-12|
    US20170114155A1|2017-04-27|
    EP2947116A3|2016-08-31|
    EP2947116A2|2015-11-25|
    US20150315363A1|2015-11-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2867540A|1955-12-30|1959-01-06|Monsanto Chemicals|Modified carbon black product and process|
    US3884285A|1971-10-08|1975-05-20|Ppg Industries Inc|Abrasion-resistant rubber compositions|
    US3994742A|1973-10-11|1976-11-30|Ppg Industries, Inc.|Rubber additive of silica and organic coupling agent|
    US4104205A|1976-01-06|1978-08-01|The Goodyear Tire & Rubber Company|Microwave devulcanization of rubber|
    JPS52100593A|1976-02-18|1977-08-23|Shigeaki Kawabata|Softening and regenerating method of vulcanized rubber|
    JPH0461022B2|1983-07-22|1992-09-29|Toyo Tire & Rubber Co|
    US4954382A|1988-11-01|1990-09-04|American Cyanamid Company|Interleaf layer in fiber reinforced resin laminate composites|
    US4861842A|1988-12-28|1989-08-29|The Goodyear Tire & Rubber Company|Cure system for sulfur vulcanizable rubber|
    EP0389978A3|1989-03-28|1991-02-27|Cytec Technology Corp.|Composite panel|
    DE4006131A1|1990-02-27|1991-08-29|Bayer Ag|Novolak-like phenol! resin used as reinforcing resin for rubber|
    US5238725A|1990-12-21|1993-08-24|E. I. Du Pont De Nemours And Company|Method for forming a structural panel with decorative facing and product thereof|
    US5284625A|1992-06-22|1994-02-08|The University Of Akron|Continuous ultrasonic devulcanization of vulcanized elastomers|
    US5294663A|1992-08-28|1994-03-15|General Tire, Inc.|Tire tread compositions of isoprene-styrene/butadiene emulsion polymers with 1,4 cis-polyisoprene rubber|
    US5770632A|1994-06-25|1998-06-23|Sekhar; Balachandra Chakkinggal|Reclaiming of elastomeric materials|
    JPH0841107A|1994-06-25|1996-02-13|Sti K Polymers Sdn Bhd|Method for reclaiming used vulcanized elastomeric material and composition for reclamation|
    US5602186A|1995-10-27|1997-02-11|Exxon Research And Engineering Company|Rubber devulcanization process|
    US5744552A|1996-09-16|1998-04-28|The Goodyear Tire & Rubber Company|Sulfur vulcanizable rubber contining sodium thiosulfate pentahydrate|
    US7704552B2|1999-08-19|2010-04-27|Ppg Industries Ohio, Inc.|Process for producing chemically treated amorphous precipitated silica|
    IL132422D0|1999-10-17|2001-03-19|Levgum Ltd|Modifier for devulcanization of cured elastomers mainly vulcanized rubber and method for devulcanization by means of this modifier|
    CA2426598C|1999-10-22|2010-05-25|Peter Alsdorf|Devulcanization product consisting of scrap rubber, a devulcanization compound, a method for producing same, the reuse thereof in fresh mixtures and the use thereof for producing injection molded parts|
    US6548560B1|2000-03-29|2003-04-15|The Goodyear Tire & Rubber Company|Process for devulcanization of cured rubbers|
    US20020121714A1|2001-03-01|2002-09-05|Preisler Darius J.|Automobile interior components that satisfy impact standards and a method for manufacturing the same|
    US6387966B1|2001-05-21|2002-05-14|Vadim Goldshtein|Method and composition for devulcanization of waste rubber|
    US7445170B2|2003-11-17|2008-11-04|Lehigh Technologies Llc|Process and apparatus for manufacturing crumb and powder rubber|
    JP2007039585A|2005-08-04|2007-02-15|Sumitomo Rubber Ind Ltd|Rubber composition and pneumatic tire using the same|
    AU2006252328A1|2006-07-13|2008-02-07|Elastomer Technologies Ltd.|Improvements in and relating to the recycling of natural and synthetic rubbers|
    US7861958B2|2007-04-05|2011-01-04|Lehigh Technologies, Inc.|Conical-shaped impact mill|
    JP5242150B2|2007-12-21|2013-07-24|ウィンテックポリマー株式会社|Composite molded body|
    WO2010050242A1|2008-10-31|2010-05-06|キョーラク株式会社|Sandwich panel, method of forming core material for sandwich panel, and method of forming sandwich panel|
    DE102009060440A1|2009-12-22|2011-06-30|nora systems GmbH, 69469|Process for producing a sheet-like rubber coating and sheet-like rubber coating|
    JP5581840B2|2010-06-22|2014-09-03|横浜ゴム株式会社|Rubber composition for tire tread and tire|
    WO2012170932A1|2011-06-08|2012-12-13|Lehigh Technologies, Inc.|Elastomeric compositions comprising reclaimed vulcanized elastomer particles of broad size distribution and chemically modified vulcanized elastomer particles|
    JP6008479B2|2011-08-19|2016-10-19|株式会社ブリヂストン|Tire, manufacturing method thereof, and rubber member for repair used in manufacturing method of tire|
    MY170049A|2012-09-12|2019-06-28|Sekhar Res Innovations Sdn Bhd|A method for producing devulcanized rubber and an apparatus therefor|
    US20140088258A1|2012-09-25|2014-03-27|Lehigh Technologies, Inc.|Elastomeric compositions comprising reclaimed vulcanized elastomer particles and improved methods of manufacture thereof|
    EP2914635B1|2012-11-02|2020-06-24|Lehigh Technologies, Inc.|Methods of functionalizing reclaimed elastomer material and compositions comprising the same|
    US9573024B2|2013-12-31|2017-02-21|Nike, Inc.|3D printed golf ball core|
    US9574069B2|2014-04-30|2017-02-21|Lehigh Technologies, Inc.|Chemically functionalized renewed rubber composition|
    US9598564B2|2014-04-30|2017-03-21|Lehigh Technologies, Inc.|Chemically functionalized renewed rubber composition|US9598564B2|2014-04-30|2017-03-21|Lehigh Technologies, Inc.|Chemically functionalized renewed rubber composition|
    US9574069B2|2014-04-30|2017-02-21|Lehigh Technologies, Inc.|Chemically functionalized renewed rubber composition|
    US9815974B2|2015-01-19|2017-11-14|Lehigh Technologies, Inc.|Recycled micronized rubber formulation having improved abrasion resistance|
    CN105949503B|2016-05-27|2019-08-09|徐州工业职业技术学院|A kind of environment-friendly type active hydrogenation butadiene-acrylonitrile-rubber vulcanized rubber powder and preparation method thereof|
    WO2018125987A1|2016-12-29|2018-07-05|Appia, Llc|Method of recycling rubber|
    IL252542A|2017-05-28|2019-06-30|Tyrec Ltd|Method for producing recycled thermoplastic rubber masterbatch with improved green strength and tack|
    JP6915431B2|2017-07-31|2021-08-04|横浜ゴム株式会社|Rubber composition for tires|
    CN109206661A|2018-08-15|2019-01-15|四川省隆昌海燕橡胶有限公司|A kind of tasteless high-intensitive reclaimed rubber|
    CN110258111B|2019-06-27|2020-07-14|四川大学|Preparation method of modified waste collagen fiber and application of modified waste collagen fiber in improving mechanical property and self-cleaning property of rubber|
    EP3769972A1|2019-07-22|2021-01-27|Continental Reifen Deutschland GmbH|Sulphur-crosslinked rubber mixture and vehicle tyre|
    JP6881627B1|2020-02-12|2021-06-02|住友ゴム工業株式会社|tire|
    法律状态:
    2015-10-27| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-05-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-08| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/04/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201461986696P| true| 2014-04-30|2014-04-30|
    US61/986,696|2014-04-30|
    US201462063801P| true| 2014-10-14|2014-10-14|
    US62/063,801|2014-10-14|
    US201562105024P| true| 2015-01-19|2015-01-19|
    US62/105,024|2015-01-19|
    [返回顶部]