RU2810337C9 - Interpenetrating elastomeric mesh obtained from particles of crushed tire rubber - Google Patents

Abstract

FIELD: methods for processing tire rubber.

SUBSTANCE: heterogeneous rubber-based matrix is proposed for production of rubber-containing products, containing an interpenetrating network of two or more elastomers, wherein said network contains sulphur-bridged, rearranged intertwined layered structures, the average distance between which is from 10 nm to 5 mcm, with each layered structure containing one of two or more elastomers selected from the group consisting of raw natural rubber, styrene-butadiene rubber, isobutylene-isoprene rubber and elastomer obtained from ground tire rubber. Sheets containing the specified matrix and layered structures made from them are also proposed.

EFFECT: proposed heterogeneous matrix is suitable for creating sheets and layered structures from them, applicable in various commercial rubber products.

12 cl, 8 dwg, 2 tbl

Description

Any and all claims of priority addressed in the application information sheet, or any amendment therein, are hereby incorporated by reference in accordance with 37 CFR 1.57. This patent application claims priority to U.S. Provisional Patent Application No. 62/489,878, filed April 25, 2017, U.S. Provisional Patent Application No. 62/541,610, filed Aug. 4, 2017, U.S. Provisional Patent Application No. 62/569,374, filed Oct. 5, 2017, U.S. Provisional Patent Application No. 62/613,744 filed Jan. 4, 2018, and U.S. Provisional Patent Application No. 62/621,465 filed Jan. 24, 2018. Each of the listed patent applications is incorporated herein by reference in its entirety, and thus each of the listed applications expressly forms a part of this specification.

TECHNICAL FIELD

Crumb rubber obtained from scrap tires is subjected to a process involving sulfide metathesis caused by phase reticulation. In this process, a reactive component is used that interferes with sulfur bonds. The resulting interlocking substitution rubber exhibits properties similar to those of the original pre-granulated composite rubber structure or other polymeric materials and is suitable for use in new tires, engineered rubber products, and rubber asphalt for use in waterproofing and paving applications.

BACKGROUND OF THE ART

In 2015, U.S. waste tire sales accounted for 87.9% by weight in end-use markets. The total volume of waste tires consumed in end-use markets in the United States was approximately 3,551 thousand tons of tires. The RMA (Rubber Manufacturers Association) estimates that approximately 4,038 thousand tons of tires were produced in the United States in 2015. Of this, 25.8% was used for the production of shredded rubber, 48.6% for the production of tire fuel, 11.4% was disposed of on land, 7.0% was used in civil engineering and 7.1% was spent for miscellaneous purposes. (0.7% in electric arc furnaces, 1.3% in reclamation systems, 2.6% was exported and 2.6% was spent on other purposes). In 1990, only eleven percent of tires were used per tire. The positive results observed in end-use markets in 2015 were primarily the result of high TDF (tire derived fuel) usage and lower exports. In the long term, the need to expand all economically viable and environmentally sound markets for waste tires is still a major challenge. Scrap tires were consumed in a variety of scrap tire markets, including tire fuel production, civil engineering, and shredded rubber industries. The remaining tires produced each year were consumed by other smaller markets and legal landfills.

Major markets for waste tires include tire-derived fuel, shredded rubber, civil construction and other markets. Tire fuel industries use waste tires as a cleaner and more economical alternative to coal as fuel in cement kilns, pulp and paper mills, and industrial and domestic boilers. The shredded rubber industries use approximately 1,020 thousand tons of waste tires, or more than 25 percent of the volume of waste tires generated annually. Shredded rubber is produced by grinding waste tires into pieces of a specific size. Industries that use shredded rubber include new rubber products, playground and other sports field surfacing, and rubber modified asphalt. Shredded rubber also includes larger pieces of rubber used as mulch in artificial landscaping and cushioning bulk material for playgrounds. The playground and mulch market was the most dynamic segment of the shredded rubber market during this period. The asphalt market uses shredded rubber to modify the asphalt binder used in paving, resulting in quieter, more durable roads. The civil construction market consumes approximately 274 thousand tons of tires per year, approximately 7.7 percent of the total tires on the market, and consists of tire pieces used in the construction of roads and landfills, septic tank leach pads, alternative intermediate fill and in other construction sectors. There are additional smaller markets for waste tires, which consume approximately 7% of the waste tires generated annually. Such markets include tires used in electric arc furnaces (in steel production), professionally engineered tire briquettes, and products stamped, extruded or die-cut from waste tires. The total amount of tire rubber consumed in shredded rubber markets is approximately 1.36 billion pounds (approximately 0.62 billion kg). The total amount of waste tires destined for these shredded rubber markets is approximately 1.02 million tons (62 million tires). The percentage of total pounds of shredded rubber consumed in the market in 2015 was: athletic field surfacing 25%, playground mulch 22%, molded/extruded products 35%, asphalt 15%, automotive 2%, and export 1% .

Historically, waste tire inventories began to build up around the 1960s and 1970s, when tires were no longer diverted to landfills and recycling markets for them failed. The reserves were susceptible to catastrophic fires, which led to air and water pollution.

The global rubber tire industry is responsible for approximately 99% of the world's end-of-life (EOL) tire waste. Approximately 1.1 billion waste tires are generated annually, which equates to approximately 12 million tons of waste tires. Due to the tough physical properties required of a new tire, tires are a carefully engineered weave of steel and fiber cords with a mineral and carbon infused rubber compound, all cross-linked to produce a highly viscous structure. Resolving an EOL tire down to its original basic elements is a challenging task. Potentially the most valuable component, rubber, is particularly difficult to regenerate due to the vulcanization process to which it is subjected. As a result of EOL, tires that are no longer suitable for vehicle use due to wear or permanent damage are typically either pyrolyzed (for example, to generate energy for use in cement production) or crushed for use as filler (for example, in asphalt road construction). coating, new tires, construction materials or materials used in the creation of artificial landscaping).

BRIEF DESCRIPTION OF THE INVENTION

Although extensive research has been devoted to developing methods for devulcanizing vulcanized rubber, such as tire rubber, a process has not yet been developed to process or convert tire rubber into a commercially viable product with properties similar to those of virgin composite rubber.

The coupled displacement method used to recover, recycle or convert natural rubber or synthetic rubber in used tires and other vulcanized rubber wastes provides a low-cost source of quality natural rubber or synthetic rubber. Such reclaimed materials may have properties similar to or even superior to those of the product from which they are derived. Rubber subjected to the processes described herein is variously referred to herein as "treated rubber", "activated rubber", "interlinked rubber", "PTR rubber", "post reactor ground tire rubber", “rubber obtained from crumb rubber of EOL tires” or the like.

One of the objectives of the methods described herein is to process vulcanized rubber products or other cross-linked rubber-containing products, such as those found in end-of-life (EOL) rubber tires, into a form suitable for use as a raw material in the manufacture of industrial products. , which are typically made from virgin natural rubber that has been vulcanized, such as in the production of new tires or other vulcanized rubber products. Vulcanized rubber subjected to the methods described herein is typically provided in the form of commonly available 30 mesh ground tire rubber particles (GTRP). Such rubber is subjected to a process whereby it is converted into a cross-linked, rearranged fragment of 5 to 10 microns in size, which micro-fragment can be remanufactured as a monolithic macrostructure characterized by an interpenetrating elastomeric network exhibiting physical properties substantially similar to the macrostructural properties of the original rubber EOL tires to reduce particle size to 30 mesh.

To achieve one or more different objectives of the methods described herein, two interdependent, parallel and nearly simultaneous, interacting processing systems are successfully implemented. To ensure the desired end result, process control may optionally include real-time data management and/or post-process analysis of the integration of the micron-sized fragment into the finished product, macrostructure(s).

In the first system, an aqueous chemical solution is provided into which the particle is immersed. The aqueous chemical solution acts to dissociate the sulfur cross-bridge from the side bond of the elastomer in a manner that promotes the formation of pre-nuclei at the side site for subsequent rearrangement and cross-linking. This dissociation allows the sulfide bridge to be largely retained as an intact and bound "tether" on a companion, parallel, non-side chain to which it was originally attached (e.g., during vulcanization).

The second system uses an electromagnetic-mechanical system that deforms the particle under the influence of stress until the subhysteresis deformation threshold is reached. This maximizes the exposure of the aqueous chemical solution to the cross-linking sites of the elastomer so that the chemical from the aqueous chemical solution can operate at picosecond speeds to effect the dissociative displacement described in the first system.

Fully vulcanized GTRP exhibits significant deformation resiliency along all three axes. Such elasticity is observed regardless of whether the external force is a mechanical compressive force, a mechanical tensile force, a mechanical torsional force, or a force of electromagnetic nature. This elasticity manifests itself in the rapid recovery of the dimensions and dielectric ground state(s) of the rubber. Such elastic deformation is the interactive product of the two interdependent processing systems described above, which are faster than the deformation-relaxation cycle, including suitable coordination.

The EU Joint Research Center (JRC) recently published a study on scarce raw materials (CRM) in December 2017, listing 27 materials that are subject to supply disruptions; interruptions that will lead to a significant loss of economic sustainability. Natural rubber (NR) was listed as one of 27 materials. The method proposed herein can provide up to 70% of the disadvantage of natural rubber mentioned in the CRM study.

According to a first aspect, a method for producing modified rubber is provided, comprising: introducing an aqueous suspension containing vulcanized rubber particles and an organometallic compound into an electromechanical reactor configured to create a phase space environment by cavitation so as to cause delamination of the rubber matrix within the vulcanized rubber particles in coordination with the breaking of sulfide bonds.

According to one embodiment of the first aspect, the proposed method additionally includes the reduction of sulfide bonds with the formation of rearranged layered structures cross-linked by sulfur bridges within the matrix.

According to one embodiment of the first aspect, the separation is caused by the fact that part of the hard sulfide bridges of the vulcanized rubber particles at the original methyl carbocation become unbound, while remaining attached to the original allylic carbocation.

According to one embodiment of the first aspect, the organometallic compound comprises a metal with an octahedral molecular geometry.

According to one embodiment of the first aspect, the organometallic compound contains a metal ion selected from the group consisting of Co ²⁺ , Cu ²⁺ , Ni ²⁺ , Zn ²⁺ and Mn ²⁺ .

According to one embodiment of the first aspect, the organometallic compound contains an organic anion as a ligand for the metal ion.

In one embodiment of the first aspect, the organic anion comprises an acetate ion.

In one embodiment of the first aspect, the organometallic compound is copper acetate.

According to one embodiment of the first aspect, the organometallic compound is a metal salt that undergoes a phase transition from a solid to a liquid or vapor state in the temperature range from 100 to 150°C.

In one embodiment of the first aspect, the temperature in the electromechanical reactor is maintained at ambient levels by means of a cooling jacket or cooling coils.

In one embodiment of the first aspect, the particle size of the vulcanized rubber crumb is greater than 200 mesh.

According to a second aspect, an electromechanical reactor is provided, comprising: a rotor having a plurality of slots; and a stator, wherein said electromechanical reactor is configured to create a phase space environment by forming a mixture of entrained air, an organometallic compound and shredded tire rubber particles in a liquid undergoing cavitation.

According to a third aspect, a heterogeneous rubber-based matrix is provided comprising an interpenetrating network of two or more elastomers, wherein said network comprises sulfur-bridged, rearranged interlocking layered structures having an average distance between 10 nm and 5 μm, each layered structure contains one of two or more elastomers.

According to one embodiment of the third aspect, soot particles are dispersed between the layered structures.

According to one embodiment of the third aspect, the two or more elastomers comprise a virgin natural rubber and an elastomer derived from ground tire rubber.

In one embodiment of the third aspect, the two or more elastomers comprise a virgin natural styrene-butadiene/butadiene rubber and an elastomer derived from ground tire rubber.

According to one embodiment of the third aspect, two of the two or more elastomers have different backbone chemical structures.

In one embodiment of the third aspect, two of two or more elastomers having different backbone chemical structures are closely woven and then cross-linked separately from each other.

According to a fourth aspect, there is provided a rubber-based heterogeneous matrix sheet according to the third aspect or any of its embodiments.

According to one embodiment of the fourth aspect, the sheet exhibits anisotropy in the ratio of length tensile strength to width tensile strength, wherein the anisotropy of length tensile strength to width tensile strength is from 1.1:1 to 3:1.

According to a fifth aspect, a layered structure comprising a plurality of sheets is provided according to a fourth embodiment.

According to one embodiment of the fifth aspect, the thickness of each of the sheets is from 10 to 70 microns.

According to one embodiment of the fifth aspect, each of the sheets is obtained by vacuum deposition and stitched to an adjacent sheet.

In one embodiment of the fifth aspect, each of the sheets is oriented at an angle of 30 to 45 degrees to the anisotropic grain of the adjacent sheet.

According to a sixth aspect, a composite structure of ground rubber tires is provided having a non-bonded, reptation internal morphology, wherein a portion of the rigid sulfide bonds contained therein are each bonded at the parent allylic carbocation and unbound at the parent methyl carbocation.

According to a seventh aspect, a vulcanized rubber is provided in which a portion of the rigid sulfide bonds contained therein are each attached to a parent allylic carbocation and unbound at a parent methyl carbocation, and in which a portion of the polymer backbone in the vulcanized rubber is replaced by an acetate moiety.

According to an eighth aspect, there is provided a rubber tire in which 3% by weight to 15% by weight of rubber in the tire is produced by a method substantially described herein.

According to a ninth aspect, there is provided a rubber tire in which from 15% by weight to 100% by weight of the rubber in the tire is produced by a method substantially described herein.

According to a tenth aspect, there is provided a tire tread comprising from 10% by weight to 50% by weight of an interconnected rubber substantially described herein.

According to an eleventh aspect, there is provided a tire sidewall comprising from 10% by weight to 100% by weight of interconnected rubber substantially described herein.

According to a twelfth aspect, there is provided a rubber-asphalt binder containing from 5% by weight to 95% by weight of interconnected rubber substantially described herein.

According to a thirteenth aspect, there is provided an asphalt emulsion containing from 5% by weight to 95% by weight of interconnected rubber substantially as described herein.

According to a fourteenth aspect, there is provided an asphalt roofing material containing from 5% by weight to 95% by weight of interlocking rubber substantially described herein.

According to a fifteenth aspect, an interconnected rubber is provided as substantially described herein.

According to the sixteenth aspect, tire tread, tire sidewall, roofing membrane, high dielectric insulating tape, tank lining, tank lining, trench support, bridge support surface, wire harness winding, self-adhesive wire harness winding, shoe soles, rubber boots, insulating tape are proposed. , foundation waterproofing material, parking garage waterproofing material, hose, belt or casting containing the interlocking rubber product described herein.

Any of the specified features of the embodiment according to the first through sixteenth aspects is applicable to all aspects and embodiments described herein. In addition, any of the listed features of an embodiment according to the first through sixteenth aspects may be independently combined, in whole or in part, with other embodiments described herein in any manner, for example, one, two, or three or more embodiments can be combined in whole or in part. . In addition, any of the features of an embodiment according to the first through sixteenth aspects may be made optional for other aspects or embodiments. Any aspect or embodiment of a method may be implemented by a system or device in accordance with another aspect or embodiment, and any aspect or embodiment of a system or device may be configured to implement a method in accordance with another aspect or embodiment.

DESCRIPTION OF GRAPHIC MATERIALS

In fig. 1 shows an electromechanical reactor environment (EMRE) comprising a rotor 101, a stator 102, and slots/cavitation portals 103 combined to create a ground tire rubber particle (GTRP) slurry flow path 104.

In fig. 2 shows the process for preparing the GTRP slurry for the EMRE shown in FIG. 1, when using the EMRE submersible top 202 in the mixing tank 201.

In fig. 3A shows the process of GTRP passing through a “phase space tunnel” in which differential cyclic, mechanical stress and steric field polarization are applied.

In fig. 3B shows a phase space tunnel 303 between the EMRE rotor 301 and the compression gate 302.

In fig. 3C shows the rapid compression-stretch-decrease effect of GTRP.

In fig. 4A illustrates the cavitation process generated by the EMRE rotor 401 and compression seal 203 as entrained air 406, GTRP 405, and aqueous metal-organic matrix 407 pass through the compression seal.

Fig. 4B contains process adjustable variables to control conditions in the phase space tunnel region.

In fig. 4C is a table listing the controllable variables of the GTRP slurry.

In fig. 4D is a table listing the EMRE process control variables.

In fig. 5A schematically depicts the chemotactic effect of sulfide bridge tethering.

In fig. 5B illustrates the stability of the carbocation.

In fig. 6A provides a brief description of the preparation of a GTRP slurry.

In fig. 6B illustrates the process of forming ligands from an organometallic compound in a method according to one embodiment.

In fig. 7A shows the morphology of ground state vulcanized GTRP, EMRE conditioned GTRP, and regenerated treated rubber interpenetrating elastomeric network.

In fig. 7B is a flow diagram for preparing a monolithic rubber macrostructure containing a regenerated interpenetrating elastomeric network.

In fig. 8A depicts a parallel flow microsynthesis reactor (PCMR).

In fig. 8B shows a compact tube configuration for, for example, a PCMR application.

DETAILED DESCRIPTION OF IMPLEMENTATION OPTIONS

The following description and examples illustrate in detail one embodiment of the present invention. Those skilled in the art will appreciate that there are numerous variations and modifications of the present invention that are included within its scope. Accordingly, the description of one embodiment should not be construed as limiting the scope of the present invention.

Introduction

Under environmental conditions, a particle of approximately 600 μm (30 mesh) end-of-life (EOL) ground tire rubber (GTR) has a cross-section corresponding to either the tread cross-section of an old tire or the sidewall cross-section of a tire, or a combination thereof. In general, such rubber can be characterized as a heterogeneous matrix of an interpenetrating, cross-linked elastomeric network filled with inorganic substances, primarily carbon. Depending on whether it is originally tread or sidewall rubber in origin, the primary entangled elastomers will be natural rubber (NR) or styrene-butadiene/butadiene rubber (BRS-BR), with BR and S-BR typically contained in a higher percentage by weight in the tread for improved wear, while in the sidewall the rubber content is shifted towards NR for improved flex properties. In general, a cross-link can be described as elemental sulfur and/or a coordination compound including sulfur as its main element, for example, a polysulfide chemical compound.

During tire manufacturing, interpenetrating elastomeric networks are formed by sequentially cross-linking a dominant elastomer (NR or S-BR) followed by cross-linking a secondary elastomer such that the secondary elastomer "flexes" to accommodate the already vulcanized primary elastomer with higher strength. This method imparts mechanical characteristics that are retained in the individual GTR particle.

One vehicle tire, after removing the steel and fiber reinforcement, will provide approximately sixteen pounds of recyclable GTR (ground tire rubber), and even more if truck tires are included. More than one billion EOL tires are produced worldwide every year. Approximately 50% is consumed as cheap fuel. Where possible, maximizing the reuse of such raw material for its recognized mechanical properties is a significant challenge, but where such a problem has been solved, recovery rates of up to 200:1 have been recorded when comparing the possible reuse of such raw material in the manufacture of new tires with consumption in the oven due to its heat content.

Notably, recent detailed studies of the environmental benefits of such an inversion of maximum EOL-GTR use predict the possibility of reducing the contribution of atmospheric carbon by an amount equivalent to closing 14 coal-fired power plants (300,000 railcars of coal), or removing six million vehicles from the roads or planting more 62 million acres of forest (approximately 25 million hectares) (equivalent to an area the size of Arizona) for carbon sequestration. Accordingly, one of the objectives of the methods and compositions described herein is to produce GTR particles such that they can be recombined with similar particles or materials to form a monolithic structure that can be integrated into a full range of industrial rubber products manufactured throughout the world. to the world.

A method is provided to achieve the goal of producing, improving and then recombining the GTR particle(s) so that the individual complex heterogeneous cross-linked fragments are incorporated into a newly entangled monolithic structure primarily consisting of the original GTR; with uniform mechanical properties that are at least equivalent to those of the rubber matrix of the whole tire before the granulation process. The achievement of this goal is demonstrated by the final product, which is reintroduced to the market as a raw material for the production of new tires and industrial rubber products.

The macro characteristics of a shredded tire rubber particle can be viewed from the point of view that it is a bit like an egg that has been beaten, and therefore it can never become unbeaten. Likewise, such a particle can be thought of as an old car that has been flattened in a recycling plant so that it can never be straightened out to its original specification. To some extent, both such metaphors have their merits. However, upon closer inspection, a list of unusual mechanical properties and conditions becomes apparent which, if exploited, provide the opportunity to extract such a complex resource in a commercial and technically viable manner; resulting in complete restoration of the resource.

In GTR, the properties and conditions for this capability include the following. There is a significant supply of unlinked eight-membered sulfur rings. Previous byproducts of the accelerator chemical reactions were decomposed so they could be weakened and would not interfere with further cross-linking processes. The existing cross-link density and sulfur bond length can be accurately determined using a chemical probe (a chemical reagent that destroys the nodes of the polymer network). Due to the loop cross-links in a single molecular backbone, there is significant, recoverable, ineffective elasticity within the interpenetration density. The original, new tire morphology has undergone severe physical challenges resulting in annealing of the remaining structure. The environmental grinding process produces a coastline with a very highly developed particle surface. The entangled polymer structure(s) leaves a significant amount of unused allylic hydrogen and carbon sites. The formation of a classical sulfur cross-bridge is well documented, providing a specialized mechanistic model for resource recovery approaches.

The strategic efforts using these properties and conditions are to 1) carefully unpack the dense GTR composite structure, 2) relocate the least stable cross-link attachment point without adversely altering the elastomer molecule or sulfur bridge, 3) install an additional primary polymer receptor at the dislocation site , then 4) after mechanically induced peeling of sub-particles, re-link the original sulfur hanging bridge at susceptible dislocation sites along the elastomer backbone.

Without assistance, elemental sulfur will slowly cross-link functional rubber polymers, but such a process is too slow and has too many end-property problems to be a commercially realistic alternative to a commercially successful vulcanization process. The vulcanization described herein refers to the accelerated sulfur vulcanization process that is used in industrial vulcanization practice.

Sulfur vulcanization was discovered by Charles Goodyear in 1839. 178 years after its development, it is generally accepted that such processes are complex and result in the formation of a sulfur cross-bridge between adjacent, interpenetrating rubber polymers.

These bridges, in turn, give the elastomeric material mechanical properties that are crucial for civilization. However, great success has been achieved and many specific elements of such progress are well known.

Although the free radical mechanism has long been thought to be the controlling phenomenon, more recently, with the advent of better ways to study hidden processes, no convincing evidence for the presence of the theoretical primary radicals needed to support such a mechanism has been found. In contrast, the ionic mechanism was predicted and confirmed using similar advanced process research techniques. Since the modern vulcanization process involves mixing many chemical components at the beginning of the said process, each component (combination) with its own chemical reaction pathway, it is likely that both radical and ionic mechanisms are active, but analysis shows that the ionic mechanism predominates.

A typical example (% by weight) of a mixture obtained from an NR-BR tire is: NR 80%, BR 20%), ZnO 5%, stearic acid 2%, silica-talc 3%, carbon black 55%, aromatic oil 10 %, elemental sulfur 1.7%, N-cyclohexyl-2-benzothiazole sulfenamide (CBS - accelerator) 1.2%, 2-(4-morpholinothio) benzothiazole (MBS - accelerator) 1.1% and N-tert-butyl -2-benzothiazole sulfenamide (TBBS - accelerator) 1.1%.

The process begins in a heated mold after the components of the tire recipe have been carefully distributed and dispersed. The vulcanization process can be observed as three sequential events: 1) formation of an accelerator complex by chemical reactions, 2) formation of a crosslinking precursor, and 3) completion of crosslinking.

Accelerator education

Using, for example, the popular 2-mercaptobenzothiazole (MBT) accelerator model, there is consensus that the sulfonamide accelerator, in the presence of sulfur, decomposes on heating to form MBT and the corresponding amine. MBT then gradually reacts with the remaining sulfenamide molecules to autocatalytically form 2,2'-dithiobenzothiazole (MBTS) and thereby release amine molecules. MBTS then reacts with elemental sulfur to form polysulfide as an active sulfitizing agent (a source of persulfonium ions). A possible mechanism for the precursor formation reaction is given below.

Preparation of cross-linking precursor

This second-stage reaction, consuming the newly formed accelerator intermediate associated with both ends of the resulting sulfur chain, begins when the sulfurizing agent reacts with a pendant structure attached to the elastomeric isoprene or butadiene molecular chain to form a persulfonium(I) ion. The resulting persulfonium ion then reacts with a second isoprene or butadiene molecule by capturing an allylic hydrogen to form a polymeric methyl carbocation. The resulting intermediate, also called a polythio-mercapbenzothiazyl group, introduces monomeric sulfur into the side group bonding position, which the new carbocation converts into a double bond by the addition of anions. Ultimately, this formation of the final double bond occurs by decomposition of the sulfenamide to form unexplored isomers near the reaction site.

Cross Link Formation

In the final step, the backbone of the adjacent rubber polymer chain is attacked at the allylic carbon position, which is sensitive to the carbocation due to the polysulfide group associated with the remaining "end" of the elemental chamois chain. The length of the sulfur chain in the final cross-linked form can be up to twenty (20) atoms, but usually does not exceed (7) atoms. The sulfur bridge can contain individual atoms, but usually contains one or more eight-membered rings of elemental sulfur (S8). Longer chains may be shortened when curing time and temperature exceed the end-crosslinking time and temperature; or during the accompanying annealing process. It is important to note that no sulfide chain can form until a "fragment" of another dissociated sulfur compound is attached to the precursor site. The punch rheometry (MDR) curve shows only the last stage of cross-linking.

Determination of final cross-linking characteristics

The density and type of crosslinking are determined using a chemical swelling method and a chemical probe, respectively; or using spectroscopy.

The cross-linking density of the elastically effective mesh chain can be calculated using the Flory-Riener equation after empirical data acquisition. The same localized sample used to determine cross-link density is then exposed to piperidine propane-2-thiol as a chemical probe (PPTCP) to determine the proportion of sulfide cross-links (S>3). Further processing of the same PPTCP sample using piperidine-hexane-1-thiol as a chemical probe reveals the ratio of disulfide and monosulfide cross-links. The percentage of each bond as a percentage of the original cross-link density can then be calculated and usefully compared to the MDR curve.

With MAS NMR spectra (magic angle spinning C-NMR spectra) are cross-validated by chemical probe method(s), detecting polysulfide and monosulfide resonance peaks at 57.5 and 50.4 ppm, respectively (type structures B2 as an example); and resonance peaks at 37.3, 44.7, 48.2, 49.6, 50.6, 52.5, 54.8 and 57.5 ppm when applying half the sum of the listed areas and obtain the crosslinking density.

Estimation of loop formation probabilities

When cross-linking occurs between adjacent polymer chains, it imparts elasticity and shear modulus to the rubber composite. However, when a cross-link is formed in the same polymer chain, it forms a loop and becomes ineffective in terms of elasticity and can be characterized as a defect or weak point in the structure of the vulcanized rubber matrix. A detailed analysis of the probability of loop formation shows that the occurrence of this undesirable condition occurs in a given commercially vulcanized rubber in the range of 5 to 15% of the total number of cross-links. Depending on the location of the unwanted cross-link, the looped polymer molecular chain can convert 5 to 20% of the rubber polymer into an ineffective cyclic hydrocarbon. It should be noted that the re-elastomeric morphology of GTRP treated with methods according to the proposed embodiments of the present invention reduced susceptibility to this phenomenon.

Common Use of Waste Rubber in Tires

Excluding rubber scraps obtained before final heating and crosslinking of new tires, it is estimated that less than 0.0004% by weight of all EOL tires are re-incorporated into the masterbatch used to produce new tires. This reincorporation using very fine, cryogenically treated shredded rubber obtained from EOL tires has been successfully accomplished at masterbatch loadings up to 3% by weight. Loading more processed shredded rubber from EOL tires than specified has not been practical until now because at higher loading levels the physical properties required by new tires are not adequate. Tire manufacturing typically begins with a basic component formula developed through the selection of raw material(s). It is then brought to a masterbatch in high shear mixing equipment. Generally, the masterbatch is produced in two stages: the main cycle and the final cycle. The main cycle combines various types of rubber, which are introduced in the form of small briquettes or sheets and mixed with fine powders of soot and minerals, as well as a small amount of process oil(s). This step is carried out at a high temperature necessary to reduce the viscosity of the rubber elements so that the poorly flowing powder elements can be evenly distributed in fairly small clusters or packets. Such clusters or packets can then be dispersed sequentially to a minimum particle size. The final cycle is performed at a lower temperature and usually under technological conditions that create a greater effect of smearing heterogeneous elements. In the final cycle, the rubber polymers are not further degraded by high temperatures as in the main cycle, and evenly distributed agglomerates of powder components are processed to such a small physical size that they are dispersed in the free molecular space of the rubber elements. Once the final cycle is completed, the masterbatch briquettes are removed from the mixer and rolled into thin sheets (this is called rolling). Rolled sheets are used to lay the tire carcass layers on specialized forming equipment before being placed in a compression press for final cross-linking through thermal and/or chemical means.

Crosslinking accelerators contain a mercapto group or a sulfur-based group (eg, elemental sulfur and/or N-tert-butyl-2-benzothiazole sulfenamide (TBBS) accelerator derivatives). Sulfur-based crosslinkers that react with sites in the masterbatch at or above a given temperature may be partially introduced in both the main cycle and the final cycle. Crosslinking during the final heating of the tire carcass causes the reactive sites in the various rubber elements to create sufficient crosslinking density to provide the final physical properties needed to withstand the long-term load and thermal environment to which the tire will be subjected.

A method has been developed to target the crosslinking precursor site, which allows for interconnected replacement of the EOL tire such that functionally rearranged recrosslinkable rubber can be obtained in the form of submicron particles. Such rubber is suitable for reintroduction into new tire production at levels up to 100% by weight relative to the weight of the masterbatch used in subsequent new tire production. New tires using such raw materials modified by EOL tires exhibit performance characteristics equivalent or similar to those achieved using materials that are all virgin materials.

Rubber from waste tires

Crumb rubber is obtained from two main types of raw materials: tire burr, tire retread by-product, whole tires and waste tire rubber. Scrap tire rubber comes from three types of tires: passenger car tires; tires for trucks; and off-road tires. The final product yield for each of these types of tires depends on the design, strength and weight of the tire. On average, one passenger car tire can yield 10 to 16 pounds (about 4.5 kg to about 7.3 kg) of scrap tire debris. Other sources of crumb rubber include products containing or manufactured from recycled crumb rubber, such as new rubber products, playground surfacing, rubber mulch, drainage aggregate, fill material, industrial waste, and the like.

Tires are composite structures containing a number of components. The tire carcass consists of a tread, bead, sidewall, shoulder area and cord layer. Tires are made from components such as natural rubber and/or synthetic rubber, cords and filler. The polymer most commonly used for tread and cord shells is a mixture of NR and S-BR copolymers. The cords form the ply and bead of the tire and provide the tensile strength needed to contain the tire's internal pressure. Cords may contain steel, natural fibers such as cotton or silk, and synthetic fibers such as nylon or Kevlar. Fillers may include silica and carbon black. A typical tire may contain one or more of: synthetic rubber, natural rubber, sulfur and sulfur-containing compounds, silica, phenolic resin, oil (aromatic, naphthenic and/or paraffinic), fabric (polyester, nylon, etc.), petroleum waxes, pigments (zinc oxide, titanium dioxide, etc.), carbon black, fatty acids, various inert materials and steel wire.

A typical passenger car tire contains 14% natural rubber, 27% synthetic rubber, 28% carbon black, 14 to 15% steel and 16 to 17% fabric, fillers, accelerators, antiozonants and other miscellaneous components. The average weight of a new passenger car tire is 25 pounds (approximately 11 kg) and a used passenger car tire is 22 pounds (approximately 10.0 kg). Truck tires typically contain 27% natural rubber, 14% synthetic rubber, 28% carbon black, 14 to 15% steel and 16 to 17% fabric, fillers, accelerators, antiozonants and other miscellaneous components. The average weight of a new truck tire is 120 pounds (approximately 54 kg), and a used truck tire is 110 pounds (approximately 50 kg). Other types of tires may contain higher amounts of synthetic and/or natural rubber, such as 70% (by weight) rubber, 15% steel, 3% fiber and 12% other materials such as inert fillers. Rubber is found in tire components, including the tread, liner, beads, belts, etc. The percentage of rubber by weight in a new passenger car tire is typically: 32.6% in the tread; 1.7% at the base, 21.9% at the side, 5.0% at the top of the bead ring, 1.2% in the bead ring insulation material, 11.8% in the fabric insulation material; 9.5% in the steel cord insulation material, 12.4% in the containment layer and 3.9% in the rubber cushion layer.

The rubber compounds used in a typical tire along with associated materials are listed in Table 1. The methods described herein are suitable for treating the tire's tread, base, sidewall, and liner, and are also suitable for treating other materials containing vulcanized ( or otherwise cross-linked) natural rubber, styrene-butadiene rubber and isobutylene-isoprene rubber. As further described herein, other components, such as carbon black, present in an EOL tire or other industrial products containing vulcanized rubber, in some embodiments, may remain in the rubber subjected to the processes described herein without treatment being carried out to affect on the properties or quantities of the other component(s). In other embodiments, the rubber may be subjected to additional processes to enrich or minimize such additional components or change their properties.

* PHR=per 100 parts of rubber, parts based on weight

* Carbon grade=ASTM classification: Particle size and structure of carbon vary.

A passenger car tire contains approximately 2.5 pounds (approximately 1.1 kg) of steel belts and bead wire. This material is made from high-carbon steel with a nominal tensile strength of 2750 MN/m ^2. The composition of a typical tire's steel tire cord is given in Table 2.

Whole tires can be shredded to produce rubber particles mixed with other tire components. Methods for producing rubber-containing particles from tires are known in the art. Used tires (or chunks or pellets) may be subjected to an optional cleaning step (eg water rinsing). Tires can be disposed of by subjecting them to an initial stage of cutting into pieces and then subjecting such pieces to a granulation process to produce a raw granulate with sizes ranging from 1 to 3 cm. Reduction can be carried out under ambient conditions (for example, in a granulator or crushing rollers) or in cryogenic conditions.

Environmental comminution is a multi-stage processing technology that uses a number of devices (usually three) to separate the rubber, metal and fabric components of a tire. Whether pelletizing equipment or crushing rollers are used, the first stage of processing typically involves reducing the size of the feedstock to fine chips. The second device in the row will grind such shavings to separate rubber from metal and fabric. The material will then be ground in a fine mill to achieve the required product specification. After each processing stage, the material is sorted using sieves that return oversized pieces to the granulator or rollers for further processing. Magnets are used to remove wire and other metal contaminants at all stages of processing.

At the last stage, tissue is removed using air separators. The rubber particles produced by the granulation process typically have a cutting surface shape and a rough texture with uniform dimensions along the cut edges.

Crushing rollers use two large rotating rollers with teeth cut into one or both of the rollers. The rotation configurations are what makes them different. Such rolls work against each other with a small permissible deviation at different speeds. The size of the product is controlled by the gap between the rollers. Crushing rollers are low-speed units operating at approximately 30 to 50 rpm. The rubber is usually passed through two or three rollers to ensure that the various particle sizes are reduced and further separates the steel and fiber components. Such rollers do not have sieves built into them and therefore the rollers themselves do not regulate the size of the final particle. A stand-alone screening system will separate the rollers' "aged" particles from the oversize granules and recycle the oversize products. The particles produced by crushing rollers are typically long and narrow in shape and have a large surface area.

Cryogenic processing uses liquid nitrogen or other materials/methods to freeze tire chips or rubber particles before reducing them to size. At temperatures below -80°C, most rubber becomes brittle or glassy. The use of cryogenic temperatures can be used at any stage of reducing the size of waste tires. Typically, the feed size corresponds to chips with a nominal size of 2 inches (approximately 5.1 cm) or smaller. To reduce the temperature of rubber or tire chips, the material can be cooled in a tunnel-type chamber, immersed in a “bath” of liquid nitrogen, or sprayed with liquid nitrogen. The cooled rubber is crushed in an impact gearbox, centrifuge or hammer mill. This process reduces the rubber to particles that pass through a 1/4 inch (about 0.64 cm) to 30 mesh screen opening, with the majority of particles from the particle distribution passing through a 1/4 inch (about 0.64 cm) screen opening. .64 cm) up to 20 mesh. Typical throughput ranges from 4,000 (approximately 1,814 kg) to 6,000 lb (approximately 2,722 kg) per hour. Cryogenic grinding prevents thermal degradation of rubber and provides a high yield of product that contains virtually no fibers or steel, which are all separated during the process.

Wet grinding is a processing technology used to produce particles 40 mesh and smaller. In the wet grinding process, partially purified crumb rubber particles are mixed with water to form a slurry. This slurry is then transported through size reduction and screening equipment. When the required size is reached, the suspension is transferred to equipment to remove most of the water and then dry. In addition to the use of water, the wet grinding process uses the same basic principles as the environmental process. The main advantage of the wet grinding process is the ability to produce crumb rubber that passes through a fine mesh screen. Although 40 mesh products are produced, most particles are 60 mesh or smaller. A percentage of the total material passed is less than 200 mesh. Another advantage of the wet grinding process is the purity and consistency of the resulting crumb rubber. In this process, the crumb rubber particles are washed. The wet grinding process removes small fiber particles from the crumb rubber, resulting in a very clean product.

The initial granulate contains steel, rubber and fabric components. To minimize rubber loss, steel is typically recovered using a multi-stage magnetic separation process. Such a process may include a first stage in which a high strength two-pole over-belt cross-belt separator magnet is used to remove metal-containing particles in the first stage. The second stage includes a magnetic drum separator or magnetic drum, which uses high-strength rare earth magnets. The axial magnetic field causes particles containing metal to fall and release the trapped rubber. For fine rubber material fed into a powder mill, a plate magnet suspended above the conveyor near the product can lift and remove small wire fragments. Additional testing can be done to determine the metal content, for example using a magnetometer.

The fiber can be recovered using a modified fiber separator known in the textile industry. Typically a two-step process is used in which the pure fiber is removed from the EOL tire crumbs using a modified cylindrical fiber separator (used in the textile industry to remove foreign matter from raw cotton). The partially cleaned chips are subjected to a second step to remove fibers that may still contain rubber particles. The resulting cleaned EOL tire chips are then collected for packaging or other uses. See, for example, W. Stanley Anthony, Applied Engineering in Agriculture, Vol. 22(4): 563-570.

The American Society for Testing and Materials (ASTM) has standards for defining different size ranges for crumb rubber, such as 30 mesh or 80 mesh. The range of particle sizes can be determined using sieve analysis, which consists of shaking and passing a measured amount of a sample of crumb rubber through a specified number of test sieves for a specified time. The amount of sample remaining on each sieve is weighed and the results are reported as the percentage of sample remaining on each sieve. A recommended procedure for sieve analysis using the Rotap method is given in ASTM 5644. Typical crumb rubber sizes targeting specific products and applications include the following sizes: molded and extruded products, 4 to 100 mesh; asphalt modification, from 16 to 40 mesh; sports field coverings, 1/4 inch (about 0.64 cm) to 40 mesh; automotive products, from 10 to 40 mesh; tires, 80 to 100 mesh; rubber and plastic mixtures, from 10 to 40 mesh; and construction, 10 to 40 mesh.

There are no uniform U.S. standards for processing crumb rubber from EOL tires; however, suitable EOL tire crumb rubber for interlocking replacement applications typically has a low fiber content (less than 0.02% of total weight), low metal content (less than 0.01% of total weight), viscous consistency, with a particle size that is preferably such that 100% of particles pass through the 16 mesh openings. In some embodiments, it may be appropriate to use larger particle sizes, such as 14, 12, or even 10 mesh. For example, crumb rubber ranging in size from 10 to 40 mesh (eg, 30 mesh or 25 to 35 mesh) provides satisfactory results when processed according to the methods described herein. Finer particles, for example 41 to 200 mesh, can be used and can provide more effective interconnected displacement; however, reducing the particle size will entail greater costs in obtaining crumbs of the specified size. Larger particles, for example, less than 10 mesh (4 to 9 mesh), can also be treated by these methods, for example, to reduce particle size.

ASTM D5603 Standard Classification for Rubber Compounding Materials - Recycled Vulcanizate Particulate, classifies particulate vulcanized rubber based on maximum particle size, size distribution, and starting materials, including whole tires, tire outer casings, tread-derived burrs, and shoulder areas of the tire, burrs derived from the tread, shoulder and sidewall of the tire, and non-tire rubber.

Determination of the characteristics of crumbs from used tires

Crumb rubber from EOL tires containing vulcanized rubber and having the desired particle sizes can be manufactured or obtained from any suitable commercial source.

As discussed above, crumb rubber from tires is typically sized such that 100% of the particles can pass through a 16 mesh screen, and furthermore, such crumb rubber may have a narrow size distribution (e.g., no less than 20 mesh and no more 16 mesh) or may have a broader size distribution (eg, significant amounts of fines and various other particles smaller than 16 mesh). Crumb rubber is typically purified from fibers and wires to 99.9 wt.% purity (that is, the fiber and wire content is 0.1 wt.% or less); however, as discussed above, in some embodiments, such foreign materials (one or more materials selected from fiber, wire, carbon black) may be left present.

If the sulfur content of EOL tire crumb rubber is unknown, representative samples of EOL tire crumb rubber can be tested to determine the sulfur content (usually measured in parts per hundredweight), so that a controlled amount of reagent can be used in the extraction process, thereby avoids overuse or underuse of reagent. However, in general, the methods of the present embodiments are suitable for use with rubber having any degree of vulcanization, so knowledge of the sulfur content is not necessary for processing vulcanized rubber. If it is necessary to determine the sulfur content, any suitable method, for example, a nitrogen compound extraction method, can be used. ASTM D4578 describes standard test methods applicable to rubber chemicals to determine the percentage of sulfur. Such test methods involve the determination of solvent-insoluble materials in a sulfur-containing sample. The two test methods are: (1) Test Method A, carbon disulfide extraction and (2) Test Method B, toluene extraction. If there are no other materials insoluble in the solvent in the sulfur-containing sample, these test methods provide a direct determination of the insoluble sulfur content. If other materials are also present, additional testing is necessary to determine what portion of the insoluble materials (eg, carbon black, silica, or other inert fillers) is insoluble sulfur.

Gray rubber stitching

At room temperature, elemental sulfur consists of cyclic molecules of eight atoms. In the presence of accelerators and activators, elemental sulfur forms sulfur fragments that react with the reactive groups of rubber in a process of interconnected substitution to form cross-links, such as:

Crumb rubber from EOL tires is chemically treated with a reagent to induce interlocking substitution. The reagent contains a metal salt having an octahedral molecular geometry and a melting point in the range from 100 to 150°C. Examples of suitable reagents include cobalt acetate (CAS 6147-53-1; Co(OAc) ₂ ), and copper acetate (CAS 6046-93-1; Cu(OAc) ₂ ), although other reagents can be used as discussed in elsewhere in this document. The reagent is usually used in an amount of 0.1 to 5.0 parts of reagent per hundred parts of vulcanized rubber (by weight); however, in certain embodiments, higher or lower amounts may also be used. The amount of reagent used can be increased or decreased depending on the sulfur content of the EOL tire crumb rubber to be treated or the desired degree of interconnected substitution to be achieved. For example, to achieve a preselected degree of interlinked substitution, a ratio of reactant molecules to sulfur bonds of 1:1, 4:6, 1:2, or any other suitable ratio can be used.

Regeneration of an interpenetrating elastomer mesh from crushed tire rubber particles

In one embodiment, sequential elements are used to regenerate the morphology of a monolithic, macrostructural, interpenetrating elastomeric network of shredded tire rubber particles. Element 1 involves providing an electromechanical reactor environment (EMRE) to support Boltzmann "phase space" mediators that decompress GTRP and then rearrange the sulfide bridging chains for final compounding. Element 2 involves obtaining a GTRP slurry for treatment by EMRE.

Element 3 involves exposing GTRP to differential cyclic mechanical stress and steric electropolarization. Element 4 involves exposing the GTRP slurry to engineered, cavitation-induced thermal and acoustic shock wave differential(s). Element 5 involves the creation of a chemotactic effect of binding sulfide bridges. Element 6 includes the production of chemical reaction products and the time scale. Element 7 involves compounding the regenerated GTRP to produce a fully integrated, monolithic, macrostructured elastomeric material.

In Element 1, the electromechanical reactor environment (EMRE) provides an efficient "phase space" environment to 1) unpack the GTRP and restart the curing precursor for 2) subsequent rearrangement of sulfide bridges, 3) with minimal modification to the native elastomeric filler matrix. In fig. Figure 1 shows the top of the EMRE. The top contains a 16-inch (approximately 40 cm) 101 stainless steel variable speed rotor with a maximum speed of 15,000 fpm (4,572 m/min). In addition, a 17-inch (about 43 cm) stainless steel stator 102 is used containing one hundred and ten slots (cavitation portals) 103. These components create a GTRP slurry flow path 104, as shown in FIG. 1. In FIG. Figure 1 shows a detailed cross-section along line “A”. Although the EMRE shown in FIG. 1 can be effectively used, other mechanical platforms can be made in the form of reactors used in the methods according to the present embodiments, for example, cavitation-type screw pumps, screw pumps, extruders or the like.

In Element 2 a GTRP suspension is obtained. In fig. 2 depicts a flow diagram for such a process, including a stainless steel mixing tank 201 containing an EMRE submersible top 202. During operation, the reservoir is typically filled to approximately 70% of the available reservoir volume. The slurry is prepared from a whole EOL tire that has been subjected to conventional metal and fiber removal processes and ground to pass through a 30 mesh (600 micron) screen. In the exemplary process shown in FIG. 2, a 300 gallon stainless steel mixing tank is used to produce a 200 gallon batch of EOL tire rubber slurry having a specific gravity of 1.03. The stainless steel tank can be uninsulated, allowing EMRE (thermal energy) energy to be dissipated. In some embodiments, cooling coils may be added to keep the batch temperature below the boiling point, or alternatively, the process vessel may be sealed to allow higher temperature operation under elevated pressure conditions. A batch of EOL tire slurry weighs 1,716 lbs (approximately 778 kg) at a 3:1 water to GTRP ratio. The components of the suspension in Fig. 2 include approximately 152 gallons (approximately 575 L) of reverse osmosis (RO) water, approximately 400 pounds (approximately 181 kg) of GTRP, and approximately 8 pounds (approximately 3.6 kg) of copper acetate (called organometallic compound or OMC), pre-dissolved in approximately 40 pounds (approximately 18 kg) of RO water. The filtered water recovered from the previous batch, including the water squeezed out of the filter cake, can be used as part of the approximately 152 gallons (approximately 575 L) of water used to produce the batch. In general, it is preferable to use fresh RO water to dissolve OMC; however, in some embodiments, recovered water can also be successfully used.

In Element 3, the GTRP of the suspension traverses a “phase space tunnel” in which differential cyclic mechanical stress and steric field polarization are applied to the GTRP. The concept of "phase space" (sometimes called a "tunnel") introduced herein was first used by Boltzmann as a "box" in which molecular structures and velocity are quantified as a function of the time interval when the "contents" of the box are exposed to external influence(s). . When the environment in the "box" is induced through entropy-enthalpy-entropy phase changes at short intervals of time-oscillation, enormous forces of energy (velocity) are released in the "box". Such a process is schematically depicted in Fig. 3A, with linear distance, GTRP geometry, velocity, and acceleration profile shown as a function of time on a time scale running from 0.000 seconds to 0.0019 seconds. Time 0.000 corresponds to the moment when the particle falls on the rotor 301 EMRE. The GTRP is then compressed in the stator (compression gate 302), exits the stator, and enters the recirculation circuit. As shown in FIG. 3B, the space between the EMRE rotor 301 and the exit from the compression gate 302 is called the phase space tunnel 303. To facilitate this process, it is optional to apply modulated alternating current to the compression gate. Electrodes 304 are used which produce a modulated alternating current. By using a frequency controller, oscillations from 0 (or no oscillation) to 100 Hz can be used, or oscillations up to 1000 Hz or more can be used. Voltages of up to 300 V or more can be applied to induce current flow through the suspension medium, causing electrons to be deposited onto the surface of the rubber particles in the phase space tunnel by rapidly changing polarity. The compression process in the stator causes the GTRP to deform such that the width to length ratio increases to 6:1. The "trampoline" effect of rapid contraction-expansion-decompression, facilitated by the flow of modulated alternating current through the stator slot, enhances the steric repulsion effect between overlapping electron clouds, followed by accelerated delamination of the associated GTRP matrix, as depicted in FIG. 3C. In the case of a 600 µm particle with approximately 1200 sulfide cross-links, 60 dislocated and re-strengthened sections of the vulcanized precursor are regenerated in one pass through the stator. It should be noted that the EMRE described in Item 1 is an implementation of the parallel flow microsynthesis reactor (PCMR) hardware described elsewhere herein, primarily because the environment eliminates the need to build and certify a pressure vessel for carrying out the process according to the present embodiments of the present invention. However, PCMR, operating at a fixed temperature along the water-to-steam conversion curve, is capable of providing similar "phase space" particle unpacking results to GTRP as the EMRE implementation in Element 1, in five "Timeline" quanta. The Linear Distance, GTRP Geometry, Velocity, and Acceleration Profile shown in FIG. 3A, by forcing the GTRP slurry through strategically placed mechanically larger orifices (such as an adjustable iris valve), allowing the slurry to be increased in volume until it enters the gas phase, and then immediately reduced back to the original pipe ID. When the suspension temperature is dependent on the pressure induced to create oscillation of the vapor-liquid-vapor cycle, the decompression efficiencies of GTRP are equivalent. With each pass through the rotor, the particle size decreases. When reduced to 200 mesh (70 µm), approximately 65% of the cross-linking bonds are broken and the particles can be mechanically exfoliated to form thin pancake-like structures (eg, "smear" into a 10 µm film). Further downsizing is usually not necessary. When decreasing to 5 to 60 µm, soot begins to be released from the particle matrix. When reduced to a size of 5 microns, carbon reduction begins to occur. In general, a particle size of 200 mesh (70 microns) is suitable for most applications such as tires, roofing and paving; however, some embodiments may require sizes as small as 10 microns.

In Element 4, the GTRP is subjected to an engineered acoustic shock wave caused by cavitation. As shown in FIG. 4A, in the phase space tunnel between the EMRE rotor 401 and the compression seal 402, a mixture 405 of GTRP, entrained air 406, and aqueous organometallic compound matrix 407 is present at a certain speed and volume. Upon exiting through the compression valve 402, the compression of the air bubbles and the acceleration of the particles cause cavitation to propagate 408. As the suspension exits, the lower pressure completes the cavitation cycle with an explosion of air cavities. In general, it is preferable that no change in the bulk phase occurs within the continuous aqueous phase of the suspension during cavitation. Therefore, differential changes in temperature and pressure occur on an atomic scale. This process creates extreme differential temperature and pressure differences in nano-regions, with a cone of cavitation ranging from 10 ² °F to 10 ¹⁵ °F (from about 38 °C to 3.8 x 10 ¹⁴ °C) for temperatures from 60 m/s to 180 m/s for the speed of the acoustic wave, and all this occurs during the time interval from 10 ³ sec ^-1 to 10 ⁸ sec ^-1 . By changing the EMRE rotor speed and/or the suspension viscosity and/or the stator gap, the energy “leverage” can be manipulated in the phase space tunnel. In fig. 4B depicts the process control variables for the GTRP and EMRE slurry. A proportional-integral differential controller (PID or three-channel controller), a control loop feedback mechanism widely used in industrial control systems and a variety of other applications requiring continuous modulated control, is used to control temperature, hole size, slurry volume, and oscillations between vapor and liquid. Other factors that can be controlled, for example by a PID controller, related to the reagents include the rubber to water ratio, OMC added (amount, dosing rate, intermittent or continuous dosing), amount of OMC residue, reduction rate. Factors associated with the device that can be adjusted, for example, using a PID controller, include the peripheral speed of the rotor and the size of the gap between the EMRE and the compression gate. In fig. 4C presents a table containing a list of selected adjustable variables of the GTRP suspension and the results of their modification. In fig. 4D presents a table containing a list of selected process controlled variable parameters of EMRE and the results of their modification.

Element 5 illustrates the dynamics of the chemotactic sulfide bridge tethering effect (SBTE). In fig. 5A schematically depicts the initial sulfide bridges, including the formation of pendant vulcanizate precursors occurring predominantly at the methyl carbocation (initially formed at approximately 140°C) and completed vulcanization occurring primarily at the allylic carbocation (subsequently formed at 160°C) . In fig. 5B shows the types of carbocations (with varying numbers of carbon atoms attached to the carbocation) in order of stability, with tertiary carbocations being the most stable, secondary carbocations being less stable, primary carbocations being even less stable, and the methyl carbocation being the least stable. Resonance increases the stability of allylic carbocations as the positive charge density is spread out, making it more stable than the secondary carbocation, as shown in FIG. 5V. Accordingly, the process of dislocation of sulfide bridges successfully occurs in the methyl carbocation, and not in the allylic carbocation. The result of this dislocation is that the rigid sulfide bridge becomes tethered at the parent allylic carbocation and becomes unbound at the methyl carbocation.

In Element 6, a chemical reaction occurs along a time scale. RO water and OMC (in this case metal acetate or MO Ac) are mixed in a 20% solution concentrate and dosed into a GTRP slurry (180°F (about 82°C), RO water to GTRP 3:1 weight ratio) as shown in fig. 6A. The resulting chemical reaction is shown in Fig. 6B. An organometallic compound dissolved in water associates with ligands including transition aqua metal compounds. In fig. 6B to refers to the mechanistic kinetics of the Boltzmann “phase space” EMRE tunnel, M ²⁺ refers to the metal ion; NH _n , CH _n , Zn _n and _Sn refer to what are believed to be isomeric "fragments" near the precursor site that are by-products of the original rubber compounding process, and OAS ^-2 refers to the acetate ion. The initial precursor to tire vulcanization, allylic hydrogen, captured by the amino group of MBTS described earlier, forms reaction byproducts. Nitrogen-sulfur compounds include ammonium disulfate (NH ₄ ) ₂ S ₂ O ₈ (ADS) molecules or their radicals, which are located and compacted in the form of isomeric fragments near the methyl carbocation. Such nitrogen-sulfur isomers, which are not noticeably formed during the final stage of the initial sulfide vulcanization at the parent carbocation of the sulfide cross-link on the adjacent polymer chain, are highly soluble in water and become powerful oxidizing agents that promote sulfide metathesis when displacing the methyl carbocation. Active OMC, the metal coordination complex, can either activate the hydration of the ADS molecule to form hydrogen peroxide (H ₂ O ₂ ) and/or become an accelerator that enhances such a reaction by targeting metathesis as an oxidizing agent in the metal carbocation. The rate of sulfide metathesis of the methyl carbocation can be achieved without any peroxide and/or other oxidizing agent when the temperature threshold at the reaction site is greater than 240°F (about 116°C), above which sulfur becomes labile during phase transition. This may be caused by either an oscillation of the phase transition at elevated pressure from water to steam, or a sudden explosion during cavitation in phase space with bursts of hyperenergy that lead to a solid-liquid-solid phase transition of both the sulfur and the OMC compound at the site -target methyl carbocation. To more fully appreciate the enormous amounts of energy released by the exploding cone of cavitation, recent CERN research on the topic has suggested that electromagnetic plasma entanglement occurs during picosecond deformation, which is very similar to the phenomenon associated with a 300-fold increase in the temperature of the solar corona compared to with the surface of the sun. By this analogy, for a 180°F (about 82°C) GTRP slurry passing through a phase space tunnel, the cavitation point temperatures at the methyl carbocation target site would be expected to be at least 54,000°F (about 30,000°C) within a very short time.

Without wishing to be bound by theory, it is believed that in such a reaction dissociative displacement of the metal acetate ion occurs at the methyl carbocation. This destroys the vulcanization precursor, and this insertion forms a new functional site in the elastomeric side structure for subsequent rearrangement of sulfide bridges. In this process, O ^2- is converted into CO ₂ under the action of charged carbon aggregate particles in the phase space. With strong interaction between M ²⁺ and S ^2-, a precipitate is formed, which releases the rigid sulfide bridge to a “tethered” state, bound only at the parent allylic carbocation. Various metal ions are suitable for use, including, but not limited to, Co ²⁺ (ligand exchange rate for the H ₂ O × metal coordination matrix is 3 × 10 ⁶ ), Cu ²⁺ (ligand exchange rate for the H ₂ coordination matrix O×metal is 5×10 ⁹ ), Ni ²⁺ (ligand exchange rate for the H ₂ O×metal coordination matrix is 3×10 ⁴ ), Zn ²⁺ (ligand exchange rate for the H ₂ O×metal coordination matrix is 2× 10 ⁷ ) and Mn ²⁺ (the ligand exchange rate for the H ₂ O×metal coordination matrix is 2×10 ⁷ ). There is actual evidence in the literature that in a heated aqueous environment the coordination number of a copper-based organometallic molecule can be up to ten (10). This coordination ability mediates the formation of a super-loose matrix that facilitates this process by trapping a ligand from an inhibitory isomeric “splinter” near the reactive site of the methyl carbocation. Ligand uptake and release rates are also many times faster than other metals. Such impressive capabilities lead to the possibility of creating various reactive copper-based isomers from the heterogeneous fragment (maw) molecules present during the GTRP-metathesis unpacking sequence. By selecting an organometallic compound that exhibits a phase transition at a temperature close to that of elemental sulfur, the metathesis reaction can be facilitated; however, organometallic compounds having different phase transition temperatures can also be used.

In Element 7, a monolithic macrostructure of rubber is obtained. In fig. 7A shows the macrostructure of ground state vulcanized GTRP (Stage 1), EMRE conditioned GTRP (Stage 2) including unbound, pre-reptation internal morphology, and a regenerated interpenetrating elastomeric network (Stage 3) containing intertwined layered structures spaced apart from each other. from 10 nm to 5 µm. One of the features of this process according to the present embodiments is that the cross-links are restored in the interpenetrating elastomeric network through a gentle process leaving the carbon black intact. This results in a slight decrease in tensile strength, but an improvement in rebound strength.

During the production process, as shown in FIG. 7B, the treated GTPR slurry is pumped out and passed through a filter cake press, and dried by centrifugation to a moisture content of less than 1% by weight. The resulting treated GTRPs can be oven dried in a drum dryer to a moisture content of less than 0.1% by weight to produce dry EMRE conditioned GTRPs. Between the press filter stage and the drum dryer stage, specially selected water-soluble or liquefied thermoplastic virgin polymers can optionally be wet mixed into the treated GTRPs. The dried GTRPs can be processed in a closed mixer (eg, Banbury mixer, Z-mixer, or the like) and/or in a microlaminated roller mill where the dry EMRE conditioned GTRPs are mixed with the polymer and crosslinking additives. The resulting product can then be packaged as a pellet, roll, briquette, scalloped sheet or the like. In certain embodiments, the treated GTPR slurry provides a valuable product for use without any additional processing steps. GTRP can be mixed with asphalt to form rolls and sheets, or melted to bind aggregate or form an emulsion. Likewise, the product obtained from any of the intermediate steps in Element 7, including press filtration, tumble drying, wet mixing, internal mixing and packaging, may itself constitute a valuable product. Accordingly, in various embodiments, any of the stages of Element 7 may be considered optional. It should be noted that when a roller mill is used, the resulting GTRP is “exfoliated” into thin pancake-like structures that form during subsequent vacuum forming, giving the resulting GTRP sheet anisotropic properties. When using a closed mixer, the resulting GTRP sheets are substantially isotropic.

A mixture of asphalt and GTRP can be produced in a variety of ways. As a first step, the GTRP is passed through a fine roller mill to a "sheet" or "full sheet reptation" form (with a particle thickness of, for example, approximately 10 microns or less at its smallest size), and then together with the asphalt is passed through a roller mill or closed mixer. Typically, a cohesive GTRP sheet (characterized by a "sheet" shape) can be obtained after 10 passes through a cold roller mill or 2 passes through a hot roller mill. Once the cohesive GTPR sheet is produced, it can be combined with asphalt. In one embodiment, asphalt is added to the cohesive GTRP sheet in a roller mill, then mixed by the roller mill to produce a mixture of 92% by weight GTRP and 8% by weight asphalt in the form of a continuous GTRP/asphalt sheet . Type IV asphalt may advantageously be used; however, asphalt with a penetration value of 5 to 200 can also be used. A crosslinking agent (eg, 0.005 phr (0.005 parts by weight per hundred parts by weight of rubber) of continuous GTRP/asphalt sheet) can optionally be added to the asphalt. Such a sheet can be advantageously rotated during the process to facilitate uniform distribution. A cohesive GTRP sheet ("sheet") or continuous GTRP/asphalt sheet can be further combined as a hot melt with asphalt in any form, such as particulate, emulsion or hot mix. Re-vulcanization can be successfully accomplished after placing the GTRP/asphalt mixture in place.

For example, in paving applications, a cohesive GTRP sheet or a continuous GTRP/asphalt sheet can be melted into asphalt to produce a composition containing from about 20 to 50% by weight GTRP, for example, suitable for use as an aggregate binder. In another example, a continuous GTRP/asphalt sheet may be applied in sheet form to a damaged pavement, then a conventional hot mix, aggregate, or aggregate/binder mixture may be applied as a topcoat to said continuous GTRP/asphalt sheet. Irradiation can be successfully used to induce cross-linking and binding of GTRP. When using GTRP in asphalt as a binder or in a support surface containing a continuous GTRP/asphalt sheet, GTRP can be successfully cured in situ on a road surface using the emitter system and associated apparatus and methodology described in US Pat. No. 8,992,118, US Pat. No. 9169606, US Patent No. 9074328, US Patent No. 9347187, US Patent No. 9481967, US Patent No. 9551117, US Patent No. 9551114, US Patent No. 9624625, US Patent No. 9637870, US Patent 9127413 and US Patent No. 9057163, the contents of each of which its entirety is incorporated herein by reference. Such an emitter system for irradiating an asphalt/concrete pavement typically includes a support frame supporting a panel of emitters configured to emit a peak wavelength of 1000 nm to 10,000 nm to soften the asphalt in the asphalt/concrete pavement. As used herein, the terms "melting" or "softening" are broad terms that are to be given to one skilled in the art in their ordinary and generally accepted meaning (and not to be limited to a specific or specialized meaning), and such terms refer to , without limitation, to describe a fluid that can move when minimal pressure is applied to a fluid body. Temperatures in the range of 190°F to 290°F (about 88°C to about 143°C), such as 250°F to 290°F (about 121°C to about 143°C), can be used successfully to induce softening of asphalt. °C). Radiation with a peak wavelength in the range of 350 nm to 700 nm can be successfully used to irradiate GTRP to promote cross-linking, and this radiation can be used in addition to radiation with a peak wavelength between 1000 nm and 10,000 nm (for example, using two peak wavelengths). Some degree of cross-linking will occur in the absence of added cross-linking agents; however, additional cross-linking agents can increase the speed and efficiency of this process. It should be noted that temperatures of 170°F (approximately 77°C) can cause crosslinking when using DIBP (diisobutyl phthalate) as a crosslinking agent, making it suitable for use in GTRP/asphalt sheet where stability and controlled crosslinking is required. When dicumyl peroxide is used as a crosslinking agent, crosslinking will occur quickly even in the absence of applied heat. Dicumyl peroxide can be used successfully as a crosslinking agent when GTRP/asphalt is in liquid form (eg, emulsion form). The paving material containing GTRP exhibits superior properties in terms of durability compared to conventional paving materials containing shredded tire rubber that has not undergone any treatment.

Continuous GTRP/Asphalt Sheet can be used in rolls and sheets for weatherproofing or roofing applications. Alternatively, cohesive GTRP sheet ("sheet") or continuous GTRP/asphalt sheet can be melted in asphalt or other solvent and the resulting mixture applied to the surface by spraying to produce a sealed and waterproof surface. The resulting particulate rubber is also of a quality suitable for use in residential shingles and roofing rolls, providing resistance to damage caused by hail, improved flexibility at low temperatures (e.g., flexibility to temperatures of at least -40°F (- 40°C)) and reduced ability to soften, spread and stain in hot weather. Roll roofing sheeting containing particulate rubber can be placed in a dry state and then subjected to irradiation causing the sheet to melt, warp, crosslink and adhere to the underlying layer (eg, insulation material or old roofing sheeting). The liquid mixture containing GTRP can be irradiated to induce cross-linking. Irradiation can be achieved using an emitter system similar to the system described above for paving (see, for example, US Patent No. 8992118, US Patent No. 9169606, US Patent No. 9074328, US Patent No. 9347187, US Patent No. 9481967, US Patent No. 9551117, U.S. Patent No. 9551114, U.S. Patent No. 9624625, U.S. Patent No. 9637870, U.S. Patent No. 9127413, and U.S. Patent No. 9057163, each of which is incorporated herein by reference in its entirety). Electromagnetic radiation of a preselected peak wavelength can be applied to the roofing or waterproofing sheet or material sprayed on site. Thermal radiation can be generated by modifying the emitter so that it emits the desired wavelength. The wavelength of electromagnetic radiation used for heating is selected based on the materials present in the roofing roll. Preferred peak wavelengths for exposure of rubber in rolled roofing are from 350 to 700 nm at power densities less than or equal to 10 W/in ² (about 15.5 kW/m ² ). Radiant energy applied to the roofing roll heats the rubber in the roofing roll while minimizing heating of the substrate. The radiation device can be manufactured to minimize costs and be suitable for field use. Field use can be achieved by powering the device using a portable generator, such as a Class 4 diesel engine, electrically coupled to one or more emitter panels located within a metal frame. The emitter can be insulated, for example, using high-density ceramics, and the panel(s) can be inserted into the ceramic cladding of the frame facing the plane of the rolled roof covering.

The GTRP post-reactor mixture can be dried to any desired degree. Moisture can be removed slowly or quickly. Gentle drying will have minimal effect on the structure of the morphology of the elastomeric network. Shear drying typically results in smaller particle sizes and faster evaporation of moisture.

Curing of the post-reactor GTRP mixture can be done slowly or quickly using chemical curing agents or by irradiation (eg, using the emitter system described elsewhere herein).

In some embodiments, it may be desirable to combine the dried post-reactor GTRP with a solid polymer (eg, virgin natural rubber) by dry mixing and then further processing to mix the components. Alternatively, with post-reactor GTRPs, latex with a certified number of reactive sites can be combined and further processed. The water can be removed later, for example by squeezing. Post-reactor GTRPs can be modified for various applications, such as thermoplastic, thermotropic or thermoset plastics. Polymer backbones are prone to vulcanization. Because post-reactor GTRPs are hydrophobic, the material is rendered hydrophilic, allowing it to be emulsified or converted into a colloidal suspension. The properties can be modified by adding a homopolymer to functionalize the backbones. To impart thermosetting properties, the particles can be coated (for example, coated with nonylphenol ethoxylate). To impart thermoplastic properties, hydrophilic regions can be introduced (for example, through a quaternary amine).

As discussed herein, exposing GTRP to oscillation throughout the vapor/water phase allows liquid to be pumped into the voids of the particles. This can result in batch saturation very quickly, for example in less than one minute. During the reactor process, water can flood the particle such that there is a significant increase in free molecular space, such as 500% or more, such as a fivefold increase. The result is dried particles that can be described as “fluffy.” Dried GTRP contains "voids" - internal spaces (free molecular spaces) in which liquids can be accommodated. Applying shear forces to GTRP can destroy such voids. When providing GTRP in the form of a colloidal suspension with the material to be mixed, the presence of voids promotes the internalization of the materials into the liquid in the GTRP voids. Such materials may include water-soluble polymers. This can result in superior dispersibility of the polymer compared to conventional solid in solid state mixing, which is the primary method of polymer mixing in the tire industry, for the resulting particles, such as superior tensile strength, hysteresis and shear. Improvements in physical strength of 200 to 300% or more can be observed compared to what is observed in rubber commonly used in the tire industry.

Based on analysis of the physical properties of samples consisting of mixtures of post-reactor GTRP with small amounts of the original styrene 1,4-cis-polybutadiene polymer, it is possible to achieve on a regular basis a cross-linking density of greater than approximately 80% compared to a compound consisting of the original carbon black masterbatch. tire compounds using dicumyl peroxide (DCP) as a catalyst, curing for two hours at 240°F (approximately 116°C). DCP provides reactive cross-linking below 240°F (about 116°C), but curing temperatures above this threshold will liquefy the tethered sulfur chain so that its labile state will allow for more efficient completion of the rearrangement. Another effective accelerator is di(tert-butylperoxyisopropyl)benzene (CAS No. 25155-25-3, also called DBPI).

Silicone rubber (SiR) grafted with high 1,2-vinyl content butadiene homopolymer functionality can be cross-linked to a mercapto group-containing catalyst. Such mixtures will provide high cross-linking densities and produce homogeneous elastomeric interpenetrating domains exhibiting the excellent hybrid properties known for both groups of rubber. Hybrid SiR, derived from carbon black masterbatch and NR/SBR (natural/styrene butadiene rubber), using regenerated EOL particles, represents a new, cost-effective innovation.

In another embodiment, in an anhydrous environment, the size of the GTRP particles decreases and rearrangement of cross-links occurs. Crumb rubber from EOL tires is preheated to a temperature of about 250°F (about 121°C) (for example, from 230°F (about 110°C) to 270°F (about 132°C), or from 240°F (about 116°C) to 260°F (about 127°C), or 245°F (about 118°C) to 255°F (about 123°C)) in a three-shaft vertical mixer or other suitable mixing device. The reactant (e.g., copper acetate or another metal salt as described herein) in solid form is preheated to a temperature of 250°F (about 121°C) (e.g., preferably above the melting point of the metal salt, e.g., 250°F ( about 121°C) or more, such as 230°F (about 110°C) to 270°F (about 132°C), or 240°F (about 116°C) to 260°F (about 127°C) C), or from 245°F (about 118°C) to 255°F (about 123°C)) in a separate vessel under an inert atmosphere (for example, a layer of nitrogen). In certain embodiments, an inert atmosphere may be optional. The heated reagent is combined with preheated crumb rubber from EOL tires. For example, the heated reactant may be sprayed, sprayed, or poured onto the preheated EOL crumb rubber while mixing to achieve uniform coating and distribution of the reactant on the preheated EOL crumb rubber to form activated EOL crumb rubber. When added directly to preheated crumb rubber from EOL tires, the reagent may preferably be obtained in the form of a finely divided powder.

Application of interconnected rubber material

As discussed herein, the interlinked rubber material of the present embodiments is suitable for use in a wide variety of applications, including tire and road surface applications as described above, or any other applications in which the original natural rubber can be used. By using various reactive adhesive matrices, e.g., hot melts (e.g., asphalt, SBR, polyisobutylene (PIB), and polyethylene (PE)) and multicomponent reactive agents (e.g., fatty acid polyols), artificial products and their properties have been studied. These properties suggest that the compounded interlinked rubber material can cost effectively compete with much more expensive silicone, urethane, epoxy and ethylene propylene diene terpolymer (EPDM) based materials. The compounded interlinked rubber material is waterproof, lightweight, abrasion resistant, resistant to salt, common chemicals and hydrocarbon-based fuels, and has excellent heat and ultraviolet resistance. An interconnected rubber material with properties tailored to a specific application can be obtained by controlling the process dynamics associated with an entangled polymer-nanoparticle composite material that is an interconnected rubber material. For example, in some cases a smaller particle size is not necessary, and there are certain morphological features described herein that can provide superior performance characteristics to the original natural rubber. Nanoparticles have a strong influence on the mechanical properties of the polymer; therefore, during operation, regulating the entropy-enthalpy interaction of host polymer molecular mobility (strain and relaxation) across all time scales can provide many benefits.

It has been found that the performance of the interconnected rubber material can drop sharply as the particle size is reduced below a size that is approximately 5 to 10 times smaller than the random coil radius of the host polymer. This is based on the model that the initial shredded tire mixture typically contains a nanoparticle:polymer cluster, biasing the statistical coil ratio (in favor of the polymer) to greater than 1.0:1.0.

Over two hundred elements that make up a tire can be found in more than 90% of the mass (by element count) of individual GTR particles, suggesting that testing the homogeneity of an interconnected rubber material is impossible, but this is not the case. A reliable method for eliminating sulfide attack, as in the methods of the present embodiments, is intentionally “mild” in disrupting the chemical and intermechanical properties of the composite material, and a system for grading uniformity is currently being developed. The puzzle(s) relating to the observation of composite material viscosity, which contradicts the Einstein-Batchelor viscosity law, will be partially resolved once the sulfide component is no longer influential. Since there is a simple way to study the resulting process yield by correlating the optimal process intensity and articulation, it is expected that the interconnected rubber material can be used in a variety of products, including high performance products. Examples of high performance products include monolithic, structural, self-insulating, in-situ foam panels. Small permanent earthquake-resistant habitats can be created from dried and ground native carbonaceous cellulose-rich vegetation using a chopped fiberglass spray gun and reclaimed GTR as the main binder (at high loads). Secondary sprayed membranes can be installed in tanks and on ships. Automatically sprayed, multi-component, chemical-resistant and pressure-resistant liners can be installed on aging sewer and water pipes without excavation. Monolithic roofing membranes that comply with the UBC (Uniform Building Code) can be fabricated in a factory or applied on site. New underground piping networks for civil infrastructure can be protected with more durable coatings made from interlocking rubber material. Marine structures of all types can be protected from corrosion using PTR-based anti-fouling composite coatings. To provide superior performance, an interlocking rubber material casing can be used to formulate almost any product currently manufactured and must be pest resistant, fuel resistant, mold resistant, bacteria resistant, light and salt resistant.

Synthesis of redesigned elastomeric polymers

A reengineered elastomeric polymer (REEP) that has been pre-crosslinked with sulfur compounds requires breaking the sulfur bonds and incorporating alternative chemical reactions if necessary to improve the final properties of the composition in which REEP is planned to be used as an essential element. Such polymers may include, for example, ground tire rubber, rubber from other sources, other elastomers such as cis-1,4-polyisoprene, trans-1,4-polyisoprene, natural polyisoprene, synthetic polyisoprene, polybutadiene, chloroprene rubber, halogenated butyl rubber non-halogenated butyl rubber, styrene-butadiene rubber, hydrogenated nitrile rubber, non-hydrogenated nitrile rubber or other unsaturated rubbers capable of being cured by sulfur vulcanization or having carbon-sulfur bonds in the polymer backbone, for example -CS _n -C, where n is an integer , equal to two or more. Re-cross-linking improves oxidation resistance and mechanical properties, thereby improving the stress-relaxation spectrum and/or performance spectrum. The final properties of REEP upon re-cross-linking can successfully impart a thermoset (rigid) or thermotropic (elastic) character to the finished composition. In addition, effective reptation (relaxation of the elastomeric polymer) during REEP treatment is more easily achieved by manipulating the internal cross-links (eg, in combination with the interlocking displacement described herein).

Sulfur-cured REEPs are predominantly composed of polysulfide bridges with binding energies of approximately 150 kJ/mol. Reduction of such bridges to a mono- or disulfide state significantly improves the oxidation resistance of the host elastomer, since the binding energies of the mono- or disulfide bridges are approximately 270 kJ/mol. The use of one-step "one-click" metathesis, in which the sulfur bond undergoes hybridization, is a desirable step in the preparation of REEP for final compounding to produce an elastomer-containing product.

The use of a parallel flow microsynthesis reactor (PCMR) to perform single-pass molecular reassembly of REEP can be based on an understanding of the efficiency of the real-time reduction-replacement action within the morphology of the resulting polymer, if necessary to provide the required, post-reactor, dynamic mechanical analytical data. The interaction of the polymer dipole moment within thin "instantaneous" cross sections with a slow flow loop of a reactor with an externally modulated electric field, while capturing both dielectric constant and field twist gradient excursions, provides point-by-point differential data regarding changes resulting from upstream metering stations. It also provides important operational instructions regarding what additional electrochemical “input menu” may be required to achieve the desired end properties when the polymer completes the PCMR rearrangement process. Similar benefits can be found in a PCMR environment using twisted gradient amplification (CGA) technology.

In fig. 8A shows a PCMR according to one embodiment that uses a loop molecular assembly propagation (L-MAP) process by twist gradient amplification. The L-MAP process described herein embeds CGA technology into an advanced modular PCMR platform with unprecedented capabilities for creating new as well as redesigned polymers. Such a reactor contains a turbo integrator 802 to which metered components 801 are added. These components may include monomers, homopolymers, polymers and/or other components. In an exemplary embodiment, to modify the interlinked rubber, the interlinked rubber may be added to the turbo integrator along with other components, for example, one or more monomers, oligomers, or polymers to be grafted onto the interlinked rubber, or one or more reagents to functionalization of interconnected-substituted rubber (for example, for blocking the end groups of the polymer chain, ionic substitution, etc.). In the described embodiment, the mixture of components is heated to 180°F (about 82°C) and supplied to a dedicated pump 803 (dedicated pump #1). The illustrated pump is configured to operate at pressures less than or equal to 100 psi (about 689 kPa) and temperatures less than or equal to 360°F (about 182°C); however, if higher pressures and/or temperatures are required for a particular mixture of components being processed, another pump that meets the specifications for the required pressure and temperature may be substituted. The mixture is then pumped into a stack of pipes 804. To minimize the footprint of the stack, the pipe is designed in a serpentine configuration and has an overall length of 800 inches (2032 cm). The embodiment shown comprises a 4 inch (about 10 cm) diameter stainless steel pipe configured as a stack of ten curved pipe segments, the stack being 120 inches (approximately 305 cm) in length. As the mixture passes through the pipe, the components of the mixture react to form a redesigned elastomeric polymer having a preselected composition and properties. The outlet stream from the pipe is directed to a second pump 805 (specialty pump #2), which pumps the reacted mixture into the drying tank 806 to recover the liquid (eg, at 205°F (about 96°C)). The configuration shown in this embodiment is capable of producing 783 gallons/hour of slurry 807 when using a set of two batteries. The reactor can be scaled to any suitable configuration. For example, one or more turbo integrators or other mixing devices known in the art may be used, optionally with heating or cooling capabilities, under elevated pressure, or while maintaining an inert atmosphere. One turbo integrator can supply one or more batteries, or multiple turbo integrators can supply one battery. One or more pumps may be used, either in series with one battery, in parallel with one battery, or one pump, by means of appropriate piping or valves, can supply several batteries. As discussed above, pumps can be selected depending on the required properties of the mixture being pumped (temperature, pressure, etc.). In some embodiments, the mixture from the battery can be used directly in downstream processes (eg, removing a dedicated #2 pump and/or drying tank from the reactor). Although the battery uses 4-inch (about 10 cm) stainless steel pipe, other diameters can be successfully used, for example, a diameter of 0.25 inches (about 0.64 cm) or less to 6 inches (about 15 cm) or Moreover, any suitable length of pipe may be used that provides sufficient residence time for the components of the mixture to react to produce the preselected product, for example, from 50 inches (127 cm) or less to 2500 inches (6350 cm) or more. In some embodiments, it may be necessary to operate multiple batteries in a series configuration, optionally using a pump located between the batteries, for example, to provide longer residence times or use pumps capable of operating at reduced pressure. The tube(s) may be equipped with a strategic static mixer and chemical injection points to facilitate reaction 804A (FIG. 8A, note 1) and integrated ports 804B for twist gradient amplification (CGA) (FIG. 8A, note 2). In addition, the pipe(s) may also be partially or completely contained within a controlled thermal space, for example a heating or cooling jacket or a temperature controlled immersion bath may be used. Alternatively, the pipe(s) may be exposed to environmental conditions.

In fig. 8B shows a compact tube configuration. In such a configuration, the tube 811 is helical and may be located in the controlled thermal space 810. The helical tube in this configuration may extend axially from the inlet end 811A to the outlet end 811B or may also be configured in a serpentine configuration to further reduce the area occupied by the battery.

The PCMR of the present embodiments can be advantageously used to functionalize or interact the interlinked-substituted product described herein in a manner similar to how the parent natural rubber is interacted or functionalized. Graft polymerization, chain end functionalization, and the like can be carried out. The resulting products may be suitable for use in asphalt cement, rubber tires, specialty rubber products, and the like.

PTR morphology

After numerous experiments, the product streams produced by an alternative batch process using a pressure stirred vessel were studied experimentally. It was discovered that the interconnected rubber material contained tiny golden fibers with a cross-section of approximately 0.002 inch to 0.005 inch and variable length. Such fibers are expected to degrade only when exposed to excessive heat (at temperatures higher than those used in the interlocking displacement process described herein and higher than those typical for hot-mix processes) and will not dissolve in trichlorethylene (TSE).

The presence of such fibers would not be expected to significantly increase the mass of the insoluble component of the submicron interlinked rubber material, but such fiber would be expected to plug the pores of the one micron filter, making the actual filter media less porous and thereby causing a false fraction reading (quanta ) filtrate concentration. Samples of the interlocking rubber material in suspension were passed through a piston diaphragm pump at high temperature and high pressure and through a high strength sintered filter capable of withstanding pressures up to 50,000 psi (345 MPa) through a 1.0 µm orifice. This additional treatment, which is believed to reduce the overall length of the fibers, produced a homogeneous mixture capable of passing through the pores of a one-micron filter. Further processing led to rapid destruction of the rubber with the formation of an easily dispersible submicron fragment with some soot release.

This fibrous component derived from a scrap tire can significantly improve the bond strength between the asphalt to which the interlinked rubber material is added (eg, as a binder or adhesive) and the aggregate, thereby improving the overall performance of the road surface and provides superior pavement performance compared to pavement made from aggregate and asphalt containing virgin natural rubber.

PTR in black-filled masterbatch

An interlinked rubber material produced using laboratory equipment similar to that shown in FIG. 1, under conditions similar to those shown in FIG. 2, was added to the main soot-filled masterbatch with known properties, containing the original natural rubber in an amount of 10 wt%. (after adjusting for aggregates in the interlinked rubber material). The resulting 10% wt. the mixture was subjected to thermogravimetric analysis and other tests. The resulting 10% blend was found to be nearly equivalent in homogenizing ability and physical properties to a master black carbon masterbatch of known properties containing the original natural rubber, such that it would not affect the final performance characteristics of a new tire, or it could be used in a master carbon black masterbatch. masterbatch at a higher loading than the 3 wt% upper limit traditionally used for fully vulcanized fine particle shredded tire rubber (200 mesh). In other words, the interconnected rubber material has been found to be suitable for tire applications as a sole source of rubber, or it can be used in combination with a basic carbon black masterbatch at loadings above 3%, e.g. 4, 5, 6, 7 , 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95% wt. or more.

It was found that the interconnected rubber material contains almost no elemental sulfur, has a morphology similar to the composite original natural rubber, has a particle size of ≤50 μm, and is characterized by significant soot retention in the elastomer. The material is suitable for use in the sidewall of new light truck and automobile tires in amounts of at least 20% and up to 50, 60%, 70, 80, 90% or more (e.g., up to 100%). In addition, such interconnected rubber material is suitable for use in membranes and industrial rubber products.

Rubber polymer IPREX

Xlink Interpenetrating Regenerative Elastomer (IPREX) Rubber Polymer (TRP) is a micro-laminated, anisotropic structured rubber sheet. It consists of several vacuum-fused and cross-linked layers, each of which has a thickness of 10 to 70 microns. This material contains carbon-filled interpenetrating polyisoprene-polybutadiene elastomeric chains, regenerative rearranged cross-links formed by sulfide cross-bridges. Individual lamellae exhibit a near-zero probability of loop formation, and an obliquely directed, parallel reptation, twisted core elastomeric chain structure(s) which, when gradually applied during construction at an angle of 30-45 degrees to the anisotropic "grain" of each previous lamina, forms the finished sheet , exhibiting superior torsional resistance and resilience comparable to isotropic sheets of similar material and section thickness. The pre-crosslinked feedstock is processed into thin slabs by passing it through a high-pressure variable-gap roller mill. IPREX rubber can be produced in two stages from a pre-crosslinked soot-filled masterbatch as feedstock obtained for the production of tires or other engineered rubber products, and/or from EOL waste of whole tires that have been subsequently separated into fine rubber particles (typically 30 mesh, environmentally ground tire rubber) which are then re-compounded according to the pre-determined process parameters of the PRISM reactor described herein. IPREX rubber can be compounded to form an interpenetrating and cross-linked elastomeric network with other elastomers, such as functionalized SiR, to improve chemical and thermal resistance. IPREX rubber is suitable for use in tire sidewall construction, code compliant adhesive tape and potting compounds, industrial belt fabric and hose, high temperature fabrics and gaskets, geotechnical underlays, roofing and waterproofing membranes, colloidal suspensions for industrial adhesives and superpave (system super-durable asphalt coating), hot-melt adhesive PG, modification of asphalt binder.

Performance characteristics of a car tire containing post-reactor GTRP

Post-reactor GTRPs have a lumpy, heterogeneous appearance when leaving the reactor. After drying and compounding with crosslinkers and other optional hybrid elastomers, typically performed in a closed high shear mixer such as a Banbury double paddle or Z-mixer, the GTRP is passed through the narrow gap of a roller mill where the particles are converted into thin sheet. Such thin sheet, unlike conventional VBMB-based elastomeric composites processed in a similar manner, can exhibit anisotropy in the ratio of lengthwise tensile strength to widthwise tensile strength of up to approximately 3:1 . Factors that may contribute to the degree of anisotropy include reactor-controlled reduction in loop formation probability, manipulation of the degree of cross-link dislocation, and/or reduction in internal mixing time.

Reactor controlled loop reduction

Such a factor can statistically add an average of 12.5% by weight of additional effective elastomer to the resulting matrix, since after the dislocation of the sulfur bridge associated with the methyl carbocation precursor with the same backbone, the elastomer is released and dynamically orients (and remains so) as in reptation -displacement, along the lateral axis of the compression stroke (perpendicular to the gap surface of the roller mill).

Manipulating the degree of cross-link dislocation

The elasticity of the remaining cross-links in the EOL tire causes variable residual resistance to dimensional reduction during compounding and production of the final sheet, with the incompletely dislocated particle resisting flattening under the pressure of the roller mill. Such an appendage acts as an anchor, being pulled along that part of the elastomeric matrix that more easily achieves reptation-like dynamics. This effect is a reptation-displacement in the transverse direction of the compression stroke between the rollers.

Reduced internal mixing time

The final size reduction of post-reactor GTRP particles is a function of the number of grinding cycles that the particle endures in a mixer (eg, a double paddle mixer). Since only minimal amounts of additives are typically used to produce GTRP used for rolling into multi-purpose sheets, excessively high shear is not required unless gradual reduction in lump size is desired. Such manipulation of mixing time may have a similar, but slightly less pronounced effect of moving the armature than the effect previously described herein.

When isotropy is appropriate, GTRP can be processed in a manner that is the inverse of these three discriminators. However, unlike VBMB, anisotropic quality can be a huge advantage in structures that must undergo constant flexing yet remain dimensionally stable, such as the sidewall of a vehicle tire.

Treated rubber for tire applications

Industry averages are approximately 15% of a vehicle's operating fuel consumption when overcoming the rolling resistance of a car tire. Much of this resistance is due to tire flex as with each rotation the tread deflects back and forth in a random sinusoidal path in the direction of travel as the tread portion of the tire comes into contact with the road surface. This deformation is contained by the elastic and torsional properties of the tire sidewall, which are transmitted to the solid rim and vehicle suspension. Tire manufacturing design and construction utilizes a reinforcing fabric angled between 15 and 90 degrees to the vertical plane of the rolling tire, which is layered between isotropic VBMB to create a composite structure that maintains a safe and efficient rolling structure. However, significant energy is required to overcome the wide range of torsional mechanisms associated with movement under various surface conditions at variable speeds.

A 40 mil (~1 mm) thick GTRP microlaminated sheet consisting of four 0.010 inch (about 0.025 cm) thick sheets laid in a four microlayer build form, with each sublayer positioned at approximately 45 degree angles to the subsequent laminate structure, demonstrates an increase of approximately 30% or more in torsional resistance compared to a similarly prepared VBMB microlaminated structure. When applying torsion mechanical models, quantified in units of lb-ft, to a tire structure that uses such an anisotropic microlaminated structure, particularly as a component in the two outermost laminate structures of the tire structure, where the stress versus dimensional radius under deformation is the largest, predict a decrease in rolling resistance per unit mass of the tire carcass by 9.5% to 16%. A ten percent (10%) reduction in tire rolling resistance based on current global fuel consumption equates to annual fuel savings of over six billion gallons (6000000000 gallons (approximately 22700000000 L)). Thus, the treated rubber of the present embodiments is particularly useful in tire applications, e.g., in the form of microlaminated sheets (e.g., 2 to 100 or more sheets, e.g., 2 to 20, 2 to 20, or 2 to 5 sheets laminated together) for use in tire sidewalls.

Treated rubber for use in high-quality products

Rubber and rubber-containing materials, according to various embodiments, can be prepared to meet one or more of the following specifications. In some embodiments, rubber and rubber products are produced that meet one or more of the MIL-R specifications listed below. Such products may include, but are not limited to, tire tread, tire sidewall, roof membrane, high dielectric insulation tape, tank liner, tank liner, trench support, bridge bearing surface, foundation waterproofing material, parking garage waterproofing material, hose, belt, casting or other rubber products derived from molded rubber or rubber sheet material (for example, gaskets, piping, shock-absorbing materials, floor mats and bead pads for vehicles, mats and flooring materials for commercial and residential construction, flooring, decking and concrete bases, soundproofing materials, etc.) Other products include rubber bands in clothing and hair ties, dishwashing gloves, toys, container sealants and tires, door mats with a welcome message, garden hoses. Other household items made from rubber include boots, raincoats, pond liners, mattresses and cushions, pillows, garden tool handles, bathtub stoppers, door closers, earplugs, heating pads, aquarium tubes, washing devices and rug pads. The rubber of these embodiments can be used to make stoppers for laboratory flasks and vials, chemical-resistant mats and pads, dentures and other specialized products and equipment, as well as rubber food and water bowls, chew toys and balls, sponge rubber mattress covers, mats , elastic veterinary capes, flea collars, work gloves and rubber combs, mouse pads, keyboards, adhesives and wheels for rolling chairs, high dynamic strength mats, carpet bases, earbuds and rubber seals, air mattresses for camping, playground tiles, rubber ducks, sportswear, diving suits, civil and military vehicle parts; parts of boats, ships and submarines for civil or military use; parts for aircraft, passenger aircraft and fighter jets, parts for railroad cars and railroad engines, products for residential and commercial buildings, in-plant or factory or industrial components, clothing and footwear components.

The treated rubber of the present embodiments can be used in rubber products that meet or exceed one or more of the following ASTM specifications, military specifications (MIL), aerospace materials specifications (AMS), and/or other specifications that are used in various industries using rubber products.

ASTM C542 (ASTM C 1166 Procedure) - Low Smoke, Low Flame, Low Toxicity Neoprene

ASTM E662 - Low Smoke, Low Flame, Low Toxicity Neoprene

ASTM D1330 Grade 1 - Premium SBR - Style 22

ASTM D1330 Grade 2 - Red Rubber SBR - Style 20

ASTM D2000 1AA 430 - Natural Rubber - Style 28

ASTM D2000 1AA 704 Z1 (11=75±5 Durometer) - Red Rubber SBR - Style 20

ASTM D2000 M1AA 407 - Butyl

ASTM D2000M 1AA 417 - Natural Rubber, Pure Gum Floating Natural Rubber, EZ Cut Non-Floating Gum Natural Rubber, Protein Free (Synthetic Polyisoprene) Natural Rubber

ASTM D2000 M1AA 503 - Commercial EPDM

ASTM D2000 M1AA 507 - Butyl

ASTM D2000M1AA 517 - Natural Rubber

ASTM D2000 M1AA 606 - Commercial EPDM

ASTM D2000 M1AA 607 - Butyl

ASTM D2000M1AA 617 - Natural Rubber

ASTM D2000M1AA703Z1 (Z1=75±5Durometer) - Specification Grade SBR (Red)

ASTM D2000 M1AA 706 - Commercial EPDM

ASTM D2000 M1AA 710 - Butyl

ASTM D2000 M4AA 407 A13 B13 C12 F17

ASTM D2000M4AA 421 F17 G21 - Tuff-Stuff® Natural Rubber

ASTM D2000 M4AA 510 A13 B13 C12 F17 - ASTM D2000 M4AA Specification Grade (EPDM)

ASTM D2000 M4AA 610 A13 B13 C12 F17

ASTM D2000 M4AA Specification Grade (EPDM)

ASTM D2000 M4AA 710 A13 B13 C12 F17

ASTM D2000 M4AA Specification Grade (EPDM)

ASTM D2000 M2BA 407 C12 F17 - Premium EPDM - Style 45

ASTM D2000 3BA 508 C12 - Commercial EPDM - Style 40

ASTM D2000 3BA 515 A14B13C12F17 - Premium EPDM - Style 45

ASTM D2000 3BA 608 C12 - Commercial EPDM - Style 40

ASTM D2000 3BA 615 A14 B13 C12 F17 - Premium EPDM - Style 45

ASTM D2000 3BA 708 C12 - Commercial EPDM - Style 40

ASTM D2000 3BA 715 A14 B13 C12 F17 - Premium EPDM - Style 45

ASTM D2000 3BA 815 A14B13C12F17-Premium EPDM - Style 45

ASTM D2000 1BC 408 - Commercial Neoprene - Style 10

ASTM D2000 1BC 508 - Commercial Neoprene - Style 10, Matte Finish Neoprene - Style 12

ASTM D2000 1BC 515 - Mid-Grade Neoprene - Style 15

ASTM D2000 1BC 609 - Commercial Neoprene - Style 10, Matte Finish Neoprene - Style 12

ASTM D2000 1BC 615 - Mid-Grade Neoprene - Style 15

ASTM D2000 1BC 710-Commercial Neoprene - Style 10, Matte Finish Neoprene - Style 12

ASTM D2000 1BC 715 - Mid-Grade Neoprene - Style 15

ASTM D2000 1BC 810 - Commercial Neoprene - Style 10, Matte Finish Neoprene - Style 12

ASTM D2000 M1BC 303 - Mid-Grade Neoprene - 5100 Series, Premium Neoprene

ASTM D2000 M1BC 403 - Mid-Grade Neoprene - 5100 Series, Neoprene Molded Slabs

ASTM D2000 M1BC 407 - Premium Neoprene

ASTM D2000 M1BC 507 - Mid-Grade Neoprene - 5100 Series, Neoprene Molded Slabs

ASTM D2000 M1BC 510 - Premium Neoprene

ASTM D2000 M1BC 607 - Mid-Grade Neoprene - 5100 Series, Neoprene Molded Slabs

ASTM D2000 M1BC 610 - Premium Neoprene

ASTM D2000 M1BC 707 - Mid-Grade Neoprene - 5100 Series, Neoprene Molded Slabs

ASTM D2000 M1BC 710 - Premium Neoprene

ASTM D2000 M1BC 807 - Mid-Grade Neoprene - 5100 Series, Neoprene Molded Slabs

ASTM D2000 M1BC 810 - Premium Neoprene

ASTM D2000 M1BC 907 - Premium Neoprene

ASTM D2000 M2BC 407 A14 B14 C12 F17 Z1 - (Z1=Fungus Resistance per MIL STD 810, Method508), Anti-Microbial Neoprene

ASTM D2000 M2BC 410 A14 B14 C12 E034 F17

ASTM D2000 M2BC Specification Grade (Neoprene)

ASTM D2000 M2BC 510 A14 B14 C12 F17 Z1 - (Z1=Fungus Resistance perMIL STD 810, Method508), Anti-Microbial Neoprene

ASTM D2000 M2BC 510 A14B14 C12E034F17

ASTM D2000 M2BC Specification Grade (Neoprene)

ASTM D2000 M2BC 610 A14 B14 C12 F17 Z1 - (Z1=Fungus Resistance per MIL STD 810, Method508), Anti-Microbial Neoprene

ASTM D2000 M2BC 610 A14 B14 C12 E034 F17

ASTM D2000 M2BC Specification Grade (Neoprene)

ASTM D2000 M2BC 710 A14 B14 C12 E034 F17

ASTM D2000 M2BC Specification Grade (Neoprene)

ASTM D2000 MICA 410 - Peroxide Cure EPDM

ASTM D2000 MICA 510 - Peroxide Cure EPDM

ASTM D2000 MICA 610 - Peroxide Cure EPDM

ASTM D2000 MICA 710 - Peroxide Cure EPDM

ASTM D2000 MICA 810 - Peroxide Cure EPDM

ASTM D2000 1BF 408 Z1 (Z1=Meets basic requirements of BFmaterials), Commercial Nitrile (Buna-N) - Style 3 5

ASTM D2000 1BF 508 Z1 (Z1=Meets basic requirements of BF materials), Commercial Nitrile (Buna-N) - Style 3 5

ASTM D2000 1BF 609 - Commercial Nitrile (Buna-N) - Style 35

ASTM D2000 1BF 710 -Commercial Nitrile (Buna-N) - Style 35

ASTM D2000 1BF 810 -Commercial Nitrile (Buna-N) - Style 35

ASTM D2000 1BG 610 - FDA Nitrile (Buna-N) - Style 37

ASTM D2000 M1BG 407 - Premium Nitrile (Buna-N)

ASTM D2000 M1BG 503 Zl (Z1=45±5 Durometer), WARCO White® FDA Nitrile (Buna-N)

ASTM D2000 M1BG 507 - Premium Nitrile (Buna-N)

ASTM D2000 M1BG 607 Z1 (Z1=55±5 Durometer), WARCO White® FDA Nitrile (Buna-N)

ASTM D2000 M1BG 610 - Premium Nitrile (Buna-N)

ASTM D2000 M1BG 707 Z1 (Z1=65±5 Durometer), WARCO White® FDA Nitrile (Buna-N)

ASTM D2000 M1BG 710 - Premium Nitrile (Buna-N)

ASTM D2000 M1BG 803 - WARCO White® FDA Nitrile (Buna-N)

ASTM D2000 M1BG 810 - Premium Nitrile (Buna-N)

ASTM D2000 M1BG 910 - Premium Nitrile (Buna-N)

ASTM D2000 5BG 613 A14 B14 E014 E014 F17 - Premium Nitrile (Buna-N) -Style 36

ASTM D2000 5BG 620 A14 B14 E034 - Transformer Oil Nitrile (Buna-N)

ASTM D2000 5BG 720 A14 B14 E034 - Transformer Oil Nitrile (Buna-N)

ASTM D2000 M5BG 407 A14 B14 E014 E034 F17 - ASTM D2000 M5BG Specification Grade (Nitrile/Buna-N)

ASTM D2000 M5BG 507 A14 B14 E014 E034 F17 - ASTM D2000 M5BG Specification Grade (Nitrile/Buna-N)

ASTM D2000 M5BG 610 A14 B14 E014 E034 F17 - ASTM D2000 M5BG Specification Grade (Nitrile/Buna-N)

ASTM D2000 M5BG 710 A14 B14 E014 E034 F17 - ASTM D2000 M5BG Specification Grade (Nitrile/Buna-N)

ASTM D2000M1HK 607-Premium Viton® A: 66% Fluorine

ASTM D2000 M1NK 707 - Premium Viton® A: 66% Fluorine, Premium Viton® B: 68% Fluorine

ASTMD2000M1HK 807-Premium Viton® A: 66% Fluorine

ASTM D2000 M1HK 807 Z1 (Z1=75±5 Durometer), Premium Viton® B: 68% Fluorine

MIL-R-900 - MIL-R-900 Specification Grade

MIL-G-1149 - MIL-G-1149 Type 1 Class 1 Grade 50-MIL-R-1149 Specification Grade (Neoprene)

MIL-G-1149 Type 1 Class 2 Grade 50 - MIL-R-1149 Specification Grade (SBR)

MIL-G-1149 Type 1 Class 5 Grade 50 - MIL-R-1149 Specification Grade (Nitrile/Buna-N)

MIL-R-2765 - MIL-R-2765 Specification Grade (Nitrile/Buna-N)

MIL-R-3065 SB 410F2-MIL-R-3065 SB Specification Grade (Nitrile/Buna-N)

MIL-R-3065 SB 515 F2 - MIL-R-3065 SB Specification Grade (Nitrile/Buna-N)

MIL-R-3065 SB 615 F2 - MIL-R-3065 SB Specification Grade (Nitrile/Buna-N)

MIL-R-3065 SB 715 F2 - MIL-R-3065 SB Specification Grade (Nitrile/Buna-N)

MIL-R-3065 SB 815 F2 - MIL-R-3065 SB Specification Grade (Nitrile/Buna-N)

MIL-R-3065 SC310F1 - MIL-R-3065 SC Specification Grade (Neoprene)

MIL-R-3065 SC 408 Z1 (Z1=350% minimum Elongation), Commercial Neoprene - Style 10

MIL-R-3065 SC 410 F2-MIL-R-3065 SC Specification Grade (Neoprene)

MIL-R-3065 SC 508 - Commercial Neoprene - Style 10, Matte Finish Neoprene -Style 12

MIL-R-3065 SC 515 F2 - MIL-R-3065 SC Specification Grade (Neoprene)

MIL-R-3065 SC 609 - Commercial Neoprene - Style 10, Matte Finish Neoprene -Style 12

MIL-R-3065 SC 615 F2 -MIL-R-3065 SC Specification Grade (Neoprene)

MIL-R-3065 SC 710 - Commercial Neoprene - Style 10, Matte Finish Neoprene -Style 12

MIL-R-3065 SC 715 F2 -MIL-R-3065 SC Specification Grade (Neoprene)

MIL-R-3065 SC 810 - Commercial Neoprene - Style 10, Matte Finish Neoprene -Style 12

MIL-R-3065 SC 815 F1 - MIL-R-3065 SC Specification Grade (Neoprene)

MIL-R-3065 RS 508 C1 - Commercial EPDM - Style 40

MIL-R-3065 RS 515 C1 F1 - Premium EPDM - Style 45

MIL-R-3065 RS 608 C1 - Commercial EPDM - Style 40

MIL-R-3065 RS 615 C1 F1 - Premium EPDM - Style 45

MIL-R-3065 RS 708 C1 - Commercial EPDM - Style 40

MIL-R-3065 RS 715 C1 F1 - Premium EPDM - Style 45

MIL-R-3065 RS 815 C1 F1 - Premium EPDM - Style 45

MIL-R-6855 Class 1 Grade40 - MIL-R-6855 Class 1 Fuel Resistant Specification Grade (Nitrile/Buna-N)

MIL-R-6855 Class 1 Grade 50 - MIL-R-6855 Class 1 Fuel Resistant Specification Grade (Nitrile/Buna-N)

MIL-R-6855 Class 1 Grade 60 - MIL-R-6855 Class 1 Fuel Resistant Specification Grade (Nitrile/Buna-N)

MIL-R-6855 Class 1 Grade 70 - MIL-R-6855 Class 1 Fuel Resistant Specification Grade (Nitrile/Buna-N)

MIL-R-6855 Class 1 Grade 80 - MIL-R-6855 Class 1 Fuel Resistant Specification Grade (Nitrile/Buna-N)

MIL-R-6855 Class 2, Grade 30 - MIL-R-6855 Class 2 Oil Resistant Specification Grade (Neoprene)

MIL-R-6855 Class2, Grade40 - MIL-R-6855 Class 2 Oil Resistant Specification Grade (Neoprene)

MIL-R-6855 Class 2, Grade 50 - MIL-R-6855 Class 2 Oil Resistant Specification Grade (Neoprene)

MIL-R-6855 Class 2, Grade 60 - MIL-R-6855 Class 2 Oil Resistant Specification Grade (Neoprene)

MIL-R-6855 Class 2, Grade 70 - MIL-R-6855 Class 2 Oil Resistant Specification Grade (Neoprene)

MIL-R-6855 Class 2, Grade 80 - MIL-R-6855 Class 2 Oil Resistant Specification Grade (Neoprene)

MIL-R-21252 - MIL-R-21252 Specification Grade (EPDM)

MIL-R-83248C Type 2 Class 1 - Fluorozone® Mil-Spec Performance FKM, Military Specification Grade Viton® A, MIL-R-83285

MIL-R-83285 Grade 80 - MIL-R-83285 Grade 80 Specification Grade (EPDM)

AMS 3205 - Aerospace Material Specification (AMS) Grade Low Temperature (Neoprene)

AMS 3208 - Aerospace Material Specification (AMS) Grade Weather Resistant (Neoprene)

AMS 3215 - Aerospace Material Specification (AMS) Grade Fuel Resistant (Nitrile/Buna-N)

AMS 3216 - Fluorozone® Mil-Spec Performance FKM, Military Specification Grade Viton® A

AMS 3301 -INFINISIL™ Spec-Grade Performance Silicone

AMS 3302 -INFINISIL™ Spec-Grade Performance Silicone

AMS 3303 - INFINISIL™ Spec-Grade Performance Silicone

AMS 3304 -INFINISIL™ Spec-Grade Performance Silicone

FDA Approved Ingredients per 21 CFR 177.2600 - FDA Neoprene, WARCO White® FDA Nitrile, Natural Rubber - Style 28, Pure Gum Floating Natural Rubber, Fluorozone® FDA Performance FKM, FDA Viton® A: 66% Fluorine, FDA Red Silicone, FDA White Silicone, FDA Approved Grade TPE (Black), FDA Approved Grade TPE (Neutral)

NSF 51 - NSF 51 & NSF 61 Approved Grade TPE

NSF 61 - NSF 51 & NSF 61 Approved Grade TPE

A-A-59588 2A & 2B - INFINISIL™ Spec-Grade Performance Silicone

SAE J200 1AA 430-Natural Rubber - Style 28

SAE J200 3BA 508 C12 - Commercial EPDM - Style 40

SAE J200 3BA 515 A14 B13 C12 F17 - Premium EPDM - Style 45

SAE J200 3BA 608 C12 - Commercial EPDM - Style 40

SAE J200 3BA 615 A14 B13 C12 F17 - Premium EPDM - Style 45

SAE J200 3BA 708 C12 - Commercial EPDM - Style 40

SAE J200 3BA 715 A14 B13 C12 F17 - Premium EPDM - Style 45

SAE J200 3BA 815 A14 B13 C12 F17 - Premium EPDM - Style 45

SAE J200 1BC 408 - Commercial Neoprene - Style 10

SAE J200 1BC 508 - Commercial Neoprene - Style 10, Matte Finish Neoprene -Style 12

SAE J200 1BC 609 - Commercial Neoprene - Style 10, Matte Finish Neoprene -Style 12

SAE J200 1BC 710 - Commercial Neoprene - Style 10, Matte Finish Neoprene -Style 12

SAE J200 1BC 810 - Commercial Neoprene - Style 10, Matte Finish Neoprene -Style 12

SAE J200 1BF 608 Z1 (Z1=40±5 Durometer) -Commercial Nitrile (Buna-N) -Style 35

SAE J200 1BF 608 Z1 (Z1=50±5 Durometer) -Commercial Nitrile (Buna-N)-Style 3 5

SAE J200 1BF 609 - Commercial Nitrile (Buna-N) - Style 35

SAE J200 1BF 710 - Commercial Nitrile (Buna-N) - Style 35

SAE J200 1BF 810 - Commercial Nitrile (Buna-N) - Style 35

AASHTO Grade 2 - AASHTO Unsupported Neoprene Bearing Pads - Style 71, AASHTO Unsupported Calendered Neoprene Bearing Pads, AASHTO Unsupported Molded Neoprene Bearing Pads, AASHTO Unsupported Neoprene Bearing Pads -Style 72

AASHTO Grade 3 - AASHTO Unsupported Calendered Neoprene Bearing Pads, AASHTO Unsupported Molded Neoprene Bearing Pads

Caltrans 51-1.14 Waterstops - Cal-Trans Strip Water Stops

Boeing BSS 7239 -Low Smoke, Low Flame, Low Toxicity Neoprene

Bombardier SMP 800-C - Low Smoke, Low Flame, Low Toxicity Neoprene

GMP.E/P.002 - General Purpose Grade TPE (Neutral)

GMP.E/P.003 - General Purpose Grade TPE (Neutral)

GMP.E/P.004 - General Purpose Grade TPE (Neutral)

GMP.E/P.005 - General Purpose Grade TPE (Neutral)

GMP.E/P.006 - General Purpose Grade TPE (Neutral)

GMP.E/P.007 - General Purpose Grade TPE (Neutral)

MSAR20A - General Purpose Grade TPE (Black)

MSAR20B - General Purpose Grade TPE (Neutral)

MSAR20C - General Purpose Grade TPE (Neutral)

MSAR20D - General Purpose Grade TPE (Neutral)

MSAR20E - General Purpose Grade TPE (Neutral)

MSAR30A - General Purpose Grade TPE (Neutral)

MSAR30B - General Purpose Grade TPE (Neutral)

MSAR40A-Flame Retardant Grade TPE

MSAR40B - Flame Retardant Grade TPE

WSD-M2D379-A1 - General Purpose Grade TPE (Neutral)

WSD-M2D380-A1 - General Purpose Grade TPE (Neutral)

WSD-M2D381-A1 - General Purpose Grade TPE (Neutral)

WSD-M2D382-A1 - General Purpose Grade TPE (Neutral)

WSD-M2D441-A-General Purpose Grade TPE (Neutral)

WSD-M2D712-A1 - General Purpose Grade TPE (Neutral)

HHP-151F - HHP-15IF Cloth-Inserted (C1), Fungus Resistant, Anti-Microbial Neoprene

General Electric EA12C11E7 - Transformer Oil Nitrile (Buna-N)

ASTM D 178-93 Type 1 Class 2 - ASTM Switchboard Type 1 Rubber Matting

ASTM D2000 1AA - Corrugated Matting, Heavy Corrugated Matting, Lightweight KleenRite® Matting, Molded Slabs

AASHTO Grade 2 - AASHTO Unsupported Molded Neoprene Bearing Pads

AASHTO Grade 3 - AASHTO Unsupported Molded Neoprene Bearing Pads

Rubber polymer PRISM™

The treated rubber, in some embodiments, can be used in PRISM™ rubber polymer, a polybutadiene-butyl rubber hybrid masterbatch material incorporating phase reticulation induced sulfide metathesis (PRISM). PRISM™ rubber polymer can be compounded to contain up to eight additional blended polymers, but typically no more than three additional polymers (e.g., SBR, natural rubber and/or EPDM), depending on the end application. PRISM™ rubber polymer comprises an interpenetrating dual elastomeric network in which two completely different backbone chemistries have been tightly woven and then cross-linked separately from each other. This process achieves superior spatial weave and superior torsional mechanical properties compared to conventional masterbatch material to provide superior stability in all applications. The benefits of PRISM™ rubber polymer include high performance/cost ratio, improved mechanical, chemical and electrical properties, excellent oxidation resistance, significant reduction in carbon footprint, sustainable polymer chemistry. PRISM™ rubber polymer is suitable for use in tire sidewalls, roofing membranes, high dielectric insulation tape, tank liner, tank lining, trench support, bridge bearing surface, foundation waterproofing material, parking garage waterproofing material, rubber hoses, rubber belts and rubber casting.

Illustrative Methods, Apparatus and Compositions

Method 1: A method for producing modified rubber, comprising: introducing an aqueous suspension containing vulcanized rubber particles and an organometallic compound into an electromechanical reactor configured to create a phase space environment by cavitation so as to cause delamination of the rubber matrix within the vulcanized rubber particles in coordination with breaking of sulfide bonds.

Method 2: The method according to Method 1, additionally including the restoration of dislocated sulfide bonds with the formation of rearranged layered structures within the matrix cross-linked by sulfur bridges.

Method 3: The method according to Method 1, in which the delamination is caused by the fact that part of the hard sulfide bridges of the vulcanized rubber particles at the original methyl carbocation become unbound, while remaining attached at the original allylic carbocation.

Method 4: The method according to Method 1, in which the organometallic compound contains a metal with an octahedral molecular geometry.

Method 5: The method according to Method 1, wherein the organometallic compound contains a metal ion selected from the group consisting of Co ²⁺ , Cu ²⁺ , Ni ²⁺ , Zn ²⁺ and Mn ²⁺ .

Method 6: The method according to Method 1, in which the organometallic compound contains an organic anion as a ligand for the metal ion.

Method 7: The method according to Method 6, in which the organic anion contains acetate ion.

Method 8: The method according to Method 1, in which the organometallic compound is copper acetate.

Method 9: The method according to Method 1, in which the organometallic compound is a metal salt undergoing a phase transition from a solid to a liquid state in a temperature range of 115 to 150°C.

Method 10: The method according to Method 1, in which the temperature in the electromechanical reactor is maintained at ambient levels using a cooling jacket or cooling coils.

Method 11: The method according to Method 1, in which the particle size of the vulcanized rubber crumb is more than 200 mesh.

Reactor 12: An electromechanical reactor comprising: a rotor having a plurality of slots; and a stator, wherein said electromechanical reactor is configured to create a phase space environment by forming a mixture of entrained air, an organometallic compound and shredded tire rubber particles in a liquid undergoing cavitation.

Matrix 13: A heterogeneous rubber-based matrix comprising an interpenetrating network of two or more elastomers, wherein said network comprises sulfur-bridged, rearranged interlaced layered structures having an average distance between 10 nm and 5 µm, wherein each layered structure contains one of two or more elastomers.

Matrix 14: Matrix according to Matrix 13, further containing carbon black particles dispersed between the layered structures.

Matrix 15: The matrix according to Matrix 13, in which two or more elastomers contain a raw material natural rubber and an elastomer obtained from ground tire rubber.

Matrix 16: A matrix according to Matrix 13, in which two or more elastomers comprise a virgin natural styrene-butadiene/butadiene rubber and an elastomer derived from ground tire rubber.

Matrix 17: A matrix according to Matrix 13 in which two of the two or more elastomers have different backbone chemical structures.

Matrix 18: A matrix according to Matrix 13 in which two of two or more elastomers having different backbone chemical structures are closely woven and then cross-linked separately from each other.

Sheet 19: Rubber-based heterogeneous matrix sheet according to Matrix 13.

Sheet 20: Sheet according to Sheet 19 showing anisotropy in the ratio of length tensile strength to width tensile strength, wherein the anisotropy of length tensile strength to width tensile strength is from 1.1:1 to 3:1.

Layered structure 21: A layered structure containing a plurality of sheets according to Sheet 19.

Layered structure 22: The layered structure according to Layered structure 21, in which the thickness of each of the sheets is from 10 to 70 μm.

Layered Structure 23: The layered structure according to Layered Structure 21, in which each of the sheets is obtained by vacuum deposition and stitched to an adjacent sheet.

Layered Structure 24: The layered structure of Layered Structure 21, in which each of the sheets is oriented at an angle of 30 to 45 degrees to the anisotropic grain of the adjacent sheet.

Structure 25: A composite structure of ground tire rubber having a non-bonded, reptation internal morphology, wherein a portion of the rigid sulfide bonds contained therein are each attached to the parent allylic carbocation and unbound at the parent methyl carbocation.

Vulcanized Rubber 26: Vulcanized rubber in which a portion of the rigid sulfide bonds contained therein are each attached to the parent allylic carbocation and unbound at the parent methyl carbocation, and in which a portion of the polymer backbone in the vulcanized rubber is replaced by an acetate moiety.

Interconnected rubber 27: Interconnected rubber substantially described herein.

Product 28: Tire tread, tire sidewall, roofing membrane, high dielectric insulation tape, tank lining, tank lining, trench support, bridge support surface, wire harness winding, self-adhesive wire harness winding, shoe soles, rubber boots, insulation tape, a foundation waterproofing material, a parking garage waterproofing material, a hose, a belt or a casting containing the interlocking rubber product described herein.

Rubber Tire 29: A rubber tire in which 3% by weight to 15% by weight of rubber in the tire is produced by a method substantially described herein.

Rubber Tire 30: A rubber tire in which from 15% by weight to 100% by weight of rubber in the tire is produced by a method substantially described herein.

Tire Tread 31: A tire tread comprising from 10% by weight to 50% by weight of interconnected rubber substantially as described herein.

Tire Sidewall 32: A tire sidewall containing from 5% by weight to 100% by weight of interconnected rubber substantially as described herein.

Rubber-asphalt binder 33: A rubber-asphalt binder containing from 5% by weight to 95% by weight of interconnected rubber substantially described herein.

Asphalt Emulsion 34: An asphalt emulsion containing from 5% by weight to 95% by weight of interconnected rubber substantially as described herein.

Asphalt Roofing Material 35: An asphalt roofing material containing from 5% by weight to 95% by weight interlocking rubber substantially as described herein.

Although the present invention has been illustrated and described in detail in the drawings and description above, such illustrations and description are to be considered as illustrative or exemplary and not limiting. The present description is not limited to the embodiments shown. Modifications to the described embodiments can be understood and implemented by those skilled in the art through practice of the claimed invention based on examination of the drawings, description, and appended claims.

All references cited herein are incorporated by reference in their entirety. To the extent that publications and patents or patent applications incorporated by reference conflict with the disclosure contained in the specification, it is intended that the specification supersede and/or take precedence over any such conflicting material.

Unless otherwise specified, all terms (including technical and scientific terms) are given to one skilled in the art in their ordinary and generally accepted meaning and are not to be limited to a special or specialized meaning unless otherwise expressly defined herein. It should be noted that the use of specific terminology in describing certain features or aspects of the present invention should not imply that such terminology is redefined herein to limit the inclusion of any specific characteristics of the features or aspects of the present invention with which such terminology is associated. The terms and phrases used in this application, and variations thereof, particularly in the appended claims, unless expressly stated otherwise, are to be construed as non-limiting and not limiting. As examples of the foregoing, the term “including” should be understood to mean “including without limitation,” “including but not limited to,” or the like; as used herein, the term “consisting of” is synonymous with “comprising,” “comprising,” or “characterized by,” and is inclusive or non-limiting and does not exclude additional, unmentioned elements or process steps; the term “having” should be understood as “having at least”; the term “includes” is to be understood as “including but not limited to”; the term “example” is used to provide illustrative examples of the subject under discussion and is not an exhaustive or limiting list; adjectives such as "famous", "normal", "standard" and terms of similar meaning should not be construed as limiting the subject matter described to a given time period or subject matter available at a given time, but instead it is to be understood that such terms includes known, conventional or standard technologies that may be available or known now or at any time in the future; and it should be understood that the use of such terms as "preferred", "preferred", "required" or "desirable" and words of similar meaning is not intended to imply that certain features are critical, essential or even important in terms of the structure or function of the present invention but instead, these terms are simply intended to emphasize alternative or additional features that may or may not be used in a particular embodiment of the present invention. Likewise, a group of items related by “and” should not be construed as requiring the presence of each and every one of those items in the grouping, but rather should be understood as “both/or” unless expressly stated otherwise. Likewise, a group of items related by “or” should not be considered to require mutual exclusivity among such a group, but rather should be understood as “and/or” unless expressly stated otherwise.

When a range of values is given, the upper and lower limits and each intermediate value between the upper and lower limits of said range are meant to be included in embodiments of the present invention.

With respect to the use of substantially any plural and/or singular terms herein, those skilled in the art may translate from plural to singular and/or from singular to plural depending on the context and/or application. Various singular/plural permutations may be explicitly stated herein for the sake of clarity. A singular noun does not exclude plurality. One processor or other device can perform the functions of several elements shown in the claims. The mere fact that certain measures are set forth in mutually distinct dependent claims does not mean that a combination of such measures cannot be used to obtain an advantage. Any reference numerals in the claims should not be construed as limiting the scope.

In addition, those skilled in the art will understand that if a specific number is implied by an inclusion in the claims, then such intent will be expressly expressed in the claim, and in the absence of such inclusion, there is no corresponding intent. For example, to facilitate understanding, the following claims may include the use of the introductory phrases “at least one” and “one or more” used to introduce inclusion in the claims. However, the use of such phrases should not be construed as implying that the inclusion of an inclusion in a claim in a single form limits any particular claim containing such inclusion to embodiments containing only one such inclusion, even when that same claim contains introductory phrases “one or more” or “at least one” and non-specific singular nouns (for example, singular nouns should generally be understood to mean “at least one” or “one or more”); the same applies to the use of specific nouns used to introduce inclusions in the claims. Moreover, even if an inclusion in a claim clearly states a specific number, those skilled in the art will understand that such inclusion should generally be interpreted to mean at least the stated number (e.g., simply including "two inclusions" without other modifiers typically means at least at least two inclusions or two or more inclusions). Moreover, where a conditional expression similar to “at least one of A, B, and C, etc.” is used, such construction is generally used in the sense that one skilled in the art would understand the specified conditional expression (for example, “a system containing at least one element of A, B and C” will include, but is not limited to, systems containing only A, only B, only C, A and B together, A and C together, B and C together and/or A, B and C together, etc.). Where a conditional expression similar to "at least one of A, B or C, etc." is used, such construction is generally used in the sense in which one skilled in the art would understand the conditional expression (e.g., "a system containing at least one element of A, B, or C" will include, but is not limited to, systems containing only A, only B, only C, A and B together, A and C together , B and C together and/or A, B and C together, etc.). In addition, those skilled in the art will appreciate that virtually any dividing word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to include consideration of the inclusion of one of the terms , either term or both terms. For example, the phrase "A or B" should be understood to include the possibilities "A" or "B" or "A and B."

All numbers expressing quantities of ingredients, reaction conditions, etc., used in the description of the invention are to be understood as being modified in all cases by the term “about.” Accordingly, unless otherwise indicated, the numerical parameters given herein are approximate values that may vary depending on the desired properties sought to be achieved. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of any claim in any application claiming priority based on this application, each numerical parameter should be considered in light of the number of significant digits and normal rounding techniques. Moreover, although the foregoing document has been described in some detail by way of illustrations and examples for the purposes of clarity and understanding, it will be apparent to those skilled in the art that certain changes and modifications may be made in practice. Accordingly, the foregoing description and examples should not be construed as limiting the scope of the invention to the specific embodiments and examples described herein, but rather to include all modifications and alternatives that fall within the true scope and spirit of the invention.

Claims (12)

1. A heterogeneous rubber-based matrix for the production of rubber-containing products, containing an interpenetrating network of two or more elastomers, wherein said network contains sulfur-bridged, rearranged interwoven layered structures, the average distance between which is from 10 nm to 5 μm, each the layered structure comprises one of two or more elastomers selected from the group consisting of virgin natural rubber, styrene-butadiene rubber, isobutylene-isoprene rubber, and ground tire rubber elastomer. 2. The matrix according to claim 1, additionally containing soot particles dispersed between the layered structures. 3. The matrix according to claim 1, in which the two or more elastomers contain the original natural rubber and an elastomer obtained from ground tire rubber. 4. The matrix of claim 1, wherein the two or more elastomers comprise a virgin natural styrene-butadiene/butadiene rubber and an elastomer derived from ground tire rubber. 5. The matrix of claim 1, wherein two of the two or more elastomers have different backbone chemical structures. 6. The matrix of claim 1, wherein two of the two or more elastomers having different backbone chemical structures are closely woven and then cross-linked separately from each other. 7. A sheet intended for use in rubber-containing products, containing a heterogeneous rubber-based matrix according to claim 1. 8. The sheet according to claim 7, showing anisotropy in the ratio of tensile strength along the length to the tensile strength across the width, wherein the anisotropy of the tensile strength along the length to the tensile strength across the width ranges from 1.1:1 to 3:1. 9. A layered structure intended for use in rubber-containing products, containing a plurality of sheets according to claim 7. 10. Layered structure according to claim 9, in which the thickness of each sheet is from 10 to 70 microns. 11. The layered structure according to claim 9, in which each of the sheets is obtained by vacuum deposition and stitched to an adjacent sheet. 12. The layered structure according to claim 9, in which each of the sheets is oriented at an angle of 30 to 45 degrees to the anisotropic grain of the adjacent sheet.