Method to produce functional NANO-size particles by antiferromagnetic metallocene reactions from end-of-life ground tire rubber

Abstract

Functional nanoparticles are prepared from end-of-life ground tire rubber (EOL-GTR). A method is provided of dissolving a metallocene to a molecular state in a solvent medium and applying the solution onto the surface of an EOL-GTR particle within a controlled reactor environment. An in-situ process is provided for extracting sulfur components within a vulcanized elastomer matrix, such that the extracted rubber may be re-synthesized into end-uses analogous to those of an original, virgin non-sulfurized polymer matrix by utilizing hyperbranched macromolecules (HMs) in which all bonds converge to a focal point or core, and which have a multiplicity of reactive chain-ends.

Description

WCOE.050WO PATENTMETHOD TO PRODUCE FUNCTIONAL NANO-SIZE PARTICLES BY ANTIFERROMAGNETIC METALLOCENE REACTIONS FROM END-OF-LIFE GROUND TIRE RUBBERFIELD

[0001] Functional nanoparticles are prepared from end-of-life ground tire rubber (EOL-GTR). A method is provided of dissolving a metallocene to a molecular state in a solvent medium and applying the solution onto the surface of an EOL-GTR particle within a controlled reactor environment. An in-situ process is provided for extracting sulfur components within a vulcanized elastomer matrix, such that the extracted rubber may be re-synthesized into end¬ uses analogous to those of an original, virgin non-sulfurized polymer matrix by utilizing hyperbranched macromolecules (HM's) in which all bonds converge to a focal point or core, and which have a multiplicity of reactive chain-ends.BACKGROUND

[0002] In 2015, end-use markets consumed 87.9% percent by weight of the scrap tires generated in the U. S, The total volume of scrap tires consumed in end use markets in the U. S, reached approximately 3551 thousand tons of tires. RMA estimates that about 4038 thousand tons of tires were generated in the U. S. in 2015. Of those tires, 25.8% were used to produce ground rubber, 48.6% for tire derived fuel, 11.4% were land disposed, 7.0% were used in civil engineering, and 7.1% went to miscellaneous uses (0.7% to electric arc furnace, 1.3% to reclamation projects, 2.6% were exported, and 2.6% went to other uses). In 1990, only eleven percent, of tires were consumed on a per tire basis. Positive end-use market results in 2015 were primarily the result of high rates of TDF use and lower exports. In the long term, the need to expand all economically viable and environmentally sound markets for scrap tires is still imperative. Scrap tires were consumed by a variety of scrap tire markets, including tire- derived fuel, civil engineering and ground rubber applications. Other smaller markets and legal landfilling consumed the remaining annually generated tires.

[0003] Key scrap tire markets include tire derived fuel, ground rubber, civil engineering and other markets. In tire derived fuel applications, scrap tires are used as a cleanerand more economical alternative to coal as fuel in cement kilns, pulp and paper mills and industrial and utility boilers. Ground rubber applications utilize approximately 1020 thousand tons of scrap tires, or over 25 percent of the volume of scrap tires generated each year. Ground rubber is produced by grinding scrap tires into size defined pieces. Ground rubber applications include new rubber products, playground and other sports surfacing and rubber-modified asphalt. Ground rubber also includes larger pieces of rubber used as landscaping mulch, and loose fill playground material. The playground and mulch market were the most dynamic segment in the ground rubber market during this period. The asphalt market uses ground rubber to modify the asphalt binder used in road paving, resulting in quieter, more durable roads. The civil engineering market consumes approximately 274 thousand tons of tires per year, about 7.7 percent of the total tires to market, and consists of tire shreds used in road and landfill construction, septic tank leach fields, alternative daily cover and other construction applications. Additional smaller markets for scrap tires exist that consume approximately 7% of annually generated scrap tires. These markets include tires consumed in electric arc furnaces (steel manufacturing), professionally engineered tire bales and products punched, pressed, or stamped from scrap tires. Total tire rubber consumed in ground rubber markets is about 1.36 billion pounds. The total scrap tires diverted to these ground rubber markets is about 1.02 million tons (62 million tires). The percentage of total pounds of ground rubber consumed in the market in 2015 is as follows: sport surfaces 25%, playground mulch 22%, molded / extruded products 35%, asphalt 15%, automotive uses 2%, and export 1%.

[0004] Stockpiles of scrap tires historically began to be created around the 1960s and 1970s when tires were diverted from landfills, but recycling markets for them were not functional. Stockpiles proved to be prone to catastrophic fires which created air and water pollution.

[0005] Worldwide rubber tire production is responsible for generating approximately 99% of worldwide, end-of-life (EOL) tire scrap. About 1.1 billion scrap tires are generated annually, corresponding to roughly 12 million tons of scrap tire. Due to the punishing physical properties required of a new tire, tires embody a carefully engineered weaving together of steel and fiber cords with a mineral and carbon-filled rubber blend, all cross linked to a highly tenacious structure. The EOL tire is challenging to breakdown to its original essential elements. The potentially highest value component - the rubber - isparticularly difficult to reclaim, due to the vulcanization process it is subjected to. As a result, EOL tires that are no longer suitable for use on vehicles due to wear or irreparable damage are typically either subject to pyrolysis (e.g., to generate energy for use in cement manufacturing), or ground up to be used as filler (e.g., in asphalt pavement, new tires, construction or landscaping materials).

[0006] The market for natural and synthetic rubber for non-tire applications was estimated at 13.9 million tons in 2021 and is expected to be 16.9 million tons by the end of 2027, with a compound average growth rate of 3.4%. The global market for natural and synthetic elastomers for non-tire applications by end use, 2023, is reported as follows: automotive and transportation 30.6%; building and construction 11.7%; industrial products 11.2%; wire and cable 9.2%; polymer modification 9.1%; electric and electronic 7.6%; footwear 5.9%; bitumen modification 4.4%; others 4.4%; coatings / sealants / adhesives 3.1%; medical / healthcare 2.7%.

[0007] While the global non-tire elastomer market is considerably smaller than the global tire market, it is far broader in both the number and the type of applications. While tire applications require a relatively small range of rubbers to execute the needs of the tireproducing industries, the non-tire industries are characterized by the wide number of elastomers currently in use, many of which find no place in the production of tires.

[0008] The main driver for elastomers is the demand for increased performance. Improvements can be desired in heat resistance, chemical resistance and, in many cases, improved compression set. Certain key areas are identified that can assist in meeting this demand. In the area of natural rubber developments, Versalis, Italy and Bridgestone Americas have signed an agreement to commercialize natural rubber derived from the guayule shrub. The agreement will enable Versalis and Bridgestone to focus on development of proprietary highly productive varieties of guayule using cuting-edge genetic technologies. While this development is focused on the production of natural rubber for tires, it is evident that non-tire applications in both Europe and the US will benefit from these initiatives. The European Union set up a program some time ago to develop production of guayule, principally for surgical gloves, and other companies and organizations are expected to also take the initiative to develop non-Asia-sourced natural rubber, the driving force being to obtain independence of supply for Europe and the US.J

[0009] Unlike paper and cardboard, which are able to replace plastics in certain applications, rubbers cannot be replaced by any other known substances. There is, of course, inter-competition amongst various types of rubber or elastomer. For example, styrene¬ butadiene rubber (SBR) in solution form has almost replaced emulsion SBR in many automotive tire applications. There is now evidence that it will begin to replace emulsion SBR in a number of non-tire applications also, due to its better abrasion resistance, superior flexibility and enhanced deformation recovery.

[0010] The rapid emergence of polyolefin elastomers (POEs) is causing some concern to suppliers of ethylene propylene diene monomer (EPDM) rubber, since POEs are now replacing EPDM for a number of applications. POEs have excellent low-temperature properties and the olefin block copolymers (OBCs) are beginning to replace EPDM in thermoplastic elastomers (TPEs).

[0011] Developments in regulations are another important factor. The most important regulation put into European law is Regulation 1907 / 2006 for the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH). The regulation requires a list to be compiled of all chemical substances used or likely to be used in the production of plastics and rubbers. A recent problem has occurred in Germany, in respect to the use of rubber in the production of hoses for the use of drinking water. It is predicted that vulcanized elastomers are likely to be banned by the German authorities for this application, due to the fact that they contain Substances of Very High Concern (SVHCs) as defined by REACH. While REACH is a purely European Union (EU) regulation, it is very likely to have knock-on impacts on multiple types of rubber goods imported into Europe. Just as the global nature of the tire trade, with trans-regional imports and exports, means that EU tire labelling regulations have a strong influence on that global industry.

[0012] Manufacturing and processing methods are another important factor. Vulcanized rubbers suffer from the drawback that they require production methods with extended curing process times to achieve their desired properties. This limitation has been accepted for many years, because the advantages of the properties of rubber compounds outweigh their disadvantages. The introduction of thermoplastic elastomers, which require no vulcanization, has sharpened the need for more efficient rubber component production processes.

[0013] For technical reasons, the vulcanization of rubber compounds cannot be accelerated so as to match the comparatively short cycles of thermoplastic processing. These problems have been addressed by on-line vulcanization and by extending the process or adding a post-curing oven to the production line.

[0014] Accordingly, there is a need for improvements in methods of producing vulcanized rubbers that address the aforementioned concerns, as well as a need for vulcanized rubber materials having superior properties or characteristics when compared to conventional materials.SUMMARY

[0015] Extensive research efforts over many years have been devoted to development of methods for devulcanizing vulcanized rubber, e.g., tire rubber, so as to transform tire rubber into a commercially viable product having properties similar to virgin composite rubber. These efforts have generally met with limited success, until the recent development of methods as documented in PCT Publ. No. WO 2018 / 200340, PCT Publ. No. WO 2019 / 135815, PCT Publ. No. WO 2019 / 028286, PCT Publ. No. WO 2022 / 146464, PCT Publ. No. WO 2021 / 225848, PCT Publ. No. WO 2021 / 178575, PCT Publ. No. WO 2021 / 141750, and PCT Publ. No. 2002 / 231807, the contents of each of which are hereby incorporated by reference in their entirety. The present methods provide an improvement to these processes and compositions, enabling the processes to be conducted with greater environmental safety, to yield products of desirable physical properties, and / or to enable the process to be conducted a more cost-efficient manner.

[0016] Functional nanoparticles are prepared from end-of-life ground tire rubber (EOL-GTR). A method is provided of dissolving a metallocene to a molecular state in a solvent medium and applying the solution onto the surface of an EOL-GTR particle within a controlled reactor environment. A progressive exfoliation ensues, such that a dimensional reduction of the larger EOL-GTR particles to sub-micron dimensions is achieved. The size reduction occurs while stabilizing the chemistry of the particles’ interpenetrating carbon / elastomer morphology. An in-situ process is provided for extracting sulfur components within a vulcanized elastomer matrix, such that the extracted rubber may be re-synthesized into end-uses analogous to those of an original, virgin non-sulfurized polymer matrix by utilizing hyperbranched macromolecules (HMs) in which all bonds converge to a focal point or core, and which havea multiplicity of reactive chain-ends. The process is useful for treating sulfur crosslinked waste streams from many sources, including new rubber article production downfall and end-of-life (EOL) scrap tires, benefiting global resource sustainability as well as the energy and carbon challenges associated with mitigating climate change.

[0017] A process for incorporating an iron-based organometallic compound (OMC) into a vulcanized rubber matrix, such as crumb rubber obtained from recycled tires or other vulcanized rubber, is provided, whereby properties of the rubber matrix are modulated. The process involves formation of iron-sulfur components by reaction with sulfur in the rubber matrix. The resulting rubber is suitable for use in applications typically utilizing virgin rubber, such as new tires, engineered rubber articles, and asphalt rubber for use in waterproofing and paving applications.

[0018] To date, Asphalt Rubber (AR) roads are proven to be America’s best, most cost-effective road design. AR roads are built to pass ASTM 20% tire rubber binder content standards. According to Cal Trans, Rubberized Asphalt Concrete (RAC = AR) long term studies, such RAC road costs about 50% more to build but when the durability and low maintenance is factored into the calculus it is “28% more cost effective”. AR roads have conventionally been so expensive to build because the binder is so stiff and prone to settling that it cannot be compounded in a central plant like most Asphalt / C on crete (A / C) road materials. Instead, it requires specially trained crews, operating an on-site, mobile train which digests the GTR into the asphalt on-the-fly, then mixes in the aggregate and immediately places it onto the road bed. Even then the AR materials must be placed at 350 - 375°F (in contrast to normal A ASHTO pavement application temperatures that are ~250°F max). If too cool, the AR road material will not properly compact and must be ripped up or ground smooth as it is easier than trying to salvage it. But, even with this degree of difficulty, the AR road can easily outlast a conventional well-built, AASHTO PG “super pave” road by two times, and have zero maintenance costs for the first 15 years of useful life. 15 years is the expected useful life of an AASHTO PG "super pave” A / C road. After 15 years it usually requires expensive overlay(s), crack sealants and pothole repairs to correct numerous safety defects which begin cropping up within a period as early as the second year of original placement.

[0019] A key innovation of the NTR binder technology disclosed herein that enables building a better road is the size of the nano tire rubber (NTR). To meet AASHTOPG standards, the rubber must be reduced to a sub-micron size but still be able to perform like the unmodified, 600 micron, ground tire element which makes the AR road adhesive so durable. A set new processing tools has been developed to bring the AR tire rubber performance qualities in-line with AASHTO PG Standards. These new tools overcome seven challenges not previously known to have been solved: 1) the ability to dissolve the scrap tire to an intact, particle small enough to pass through a one micron filter, 2) the ability to keep the scrap tire at the AR prescribed approximate 20% loading of the binder weight, 3) the ability to make the final, compounded asphalt-based adhesive viscosity’ to be easily installed at / or below' 300°F, 4) the ability to maintain the three properties of high temperature stiffness, low' temperature flexibility and resilience to the accelerated aging of the RTFO and PAV test, 5) the ability to remain homogenous during long term storage, 6) the ability to pass a bevy of water resistance and anti-stripping tests, and 7) the ability to maintain, installed-cost- equivalency with standard PG binder systems. The NTR binder technology provides solutions to one or more of the aforementioned problems.

[0020] Of the seven challenges outlined above, the one which has proved the most difficult to overcome by conventional means is particle size reduction, e.g., a 600 x particle size reduction (comminution) that is achieved without destroying the original GTR resilience. Accordingly, a particle size of, e.g., 30 mesh can be taken down to 25 microns or less. When heated, paving-grade asphalt is a sticky but amorphous chemical with good tire rubber-swelling properties, while not effective at intact comminution. SARA fraction analysis has been divided into two categories: maltenes (MALT) and asphaltenes (ASPT). The sticky, ductile and dissolving category' is MALT and the hard, mostly brittle category' is the ASPT. The ultimate value-add, the core feature for the performance grading (PG) of a binder, is rooted in the crude oil source and how' it is refined. To meet AASHTO PG Standards for unmodified grades, the asphalt’s variability' is seldom adequate without cross blending, and it can be impossible to achieve by conventional means both a solvent quality for digesting GTR as well as all the other prescriptive requirements of the PG Standard associated with polymer modified grades.

[0021] The process of using select fatty acid bio-resins such as soybean or canola oil has become a tool to make a better A / C binder. With just the right balance of short and long carbon chains, endowed with reactive, double-carbon bonds, this tool’s chemistry effectively implements intact size-reduction of the GTR to the sub-micron moiety’ required by AASHTO'ssolubility test. The bio-chemistry and process method(s) may be customized to augments the variety of asphalt(s) available across the world of crude oil sources and petroleum refineries, while also providing the natural chemistry to be cross linked (XLNK), with fractional amounts of carefully chosen chemicals and process methods. Upon tire particle size-reduction to such a tiny speck, the NTR technology reliably re-synthesizes all the elements into a high performance whole, thereby meeting the needed robustness and durability as specified by both A STM and AASHTO Standards.

[0022] The NTR 20% tire rubber road binder prepared according to the methods herein presents none of problems of the construction and extra costs associated with conventional AR roads, and may perform as well or better than conventional AR roads. Critical new' added values may include fast track high performance designs that can cut traffic delays, performance exceeding the performance of all current conventional A / C binders, a substantial reduction in carbon footprint to build and maintain road systems, highly sustainable construction materials, and a universal binder chemistry. Use of the ferrocene and norbornene technologies described herein, along with the use of unsaturated oils, such as soybean oil and canola oil, enables production of NTR that meets the challenges of building better roads, and provides a rubber material that is useful in other applications as described herein.

[0023] One of the objects of certain methods described herein include production of functional (nano)particles (e.g., NTR) from end-of-life ground tire rubber or other cross¬ linked rubber containing products, e.g., as found in end-of-life (EOL) rubber tires or other vulcanized rubber goods or vulcanized materials. The object of certain of these methods is to produce, with greater efficiency and / or cost effectiveness and / or precision and / or yield, functional nanoparticles of EOL-GTR having desired properties. The functional nanoparticles can be sui table for use as a raw material in the fabrication of articles of manufacture that would conventionally be fabricated from virgin rubber subjected to vulcanization, e.g., new tires or other vulcanized rubber products. In certain embodiments, the functional nanoparticles, when used in the production of rubber articles, can offer superior or advantageous properties, either in the end product or the method of manufacture thereof, when compared to conventional materials and methods using virgin rubber or recycled vulcanized rubber. The vulcanized rubber starting material subjected to the methods described herein is typically provided as aconventionally available, 30 mesh, end-of-life, ground tire rubber particle (GTRP), or smaller particle size material. The methods described herein can be employed to achieve the object of transforming EOL-GTR into a functional particle having desirable properties. Another object of the methods of selected embodiments is to produce certain rubber chemistries that can deliver a stabilized elastomer that does not contain extractable SVHCs pursuant to REACH.

[0024] One of the objects of certain methods described herein is to process, with greater efficiency, greater cost effectiveness, reduced environmental impact, and / or increased sustainability, products derived from vulcanized rubber or other sulfur cross-linked elastomer containing products, e.g., as found in end-of-life (EOL) rubber tires, into a form suitable for use as a starting material in the fabrication of articles of manufacture that would conventionally be fabricated from virgin rubber or elastomer subjected to vulcanization, e.g., new' tires or other vulcanized rubber products. The methods described herein can be employed, e.g., to transform EOL tire rubber into an elastomer product having desirable properties, e.g., a similarity of selected properties to virgin elastomer, or even superior properties.

[0025] One of the objects of certain methods described herein is to process, with greater efficiency and / or cost effectiveness, vulcanized rubber products or other crosslinked rubber containing products, e.g., as found in end-of-life (EOL) rubber tires, into a form suitable for use as a raw material in the fabrication of articles of manufacture that would conventionally be fabricated from virgin rubber subjected to vulcanization, e.g., new' tires or other vulcanized rubber products. The vulcanized rubber subjected to certain of the methods described herein is typically provided as a conventionally available, 30 mesh, end-of-life, ground tire rubber (GTR) particle (GTRP), or smaller particle size material. The methods described herein can be employed to transform EOL tire rubber into a rubber product (referred to variously herein as “ PTR”) having desirable properties.

[0026] Accordingly, in a generally applicable first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a method is provided for preparing an elastomer product, comprising: combining, under pressure, a mixture of sulfur-crosslinked elastomer and a hyperbranched macromolecule having a plurality of reactive chain ends, whereby resident sulfur in rubber crosslinks of the sulfur-crosslinked elastomer matrix is removed, whereby an elastomer product is obtained.

[0027] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), wherein 1-20 wt. %, optionally 2-10 wt. %, optionally 5 wt. % of the mixture is the hyperbranched macromolecule.

[0028] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the sulfur-crosslinked elastomer is an end-of-life tire particle, optionally, having a size of 100-1000 microns, optionally a size of 500-700 microns, optionally a size of 600 microns.

[0029] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the sulfur-crosslinked elastomer is vulcanized rubber.

[0030] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the sulfur-crosslinked elastomer is coated with the hyperbranched macromolecule in a pug mill.

[0031] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture is generated in a co-rotating, intermeshing twin screw extruder-reactor.

[0032] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture is generated in a co-rotating reactor, optionally a co-rotating reactor comprising an annular cavity wherein a series of rotating lobes create pressure impingement upon the mixture as it progresses through the co¬ rotating reactor.

[0033] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture is generated in a co-rotating reactor compression bars adapted to subject the mixture to pressure pulses.

[0034] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture is generated in a multi-lobe, co-rotating mixer extruder.

[0035] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), pressure is applied in a series of pulses, wherein each particle of the mixture encounters 120,000 or more pulses in production of the rubber-based elastomer.

[0036] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), pressure is applied by passing the mixture between two rollers.

[0037] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture passes between the two rollers from 3 to 100 times.

[0038] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture passes between the two rollers from 3 to 10 times.

[0039] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture passes between the rollers from 3 to 5 times.

[0040] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the two rollers have a nip of 0.007 inches to about 0.050 inches.

[0041] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), one of the two rollers rotates faster than the other.

[0042] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), one of the two rollers rotates faster than the other, optionally up to 1.15 times faster than the other.

[0043] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), one of the two rollers has a variable speed of from 5 to 150 rpm.

[0044] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the two rollers have a variable speed of from 5 to 150 rpm.

[0045] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), pressure is applied in a series of pulses, wherein a temperature of the mixture rises to over 200°C at a peak pressure in a pulse and then subsides until a next pulse.

[0046] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the pressure is from 100-400 megapascals.

[0047] In an embodiment of the first aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture further comprises one or more of a virgin rubber or a virgin elastomer or a synthetic rubber.

[0048] In a second aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a mixture is processed in a continuous process comprising: coating ground tire rubber particles with hyperbranched macromolecules having a plurality of reactive chain ends in a spray-mixing auger or pugmill to obtain coated ground tire rubber particles; and feeding the coated ground tire rubber particles through a screw reactor to obtain processed particles, whereby rubber-based elastomer particles are obtained.

[0049] In an embodiment of the second aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the reactor is a twin-screw reactor.

[0050] In an embodiment of the second aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the processed particles are squeezed with a screw through a high shear knife-die assembly, whereby an elastomer product comprising 50-75 micron-sized rubber particles is obtained.

[0051] In an embodiment of the second aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture is processed using a single screw extruder, armed with one or more tiny orifice breaker plates, and run at pressures of from 400-600 bars, whereby an elastomer product comprising approximately 10 micron-sized rubber particles is obtained.

[0052] In an embodiment of the second aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture comprises 1-10% by weight hyperbranched macromolecules.

[0053] In an embodiment of the second aspect (i. e., independently combinable with any of the aspects or embodiments identified herein), the mixture comprises 5% by weight hyperbranched macromolecules.

[0054] In a generally applicable third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), an elastomer product is provided prepared by the method of any of the first or second aspects or embodiments thereof.

[0055] In an embodiment of the third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product is subjected to cross-linking.

[0056] In an embodiment of the third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product is fabricated into a rubber-containing article.

[0057] In an embodiment of the third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the rubber-containing article is a new tire.

[0058] In an embodiment of the third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the rubber-containing article is an engineered rubber article.

[0059] In an embodiment of the first, second, or third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture further comprises a virgin elastomer.

[0060] In an embodiment of the first, second, or third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the virgin elastomer comprises natural rubber, styrene-butadiene rubber, or a mixture thereof.

[0061] In an embodiment of the first, second, or third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product is a rubber-based elastomer molded into a molded rubber product.

[0062] In an embodiment of the first, second, or third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the sulfur-crosslinked elastomer is in a form of ground tire rubber having an average particle size of approximately 600 microns.

[0063] In an embodiment of the first, second, or third aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the ground tire rubber is end-of-life tire rubber.

[0064] In a generally applicable fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a method is provided for preparing an elastomer product, comprising: combining a mixture of sulfur-crosslinked elastomer and hyperbranched macromolecules having a plurality of reactive chain ends, whereby resident sulfur in rubber crosslinks of the sulfur-crosslinked elastomer matrix is removed, whereby an elastomer product is obtained.

[0065] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), combining is conducted under conditions of elevated temperature and / or pressure.

[0066] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the reactive chain ends comprise sulfonium moieties.

[0067] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), 1-20 v. %, optionally 2-10 wt. %, optionally 5 wt. % of the mixture is the hyperbranched macromolecule.

[0068] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the sulfur-crosslinked elastomer is an end-of-life tire particle, optionally, having a size of 100-1000 microns, optionally a size of 500-700 microns, optionally a size of 600 microns.

[0069] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the sulfur-crosslinked elastomer is vulcanized rubber.

[0070] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the sulfur-crosslinked elastomer is coated with the hyperbranched macromolecule in a pug mill.

[0071] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture is generated in a co-rotating, intermeshing twin screw extruder-reactor.

[0072] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture further comprises one or more of a virgin rubber or a virgin elastomer or a synthetic rubber.

[0073] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product is combined with one or more of a virgin rubber or a virgin elastomer or a synthetic rubber.

[0074] In an embodiment of the fourth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the sulfur-crosslinked elastomer is ground rubber tire particles, the method further comprising: coating the ground tire rubber particles with the hyperbranched macromolecules in a spray-mixing auger or pugmill to obtain coated ground tire rubber particles; and feeding the coated ground tire rubber particles through a screw reactor to obtain processed particles, whereby rubber-based elastomer particles are obtained.

[0075] In a generally applicable fifth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), an elastomer product is provided prepared by the method of the fourth aspect or any of its embodiments.

[0076] In an embodiment of the fifth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product is subjected to cross-linking.

[0077] In an embodiment of the fifth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product is fabricated into a rubber-containing article.

[0078] In an embodiment of the fifth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product comprises a component of a new tire.

[0079] In an embodiment of the fifth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product comprises an engineered rubber article.

[0080] In an embodiment of the fifth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product further comprises a virgin elastomer.

[0081] In an embodiment of the fifth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the virgin elastomer comprises natural rubber, styrene- butadiene rubber, or a mixture thereof.

[0082] In an embodiment of the fifth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer product comprises a molded rubber product.

[0083] In a generally applicable sixth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a colloid suspension is provided comprising the elastomer product of the fifth aspect or any embodiments thereof.

[0084] In an embodiment of the sixth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the colloid suspension comprises a suspension of <25 micron-sized rubber particles.

[0085] In an embodiment of the sixth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the <25 micron-sized rubber particles have similar physical properties to those exhibited in an original tire composite from which they are derived.

[0086] In a generally applicable seventh aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a process substantially as described herein is provided.

[0087] In a generally applicable seventh aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a product substantially as described herein is provided.

[0088] In a generally applicable eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a method for preparing a functional rubber is provided, comprising: exfoliating end-of-life rubber particles by reaction with a metallocene, whereby a particle size of the exfoliated end-of-life rubber particles is reduced while maintaining a vulcanizing property and an inner structure of the exfoliated end-of-life rubber particles, whereby a functional rubber is obtained.

[0089] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the metallocene is ferrocene.

[0090] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a surface area of the exfoliated end- of-life rubber particles is 1000-fold greater than a surface area of the end-of-life rubber particles.

[0091] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the ferrocene is provided in a form of a solution in a solvent.

[0092] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), at least a portion of the solvent is recovered after exfoliating.

[0093] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), at least a portion of the solvent is recycled for further use in exfoliating.

[0094] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the solvent is dichloromethane.

[0095] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the exfoliating is conducted in a stator-rotor reactor.

[0096] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), two or more stator-rotor reactors in sequence are provided, such that a sequential series of exfoliating steps is performed.

[0097] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the solution is sprayed into a stream of the end-of-life rubber in the stator-rotor reactor.

[0098] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the solution is ferrocene in dichloromethane at a temperature of approximately 50°F and the stream of the end-of-life rubber particles is at a temperature greater than 270°F.

[0099] In an embodiment of the eighth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a dwell time in the stator-rotor reactor is 20-50 ms.

[0100] In a generally applicable ninth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a functional rubber prepared by the method of the eighth aspect is provided.

[0101] In an embodiment of the ninth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the functional rubber is subjected to cross-linking.

[0102] In an embodiment of the ninth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the functional rubber is provided with one or more functional groups or reactive groups.

[0103] In an embodiment of the ninth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the functional rubber is fabricated into a rubber-containing article.

[0104] In an embodiment of the ninth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the rubber-containing article is a component of a tire.

[0105] In an embodiment of the ninth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the rubber-containing article is a coating.

[0106] In an embodiment of the ninth aspect (i.e,, independently combinable with any of the aspects or embodiments identified herein), the rubber-containing article is a sheet,

[0107] In an embodiment of the ninth aspect (i.e,, independently combinable with any of the aspects or embodiments identified herein), the rubber-containing article is an engineered rubber article.

[0108] In a generally applicable tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a method is provided for preparing a rubber¬ based elastomer, comprising: applying pressure to a mixture comprising sulfur-crosslinked rubber particles and an iron-based organometallic compound, then releasing the pressure, whereby a rubber-based elastomer is obtained.

[0109] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the iron-based organometallic compound is derived from iron oxide nanoparticles.

[0110] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the iron-based organometallic compound is derived from superparamagnetic iron sulfide nanoparticles.

[0111] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the iron-based organometallic compound is a ferrocene.

[0112] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the iron-based organometallic compound is prepared by reacting cyclopentadiene monomer with soybean oil in a presence of iron oxide nanoparticles having a diameter of from about 1 to 100 nanometers, optionally from about 2 to 20 nanometers.

[0113] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the iron-based organometallic compound is prepared by reacting cyclopentadiene monomer with soybean oil in a presence of superparamagnetic iron sulfide nanoparticles having a diameter of from about 2 to 20 nanometers.

[0114] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the iron-based organometallic compound is present in the mixture at from 1 to 10 % by weight of the mixture.

[0115] In an embodiment of the tenth aspect (i.e,, independently combinable with any of the aspects or embodiments identified herein), the iron-based organometallic compound is present in the mixture at about 5 % by weight of the mixture.

[0116] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the rubber-based elastomer is combined with asphalt as an asphalt modifier.

[0117] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the mixture further comprises a virgin elastomer.

[0118] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the virgin elastomer comprises natural rubber, styrene-butadiene rubber, or a mixture thereof.

[0119] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the rubber-based elastomer is molded into a molded rubber product.

[0120] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the sulfur-crosslinked rubber particles are in a form of ground tire rubber having an average particle size of approx. 600 microns.

[0121] In an embodiment of the tenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the ground tire rubber is end-of-life tire rubber.

[0122] In an eleventh aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), an elastomer prepared by the method of the tenth embodiment or any aspect thereof is provided.

[0123] In an embodiment of the eleventh aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer is subjected to cross¬ linking.

[0124] In an embodiment of the eleventh aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the elastomer is fabricated into a rubber¬ containing article.

[0125] In an embodiment of the eleventh aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the rubber-containing article is a new' tire.

[0126] In an embodiment of the eleventh aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the rubber-containing article is a floor mat.

[0127] In an embodiment of the eleventh aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the rubber-containing article is an engineered rubber article.

[0128] In a twelfth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a material substantially as described herein.

[0129] In a thirteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a process substantially as described herein.

[0130] In a fourteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), an apparatus substantially as described herein.zo

[0131] In a fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a method is provided for preparing a functional rubber material, comprising: reacting a vulcanized rubber with an unsaturated oil in the presence of a ferrocene catalyst, whereby a functional rubber material is obtained.

[0132] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the unsaturated oil is soybean oil, optionally high oleic soybean oil.

[0133] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the unsaturated oil is canola oil.

[0134] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a weight ratio of unsaturated oil to ferrocene is 96:4.

[0135] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the vulcanized rubber is ground tire rubber, optionally having a particle size of 30 mesh.

[0136] In an embodiment of the fifteenth aspect (i.e,, independently combinable with any of the aspects or embodiments identified herein), from 75-95 parts by weight of vulcanized rubber is present in the functional rubber material.

[0137] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), 80 parts by weight, of vulcanized rubber is present to 20 parts by weight of a combination of the unsaturated oil and the ferrocene catalyst.

[0138] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), 85 parts by weight, of vulcanized rubber is present to 15 parts by weight of a combination of the unsaturated oil and the ferrocene catalyst.

[0139] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises combining the functional rubber material with an asphalt.

[0140] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises addinga crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

[0141] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises adding a styrene-butadiene-styrene block copolymer to the functional rubber material.

[0142] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

[0143] In an embodiment of the fifteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises fabricating the functional rubber material into a rubber-containing article.

[0144] In a sixteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a functional rubber material is provided that is prepared by the method of the fifteenth aspect.

[0145] In a seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a method is provided for preparing a functional rubber material, comprising: reacting a vulcanized rubber with an unsaturated oil in the presence of a norbornene, whereby a functional rubber material is obtained.

[0146] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the unsaturated oil is soybean oil, optionally high oleic soybean oil.

[0147] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the unsaturated oil is canola oil.

[0148] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a weight ratio of unsaturated oil to norbornene is 50:50.

[0149] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the vulcanized rubber is ground tire rubber, optionally having a particle size of 30 mesh.

[0150] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), from 75-95 parts by weight of vulcanized rubber is present in the functional rubber material.

[0151] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), 80 parts by weight of vulcanized rubber is present to 20 parts by weight of a combination of the unsaturated oil.

[0152] In an embodiment of the seventeenth aspect (i. e., independently combinable with any of the aspects or embodiments identified herein), 85 parts by weight of vulcanized rubber is present to 15 parts by weight of a combination of the unsaturated oil.

[0153] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises combining the functional rubber material with an asphalt.

[0154] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

[0155] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises adding a styrene-butadiene-styrene block copolymer to the functional rubber material.

[0156] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.Z3

[0157] In an embodiment of the seventeenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), the method further comprises fabricating the functional rubber material into a rubber-containing article.0158] In a eighteenth aspect (i.e., independently combinable with any of the aspects or embodiments identified herein), a functional rubber material prepared by the method of the seventeenth aspect is provided.

[0159] Any embodiment of any aspect may be combined, in whole or in part, with any other embodiment of any other aspect(s) or embodiment(s). Likewise, any feature of an embodiment or aspect may be combined, in whole or in part, with any other embodiment(s) or aspect(s).BRIEF DESCRIPTION OF THE DRAWINGS

[0160] FIG. 1A provides a top view and end view of an embodiment of a horizontal compression reactor.

[0161] FIG. 1B provides an exploded view of the horizontal compression reactor of FIG. 1A.

[0162] FIG. 1C provides a top view of the horizontal compression reactor of FIG.1A.

[0163] FIG. 1D provides an end view of the horizontal compression reactor of FIG.1A.

[0164] FIG. 2 provides schematics of the process of compressing rubber crumb precoated with reactant in a horizontal compression reactor.

[0165] FIGS. 3A-3C provide views of an embodiment of a micro-compounding reactor incorporating twin counter rotating screws. FIG. 3 A provides a view of the barrel, FIG.3B provides a view of the end plate, and FIG. 3C provides a view of one of the rotating screws.

[0166] FIGS. 4A and 4B depict view's of an interfusion reactor 1700 incorporating a shaft collar 1701, four thrust bearings 1702, a ’4 meh shaft 1703, an oilite bearing 1704, a ’4 meh stainless steel (ss) housing lid 1705, a shaft collar 1706, a 3 / 8 inch stainless steel rotor 1707, shims 1708 (as needed), a 3 / 8 meh stainless steel spacer 1709, a 3 / 8 meh stainless steel stator 1710, an oilite bushing 1711, and a A meh bushing plate 1712.

[0167] FIG. 5A depicts a standard mixing lobe design including a first lobe 5001 with side view 5003, and a second lobe 5002.

[0168] FIG. 5B depicts a modified lobe design and a modified barrel design. The design includes a first lobe 5001 and a second lobe 5002. The barrel (jacketed barrel 5011) is a two-piece clamshell barrel 5005. Three alternative Stress-Strain Lug (SSL) designs 5006 are depicted. Piezoelectric transducer driven acoustic horns 5007 are provided, which are associated with an area of quantum field activity 5008. The gap 5009 between paired lobes is 0.015” and the gap 5010 between a lobe and the barrel is 0.050”.

[0169] FIG. 5C is a photograph showing details of the paired lobes of the CPE.

[0170] FIG. 5D is a photograph of the CPE with half of the clamshell barrel removed, exposing the interior and showing the arrangement of lobes and rotating screws.

[0171] FIG. 5E depicts a modified lobe design and a modified barrel design similar to that depicted in FIG. 5B, showing the engagement of the lobes 5001 and 5002. The design includes an upper one-half reactor tunnel 5020, a lower one-half reactor tunnel 5021, ultrasonic transducers 5022, and alternating ports (not depicted) at upper and lower work positions for liquid nitrogen injection. The liquid nitrogen mitigates, by cold temperature embrittlement, the otherwise flexible ground tire rubber particle. This achieves quicker and more complete size reduction when coordinated with the ultrasonic transducer pulses from the piezoelectric transducer driven acoustic horns.

[0172] FIG. 6 depicts an RPA (Rubber Process Analyzer) curing curve and associated data for an exemplary rubber formula.

[0173] FIG. 7A depicts a force-displacement curve and FIG. 7B depicts a stress-strain curve for an exemplary rubber formula.

[0174] FIG. 8 depicts a DMA (Dynamic Mechanical Analysis) temperature sweep test graph for an exemplary rubber formula.

[0175] FIG. 9 is a process flow chart depicting the process of preparing a colloid suspension of rubber particles derived from recycled vulcanized rubber (e.g., ground tire rubber).

[0176] FIG. 10 provides a reaction sequence for the ring opening metathesis polymerization (ROMP) / radical polymerization (RP) between cyclopentadienyl ferrocene complex (cpFe) and a sulfur bridge (S8) of an EOL-GTR.

[0177] FIG. 11 provides a dra wing of a reactor configured to generate a functional (nano)particle rubber from EOL-GTR.

[0178] FIG. 12 provides IDEAL-CT test results for SJR modified binders.0179] FIG. 13 provides IDEAL-CT test results for SJR modified binders and reference binders.

[0180] FIG. 14 provides IDEAL-CT test results alongside IDEAL-RT test results for SJR modified binders and reference binders.DETAILED DESCRIPTION OF THE EMBODIMENTS

[0181] The following description and examples illustrate an embodiment of the present technology in detail. Those of skill in the art will recognize that there are numerous variations and modifications of this technology that are encompassed by its scope. Accordingly, the description of an embodiment should not be deemed to limit the scope of the present technology.AbbreviationsAASHTO - American Association of State Highway Transportation Officials APART - Asphalt Pavement & Recycling Technologies, Inc.ASPT - AsphaltenesAFM - Anti-ferromagneticASTM - American Standard Testing MaterialsCANO - Canola OilCAT - CatalystCRPM - Counter Rotating Pug MillDCPD - DicyclopentadieneER - Elastic RecoveryFc - FerroceneGTR - Ground Tire RubberIDEAL-CT - Indirect Tensile Cracking TestLSPS - Low Speed Propeller StirMALT - MaltenesMER - Mixer Extruder ReactorNAPA - National Asphalt Pavement AssociationNBE - NorborneneNTR - Nano Tire RubberOMC - Organo Metallic CompoundPa*s - Pascal SecondsPAV - Pressure Aging VesselPG - Performance GradeREOB - Recycled Engine Oil BotomsRT - Room TemperatureRTFO - Rolling Thin Film OvenRV - Rotational ViscositySARA - Saturates, Aromatics, Resins, AsphaltenesSBO - Soybean OilSBO-HO - Soybean Oil High OleicSBS - Styrene Butadiene Styrene (General Polymer 1000)SIR - San Joaquin RefiningTBAc - Tert Butyl AcetateTCE - TrichloroethyleneTTI - Texas Transportation InstituteXI NR - CrosslinkZ c - Zinc AcetateZDTC - Zinc Diethyl-DithioCarbamateIntroduction

[0182] Extensive research efforts over many years have been devoted to development of methods for devulcanizing vulcanized rubber, e.g., tire rubber, so as to transform tire rubber into a commercially viable product having properties similar to virgin composite rubber. These efforts have generally met with limited success, until the recent development of methods as documented in PCT Publ. No. WO 2018 / 200340, PCT Publ. No. WO 2019 / 135815, PCT Publ. No. WO 2019 / 028286, PCT Publ. No. WO 2019 / 135815, PCT Publ. No. WO 2021 / 178575, PCT Publ. No. WO 2021 / 225848, PCT Publ. No. WO 2021 / 225848, PCT Publ. No. WO 2021 / 225848, and PCT Publ. No. WO 2022 / 231807, the contents of each of which are hereby incorporated by reference in their entireties. The present methods provide an improvement to these processes and compositions, enabling the processes to be conducted with, e.g., greater environmental safety, higher efficiency, to yield products ofdesirable physical properties, and / or to enable the process to be conducted in a more cost- effective manner.

[0183] Metallocene molecular complex(s) formed from the reaction of metals such as nickel (Ni), cobalt (Co), and in particular iron (Fe) consist of three cells: an upper (outer) layer consisting of two non-symmetrical, tilted cyclopentadienyl (cp) rings and a core with three symmetrical elements arranged with a metal ion at the center. This symmetrical configuration mismatch induces the upper layer of the metallocene molecule to exhibit ground state anti- ferromagnetism. By dissolving the metallocene to a molecular state in a solvent medium and applying the solution onto the surface of an EOL-GTR particle, within a controlled reactor environment, a progressive exfoliation ensues, such that a dimensional reduction of the larger particles, e.g., by up to 1000 times or more, to sub-micron dimensions is achieved. This exfoliation occurs while stabilizing the chemistry of the interpenetrating carbon / elastomer morphology.

[0184] The Joint Research Council (JRC) for the EC recently published a Critical Raw Material (CRM) study in December 2017 listing 27 materials subject to supply disruption; a disruption that would result in significant loss of economic sustainability. Natural rubber (NR) was listed as one of the 27 materials. The process disclosed herein can provide up to 70% of the natural rubber gap referred to in the CRM study.

[0185] An ambient, end of life (EOT.), ground tire rubber (GTR) particle in the size range of approximately 600 microns (30 mesh), also referred to as a ground scrap tire moiety (GSTM), has a cross section composed of either the old tire tread or the tire side wall or a combination of the two. It may be generally characterized as a heterogeneous matrix of an interpenetrating, cross linked, elastomer network filled with inorganic substances, primarily carbon. Depending upon whether it is primarily tire tread or sidewall in origin the primary- entangled elastomers will be natural rubber (NR) or styrene butadiene / butadiene rubber (BR S-BR), with the BR and S-BR typically having the larger mass component in the tread for better wear and the sidewall having an NR bias for improved flexural qualities. The crosslink may generally be described as elemental sulfur and / or a complex compound incorporating sulfur as its principal element, e.g., a polysulfidic chemical.

[0186] During tire construction the interpenetrating elastomer networks are formed using a sequential crosslink of the predominant elastomer (NR or S-BR ) followed by thecrosslink of the secondary elastomer, such that the secondary elastomer is “bent” to conform to the already vulcanized, higher strength primary elastomer. This technique imparts mechanical characteristics that are retained in the individual GTR particle.0187] A single vehicle tire, after being stripped of steel and fiber reinforcement wall yield approximately sixteen pounds (16 lbs.) of reusable GTR, with truck tires yielding more. Over one billion EOL tires are generated worldwide annually. About 50% are consumed as low value fuel. Where possible, maximizing the reuse of this raw material for its proven mechanical properties represents a substantial challenge, but to the extent achieved, a resource recovery value of as much as 200: 1 is observed when comparing its possible re-use in new tire construction to being consumed in a furnace for its BTU content.

[0188] Notably, recent detailed studies of the environmental advantages such a reversal of EOL-GTR. usage, maximized, predicts that atmospheric carbon contribution might be reduced by the equivalent of shutting down 14 coal fired power plants (300,000 rail cars of coal) or removing six million vehicles from the roads or planting an additional 62 million acres of forests (equivalent to an area the size of the state of Arizona) for carbon sequestration. Accordingly, one object of the methods and compositions discussed herein is to prepare the GTR particle so that it may be integrated into the full spectrum of industrial rubber goods manufactured worldwide.

[0189] Unassisted, elemental sulfur will slowly crosslink functional rubber polymers, but the process is too slow and has too many end property difficulties to be a commercially realistic alternative to a commercially successful vulcanization. Vulcanization as discussed herein regards an accelerated sulfur vulcanization process as is practiced in commercial vulcanization.

[0190] Sulfur vulcanization was discovered by Charles Goodyear in 1839. After 178 years of development, it is universally agreed that the processes are complex which result in the formation of the transverse sulfuric bridge between adjacent, interpenetrating rubber polymers. These bridges in turn yield mechanical properties in an elastomeric material which are critical to civilization. However, much progress has been made and many definitive elements of the progression are well established.

[0191] While a free-radical mechanism had long been assumed to be the controlling phenomena, more recently, with the advent of more advanced methods of discreet processcharacterization, a convincing presence has not been detected of the primary, theoretical radicals necessary to validate that mechanism. In contrast, an ionic mechanism has been predicted and validated using similar advanced process characterization methods. Since the modern vulcanization process involves many chemical components being mixed together at the start of the process, each (combination) with its own chemical reaction pathway, it is likely that both radical and ionic mechanisms are active, but analysis reveals that the ionic mechanism is predominant.

[0192] A typical example (by wt. %) of an NR-BR tire compound is: NR 80%, BR 20%, ZnO 5%, steric acid 2%, silica-talc 3%, carbon black 55%, aromatic oil 10%, elemental sulfur 1.7%, N-Cyclohexyl-2-benzothiazole sulfenamide (CBS - an accelerator) 1.2%, 2-(4-Morpholinothio)-benzothiazole (MBS - an accelerator) 1.1%, and N-tert-butyl-2- benzothiazole sulfenamide (TBBS - an accelerator) 1.1%.

[0193] The process begins in a heated mold, after the tire recipe components have been thoroughly distributed and dispersed. The vulcanization process may be seen in three sequential events: 1) formation of the accelerator complex chemistry, 2) formation of the crosslink precursor, and 3) completion of the crosslink.Conventional Usage of Scrap Rubber in Tire

[0194] Excluding the rubber trimmings generated prior to the final heating and cross linking of new tires, it is estimated that less than 0,004% by weight of all EOT tires are reincorporated into a new tire master batch. Such reincorporation has been successfully- accomplished at master batch loadings for passenger car tires of up to 3% by weight utilizing very fine, cryogenically processed ground rubber obtained from EOL tires. A loading of EOL tire-derived processed ground rubber greater than this has thus far not been feasible, in that the physical properties required of new tire applications are not met at higher loading levels. Tire production typically begins with a base formula of components, with the base formula developed by selection of raw material(s). This is then reduced to a master batch in high shear mixing equipment. Typically, the master batch is done in two phases: the master pass and the finish pass. The master pass combines various rubber species which are introduced as small bales or sheets and are blended with fine powders of carbon black and minerals, as well as a small quantity of process oil(s). This step is performed at the high temperature required to lower the viscosity of the rubber elements such that the flow-resistant powder elements can beuniformly distributed in sufficiently small clusters or packets. These clusters or packets can then be subsequently dispersed to a minimal particle size. The finish pass is done at a lower temperature and usually under process conditions that create more of a smearing action of the heterogeneous elements. In the finish pass, rubber polymers are not further degraded by high temperatures as in the master pass, and the uniformly distributed agglomerates of powder components are worked into such small physical size that they become dispersed within the free molecular space of the rubber elements. Once the finish pass is completed, the master batch bales are ejected from the mixer and rolled into thin sheets (referred to as milling). The milled sheets are used to lay up, on specialized forming equipment, the tire carcass prior to being placed in a compression molding press for final crosslinking by thermal and / or chemical means.

[0195] Crosslinking accelerants include mercapto group or sulfur-based (e.g., elemental sulfur and / or, accelerator derivatives of N-tert-butyl-2-benzothizolesulfenamide (TBBS)). The sulfur-based crosslinking agents which react with sites in the master batch at or above a prescribed temperature may be partially introduced at both the master pass and the finish pass phase. The crosslinking during the final heating of the tire carcass causes the reactive sites in the various rubber elements to build a sufficient crosslink density to achieve the final physical properties required to meet the sustained load and heat environment to which the tire will be subjected.Rubber from End-of-Life Tire Scrap

[0196] Rubber-containing crumb is manufactured from two primary feedstocks: tire buffings, a byproduct of tire retreading, whole tire, and scrap tire rubber. Scrap tire rubber comes from three types of tires: passenger car tires; truck tires; and off-the-road tires. End product yields for each of these tire types are affected by the tire’s construction, strength, and weight. On average, 10 to 16 pounds of end-of-life tire crumb can be derived from one passenger tire. Other sources of rubber-conta ining crumb include products containing or made using recycled rubber-containing crumb, e.g., new rubber products, playground surfacing, rubber mulch, drainage aggregate, construction fill material, scraps from manufacturing, and the like.

[0197] Tires are composite structures containing a number of components. The tire carcass is composed of the tread, bead, sidewall, shoulder, and ply. Tires are formed fromcomponents such as natural and / or synthetic rubber, cords, and filler. The polymer most commonly employed for the tread and encasement of the cords is a blend of NR and S-BR copolymer. Cords form the ply and bead of the tire and provide tensile strength necessary to contain the inflation pressure. Cords can comprise steel, natural fibers such as cotton or silk, and synthetic fibers such as nylon or Kevlar. Fillers can include silica and carbon black. A representative tire can comprise 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, miscellaneous inert materials, and steel wire.

[0198] The typical passenger tire comprises 14% natural rubber, 27% synthetic rubber, 28% carbon black, 14-15% steel, and 16-17% fabric, fillers, accelerators, antiozonants, and other miscellaneous components. The average weight of a new passenger car tire is 25 lbs., and for a scrap passenger tire 22 lbs. Truck tires typically contain 27% natural rubber, 14% synthetic rubber, 28% carbon black, 14-15% steel, and 16-17% fabric, fillers, accelerators, antiozonants, and other miscellaneous components. The average weight of a new truck tire is 120 lbs,, and for a scrap truck tire 110 lbs. Other types of tires can contain higher amounts of synthetic and / or natural rubber, e.g., 70% (by weight) rubber, 15% steel, 3% fiber, and 12% of other materials such as inert fillers. Rubber is found in tire components including tread, innerliner, beads, belts, and the like. The percent rubber by weight in a new passenger tire is typically as follows: 32.6% m tread; 1.7% in base, 21.9% in sidewall, 5.0% in bead apex, 1.2% in bead insulation, 11.8% in fabric insulation, 9.5% in insulation of steel cord, 12.4% in innerliner, and 3.9% in undercushion.

[0199] The rubber compounds employed in a typical tire, along with associated materials, are set forth in Table 1. The methods described herein are suitable for processing tire tread, base, sidewall, as well as innerliner, and are also suitable for processing other materials containing vulcanized (or otherwise cross linked) natural rubber, styrene-butadiene rubber, and isobutylene-isoprene rubber. As further described herein, the other components, e.g., carbon black, present in EOL tire or other vulcanized rubber containing articles of manufacture may in some embodiments remain in the rubber subjected to the processes described herein, with no processing conducted to impact the properties or amounts of the othercomponent(s). In other embodiments, the rubber may be subjected to further processes to enrich or minimize these additional components or change their properties.TABLE I.Tread Base (PHR) Sidewall Innerliner (PHR.) (PHR) (PHR) Natural Rubber 50.0 100.0 75.0Styrene-Butadiene Rubber 50.0 25.0Isobutylene-Isoprene Rubber 100.0 Carbon Black (Grade N110) 50.0 15.0 20.0Carbon Black (Grade N330) 25.0 35.0Carbon Black (Grade N765) 50.0 Processing Oil 7.5 5.0 5.0 3.0 Antioxidant 1.0 0.75 1.0 1.0 Antioxidant Wax 2.0Stearic Acid 2.0 4.0 3.0 1.5 Zinc Oxidant 5.0 5.0 5.0 5.0 Accelerator (High) 1.0 0.7Accelerator (Middle) 1.25 0.4 Accelerator (Low) 0.4Sulfur 2.5 3.0 2.8 2.0 *PHR = Per Hundred Rubber, parts on a weight basis* Carbon grade = ASTM grading: Particle size and structure of carbon are different.

[0200] There are approximately 2.5 pounds of steel belts and bead wire in a passenger car tire. This material is made from high carbon steel with a nominal tensile strength of 2750 MN / m2The steel tire cord composition of a typical tire is set forth in Table 2.TABLE 2.Steel Belts Bead Wire Carbon 0.67 - 0.73% 0.60% mm.Manganese 0.40 - 0.70% 0.40 - 0.70% Silicon 0.15 - 0.03% 0.15 - 0.30% Phosphorus 0.03% max. 0.04% max.Sulfur 0.03% max. 0.04% max.Copper Trace Trace Chromium Trace Trace Nickel Trace Trace Coating 66% Copper 98% Brass34% Zinc 2% Tin

[0201] Whole tires can be ground to yield rubber particles mixed with other components of the tire. Methods for producing rubber containing particles from tires are known in the art. The used tires (or shreds or granules thereof) can be subjected to an optional cleaningstep (e.g., a water wash). Tires can be recycled by subjecting them to an initial shredding step, then subjecting the shreds to a granulation process to yield an initial granulate having dimensions of 1-3 cm. Grinding can be conducted under ambient conditions (e.g., in a granulator or a cracker mill) or cryogenic conditions.

[0202] Ambient grinding is a multi-step processing technology that uses a series of machines (usually three) to separate the rubber, metal, and fabric components of the tire. Whether using granulation equipment or cracker mills, the first processing step typically reduces the original feedstock to small chips. The second machine in the series will grind the chips to separate the rubber from the metal and fabric. Then a finishing mill will grind the material to the required product specification. After each processing step, the material is classified by sifting screens that return oversize pieces to the granulator or mill for further processing. Magnets are used throughout the processing stages to remove wire and other metal contaminants.

[0203] In the final stage, fabric is removed by air separators. Rubber particles produced in the granulation process generally have a cut surface shape and rough texture, with similar dimensions on the cut edges.

[0204] Cracker mills use two large rotating rollers with serrations cut in one or both of them. The roll configurations are what make them different. These rollers operate face-to- face in close tolerance at different speeds. Product size is controlled by the clearance between the rollers. Cracker mills are low speed machines operating at about 30-50 RPM. The rubber usually passes through two to three mills to achieve various particle size reductions and to further liberate the steel and fiber components. These mills do not have screens built into the mill and as such the mill itself does not control the final particle. A stand-alone screening system will separate “sized” particles from oversize granules following the mill and re¬ circulate the oversize products. The particles produced by the cracker mill are typically long and narrow in shape and have a high surface area.

[0205] Cryogenic processing uses liquid nitrogen or other matenals / methods to freeze tire chips or rubber particles prior to size reduction. Most rubber becomes embrittled or “glass-like” at temperatures below -80°C. The use of cryogenic temperatures can be applied at any stage of size reduction of scrap tires. Typically, the size of the feed material is a nominal 2-inch chip or smaller. The material can be cooled in a tunnel style chamber, immersed in a“bath” of liquid nitrogen, or sprayed with liquid nitrogen to reduce the temperature of the rubber or tire chip. The cooled rubber is size reduced in an impact type reduction unit, centrifuge, or hammer mill. This process reduces the rubber to particles ranging from 1 / 4 inch down to 30 mesh, with the majority of the particle distribution between 1 / 4 inch and 20 mesh. A typical throughput is 4,000 to 6,000 pounds per hour. Cryogenic grinding avoids heat degradation of the rubber and produces a high yield of product that is free of almost all fiber or steel, which is liberated during the process.

[0206] Wet grinding is a processing technology used to manufacture particles that are 40 mesh and finer. The wet grind process mixes partially refined crumb rubber particles with water creating a slurry. This slurry is then conveyed through size reduction and classification equipment. When the desired size is achieved, the slurry’ is conveyed to equipment for removing the majority of the water and then drying. Aside from the use of water, the same basic principles that are used in an ambient process are utilized in a wet grinding process. The major advantage for a wet grind process is the ability to create fine mesh crumb rubber. While products as coarse as 40 mesh are produced, the majority of the particles are 60 mesh and finer. A percentage of the overall throughput is finer than 200 mesh. Another advantage for a wet grind process is the cleanliness and consistency of the crumb rubber produced. The process washes the crumb rubber particles. The wet process removes the fine particles of fiber from the crumb rubber making a very' clean product.

[0207] The initial granulate contains steel, rubber, and textile components. The steel is typically recovered using a multistage magnetic separation process to minimize the loss of rubber. This can entail a first step utilizing a high strength twin pole overband cross belt separator magnet to remove metal containing particles in a first step. The second step involves a magnetic drum separator or magnetic pulley utilizing high strength rare earth magnets. The axial magnetic field causes the metal containing particles to tumble and release entrapped rubber. For fine rubber material that is fed into a powder grinder, a plate magnet suspended close to the product over the conveyor can lift and remove fine wire fragments. Testing can be conducted to determine metal content, e.g., by using a magnetometer.

[0208] The fiber can be recovered using modified gm machinery as known in the textile industry. A two-step process is typically employed, where clean fiber is removed from EOL tire crumb using a modified gm cylinder cleaner (used in the textile industry to removeforeign matter from seed cotton). Partially cleaned crumb is subjected to a second step to remove fiber, which can still contain some rubber particles. The resulting cleaned EOL tire crumb is then collected for packaging or other use. See, e.g., W. Stanley Anthony, Applied Engineering in Agriculture, Vol. 22(4): 563-570.

[0209] American Society for Testing and Materials (ASTM) has standards for specifying different size ranges of crumb rubber, such as 30 mesh or 80 mesh. The range of particle sizes can be determined by sieve analysis, consisting of shaking and tapping a measured quantity of a crumb rubber sample through a specified number of test sieves over a specified time. The amount of sample retained on each screen is weighed and results are given as the percentage of sample retained on each screen. The recommended procedure for sieve analysis using the Rotap method is provided in ASTM 5644. Typical crumb rubber sizes directed to certain products and uses include the following: molded and extruded products, 4 - 100 mesh; asphalt modification, 16 - 40 mesh; sport surfacing, 1 / 4” - 40 mesh; automotive products, 10 - 40 mesh; tires, 80 - 100 mesh; rubber and plastic blends, 10 - 40 mesh; and construction, 10 - 40 mesh.

[0210] There are no unified U. S. standards for processing EOL. tire rubber crumb; however, a suitable EOL tire rubber crumb for use in interlinked substitution typically has a low fiber content (less than 0.02 % of total weight), low metal content (less than 0.01 % of total weight), high consistency, and the particles are generally sized for 100% pass through 16 mesh. In some embodiments, it may be acceptable to have particles of larger size, e.g., 14, 12, or even 10 mesh. For example, 10-40 mesh crumb rubber (e.g., 30 mesh, or 25-35 mesh) yields satisfactory results when processed according to the methods described herein. Smaller particles, e.g., 41-200 mesh, can be employed and may enable more efficient interlinked substitution; however, a reduction in particle size will incur greater expense in manufacture of the crumb of the specified size. Larger particles, e.g., less than 10 mesh (4-9 mesh) can also be subjected to the methods, e.g., for particle size reduction purposes.

[0211] ASTM D5603 Standard Classification for Rubber Compounding Materials - Recycled Vulcanizate Particulate, classifies vulcanized particulate rubber according to maximum particle size, size distribution and parent materials including whole tires, tire peels, buffings generated from the tire tread and shoulder, buffings generated from tire tread, shoulder and sidewall and non-tire rubber.

[0212] End-of-Life Tire Crumb Characterization ELT crumb containing vulcanized rubber and having the desired particle sizes can be manufactured or obtained from any suitable commercial source.

[0213] The ELT crumb is typically of such a size that 100% can pass through a 16 mesh screen, and may have a narrow size distribution (e.g., no smaller than 20 mesh and no larger than 16 mesh) or may have a broader size distribution (e.g., significant contents of fines and various other particle sizes less than 16 mesh). The crumb rubber is typically cleaned of fiber and wire to a purity of 99.5 wt. % (i.e., 0.5 wt. % or less of fiber and wire).

[0214] If the sulfur content of the ELT crumb is unknown, representative samples of the ELT crumb can be tested to determine sulfur content (typically measured in parts per hundred weight), such that a controlled amount of reactant can be used in the extraction process, thereby avoiding overutilization or underutilization of reactant. A stoichiometric amount of reactant to sulfur is typically employed; however, larger or smaller amounts can also be advantageously employed. Any suitable method can be employed to determine the sulfur compound; however, a nitric compound extraction process can be advantageously employed. ASTM D4578 describes standard test methods applied to rubber chemicals for determination of percent sulfur. These test methods cover the determination of solvent insoluble materials in a sulfur-containing sample. The two test methods are: (1) Test Method A, Extraction by Carbon Disulfide, and (2) Test Method B, Extraction by Toluene. If there are no other solvent insoluble materials present in the sulfur-containing sample, the test methods determine the insoluble sulfur content directly. If other materials are also present, additional testing is necessary to identify what portion of the insolubles (e.g., carbon black, silica, or other inert fillers) is insoluble sulfur.Sulfur Crosslinking of Rubber

[0215] Elemental sulfur has cyclic eight atoms molecules at room temperature. In the presence of accelerators and activators, elemental sulfur generates sulfur fragments that react with reactive groups of rubbers in the process of interlinked substitution to create cross¬ links such as:■w OH,- CH “Ci H-CH ** s. - > HSi1 'S' s X ^CH - CH -CH~< H,*'* -w CH~ < H - CH~ OH,w< -w5H~Crx~Cxsr H2** *, ~ S'xI ^CK - OH«CH-CH.iw' OH,"' C«- CH~ CH?wTx** CH~ CH = CH~ CH?wDendritic Polymers

[0216] Dendritic polymers have been classified into categories: dendrimers, dendrigrafts, and hyperbranched polymers or macromolecules. A dendrimer is characterized by a perfect symmetrical globular shape that results from a stepwise controlled process giving a monodisperse molecular weight distribution. Hyperbranched polymers (also referred to as hyperbranched macromolecules) are attractive because they resemble dendrimers (their difference lies in their polydispersity and the less-perfect globular shape) but they can be produced more easily on a larger scale and at a reasonable cost, thus making them commercially available in large quantities. All types of dendritic polymers, including dendrimers, dendrigrafts, and hyperbranched polymers or macromolecules, are suitable for use in the processes and products described herein. When one term is employed, e.g., “hyperbranched macromolecule1’, it is understood that a dendrimer or other dendritic polymer may alternatively be employed. Similarly, one kind of hyperbranched macromolecule can be employed, or a mixture of two or more different (e.g., different backbone, different end groups, different molecular weight, or the like) dendritic polymers can be employed. Likewise, a single hyperbranched macromolecule may contain two or more different backbones and / or two or more different end groups. Unlike conventional polymers, the high number of end groups and their nature participate actively in the physical properties (solubility, glass transition temperature, and viscosity) in combination with the backbone structures. This characteristicleads to the possibility of designing the macromolecule with the combination of many different end groups and / or backbone structures and / or degrees of branching.

[0217] Dendritic polymers are hyperbranched macromolecules characterized by a treelike architecture, incorporating multiple branching levels. Dendritic polymers are highly branched structures which can provide potential anchor points to various compounds and contain large numbers of functional end groups capable of forming, e.g., van der Waals, dipole and donor-acceptor forces. This class of materials has a combination of features including a compact globular topology with diameters ranging from 1 nm to over 100 nm, more typically from 1 to 15 nm, the presence of internal cavities, and a large number of functional groups at the periphery. The significant advantages of dendritic polymer architecture over nondendritic nanocarriers of functional groups reside mainly in the multivalency of dendritic molecules. Dendritic polymers can be divided into three main groups: dendrimers (well-controlled structures, including dendritic-linear hybrids), dendrigraft (semi-controlled structure) polymers; and hyperbranched (statistically branched) polymers. Well controlled dendritic hyperbranched or star polymers have symmetric structures with narrow molecular weight distributions. Polymer chains are radiated from the same core and have two or more polymer chains at each branch point. Dendritic polymers are typically obtained by reacting a polyfunctional core with ABx monomers, typically AB2 monomers (glutamic acid, lysine, uronic acids, caffeic acid, etc ), yielding amorphous structures. The obtained macromolecules are thus characterized by an exponential growth in both molecular weight and in end-group functionalities.

[0218] Dendritic polymers have been shown to possess unique properties compared to their linear analogs. They behave, both in solution and in the melt, as Newtonian, nonentangled systems, i.e., no shear thinning or shear thickening. The melt viscosity is lower compared to their linear analogs, especially at higher molecular weights where linear macromolecules start to display properties characteristic of entanglements. Their high solubility in various solvents together with low viscosity make dendritic polymers suitable for thermoset resins where a high molecular weight is often desired before cross-linking in combination with a low viscosity. The viscosity for one specific hyperbranched polymer can also be changed to a large extent by modification of the end-group structure. Hyperbranched polymers have also been demonstrated to be suitable as processing aids in extrusion processes.

[0219] Dendronized polymers are linear polymers to every repeat unit of which dendrons are attached. Dendrons are regularly branched, tree-like fragments and for larger ones the polymer backbone is wrapped to give sausage-like, cylindrical molecular objects. An exemplary dendronized polymer is depicted as follows, with the dendrons depicted as wedges. In the example, the dendronized polymer has a polymethylmethacrylate (PMMA) backbone, the methyl group of which is replaced by a dendron of the third generation (three consecutive branching points). The peripheral amine groups are modified by a substituent X which often is a protection group. Upon deprotection and modification substantial property changes can be achieved. The subscript n denotes the number of repeat units.

[0220] Dendronized polymers can contain several thousands of dendrons in one macromolecule and have a stretched out, anisotropic structure. In this regard they differ from the more or less spherically shaped dendritic polymers, where a few dendrons are attached to a small, dot-like core resulting in an isotropic structure. Depending on dendron generation, the polymers differ in thickness. Neutral and charged dendronized polymers are highly soluble in organic solvents and in water, respectively. This is due to their low tendency to entangle. Dendronized polymers have been synthesized with, e.g., polymethylmethacrylate, polystyrene, polyacetylene, polyphenylene, polythiophene, polyfluorenepoly(phenylene vinylene), polyfphenylene acetylene), polysiloxane, polyoxanorbornene, polylethylene imine) (PEI)backbones. Molar masses up to 200,000,000 g / mol have been obtained. Dendronized polymers have been investigated for / as bulk structure control, responsivity to external stimuli, single molecule chemistry, templates for nanoparticle formation, catalysis, electro-optical devices, and bio-related applications. Water-soluble dendronized polymers can be used for the immobilization of enzymes on solid surfaces (inside glass tubes or microfluidic devices) and for the preparation of dendronized polymer-enzyme conjugates.

[0221] A metallodendrimer is a type of dendritic polymer with incorporated metal atoms. The metal can be situated in the repeat unit, the core or at the extremities as end-group. Elements often encountered are palladium and platinum. These metals can form octahedral six-coordinate M(IV) linking units from organic dihalides and the corresponding 4-coordinate M(II) monomers. Ferrocene-containing dendritic polymers and dendritic polymers with cobaltocene and arylchromiumtricarbonyl units have been reported in end-functional dendritic polymers. Metallodendrimers can form as metal complexes with dendritic counter ions, for example by hydrolysis of ester terminated PAMAM dendrimers with sodium hydroxide. Metallodendrimers have been investigated as equivalents to nanoparticles. Applications can be expected in the fields of catalysis, as chemical sensors in molecular recognition, for example of bromine and chloride anions, or as materials capable of binding metals. Metallodendrimers can also mimic certain biomolecules, for example hemoprotein in dendrimer with a porphyrin core. Further uses are reported as electrocatalyst. Examples of metallodendrimer heterogeneous catalysis are a nickel-containing dendrimer active in the Kharasch addition, palladium-containing dendritic polymers active in ethylene polymerization and in the Heck reaction.

[0222] Ferrocene-containing dendritic polymers are dendritic polymers that contain ferrocene substituents. Some ferrocene-containing dendritic polymers feature ferrocene cores and others do not. All feature peripheral ferrocene groups. Ferrocene-containing dendritic polymers can be synthesized by both convergent and divergent methods. Some of the dendritic polymers of this type can be made by attaching ferrocene units to small silicon containing dendritic polymers. Dendritic polymers with peripheral ferrocene groups are usually synthesized by attaching ferrocene to the core by either olefin metathesis or by hydrosilylation. As an example, tetraallylsilane undergoes Pt-catalyzed hydrosilylation to form the core. This core was then reacted with ferrocenyllithium in the synthesis depicted below toyield dendritic polymer 1. Convergent approaches can also be used to make dendritic polymers with peripheral ferrocene., / s s¥ i•< mwt w \?,

[0223] As an example, a 10-ferrocene dendritic polymer can be synthesized by a fast convergent approach.A 10-ferrocene dendritic polymer

[0224] Dendritic polymers have been prepared via click chemistry, employing Diels-Alder reactions, thiol-ene and thiol-yne reactions and azide-alkyne reactions. Poly(amido amine) (PAMAM) dendrimers with amine surface groups have the advantage of being able to be conjugated to other molecules via an amide linkage. Poly(propylene imine)-dendrimers (PPI-dendrimers) and carbazole-phenylazomethine dendrimer with a porphyrin core are other examples of dendritic polymers.

[0225] Various functional groups can be incorporated in dendritic polymers, e.g., NHBoc, azide, acetylene, hydroxyl, disulfide, carboxyl, polyethylene glycol, ammonium, amine, fatty acids, etc. Protecting groups may also be incorporated in selected applications. The terms “protecting group” and “protecting groups” as used herein refer to any atom or group of atoms that is added to a molecule in order to prevent existing groups in the molecule from undergoing unwanted chemical reactions. Examples of protecting group moieties are described in T. W. Greene and P. G. M. Wilts, Protective Groups in Organic Synthesis, 3. Ed. John Wiley & Sons, 1999, and in J. F. W. McOmie, Protective Groups in Organic Chemistry Plenum Press, 1973, both of which are hereby incorporated by reference for the limited purpose of disclosing suitable protecting groups. The protecting group moiety may be chosen in such a way, that they are stable to certain reaction conditions and readily removed at a convenient stage using methodology known from the art, A non-limiting list of protecting groups include benzyl; substituted benzyl; alkylcarbonyls and alkoxycarbonyls (e.g., t-butoxycarbonyl (BOC), acetyl, or isobutyryl); arylalkylcarbonyls and arylalkoxycarbonyls (e.g., benzyloxycarbonyl); substituted methyl ether (e.g. methoxymethyl ether); substituted ethyl ether; a substituted benzyl ether; tetrahydropyranyl ether, silyls (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl, t-butyldimethylsilyl, tri -isopropyl silyloxy methyl, [2-(trimethylsilyl)ethoxy]methyl or t- butyldiphenylsilyl); esters (e.g. benzoate ester), carbonates (e.g. methoxymethyl carbonate); sulfonates (e.g. tosylate or mesylate); acyclic ketal (e.g. dimethyl acetal), cyclic ketals (e.g., 1,3-dioxane, 1,3-dioxolanes, and those described herein), acyclic acetal; cyclic acetal (e.g., those described herein); acyclic hemiacetal; cyclic hemiacetal; cyclic dithioketals (e.g., 1,3- dithiane or 1,3-dithiolane); orthoesters (e.g., those described herein) and triarylmethyl groups (e.g., trityl; monomethoxy trityl (MMTr); 4,4'-dimethoxytrityl (DMTr); 4,4',4”- trimethoxy trityl (TMTr); etc.).

[0226] The dendritic polymer can incorporate various functional groups or other substituents. Whenever a group is described as being “optionally substituted” that group may be unsubstituted or substituted with one or more of the indicated substituents. Likewise, when a group is described as being “unsubstituted or substituted” if substituted, the substituent(s) may be selected from one or more of the indicated substituents. If no substituents are indicated, it is meant that the indicated “optionally substituted” or “substituted” group may be substituted with one or more group(s) individually and independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, heteroaralkyl, (heteroalicyclyl)alkyl, hydroxy, protected hydroxyl, alkoxy, aryloxy, acyl, mercapto, alkylthio, arylthio, cyano, halogen, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, protected C- carboxy, O-carboxy, isocyanato, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl, trihalomethanesulfonamido, an amino, a mono-substituted ammo and a di-substituted ammo group, and protected derivatives thereof.

[0227] As used herein, “Cato Cb” in which “a” and “b” are integers refer to the number of carbon atoms in an alkyl, alkenyl or alkynyl group, or the number of carbon atoms in the ring of a cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl or heteroalicyclyl group. That is, the alkyl, alkenyl, alkynyl, ring of the cycloalkyl, ring of the cycloalkenyl, ring of the cycloalkynyl, ring of the aryl, ring of the heteroaryl or ring of the heteroalicyclyl can contain from “a” to “b”, inclusive, carbon atoms. Thus, for example, a “Ci to Ci alkyl” group refers to all alkyl groups having from I to 4 carbons, that is, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, CH3CH2CH(CH3)- and (CH3)3C-. If no “a” and “b” are designated with regard to an alkyl, alkenyl, alkynyl, cycloalkyl cycloalkenyl, cycloalkynyl, aryl, heteroaryl or heteroalicyclyl group, the broadest range described in these definitions is to be assumed.

[0228] . As used herein, “alkyl” refers to a straight or branched hydrocarbon chain that comprises a fully saturated (no double or triple bonds) hydrocarbon group. The alkyl group may have 1 to 20 carbon atoms (whenever it appears herein, a numerical range such as “1 to 20” refers to each integer in the given range; e.g., “I to 20 carbon atoms” means that the alkyl group may consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including20 carbon atoms, although the present definition also covers the occurrence of the term “alkyl” where no numerical range is designated). The alkyl group may also be a medium size alkyl having 1 to 10 carbon atoms. The alkyl group could also be a lower alkyl having 1 to 6 carbon atoms. The alkyl group of the compounds may be designated as “C1-C4 alkyl” or similar designations. By way of example only, “C1-C4 alky l” indicates that there are one to four carbon atoms in the alkyl chain, i.e., the alkyl chain is selected from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and t-butyl. Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary’ butyl, pentyl and hexyl. The alkyl group may be substituted or unsubstituted.

[0229] As used herein, “alkenyl” refers to an alkyl group that contains in the straight or branched hydrocarbon chain one or more double bonds. An alkenyl group may be unsubstituted or substituted.

[0230] As used herein, “alkynyl” refers to an alkyl group that contains in the straight or branched hydrocarbon chain one or more triple bonds. An alkynyl group may be unsubstituted or substituted.

[0231] As used herein, “cycloalkyl” refers to a completely saturated (no double or triple bonds) mono- or multi- cyclic hydrocarbon ring system. When composed of two or more rings, the rings may be joined together in a fused fashion. Cycloalkyl groups can contain 3 to 10 atoms in the ring(s) or 3 to 8 atoms in the ring(s). A cycloalkyl group may be unsubstituted or substituted. Typical cycloalkyl groups include, but are in no way limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0232] As used herein, “cycloalkenyl” refers to a mono- or multi- cyclic hydrocarbon ring system that contains one or more double bonds in at least one ring; although, if there is more than one, the double bonds cannot form a fully delocalized pi-electron system throughout all the rings (otherwise the group would be “aryl,” as defined herein). When composed of two or more rings, the rings may be connected together in a fused fashion. A cycloalkenyl group may be unsubstituted or substituted.

[0233] As used herein, “cycloalkynyl” refers to a mono- or multi- cyclic hydrocarbon ring system that contains one or more triple bonds in at least one ring. If there is more than one triple bond, the triple bonds cannot form a fully delocalized pi-electron systemthroughout all the rings. When composed of two or more rings, the rings may be joined together in a fused fashion. A cycloalkynyl group may be unsubstituted or substituted.

[0234] As used herein, “aryl” refers to a carbocyclic (all carbon) monocyclic or multicyclic aromatic ring system (including fused ring systems where two carbocyclic rings share a chemical bond) that has a fully delocalized pi-electron system throughout all the rings. The number of carbon atoms in an aryl group can vary. For example, the aryl group can be a C6-C14 aryl group, a Cs-Cio aryl group, or a Cs aryl group. Examples of aryl groups include, but are not limited to, benzene, naphthalene and azulene. An aryl group may be substituted or unsubstituted.

[0235] As used herein, “heteroaryl” refers to a monocyclic or multicychc aromatic ring system (a ring system with fully delocalized pi-electron system) that contain(s) one or more heteroatoms, that is, an element other than carbon, including but not limited to, nitrogen, oxygen and sulfur. The number of atoms in the ring(s) of a heteroaryl group can vary. For example, the heteroaryl group can contain 4 to 14 atoms in the ring(s), 5 to 10 atoms in the ring(s) or 5 to 6 atoms in the ring(s). Furthermore, the term “heteroaryl” includes fused ring systems where two rings, such as at least one aryl ring and at least one heteroaryl ring, or at least two heteroaryl rings, share at least one chemical bond. Examples of heteroaryl rings include, but are not limited to, furan, furazan, thiophene, benzothiophene, phthalazine, pyrrole, oxazole, benzoxazole, 1,2,3-oxadiazole, 1,2, 4- oxadi azole, thiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, benzothiazole, imidazole, benzimidazole, indole, indazole, pyrazole, benzopyrazole, isoxazole, benzoisoxazole, isothiazole, triazole, benzotriazole, thiadiazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, purine, pteridine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, and tri azine. A heteroaryl group may be substituted or unsubstituted.

[0236] As used herein, “heterocyclyl” or “heteroalicyclyl” refers to three-, four-, five-, six-, seven-, eight-, nine-, ten-, up to 18-membered monocyclic, bicyclic, and tricyclic ring system wherein carbon atoms together with from I to 5 heteroatoms constitute said ring system. A heterocycle may optionally contain one or more unsaturated bonds situated in such a way, however, that a fully delocalized pi-electron system does not occur throughout all the rings. The heteroatom(s) is an element other than carbon including, but not limited to, oxygen, sulfur, and nitrogen. A heterocycle may further contain one or more carbonyl or thiocarbonylfunctionalities, so as to make the definition include oxo-systems and thio-systems such as lactams, lactones, cyclic imides, cyclic thioimides and cyclic carbamates. When composed of two or more rings, the rings may be joined together in a fused fashion. Additionally, any nitrogens in a heteroalicyclic may be quaternized. Heterocyclyl or heteroalicyclic groups may be unsubstituted or substituted. Examples of such “heterocyclyl” or “heteroalicyclyl” groups include but are not limited to, 1,3-dioxin, 1,3-dioxane, 1,4-dioxane, 1,2-dioxolane, 1,3- dioxolane, 1,4-dioxolane, 1,3-oxathiane, 1,4-oxathiin, 1,3-oxathiolane, 1,3-dithiole, 1,3- dithiolane, 1,4-oxathiane, tetrahydro- 1,4-thiazine, 2H-l,2-oxazine, maleimide, succinimide, barbituric acid, thiobarbituric acid, dioxopiperazine, hydantoin, dihydrouracil, trioxane, hexahydro-1, 3, 5-triazine, imidazoline, imidazolidine, isoxazoline, isoxazolidine, oxazoline, oxazolidine, oxazolidinone, thiazoline, thiazolidine, morpholine, oxirane, piperidine N-Oxide, piperidine, piperazine, pyrrolidine, pyrrolidone, pyrrolidione, 4-piperidone, pyrazoline, pyrazolidine, 2-oxopyrrolidine, tetrahydropyran, 4H-pyran, tetrahydrothiopyran, thiamorpholine, thiamorpholine sulfoxide, thiamorpholine sulfone, and their benzo-fused analogs (e.g., benzimidazolidinone, tetrahydroquinoline, 3,4-methylenedioxyphenyl).

[0237] As used herein, “aralkyl” and “aryl(alkyl)” refer to an aryl group connected, as a substituent, via a lower alkylene group. The lower alkylene and aryl group of an aralkyl may be substituted or unsubstituted. Examples include but are not limited to benzyl, 2-phenylalkyl, 3 -phenylalkyl, and naphthylalkyl.

[0238] As used herein, “heteroaralkyl” and “heteroaryl(alkyl)” refer to a heteroaryl group connected, as a substituent, via a lower alkylene group. The lower alkylene and heteroaryl group of heteroaralkyl may be substituted or unsubstituted. Examples include but are not limited to 2-thienylalkyl, 3-thienylalkyl, furylalkyl, thienylalkyl, pyrrolylalkyl, pyridylalkyl, isoxazolylalkyl, and imidazolylalkyl, and their benzo-fused analogs.

[0239] A “(heteroalicyclyl)alkyl” and “(heterocyclyl)alkyl” refer to a heterocyclic or a heteroalicyclyl ic group connected, as a substituent, via a lower alkylene group. The lower alkylene and heterocyclyl of a (heteroalicyclyl)alkyl may be substituted or unsubstituted. Examples include but are not limited tetrahydro-2H-pyran-4-yl)methyl, (piperidin-4-yl)ethyl, (piperidin-4-yl)propyl, (tetrahydro-2H-thiopyran-4-yl)methyl, and (1,3-thiazinan-4-y Ijmethyl.

[0240] As used herein, “Lower alkylene groups” are straight-chained -CH?- tethering groups, forming bonds to connect molecular fragments via their terminal carbonatoms. Examples include but are not limited to methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), and butylene (-CH2CH2CH2CH2-). A lower alkylene group can be substituted by replacing one or more hydrogen of the lower alkylene group with a substituent(s) listed under the definition of “substituted.”

[0241] As used herein, “alkoxy” refers to the formula -OR wherein R is an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a cycloalkenyl or a cycloalkynyl is defined as above. A non-limiting list of alkoxys are methoxy, ethoxy, n-propoxy, 1 -methylethoxy (isopropoxy), n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy. An alkoxy may be substituted or unsubstituted.

[0242] As used herein, “acyl” refers to a hydrogen, alkyl, alkenyl, alkynyl, or aryl connected, as substituents, via a carbonyl group. Examples include formyl, acetyl, propanoyl, benzoyl, and acryl. An acyl may be substituted or unsubstituted.

[0243] As used herein, “hydroxyalkyl” refers to an alkyl group in which one or more of the hydrogen atoms are replaced by a hydroxy group. Exemplary hydroxyalkyl groups include but are not limited to, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, and 2,2-di hydroxy ethyl. A hydroxyalkyl may be substituted or unsubstituted.

[0244] As used herein, “haloalkyl” refers to an alkyl group in which one or more of the hydrogen atoms are replaced by a halogen (e.g., mono-haloalkyl, di-haloalkyl and tri- haloalkyl). Such groups include but are not limited to, chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, l-chloro-2-fluoromethyl, and 2-fluoroisobutyl. A haloalkyl may be substituted or unsubstituted. As used herein, “haloalkoxy” refers to an alkoxy group in which one or more of the hydrogen atoms are replaced by a halogen (e.g., mono-haloalkoxy, di- haloalkoxy and tri- haloalkoxy). Such groups include but are not limited to, chloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy and l-chloro-2-fluoromethoxy, 2-fluoroisobutoxy. A haloalkoxy may be substituted or unsubstituted.

[0245] As used herein, “aryloxy” and “arylthio” refers to RO- and RS-, in which R is an aryl, such as but not limited to phenyl. Both an aryloxy and arylthio may be substituted or unsubstituted.

[0246] A “sulfenyl” group refers to an “-SR” group in which R can be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl. A sulfenyl may be substituted orunsubstituted. A “sulfinyl” group refers to an “-S(:;=O)-R” group in which R can be the same as defined with respect to sulfenyl. A sulfinyl may be substituted or unsubstituted. A “sulfonyl” group refers to an “SOzR” group in which R can be the same as defined with respect to sulfenyl. A sulfonyl may be substituted or unsubstituted.

[0247] An “O-carboxy” group refers to a “RC(:=:())0-” group in which R can be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl, as defined herein. An O-carboxy may be substituted or unsubstituted.

[0248] The terms “ester” and “C-carboxy” refer to a “~C(=O)OR” group in which R can be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyi)alkyl. An ester may be substituted or unsubstituted. A “thiocarbonyl” group refers to a “-C(=S)R” group in which R can be the same as defined with respect to O-carboxy. A thiocarbonyl may be substituted or unsubstituted. A “trihalomethanesulfonyl” group refers to an “X3CSO2-” group wherein X is a halogen. A “trihalomethanesulfonamido” group refers to an “XSCS(O)2N(RA)-” group wherein X is a halogen and RA hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl. The term “ammo” as used herein refers to a -NH2 group. As used herein, the term “hydroxy” refers to a -OH group. A “cyano” group refers to a “-CN” group. The term “azido” as used herein refers to a -N3group. An “isocyanato” group refers to a “-NCO” group. A “thiocyanato” group refers to a “-CNS” group. An “isothiocyanate” group refers to an “ -NCS” group. A “mercapto” group refers to an “-SH” group. A “carbonyl” group refers to a C=O group. An “S-sulfonamido” group refers to a “-SO2N(RARB)” group in which RA and RB can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl. An S-sulfonamido may be substituted or unsubstituted. An “N-sulfonamido” group refers to a “RSO2N(RA)-“ group in which R and RA can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl. An N-sulfonamido may be substituted or unsubstituted. An “O-carbamyl” group refers to a “-OC(=O)N(R RB)” group in which RA and RB can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl.An O-carbamyl may be substituted or unsubstituted. An “N-carbamyi” group refers to an “ROC(“O)N(R ) group in which R and RA can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl. An N-carbamyl may be substituted or unsubstituted. An “O-thiocarbamyl” group refers to a ‘■‘-OC(=S)-N(RARB)” group in which RA and RB can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl. An O-thiocarbamyl may be substituted or unsubstituted. An “N-thiocarbamyl” group refers to an “ROC(=S)N(RA)-“ group in which R and RA can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl. An N-thiocarbamyl may be substituted or unsubstituted.

[0249] A “C-amido” group refers to a “-C(=O)N(RARB)’’ group in which RA and RB can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl. A C-amido may be substituted or unsubstituted. An “N-amido” group refers to a “RC(=O)N(RA)-“ group in which R and RA can be independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, or (heteroalicyclyl)alkyl. An N-amido may be substituted or unsubstituted.

[0250] The term “halogen atom” or “halogen” as used herein, means any one of the radio-stable atoms of column 7 of the Periodic Table of the Elements, such as, fluorine, chlorine, bromine and iodine.

[0251] The term “alcohol” as used herein is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to any compound as described herein incorporating one or more hydroxy groups, or being substituted by or functionalized to include one or more hydroxy groups.

[0252] A fatty acid is a carboxylic acid with an aliphatic chain, which is either saturated or unsaturated. Most fatty acids are even chained, e.g. stearic (Cl 8) and oleic (Cl 8), meaning they are composed of an even number of carbon atoms. Some fatty acids have odd numbers of carbon atoms; they are referred to as odd-chained fatty acids (OCFA). Most common fatty acids are straight- chain compounds, with no additional carbon atoms bonded asside groups to the main hydrocarbon chain. Branched-chain fatty acids contain one or more methyl groups bonded to the hydrocarbon chain. The term “short-chain fatty acid” as used herein is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a fatty acid with 2-6 carbon atoms. The term “medium-chain fatty acid” as used herein is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a fatty acid with 7-12 carbon atoms. The term “long-chain fatty acid” as used herein is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a fatty acid with 13-22 carbon atoms. The term “very long chain fatty acid” as used herein is a broad term, and is to be given its ordinary and customary meaning to a person of ordinary skill in the art (and is not to be limited to a special or customized meaning), and refers without limitation to a fatty acid with 23 or more carbon atoms.

[0253] Where the numbers of substituents are not specified (e.g. haloalkyl), there may be one or more substituents present. For example, “haloalkyl” may include one or more of the same or different halogens. As another example, “C1-C3 alkoxyphenyl” may include one or more of the same or different alkoxy groups containing one, two or three atoms.

[0254] As used herein, the abbreviations for any compounds, are, unless indicated otherwise, in accord with their common usage.

[0255] Nomenclature for dendritic molicules is described in Jorg H. Friedhofen and Fritz Vogtle “Detailed nomenclature for dendritic molecules” New J. Chem., 2006, 30, 32-43.

[0256] In certain embodiments, the hyperbranched macromolecule has a three- dimensional structure with numerous terminal functional groups. These terminal functional groups (also referred to as end groups) are selected to achieve predetermined thermo¬ mechanical propertie(s) within the substance of final compounding. Principal synthesis methods to create the HBP include condensation polymerization (CP), ring opening polymerization (ROP), and free radical polymerization (FRP) reactions.

[0257] Creation of poly-sulfur molecular hub-based HBP(s) can be accomplished via single-pot synthesis reactions or multi-step compounding processes inclusive of multipletransition states. Although high molar mass polymers are readily formed via ROP of Ss (polymeric sulfur), such polymers are chemically unstable at temperatures above 159°C Tr (namely, under equilibrium polymerization conditions), since terminal sulfur radicals promote depolymerization back to cyclic monomeric sulfur. However, rapid quenching of the equilibrium melt polymerization of Ss has been demonstrated to preserve the polymeric form of sulfur (plasticized with small molecules of Ss and Sn where n 8) for an extended period of time when the temperature is kept below' the glass transition temperature of the mixture (Tg, - 30°C). At temperatures exceeding the Tg, the amorphous mixture becomes elastic and crystallizes rapidly, ultimately leading to the polymer undergoing breakdown into cyclic species over time, even at low temperatures.

[0258] Polysulfides are a class of high sulfur content polymers which are structurally similar to polymeric sulfur, but with improved stability and processing capabilities. Condensation copolymerization of elemental sulfur may generate high sulfur content polysulfides by: a) reaction of a, ro-alkyl dihalides with sodium polysulfides; b) base catalyzed reaction of alkyl dithiols and sulfur; c) thermally or lithium metal-initiated reaction of di chlorobenzene and sulfur; d) anionic generation of dicarbanionic oligomers followed by condensation with sulfur. Synthesis of high sulfur content polysulfides via a polycondensation reaction of a, G)-alkyl halides and inorganic polysulfides (e.g,, Na2Sx, x = 4-6) generates high molecular weight rubbers with good solvent and wear resistance. An emulsion condensation polymerization between the aqueous polysulfide solutions and organic alkyl halides is utilized to aid in the processing of the resulting polymer. Several alkyl halide comonomers are applicable to the condensation reaction and sulfur content in the polymer is easily varied during the emulsion polymerization step by controlling the sulfur rank of the inorganic polysulfides. In turn, the sulfur rank within the inorganic polysulfide is determined by the molar ratio of sodium sulfide and sulfur, although the distribution of rank can be affected by pH, temperature, and concentration.

[0259] Thermal or alkali metal-initiated reaction between sulfur and either 1,3- di chlorobenzene or 1,4-dichlorobenzene generates crosslinked or linear polysulfides, respectively. The linear high molecular weight materials are high-performance thermoplastics that possess excellent thermal stability and solvent resistance. Kinetic profiles reveal that control over sulfur content and polymer structure may be achieved by control of S8 in thecomonomer feed. Additionally, carbanion is found to react at different rates with vinylic monomers and the rate of Ss consumption is observed to dominate in the initial stages over vinylic polymerization, thereby allowing a new class of sulfur containing polymers based upon poly(aminosulfides) to be prepared.

[0260] Synthesis of high sulfur-content allotropes and macrocycles through activated sulfur-precursors may be achieved by: a) utilization of bis(p- cyclopentadienyl)titanium pentasulfide (Cp2TiS5) as the starting material to generate several homocyclic sulfur allotropes; b) utilization of the tetramethylethylenediamine zinc hexasulfido complex as the starting material to generate cyclo-tetradecasulfur (Su) as well as other cyclic polysulfide molecules. High sulfur rank cyclic polysulfide using organometallic metallocene precursors can also be prepared. The synthesis of sulfur-rich macrocycles in commercial settings has provided a strong precedence for the generation of high sulfur-content hyper¬ branched copolymers by ring opening polymerizations with Ss comonomers. Thermally initiated copolymerization of cyclic arylene disulfides oligomers with sulfur, generate high sulfur content copolymers with high molecular weights,

[0261] The atom-efficient, free-radical, click copolymerization between sulfur and a variety of unsaturated molecules are a means of generating high sulfur content, highly branched polysulfides. Examples include vinylics (styrene, methyl methacrylate, methyl acrylate, vinyl acetate, tetrafluoroethylene, 2-chloroprene, butadiene); cyclic olefins (cyclododeca- 1,5,9- triene, cyclohepta- 1, 3, 5-triene, cycloocta- 1,3-diene, cyclohexene, 1- methylcyclohexene, norbornene, di cyclopentadiene, tri cyclopentadiene); and terpenoids (limonene, 2,6- dimethylocta-2,4,6-triene, 7-methyl-3 -methyleneocta- 1,6-diene, 3,7- dimethylocta-l,6-diene, 2,6-dimethylhepta-l,5-diene). In certain embodiments a fatty acid or fatty acid ester (e.g., a triglyceride), e.g., a soybean oil, can be employed as the unsaturated molecule. Commercially available soybean oil is composed of five fatty acids: palmitic acid (16:0), stearic acid (18:0), oleic acid (18:1), linoleic acid (18:2), and linolenic acid (18:3). The percentage of these five fatty acids in soybean oil averages 10%, 4%, 18%, 55%, and 13%, respectively. The main component of soybean oil is triglyceride oil or triacylglycerol (TAG). While soybean oil is readily available and can be used as the sole unsaturated molecule(s), as an inexpensive reactant, other materials can also be employed. One such material is an unsaturated fatty acid or unsaturated fatty acid ester. Any suitable unsaturated fatty acid orunsaturated faty acid ester may be used, e.g., an unsaturated C6-30 carboxylic acid or ester thereof. Depending upon the chain length, such fatty acids or fatty acid esters can contain 1 or more double bonds, e.g., 1, 2, 3, 4, or 5 or more double bonds. Fatty acids and faty acid esters include, but are not limited to, linear and branched carboxylic acids, and can include fatty acids or olefins from the stearoyl family such as arachidonic acid, eicosapentaenoic acid, linoleic acid, alpha linolenic acid, gamma linolenic acid, oleic acid, palmitoleic acid, and combinations thereof. One suitable material is a purified vegetable oil, such as soy oil, which contains a certain content of oleic acid. In an exemplary embodiment, a purified soy oil having a 22% oleic acid content is employed; however, oils having higher or lower oleic acid content may also be advantageously employed, as can oils which contain other unsaturated fatty acids. In other embodiments, an unsaturated polyester (e.g., C16H16O9; CAS No. 26123-45-5) can be employed as the unsaturated molecule. Unsaturated polyesters are condensation polymers formed by the reaction of polyols (also known as polyhydric alcohols), organic compounds with multiple alcohol or hydroxy functional groups, with unsaturated or saturated dibasic acids. Typical polyols are glycols including ethylene glycol, propylene glycol, and diethylene glycol. Typical acids are phthalic acid, isophthalic acid, terephthalic acid, and maleic anhydride. Maleic anhydride-phthalic anhydride-diethylene glycol polymer is an example of a suitable unsaturated polyester as the unsaturated molecule. It can be used in combination with a soybean oil, or instead of a soybean oil. The general triglyceride structure of canola oil, soybean oil, and high oleic soybean oil is provided below.

[0262] GENERAL TRIGLYCERIDE, STRUCTURESFatty Acid % Composition 16:0 18:0 18:1 18:2 18:3 20:0 20:1 Canola 4.1 1.8 60.9 21.0 8.8 0.7 1.0 Soybean 11.0 4.0 23.1 53.2 7.8 0.3 0.0 High Oleic Soybean 6.4 3.1 82.6 2.3 3.7 0.2 0.4x:y = chain carbon atoms: number of unsaturations

[0263] In solution-based copolymerizations conducted at temperatures commonly used for free radical polymerizations of vinylic comonomers (e.g., at 60-90°C), S8 may act as an inhibitor due to the significant chain transfer rate between the carbon radical and sulfur. The high rate of chain transfer to sulfur, coupled with a low rate of attack on vinylic bonds by sulfur radicals ultimately leads to a majority of the materials having low sulfur content (<10 wt. %).

[0264] Free-radical copolymerization of sulfur with various olefin comonomers can generate chain extending or dendritic polysulfide copolymers. In order to obtain polymeric materials with higher molecular weights and increased functional-sulfur content, bulk copolymerization methodologies generally afford improved materials due to the higher reactivity ratio of the monomers when compared to solution-based methods.

[0265] The side-products of free-radical copolymerization between sulfur and olefins (e.g., norbornene and di cyclopentadiene) are small sulfur-containing molecules, such as, tri- and penta-thiacyclic derivatives. These molecules and other cyclic sulfides (e.g., thiiranes) are observed to readily copolymerize with elemental sulfur under anionic conditions to generate linear polysulfides. Anionic copolymerization of Sx with thiiranes can be manipulated at dendritic sites as well. The sulfur content and nieta-structure location in these copolymers can be tailored by controlling the sequence of the comonomer feed ratios and reaction temperature.

[0266] Sulfur can also undergo copolymerization via cationic conditions, as the S- S bond has demonstrated to be susceptible to attack by electrophiles.

[0267] Typical process conditions for these HBP(s) advantageously include a stirred, reactor kettle at > 160°C under nitrogen blanket, although other reaction conditions can also be employed, as desired. Sulfonium end groups can advantageously be employed, although other end groups may also be utilized, as discussed elsewhere herein in the context of functional groups.Hyperbranched Macromolecule Reaction with Vulcanized Rubber

[0268] The hyperbranched macromolecule can be employed directly for reaction with a vulcanized rubber or other vulcanized elastomer matrix, such as vulcanized rubber, e.g., ground tire rubber (GTR), e.g., end-of-life (EOL) tire rubber. The hyperbranched macromolecule can be in a form of a liquid which is poured, sprayed, or otherwise combined with a sulfur-crosslinked elastomer, e.g., GTR, EOL-GTR or other vulcanized rubber in crumb form. Mixing in a pug mill can advantageously be employed as a pre-reaction step, or the mixing can occur directly in a reactor, e.g., a twin screw reactor, an auger reactor, a roll mill reactor, a twin arm Banbury mixer, or sigma blade mixer, or any other similar reactor or a reactor as described herein.

[0269] When vulcanized rubber is to be employed for use in preparing a molded rubber product, it is processed principally through the addition and compounding of interpenetrating virgin elastomers, such as natural rubber (NR) and / or styrene butadiene rubber (SBR). These can be included in the vulcanized elastomer / hyperbranched macromolecule mixture or added later after reaction of the vulcanized elastomer and hyperbranched macromolecule. The hyperbranched macromolecule typically comprises from 1-20% by weight, optionally 2-10% by weight, optionally 4-6% by weight, optionally about 5% by weight of the vulcanized rubber-containing mixture to be processed, although in certain embodiments more or less hyperbranched macromolecule can be employed. The amount / s) of hyperbranched macromolecule(s) employed may vary depending upon certain properties of the hyperbranched macromolecule, e.g., number and / or types of endgroups, degree of branching, molecular weight, etc. Dendritic polymers are classified by generation, which refersOther Components and HBP Products Containing Same

[0270] The HBPs provided are useful in fabricating rubber-based goods and materials, including those prepared using GTR or other vulcanized rubber as a starting material. Other components can be employ ed in preparing such goods and materials, includingthose as are conventionally employed in the preparation of rubber-based goods or materials utilizing virgin rubber as a starting material. Other components of the rubber materials can optionally include white mineral oil and / or other oils, including but not limited to synthetic oils and vegetable oils, e.g., polyalphaolefins, diesters, polyolesters, phosphate esters, polyalkylene glycols, and silicones. In certain embodiments a soybean oil can be employed as a process oil. Commercially available soybean oil is composed of five fatty acids: palmitic acid (16:0), stearic acid (18:0), oleic acid (18:1), linoleic acid (18:2), and linolenic acid (18:3). The percentage of these five fatty acids in soybean oil averages 10%, 4%, 18%, 55%, and 13%, respectively. The main component of soybean oil is triglyceride oil or triacylglycerol (TAG). While soybean oil is readily available and inexpensive, other materials can also be employed. One such material is an unsaturated fatty acid or unsaturated fatty acid ester. Any suitable unsaturated fatty acid or unsaturated fatty acid ester may be used, e.g., an unsaturated C6-30 carboxylic acid or ester thereof. Depending upon the chain length, such fatty acids or fatty acid esters can contain 1 or more double bonds, e.g., 1, 2, 3, 4, or 5 or more double bonds. Fatty acids and fatty acid esters include, but are not limited to, linear and branched carboxylic acids, and can include fatty acids or olefins from the stearoyl family such as arachidonic acid, eicosapentaenoic acid, linoleic acid, alpha linolenic acid, gamma linolenic acid, oleic acid, palmitoleic acid, and combinations thereof. One suitable material is a purified vegetable oil, such as soy oil, which contains a certain content of oleic acid. In an exemplary embodiment, a purified soy oil having a 22% oleic acid content is employed; however, oils having higher or lower oleic acid content may also be advantageously employed, as can oils which contain other unsaturated fatty acids. In other embodiments, an unsaturated polyester (e.g., C16H16O9; CAS No. 26123-45-5) can be employed as a process oil. Unsaturated polyesters are condensation polymers formed by the reaction of polyols (also known as polyhydric alcohols), organic compounds with multiple alcohol or hydroxy functional groups, with unsaturated or saturated dibasic acids. Typical polyols are glycols including ethylene glycol, propylene glycol, and diethylene glycol. Typical acids are phthalic acid, isophthalic acid, terephthalic acid, and maleic anhydride. Maleic anhydride-phthalic anhydride-diethylene glycol polymer is an example of a suitable unsaturated polyester as a process oil. It can be used instead of soybean oil as the sole process oil, or in combination with soybean oil or any other process oil.

[0271] Other polymeric components can be utilized, e.g., natural or synthetic rubber or other elastomers, e.g., polybutylenes, polyisobutylenes, polystyrenes, or the like, or polymers such as polypropylene or polyethylene, or other polymers as are typically present in a recycled plastics stream. Fillers such as limestone, calcium carbonate. Kaolin, magnesium hydroxide, glass, fly ash, Wollastonite (CaSiOs), mica, silica, carbon black, dolomite, barium sulfate, Al(OH)3,, diatomaceous earth, magnetite / hematite, Halloysite, zinc oxide, and titanium dioxide can also be present. Other components can include antioxidants, such as primary antioxidants, secondary antioxidants, and antiozonants, one or more deodorants and / or reodorants, or the like.

[0272] The rubber materials manufactured can be utilized in a variety of goods and products such as are known in the art. These can include rubberized asphalt, asphalt emulsions, rubber paving materials, as well as engineered goods, e.g., manufactured to meet one or more industry’ or military specifications. Such specifications may include but are not limited to ASTM specifications, military specifications (MIL), aerospace material specifications (AMS), and / or other specifications as are employed in various industries utilizing rubber goods. Such goods include but are not limited to tires and tire components; floor mats and bed liners for vehicles; mats and flooring materials for commercial and residential use; chemical-resistant mats and pads for industrial or laboratory use; anti-fatigue mats; tiles, e.g., interlocking tiles for exercise rooms or daycare; tire treads; tire sidewalls; wheels; roofing membranes; roofing materials; electrical tapes; liners for plastic or metal goods; pond liners; tank linings; reservoir linings, trench linings; bridge underlayments; foundation waterproofing sheets and coatings; parking garage waterproofing sheets and coatings, vehicle components for civilian and military use; boat, ship, and submarine components for civilian or military use; airplane, passenger plane, and fighter jet components; railcar and train engine components, residential and commercial building products, factory, industrial, and manufacturing components; clothing and footwear components; hoses, belts, stoppers, grips, moldings, and other rubber goods prepared from molded rubber or rubber sheeting (e.g., gaskets, washers, tubing, shock absorbing materials, underlayments for carpets, floors, decking, and concrete, sound proofing, etc.).

[0273] Such goods can advantageously be manufactured utilizing techniques for processing rubber as known in the art, such as molding techniques. Molding techniques includerubber transfer molding, which utilizes a closed mold. For example, mold forms are loaded into a pot and then compressed, e.g., with pistons. All of the rubber is forced through sprues to completely fill one or more cavities produced in the forms. This method is advantageous in that it can produce tight dimensional tolerances. In rubber compression molding, a rubber blank that that roughly matches the shape of the product is provided and loaded into an open mold, where the rubber cures before it is removed. The resulting material can exhibit a high degree of strength. Injection molding techniques, however, are generally preferred. These techniques utilize one or more nozzles and strategically placed sprues and runners to distribute uncured rubber feedstock through a mold. The rubber flows into hold cavities and cures. Commonly employed injection techniques include organic rubber injection, liquid injection molding, and thermoplastic rubber injection.Reactor Designs

[0274] Reactors as depicted in FIGS. 1A-1D, 3A-3C, 4A-4B, and 5A-5E can advantageously be employed in certain embodiments for reacting sulfur cross-linked elastomer(s) and hyperbranched macromolecule(s). These nonlimiting examples of exemplary reactors each apply compression (pressure) to a mixture of sulfur cross-linked elastomer(s) and hyperbranched macromol ecule(s). Other reactor designs, as known in the art for applying compression (pressure) to solids can alternatively be employed.

[0275] The reactors depicted in FIGS. 1A-1D and 3A-3C are horizontal compression reactors. FIG. 1 A depicts a top view and a side view of a small-scale reactor and its gears 1000. The gears as provided 1008 are steel and are machined to include machined grooves 1010 to the root of pitch. In operation, the grooves of both gears match when the gears mesh and maintain ~ 0.040 inches of clearance 1007 (between the gear with dowel pin placement and the housing) which locates the end plates. Ten gear segments of equal length (e.g., one segment up to any desired plurality of segments, e.g., up to 10, 20, 30, 40, 50 or more) are employed with nine 1 / 8-inch grooves equally spaced. The number of grooves and the configuration or depth of the grooves can be adjusted depending upon processing conditions. The gears are placed in a split stainless-steel tube 1004 having threaded holes 1003 and welded to stainless steel plates 1001 including dowel pins 1002. A removable pin 1005 fitted into a hinge assembly 1006 secures the apparatus for operation. FIG. IB provides an exploded view' of a horizontal compression reactor showing detail of the gears 1000 of FIG.1A. The gears, as shown in top view in FIG. 1C include eleven sets of gear segments 1030 with twenty-four grooves 940 and a 0.200” compression relief 1014 for each gear segment. FIG. ID shows a view of the end plates 1013 (and transparent view of endplates showing details of gear behind) including taps 1016 and plate 1015 including taps 1017. While the apparatus depicted in the figures can be employed to provide pressure to a mixture of vulcanized rubber and hyperbranched macromolecules as reactant, other configurations are also envisioned, as will be appreciated by one of skill in the art, e.g., mortar and pestle, ribbon mixers, high shear dispersers, or the like. In one embodiment, instead of meshing gears, smooth rollers in opposing configuration can be employed.

[0276] FIG. 2 depicts detail of the meshing gears of the drive roll in operation. The gears are converging compression rolls with machined relief to allow lateral flow 1106 of the reactant coated crumb rubber. A 20-mesh crumb rubber pre-coated with reactant 1103 fills the space between the gears at a pressure of less than 5 psi. As the gears 1101 mesh, the pre-coated crumb rubber 1105 is compressed to approximately 100 psi (e.g., 50 psi to 200 psi, or 75 psi to 150psi, or 80 psi to 125 psi, or higher or lower, depending upon reaction conditions). Ten rotations of the gears (10 applications of compression) reduce the particle size (as determined by screening through a particular mesh size) from 20 mesh to less than 200 mesh 1107. Fifty rotations of the gears (50 applications of compression) reduce the particle size from 20 mesh to approximately 2 gm. The drive roll incorporates a dynamic brake to control back pressure. The resulting product can be processed until a desired particle size less than that of the starting crumb rubber is obtained, e.g., 30 mesh, 40 mesh, 50 mesh, 100 mesh, 200 mesh, 10 gm, 5 gm, 2 gm, 1 gm, or less than 1 gm.

[0277] Another reactor design incorporates twin counter rotating screws. The twin screws are in a close intermesh configuration and are situated in a pair of partial barrels joined together. FIG. 3 A shows a side view of one of the barrels 1200. The barrel depicted has a 3- inch outer diameter and a 2-inch inner diameter, is 30 inches in length, and contains a rotor 1202. FIG 3B shows one of the two end plates 1213 with hold holes 1220, 1221, illustrating the joined barrels configured to enclose the close-intermeshed twin counter rotating screws. The critical dimension 1222 is based upon the Boston Gear pitch diameter. A clearance of approximately 0.010 inches between the rotors of the screws and the barrel wall is provided. FIG 3C depicts one of the screws, a.500 Roton Screw 1232 with cold rolled steel thread. FIG.3C depicts thrust surface 1230, bronze bearing journal 1235, and. ANSI keyway 1234. While the reactor depicted in FIGS. 3A-C includes specific dimensions or materials, the dimensions can be reduced or increased as needed to provide a larger or smaller reactor, and other suitable materials can be substituted.

[0278] In certain embodiments, an interfusion reactor (IFR) can be employed. It has been engineered to have two, otherwise unexpected capabilities: 1) the high-speed mixing action of an open blade mixer, and 2) the impinging wedge action of a mixing extruder. A single stage interfusion reactor is depicted in FIGS. 4A and 4B.

[0279] Continuous processing equipment (CPE) including elliptical mixing lobe pairs can also be employed. The CPE base design is a 5" x 36", twin shaft, counter-rotating device powered by a 20 hp, 480v, 3ph motor manufactured by Teledyne Readco in York Pennsylvania, now known as Kurimoto Readco. The twin shafts are configured to accept slide on-and-off spiral transfer flights and 1 " thick elliptical mixing lobe pairs (FIG. 5 A) typically made of corrosion resistant, 304 stainless steel or Hastelloy steel.

[0280] The spiral and lobe work appliances match to orchestrate the movement and compounding action desired for a particular material, whether it be a power-liquid, powder-powder, or liquid-liquid medium. Square shaft openings in the individual appliances are oriented at 90 degrees or 45 degrees such that when mounted in an alternating position on the shaft(s) they provide a helical progression of pushing or mixing of the material from the barrel entrance, known as a stuffing box, to and through the barrel exit which may be a free flowing or regulated gate.

[0281] Typical, original sweep clearances between the barrel surface and the rotating surfaces of the outer circumference of the spiral flights and / or the tips of the rotating lobe(s) is in the range of 0.050“ - 0.060", dependent upon the materials being processed; however, larger or smaller clearances can be employed. Clearances between the moving surfaces of the intermeshing lobes are usually closer than between the rotating surfaces and the barrel, for example, in the range of 0.040" - 0.050" (FIG. 5B). FIG. 5C is a photograph showing details of the intermeshing lobes.0282] The barrel design is typically made of corrosion resistance 304 stainless steel with a chrome inner surface. It is a clamshell configuration and provides thermal controlof the process through full length and circumference jacketing. FIG. 5D is a photograph showing details of the spiral flights and the rotating lobes as seated in half of the barrel.

[0283] Two primary modifications to the CPE base design are incorporated in an embodiment suitable for reaction of hyperbranched macromolecules (or other reactant, e.g., OMC as described elsewhere herein) with vulcanized rubber. The design modifications are mutual, reciprocal and complimentary to achieve Atomic-Scale, Particle Interaction (ASPI). The ASPI is achieved by (ONE) a coordinated, substantial increase in: 1) mechanical stress-strain, 2) rate of shearing, 3) pulsed-timed micro-mechanical stress-strain, all modulated by (TWO) an intersecting, variable, high frequency acoustic, quantum field.

[0284] ONE consists of providing a series of raised lugs across the width of the original lobe design (see FIG. 5B). These are referred to as stress-strain lugs (SSLs) The height and shape of the lug can vary depending upon the material being processed. Its construction can be achieved by machining the profile desired from a raw blank lobe: three alternatives are shown. Typically, the barrel-to-lobe gap remains the same as the Original Equipment Manufacture (OEM) design. The lobe-tip-to-lug, primary surface can also remain the same as the OEM design, but the closure gap between the raised surface of the lug and the lobe tip can be in the range of 0.10" - 0,15"; however higher or lower closure gaps can be employed. The number of lobes and the shape are empirically established, and can vary' depending upon application, e.g,, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more lobes.

[0285] TWO consists of the insertion of piezoelectric transducer driven acoustic horn(s) arranged along the outer barrel and penetrating the barrel through a series of vibration- isolated ports which traverse the barrel jacket and are located at positions selected to strategically influence the ASPI. The high frequency emitters (HFE) operate in the range of 1,000 - 50,000 Hz.

[0286] The following discussion is in the context of processing a hyperbranched macromolecules-coated (or other reactant-coated, e.g., OMC-coated, as described elsewhere herein) ground rubber particle (GRP) with a beginning average diameter of 600 microns and an intended, exiting final diameter in the range of 500 nm - 10 microns.

[0287] At an operating motor speed of 3,500 rpm driven through a 17:1 gearbox the shaft(s) rate of rotation is 205 rpm (however, higher or lower rpm can be employed in certain embodiments). With the shaft-pair configuration of three sets of three pairs of lobes(workstations) pressurized by the forward-squeezing, transfer spirals aiong the 36" length of the CPE; the number of pulsed, SSL interactions between the Ground Rubber Particle (GRP) and the lugs is 44,280 / min.0288] The spiral feed system, with no workstations or exit valving will, at 205 shaft rpm, free flow approximately 200 pounds per minute of free-flowing GRP. With workstations as described herein and a gate valve at the exit, a 20 hp motor will move about 20 pounds of processed GRP. This equates to subjecting the bulk rubber particle to 442,800 SSLs / min.

[0289] Six HFE located three above and three below' (FIG. 5B) per workstation, emitting approximately 30,000 pulses per second, provides an accelerated chemical bond disruption.

[0290] The “Area of Quantum Field Activity” (FIG. 5B) is a Particle Vortex Cavity (PVC) which is formed by the confluence of the flow of materials along three axis within the CPE barrel: 1) a push- flow from the spiral feed flights which is parallel to the annular cavity axis of the barrel, 2) an upward sweeping motion induced by the left hand lobe perpendicular to the axial push-flow of (1) and 3) a downward sweeping motion induced by the right hand lobe, also perpendicular to the axial push-flow but opposing the flow of (2). Positioning a three HFE acoustic horns (sonotrode) cluster to radiate an acoustic wave into the PVC directly below and above the three-lobe workstation creates an opportunity to significantly influence efficiency of the mixing, chemical reaction(s) and size-dissociation of the materials being processed.

[0291] The GRP being subjected to the CPE (by way of example) is pre-coated with a hyperbranched macromolecule (or other reactant, e.g., OMC, as described elsewhere herein) in a separate operation, prior to being fed into the CPE. The cluster timed, HFE propagated ultra-sonic wave will travel through air space between the particles and, upon striking innumerable particle surface(s), interact with the liquid component of the coating thereby forming a cavitation bubble. The formation, growth and sudden collapse of the bubble forms a shockwave. The collapsing bubble shockwave operates at super-sonic speed. The HFE ultra-sonic wave and the particles, both upstream and downstream of the bubble collapse, are moving at sub-sonic speed. This flow of materials around the collapsing bubble are considered isentropic, i.e., they satisfy the Rankine-Hugoniot conditions, and therefore the supersonicshockwave is as adiabatic process transferring no heat or mass between an otherwise thermodynamic system.

[0292] The sudden nature of the cavitation shockwave relative to the conditions within which it occurs in the PVC provides an overlapping, electrodynamic force which may be engineered as to amplitude and frequency by tuning the HFE wavelength and timing. One critical measurement of the H FE efficiency is the comparison of the final particle size emitted from the CPE measured against the power consumed by the main CPE drive train. A higher ratio of small particles to constant power consumption is a bulk indication that the settings of HFE by tuning is optimizing its influence.

[0293] Each of the aforementioned reactor designs can readily be modified, as will be understood to one of skill in the art, to account for desired throughput, particulars of the reactant mix, footprint requirements, energy requirements, environmental concerns, and the like. While the above reactor designs can advantageously be employed, other reactor designs, as are known in the art for use in processing, e.g., plastics and other polymeric materials, can be adapted for use in the methods herein, including methods related to Fe-OMC and metallocene chemistries such as ferrocene chemistries.Exemplary Process Steps for Production of Hyperbranched Polymers

[0294] More than ninety seven percent (97%) of the matrix mass of pre-vulcanized or vulcanized rubber compounds, utilizing long established sulfur crosslink technology(s), consist of a blend of filled, synthetic elastomers and / or natural rubber. The remaining, less than three percent (3%) reactive sulfur / accelerator package pre-disposes such filled elastomeric compounds to primarily a thermoset-bias, end-use.

[0295] An in-situ innovation of precision extraction by a high yield, co-polymerization processing of the ubiquitous, incipient sulfur component within these compounds completely liberates the filled elastomer(s), such that they may be re-synthesized into as broad a spectrum of end-use opportunities as an analogous original, virgin non-sulfurized matrix. This innovation will provide significantly greater end-use options for millions of tons of annually generated, sulfur crosslinked waste streams from many sources, including new rubber article production downfall and end-of-life (EOL) scrap tires. It will also substantially benefit global resource sustainability as well as the energy and carbon challenges associated with mitigating climate change.

[0296] Hyperbranched macromolecules (HMs, also called hyperbranched polymers) are highly branched three-dimensional (3D) structures in which all bonds converge to a focal point or core, and which have a multiplicity of reactive chain-ends. Compared to linear analogues, the globular and dendritic architectures of HMs endow new characteristics, such as abundant functional groups, intramolecular cavities, low viscosity, and high solubility.

[0297] Utilizing advanced, hyperbranched (HB) polymer chemistry applied within the existing, ambient temperature, medium pressure applied by a co-rotating, intermeshing twin screw extruder-reactor process equipment, a new approach to the management of sulfur has emerged. That approach is to engage the most vulnerable sulfur molecular geometries existent within the original GTR with a multi-functional, hyper-branched polymer (HBP) (those sulfur molecules with chemical bonds to other than the sulfur molecules requiring less than approximately 150 kcal / mole to scission) which is tailored to initiate sulfur geometry ring opening and then crosslink the sulfur into a non-reactive polymer.

[0298] In an exemplary process, a continuous stream of 600-micron (30 mesh) ground tire rubber (GTR) is coated in a pug mill at approximately 5% by weight with an HB EIT (HyperBranched Environmentally Inert Technology) polymer supplied by Ecostar Science Technology, Inc. of Wrightwood, California. The HB EIT is a chemical reaction initiating, functional polymer with an integral catalyst that reacts with and crosslinks sulfur via a sulfonium group. At room temperature, the HB EIT polymer is a low viscosity oily liquid that readily penetrates the GTR powder surface.

[0299] As the coated GTR progresses through the reactor, the HB polymer is pressure driven deep into the inter molecular space of the rubber particle where it engages the sulfur element initiating a rapid sequence of ring opening, catalysis and co-polymerization with the HB EIT. As the sulfur is copolymerized the elastomer crosslink bridge dissolves allowing the ground tire rubber to become facile which facilitates a thorough splaying open of the rubber powder for the full collision of the sulfur and the HB EIT reaction. This accomplishes the following: I) Much lower post-process viscosity for the permitted tire rubber, i.e., the tire rubber becomes fully thermoplastic. All the sulfur contained in the mid-span of the crosslink bridges are eliminated; 2) Elimination of virtually all, old sulfur bridging without disrupting the original sulfonium-carbon-carbon elastomer attachment point from the original tire rubber sulfur vulcanization bridge, i.e., bridge attachment points are left intact; 3) HB polymerdendritic structures may be engineered to intelligently, pre-functionalize numerous carbon and elastomer components throughout the tire rubber to more efficiently react and create high performance properties in all future re-compounding applications; and 4) HB polymer can be designed for superior, controlled cross linking of end use materials; using the original sulfonium C-C sites and / or initiating new crosslink sites.

[0300] Test data demonstrated that using an HB EIT polymer / re-synthesized ground tire blend with virgin tire rubber improved cured physical properties of the tire rubber compound.

[0301] In an exemplary tensile strength graph, a comparison is provided of a 15 wt. % loading of HB EIT polymer / re-synthesized ground tire blend in an otherwise conventional tire manufacturer rubber formula versus an unmodified baseline formula. The addition of 15 wt. % HB EIT polymer / re-synthesized ground tire blend to the rubber formula substantially improved the tensile strength, e.g., approximately a 24% increase at 15 wt. % loading) when compared to that of the baseline (no HB EIT polymer / re-synthesized ground tire blend) formula. Higher and lower loadings, e.g., 16-99 wt. % loadings and 1-14% loadings may yield significant improvements in dynamic physical performance. Generally, from 10-20 wt. %, optionally 15 wt. % loadings can advantageously be employed, with the remainder virgin polymer-based rubber formula, however the amount of loading can be adjusted as desired for a balance of cost effectiveness and improved properties.

[0302] The HB EIT polymer / re-synthesized ground tire blend can be advantageously employed in, e.g., the manufacture of tires, engineered rubber products, rubberized asphalt, and any other manufactured goods where virgin elastomer is employed. The HB EIT polymer / re-synthesized ground tire blend can advantageously be employed in black masterbatch. A 15 wt. % HB EIT polymer / re-synthesized ground tire blend in conventional black master batch is observed to be an acceptable substitute for a conventional base black master batch of virgin rubber, providing improved performance features, and advantageously being used at a higher loading than the upper limit of 3 wt. % that has traditionally been employed for small-particle (200 mesh), fully-vulcanized, ground tire rubber m such formulas. In other words, the HB EIT polymer / re-synthesized ground tire blend is observed to be suitable for use in fabricating tires as the sole rubber source, or it can be usedin combination with base black master batch 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.

[0303] The HB EIT polymer / re-synthesized ground tire blend is observed to have a morphology similar to that of composite virgin rubber, to be < 50 micron in particle size, with substantial elastomer retention of the carbon black. The material is suitable for use as at least 20% and up to 50, 60%, 70, 80, 90%, or more (e.g., as much as 100%) of the sidewall of new, light truck and auto tires. Such HB EIT polymer / re-synthesized ground tire blend material is also suitable for use in membranes and industrial rubber goods.

[0304] The HB EIT polymer / re-synthesized ground tire blend and other rubbers and rubber-containing materials of the various embodiments may be manufactured, e.g., into articles or useful materials, as described herein, including but not limited to rubber and rubber goods meeting one or more MIL-R specifications or other specifications.Hyperbranched Polymer Example 1

[0305] In an exemplary embodiment, a mixture was provided in a pug mill of 5 wt.% HB EIT polymer and 95 wt. % particles of ground tire rubber (GTR) having an average particle size of approximately 600 microns. The HB EIT polymer 'as combined with the GTR while simultaneously being vigorously mixed within counter-rotating tines in a pug mill, e.g., approximately 1-3 minutes.

[0306] Thereafter, the coated / penetrated rubber particles were dropped into a stuffing box of a co-rotating, intermeshing twin screw extruder-reactor where it. is pushed, under pressure through the reactor, creating a high-pressure impingement upon the coated / penetrated rubber particles as they progressed through the reactor structure. The resulting elastomer product (referred to herein as EIT-PTR) was then combined with a conventional tire manufacturer rubber formula, which was subject, to curing to yield a molded rubber matrix subjected to testing. Standard batching procedure involves first scissioning the sulfur from the vulcanization bridge position, and immediately thereafter the rubber moiety is moved into a nitrogen blanketed, stirred chamber where the scissioned, sulfonated compound is grafted by ROP with one of the many pre-prepared HB polymer compounds as disclosed herein.

[0307] An RPA (Rubber Process Analyzer) curing curve for the molded rubber matrix (Compound: PTR3:(NR / PBR)) was determined and is provided in FIG. 6. The data for the compound is presented in Table 3 below.TABLE 3.Strain 13.95 (%)Frequency 1.7 [Hz]Test Temperature 160.00 [C°]Offset 0.00 [%]Closing Pressure 4.01 [bar]Range 0-200 [dNm]Time / Step 30.00 [min]IsothermS' max [dNm] 27.37S’ min [dNm] 3.19S’ 1.0' test time [dNm] 3.28S' @ 10.0’ test time [dNm] 27.33S' @ 20.0' test time [dNm] 25.52S’ @ 50% test time [dNm] 26.63TC 10 [min] 3.80TC 20 [min] 4.32TC 50 [min] 5.29TC 90 [min] 7.27 Scorch time (ts 1) [min] 3.22 Scorch time (ts 2) [min] 3.69Peak rate (s’ / min) [dNm / min] 8.16

[0308] Tensile strength was measured, and a force-displacement curve and stress¬ strain curve were generated. The product contained 5 wt. % EIT-PTR in a conventional rubber formula. The Speed was 500 mm / min and the Ext. 1 Gauge Length was 25mm. Data, was as presented in TABLE 4 for two samples: Sample A #1 and Sample A #2, cured at 160°C. AForce- Displacement Curve for the two samples is presented in FIG. 7 A and a Stress-Strain Curve for the two samples is presented in FIG. 7B.TABLE 4.Name UTS Break Ext. Strain Modulus Stress 100 Elong Stress 100 Elong Stress 100 Elong Parameters Sensitivity: 10 Sensitivity: 10 Force 0-1 ON Ext. Strain 100 Ext. Strain 100 Ext. Strain 100 Unit % % MPa % % %MPa MPa MPa Sample A #1 16.3861 400.480 4.76585 2.53779 6.37649 11.6816 Sample A #2 15.9601 397.700 4.95300 2.55834 6.34159 11.5331 Average 16.1731 399.090 4.85943 2.54807 6.35904 11.6074 Standard Deviation 0.30123 1.96576 0.13234 0.01453 0.02468 0.10501 Maximum 16.3861 400.480 4.95300 2.55834 6.37649 11.6816

[0309] A sample containing 15 wt % EIT-PTR and 85 wt. % conventional rubber formula was prepared and subjected to a tension temperature sweep, 2% Strain @ 10Hz, ambient temperature to 80°C. The results are presented in FIG. 8.Environmentally Inert Technology Polymer Example 2Micronized End-of-Life Tire, Colloidal Suspension

[0310] Exfoliation of micronized EOL tire rubber can be performed to generate a colloidal suspension suitable for use in a variety of applications, e.g., roofing, paving materials, tires, and the like.Overview

[0311] As depicted in the Process Flow Chart of FIG. 9, this exfoliation process is the second stage of reducing an approximately 600 micron sized ground tire rubber particle to a high surface area (approximately <25 micron sized particle) while minimizing the separation of the embedded carbon (30% of the particle, the carbon comprising carbon black) from the inter-penetrating elastomeric matrix of the GTR such that the smaller particle has similar physical properties to those exhibited in the original tire composite.

[0312] The mechanism that results in the exfoliation of the ground tire rubber, successfully avoiding measurable scissionmg of the principal composite morphology, focuses the shearing and chemical additive environment primarily upon the incipient, vulnerable weakness associated with the original tire matrix construction. That weakness is the mechanical changes induced by thermo-mechanical aging, technically referred to as the Payne Effect.

[0313] The mechanism leads to full exfoliation and dispersion of organophilic clays when mixed with molten hydrophilic polymers. This process is of fundamental importance for the production of clay-polymer nanocomposites with enhanced materials properties. The chemically specific nature of the multiscale approach used herein allows determination of how chemistry, in combination with processing conditions, produces such materials properties at the mesoscale and beyond. In general agreement with experimental observations, it is found that a higher grafting density of charged quaternary ammonium surfactant ions promotes exfoliation by a mechanism whereby the clay sheets slide transversally over one another. The elastic properties of these nanocomposites can bedetermined, and exfoliated and partially exfoliated morphologies lead to substantial enhancement of the Young’s modulus of the <25 micron-sized particle, as found experimentally.The Payne Effect

[0314] Physically, the Payne Effect can be attributed to a thermo-oxidative, deformation-induced change in the material's microstructure, i.e., to breakage and recovery of weak physical bonds linking adjacent filler clusters. With increasing time of aging, a general consensus is that the crosslink density of rubber-like materials changes, which results in a change in mechanical behavior. The crosslink density of the carbon black (CB) filled rubber vulcanizates, time and use aged at 50-100°C, measured by equilibrium swelling method, increases.

[0315] However, it is recognized that there are two competitive mechanisms during time and use aging: chain crosslinking and chain scission. This crosslink density change ultimately results in a net loss of crosslink density, whereupon the formation of nanoscopic fracture points, composed primarily from the migration of elastomeric-starved CB into the propagation of fence(s). These non-load transferring, fence-like anomalies disrupt the tire body’s cyclic stress-strain equilibrium ultimately resulting in the loss of overall tire performance.

[0316] The CB fences exhibit weak intermol ecular forces - at least two orders of magnitude less as compared to the CB clusters that are elastomer bound. The shearing action of the colloid mill acts to distort the rubber particle(s) as each passes between the rotor and stator, whereupon the chemical elements of the formula “6) Process Aids” (see Table 5), coming in dynamic shearing contact with the exposed CB flaws, act to deflocculate these CB fences.

[0317] The dissolving and peripheral scissoring of these weakening flaws result in an effective exfoliation of the large rubber particle to a smaller but more robust particle. The elimination of the weaknesses combined with higher surface area of a more robust morphology present an improved version of the EOL ground tire rubber such that its use is substantially improved over that which might otherwise be case with cryogenic or cracker mill generated scrap tire moieties.Preparation of Colloid Suspension

[0318] A tire rubber-based colloid suspension can be prepared using as a base material a rubber (referred to herein as Environmentally Inert Technology (EIT) PTR or “EIT- PTR”) prepared according to the method of Example I. The resulting product is then combined with an amine-silane (or other functionalizing agent), optionally other components, then with asphalt. The resulting product is a thermoplastic medium. The thermoplastic medium is then combined with a surfactant system, process aids, and water to yield an aqueous medium (as a colloidal suspension). The overall process is depicted in FIG. 9. The EIT-PTR is prepared by mixing ground tire rubber (GTR) with HB EIT or another EIT using paired rollers 901, then heated, e.g., by heating coils 909, and passed into a mechanical extruder (M / E) 902 operated at 50 HP by a motor 903. The resulting product (referred to as “EIT-PTR”) can be combined with process aids, if necessary’, and employed in manufacturing tires, specialty end uses, or hot melt roofs / roads applications. The EIT-PTR can also be subjected to processing in a colloid mill 904 where it is combined with water and process aids under air suppression 905, then passed through a 325-mesh sieve 906. The particles that fail are combined with additional process aids then corrected in a high-speed disintegrator 907 then passed along with the particles that pass the 325-mesh sieve 906. The resulting package (PKG) colloid suspension in 70% liquid can be stored in tank farm 908 where it is drawn from for use in multiple products.

[0319] Some of the components employed in the process include “#3) Amine Silane” (see Table 5). In the example, this is N-2-(aminoethyl)-3aminopropyltrimethoxysilane, CAS # 1760-24-3. (3-Aminopropyl)tri ethoxysilane (APTES) is an aminosilane frequently used in the process of silanization, the functionalization of surfaces with alkoxysilane molecules. It is a silane widely used to supply amino groups for further modifications on various materials. While N-2-(aminoethyl)-3aminopropyltrimethoxysilane is employed in the example, other aminosilanes can also be employed, including di-amino silanes, tri-amino silanes, piperazinyl silanes, cyclohexyam ino silanes, dimethyamino silanes, diethylamino silanes and butylamino silanes, e.g., 3-aminopropyltriethoxysilane, 3-aminopropylsilane, bis[(3-triethoxysilyl)propyl]amine, bis[(3-trimethoxysilyl)propyl]amine, 3-ammopropylmethyldimethoxysilane, aminoethylaminopropyltrimethoxy silane, aminoethylaminopropyltriethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethyldiethoxysilane, diethylenetriaminopropyltrimethoxysilane, diethylenetriaminopropylmethyldimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N- cyclohexyl-3-aminopropylmethyldimethoxysilane, phenylaminomethyltrimethoxysilane, phenylaminomethyltriethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, diethylaminomethyltriethoxysilane, diethylaminopropyltrimethoxysilane, diethylaminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, 3-(N, N- dimethylaminopropyl)-aminopropyl-methyldimethoxysilane, N-(n-butyl)-3-aminopropyltrimethoxysilane, amino silane hydrolysate, oligomeric diamino-silane, diamino functional oligomeric siloxane, and the like. Other monomers yielding different functional groups as described herein can be employed instead of amine silanes in certain embodiments.

[0320] Another component of the process is “#5) Surfactant System” (see Table 5). In the example, this is Redicote® E-7000, an amphoteric emulsifier comprising a proprietary mixture of alkyl amines salts, water, sodium chloride, proprietary acid, and proprietary amine. Other amphoteric emulsifiers can also be employed. An emulsifier is a surfactant that stabilizes emulsions. Amphoteric emulsifiers are surfactant emulsifiers simultaneously carrying an anionic and cationic hydrophilic group with its structure containing simultaneously ions which are able to form cations or anions according to ambient conditions such as pH changes. The cationic part is typically an amine salt or quaternary ammonium hydrophilic group while the anionic moiety is typically a carboxylate, sulfonate, or phosphate hydrophilic group, especially the amino acid type amphoteric surfactants that contains both amino and carboxy group or the intramolecular ammonium salt type amphoteric surfactants consisting of carboxyl group and a quaternary ammonium group. Various types of amphoteric surfactants include hydroxyimidazoline and N-alkyl betaine types, which exhibit cationic properties upon acidity. Other examples include sulfonic acid type betaine and phosphonyl group betaine amphoteric surfactants, which exhibit anionic properties at all pHs, and phospholipid-type amphoteric surfactants, alkyl group glycines (diamine- ethyl- group) and di (alkyl amino-ethyl group) glycines, quaternized fatty acid amides glycines, lauryllactam imidazolium salts, and amido propyl betaine, Amphoteric surfactants can be used in combination with fatty alcohol sulfates in order to improve solubility. Commonly used amphoteric emulsifiers include amino acid emulsifiers, imidazoline emulsifiers, and betaine emulsifiers. Examples of amphoteric emulsifiers include lauryl betaine; betaine citrate; sodium lauroamphoacetate; fatty acids, C10- 20 and C16-18-unsatd., reaction products with triethanolamine, di-Me sulfate-quaternized;sodium hydroxymethylglycinate; iauramidopropyl betaine; rennin; betaines, cocoalkyldimethyl; (carboxymethyl)dimethyloleylammonium hydroxide; cocoamidopropyl betaine, ( carboxy latomethyl)dimethyl(octadecyl)ammonium. In certain embodiments, other surfactant (emulsifier) systems can be employed.

[0321] Another component of the process is “#6) Process Aids”. In the example this is BYK 151, a solution of an alkylol ammonium salt of a polyfunctional polymer with anionic character in (2-methoxymethylethoxy)propanol. Other wetting agents, solvents, or processing aids as known for use in rubber processing for various end uses can also be employed. Wetting agents ease the wetting of solid particles, and dispersing agents ensure the stability’ of a dispersion over time. These are employed to aid in forming a stable colloid suspension. A wetting agent is a surface-active molecule used to reduce the surface tension of water. The chemical structure of wetting agent molecules can include a hydrophilic head and a long hydrophobic tail. Its distinct amphiphilicity allows it to bury’ its hydrophilic head in an aqueous bulk phase and hydrophobic part in the organic bulk phase respectively. Wetting solution molecules break the intermolecular forces between each molecule in the organic phase and each water molecule in the aqueous phase by displacement. Due to the lowered attractive forces, the surface tension is reduced. Upon adding more wetting solution, the elevated concentration of wetting solution molecules leads to a further decrease in surface tension and makes the molecules at the surfaces become more crowded. The molecules will be forced to remain in the aqueous phase when there are no more vacancies for them to stay on the surface. At this point, the surface tension is maximally lowered and is termed as the critical micelle concentration (CMC). The lower the CMC, the more efficient the wetting solution is in reducing surface tension. Any additional wetting solution molecules will undergo self¬ aggregation into several special structures called micelles. Micelles are spheres with a hydrophobic core formed by the non-polar tail of wetting solution molecules and are surrounded by a hydrophilic layer arising from the molecules’ polar heads. Extra wetting solution molecules are forced to form micelles instead of adhering to the surface, such that the surface tension remains constant. Due to the minimized surface tension, the droplet can spread thoroughly and form a thin film on the surface. Generally, the wetting solution molecules consist of a hydrophilic head and a long hydrophobic tail. The hydrophobic region usually contains saturated or unsaturated hydrocarbon chains, heterocyclic rings or aromatic rings.Despite the similar amphiphilic composition, the molecules can be divided into four classes with respect to the nature of the hydrophilic group, namely, non-ionic, anionic, cationic and zwitterionic. Other processing agents can be employed in certain embodiments.0322] The components that were employed in preparing a colloid suspension are set forth in Table 5. The resulting colloid suspension exhibited properties indicating suitability for use in a variety of applications, including tires, specialty end uses (e.g., engineered rubber goods), and hot melt roof and road compositions. The relative proportions (on a weight basis) of the colloid suspension that was prepared are set forth in Table 5. It is contemplated that other relative proportions may also be employed in various embodiments of colloid suspensions, e.g.: 40-70 parts by weight GTR, 1-5 parts by weight HB FIT, 0.25-3 parts by weight amine-silane, 2 to 10 parts by weight asphalt (either VTB or other asphalt based product(s)), 1 to 5 parts by weight surfactant system, and 1 to 7 parts by weight process aids. In certain embodiments, one or more of the Elements 3), 4), 5), and 6) may be optional in the preparation of a product comprising the product of EIT-PTR. While in certain embodiments EIT-PTR is employed as a rubber component, other rubbers can also be employed, e.g., rubber components prepared by EITs other than HB EIT, or rubbers prepared as in the methods of PCT Publ. WO 2018 / 200340, PCTPubl. WO 2019 / 135815, PCTPubl. No. WO 2019 / 028286, PCT Publ. No. WO 2022 / 146464, PCT Publ. No. WO 2021 / 225848, PCT Publ. No. WO 2021 / 178575, and PCT Publ, No. WO 2021 / 141750, the contents of each of which are hereby incorporated by reference in their entirety. While the methods of the embodiments are described as being employed with rubber components derived from EOL rubber tires, in certain embodiments rubber components containing both a virgin rubber and a recycled rubber can be employed, as can a virgin rubber component.TABLE 5.Element Formula Chemistry or sourceWt (lb)1) GTR 30 mesh 56.00 CRM of Mesa, AZ; Genan Inc. of Houston, TX, and / or Liberty Tire Recycling of Pittsburgh, PA 2) HB EIT | 2.80 EcoStar Technology of Wrightwood, CA3) Amine-silane 0.56 N-2-(Aminoethyl)-3- aminopropyltrimethoxysilane, CAS # 1760-24-3 4) Asphalt 5.32 E.g., Vacuum Tower Distillation Bottoms (VTB) asphalt from Calumet Specialty Products Partners of Shreveport, LA5) Surfactant 1.96 Redicote® E-7000 from Akzo Nobel Surface System Chemistry LLC of Chicago, IL, amphoteric emulsifier comprising a proprietary mixture of alkyl amines salts, water, sodium chloride, proprietary acid, and proprietary amine.6) Process Aids 3.50 BYK 151 Solution of an alkylol ammonium salt of a polyfunctional polymer with anionic character, BYK-Chemie GmbH of Wesel, Germany and (2-methoxymethylethoxy)propanol CAS # 34590- 94-87) Water 29.86 Potable water, municipal water supplyFerrocene and other Cyclopentadiene Metallocene Complexes

[0323] The asymmetrical electronic structure of the cyclopentadiene metallocene complex provides an unparalleled opportunity to form new compounds from the existing inorganic and organic spectrum which exhibit advanced physical properties. The pendant ferrocenyl unit can become a redox center to impart one or more properties, e.g., high torsional mobility, thermal stability, polar switching, hydrophobicity, hydrophilicity, broad copolymerization, electrical resistivity, electrical conductivity, facilitate n and p junction doping, self-healing composites, electrical switching, manipulable logic gates, and stimuli- responsive polymers, to name a few.

[0324] The electronic structure of ferrocene is as follows. The two cyclopentadienyl (Cp) rings of ferrocene may be orientated in the two extremes of either an eclipsed ( sh) or staggered (Dsd) conformation. The energy of rotation about the Fe-Cp axis is very small 4 kJmol’1) and ground state structures of ferrocene may show either of these conformations. There is also very little difference in electronic states between the D5h and D5dsymmetries however the Did point group irreducible representations are used here in the description of the electronic structure of ferrocene as they simplify the symmetry matching of ligand molecular orbitals (SALCs) and metal atomic orbitals. The primary orbital interactions that form the metal-ligand bonds in ferrocene occur between the Fe d orbitals and the n-orbitals of the Cp ligand. If D5d symmetry is assumed, so that there is a center of symmetry in the ferrocene molecule through the Fe atom there will be centro-symmetric (g) and anti-symmetric (u) combinations.0325] The n MOs of cyclopentadienyl, (MOs), are as follows. CsHs' has three pairs of electrons delocalized in a n system extending around the pentagonal ring. The five 2p orbitals perpendicular to the ring on the five carbon atoms combine to form three bonding (rr1, TT2, 7t3) and three antibonding (a:4*, it5*, TT6*) MOS. The symmetries and forms of these MOs can be deduced by applying the operations of the point groupto a set of five vectors perpendicular to the ring, one at each carbon, to generate a reducible representation r^.1! MOs of Cyclopentadienyl, C5H5~, D5 / ;£ 2G 2Cf 5C > 2S524 / 5< TV.u 5 0 0 -1 -5 0 0 15 0 0 -5 -5 0 0 5 0 0J. 5 0 0 5 -5 0 0 -5 0 0£? 10 0 0 0 -10 0 0 0 0 0E2‘ 10 0 0 0 -10 0 0 0 0 05 0 0 -5 5 0 0 -5 0 0X 5 0 0 5 5 0 0 5 20 2£?' 10 0 0 0 10 0 0 0 20£. / 10 0 0 0 10 0 0 0 20T~ = X’ + * £2w£ / r- ] 4- 2 4- 2 - 5

[0326] The five p-orbitals on the planar Cp ring (DSH symmetry) can be combined to produce five molecular orbitals according to the reducible representation:r u n„ = A7+ E + E7«£ K‘

[0327] One combination has the full symmetry of the ring (az”). There are two doubly degenerate combinations (ei" and ez") having one and two planar nodes at right angles to the plane of the ring. The relative energies of these orbitals increase as the number of nodes increases. The az” and ei" orbitals are both fully occupied in the electronic configuration of the Cp’ anion whereas the ez" orbitals are net anti-bonding and are unfilled.The π-molecular orbitals of the cyclopentadienyl ring0328] The five p-orbitals on the planar Cp ring (Dsh symmetry) can be combined to produce five molecular orbitals. For a bis-cyclopentadienyl metal complex (p5-Cp)2M, such as ferrocene, the n-orbitals of the two Cp ligands are combined pairwise to form the symmetry adapted linear combination of molecular orbitals (SALCs) which are described by the irreducible representations of the D5d point group.Γπ= A1g+ A2g+ E1g+ E2g+ A1u+ A2u+ E1u+ E2udΓ= 1 + 2 + 2 + 1 + 2 + 2 = 10

[0329] The ΓπSALCs of the (Cp)2framework are also defined by the sum and difference of SALCs from the two contributing Cp ligands whose results must correspond to the irreducible components of Γπ(Cp)2i.e.(ψ1+ψ1), (ψ1-ψ1); (ψ2+ψ2), (ψ2-ψ2) ... etc. where, for example, 'ψ1+ψ1' gives rise to a molecular orbital of A1gsymmetry.

[0330] This gives rise to three sets of ligand molecular orbitals of gerade (g) and ungerade (u) symmetry with respect to the center of inversion, a low lying filled bonding pair of A1gand A2usymmetry; a filled weakly bonding pair of E1gand E1usymmetry, and an unfilled anti-bonding pair of E2gand E2usymmetry.SALCs for a (η5-Cp)2M complex

[0331] Using the reducible representation of SALCs the corresponding metal AOs are found:Γπ= A1g+ E1g+ E2g+ A2u+ E1u+ E2u

[0332] Thus, in D5dthe bonding metal orbitals transform as:A1g:: (s, dz2)A2u: (pz)(px, py)

[0333] By considering the AO and SALC symmetries and how overlap can be affected the MO bonding picture of ferrocene can be constructed. Each combination of AOs and SALCs leads to a bonding molecular orbital | ( HA and molecular orbital )^('Pmetal atomic orbital )] and a COlieSpOndin ant -bonding molecular orbital [{JEligand molecular orbital)“dPmetal atomic orbital)] providing that the energies of the two component sets are sufficiently close for overlap.Symmetry matching of the SALC's with the metal atomic orbitals<>3s

[0334] Due to a difference in energies the lowest energy e1gmolecular orbital is mainly ligand based with a slight admixture of the Fe 4s and 3dz2orbitals. Similarly, thelevel has little if any metal character due to higher lying Fe 4pzorbital with which it is formally able to combine. The e1gmolecular orbital arises from the bonding combination of the ligand e1gorbitals with the Fe 3dxzand 3dyzorbitals. This is the only symmetry combination of orbitals in the two Cp rings that has appreciable overlap with the metal 3d orbitals to act as an efficient donor and it is thus this interaction which is mainly responsible for the stability of the complex. The corresponding anti-bonding orbitals, e1g*, are unfilled in the ground state of ferrocene but they are involved in excited state transitions. The e1ubonding molecular orbitals are again mainly ligand based but with a small contribution from the higher energy Fe 3px, pyorbitals. The a1gHOMO mostly consists of the Fe 3dz2orbital as the a1gSALC and the metal dz2orbital result in little or no overlap. The e2g(dx2-dy2, dxy) metal orbitals are considered weakly-bonding due to poor overlap with the e2gSALC orbitals. Since the occupied orbitals are of either a1g, e1gor e2gtype symmetry no intrinsic barrier to internal rotation is predicted aseach of these molecular orbitals are symmetric about the axis of rotation. The very low values observed for this rotation (~ 4 kJmol-1) may be attributed to van der Waals forces between the two Cp rings. The attachment of additional groups or ligands destroys the D5d / D5hsymmetry of ferrocene thus significantly altering the MO diagram.

[0335] The electronic structure of bisbenzenechromium Cr(η6-C6H6)2is as follows. Similar to ferrocene, primary orbital interactions that form the metal-ligand bonds in occur between the Cr d orbitals and the rc-orbitals of the benzene ligand. The two benzene rings of Cr(η6-C6H6)2are ideally orientated in an eclipsed (D6h) conformation.K MOs of Benzene, C6H6

[0336] For (η6-C6H6)2M the π-orbitals of the two benzene ligands are combined pairwise to form the SALCs which are described by the irreducible representations of the D6hpoint group.P ix J 4- h 4- A. 4* r > 4* 4 -> 4* 4~ -r?f-r

[0337] Using the reducible representation of SALCs the corresponding metal AOs are found:FΓπ= A1g+ E1g+ E2g+ B2g+ A2u+ E1u+ E2u+ B1u

[0338] In D6hthe bonding metal orbitals transform as:: (s, dz2)E1g: (dxz, dyz)^g 'A2u: (pz)£E1u: (px, py)

[0339] The metal s, p and d orbitals all transform in D6hin a similar manner as found for the D5dferrocene metal AOs, thus a similar LCAO can be earned out.Symmetry matching of the SALC's with the metal atomic orbitals

[0340] Metallocenes are a class of organometallic compounds that consist of a transition metal atom sandwiched between two cyclopentadienyl (Cp) ligands. Ferrocene is a specific type of metallocene that contains an iron (Fe) atom sandwiched between two Cp ligands. Ferrocene is one of a large number of compounds of transition metals with the cyclopentadienyl anion. Other metals that form sandwich-type structures similar to ferrocene include nickel, titanium, cobalt, ruthenium, zirconium, and osmium. The stability of metallocenes varies greatly with the metal and its oxidation state. Ferrocene, ruthenocene, and osmocene are particularly stable because in each the metal achieves the electronic configuration of an inert gas. In (CsHs^Co®, the cobalticinium ion, the metal has the 18 outer¬ shell electrons characteristic of krypton.

[0341] Many other unsaturated organic compounds can form n complexes with transition metals. A substance that is in some ways analogous to ferrocene is the complex of two benzene molecules with chromium metal, called dibenzenechromium. The bondinginvolves zerovalent chromium and the n electrons of the two benzene rings. In dibenzenechromium, the electronic configuration of the chromium atom is similar to that of krypton:

[0342] Although dibenzenechromium is thermally quite stable, it is less so than ferrocene and melts with decomposition at 285°C to give benzene and metallic chromium. Furthermore, it appears to lack the aromatic character of either benzene or ferrocene as judged by the fact that it is destroyed by reagents used for electrophilic substitution reactions. Several transition-metal complexes of cyclobutadiene have been prepared. Reactions that logically should lead to cyclobutadiene give dimeric products instead. Thus, 3,4-dichlorocyclobutene has been dechlorinated with lithium amalgam in ether, and the hydrocarbon product is a dimer of cyclobutadiene, 5. However, 3,4-dichlorocyclobutene reacts with diiron nonacarbonyl, Fe2(CO)9, to give a stable iron tricarbonyl complex of cyclobutadiene, whose structure has been established by x-ray analysis. The ^-electron system of cyclobutadiene is stabilized by complex formation with iron, which again attains the electronic configuration of krypton.

[0343] Oxidation of 6 with ceric iron, Ce(IV), releases cyclobutadiene which quickly dimerizes, but can be trapped by good dienophiles such as ethyl propynoate to give acycloadduct. Many metallocene derivatives are known of other conjugated cyclic polyenes. Examples are bis(cyclooctatetraene)uramum (uranocene, 7) and bis(pentalenylnickel):

[0344] Many of the metallocene compounds display unusual reactivities and reactions, such as the absorption of dinitrogen, N2N2, by titanocene, (C2H5)2Ti, to form a complex or complexes that can be reduced easily to form ammonia. The nature of these complexes is in doubt, but the structure of the complex 9 formed from decamethylzirconocene and dinitrogen is believed to be:9 (for clarity, the 20 methyl groups on the ring

[0345] This complex treated with acids yields NH2−NH2 and some NH3.

[0346] Iron(O) has 8 electrons in the 45 and 3d orbitals. Ferrous iron (Fe2+) has 6 outer-shell electrons. This 6 plus the 12 TT electrons of the two cyclopentadienide rings makes the 18-electron total and the krypton electronic configuration.

[0347] Ferrocene is soluble in many organic solvents, including methanol, ethanol, ethyl ether, petroleum ether, gasoline, kerosene, diesel oil, methylene chloride (dichloromethane), benzene, toluene, and xylene. Any suitable solvent may be employed in the methods described herein for ferrocene or other metallocenes. While a fully saturated solution can be advantageously employed, in certain embodiments a solution that is less than fully saturated with the metallocene may also be employed, as may a supersaturated or oversaturated solution. Similarly, while an organic solvent is advantageously employed to provide the metallocene, other carrier fluids may also be employed, e.g., certain carrier gases, certain inorganic solvents, or the like. In certain embodiments, the metallocene can be provided in the form of a powder suitable for being sprayed or otherwise conveyed into the EOL-GTR to be treated.

[0348] In certain embodiments, a metallocene can be incorporated into a dendritic polymer, as described elsewhere herein, e.g., a ferrocenyl HB polymer.Uses of EOL-GTR Derived Rubbers (e.g., Permutated EOL-GTR or Iron-Based OMC-GTR Reaction Product)

[0349] The rubbers and rubber-containing materials of the various embodiments are suitable for use in a variety of products conventionally prepared from virgin rubber, e.g., rubberized asphalt, black master batch, roofing materials, paving materials, asphalt emulsions, tires, tire retreads, membranes, industrial rubber goods, and engineered rubber products such as floor mats, tire wall construction, code compliant electrical tape, potting compounds, industrial belting and hoses, high temperature fabrics and gaskets, geo-liners, roofing and waterproofing membranes, colloidal suspensions for industrial adhesives, and super-pave, PG hot-melt, asphalt binder modification. The material is suitable for use as the sole rubber component in such articles of manufacture or may be used in combination with virgin rubber and / or other elastomers.

[0350] The rubbers and rubber-containing materials of the various embodiments (e.g., HB EIT polymer / re-synthesized ground tire blend, permutated rubber, OMC rubbers, or other elastomers as described herein) may be manufactured, e.g., into articles or useful materials. In certain embodiments, rubber and rubber goods meeting one or more MIL-R specifications are provided. The articles (e.g., engineered articles) can include but are not limited to tire tread, tire sidewall, roofing membrane, high dielectric electrical tape, tank lining, reservoir lining, trench lining, bridge underlayment, foundation waterproofing, parking garage waterproofing, hose, belt, molding, or other rubber goods prepared from molded rubber or rubber sheeting (e.g., gaskets, tubing, shock absorbing materials, floor mats and bed liners for vehicles, mats and flooring materials for commercial and residential construction, underlayments for floors, decking, and concrete, sound proofing, etc. ). Other products include elasticized bands in clothing and hair ties, dishwashing gloves, toys, jar seals and tires, welcome mats, garden hoses. Other household rubber items include shoe soles, boots, raincoats, pond liners, mattresses and cushions, pillows, grips on garden tools, bathtub plugs, doorstops, earplugs, hot water bottles, aquarium tubing, faucet washers and backing for rugs. Stoppers for lab flasks and vials, chemical resistant mats and pads, prosthetics and other specialized products and equipment can be made from the rubber of the embodiments, as canrubber food and water bowls, chew toys and balls, foam rubber mattress pads, stall mats, elasticized vet wraps, flea collars, shed mitts and rubber combs, mouse pads, keyboards, adhesives and rolling chair wheels, anti-fatigue mats, carpet underlayment, head phone pads and rubber stamps, inflatable beds for camping, playground tiles, rubber ducks, sportswear, scuba suits, vehicle components for civilian and military use; boat, ship, and submarine components for civilian or military use; airplane, passenger plane, and fighter jet components, railcar and train engine components, residential and commercial building products, factory or industrial or manufacturing components, clothing and footwear components.Functional Nanoparticle Example 3

[0351] A functional nanoparticulate rubber derived from EOL-GTR (NTR) was prepared according to the reaction sequence of FIG. 10 in a reactor as depicted in FIG. 11. While the depicted reactor can be advantageously employed, other reactor configurations may also be suitable for use, as one of skill in the art will understand, in that they are able to provide the metallocene to the vulcanized rubber particles to be exfoliated in a suitable manner so as to achieve exfoliation.

[0352] FIG. 10 provides a reaction sequence for the ring opening metathesis polymerization (ROMP) / radical polymerization (RP) (III) between cyclopentadienyl ferrocene complex (cpFe) (I) and a sulfur bridge Ss (II) of an EOL-GTR Thermal catalysis operates on a “click” time scale. The thermally initiated thiol ene reaction yields a pendant ferrocenyl (or backbone ferrocenyl). Pendant ferrocenyl units can act as redox centers to impart physical properties such as high torsional mobility, thermal stability, polar switching, hydrophobicity, hydrophilicity, copolymerization (broad), electrical resistivity, electrical conductivity, facilitate n and p junction doping, self-healing composites, electrical switching, logic gates (manipulable), and stimuli responsive polymers.

[0353] FIG. 11 provides a drawing of a reactor configured to generate a functional (nano)particle rubber from EOL-GTR. In Stage I, EOL-GTR was processed by a variable speed mixer (2 hp operating at 3050 rpm) 11101 with a stainless steel (SS) bowl 11102 with ten- pound (10 lb) process volume for 30 mesh EOL-GTR. The mixer utilized counterrotating intermeshing mixer ribbons 11103 in a reactor equipped with 3000-watt heating straps 11104 and a regulating valve 11105 for passage of EOL-GTR to a multistage stator / rotor assembly 11106. The stator / rotor assembly (Stage 2) 11106 was equipped with 0.060- inch slots 11107then 0.020-inch slots 11108 and was equipped to receive the cpFe via insulated pressurized fluid lines with metering (Stage 1) 11109. The stator / rotor assembly 1106 was powered by a 5 hp motor 11110 operating at 3500 rpm. As shown in Detail “A”, each slotted stator 11114 of the stator / rotor assembly was equipped with an outer housing 11111 enclosing multiple spray ports 11112 at the stator / rotor gap 11113 and provided a flow passage 11115 for EOL-GTR Rotation of the rotor 11117 is depicted. The stator gap 11113 was adjustable. As shown in Detail “B”, the metered cpFe (fluid) at approx. 50°F was metered into the spray ports 11112 of the stator / rotor where it contacted EOL-GTR particles at a temperature of >290°F under a partial vacuum. The dwell time for the cpFe and EOL-GTR particles was approximately 50- 90 msec, during which time the “click” reaction formed pendant (or backbone) ferrocenyl units. The product of the first level stator / rotor 11107 was suitable for utilization as formed, or suitable for passage through to one or more additional levels of stator / rotor 11108 where further reaction between EOL-GTR and cpFe could occur. Exfoliated (permutated) EOL-GTR was collected from the stator / rotor assembly via a permutated EOL-GTR collection system 11116.

[0354] The reaction sequence was conducted as follows. A solution of ferrocene (cpFe) in di chloromethane (DCM) was prepared. The relative percentages by weight, were as follows: ferrocene blend (CAS No. 102-54-5; melting point 350°F) at 75 wt. % and di chloromethane (CAS No, 752-09-2; boiling point 103 °F) at 25 wt. %. The solution (or cpFe- solvent mixture) was stored and handled at a temperature in a range of 50-70°F (typical ambient, temperatures).

[0355] 30 mesh EOL-GTR particles were provided and preheated in reactor Stage 1 to 150-200°F and released, at an optimized timed rate (50-90 msec dwell time), into reactor Stage 2 (of I and II), where they were subjected to exfoliation by cpFe in a “click” reaction. The DCM / cpFe fluid phase changed to gas at approx. 105-110°F. Transfer as a fluid phase to the reactor through one or more insulated tube(s) 11120 and atomization nozzle(s) 11121 above approx. 50 psi assured adequate diffusion into the EOL-GTR. To maintain uniform reaction and optimized, progressive exfoliation, the balance between stator / rotor chamber density of the rubber, atomized DCM / cpFe, exit temperature, and mass flow rates were maintained tokeep pace with the rate of the click reaction between the cpFe and the accessible, thermally fluidized sulfur of the EOL-GTR.

[0356] The total throughput of exfoliated rubber from 30 mesh down to submicron (<1 um) size rubber was 400 Ib / hr.

[0357] The method of the example offers advantages over other methods of processing, recovering, or recycling a vulcanized rubber such as EOL-GTR. The ferrocene attacks the sulfidic bridges of the surface of the EOL-GTR particle in a controlled manner, such that the topmost layer of the particle is “exfoliated” while leaving deeper layers unaffected (maintaining the structure of the vulcanized rubber and its vulcanizing properties). This exfoliation process acts layer by layer, as the reaction is maintained, progressively reducing the particle size, similar to the process of peeling an onion layer by layer. The exfoliation can be conducted to increase the surface area of the particle, e.g., by 1000-fold or more. The process greatly increases the surface area of the particles, enabling the carbon black and functional groups of the EOL-GTR to be accessed for utilization, yielding particles of a small, desired size, e.g., 500 nm to 25 microns. While not wishing to be bound by theory, it is believed that the superconducting nature of the metallocene (cpFe) results in a rate of reaction with the sulf idic bridge of 20-100 ns. The ferrocene is released into the reactor at a controlled rate to react with the EOL-GTR to exhaust the chemistry', then the exfoliated particle is moved to a next stage for further reaction. The reaction offers the advantage of avoiding flammability issues, and a large portion (as much as 99.9% by weight or more) of the solvent can be recovered / recycled for continued use in the process. With respect to the functional (nano)particle resulting from the process, it can agglomerate, it can be functionalized (e.g., using a disperser modified water), it can be spray dried, it can be spun into a fiber, it can be used in 3-d printing, and it can be used to coat 2 dimensional structures. The method provides a way to prepare highly carbon impacted elastomer with various levels of functional groups inexpensively.Iron-Based Organometallic Reactant

[0358] One of the components utilized in preparing certain iron-based organometallic reactant compounds are iron oxide nanoparticles. Iron oxides are common natural compounds and can also easily be synthesized in the laboratory. There are sixteen iron oxides, including oxides, hydroxides, and oxide-hydroxides. Iron oxides can form as a resultof aqueous reactions under various redox and pH conditions. Iron oxides have the basic composition of Fe, O, and / or OH, but differ in the valency of iron and overall crystal structure. Some of the important iron oxides are goethite, akaganeite, lepidocrocite, magnetite, and hematite.

[0359] Commercially available iron oxide nanoparticles include maghemite (γ-Fe2O3) and / or magnetite (Fe3O4) particles with diameters of from 1 to 100 nanometers. In nanoparticles, the surface area to volume ratio is typically much larger than for larger particles. This allows a considerably higher binding capacity and excellent dispersibility of the iron oxide nanoparticles in liquids. Magnetic iron oxide nanoparticles with sizes of from 2 to 20 nm display superparamagnetism (i.e., their magnetization is zero in the absence of an external magnetic field, and they can be magnetized by an external magnetic source). This property provides additional stability for the magnetic nanoparticles in liquids. Magnetite has an inverse spinel structure with oxygen forming a face-centered cubic crystal system. In magnetite, all tetrahedral sites are occupied by FeJ fand octahedral sites are occupied by both Fe^ and Fe2". Maghemite differs from magnetite in that all or most of the iron is in the trivalent state (Fe3+) and by the presence of cation vacancies in the octahedral sites. Maghemite has a cubic unit cell in which each cell contains 32 oxygen ions, 21⅓ Fe3+ions and 2⅔ vacancies. The cations are distributed randomly over the eight tetrahedral and sixteen octahedral sites. Due to its four unpaired electrons in the 3d shell, an iron atom has a strong magnetic moment. Fe also has four unpaired electrons in 3d shell and Fe3" has five unpaired electrons in 3d shell. Therefore, when crystals are formed from iron atoms or the ions Fe2+and Fe3" they can be in ferromagnetic, antiferromagnetic, or ferrimagnetic states. In the paramagnetic state, the individual atomic magnetic moments are randomly oriented, and the substance has a zero net magnetic moment if there is no magnetic field. These materials have a relative magnetic permeability greater than one and are attracted to magnetic fields. The magnetic moment, drops to zero when the applied field is removed. But in a ferromagnetic material, all the atomic moments are aligned even without an external field. A ferrimagnetic material is similar to a ferromagnet but has two different types of atoms with opposing magnetic moments. The material has a magnetic moment because the opposing moments have different strengths. If they have the same magnitude, the crystal is antiferromagnetic and possesses no net magnetic moment. When an external magnetic field is applied to a ferromagnetic material, themagnetization (AT) increases with the strength of the magnetic field (H) until it approaches saturation. Over some range of fields, the magnetization has hysteresis because there is more than one stable magnetic state for each field. Therefore, a remanent magnetization will be present even after removing the external magnetic field. A single domain magnetic material (e.g., a magnetic nanoparticle) that has no hysteresis loop is said to be superparamagnetic. The ordering of magnetic moments in ferromagnetic, antiferromagnetic, and ferrimagnetic materials decreases with increasing temperature. Ferromagnetic and ferrimagnetic materials become disordered and lose their magnetization beyond the Curie temperature and antiferromagnetic materials lose their magnetization beyond the Neel temperature. Magnetite is ferrimagnetic at room temperature and has a Curie temperature of 850 K. Maghemite is ferrimagnetic at room temperature, unstable at high temperatures, and loses its susceptibility with time. (Its Curie temperature is hard to determine). Both magnetite and maghemite nanoparticles are superparamagnetic at room temperature. This superparamagnetic behavior of iron oxide nanoparticles can be attributed to their size. When the size gets small enough (<10 nm), thermal fluctuations can change the direction of magnetization of the entire crystal. A material with many such crystals behaves like a paramagnet, except that the moments of entire crystals are fluctuating instead of individual atoms.

[0360] Iron oxide nanoparticles can be prepared by a variety of methods and are commercially available. The preparation method has an impact on shape, size distribution, and surface chemistry of the particles. The preparation method also determines to a great extent the distribution and type of structural defects or impurities in the particles. All these factors affect magnetic behavior. Recently, many attempts have been made to develop processes and techniques that would yield "monodisperse colloids" consisting of nanoparticles uniform in size and shape.

[0361] The most common method for preparing iron oxide nanoparticles is coprecipitation. This method can be further divided into two types. In the first, ferrous hydroxide suspensions are partially oxidized with different oxidizing agents. For example, spherical magnetite particles of narrow size distribution with mean diameters between 30 and 100 nm can be obtained from a Fe(II) salt, a base and a mild oxidant (nitrate ions). The other method consists of ageing stoichiometric mixtures of ferrous and ferric hydroxides in aqueousmedia, yielding spherical magnetite particles homogeneous in size. In the second type, the following chemical reaction occurs:2 Fe3++ Fe2++ 8 OH−→ Fe3O4+ 4 H2O

[0362] Optimum conditions for this reaction are pH between 8 and 14, Fe3+ / Fe2+ratio of 2:1 and a non-oxidizing environment. Being highly susceptible to oxidation, magnetite (Fe3O4) is transformed to maghemite (γFe2O3) in the presence of oxygen:2 Fe3O4 + O2 → 2 γFe2O3The size and shape of the nanoparticles can be controlled by adjusting pH, ionic strength, temperature, nature of the salts (perchlorates, chlorides, sulfates, and nitrates), or the Fe(II) / Fe(III) concentration ratio.

[0363] Hydrothermal synthesis is a common wet chemical method for forming various magnetic nanoparticles, including magnetite and manganese or cobalt ferrites. The main advantage of this method is the ability to increase solutions temperatures above their boiling point, and it helps to form small size and crystalline nanoparticles.

[0364] A microemulsion is a stable isotropic dispersion of two immiscible liquids consisting of nanosized domains of one or both liquids in the other stabilized by an interfacial film of surface-active molecules. Microemulsions may be categorized further as oil-in-water (o / w) or water-in-oil (w / o), depending on the dispersed and continuous phases. Water-in-oil is more popular for synthesizing many kinds of nanoparticles. The water and oil are mixed with an amphiphilic surfactant. The surfactant lowers the surface tension between water and oil, making the solution transparent. The water nanodroplets act as nanoreactors for synthesizing nanoparticles. The shape of the water pool is spherical. The size of the nanoparticles will depend on the size of the water pool to a great extent. Thus, the size of the spherical nanoparticles can be tailored and tuned by changing the size of the water pool.

[0365] The decomposition of iron precursors in the presence of hot organic surfactants results in samples with good size control, narrow size distribution (5-12 nm) and good crystallinity; and the nanoparticles are easily dispersed. Viable iron precursors include Fe(Cup)3, Fe(CO)5, or Fe(acac)3 in organic solvents with surfactant molecules. A combination of xylenes and sodium dodecylbenzenesulfonate as a surfactant are used to create nanoreactors for which w'ell dispersed iron(II) and iron (III) salts can react.

[0366] The iron oxide nanoparticle is subject to reaction to form a ferrocene. In one embodiment, dicyclopentadiene (DCPD) is subject to cracking at 200°C into cyclopentadiene (CPD) monomer. Soybean oil is added to the monomer, where the carbon-carbon double bonds of the soybean oil react with the monomer in a ring opening metathesis. Iron oxide nanoparticles are then added to the reaction mixture, where iron graft between CPD rings forms a ferrocene. The resulting iron-based OMC scavenges sulfur in a vulcanized rubber matrix to yield ferrous sulfur.

[0367] Commercially available soybean oil is composed of five fatty acids: palmitic acid (16:0), stearic acid (18:0), oleic acid (18:1), linoleic acid (18:2), and linolenic acid (18:3). The percentage of these five fatty acids in soybean oil averages 10%, 4%, 18%, 55%, and 13%, respectively. The main component of soybean oil is triglyceride oil or triacylglycerol (TAG). While soybean oil is a readily available, inexpensive reactant in the OMC synthesis, other materials having a reactive carbon-carbon double bond can also be employed. One such material is an unsaturated fatty acid or unsaturated fatty acid ester. Any suitable unsaturated fatty acid or unsaturated fatty acid ester may be used, e.g., an unsaturated Ce-oo carboxylic acid or ester thereof. Depending upon the chain length, such fatty acids or fatty acid esters can contain 1 or more double bonds, e.g., 1, 2, 3, 4, or 5 or more double bonds. Fatty acids and fatty acid esters include, but are not limited to, linear and branched carboxylic acids, and can include fatty acids or olefins from the stearoyl family such as arachidonic acid, eicosapentaenoic acid, linoleic acid, alpha linolenic acid, gamma linolenic acid, oleic acid, palmitoleic acid, and combinations thereof One suitable material is a purified vegetable oil, such as soy oil, which contains a certain content of oleic acid. In an exemplary embodiment, a purified soy oil having a 22% oleic acid content is employed; however, oils having higher or lower oleic acid content may also be advantageously employed, as can oils which contain other unsaturated fatty acids.

[0368] Any suitable ratio of soybean oil to iron oxide nanoparticle can be employed, e.g., 1 part by weight of iron oxide to 10 to 100 parts by weight soybean oil, optionally 40 parts by weight soybean oil; however, in certain embodiments higher or lower amounts of soybean oil to iron oxide nanoparticle can be employed. Any suitable ratio of soybean oil to DCPD can be employed, e.g., 1 part by weight of DCPD to 1 to 10 parts byweight soybean oil, optionally 4 parts by weight soybean oil; however, in certain embodiments higher or lower amounts of soybean oil to DCPD can be employed.

[0369] Iron-based OMC (FeOMC), e.g., ferrocene, is typically employed at from 0.1 to 10.0 parts reactant per 100 parts by weight vulcanized rubber (by weight), optionally 1 part by weight to 10 parts by weight of reactant to 100 parts by weight vulcanized rubber, optionally 5 parts by weight OMC to 95 parts by weight of vulcanized rubber; however, higher or lower amounts may also be employed in certain embodiments.Iron Sulfide-Based Nanoparticles

[0370] One of the components utilized in preparing certain FeOMCs is iron sulfide nanoparticles. These nanoparticles can exhibit superparamagnetic properties. Solid phases of iron sulfides principally comprise FeS (mackinawite), Fe1-xS (pyrrhotite), FeS2p (pyrite), FeS2m (marcasite), Fe3S4 (greigite), and Fe6S8 (smythite). See, e.g., “Nano-Sized Iron Sulfide: Structure, Synthesis, Properties, and Biomedical Applications”, Ye Yuan et al. Front. Chem., 10 September 2020, Sec. Nanoscience https: / / doi.org / 10.3389 / fchem.2020.00818.

[0371] The content of iron within these materials influences its phase, shape, and physical and chemical properties. FeS naturally has a tetragonal structure, with each iron atom coordinated to four sulfurs. For Fe1-xS, a monoclinic hexagonal is present. FeS2P forms stable iron (II) disulfides with cubic structures, FeS2m differs from FeS2P as an orthorhombic metastable iron (II) disulfide, whilst Fe3S4 is a cubic metastable Fe (II) Fe (III) sulfide. Hexagonal Fe6S8 is related to the Fe1-xS phase. FeS possesses a tetragonal layered structure in which the iron atoms are linked through tetrahedral coordination to four equidistant sulfur atoms. A single iron atom is coordinated to four equidistant sulfur atoms. The distance of Fe- Fe is 2.5967 A. In addition, Fe-Fe bonding is substantial in FeS. To assess the effects of van der Waals forces resulting from the S atoms, sheets including Fe are stacked along the C-axis. The spacing of these layers is 5 A. The structure of Fe2S3 is close to FeS. The structure of FeS2 is similar to that of NaCl in which S2−is located at the center of a cube. The cubic structure has a low symmetry. In addition, FeS2 exhibits chirality through absorbed organic molecules. Fe3S4 has an inverse spinel structure in which 8 Fe atoms are located at the tetrahedral A-sites and 16 Fe atoms are located at the B-sites of the octahedron. The unit cell of Fe3S4 is 9.876 Å. In addition, the cubic structure of Fe3S4 forms a closely packed array of S molecules linked by smaller Fe units. It has been established that the Fe6S8 structure is a hexagonal supercell. Theviable distribution of vacancy sites ideal for the base structure of NiAs was observed to describe the structure of FesSio.

[0372] Various methods for synthesizing iron sulfide compositions are known. Thermal decomposition is the most commonly used hydrothermal reaction for iron sulfide production. The typical solvothermal synthesis method of nFeS uses FeCh 6H2O as a starting material. Generally speaking, the product obtained by the hydrothermal method has better dispersibility and controllability than by other methods, but iron oxide impurities can also appear during the synthesis of iron sulfide. Meanwhile, multiphase iron sulfide appears to occur easily, as assessed by X-ray diffraction (XRD) patterns for hydrothemially synthesized samples.

[0373] Microwave-assisted methods can be used instead of conventional heating to achieve reduced reaction time, smaller particle size distribution, and higher purity.

[0374] Chemical co-precipitation methods do not introduce impurities. The operation is performed under mild conditions and is typically synthesized using FesSr methods, in which iron (II) sulfate heptahydrate and sodium sulfide are dissolved in ultrapure deionized water. The conditions of synthesis required by co-precipitation are harsher than those of other methods, and the products obtained may show poor homogeneity.

[0375] Chemical synthesis methods using high temperatures have been reported for FeS2. For example, iron (II) acetylacetonate (Felacach), trioctylphosphine oxide (TOPO) and oleyamme (OLA) can be used as starting materials to produce FeS2 nanoplates. Synthesis methods for Fei-xS and FesSr have also been reported. The rapid injection method has been used to reduce the size of FesSr. This method of synthesis is highly sensitive to experimental conditions.

[0376] FeS sonochemical synthesis utilizes FeSOvTILO as a starting material. Other methods include low temperature synthesis utilizing FeCLz and NazSx as starting materials. Biosynthesis of iron sulfide is also employed.

[0377] The ferromagnetism of FezSs can be explained by Fe3" ions with excess sulfur. The magnetic susceptibility % of natural FeSz was found to be 64 x 10“668 * 10”6cm3 / moles between 4.2 and 380 K. Magnetic ordering in FeS was inferred and used to prove strong itinerant spin fluctuations. FeS can also be used as a superconductor. Even when the structure of FeS is changed from troilite to the MnP-type under high pressure, the antiferromagneticproperties are preserved until the monoclinic structure is formed. The magnetic moment then disappears and tetragonal-phase FeS (Tc: 5K) was observed for the same structure as the superconductor FeSe (Tc: 8 K). FesS4 displays high Mrs / %, (Mrs / 'x: the saturation isothermal remnant magnetization: magnetic susceptibility) and its MrsMs (hysteresis ratios) and Bcr / Bc are 0.5 and 1.5 (Ms: saturation magnetization; Be: the coercive force; Bcr: the coercivity of remanence). Fe3§4 also displays unique high-temperature properties, with a clear drop in magnetization from 270 to 350°C. Synthesized Fei. Sr contains various crystals from small superparamagnetic grains (non-remanence) to large multi-domain grains. The magnetic hysteresis properties of FerSs have also been studied. The relationship between structure and magnetic properties has been reported within variable temperatures. Magnetic transitions occurred within the transformation of the structure. The magnetocaloric conversion ability of Fe?, S4 nanoparticles has been measured under an alternating magnetic field (AMF). Meanwhile, the excellent physical and chemical properties provide magnetothermal thrombolytic ability in medical applications.

[0378] In certain of the embodiments, the superconductor parent compound is a mackinawite Fei-xS tetragonal structure, prepared by a solvothermal method incorporating a diamine, endo-intercalation atomic structure pressure transformed to a stabilized, interorbital hexagonal troilite phase (P62c space group).

[0379] While iron is advantageously employed in conjunction with OMCs, other metals such as those described elsewhere herein can also be employed, e.g., nickel, titanium, cobalt, ruthenium, zirconium, and osmium.Dual System Crosslinking

[0380] Dual system crosslinking of thermoplastic elastomers (TPEs) may compete with thermosetting elastomers (TSE). Up until recently, the concept of double network elastomers was confined to studies of the physical ageing of elastomers. In the last two decades, many studies probed the physical properties of double networks, with the intent of applying them to practical applications. Recent attention has been given to the thermal and thermo¬ mechanical behavior of TPE's, examining their significance in applications such as o-rings, actuators, encapsulants, and dampers.

[0381] Thermoplastic elastomers (TPEs) have recently been studied as a possible replacement for traditionally cured thermosetting elastomers (TSE). They follow thethermodynamic behavior similar to traditional elastomers, and their deformational behavior has been studied in this category. TPEs are generally block copolymers, having hard and soft segments. In contrast to the traditionally cured TSE's, which once cured cannot be reshaped. TPEs provide ease of processibility to give rubbery materials which can be reshaped again, like other thermoplastics. However, TPEs lack thermal stability and their rigidity is limited by the stiffness of hard block. Thermoplastic vulcanizates (TPVs), such as can be prepared by the methods of the embodiments, partially fill tins gap.

[0382] Traditional curing of a rubber or elastomer results in isotropic networks and properties. From the kinetic theory’, the elasticity of rubber has been attributed to the changes in the conformations and configurational entropy of a system of long-chain molecules. When the chains undergo deformation, the internal energy is considered to remain constant. Hence, when loading and unloading the network, the heat exchange with the surroundings is due primarily to entropic contributions.

[0383] A general schematic of an elastomer’s heat exchange with its surroundings, during deformation, may be charted. Heat is given out from the elastomer to the surroundings while loading and is absorbed while unloading.

[0384] This heat exchange substantially governs the mechanical and thermal properties of these networks. If a partially cured TPE is first deformed and then subjected to additional crosslinking, a second crosslinked network can be formed within the initial network. This results in materials with unusual and enhanced properties which have been termed “double network elastomers.” These properties arise from a competition between these two networks during small deformations, where heat released by one network is being absorbed by the other network. Thus, a lower modulus of elasticity can be obtained in this low strain, competitive regime relative to a single network system. At higher elongations, these networks work in parallel to each other to provide collaborative behavior, and consequently a higher modulus of elasticity than in a single network system can be obtained.

[0385] Because of entropic dependence of these elastomers, the stretched rubber is observed to have a lower coefficient of thermal expansion in the stretched direction. Therefore, these systems can be very useful in applications where positive thermal expansion must be reduced, without using a composite material exhibiting a negative coefficient of thermal expansion.Cellulosic Nanofiber0386] A robust and feasible strategy is provided to process cellulose nano fibers (CNFs) into a high performance bulk structural material with low density, outstanding strength and toughness, and great thermal dimensional stability. It offers a green paradigm shift for the reinforcement of large-scale materials such as portland concrete, plastic articles such as car parts and articles for use in a marine environment, as well as impact elastomers.

[0387] Cellulose nanomaterials are conventionally produced by various methodologies, including electrospinning, bacterial generation, acid digestion, and a variety’ of mechanical defibrillation techniques. The morphology of the nanomaterial produced is specific to the production process. Feedstocks range from various forms of woody biomass to fungi. The type of feedstock can impact the properties of the resulting product. A mechanical defibrillation technique is advantageously employed to continuously’ break down cellulose fibers suspended in water via segmentation and defibrillation through grinding and refining. The process is typically operated until a desired level of fines is achieved in the resultant slurry' of cellulose nanofiber (CNF, alternatively referred to as “cellulose nanofibril”). Mechanical defibrillation processes can be built to produce several liters in a small batch system, and up to tons per day in a continuous pilot scale refinery'- system.

[0388] Following initial dehydration, the untreated CNF is processed by consecutive spray-roller-squeezing application of poly vinyl alcohol (PVA), followed by silicic acid solution. Other chemical coatings may be employed with this application method, such as tetramethylpipendinyl-oxyl (TEMPO). Depending upon the composite structure within which the CNF compounded is to be utilized, such as polypropylene and / or inorganic materials such as calcium bentonite, the coating can be adjusted to achieve desired final specifications.

[0389] The Coated CNF is then dried / crosslmked in a continuous oven. The resulting product is useful in preparing various composite materials.

[0390] Where CNFs are the basic building blocks of a material, hydrogen bonds are the main interaction that bind them together. The strength (at least 2 GPa) and Young’s modulus (about 138 GPa) of individual CNFs can be almost as high as those of steel and Kevlar, and those superior nanoscale properties can be scaled to the macro level, mainly due to the strong interaction between CNFs and the matrix within which the fiber is utilized, such as portland concrete, plastic, or rubber.

[0391] An outstanding performance standard for lightweight biopolymers is exhibited by dragline silk. CNFs prepared as described herein can outperform dragline silk 8 in terms of stiffness, and with similar strengths. Properly compounded, CNFs may exceed the physical strengths of metals, alloy s and silica-based E-glass fibers.

[0392] In certain embodiments, the CNFs can be reacted to form a ferro material. This process starts by modifying soybean oil (SBO) in a first reactor via a ring opening metathesis using a Diels-Alder reaction between the SBO and tetracycanoethylene yielding a norbornene ligand. Then, within a second reactor a second stage reaction is conducted by grafting one or more of the numerous species of crystallized nano-cellulose to the norbornene ring. In a third reactor, the two reactor polymers are titrated for optimal results. An iron species, e.g., iron oxide nanoparticle or nano iron sulfide superconductor, is then added into the resulting polymer mix to yield a ferro-cellularized soybean oil (FC-SBO, available from Natural Composites, LLC, Bullhead City, AZ).

[0393] The FC-SBO exhibits sulfur scavenging activity in vulcanized materials and can be employed in reaction with ground tire rubber (GTR). A material compounded from ferro-cellularized soybean oil (FC-SBO, available from Natural Composites, LLC, Bullhead City, AZ) and ground tire rubber (in a 5:95 mass ratio) is provided offering advantageous properties. The FC-SBO adds considerable hydrogen sites to the permutated GTR, resulting in a significant gain in the recompounded tensile and elongation properties of the permutated GTR.

[0394] In applications such as portland concrete, the FC-SBO is not employed as a sulfur scavenger, and can be used at lower levels, e.g., a mass ratio of FC-SBO to portland concrete of 2:98. The FC-SBO imparts repelling forces to the fibers in the portland concrete, thereby reducing clumping and enabling fiber loading to increase from the 1% by weight conventionally employed to as much as a 10% by weigh loading levels or more (e.g., 2 to 10% by weight, optionally 5 to 10% by weight).Reaction with Vulcanized Rubber

[0395] The FeOMC can be employed directly for reaction with a vulcanized rubber or other vulcanized elastomer matrix, such as vulcanized rubber, e.g., ground tire rubber (GTR), e.g., end-of-life (EOL) tire rubber, or it can advantageously be provided with other components commonly employed in the preparation of rubber articles of manufacture, e.g.,stabilizers, antioxidants, accelerators, reducing agents, curing agents, fillers, pigments, plasticizers, processing aids and the like. Auxiliary polymers can also be present. The auxiliary polymer can be an elastomer, e.g., butadiene, natural rubber, styrene butadiene rubber, isobutylene-isoprene rubber, styrene-l,4-cis polybutadiene polymer, trans- 1,4-poly isoprene, cis-l,4-polyisoprene, natural poly isoprene, synthetic polyisoprene, chloroprene rubber, halogenated butyl rubber, nonhalogenated butyl rubber, silicone rubber, hydrogenated nitrile rubber, nonhydrogenated nitrile rubber, or 1,2-high vinyl butadiene.

[0396] In an exemplar}' embodiment, the FeOMC is combined with a sulfur- crosslinked elastomer, e.g., GTR, EOL-GTR, or other vulcanized rubber in crumb form. Mixing the FeOMC and GTR at a weight ratio of 5:95; while simultaneously vigorously mixing, e.g., within counter-rotating tines in a pug mill, can advantageously be employed as a pre-reaction step, or the mixing can occur directly in a reactor as described herein or as similar to those described herein.

[0397] Thereafter, the mixture is dropped into a stuffing box of a co-rotating reactor where it is pushed, under pressure through an annular cavity whereupon a series of rotating lobes create a high-pressure impingement upon the coated rubber as it progresses through the annular reactor structure.

[0398] The surface of the rotating lobes of the reactor are outfitted with compression bars which subject the rubber to ven,' high-pressure pulses. The temperature momentarily rises to over 200 °C at the peak pressure, then subsides until the next compression bar is encountered. During the approx. 36 inches of travel from the stuffing box to the opposite end of the reactor journey, each rubber particle encounters upwards of 120,000 such pulses.

[0399] In certain embodiments, a twin-screw reactor, an auger reactor, a roll mill reactor, a twin arm Banbury shaft, co-rotating mixer extruder including elliptical-shaped lobes can be employed. In one embodiment, the mixer, or any other similar reactor or a reactor as described herein extruder includes twelve (12) equally spaced raised, ladder type bar / lugs machined onto the circumference of the lobe such that as the lobes pass over the respective profile of the opposing lobe the mixture is impinged into a 0.010" nip for about 1 / 4" of the travel. Any suitable number of lobes can be provided, e.g., fewer than 12 or more than 12, e.g., 6-24 lobes, 3-36 lobes, etc. Other nip distances can also be employed, e.g., 0.005” to 0.1,” 0.005” to 0.05.” Other distances of travel can be employed as well, e.g., 1 / 8” to 1 / 2”, 1 / 6” to1 / 3”, etc. While mixer extruders as described herein can be employed, other reactor configurations described herein can also be employed, e.g., horizontal compression reactors or the like. Reactors as depicted in FIGS. 1 A-1D, 3A-3C, 4A-4B, and 5A-5E can advantageously be employed in certain embodiments While the apparatus depicted in the figures can be employ ed to provide the pressure to the mixture of vulcanized rubber and FeOMC (or other reactant), other configurations are also envisioned, as will be appreciated by one of skill in the art, e.g., mortar and pestle, ribbon mixers, high shear dispersers, or the like. In one embodiment, instead of meshing gears, smooth rollers in opposing configuration can be employed.OMC Example 4

[0400] An FeOMC was prepared by the following process. A reactor vessel (fabricated from 304 stainless steel (non- magnetic), having a stirrer, pressure relief valve, temperature and pH monitors, and loading ports) was charged with 500 grams CPD Dimer (97%) (Parchem, Inc., New Rochelle, NY) that was subjected to thermal cracking to the corresponding monomer at a temperature of 200°C for 30 min (under some conditions sufficient cracking can be achieved in less time, e.g., 10-30 min). The baseline reactor pressure after thermal cracking was noted. The reactor vessel was then charged with 2000 grams soybean oil (Cargill, Inc., Minneapolis, MN) which was mixed into the reactor vessel contents. The reactor vessel contents were stirred at 50 rpm at a temperature of 200°C, such that the carbon-carbon double bonds of the monomer underwent an exothermic ring opening metathesis, causing the pressure within the reaction vessel to rise to approximately 45 psi. The pressure within the reaction vessel was monitored for a pressure drop, indicating that the reaction was complete with early formation of norbornylene ligands (NL). The reaction vessel was then slowly charged with 50 grams of nano iron oxide (FeO of diameter 2-20nm, Cerion, LLC, Rochester, NY). The stirring speed was increased to 150 rpm and the temperature held at 200°C as an exothermic reaction progressed with a pressure rise as iron was grafted between CPD rings to form a ferrocene. The reaction was deemed complete upon a pressure drop to baseline (i.e., the baseline reactor pressure after thermal cracking was completed). Upon restoration of baseline pressure, the reactor vessel was allowed to cool to room temperature then the FeOMC contents was discharged.

[0401] The iron oxide nanoparticle-based OMC thus prepared was a functional liquid (having a viscosity of approximately 150 cps at room temperature (approximately 20°C)). The OMC was capable of being pre-compounded with numerous ligands to achieve improved performance of the resulting rubber produc t prepared from (typically 30 mesh) GTR.

[0402] A reactor was provided for subjecting the OMC (or alternative to OMC) and GTR to reaction. The reactor was a custom fabricated, jacketed, counterclockwise rotating (CCR), intermeshing twin screw mixer extruder. The reactor utilized twin, 36” long x 5” elliptical, clamshell, parallel stator cavities powered by a 50hp motor driving the rotor shafts through a 20: 1 splitter gearbox. The rotors accommodated sliding on mixing, stainless steel (SS) lobes and feed flights. The lobes had six tangential compression bars on each side of the mixing surface such that when the lobes rotated, the tips of the opposing, intermeshing lobes captured the GTR. The 36” long rotor assembly was set up with three, three lobe work centers interspaced with transfer screw sections. The OMC was uniformly pre-mixed with dry GTR at a ratio of 5 mass units OMC to 95 mass units GTR. The mixture was fed into the stuffing box at approximately 20-100 rpm, at a feed rate that allowed the top of the feed screws to remain visible. A jacket temperature was maintained within a range of 149°C to 177°C. The flow of material, as it passed through the mix stages, was captured and compressed in the compression bar nip, causing the pressure to rise to a pressure of between 0,4 - 9.5 GPa, This opened up the GTR moiety7such that the OMC collided and exothermically reacted with the liquified sulfur component of GTR vulcanizate such that the exothermic sulfur rings were scissioned forming FexS (or variations thereof’), thereby freeing the intermeshing elastomer-carbon matrix to be easily broken down into increasing smaller particles. This was an intense mixing and shearing process winch caused some de-composition of the GTR elastomer chemistry and generated varying degrees of smoke which was captured and filtered. The resulting late-stage material was soft and gooey, and exited the mixing-extruding reactor as a hot, somewhat gummy maw of clusters of sub-micron rnoieties capable of being pelletized or further processed with other polymers.

[0403] In variations of this reaction not involving ferrocene formation, the dicyclopentadiene (DCPD) is reacted with maleic anhydride (MAH) to yield maleic- dicyclopentadiene (M-DCPD) functional groups. Typically, a mixture of 95 wt. % DCPD is combined with 5 wt. % MAH and subjected to a grafting reaction in the presence of dicumylperoxide (DCP) at a temperature of 200°C for 2 hours to yield M-DPCD functional groups. This product (OMC alternative) can be used as an alternative to an iron-based OMC.FeOMC Example 50404] An FeOMC was prepared by the following process. A reactor vessel (fabricated from 304 stainless steel (non-magnetic), having a stirrer, pressure relief valve, temperature and pH monitors, and loading ports) was charged with 500 grams CPD Dimer (97%) (Parchem, Inc., New Rochelle, NY) that was subjected to thermal cracking to the corresponding monomer at a temperature of 200°C for 30 min (under some conditions sufficient cracking can be achieved in less time, e.g., 10-30 min). The baseline reactor pressure after thermal cracking was noted. The reactor vessel was then charged with 2000 grams soybean oil (Cargill, Inc., Minneapolis, MN), which was mixed into the reactor vessel contents. The reactor vessel contents were stirred at 50 rpm at a temperature of 200°C, such that the carbon-carbon double bonds of the monomer underwent an exothermic ring opening metathesis, causing the pressure within the reaction vessel to rise to approximately 45 psi. The pressure within the reaction vessel was monitored for a pressure drop, indicating that the reaction was complete. When the pressure drop was complete, the reaction vessel contents was allowed to cool to 80°C. The reaction vessel was then slowly charged with 20 grams of nano iron sulfide superconductor (Fei-xS having a 2-5nm diameter, spherical in shape, room temperature (RT) stabilized superconductor, Avantama Labs, Zurich, Switzerland). The stirring speed was increased to 150 rpm and the temperature held at 80°C to achieve full homogenization. The reaction vessel contents were allowed to cool to room temperature (approximately 20°C) and then discharged.

[0405] The nano iron sulfide superconductor-based OMC thus prepared was a functional liquid (having a viscosity of approximately 150 cps at room temperature (approximately 20°C)). The OMC was a norbornene functional compound containing a thermally activated, ring-opening initiator capable of being pre-compounded with other functional group as ligands to achieve improved performance of the resulting rubber product prepared from (typically 30 mesh) GI'R.

[0406] A reactor was provided for subjecting the OMC (or alternative to OMC) and GTR to reaction. The reactor was a custom fabricated, jacketed, counterclockwise rotating (CCR), intermeshing twin screw mixer extruder (also referred to as a continuous mixerextruder or CME). The reactor utilized twin, 36” long x 5” elliptical, clamshell, parallel stator cavities powered by a 50hp motor driving the rotor shafts through a 20:1 splitter gearbox. The rotors accommodated sliding on mixing, stainless steel ( SS) lobes and feed flights. The lobes had six tangential compression bars on each side of the mixing surface such that when the lobes rotated, the tips of the opposing, intermeshing lobes captured the GTR. The 36” long rotor assembly was set up with three, three lobe work centers interspaced with transfer screw sections. The OMC was uniformly pre-mixed with dry GTR at a ratio of 5 mass units OMC to 95 mass units GTR. The mixture was fed into the stuffing box at approximately 20-100 rpm, at a feed rate that allowed the top of the feed screw's to remain visible. A jacket temperature was maintained within a range of 85°C to 100°C. The flow' of material, as it passed through the mix stages, was captured and compressed in the compression bar nip, causing the pressure to rise to a pressure of between 0.4 - 9.5 GPa, such that the Fei-xS nano-superconductor component acted as an electromagnetically, resistance-free thermal transport moiety focusing the significant energy developed during the compression cycle. This focusing of the high energy dynamic caused a catalytic opening of the norbornene ring and all proximate sulfur rings whereupon the formation of a sulfonated norbornene polymer occurred, thereby freeing the intermeshing elastomer-carbon matrix to be easily broken down into increasing smaller particles and / or long, non-bound elastomeric strands. The resulting late-stage material was a black, soft, semi-sticky clumped rubbery yarn with noticeable bounce and exited the mixingextruding reactor as a warm, somewhat agglomerating maw of a clusters of micron range moieties capable of being pelletized or further processed with other polymers.

[0407] The methods of Example 5 and Example 4 can offer different advantages. When a permutated GTR is to be homogenized as an aqueous colloid suspension, the individual particle is reduced to a size of between 600 nm and 5 microns, such that the method of Example 4 can advantageously be employed. In other embodiments, the method of Example 5 can offer one or more of the following advantages. No pre-heating or process energy is necessary for the GTR beyond power for driving the mam shafts of the mixer-extruder, such that the method of Example 5 uses 85% less energy. The complete scavenging of crosslink sulfur is accomplished at a much lower annular travel distance at a power setting, such that the method of Example 5 has a mechanical investment that is 75% lower as a capital expenditure. Minimal damage to the interpenetrating elastomer network in the method of Example 5 provides a much higheraverage molecular weight per individual moiety (e.g., > 5x), which offers a superior starting point for manufacturing lower cost, higher performance end products. The method of Example 5 has a base value estimated to be 2x greater. The method of Example 5 is more sustainable as the basic permutated GTR requires less virgin material to compete for commercial applications. The sulfonated norbornene and non-sulfonated norbornene structures generated in the method of Example 5 provide added crosslink and grafting sites for dual crosslinking and grafting, providing probable higher final performance characteristics. Higher loading of the nano Fei-xS superconductor moiety in the method of Example 5 may substantially mitigate heat buildup in articles such as truck and car tires. Finally, possible intra and inter- combinatorial chemistry in the method of Example 5 may provide unusual properties via dual¬ cross linking of the systems of Example 5 and Example 5 (inclusive of virgin hybridization) using, by way of example, sulfur and / or peroxide curing packages.Ferrocene Example 6

[0408] Elementary’ electron spin excitations, collectively, are electron derivations or spin waves and quantitatively are magnons. The introduction of antiferromagnetic, magnonic spin current (AFMSC) into the formation of novel chemical compounds has two essential advantages: they are insensitive to external magnetic perturbances; and they promote ultrafast transition state dynamics. The basic process and chemical elements which demonstrate the AFMSC effective influence are presented herein. The absence of the advantages of the integration of AFMSC in an earlier process utilizing selected other organometallic compounds (OMCs) are also apparent within the context of the substantial shortfall in performance testing.

[0409] The process involved a variable speed, 50 hp, twin shaft, counter rotating, continuous mixer-extruder (CME), as previously described, is the primary mechanical compounding device. A machine with five-inch (5 in), intermeshing stainless steel (SS) lobes had, (per lobe) fourteen raised lugs which impinged, creating a mixing high shear and compression onto the GTR particle surface, thereby imparting an exfoliation of the chemically treated rubber moiety.

[0410] The shafts had exchangeable elements, and in this configuration consisted of a stuffing box transfer screw followed by three sets of workstation lobes being separated and fed by upstream screw segments which advanced the material from the previous workstation. The stainless steel CME (SS-CME) barrel can be jacketed in segments and the upper, clam-shell can be penetrated by multiple injection ports (M1P) whereby chemicals and / or magnetic media may be installed, providing progressively additive value during the exfoliation process to engineer and / or adjust for a desired result in the GI'R particle size and functionality.

[0411] The chemical elements of the process are as follows.

[0412] Step One (SI): Preparation of solvent-borne AFM metallocene liquid. Ferrocene powder (FP) is mixed, using a low speed propeller mixer in a suitable vessel, directly into methylene chloride (MC) at approximately a 12:1 mass ratio at 25°C. The deployment of this mixture of ferrocene powder / methylene chloride (FPMC), where used individually, is as described above. It also may be complexed during CME compounding via multiple injection ports (MIPs) into the following Steps as shown. This solution reduced the FP to a single molecular entity / moiety and exhibited a strong AFMSC influence well of approximately 100 nm.

[0413] Step Two (S2): Preparation of vegetable triglyceride monomer(s) (ambient and facile). To a soybean oil (SBO) was slowly added an initiator / catalyst. The initiator / catalyst was Norway fish oil ethyl ester (NFO), added under vigorous agitation at 25-30°C. Thereafter stabilized dicyclopentadiene (DCP) was added at various mass-on-mass ratios. For purposes of this Example, an SBO: NFO: DCP mixture (62:3:35 by weight) resulted in the performance Example presented below. The C==C bonds in the SBO are electrophilic sites for attack by the reactive species. Other initiators and ratios have been tested and were found to offer improved performance in different end-product applications. Accordingly, other initiator / catalysts can be employed and other weight ratios can be utilized depending upon the desired end-product application. Suitable initiator / catalysts include the unsaturated fatty acids and unsaturated fatty acid esters as described elsewhere herein, as well as certain other compounds including a carbon-carbon double bond (C C bond) or other electrophilic site amenable to attack by a reactive species such as dicyclopentadiene.

[0414] Step Three (S3): Preparation of vegetable triglyceride (high temp / pressurereactor based). To SBO was added DCP (67:33), under slow- addition and then vigorous agitation at 25-30°C. The mixed liquid 'as added to a stirred, heated, pressure rated, stainless steel (SS) reactor. Under slow agitation, the process temperature was slowly raised and held at 230°C. An exothermic reaction occurred between 150°C and 230°C where the formation of anorbornyl functionality replaced SBO C=C bonds. Stirring and vessel heat were adjusted to hold the reaction pressure below 40 psi, as above 40 psi high molecular weight oligomers form, thus reducing polymer value. The reaction was complete when no more exotherm / pressure rise was recorded.

[0415] Step Four (S4): Compounding of Steps Two and Three Modifier Resin (2-3MR) and application onto 30 mesh ground tire rubber (GTR). S2 and S3 reactive compounds were pre-mixed (50:50) at ambient temperature. This mixture was slowly sprayed into a high shear pug mill and mixed onto the surface of ambient temperature GTR to a uniform coating. The range of mass-on-mass (GTR:2-3MR) is preferably (94:6 to 92:8), and a mass ratio in this range was employed. The coated GTR was then fed into the stuffing box of the CME, whereupon it was, as it passed through the work centers, exfoliated at a temperature in a range of 140-150°C to a maximum target size of one micron (a 600 x size reduction from the 30 mesh beginning size). Other ratios of (GTR:2-3MR) can dramatically change the ultimate physical and chemical characteristics of this blended material and final compound performance. Accordingly, in certain embodiments other ratios can be employed depending upon the desired physical and chemical characteristics of the final product. Utilizing the injection ports described herein, tiny amounts of the FPMC (<0.0001% total mass) may be used to synergize chemical reactions. As well, the FPMC can enhance the addition of multiple functionalities to the rubber moiety and the improvement of the energy efficiency and product consistency may be achieved with the Polymer-hybrid ized Nanometer-sized Tire Rubber (PNTR) process.

[0416] Step Five (S5): Compounding a Polymer-Hybridized Tire Rubber as prepared according to S4. As a separate operation, virgin elastomer(s) may be grafted to the properly functionalized PNTR through a stand-alone, separate CME or other devices known to industry. A PNTR and butadiene rubber (BR) compound (at a weight ratio of PNTR to BR of 89:9) plus a 2% conventional crosslink package can be made into a new automobile tire with superior performance over virgin materials, at a lower cost.

[0417] A PNTR was made according to S1-S4 and compared to a PTR-based material prepared by a different process. The PTR-based material comprises a PTR prepared from 95% GTR with 5% zinc acetate (OMC). The PTR: Virgin Rubber in a ratio by weight of 25 to 75 was compounded using standard rubber process equipment then tested using RP A and DMA lab equipment.Mechanical Properties PNTR (89:9:2) PTR (25:75) Glass Transition (C) -22.50 -31.00Crosslink Density (mol / m-3) 1.29 1.00Tan delta (max) 1.08 1.32Ultimate Strength (MPa) 15.20 14.10Ferrocene Example 7

[0418] An alternate, “touch-less” method to ‘gently’ reduce the ground tire rubber (GTR.) particle from a 30 mesh (600 micron) particle size to a 0.500 - 10 micron range is provided. The method includes the following five (5) steps:

[0419] Step 1) Prepare a solution of ferrocene (Fc) and 1,2-dimethoxy ethane (DME) at a mass ratio of 3:97 Fc: DME to yield a DMEFc fluid. While the specified mass ratio is generally preferred, in certain embodiments different ratios can be employed, e.g., (1 -6 parts by weight Fc (or higher or lower) in the DMEFc solution). While DME can advantageously be employed, other polar aprotic solvents, e.g., ones at least slightly miscible with water, can also be employed in certain embodiments, such as tetrahydrofuran (THF), 2-butoxyethanol, acetonitrile, or the like.

[0420] Step 2) Immerse GTR powder in the DMEFc fluid at a mass ratio of GTR.: DMEFc of 5:95 under ambient conditions. While ambient temperature conditions (e.g., 5-45°C) are generally desirable, under certain circumstances higher or lower temperatures can be employed. Likewise, ambient atmospheric conditions can advantageously be employed, however, under certain circumstances it may be desirable to conduct the step under an inert atmosphere (e.g., nitrogen or argon).

[0421] Step 3) Pump the GTR: DMEFc fluid (“Fluid”) through a transparent, borosilicate glass tube-loop, under a select, process controlled photon barrage (light) having a spectrum of wavelengths in the range of 380 - 675 nm, the Fluid traveling at approx. 20-40 meters per second (mps). The light spectrum can include a distribution of wavelengths, or can employ one or more selected wavelengths in the specified range. While a fluid travel speed of 20-40 nips is generally preferred, in certain embodiments higher or lower speeds can also be employed. The borosilicate glass tubing can be in any suitable configuration, e.g., a spiral configuration is advantageous for having a compact footprint, but in certain embodiments otherconfigurations can be employed, e.g., a straight run. One tube can be employed, or the Fluid can be directed to a collection of a plurality of tubes provided to process Fluid in parallel. The photon source can be provided in any suitable configuration, e.g., in a center of a spiral configured tube, or in the center of a collection of a plurality of tubes or otherwise adjacent to the tube(s). The photon source could also be immersed in the Fluid. One photon source can be employed, or multiple photon sources can be employed. While borosilicate glass is generally preferred, other types of glass or other materials may also be employed in certain embodiments, e.g., fused silica glass, tempered glass, or soda-lime silicate glass, or even certain thermoplastics. The diameter of the tube can be any suitable diameter, e.g., 0.1 cm or less to 2.5 cm or more.

[0422] Step 4) Simultaneous to the exposure of the Fluid to the photon barrage, it is subjected, at approximately every 0.30 meters (or, in certain embodiments, to larger or smaller spacings, e.g., 0.1 meters or less to 1 meter or more), to a pulsing magnetic field by way of one centimeter wide, electro-magnetic bands. The magnetic field is process-controlled as to pulse width, field strength (Ga) and polarity, with such parameters adjusted to achieve a predetermined rate of particle size reduction. Pulse width equals the time between field shift from off-on-off and is typically, e.g., 1-500 milliseconds, although in certain embodiments larger or smaller pulse widths can be employed. Field strength range can be 60 to 600 Gauss (1 Ga + 80 Amps / meter), although in certain embodiments stronger or weaker field strengths can be employed. Polarity refers to reversing the magnetic poles, i.e., north becomes south and south becomes north. Pulse width can refer to both field strength and switching frequency of polar phase(s). Pulsed magnetic field generators as are commercially available can be employed, or can readily be manufactured using materials and techniques as are known in the art.

[0423] Step 5) Upon reduction to a uniform size, the Fluid, which comprises a solid rubber component and a solvent-comprising liquid component, is separated by means of a three-step filtering system: 1) tangential disc separator, then 2) a polytetrafluoroethylene (PTFE) candle-style, reversible flushing fine filter, and for the resulting cake (comprising a rubber material), processing in a 3) thermal evaporator. The cleansed / recovered DMEFc is returned to service, e.g., recycled for use in mixing with GI'R, e.g., in Step 2. While thespecified filtration and separation apparatus can be employed, other filtration and separation apparatus as known in the art can be adapted for use as well.

[0424] The estimated materials costs and energy costs associated with a thousand¬ fold reduction in size (e.g., a 1000:1 size reduction) of the GTR particles according to this scheme is approximately $0,015 (materials cost) and approximately $0,025 (energy cost) respectively. The resultant moiety is nearly unchanged as to the sulfidic crosslink, i.e., the sulfur vulcanizing bridges remain in-place and the orphaned elastomer bundles, formed at the time the composite rubber was first manufactured, are liberated as ganglionic appendages which may be easily functionalized for substantial increases in the four categories of physical properties of modulus, tensile, elongation and resilience.

[0425] Using the Taguchi method, e.g., as described in the technical publication Kiss L, Molnar MJ, Meszaros L. Improving the mechanical properties of vulcanizates containing ground tire rubber: Recipe optimization with the Taguchi method. Polym Adv Technol. 2024; 35(4):e6389. doi:10.1002 / pat.6389, an over 107% increase in all four categories is achievable While it can be difficult to explore the processes between the GTR and additives, with the help of the Taguchi method it is possible to determine how the amount of different components should be changed when one wishes to enhance a specific mechanical property in such a mixture. The method is essentially based on fractional factorial experimental design, which is essentially a standardized experimental design method. First, an appropriate orthogonal matrix is selected, then the corresponding column-factor pairs are created according to specified rules. With this, the degree of the effects of the individual factors can be determined, and, if applicable, also the degree of interaction between factors. The Taguchi method can be employed for the development of recipes containing GTR in vulcanized materials, because it is simple to apply and clear (especially when graphical representation is used). The application of the Taguchi method is effective in cases where the optimization of the combined effects of multiple factors is the goal.Ferrocene Example 8

[0426] A method to produce very fine rubber particles (“NTR” Nano Tire Rubber, e.g., 0.500 - 10 micron particle size range) suitable for a variety of applications, including but not limited to tire components such as tread and sidewall, is provided. The method utilizes as a starting material ground tire rubber (GTR) of 30 mesh. While 30 mesh GTR isadvantageously employed, in certain embodiments higher or lower mesh GTR can be employed, e.g., 10 mesh or lower to 80 mesh or higher, e.g., 10 Mesh, 24 mesh, 40 mesh, 60 mesh, 80 mesh, or other commercially available mesh size. The method includes the following steps:

[0427] A mixture of ferrocene ( Fc) and dimethylcarbonate (DMC) at a mass ratio of 2:1423 Fc: DMC is pre-reacted to yield a first intermediate mixture (1425 mass units). The reaction is conducted at a temperature of 25°C. While the specified mass ratio is generally preferred, in certain embodiments different ratios can be employed, e.g., (0.1 to 10 parts by weight Fc (or higher or lower) to 1423 parts by weight DMC). While DMC can advantageously be employed, other polar aprotic solvents, e.g., ones at least slightly miscible with water, can also be employed in certain embodiments, such as other carbonate esters, DME, tetrahydrofuran (THF), 2- butoxy ethanol, acetonitrile, or the like.

[0428] A mixture of a vegetable oil (canola oil containing a minimum of 70% oleic) and Fc at a mass ratio of 2:68 is pre-reacted to yield a second intermediate mixture (70 mass units). The reaction is conducted at a temperature of 80°C. While the specified mass ratio is generally preferred, in certain embodiments different ratios can be employed, e.g., (0.1 to 10 parts by weight Fc (or higher or lower) to 68 parts vegetable oil). Any suitable high oleic acid oil, e.g., high oleic acid seed oil, including vegetable oils, such as canola, sunflower and soybean oils can advantageously be employed, either in pure form or mixed with carrier components, such as CAN 70 canola oil.

[0429] The first intermediate mixture and the second intermediate mixture are combined yielding a final reaction mixture (195 mass units) which is reacted at approximately 75°C under shear, with the reaction terminated with a viscosity increase of approximately 1000 cps.

[0430] The final reaction mixture is combined with ground tire rubber (e.g., clean 30 mesh) under shear with a stator-rotor at 3300 fpm with a phase cavitation design. The stator¬ rotor is maintained at a mechanical temperature of < 85°C, and the batch temperature is maintained at < 60°C for approximately 30 minutes, or until a de-volatized, draw sample achieves a two-roll mill sheet with a maximum thickness of 45 microns.

[0431] Post-treatment of the batch by complete desorption of liquid phase yields an approximately 1.90% by weight increase over the starting GTR weight. The liquid phasecan be perpetually reutilized with replenishment of chemistries extracted during the permutation of GTR to NTR. The batch can be efficiently processed by making a filter cake of the NTR having approximately 1-2 % by weight volatile content, then flash evaporating the remainder of the volatile content. Very fine rubber particles may be removed from the liquid phase by using a crossflow, disc filtration system, however, in certain embodiments other filtration systems can advantageously be employed, e.g., a mesh filter, or other separation means, e.g., centrifugation, etc.

[0432] The resulting NTR can include a crosslink package which varies depending upon the end use of the functionalized NTR.Rubberized Asphalt Example 9

[0433] 75% by mass elemental sulfur was combined with 25% by mass zinc diethyldithiocarbamate. Both components were thoroughly mixed as dry powders at room temperature in a counter rotating pug mill to yield XLNK XSZ31, a crosslinking agent.

[0434] Fc powder was pre-reacted and dissolved into soybean oil in a weight ratio of soybean oil to Fc of 96:4 at room temperature with a low speed propeller stir to yield a clear solution. 20 wt. % of the resulting clear solution was combined with 80 wt % ground tire rubber (30 mesh, dry powder) to yield a uniform mixture at room temperature in a counter rotating pug mill, and then fed through a mixer extruder reactor at a temperature of 250-275°F to yield AR-NTR-8282FD, a rubber component. It is believed that the reaction pathway for polymerization by inverse vulcanization of soybean oil in the preparation of NTR-8282FD is as depicted below; showing the structure of the high-oleic portion of SBO-HO with ring opened sulfur copolymer yield.

[0435] 20.0% AR-NTR-8282FD was mixed into 80.0 wt. % SJR PG 64-10 base asphalt (from San Joaquin Refining Co, of Bakersfield, CA) at a temperature of 300°F using a Silverson Mixer at a rate of 1500 RPM. After 90 minutes, 0.625 wt. % of XLNK XSZ31 was added to the blend and mixed using the Silverson Mixer at a temperature of 300°F and a shear rate of 750 RPM (just enough to create a vortex). The blend was allowed to mix for one hour. The total mixing time was 2.5 hours. After mixing, the rotational viscosity and solubility in trichloroethylene of the blend was determined using protocols as known in the art.AASHTO Test Method Test Result Rotational Viscosity 135°CPa*s T316 1.840 Solubility in Trichloroethylene, wt. % T44 95.83Rubberized Bitumen Example 10

[0436] 75% by mass elemental sulfur was combined with 25% by mass zinc diethyldithiocarbamate. Both components were thoroughly mixed as dry powders at room temperature in a counter rotating pug mill to yield XLNK XSZ31, a crosslinking agent.

[0437] 85 wt. % ground tire rubber (30 mesh, dry powder) was mixed with 15 wt. % canola oil to yield a uniform mixture at room temperature in a counter rotating pug mill, and then fed through a mixer extruder reactor at a temperature of 250-275°F to yield NTR C-85, a rubber component.

[0438] Norbornene was combined with canola oil at a weight ratio of 50 parts by¬ weight norbornene to 50 parts by weight canola oil. The norbornene and canola oil mixturewas heated to 150°F then uniformly mixed / reacted with a low speed propeller stir. 7.50 wt. % of the norbornene / canola oil mixture was then combined with 36.50 wt % SBS (GP-1000, General Industrial Polymers, styrene-butadiene block copolymer having a radial molecular structure, 30% by weight styrene content and 70% by weight butadiene content, powder form) at room temperature in a counter rotating pug mill. 56 wt. % of the NTR C-85 was added to the mixture and uniformly blended in at room temperature in a counter rotating pug mill, then fed through a mixing extruder reactor at 250-275°F to yield NTR Poly 5644 N, a rubber / polymer material. Polymerization by norbornyl ization of canola oil is believed to proceed according to the following reaction, showing the synthesis of fatty acid by norbornene ROMP substitution.

[0439] 92.0% by weight THMTxPG / (30:70) (from THP Operating LLC Oil Wells and Leases, a Texas PG 30:70 bitumen) was blended with 8.0% by weight NTR Poly 5644. XLNK XSZ31 was added to the blend and mixed using the Silverson Mixer at a temperature of 300°F and a shear rate of 500 RPM (just enough to create a vortex) to yield a blend containing 0.375 wt. % of XLNK XSZ31. The blend was allowed to mix for one hour. After mixing, the blend was tested for grade determination as per AASHTO R29.AASHTO Test Result Modified Test Method Specification Rotational Viscosity 135°CPa*s T316 2.688 3.0 Max. Flash, COC, °C T48 292 230 Mm. Solubility in Trichloroethylene, % T44 99.64 97.5 Mm. Dynamic Shear Rheometer, °C T315 76 82 88G*, kPa 1.882 1.008 0.580Phase Angle, 8, ° 79.6 80.5 81.3G* / Sin 6, kPa 1.913 1.022 0.586 1.00 Min. Critical Temperature, °C(1)82.2RTFO-Aged T240Mass Loss, w % T240 0.336 1.0 Max. Dynamic Shear Rheometer, °C T315 76 82G*, kPa 2.734 1.444Phase Angle, 5, ° 77.7 79.3G* / Sin 5, kPa 2.798 1.470 2.20 Min. Critical Temperature, °C(1)78.2Phase Angle at 2.2 kPa, 8, ° T315 78.3 80.0 Max. Elastic Recovery, 25°C, % T301 67.5P AV- Aged, °C R28 110Dynamic Shear Rheometer, °C T315 31 28G*, kPa 4910 7290Phase Angle, 8, ° 48.1 45.8G* / Sin 6, kPa 3655 5226 5000 Max. Critical Temperature, °C(1)28.4Bending Beam Rheometer, °C T313 -12 -18Stiffness, MPa 297 567 300 Max. Critical Temperature, °C(1)-12.1Bending Beam Rheometer, °C T313 -12 -18m- value 0.304 0.250 0.300 Mm. Critical Temperature, °C(1)-12.4PG Grade 76-22True Grade 78.2-22.1

[0440] (1) Critical temperature is the temperature at which the values of the material will be at the specification limit.Rubberized Asphalt Example 11

[0441] 75% by mass elemental sulfur was combined with 25% by mass zinc diethyldithiocarbamate. Both components were thoroughly mixed as dry powders at room temperature in a counter rotating pug mill to yield XLNK XSZ31, a crosslinking agent.0442] 80 wt. % ground tire rubber (30 mesh, dry powder) was mixed with 20 wt. % canola oil to yield a uniform mixture at room temperature in a counter rotating pug mill, and then fed through a mixer extruder reactor at a temperature of 250-275°F to yield NTR C-80, a rubber component.

[0443] 85 wt. % ground tire rubber (30 mesh, dry powder) was mixed with 15 wt. % canola oil to yield a uniform mixture at room temperature in a counter rotating pug mill, and then fed through a mixer extruder reactor at a temperature of 250-275°F to yield NTR C-85, a rubber component.

[0444] Norbornene was combined with canola oil at a weight ratio of 50 parts norbornene to 50 parts canola oil. The norbornene and canola oil was heated to 150°F then uniformly mixed / reacted with a low speed propeller stir. 7.50 v. % of the norbornene / canola oil mixture was then combined with 36.50 wt. % SBS (GP-1000, General Industrial Polymers, styrene-butadiene block copolymer having a radial molecular structure, 30% by weight styrene content and 70% by weight butadiene content, powder form) at room temperature in a counter rotating pug mill. 56 wt. % of the NTR C-85 was added to the mixture and uniformly blended in at room temperature in a counter rotating pug mill, then fed through a mixing extruder reactor at 250-275°F to yield NTR Poly 5644 N, a rubber / polymer material.

[0445] A mixture of 50 parts by weight NTR Poly 5644 N and 50 parts by weight NTR C-80 was prepared to yield Poly 5644N: NTR C80.

[0446] 10.0 parts by weight Poly 5644N: NTR C80 and 10 parts by weight NTR C- 80 were blended into 80.0 parts by weight PEMEX PG 64-22 asphalt base stock (from Mexico) at a temperature of 300°F using a Silverson mixer at a rate of 1500 RPM. After one hour of blending, the blend was tested for RV.AASHTO Test Method Test Result Rotational Viscosity 135°C Pa*s T316 1.486

[0447] XLNK XSZ31 was added to the blend (0.125% by weight) and mixed using a Silverson Mixer at a temperature of 300°F and a shear rate of 500 RPM (just enough to create a vortex). The blend was allowed to mix for one hour and then tested for RV.AASHTO Test Method Test Result Rotational Viscosity 135°C Pa*s T316 2.225

[0448] Additional XLNK XSZ31 was added to the blend (0.125% by weight for a total of 0.250% by weight in the blend) and mixed using a Silverson Mixer at a temperature of 300°F and a shear rate of 500 RPM (just enough to create a vortex). The blend was allowed to mix for one hour and then tested for RV.AASHTO Test Method Test Result Rotational Viscosity 135°C Pa*s T316 2.834

[0449] Once the RV was near 3.0 Pa*s, no additional XLNK XSZ31 was added. Because the RV was near the desired target, the blend was tested for grade determination as per AASHTO R29.AASHTO Test Result Modified Test Method Specification Rotational Viscosity 135°C Pa*s T316 2.834 3.0 Max. Flash, COC, °C T48 284 230 Min. Solubility in Trichloroethylene, % T44 97.98 97.5 Min. Dynamic Shear Rheometer, °C T315 82 88G*. kPa 1.65 0.950Phase Angle, 5, ° 77.5 80.5G* / Sin δ, kPa 1.69 0.963 1.00 Min. Critical Temperature, °C(1)87.6RTFO-Aged T240Mass Loss, w % T240 0.704 1.0 Max. Dynamic Shear Rheometer, °C T315 82 88G*, kPa 2.11 1.26 Phase Angle, 5, ° 65.7 69.5G* / Sin 5, kPa 2.31 1.35 2.20 Min. Critical Temperature, °C(1)82.5Phase Angle at 2.2 kPa, 5, ° T315 66.0 80.0 Max. Elastic Recovery, 25°C, % T301 65.0P AV- Aged, °C R28 110Dynamic Shear Rheometer, °C T315 7 4G*, kPa 8346 11239Phase Angle, 5, ° 33.4 32.5G* / Sin 5, kPa 4594 6039 5000 Max. Critical Temperature, °C(1)6.1Bending Beam Rheometer, °C T313 -18 “24 -30Stiffness, MPa 77 163 337 300 Max. Critical Temperature, °C(1)-29.0Bending Beam Rheometer, °C T313 -18 -24 -30m- value 0.303 0.264 0.227 0.300 Min. Critical Temperature, °C(1)-18.5PG Grade 82-28True Grade 82.5-28.5

[0450] (1) Critical temperature is the temperature at which the values of the material will be at the specification limit.Rubberized Asphalt Example 12

[0451] Fc powder was pre-reacted and dissolved into soybean oil in a weight ratio of soybean oil to Fc of 96:4 at room temperature with a low speed propeller stir to yield a clear solution. 20 wt. % of the resulting clear solution was combined with 80 wt. % ground tire rubber (30 mesh, dry powder) to yield a uniform mixture at room temperature in a counter rotating pug mill, and then fed through a mixer extruder reactor at a temperature of 250-275°F.0.5 wt. % SBS (GP-1000, General Industrial Polymers, styrene-butadiene block copolymer having a radial molecular structure, 30% by weight styrene content and 70% by weight butadiene content, powder form) was mixed in to yield NTR 73FNV2.0452] A mixture of 400.0 grams SJR PG 64- 10 asphalt and 116.0 g NTR 73FNV2 was blended using a Silverson Mixer at a rate of 1500 RPM. The blend appeared fully dispersed after 25 minutes. The blend was allowed to mix for an additional 35 minutes to ensure full dispersion and homogeneity. The Rotational Viscosity and Solubility of the blend in trichloroethylene was determined.AASHTO Test Method Test Result Rotational Viscosity 135°C Pa*s T316 0.515 Solubility in Trichloroethylene, w% T316 97.12

[0453] 30.8 g of NTR 73FNV2 were added to the blend and mixed using the Silverson Mixer at a temperature of 300°F and a shear rate of 1500 RPM. The blend was allowed to mix for one hour. 0.75% of XLNK XSZ31 was mixed in using the Silverson Mixer at a temperature of 300°F at a shear rate of 750 RPM (just enough to create a vortex). The blend was then allowed to mix for one hour. After mixing, the PG grade was determined.AASHTO Test Result Modified Test Method Specification Rotational Viscosity 135°C Pa*s T316 26.035 3.0 Max. Flash, COC, °C T48 262 230 Min. Solubility in Trichloroethylene, % T44 93.74 97.5 Min. Dynamic Shear Rheometer, °C T315 76 82 88G*, kPa 2.6 1.12 0.598Phase Angle, 5, ° 58.8 60.4 62.1G* / Sin δ, kPa 2.52 1.29 0.676 1.00 Min. Critical Temperature, °C(1)84.4RTFO-Aged T240Mass Loss, w % T240 1.320 1.0 Max. Dynamic Shear Rheometer, °C T315 76 82G*, kPa 2.23 1.17 Phase Angle, 5, ° 78.3 80.7G* / Sin 5, kPa 2.28 1.19 2.20 Min. Critical Temperature, °C(1)76.3Phase Angle at 2.2 kPa, 5, ° T315 78.4 80.0 Max. Elastic Recovery, 25°C, % T301 75.0PAV-Aged, °C R28 110Dynamic Shear Rheometer, °C T315 25 22G*, kPa 5672 8889Phase Angle, 5, ° 52.6 49.8G* / Sin 5, kPa 4506 6789 5000 Max. Critical Temperature, °C(1)24.3Bending Beam Rheometer, °C T313 -12 -18Stiffness, MPa 220 487 300 Max. Critical Temperature, °C(1)-14.3Bending Beam Rheometer, °C T313 -12 -18m- value 0.320 0.254 0.300 Min. Critical Temperature, °C(1)-13.8PG Grade 76-22True Grade 76.3-23.8

[0454] (1) Critical temperature is the temperature at which the values of the material will be at the specification limit.Modified Binders Example 13

[0455] Preparation, conditioning, and testing of asphalt mixture specimens in the indirect tensile cracking test (IDEAL-CT) was conducted using two modified binder samples. The binders contained AR-NTR-8282FD was prepared in Example 9. The first test specimen identified as “10% SIR, 90% PG 64-10” contained a blend of 10.0 parts by weight AR-NTR- 8282FD to 90 parts by weight SIR PG 64-10 base asphalt. The second test specimen identified as “20% SIR, 80% PG 64-10” contained a blend of 20 parts by weight AR-NTR-8282FD to80.0 parts by weight SJR PG 64-10 base asphalt. The first and second test specimens each included 0.625 wt. % of XLNK XSZ31. Comparative IDEAL-CT test results from specimens fabricated using the same mix design with Texas supplied binders (PG 64-22, PG 70-22, PG 70-28, and PG 76-28). The Texas supplied binders complied with the requirements of the Texas Department of Transportation (TxDOT) Designation Tex-545-C, “Asphalt Binder Quality Program.”

[0456] A dense graded mix design was used, designed according to the TxDOT specification SS-3077-SP-C. A dolomite limestone aggregate was used. The mixture was designed to 50 gyrations, 5.0% optimum asphalt content, and using 12% reclaimed asphalt pavement (RAP).

[0457] Aggregate and binder were combined in a drum mixer and mixed until all aggregates were coated in binder. The loose mix was then short-term oven aged (STOA) at 135°C for 2 hours before compacting. Specimens were compacted using the superpave gyratory compactor. The target thickness was 62mm and the target air void content was 7% by volume. The thickness was measured after compaction was completed and no notable expansion was observed. Specimens were cooled and tested using the same procedure for all binder types. Specimens were tested according to ASTM D8225 at 25°C (IDEAL-CT). Test results for both binder types are shown in FIG. 12. FIG. 13 shows the two binder results with four reference binder types (PG 64-22, PG 70-22, PG 70-28, and PG 76-28). The whiskers indicate ± 1 standard deviation. A higher IDEAL-CT index result indicates higher cracking resistance. For reference, Texas preliminarily recommends a mixture meet a threshold > 80 on the IDEAL-CT Index.

[0458] Additional test specimens were created and evaluated according to ASTM D8360 at 50°C (IDEAL. -RT). The IDEAL-RT Index provides an indication of a mixture’s resistance to rutting, with Texas setting a preliminary threshold of 65 for most regions. The results are graphed alongside the IDEAL-CT data in FIG. 14. The upper right hand quadrant of the graph represents the “balanced” region, where both cracking and rutting performance thresholds are met. The same four reference binder types are also plotted on the graph.

[0459] The SJR modified binders appeared to perform well on the selected mixture tests and both performed most similarly to the PG 70-28 reference binder. The variability of the test results appeared to be within normal ranges.Discussion0460] The testing reports for the polymer modified asphalts (PMAs) of Examples 9-14 establish that the disclosed formulary can be adjusted to make a specification-compliant PMA from a broad spectrum of asphalts, refined at diverse locations. These reports cover the SARA differentials associated with asphalt feed stock from refiners using California (San Joaquin Valley Crude), Texas (Permean Basin Crude) and Mexico oil fields. The test results also affirm that especially difficult PMA binder specifications, such as the Federal Aviation Administration’s (FAA’s) 401 / 404 PG 82-28 specification, can be achieved using a modified GTR as the principal polymer. Such PMAs also exhibit the rutting and crack resistance associated GTR utilization but with the handling and install characteristics of conventional polymers (which conventionally do not perform as well as GTR-based formulations long term).Exemplary Methods, Materials, and Apparatus

[0461] Method 1: A method for preparing a functional rubber material, comprising: reacting a vulcanized rubber with an unsaturated oil in the presence of a ferrocene catalyst, whereby a functional rubber material is obtained.

[0462] Method 2: The method of Method 1, wherein the unsaturated oil is soybean oil, optionally high oleic soybean oil.

[0463] Method 3: The method of Method 1, wherein the unsaturated oil is canola oil.

[0464] Method 4: The method of Method 1, wherein a weight ratio of unsaturated oil to ferrocene is 96:4.

[0465] Method 5: The method of Method 1, wherein the vulcanized rubber is ground tire rubber, optionally having a particle size of 30 mesh, optionally wherein a particle size of the functional rubber material is 25 microns or less.

[0466] Method 6: The method of Method 1, wherein from 75-95 parts by weight of vulcanized rubber is present in the functional rubber material.

[0467] Method 7: The method of Method 1, wherein 80 parts by weight of vulcanized rubber is present to 20 parts by weight of a combination of the unsaturated oil and the ferrocene catalyst.

[0468] Method 8: The method of Method 1, wherein 85 parts by weight of vulcanized rubber is present to 15 parts by weight of a combination of the unsaturated oil and the ferrocene catalyst.

[0469] Method 9: The method of Method 1, further comprising combining the functional rubber material with an asphalt.

[0470] Method 10: The method of Method 9, further comprising adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

[0471] Method 11: The method of Method 1, further comprising adding a styrene- butadiene-styrene block copolymer to the functional rubber material.

[0472] Method 12: The method of Method 11, further comprising adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

[0473] Method 13: The method of Method 1, further comprising fabricating the functional rubber material into a rubber-containing article,

[0474] Functional Rubber Material 14: A functional rubber material prepared by the method of Method 1.

[0475] Method 15: A method for preparing a functional rubber material, comprising: reacting a vulcanized rubber with an unsaturated oil in the presence of a norbornene, whereby a functional rubber material is obtained.

[0476] Method 16: The method of Method 15, wherein the unsaturated oil is soybean oil, optionally high oleic soybean oil.

[0477] Method 17: The method of Method 15, wherein the unsaturated oil is canola oil.

[0478] Method 18: The method of Method 15, wherein a weight ratio of unsaturated oil to norbornene is 50:50.

[0479] Method 19: The method of Method 15, wherein the vulcanized rubber is ground tire rubber, optionally having a particle size of 30 mesh, optionally wherein a particle size of the functional rubber material is 25 microns or less.0480] Method 20: The method of Method 15, wherein from 75-95 parts by weight of vulcanized rubber is present in the functional rubber material.

[0481] Method 21: The method of Method 15, wherein 80 parts by weight of vulcanized rubber is present to 20 parts by weight of a combination of the unsaturated oil.

[0482] Method 22: The method of Method 15, wherein 85 parts by weight of vulcanized rubber is present to 15 parts by weight of a combination of the unsaturated oil.

[0483] Method 23: The method of Method 15, further comprising combining the functional rubber material with an asphalt.

[0484] Method 24: The method of Method 23, further comprising adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

[0485] Method 25: The method of Method 15, further comprising adding a styrene- butadiene-styrene block copolymer to the functional rubber material.

[0486] Method 26: The method of Method 25, further comprising adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

[0487] Method 27: The method of Method 15, further comprising fabricating the functional rubber material into a rubber-containing article.

[0488] Functional Rubber Material 28: A functional rubber material prepared by the method of Method 15.

[0489] Method 29: A method for preparing an elastomer product, comprising: combining a mixture of sulfur-crosslinked elastomer and hyperbranched macromolecules having a plurality of reactive chain ends, whereby resident sulfur in rubber crosslinks of the sulfur-crosslinked elastomer matrix is removed, whereby an elastomer product is obtained.

[0490] Method 30: A method for preparing a functional rubber, comprising: exfoliating end-of-life rubber particles by reaction with a metallocene, whereby a particle size of the exfoliated end-of-life rubber particles is reduced while maintaining a vulcanizing property and an inner structure of the exfoliated end-of-life rubber particles, whereby a functional rubber is obtained.

[0491] Method 31: A method for preparing a rubber-based elastomer, comprising: applying pressure to a mixture comprising sulfur-crosslinked rubber particles and an iron¬ based organometallic compound, then releasing the pressure, whereby a rubber-based elastomer is obtained.

[0492] Method 32: A material substantially as described herein.

[0493] Method 33: A process substantially as described herein.

[0494] Method 34: An apparatus substantially as described herein.

[0495] While the disclosure has been illustrated and described in detail in the drawings and foregoing description, such illustration and description are to be considered illustrative or exemplary and not restrictive. The disclosure is not limited to the disclosed embodiments. Variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed disclosure, from a study of the drawings, the disclosure and the appended claims.

[0496] All references cited herein are incorporated herein by reference in their entirety. To the extent publications and patents or patent applications incorporated by reference contradict the disclosure contained in the specification, the specification is intended to supersede and / or take precedence over any such contradictory material.

[0497] Unless otherwise defined, all terms (including technical and scientific terms) are to be given their ordinary and customary meaning to a person of ordinary skill in the art and are not to be limited to a special or customized meaning unless expressly so defined herein. It should be noted that the use of particular terminology when describing certain features or aspects of the disclosure should not be taken to imply that the terminology is being re-defined herein to be restricted to include any specific characteristics of the features or aspects of the disclosure with which that terminology is associated. Terms and phrases used in this application, and variations thereof, especially in the appended claims, unless otherwise expressly stated, should be construed as open ended as opposed to limiting. As examples ofthe foregoing, the term ‘including’ should be read to mean ‘including, without limitation,’ ‘including but not limited to,’ or the like; the term ‘comprising’ as used herein is synonymous with ‘including,’ ‘containing,’ or ‘characterized by,’ and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps; the term ‘having’ should be interpreted as ‘having at least;’ the term ‘includes’ should be interpreted as ‘includes but is not limited to;’ the term ‘example’ is used to provide exemplary instances of the item in discussion, not an exhaustive or limiting list thereof; adjectives such as ‘known’, ‘normal’, ‘standard’, and terms of similar meaning should not be construed as limiting the item described to a given time period or to an item available as of a given time, but instead should be read to encompass known, normal, or standard technologies that may be available or known now or at any time in the future; and use of terms like ‘preferably,’ ‘preferred,’ ‘desired,’ or ‘desirable,’ and words of similar meaning should not be understood as implying that certain features are critical, essential, or even important to the structure or function of the present technology, but instead as merely intended to highlight alternative or additional features that may or may not be utilized in a particular embodiment of the present technology. Likewise, a group of items linked with the conjunction ‘and’ should not be read as requiring that each and every' one of those items be present in the grouping, but rather should be read as ‘and / or’ unless expressly stated otherwise. Similarly, a group of items linked with the conjunction ‘or’ should not be read as requiring mutual exclusivity among that group, but rather should be read as ‘and / or’ unless expressly stated otherwise.

[0498] Where a range of values is provided, it is understood that the upper and lower limit, and each intervening value between the upper and lower limit of the range is encompassed within the embodiments.

[0499] With respect to the use of substantially any plural and / or singular terms herein, those having skill in the art can translate from the plural to the singular and / or from the singular to the plural as is appropriate to the context and / or application. The various singular / plural permutations may be expressly set forth herein for sake of clarity. The indefinite article “a” or “an” does not exclude a plurality. A single processor or other unit may fulfill the functions of several items recited in the claims. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measurescannot be used to advantage. Any reference signs in the claims should not be construed as limiting the scope.

[0500] It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and / or “an” should typically be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, typically means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc. ). It will be further understood by those within the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” wall be understood to include the possibilities of “A” or “B” or “A and B.”

[0501] All numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification are to be understood as being modified in all instances by the term ‘about.’ Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of any claims in any application claiming priority to the present application, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.

[0502] Furthermore, although the foregoing has been described in some detail by way of illustrations and examples for purposes of clarity' and understanding, it is apparent to those skilled in the art that certain changes and modifications may be practiced. Therefore, the description and examples should not be construed as limiting the scope of the present technology to the specific embodiments and examples described herein, but rather to also cover all modification and alternatives coming with the true scope and spirit of the present technology.

Claims

WHAT IS CLAIMED IS:

1. A method for preparing a functional rubber material, comprising:reacting a vulcanized rubber with an unsaturated oil in the presence of a ferrocene catalyst, whereby a functional rubber material is obtained.

2. The method of Claim 1, wherein the unsaturated oil is soybean oil, optionally high oleic soybean oil.

3. The method of Claim 1, wherein the unsaturated oil is canola oil.

4. The method of Claim 1, wherein a weight ratio of unsaturated oil to ferrocene is 96:4.

5. The method of Claim 1, wherein the vulcanized rubber is ground tire rubber, optionally having a particle size of 30 mesh, optionally wherein a particle size of the functional rubber material is 25 microns or less.

6. The method of Claim 1, wherein from 75-95 parts by weight of vulcanized rubber is present in the functional rubber material.

7. The method of Claim 1, wherein 80 parts by weight of vulcanized rubber is present to 20 parts by weight of a combination of the unsaturated oil and the ferrocene catalyst.

8. The method of Claim 1, wherein 85 parts by weight of vulcanized rubber is present to 15 parts by weight of a combination of the unsaturated oil and the ferrocene catalyst.

9. The method of Claim 1, further comprising combining the functional rubber material with an asphalt.

10. The method of Claim 9, further comprising adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

11. The method of Claim 1, further comprising adding a styrene-butadiene-styrene block copolymer to the functional rubber material.

12. The method of Claim 11, further comprising adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zincdiethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

13. The method of Claim 1, further comprising fabricating the functional rubber material into a rubber-containing article.

14. A functional rubber material prepared by the method of Claim 1.

15. A method for preparing a functional rubber material, comprising:reacting a vulcanized rubber with an unsaturated oil in the presence of a norbornene, whereby a functional rubber material is obtained.

16. The method of Claim 15, wherein the unsaturated oil is soybean oil, optionally high oleic soybean oil.

17. The method of Claim 15, wherein the unsaturated oil is canola oil.

18. The method of Claim 15, wherein a weight ratio of unsaturated oil to norbornene is 50:50.

19. The method of Claim 15, wherein the vulcanized rubber is ground tire rubber, optionally having a particle size of 30 mesh, optionally wherein a particle size of the functional rubber material is 25 microns or less,20. The method of Claim 15, wherein from 75-95 parts by weight of vulcanized rubber is present in the functional rubber material.

21. The method of Claim 15, wherein 80 parts by weight of vulcanized rubber is present, to 20 parts by weight of a combination of the unsaturated oil.

22. The method of Claim 15, wherein 85 parts by weight of vulcanized rubber is present, to 15 parts by weight of a combination of the unsaturated oil.

23. The method of Claim 15, further comprising combining the functional rubber material with an asphalt.

24. The method of Claim 23, further comprising adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

25. The method of Claim 15, further comprising adding a styrene-butadiene-styrene block copolymer to the functional rubber material.

26. The method of Claim 25, further comprising adding a crosslinking agent to a mixture of the functional rubber material and the asphalt, whereby a rubberized asphalt is obtained, optionally wherein the crosslinking agent is a mixture of elemental sulfur and zinc diethyldithiocarbamate, optionally with a weight ratio of the elemental sulfur to the zinc diethyldithiocarbamate of 75:25.

27. The method of Claim 15, further comprising fabricating the functional rubber material into a rubber-containing article.

28. A functional rubber material prepared by the method of Claim 15.

29. A method for preparing an elastomer product, comprising:combining a mixture of sulfur-crosslinked elastomer and hyperbranched macromolecules having a plurality of reactive chain ends, whereby resident sulfur in rubber crosslinks of the sulfur-crosslinked elastomer matrix is removed, whereby an elastomer product is obtained.

30. A method for preparing a functional rubber, comprising:exfoliating end-of-life rubber particles by reaction with a metallocene, whereby a particle size of the exfoliated end-of-life rubber particles is reduced while maintaining a vulcanizing property and an inner structure of the exfoliated end-of-life rubber particles, whereby a functional rubber is obtained.

31. A method for preparing a rubber-based elastomer, comprising:applying pressure to a mixture comprising sulfur-crosslinked rubber particles and an iron-based organometallic compound, then releasing the pressure, whereby a rubber-based elastomer is obtained.

32. A material substantially as described herein.

33. A process substantially as described herein.

34. An apparatus substantially as described herein.

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