Resin from junked tires

Abstract

Resin from junked tires. The hydrocarbon resin includes a reaction product of a polymerization reaction of a junked tire (ELT) oil monomer, and has a Tg of about-30 DEG C to about 140 DEG C, a softening point of about 10 DEG C to about 170 DEG C, and a molecular weight Mw of between 100 and 5000 Da.

Description

Technical Field

[0001] The present application relates to hydrocarbon resins, tires, and a method of forming resins from ELT oils. Background Art

[0002] Used tires ("waste" tires or "ELTs") can be thermally decomposed to separate organic and inorganic materials therefrom. Products obtained from the thermal decomposition of tires can include carbon black, steel, sulfur (isolated as sulfur-containing compounds), one or more gaseous and / or liquid oily products.

[0003] US Pat. No. 7,628,892 to PRTI Corporation discloses a process for producing a two-phase fluid mixture by depolymerizing the phases of rubber products, such as worn tires. The '892 process involves depolymerization and separation of a primary gaseous phase having physicochemical properties suitable for use in conventional diesel engines. Liquid hydrocarbons are also collected using the '892 process (hereinafter referred to as "ELT-oil").

[0004] Typical tire recycling technologies produce low-quality materials with limited use in new tire production. It has now been discovered that the depolymerization process can be optimized to maximize the availability of suitable organic hydrocarbon molecules such as C5, C9, limonene and other resin precursors such as styrenic monomers in the liquid ELT oil phase.

[0005] It is desirable to use the hydrocarbons of liquid ELT-oil to produce hydrocarbon resins. The present disclosure provides one or more resins and methods of polymerizing the resins using ELT oil collected from depolymerization of tire / rubber products. Summary of the Invention

[0006] One embodiment of the present disclosure is directed to a hydrocarbon resin comprising the reaction product of a polymerization reaction of an ELT oil monomer. The reaction product is characterized by a glass transition temperature (Tg) of about -30°C to about 140°C, a softening point of about 10°C to about 170°C, and a molecular weight (Mw) of 100 to 5000 Da.

[0007] Another embodiment of the present disclosure is directed to a tire having a tread and / or carcass compound comprising at least one rubber selected from natural rubber, rubber derived from diene monomers, and mixtures thereof, and an ELT hydrocarbon-based resin.

[0008] Another embodiment of the present disclosure relates to a method for forming a resin from ELT oil. The method includes the steps of obtaining an ELT oil obtained by thermal depolymerization of ELTS and polymerizing the ELT oil to produce an ELT hydrocarbon-based resin.

[0009] The present invention discloses the following embodiments:

[0010] 1. A hydrocarbon resin comprising the reaction product of the polymerization of waste tire (ELT) oil monomers and having a Tg of about -30°C to about 140°C, a softening point of about 10°C to about 170°C, and a molecular weight Mw of 100 to 5000 Da.

[0011] 2. The resin of embodiment 1, wherein the ELT oil is derived from thermal depolymerization of tires and / or other rubber products.

[0012] 3. The resin of embodiment 2, wherein the ELT oil is derived from the thermal depolymerization of substantially whole tires.

[0013] 4. The resin of embodiment 1, wherein the ELT oil is derived from thermal depolymerization of cured and / or uncured rubber production plant waste.

[0014] 5. The resin of embodiment 1, wherein the hydrocarbon resin is formed solely from ELT oil monomers.

[0015] 6. The resin according to embodiment 1, wherein the hydrocarbon resin is formed by copolymerizing ELT oil monomers with other hydrocarbon fractions.

[0016] 7. The resin according to embodiment 6, wherein the hydrocarbon fraction is selected from the group comprising C5, C9, AMS, DCPD, rosin, phenol, epoxy resin, sole or mixtures thereof.

[0017] 8. The resin of embodiment 1, wherein the resin is hydrogenated.

[0018] 9. The resin of embodiment 1, wherein the resin is a liquid.

[0019] 10. The resin of embodiment 1, wherein the resin is a solid.

[0020] 11. The resin of embodiment 1, wherein the resin is incorporated into a rubber article.

[0021] 12. The resin of embodiment 11, wherein the rubber article is a tire component.

[0022] 13. The resin of embodiment 1, wherein the resin is incorporated into an adhesive formulation.

[0023] 14. A tire having a tread and / or a carcass compound, the tread and / or carcass compound comprising:

[0024] at least one rubber selected from the group consisting of natural rubber, rubber derived from diene monomers, and mixtures thereof; and

[0025] The ELT oleyl hydrocarbon-based resin of embodiment 1.

[0026] 15. The tire according to embodiment 11, wherein the ELT oil is derived from thermal depolymerization of waste tires (ELT).

[0027] 16. A method of forming a resin from an ELT oil, the method comprising the steps of:

[0028] Obtaining ELT oil obtained by thermal depolymerization of waste tires (ELTS); and

[0029] ELT oils are polymerized to produce ELT hydrocarbon-based resins.

[0030] 17. The method of embodiment 16, further comprising:

[0031] The ELT oil is optionally refined to the desired hydrocarbon composition.

[0032] 18. The method of embodiment 16, wherein the polymerization comprises:

[0033] The monomers of the ELT oil are polymerized to produce an ELT hydrocarbon-based resin.

[0034] 19. The method of embodiment 16, wherein the polymerization comprises:

[0035] The monomers of the ELT oil are copolymerized with other hydrocarbon fractions to produce ELT hydrocarbon-based resins. DETAILED DESCRIPTION

[0036] The present invention relates to novel synthetic resins and methods for their preparation. Another object of the present invention is to provide novel and useful copolymers prepared from hydrocarbons formed by depolymerization of ELT, and to provide methods for their preparation.

[0037] In one embodiment, ELT oil is produced using the operations described in U.S. Pat. No. 7,628,892, entitled "SYSTEM AND PROCESS FOR THE PRODUCTION OF COMBUSTABLE SUBSTANCES BY DEPOLYMERIZATION OF RUBBER PRODUCTS," the entire contents of which are incorporated herein by reference. The '892 patent discloses a method and apparatus for producing a liquid and storable combustible substance by depolymerization of ELT. Entire tires or parts thereof may be used. The '892 process produces a carbonaceous fuel product and a gaseous product by: (S1) introducing calcium oxide into the tire in a depolymerization apparatus; (S2) activating the tire for combustion; (S3) performing a thermal treatment process to form a two-phase mixture containing combustible particulates (i.e., oily particles in the form of droplets) resulting from the depolymerization; (S4) physically separating the solid phase from the liquid phase using condensation; and (S5) and burning the gaseous phase while containing the liquid as the combustible substance.

[0038] The amount of flammable liquid product will vary; however, the total liquid product content (ie, the "oil content" in the tire rubber) using the '892 process is 35% to 40% of the tire weight and has the physicochemical properties shown in Table 1 of the '892 patent.

[0039] Hydrocarbon products having five or more carbon atoms in their chains are liquid at room temperature. In one embodiment, liquid hydrocarbon products are produced using the procedures described in US Patent No. 10,703,876, entitled "APPARATUS AND METHOD FOR THERMALLY DEMANUFACTURING TIRES AND OTHER WASTE PRODUCTS," incorporated herein by reference in its entirety. The '876 patent discloses a method and apparatus for producing a liquid and storable combustible material by ELT depolymerization. Entire tires or components thereof may be used. The '876 process produces a carbonaceous fuel product and a gaseous product by: (S1) introducing oxygen or air through a register onto which the material to be depolymerized (e.g., a tire) is placed; (S2) partially burning or smoldering the material while allowing the burner to generate heat using air; (S3) separating the liquid hydrocarbon product from the gaseous product using a condenser that reduces the temperature of the gas stream to obtain a liquid stream and a gas stream; and (S4) collecting the cooled liquid product.

[0040] There is no limitation on the type of oil (e.g., pyrolysis, ELT) provided to the resin synthesis of the present disclosure. Preferred embodiments contemplate the use of methods similar to those described above, using thermal decomposition, pyrolysis manufacturing and / or thermal depolymerization of cured and / or uncured rubber products and waste to produce ELT oil. Thermal depolymerization is distinguishable from conventional pyrolysis in that it uses an oxidant, i.e., air, to continue the combustion of the tire. Such an oxidant is not present in pyrolysis, such as the one described in US20230407184 to Michelin, where a temperature ramp separates the pyrolysis oil from gaseous (below 150°C) and solid (above 260°C) effluents. In '184, the pyrolysis oil is an intermediate fraction supplied to the resin synthesis.

[0041] However, during thermal depolymerization, condensation occurs and the resulting liquid effluent is introduced into a container. This liquid effluent (i.e., liquid hydrocarbon) is defined herein as a "base ELT oil" formed from ELT monomers. The base ELT oil can be used as is or undergo one or more distillations to produce a refined ELT oil. As used herein, "refined ELT oil" may include distilled ELT oil or oil purified by other means known to those of ordinary skill in the art. "Distilled ELT oil" is a "refined ELT oil," but the refined ELT oil may or may not contain distilled ELT oil.

[0042] As used herein, "ELT oil," "oil," "liquid effluent," "liquid phase," or hydrocarbons are interchangeable and used synonymously hereinafter. As described above, "base ELT oil" specifically refers to oil produced using thermal depolymerization of rubber products. Although not limiting, these products are expected to include all or part of tires (new or used) and production plant waste. In one embodiment, it does not include oil produced by pyrolysis. On the other hand, "ELT oil" can refer to oil produced using methods such as pyrolysis or thermal depolymerization.

[0043] The process of the '876 patent is operated under the conditions to obtain a product containing at least 15 wt% C4-C 12 Olefinic monomers, preferably at least 20 wt% C4-C 12 ELT oil based on olefinic monomers.

[0044] "Olefinic monomers" refer to hydrocarbon-containing compounds that contain unsaturated carbon-carbon bonds and are polymerizable under appropriate conditions. Examples of these olefinic monomers include limonene, terpenes, aromatic olefins such as styrene, α-methylstyrene, indene, benzofuran, and linear or cyclic olefins such as dicyclopentadiene.

[0045] Further refining of the base ELT oil can be carried out by any method known to those skilled in the art. It has been found that the total olefin content of the ELT oil, as defined above, does not vary much between the base ELT oil and the refined ELT oil. However, it has been found that the limonene content of the distilled ELT oil becomes richer after each distillation cycle. It is further believed that by using ELT with a high content of polyisoprene elastomer, such as natural rubber, as a raw material and by optimizing the thermal reaction conditions, such as pressure, temperature, and steam residence time, the limonene content can be maximized. This raw material is beneficial for the production of limonene monomer.

[0046] Base ELT oils primarily comprise a mixture of hydrocarbons having a broad boiling point range. Most of these compounds form part of the family of alkanes, alkenes, naphthenes (cycloalkanes) and aromatic compounds.

[0047] More particularly, the base ELT oil is characterized by comprising at least 20 wt% of C4-C 12 Olefinic monomers, including at least styrenes, limonenes, and indenes. Certain heteroatom-containing substances may also be present. Analysis of a sample of base ELT oil revealed that this oil is also characterized by over 30 components present in trace amounts of approximately 1%.

[0048] It has been found that the base ELT oil can be further refined to modify the distribution of components. It has been found that treating the base ELT oil by distillation can yield ELT oil samples containing a higher limonene content. It is contemplated that additional distillations can be performed to achieve the desired purity.

[0049] The present invention relates to a method for forming a resin using ELT oil. The method comprises the following steps:

[0050] Polymerization reaction

[0051] In the practice of the present invention, an untreated resin material is prepared by polymerizing a hydrocarbon mixture comprising 50-95 wt% ELT oil and 5-50 ppm methanol initiator in the presence of an anhydrous metal halide catalyst, which may serve as a co-initiator. In a preferred embodiment, the mixture to be polymerized comprises 65-95 wt% ELT oil and 5-35 wt% inert solvent. In one embodiment, about 0.5 wt% to about 5 wt%, and more preferably about 1 wt% to about 3 wt%, of the anhydrous metal halide catalyst may be used.

[0052] In fact, various anhydrous metal or boron halide catalysts can be used to prepare the untreated resin material. Representative examples of such catalysts are fluorides, chlorides, bromides and iodides of aluminum, tin and boron. Such catalysts include, for example, aluminum chloride, tin chloride and boron trifluoride. Aluminum chloride and tin chloride are preferred.

[0053] When carrying out polyreaction, hydrocarbon mixture is contacted with anhydrous metal halide catalyst.Usually, catalyst is used or is loaded on light granular and preferably porous particle with particle form.Usually, use the particle of 5-200 mesh particle size, although can use bigger or smaller particle.The consumption of catalyst is not critical, although must use enough catalyst to cause the generation of polyreaction.In the embodiment of expectation, enough catalyst can be roughly about 200 to about 500ppm methanol.

[0054] Catalyst can be added to the hydrocarbon mixture, or the hydrocarbon mixture can be added to the catalyst. If desired, catalyst and hydrocarbon mixture can be added to the reactor simultaneously or intermittently. Reaction can be carried out continuously or by batch process technology commonly known to those skilled in the art.

[0055] The polymerization reaction is carried out in an organic solvent. Various inert solvents that do not participate in the polymerization reaction can be used. Representative examples of inert solvents are aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as toluene and benzene, and unreacted residual hydrocarbons from the reaction. Particularly preferred polar solvents are selected from benzene, toluene, xylene, chlorobenzene and methylene chloride.

[0056] Non-polar organic solvents, although not preferred, may also be used in combination with polar solvents. Non-polar solvents may be selected from hexane, pentane, cyclohexane, napthas, and olefins that are relatively inert under the conditions involved in the reaction, such as cyclopentene.

[0057] The total volume ratio of solvent to ELT oil in the reaction mixture may be from about 1:2 to about 1:6.

[0058] Preferably, the solvent and catalyst are added to the reaction vessel and the ELT oil is then added to the reaction vessel over time while the reaction mixture is stirred. However, the ELT oil and catalyst may be added to the reaction vessel substantially simultaneously, particularly when conducting a continuous polymerization reaction.

[0059] The polymerization reaction can be carried out at a wide range of temperatures. The polymerization can be carried out at a temperature of 20°C to 1000°C, although typically the reaction is carried out at a temperature of 0°C to 500°C. The polymerization reaction pressure is not critical and can be atmospheric pressure or above or below atmospheric pressure.

[0060] In general, satisfactory polymerization can be carried out when the reaction is carried out at about the autogenous pressure generated in the reactor under the operating conditions employed. The reaction time is generally not critical and can range from a few seconds to 12 hours or more.

[0061] washing

[0062] After the polymerization reaction is substantially complete, the reaction product mixture is quenched with water to a temperature of about 15°C to about 40°C and heated to a temperature of about 50°C to about 90°C.

[0063] Vacuum distillation and nitrogen sparging

[0064] After washing, the organic phase is distilled and sparged according to the method disclosed in US6121392 of Arizona Chem Co., the entire contents of which are incorporated herein by reference. In a contemplated embodiment, the separated organic phase can be washed with a blend of alcohol and water at elevated temperature to remove traces of catalyst and other impurities. The organic phase is distilled from the product at a temperature of 240°C under atmospheric pressure. The crude resin is then purged with nitrogen at 240°C to remove dimers and obtain the lowest molecular weight resin (hereinafter referred to as "ELT resin"), as determined by the ring and ball method of ASTM E-28-58T. This is to separate the aqueous phase from the organic phase. In alternative embodiments, it can be carried out by well-known phase separation techniques such as decantation, centrifugation, extraction, drying, etc.

[0065] In one embodiment, the ELT resin is a hydrocarbon resin. The hydrocarbon resin can be, for example, an aromatic and / or non-aromatic based resin. The difference in resins is primarily due to the olefins contained in the ELT based feedstock from which the resin is derived.

[0066] In one embodiment, the ELT resin is a terpene resin from the group dipentene (D,L-limonene).The terpene resin may comprise, for example, a polymer of limonene and have a softening point of about 60°C to 170°C.

[0067] In another embodiment, terpenes can be used with other petroleum-based monomers such as styrene to form a resin product. Any method known to those of ordinary skill in the art can be used. More particularly, terpenes or ELT resins can be copolymerized with other hydrocarbon fractions such as C5 (olefins and dienes containing an average of five carbon atoms), C9 (olefins and dienes containing an average of nine carbon atoms), alpha-methylstyrene (AMS), or mixtures thereof. In other embodiments, terpenes can be copolymerized with phenolic monomers to form terpene-phenol resins. Exemplary terpene-phenol resins can be copolymers of phenol monomers with limonene. Polymer resin materials containing units derived from limonene and more than one of DCPD, indene, tert-butylstyrene, indene AMS, vinyltoluene, dimethyl-dicyclopentadiene are also contemplated. The resin compound can be liquid or solid.

[0068] In contemplated embodiments, the resin may comprise a traction resin or a plasticizing resin, or a tackifying resin. In one embodiment, the resin may be partially or fully hydrogenated. In one embodiment, the resin may undergo further hydrogenation to obtain the desired degree of saturation according to methods known to those of ordinary skill in the art.

[0069] In summary, the ELT fractions can be copolymerized to synthesize desired grades, oil fractions, or possible resins within a blend. The present invention relates to a resin consisting essentially of the reaction product of a polymerization reaction between ELT oil monomers and having a glass transition temperature (Tg) of about -30°C to about 140°C, a softening point of about 10°C to about 170°C, and a molecular weight Mw of 100 to 5000 Daltons (Da).

[0070] The resins of the present invention are particularly useful as modifiers for natural rubber and various synthetic rubber compositions. According to the present invention, various articles such as tires and industrial rubber products can be prepared using this rubber composition. Upon vulcanization, this rubber composition can be incorporated into pneumatic or non-pneumatic tires, belts, hoses, air springs, footwear products, or engine mounts. In the case of tires, the rubber composition can be incorporated into various rubber tire components such as treads (including tread caps and / or tread bases), sidewalls, apex rubber, bead fillers, sidewalls, inserts, wire lagging, and / or innerliners. In one embodiment, the compound is a tread. It is expected that current ELT oil-derived resins are used as traction resins in silica tread compounds to provide balanced performance. In one embodiment, the disclosed resins are contemplated for use in high-performance tire compounds comprising one or both of high silica and high resin loadings. In further embodiments, the ELT hydrocarbon-based resins disclosed herein can be used in adhesives.

[0071] The tire of the present invention can be a racing tire, a passenger car tire, an aircraft tire, an agricultural tire, a bulldozer tire, an off-road tire, a truck tire, etc. The tire can also be radial or bias ply.

[0072] The resins can be used as partial or complete replacements for conventional plasticizers and blends commonly used in tire & technical commodity compounds, such as traction resins, tackifiers, and processing resins, and can be used in combination with other resins such as hydrocarbon or bio-based resins, oils, processing aids, and blends thereof. In one embodiment, the ELT hydrocarbon-based resins can be used as extenders in synthetic polymers such as styrene butadiene (SSBR) and polybutadiene (BR), by replacing extender oils.

[0073] The following examples further illustrate the present invention but are not intended to be limiting. In these examples, parts and percentages are in grams unless otherwise indicated.

[0074] Example

[0075] The reactants, reaction conditions, and product characteristics (Sample 1) are given in Table II.

[0076] Example 1: Limonene resin

[0077] To a 3-liter, necked flask equipped with a mechanical stirrer, nitrogen, and a thermocouple, 210 mL of toluene, 175 mL of isooctane, and 11.8 g of aluminum chloride were added. The reaction mixture was cooled to 14°C in a water bath. 50 mL of limonene and 0.12 g of methanol initiator were then added to the mixture. The temperature was raised to 29°C, and the mixture turned orange-amber. The mixture was allowed to cool to 20°C, after which additional portions of limonene were added. This process was repeated until a total of 500 mL of limonene had been added. An additional 2.4 g of aluminum chloride was added, and the mixture was reacted for four hours with continuous stirring.

[0078] The reaction was quenched with 500 mL of 30% aqueous isopropanol. The aqueous layer was siphoned off and the mixture was washed with two additional 500 mL portions of aqueous isopropanol. The hydrocarbons were slowly and incrementally removed by vacuum distillation (rotary evaporator) until the final temperature was 90°C and the vacuum was 10-15 torr. Finally, the resin was refined by high temperature nitrogen sparging as described in US6121392 to Arizona Chemical Company, the entire contents of which are incorporated herein by reference. The resulting resin was a hard, off-white solid characterized by a softening point of 133°C as determined by the ring and ball method of ASTM E-28-58T and a glass transition temperature of 87.4°C as determined by DSC differential scanning calorimetry at a heating rate of 10 K / min.

[0079] Example 2: Resin from 8% Limonene ELT Oil

[0080] To a 3-liter neck flask equipped with a mechanical stirrer, nitrogen, and a thermocouple, 210 mL of toluene, 175 mL of isooctane, and 11.8 grams of aluminum chloride were added. The reaction mixture was cooled to 14°C in a water bath. 50 mL of ELT oil and 0.12 g of methanol initiator were then added to the mixture. The temperature was raised to 29°C, and the mixture turned orange-amber. The mixture was cooled to 20°C, and then additional portions of ELT oil were added. This process was repeated until a total of 500 mL of ELT oil had been added. An additional 2.4 grams of aluminum chloride was added, and the mixture was reacted for four hours under continuous stirring.

[0081] The reaction was quenched with 500 mL of 30% aqueous isopropanol. The aqueous layer was siphoned off and the mixture was washed with two additional 500 mL portions of aqueous isopropanol. The hydrocarbons were slowly and incrementally removed by vacuum distillation (rotary evaporator) until the final temperature was 90°C and the vacuum was 10-15 Torr. Finally, the resin was purified by high temperature nitrogen sparging as described in U.S. Pat. No. 6,121,392 to Arizona Chemical Company, the entire contents of which are incorporated herein by reference. The resulting resin was a hard, off-white solid characterized by a softening point of 75.5°C as measured by the ring and ball method of ASTM E-28-58T and a glass transition temperature of 19.9°C as measured by DSC differential scanning calorimetry at a heating rate of 10 K / min.

[0082] Example 3: Resin from 15% Limonene ELT Oil

[0083] The samples were prepared as described in Example 2, with ELT oil distilled twice to have a 15% limonene content.

[0084] The resulting resin is a semi-hard amber solid characterized by a softening point of 66.9° C. as determined by the ring and ball method of ASTM E-28-58T and a glass transition temperature of 14.1° C. as determined by DSC (differential scanning calorimetry) at a heating rate of 10 K / min.

[0085] Table II

[0086]

[0087]

[0088] Table III characterizes exemplary resin materials according to aspects of the exemplary embodiments.

[0089] Table III

[0090]

[0091] Based on the description provided herein, the present invention can be varied. Although certain representative embodiments and details have been shown for the purpose of illustrating the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the scope of the present invention. Therefore, it should be understood that changes can be made in the specific embodiments described, and these changes will be within the full expected scope of the present invention as defined by the appended claims.

Claims

1. A hydrocarbon resin comprising the reaction product of the polymerization of waste tire (ELT) oil monomers and having a Tg of about -30°C to about 140°C, a softening point of about 10°C to about 170°C, and a molecular weight Mw of 100 to 5000 Da.

2. The resin of claim 1, wherein the ELT oil is derived from thermal depolymerization of tires and / or other rubber products.

3. The resin of claim 2, wherein the ELT oil is derived from the thermal depolymerization of substantially whole tires.

4. The resin of claim 1, wherein the ELT oil is derived from thermal depolymerization of cured and / or uncured rubber production plant waste.

5. The resin according to claim 1, wherein the hydrocarbon resin is formed only from ELT oil monomers.

6. The resin according to claim 1, wherein the hydrocarbon resin is formed by copolymerizing ELT oil monomers with other hydrocarbon fractions.

7. The resin according to claim 6, wherein the hydrocarbon fraction is selected from the group comprising C5, C9, AMS, DCPD, rosin, phenol, epoxy resin, sole or mixtures thereof.

8. The resin of claim 1, wherein the resin is hydrogenated.

9. A tire having a tread and / or a carcass compound, the tread and / or carcass compound comprising: at least one rubber selected from the group consisting of natural rubber, rubber derived from diene monomers, and mixtures thereof; and The ELT oleyl hydrocarbon-based resin of claim 1.

10. A method of forming a resin from ELT oil, the method comprising the steps of: Obtaining ELT oil obtained by thermal depolymerization of waste tires (ELTS); and ELT oils are polymerized to produce ELT hydrocarbon-based resins.

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