Methods for synthesizing polar waxes and polyketones

Abstract

A method for producing oxidized forms of waxes (polar waxes) or polyketones containing oxygen functional groups from polypropylene (PP), polystyrene (PS), and / or polyethylene (PE), which can be used as lubricants, adhesives, coating agents, etc. In one or more examples, hydroperoxides were used as oxidants to cleave C-C and C-H bonds at mild temperatures (e.g., 150°C). C-C bond cleavage reduces the number average molecular weight (M n ) is reduced to 500-5000 g / mol. This method has been successfully applied to the conversion of post-consumer polyolefin waste to produce polar waxes or polyketones.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of commonly assigned, co-pending U.S. Provisional Application No. 63 / 433,849 entitled "METHOD OF SYNTHESIZING POLAR WAXES," filed December 20, 2022 by Hyunjin Moon, Fumihiko Shimizu, Kazuki Fukumoto, and Susannah L. Scott, which is incorporated herein by reference.

[0002] Background of the Invention 1. Field of the Invention The present disclosure relates to methods for synthesizing polar waxes (e.g., those containing carbonyl groups) and polyketones from polyolefins, for example, by oxidative cleavage of polyolefins. [Background technology]

[0003] 2. Description of Related Technology Polyolefins are essential in our daily lives due to their excellent chemical stability and physical properties that can be tailored to various applications through inexpensive manufacturing methods. However, the use of single-use plastics by consumers leads to undesirable plastic waste, which has relatively low biodegradability. To reduce the environmental impact of this waste, plastics can be recovered and mechanically recycled, but this process reduces the thermal and mechanical robustness of the recycled plastics and only delays the time for landfilling for non-biodegradable plastic waste. This drawback limits the range of applications for recycled plastics and reduces the incentive for this type of recycling. Therefore, there is a need for plastic upcycling technologies that convert discarded plastics into value-added products and also decompose relatively quickly under natural conditions. The present disclosure simultaneously meets both of these needs. Summary of the Invention [Means for solving the problem]

[0004] Summary of the Invention This invention presents a method for producing oxidized forms of wax by converting polypropylene (PP), polystyrene (PS), or polyethylene (PE). The process is carried out at mild reaction temperatures (e.g., 150°C) using a peroxide (e.g., tert-butyl hydroperoxide (TBHP)) solution in a sealed reactor filled with either air or an inert gas. The presence of oxygen-containing functional groups, such as carbonyls, acids, esters, and alcohols, in the oxidation products was confirmed by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy, as well as elemental analysis and titration. Oxidized waxes impart various functionalities by blending with or in combination with other types of materials and / or by further converting the oxygen-containing groups to other functional groups. For example, oxidized waxes, which are more polar than hydrophobic waxes, can be used as additives added to or mixed with polar materials to obtain compositions with new properties (e.g., mechanical properties).

[0005] Exemplary embodiments of the present invention include, but are not limited to, the following. 1. A method for synthesizing a wax or polyketone, comprising: A method comprising reacting a polyolefin with a peroxide in the presence of a solvent under conditions including a temperature of less than 200°C, wherein at least one of a carbon-carbon bond or a carbon-hydrogen bond of the polyolefin is cleaved by oxidation with the peroxide to form a polyketone or a wax comprising an oxidized polyolefin. 2. The method of embodiment 1, further comprising catalyzing said reaction with a catalyst that decomposes said peroxide so that oxygen from said peroxide can more readily react with said polyolefin. 3. The method of embodiment 1, further comprising catalyzing said reaction using [Fe(III)SO4] or MnBr2. 4. The method of embodiment 2 or 3, wherein the peroxide is hydrogen peroxide, the solvent is water, and the reaction forms a polyketone. 5. The method of claim 2 or 3, wherein the peroxide is TBHP, the solvent is water, and the reaction forms a wax. 6. The method of embodiment 5, wherein the wax has a molecular weight of 500 or less, or 1000 or less. 7. The method of embodiment 1, further comprising controlling at least one of the composition of the peroxide, the temperature, and the duration of the reaction to select the wax or the polyketone. 8. The method of embodiment 1, wherein the peroxide comprises a hydroperoxide and the polyolefin comprises at least one of polyethylene, polystyrene, or polypropylene. 9. The method of embodiment 1 or 8, further comprising selecting the weight percent of the peroxide in the solution relative to the mass of the polyolefin to achieve a desired molecular weight of the oxidized polyolefin, a lower weight percent of the peroxide resulting in a higher molecular weight of the oxidized polyolefin. 10. 10 wt% to 200 wt% of the peroxide in the solution relative to the mass of the polyolefin in the solution; or contacting said peroxide with said polyolefin in a molar ratio comprising moles of monomer units (in said polyolefin) divided by moles of said peroxide in a range of from about 0.5 to about 20; 10. The method of any of embodiments 1-9, comprising: 11. The method of any of embodiments 1 or 7-10, wherein the solvent comprises any hydrocarbon solvent capable of at least partially dissolving the polyolefin. 12. The method of embodiment 1, wherein the peroxide comprises a hydroperoxide, the solvent comprises water, and the polyolefin comprises polyethylene. 13. The method of any of embodiments 1 or 7-12, wherein the oxidized polyolefin comprises a carbonyl. 14. The method of any of embodiments 1 or 7-13, wherein the oxidized polyolefin comprises a ketone oxygen content greater than its ester and carboxylic acid oxygen content. 15. The one or more waxes have a number average molecular weight (M n 15. The method of any of embodiments 1 or 7-14, wherein the amount of peroxide and the reaction time of the reaction are selected so as to have a polydispersity in the range of 1.2 to 2.5. 16. The method of any of embodiments 1 or 7-15, wherein the temperature is greater than 100°C and less than 200°C. 17. One or more waxes synthesized by the method of any of embodiments 1-3 or 5-16. 18. The method of any one of claims 1 to 17, further comprising contacting untreated plastic waste comprising at least the polyolefin (and, e.g., optionally, at least one of any additives, impurities, or other polyolefins) with the solvent. 19. A composition of matter comprising an oxidized polyolefin having at least one of the following: a number average molecular weight in the range of 500 to 5000 g / mol and optionally a dispersity index in the range of 1.2 to 2.5, an oxygen content characterized by a saponification value in the range of 30 to 200 (30≦saponification value≦200) or 30 to 150 (30≦saponification value≦150), wherein the saponification value is the amount of potassium hydroxide in milligrams required to saponify 1 gram of the oxidized polyolefin; an oxygen content characterized by an acid value in the range of 15 to 100, the acid value being the amount in milligrams of potassium hydroxide required to neutralize 1 g of oxidized polyolefin dissolved in xylene; The oxygen content is 3 to 15 wt.% relative to the mass of the oxidized polyolefin (for example, 3 wt.%≦oxygen content≦15 wt.%) a ketone oxygen content greater than the ester and carboxylic acid oxygen content, or Alcohol oxygen content of approximately 1-4 wt%. 20. The composition of embodiment 19, wherein the oxidized polyolefin has a melting point in the range of 70 to 120°C. 21. The composition of embodiment 19 or 20, wherein the oxidized polyolefin is characterized by a saponification number that is equal to or higher than the saponification number of an oxidized polyolefin formed by oxidation of a molten polyolefin by melt oxidation, oxidation of said polyolefin in an aqueous dispersion, or oxidation of said polyolefin in solid form. 22. The composition of any of claims 19-21, wherein the oxidized polyolefin comprises oxidized polypropylene, oxidized polyethylene, or oxidized polystyrene. 23. A lubricant, adhesive, or coating comprising the wax according to any one of claims 19 to 22. 24. An oxidized polyolefin having the structure: Methyl ketone [ka] , internal ketone [ka] , carboxylic acid [ka] , t-butyl ester [ka] , tert-alcohol [ka] , sec-alcohol [ka] 24. The composition of any of embodiments 19-23, comprising: 25. The composition of any of embodiments 19-24, synthesized using the method of any of claims 1-3 or 6-18, wherein the polyolefin comprises at least one of polypropylene, polyethylene, or polystyrene. 26. Precursors from which oxidized polyolefins can be synthesized, Untreated plastic waste containing polyolefins, and a solution containing peroxide and polyolefins at least partially dissolved in a solvent Precursors, including: 27. A mixture comprising the precursor of embodiment 26 and an oxidized polyolefin formed by oxidation of said polyolefin with said peroxide. A polyketone with an oxygen content greater than 28.4 wt %, the ketone content being greater than the content of said ester. 29. The polyketone of embodiment 28 synthesized by the method of any one of claims 1-4, wherein the polyolefin comprises LDPE. 30. The following structure: [ka] 30. The polyketone of any one of embodiments 28 to 29. 31. A reactor for synthesizing oxidized polyolefins from plastic waste, comprising: a container for containing a solution comprising peroxide and said polyolefin; a temperature sensor connected to the pressure vessel for regulating the temperature of the solution; one or more openings in the pressure vessel for transferring at least one of the solution or the solvent into the pressure vessel; a control circuit for controlling the temperature and reaction time of an oxidation reaction in which carbon-carbon and / or carbon-hydrogen bonds of the polyolefin are cleaved by oxidation with the peroxide to form a polyketone or one or more waxes including an oxidized polyolefin; and an opening for removing the oxidized polyolefin from the pressure vessel; A reactor comprising: 32. The method or composition of any of the embodiments, wherein said oxidized polyolefin has a molecular weight of 2000 g / mol or less. 33. The solvent comprises at least completely or partially dissolving the polyolefin before or after the oxidation is initiated; or Swelling and / or softening the polyolefin before or after the oxidation is initiated. 33. The method of any of embodiments 1-32, wherein the rate of the oxidation reaction is increased by: 34. The method of any of embodiments 1-33, wherein the solvent dissolves the peroxide. 35. The method of any of embodiments 1-34, wherein the solvent at least increases the rate of the oxidation or decreases the temperature at which the oxidation occurs.

[0006] Reference will now be made to the drawings, in which like reference numbers represent corresponding parts throughout. [Brief explanation of the drawings]

[0007] [Figure 1] (a) Molecular weight distributions of oxidized iPP obtained after reaction with iPP (green) and 1.0 mL of TBHP solution (5.5 M in n-decane) at 150 °C: one 24-h period (purple) and two 24-h periods (blue). 0.4 g of iPP (Mn 54,000 g / mol, Mw = 340,000 g / mol) was used. (b) Molecular weight distributions of various PPs before (solid line) and after (dotted line) oxidation. Reaction conditions: 0.4 g PP, 1.0 mL of TBHP (5.5 M, decane), 150 °C, 24 h.

[0008] [Figure 2]Molecular weight distribution of oxidized PP (red) obtained from a mixture of iPP and aPP. Reaction conditions: 0.133 g each of low MW iPP, high MW iPP, and aPP, 1.0 mL of TBHP (5.5 M in decane), 150 °C, 24 h.

[0009] [Figure 3] Evolution of (a) molecular weight (Mn) and (b) polydispersity (D) over time for high / low MW iPP. Reaction conditions: 0.4 g iPP, 1.0 mL TBHP (5.5 M in decane), 150 °C.

[0010] [Figure 4] IR spectra of iPP (0.400 g, Mn 54,000 g / mol, D = 6.5): (a) before and (b–d) after 24 h of reaction at 150 °C. Reaction conditions: (b) TBHP (1.0 mL, 5.5 M in n-decane) in air, (c) TBHP (1.0 mL, 5.5 M in n-decane) in N, and (d) n-decane (1.0 mL) in air.

[0011] [Figure 5] (a) IR spectra of oxy-iPP1 and oxy-iPP2. (b) Expanded region showing the different carbonyl groups.

[0012] [Figure 6] (a) 1H and (b) 13C NMR spectra of oxidized iPP in solution. Reaction conditions: 0.4 g of iPP (Mn 54,000, D = 6.5), 1.0 mL of TBHP (5.5 M in decane), 150 °C, 24 h.

[0013] [Figure 7] 1H-13C 2D HSQC NMR of oxy-iPP1. Reaction conditions: 0.4 g of iPP (Mn 54,000 and Mw 350,000 g / mol), 1.0 mL of TBHP (5.5 M in decane), 150 °C, 24 h.

[0014] [Figure 8]1H-13C 2D HMBC NMR spectrum of oxy-iPP1. Peaks marked with red circles indicate correlations between methyl protons and tertiary alcohol carbons, as shown in the chemical structure. Reaction conditions: 0.4 g iPP (Mn 54,000, Mw 350,000 g / mol), 1.0 mL TBHP (5.5 M in decane), 150 °C for 24 h.

[0015] [Figure 9-1] Effect of TBHP:PP ratio on the IR spectra of PP and oxy-PP for (a) low-MW iPP (Mn 8,300 g / mol, D 2.8), (b) high-MW iPP (Mn 54,000 g / mol, D 6.5), and (c) aPP (Mn 6,700 g / mol, D 4.1). [Figure 9-2] Effect of TBHP:PP ratio on the IR spectra of PP and oxy-PP for (a) low-MW iPP (Mn 8,300 g / mol, D 2.8), (b) high-MW iPP (Mn 54,000 g / mol, D 6.5), and (c) aPP (Mn 6,700 g / mol, D 4.1).

[0016] [Figure 10] Effect of TBHP:PP ratio on GPC analysis of various PP and oxy-PP.

[0017] [Figure 11] IR spectrum of oxidized post-consumer PP. Reaction conditions: 0.4 g of post-consumer PP, 1.0 mL of TBHP (5.5 M in decane), 150 °C, 24 hours.

[0018] [Figure 12ab] (a) Information on the molecular weight of used PP before and after oxidation. (b) Changes in molecular weight distribution of used PP before and after oxidation. Reaction conditions: 0.4 g used PP, 1.0 mL TBHP (5.5 M in decane), 150 °C, 24 hours. (c) Formation of methyl ketones, alcohol esters, esters, and peresters by oxidation of PP. [Figure 12c](a) Information on the molecular weight of used PP before and after oxidation. (b) Changes in molecular weight distribution of used PP before and after oxidation. Reaction conditions: 0.4 g used PP, 1.0 mL TBHP (5.5 M in decane), 150 °C, 24 hours. (c) Formation of methyl ketones, alcohol esters, esters, and peresters by oxidation of PP.

[0019] [Figure 13ab] (a) Molecular weight distribution and (b) IR spectroscopic characterization of various PEs and their oxidation products. (c) Expanded region showing the OH stretch of alcohols. The IR spectrum of oxy-PE shows the ketone stretch at 1712 cm-1. Reaction conditions: 0.27 g PE, 1.0 mL TBHP (5.5 M, decane), 150 °C, 24 h. [Figure 13c] (a) Molecular weight distribution and (b) IR spectroscopic characterization of various PEs and their oxidation products. (c) Expanded region showing the OH stretch of alcohols. The IR spectrum of oxy-PE shows the ketone stretch at 1712 cm-1. Reaction conditions: 0.27 g PE, 1.0 mL TBHP (5.5 M, decane), 150 °C, 24 h.

[0020] [Figure 14] IR spectra of various grades of PE and their oxidation products, expanded in the 1800–1600 cm-1 region for oxy-LDPE1, oxy-HDPE1, and oxy-UHMWPE. Reaction conditions: 0.267 g PE, 1.0 mL TBHP, 150 °C, 24 h.

[0021] [Figure 15] IR spectra of oxidized (a) HDPE and (b) LDPE (reaction conditions: PE 0.267 g, TBHP 1.0 mL, 150 °C, 24 h). Further oxidation with TBHP gave oxy-HDPE2 and oxy-LDPE2.

[0022] [Figure 16]Molecular weight distribution of oxidized (a) HDPE and (b) LDPE (reaction conditions: PE 0.267 g, TBHP 1.0 mL, 150 °C, 24 h). Further oxidation with TBHP gave oxy-HDPE2 and oxy-LDPE2.

[0023] [Figure 17] 1H-13C 2D HSQC NMR of oxidized HDPE. Reaction conditions: HDPE 0.267 g (Mn 18,000 g / mol, D=16), TBHP (5.5 M in decane) 1.0 mL, 150 °C, 24 h.

[0024] [Figure 18] H-C 2D HSQC NMR of oxidized (a) HDPE and (b) LDPE. Correlations between methine protons and secondary carbons of the alcohol are marked with red circles. Reaction conditions: 0.267 g HDPE (or LDPE), 1.0 mL TBHP (5.5 M in decane), 150 °C, 24 h.

[0025] [Figure 19a] a. IR spectra of PE oxidized with H2O2 solution at various temperatures. Reaction conditions: 0.267 g of PE (Mn 1740 g / mol, D 2.5), 1.0 mL of H2O2 (30 wt% in H2O), 24 h. b. Oxidation of PE to form internal ketones, alcohols, carboxylic acids, and ester chain ends. [Figure 19b] a. IR spectra of PE oxidized with H2O2 solution at various temperatures. Reaction conditions: 0.267 g of PE (Mn 1740 g / mol, D 2.5), 1.0 mL of H2O2 (30 wt% in H2O), 24 h. b. Oxidation of PE to form internal ketones, alcohols, carboxylic acids, and ester chain ends.

[0026] [Figure 20](a) GPC results of polystyrene (PS) and oxidized PS products. (b) IR spectra of PS and oxidized PS. The shaded region at approximately 1700 cm-1 indicates the formation of carbonyl groups (e.g., carboxylic acids, phenyl ketones). The broad peak at 3400 cm-1 indicates the formation of alcohol groups on the chain. Reaction conditions: 0.40–0.99 g of PS (Mn 112,000 g / mol, D 2.3), 1.0 mL of TBHP (5.5 M in n-decane), 150 °C, 24 h.

[0027] [Figure 21] Characterization of oxy-PP / PE by (a) IR and (b) GPC. GPC analysis of the starting polymer is also shown. Reaction conditions: 0.100 g each of high and low molecular weight iPP, LDPE, and HDPE (total 0.400 g), 1.5 mL of TBHP (5.5 M in decane), 150 °C, 24 hours.

[0028] [Figure 22] (a) HDPE / iPP (white HDPE and green iPP bottles, labeled) tested for oxidative cleavage to polar waxes. Molecular weights before (black) and after (blue) the oxidation reaction are shown. (b) IR characterization of oxy-PP / PE obtained from a blend of post-consumer HDPE and PP.

[0029] [Figure 23] General reaction scheme for the selective catalytic oxidation of LDPE.

[0030] [Figure 24a] IR spectrum of oxy-LDPE. Reaction conditions: 0.05 g LDPE (Mw 56,000, D 6.1), 1 mL tBuOOH (70 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 24 hours.

[0031] [Figure 24b]Deconvolution of the C=O stretching (carbonyl) peak centered at 1716 cm-1. IR spectrum of oxy-LDPE. Reaction conditions: 0.05 g LDPE (Mw 56,000, D 6.1), 1 mL tBuOOH (70 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 24 hours.

[0032] [Figure 25] (a) Evolution of molecular weight (MW) of oxy-LDPE over time obtained by GPC analysis. (b) IR spectrum showing evolution of carbonyl peak intensity over time. Reaction conditions: 0.05 g LDPE (MW 56,000, D 6.1), 1 mL tBuOOH (70 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 24 h.

[0033] [Figure 26] (a) IR spectrum showing the evolution of the carbonyl peak intensity of oxy-LDPE over time. (b) GPC Mw evolution over time. Reaction conditions: 0.05 g LDPE (Mw 56,000, D 6.1), 1 mL H2O2 (30 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 15–24 h.

[0034] [Figure 27a] Solution-state NMR spectra of oxidized LDPE: (a) 1H NMR and (b) 2D 1H-13C HSQC NMR. Reaction conditions: 0.05 g LDPE (MW 56,000, D 6.1), 1 mL H2O2 (30 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 15–24 h. [Figure 27b] Solution-state NMR spectra of oxidized LDPE: (a) 1H NMR and (b) 2D 1H-13C HSQC NMR. Reaction conditions: 0.05 g LDPE (MW 56,000, D 6.1), 1 mL H2O2 (30 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 15–24 h.

[0035] [Figure 28]IR spectra of LDPE (green) and oxy-LDPE prepared by oxidation with TBHP (light blue) or H2O2 (dark blue). Reaction conditions: 0.05 g LDPE (MW 56,000, D 6.1), oxidant (1 mL of 30 wt% H2O2 in H2O or 1 mL of 70 wt% TBHP in H2O), 2.5 wt% MnBr2, 110°C for 24 hours.

[0036] [Figure 29] GPC of oxy-LDPE prepared by oxidizing LDPE with TBHP (light blue) or H2O2 (dark blue).

[0037] [Figure 30-1] Comparison of IR spectra of oxy-LDPE obtained with various catalysts: (a) Anion effect: MnBr2 (light blue), Mn(NO3)2 (gray-blue), and no catalyst (green). (b) Cation effect: MnBr2 (light blue), KBr (green), and no catalyst (purple). Reaction conditions: 0.05 g LDPE (MW 56,000, D 6.1), oxidant (1 mL of 30 wt% H2O2 in H2O or 1 mL of 70 wt% TBHP in H2O), 2.5 wt% catalyst, 110 °C for 24 h. [Figure 30-2] Comparison of IR spectra of oxy-LDPE obtained with various catalysts: (a) Anion effect: MnBr2 (light blue), Mn(NO3)2 (gray-blue), and no catalyst (green). (b) Cation effect: MnBr2 (light blue), KBr (green), and no catalyst (purple). Reaction conditions: 0.05 g LDPE (MW 56,000, D 6.1), oxidant (1 mL of 30 wt% H2O2 in H2O or 1 mL of 70 wt% TBHP in H2O), 2.5 wt% catalyst, 110 °C for 24 h.

[0038] [Figure 31] Proposed mechanism for the oxidation of LDPE. [Figure 32a]Comparison of IR spectra of oxy-LDPE prepared by oxidation with excess H2O2 (red) or oxy-substoichiometric H2O2 (orange). Reaction conditions: 0.05 g LDPE (MW 56,000, D 6.1), oxidant (1 mL of 30 wt% H2O2 in H2O), 2.5 wt% MnBr2, 110 °C for 24 hours. Excess H2O2: 5.5 equivalents of H2O2 (9.8 mmol, 1 mL of 30 wt% H2O2 in H2O) for 1 equivalent of LDPE (1.8 mmol, 50 mg). Substoichiometric amount of H2O2: 0.5 equivalents of H2O2 (0.75 mmol, 0.08 mL of 30 wt% H2O2 in H2O) for 1 equivalent of LDPE (1.8 mmol, 50 mg).

[0039] [Figure 32b] IR spectra of oxy-LDPE. Reaction conditions: 0.05 g LDPE (MW 56,000, D 6.1), 1 mL tBuOOH (70 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 8 hours (orange spectrum); 0.05 g LDPE (MW 56,000, D 6.1), 1 mL H2O2 (30 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 24 hours (blue spectrum).

[0040] [Figure 32c] Molecular weight (MW) of oxy-LDPE obtained by GPC analysis. Reaction conditions: 0.05 g LDPE (MW 56,000, D 6.1), 1 mL tBuOOH (70 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 8 hours (blue line), 0.05 g LDPE (MW 56,000, D 6.1), 1 mL H2O2 (30 wt% in H2O), 2.5 wt% MnBr2, 110 °C for 24 hours (green line).

[0041] [Figure 33a](a) IR spectroscopic characterization of LDPE (blue) and oxy-LDPE (orange) prepared by reacting LDPE with TBHP in isooctane (0.5 mL) with FeSO4 as a catalyst at 100 °C for 24 h. The ketone stretching mode appears at 1714 cm-1. (b) GPC analysis of the CHCl3-soluble fraction of oxy-LDPE. [Figure 33b] (a) IR spectroscopic characterization of LDPE (blue) and oxy-LDPE (orange) prepared by reacting LDPE with TBHP in isooctane (0.5 mL) with FeSO4 as a catalyst at 100 °C for 24 h. The ketone stretching mode appears at 1714 cm-1. (b) GPC analysis of the CHCl3-soluble fraction of oxy-LDPE.

[0042] [Figure 34] IR spectroscopic characterization of LDPE (green), oxy-LDPE (a) prepared by reacting LDPE (0.05 g) with TBHP (1 mL, 70 wt% in H2O) + MnBr2 (2.5 wt%) at 110 °C for 24 h, and oxy-LDPE (b) prepared by reacting LDPE (0.05 g) with H2O2 (0.5 mL, 30 wt% in H2O) + MnBr2 (2.5 wt%) at 110 °C for 24 h. The ketone stretching mode appears at 1714 cm-1.

[0043] [Figure 35] Solution-state NMR spectrum of oxidized LDPE: 1D 1H NMR in CDCl3. Reaction conditions: LDPE (0.05 g) was reacted with TBHP (1 mL, 70 wt% in H2O) + MnBr2 (2.5 wt%) at 110 °C for 24 h.

[0044] [Figure 36] Solution-state NMR spectrum of oxidized LDPE: 2D 1H-13C HSQC NMR in CDCl3. Reaction conditions: LDPE (0.05 g) was reacted with TBHP (1 mL, 70 wt% in H2O) + MnBr2 (2.5 wt%) at 110 °C for 24 h.

[0045] [Figure 37] Comparison of the IR spectra of LDPE before (blue) and after (orange) oxidation of LDPE (0.05 g) with a solution of Ti(OPri)4 (10 wt%) and TBHP (1 mL, 5.5 M in n-decane) at 100 °C for 24 h.

[0046] [Figure 38] Comparison of the IR spectrum of oxy-LDPE (orange) prepared using the heterogeneous Ti-sylopol catalyst and H2O2 with that of oxy-LDPE (blue) obtained using Ti(OPri)4 and TBHP.

[0047] [Figure 39] reported 4 thermal oxidation of PE using O2 in scCO2.

[0048] [Figure 40] Comparison of IR of oxy-LDPE (orange) obtained by reaction with H2O2 in scCO2.

[0049] [Figure 41] 1 is a flow chart showing a method for synthesizing waxes or polyketones. DETAILED DESCRIPTION OF THE INVENTION

[0050] Detailed Description of the Invention In the following description of the preferred embodiment, reference is made to the accompanying drawings, which form a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention. Technical Description

[0051] The present disclosure describes a method for synthesizing a wax, the method comprising forming a solution comprising a peroxide and a polyolefin at least partially dissolved in a solvent, and initiating a reaction between the polyolefin and the peroxide under conditions comprising a temperature of less than 200° C., wherein carbon-carbon bonds of the polyolefin are cleaved by oxidation with the peroxide to form one or more waxes comprising oxidized and cleaved polyolefins. The following sections describe various embodiments of the method. [Example]

[0052] First Example Depolymerization of PP by oxidative cleavage. The first example demonstrates a new approach to the oxidative cleavage of various PPs under uncatalyzed reaction conditions using tert-butyl hydroperoxide (TBHP) as the oxidant. TBHP solution (5.5 M in n-decane) can dissolve the starting isotactic PP (iPP) at 150 °C.

[0053] GPC analysis of the oxy-iPP product obtained by TBHP-mediated oxidation revealed that the oxidation reaction resulted in the number-average molecular weight (M n ) and weight average molecular weight (M w ) are both M n 54,000 (D=6.5) to M n The molecular weight of oxy-iPP1 was dramatically reduced to 1,620 g / mol (D = 1.8) (Figure 1a), indicating that TBHP cleaves the C-C bond of iPP. To further reduce the molecular weight, oxy-iPP1 recovered after 24 hours of reaction at 150 °C was heated overnight at 70 °C in an oven to remove volatiles (unreacted TBHP, decane, t-butanol, and decane oxygenates). After a second reaction at 150 °C for 24 hours with the same amount of TBHP, the molecular weight of oxy-iPP1 was reduced to 1,620 g / mol (D = 1.8). n 1,620 g / mol (D = 1.8) to the M of oxy-iPP2 n It decreased to 900 g / mol (D = 1.7) (Fig. 1a).

[0054] The same reaction was carried out for low / high MW iPP and atactic PP. As shown in the molecular weight distributions in Figure 1b, the oxidized PPs exhibited similar M regardless of their initial molecular weight, dispersity, and tacticity. n The results show that the longer the chain, the more C-C bond cleavage events occur, while the shorter the chain, the fewer C-C bond cleavage events occur. Therefore, the results suggest that TBHP-mediated oxidation of PP is beneficial for the treatment of waste PP, as this oxidation reaction yields oxidation products with similar molecular weights, as shown in Figure 2.

[0055] The following sections describe various characterizations of the wax formed according to the first example.

[0056] 1. The molecular weight of the wax product decreases with increasing reaction time.

[0057] Random chain cleavage should result in an initial rapid decrease in average chain length, followed by a gradually smaller decrease as the number of chains increases. n The initial decrease in iPP was rapid, from 54,000 g / mol to approximately 4,000 g / mol within the first hour, followed by a much slower decrease to approximately 1,600 g / mol after 24 hours (Figure 3a). This slower decrease is due to the slower rate of TBHP consumption for the oxidation of iPP (0.92 mmol / h before 1 hour compared to 0.02 mmol / h between 3 and 6 hours). Thus, the majority of the oxidation reaction was complete within 6 hours. 2. Identification of oxidants

[0058] The IR spectra of iPP and oxy-iPP1 are compared in Figure 4. In the spectrum of oxy-iPP, the peak at 1714 cm -1 A strong new peak with a maximum at 3400 cm is characteristic of the carbonyl group (Figure 4b). -1The broad peak of oxy-iPP1 near 1712 cm indicates the formation of an alcohol. Control experiments were performed under N2 with TBHP and in air without TBHP to identify the oxidant. The product generated under N2 by TBHP is indeed at 1712 cm. -1 In contrast, the IR spectrum of the product obtained without the use of TBHP has a strong peak at approximately 1712 cm -1 (Fig. 4d) Therefore, only TBHP, not air, is involved in the formation of the carbonyl group and presumably the associated C-C bond cleavage. 3. Characterization of carbonyl functional groups in oxidized PP by IR spectroscopy

[0059] The IR spectra of oxy-iPP1 and oxy-iPP2 are shown in Figure 5a. Increased carbonyl and hydroxyl peak intensities were observed in oxy-iPP2. The carbonyl group peak region is enlarged in Figure 5b. -1 In addition to the ketone peak with a maximum intensity at 1740 cm, the ester peak (approximately 1740 cm) -1 ), peresters and / or γ-lactones (approximately 1760–1790 cm -1 ) are present, representing carboxylic acids (approximately 1700 cm -1 ) overlaps with the IR signal of the ketone group. 4. Characterization of oxy-iPP1 using NMR spectroscopy

[0060] The chemical structure of oxy-iPP1 is shown below. 1 H and 13 Oxy-iPP1 was characterized by C NMR spectroscopy. 1 In the H NMR spectrum, a sharp peak at approximately 2.1 ppm and a small peak at approximately 2.4 ppm were assigned to the methyl and methylene protons adjacent to the terminal (methyl) ketone (Figure 6a), which is consistent with TBHP cleavage of the CC backbone of PP. 13In the C NMR spectrum, apart from the three carbon resonances typical of iPP, additional small peaks at approximately 30 and 51 ppm were observed (Figure 6b), which are attributed to the primary and secondary carbons located adjacent to the terminal ketone, respectively.

[0061] The assignment of the methyl ketone was confirmed by 2D HSQC NMR, which shows a strong correlation between the signals of the methyl protons and the methyl carbons attached to the ketone (red circles, Figure 7). The peaks marked with blue circles show correlation between the methylene protons and the methylene carbons attached to the ketone (Figure 7).

[0062] In the HSQC NMR spectrum, 2.3 / 34 ppm ( 1 H / 13 A correlation in C) is also evident (Figure 7a, orange circle), which is assigned to the methylene group adjacent to the ester carbonyl. 1 The H signal is due to the methyl proton of the tBu ester. The tBu group originally comes from TBHP. This is 1.4 / 28( 1 H / 13 The carbon peak (green circle) at 1.2 / 74 (C) ppm correlates with the carbon peak at 1.2 / 74 (C) ppm. Comparison with the chemical shifts of t-butyl propionate confirmed the assignment to the tBu ester. In addition, the 2D HMBC NMR spectrum showed a 1.2 / 74 ( 1 H / 13 C) shows the correlation between the methyl protons and the tertiary carbon attached to the alcohol group in ppm (Figure 8). 5. Effect of TBHP:PP ratio

[0063] To optimize the TBHP:PP ratio, experiments were performed using 400 mg of PP and TBHP volumes ranging from 0.5 mL to 1.5 mL. For all three PP materials (low / high MW iPP and aPP), increasing the amount of TBHP from 0.5 mL to 1.0 mL resulted in a peak of approximately 1700 cm. -1The relative intensity of the C=O stretching mode in the PP-1000 series increased (Figure 9). However, further increasing the concentration to 1.5 mL did not result in a further increase in peak intensity. The GPC results are consistent with this interpretation of the IR spectra: the use of 0.5 mL of TBHP resulted in a significant increase in the M of the three types of oxy-PP. n At 1.0 mL of TBHP, values ​​of 1900, 2100, and 2300 g / mol were observed, with further reductions for all PP types, but at 1.5 mL of TBHP, further reductions were found to be negligible (Figure 10). Higher amounts of TBHP result in more C-C bond cleavage overall, but a corresponding increase in the amount of decane solvent also results in more decane oxygenates.

[0064] The TBHP:PP ratio can also be expressed as wt.%, so the experiments described above correspond to 10-200 wt.% TBHP (relative to the mass of PP). However, as previously mentioned, this range can be adjusted depending on the desired molecular weight of the oxidized PP. For example, at 60 wt.% TBHP, the MW of the wax product was approximately 2300 g / mol. Using a lower amount of peroxide results in a higher final molecular weight of the wax. 6. Expansion to used PP

[0065] The oxidation of PP with TBHP can be applied to post-consumer PP. Various PP samples (white and blue disposable masks, white or black disposable coffee cup lids, coffee capsules, and centrifuge tubes) were subjected to the reaction conditions described above. The IR spectra of each oxidized material showed a strong carbonyl peak (approximately 1700 cm). -1 ) was observed (Figure 11), consistent with the results for pure PP. Even in the presence of unknown additives, the oxidized post-consumer PP showed a significant decrease in molecular weight after the oxidation reaction (an M of approximately 2,400 g / mol for the coffee cup lid and coffee capsule). n , and a mixture of centrifuge tubes and white and blue disposable masks had an M of approximately 1,600 g / mol. n )(Figure 12). Second Example Oxidative cleavage of polyethylene (PE)

[0066] Oxidative cleavage of PE with TBHP was carried out at 150 °C. As shown by GPC (Figure 13a), significant chain scission was observed for various PE grades (LDPE, HDPE, and ultra-high MW PE), with similar final molecular weights (M of approximately 1,000 g / mol). n ) The IR spectrum of oxy-PE confirms the presence of both carbonyl groups (Figure 13b) and alcohol groups (Figure 13c).

[0067] When the peak region of the carbonyl group of oxidized PE is enlarged (Figure 14), the peak at 1714 cm -1 The ketone peak at 1700 cm -1 ), ester (approximately 1740 cm -1 ), and perester / γ-lactone (approximately 1780 cm -1 ) is clearly overlapped with an additional peak of carboxylic acid. The origin of the carboxylic acid may be the formation of an aldehyde end group resulting from C-C bond cleavage, followed by further oxidation of the aldehyde to a carboxylic acid. Further reaction of the oxidized PE with TBHP resulted in a higher carbonyl peak intensity (Figure 15) and a decrease in molecular weight from approximately 1000 g / mol to approximately 500 g / mol (Figure 16). Therefore, the oxygen content and chain length can be easily adjusted by the amount of TBHP used in the reaction.

[0068] The HSQC NMR of oxy-HDPE shows correlations between the CH2 groups adjacent to the ketone (red circle, Figure 17), as well as between the CH2 groups adjacent to the ester and carboxylic acid groups (orange circle). The correlation between the CH3 groups of the t-butyl ester (green circle) suggests that some ester groups are formed by the reaction of the carboxylic acid groups with t-butanol. The methine proton peak and the 3.6 / 72 ( 1 H / 13 C) The correlation between the carbons of the secondary alcohols in ppm (Figure 18) confirms the formation of these alcohol groups. Third Example Use of different solvents and peroxides

[0069] In one example, PE(M n 1740 g / mol, PDI 2.5) or LDPE (M n When 10,500 g / mol (PDI 8.1) of ethylenediamine diisopropyl ether (PE) was reacted with HO (30 wt%) in HO (solvent) at 150 °C, oxidized PE was formed, as confirmed by IR spectroscopy (Figure 19). Under these conditions, a homogeneous solution was also achieved. Cumene hydroperoxide and TBHP were also successfully used together as peroxide sources to form oxidized PE.

[0070] We screened multiple solvents to find one that solubilizes LDPE at T ≤ 150°C. The results are shown in Table 1. Ideally, a good solvent should be less easily oxidized than the polymer. Given the competitive oxidation reactions between the solvent and the polymer substrate, the goal is to solubilize the substrate in as little solvent as possible.

[0071] LDPE was found to be soluble in isooctane and partially soluble in DCE at 100°C. Consequently, isooctane was chosen for the oxidation of LDPE with peroxide to study the effect of low temperature on chain scission and incorporation of oxygen into the polymer chain. [Table 1] Fourth Example Polystyrene oxidation

[0072] PS can also be oxidized with peroxide in a similar manner. Figure 20a shows that the molecular weight of PS changes from 112,000 g / mol to several thousand g / mol after oxidation with TBHP. The IR spectrum of oxidized PS shows a peak at 1700 cm -1 A new peak at 3400 cm was observed, indicating the formation of carbonyl groups such as carboxylic acids and phenyl ketones (Figure 20b). -1 The broad peak at confirms the formation of alcohol groups on the chain. Fifth Example Oxidation of PP-PE mixtures

[0073] In one example, a mixture of PP and PE was simultaneously oxidized and converted to a polar wax. A mixture made from high and low molecular weight iPP, LDPE, and HDPE (0.100 g each, 0.400 g total) was heated with TBHP (1.5 mL, 5.5 M in n-decane) at 150 °C for 24 hours. IR spectra of the product confirmed that it contained a mixture of oxy-iPP and oxy-PE (Figure 21a). GPC analysis confirmed that the oxy-PP / PE mixture had a low molecular weight and a narrow molecular weight distribution (M n 1,430 g / mol, D = 2.3, Figure 21b). Thus, PP and PE can be processed together to produce polar waxes. Sixth Example Oxidation of post-consumer HDPE and iPP blends

[0074] A mixture of HDPE and iPP bottles containing color additives and labels (Figure 22a) was oxidized. n The oxidative cleavage of PP and PE wastes with TBHP is applicable to the conversion of these wastes to oxidized wax under relatively mild conditions without the need for a catalyst. Seventh Example Determination of saponification degree, acid value, and total oxygen content

[0075] Table 1 shows the results of measuring the saponification number and acid number, as well as the total oxygen content, of various oxidized polyolefins. The method for obtaining molecular weight (MW) is explained in Appendix B of the priority application, U.S. Provisional Application No. 63,433,849. [Table 2]

[0076] Reaction conditions: Oxy-iPP1: 0.4 g iPP, 1.0 mL TBHP (5.5 M in decane), 150 °C, 24 h. Oxy-HDPE1 and Oxy-LDPE1: 0.267 g HDPE or LDPE, 1.0 mL TBHP (5.5 M in decane), 150 °C, 24 h. Oxy-PP / PE: 0.1 g each of low and high MW iPP, 0.1 g HDPE, 0.1 g LDPE, 1.5 mL TBHP (5.5 M in decane), 150 °C, 24 h. Oxy-iPP2, Oxy-HDPE2, and Oxy-LDPE2: After drying the reactor containing the oxidation product, an additional 1 mL of TBHP was added. The reaction was again carried out at 150 °C for 24 h.

[0077] The saponification number is the amount of potassium hydroxide in milligrams required to saponify one gram of oxidized polyolefin. KOH reacts with both the carboxylic acid and ester groups of the oxidized polyolefin. The amount of KOH that reacts is the saponification number. By varying the amount of peroxide and the duration of the oxidation reaction, or the number of times the reaction is repeated, the saponification number can be varied within the range of (30≦saponification number≦200).

[0078] The acid number is the amount of potassium hydroxide, in milligrams, required to neutralize 1 gram of oxidized polyolefin dissolved in xylene. By varying the amount of peroxide and the duration of the oxidation reaction, or the number of times the reaction is repeated, the acid number can be varied from 15 to 100.

[0079] To estimate the oxygen content of alcohol groups, an acetylation reaction was carried out. Acetylation converts alcohol groups into esters. The increase in the amount of esters was obtained by measuring the saponification number of the acetylated product.

[0080] Total oxygen content was determined by CHN (carbon, hydrogen, nitrogen) elemental analysis. Since the material does not contain nitrogen, the wt% of oxygen in the oxidation product was calculated by subtracting the carbon and hydrogen contents from 100 wt%. Eighth Example Investigation of the dissolution process

[0081] Without being bound to any particular scientific theory, oxidation and dissolution can proceed according to a wide variety of scenarios.

[0082] First scenario: Polyolefins can dissolve in solvents at a set temperature and then react with peroxide oxidants.

[0083] Second scenario: Polyolefin is partially dissolved in the solvent at a set temperature, and the dissolved part reacts first, then the undissolved part dissolves and reacts in the same process. Evidence: At 140°C, iPP (Mn: 97kJ, M w :340kJ) was not completely dissolved in 1.0 mL of TBHP (5.5 M decane) at 140 C. Therefore, in the case of oxidation of iPP, iPP was partially dissolved.

[0084] Third scenario: The polyolefin softens and swells or melts in the solvent, forming two liquid phases with the solvent. The peroxide penetrates and reacts with the polymer, oxidizing it. The partially oxidized polymer and solvent form a homogeneous solution. Solubility and oxidation [Table 3]

[0085] Our data show that iPP is solid in H2O2 / H2O at 150 °C. However, PE melts at 150 °C, resulting in the separation of PE and H2O2 / H2O phases. When the PE chains are oxidized by H2O2, a homogeneous solution of oxidized PE and water is achieved. Additionally, even though PE is only partially soluble in decane at 150 °C, the PE chains are oxidized by TBHP, resulting in the formation of a homogeneous solution of oxidized PE chains and decane during the reaction. For oxidized iPP in the liquid state, no improvement in oxidation is achieved with a TBHP / H2O solution. Therefore, for iPP, "dissolution" is required for oxidation. Therefore, our data (see, for example, slides 22-26 of Appendix C of the priority application, U.S. Provisional Application No. 63,433,849) indicate that effective oxidation using peroxide requires PP / PE in a solution or melt. PE can be efficiently oxidized by peroxides both in solution and in the melt due to its relatively low melting temperature (approximately 160°C for iPP, approximately 110°C for LDPE, and 130°C for HDPE). However, much higher temperatures (>160°C) are required to melt iPP; however, at such high temperatures, peroxides rapidly decompose, making the reaction ineffective. Therefore, oxidation of polyolefins in hydrocarbon solvents can be used to lower the reaction temperature to obtain commercially reasonable reaction rates while avoiding undesirably high temperatures at which peroxides may decompose.

[0086] Since both PP and PE are at least partially soluble in hydrocarbon solvents such as decane under the experimental conditions (temperature, loading, etc.), the use of hydrocarbon solvents can be useful to enhance oxidation at relatively low temperatures. Ninth Example

[0087] An approach has been discovered for the selective oxidation of LDPE. This method uses peroxide as the oxidant, water as the reaction medium, and MnBr2 as the catalyst at 110°C (Figure 23). When the oxidant is tert-butyl hydroperoxide (TBHP), oxidation occurs primarily at the tertiary carbons of the LDPE branch points, resulting in the cleavage of C-C bonds along the polymer backbone and the formation of oligomers (M) with ester and ketone functional groups. w <600 g / mol, D=1.2). By changing the oxidant to H2O2, this process redirects the selective cleavage to the C-H bond of the secondary carbon, resulting in a polyketone-like product with an internal ketone on the backbone and a methyl ketone on the branch. Small amounts of esters are also formed. This innovative oxidation process of LDPE using H2O2 represents the first synthetic strategy for obtaining polyketone-like structures by direct oxidation of PE. Results and Discussion 1. Product Characterization

[0088] At the beginning of the reaction (time = 0), LDPE is insoluble in the reaction medium (water) under the reaction conditions (110 °C). However, as oxidation progresses, the solubility of LDPE increases. After 24 hours, the solution appears homogeneous. When the reaction mixture is cooled to room temperature, the product begins to precipitate as a white solid. (i) Using TBHP as the oxidant to obtain small oxygenated oligomers

[0089] 0.05g of LDPE (M w The data were obtained using reaction conditions of 110 °C for 24 hours using 56,000, D6.1), 1 mL of tBuOOH (70 wt % in H2O), and 2.5 wt % MnBr2.

[0090] IR analysis of oxy-LDPE obtained as a result of MnBr2-catalyzed oxidation of LDPE with TBHP at 110 °C for 24 h showed a band at 1714 cm corresponding to the carbonyl stretching mode. -1 A sharp peak at 3300–2500 cm -1A closer look at the carbonyl region reveals the most intense peak (1712 cm) assigned to the ketone. -1 ), plus esters (approximately 1740 cm -1 ) and carboxylic acids (1700cm -1 ) is evident. [1] The presence of carboxylic acid groups is also consistent with OH stretching.

[0091] The intensity of the carbonyl peak in the IR spectrum is directly proportional to the level of oxygen incorporation into oxy-LDPE. Figure 25b shows how the intensity of this peak increases with reaction time, indicating a gradual increase in oxygen content from 8 to 24 hours. These results from Figures 25a and 25b suggest that oxidation proceeds by cleavage of C-C bonds in the polymer backbone, i.e., by a β-scission mechanism. Figures 25a and 25b show that oxidation of M w It clearly shows that the β-saturation decreases over time with increasing oxygen content.

[0092] The data in Figures 25a and 25b are w This indicates that the low molecular weight wax, D = 570, D1.2, has alternating ketones, terminal ketones, esters, and internal ketones containing hydroxy groups. Surprisingly, no acid groups were detected by NMR and titration. 1 As identified by H NMR and hypothesized from IR analysis, traces of lactone groups are present in the wax (Figure 24b). From elemental analysis, the wax has a total oxygen content of 14.3 wt% and a saponification number of 124 mg KOH / g. For these results, 0.05g of LDPE was used in the oxidation reaction. Different amounts and ratios were studied, but the standard condition was 50mg of LDPE. (ii) Use of H2O2 as an oxidant to obtain polyketones

[0093] The data were obtained using reaction conditions of 50 mg LDPE + 2.5 wt% MnBr2 + 1 mL H2O2 (30 wt% in H2O) at 110 °C for 24 hours.

[0094] When TBHP is replaced with H2O2, the IR spectrum of the oxy-LDPE product shows a gradual increase in the carbonyl peak intensity over time (Figure 26a). However, the molecular weight remains almost unchanged as the reaction proceeds (Figure 26b). (The molecular weight M of the polyketone under these reaction conditions is w is 49000 with D = 6.1). In this case, oxygen was incorporated onto the polymer backbone without significant chain scission, suggesting a C-H bond cleavage mechanism.

[0095] The chemical structure of oxy-LDPE is 1 The compound was further characterized by H NMR (Figure 27a). A strong multiplet at approximately 2.4 ppm is assigned to the methylene protons α to the internal carbonyl. This signal is consistent with a C—H bond cleavage mechanism. 1 No H NMR peaks are observed. Interestingly, at 2.2 ppm there is a sharp singlet characteristic of a methyl proton adjacent to a ketone. The methyl ketone may arise from oxidation of a branch in the LDPE structure.

[0096] In the 2D HSQC NMR, strong correlations are observed for the methylene groups α and β to the internal ketone (green circles, Figure 27b). Cross-peaks at 2.1 ppm and approximately 30 ppm are assigned to the methyl groups α to the terminal ketone (yellow circles, Figure 27b). Ester groups are also present. Thus, oxy-LDPE has a polyketone-like structure with both internal ketones on the backbone, ester groups at the chain ends, and methyl ketones at the branch ends.

[0097] Thus, the data indicates that the polyketone has ester and ketone groups (non-alternating), the majority of the ketone groups are internal ketones, and the total oxygen content in the polyketone is 4.2 wt%.

[0098] The composition of this polyketone indicates that it has application as a barrier polymer or any application where improved adhesion is required. We hypothesize that this polyketone is biodegradable, considering (4) (e.g., soil, marine, compost, or landfill environments).

[0099] Under the reaction conditions of 50 mg LDPE + 2.5 wt% MnBr + 1 mL H2O2 (30 wt% in H2O) at 130 °C for 24 h, the carbonyl peak has the same intensity as when TBHP is used at 110 °C for 24 h, indicating that higher oxidation efficiency and increased oxygen content are achieved by increasing the reaction temperature.

[0100] For these results, 0.05g of LDPE was used in the oxidation reaction. Different amounts and ratios were studied, but the standard condition was 50mg of LDPE. (iii) Role of oxidants

[0101] Figure 28 shows the IR spectra of oxy-LDPE products made using TBHP or H2O2 at 1712 cm -1 The intensities of the carbonyl stretching peaks in HCl and HCl are compared after 24 hours of reaction. TBHP clearly gives a product with a higher carbonyl content than HO. Also, the products made with different peroxides have significantly different molecular weights (Figure 29).

[0102] Therefore, the selectivity of the process is strongly influenced by the choice of peroxide. When TBHP is used, the reaction leads to oxidative C-C bond cleavage. In contrast, when H2O2 is utilized, no significant chain scission occurs. This difference may be due to the conformation of the polymer chains in the two reaction solutions. A more extended or open conformation should provide better access to internal sites on the polymer chain, promoting more extensive oxidation and chain scission, whereas a folded or closed conformation may only allow access to external surface sites on the polymer, limiting the extent to which the polymer chains are oxidized. 2. The role of catalysts

[0103] The role of the catalyst was studied by varying both the metal and the anion. LDPE was oxidized with TBHP in water at 110 °C for 24 h. When the catalyst was Mn(NO3)2 (i.e., no bromide), the intensity of the carbonyl peak was significantly reduced compared to the reaction catalyzed by MnBr2 (Figure 30a). A similar reduction was observed when the catalyst was KBr (Figure 30b). Thus, both Mn(II) and bromide appear to play a role in the catalytic cycle.

[0104] Oxidation mechanism: Based on results already obtained in our laboratory, we propose a possible mechanism for the oxidation of LDPE: Mn(II) is oxidized to Mn(III) by peroxides, and Mn(III) is oxidized to Br - The oxidation of the polymer is initiated by the Br radical abstracting an H atom from the LDPE backbone, resulting in secondary and / or tertiary carbon-based radicals (Scheme 1) [2]. This reaction also converts Br to Br - Reduce to. [ka] Scheme 1. Initiation steps in the oxidation of LDPE

[0105] Depending on the nature of the polymer radical generated, there are several possible propagation paths. If a tertiary carbon-centered radical is generated, the radical can be captured by O2 (formed by peroxide disproportionation) and ultimately form a tertiary alkoxy radical that undergoes β-scission, resulting in an alkyl ketone-terminated chain and a new primary radical (Figure 31). Secondary carbon-centered radicals are oxidized to secondary alkoxy radicals, which can undergo C-H bond cleavage to give an internal ketone, H-atom abstraction to give a tertiary alcohol, or C-C bond cleavage to give an aldehyde-terminated chain and a new alkyl radical [3]. Further oxidation of the aldehyde gives a carboxylic acid, which can react with an alcohol (such as tert-butanol) present in the reaction mixture to give an ester.

[0106] When TBHP is used as the oxidant, the reaction proceeds primarily by oxidative C-C bond cleavage, suggesting that the major pathway involves tertiary alkoxy radicals undergoing β-scission. In contrast, when H2O2 is used as the oxidant, the reaction proceeds primarily by C-H bond cleavage, suggesting that the major pathway involves secondary alkoxy radicals.

[0107] 2.5 wt% of the catalyst MnBr2 was determined to be the optimum catalyst amount for forming wax and polyketone. 3. Role of peroxides and oxidants

[0108] Peroxides (either TBHP or H2O2) convert Mn(II) to Mn(III) and / or Br -Peroxide can act as an initiator by oxidizing HO to Br·. Peroxide can also serve as an oxygen source for LDPE. In the benchmark reaction conditions, peroxide is used in excess. When the amount of HO was reduced to a substoichiometric amount of 0.5 (0.5 equivalents per ethylene monomer repeat unit), the degree of oxidation decreased dramatically. When peroxide was not present in excess, the intensity of the carbonyl stretching peak decreased significantly (Figure 32a). This indicates that HO is the primary oxygen source in the reaction. Similar results were obtained with TBHP. 4. Study of model compounds to gain insight into reaction mechanisms

[0109] From our study of the oxidation of n-octadecane, we conclude that at low conversions, the selectivity is the same for both peroxides (i.e., after 1 hour of reaction with TBHP and after 24 hours of reaction with HO). In both cases, the initial oxidation product is formed by C-H bond cleavage. The origin of the large rate difference may simply be the higher solubility of alkanes in aqueous TBHP compared to aqueous HO. Although both oxidants are soluble in water, the presence of high concentrations of TBHP (and tBuOH as the reaction progresses) likely increases the solubility of the alkanes and therefore their apparent reactivity.

[0110] To understand how chain branching affects the mechanism, we studied the oxidation of squalane as a model compound. The organic products were identified by GC-MS. After 24 h, the conversion was approximately 85%, similar to that obtained for the oxidation of C-18 (n-octadecane) under the same conditions. However, the squalane products differed from those obtained with C-18. Specifically, methyl ketones, esters, and carboxylic acids were present, but internal ketones were not detected. These products suggest that in the presence of branching, H-atom abstraction occurs primarily at tertiary carbons. The preferential formation of tertiary radicals is favored, and their subsequent oxidation leads to the production of methyl ketones via β-scission. We also investigated the reaction of squalane with HO. After 24 h at 110 °C, the conversion was approximately 5%. Oxidative cleavage of the C-C bond was minimal. As a result, TBHP appears to be more reactive toward squalane than HO.

[0111] Our model compound studies provide valuable insight into the unexpected difference in selectivity in the oxidation of LDPE by the two peroxides. During the early stages of TBHP oxidation, the abundant methylene carbons undergo rapid oxidation via C-H bond cleavage. The methine carbons, which are more reactive but less abundant, are oxidized more slowly. Reaction of the methine carbons results in extensive chain scission. In contrast, when H2O2 is used, oxidation is slower and limited to the more abundant methylenes. 5. Adjusting the reaction duration

[0112] As described above, selective oxidation in low-density polyethylene (LDPE) can be tuned through strategic selection of oxidant and reaction duration. In this example, we compare the effects of H2O2 and TBHP on the oxidation of LDPE using MnBr2 as a catalyst at 110 °C. Both oxidants initiate the oxidation of LDPE similarly through C-H bond cleavage, resulting in comparable levels of oxy-LDPE with similar oxygen content and molecular weight. However, extended reaction with TBHP uniquely induces further oxidation through C-C bond β-scission. These insights demonstrate the potential for controlling the selectivity and extent of LDPE oxidation and provide a route for synthesizing tailored polyketone-like materials by adjusting the type of oxidant and reaction time. These findings are consistent with observations obtained through analyses using model compounds.

[0113] IR spectroscopic analysis of oxidized LDPE (oxy-LDPE) produced by the MnBr2-catalyzed oxidation of LDPE with H2O2 at 110 °C for 24 h, and oxy-LDPE produced from the MnBr2-catalyzed oxidation of LDPE with TBHP at 110 °C for 8 h (Figure 32b), showed a peak at 1714 cm -1 A prominent peak at 0°C was revealed, which is indicative of the carbonyl stretching mode and showed similar intensities in both samples.

[0114] The intensity of the carbonyl peak in the IR spectrum is directly proportional to the degree of oxygen incorporation into oxy-LDPE. Consequently, these experimental findings suggest that the oxygen content of both oxy-LDPE samples is remarkably similar. [Table 4]

[0115] GPC analysis of the oxy-LDPE samples (Figure 32c, Table 4) also revealed that their molecular weights were remarkably similar, thereby suggesting that the initial stage of oxygen incorporation into the LDPE matrix occurs primarily through C-H bond cleavage, regardless of whether TBHP or H2O2 is used as the oxidant. However, prolonging the reaction with TBHP beyond 8 hours leads to further oxidation of LDPE through beta-scission of C-C bonds, resulting in the formation of small oxygenated oligomers. In contrast, when H2O2 is utilized, the reaction occurs primarily through C-H bond cleavage.

[0116] In both scenarios, the primary oxidation product is generated by C-H bond cleavage. The significant variation in reaction rates may be due to the higher affinity of LDPE for TBHP solution compared to aqueous H2O2. Although both oxidants are solubilized in water, TBHP is more easily integrated into the hydrophobic polymer matrix and therefore ostensibly exhibits enhanced reactivity.

[0117] Without being bound to any particular scientific theory, it is possible to synthesize polyketone-like materials by fine-tuning the selection of oxidant and the duration of the reaction. Tenth Example Use of different types of catalysts and reaction media 1. Oxidation catalyzed by iron [Fe(III)SO4]

[0118] Fenton and Fenton-like oxidations have been reported to degrade microplastics. A typical Fenton-like reaction of Fe(III) salts with TBHP, which generates alkoxy and peroxy radicals, is shown in Scheme 2. [ka] Scheme 2. Fenton-like mechanism for TBHP activation

[0119] LDPE (0.05 g) was heated with 0.5 mL of TBHP (1 mL, 5.5 M in n-decane) in decane in the presence of an Fe(III) catalyst (1 wt%) at 100 °C for 24 h. IR of the oxy-LDPE product confirms the presence of C=O stretching typical of ketones (Figure 33a). This oxy-LDPE, which is slightly soluble in CHCl3, was analyzed by GPC. The results show significant chain scission (Figure 33b), and the yield of the soluble fraction appears to be approximately 40%. However, high-temperature GPC is required to properly quantify the extent of CC scission. 2. MnBr2-catalyzed oxidation

[0120] Inspired by a recent report on the use of an AMOCO-like process for the oxidative depolymerization of mixed plastic waste [2], we explored the oxidation of LDPE with peroxide using MnBr2 as a catalyst. After initial optimization of the reaction conditions, the best conditions involved reacting LDPE (0.05 g) with either TBHP (1 mL, 70 wt% in H2O) + MnBr2 (2.5 wt%) or H2O2 (0.5 mL, 30 wt% in H2O) + MnBr2 (2.5 wt%) at 110 °C for 24 h.

[0121] In both reactions, oxy-LDPE was recovered as a soft white solid. The product was analyzed by IR (Figure 34) and 1 The compound was analyzed by H NMR (Figures 27a and 35). Both IR spectra showed a peak at 1712 cm -1 The relative intensity is stronger when the oxidant is TBHP than when it is H2O2. 1 The H NMR spectrum shows signals for methylene (approximately 2.38 ppm) and methyl (approximately 2.16 ppm) protons located α to the internal ketone and methyl ketone chain ends. 1In the H NMR spectrum, a proton located β to the ester group is detected. From the relative peak integrations, we can state that the amount of internal ketones generally exceeds that of terminal methyl ketones, and the ratio is higher when the oxidant is TBHP compared to HO. The latter finding is consistent with TBHP inducing more extensive C-C bond cleavage than HO, which is likely a way to adjust the target molecular weight of oxy-LDPE.

[0122] Figure 36 13 In the C NMR spectrum, the signal at approximately 42 ppm is associated with a secondary carbon located alpha to the internal ketone. 3. Oxidation catalyzed by Ti(OiPr)4

[0123] Ti complexes catalyze the oxidation of olefins with peroxides. Specifically, Ti(OPr i )4 (titanium isopropoxide, or Ti(OiPr)4) catalyzes the oxidation of olefins with TBHP in solution at room temperature. [3] In this section, we decided to explore homogeneous Ti catalysts for the oxidation of LDPE.

[0124] LDPE (0.05 g) was mixed with a solution of Ti(OiPr)4 (1 wt%) and TBHP (1 mL, 5.5 M in n-decane) at 100 °C for 24 h. The oxy-LDPE product, recovered as a pale yellow solid, was analyzed by IR and 1 The IR spectrum (Figure 37) showed a peak at 1712 cm -1 The peak shows a strong ketone peak at 1.5, its broadness and lack of symmetry suggesting overlapping ester peaks. 1The H NMR spectrum was initially recorded in CDCl3, in which only a portion of the solid product was soluble. The presence of the ester was confirmed by a singlet at 1.45 ppm. Other peaks at 2.4 ppm and 2.1 ppm were assigned to methylene and methyl protons located α to the internal ketone and methyl ketone chain ends. A sharp peak at approximately 2.16 ppm, assigned to the methyl proton adjacent to the terminal ketone chain end, indicates C—C bond cleavage on the PE backbone. Peak integration of the terminal methyl and methylene protons reveals that the ketone is primarily located on the PE backbone. In fact, the integral for the proton α to the internal ketone is five times larger than the integral for the methyl proton α to the ketone chain end. The peaks characteristic of aldehydes, ethers, and carboxylic acids are 1 No 1 H NMR peaks were observed.

[0125] To better solubilize oxy-LDPE, NMR experiments were also performed on a 1:1 mixture of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and C6D6. The presence of methylene and methyl protons alpha to the internal ketone and chain-terminal ketone groups was confirmed, but the signals appeared to overlap, causing integration problems. Additionally, a peak of unknown origin was present at 1.81 ppm.

[0126] These results reveal a predominantly internal ketone compared to oxidation with TBHP, which at 150 °C gave primarily terminal ketones. 4. Ti-Sylopol catalyzed oxidation

[0127] Titanium silicalite (TS-1) was reported to catalyze the oxyfunctionalization of alkanes to alcohols and ketones with aqueous H2O2 [4]. Based on this, we decided to explore heterogeneous Ti catalysts for the oxidation of LDPE.

[0128] Because the micropores of TS-1 are difficult to access for macromolecules such as LDPE, we synthesized a Ti-coated mesoporous silica catalyst by reacting TiCl4 with Sylopol at room temperature. After the reaction, the material was calcined at 500°C.

[0129] LDPE (0.05 g) and HO (0.5 mL, 30 wt % in HO) were reacted in the presence of Ti / silica catalyst (10 wt %) at 100 °C for 24 h. After 24 h, the spent solid catalyst was separated from the reaction mixture by centrifugation, and the oxy-LDPE product was recovered as a white solid. Its IR spectrum is shown in Figure 38 (orange line), which confirms the presence of the C=O stretch typical of ketones. However, the carbonyl peak is not present in Ti(OPr i ) 4 (Figure 38, blue line).

[0130] The reactivity obtained in heterogeneous phase experiments is promising. However, the product is insoluble in both CHCl3 and HFIP / C6H6 (1 / 1). More suitable solvents and reaction conditions (oxygen source, reaction time) can be used. 5. Supercritical CO2 as a reaction medium

[0131] Recent literature has shown that O2 dissolved in supercritical CO2 (scCO2) is effective for the thermal oxidation of polyethylene at 140 °C (Figure 39[5]).

[0132] After 24 hours, the products were ethylene oligomers (whose oxygen content was not specified) and small molecules such as acetic acid, formic acid, and propionic acid. Based on this, we decided to use scCO as the reaction medium in our system and to use H2O2 as the oxidant instead of O2 for safety reasons and because it is likely to be effective at lower reaction temperatures.

[0133] To achieve supercritical conditions, the Parr reactor was connected to a high-pressure CO2 tank.

[0134] A 30 mL Parr reactor was charged with LDPE (50 mg) and HO (1 mL, 30 wt % in HO), then pressurized with CO (1058 psi). The reaction was carried out at 110 °C. After 24 h, the reactor headspace was analyzed by GC-MS. The only hydrocarbon product detected was a trace of CH. The IR spectrum of the recovered white solid is shown in Figure 41.

[0135] 1714cm -1 The peak at indicates the presence of carbonyl groups in the oxy-LDPE product, but its low intensity suggests limited oxygen incorporation. Nevertheless, the presence of scCO2 enhanced the degree of oxidation, as no carbonyl signal was detected when the same reaction was carried out without scCO2. We believe this process is a promising candidate for further study. Process Step Examples

[0136] FIG. 41 is a flow chart illustrating a method for synthesizing a wax or polyketone according to one or more embodiments.

[0137] Block 4100 represents reacting a polyolefin with a peroxide in the presence of a solvent under conditions including a temperature of less than 200°C, wherein at least one of the carbon-carbon or carbon-hydrogen bonds of the polyolefin is cleaved by oxidation with the peroxide to form a polyketone, or a wax comprising an oxidized polyolefin.

[0138] This step may include contacting one or more peroxides and one or more polyolefins (e.g., polypropylene, polyethylene, or polystyrene) with a solvent (the solvent may be a co-solvent), or obtaining a composition comprising a solvent and peroxide and / or polyolefin. In one or more examples, this step includes obtaining untreated plastic waste (including one or more polyolefins) and contacting the plastic waste (including polyolefins, and optionally any additives, impurities, other polyolefins) with a solvent, e.g., to form a solution. In one or more examples, the polyolefin is contacted with a solution already containing dissolved peroxide. In other examples, the solution may include a homogeneous solution of peroxide and polyolefin.

[0139] In one example, the step includes selecting the weight percent of peroxide in the solution relative to the weight of the polyolefin to achieve a desired molecular weight of the wax containing the oxidized polyolefin. A lower weight percent of peroxide results in a higher molecular weight oxidized polyolefin. In one or more examples, based on the experimental data presented herein, 10 wt% to 200 wt% or 60 wt% to 2000 wt% of peroxide in the solution relative to the weight of the polyolefin may be used. In one or more further examples, the molar ratio of monomer units in the polyolefin to peroxide ranges from about 0.1 to about 10, or from 0.5 to about 20 (where lower values ​​indicate a higher amount of peroxide. For the data in Figure 19, PE and HO were used, and the molar ratio of monomer to peroxide in this experiment is about 2).

[0140] In some examples, a variety of solvents can be used, including, but not limited to, any hydrocarbon solvent capable of dissolving the polyolefin as the oxidation proceeds (e.g., decane, nonane, cyclohexane, methylcyclohexane, isooctane, toluene, and p-xylene).

[0141] Peroxides may include, but are not limited to, hydrogen peroxide, lithium peroxide, sodium peroxide, calcium peroxide, barium peroxide, zinc peroxide, or organic peroxides (e.g., cumene hydroperoxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, lauroyl peroxide, 2-butanone peroxide, benzyl peroxide).

[0142] The temperature at which a polyolefin dissolves in a solvent can depend on the polyolefin, solvent, oxidation, and amount of polyolefin. In one or more examples, 150°C is the lower limit of the temperature used to dissolve PP in decane. However, by increasing the amount of solvent and decreasing the amount of PP, the temperature at which the polyolefin becomes soluble can be lowered (e.g., to 120°C). Furthermore, under some conditions, PE or PP can be dissolved at temperatures lower than 150°C, such as 80°C (for PE in 1,2-dichloroethane) or 85°C (for PP in cyclohexane).

[0143] The conditions (including the temperature range) under which the oxidation reaction (and / or dissolution) of block 4100 is carried out can be selected depending on the desired rate of oxidation, dissolution, and / or decomposition of the reagent(s). In some examples, the oxidation reaction is carried out in a temperature range having a lower limit (e.g., 100°C) that allows the oxidation reaction rate to exceed a desired threshold, and an upper limit (e.g., 180-200°C) above which the oxidation rate does not increase significantly and / or the concentration of peroxides decreases below undesirable levels (due to the increased decomposition rate of peroxides at higher temperatures) and / or does not increase so much that such peroxide sources become explosive or otherwise uncontrollable. For example, at temperatures above 200°C, some peroxides may decompose into by-products that prevent the desired oxidation and cleavage of polyolefins (Type 1 decomposition) or into radical species that may still lead to the oxidation and cleavage of polyolefins (see, e.g., Equations 1-3, Type 2 decomposition, in Appendix A of U.S. Provisional Application No. 63,433,849, which is a priority application). Thus, the upper limit may be selected to avoid Type 1 decomposition, which would prevent oxidation, and / or to avoid excessively rapid decomposition / oxidation involving radical species (Type 2 decomposition), which leads to uncontrolled or undesirable side reactions. Because most decomposition / oxidation reactions are exothermic, excessively rapid reactions involving radicals at temperatures above 200°C can lead to thermal runaway or, in extreme cases, explosion. Thus, in one or more examples, the temperature ranges from 100 to 200°C.

[0144] Without being bound to any particular scientific theory, the polyolefin may be dissolved in a solvent prior to and / or during the oxidation reaction.

[0145] In one or more examples, the peroxide is added to the solution slowly or in multiple steps to maximize the reaction of the peroxide with the polyolefin and avoid excess peroxide decomposing before reacting.

[0146] In one or more examples, the amount of peroxide, solvent, and reaction time of the reaction are adjusted to provide a wax product with a number average molecular weight (M) in the range of 500 to 5000 g / mol. n ) and the polydispersity is selected to be in the range of 1.2 to 2.5 or 1.5 to 2.5.

[0147] In one or more further examples, the amounts of polyolefin and peroxide are adjusted to control at least one of the saponification number or acid number of the resulting oxidized polyolefin.

[0148] A catalyst can be added to aid in the decomposition of the oxidizing agent (e.g., peroxide). The composition of the oxidizing agent, the amount of oxidizing agent, the reaction temperature, and / or the duration of the reaction can then be selected to affect the selectivity of the reaction toward polyketone or wax as the product. Examples of catalysts include, but are not limited to, using [Fe(III)SO4] or MnBr2 to catalyze the reaction. In certain catalyzed reaction temperature embodiments where the peroxide is hydrogen peroxide and the solvent is water, the reaction forms a polyketone. In certain catalyzed reaction temperature embodiments where the peroxide is TBHP and the solvent is water, the reaction forms a wax (e.g., having a molecular weight of 500 or less, or 1000 or less).

[0149] Block 4102 represents the final result, i.e., the composition of the oxidized polyolefin formed by oxidizing the polyolefin. Examples of compositions include, but are not limited to, the following: 1. A composition comprising an oxidized polyolefin (polystyrene, polyethylene, and / or polypropylene, or a mixture thereof), wherein the oxidized polyolefin is: a number average molecular weight in the range of 500 to 5000 g / mol and optionally a dispersity in the range of 1.2 to 2.5; an oxygen content characterized by a saponification value in the range of 30 to 200 or 30 to 150, the saponification value being the amount of potassium hydroxide in milligrams required to saponify 1 gram of oxidized polyolefin; an oxygen content characterized by an acid value in the range of 15 to 100, the acid value being the amount in milligrams of potassium hydroxide required to neutralize 1 g of oxidized polyolefin dissolved in xylene; a total oxygen content of 3 to 15 wt.% relative to the mass of the oxidized polyolefin (e.g., 3 wt.%≦oxygen content≦15 wt.%); a ketone oxygen content greater than the sum of the ester and carboxylic acid contents, or Alcohol oxygen content of 1-4 wt% The composition having at least one of: 2. The composition of Example 1, wherein the oxidized polyolefin is characterized by a saponification number greater than the saponification number of a wax formed by oxidation of the polyolefin in molten form (melt oxidation), oxidation of the polyolefin in an aqueous dispersion, or oxidation of the polyolefin in solid form. 3. The composition of Examples 1 or 2, wherein the oxygen content is 2 to 5 times (typically 3 to 4 wt%) the oxygen content in the oxidized polyolefin formed by oxidation of the polyolefin in molten form. 4. The composition of Examples 1 or 2 or 3, wherein the oxidized polyolefin has a melting point in the range of 70 to 120°C (e.g., as measured by DSC). 5. The composition of Example 1, wherein the oxidized polyolefin is characterized by a polydispersity that is narrower than the polydispersity of a wax formed by oxidation of the polyolefin in molten form (melt oxidation), oxidation of the polyolefin in an aqueous dispersion, or oxidation of the polyolefin in solid form. 6. The composition of Example 1, comprising said oxidized polyolefin in which the amount of ketone is greater than the amount of ester and carboxylic acid according to the intensity of the carbonyl peak in the IR spectrum. 7. The composition of Example 1, wherein the oxidized polyolefin comprises oxy-PE, and the amount of carboxylic acid is similar to the amount of ester according to acid number and saponification number. 8. The composition of Example 1, wherein the oxidized polyolefin comprises oxy-iPP having an amount of acid greater than the amount of ester, or an amount of ester greater than the amount of acid. Thus, the amount of ester and acid can be controlled based on the reaction conditions. 9. The composition or method of any of the Examples, wherein the oxidation is catalyzed using, for example, [Fe(III)SO4] or MnBr2, or a transition metal-based catalyst (e.g., containing nickel or Cr, Mn, Co, Ti) as the active agent, for example, in combination with bromine, or using supercritical CO2 as the reaction medium. 10. The composition or method of any of the Examples, wherein the solvent, e.g., an organic solvent, dissolves the catalyst and plastic at the reaction temperature, allowing for a more homogeneous mixture and oxidation. In one or more embodiments, if the solvent is HO and the polymer is not dissolved at the start of the reaction, the reaction mixture appears homogeneous after several hours (e.g., >5 hours). 11. The composition of any of the Examples, wherein the organic solvent, and amount of solvent, is selected (making a trade-off) to dissolve the plastic and / or catalyst and oxidant while simultaneously reducing reaction of the solvent with the oxidant. 12. In one embodiment, peroxide (oxidizing agent) and water (solvent) are used to form polyketones after at least 24 hours at a reaction temperature of 100-200° C. The higher the temperature at which the reaction is carried out, the shorter the reaction time can be. 13. In one embodiment, the selection of polyketone and wax products for the oxidation of LDPE is as follows: As the oxidant, hydrogen peroxide can be used for at least 24 hours or TBHP for up to 8 hours to make polyketones by C—H cleavage. For TBHP, extending the reaction time beyond 8 hours will result in more TBHP being oxidized and waxes being formed by C—C cleavage (longer times will result in lower MW waxes). A polyketone having an oxygen content greater than 14.4 wt.% (e.g., 4 wt.%≦oxygen content≦4.2 wt.%, 4 wt.%≦oxygen content≦5 wt.%, 4 wt.%≦oxygen content≦5.5 wt.%, e.g., 4 wt.%≦oxygen content≦6 wt.%), wherein the ketone content is greater than the ester content. 15. The polyketone of embodiment 14, having a molecular weight change of less than 15% compared to the LDPE from which it is oxidized to the polyketone. 16. The polyketone of embodiments 14-15 synthesized by the method of any of the catalyzed embodiments, wherein the polyolefin comprises LDPE. 17. Structure: [ka] The polyketone of any one of embodiments 14 to 16. 18. The polyketone of any of embodiments 14-17, comprising a random distribution of ketones. 19. The polyketone of any of embodiments 14-18, comprising non-alternating ketone groups. 20. The polyketone of any of embodiments 14-19, wherein the amount and / or temperature of oxidation is controlled (e.g., increased) to increase the oxygen content within the limits where increasing oxidation and temperature increases C—C scission and decreases the molecular weight of the polymer, and thus, said oxidation can be increased as long as the molecular weight does not decrease below a predetermined threshold level. 21. The polyketone of any of embodiments 14-20, wherein (e.g., oxidation and / or reaction temperature and / or reaction duration) are such that the oxygen content and molecular weight of the polyketone are within controlled, predetermined ranges, and / or the molecular weight does not decrease by more than 15% compared to the molecular weight of the polyolefin (e.g., LDPE, PP, PE) from which it was oxidized to the polyketone. 22. The polyketone of any of embodiments 14-19, wherein the oxygen content is 4 wt%≦oxygen content≦4.2 wt%, 4 wt%≦oxygen content≦5 wt%, 4 wt%≦oxygen content≦5.5 wt%, for example, 4 wt%≦oxygen content≦6 wt%, and wherein the molecular weight is not reduced by more than 15% compared to the molecular weight of the polyolefin from which it was oxidized to the polyketone. 23. The polyketone or wax of any of embodiments 1-22, wherein the wt% oxygen content assumes that the product consists only of carbon, hydrogen, and oxygen, and the carbon and hydrogen contents are obtained using an elemental analyzer, and the amount of oxygen in the polyketone is calculated by subtracting the carbon and hydrogen contents from 100 wt%. 24. The polyketone or wax of any of embodiments 1-22, wherein the acid number, saponification number, alcohol content, or oxygen content is determined using the method described under the heading "3. Characterization Methods for Oxidized PP and PE" on pages 36-37 of the present application. 25. The method or composition of any of embodiments 1-14, wherein various reaction parameters (e.g., amount of oxidant, temperature, reaction time, and solvent) are selected to affect the oxygen content and molecular weight of the polyketone or wax (e.g., to control the fraction of CH and CC cleavages) to form polyketones and waxes with controlled oxygen content and molecular weight. 26. The method or composition of embodiment 25, wherein said increased oxidation increases both CH and CC cleavage, thereby decreasing the molecular weight of the polyketone. Block 4104 represents utilizing the composition for use as, for example, an additive, lubricant, adhesive, or coating reagent. Reactor Example

[0150] In a typical example, a reactor for synthesizing oxidized polyolefins from plastic waste includes a vessel (e.g., a pressure vessel) for containing a solution comprising peroxide and a polyolefin at least partially dissolved in a solvent. In one or more embodiments, the vessel is a pressure vessel or a sealed vessel (e.g., a glass pressure vessel) so that TBHP cannot escape from the reactor (the boiling point of TBHP is only 89°C at 1 atmosphere [4], so a sealed vessel can be used to prevent TBHP leakage in the reaction temperature range of 100-200°C). In another example, the vessel includes an open vessel connected to a condenser.

[0151] The reactor further comprises a temperature sensor, a heater, and a temperature control system (e.g., a cooler and / or heater) connected to the pressure vessel for regulating the temperature of the solution. One or more openings in the pressure vessel are used to transfer at least one of the solution or solvent to the pressure vessel. A control circuit (e.g., a computer controller) is used to control the temperature and reaction time of the oxidation reaction in which the carbon-carbon bonds of the polyolefin are cleaved by oxidation with peroxide to form one or more waxes, including the oxidized polyolefin. One or more openings are further used to remove the oxidized polyolefin from the pressure vessel.

[0152] The reactor can be configured to perform the method (or synthesize a composition) of any of Embodiments 1-26, or to perform the method of Figure 41. The reactor can include a computer / controller / circuitry for controlling the amount of oxidant, temperature, and reaction time. Advantages and Improvements

[0153] Conventional wax materials are produced in a similar manner to the production of polyolefins, using ethylene / propene as monomer units and a catalyst to link them together. Additionally, polar forms of wax are typically obtained from molten polyethylene using dioxygen as the oxygen source. In contrast, the present inventors have developed a process for producing wax by converting plastic waste (PE, PP, PS, and even their mixtures) by using a hydroperoxide source without an additional catalyst, making this process more affordable for industrial applications. Oxidized waxes derived from plastic waste can be easily controlled to a narrow molecular weight distribution, making them suitable for a variety of applications, such as lubricants, adhesives, paint additives, dispersants, and resin modifiers.

[0154] A similar process can also be used to produce polyketones by catalytic oxidation of LDPE while controlling the reaction solvent, time, temperature and oxidant loading. Supplementary Information: Materials and Methods Used to Obtain the Data in Examples 1-8 1. Chemicals

[0155] Two types of isotactic polypropylene (M n 54,000g / mol, D=6.5 (SKU-427861) and M n 8,300 g / mol, D = 2.8 (SKU: 428116)), amorphous polypropylene (M n6,700 g / mol, D = 4.1 (SKU-428175), high-density polyethylene (SKU-547999), low-density polyethylene (SKU-428043), ultra-high molecular weight polyethylene (SKU-429015), tert-butyl hydroperoxide solution (5.5 M in decane), n-decane (anhydrous, ≥ 99%), nonanal (95%), meta-chloroperbenzoic acid (≤ 77%), 4-methyl-2-pentanone (≥ 98.5%), benzaldehyde (≥ 98.5%), methyl 10-undecenoate (96%), 3-methylpentane (≥ 99%), squalane (96%), 2-methoxyethanol (99.9%), dihexyl ketone (97%), and lauric acid (≥ 98%) were purchased from Sigma-Aldrich. Chloroform-D (99.8%) was purchased from Cambridge Isotope Laboratories. Ethanol (200 proof) was obtained from Rossville Gold Shield. Xylene was purchased from MP Biomedicals. Potassium hydroxide (P250-500) was obtained from Fisher Chemical. Hydrochloric acid (36.5-38.0 wt%) was obtained from Millipore Corporation (Billerica, MA). All chemicals were used as received. 2. TBHP-Mediated Oxidation of Polyolefins and Model Chemicals

[0156] 0.400 g of PP and 0.5–1.5 mL of TBHP (5.5 M in n-decane) solution were added to a 15 mL glass pressure reactor, and the reactor opening was sealed with a bushing and a Kalrez O-ring. The glass pressure reactor was placed in an oil bath at the desired temperature and reaction time. After the reaction, the glass pressure reactor was cooled to room temperature using a water bath. The solid product was transferred to a glass vial with the aid of ethanol. The ethanol, decane, unreacted TBHP, and decane oxygenates were removed by RotaVap (130 mbar, 30 °C, approximately 20 min), followed by vacuum (0.1 mTorr, room temperature, overnight), and then drying at 70 °C for 8 h. This last step did not change the chemical composition of the oxidation product but only served to remove residual decane and decane oxygenates.

[0157] For the oxidative cleavage of PE, 0.267 g of PE was added to a glass pressure reactor containing a TBHP (5.5 M in n-decane) solution, and the subsequent procedure was the same as for the oxidative cleavage of PP.

[0158] For the PP model chemical, 3-methylpentane (3.9 mmol) or squalane (0.96 mmol) was added to a glass pressure reactor containing TBHP solution. The reactor opening was sealed with a bushing and a Kalrez O-ring. The reactor was placed in an oil bath at 150 °C for 24 h. For the oxidation of unbranched model hydrocarbons, a TBHP (5.5 M in n-decane) solution was heated under the same conditions. For GC analysis of the liquid-phase products, the products were diluted with ethanol. For NMR analysis, the products were diluted with CDCl3.

[0159] For analysis of gas-phase products obtained from the oxidation of polyolefins or model chemicals, a glass reactor with a side arm was used to collect the gas-phase products. After the reaction, the reactor was cooled to room temperature, and a rubber septum was fitted to the outlet of the side arm. The gas-phase products were extracted with a gas-tight syringe for GC-FID measurement. 3. Characterization Methods for Oxidized PP and PE

[0160] Gel Permeation Chromatography. To prepare for room-temperature gel permeation chromatography (RT-GPC), 4–6 mg of oxidized PP and 2.0 mL of chloroform containing 0.25% triethylamine (TEA) were added to a glass vial. The glass vial was placed in an oven at 80 °C for several minutes to completely dissolve the product. After the vial was cooled to room temperature, the solution was passed through a 0.45 μm filter for GPC analysis. GPC analysis was performed on a Waters Alliance HPLC system equipped with a 2690 Separation Module. The sample solution was passed through two Tosoh TSKgel SuperHZM-N columns and guards (MW linear range 200–700,000 g / mol). Analysis was performed using a Waters 2410 differential refractometer and a Waters 2998 photodiode array detector. A calibration curve was generated using polystyrene (PS) standards ranging from 162 to 1,044,000 g / mol.

[0161] A high-temperature GPC (HT-GPC) system was used to obtain the molecular weights of chloroform-insoluble oxidized PP, oxidized PE, pristine PP and PE provided by Sigma-Aldrich, and used iPP and HDPE. The samples were wrapped in a 26 μm metal mesh filter, prepared in a 0.1 wt% solution in o-dichlorobenzene (containing 0.5 g / L butylated hydroxytoluene), dissolved at 135 °C for 30 min, and filtered. Experiments were performed on an EcoSEC HLC-8321GPC / HT (Tosoh Biosciences) equipped with a TSKgel guard column HHR-HT (7.5 mm x 7.5 cm) and a TSKgel GPC column (GMHHR-H, 300 mm x 7.8 mm) calibrated with monodisperse polystyrene standards.

[0162] Molecular weights obtained based on polystyrene standards were converted to PP and PE standards using equation (S1).

number

[0163] M PSis the molecular weight obtained using PS standards. PS and a PS is the Mark-Houwink constant for polystyrene. K x and a PS is the Mark-Houwink constant for PP or PE, and M x is the converted molecular weight. Previously reported values ​​for these constants are used. 1~3 For the mixtures of oxidized PP and PE, the molecular weights reported in this paper were based on PP standards. The converted molecular weights by PE standards are presented in Figure S39.

[0164] Gas chromatography. The products in the liquid phase after the oxidation reaction and the reaction of the model compounds were qualitatively analyzed on a Shimadzu GC-2010 gas chromatograph equipped with an Agilent DB-1 capillary column (dimethylpolysiloxane, 30 m × 0.25 mm × 0.25 μm) connected to a QP2010 mass spectrometer. The injector and detector temperatures were 250 °C. The temperature program was 60 °C (hold for 2 min), then ramp to 270 °C at 15 °C / min (hold for 35 min).

[0165] The products in the gas phase were also analyzed using a Shimadzu GC-2010 gas chromatograph equipped with a capillary column (Supelco Alumina Sulfate plot, 30 m × 0.32 mm) and a flame ionization detector (FID). The relative carbon response factor was assumed to be 1.0. The injector and detector temperatures were 200 °C. The temperature program was 90 °C (hold for 5 min), then 10 °C / min to 150 °C (hold for 20 min).

[0166] NMR spectroscopy. Oxidized PP samples for NMR measurements were prepared by combining approximately 5 mg of oxidized sample with 1.0 mL of CDCl3 in a glass vial. The glass vial was placed in an oven at 80 °C for several minutes. After cooling to room temperature, approximately 700 μL of the solution was analyzed using an 800 MHz SB Bruker Avance spectrometer. 1 was used for collection of 1 H NMR spectra. 13 C.13 C DEPT-135, 2D 1 H- 13 C HSQC and HMBC NMR spectra were recorded on a Bruker Avance NEO 500 MHz spectrometer. For oxidized PE samples, NMR measurements were performed at 50 °C. Chemical shifts were measured using the internal solvent (CDCl3, δ( 1 H) 7.26 ppm and δ( 13 C) 77.5 ppm). The spectra obtained were analyzed using MestReNova (v14.2.0, Mestrelab Research SL).

[0167] IR spectroscopy. Fourier transform infrared (FT-IR) spectra of the samples were obtained using a Thermo Scientific Nicolet iS10 FT-IR spectrometer equipped with a Smart Orbit (diamond) attenuated total reflectance (ATR) accessory. 4 cm -1 A resolution of 1000 nm and 32 scans per sample were used.

[0168] Differential Scanning Calorimetry (DSC). DSC measurements were performed on a TA Instruments DSC 2500. Each polymer sample (approximately 3 mg) was placed in a Tzero aluminum pan. DSC measurements were performed at a heating and cooling rate of 10°C / min. Melting temperature (T m ) was obtained from the second heating cycle.

[0169] Thermogravimetric analysis (TGA). TGA measurements were performed on a TA Instrument TGA5500 thermogravimetric analyzer in the temperature range of 50 to 300 °C (heating rate: 10 °C min ) under air flow. -1 ) was performed.

[0170] Viscosity. Viscosity values ​​of the oxidation products were measured at 140°C under N2 atmosphere using an ARES-G2 rheometer equipped with a 25 mm plate.

[0171] Acid Number (AN). 0.5 g of the oxidation product and 25 mL of xylene are added to a round-bottom flask and heated to 75°C at 100 rpm. After the product dissolves, 12 mL of ethanol is slowly added to the flask. The solution is titrated with 0.1 M KOH in 2-methoxyethanol and phenolphthalein indicator. The volume of the added KOH solution is designated as V1. AN is calculated by Equation S2, where M1 is the molar concentration of KOH and m is the mass of the sample in grams.

number

[0172] Saponification Number (SN). 0.5 g of the oxidation product and 10 mL of xylene are added to a round-bottom flask equipped with a condenser, and the flask is heated to 100 °C until the oxidation product dissolves. After cooling the flask, 15 mL of 0.1 M KOH in 2-methoxyethanol is added, and the solution is heated at 130 °C for 2 hours at 100 rpm. After setting the temperature of the flask to 60 °C, the solution is titrated with 0.3 M aqueous HCl using phenolphthalein indicator. The added HCl solution is designated as V2. The titration is performed without adding the oxidation product, and the volume of the HCl solution for the titration is designated as V3. The SN number is calculated according to equation S3, where M2 is the molar concentration of the HCl solution, and m is the mass in grams of the sample used.

number

[0173] The ester number (EN) is obtained by subtracting the AN from the SN.

[0174] Alcohol content. The mass percentage of oxygen attributed to the presence of alcohol was obtained by measuring the increased ester value after the acetylation reaction. To consume the alcohol group through the acetylation reaction, 60 mg of the oxidation product and 4.4 mmol of acetyl chloride were added to a glass pressure reactor containing 12 mL of CHCl. ​​The reaction was carried out at 70 °C for 15 h. After the reaction, the reactor was cooled to room temperature, and the solvent and residual acetyl chloride in the solution were removed using a RotaVap (50 °C, 350 mbar). The product was further dried under vacuum (0.2 mTorr) for 8 h. 4 mL of xylene and 13 mL of 0.025 M KOH 2-methoxyethanol were added, and the solution was heated at 130 °C for 2 h. After cooling to 60 °C, titration was performed with 0.02 M aqueous HCl using phenolphthalein as the indicator to obtain the saponification value. The increase in ester value corresponding to the amount of alcohol reacted is given by Equation S4. Increased EN = SN of acetylated product - EN before reaction - 2 × (AN before reaction) (S4).

[0175] Oxygen content. The mass fraction of oxygen was obtained assuming that the product consisted only of carbon, hydrogen, and oxygen. The carbon and hydrogen contents were obtained using an EAI CE-440 elemental analyzer (EAI Co. Ltd.). The amount of oxygen in the oxidation product was calculated by subtracting the carbon and hydrogen contents from 100 wt%. References for Examples 1-8 The following references are incorporated herein by reference: [1]Renewable ketone waxes with unique carbon chain lengths and polarities.(WO2019 / 070422A1) [2]Green Chemistry, 2021, 23, 7137-7161 [3]In Ullmann's Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA, Ed.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2015; pp 1-63 [4]https: / / pubchem.ncbi.nlm.nih.gov / compound / Tert-butyl-hydroperoxide#section=Boiling-Point References for Example 9

[0176] The following references are incorporated herein by reference: (1) Adams, JH Analysis of the Nonvolatile Oxidation Products ofPolypropylene I. Thermal Oxidation. J Polym Sci A1 1970, 8 (5),1077-1090.https: / / doi.org / 10.1002 / POL.1970.150080505. (2) Perez, E.; Fraga-Dubreuil, J.; Garcia-Verdugo, E.; Hamley, PA; Thomas,ML; Yan, C.; Thomas,WB; Housley, D.; Partenheimer, W.; Poliakoff, M. Selective Aerobic Oxidation of Para-Xylene in Sub-and Supercritical Water. Part 2. The Discovery of Better Catalysts. 2011, 13 (9), 2397-2407. https: / / doi.org / 10.1039 / C1GC15138J. (3) Gardette, M.; Perthue , A. ; Gardette , JL ; Janecska , T. ; Foldes, E.; Pukanszky,B.; Therias, S. Photo-and Thermal-Oxidation of Polyethylene: Comparison of Mechanisms and Influenceof Unsaturation Content. PolymDegrad Staff 2013, 98(11), 2383–2390. https: / / doi.org / 10.1016 / J.POLYMEGRADESTAB.2013.07.017. (4) A. Sen, Adv. Polym. Sci. 73-74,125 (1986). Check out the top 10 ingredients The design of one of these is based on a slightly smooth surface.

[0177] (1) Hu, K.; Zhou, P.; Yang, Y.; Hall, T.; Nie, G.; Yao, Y.; Duan, X.;Wang, S. Degradation of Microplastics by a Thermal Fenton Reaction. ACS ES and TEngineering 2022 , 2 ( 1 ) , 110 - 120 . (2) Sullivan, KP; Werner , AZ ; Ramirez , KJ ; Ellis , LD ; Bussard,JR; Black, BA; Brandner , DG ; Bratti , F. ; Buss , BL ; Dong, X.; Haugen , SJ ; Ingraham, MA; Konev, M. O.; Michener, W. E.; Miscall, J.; Pardo, I.; Woodworth, S. P.; Guss, A.M.; Roman- Leshkov, Y.; Stahl, S. S.; Beckham,G. T. Mixed Plastics Waste Valorization through Tandem Chemical Oxidation andBiological Funneling. Science (1979) 2022, 378 (6616). https: / / doi.org / 10.1126 / SCIENCE.ABO4626 / SUPPL_FILE / SCIENCE.ABO4626_DATA_S 1.ZIP. (3) Fujiwara, M.; Xu, Q.; Souma, Y.; Kobayashi, T. Oxidation of Alkanes byTBHP in thePresence ofSoluble Titanium Complexes. J Mol Catal A Chem 1999, 142 (1), 77-84. https: / / doi.org / 10.1016 / S1381-1169(98)00284-2. (4) Huybrechts, D. R. C.; Bruycker, L. De; Jacobs, P. A.; Huybrechts, D.R. C.; Bruycker, L. De; Jacobs, P. A. Oxyfunctionalization of Alkanes with HydrogenPeroxide on Titanium Silicalite. Natur 1990, 345 (6272), 240-242.https: / / doi.org / 10.1038 / 345240A0. (5) Elmanovich, IV; Stakhanov, AI; Kravchenko, EI; Stakhanova, SV; Pavlov, AA; Ilyin, MM; Kharitonova, EP; Gallyamov, MO; Khokhlov, AR Chemical Recycling of Polyethylene inOxygen-Enriched Supercritical CO2. J Supercrit Fluids 2022, 181,105503. https: / / doi.org / 10.1016 / J.SUPFLU.2021.105503. conclusion

[0178] This concludes the description of the preferred embodiments of the present invention. The foregoing description of one or more embodiments of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teachings. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.

Claims

1. 1. A method for synthesizing a wax or polyketone, comprising: The method comprises reacting a polyolefin with a peroxide in the presence of a solvent under conditions comprising a temperature of less than 200°C, wherein at least one of a carbon-carbon bond or a carbon-hydrogen bond of the polyolefin is cleaved by oxidation with the peroxide to form a polyketone or a wax comprising an oxidized polyolefin.

2. 10. The method of embodiment 1, further comprising catalyzing the reaction with a catalyst that decomposes the peroxide so that oxygen from the peroxide can more readily react with the polyolefin.

3. [Fe(III)SO ４ ] or MnBr ２ 10. The method of claim 1, further comprising catalyzing the reaction using

4. 4. The method of claim 2 or 3, wherein the peroxide is hydrogen peroxide, the solvent is water, and the reaction forms the polyketone.

5. 4. The method of claim 2 or 3, wherein the peroxide is tert-butyl hydroxypropyl ether, the solvent is water, and the reaction forms the wax.

6. 6. The method of claim 5, wherein the wax has a molecular weight of 500 or less, or 1000 or less.

7. 10. The method of claim 1, further comprising controlling at least one of the composition of the peroxide, the temperature, and the duration of the reaction to select the wax or the polyketone.

8. 10. The method of claim 1, wherein the peroxide comprises a hydroperoxide and the polyolefin comprises at least one of polyethylene, polystyrene, or polypropylene.

9. 10. The method of claim 1 or 8, wherein the method further comprises selecting a weight percent of the peroxide in solution relative to the mass of the polyolefin to achieve a desired molecular weight of the oxidized polyolefin, a lower weight percent of the peroxide resulting in a higher molecular weight of the oxidized polyolefin.

10. 10 wt % to 200 wt % of the peroxide in the solution, based on the weight of the polyolefin in the solution; or contacting said peroxide with said polyolefin in a molar ratio comprising moles of monomer units (in said polyolefin) divided by moles of said peroxide in a range of from about 0.5 to about 20; The method of claim 1 , comprising:

11. 11. The method of claim 1 or 10, wherein the solvent comprises any hydrocarbon solvent capable of at least partially dissolving the polyolefin.

12. 10. The method of claim 1, wherein the peroxide comprises a hydroperoxide, the solvent comprises water, and the polyolefin comprises polyethylene.

13. 10. The method of claim 1 or 7, wherein the oxidized polyolefin comprises a carbonyl.

14. 10. The method of claim 1 or 7, wherein the oxidized polyolefin has a ketone oxygen content greater than its ester and carboxylic acid oxygen content.

15. The one or more waxes have a number average molecular weight (M ｎ 15. The method of claim 1 or 14, wherein the amount of peroxide and the reaction time of the reaction are selected to have a polydispersity of 1.2 to 2.

5.

16. 16. The method of claim 1 or 15, wherein the temperature is greater than 100°C and less than 200°C.

17. 17. One or more waxes synthesized by the method of any of claims 1-3 or 5-16.

18. 10. The method of claim 1, further comprising contacting untreated plastic waste comprising at least said polyolefin (and optionally at least one of any additives, impurities, or other polyolefins) with said solvent.

19. A composition comprising an oxidized polyolefin having at least one of the following: a number average molecular weight in the range of 500 to 5000 g / mol and optionally a dispersity index in the range of 1.2 to 2.5, an oxygen content characterized by a saponification number in the range of 30 to 200 (30≦saponification number≦200) or 30 to 150 (30≦saponification number≦150), wherein the saponification number is the amount of potassium hydroxide in milligrams required to saponify 1 gram of the oxidized polyolefin; an oxygen content characterized by an acid number in the range of 15 to 100, said acid number being the amount of potassium hydroxide in milligrams required to neutralize 1 g of oxidized polyolefin dissolved in xylene; an oxygen content of 3 to 15 wt. % relative to the mass of the oxidized polyolefin (e.g., 3 wt. %≦oxygen content≦15 wt. %); a ketone oxygen content greater than the ester and carboxylic acid oxygen content, or Alcohol oxygen content of approximately 1-4 wt%.

20. 20. The composition of claim 19, wherein the oxidized polyolefin has a melting point in the range of 70 to 120°C.

21. 21. The composition of claim 19 or 20, wherein the oxidized polyolefin is characterized by a saponification number that is equal to or higher than the saponification number of the oxidized polyolefin formed by oxidation of a molten polyolefin by melt oxidation, oxidation of the polyolefin in an aqueous dispersion, or oxidation of the polyolefin in solid form.

22. 20. The composition of claim 19, wherein the oxidized polyolefin comprises oxidized polypropylene, oxidized polyethylene, or oxidized polystyrene.

23. 23. A lubricant, adhesive or coating comprising the wax of claim 22.

24. The oxidized polyolefin has the structure: Methyl ketone 【Chemistry 11】 , internal ketone 【Chemistry 12】 , carboxylic acid 【Chemistry 13】 , t-butyl ester 【Chemistry 14】 , tert-alcohol 【Chemistry 15】 , sec-alcohol 【Chemistry 16】 20. The composition of claim 19, comprising:

25. 20. The composition of claim 19 synthesized using the method of claim 1, wherein the polyolefin comprises at least one of polypropylene, polyethylene, or polystyrene.

26. Precursors from which oxidized polyolefins can be synthesized, Untreated plastic waste containing polyolefins, and a solution containing the polyolefins at least partially dissolved in peroxide and a solvent. Precursors, including:

27. 27. A mixture comprising the precursor of claim 26 and an oxidized polyolefin formed by oxidation of said polyolefin with said peroxide.

28. A polyketone with an oxygen content greater than 4 wt %, the ketone content being greater than the ester content.

29. 29. The polyketone of claim 28 synthesized by the method of any one of claims 1 to 4, wherein the polyolefin comprises LDPE.

30. The following structure: 【Chemistry 17】 29. The polyketone of claim 28.

31. A reactor for synthesizing oxidized polyolefins from plastic waste, comprising: a container for containing a solution comprising peroxide and said polyolefin; a temperature sensor connected to the pressure vessel for regulating the temperature of the solution; one or more openings in the pressure vessel for transferring at least one of the solution or solvent into the pressure vessel; a control circuit for controlling the temperature and reaction time of an oxidation reaction in which carbon-carbon bonds and / or carbon-hydrogen bonds of the polyolefin are cleaved by oxidation with the peroxide to form one or more waxes, including polyketones or oxidized polyolefins; and an opening for removing the oxidized polyolefin from the pressure vessel; A reactor comprising:

32. 29. The method of claim 1, or the composition of claim 19 or 28, wherein the oxidized polyolefin has a molecular weight of 2000 g / mol or less.

33. The solvent is at least completely or partially dissolving the polyolefin before or after the oxidation is initiated; or Swelling and / or softening the polyolefin before or after the oxidation is initiated.

2. The method of claim 1, wherein the rate of the oxidation reaction is increased by:

34. The method of claim 1 , wherein the solvent dissolves the peroxide.

35. 10. The method of claim 1, wherein the solvent at least increases the rate of the oxidation or decreases the temperature at which the oxidation occurs.

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