CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application No.

63/393,431, filed July 29, 2022; the contents of the above-identified application are hereby fully incorporated herein by reference in their entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with government support under grant number 2139899 awarded by the National Science Foundation. The government has certain rights in the invention.

BACKGROUND OF THE DISCLOSURE

[0003] Polyethylene terephthalate (PET) textiles are among the largest categories of inproduction plastics. Because they are blended with other components, such as cotton, dyes, and additives, depolymerizing these PET blends leave impurities trapped in the extracted monomers (terephthalic acid, “TP A”). PET is a major contributor to global plastic waste. Recycling has the potential to alleviate this concern. However, existing approaches (mechanical recycling) need clean starting materials. While clean PET bottles can be mechanically recycled through a series of cleaning steps, blended PET products such as textiles, which contain dyes and other additives, are not yet suitable for mechanical recycling approaches. Chemical recycling, which uses reagents to depolymerize PET into monomers, can depolymerize blended plastics; however, separating the impurities post-depolymerization is not straightforward. Considering that the textile industry produces over 60% of global PET supply, devising a strategy to separate impurities from recycled monomers is a key step toward mitigating their environmental impact, especially given the growing trend of fast fashion.

[0004] Polyester and cotton (polycotton) blended fabrics are among the most common textiles being produced. Palme et al. reported that alkaline hydrolysis can chemically recycle the PET fibers in polycotton to form terephthalic acid (TP A) and ethylene glycol (EG) monomers while leaving cotton intact. Cosimbescu et al. similarly found that alkaline hydrolysis can depolymerize colored PET bottles; however, the impurities present in the starting material stayed attached to the recycled TPA (rTPA) even after the purification step. These impurities are a significant concern given that they can affect the quality, appearance, and safety of the recycled products.

[0005] The methods for purifying TP A are energy and reagent intensive. The most common approach is to take advantage of the temperature-dependent solubility of TPA. With limited solubility in water, the water-based method requires a controlled cooling step from an autoclave for impurity rejection. Alternatively, one can take advantage of the increased solubility of TPA in organic solvents such as N,N-dimethylacetamide. The drawback of this approach is the need for a solvent recovery system. Another possibility is to add excess methanol in the depolymerization process (‘methanolysis’) to form dimethyl terephthalate (DMT) that has a lower melting temperature than TPA. This approach allows DMT purification via crystallization; however, it requires the methanol recovery system.

SUMMARY OF THE DISCLOSURE

[0006] The present disclosure provides, inter alia, methods of forming one or more purified monomer(s) and polymers formed from at least a purified monomer or purified monomers formed by a method of the present disclosure. The present disclosure also provides articles of manufacture comprising one or more of the polymers. Non-limiting examples of the methods, the purified monomers, the polymers, and the articles of manufacture are provided herein.

[0007] In various examples, the present disclosure provides a method of forming one or more purified monomer(s) comprises forming one or more metal complex(es), one or more metal organic framework(s) (MOF(s)), one or more coordination polymer network(s), or any combination thereof using one or more impure monomer(s), structural analog(s) thereof, or any combination thereof; optionally, isolating the metal complex(es), one or more metal organic framework(s) (MOF(s)), coordination polymer network(s); optionally, decomposing the metal complex(es), metal organic framework(s), coordination polymer network(s), where purified monomer(s), or structural analog(s) thereof are formed; and optionally, isolating the purified monomer(s) the structural analog(s) thereof. In various examples, the method further comprising providing the impure monomer(s). In various examples, the polymer(s) is/are chosen from organic polymers, biopolymers, and the like, and any combination thereof. In various examples, the impure monomer(s) is/are organic acid(s), polyol(s), amine(s), or the like, or any combination thereof. In various examples, the impure monomer(s) is/are formed from a textile, an article of manufacture), or the like, or any combination thereof. In various examples, the forming the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like, or any combination thereof comprises contacting the impure monomer(s)) with one or more metal precursor(s), wherein the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like are formed. In various examples, the decomposing the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like, or any combination thereof comprises contacting the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like, or any combination thereof with one or more acid(s), one or more base(s), one or more organic solvent(s), or one or more ionic liquid(s), or any combination thereof. In various examples, the decomposing the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like, or any combination thereof comprises contacting the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like, or any combination thereof with one or more acid(s), wherein metal precursor(s), or structural analog(s) thereof are formed. In various examples, the impure monomer(s) comprise one or more impurit(ies) and the purified monomer(s) is/are substantially free or free of the impurit(ies) and/or the impure monomer(s) comprise one or more additive(s) and the purified monomer(s) is/are substantially free or free of the additive(s). In various examples, the impure monomers are less than 99% pure by weight. In various examples, the impure monomers are less than 90% pure by weight. In various examples, the purified monomer(s) is/are substantially colorless or colorless. In various examples, the method further comprises polymerizing the purified monomer(s) or structural analog(s) thereof.

[0008] In various examples, the present disclosure provides a polymer formed from at least a purified monomer or purified monomers formed by a method of the present disclosure. In various examples, the polymer is a homopolymer or a copolymer. In various examples, the polymer is chosen from organic polymers and biopolymers, and the like. In various examples, the polymer is a polyester (such as, for example, a poly(terephthalate), a polypropylene terephthalate), a poly(butylene terephthalate), a polylactic acid, or the like), a polyamide (such as, for example, a nylon or the like), a polyalcohol, a polyurethane, a polyurea, a polycarbonate, a polyether ether ketone, a polyether ether ketone ketone, a poly ether ketone ketone, a polyetherimide, a polystyrene, or the like, or any combination thereof. In various examples, the polymer is in the form of a textile, an article of manufacture (such as, for example, a container (such as, for example, a bottle, a food tray, a food packaging, or the like), a rug/carpet(s), a structural element, a surface element (such as, for example, a component or part from an automobile, a plane, or the like), or the like. In various examples, the polymer is substantially free of impurit(ies) and/or additive(s) present in the impure monomer(s) from which purified monomer(s) was/were formed.

[0009] In various examples, the present disclosure provides an article of manufacture comprising one or more polymer(s) of the present disclosure (e.g., formed from at least a purified monomer or purified monomers formed by a method of the present disclosure). In various examples, the article of manufacture is a container, a structural element, or a surface element, or the like. In various examples, the container is a bottle, a food tray, or a food packaging, or the like. In various examples, the surface element is a component or part from an automobile, or a plane, or the like.

BRIEF DESCRIPTION OF THE FIGURES

[0010] For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures.

[0011] FIG. 1 shows a schematic of the purification cycle of terephthalic acid recovered from waste textiles.

[0012] FIG. 2 shows (a) Powder X-ray diffraction of recycled TPA from red polycotton (“rTPA”), MIL-53(Ga) MOF synthesized from rTPA (“MOF”), and purified TPA from MOF disassembly (“pTPA”), (b) photo, and (c) UV-Vis spectra of of rTPA and pTPA in DMSO.

[0013] FIG. 3 shows (a) photo and (b) UV-Vis spectra of rTPA obtained from blue polycotton and the corresponding pTPA in DMSO. (c) photo and (d) UV-Vis spectra of rTPA obtained from green polycotton and the corresponding pTPA dissolved in DMSO.

[0014] FIG. 4 shows PXRD patterns (X = 1.5406 A) of MIL-53(Ga) synthesized from rTPA (showing here rTPA from red fabric) and reference MIL-53(Ga) pattern (Vougo-Zanda et al).

[0015] FIG. 5 shows TGA curves of recycled TPA (rTPA), purified TPA (pTPA), and commercial TPA (cTPA) for TPA from (a) red fabric, (b) blue fabric, and (c) green fabric. The thermogravimetric decomposition profiles were collected on a TA Instruments TGA Q5000 under an atmosphere of N2 and with a ramp rate of 3 °C/min.

[0016] FIG. 6 shows FTIR infrared spectra of recycled TPA (rTPA), purified TPA (pTPA), and commercial TPA (cTPA) for TPA from (a) red fabric, (b) blue fabric, and (c) green fabric. The spectra were collected on a Bruker Tensor II IR spectrometer equipped with a diamond Attenuated Total Reflectance (ATR) attachment. [0017] FIG. 7 shows (a) ¹ H NMR and (b) ¹³ C NMR (500 MHz, DMSO-tL) of recycled TPA (rTPA), purified TPA (pTPA), and commercial TPA (cTPA) for TPA from red fabric. Peaks are color-coded based on corresponding protons and carbons in the TPA molecule. [0018] FIG. 8 shows SEM images (Zeiss Gemini 500 Scanning Electron Microscope) of MIL-53(Ga) crystals synthesized from (a) rTPA from red fabric, (b) rTPA from blue fabric, and (c) rTPA from green fabric. Samples are carb on- sputtered.

[0019] FIG. 9 shows TPA purification with no organic solvents, (a) Powder X-ray diffraction patterns ( = 1.5406 A) of purified TPA from MOF disassembly (“pTPA”) and MIL-53(Ga) MOF synthesized from rTPA (“MIL-53 (Ga)”), (b) photo of rTPA versus pTPA in DMSO, and (c) UV-Vis spectra of commercial TPA and pTPA.

[0020] FIG. 10 shows PXRD pattern ( = 1.5406 A) of MIL-53(Ga) made from recycled GafNOsjs and rTPA from red polycotton fabric. The recycled GafNOsjs was obtained by evaporating the excess liquid from the effluent of a MIL-53(Ga) disassembly from an earlier experiment of reactive crystallization.

[0021] FIG. 11 shows X-ray photoelectron spectroscopy (XPS) of pTPA from red polycotton fabric showing less than 0.1 at% Ga impurities. Samples were analyzed using a Scienta Omicron ESCA-2SR Spectrometer with operating pressure ca. IxlO' ⁹ Torr. Monochromatic Al Ka x rays (1486.6 eV) with photoelectrons collected from a 1.1 mm diameter analysis spot. Photoelectrons were collected at a 90° emission angle with source to analyzer angle of 54.7°. A hemispherical analyzer determined electron kinetic energy, using a pass energy of 200 eV for wide/survey scans, and 50 eV for high resolution scans. A flood gun was used for charge neutralization of non-conductive samples.

[0022] FIG. 12 shows an example of a system of the present disclosure.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0023] Although claimed subject matter will be described in terms of certain examples and embodiments, other examples and embodiments, including examples that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. Various structural, logical, and process step changes may be made without departing from the scope of the disclosure.

[0024] As used herein, unless otherwise indicated, “about”, “substantially”, or “the like”, when used in connection with a measurable variable (such as, for example, a parameter, an amount, a temporal duration, or the like) or a list of alternatives, is meant to encompass variations of and from the specified value including, but not limited to, those within experimental error (which can be determined by, e.g., a given data set, an art accepted standard, etc. and/or with, e.g., a given confidence interval (e.g. 90%, 95%, or more confidence interval from the mean), such as, for example, variations of +/- 10% or less, +/-5% or less, +/-1% or less, and +/-0.1% or less of and from the specified value), insofar such variations in a variable and/or variations in the alternatives are appropriate to perform in the instant disclosure. As used herein, the term “about” may mean that the amount or value in question is the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, compositions, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error, or the like, or other factors known to those of skill in the art such that equivalent results or effects are obtained. In general, an amount, size, composition, parameter, or other quantity or characteristic, or alternative is “about” or “the like,” whether or not expressly stated to be such. It is understood that where “about,” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0025] Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include the lower limit value, the upper limit value, and all values between the lower limit value and the upper limit value, including, but not limited to, all values to the magnitude of the smallest value (either the lower limit value or the upper limit value) of a range. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “0.1% to 5%” should be interpreted to include not only the explicitly recited values of 0.1% to 5%, but also, unless otherwise stated, include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5% to 1.1%; 0.5% to 2.4%; 0.5% to 3.2%, and 0.5% to 4.4%, and other possible sub-ranges) within the indicated range. It is also understood (as presented above) that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about, it will be understood that the particular value forms a further disclosure. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0026] The present disclosure provides, inter alia, methods of obtaining one or more purified monomer(s) or obtaining one or more molecul(es) of interest from one or more polymer(s). The present disclosure also provides uses of monomer(s) and molecule(s) of interest obtained using the methods.

[0027] In an aspect, the present disclosure provides obtaining one or more purified monomer(s) or obtaining one or more molecule(s) of interest from one or more polymer(s). In various examples, the methods are polymer recycling methods. In various examples, a method recycles one or more polymer(s) (e.g., purifies recycled monomer(s) obtained from polymer(s)). In various examples, a method comprises one or more reactive crystallization(s) or the like. In various examples, a reactive crystallization comprises forming crystals comprising (or of) metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like, or any combination thereof at or about a purification temperature (e.g., a temperature at which substantially all or all of the impurit(ies) and/or additive(es) of the impure monomer(s) are not trapped in the crystals during crystallization or during cooling of the crystals). In various examples, a method does not comprise any other monomer purification process(es) or step(s) (such as, for example, monomer pre-purification process(es) or step(s) or the like). In various examples, a purified monomer or monomers (or a composition comprising one or more monomer(s)) (e.g., recycled monomer(s)) is/are formed by a method of the present disclosure. Non-limiting examples of the methods are disclosed herein.

[0028] A method can recycle various polymers. In various examples, a polymer is a homopolymer, a copolymer, or the like. In various examples, a method is used to recycle a plurality of polymers, where each polymer is structurally distinct from the other polymers. In various examples, polymer(s) is/are chosen from polyester(s) (such as, for example, poly(terephthalate)(s), polypropylene terephthalate)(s), poly(butylene terephthalate)(s), polylactic acid(s), and the like), polyamide(s) (such as, for example, nylon(s) and the like), polyalcohol(s), polyurethane(s), polyurea(s), polycarbonate(s), polyether ether ketone(s), polyether ether ketone ketone(s), polyether ketone ketone(s), polyetherimide(s), polystyrene(s), and the like, and any combination thereof, and/or the impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest), structural analog(s) thereof, or any combination thereof is/are chosen from organic acids (such as, for example, terephthalic acid, isophthalic acid, adipic acid, lactic acid, adipic acid, and the like), polyols (which may be diols or the like) (such as, for example, ethylene glycol, propanediol, butanediol, and the like), organic amines (which may be organic diamines or the like) (such as, for example, methylenedianiline, hexamethylenediamine, and the like), bisphenol A, hydroquinone, structural analogs thereof, and the like and any combination thereof.

[0029] In various examples, a method recycles one or more textile(s), one or more article(s) of manufacture (such as, for example, container(s) (such as, for example, bottle(s), food tray(s), food packaging(s), or the like), rug(s)/carpet(s), structural element(s), surface element(s) (such as, for example, component s) or part(s) from an automobile, a plane, or the like), or the like, or any combination thereof.

[0030] In various examples, a method of recycling one or more polymer(s) (e.g., purifying recycled monomer(s) obtained from polymer(s)) (or obtaining one or more molecule(s) of interest (e.g., from a polymer/polymers or the like)) comprises: forming one or more metal complex(es), one or more metal organic framework(s) (MOF(s)), one or more coordination polymer network(s), or the like, or any combination thereof comprising one or more impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest), structural analog(s) thereof, or any combination thereof; optionally, isolating the metal complex(es), one or more metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like; optionally, decomposing the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like, where purified monomer(s) (e.g., free monomer(s) or the like) (or purified molecule(s) of interest), or structural analog(s) thereof are formed; and optionally, isolating the purified monomer(s) (or purified molecule(s) of interest) or the structural analog(s) thereof.

[0031] In various examples, a reaction comprises one or more reactive crystallization(s). In various examples, a method recycles (or obtains one or more molecule(s) of interest from) a polymer/polymers (such as, for example, polyester(s) (such as, for example, poly(terephthalate)(s), polypropylene terephthalate)(s), poly(butylene terephthalate)(s), polylactic acid(s), or the like), polyamide(s) (such as, for example, nylon(s) and the like), polyalcohol(s), polyurethane(s), polyurea(s), polycarbonate(s), polyether ether ketone(s), polyether ether ketone ketone(s), polyether ketone ketone(s), polyetherimide(s), polystyrene(s), or the like, or any combination thereof, lignins, starches, celluloses, or the like, or any combination thereof). In various examples, a method for recycling polymer(s) (or obtaining one or more molecule(s) of interest from) a polymer/polymers (such as, for example, polyester(s) (such as, for example, poly(terephthalate)(s), polypropylene terephthalate)(s), poly(butylene terephthalate)(s), polylactic acid(s), or the like), polyamide(s) (such as, for example, nylon(s) and the like), polyalcohol(s), polyurethane(s), polyurea(s), polycarbonate(s), polyether ether ketone(s), polyether ether ketone ketone(s), polyether ketone ketone(s), polyetherimide(s), polystyrene(s), or the like, or any combination thereof, lignin(s), starche(s), cellulos(es), or the like, or any combination thereof) comprises reactive crystallization.

[0032] A method can use various monomers (such as, for example, impure monomers or the like). In various examples, monomer(s) is/are obtained from one or more polymer(s) described herein.

[0033] In various examples, impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest) are terephthalic acid and adipic acid (which may obtained from depolymerization of polyester-nylon blend textiles or the like). After obtaining (e.g., isolating or the like) at least a portion of the isolating terephthalic acid, the remaining reaction mixture is subjected to a second forming reaction (e.g., formation of a second metal complex and/or metal-organic-framework and/or coordination polymer network or the like) and second decomposition to obtain (e.g., isolate or the like) at least a portion of the adipic acid.

[0034] In various examples, impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest) comprise one or more impurit(ies) and the purified monomer(s) (which may be free monomer(s) or the like) (or purified molecule(s) of interest) is/are substantially free or free of the impurit(ies) and/or the impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest)) comprise one or more additive(s) and the purified monomer(s) (which may be free monomer(s) or the like) (or purified molecule(s) of interest) is/are substantially free or free of the additive(s).

[0035] The presence (e.g., quantity) and/or absence of impurit(ies) and/or additive(s) can be determined by methods known in the art. In various examples, the presence (e.g., quantity) and/or absence of impurit(ies) and/or additive(s) is determined by spectroscopic method(s) (such, as for example, UV-VIS spectroscopy, IR spectroscopy, NMR spectroscopy (e.g., NMR spectroscopy, ¹³ C NMR spectroscopy, or the like), spectrometric methods (e.g., mass spectrometry, GC-MS, LC-MS, or the like), liquid chromatography (such as, for example, high performance liquid chromatography (HPLC) or the like), thermogravimetric analysis (TGA), Platinum-Cobalt Color, acid number, inductively Coupled Plasma Optical Emission spectroscopy (ICP-OES), energy-dispersive x-ray spectroscopy (EDS), or the like, or any combination thereof. In various examples, the recycled monomer(s) comprise 5% or less, 2.5% or less, 1% or less, 0.1% or less. 0.05% or less by weight (based on the total weight of the recycled monomer(s) of impurit(ies) and/or additive(s)) as determined by one or more of the foregoing methods.

[0036] In various examples, the presence (e.g., quantity) and/or absence of impurit(ies) and/or additive(s) is below the detection limit of spectroscopic method(s) (such, as for example, UV-VIS spectroscopy, IR spectroscopy (e.g., FTIR or the like), NMR spectroscopy (e.g., 'H N R spectroscopy, ¹³ C NMR spectroscopy, or the like), spectrometric methods (e.g., mass spectrometry, GC-MS, LC-MS, or the like), thermogravimetric analysis (TGA), acid number, or the like, or any combination thereof.

[0037] Metal complex(es), metal organic framework(s), coordination polymer network(s), or the like can be formed in various ways. In various examples, forming metal complex(es), metal organic framework(s), coordination polymer network(s), or the like, or any combination thereof comprises contacting impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest, or any combination thereof with one or more metal precursor(s), where the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like are formed. In various examples, the yield of a forming is 10% or higher.

[0038] Various metal precursors can be used. In various examples, a metal precursor is a salt or the like. In various examples, metal precursor(s) is/are chosen from metal salt(s), metal-containing clusters, metal particles (such as, for example, metal nanoparticles and the like), and the like, and structural analogs thereof, and any combination thereof. In various examples, the metal salt(s), independently, comprise one or more anion(s) chosen from F", Cl , Br", I', S', CN’, NH ₂ -, OCN’, SCN’, C2O4 ² ; OH", MnOr, PO ₄ ³ ', SO ', NO ₃ ', NO2/ ClOF, CIO3; CIO2; OCF, IO ₃ ; BrCh', OBr", CO3 ² ; CrO ₄ ² ', CnO? ² ', CH3COO; HCOO; ), and the like and/or one or more cation(s) chosen from transition metal cations (e.g., Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Ag, Zr, W cations, and the like), Group 13 cations (e.g., Al, Ga, In cations, and the like), alkaline earth cations (e.g., Mg, Ca, Sr, Ba cations, and the like), lanthanide cations(s), and the like. In various examples, the metal precursor(s) is/are chosen from gallium nitrate (which may be a hydrate or anhydrous), gallium nanoparticles, gallium clusters, and the like, and any combination thereof.

[0039] Various amounts of metal precursor(s) can be used. In various examples, metal salt(s) is/are present (e.g., in a forming reaction mixture) at about 1 to about 20 wt%, including all 0.1 wt% values and ranges therebetween (e.g., about 3 to about 10 wt% or about 5 wt%), based on the total weight of a forming reaction mixture.

[0040] A forming may be carried out in a solvent or a mixture of solvents. In various examples, forming metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like is carried out in an aqueous solvent (e.g., water or the like). In various examples, forming metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like is carried out in solvent(s) chosen from water, organic solvents (e.g., dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, cyrene, formic acid, acetone, or the like), ionic liquids, and the like, and any combination thereof.

[0041] Various amounts of solvent(s) may be used. In various examples, solvent(s) is/are present (e.g., in a forming reaction mixture) at about 50 to about 95 wt%, including all 0.1 wt% values and ranges therebetween (e.g., about 75 to about 90 wt% or about 90 wt%), based on the total weight of a forming reaction mixture.

[0042] A reaction forming metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like can be carried out under various reaction conditions.

[0043] A forming reaction can comprise one or more steps and each step can be performed under the same or different reaction conditions as other steps. A reaction can be carried out at various temperatures. In various examples, a reaction is carried out at about room temperature (e.g., from about 20 °C to about 22 °C, including all 0.1 °C values and ranges therebetween) to about 600 °C (e.g., about 80 °C to about 600 °C), including all 0.1 °C values and ranges therebetween) above, or any combination thereof (e.g., where each reaction is performed at the same or different temperature as other steps). In various examples, a reaction is carried out at about 50 °C to about 400 °C, including all 0.1 °C values and ranges therebetween (e.g., about 100 °C to about 300 °C or about 200 °C to about 250 °C).

[0044] A forming reaction can be carried out at various pressures. In various examples, a reaction is carried out at below atmospheric pressure (e.g., about 1 bar), at about atmospheric pressure, or at greater than atmospheric pressure (e.g., heating in a sealed pressurized reaction vessel and the like). In various examples, a reaction is carried out at from about 1 bar to about 100 bar, including all 0.1 bar values and ranges therebetween, or any combination thereof (e.g., where each step is performed at a different pressure as other steps). In various examples, a reaction is carried out at from about 0.1 MPa to about 10 MPa, including all 0.1 MPa values and ranges therebetween (e.g., about 1 MPa to about 6 MPa or about 3 MPa. In various examples, each step is performed at the same or different pressure as other steps. [0045] A forming reaction can be carried out for various times. Reaction time can depend on factors such as, for example, temperature, pressure, reaction component concentration(s), presence and/or intensity of an applied energy source, mixing (e.g., stirring or the like), or the like, or a combination thereof. In various examples, reaction time ranges from about minutes (e.g., 5 minutes) to about 3 days (or more), including all integer second values and ranges therebetween, or any combination thereof (e.g., where each step is performed at a different time as other steps). In various examples, reaction time is about one hour to about 3 days, including all integer second values and ranges therebetween (e.g., about 3 hours to about 9 hours or about 5 hours)

[0046] In various examples, a reaction is a hydrothermal reaction (e.g., carried out at about 210 °C and/or for about 5 hours or the like). In various examples, a method is carried out in air or an inert atmosphere.

[0047] In various examples, at least a portion of the, one or more, or all metal complex(es), metal organic framework(s), coordination polymer network(s), or the like are crystalline. In various examples, at least a portion or all metal complex(es), metal organic framework(s), coordination polymer network(s), or the like comprise a linear dimension or all linear dimensions of about 5 mm or less. In various examples, at least a portion of the, one or more, or all metal complex(es), metal organic framework(s), coordination polymer network(s), or the like are amorphous. In various examples, at least a portion of the, one or more, or all metal complex(es), metal organic framework(s), coordination polymer network(s), or the like are crystalline and/or at least a portion of one or more of the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like are amorphous. In various examples, metal complex(es), metal organic framework(s), coordination polymer network(s), or the like are not amorphous.

[0048] In various examples, metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like are isolated from a forming reaction mixture. Non-limiting examples of isolation include filtration (e.g., vacuum filtration and the like), centrifugation, and the like.

[0049] Various impure monomers can used to form one or more metal complex(es), one or more metal organic framework(s) (MOF(s)), one or more coordination polymer network(s), or the like, or any combination thereof. In various examples, impure monomer(s) (which may be recycled monomer(s) or the like), structural analog(s) thereof, or any combination thereof (or molecules of interest) are, independently, ligands(s) of the metal complex(es) or linker(s) metal organic framework(s) or coordination polymer network(s), or the like.

[0050] In various examples, impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest), or structural analog(s) thereof have a purity of 99.9% or less, 99% or less, or 90% or less. In various examples, the impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest), or structural analog(s) thereof comprise impurit(ies) and/or additive(es) 0.1 to 15 wt%, including all 0.1 wt% values and ranges therebetween, based on the total weight of impure monomer(s) and impurit(ies) and/or additive(es). In various examples, impure monomer(s) comprise less than or at least 1 weight percent (wt%) impurit(ies) and/or additive(es). Nonlimiting examples of impurities include impurities typically found in commercial polymers, articles of manufacture comprising commercial polymers, and the like (such as, for example, pigments, dyes, and the like, and any combination thereof). Non-limiting examples of additives include additives typically found in commercial polymers, articles of manufacture comprising commercial polymers, and the like (such as, for example, surface additives, plasticizers, and the like, and any combination thereof).

[0051] In various examples, impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest), or structural analog(s) thereof exhibit an absorbance at one or more visible wavelength(s) (e.g., about 380 nm to about 700 nm, including all 0.1 nm values and ranges therebetween) of about 0.01 to about 1.5, including all 0.01 values and ranges therebetween, measured at a impure monomer(s) concentration of about 1 micromolar to about 200 millimolar (e.g., about 1 millimolar or 10 millimolar), including all 0.1 microlmolar values and ranges therebetween, and path length of about 1 centimeter (cm).

[0052] Various amounts of impure monomer(s) can be used. In various examples, impure monomer(s) is/are present (e.g., in a forming reaction mixture) at about 1 to about 20 wt%, including all 0.1 wt% values and ranges therebetween (e.g., about 1 to about 10 wt% or about 3 wt%), based on the total weight of a forming reaction mixture.

[0053] Various MOFs can be formed. In various examples, metal organic framework(s) are chosen from gallium MOFs (e.g., MIL-53 (Ga) and the like), UiO-66(Zr), UiO-66(Hf), MIL-53(A1), MIL-47(V), Cr-MOF20, MIL-47(V), MIL-53(Cr), MIL-53(Fe), MIL-53(Ga), MIL-lOl(Cr), MIL-lOl(Fe), MOF-2, MOF-5, and copper terephthalates, and the like, and any combination thereof. In various examples, the MOF(s), independently (in the case of combinations of MOFs), have a linear dimension (e.g., a diameter or the like), which may be a longest linear dimension, of about 0.1 micrometers to about 100 micrometers, including all 0.01 micrometer values and ranges therebetween.

[0054] In various examples, a method further comprises providing impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest) or the like. In various examples, impure monomer(s) (which may be recycled monomer(s) or the like) is/are provided by degradation (e.g., depolymerization or the like) of polymer(s). In various examples, one or more impure monomer(s) (which may be recycled monomer(s) or the like) is/are provided by solvolysis (such as, for example, a hydrolysis, methanolysis, glycolysis, or the like) of one or more polymer(s) (e.g., alkaline hydrolysis, acid hydrolysis, glycolysis, alcoholysis, aminolysis, or the like, or any combination thereof).

[0055] In various examples, impure monomer(s) (which may be recycled monomer(s) or the like) is/are provided by solvolysis (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like) or the like of one or more polymer(s). In various examples, solvolysis (such as, for example, a hydrolysis, methanolysis, glycolysis, or the like) of one or more polymer(s) comprises forming a mixture comprising one or more base(s) and one or more polymer(s). A solvolysis reaction (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like) can be performed under various reaction conditions.

[0056] Various bases or acids may be used in a solvolysis reaction (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like). Combinations of bases or acids can be used. Non-limiting examples of basis include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, and the like, and any combination thereof. Non-limiting examples of acids include mineral acids (such as, for example, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, and the like) and organic acids (such as, for example, acetic acid, trifluoroacetic acid, formic acid, and the like), and the like, and any combination thereof.

[0057] Various amounts of base(s) or acid(s) can be used in a solvolysis reaction (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like). In various examples, base(s) or acid(s) is/are present (e.g., in the hydrolysis reaction mixture) at about 1 to about 20 wt%, including all 0.1 wt% values and ranges therebetween (e.g., about 3 to about 10 wt% or about 5 wt%), based on the total weight of the solvolysis reaction mixture. [0058] In various examples, a polymer or polymers is/are present in a raw material. In various examples, a raw material comprises (or is) a textile, an article of manufacture (such as, for example, a container (such as, for example, a bottle, a food trays, a food packaging, or the like), a rug/carpet, a structural element, a surface element (such as, for example, a component or part in an automobile, a plane, or the like), or the like, or any combination thereof. In various examples, a raw material comprises (or is) a waste textile, a waste article of manufacture (such as, for example, a waste container (such as, for example, a waste bottle, a waste food tray, a waste food packaging, or the like), a waste rug/carpet, a waste structural element, a waste surface element (such as, for example, a component or part in an automobile, a plane, or the like), or the like, or any combination thereof.

[0059] Various amounts of polymer(s) (e.g., raw material(s), which may be waste material(s)) can be used. In various examples, polymer(s) (e.g., raw material(s)) is/are present (e.g., in a hydrolysis reaction mixture) at about 1 to about 50 wt%, including all 0.1 wt% values and ranges therebetween (e.g., about 1 to about 20 wt% or about 1 wt%), based on the total weight of the hydrolysis reaction mixture.

[0060] A solvolysis reaction (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like) may be carried out in a solvent or a mixture of solvents. In various examples, a solvolysis reaction (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like) is carried out in an aqueous solvent (e.g., water or the like). In various examples, a (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like) is carried out in solvent(s) chosen from water, organic solvents (e.g., alcohols, glycols, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, cyrene, formic acid, acetone, or the like), ionic liquids, and the like, and any combination thereof.

[0061] Various amounts of solvent(s) may be used. In various examples, solvent(s) is/are present (e.g., in a hydrolysis reaction mixture) at about 50 to about 95 wt%, including all 0.1 wt% values and ranges therebetween (e.g., about 75 to about 95 wt% or about 95 wt%), based on the total weight of the hydrolysis reaction mixture.

[0062] A solvolysis reaction (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like) can be carried out at various temperatures. In various examples, a solvolysis reaction is carried out at about 50 °C to about 100 °C, including all 0.1 °C values and ranges therebetween (e.g., about 80 °C to about 100 °C or about 90 °C). [0063] A solvolysis reaction (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like) can be carried out at various pressures. In various examples, a solvolysis reaction is carried out at from about 0.1 MPa to about 1 MPa, including all 0.1 MPa values and ranges therebetween (e.g., about 0.1 MPa to about 0.5 MPa or about 0.1 MPa.

[0064] A solvolysis reaction (such as, for example, a hydrolysis reaction, methanolysis reaction, glycolysis reaction, or the like) can be carried out for various times. Reaction time can depend on factors such as, for example, temperature, pressure, reaction component concentration(s), presence and/or intensity of an applied energy source, mixing (e.g., stirring or the like), or the like, or a combination thereof. In various examples, reaction time is about one hour to about 12 hours, including all integer second values and ranges therebetween (e.g., about 2 hours to about 8 hours or about 3 hours).

[0065] In various examples, polymer(s) is/are chosen from organic polymers, biopolymers, and the like, and any combination thereof. In various examples, an organic polymer is a polyester (such as, for example, a poly(terephthalate), a polypropylene terephthalate), a poly(butylene terephthalate), a polylactic acid, or the like), a polyamide (such as, for example, a nylon or the like), a polyalcohol, a polyurethane, a polyurea, a polycarbonate, a polyether ether ketone, a polyether ether ketone ketone, a poly ether ketone ketone, a polyetherimide, a polystyrene, or the like, or any combination thereof. In various examples, a biopolymer is a lignin, a starch, a cellulose, or the like, or any combination thereof.

[0066] In various examples, impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest) comprise (or is/are) organic acid(s), polyol(s), amine(s) (which may be diamines or the like), any of which may, independently, are protonated or deprotonated, or the like, or any combination thereof. In various examples, impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest) and/or free monomer(s) (or purified molecule(s) of interest) comprise one or more organic acid(s), one or more polyol(s), one or more amine(s), or structural analog(s) thereof is/are, independently, a deprotonated (e.g., a salt) or protonated structural analog of the organic acid(s), polyol(s), amine(s), or any combination thereof. In various examples, the organic acid(s) is/are chosen from terephthalic acid, isophthalic acid, phthalic acid, adipic acid, and the like, and structural analogs thereof, and any combination thereof. In various examples, the polyol (s) is/are chosen from diols (such as, for example, ethylene glycol, propane diol, butanediol, and the like), and the like, and structural analogs thereof, and any combination thereof. In various examples, the organic amine(s) is/are chosen from diamines (such as, for example, methylenediamine, hexamethyldiamine, and the like), and the like, and structural analogs thereof, and any combination thereof.

[0067] In various examples, impure monomer(s) (which may be recycled monomer(s) or the like) is/are formed from a textile, an article of manufacture (such as, for example, a container (such as, for example, a bottle, a food trays, a food packaging, or the like), a rug/carpet, a structural element, a surface element (such as, for example, a component or part in an automobile, a plane, or the like), or the like, or any combination thereof.

[0068] In various examples, a method comprises (or further comprises) isolating metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like, or any combination thereof. Metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like can be isolated by methods known in the art.

[0069] In various examples, a method comprises (or further comprises) contacting (such as, for example, washing or the like) metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like, or any combination thereof (which may be isolated) with one or more solvent(s) (examples of which are disclosed herein with respect to formation of ) metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like, or any combination thereof). In various examples, contacting repeated a desired number of times.

[0070] In various examples, a method comprises (or further comprises) decomposing metal complex(es), metal organic framework(s), coordination polymer network(s), or the like, where purified monomer(s) (e.g., free monomer(s) or the like) (or purified molecule(s) of interest), or structural analog(s) thereof are formed.

[0071] In various examples, decomposing metal complex(es), metal organic framework(s), coordination polymer network(s), or the like comprises contacting (e.g., forming a mixture (which may be a solution or the like) or the like with) metal complex(es), metal organic framework(s), coordination polymer network(s), or the like with one or more acid(s), one or more base(s), optionally, one or more organic solvent(s), one or more ionic liquid(s), or the like, or any combination thereof. In various examples, decomposing metal complex(es), metal organic framework(s), coordination polymer network(s), or the like comprises contacting the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like with one or more acid(s) forms metal precursor(s), structural analog(s) thereof, or the like. In various examples, decomposing comprises heating the metal complex(es), the metal organic framework(s), coordination polymer network(s), or the like (e.g., heating at about 100 °C in a mineral acid (such as, for example, nitric acid or the like) for about 6 hours).

[0072] Various amounts of MOF(s) can be used. In various examples, MOF(s) is/are present (e.g., in a decomposition reaction mixture) at about 1 to about 15 wt%, including all 0.1 wt% values and ranges therebetween (e.g., about 5 to about 15 wt% or about 15 wt%), based on the total weight of the reaction mixture.

[0073] In various examples, a decomposing is carried out in the absence of added solvent(s). In various examples, decomposing is carried out in one or more solvent(s). Nonlimiting examples of solvents include aqueous solvents (e.g., water, acids, bases, and the like), organic solvents (e.g., dimethylformamide, dimethyl sulfoxide, N-methyl-2- pyrrolidone, cyrene, formic acid, acetone, or the like), ionic liquids, and the like.

[0074] In various examples, decomposing is carried out in presence of one or more additive(s). Non-limiting examples of additives include acids, bases, and the like. Nonlimiting examples of acids include nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, perchloric acid, and the like, and any combination thereof. Non-limiting examples of bases include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, tripotassium phosphate, and the like, and any combination thereof.

[0075] Various amounts of acid(s) or base(s) can be used. In various examples, acid(s) or base(s) is/are present (e.g., in decomposition reaction mixture) at about 85 to about 98 wt%, including all 0.1 wt% values and ranges therebetween (e.g., about 85 to about 90 wt% or about 85 wt%), based on the total weight of a decomposition reaction mixture.

[0076] Decomposing can be carried out at various pH values. In various examples, decomposing is carried out at (or a decomposition reaction mixture comprises) a pH of 0-14, including all 0.1 pH units and ranges therebetween.

[0077] A decomposing metal complex(es), metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like can be performed under various reaction conditions. A decomposing reaction can comprise one or more steps and each step can be performed under the same or different reaction conditions as other steps.

[0078] A decomposing reaction can be carried out at various temperatures. In various examples, a decomposing reaction is carried out without exogenous heating or with exogenous heating. In various examples, a decomposing reaction is carried out at about room temperature (e.g., from about 20 °C to about 22 °C, including all 0.1 °C values and ranges therebetween), or above room temperature (e.g., above room temperature up to or about a boiling point of the solvent(s), if present) (e.g., from above room temperature to about 600 °C or above, or any combination thereof (e.g., where each decomposing reaction is performed at the same or a different temperature as other steps). In various examples, a decomposing is carried out at or about the boiling point of the acid(s) (e.g., mineral acid(s) or the like), base(s), organic solvent(s), or the like. In various examples, a decomposing reaction is carried out at about 25 °C to about 100 °C, including all 0.1°C values and ranges therebetween (e.g., about 50 °C to about 100 °C or about 100 °C).

[0079] A decomposing reaction can be carried out at various pressures. In various examples, a decomposing reaction is carried out at below atmospheric pressure (e.g., about 1 bar), at about atmospheric pressure, or at greater than atmospheric pressure (e.g., heating in a sealed pressurized reaction vessel and the like). In various examples, a decomposing reaction is carried out at from about 1 bar to about 100 bar, including all 0.1 bar values and ranges therebetween, or any combination thereof (e.g., where each step is performed at a different pressure as other steps). In various examples, a reaction is carried out at from about 0.1 MPa to about 1 MPa, including all 0.1 MPa values and ranges therebetween (e.g., about 1 MPa to about 0.5 MPa or about 0.1 MPa.

[0080] A decomposing reaction can be carried out for various times. Reaction time can depend on factors such as, for example, temperature, pressure, reaction component concentration(s), presence and/or intensity of an applied energy source, mixing (e.g., stirring or the like), or the like, or a combination thereof. In various examples, reaction times range from about minutes (e.g., 5 minutes) to about 3 days (or more), including all integer second values and ranges therebetween, or any combination thereof (e.g., where each step is performed at a different time as other steps). In various examples, decomposition reaction time is about one hour to about 24 hours, including all integer second values and ranges therebetween (e.g., about 1 hour to about 8 hours or about 6 hours).

[0081] In various examples, a method forms purified monomers. In various examples, at least a portion or all of the purified monomer(s) (which may be free monomer(s) or the like) (or purified molecule(s) of interest) is/are substantially colorless or colorless. The presence (e.g., quantity) and/or absence of color can be determined by methods known in the art. In various examples, the presence (e.g., quantity) and/or absence of color is determined by spectroscopic method(s) (such, as for example, UV-VIS spectroscopy or the like, or any combination thereof), Platinum-Cobalt Color, acid number, or the like, or any combination thereof. In various examples, the purified monomer(s) do not have detectible absorbance and/or 98% or greater, 99% or greater, 99.5% or greater, 99.9% or greater or substantially 100% transmittance of visible light wavelengths (e.g., about 400 nanometers to about 700 nanometers).

[0082] In various examples, purified monomer(s) (which may be free monomer(s)) or structural analog(s) thereof (or purified molecule(s) of interest (e.g., terephthalic acid or the like or any combination thereof) has higher purity than the impure monomer(s) (which may be a recycled monomer) (or impure molecule(s) of interest) used to produce the purified monomer(s) (which may be free monomer(s)) (or purified molecule(s) of interest). In various examples, purified monomer(s) (or purified molecule(s) of interest) purity level exhibit(s) high-purity appearance (such as, for example, white-transparent powders in the case of terephthalic acid). In various examples, purified monomer(s) (which may be free monomer(s)(or purified molecule(s) of interest) purity level exhibit(s) substantially the same or the same thermogravimetric or spectroscopic features as the corresponding analytical- grade molecules. In various examples, purified monomer(s) (which may be free monomer(s) or purified molecule(s) of interest) exhibit(s) a transparent color profile (e.g., that shows no features substantially different or different than the same monomer(s) signal(s) when tested using liquid chromatography or the like).

[0083] In various examples, a method further comprises isolating purified monomer(s) (or purified molecule(s) of interest) or the structural analog(s) thereof. In various examples, purified monomer(s) (e.g., free monomer(s) or the like) (or purified molecule(s) of interest) are isolated from the decomposition reaction mixture. Non-limiting examples of isolation include filtration (e.g., vacuum filtration and the like), centrifugation, and the like, which may remove substantially all or all of the solid(s) from the decomposition reaction mixture. Other non-limiting examples of isolation include distillation (e.g., vacuum distillation and the like, and the like, which may remove substantially all or all of the purified monomer(s) (e.g., free monomer(s) or the like) (or purified molecule(s) of interest) from the decomposition reaction mixture.

[0084] In various examples, in the case where not all impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest) are reacted in the forming reaction and/or decomposing reactions, the reaction mixture remaining after isolation of the purified monomer(s) (which may be free monomer(s) or the like) (or impure molecule(s) of interest) is subjected to additional/subsequent forming and/or decomposing reaction(s). In various examples, a method further comprises a second forming and/or second decomposing. In various examples, one or more or all of the additional forming and/or decomposing reaction(s) (e.g., the second forming and/or the second decomposing or the like) are carried out under the same conditions as the initial (e.g., first) forming and/or initial (e.g., first) decomposing. In various examples, one or more of all of the additional forming and/or decomposing reaction(s) (e.g., the second forming and/or the second decomposing or the like) are carried out under different conditions (e.g., different reactant(s), different reactant concentration(s), different reaction time and/or temperature, or the like, or any combination thereof) from the initial (e.g., first) forming and/or initial (e.g., first) decomposing or two or more or all of the other additional/subsequent forming and/or decomposing reaction(s). Forming and/or decomposing can be carried out a desired number of times.

[0085] In various examples, a method comprises (or further comprises) use of purified monomer(s) (which may be free monomer(s)) or structural analog(s) thereof in a polymerization reaction. In various examples, polymerization forms a polymer described herein. In various examples, polymerization forms a polyester (such as, for example, a poly(terephthalate), a polypropylene terephthalate), a poly(butylene terephthalate), a polylactic acid, or the like), a polyamide (such as, for example, a nylon or the like), a polyalcohol, a polyurethane, a polyurea, a polycarbonate, a polyether ether ketone, a polyether ether ketone ketone, a polyether ketone ketone, a polyetherimide, a polystyrene, or the like, or any combination thereof.

[0086] In various examples, one or more or all purified monomer(s) is/are subjected to one or more purification(s) (which are not a purification method of the present disclosure) prior to use in a polymerization reaction. Non-limiting example of purification include solvent extraction, distillation, crystallization, trituration, chromatography, and the like, and any combination thereof.

[0087] In various examples, a method comprises (or further comprises) isolation (such as, for example, recycling or the like) of at least a portion of or substantially all (or all) of the acid(s) or base(s) or metal ions (of the metal precursor(s), which may be in the form of metal salt(s)), or both used to form the metal complex(es), the MOF(s), the coordination polymer network(s), or the like, or any combination thereof. In various examples, at least a portion of or substantially all (or all) of the acid(s) or base(s) are isolated by distillation or the like and/or at least a portion of or substantially all (or all)of the metal ion(s) (such as, for example, metal salt(s) or the like) are isolated by solvent removal (such as, for example, evaporation, distillation, or the like. In various examples, the isolated acid(s) or base(s) and/or isolated metal precursor(s) used in a subsequent method of the present disclosure (e.g., are recycled). [0088] In various examples, a method comprises (or further comprises) isolation (such as, for example, recycling or the like) of at least a portion of or substantially all (or all) of the acid(s) or base(s) or metal ions (of the metal precursor(s), which may be in the form of metal salt(s)), or both used to form the metal complex(es), the MOF(s), the coordination polymer network(s), or the like, or any combination thereof. In various examples, at least a portion of or substantially all (or all) of the acid(s) or base(s) are isolated by distillation or the like and/or at least a portion of or substantially all (or all)of the metal ion(s) (such as, for example, metal salt(s) or the like) are isolated by solvent removal (such as, for example, evaporation, distillation, or the like. In various examples, the isolated acid(s) or base(s) and/or isolated metal precursor(s) used in a subsequent method of the present disclosure (e.g., are recycled). [0089] In various examples, a method or a portion thereof is carried out in a batch process, a continuous process, a semi-continuous process, or the like, or any combination thereof.

[0090] In various examples, a method or a portion thereof is carried out in a system. An example of a system is shown in FIG. 12.

[0091] In the system of FIG. 12, a first chamber 100 is configured to carry out formation of one or more metal complex(es), one or more metal organic framework(s) (MOF(s)), one or more coordination polymer network(s), or the like, or any combination thereof and isolation of same and disassembly of same. A second chamber 200 is configured to recover metal salt(s) formed by the disassembly process. In various examples, a first chamber and a second chamber are in fluid connection.

[0092] In an aspect, the present disclosure provides methods of making one or more metal complex(es), one or more metal organic framework(s) (MOF(s)), one or more coordination polymer network(s), or the like, or any combination thereof. Non-limiting examples of the methods are disclosed herein.

[0093] In various examples, a method of making one or more metal complex(es), one or more metal organic framework(s) (MOF(s)), one or more coordination polymer network(s), or the like, or any combination thereof is as described herein. In various examples, a method of making one or more metal complex(es), one or more metal organic framework(s) (MOF(s)), one or more coordination polymer network(s), or the like, or any combination thereof comprises: forming one or more metal complex(es), one or more metal organic framework(s) (MOF(s)), one or more coordination polymer network(s), or the like, or any combination thereof comprising one or more impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest), structural analog(s) thereof, or any combination thereof; and optionally, isolating the metal complex(es), one or more metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like.

[0094] In an aspect, the present disclosure provides uses of purified monomer(s) (or purified molecule(s) of interest) or structural analog(s) thereof. In various examples, purified monomer(s) (or purified molecule(s) of interest) or the structural analog(s) thereof are made by a method of the present disclosure. Non-limiting examples of uses of purified monomer(s) (or purified molecule(s) of interest) or the structural analog(s) thereof.

[0095] Purified monomer(s) or structural analog(s) thereof can be used in various polymerization reactions and/or to produce various polymers. In various examples, a polymer is a homopolymer, a copolymer or the like. In various examples, a polymer comprises one or more polymerized recycled monomer(s). Non-limiting examples of polymerization reactions and polymers are described herein.

[0096] In various examples, a polymer is formed from at least one purified monomer (e.g., a monomer or monomers produced by a method of the present disclosure). In various examples, a polymer is formed from two or more purified monomers (e.g., monomers produced by a method of the present disclosure). In various examples, a polymer further comprises one or more monomer(s) that are not purified monomer(s) (e.g., a monomer or monomer(s) not produced by a method of the present disclosure).

[0097] In various examples, a polymer comprises (or is chosen from) organic polymers, biopolymers, and the like, and any combination thereof. In various examples, an organic polymer is a polyester (such as, for example, a poly(terephthalate), a polyethylene terephthalate), a polypropylene terephthalate), a poly(butylene terephthalate), a polylactic acid, or the like), a polyamide (such as, for example, a nylon or the like), a polyalcohol, a polyurethane, a polyurea, a polycarbonate, a polyether ether ketone, a polyether ether ketone ketone, a polyether ketone ketone, a polyetherimide, a polystyrene, or the like, or any combination thereof. In various examples, a biopolymer is a lignin, a starch, a cellulose, or the like, or any combination thereof.

[0098] In various examples, purified monomer(s) is/are chosen from organic acid(s), polyol(s), amine(s) (which may be diamines or the like), any of which may, independently, are protonated or deprotonated, or the like, or any combination thereof. In various examples, organic acid(s) is/are chosen from terephthalic acid, isophthalic acid, phthalic acid, adipic acid, and the like, and structural analogs thereof, and any combination thereof. In various examples, polyol (s) is/are chosen from diols (such as, for example, ethylene glycol, propane diol, butanediol, and the like), and the like, and structural analogs thereof, and any combination thereof. In various examples, organic amine(s) is/are chosen from diamines (such as, for example, methylenediamine, hexamethyldiamine, and the like), and the like, and structural analogs thereof, and any combination thereof.

[0099] In various examples, a polymer does not comprise one or more impurit(ies) and/or additive(s) present in the impure monomer(s) from which purified monomer(s) was/were formed. In various examples, a polymer is substantially free or free of the impurit(ies) and/or additive(s) present in the impure monomer(s) from which purified monomer(s) was/were formed.

[0100] The presence (e.g., quantity) and/or absence of impurit(ies) and/or additive(s) in a polymer can be determined by methods known in the art. In various examples, the presence (e.g., quantity) and/or absence of impurit(ies) and/or additive(s) is determined by spectroscopic method(s) (such, as for example, UV-VIS spectroscopy, IR spectroscopy, NMR spectroscopy (e.g., spectroscopy, ¹³ C NMR spectroscopy, or the like), spectrometric methods (e.g., mass spectrometry, gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), or the like), liquid chromatography (such as, for example, high performance liquid chromatography (HPLC) or the like), thermogravimetric analysis (TGA), Platinum-Cobalt Color, acid number, inductively Coupled Plasma Optical Emission spectroscopy (ICP-OES), energy-dispersive x- ray spectroscopy (EDS), or the like, or any combination thereof. In various examples, a polymer comprises 5% or less, 2.5% or less, 1% or less, 0.1% or less. 0.05% or less by weight (based on the total weight of the polymer, impurit(ies) and/or additive(s)) as determined by one or more of the foregoing methods.

[0101] In various examples, the presence (e.g., quantity) and/or absence of impurit(ies) and/or additive(s) in a polymer is below the detection limit of spectroscopic method(s) (such, as for example, UV-VIS spectroscopy, IR spectroscopy (e.g., FTIR or the like), NMR spectroscopy (e.g., NMR spectroscopy, ¹³ C NMR spectroscopy, or the like), spectrometric methods (e.g., mass spectrometry, GC-MS, LC-MS, or the like), thermogravimetric analysis (TGA), acid number, or the like, or any combination thereof.

[0102] Purified monomer(s) or the structural analog(s) thereof (e.g., polymer(s) produced using the purified monomer(s) or the structural analog(s) thereof) can be used to form various articles of manufacture. Non-limiting examples of articles of manufacture (e.g., comprising one or more polymer(s) produced using the purified monomer(s) or the structural analog(s) thereof of the present disclosure) are described herein. [0103] The following Statements provide examples of methods and polymers of the present disclosure:

Statement 1. A method of recycling one or more polymer(s) (e.g., purifying recycled monomer(s) obtained from polymer(s)) (or obtaining one or more molecule(s) of interest (e.g., from a polymer/polymers or the like)) comprising forming one or more metal complex(es), one or more metal organic framework(s) (MOF(s)), one or more coordination polymer network(s), or the like, or any combination thereof comprising one or more impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest), structural analog(s) thereof, or any combination thereof; optionally, isolating the metal complex(es), one or more metal organic framework(s) (MOF(s)), coordination polymer network(s), or the like; optionally, decomposing the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like, where purified monomer(s) (e.g., free monomer(s) or the like) (or purified molecule(s) of interest), or structural analog(s) thereof are formed; and optionally, isolating the purified monomer(s) (or purified molecule(s) of interest) or the structural analog(s) thereof.

Statement 2. A method according to Statement 1, the method further comprising providing impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest) or the like.

Statement 3. A method according to Statement 1 or 2, where the polymer(s) is/are chosen from organic polymers, biopolymers, and the like, and any combination thereof.

Statement 4. A method according to any one of the preceding Statements, where the impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest) is/are organic acid(s), polyol(s), amine(s) (which may be diamines or the like), any of which may, independently, are protonated or deprotonated, or the like, or any combination thereof.

Statement 5. A method according to any one of the preceding Statements, where the impure monomer(s) (which may be recycled monomer(s) or the like) is/are formed from a textile, an article of manufacture (such as, for example, a container (such as, for example, a bottle, a food trays, a food packaging, or the like), a rug/carpet, a structural element, a surface element (such as, for example, a component or part in an automobile, a plane, or the like), or the like, or any combination thereof.

Statement 6. A method according to any one of the preceding Statements, where the forming the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like comprises contacting the impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest, or any combination thereof with one or more metal precursor(s), where the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like are formed.

Statement 7. A method according to any one of the preceding Statements, where the decomposing the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like comprises contacting (e.g., forming a mixture (which may be a solution or the like) or the like with) the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like with one or more acid(s), one or more base(s), one or more organic solvent(s), one or more ionic liquid(s), or the like, or any combination thereof.

Statement 8. A method according to any one of the preceding Statements, where the decomposing the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like comprises contacting the metal complex(es), metal organic framework(s), coordination polymer network(s), or the like with one or more acid(s) forms metal precursor(s), structural analog(s) thereof, or the like.

Statement 9. A method according to any one of the preceding Statements, where the impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest) comprise one or more impurit(ies) and the purified monomer(s) (which may be free monomer(s) or the like) (or purified molecule(s) of interest) is/are substantially free or free of the impurit(ies) and/or the impure monomer(s) (which may be recycled monomer(s) or the like) (or impure molecule(s) of interest)) comprise one or more additive(s) and the purified monomer(s) (which may be free monomer(s) or the like) (or purified molecule(s) of interest) is/are substantially free or free of the additive(s).

Statement 10. A method according to any one of the preceding Statements, where the purified monomer(s) (which may be free monomer(s) or the like) (or purified molecule(s) of interest) is/are substantially colorless or colorless.

Statement 11. A method according to any one of the preceding Statements, further comprising use of the purified monomer(s) (which may be free monomer(s)) or structural analog(s) thereof in a polymerization reaction.

Statement 12. A polymer formed from at least a monomer or monomers provided by a method according to any one of the preceding Statements.

[0104] The steps of the methods described in the various embodiments and examples disclosed herein are sufficient carry out the methods of the present disclosure. Thus, in an embodiment, a method consists essentially of a combination of the steps of the methods disclosed herein. In another embodiment, a method consists of such steps.

[0105] The following Example is presented to illustrate the present disclosure. It is not intended to be limiting in any manner.

EXAMPLE

[0106] This example provides a description of methods and purified monomers of the present disclosure, and uses thereof.

[0107] Reactive Crystallization through Metal-Organic-Framework Intermediate Purifies Terephthalic Acid from Textile Impurities. Methods were developed for purifying TP A by crystallization that works in water and does so by forming crystals at the purification temperature (to avoid trapping the impurities at the cooling stage).

[0108] MOFs are compounds consisting of metal ion clusters coordinated to organic ligands to form three-dimensional crystalline structures. TPA derived from PET waste has been used to prepare MOFs, including UiO-66(Zr), MIL-53(A1), and MIL-47(V). In some cases, PET waste can be directly used as the synthesis reagent, including Cr-MOF, MIL- 47(V), MIL-53(Cr), MIL-53(A1), MIL-53(Ga), and MIL-lOl(Cr). This work demonstrated that the MOF disassembly can separate TPA from its impurities. MOFs were selected that can undergo decomposition in strong acid, with the intention to create a final solution resembles the solution at start. It was shown that recycled TPA from blended PET waste can be reversibly assembled as the organic linker of MIL-53(Ga) and its disassembly results in pure TPA. Furthermore, it was shown that the metal salt that can be circularly recycled for the further crystallization (FIG. 1).

[0109] Results and Discussion. Powder X-ray diffraction (PXRD) confirms the formation of rTPA from a red poly cotton (65/35 polyester/cotton blend) fabric after alkaline hydrolysis (FIG. 2a and FIG. 4). All observed PXRD peaks are in good agreement with the TPA crystal structure. Repeated water washing, however, did not remove the fabric dyes from rTPA. The leftover impurity was visually recognizable through the color of the TPA and its solution in DMSO (FIG. 2b) but below the detection limit of Nuclear Magnetic Resonance (NMR), Thermogravimetric Analysis (TGA), or Fourier-Transform Infrared Spectroscopy (FTIR) (see FIGS. 5-7). A mixture of rTPA, Ga(NCh)3 and water was heated in an autoclave at 210°C for 5 hours to synthesize MIL-53(Ga) (see FIG. 9-11). The PXRD spectra of the prepared MIL-53(Ga) (FIG. 4) matches well with literature, confirming that rTPA can serve as the organic linker in a metal organic framework synthesis. The particle sizes were on the order of 10-100pm (see FIG. 8). The MIL-53(Ga) crystals were subjected to boiling HNCh to form purified TPA (pTPA). FIG. 2a shows the PXRD of rTPA obtained after the MIL-53 (Ga) disassembly. The peak positions match well the TPA crystal structure and have sharper FWHM than rTPA, indicating the higher degree of crystallinity.

[0110] The comparison between rTPA and pTPA dissolved in DMSO shows visual evidence of color change (FIG. 2b). The rTPA solution had a red tint, indicating the presence of dyes and other impurities from the red fabrics, while the pTPA solution was clear and colorless, indicating no dye impurities. Given that the impurity was recognizable through the color of the solution but not detectable by NMR, TGA, or FTIR, the cleanliness of the TPA was quantified using UV-vis spectroscopy after dissolving the solids in DMSO (FIG. 2c.) Comparing the absorbance of rTPA and pTPA to commercial TPA, all three have a peak characteristic of TPA at 300 nm. Commercial TPA has no absorbance other than the characteristic TPA feature at 300 nm. In contrast, rTPA has absorbance peaks that extend as far as 600 nm. These peaks were assigned to the impurities in rTPA, most likely dyes and colorants. The absorbance peaks disappear in pTPA, whose absorbance spectrum matches closely with that of the commercial TPA. This observation suggests that pTPA has purity close to the commercial TPA monomers, validating our hypothesis that reactive crystallization via the MIL-53(Ga) formation rejects textile impurities in recycled monomers. [OHl] The TPA purification process works irrespective of the color of the starting textile. The reactive crystallization approach was applied to polycotton dyed with different colors (blue: FIG. 3a-b, green: FIG. 3c-d). The photographs of rTPA dissolved in DMSO from the blue and green fabrics showed a tinted solution, indicating the presence of impurities, similar to the red polycotton sample. This effect was quantified using UV-Vis spectroscopy. FIG. 3b, d compares the spectra of rTPA, pTPA, and commercial TPA, where pTPA went through the same methodology as red polycottons. The results showed the same outcome: the rTPA showed only the 300 nm peak that is the characteristic absorption of TPA, and no other absorbance features. It is noteworthy that the base absorbance of the rTPA was slightly higher than the commercial TPA, although it was difficult to quantify given that it presented as a very weak signal.

[0112] In summary, the purification of recycled TPA from waste polyester textiles through reactive crystallization was demonstrated. The instant approach crystallizes recycled TPA with Ga nitrate to form a MIL-53 (Ga) MOF intermediate, which we subsequently disassembled in nitric acid to extract purified TPA. The reported process is water-based and does not require organic solvents. Colorimetric analysis using DMSO as a solubilizing solvent showed that purified TPA produced a clear solution. This observation is in contrast to the tint pre-purified TPA solution, which contained dyes from the depolymerization step. This result confirmed the removal of impurities such as textile colorants. The processs produced in addition to purified TPA, Ga nitrate and excess nitric acid that can be reused in the future reactive crystallization step. This work demonstrated an aqueous method for purifying TPA from impurities and contribute a technique for purifying recycled waste textiles to enable circular polyesters.

[0113] Experimental Details. Reagents and Chemicals. Gallium (III) nitrate hydrate (Ga(NO3)3-xH2O, Beantown Chemical, 99.9%), terephthalic acid (BDC, Sigma Aldrich, 98%), sodium hydroxide (NaOH, Macron Fine Chemicals), polyester/cotton shirts (Port & Company, 65% polyester 35 % cotton), acetone (Sigma- Aldrich, 99.9%), methanol (Sigma- Aldrich, 99.8%), sulfuric acid (Honeywell, 95.0-98.0 %), and nitric acid (LabChem, 50% v/v) were used as-received. All water used was deionized (MilliporeSigma, Direct-Q 5UV-R). [0114] Depolymerization of PET Textile Wastes. The polyester cotton fabric was depolymerized following an alkaline hydrolysis procedure from Palme et al. 20 g NaOH and 480 g deionized water were combined in a 500 mL round bottom flask to make a 10 wt% NaOH alkaline hydrolysis solution. 5g of either red, green, or blue 65/35 polyester/cotton fabric was cut into 1 in x 1 in pieces and put into the reaction flask. The solution was heated to 100 C and stirred for 200 min. The round bottom flask was cooled to room temperature. The liquid fraction was extracted using a vacuum filtration using a glass microfiber filter. To the liquid phase sulfuric acid was added to precipitate TPA solids. TPA was filtered off using vacuum filtration with a glass microfiber filter and washed with deionized water. Prior to PXRD, TPA was dried at 150 °C overnight.

[0115] Synthesis of MIL-53 (Ga). MIL-53 (Ga) was hydrothermally synthesized under autogenous pressure from a mixture of 0.525 g Ga nitrate, 0.38 g terephthalic acid, and 10 g deionized water. The reactants were mixed together in a 100 mL Teflon-lined autoclave, which was heated at 210 C for 5 hr. After the reaction, the product was washed with N,N- dimethylformamide (DMF) to remove excess TPA and acetone to help the product dry more quickly. Without using DMF, PXRD showed that the resulting product contained excess TPA.

[0116] Disassembly of MIL-53(Ga). MIL-53(Ga) was disassembled to purified TPA by stirring the MOF with the 2 mole-equivalent amount of nitric acid. The mixture was stirred at 100 °C for 6 hr in a lidded glass vial with a needle vent. After cooling to room temperature, the mixture was centrifuged 3 times with water to remove remaining nitric acid and once with MeOH to help dry the product more quickly. The product was then dried and prepared for characterization. [0117] Characterization. The Bruker D8 Advance ECO powder diffractometer with a

IkW Cu-Ka source was used to collect PXRD in the range of 29 = 3 - 50° at a scanning rate of 0.02° s' ¹ . All samples were dried overnight. UV-Vis spectra was recorded on UV-Vis spectrometer (Shimadzu) in the range of 200 - 900 nm. Blank DMSO as a background for all UV-Vis experiments. [0118] Although the present disclosure has been described with respect to one or more particular embodiments and/or examples, it will be understood that other embodiments and/or examples of the present disclosure may be made without departing from the scope of the present disclosure.