WO2024133398A1

WO2024133398A1 - Repeatedly recyclable-elastomer copolymer mimics (rr-ecpms) of polyolefin elastomers (poe) copolymers

Info

Publication number: WO2024133398A1
Application number: PCT/EP2023/086855
Authority: WO
Inventors: Sivadinarayana Chinta; Kaiwalya SABNIS; Ganesh Kannan; Lidia JASINSKA-WALC; Robbert Duchateau; Girish KORIPELLY; Alexander Stanislaus; Ravichander Narayanaswamy; Maria Soliman; Bart Albertus Hubertus ESSCHERT VAN DEN
Original assignee: Sabic Global Technologies B.V.
Priority date: 2022-12-24
Filing date: 2023-12-20
Publication date: 2024-06-27

Abstract

A composition and methods of making the composition are described. The composition can include a repeatedly recyclable-elastomer copolymer mimic (RR-ECPM) of a polyolefin elastomer (PoE) copolymer(s). The RR-ECPM can be a reaction product of a difunctional oligomer and a difunctional linker obtained from a liquefied article.

Description

REPEATEDLY RECYCLABLE-ELASTOMER COPOLYMER MIMICS (RR- ECPMS) OF POLYOLEFIN ELASTOMERS (PoE) COPOLYMERS

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of the filing date of India Provisional Patent Application No. 202241075169, filed December 24, 2022, and India Provisional Patent Application No. 202341063917, filed September 22, 2023, which are incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

A. Field of the Invention

[0001] The invention generally relates to repeatedly recyclable-elastomer copolymer mimics (RR-ECPMs) of polyolefin elastomer (PoE) copolymers.

B. Description of Related Art

[0002] Polyolefins have multiple industrial uses. Polyolefins such as polyolefin elastomers constitute the largest volume of synthetic plastic produced worldwide. Polyolefin elastomer copolymers are used in wide variety of articles, such as films, sheets, foams, fibers, toys, bottles, containers, furniture, electronic parts, and plumbing materials. One of the issues with the wide-spread use of PoE is what to do with the articles once they reach the end of their useability. One solution is to simply discard the articles (“single use articles”) and prepare new ones from new chemicals. A problem with this approach is the use of landfills and/or incinerators to discard and/or destroy the articles. Landfills are reaching capacity, and incinerators can create pollution. Still further, the use of new chemicals can be wasteful and/or increase the carbon footprint of the resulting article.

[0003] An alternative solution to discarding articles made with PoE is to mechanically recycle the articles. Mechanical recycling efforts physically alter an article into another form without recreating the material for new applications. The stress and energy input to physically alter the article (e.g., melt the article and reform it into a new article) can oftentimes degrade the PoE such as by damaging the copolymer chains (e.g., chain scission, chain branching, crosslinking, etc.). The mechanically recycled PoE can have reduced chemical and/or physical properties when compared with its native/virgin form. This damage oftentimes limits the amount of mechanically recycled PoE that can be used to re-produce new articles. For example, virgin PoE is often blended with the mechanically recycled PoE to create new articles. The use of additional materials such as virgin PoE can be cost-inefficient and/or increase the carbon footprint of the resulting article.

[0004] An alternative solution to mechanically recycling articles made with PoE is to chemically recycle the PoE within the articles. Typical chemical PoE recycling technologies subject the material to pyrolysis (cracking) and/or gasification reactions to chemically break down the PoE into various smaller hydrocarbon products (e.g., smaller alkanes, alkene, or dienes). The chemical recycling process of PoE typically results in production of a fraction of olefins, which can be used to make chemically recycled PoE. The additional hydrocarbon products can be used as intermediates in petrochemical plants, as fuels or fuel components, or as specialty chemicals. Examples of chemical recycling of polyolefins are described in International Patent Application Publication No. WO 2003/054061 to Maeharae/ o/.. European Patent Application Publication No. EP 3907250 to Mecking et al., and U.S. Patent No. 5,643,998 to Nakano et al.

SUMMARY OF THE INVENTION

[0005] A discovery has been made that provides a solution to at least one or more of the problems that may be associated PoE recycling. The discovery relates to the use of a repeatedly recyclable elastomer copolymer mimic (RR-ECPM) of a polyolefin elastomer (PoE) copolymer, which, once made into an article, can repeatedly be recreated from the article, and reused to make additional articles. The RR-ECPM can be the reaction product of a difunctional oligomer with an optional comonomer and a difunctional linker obtained by depolymerization of an article into a liquified article comprising mixtures of difunctional linkers and difunctional oligomers of the RR-ECPM. The liquified article can be obtained by, for example, melting and depolymerizing a previously manufactured and/or used article having the RR-ECPM. Nonlimiting examples of articles can include consumer goods, packaging products, dispensing bottles, wash bottles, tube, bags, electronic components, other molded articles, pharmaceutical containers, bottles, caps, closures, liners, trash bags, food packaging film and/or materials, laminations, pipes, hoses, fittings, etc. Advantageously, the RR-ECPM of the present invention can be repeatedly and directly recreated (e.g., 2 to 500 times or more) from an article made from the copolymer at amounts that are substantially the same as present in the article being recycled. For example, at least 90 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, or 100 wt. % of the RR-ECPM from the article being recycled can be depolymerized into difunctional oligomers and difunctional linkers, repolymerized into recreated RR-ECPM, and re-used in the newly produced article. This high recycling efficiency can reduce or avoid the need to use additional materials (e.g., virgin RR-ECPM) to produce new articles. For example, the high recycling efficiency of the RR-ECPM can reduce or avoid having to use feed stock (e.g., virgin RR-ECPM feed stock) to produce additional article(s) from the recycled article(s). In some aspects, 5, 4, 3, 2, 1, 0.5, or 0 wt. % of feed stock (e.g., virgin RR-ECPM feed stock) can be used after 2, 3, 4, 5, 6, 7, 8, 9, 10, or more use cycles of the RR-ECPM. Additionally, the recreated RR-ECPM obtained from the article can have the same or substantially the same chemical and/or physical properties of the RR-ECPM present in the unrecycled article. The RR-ECPM(s) containing compositions, articles, and/or methods of the present invention provide for a recycling efficiency that can advantageously result in reduced costs of recycling articles, increased recycling efforts, and/or reduced amount of additional materials used to produce new articles. Still further, the recycling efficiency of the RR-ECPM(s) can result in a reduced carbon footprint for the produced articles.

[0006] One aspect of the present invention describes compositions that include RR-ECPMs. In one aspect, a composition can include a repeatedly recyclable-elastomer copolymer mimic (RR-ECPM) of a polyolefin elastomer copolymer, and an additive. The RR-ECPM can be a reaction product of a difunctional oligomer and a difunctional linker of a liquefied article (e.g., a consumer good, a packaging product, a pharmaceutical container, a bottle, a cap, a closure, a liner, a trash bag, a food packaging film, a lamination; a pipe, a hose, a fitting, or a combination thereof). The difunctional oligomer can include a difunctional oligomer having from 40 to 2000 carbon atoms (C40 to C2000), preferably C60-C1500, more preferably C80-C1100, and a functionality “F” of 2.0 ± 0.3. The difunctional oligomer can have a degree of saturation of 98% to 100%. In some aspects, the difunctional oligomer of the RR-ECPM can have branched C40 to C2000 polyethylene or polypropylene. The difunctional oligomer can be a branched and can have a degree of branching of 5% up to 60%. The difunctional oligomer can include a comonomer. The difunctional linker can have a carbon chain of 2 to 13 carbon atoms (C2-C13) and “F” of 2.0 ±0.3. For both the difunctional oligomer and difunctional linker, “F” can be an amine (-NH2), an alcohol (-OH), a carboxylic acid (-COOH), or a combination thereof. The difunctional oligomer “F” and the difunctional linker “F” can be the same or different as long as they can react to form a condensation product. The carboxylic acid can be a cyclic acid (e.g, anhydride), acyclic acid, a masked acid (e.g, an ester), or a combination thereof. In some embodiments, the carboxylic acid difunctionality is a combination of an acid and an ester. In a preferred aspect, the difunctional oligomer(s) can be diol(s) and the difunctional linker(s) can be a carboxylic acid(s). The number average molecular weight (M_n) of the RR-ECPM can be 20,0000 to 1,000,000 g/mol. The M_n can be determined using gas permeation chromatography (GPC). More particularly, the M_n can be determined as the polyethylene equivalent molecular weight by high temperature size exclusion chromatography performed at 160 °C in trichlorobenzene using polyethylene standards. A density of the RR-ECPM can be 0.799 g/cm³ to 0.95 g/cm³. The RR-ECPM(s) can have a melt temperature (Tm) of 40 °C to 110 °C, 50 °C to 100 °C, or any value or range there between as measured by DSC at a heating rate of 10 °C per min. In some aspects, the composition does not include homopolymers of high-density polyethylene (HDPE) homopolymer, low density polyethylene (LDPE) homopolymer, linear low-density polyethylene (LLDPE) homopolymer and/or polypropylene (PP) homopolymer or combinations thereof. In some aspects, the composition can include at least 95 wt.%, preferably at least 98 wt. %, of the RR-ECPM(s) and greater than 0 wt. to 5 wt. %, preferably at least 0.01 wt. % to 0.2 wt. %, or more preferably 0.05 wt. % to 0.15 wt. %, of an article additive. In another aspect, the composition can include an article additive (e.g., an additive present in the article being liquified) in an amount ranging from more than 0 wt. % to less than 0.01 wt.%, based on the weight of the RR-ECPM. In some aspects, the difunctional oligomer and the difunctional linkers of the liquefied article have a weight percentage that is at least 95 wt.% of the RR-ECPM.

[0007] The composition can be an ethylene comonomer based RR-ECPM. In some aspects, the composition can be a propylene comonomer based RR-ECPM. In some aspects, the RR- ECPM is an ethylene-based RR-ECPM, a propylene-based RR-ECPM, or a combination thereof. In some aspects, the composition can include an ethylene olefin and a linear alpha olefin (e.g, propene, butene, pentene and the like), preferably 40 wt. % to 95 wt. % of the ethylene olefin and 5 wt. % to 60 wt. % of the linear alpha olefin. The composition can include a propylene olefin and a linear alpha olefin, preferably 40 wt. % to 95 wt. % of the propylene olefin and 5 wt. % to 60 wt. % of the linear alpha olefin. In some aspects, the composition can include an ethylene olefin and a butylene olefin, preferably 40 wt. % to 95 wt. % of the ethylene olefin and 5 wt. % to 60 wt. % of the butylene olefin. The composition can include a propylene olefin and a butylene olefin, preferably 40 wt. % to 95 wt. % of the propylene olefin and 5 wt. % to 60 wt. % of the butylene olefin.

[0008] In one preferred aspect of the present invention, the RR-ECPM can have the following formula:

(I) (II)

Z can be an aliphatic group and n can be an integer ranging from 2 to 13. X and X' can be the same or different. X can include a polyolefin backbone (e.g., derived from the difunctional oligomer) that can include 40 to 2000 carbon atoms, preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms. When X or X' is a propylene oligomer, a methyl group is usually present. X can include an optional co-monomer of an ethylene olefin or a propylene olefin and a 1 -alkene. The 1 -alkene can include 3 to 13 carbon atoms. The comonomer can include 40 wt.% to 95 wt.% of the ethylene or propylene olefin and 5 wt.% to 60 wt. % of the 1 -alkene. The RR-ECPM(s) can have more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units.

[0009] X' can each independently include a polyolefin backbone (e.g, derived from the difunctional oligomer) that can include 40 to 2000 carbon atoms, preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms. X' can include an optional co-monomer of an ethylene olefin or a propylene olefin and a 1 -alkene. The 1 -alkene can include 3 to 13 carbon atoms. The comonomer can include 40 wt.% to 95 wt.% of the ethylene or propylene olefin and 5 wt.% to 60 wt.% of the 1-alkene. The RR-ECPM(s) can have more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units.

[0010] A composition of the present invention can include: (a) a repeatedly recyclable- elastomer copolymer mimic (RR-ECPM) of a polyolefin elastomer (PoE) copolymer and (b) an article additive. The RR-ECPM is a reaction product of a difunctional oligomer with a comonomer and a difunctional linker. The difunctional oligomer and the difunctional linker are both from a liquefied article. The difunctional oligomers and the difunctional linkers of the liquefied article can have a weight percentage that is at least 95 wt.% of the RR-ECPM. The composition does not include any homopolymer of high-density polyethylene (HDPE), low density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and polypropylene (PP), and combinations thereof. The difunctional oligomer and the difunctional linker of the liquefied article can have weight percentage that is at least 95 wt.% of the RR-ECPM.

[0011] In some aspects of the present invention composites are described. A composite can include the RR-PoP composition of the present invention. The composite can include a plurality of fillers. Non-limiting examples of fillers include fibers, glass fibers, aramid fibers, polyester fibers, polyamide fibers basalt fibers, steel fibers, or combination thereof. In embodiments where the composite includes fibers, the fibers can be sized. The sizing can be a RR-PoP or a RR-ECPM.

[0012] In other aspects of the present invention, stacked polymeric compositions are described. The stacked polymeric composition can include a composite or composition of the present invention (first layer) and a second layer. The second layer can include a composite or composition of the present invention. In some aspects, the first and second layers can be coupled together via a coupling agent (tie layer).

[0013] In some aspect of the present invention, a fiber that includes a RR-ECPM sizing disposed about the fiber is described. The fiber can be included in a tow of fibers. The fiber can be incorporated in a composite or composition that includes a polymeric matrix material. The polymeric matrix material can be repeatedly recycled polymer mimic polymer matrix, a thermoplastic polymer matrix, or a thermoset polymer matrix. Upon recycling the composite, laminate or composition containing the PoP sized fiber, the fiber can be separated from the PoP material and reused.

[0014] In yet other aspects of the present invention, an article comprising a composition of the present invention are described. The article can be recycled by the processes of the present invention and can be remade into another article (e.g., the article and the another article can be a cup, or the article can be a cup and the another article can be a plastic utensil). Notably, the article and the another article can include similar mechanical and/or functional properties due to the chemical recycling of the RR-ECPM of the present invention.

[0015] Certain aspects are directed to a method for making the composition of the present invention. A method can include liquefying (e.g., melting) an article made from a composition of the present invention. The RR-ECPM in the composition can be depolymerized into a mixture containing the difunctional oligomers and the difunctional linkers. In one aspect, depolymerization can be performed by hydrolysis and/or solvolysis by contacting the liquified article composition with water and/or solvent to obtain the difunctional oligomer and the difunctional linker. In some aspects, the difunctional oligomer and the difunctional linker in the mixture can be separated prior to repolymerization. Reaction of the difunctional oligomer and the difunctional linker can produce the composition of the present invention that includes a RR-ECPM(s). The composition can be formed into an article. The article can be used by consumers and then recycled to produce the composition of the present invention to continue the cycle. The cycle can be repeated at least two times, preferably 2 to 500 times.

[0016] Also disclosed in the context of the present invention is a method of closed-loop recycling that encompasses a combination of mechanical and chemical recycling events. The method can include any one or any combination or all of the following steps: (1) obtaining an article comprising the RR-ECPM; (2) liquifying the article (e.g., melting the article) to obtain a liquified article composition; and/or (iii) forming a second or new article of manufacture from the liquified polymeric composition. This mechanical recycling process can be performed without having to use virgin RR-ECPM or using minimal amounts of virgin RR-ECPM (e.g., 10, 5, 4, 3, 2, 1, or 0 wt.% of virgin RR-ECPM). Advantageously, at least 90, 95, 96, 97, 98, 99, or 100 wt.% of the RR-ECPM from the article being liquified can be reused in the newly created article. The article can include an article additive (e.g., greater than 0 wt.% to 5 wt.%, preferably at least 0.01 wt. % to 0.2 wt. %, or more preferably 0.05 wt. % to 0.15 wt. %, of an article additive). The composition of the present invention can be recycled multiple times and retain its mechanical and/or functional properties. In some aspects, the recycled composition may include increasing article additive loadings for each round of recycling, which could affect the mechanical and/or functional properties due to increased article additive loadings.

[0017] In yet another aspect of the present invention, the RR-ECPM can have similar functional properties to conventional PoE and/or to virgin RR-ECPM. This provides a solution to the problems associated with recycling conventional PoE (e.g., articles made with conventional PoE can be made with the RR-ECPM of the present invention while having a high recycling efficiency). Still further, by maintaining its functional properties after 1, 2, 3, 4, 5, or more use cycles, the RR-ECPM of the present invention can continuously be reused, which can reduce and/or avoid the need to produce additional RR-ECPM or to produce conventional RR-ECPM.

[0018] In still another aspect of the present invention, there is disclosed a composition comprising a polymer, wherein the polymer comprises moieties derived from any one of the difunctional oligomers and from any one of the difunctional linkers disclosed throughout the specification. The composition can include an additive (e.g., any one of the additives disclosed throughout the specification). The additive can be an article additive. The composition can also include any one of the additional components, ingredients, features, and/or amounts of ingredients disclosed throughout this specification. The composition can have structural and/or functional characteristics similar to virgin PoE. [0019] Other embodiments of the invention are discussed throughout this application. Any embodiment discussed with respect to one aspect of the invention applies to other aspects of the invention as well and vice versa. Each embodiment described herein is understood to be embodiments of the invention that are applicable to other aspects of the invention. It is contemplated that any embodiment discussed herein can be implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.

[0020] The following includes definitions of various terms and phrases used throughout this specification.

[0021] “Article Additive” means an additive from an article being recycled. For example, if an article is being recycled in the context of the present invention, an additive from the recycled article is an article additive. Therefore, a composition and/or article produced from a recycled article of the present invention can include an additive or additive package from the recycled article.

[0022] “Repeatedly-Recyclable Elastomer Copolymer Mimic” or “RR-ECPM” means a copolymer that is a mimic of a polyolefin elastomer (PoE). The RR-ECPM is a reaction product of difunctional oligomer(s) and difunctional linker(s). The difunctional linker(s) and the difunctional oligomer(s) are obtained from a liquefied article that includes the difunctional oligomer(s) and the difunctional linker(s). The difunctional oligomer can include a comonomer. The RR-ECPM can be made into an article that is then liquefied by being heated and depolymerized into a mixture of difunctional oligomer(s) and difunctional linker(s). The difunctional oligomer(s) (with optional comonomer) and difunctional linker(s) can then be repolymerized into another RR-ECPM and re-used to produce another article. The process of the present invention can be repeated multiple times (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more) so that at least two additional or new articles can be made from the RR-ECPM starting material that was obtained from the recycled article.

[0023] The term “linker” means an aliphatic group (e.g., “Z”) that can couple and decouple to a RR-ECPM oligomer (e.g., “X”).

[0024] “Virgin Repeatedly-Recyclable Elastomer Copolymer Mimic” or “virgin RR- ECPM” is newly made directly from difunctional oligomers and difunctional linkers (and have not been obtained from an article). Virgin RR-ECPM has not previously been depolymerized and repolymerized. [0025] “Use Cycle” indicates how many times an RR-ECPM can be used to make different articles. The different article can be a new article made from the RR-ECPM, and the new article can be the same type of article (e.g., the article to be recycled and the recycled article can both be the same type of article (e.g., a cup)), or the new article can be another type of article (e.g., the article to be recycled can be a cup and the recycled article can be a utensil). For instance, for a RR-ECPM having a Use Cycle 0 rating, the RR-ECPM is a “virgin RR-ECPM”, and, therefore, the virgin RR-ECPM is made directly from a difunctional oligomer(s) and a difunctional linker(s) of the present invention (the virgin RR-ECPM has not been used to make an article). A RR-ECPM having a Use Cycle 1 rating means that the RR-ECPM has been used once to make an article. A RR-ECPM having a Use Cycle 2 rating means the RR-ECPM has been used twice to make, for example, two different articles. A RR-ECPM at Use Cycle 3 means the RR-ECPM has been used three times to make, for example, three different articles. As such, a RR-ECPM having a Use Cycle “n” means that the RR-ECPM can been used n times to make n different articles and impart substantially similar to identical functional properties. FIG. 2 provides a non-limiting example of a visually depiction of a Use Cycle of a RR-ECPM of the present invention.

[0026] The term “branching” refers the regular or random attachment of side chains to a polymer’s backbone chain.

[0027] The term “degree of branching (DB)” of a group/oligomer/polymer refers to % of branched carbons in the backbone of the group/oligomer/polymer. For example, the following group having the formula of Formula (II), has a degree of branching of 20 to 30 %. The branched carbons in the backbone of the group of Formula II is marked with a *. R' in Formula II is a branching group, can be an alkyl group, and y is an integer and denotes number of repeat units.

[0028] The term “linear hydrocarbon” refers to a hydrocarbon having a continuous carbon chain without side chain branching. The continuous carbon chain may be optionally substituted. The optional substitution can include replacement of at least one hydrogen atom with a functional group, such as hydroxyl, acid, amine, or halogen group; and/or replacement of at least one carbon atom with a heteroatom.

[0029] The term “branched hydrocarbon” refers to a hydrocarbon having a linear carbon chain containing branches, such as substituted and/or unsubstituted hydrocarbyl branches, bonded to the linear carbon chain. Optionally, the linear carbon chain can contain additional substitution. Optional additional substitutions can include replacement of at least one carbon atom in the linear carbon chain with a heteroatom and/or replacement of at least one hydrogen atom directly bonded to a carbon atom of the linear chain with a functional group, such hydroxyl, acid, amine, or halogen group.

[0030] The term “elastomer” refers to a copolymer that exhibits elastic properties, which means it can stretch and deform under stress and return to its original shape when the stress is released.

[0031] The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0032] The terms “wt.%,” “vol.%,” or “mol.%” refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, which includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.

[0033] The term “substantially” and its variations are defined to include ranges within 10 %, within 5 %, within 1 %, or within 0.5 %.

[0034] The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0035] The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0036] The use of the words “a” or “an” when used in conjunction with any of the terms “comprising,” “including,” “containing,” or “having” in the claims, or the specification, may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0037] The phrase “and/or” means “and” or “or”. To illustrate, A, B, and/or C includes: A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C.

[0038] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0039] The compositions of the present invention can “comprise,” “consist(s) essentially of,” or “consist of’ particular groups, compositions, etc. disclosed throughout the specification. In one aspect of the present invention, and with reference to the transitional phrase “consist(s) essentially of’ or “consisting essentially of,” a basic and novel characteristic of the present invention can include a RR-ECPM obtained from a liquified article that can be depolymerized into difunctional oligomers and difunctional linkers, repolymerized into RR-ECPM, and/or used to produce a new article. The newly produced article can be substantially produced from the repolymerized (e.g., at least 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 wt. % of the newly produced article can be from the RR-ECPM obtained from the liquified article). Alternatively, the difunctional oligomer and the difunctional linkers of the liquefied article can have a weight percentage that is at least 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 wt.% of the RR-ECPM.

[0040] Other obj ects, features and advantages of the present invention will become apparent from the following detailed description and examples. It should be understood, however, that the detailed description and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.

[0042] FIG. 1 is an illustration of the system and method to make the composition of the present invention that includes a RR-ECPM(s).

[0043] FIG. 2 is an illustration of a closed loop Use Cycle of a RR-ECPM of the present invention.

[0044] FIG. 3 is an illustration of a stacked polymeric composition of the present invention that includes four fiber-reinforced composites of the present invention.

[0045] FIG. 4 is an illustration of a stacked polymeric composition of the present invention that includes 2 fiber-reinforced composites of the present invention and a coupling layer.

[0046] FIG. 5 is cross-sectional view of an illustration of a polymeric matrix that includes a fiber sized with RR-ECPM of the present invention.

[0047] FIG. 6 is an illustration of the closed-loop recycling process of the present invention that include the RR-ECPMs.

[0048] FIG. 7 shows the ¹³C-NMR of virgin RR-ECPM and RR-ECPM of the present invention.

[0049] FIG. 8 is a graphical representation of the differential scanning calorimetry (DSC) data of virgin RR-ECPM of the present invention.

[0050] FIG. 9 shows X-ray diffraction (XRD) patterns of virgin RR-ECPM.

[0051] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION

[0052] A discovery has been made that provides a solution to at least one or more of the problems associated with chemical recycling of polyolefin copolymers such as PoE. In one aspect of the present invention, the RR-ECPM of the present invention can be repeatedly and directly recreated (e.g., 2 to 500 times or more) from an article made from the copolymer(s) at an amount that is substantially the same as in the article. For example, at least 90 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, or 100 wt. % of the RR-ECPM from the article being recycled can be depolymerized, repolymerized into RR-ECPM, and re-used in the newly produced article. This recycling efficiency of the RR-ECPM containing compositions and articles made therefrom can advantageously result in reduced costs of recycling articles, increased recycling efforts, and/or reduced amount of additional materials used to produce new articles. Additionally, the recycling efficiency can result in a reduced carbon footprint for the produced articles. Notably, the RR-ECPM can have similar functional properties to conventional RR-ECPM and/or to virgin RR-ECPM. Also, the RR-ECPM can be used in such a manner that additional feed stock (e.g., virgin RR-ECPM) is not used or used in limited amounts (e.g., 5, 4, 3, 2, 1, or less wt. %) after multiple use cycles (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more use cycles).

[0053] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections with reference to the Figures.

A. Composition

[0054] The composition can include a RR-ECPM of the present invention and an article additive. In some aspects, the composition can include at least 95 wt.% to 100 wt.% (e.g., 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, 100 wt.% or any value or range there between) of the RR-ECPM(s). In some aspects the composition does not include any homopolymers of high-density polyethylene (HDPE), low density polyethylene (LDPE), linear low-density polyethylene (LLDPE) and/or polypropylene (PP), and/or combinations thereof. i. RR-ECPM

[0055] The RR-ECPM can include repeating units of a difunctional linker (Z) and a difunctional oligomer (X) obtained from a liquified article. In some aspects, the number average molecular weight (M>) of the RR-ECPM can be 20,000 g/mol to 1,000,000 g/mol, 20,000 to 3,000,000 g/mol, 40,000 to 1,000,000 g/mol or 20,000 g/mol, 40,000 g/mol, 30,000 g/mol, 40,000 g/mol, 50,000 g/mol, 100,000 g/mol, 200,000 g/mol, 300,000 g/mol, 400,000 g/mol, 500,000 g/mol, 600,000 g/mol, 700,000 g/mol, 800,000 g/mol, 900,000 g/mol, 1,000,000 g/mol, or any range or value there between. The M_n can be determined as the polyethylene equivalent molecular weight by high temperature size exclusion chromatography performed at 160 °C in trichlorobenzene using polyethylene standards. The RR-ECPM(s) can have a melt temperature (T_m) of 40 °C to 110 °C, 45 °C to 105 °C, or 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, or any value or range there between as measured by DSC at a heating rate of 10 °C per min. A density of the RR-ECPM(s) can be 0.799 g/cm³ to 0.95 g/cm³ or 0.799 g/cm³, 0.80 g/cm³, 0.85 g/cm³, 0.90 g/cm³, 0.95 g/cm³ or any range or value there between. In some aspects, the copolymer(s) can have a poly dispersity index (PDI), of 1 to 5, or equal to any one of, at least any one of, or between any two of 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, and 5.

[0056] In some preferred aspects, the RR-ECPM can include polymers having Formula (I) and/or Formula (II):

(I) (II)

Although ketones are illustrated as side groups in Formulas (I) and (II), the one or more side functional groups of Z can be one or more of hydroxyl (-0H), carboxylic acid (CO2H), amine (NH2), or a combination thereof and the oxygens bonded to X can be ketones, amines etc. In some aspects, the functional groups can contain hydrocarbon groups linking the functional group to the backbone of Z. In certain aspects, Z can vary randomly between the repeating units of Formula I. Although ketones are illustrated as side groups in Formula (I), the one or more side functional groups of Z can be one or more of hydroxyl (-0H), carboxylic acid (CO2H), amine (NH2), or a combination thereof and the oxygens bonded to X can be ketones, amines etc. A non-limiting example of the copolymer, when Z includes hydroxyl groups, and X includes ketones is represented in Formulas (lb) and (lib).

(lb) (lib)

[0057] In Formulas (la), (lb), (Ila), and (lib), Z can be an aliphatic group and represents the carbon backbone of the difunctional linker. Z can contain up to 13 carbon atoms, or equal to any one of, at least any one of, or between any two of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 carbon atoms. In certain aspects, Z can contain 2 to 13 carbon atoms. In certain aspects, Z can be a Cl to Cl 3 aliphatic group. In some aspects, Z can be a linear or a branched hydrocarbon. In some aspects, Z can be a branched hydrocarbon. In some aspects, Z can be a polyethylene group. In certain aspects, the number of carbon atoms in the Z groups can vary randomly between the repeating units of Formulas (la), (lb), (Ila), and (lib). In some aspects, n is 2 and the copolymer can have the structure represented by Formulas (Ic) and (lie).

(Ic) (lie)

[0058] In Formulas (la), (lb), (Ic), (Ila), (lib) and (lie), X can be an aliphatic group. X can contain at least 40 carbon atoms. In certain aspects, X can vary randomly between the repeating units of Formula I and Formula (II), such as number of carbon atoms and/or DB of the X groups in the copolymer(s) can vary randomly. In certain aspects, X does not vary between the repeating units of Formula I. In some aspects, X can include 40 to 2,000, or equal to any one of, at least any one of, or between any two of 40, 45, 50, 55, 60, 65, 70, 80, 90, 100, 150, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 carbon atoms. In some aspects, X can include 60 to 1500 carbon atoms. In another aspect, X can include 80 to 1100 carbon atoms. In some aspects, X can be a branched polyolefin having a DB of 5% to 50 %, or equal to any one of, at most any one of, or between any two 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45 and 50 %. In some aspects, X can contain Cl to C13 branches (e.g., on the hydrocarbon backbone). In some aspects, X can contain Cl to C13 alkyl group branches.

[0059] In some aspects, X can be a polyolefin having the formula of Formula (III):

can be an integer from 40 to 2,000 and denotes number of repeat units. R can be -H or a Ci to Cio alkyl group, and varies independently (e.g., between -H and the Ci to C io alkyl group) in the repeating units -CHR-. In some aspects, m can be equal to any one of, at least any one of, or between any two of 40 45, 50, 55, 60, 65, 70, 80, 90, 100, 150, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, and 2,000. The -(CHR)_m’- group can have regular branching. In some aspects, m can vary randomly between the repeating units of Formula II, and X can optionally contain one or more side functional groups. In some aspects, the one or more side functional groups can be one or more of hydroxyl, acid, or amine groups. The functional groups can include hydrocarbon groups linking the functional group to the hydrocarbon backbone of X. X can have a degree of saturation 97 to 100 %, or equal to any one of, at most any one of, or between any two 97, 97.5, 98, 98.5, 99, 99.5 and 100 %.

[0060] In some aspects, the polyolefin group of X can be a polyethylene, polypropylene, poly(ethylene-co-propylene), or poly(ethylene-co-a-olefm) group. In some aspects, a-olefin of the poly(ethylene-co-a-olefm) group of X can independently be a propylene, 1 -butene, 4- methyl-1 -pentene, 1 -hexene, styrene, vinylcyclohexane, 1 -octene, norbomene, 5-vinyl-2- norbomene, 5-ethylidene-2-norbomene or 1 -decene. In some aspects, X can be an atactic, isotactic, or syndiotactic polyethylene group. In another aspects, X can be an atactic, isotactic, or syndiotactic polypropylene group.

[0061] In some aspects, X can include of a comonomer of an ethylene olefin or a propylene olefin and a 1 -alkene. The 1 -alkene can include 3 to 13 carbon atoms. The comonomer can include 40 wt. % to 95 wt. % of the ethylene or propylene and 5 wt. % to 60 wt. % of the 1- alkene. An amount of comonomer in X can be more than 0 wt.% to 5 wt.% or more than 0, 1, 2, 3, 4, 5 wt.% or any range or value therein.

[0062] In Formulas (la), (lb), (Ic), (Ila), (lib) and (lie), X' can be an aliphatic group. X' can contain at least 40 carbon atoms. In certain aspects, X' can vary randomly between the repeating units of the Formulas such as number of carbon atoms and/or DB of the X' groups in the copolymer(s) can vary randomly. In certain aspects, X' does not vary between the repeating units of the Formulas. In some aspects, X' can include 40 to 2,000, or equal to any one of, at least any one of, or between any two of 40, 45, 50, 55, 60, 65, 70, 80, 90, 100, 150, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 carbon atoms. In some aspects, X' can include 60 to 1500 carbon atoms. In another aspect, X' can include 80 to 1100 carbon atoms. In some aspects, X' can be a branched polyolefin having a DB of 5% to 50 %, or equal to any one of, at most any one of, or between any two 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45 and 50 %. In some aspects, X' can contain Cl to C13 branches (e.g., on the hydrocarbon backbone). In some aspects, X' can contain Cl to Cl 3 alkyl group branches. [0063] In some aspects, X can be a polyolefin having the formula of Formula (III):

can be an integer from 40 to 2,000 and denotes number of repeat units. R' can be -H or a Ci to Cio alkyl group, and varies independently (e.g., between -H and the Cl to Cl 3 alkyl group) in the repeating units -CHR-. In some aspects, m can be equal to any one of, at least any one of, or between any two of 40 45, 50, 55, 60, 65, 70, 80, 90, 100, 150, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, and 2,000. The -(CHR)_m - group can have regular branching. In some aspects, m can vary randomly between the repeating units of Formula III, and X' can optionally contain one or more side functional groups. In some aspects, the one or more side functional groups can be one or more of hydroxyl, acid, or amine groups. The functional groups can include hydrocarbon groups linking the functional group to the hydrocarbon backbone of X'. X can have a degree of saturation 97 to 100 %, or equal to any one of, at most any one of, or between any two 97, 97.5, 98, 98.5, 99, 99.5 and 100 %.

[0064] In some aspects, the polyolefin group of X' can be a polyethylene, polypropylene, poly(ethylene-co-propylene), or poly(ethylene-co-a-olefm) group. In some aspects, a-olefin of the poly(ethylene-co-a-olefm) group of X' can independently be a propylene, 1 -butene, 4- methyl-1 -pentene, 1 -hexene, styrene, vinylcyclohexane, 1 -octene, norbomene, 5-vinyl-2- norbomene, 5-ethylidene-2 -norbomene or 1 -decene. In some aspects, X' can be an atactic, isotactic, or syndiotactic polyethylene group. In another aspects, X' can be an atactic, isotactic, or syndiotactic polypropylene group.

[0065] In some aspects, X' can include of a comonomer of an ethylene olefin or a propylene olefin and a 1 -alkene. The 1 -alkene can include 3 to 13 carbon atoms. The comonomer can include 40 wt. % to 95 wt. % of the ethylene or propylene and 5 wt. % to 60 wt. % of the 1- alkene. An amount of comonomer in X' can be 0 wt.% to 5 wt.% or 0, 1, 2, 3, 4, 5 wt.% or any range or value therein.

[0066] In some aspects, X and X' can be poly(ethylene-co-l -butene) groups where the mol.% of 1 -butene in X and X' are different. In some aspects, X and X' can be poly(ethylene- co-l-octene) groups where mol.% of 1-octene in X and X' are different. In some aspects, X can be a linear or branched polyethylene group, and X' can be a poly(ethylene-co-l -butene) group. In some aspects, X can be a linear or branched polyethylene group, and X' can be a poly(ethylene-co-l -octene) group. In some aspects, X can be a poly(ethylene-co-a-olefm) group, and X' can be a polypropylene group.

[0067] In some aspects, X' can be a polyethylene group while X is a polyolefin or vice versa. The polyethylene group can contain 3 to 1,000 atoms, or equal to any one of, at least any one of, or between any two of 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 80, 90, 100, 150, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 650, 700, 750, 800, 850, 900, 950, and 1,000 atoms (e.g. carbon and oxygen atoms in total) in the polymer backbone. The polyethylene can be a linear or a branched polypropylene. The branched polyethylene can contain Cl to Cl 3 hydrocarbon branches. In some aspects, the branched polyethylene can contain Cl to C 13 alkyl group branches.

[0068] In some aspects, X' can be a polyethylene copolymer group while X is a polyolefin or vice versa. In some aspects, X' can contain at least 45 carbon atoms, and can have a degree of saturation of the main chain of 60 to 100 %, such as 75 to 100 %. In some aspects, X' can contain 45 to 1,000 carbon atoms, or equal to any one of, at least any one of, or between any two of 45, 50, 55, 60, 65, 70, 80, 90, 100, 150, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 650, 700, 750, 800, 850, 900, 950, and 1,000 carbon atoms.

[0069] In some aspects, X' can be a polypropylene group while X is a polyolefin or vice versa. The polypropylene group can contain 3 to 1,000 atoms, or equal to any one of, at least any one of, or between any two of 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 80, 90, 100, 150, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 650, 700, 750, 800, 850, 900, 950, and 1,000 atoms (e.g. carbon and oxygen atoms in total) in the polymer backbone. The polypropylene can be a linear or a branched polypropylene. The branched polypropylene can contain Cl to C13 hydrocarbon branches. In some aspects, the branched polypropylene can contain Cl to C13 alkyl group branches.

[0070] In some aspects, X' can be a polypropylene copolymer group while X is a polyolefin or vice versa. In some aspects, X' can contain at least 45 carbon atoms, and can have a degree of saturation of the main chain of 60 to 100 %, such as 75 to 100 %. In some aspects, X' can contain 45 to 1,000 carbon atoms, or equal to any one of, at least any one of, or between any two of 45, 50, 55, 60, 65, 70, 80, 90, 100, 150, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 650, 700, 750, 800, 850, 900, 950, and 1,000 carbon atoms.

[0071] In some aspects, X and X' can be same or different, e. g. can have same or different chemical formula. In some aspects, X of the first unit (e.g, Formula I) and the second unit (e.g, Formula II) can have the same formula. In certain aspects, the ratio of mol.% of the first unit and second unit in the copolymer can be 9: 1 to 999: 1, or equal to any one of, at least any one of, or between any two of 9: 1, 10: 1, 15: 1, 20: 1, 25: 1, 30: 1, 35: 1, 40: 1, 45: 1, 50:1, 55: 1, 60: 1, 65: 1, 70: 1, 75: 1, 80: 1, 85: 1, 90: 1, 95: 1, 100: 1, 200: 1, 300: 1, 400: 1, 500: 1, 600: 1, 700: 1, 800: 1 , 900: 1 , and 999: 1. Although two units are shown in the Formulas, it should be understood that the copolymer can have more than 2 units (e.g, 2, 3, 4, 5, etc.) of varying Formulas described herein.

[0072] The RR-ECPM(s) of the present invention can be a reaction product of a difunctional linker and a difunctional oligomer from a depolymerization process. The difunctional linker

R^1-^- Z-) — R² can having the formula ' 'ⁿ , “R^J-Z-R² ”, where R¹ and R² are each OH, CO2H, NH2, or a combination thereof, and n is 2 to 13 carbon atoms. In some instances, Z can have a carbon chain of 2 to 13 carbon atoms (C2-C13), 2 to 10, or 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or any value or range there between. The two functional groups, R¹ and R² can be an amine (-NH2), an alcohol (-OH), a carboxylic acid (-COOH), or a combination thereof. In some instances, the difunctional linker is a cyclic acid, a cyclic amide, a diester, or a combination of a monoacid and an ester. The functionality “F” of the difunctional linker can be a statistical value of 2.0 ± 0.3, or 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3 or any value or range there between. Functionality can be measured using known chemical analysis, for example, titration methods. In some aspects, the difunctional linker can be oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, aconitic acid, isocitric acid, propane-1, 2, 3 -tricarboxylic acid, pentane- 1, 3, 5-tricarboxy lie acid, or any combinations thereof.

R3 _L_ _J _ R4

[0073] The difunctional oligomer can have a formula of ' 'ⁿ , (“R³-X-R⁴”) where R³ and R⁴ are each OH, CO2H, NH2, or a combination thereof and n can be 40 to 2000. In some aspects, X is a polyethylene or polypropylene polymer have 40 to 2000 carbon atoms, 60 to 1500 carbon atoms 80 to 1100 carbon atoms, or 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 or any value or range therebetween of carbon atoms. X can have a degree of saturation of 98% to 100% or 98%, 98.5%, 99%, 99.5%, 99.9%, 100% or any value or range there between. In some aspects, X can be regular branched. Regular branching in the polyethylene backbone can provide the linear structure to the RR-ECPM. The two functional groups, R³ or R⁴ can be an amine (-NH2), an alcohol (-OH), a carboxylic acid (-COOH), or a combination thereof. The functionality “F” of the difunctional oligomer can be a statistical value of 2.0 ± 0.3, or 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3 or any value or range there between. Functionality can be measured using known chemical analysis, for example, titration methods.

R^5-r— X'T — R⁶ [0074] If a second difunctional oligomer is used it can have a formula of ' 'ⁿ (“R⁵-X'-R⁶”) where R⁵ and R⁶ are each OH, CO2H, NH2, or a combination thereof and n can be 40 to 2000. In some aspects, X' is a polyethylene or polypropylene polymer have 40 to 2000 carbon atoms, 60 to 1500 carbon atoms 80 to 1100 carbon atoms, or 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000 or any value or range therebetween of carbon atoms. X' can have a degree of saturation of 98% to 100% or 98%, 98.5%, 99%, 99.5%, 99.9%, 100% or any value or range there between. In some aspects, X' can be regular branched. Regular branching in the polyethylene backbone can provide the linear structure to the RR-ECPM. The two functional groups, R⁵ or R⁶ can be an amine (-NH2), an alcohol (-OH), a carboxylic acid (-COOH), or a combination thereof. The functionality “F” of the difunctional oligomer can be a statistical value of 2.0 ± 0.3, or 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3 or any value or range there between. Functionality can be measured using known chemical analysis, for example, titration methods. ii. Additives

[0075] The compositions of the present invention can include at least one article additive. The at least one article additive can be added when a RR-ECPM is made into an article. Examples of such additives can include catalysts and additive that are useful for making articles. Non-limiting examples of article additives can include, but are not limited to, an antioxidant, a metal deactivator, a processing aid, a UV stabilizer, a pigment, a phosphite, a phosphinate, a colorant, or mixtures thereof. In some embodiments, combinations of the article additives can be combined as an article package to be added to the composition. The choice of additive packages may be driven by the specific type of article being made and its intended use. For use in pipes intended for use with chlorinated water, for instance, additive packages comprising certain types of antioxidants can lead to synergistic results. Other articles can preferably be made with specific types of additive packages.

[0076] Non-limiting examples of article antioxidant additives can include 3,3'3",5,5',5'- hexatert-butyl-alpha,alpha',alpha,"-(mesitylene-2,4,6-triyl )tri-p-cresol (CAS 1709-70-2) commercially known as Irganox 1330 (Ciba Specialty Chemicals) or Ethanox 330 (Albemarle Corporation); pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (CAS 6683-19-8) available as Irganox 1010 (Ciba Specialty Chemicals); octadecyl-3-(3. 5-di- tert.butyl-4-hydroxyphenyl)-propionate (CAS 002082 79-3) available as Irganox 1076; 1,3,5- tris(3,5-di-tert-butyl 4-hydroxybenzyl)-l,3,5-triazine-2,4,6(lH.3H,5H)-trione (CAS 2767-62- 6) available as Irganox 3114; 1 ,3,5-tris(4- tert-butyl-3-hydroxy-2,6-dimethyl benzyl) 1,3,5- triazine-2, 4,6-(lH,3H,5H)-trione (CAS 040601-76) available as Cyanox 1790 (CyTech Industries); ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (CAS 36443-68-2) available as Irganox 245; 1.6-hexamethylene bis (3,5-di(tert)-butyl-4- hy dr oxy hydrocinnamate (CAS35074-77-2) available as Irganox 259: thiodiethylene bis3-(3,5- di-tert-butyl-4-hydroxyphenyl) propionate (CAS 41484-35-9) available as Irganox 1035; tris(2,4-ditert-butylphenyl)phosphate (CAS 31570-04-4) available as Irgafos™ 168 and mixtures thereof.

[0077] Non-limiting examples of metal deactivators can include 2',3-bis(3-3,5-di-tert-butyl- 4-hydroxyphenylpropionylpropionohydrazide. (CAS 32687-78-8) available as Irganox™ MD 1024 and 2,2'-oxalyldiamidobis ethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (available as Naugard™ XL1), and mixtures thereof.

[0078] For every Use Cycle a RR-ECPM is produced from a liquified article, a new article additive and/or package can be used prior to making a new article so that the next RR-ECPM that is made and used to make the new article, the new article can have a higher amount of additive(s) when compared with the initial (prior to adding more additive) RR-ECPM obtained from the liquified article. At very high Use Cycle rating, when the amount additive(s) in a RR- ECPM are so much that the amount of additive(s) can affect the functional properties of the polymer made, the RR-ECPM may not be substantially similar to the functional properties of virgin RR-ECPM or virgin PoE. In some aspects, at some point, there may be so much additive in the RR-ECPM that the recycled RR-ECPM may no longer function similar to the virgin RR- ECPM or conventional PoE. [0079] The amount of additives used to make an article can vary by application and can be from greater than 0 wt.% to 5 wt. %, or 0.00001 wt. %, 0.0001 wt. %, 0.001 wt. %, 0.01 wt. 0.05 wt. %, 0.06 wt. %, 0.07 wt. %, 0.08 wt. %, 0.09 wt. %, 0.1 wt. %, 0.2 wt. %, 0.3 wt. %, 0.4 wt. %, 0.5 wt.%, 0.6 wt. %, 0.7 wt. %, 0.8 wt. %, 0.9 wt. 1, 1 wt. %, 2 wt. %, 3 wt. % 4 wt. %, or 5 wt. %, or any number or range there between.

[0080] The composition can include one or more optional additives. Non-limiting examples of an optional additive can include a scratch-resistance agent, an antioxidant, a flame retardant, an UV absorber, a photochemical stabilizer, a filler such as glass and/or mineral filler, an optical brightener, a surfactant, a processing aid, a mold release agent, a pigment, flow modifiers, foaming agents or any combinations thereof. In some aspects, the composition can include at least 95 wt.% to 100 wt.% (e.g., 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, 100 wt.% or any value or range there between) of the RR-ECPM(s) and an optional additive. An amount of optional additive can be from greater than 0 to 5 wt. %, or 0.00001 wt. %, 0.0001 wt. %, 0.001 wt. %, 0.01 wt. 0.05 wt. %, 0.06 wt. %, 0.07 wt. %, 0.08 wt. %, 0.09 wt. %, 0.1 wt. %, 0.2 wt. %, 0.3 wt. %, 0.4 wt. %, 0.5 wt.%, 0.6 wt. %, 0.7 wt. %, 0.8 wt. %, 0.9 wt. 1, 1 wt. %, 2 wt. %, 3 wt. % 4 wt. %, or 5 wt. %, or any number or range there between. In some preferred aspects, the amount of the optional additive in the composition can be 0.0 wt.% to 0.2 wt.% or 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.15 wt.%, 0.2 wt.% or any value or range there between. In some embodiments, the composition include at least 0.01 % to 0.2 %, preferably 0.05 % to 0.15 %, of an article additive and 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, 100 wt.% of the RR-ECPM(s).

B. Method of Making the Composition

[0081] Certain aspects are directed to a method for making the composition of the present invention that includes the RR-ECPM(s) of the present invention. Referring to FIG. 1, a system and method of making the composition of the present invention is illustrated. In a preferred aspect, FIG. 1 illustrates a closed loop system and method of recycling a RR-ECPM(s) of the present invention. System 100 can include liquification unit 102, depolymerization unit 104, and polymerization unit 106. Plastic article 108 can enter liquification unit 102. Plastic article 108 can include or be a consumer product that includes RR-ECPM(s) and/or a composition of the present invention that includes a RR-ECPM(s). In some preferred aspects, the article 108 is a plastic article. Non-limiting examples of consumer goods can include a packaging product, a pharmaceutical container, a bottle, a cap, a closure, a liner, a trash bag, a food packaging film, a lamination, a pipe, a hose, a fitting, or a combination thereof. In some aspects, the composition can contain a blend of the RR-ECPM(s) of varying molecular weight. Plastic article 108 can be optionally cleaned of contaminants (e.g., inert materials) and shredded into smaller pieces prior to being fed to liquification unit 102. In liquification unit 102, plastic article 108 can be heated to melt the article (e.g., heated to a temperature of 120 °C to 250 °C) and produce a liquified article composition 110. Liquification unit 102 can be an extruder, stirred tank and/or a combination thereof. Liquified article composition 110 can include the RR- ECPM(s) and an article additive.

[0082] Liquified article composition 110 can exit liquification unit 102 and enter depolymerization unit 104. In some instances, liquification unit 102 and depolymerization unit 104 can be the same unit. In depolymerization unit 104, liquified article composition 110 can be subjected to conditions to depolymerize the RR-ECPM(s) in the liquified article composition to produce a liquified article comprising a mixture of difunctional oligomers and difunctional linkers. Depolymerization conditions can include temperature and pressure. Depolymerization temperature can be from 190 °C to 350 °C or 190 °C, 195 °C, 200 °C, 225 °C, 250 °C, 275 °C, 300 °C, 325 °C, 350 °C, or any range or value there between. A depolymerization pressure can range from 3 MPa to 4.5 MPa, or 3 MPa, 3.1 MPa, 3.2 MPa, 3.3 MPa, 3.4 MPa, 3.5 MPa, 3.6 MPa, 3.7 MPa, 3.8 MPa, 3.9 MPa, 4.0 MPa, 4.1 MPa, 4.2 MPa, 4.3 MPa, 4.4 MPa, 4.5 MPa, or any range or value there between. In some aspects, the depolymerization can be performed at an inert atmosphere. In some instances, the depolymerization conditions can be 195 °C to 205 °C at 3.8 to 4.0 MPa. At these reaction conditions, the RR-ECPM(s) depolymerizes and forms the difunctional oligomers and difunctional linkers. The difunctional oligomer can be a solid, liquid, or a combination thereof. The difunctional linkers can be a solid, liquid, or combination thereof. Depolymerization can include hydrolysis and/or solvolysis (e.g., alcoholysis) of the copolymer(s) to obtain the difunctional oligomer R³-X-R⁴, and/or R⁵-X'-R⁶, where R³, R⁴ R⁵, and R⁶ are each OH, CO2H, NH2, or a combination thereof, and the difunctional linker R'-Z-R². where R² and R² are each OH, CO2H, NH2, or a combination thereof. In certain aspects, the depolymerization method can include methanolysis of the composition under conditions suitable to obtain the difunctional oligomer (e.g, R³-X-R⁴, and/or R⁵-X'-R⁶, where R³, R⁴ R⁵, and R⁶ are each OH,), and a methyl ester of the difunctional linker (e.g, R'-Z-R². where R¹ and R² are masked acid (e.g, CH3O2C-Z-CO2CH3)). Non-limiting examples of a catalyst used for methanolysis depolymerization can include a mineral acid, organic acid, organic base, and/or metallic compound. Non-limiting examples of metallic compounds can include a metal complexed or bonded to a hydrocarbyl, an oxide, a chloride, a carboxylate, an alkoxide, an aryloxide, an amide, a salen ligan, a [3-ketiminato ligand, or a guanidinato ligan. In some aspects, the metal can be Li, Na, K, Mg, Ca, Sc, Y, lanthanides, Ti, Zr, Zn, Mo, Mn, Al, Ga, Bi, Sb, or Sn. In some aspects, the catalyst can be Ti(OiPr)4, Ti(OBu)4, Al(OiPr)s, Sn(2-ethyl-hexanoate)2, MoOs, or any combinations thereof.

[0083] In some instances, depolymerization unit 104 can include one or more separation/purification units. The separation/purification units can be a part of depolymerization unit 104 or a separate unit (not shown). The separation units can separate the difunctional oligomers from the difunctional linkers from the depolymerization composition. For example, the difunctional oligomer(s) can be a solid and the difunctional linker(s) can be a liquid or vice versa. In such instances, the solid can be separated from the depolymerization composition using filtration, centrifugation, precipitation, or other known separation techniques. In some instances, the liquid component can be separated from the depolymerization composition using distillation methods. In other instances, both the difunctional oligomer and difunctional linker are both liquids or both solids and solid/solid or liquid/liquid separation/purification methods can be used to isolate the solids or liquids. In some instances, the comonomer can be produced during depolymerization, be separated from the difunctional oligomer and difunctional linker, and then recycled. Separation units can help to remove impurities and/or other unwanted items prior to repolymerization. In some aspects, oligomers, and linkers from other RR-ECPM processes that are desired can be separated from the desired oligomers and linkers. For example, any homopolymers of PP, LDPE, HDPE or LLDPE, or a combination thereof can be separated from the RR-ECPM difunctional oligomers.

[0084] Difunctional oligomer stream 112 and/or difunctional linker stream 114 can exit depolymerization unit 104 and enter polymerization unit 106. In some instances, difunctional oligomer stream 112 and difunctional linker stream 114 exit depolymerization unit 104 as a single stream. In some aspects, the article additive is included in oligomer stream 112 and/or linker stream 114. In some instances, depolymerization unit 104 and polymerization unit 106 are the same unit. In another instance, liquification unit 102, depolymerization unit 104, and polymerization unit 106 can be the same unit. In polymerization unit 106, difunctional oligomer 112 and difunctional linker 114 can be subjected to conditions to produce RR-ECPM(s). Said another way, the difunctional oligomers and difunctional linkers in stream 112 and 114 can be repolymerized to form a recycled RR-ECPM(s). In polymerization unit 106, the difunctional oligomers (with comonomer) and difunctional linkers can be reacted at i) a temperature of 90 °C to 250 °C, or equal to any one of, at least any one of, or between any two of 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, and 250 °C, and/or ii) under inert atmosphere and/or vacuum. In some aspects, the reaction can include esterification at 90 °C to 250 °C, and/or under inert atmosphere, followed by polycondensation at 90 °C to 250 °C, and/or under vacuum, e.g., at pressure below 0.0005 MPa, below 0.0001 MPa, below 0.00005 MPa. The difunctional oligomers (e.g, diol) can be reacted with the difunctional linker (c.g. acid, ester, or anhydride) at a mole ratio of 95:5 to 5:95, or equal to any one of, at least any one of, or between any two of, 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, 50:50, 45:55, 40,:60, 35:65, 30:70, 25:75, 20:80, 15:85, 10:90, and 5:95. In some instances, the polymerization (repolymerization) can be performed in presence of a catalyst. Non-limiting examples of catalysts include mineral acid, organic acid, organic base, and/or metallic compound. Nonlimiting examples of metallic compounds can include a metal complexed or bonded to a hydrocarbyl, an oxide, a chloride, a carboxylate, an alkoxide, an aryloxide, an amide, a salen ligan, a -ketiminato ligand, or a guanidinato ligand. In some aspects, the metal can be Li, Na, K, Mg, Ca, Sc, Y, lanthanides, Ti, Zr, Zn, Mo, Mn, Al, Ga, Bi, Sb, or Sn. In some aspects, the catalyst can be Ti(OiPr)4, Ti(OBu)4, Al(OiPr)s, Sn(2-ethyl-hexanoate)2, MoOs, or any combinations thereof. In certain aspects, a combination of catalysts can be used.

[0085] In some aspects, the difunctional oligomer (e.g, HO-X-OH and/or HO-X'-OH) obtained from a liquefied article can be repolymerized with a difunctional linker (e.g, HO2C- Z-CO2H, an ester, and/or cyclic anhydride thereof (e.g., of the acid of HO2C-Z-CO2H)). In some instances, a comonomer is reacted with the difunctional oligomer and/or difunctional linker. In some aspects, the difunctional oligomer can be repolymerized with i) a first diacid having the formula of HO2C-Z-CO2H (and/or an ester, and/or cyclic anhydride thereof) and/or ii) a second diacid having the formula of HO2C-Z -CO2H (and/or an ester, and/or cyclic anhydride thereof), wherein Z is different than the Z', but both diacids are obtained from the depolymerization process.

[0086] In some aspects, the first acid can be oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or any combinations thereof. In some aspects, the second acid can be citric acid, aconitic acid, isocitric acid, propane-1, 2, 3 -tricarboxylic acid, pentane-l,3,5-tricarboxylic acid, or any combinations thereof. In certain aspects, the compound HO-X-OH can be polymerized with more than two acids selected from oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, aconitic acid, isocitric acid, propane- 1,2, 3 -tricarboxy lie acid, and pentane-l,3,5-tricarboxylic acid, and/or esters, and/or anhydride thereof obtained from a RR-ECPM recreated from an article comprising difunctional oligomers and difunctional linkers.

[0087] RR-ECPM(s) 116 can exit polymerization unit 106 and be sold, transported, or formed into a consumer product. In some aspects, the article additive is included in the RR- ECPM(s). In some aspects, RR-ECPM 116 is formed into a pellet to be sold, transported, or converted into a consumer product. As shown in FIG. 1, RR-ECPM(s) exits polymerization unit 106 and enters converting unit 118. Converting unit 118 can be onsite or offsite. Converting unit 118 can be a commercial manufacture of consumer goods and/or articles of manufacture. In converting unit 118, RR-ECPM(s) 116 can be formed into RR-ECPM article 120 that includes the RR-ECPM(s) of the present invention. For example, RR-ECPM(s) 116 can be molded (e.g, extruded, injection molded, blow molded, compression molded, rotational molded, thermoformed and/or 3-D printed) to form RR-ECPM article 120. In some aspects, RR-ECPM article 120 can be comprised in or in the form of a foam, a film, a layer, a sheet, a molded article, a welded article, a filament, a fiber, a wire, a cable, or a powder. In one example, the composition is incorporated into a film. In some instances, the film may include at least one film layer that includes the composition. In some aspects, an article additive can be combined with the RR-ECPM(s) 116 prior to being sent to the converting unit 118. The additive can be an article additive package that is typically used with the article to be produced. In some aspects, an article additive is not combined with the RR-ECPM(s) 116 prior to being sent to the converting unit 118, which may be advantageous if the article being recycled, and the article being made are the same type or class of articles. In such an aspect, the additive present in the article being liquified in liquification unit 102 can be preserved throughout the liquification, depolymerization, and re-polymerization steps, such that no or reduced amounts of additive is added prior converting unit 118.

[0088] In some aspects, RR-ECPM article 120 can contain a blend of the RR-ECPM(s) of varying molecular weight. In some aspects, RR-ECPM article 120 can further include one or more additives. The additives can be added in polymerization unit 106 and/or converting unit 118. Non-limiting examples of additives can include, a scratch-resistance agent, an antioxidant, a flame retardant, an UV absorber, a photochemical stabilizer, a filler such as glass and/or mineral filler, an optical brightener, a surfactant, a processing aid, a mold release agent, a pigment, flow modifiers, foaming agents or any combinations thereof. [0089] RR-ECPM article 120 can exit converting unit 118 and be sold, transported, used, and/or stored. RR-ECPM article 120 can be used and collected by consumers 122. After use, used RR-ECPM article 124 containing RR-ECPM can be provided to liquification unit 102, and a new cycle can be started. The cycle of the present method can be continuously repeated (e.g., 2 to 500 times (e.g., 2, 5, 10, 15, 20, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, or 500 times, or any value or range there between)). In one aspect, a closed-loop recycling of the RR-ECPM(s) can now be realized.

C. Articles

[0090] Compositions of the present invention that include the RR-ECPM and/or additives can be shaped into useful articles by a variety of methods (e.g., injection molding, extrusion molding, rotation molding, foam molding, calendar molding, blow molding, thermoforming, compaction, melt spinning, and the like). Non-limiting examples of articles include consumer goods, packaging products, pharmaceutical containers, bottles, caps, closures, liners, trash bags, food packaging film and/or materials, laminations, pipes, hoses, or fittings.

[0091] Some additional non-limiting examples include: external and/or internal components (e.g., panels, quarter panels, rocker panels, trim, fenders, doors, decklids, trunk lids, hoods, bonnets, roofs, bumpers, fascia, grilles, mirror housings, pillar appliques, cladding, body side moldings, wheel covers, hubcaps, door handles, spoilers, window frames, headlamp bezels, headlamps, tail lamps, tail lamp housings, tail lamp bezels, license plate enclosures, roof racks, and running boards) for transportation vehicles (e.g., aircraft, automotive, truck, military vehicle (including automotive, aircraft, and water-borne vehicles), scooter, and motorcycle); enclosures, housings, panels, and parts for outdoor vehicles and devices; enclosures for electrical and telecommunication devices; outdoor furniture; aircraft components; boats and marine equipment, including trim, enclosures, and housings; outboard motor housings; depth finder housings, personal water-craft; jet-skis; pools; spas; hot-tubs; steps; step coverings; building and construction applications such as glazing, roofs, windows, floors, decorative window furnishings or treatments; treated glass covers for pictures, paintings, posters, and like display items; wall panels, and doors; counter tops; protected graphics; outdoor and indoor signs; enclosures, housings, panels, and parts for automatic teller machines (ATM); computer; desk-top computer; portable computer; lap-top computer; palm- held computer housings; monitor; printer; keyboards; FAX machine; copier; telephone; phone bezels; mobile phone; radio sender; radio receiver; enclosures, housings, panels, and parts for lawn and garden tractors, lawn mowers, and tools, including lawn and garden tools; window and door trim; sports equipment and toys; enclosures, housings, panels, and parts for snowmobiles; recreational vehicle panels and components; playground equipment; shoe laces; lids for containers; articles made from plastic-wood combinations; golf course markers; utility pit covers; light fixtures; lighting appliances; network interface device housings; transformer housings; air conditioner housings; cladding or seating for public transportation; cladding or seating for trains, subways, or buses; meter housings; antenna housings; cladding for satellite dishes; coated helmets and personal protective equipment; coated synthetic or natural textiles; coated painted articles; coated dyed articles; coated fluorescent articles; coated foam articles; and like applications.

[0092] Additionally, the RR-ECPM compositions (with or without additives) can also be formed into films or sheets as well as components of laminate systems. The sheet can be a foam sheet, paper sheet, or fabric sheet. Articles include, for example, fibers, sheets, films, multilayer sheets, multilayer films, molded parts, extruded profiles, coated parts and foams, windows, luggage racks, wall panels, chair parts, lighting panels, diffusers, shades, partitions, lenses, skylights, lighting devices, reflectors, ductwork, cable trays, conduits, pipes, cable ties, wire coatings, electrical connectors, air handling devices, ventilators, louvers, insulation, bins, storage containers, doors, hinges, handles, sinks, mirror housing, mirrors, toilet seats, hangers, coat hooks, shelving, ladders, hand rails, steps, carts, trays, cookware, food service equipment, communications equipment and instrument panels.

[0093] In one aspect the RR-ECPM is comprised in

D. RR-ECPM Use Cycles

[0094] In some aspects, the RR-ECPM of the present invention exhibits favorable Use Cycle ratings such that the RR-ECPM can be made into different articles such that instead discarding each article can be liquefied and repolymerized into another RR-ECPM material. FIG. 2 is an illustration of Use Cycle 200. In Block 202, RR-ECPM_n is shown, where n is an integer (e.g., 0 to 10000, or more). In Block 204, an Articlen can be made from Block 202 RR- ECPMn. When n is 1, this can represent Use Cycle 1. In Block 206, the Articlen from Block 204 made from RR-ECPMn can be liquefied by heating and depolymerization as described above to produce difunctional oligomer(s) and difunctional(s) linkers of Articlen. In Block 208, the liquified Articlen of Block 206 (e.g., the difunctional oligomer(s) and difunctional linker(s) of the present invention) can be polymerized to produce RR-ECPM_n+i. In Block 210, the Articlen+i can be produced from the RR-ECPMn+i of Block 208. When n is 2, this represents a Use Cycle of 2. Generally, the RR-ECPM has a Use Cycle rating of at least 2. In Block 212, the process can be continued, where Article_n+i of Block 210 can be liquefied by heating and depolymerization as described above to produce difunctional oligomer(s) and difunctional(s) linkers. In Block 214, the liquified Articlen+i of Block 212 (e.g., the difunctional oligomer(s) and difunctional linker(s) of the present invention) can be polymerized to produce a new RR- ECPM material to continue the cycle. In one embodiment, the RR-ECPM has a Use Cycle rating ranging from 2 to 1000. In another embodiment, the RR-ECPM has a Use Cycle rating ranging from 2 to 500. In another embodiment, the RR-ECPM has a Use Cycle rating ranging from 2 to 400. In another embodiment, the RR-ECPM has a Use Cycle rating ranging from 2 to 300. In another embodiment, the RR-ECPM has a Use Cycle rating ranging from 2 to 300. In another embodiment, the RR-ECPM has a Use Cycle rating ranging from 2 to 200. In another embodiment, the RR-ECPM has a Use Cycle rating ranging from 2 to 100. In some aspects, the Use Cycle rating can be greater than 1000 (e.g., 1500, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, or more). In some aspects, the US Cycle rating can be 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, or more, or any range or number therein.

[0095] Advantageously, the Use Cycle ratings can be achieved without having to use additional feed stock (e.g., virgin RR-ECPM feed stock) or by using a limited amount of additional feed stock (5, 4, 3, 2, 1, 0.5, or 0 wt. % of virgin RR-ECPM feed stock).

[0096] Remarkably, it is now possible to make a copolymer(s) that is functionally similar to conventionally made RR-ECPM, or a virgin RR-ECPM, and that can be repeatedly reused. This can reduce or eliminate the use of single use plastics and/or increase the efficiency of traditional chemical recycling processes. Instead of using the traditional process of making a copolymer(s) from monomers, the compositions, RR-ECPM, and articles of the present invention can be made from difunctional oligomers and difunctional linkers obtained from a recycled article that would have typically been discarded into a landfill or incinerated. Advantageously, the compositions, RR-ECPM, articles, and/or processes of the present invention are highly efficient at being recycled and made into new articles (e.g., at least 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 %, of RR-ECPM obtained from an article can be recycled to produce a new article.

E. RR-ECPM Composites [0097] The RR-ECPM compositions of the present invention can be included in composites. Composites can be made into stacked polymeric compositions (e.g, laminates) used to form structures having advantageous structural characteristics, such as high strength, high stiffness and/or relatively low weight when compared to similar structures formed from conventional materials.

[0098] RR-ECPM composites or compositions of the present invention can be formed into any structure. Non-limiting examples of structures include sandwich-type structures, multilayered (stacked) composites and the like. The composite or compositions of the present invention can be dimensioned and shaped according to respective applications. Non-limiting examples of shapes include rectangular, triangular, square, polygonal (whether having sharp and/or rounded comers), circular, elliptical, or otherwise rounded, or can have an irregular shape or otherwise. The overall thickness of the composite or compositions can be up to and even exceeding several millimeters. Some embodiments of the present composites or compositions can include one or more openings, notches, and/or the like, which can facilitate incorporation of the composite into a structure. Composites or compositions of the present invention can have any thickness.

[0099] In some embodiments, the composite, compositions and/or stacked polymeric composition of the present invention can be decorated. In use, a surface of the composite or stacked polymeric compositions can be subjected to printing with ink. In an embodiment, an exposed surface of the composite or a stacked polymeric composition surface opposite the surface adjacent to the core can be subsequently decorated, in particular printed with markings such as alphanumerics, graphics, symbols, indicia, logos, aesthetic designs, multicolored regions, and a combination that includes at least one of the foregoing. In some embodiments, each composite can be decorated. In some embodiments, one of the exposed (or outer) surfaces of the composite can be subjected to common curing and/or surface modification processes. Non-limiting examples of such processes can include heat-setting, texturing, calendaring, embossing, corona treatment, flame treatment, plasma treatment, and vacuum deposition.

[0100] In some embodiments, the composite can include a cap layer material. The cap layer can be a film material made from a different polymer and process than the composite stacks (e.g, laminates). By way of example, it can be an extruded film material, which is for example chemical resistant to cleaning agents. Film materials used can include polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), poly(methylmethacrylate) (PMMA), multilayered combinations and blends thereof. These film materials can be applied by roller lamination or double belt press lamination equipment. Also, aesthetic film materials can be used to produce, for example, a wood grain or metallic surface. The cap layer can be created by co-extrusion (single or multi-manifold). In some embodiments, an anti-microbial surface can be created by co-extrusion of film materials with silver or other germicides. In some embodiments, the cap layer can be made by screen-printing an aesthetic or functional ink layer. In most instances, these cap layers will be thermoformable.

[0101] The composites can be made using known panel consolidation techniques. By way of example, the composite can be made using continuous systems that include one or more machines capable of cutting, cooling, stacking, wrapping, or the like (for example, static heated presses, double belt presses and the like). In some embodiments, the composites and/or stacked polymeric compositions of the present invention can include at least 2 or 3, 4, 5, 6, 7, 8, 9, 10 or more RR-ECPM composites of the present invention having a thickness of about 0.1 to 10 mm, or 0.25 to 5 mm. In some embodiments, when a core is present, the core density can be reduced to a desired density by patterning the core thermoplastic layer. In some embodiments, a stack of RR-ECPM composites can be formed by heating and pressing more than one RR- ECPM composites together. By way of example the composite stack can enter a first zone of a double belt press at a pressure of 5 to 15 N/cm², or (0.5 to 1.5 MPa, or 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5 MPa or any value or range there between) and then heated to a temperature of 140 to 150 °C, (e.g., about 145 °C). The pressed stack can enter a second zone, be pressed, and the heated to 145 to 155 °C (e.g., about 150 °C). The pressed stack can enter a third zone, be pressed, and then heated at a temperature of 150 to 160 °C (e.g, about 155 °C) to form a composite of the present invention. In some embodiments, the surface of one RR-ECPM composite can be treated with a coupling agent prior to assembling the stack. In some embodiments, the coupling agent can be a RR-PoP composition.

[0102] Non-limiting examples of core materials can include RR-ECPM compositions of the present invention, polyethylene terephthalate (PET), a fire-retardant polypropylene (PP) or copolymer thereof, a polycarbonate (PC) or a copolymer thereof, a polyimide/poly etherimides or a copolymer thereof, a polyethersulfone (PES), a polyurethane (PU), or a polyphenyl ether (PPO)Zstyrene blend, a PPO/polyamide blend, a PPE/poly styrene blend, a PPO/polypropylene blend a PPO-Si/polyamide blend, a PPO-Si/polystyrene blend, a PPO-Si/polypropylene blend, or any combination thereof. Thermoplastic cores can be produced or are available from various commercial sources. By way of example, a PET core can be obtained from commercial sources such as Armacell Benelux S. A. (Beligum) under the tradename of ArmaFORM®, or from Diab Group (Sweden) under the tradename of Divinylcell P. Fire-retardant polypropylene honeycomb cores can be obtained from EconCore N.V. (Belgium.) under the tradename ThermHex. Polyimide cores can be obtained from commercial suppliers such as DuPont™ (U.S.A.), Hexcel Corporation (U.S.A.), and the like.

[0103] In some embodiments, a fiber reinforced composite of the present invention can include the RR-ECPM of the present invention, additives, fibers, and a coupling agent. More than one composite or composition of the present invention can be assembled to produce a stack (e.g., a laminate). A fiber-reinforced composite includes greater than or substantially equal to any one of, or between any two of 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 49.5, 49.9, or 49.95 wt.% of RR-ECPM, based on the total weight of the fiber-reinforced composite.

[0104] Non-limiting examples of fibers include glass fibers, carbon fibers, aramid fibers, thermoplastic fibers, ceramic fibers, basalt fibers, steel fibers, and/or the like. Non-limiting examples of thermoplastic fibers include polyethylene fibers, polyester fibers, polyamide fibers with or without fire retardant additives (FR thermoplastic fibers) incorporated into the fiber. The fiber-reinforced composite can include, based on the total weight of the fiber-reinforced composite, 50 to 80 wt.% fibers or greater than or substantially equal to any one of, or between any two of: 50, 55, 60, 65, 70, 75, 80 wt.% fibers. Fibers (e.g., fibers 310 in FIG. 3) of a composite (e.g, composite 302, 304, 306, 308 in FIG. 3) can be provided in bundles (e.g, bundles of carbon, ceramic, carbon precursor, ceramic precursor, glass, and/or the like fibers). Such bundles may include any number of fibers, such as, for example, 400, 750, 800, 1,375, 1,000, 1,500, 3,000, 6,000, 12,000, 24,000, 50,000, 60,000, or more fibers. Fibers in a bundle can have an average filament diameter of 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, or more microns (e.g., from 5 to 30 microns, 10 to 20 microns, 12 to 15 microns, or any range there between). Fibers can be provided with a sizing (e.g., a coating of an organic polymer, such as an organosilane), a pigment, and/or the like. Fibers can also be provided as a woven mat.

[0105] In some embodiments, fillers (e.g., fibers) in the composite or compositions of the present invention can be sized. The sizing can include RR-PoP, RR-ECPM, or a combination thereof. The sizing can range from about 0.01 wt.% to about 30 wt.% of the fiber component, or from about 0.1 wt.% to about 10 wt. % of the fiber component, or from about 1 wt.% to about 5 wt.% of the fiber component.

[0106] Fiber-reinforced composites can be made by dispersing fibers (sized with RR-ECPM or unsized) in a RR-ECPM matrix of the present invention using know fiber-reinforced composite methodology. For example, methods to prepare fiber-reinforced composites are described in International Application Publication No. WO 2016/142786 to Prins et al. In such a method, a sheet or film that includes the RR-ECPM (polymer composition) can be supplied between a first and a second spreaded fiber layers. Heat can be applied to the fiber layer/polymer composition/fiber layer material, followed by pressing the fiber layers into the polymer composition. In some embodiments, after pressing is completed, the first or second fiber layers can be rubbed. In some embodiments, the fibers are not spread prior to heating. In another embodiment, the composites can be made by using known impregnation techniques. For example, Miller et al. in Polymers & Polymer Composites, 1996, Vol. 4, No. 7 describes impregnation techniques for thermoplastic matrix composites. One such method can include providing suppling fibers to one or more solution baths (e.g., RR-ECPM in one or two baths) to form resin impregnated fibers, drying the fibers, and then pressing the fibers to produce a fiber-reinforced composite (e.g, prepreg sheets). In another embodiment, the RR-ECPM and fibers can be stacked together, heated, and then pressed causing the resin to flow transverse to the fibers to from prepreg sheets of reinforced thermoplastic materials. Typically, the width and the length of the non-woven fibrous region are substantially similar to the width and the length, respectively, of the fiber-reinforced composite. Such fiber-reinforced composites can include, by volume, at least 35 to 70% of the plurality of continuous fibers.

[0107] In some aspects, a fiber-reinforced composite (e.g, a ply) or compositions of the present invention can be used to make a stacked polymeric composition (e.g, a laminate). In a plurality of fiber-reinforced composites, the fiber-reinforced composites can have a length and a width that is perpendicular to and smaller than the length, where the length and the width are each a distance between outer edges of the fiber-reinforced composite measured along a straight line. The length can be, but need not be, the largest such distance. Each of the fiber- reinforced composites can have a shape and dimensions that correspond to the shape and dimensions of the final material. To further illustrate, the largest face of each of the fiber- reinforced composites can have a surface area that is substantially equal to a surface area of the largest face of the final material. To illustrate yet further, each of the fiber-reinforced composites can be rectangular. In other embodiments, one or more fiber-reinforced composites of a stacked polymeric composition (e.g., a laminate) can have a shape and/or dimensions that differ from the shape and/or dimensions of the laminate; such fiber-reinforced composites can, for example, be used to add stiffness and strength to a portion of the laminate that is smaller than the entirety of the laminate. In some aspects, a mixture of fiber-reinforced composites and unreinforced composites are used to make stacked polymeric compositions. In a preferred aspects, the stacked polymeric composition is made of only RR-ECPM composites of the present invention having fibers or sized fibers dispersed therein.

[0108] Referring to FIG. 3, composite 300 can be a stacked polymeric composition (e.g, a laminate) and include at least two fiber-reinforced composites. For example, four fiber- reinforced composites (e.g., fiber-reinforced composites 302, 304, 306 and 308). At least one fiber-reinforced composite can include a RR-ECPM polymeric matrix having a plurality of fibers 310 dispersed therein. Some embodiments of the present methods include producing a laminate (e.g., 300) at least by stacking two or more fiber-reinforced composites (e.g., including one or more of fiber-reinforced composites or composites in a 0/90 orientation). By way of example, at least 2 or 3, 4, 5, 6, 7, 8, 9, 10 or more RR-ECPM composites (e.g., fiber-reinforced composites and/or non-fiber containing composites) having a thickness of about 0.1 to 10 mm, or 0.25 to 5 mm can be stacked. During such stacking, any number of the laminates can be formed by placing sections (e.g., fiber-reinforced composites 302 and 304) of fiber-reinforced composite material, such as, for example, sections of unidirectional fiber composites, adjacent to one another. In some methods, the two or more polymeric composites include two or more unidirectional first fiber-reinforced composite and one or more unidirectional second fiber-reinforced composite, and the stacking is performed such that: (1) fibers of the first fiber-reinforced composite are aligned in a first direction; (2) fibers of the one or more second fiber-reinforced composite are aligned in a second direction that is perpendicular to the first direction; and (3) the one or more second fiber-reinforced composites are disposed in contact with one another and between two of the first fiber-reinforced composites.

[0109] Composites (e.g., 302, 304', 306, 308, etc.) that include fibers (e.g., fibers 310) can have a pre-consolidation fiber volume fraction (Vf) that is greater than or substantially equal to any one of, or between any two of: 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90%. In some embodiments of the present laminates, one or more fiber-reinforced composites may not include fibers; such fiber-reinforced composite can, for example, include a sheet of thermoplastic polymer material.

[0110] The laminates can be prepared using known lamination methods. It should be understood that laminates (e.g., laminate 300) can be made of fiber-reinforced composites having the same or different compositions. By way of example, fiber-reinforced composites 302, 304, 306 and 308 can each have a different composition or fiber-reinforced composites 302, 304, 306, and 308 can have the same or different compositions.

[oni] One or all of the fiber-reinforced composites (e.g., 302, 304, 306, 308, etc.) can include fibers (e.g, fibers 310) dispersed within a matrix material or pressed into the polymer matrix material. By way of example, the laminates can be prepare using a double belt press with integrated contact heating and cooling supplied by, for example Meyer® (Maschinenfabrik, Herber Meyer GmbH, Germany). The different fiber-reinforced composites (e.g., fiber-reinforced composites 302 and 304) can enter the heat press unit in a defined stacking sequence at a rate of 1.5 m/min. The fiber-reinforced composites stack can be pressed together in a first zone at a pressure of 0.1 to 0.4 N/cm², or (1 to 4 kPa, or 1, 1.5, 2, 2.5, 3, 3.5, 4 kPa or any value or range there between) and then heated to a temperature of 170 to 185 °C, (e.g., about 180 °C). The pressed stack can enter a second zone, pressed, and the heated to 190 to 200 °C (e.g., about 195 °C). The pressed stack can enter a third zone, be pressed at a lower temperature of 185 to 195 °C (e.g, about 190 °C) to form the stack (e.g., laminate 300). Heating and cooling can be maintained without release of pressure. In some embodiments, a static heated press can be used.

[0112] In stack 300, each of the fiber-reinforced composites (e.g., plies 302, 304, 306, 308 etc.) can be a unidirectional fiber-reinforced composite, or a fiber-reinforced composite having fibers (e.g., fibers 310), substantially all of which are aligned in a single direction. More particularly, in each of the fiber-reinforced composites, the fibers can be aligned with either the length of stack 300 (e.g., fiber-reinforced composites 302, 308 of FIG. 3 each of which may be characterized as a 0-degree unidirectional fiber-reinforced composites) or the width of the stack (e.g., fiber-reinforced composites 304 and 306 of FIG. 3 each of which may be characterized as a 90-degree unidirectional ply). The phrase, "aligned with" means within 10 degrees of parallel. Other embodiments of the present polymeric stacks of the present invention can include one or more unidirectional fiber-reinforced composites, each having fibers that are aligned in any suitable direction. For example, a unidirectional fiber-reinforced composite can include fibers aligned in a direction, where the smallest angle between the direction and a length of a stack including fiber-reinforced composite can be greater than or substantially equal to any one of, or between any two of: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 degrees.

[0113] Some embodiments of the present polymeric stacks can include one or more fiber- reinforced composites, each having fiber-reinforced composites that define a woven structure (e.g., as in a fiber-reinforced composite having a plane, twill, satin, basket, leno, mock leno, or the like weave). For example, a fiber-reinforced composite can include a first set of fibers aligned in a first direction and a second set of fibers aligned in a second direction that is angularly disposed relative to the first direction, where the first set of fibers is woven with the second set of fibers. A smallest angle between first direction and second direction can be greater than or substantially equal to any one of, or between any two of: 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 degrees. The smallest angle between first direction and a length of a stack including such a fiber-reinforced composite can be greater than or substantially equal to any one of, or between any two of: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 degrees.

[0114] Some embodiments of the present stacks can include one or more polymeric composite, each formed from sections of fiber-reinforced composites material. For example, a unidirectional fiber-reinforced composite can be formed from sections of unidirectional fiber material that has been placed adjacent to one another. To form such a fiber-reinforced composites, sections of fiber-reinforced composites material can be placed adjacent to one another manually and/or by an automated material laying machine.

[0115] Some embodiments of the present stacked polymeric compositions (e.g., laminates) can include 0-degree unidirectional fiber-reinforced composites (e.g., plies) and 90-degree unidirectional fiber-reinforced composites stacked such that the 0-degree unidirectional plies are in contact with one another (meaning each is in contact with at least one other) and are disposed between two of the 90-degree unidirectional plies. In some embodiments, composites of the present invention (e.g., laminates) can include first and second sub-stacks of 90-degree unidirectional fiber-reinforced composites and a third sub-stack of 0-degree unidirectional fiber-reinforced composites, where the third sub-stack is disposed between the first and second sub-stacks. In some embodiments, each of the sub-stacks can include three fiber-reinforced composites. However, in other embodiments, such sub-stacks can each be replaced with a single fiber-reinforced composite or can include 2, 3, 4, 5, 6, 7, 8, 9, or more fiber-reinforced composites . Other embodiments of the present stacked polymeric compositions can include any suitable fiber-reinforced composites (e.g., including one or more of any fiber-reinforced composite described above) stacked in any suitable configuration (e.g., balanced, symmetric, asymmetric, and/or the like).

[0116] Stacked polymeric compositions of the present invention can include coupling agents (e.g, tie layers) to adhere the composites together. FIG. 4 illustrates stacked polymeric composition 400. Stacked polymeric composition 400 can include fiber-reinforced composite layers 402 and 404 with tie layer 406. Composite layers 402 and 404 can include fibers 408 dispersed in a RR-ECPM polymer matrix. Non-limiting examples of coupling agents (tie layer) can include RR-ECPM, maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene copolymer, citric acid, styrene ethylene/butylene block copolymer with high styrene content, or a combination that includes at least one of the foregoing. The stacked polymeric composition can include, based on the total weight of the stack, 0.1 to 2 wt.% coupling agent or greater than or substantially equal to any one of, or between any two of: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2 wt.% of coupling agent. In a preferred instance, no coupling agent is necessary.

[0117] The stacked polymeric compositions and/or composites can be recycled as described throughout this specification. When the composites or stacked polymeric compositions include fibers, the fibers can be removed after liquification of the RR-ECPM composite/stacked composition. For example, referring to FIG. 1, fibers and/or other fillers can be removed in liquefication unit 102 and/or in depolymerization unit 104.

F. RR-ECPM Sizing Agent

[0118] In some aspects of the present invention the RR-ECPM can be used as a sizing agent for fibers. FIG. 5 is an illustration of a cross-sectional view of polymer composition 500 that includes fiber 502, RR-ECPM sizing 504 and a polymer matrix 506. The fibers prepared with the RR-ECPM sizing agent can be used in filaments, fiber tows, composites, and in other hierarchical structures. The sized fibers manufactured with the sizing formulations of the invention can be spooled and/or collated into fiber tows (yams) and the like and packaged for transport, allowing for further processing of the fibers in downstream applications at other facilities. [0119] Fibers can be spun into filaments, string, ropes, yams and the like and used as a component of composite materials or matted into sheets to make paper or felted products. Nonlimiting examples of fibers to which the RR-ECPM composition can be applied as sizing or as an adjunct to existing sizing include, can include fiberglass, carbon fiber, ceramic fiber, aramid fibers and other organic fibers, metal fibers and combinations thereof. Particular fibers include, for example, carbon (as4 and IM7-pitch and PAN based), glass (E, S, D, C, R, A types), Kevlar, Alumina (Nextel), and SiC. The sized fiber can be incorporated into a fiber tow. In some embodiments the fiber tow can incorporate a single type of sized fiber, while in other embodiments, the fiber tow can include two or more types of sized fibers. In still further embodiments, fibers of the present invention can be incorporated into a composite that includes a matrix material. Such matrix material can include thermoset polymers, thermoplastic polymers, copolymers thereof, or blends thereof. In a preferred aspect, the RR-ECPM sized fibers can be incorporated into a repeatedly recycled polymer mimic composites.

[0120] Non-limiting examples of thermoplastic polymers include polyethylene terephthalate (PET), polycarbonates (PC), polybutylene terephthalate (PBT), poly(l,4- cyclohexylidene cyclohexane-l,4-dicarboxylate) (PCCD), glycol modified poly cyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine or polyetherimide (PEI) or derivatives thereof, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamides (PA), polysulfone sulfonate (PSS), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), acrylonitrile butyldiene styrene (ABS), polyphenylene sulfide (PPS), co-polymers thereof, or blends thereof. More preferred thermoplastic polymers include polypropylene, polyamides, polyethylene terephthalate, polycarbonates (PC), polybutylene terephthalate, poly(phenylene oxide) (PPO), polyetherimide, polyethylene, co-polymers thereof, or blends thereof. Even more preferred thermoplastic polymers include polypropylene, polyethylene, polyamides, polycarbonates (PC), co-polymers thereof, or blends thereof.

[0121] Non-limiting examples of thermoset polymers suitable for use as a matrix material in the present fiber-reinforced composites include unsaturated polyester resins, polyurethanes, bakelite, duroplast, urea-formaldehyde, diallyl-phthalate, epoxy resin, epoxy vinylesters, polyimides, cyanate esters of polycyanurates, dicyclopentadiene, phenolics, benzoxazines, co- polymers thereof, or blends thereof. A polymeric matrix of one of the present fiber-reinforced composites can be included in a composition along with one or more additives. Non-limiting examples of such additives include coupling agents to promote adhesion between the polymeric matrix and continuous fibers, antioxidants, heat stabilizers, flow modifiers, flame retardants, UV stabilizers, UV absorbers, impact modifiers, cross-linking agents, colorants, or a combination thereof.

[0122] The fiber can be sized by applying a RR-ECPM composition or a RR-ECPM solution to a fiber during manufacture of the fiber. When a RR-ECPM solution is used, the RR- ECPM is blended with a solvent to reduce the viscosity of the RR-ECPM. After application to the fiber the solvent can be removed. For example, to form a sized glass fiber, molten glass is drawn through a die that sets the dimensions of the fiber. The fiber is allowed to cool after being drawn and the sizing formulation is added to the fiber as it cools. After addition of the sizing formulation, the fiber is heated or “baked” to flash off water or other solvents.

[0123] In other aspects, the application of the RR-ECPM sizing can be accomplished by spraying the RR-ECPM or by dip bath techniques. Application of the sizing formulation to the fiber can be incorporated in a continuous process for sized fiber production. In some embodiments, other sizing agents can be used and are applied sequentially or all at once. In some embodiments, the sizing agent can include nanoparticles. The nanoparticles can be applied first to assure contact between the nanoparticles and the fiber surface. In other embodiments, the sizing agent containing the nanoparticles can be applied after any number of other sizing agents. In operation, drawn fiber can be fed into a dip bath and subsequently sent to a vacuum and/or heating chamber to remove solvent from the sizing formulation. The fiber with cured sizing can be spooled, processed into fiber tows, incorporated into composites, or the like.

[0124] As described above, sizing can be “cured” by removal of solvent from the RR-ECPM solution. This can be accomplished under vacuum, by heating, or combinations of the two techniques. The exact conditions for solvent removal will depend on the nature of the solvent being removed and the sensitivity of the fiber to high temperatures, for example. Temperatures for curing can range, for example, from 40° C.-l 10° C. for 1-24 hours.

[0125] Compositions that include fibers sized with RR-ECPM can be recycled as described herein. For example, the fibers can be removed after liquification of the polymeric material. The RR-ECPM material can be separated from other polymers and recycled as described throughout this specification. For example, referring to FIG. 1, fibers and/or other fillers can be removed in liquefication unit 102 and/or in depolymerization unit 104.

G. RR-ECPM Coupling Agent

[0126] In some embodiments, the RR-ECPM composition can be used as a coupling layer to adhere two polymer compositions together. For example, RR-ECPM compositions can adhere repeatedly recycled polymer compositions thermoset polymers, thermoset polymers, copolymers thereof together. In other embodiments, the RR-ECPM can adhere a non-polymeric material (e.g., an aluminum sheet) to a polymeric material. When used in composites, the polymeric material can include fillers such as, for example, fibers. The coupling agent can be used in amount from 0.1 to 2 wt.% coupling agent or greater than or substantially equal to any one of, or between any two of: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2 wt.% based on the weight of the total composition (e.g., a stacked polymer composition).

[0127] The materials having RR-ECPM as a coupling agent can be recycled When the polymeric materials include fibers or non-polymeric materials, the fibers or non-polymeric materials can be removed after liquification of the compositions that include the RR-ECPM as a coupling agent. The RR-ECPM can be recycled as described herein. The RR-ECPM can be isolated from other thermoplastic or thermoset polymeric materials.

EXAMPLES

[0128] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters, which can be changed or modified to yield essentially the same results.

Instrumentation

[0129] Thermal analysis was carried out on a DSC Q100 from TA Instruments at a heating rate of 10 °C per minute. First and second runs were recorded after cooling down to about - 40 °C. The melting temperatures reported correspond to second runs.

[0130] HT-SEC Procedure. The molecular weight and dispersity were determined by means of high temperature size exclusion chromatography (HT-SEC) performed at 150 °C in a HT- SEC-IR instrument equipped with a IR4 detector (PolymerChar, Valencia, Spain). Three Polymer Laboratories 13 pm PLgel Olexis columns constitute the set. 1 ,2-di chlorobenzene (o- DCB) was purchased from VWR and used as an eluent at flow rate of 1 mL*min-l. Molecular weights and corresponding dispersities were calculated from HT-SEC analysis with respect to narrow polystyrene standards (PSS, Mainz, Germany).

[0131] The purpose of these examples was to make a repeatedly recyclable-polyethylene elastomer (RR-ECPM) polymer (a reaction product of a difunctional oligomer and a difunctional linker) from a liquefied article containing the difunctional oligomers and the difunctional linkers. The purpose was also to (i) compare properties of the RR-ECPM with the properties of a virgin RR-ECPM that is made directly from a difunctional oligomer and a difunctional linker and (ii) whether an article made from a conventional process could be also used to make a repeatedly recyclable polymer. FIGs. 2 and 6 show an overview of the closed loop process that makes possible, where RR-ECPM can made from articles that are liquefied multiple times.

[0132] Materials. Table 1 lists the materials used to make repeatedly recyclable oligomers and RR-ECPM from the oligomers.

Table 1

Example 1

((Method of liquifying a RR-ECPM article by heating and depolymerizing the RR- ECPM article to obtain difunctional oligomers and difunctional linkers)

[0133] A RR-ECPM article (27.5 g) and methanol (300 g) were weighed and transferred to a clean reactor (600 ml Parr vessel). Titanium isopropoxide catalyst (750 mg) was weighed and transferred into the vessel under a nitrogen environment. The reactor was then reassembled, fittings tightened and purged with nitrogen twice. The inlet and vent line valves were closed, and the reactor was heated till the reactor attained a steady temperature of 200 °C to 220 °C. The stirrer speed was set at 225 rpm throughout the experiment. The reactor was maintained at this temperature for 3 hrs during which the depolymerization was completely occurred. After 3 hrs of depolymerization, the heating was stopped, and reactor was allowed to cool down to room temperature.

[0134] After the reactor was cooled to room temperature, the reactor was disassembled, and the two-layer reaction mixture was processed. The top layer was a methanol layer, and the bottom layer was a diol layer that was insoluble in methanol. The methanol layer was decanted and transferred into a beaker. The methanol layer contained the dimethyl ester of the difunctional linker (succinic acid) and residual catalyst. The ester/methanol was vacuum distilled using a laboratory Roto-vac to remove the solvent completely. The dimethyl succinate (1.6 g) was recovered with some catalyst remains (e.g., TiO2 and Ti(OH)4). The viscous diol layer at the bottom of the reactor was washed twice with methanol (total of 25 ml) and the washings transferred to the decanted methanol layer. Toluene (200 g) was added to the reactor containing the diol and stirred for 10 min. The diol dissolved in the toluene solvent layer at room temperature. The diol/solvent mixture was filtered and transferred to a distillation flask. The diol/solvent mixture was vacuum distilled using a laboratory Roto-vac to remove the solvent completely. The dimethyl succinate (1.6 g) was recovered with some catalyst remains (e.g., TiO2 and Ti(OH)4). The difunctional oligomer (diol) (24.7 g) was recovered from the toluene layer and analyzed for purity by NMR. The C20 to C2000 oligomer had carbon branching of more than 0 to 26 with a branching carbon chain length of 2 to 13 carbon atoms.

Example 2

(Method of making RR-ECPM from the liquified article containing a mixture of the difunctional oligomers and difunctional linkers of Example 1)

[0135] The difunctional oligomers and the difunctional linkers of the mixture obtained from Example 1 were reacted to produce a RR-ECPM composition.

[0136] The difunctional oligomer (Example 1 oligomer, 12.0 g, 8.2 mmol), the difunctional linker succinic acid (Example 1, 0.96 g, 8.2 mmol) and a catalyst (titanium tetra-isopropoxide) that was present in the Example 1 article (0.12 g) were introduced into the reactor and the reactor was then heated to 190 °C under stirring and in the presence of nitrogen atmosphere. The first stage esterification was carried out for 2.5 hrs at atmospheric pressure and at 190 °C. After that, the second stage, polycondensation was started by turning off the nitrogen and by dually reducing the pressure down to about 0.05 mbar and the temperature was raised to 220 °C. After polycondensation reaction for 3.0 hrs, the vacuum was released by bleeding in Nitrogen and RR-ECPM was collected. The RR-ECPM was characterized by Solid state NMR.

Example 3

(Method of making Virgin RR-ECPM)

[0137] To evaluate the properties of the RR-ECPM of our invention, the RR-ECPM's properties were compared to a virgin polymer that is a reaction product of a difunctional oligomer and a difunctional linker.

[0138] The diol oligomers was synthesized via Synthetic scheme A for a,co-dihydroxy polyethylene. Synthesis of hydroxyl terminated a,co-dihydroxy polyethylene.

[0139] 1,3-butadiene solution (13.33 g, 36.97 mmol of 15 wt.% solution in n-hexane) was added to a Schlenk tube under argon atmosphere. Then /-BDMSOPrLi solution (1 mL, 0.5 mmol of 0.5 mol/L see above for analysis method) was added to the reaction mixture under stirring. After complete addition, the reaction mixture was heated to 50 °C and stirred at this temperature for 5 hours. After 5 hours, the reaction mixture was cooled to room temperature and ethylene oxide (15.6 mL, 12.5 mmol of 0.8mol/L in hexane) was added and allowed the reaction mixture to stir for another 2 h at room temperature. Finally, the reaction mixture was terminated by the addition of degassed (degassing done by freeze-pump-thaw method, see Appendix 2) methanol (1.5 mL) to form hydroxy end group in polybutadiene. The solution was concentrated and precipitated into an excess of methanol to obtain polybutadiene with one hydroxy end group as a white viscous liquid.

[0140] Step 2: Synthesis of dihydroxy terminated polybutadiene as shown below.

The polybutadiene (1 g) with one hydroxy end group (obtained from step 3) was dissolved in THF (10 mL). Subsequently, excess Tetrabutylammonium Fluoride (TBAF, 1 M in THF); was added to the solution ([TBAF]/[TBDMS] 3:1 weight ratio) at room temperature under stirring and allowed to react for 24 h to obtain the hydroxyl groups at both ends of the polybutadiene. Finally, the polymer was precipitated in methanol and residual solvent was evaporated.

[0141] The crude product was dissolved in 50 mL of suitable solvent (according to its solubility, either in hexane/cyclohexane/dichloromethane) and washed with water (2 x 50 mL) to remove any salts present in the crude mixture. The solvent was dried over anhydrous sodium sulfate (about 10 g), filtered and the solvent was evaporated using a rotary evaporator.

[0142] Step 3: Hydrogenation of unsaturated OH-PB-OH as shown in the reaction scheme below.

Saturated OH-PB-OH

Unsaturated OH-PB-OH

In a 600 mL Parr vessel, transfer/weigh 24 gm of hydrogenate diol (Mw-3000) into a conical flask and add 150 ml of cyclohexane into conical flask. Mix the contents in the conical flask thoroughly and then transfer the contents into the Parr vessel. The remaining 150 ml of cyclohexane was added into conical flask. The contents in the conical flask were mixed thoroughly and then transferred into the Parr vessel. Hydrogenation catalyst (2.4 g of 3 wt.% Pd/CaCCh) was added directly into the Parr vessel. The vessel was sealed under a hydrogen atmosphere and heated at 75 °C and 6 MPa until hydrogenation was complete.

[0143] Reaction of the difunctional oligomer with the difunctional linker to form the RR- ECPM of the present invention was preformed using known copolymer condensation methods. In general, the difunctional oligomer, the difunctional linker, and titanium tetra-isopropoxide (0.12 g, 1 wt. % of polymer) were introduced into the reactor and the reactor was then heated to 190 °C under stirring and in the presence of a nitrogen atmosphere. The reaction was held for 2.5 hrs at atmospheric pressure, then the nitrogen was discontinued to gradually reduce the pressure down to about 0.05 mbar and the temperature was raised to 220 °C. The reaction was held for 6 hrs until polycondensation was complete; the vacuum was released by bleeding in nitrogen and the polymer was collected.

[0144] FIG. 7 shows the 13C-NMR of virgin RR-ECPM. FIG. 8 shows the DSC of the virgin RR-ECPM. The virgin RR-ECPM showed a Tm lower than conventional RR-ECPM. The lower Tm was due to the ester groups in the virgin RR-ECPM.

[0145] FIG. 9 shows XRD patterns of virgin RR-ECPM. The XRD Peaks at 20 « 21.7° and 29~ 23.8° due to (110) and (200) reflections, are characteristics peaks of conventional PoE- C0570 and virgin RR-ECPM. Weak/broad shoulder band at « 19° represents a semi-amorphous phase. The amorphous phase in the RR-ECPM was higher hence the percentage crystallinity was lower than expected. The percent crystallinity of the virgin RR-ECPM was determined to be amorphous which is the same as conventional PoE-C0570 grade.

Example 4

(Method of making a new RR-ECPM composition from the Virgin RR-ECPM composition made in Example 3)

[0146] An article made from virgin RR-ECPM was extruded by adding an article additive( about 1000 ppm of Irganox 1010 and about 1000 ppm of Irgafos™ 168) at about 240 °C for a duration of 0.5 mins to 2 mins. The article was then liquefied by placing the article into a reactor along with methanol and heating the article and methanol to about 220 °C at an autogenous pressure of 39 bar until a mixture containing difunctional oligomers and difunctional linkers formed. The difunctional oligomers and the difunctional linkers were separated from the methanol mixture and reacted to produce the RR-ECPM composition as described above in Example 2. Example 4 illustrates a RR-ECPM exhibiting a Use Cycle 1 rating.

Example 5

(Method of making an article and a new RR-ECPM composition from the RR-ECPM composition made in Example 4)

[0147] The virgin RR-ECPM composition obtained in Example 4 was extruded into an article, in accordance with the procedure RR-ECPM of Example 4. The article was then liquefied into a mixture containing difunctional oligomers and difunctional linkers and the difunctional oligomers and the difunctional linkers reacted to produce another RR-ECPM composition in accordance with the procedures described above. The RR-ECPM composition was then tested for properties and compared to the properties of the virgin RR-ECPM. Example 5 illustrates a RR-ECPM exhibiting a Use Cycle 2 rating.

[0148] Table 2 lists the GPC molecular weight data. The purities of the difunctional oligomers, difunctional linkers, and RR-LLDPE are listed in Table 3. In Table 4, the weight % of the RR-LLDPE made the article and the weight % of the article were compared and are summarized. Table 2

Table 3

Table 4

[0149] The results evidenced by Examples 4-5 show that an RR-ECPM can be repeatedly recycled, e.g., the RR-ECPM can effectively be made from the reaction product of difunctional linkers and difunctional diols of an article that was liquefied into a mixture containing difunctional linkers and difunctional diols-even if the article is liquefied multiple times. The results show that the properties of RR-ECPM obtained from mixtures of difunctional diols and difunctional linkers of liquefied articles were substantially similar to the properties of a virgin- RR-ECPM. The results also show that the process of the present invention was highly efficient, as substantially all of the material of the article was reused and converted into the RR-ECPM without the need of using additional materials. In other words, the results show that that the mass of the article was substantially similar to the mass of the RR-ECPM. Remarkably, substantially all of the material of the article was used to make the RR-ECPM, thereby eliminating the need to use additional materials. Advantageously, the difunctional oligomers and the difunctional linkers of the liquefied article had a wt. % that is at least 95% wt.% of the RR-ECPM Use Cycles 1-2.

[0150] The data evidence that the RR-ECPM made by this method have demonstrated clearly a “closed loop recycling” in a unique way. This closed loop recycling of repeatedly recyclable article to its repeatedly recyclable oligomer and back to repeatedly recyclable article is novel and depends less on the fresh feedstocks and raw materials at every cycle and can continue for a number of cycles.

Example 6 (Comparative example using conventionally made PoE)

[0151] The purpose of this Example was to evaluate whether a conventionally made PoE could be repeatedly recyclable. A conventional PoE (SABIC® C0570) extruded into an article using the procedure of Example 4. The PoE article was processed and prepared for “liquification”. The article was chopped into pellets and loaded into a reactor along with solvent. The reactor was heated to about 220 °C for the liquefied and prepared article for liquification in presence of a solvent. The polymer was in a molten phase at 220 °C and was inert (could not react) with methanol (solvent) in the reactor at reaction temperature hence could not be depolymerized. Since the PoE polymer could not be depolymerized, it could not participate in any of the further processing methods, and it had a Use Cycle 1 rating. Once the molten PoE polymer was removed from the reactor it is solid again and has conventional defects which demonstrates difficulties in reprocessing. Hence cannot be “repeatedly recycled” for “closed loop recycling” hence has properties of single use applications. The conventionally made PoE did not have a Use Cycle Rating of at least 2. The conventional PoE was not able to be effectively liquefied by heating and depolymerization into difunctional oligomers and difunctional linkers and, as such, could not be polymerized into a PoE polymer. In other words, the conventional PoE had a single use utility. [0152] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions, and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

1. A composition comprising:

(a) a repeatedly recyclable-elastomer copolymer mimic (RR-ECPM) of a polyolefin elastomer (PoE), wherein the RR-ECPM is a reaction product of a difunctional oligomer and a difunctional linker, wherein the difunctional oligomer and the difunctional linker are both from a liquified article; and

(b) an article additive.

2. The composition of claim 1, wherein the difunctional oligomer has 40 to 2000 carbon atoms (C40 to C2000) and a functionality (F) of 2.0 ± 0.3, and the difunctional linker has a carbon chain of two to thirteen carbon atoms (C2 to Cl 3) and a F of 2.0 ±0.3, where each F is independently selected from an amine (-NH2), an alcohol (-OH), a carboxylic acid (-COOH), and combinations thereof.

3. The composition of any one of claims 1 to 2, wherein the composition does not include any homopolymer selected from the group of high-density polyethylene (HDPE), low density polyethylene (LDPE), linear low-density polyethylene (LLDPE), polyolefin plastomer (PoP), and polypropylene (PP), and combinations thereof.

4. The composition of any one of claims 1 to 3, wherein the RR-ECPM comprises a comonomer, wherein the comonomer is an ethylene-based comonomer, a propylene- based comonomer, or a combination thereof.

5. The composition of claim 4, wherein the RR-ECPM is an ethylene or a propylene comonomer-based RR-ECPM.

6. The composition of any one of claims 4 to 5, wherein comonomer comprises:

(i) an ethylene or propylene olefin and a linear alpha olefin, preferably 40 wt. % to 95 wt. % of the ethylene and 5 wt. % to 60 wt. % of the linear alpha olefin;

(ii) an ethylene or propylene olefin and a butylene olefin preferably 40 wt. % to 95 wt.% of the ethylene olefin and 5 wt.% to 60 wt.% of the butylene olefin; or

7. The composition any one of claims 1 to 6, wherein:

(a) the RR-ECPM comprising repeating units according to Formulas I and/or II:

where:

Z is an aliphatic group;

X and X’ each independently comprise a polyolefin backbone comprising 40 to 2000 carbon atoms, preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms, and an optional comonomer of an ethylene olefin and a 1- alkene, wherein the 1 -alkene comprises 3 to 13 carbon atoms, and the comonomer comprises 40 wt.% to 95 wt.% of the ethylene or propylene and 5 wt.% to 60 wt. % of the 1 -alkene and X and X’ are the same or different, wherein the RR-ECPM has more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units, and the RR-ECPM has a density of 0.799 g/cm³ to 0.95 g/cm³.

8. The composition of any one of claims 1 to 7, comprising:

(a) at least 95 wt.%, preferably at least 98 wt. %, of the RR-ECPM; and

(b) at least 0.01 % to 5 %, preferably 0.05 % to 0.15 %, of the article additive.

9. The composition of any one of claims 1 to 8, wherein the composition comprises the article additive in an amount ranging from at least 0.01 % to 5 %, preferably 0.05 % to 0.15 %, or more preferably greater than 0 to less than 0.01 wt.%, based on the weight of the RR-ECPM.

10. The composition of any one of claims 1 to 9, wherein the RR-ECPM comprises a molecular weight ranging from 20,000 g/mol to 1,000,000 g/mol and a density ranging from 0.799 to 0.95 g/cm³.

11. The composition of any one of claims 1 to 10, wherein the RR-ECPM comprises a melt temperature (7_m) of 40 °C to 110 °C as measured by DSC at a heating rate of 10 °C per min.

12. The composition of any one of claims 1 to 11, wherein the difunctional oligomer has a degree of saturation of 98% to 100%.

13. The composition of any one of claims 1 to 12, wherein difunctional oligomer is a branched co-polymer having a carbon number of C40 to C2000, wherein the difunctional oligomer has a degree of branching of 5% up to 60%.

14. The composition of any one of claims 1 to 13, wherein the article is a consumer good, a packaging product, a pharmaceutical container, a bottle, a cap, a closure, a liner, a trash bag, a food packaging film, a lamination; a pipe, a hose, a fitting, or a combination thereof.

15. The composition of any one of claims 1 to 14, wherein the difunctional oligomer copolymer and the difunctional linkers of the liquefied article have a weight percentage that is at least 95 wt.% of the RR-ECPM.

16. A composition comprising

(a) a repeatedly recyclable-elastomer copolymer mimic (RR-ECPM) of a polyolefin elastomer (PoE) copolymer, wherein the RR-ECPM is a reaction product of a difunctional oligomer with a comonomer and a difunctional linker, wherein the difunctional oligomer and the difunctional linker are both from a liquefied article; and

(b) an article additive; wherein the composition does not include any homopolymer selected from the group of high-density polyethylene (HDPE), low density polyethylene (LDPE), linear low-density polyethylene (LLDPE), a polyolefin plastomer (PoP) and polypropylene (PP), and combinations thereof; and wherein the difunctional oligomer co-polymer and the difunctional linkers of the liquefied article have a weight percentage that is at least 95 wt.% of the RR-ECPM.

17. A method for making the composition of any one of the claims 1 to 16 the method comprising:

(a) liquefying an article made from the composition of any one of claims 1 to 16 into a mixture containing difunctional oligomers and difunctional linkers; and

(b) reacting the difunctional oligomers and the difunctional linkers to produce the composition.

18. The method of claim 17, wherein: the article is liquified by melting; and the composition from the liquified article is depolymerized prior to step (b) by hydrolysis and/or solvolysis by contacting the composition with water and/or a solvent to obtain the difunctional oligomers and difunctional linkers, wherein the method optionally further includes forming an article from the composition produced in step (b).

19. The method of any one of claims 17 to 18, wherein the method is repeated at least two times, preferably 2 to 500 times and wherein the article is obtained from a consumer product made from a composition of any one of claims 1 to 16.

20. A composite comprising the composition of any one of claims 1 to 16.

21. The composite of claim 20, further comprising a plurality of fillers dispersed in the composition, preferably fibers, glass fibers, aramid fibers, polyester fibers, polyamide fibers basalt fibers, steel fibers, or combination thereof.

22. The composite of claim 21 , wherein the plurality of fillers comprise a plurality of fibers and the composite further comprises sizing to promote adhesion between the plurality of fibers and the composition of any one of claims 1 to 16, preferably the sizing comprises RR-ECPM.

23. A stacked polymeric composition comprising a composition of any one of claims 1 to 16 or a composite of any one of claims 20 to 22 and a second layer, the second layer preferably comprising a composition of any one of claims 1 to 16 or a composite of any one of claims 20 to 22.

24. A sized fiber comprising a fiber having a sizing agent disposed about the fiber, the sizing agent comprising a RR-PCPM composition of any one of claims 1 to 16.