Blends of repeatedly recyclable-plastomer copolymer mimics (RR-pcpms) of polyolefin plastomer copolymers

Abstract

A composition and methods of making the composition are described. The composition can include a repeatedly recyclable-polyolefin plastomer (RR-PCPM) copolymer(s) that is a reaction product of a difunctional oligomer and a difunctional linker of a liquefied article and a second polymer. The second polymer can be a polyolefin plastomer.

Description

BLENDS OF REPEATEDLY RECYCLABLE-PLASTOMER COPOLYMER MIMICS (RR-PCPMS) OF POLYOLEFIN PLASTOMER COPOLYMERS

[0001] This application claims priority to and the benefit of the filing date of India Provisional Patent Application No. 202341063915, filed September 22, 2023, and European Patent Application No. 24151246.6, filed January 10, 2024, both of which are incorporated herein by reference in their entirety.BACKGROUND OF THE INVENTIONA. Field of the Invention

[0002] The invention generally relates to blends that include repeatedly recyclable plastomer copolymer mimics (RR-PCPMs) of polyolefin elastomer (PoP) copolymers and a second polymer. The second polymer can include PoP (e.g., mechanically recycled, or virgin PoP).B. Description of Related Art

[0003] Polyolefins have multiple industrial uses. Polyolefins such as polyolefin plastomers constitute the largest volume of synthetic plastic produced worldwide. Polyolefin plastomer 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 PoP 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.

[0004] An alternative solution to discarding articles made with PoP 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 PoP such as by damaging the copolymer chains (e.g., chain scission, chain branching, crosslinking, etc.). The mechanically recycled PoP can have reduced chemical and / or physical properties when compared with its native / virgin form. This damage oftentimes limits the amount of mechanically recycled PoP that can be used to re-produce new articles. For example,virgin PoP is often blended with the mechanically recycled PoP to create new articles. The use of additional materials such as virgin PoP can be cost-inefficient and / or increase the carbon footprint of the resulting article. Further, the use of non-PoP based polymers to blend with PoP (mechanical or virgin) can oftentimes be problematic due to the two materials not sufficiently blending together.

[0005] An alternative solution to mechanically recycling articles made with PoP is to chemically recycle the PoP within the articles. Typical chemical PoP recycling technologies subject the material to pyrolysis (cracking) and / or gasification reactions to chemically break down the PoP into various smaller hydrocarbon products (e.g., smaller alkanes, alkene, or dienes). The chemical recycling process of PoP typically results in production of a fraction of polyolefins, which can be used to make chemically recycled PoP. 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 Maehara et al., 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

[0006] A discovery has been made that provides a solution to at least one or more of the problems that may be associated with PoP recycling. In one aspect, the discovery relates to the use of a blend of a repeatedly recyclable-plastomer copolymer mimic (RR-PCPM) of a PoP with a second polymer. In one aspect, the second polymer can be mechanically recycled PoP and / or virgin PoP. The blend can be used to make an article. The RR-PCPM within the blend and / or within the article can repeatedly be recycled and reused to make additional articles. In one aspect, the RR-PCPM can be the reaction product of a difunctional oligomer and a difunctional linker of the present invention. The RR-PCPM can be blended with the second polymer in an 80:20 to 20:80 weight ratio based on the total weight of the RR-PCPM / second polymer blend. Notably, the blend can be co-continuous in these ranges, which can be advantageous in that the RR-PCPM and the second polymer sufficiently blend together. By varying the ratio of the blend, properties of the blend can be tuned to meet various polymer parameters (e.g., tensile strength, modulus, crystallinity, and the like). Also, varying the blend ratios allows the blend or compositions comprising the blend to have similar structural and / or functional properties to virgin PoP and / or virgin PoP / mechanically recycled PoP blends.

[0007] An additional advantage of the present invention is that the RR-PCPM within the blend can be repeatedly and directly recreated (e.g., 2 to 500 times or more) from an article made from the blend. At least 90 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, or 100 wt.% of the RR-PCPM present in the article to be recycled can be depolymerized into difunctional oligomers and difunctional linkers and then repolymerized into a RR-PCPM. The repolymerized RR-PCPM can then be blended with a second polymer and used to create a newly produced article. The RR-PCPM / second polymer blend provides 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-PCPM / second polymer blend can result in a reduced carbon footprint for the produced articles.

[0008] One aspect of the present invention describes compositions that include RR-PCPMs and a second polymer in weight ratios of 80:20 to 20:80. The composition includes a co- continuous phase of RR-PCPM and the second polymer (e.g., PoP such as virgin or mechanically recycled PoP). In one aspect, a composition can include a RR-PCPM copolymer that that is a reaction product of a difunctional oligomer and a difunctional linker obtained from 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 thereol). The difunctional oligomer can include a difunctional oligomer having from 40 to 2000 carbon atoms (C40 to C2000), preferably Ceo-Cisoo, more preferably Cso-Cnoo, 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- PCPM can have branched C40 to C2000 polyethylene or polypropylene. The difunctional oligomer can be 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. Functionality can be determined using known titration methods. 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 thedifunctional linker(s) can be a carboxylic acid(s). The number average molecular weight (Mn) of the RR-PCPM can be 20,0000 to 1,000,000 g / mol. The Mn can be determined using gas permeation chromatography (GPC). More particularly, the Mncan be determined as the polyethylene equivalent molecular weight by high temperature size exclusion chromatography performed at 160 °C in tri chlorobenzene using polyethylene standards. A density of the RR- PCPM can be 0.799 g / cm3to 0.95 g / cm3. The RR-PCPM 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. Density, specific gravity, and Tmcan be determined using known chemical testing methods. For example, Tm can be measured according to ISO-11357- 1 using DSC at a heating rate of 10 °C per minute. In some aspects, the composition can include at least 95 wt.%, preferably at least 98 wt. %, of the PCPM / second polymer 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 additive or article additive (e.g., an additive present in the article being liquified). In one particular aspect, the composition can include an article additive in an amount ranging from more than 0 wt. % to less than 0.01 wt.%, based on the weight of the RR-PCPM. In some aspects, the difunctional oligomer and the difunctional linker of the liquefied article can have a weight percentage that is at least 95 wt.% of the RR-PCPM.

[0009] In some aspects, compositions of the present invention can include an ethylene comonomer based RR-PCPM. In some aspects, the compositions can include a propylene comonomer based RR-PCPM. In some aspects, the RR-PCPM is an ethylene-based RR-PCPM, a propylene-based RR-PCPM, or a combination thereof. In some aspects, the compositions 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 compositions 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 compositions 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 compositions 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.

[0010] In one preferred aspect of the present invention, the RR-PCPM 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-PCPM can have more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units. 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-PCPM can have more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units.

[0011] A composition of the present invention can include (a) a repeatedly recyclable- elastomer copolymer mimic (RR-PCPM) of a polyolefin elastomer copolymer(s), and (b) a second polymer (e.g., PoP). The RR-PCPM can be a reaction product of a difunctional oligomer and a difunctional linker obtained from a liquefied article. The difunctional oligomer and the difunctional linker of the liquefied article can have weight percentage that is at least 95 wt.% of the RR-PCPM.

[0012] In some aspects of the present invention composites are described. A composite can include the RR-PCPM 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-PCPM or a PoP.

[0013] In other aspects of the present invention, stacked polymeric compositions are described. The stacked polymeric composition can include a composite or composition of thepresent 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).

[0014] In some aspect of the present invention, a fiber that includes a RR-PCPM composition 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 a repeatedly recycled polymer mimic polymer matrix, a thermoplastic polymer matrix, or a thermoset polymer matrix. Upon recycling the composite, laminate, or composition containing the RR-PCPM composition sized fiber, the fiber can be separated from the RR-PCPM material and reused.

[0015] 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-PCPM of the present invention.

[0016] 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-PCPM from the article 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, the difunctional linker, and an optional comonomer. In some aspects, the difunctional oligomer and the difunctional linker in the mixture can be separated prior to repolymerization. If fibers are present, the fibers can be separated and reused. Reaction of the difunctional oligomer with an optional comonomer (recycled or new) and the difunctional linker can produce the composition of the present invention that includes a RR-PCPM. 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.

[0017] 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. Themethod can include any one or any combination or all of the following steps: (a) liquifying the article (e.g., melting the article) to obtain a mixture containing difunctional oligomers, difunctional linkers, and the second polymer; (b) separating second polymer from the difunctional oligomers and difunctional linkers; and (c) reacting the difunctional oligomers and difunctional linkers to produce a RR-PCPM. A recycled second polymer or a third polymer can be added to the RR-PCPM to form a composition of the present invention. The third polymer can be the same or different than the second polymer or the separated second polymer. In some embodiments, the third polymer can include the separated second polymer obtained during the recycling process. The RR-PCPM from the article in step (a) can be depolymerized by hydrolysis and / or solvolysis by contacting the liquified composition from step (a) with water and / or a solvent to obtain the difunctional oligomers and difunctional linkers. A second article can be formed from the RR-PCPM composition produced in step (c). Advantageously, at least 20%, 30%, 40%, 50%, 60%, 70%, 80% wt.% of the RR-PCPM from the article being liquified can be blended with the second polymer. Advantageously, 90%, 95%, or 100 wt.% of the inventive composition can be reused in the newly created article. The article can include an article additive (e.g., greater than 0 wt.% to 2 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 RR-PCPM in the compositions of the present invention can be recycled multiple times and retain its mechanical and / or functional properties. In some aspects, the recycled RR-PCPM 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.

[0018] In another aspect of the present invention a method of making the composition of the present invention is described. The method can include blending RR-PCPM and the second polymer at a temperature of 150 °C to 200 °C. The RR-PCPM can be a reaction product of a difunctional oligomer and a difunctional linker of a liquefied article comprising the difunctional oligomer and difunctional linker.

[0019] In yet another aspect of the present invention, the RR-PCPM composition of the present invention can have similar functional properties to conventional PoE and / or to virgin RR-PCPM or blends thereof. Advantageously, this provides a solution to the problems associated with recycling conventional PoP or blends of PoP (e.g., articles made with conventional PoP can be made with the RR-PCPM composition of the present invention at high recycling efficiency). Still further, by maintaining its functional properties after 1, 2, 3, 4, 5, or more use cycles, the RR-PCPM composition of the present invention can continuously bereused, which can reduce and / or avoid the need to produce additional RR-PCPM or to produce conventional PoP.

[0020] In still another aspect of the present invention, there is disclosed a composition comprising a first polymer and a second polymer. The first polymer can comprise moieties derived from any one of the difunctional oligomers and from any one of the difunctional linkers disclosed throughout the specification. The second polymer can include a polyolefin (e.g., PoP such as virgin or mechanically recycled PoP). 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 PoP or blends comprising virgin PoP.

[0021] Other aspects describe compositions, methods of making the composition, composites, stacked polymeric composition, and / or sizing of the present invention. Aspect 1 describes a composition comprising: (a) a repeatedly recyclable plastomer copolymer mimic (RR-PCPM) of a polyolefin plastomer (PoP) copolymer, wherein the RR-PCPM 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) a second polymer, wherein the weight ratio of (a) to (b) is 20:80 to 80:20, and wherein the composition comprises a co- continuous phase of (a) and (b). Aspect 2 describes the composition of aspect 1, wherein the second polymer is a polyolefin plastomer (PoP). Aspect 3 describes the composition of any one of aspects 1 to 2, 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 C13) 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. Aspect 4 describes the composition of any one of aspects 1 to 3, wherein the RR-PCPM is an ethylene or a propylene co-monomer-based RR-PCPM, the second polymer is a PoP, and the PoP is an ethylene or a propylene co-monomer-based PoP, or a combination thereof. Aspect 5 describes the composition of any one of aspects 1 to 4, wherein RR-PCPM further comprises a comonomer, preferably the comonomer is ethylene-based, a propylene-based, or a combination thereof, more preferably the 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 olefinand a butylene olefin preferably 40 wt. % to 95 wt.% of the ethylene olefin and 5 wt.% to 60 wt.% of the butylene olefin. Aspect 6 describes the composition any one of aspects 1 to 5, wherein the composition comprises: (a) the RR-PCPM comprising repeating units according to Formulas I and / or II:where: Z is an aliphatic group and n is ; 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 or a propylene 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-PCPM has more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units, and the RR-PCPM has a density of 0.799 g / cm3to 0.95 g / cm3, wherein at least 20 wt.%, preferably at least 80 wt. %, of the composition is RR-PCPM; less than 80 wt.%, preferably 20 wt.% of the composition is a second polymer; and at least 0.01 % to 5 %, preferably 0.05 % to 0.15 %, of the composition is an article additive. Aspect 7 describes the composition of any one of claims 1 to 6, wherein the RR-PCPM 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, a melt temperature (7 m) of 40 °C to 110 °C as measured by DSC at a heating rate of 10 °C per min, or a combination thereof. Aspect 8 describes the composition of any one of claims 1 to 7, wherein the difunctional oligomer has a degree of saturation of 98% to 100%, the 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%, or a combination thereof. Aspect 9 describes the composition of any one of aspects 1 to 8, 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.

[0022] Aspect 10 describes a method for making the composition of any one of the aspects 1 to 9, the method comprising: (a) liquefying an article made from the composition of any one of claims 1 or 2 into a mixture containing difunctional oligomers and difunctional linkers; (b) separating the second polymer from the difunctional oligomers and difunctional linkers; and (c) reacting the difunctional oligomers and the difunctional linkers to produce the RR-PCPM.Aspect 11 describes the method of aspect 10, wherein 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 article is liquefied by melting, and wherein forming an article from the composition produced in step (b). Aspect 12 describes the method of any one of aspects 10 or 11, 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 aspects 1 to 9.

[0023] Aspect 13 describes a method of making a composition of any one of the aspects 1 to 9, the method comprising extruding at a temperature of 150 °C to 200 °C: (a) a repeatedly recyclable plastomer copolymer mimic (RR-PCPM) of a polyolefin plastomer polymer, wherein the RR-PCPM 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 liquified article; and (b) a second polymer, preferably PoP, wherein the weight ratio of (a) to (b) is 20:80 to 80:20.

[0024] Aspect 14 describes a composite comprising the composition of any one of aspects 1 to 9. Aspect 15 describes the composite of aspect 14, 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, wherein the plurality of fillers comprise a plurality of fibers and the composite further comprise sizing to promote adhesion between the plurality of fibers and the composition of any one of aspects 1 to 9, preferably the sizing comprises a repeatedly recycled polyolefin plastomer (PoP).

[0025] Aspect 16 describes a stacked polymeric composition comprising a composition of any one of aspects 1 to 9 or a composite of any one of aspects 14 to 15 and a second layer, the second layer preferably comprising a composition of any one of aspects 1 to 9 or a composite of any one of aspects 14 to 15.

[0026] Aspect 17 describes 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 aspects 1 to 9.

[0027] 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 iscontemplated 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.

[0028] The following includes definitions of various terms and phrases used throughout this specification.

[0029] “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.

[0030] “Repeatedly-Recyclable Plastomer Copolymer Mimic” or “RR-PCPM” means a copolymer that is a mimic of a polyolefin plastomer (PoP) copolymer. The RR-PCPM is a reaction product of difunctional oligomer(s) and difunctional linker(s). The difunctional linker(s) and the difunctional oligomer(s) can be 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-PCPM 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-PCPM 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-PoP starting material that was obtained from the recycled article.

[0031] The term “linker” means an aliphatic group (e.g., “Z”) that can couple and decouple to a RR-ECPM oligomer (e.g., “X”).

[0032] “Repeatedly-Recyclable Plastomer Copolymer Mimic” or “virgin RR-PCPM” is newly made directly from difunctional oligomers and difunctional linkers (and have not been obtained from an article). Virgin RR-PCPM has not previously been depolymerized and repolymerized.

[0033] “Use Cycle” indicates how many times a RR-PCPM composition of the present invention can be used to make different articles. The different article can be a new article made from the RR-PCPM, 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 newarticle 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-PCPM having a Use Cycle 0 rating, the RR- PCPM is a “virgin RR-PCPM”, and, therefore, the virgin RR-PCPM of the composition is made directly from a difunctional oligomer(s) and a difunctional linker(s) of the present invention (the virgin RR-PCPM has not been used to make an article). A RR-PCPM of the composition having a Use Cycle 1 rating means that the RR-PCPM has been used once to make an article. A RR-PCPM having a Use Cycle 2 rating means the RR-PCPM has been used twice to make, for example, two different articles. A RR-PCPM at Use Cycle 3 means the RR-PCPM has been used three times to make, for example, three different articles. As such, a RR-PCPM having a Use Cycle “n” means that the RR-PCPM can been used n times to make n different articles and impart substantially similar to identical functional properties. FIGS. 2A and 2B provides a non-limiting examples of a visually depiction of a Use Cycle of a RR-PCPM of the present invention.

[0034] The term “branching” refers the regular or random attachment of side chains to a polymer’s backbone chain.

[0035] 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. Branching can be determined usingJH NMR.

[0036] 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.

[0037] 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.

[0038] The terms “fiber” or “filament” refers to any of a class of materials that include continuous filaments or discrete elongated materials. “Fiber” can be used interchangeably with the term “filament.” Thus, modifications made in the manufacture of fibers as disclosed herein, apply equally to other filamentous materials as well. Fibers of the present invention can be of any scale including micron and nanometer scale fibers. Fibers can include natural fibers, as well as synthetic fibers made from inorganic or organic materials. Fibers can be high temperature fibers or low temperature fibers.

[0039] The term “plastomer” refers to a copolymer that exhibits plastic properties which means it can be molded or shaped under heat and pressure, but it is not as elastic as elastomers. Plastomers are typically harder and less flexible than elastomers.

[0040] 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%.

[0041] 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.

[0042] The term “substantially” and its variations are defined to include ranges within 10 %, within 5 %, within 1 %, or within 0.5 %.

[0043] 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.

[0044] The term “effective,” as that term is used in the specification and / or claims, means adequate to accomplish a desired, expected, or intended result.

[0045] 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.”

[0046] 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.

[0047] 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.

[0048] 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 blend of a RR-PCPM and a second polymer, where the RR-PCPM can be obtained from a liquified article that can be depolymerized into difunctional oligomers and difunctional linkers. The difunctional oligomers and difunctional linkers can be repolymerized into a RR-PCPM, blended with a second polymer, and / or used to produce a new article. The newly produced article can be substantially produced from the repolymerized RR-PCPM and second polymer. Alternatively, the difunctional oligomer and the difunctional linkers of the liquefied article can have a weight percentage that is at least 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.% of the RR-PCPM composition of the present invention (e.g., blend) or at least 95 wt.% of the RR-PCPM.

[0049] 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 otherembodiments. 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

[0050] 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.

[0051] FIG. 1 is an illustration of the system and method to make the composition of the present invention that includes a RR-PCPM(s).

[0052] FIGS. 2A and 2B are illustrations of closed loop Use Cycles of a RR-PCPM composition of the present invention.

[0053] FIG. 3 is an illustration of a stacked polymeric composition of the present invention that includes four fiber-reinforced composites of the present invention.

[0054] 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.

[0055] FIG. 5 is cross-sectional view of an illustration of a polymeric matrix that includes a fiber sized with RR-PCPM compositions of the present invention.

[0056] FIG. 6 is an illustration of the closed-loop recycling process of the present invention that include the RR-PCPM compositions of the present invention.

[0057] 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

[0058] A discovery has been made that provides a solution to at least one or more of the problems associated with chemical recycling of PoP copolymers. In one aspect of the present invention, there is disclosed a blend of a repeatedly recyclable plastomer copolymer mimic (RR-PCPM) of polyolefin plastomer (PoP) copolymer with a second polymer. Compositions that include this blend can be more efficiently recycled, as the RR-PCPM can be repeatedly and directly recreated (e.g., 2 to 500 times or more) from an article comprising the RR-PCPM. For example, at least 90 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, or 100 wt. %of the RR-PCPM obtained from the article being recycled can be depolymerized, repolymerized into a new RR-PCPM, and re-used with a second polymer or a third polymer or more polymers in the newly produced article. This recycling efficiency of the RR-PCPM 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-PCPM / second polymer blends can have similar functional properties to conventional PoP or to virgin RR-PCPM. Advantageously, the second polymer can be separated from the RR-PCPM composition during recycling of the article and then reused.

[0059] 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

[0060] The composition of the present invention can include a RR-PCPM and a second polymer. In some instances, an additive is present. The additive can be an article additive and / or a blend additive (e.g., an additive added to a blend of the RR-PCPM and the second polymer composition). In some aspects, the RR-PCPM / second polymer blend can include at least 20 wt.% to 80 wt.% (e.g., 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, or 80 wt.%, or any value or range there between) of the RR-PCPM. In some aspects the composition includes 20 wt.% to 80 wt.% of a second polymer or a third polymer (e.g., 20 wt.%, 30 wt.%, 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, or 80 wt.%, or any value or range there between based on the total weight of the RR-PCPM / second polymer blend. The second polymer can be virgin PoP or recycled PoP (e.g., mechanical, or chemically recycled PoP). For example, 80 wt.% RR-PCPM and 20 wt.% second polymer, 70 wt.% RR-PCPM and 30 wt.% second polymer, 65 wt.% RR- PCPM and 35 wt.% second polymer, 60 wt.% RR-PCPM and 40 wt.% second polymer, 50 wt.% RR-PCPM and 50 wt.% second polymer, 40 wt.% RR-PCPM and 60 wt.% second polymer, 30 wt.% RR-PCPM and 70 wt.% second polymer, or 20 wt.% RR-PCPM and 80 wt.% second polymer or any range or value there between, based on the total weight of the RR- PCPM / second polymer blend. i. RR-PCPM

[0061] The RR-PCPM can include repeating units of a difunctional linker (Z) and a difunctional oligomer (X). In some aspects, the number average molecular weight (M>) of the RR-PCPM can be 20,000 g / mol to 1,000,000 g / mol, 20,000 to 3,000,000 g / mol, 40,000 to1,000,000 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 Mncan be determined as the polyethylene equivalent molecular weight by high temperature size exclusion chromatography performed at 160 °C in tri chlorobenzene using polyethylene standards. The RR-PCPM(s) can have a melt temperature (Tm) 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-PCPM(s) can be 0.799 g / cm3to 0.95 g / cm3or 0.799 g / cm3, 0.80 g / cm3, 0.85 g / cm3, 0.90 g / cm3, 0.95 g / cm3or 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.

[0062] In some preferred aspects, the RR-PCPM 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 (-OH), carboxylic acid (CO2H), amine (NH2), or a combination thereof and the oxygens bonded to X and 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 (-OH), carboxylic acid (CO2H), amine (NH2), or a combination thereof and the oxygens bonded to X can be ketones, amines etc. In some aspects, X and X have different carbon lengths. Different carbon lengths provide the advantages of tunable mechanical properties, improved mechanical properties, and / or recycling processability. A non-limiting example of the copolymer, when Z includes hydroxyl groups, and X and X' includes ketones is represented in Formulas (lb) and (lib):

[0063] 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)

[0064] In Formulas (la), (lb), and (Ic), 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.

[0065] In some aspects, X can be a polyolefin having the formula of Formula (Illa):R-H- - m (Illa) where m 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 Cio 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 4045, 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 %.

[0066] 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.

[0067] 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.

[0068] In Formulas (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 C13 alkyl group branches.

[0069] In some aspects, X' can be a polyolefin having the formula of Formula (Illb):(Illb) where m 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 %.

[0070] 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.

[0071] 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.

[0072] 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- 1-octene) group. In some aspects, X can be a poly(ethylene-co-a-olefm) group, and X' can be a polypropylene group.

[0073] 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 C13 hydrocarbon branches. In some aspects, the branched polyethylene can contain Cl to C 13 alkyl group branches.

[0074] 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.

[0075] 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 Cl 3 hydrocarbon branches. In some aspects, the branched polypropylene can contain Cl to Cl 3 alkyl group branches.

[0076] 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.

[0077] 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.

[0078] The RR-PCPM(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 can having the formula?■ R'-Z-R2”, where R1and R2are 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, R1and R2can 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 -tricarboxy lie acid, pentane-1, 3, 5-tri carboxylic acid, or any combinations thereof.

[0079] The difunctional oligomer can have a formula of, (“R3-X-R4”) where R3and R4are 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-PCPM. The two functional groups, R3or R4can 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.R5-r~ X'T — R6

[0080] If a second difunctional oligomer is used it can have a formula of ' 'n(“R5-X'-R6”) where R5and R6are 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-PCPM. The two functional groups, R5or R6can 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

[0081] The compositions of the present invention can include at least one additive. The additive can be an article additive (e.g., an additive obtained from a liquified article) or a blend additive. The article or blend additive can be added when a RR-PCPM and a second polymer is blended and / or the RR-PM composition 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.

[0082] 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)-propi onate)(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.

[0083] 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.

[0084] Every time a RR-PCPM gets made from a liquified article, a new additive package can be used prior to making a new article so that the next RR-PCPM that is made and used in an article can have a higher amount of additive(s) when compared with the initial (prior to adding more additive) RR-PCPM obtained from the liquified article. When the amount additive(s) in a RR-PCPM are so much that the amount of additive(s) affects the functional properties of the copolymer(s) made, the RR-PCPM may not be substantially similar to the functional properties of virgin RR-PCPM or conventional PoP. In some aspects, at some point, there may be so much additive in the RR-PCPM that the recycled polyethylene may no longer function similar to the virgin RR-PCPM.

[0085] 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.

[0086] 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-PCPM(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 %, preferably0.05 % to 0.15 %, of an article additive from a liquified article and 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, 100 wt.% of the RR-PCPM(s). iii. Second Polymer

[0087] The second polymer (third polymer, fourth polymer, etc.) can be virgin PoP or recycled PoP obtained from the recycling process of the present invention. PoP can be obtained from various commercial manufactures. Non-limiting examples of PoP manufacturers include SABIC, ExxonMobil Chemical, LyondellBasell, Dow, Chevon Phillips Chemical, and the like. PoP can have a density of 0.86 g / cc to 0.912 g / cc. The second polymer can be supplied in any form (e.g., pellets, sheet, film, etc.). In a preferred aspect, the second polymer is a pellet.B. Method of Making the Composition

[0088] Certain aspects are directed to a method for making the composition of the present invention that includes a RR-PCPM and a second polymer. The composition of the present invention can be made by blending a RR-PCPM and a second polymer in a weight ratio of 20:80 to 80:20. In some aspects, an additive can be added to the blend. Examples of additive are listed in Section A(ii). The amount of additives used to make the blend 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. Blending conditions can include a temperature of 150 °C to 200 °C or 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, or any range or value there between.

[0089] 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-PCPM / second polymer blends 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 a second polymer, RR-PCPMs and / or a composition of the present invention that includes a RR-PCPM and a second polymer. Plastic article 108 can include one or more article additives. In some embodiments, the article only include RR-PCPMs. In some aspects, the composition can contain a blend of the RR-PCPMs of varying molecular weight and a second polymer. In some preferred aspects, the article 108 is a plastic article. Nonlimiting examples of consumer goods can include a packaging product, a pharmaceuticalcontainer, 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-PCPM(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-PCPM(s) and an article additive. In some aspects, composition 110 includes the RR-PCPM, a second polymer and an optional additive.

[0090] 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-PCPM(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-PCPM(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, R4R5, and R6are each OH, CO2H, NH2, or a combination thereof, and the difunctional linker R'-Z-R2. where R2and R2are 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, R4R5, and R6are each OH,), and a methyl ester of the difunctional linker (e.g., R^Z-R2, where R1and R2are 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 P-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.

[0091] 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, comonomer can be produced during depolymerization, be separated from the difunctional linker and difunctional oligomer, 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-PCPM processes that are desired can be separated from the desired oligomers and linkers. For example, any PoP copolymers, PoE copolymers, homopolymers of PP, LDPE, HDPE or LLDPE, or a combination thereof can be separated from the RR-PCPM difunctional oligomers.

[0092] 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-PCPM(s). Saidanother way, the difunctional oligomers with a comonomer and difunctional linkers in stream 112 and 114 can be repolymerized to form a recycled RR-PCPM(s). In some instances, the comonomer is not present. In polymerization unit 106, the difunctional oligomers and difunctional linkers, and comonomer if present, 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 (e.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. 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 -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.

[0093] 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 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 HChC-Z’-CChH (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.

[0094] 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, isocitricacid, propane- 1,2, 3 -tricarboxy lie 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-tri carboxylic acid, and pentane-l,3,5-tricarboxylic acid, and / or esters, and / or anhydride thereof obtained from a RR-PCPM recreated from an article comprising difunctional oligomers and difunctional linkers.

[0095] RR-PCPM(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- PCPM(s) 116. In some aspects, RR-PCPM 116 is formed into a pellet to be sold, transported, or converted into a consumer product. As shown in FIG. 1, RR-PCPM(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-PCPM(s) 116 can be blended with the recycled second polymer or virgin second polymer compositions 122 (e.g., recycled conventional PoP, or virgin PoP) and formed into RR-PCPM article 120 that includes the RR-PCPM(s) and second polymer. For example, RR-PCPM(s) / second polymer can be molded (e.g., extruded, injection molded, blow molded, compression molded, rotational molded, thermoformed and / or 3-D printed) to form RR-PCPM article 120. In some aspects, RR-PCPM 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-PCPM(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-PCPM(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 liquifi cation unit 102 can be preserved throughout the liquifi cation, depolymerization, and repolymerization steps, such that no or reduced amounts of additive is added prior converting unit 118.

[0096] In some aspects, RR-PCPM article 120 can contain a blend of the RR-PCPM(s) and second polymer of varying molecular weight. In some aspects, RR-PCPM article 120 canfurther 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 scratchresistance 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.

[0097] RR-PCPM article 120 can exit converting unit 118 and be sold, transported, used, and / or stored. RR-PCPM article 120 can be used and collected by consumers 124. After use, used RR-PCPM article 126 containing RR-PCPM 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-PCPM(s) can now be realized.C. Articles

[0098] Compositions of the present invention that include the RR-PCPM 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.

[0099] 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.

[0100] Additionally, the RR-PCPM 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.D. RR-PCPM Use Cycles

[0101] In some aspects, the RR-PCPM of the present invention exhibits favorable Use Cycle ratings such that the RR-PCPM can be made into different articles such that instead discarding each article can be liquefied and repolymerized into another RR-PCPM material, or blended with the recycled second polymer or virgin second polymer compositions 122 (e.g., recycled PoP, or virgin PoP) to form RR-PCPM composition as described above. Referring to FIG. 2A, In Block 202, RR-PCPMnis 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-PCPMn. When n is 1, this can represent Use Cycle 1. In Block 206, the Articlen from Block 204 made from RR-PCPMn 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-PCPMn+i. In Block 210, the Articlen+i can be produced from the RR-PCPMn+i of Block 208 and a second polymer. When n is 2, this represents a Use Cycle of 2. Generally, the RR-PCPM has a Use Cycle rating of at least 2. In Block 212, the process can be continued, where Articlen+i of Block 210 can be liquefied by heating and depolymerization as described above to produce difunctional oligomer(s) and difunctional(s) linkers, and the second polymer can be separated from the other components. 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-PCPMn+2 material and a second polymer (or third polymer) can be added to the RR-PCPMn+2 material.

[0102] Referring to FIG. 2B, in Block 218, RR-PCPMn and a second polymer is shown, where n is an integer (e.g., 0 to 10000, or more). In Block 220, an Articlen can be made from Block 218 RR-PCPMn and the second polymer. When n is 1, this can represent Use Cycle 1. In Block 222, the Articlen from Block 218 made from RR-PCPMn and the second polymer can be liquefied by heating and depolymerization as described above to produce difunctional oligomer(s) and difunctional(s) linkers of Articlen. In Block 224, the liquified Articlen of Block 222 (e.g., the difunctional oligomer(s) and difunctional linker(s) of the present invention) can be polymerized to produce RR-PCPMn+1. The second polymer can be removed prior to the polymerization process. In Block 224, the Articlen+1 can be produced from the RR-PCPMn+1 of Block 222 and the used second polymer or a virgin second polymer (e.g., third polymer). When n is 2, this represents a Use Cycle of 2. Generally, the RR-PCPM composition has a Use Cycle rating of at least 2. In Block 226, the process can be continued, where Articlen+1 of Block 224 can be liquefied by heating and depolymerization as described above to produce difunctional oligomer(s) and difunctional(s) linkers. In Block 228, the liquified Articlen+1 of Block 230 (e.g., the difunctional oligomer(s) and difunctional linker(s) of the present invention) can be polymerized to produce a new RR-PCPMn+2 material to continue the cycle.

[0103] In one embodiment, the RR-PCPM composition has a Use Cycle rating ranging from 2 to 1000. In another embodiment, the RR-PCPM composition has a Use Cycle rating rangingfrom 2 to 500. In another embodiment, the RR-PCPM composition has a Use Cycle rating ranging from 2 to 400. In another embodiment, the RR-PCPM composition has a Use Cycle rating ranging from 2 to 300. In another embodiment, the RR-PCPM composition has a Use Cycle rating ranging from 2 to 300. In another embodiment, the RR-PCPM composition has a Use Cycle rating ranging from 2 to 200. In another embodiment, the RR-PCPM composition 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 USE 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.

[0104] Remarkably, the present invention allows for the manufacture of a polymer that is functionally similar to conventionally made PoP, or a virgin RR-PCPM, and that can be repeatedly reused / recycled. The addition of a second polymer to the RR-PCPM allows for tuning of the properties of the RR-PCPM during the recycling process. 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 polymer from monomers, the compositions, RR-PCPM, 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-PCPM, 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-PCPM obtained from an article can be recycled to produce a new article).E. RR-PCPM Composites

[0105] The RR-PCPM 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.

[0106] RR-PCPM 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-limitingexamples 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.

[0107] 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.

[0108] 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.

[0109] 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 moremachines capable of cuting, 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-PCPM 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 paterning the core thermoplastic layer. In some embodiments, a stack of RR-PCPM composites can be formed by heating and pressing more than one RR- PCPM 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- PCPM composite can be treated with a coupling agent prior to assembling the stack. In some embodiments, the coupling agent can be a repeatedly recycled elastomer copolymer mimic of a polyolefin elastomer.

[0110] Non-limiting examples of core materials can include RR-PCPM 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 / polystyrene 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.[OHl] In some embodiments, a fiber reinforced composite of the present invention can include the RR-PCPM of the present invention, additives, fibers, and a coupling agent. Morethan 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-PCPM, based on the total weight of the fiber-reinforced composite.

[0112] 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.

[0113] In some embodiments, fillers (e.g., fibers) in the composite or compositions of the present invention can be sized. The sizing can include RR-PCPM, PoE, or a PoE mimic, 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.

[0114] Fiber-reinforced composites can be made by dispersing fibers (sized with RR-PCPM or unsized) in a RR-PCPM 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-PCPM (polymer composition) can be supplied between a first and a second spreaded fiber layers. Heat can be applied to the fiberlayer / 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-PCPM 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-PCPM 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.

[0115] 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-PCPM composites of the present invention having fibers or sized fibers dispersed therein.

[0116] 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-PCPM 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-PCPM 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.

[0117] PoP-composites (e.g., 302, 304', 306, 308, etc.) that include fibers (e.g., fibers 310) can have a pre-consolidation fiber volume fraction (VI) 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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, orthe 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.

[0122] 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.

[0123] 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).

[0124] Stacked polymeric compositions of the present invention can include coupling agents (e.g., tie layers) to adhere the composites together. FIG. 4 illustrates stacked polymericcomposition 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-PCPM polymer matrix. Non-limiting examples of coupling agents (tie layer) can include PoE, 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.

[0125] The stacked polymeric compositions and / or composites can be recycled as described in Section D. When the composites or stacked polymeric compositions include fibers, the fibers can be removed after liquification of the RR-PCPM 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-PCPM Sizing Agent

[0126] In some aspects of the present invention the RR-PCPM compositions 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-PCPM composition sizing 504 and a polymer matrix 506. The fibers prepared with the RR-PCPM composition 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.

[0127] 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-PCPM 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 otherembodiments, 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-PCPM sized fibers are incorporated into a repeatedly recycled polymer mimic composite.

[0128] Non-limiting examples of thermoplastic polymers include polyethylene terephthalate (PET), polycarbonates (PC), polybutylene terephthalate (PBT), poly (1,4- 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.

[0129] 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, copolymers 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.

[0130] The fiber can be sized by applying a RR-PCPM composition or a RR-PCPM solution to a fiber during manufacture of the fiber. When a RR-PCPM solution is used, the RR-PCPMis blended with a solvent to reduce the viscosity of the RR-PCPM. 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.

[0131] In other aspects, the application of the RR-PCPM composition sizing can be accomplished by spraying the RR-PCPM composition 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.

[0132] As described above, sizing can be “cured” by removal of solvent from the RR-PCPM composition 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.

[0133] Compositions that include fibers sized with RR-PCPM composition can be recycled as described herein. For example, the fibers can be removed after liquification of the polymeric material. The RR-PCPM material can be separated from other polymers and recycled as described in Section D. 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-PCPM Coupling Agent

[0134] In some embodiments, the RR-PCPM composition can be used as a coupling layer to adhere two polymer compositions together. For example, RR-PCPM compositions can adhere repeatedly recycled polymer compositions, thermoset polymers, thermoset polymers, copolymers thereof together. In other embodiments, the RR-PCPM can adhere a non-polymericmaterial (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).

[0135] The materials having RR-PCPM compositions 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- PCPM composition as a coupling agent. The RR-PCPM composition can be recycled as described herein. The RR-PCPM can be isolated from other thermoplastic or thermoset polymeric materials.EXAMPLES

[0136] 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

[0137] Thermal analysis was conducted 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.

[0138] HT-SEC Procedure. The molecular weight and dispersity were determined by means of high temperature size exclusion chromatography (HT-SEC) performed at 150 °C to 160 °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- dichlorobenzene (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).

[0139] The purpose of these examples was to make a repeatedly recyclable-plastomer copolymer mimic (RR-PCPM) of a polyethylene plastomer (PoP) copolymer. The RR-PCPMwas a reaction product of a difunctional oligomers and a difunctional linkers from a liquefied article that contained the difunctional oligomers and the difunctional linkers. The purpose was also to (i) compare properties of the RR-PCPM with the properties of a virgin RR-PCPM 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-PCPM can made from articles that are liquefied multiple times.

[0140] Materials. Table 1 lists the materials used to make repeatedly recyclable oligomers and RR-PCPM from the oligomers.Table 1Example 1((Method of liquifying a RR-PCPM article by heating and depolymerizing the RR- PCPM article to obtain difunctional oligomers and difunctional linkers)

[0141] A RR-PCPM 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.

[0142] 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 thebottom 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-PCPM from the liquified article containing a mixture of the difunctional oligomers and difunctional linkers of Example 1)

[0143] The difunctional oligomers and the difunctional linkers of the mixture obtained from Example 1 were reacted to produce a RR-PCPM composition.

[0144] 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 conducted 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-PCPM was collected. The RR-PCPM was characterized by solid state NMR.

[0145] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions, and alterationscan 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

CLAIMS1. A composition comprising:(a) a repeatedly recyclable plastomer copolymer mimic (RR-PCPM) of a polyolefin plastomer (PoP) copolymer, wherein the RR-PCPM 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) a second polymer, wherein the weight ratio of (a) to (b) is 20:80 to 80:20, and wherein the composition comprises a co-continuous phase of (a) and (b).

2. The composition of claim 1, wherein the second polymer is a polyolefin plastomer (PoP).

3. The composition of any one of claims 1 or 2, 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, and / or the RR- PCPM 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, a melt temperature (7 m) of 40 °C to 110 °C as measured by DSC at a heating rate of 10 °C per min, or a combination thereof.

4. The composition of any one of claims 1 or 2, wherein the RR-PCPM is an ethylene or a propylene co-monomer-based RR-PCPM, the second polymer is a PoP, and the PoP is an ethylene or a propylene co-monomer-based PoP, or a combination thereof.

5. The composition of any one of claims 1 or 2, wherein RR-PCPM further comprises a comonomer, preferably the comonomer is ethylene-based, a propylene-based, or a combination thereof, more preferably the 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.

6. The composition any one of claims 1 or 2, wherein the composition comprises:(a) the RR-PCPM comprising repeating units according to Formulas I and / or II:where:Z is an aliphatic group and n is ;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 or a propylene 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-PCPM has more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units, and the RR-PCPM has a density of 0.799 g / cm3to 0.95 g / cm3, wherein at least 20 wt.%, preferably at least 80 wt. %, of the composition is RR-PCPM; less than 80 wt.%, preferably 20 wt.% of the composition is a second polymer; and at least 0.01 % to 5 %, preferably 0.05 % to 0.15 %, of the composition is an article additive.

7. The composition of any one of claims 1 or 2, wherein the difunctional oligomer has a degree of saturation of 98% to 100%, the difunctional oligomer is a branched copolymer having a carbon number of C40 to C2000, wherein the difunctional oligomer has a degree of branching of 5% up to 60%, or a combination thereof.

8. The composition of any one of claims 1 or 2, 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.

9. A method for making the composition of any one of the claims 1 or 2, the method comprising:(a) liquefying an article made from the composition of any one of claims 1 or 2 into a mixture containing difunctional oligomers and difunctional linkers;(b) separating the second polymer from the difunctional oligomers and difunctional linkers; and(c) reacting the difunctional oligomers and the difunctional linkers to produce the RR-PCPM.

10. The method of claim 9, wherein 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 article is liquefied by melting, and wherein forming an article from the composition produced in step (b), and / or 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 or 2.

11. A method of making a composition of any one of the claims 1 or 2, the method comprising extruding at a temperature of 150 °C to 200 °C:(a) a repeatedly recyclable plastomer copolymer mimic (RR-PCPM) of a polyolefin plastomer polymer, wherein the RR-PCPM 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 liquified article; and(b) a second polymer, preferably PoP, wherein the weight ratio of (a) to (b) is 20:80 to 80:20.

12. A composite comprising the composition of any one of claims 1 or 2.

13. The composite of claim 12, 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, wherein the plurality of fillers comprise a plurality of fibers and the composite further comprise sizing to promote adhesion between the plurality of fibers and the composition of any one of claims 1 or 2, preferably the sizing comprises a repeatedly recycled polyolefin plastomer (PoP).

14. A stacked polymeric composition comprising a composition of any one of claims 1 or 2 or a composite of any one of claims 12 or 13 and a second layer, the second layer preferably comprising a composition of any one of claims 1 or 2 or a composite of any one of claims 12 or 13.

15. 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 or 2.

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