Blends of repeatedly recyclable-polymer mimics of low-density polyethylene (LDPE) polymers

Abstract

A composition and methods of making the composition are described. The composition can include a second polymer, and a repeatedly recyclable-polymer mimic (RR-PM) of a low- density polyethylene polymer. The RR-PM is a reaction product of a difunctional oligomer and a difunctional linker. The difunctional oligomer and difunctional linker are both from a liquefied article. The second polymer can be LDPE.

Description

BLENDS OF REPEATEDLY RECYCLABLE-POLYMER MIMICS OF LOW- DENSITY POLYETHYLENE (LDPE) POLYMERS

[0001] This application claims priority to and the benefit of the filing date of India Provisional Patent Application No. 202341063911, filed September 22, 2003 and European Patent Application No. 24151245.8, all 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-polymer mimics (RR-PMs) of low-density polyethylene (LDPE) polymers and a second polymer. The second polymer can include LDPE (e.g., mechanically recycled, or virgin LDPE).B. Description of Related Art

[0003] Polyolefins have multiple industrial uses. Polyolefins such as polyethylene constitute the largest volume of synthetic plastic produced worldwide. Polyethylene such as low-density polyethylene (LDPE) is 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 LDPE 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 LDPE 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 LDPE such as by damaging the polymer chains (e.g., chain scission, chain branching, crosslinking, etc.). The mechanically recycled LDPE can have reduced chemical and / or physical properties when compared with its native / virgin form. This damage oftentimes limits the amount of mechanically recycled LDPE that can be used to re-produce new articles. For example, virgin LDPE is often blended with the mechanically recycled LDPE to create newarticles. The use of additional materials such as virgin LDPE can be cost-inefficient and / or increase the carbon footprint of the resulting article. Further, the use of non-LDPE polymers to blend with LDPE (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 LDPE is to chemically recycle the LDPE within the articles. Typical chemical LDPE recycling technologies subject the material to pyrolysis (cracking) and / or gasification reactions to chemically break down the LDPE into various smaller hydrocarbon products (e.g., smaller alkanes, alkene, or dienes). The chemical recycling process of LDPE typically results in production of a fraction of ethylene, which can be used to make chemically recycled LDPE. 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 LDPE recycling. In one aspect, the discovery relates to the use of a blend of a repeatedly recyclable-polymer mimic (RR-PM) of LDPE with a second polymer. In one aspect, the second polymer can be mechanically recycled LDPE and / or virgin LDPE. The blend can be used to make an article. The RR-PM within the blend and / or within the article can repeatedly be recycled and reused to make additional articles. In one aspect, the RR-PM can be the reaction product of a difunctional oligomer and a difunctional linker of the present invention. The RR-PM can be blended with the second polymer in an 80:20 to 20:80 weight ratio based on the total weight of the RR-PM / second polymer blend. Notably, the blend can be co-continuous in these ranges, which can be advantageous in that the RR-PM 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 LDPE and / or virgin LDPE / mechanically recycled LDPE blends. In certain aspects, the blends and compositions that include the blends can have a peak melting temperature (Tm) of 104 °C to 125 °C, preferably 114 °C to 120 °C, or more preferably 112.8 °C. In some embodiments, theblend and compositions that include the blend can have a crystallinity temperature (Tc) of 88 °C to 100 °C, preferably 87 °C to 109 °C, or more preferably 95.8 °C. The blend and compositions that include the blend can have a glass transition peak temperature (Tg) of -112 °C to -108 °C, preferably -111 °C to -109 °C, or more preferably -110 °C. Tm, Tc and / or Tg can be determined using ISO-11357-1 by differential scanning calorimetry (DSC) at a heating rate of 10 °C per minute.

[0007] An additional advantage of the present invention is that the RR-PM 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-PM present in the article to be recycled can be depolymerized into difunctional oligomers and difunctional linkers and then repolymerized into a RR-PM. The repolymerized RR-PM can then be blended with a second polymer and used to create a newly produced article . The RR-PM / 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-PM / 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-PMs and a second polymer in weight ratios of 80:20 to 20: 80. The composition includes a co-continuous phase of RR-PM and the second polymer (e.g., LDPE such as mechanically recycled LDPE and / or virgin LDPE). In one aspect, a composition can include a repeatedly recyclable polymer mimic (RR-PM) of a low-density polyethylene polymer. The RR-PM can be 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 thereof) . The difunctional oligomer can include a difunctional oligomer having from 40 to 2000 carbon atoms (C40 to C2000), preferably C60-C1500, more preferably C80-C1100, and a functionality “F” of 2.0 ± 0.3. The difunctional oligomer can have a degree of saturation of 98% to 100%. In some aspects, the difunctional oligomer of the RR-PM can be a randomly branched C40 to C2000 polyethylene. The difunctional oligomer can have an entanglement structure due to the random branching on the polyethylene backbone. The difunctional linker can have a carbon chain of 2 to 13 carbon atoms (C2-C13) and “F” of 2.0 ±0.3. For both the difunctional oligomer and difunctional linker, “F” can be an amine (-NH2), an alcohol (-OH),a carboxylic acid (-COOH), or a combination thereof. The difunctional oligomer “F” and the difunctional linker “F” can be the same or different as long as they can react to form a condensation product. The carboxylic acid can be a cyclic acid (e.g., anhydride), acyclic acid, a masked acid (e.g., an ester), or a combination thereof. In some embodiments, the carboxylic acid difunctionality is a combination of an acid and an ester. In a preferred aspect, the difunctional oligomer is a diol and the difunctional linker is a carboxylic acid. The number average molecular weight (Mn) of the RR-PM can be 20,0000 to 6,000,000 g / mol. The Mn can be determined using gas permeation chromatography (GPC) (e.g., according to ISO-16014-4 and / or ASTM D6575). More particularly, the Macan be determined as the polyethylene equivalent molecular weight by high temperature size exclusion chromatography performed at 160 °C in trichlorobenzene using polyethylene standards. A density of the RR-PM can be 0.7 g / cm3to 0.99 g / cm3. Density can be determined using known methods, such as ASTM D 792 and / or ISO 1183. The RR-PM can have a melt temperature (Tm) of 60 °C to 135 °C, 75 °C to 130 °C, 80 °C to 125 °C, or 85 °C to 120 °C or any value or range there between as measured by DSC at a heating rate of 10 °C per min. In some aspects, the composition can include at least 20 wt.%, to 80 wt. %, of the RR-PM, 80 wt.% to 20 wt.% of a second polymer, and 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 additive or an article additive. In some aspects, the difunctional oligomer and the difunctional linkers of the article can have a weight percentage that of 20 wt.% to 80 wt.% of the RR-PM and 80 wt.% to 20 wt.% of a second polymer.

[0009] In another aspect, the compositions of the present invention can include an article additive (e.g., an additive present in the article being recycled) in an amount ranging from more than 0 wt.% to less than 0.01 wt.%, based on the total weight of the RR-PM or of the composition containing the RR-PM. In one preferred aspect of the present invention, the RR- PM can have the following formula:where Z is an aliphatic group, n is an integer ranging from 2 to 13, and X is a polyethylene backbone that includes 40 to 2000 carbon atoms, preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms. The RR-PM can have more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units. The RR-PM of Formula (I) can have a density of 0.70 g / cm3to 0.99 g / cm3.

[0010] In one particular aspect, a composition of the present invention can include a repeatedly recyclable-polymer mimic(RR-PM) of a low-density polyethylene polymer and a second polymer. The RR-PM can be a reaction product of a difunctional oligomer and a difunctional linker that both can be from an article of the present invention being recycled. The difunctional oligomer and the difunctional linkers of the article can have a weight percentage that is at least 95 wt.% of the RR-PM. The composition can include (i) the RR-PM having a structure according to Formula I:where: n is an integer ranging from 2 to 13; Z is an aliphatic group; and X is a polyethylene backbone that can include 40 to 2000 carbon atoms, preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms, (ii) a second polymer, and (iii) an article additive. The RR-PM has more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units; and the RR-PM of Formula (I) can have a density of 0.70 g / cm3to 0.99 g / cm3.

[0011] In some aspects of the present invention composites are described. A composite can include the RR-PM / second polymer 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.

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

[0013] In yet other aspects of the present invention, an article that includes a composition of the present invention is 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-PM of the present invention.

[0014] Certain aspects of the present invention 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-PM in the composition can be depolymerized into a mixture containing the difunctional oligomer and the difunctional linker. In one aspect, depolymerization can be performed by hydrolysis and / or solvolysis by contacting the liquified article composition with water and / or solvent to obtain the difunctional oligomer and the difunctional linker. In some aspects, the difunctional oligomer and the difunctional linker in the mixture can be separated prior to repolymerization. Reaction of the difunctional oligomer and the difunctional linker can produce the composition of the present invention that includes a RR-PM. A second polymer can be added to the RR-PM to produce a RR-PM / second polymer composition (e.g., a blended composition). The resulting composition can be formed into a new 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.

[0015] Also disclosed in the context of the present invention is a method of closed loop recycling that encompasses a combination of mechanical and chemical recycling events. The method can include any one or any combination or all of the following steps: (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-PM. A recycled second polymer or a third polymer can be added to the RR-PM 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-PM 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 difimctional linkers. A second article can be formed from the RR-PM composition produced in step (c). Advantageously, at least 20%, 30%, 40%, 50%, 60%, 70%, 80% wt.% of the RR-PM 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 article additive can befrom the liquified article used in liquifying step (a). The RR-PM 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-PM may include increasing article additive loadings (e.g., article additives from each liquified articles) for each round of recycling, which could affect the mechanical and / or functional properties due to increased article additive loadings.

[0016] 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-PM and the second polymer at a temperature of 150 °C to 200 °C. The RR-PM can be a reaction product of a difunctional oligomer and a difunctional linker of a liquefied article that includes the difunctional oligomer and difunctional linker.

[0017] In yet another aspect of the present invention, the RR-PM composition of the present invention can have similar functional properties to conventional LDPE and / or to virgin RR- PM or blends thereof. Advantageously, this provides a solution to the problems associated with recycling conventional LDPE or blends of LDPE (e.g., articles made with conventional LDPE can be made with the RR-PM 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-PM composition of the present invention can continuously be reused, which can reduce and / or avoid the need to produce additional RR-PM or to produce conventional LDPE.

[0018] In still another aspect of the present invention, there is disclosed a composition that includes a first polymer and a second polymer. The first polymer can include 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., LDPE such as virgin or mechanically recycled LDPE). The composition can include an additive (e.g., any one of the additives disclosed throughout the specification). The additive can be an article additive (e.g., an additive from the liquified article). 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 LDPE or blends comprising virgin LDPE.

[0019] 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 polymer mimic (RR-PM) of alow-density polyethylene (LDPE) polymer, wherein the RR-PM is a reaction product of a difunctional oligomer and a difunctional linker that 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 low-density polyethylene (LDPE). Aspect 3 describes the composition of any one of aspects 1 to 2, wherein the composition has a peak melting temperature (Tm) of 104 °C to 125 °C, preferably 114 °C to 120 °C, or more preferably 112.8 °C, a crystallinity temperature (Tc) of 88 °C to 100 °C, preferably 87 °C to 109 °C, or more preferably 95.8 °C, a glass transition peak temperature (Tg) of -112 °C to - 108 °C, preferably -111 °C to -109 °C, or more preferably -110 °C, or a combination thereof. Aspect 4 describes the composition of anyone of aspects 1 to 3, 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. Aspect 5 describes the composition of any one of aspects 1 to 4, wherein the difunctional oligomer has a degree of saturation of 98 % to 100%, the difunctional oligomer is a branched polyethylene having a carbon number of C40 to C2000, or a combination thereof. Aspect 6 describes the composition of any one of claims 1 to 5, wherein the RR-PM has a structure of:wherein n is an integer ranging from 2 to 13, Z is an aliphatic group, and X is a polyethylene comprising 40 to 2000 carbon atoms, preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms, wherein, the RR-PM has more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units, and the RR-PM has a density of 0.70 g / cm3to 0.99 g / cm3, and a molecular weight ranging from 20,000 g / mol to 6,000,000 g / mol. Aspect 7 describes the composition of any one of aspects 1 to 6, wherein the composition comprises at least 0.001 wt.% to 3 wt.%, preferably 0.015 % to 0.15 %, of an article additive. Aspect 8 describes the composition of any one of aspects 1 to 7, 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 fdm, a lamination, a pipe, a hose, a fitting, or a combination thereof. Aspect 9 describes the composition of any one of aspects 1 to 8, wherein the difunctional oligomer andthe difunctional linkers of the liquefied article have a weight percentage that is at least 95 wt.% of the RR-PM.

[0020] Aspect 10 describes a method of recycling 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 aspects 1 to 9 into a mixture containing difimctional oligomers, difimctional linkers, and the second polymer; (b) separating the second polymer from the difimctional oligomers and difunctional linkers; and (c) reacting the difimctional oligomers and the difimctional linkers to produce the repeatedly recyclable polymer mimic (RR-PM). Aspect 11 describes the method of aspect 10, wherein: the RR-PM from the article in step (a) is depolymerized prior to step (b) 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; the article in step (a) is liquefied by melting the article; or a combination therein; and forming a second article from the composition produced in step (c). Aspect 12 describes the method of any one of aspects 10 to 11, wherein the method is repeated at least two times, preferably 2 to 500 times. Aspect 13 describes the method of any one of aspects 10 to 12, further comprising adding a third polymer with the produced RR-PM to obtain the composition of any one of aspects 1 to 9, the third polymer comprising LDPE and / or the second polymer. Aspect 14 describes the method of any one of aspects 10 to 13, further comprising obtaining the article in step (a) from a consumer product made from a composition of any one of aspects 1 to 9.

[0021] Aspect 15 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) repeatedly recyclable polymer mimic (RR-PM) of a low-density polyethylene (LDPE) polymer, wherein the RR-PM is a reaction product of a difunctional oligomer and a difimctional linker that are both from a liquified article; and (b) a second polymer, preferably LDPE, wherein the weight ratio of (a) to (b) is 20:80 to 80:20.

[0022] Aspect 16 describes a composite comprising the composition of any one of aspects 1 to 9. Aspect 17 describes the composite of aspect 16, comprising a filler having a surface in contact with the composition. Aspect 18 describes the composite of aspect 17, wherein the filler is dispersed in the composition. Aspect 19 describes the composite of any one of aspects 17 to 18, wherein the filler is a continuous fiber or discontinuous fibers, preferably the fiber is a glass fiber, an aramid fibers a polyester fiber, a polyamide fiber, a basalt fiber, or a steel fiber, or combination thereof.

[0023] Aspect 20 describes a laminate comprising a first layer comprising the composition of any one of aspects 1 to 9 or the composite of any one of aspects 16 to 19 and a second layer, preferably the second layer comprises the composition of any one of aspects 1 to 9 or the composite of any one of aspects 16 to 19.

[0024] Other embodiments of the invention are discussed throughout this application. Any embodiment discussed with respect to one aspect of the invention applies to other aspects of the invention as well and vice versa. Each embodiment described herein is understood to be embodiments of the invention that are applicable to other aspects of the invention. It is contemplated that any embodiment discussed herein can be implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.

[0025] The following includes definitions of various terms and phrases used throughout this specification.

[0026] ‘ ‘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. For example, an additive from liquified recycled article.

[0027] “Repeatedly-Recyclable Polymer Mimic (RR-PM) ” or “RR-PM” means a polymer that is a mimic of a low-density polyethylene. The RR-PM is a reaction product of difiinctional oligomer(s) and difiinctional linker(s). The difunctional linker(s) and the difunctional oligomer(s) can be obtained from a liquefied article that includes the difiinctional oligomer(s) and the difunctional linker(s). The RR-PM can be made into an article that is then liquefied by being heated and depolymerized into a mixture of difunctional oligomer(s) and difiinctional linker(s). The difiinctional oligomer(s) and difiinctional linker(s) can then be repolymerized into another RR-PM 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-PM starting material that was obtained from the recycled article.

[0028] The term “linker” means an aliphatic group (e.g., “Z”) that can couple and decouple to a RR-PM oligomer (e.g., “X”).

[0029] “Virgin Repeatedly Recyclable-Polymer Mimic” or “virgin RR-PM” is newly made directly from difunctional oligomers and difunctional linkers (and have not been obtained from an article). Virgin RR-PM has not previously been depolymerized and repolymerized.

[0030] ‘ ‘Use Cycle” indicates how many times a RR-PM composition of the present invention can be used to make different articles. The different article can be a new article made from the RR-PM, and the new article can be the same type of article (e.g., the article to be recycled and the recycled article can both be the same type of article (e.g., a cup)), or the new article can be another type of article (e.g., the article to be recycled can be a cup and the recycled article can be a utensil). For instance, for a RR-PM having a Use Cycle 0 rating, the RR-PM is a “virgin RR-PM”, and, therefore, the virgin RR-PM of the composition is made directly from a difunctional oligomer(s) and a difunctional linker(s) of the present invention (the virgin RR- PM has not been used to make an article). A RR-PM of the composition having a Use Cycle 1 rating means that the RR-PM has been used once to make an article. A RR-PM having a Use Cycle 2 rating means the RR-PM has been used twice to make, for example, two different articles. A RR-PM at Use Cycle 3 means the RR-PM has been used three times to make, for example, three different articles. As such, a RR-PM having a Use Cycle “n” means that the RR-PM 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-PM of the present invention.

[0031] The term “branching” refers the regular or random attachment of side chains to a polymer’s backbone chain.

[0032] 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 25%. 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. Degree of branching can be determined usingJH NMR.

[0033] 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.

[0034] 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.

[0035] 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%.

[0036] 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.

[0037] The term “substantially” and its variations are defined to include ranges within 10 %, within 5 %, within 1 %, or within 0.5 %.

[0038] 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.

[0039] The term “effective,” as that term is used in the specification and / or claims, means adequate to accomplish a desired, expected, or intended result.

[0040] 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.”

[0041] 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.

[0042] 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.

[0043] 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-PM and a second polymer, where the RR-PM 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-PM, 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-PM 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-PM composition of the present invention (e.g., blend) or at least 95 wt.% of the RR-PM.

[0044] Other objects, features and advantages of the present invention will become apparent from the following detailed description and examples. It should be understood, however, that the detailed description and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0045] 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.

[0046] FIG. 1 is an illustration of the system and method to make the composition of the present invention that includes a RR-PM composition of the present invention.

[0047] FIGS. 2A and 2B are illustrations of closed loop Use Cycles of a RR-PM compositions of the present invention.

[0048] FIG. 3 is an illustration of a stacked polymeric composition of the present invention that includes four fiber-reinforced composites of the present invention.

[0049] 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.

[0050] FIG. 5 is an illustration of the closed-loop recycling process of the present invention that include the RR-PM.

[0051] FIG. 6 is proton nuclear magnetic resonance (1H NMR) of virgin RR-PM.

[0052] FIG. 7 is a graphical representation of the differential scanning calorimetry (DSC) data of virgin RR-PM.

[0053] FIG. 8 is a graphical representation of the Thermal Graphical Analysis (TGA) under a nitrogen atmosphere of virgin RR-PM.

[0054] 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

[0055] A discovery has been made that provides a solution to at least one or more of the problems associated with chemical recycling of LDPE polymers. In one aspect of the present invention, there is disclosed a blend of a repeatedly recyclable -polymer mimic (RR-PM) of LDPE with a second polymer. Compositions that include this blend can be more efficiently recycled, as the RR-PM can be repeatedly and directly recreated (e.g., 2 to 500 times or more) from an article comprising the RR-PM. For example, at least 90 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, or 100 wt. % of the RR-PM obtained from the article being recycledcan be depolymerized, repolymerized into a new RR-PM, and re-used with a second polymer or a third polymer or more polymers in the newly produced article. The article can include an additive that is present throughout the recycling process. This recycling efficiency of the RR- PM 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-PM / second polymer blends can have similar functional properties to conventional LDPE or to virgin RR-PM. Advantageously, the second polymer can be separated from the RR-PM composition during recycling of the article and then reused.

[0056] 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

[0057] The composition of the present invention can include a RR-PM 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-PM and the second polymer composition). The article additive can be obtained from the liquified article used in the recycling process. In some aspects, the RR-PM / 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-PM. 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-PM / second polymer blend. The second polymer can be virgin LDPE or recycled LDPE (e.g., mechanical, or chemically recycled LDPE). For example, 80 wt.% RR- PM and 20 wt.% second polymer, 70 wt.% RR-PM and 30 wt.% second polymer, 65 wt.% RR- PM and 35 wt.% second polymer, 60 wt.% RR-PM and 40 wt.% second polymer, 50 wt.% RR- PM and 50 wt.% second polymer, 40 wt.% RR-PM and 60 wt.% second polymer, 30 wt.% RR- PM and 70 wt.% second polymer, or 20 wt.% RR-PM and 80 wt.% second polymer or any range or value there between, based on the total weight of the RR-PM / second polymer blend. The RR-PM composition can have a melt temperature (Tm) of 104 °C to 125 °C, 105 °C to 120 °C, 114 °C to 120 °C, or 104 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, or any value or range there between as measured by DSC at a heating rate of 10 °C per min. The RR- PM / second polymer composition can have a crystallinity temperature (Tc) of 88 °C to 100 °C, 87 °C to 109 °C, or 95.8 °C, or 88 °C, 89 °C, 90 °C, 91 °C, 92 °C, 93 °C, 94 °C, 95 °C, 96 °C,97 °C, 98 °C, 99 °C, 100 °C or any range or value there between. The composition has a glass transition peak temperature (Tg) of -112 °C to -108 °C, -111 °C to -109 °C, or -110 °C, or - 112 °C, -111 °C, -110 °C, -109 °C, -108 °C or any range or value there between. i. RR-PM

[0058] The RR-PM can include repeating units of a difunctional linker (Z) and a difunctional oligomer (X). In some aspects, the number average molecular weight (An) of the RR-PM can be 20,000 g / mol to 6,000,000 g / mol, 20,000 to 3,000,000 g / mol, 40,000 to 1,000,000 g / mol or 20,000 g / mol, 40,000 g / mol, 30,000 g / mol, 40,000 g / mol, 50,000 g / mol, 100,000 g / mol, 200,000 g / mol, 300,000 g / mol, 400,000 g / mol, 500,000 g / mol, 600,000 g / mol, 700,000 g / mol, 800,000 g / mol, 900,000 g / mol, 1,000,000 g / mol, 2,000,000 g / mol, 3,000,000 g / mol, 4,000,000 g / mol, 5,000,000 g / mol, 6,000,000 g / mol or any range or value there between. The Macan be determined as the polyethylene equivalent molecular weight by high temperature size exclusion chromatography performed at 160 °C in trichlorobenzene using polyethylene standards. A density of the RR-PM can be 0.7 g / cm3to 0.99 g / cm3or 0.7 g / cm3, 0.75 g / cm3, 0.8 g / cm3, 0.85 g / cm3, 0.9 g / cm3, 0.95 g / cm3, 0.99 g / cm3or any range or value there between. In some aspects, the polymer composition can have a polydispersity index (PDI), of 1 to 4.0, 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, and 4. PDI can be measured according to ISO 16014-4 and / or ASTM D 6574 methods using high temperature size exclusion chromatography at 160 °C.

[0059] In some preferred aspects, the RR-PM can have the following formula: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. 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. A non-limiting aspect, of the RR-PM is shown in formula (lb):where Z is an aliphatic group, n is an integer ranging from 2 to 13, and X is a polyethylene that includes 40 to 2000 carbon atoms, preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms. Notably, X and Z have different carbon lengths. Different carbon lengths provide the advantages of tunable mechanical properties, improved mechanical properties, and / or recycling processability. The RR-PM can have more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units.

[0060] 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. In certain aspects, the number of carbon atoms in the Z groups can vary randomly between the repeating units of Formula I. In certain aspects, Z does not vary between the repeating units of Formula I. In some aspects, n can be 2 and Z can have the formula of Formula (1), and the polymer can contain repeating units of Formula Ic:

[0061] In Formulas (la-c), 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, such as number of carbon atoms and / or DB of the X groups in the polymer 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 certain aspects, X can be a highly branched hydrocarbon having a random branching pattern. In some aspects, the branched hydrocarbon can contain saturated Cl to CIO branches(e.g., on the hydrocarbon backbone). In some aspects, the branched hydrocarbon can contain Cl to CIO alkyl group branches. In some aspects, X can be a polyolefin having the formula of Formula (III):can be an integer from 40 to 2,000 and denotes number of repeat units. R can be -H or a Ci to Cio alkyl group, and varies independently (e.g., between -H and the Ci to 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 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 random 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 %.

[0062] The RR-PM of the present invention can be a reaction product of a difunctional linker and a difunctional oligomer from a depolymerization process. The difunctional linkerR1-^- Z- — R2can having the formula ' '11, 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 -tricarboxylic acid, pentane-l,3,5-tricarboxylic acid, or any combinations thereof.

[0063] 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 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 branched. Branching in the polyethylene backbone can provide an entanglement structure to the RR-PM. 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.

[0064] Reaction scheme A below is a non-limiting example of a reaction of a linker (diacid) with an oligomer (diol) to produce a RR-PM of the present invention.ii. Additives

[0065] The compositions of the present invention can include at least one additive. The additive can be an article additive or a blend additive. The article or blend additive can be added when a RR-PM 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 phosphate, 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 ofadditive 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.

[0066] Non-limiting examples of 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; l,3,5-tris(4- tert-butyl-3-hydroxy-2,6-dimethyl benzyl) l,3,5-triazine-2, 4,6- (lH,3H,5H)-trione (CAS 040601-76) available as Cyanox 1790 (CyTech Industries); ethylenebis(oxyethylene)bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate) (CAS 36443-68- 2) available as Irganox 245; 1.6-hexamethylene bis (3,5-di(tert)-butyl-4- hydroxyhydrocinnamate (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.

[0067] 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.

[0068] For every Use Cycle a RR-PM is produced from a liquified article, a new article additive and / or package can be used prior to making a new article so that the next RR-PM that is made and used to make the new article, the new article can have a higher amount of additive(s) when compared with the initial (prior to adding more additive) RR-PM obtained from the liquified article. At very high Use Cycle rating, when the amount additive(s) in a RR- PM are so much that the amount of additive(s) affects the functional properties of the polymer made, the RR-PM may not be substantially similar to the functional properties of virgin RR- PM or virgin EDPE. In some aspects, at some point, there may be so much additive in the RR- PM that the recycled polyethylene may no longer function similar to the virgin RR-PM or conventional LDPE.

[0069] The amount of additives used to make an article can vary by application and 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.

[0070] The composition can include one or more blend additives. Non-limiting examples of a blend 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-PM / second polymer composition and blend additive. An amount of blend 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 blend additive in the composition can be 0.0 wt.% to 0.2 wt.% or 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.15 wt.%, 0.2 wt.% or any value or range there between. In some embodiments, the composition include at least 0.01 % to 0.2 %, preferably 0.05 % to 0.15 %, of a blend additive and 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, 100 wt.% of the RR-PM / second polymer composition. iii. Second Polymer

[0071] The second polymer can be virgin LDPE or recycled LDPE obtained from the recycling process of the present invention. The second polymer can be a third polymer, fourth polymer etc., depending on the Use cycle. LDPE can be obtained from various commercial manufactures. Non-limiting examples of LDPE manufacturers include SABIC, ExxonMobil Chemical, LyondellBasell, Chevon Phillips Chemical and the like. LDPE can have a density of 0.915 g / cc to 1.13 g / cc (for example, 0.915 g / cc, 0.925 g / cc, 0.95 g / cc, 0.975 g / cc, 1.0 g / cc, 1.10 g / cc, or 1.13 g / cc or any range or value there between) . The specific gravity of LDPE can be 0.92. Tensile strength of LDPE can range from 7 MPa to 12 MPa (e.g., 7, MPa, 8 MPa, 9 MPa, 10 MPa, 11 MPa, 12 MPa or any value or range there between). The LDPE can have a melting point from 115 °C to 135 °C (e.g., 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, or any range or value there between). The LDPE can have a melt temperature (Tm) of 104 °C to 125 °C,105 °C to 120 °C, 114 °C to 120 °C, or 104 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °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 LDPE can be 0.7 g / cm3to 0.99 g / cm3or 0.7 g / cm3, 0.75 g / cm3, 0.8 g / cm3, 0.85 g / cm3, 0.9 g / cm3, 0.95 g / cm3, 0.99 g / cm3or any range or value there between. In some aspects, the polymer can have a polydispersity index (PDI), of 1 to 4.0, 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, and 4. The second polymer can be supplied in any form (e.g., pellets, sheet, fdm, etc.). In a preferred aspect, the second polymer is a pellet. Density, specific gravity, Tm, Tc, PDI and other properties can be determined using known chemical testing methods. For example Tm and / or Tccan be measured according to ISO-11357-1 using DSC at a heating rate of 10 °C per minute. PDI can be measured according to ISO 16014-4 and / or ASTM D6474 using HT-SEC at 160 °C.B. Method of Making the Composition

[0072] Certain aspects are directed to a method for making the composition of the present invention that includes a RR-PM and a second polymer. The composition of the present invention can be made by blending a RR-PM 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.

[0073] Referring to FIG. 1, a system and method of making the composition from an article of the present invention is illustrated. In a preferred aspects, FIG. 1 illustrates a closed loop system and method of recycling the RR-PM / 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 RR-PMs and / or a composition of the present invention that includes a RR-PM and a second polymer. In some aspects, plastic article also includes one or more article additives. In some embodiments, the article only includes RR-PMs. In some aspects, the composition can contain a blend of the RR-PMs of varying molecular weights and a second polymer of varying molecular weights. In some preferred aspects, the article 108 is aplastic article. Non-limiting examples of consumer goods can include a packaging product, a pharmaceutical container, a bottle, a cap, a closure, a liner, a trash bag, a food packaging fdm, a lamination, a pipe, a hose, a fitting, or a combination thereof. 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-PM and an article additive.

[0074] 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-PM 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-PM depolymerizes and forms the difunctional oligomer and difunctional linker. The difunctional oligomer can be a solid, liquid, or a combination thereof. The difunctional linker can be a solid, liquid, or combination thereof. Depolymerization can include hydrolysis and / or solvolysis (e.g., alcoholysis) of the polymer to obtain the difunctional oligomer R'-X-R2. where R1and R2are each OH, CO2H, NH2, or a combination thereof, and the difunctional linker R3-Z-R4, where R3and R4are 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., R'-X-R2. where R1and R2are OH), and a methyl ester of the difunctional linker (e.g., R3-Z-R4, where R3and R4are 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-limitingexamples of metallic compounds can include a metal complexed or bonded to a hydrocarbyl, an oxide, a chloride, a carboxylate, an alkoxide, an aryloxide, an amide, a salen ligan, a [3- ketiminato ligand, or a guanidinato ligan. In some aspects, the metal can be Li, Na, K, Mg, Ca, Sc, Y, lanthanides, Ti, Zr, Zn, Mo, Mn, Al, Ga, Bi, Sb, or Sn. In some aspects, the catalyst can be Ti(OiPr)4, Ti(OBu)4, Al(OiPr)3, Sn(2-ethyl-hexanoate)2, MoOs, or any combinations thereof.

[0075] 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 (e.g., second polymer). For example, the difunctional oligomer(s) and / or second polymer can be a solid and the difunctional linker(s) can be a liquid or vice versa. In such instances, the solid(s) 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, difunctional linker, and second polymer are both liquids or both solids and solid / solid or liquid / liquid separation / purification methods can be used to isolate the solids or liquids. Separation units can help to remove impurities and / or other unwanted items prior to repolymerization. In some aspects, oligomers and linkers from other LDPE processes that are desired can be separated from the desired oligomers and linkers. For example, oligomers that are derived from PP, LDPE, LLDPE, HDPE or PoP and PoE, or a combination thereof can be separated from the RR-PM difunctional oligomers. The LDPE can be isolated and reused to make an article that includes the RR-PM and additional polymers.

[0076] 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 preferred 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-PM. Said another way, the difunctional oligomers and difunctional linkers in stream 112 and 114can be repolymerized to form a recycled RR-PM. In polymerization unit 106, the difunctional oligomers and difunctional linkers can be reacted at i) a temperature of 90 °C to 250 °C, or equal to any one of, at least any one of, or between any two of 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, and 250 °C, and / or ii) under inert atmosphere and / or vacuum. In some aspects, the reaction can include esterification at 90 °C to 250 °C, and / or under inert atmosphere, followed by polycondensation at 90 °C to 250 °C, and / or under vacuum, e.g., at pressure below 0.0005 MPa, below 0.0001 MPa, or 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 P-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)3, Sn(2-ethyl-hexanoate)2, MoOv or any combinations thereof. In certain aspects, a combination of catalysts can be used.

[0077] In some aspects, the difunctional oligomer (e.g., 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.

[0078] In some aspects, the first acid can be oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or any combinations thereof. In some aspects, the second acid can be citric acid, aconitic acid, isocitric acid, propane-1, 2, 3 -tricarboxylic acid, pentane-l,3,5-tricarboxylic acid, or any combinations thereof. In certain aspects, the compound HO-X-OH can be polymerized with more than two acids selected from oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, aconitic acid, isocitric acid, propane- 1,2, 3 -tricarboxylic acid, and pentane-l,3,5-tricarboxylic acid, and / or esters, and / or anhydride thereof obtained from a RR-PM recreated from an article comprising difunctional oligomers and difunctional linkers.

[0079] RR-PM 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 RR-PM 116. In some aspects, RR-PM 116 is formed into a pellet to be sold, transported, or converted into a consumer product. As shown in FIG. 1, RR-PM 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-PM 116 can be blended with the recycled second polymer or virgin second polymer compositions 122 (e.g., recycled LDPE, or virgin LDPE) to form RR-PM compositions and formed into RR-PM article 120. For example, RR-PM compositions can be molded (e.g., extruded, injection molded, blow molded, compression molded, rotational molded, thermoformed and / or 3-D printed) to form RR-PM article 120 that includes the RR-PM and a second polymer. In some aspects, RR-PM article 120 can be comprised in or in the form of a foam, a fdm, 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 and / or blend additive can be combined with the RR-PM 116 and second polymer 122 prior to being sent to the converting unit 118. The article 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-PM 116 prior to being sent to the converting unit 118, which may be advantageous if the article being recycled, and the article being made are the same type or class of articles. In such an aspect, the additive present in the article being liquified in liquification unit 102 can be preserved throughout the liquification, depolymerization, and re -polymerization steps, such that no or reduced amounts of additive is added prior converting unit 118.

[0080] In some aspects, RR-PM article 120 can contain a blend of the RR-PMs of varying molecular weights and a second polymer of varying molecular weights. In some aspects, RR- PM article 120 can further include one or more blend or processing additives. The additives can be added in polymerization unit 106 and / or converting unit 118. Non-limiting examples of additives can include, a scratch-resistance agent, an antioxidant, a flame retardant, an UVabsorber, 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.

[0081] RR-PM article 120 can exit converting unit 118 and be sold, transported, used, and / or stored. RR-PM article 120 can be used and collected by consumers 124. After use, used RR- PM article 126 containing RR-PM 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-PM can now be realized.C. Articles

[0082] Compositions of the present invention that include the RR-PM, second polymer, 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. In a non-limiting example, a packaging product can include RR-PM bags containing aluminum sheets (e.g., a chip bag).

[0083] 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 likedisplay 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.

[0084] Additionally, the RR-PM compositions of the present invention (with or without additives) can also be formed into films or sheets as well as components of stacked polymeric materials (e.g., laminates). 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-PM Use Cycles

[0085] In some aspects, the RR-PM of the present invention exhibits favorable Use Cycle ratings such that the RR-PM can be made into different articles such that instead discarding each article can be liquefied and repolymerized into another RR-PM material. FIGS. 2A and 2B are an illustration of Use Cycles 200 and 216. Referring to FIG. 2A, in Block 202, RR-PMnis 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-PMn. When n is 1, this can represent Use Cycle 1. In Block 206, theArticlen from Block 204 made from RR-PMncan be liquefied by heating and depolymerization as described above to produce difunctional oligomer(s) and difiinctional(s) linkers of Articlen. In Block 208, the liquified Articlen of Block 206 (e.g., the difimctional oligomer(s) and difimctional linker(s) of the present invention) can be polymerized to produce RR-PMn+i. In Block 210, the Articlen+i can be produced from the RR-PMn+i of Block 208 and a second polymer. When n is 2, this represents a Use Cycle of 2. Generally, the RR-PM 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 difimctional oligomer(s) and difimctional(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 difimctional oligomer(s) and difimctional linker(s) of the present invention) can be polymerized to produce a new RR-PMn+2 material and a second polymer (or third polymer) can be added to the RR- PMn+2 material to continue the cycle.

[0086] Referring to FIG. 2B, in Block 218, RR-PMnand 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-PMn 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-PMn, and the second polymer can be liquefied by heating and depolymerization as described above to produce difunctional oligomer(s) and difiinctional(s) linkers of Articlen. In Block 224, the liquified Articlen of Block 222 (e.g., the difunctional oligomer(s) and difimctional linker(s) of the present invention) can be polymerized to produce RR-PMn+i. The second polymer can be removed prior to the polymerization process. In Block 224, the Articlen+i can be produced from the RR-PMn+i 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-PM composition has a Use Cycle rating of at least 2. In Block 226, the process can be continued, where Articlen+i of Block 224 can be liquefied by heating and depolymerization as described above to produce difimctional oligomer(s) and difiinctional(s) linkers. In Block 228, the liquified Articlen+i of Block 230 (e.g., the difimctional oligomer(s) and difimctional linker(s) of the present invention) can be polymerized to produce a new RR-PMn+2 material to continue the cycle.

[0087] In one embodiment, the RR-PM composition has a Use Cycle rating ranging from 2 to 1000. In another embodiment, the RR-PM composition has a Use Cycle rating ranging from 2 to 500. In another embodiment, the RR-PM composition has a Use Cycle rating ranging from 2 to 400. In another embodiment, the RR-PM composition has a Use Cycle rating ranging from2 to 300. In another embodiment, the RR-PM composition has a Use Cycle rating ranging from2 to 300. In another embodiment, the RR-PM composition has a Use Cycle rating ranging from2 to 200. In another embodiment, the RR-PM composition has a Use Cycle rating ranging from2 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.

[0088] Remarkably, the present invention allows for the manufacture of a polymer that is functionally similar to conventionally made UDPE, or a virgin RR-PM, and that can be repeatedly reused / recycled. The addition of a second polymer to the RR-PM allows for tuning of the properties of the RR-PM 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-PM, 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-PM, 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-PM obtained from an article can be recycled to produce a new article).E. RR-PM Composites

[0089] The RR-PM 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.

[0090] RR-PM compositions or RR-PM composites of the present invention can be formed into any structure. Non-limiting examples of structures include sandwich-type structures, multi-layered (stacked) composites and the like. The composite or compositions of the present invention can be dimensioned and shaped according to respective applications. Non-limiting examples of shapes include rectangular, triangular, square, polygonal (whether having sharp and / or rounded comers), circular, elliptical, or otherwise rounded, or can have an irregularshape 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 of the present invention can have any thickness.

[0091] In some embodiments, the composite 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.

[0092] 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.

[0093] The composites can be made using known panel consolidation techniques. By way of example, the composite can be made using continuous systems that include one or more machines capable of cutting, cooling, stacking, wrapping, or the like (for example, static heated presses, double belt presses and the like). In some embodiments, the composites and / or stacked polymeric compositions of the present invention can include at least 2 or 3, 4, 5, 6, 7, 8, 9, 10or more RR-PM composites of the present invention having a thickness of about 0. 1 to 10 mm, or 0.25 to 5 mm. In some embodiments, when a core is present, the core density can be reduced to a desired density by patterning the core thermoplastic layer. In some embodiments, a stack of RR-PM composites can be formed by heating and pressing more than one RR-PM 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-PM composite can be treated with a coupling agent prior to assembling the stack. In some embodiments, the coupling agent can be a repeatedly recycled plastomer / elastomer copolymer mimic of a polyolefin plastomer / elastomer copolymer.

[0094] Non-limiting examples of core materials can include RR-PM 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 / polyetherimides 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.

[0095] In some embodiments, a fiber reinforced composite of the present invention can include the RR-PM of the present invention, additives, fibers, and a coupling agent. More than one composite can be assembled to produce a stack (e.g., a laminate). The 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.% ofRR-PM, based on the total weight of the fiber-reinforced composite.

[0096] 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.

[0097] In some embodiments, fillers (e.g., fibers) in the composite can be sized. The sizing can include polyolefin plastomers / elastomers mimics, conventional PoP, conventional PoE, 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.

[0098] Fiber-reinforced composites can be made by dispersing fibers in a RR-PM 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-PM (polymer composition) can be supplied between a first and a second spreaded fiber layers. Heat can be applied to the fiber layer / polymer composition / fiber layer material, followed by pressing the fiber layers into the polymer composition. In some embodiments, after pressing is completed, the first or second fiber layers can be rubbed. In some embodiments, the fibers are not spread prior to heating. In another embodiment, the composites can be made by using known impregnation techniques. For example, Miller et al. in Polymers& Polymer Composites, 1996, Vol. 4, No. 7 describes impregnation techniques for thermoplastic matrix composites. One such method can include providing suppling fibers to one or more solution baths (e.g., RR-PM / second polymer composition 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-PM compositions 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.

[0099] In some aspects, a fiber-reinforced composite (e.g., a ply) 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-PM composites of the present invention having fibers or sized fibers dispersed therein.

[0100] 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-PM composition polymeric matrix having a plurality of fibers 310 dispersed therein. Some embodiments of the present methods includeproducing 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-PM composition 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.

[0101] RR-PM 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.

[0102] 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. In some embodiments, laminates are made with the RR-PM compositions of the present invention or a composite of the present invention and a second polymer. The second polymer can be a RR-PM composition of the present invention or a RR-PM composite of the present invention. For example, a RR- PM fiber containing composite and a RR-PM composition.

[0103] 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 polymermatrix 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.

[0104] 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.

[0105] Some embodiments of the present polymeric stacks can include one or more fiber- reinforced composites, each having fiber-reinforced composites that define a woven structure (e.g., as in a fiber-reinforced composite having a plane, twill, satin, basket, leno, mock leno, or the like weave). For example, a fiber-reinforced composite can include a first set of fibers aligned in a first direction and a second set of fibers aligned in a second direction that isangularly 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.

[0106] 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.

[0107] 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). In some embodiments, the stacked polymeric compositions include composites of the present invention and a layer comprising RR-PM of the present invention.

[0108] 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-PM matrix. Non-limiting examples of coupling agents can include mimics of polyolefin plastomers / elastomers, 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.

[0109] 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-PM 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.EXAMPLES

[0110] 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[oni] 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.

[0112] HT-SEC Procedure. The molecular weight and dispersity were determined by means of high temperature size exclusion chromatography (HT-SEC) performed at 150 °C in a HT- SEC-IR instrument equipped with a IR4 detector (PolymerChar, Valencia, Spain). Three Polymer Laboratories 13 pm PLgel Olexis columns constitute the set. 1,2-dichlorobenzene (o- DCB) was purchased from VWR and used as an eluent at flow rate of 1 mL*min-l . Molecularweights and corresponding dispersities were calculated from HT-SEC analysis with respect to narrow polystyrene standards (PSS, Mainz, Germany).

[0113] The purpose of these examples was to make a repeatedly recyclable polymer mimic (RR-PM) of a LDPE polymer. The RR-PM was a reaction product of a difunctional oligomer and a difunctional linker obtained from a liquefied article. The obtained RR-PM was blended with virgin LDPE at various ratios. The purpose was also to (i) compare properties of the RR- PM / LDPE compositions with the properties of a virgin RR-PM / virgin LDPE blends where the virgin RR-PM was made directly from a difunctional oligomer and a difunctional linker and (ii) whether an article made from the composition of the present invention can be used to make a repeatedly recyclable polymer. FIGs. 2 and 5 show an overview of the closed loop process that makes possible, where RR-PM compositions of the present invention can made from articles that are liquefied multiple times.

[0114] Materials. Table 1 lists the materials used to make repeatedly recyclable oligomers and RR-PM from the oligomers.Table 1Example 1(Method of liquifying a RR-PM article by heating and depolymerizing a RR-PM article to obtain difunctional oligomers and difunctional linkers)

[0115] A RR-PM 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 atthis 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.

[0116] After the reactor was cooled to room temperature, the reactor was disassembled, and the two-layer reaction mixture was processed. The top layer was a methanol layer, and the bottom layer was a diol layer that was insoluble in methanol. The methanol layer was decanted and transferred into a beaker. The methanol layer contained the dimethyl ester of the difunctional linker (succinic acid) and residual catalyst. The ester / methanol was vacuum distilled using a laboratory Roto-vac to remove the solvent completely. The dimethyl succinate (1.6 g) was recovered with some catalyst remains (e.g., TiO2 and Ti(OH)4). The viscous diol layer at the bottom of the reactor was washed twice with methanol (total of 25 ml) and the washings transferred to the decanted methanol layer. Toluene (200 g) was added to the reactor containing the diol and stirred for 10 min. The diol dissolved in the toluene solvent layer at room temperature. The diol / solvent mixture was filtered and transferred to a distillation flask. The diol / solvent mixture was vacuum distilled using a laboratory Roto-vac to remove the solvent completely. The dimethyl succinate (1.6 g) was recovered with some catalyst remains (e.g., TiO2 and Ti(OH)4). The difimctional oligomer (diol) (24.7 g) was recovered from the toluene layer and analyzed for purity by NMR. The oligomer was a, co-dihydroxy polyethylene having C40 to C2000 carbon atoms.Example 2(Method of making a RR-PM containing a mixture of the difunctional oligomers and difunctional linkers obtained from the liquified article of Example 1)

[0117] The difimctional oligomers and the difimctional linkers of the mixture obtained from Example 1 were reacted to produce a RR-PM composition.

[0118] The difimctional 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-PM was collected. The RR-PM mimic was characterized by Solid state NMR.Example 3(Method of making a Virgin RR-PM)

[0119] To evaluate the properties of the RR-PM of our invention, the RR-PM's properties were compared to a virgin polymer that is a reaction product of a difimctional oligomer and a difimctional linker.

[0120] The diol oligomers was synthesized via Synthetic scheme B for a, co-dihydroxy polyethylene.

[0121] Cis- l,4-diacetoxy-2 -butene (2.07 g, 61 12.0 mmol) was added to THF (135 mb) in a two-neck 500 mb Schlenk flask under argon purging. The flask was then transferred to a 35 °C oil bath, and cis-cyclooctene (30 g, 272.2 63 mmol) was added dropwise over 30 min. The addition of a second-generation Grubbs catalyst (101.86 mg, 0.12 mmol) solution in THF (3 mL) was started after adding 1 mb cis cyclooctene. After 6 hours of reaction, the mixture was precipitated into acidic methanol (1.2 L with 35% HC1 (1.5 g) solution in water (13.5 g). The precipitated polymer, a,co-diacetoxy terminated polycyclooctene was collected and dried under vacuum for two days.

[0122] To convert the end acetoxy groups in repeatedly recyclable oligomer (a,co-diacetoxy terminated polycycloocene) into hydroxy groups, the repeatedly recyclable oligomer was dissolved in THF (137.5 mL) at 40 °C and 25 wt.% NaOMe (2.97 g, 55.0 mmol) solution in methanol was added. The solution was stirred for 20 hours and precipitated into methanol (2.72 L) with 35%HC1 (1.5 g) solution in water (13.5 g). The isolated repeatedly recyclable oligomer (a, co-dihydroxy poly cyclooctene) was dried under vacuum.

[0123] The oligomer (a, co-dihydroxy polycyclooctene) (HO-PCOE-OH) was hydrogenated. The HO-PCOE-OH oligomer (10 g, 90.7 mmol double bonds), p-toluenesulfonyl hydrazide (52.4 g, 281.3 mmol), tributylamine (75.6 mb, 317.6 mmol), butylated hydroxytoluene (50 mg, 0.22 mmol), and o-xylene (385.76 mb) were added to a 1000 mb three-neck round-bottom flask. The mixture was heated to 140 °C and refluxed for 6 hours. After cooling to room temperature, the reaction mixture was poured into methanol. The obtained precipitate was washed with methanol (2 x 500 mb). The isolated white powder was dried under vacuum the extent of hydrogenation was determined by 1H-NMR and found to be > 99%.

[0124] Alternative method for hydrogenation procedure is described as follows. The hydrogenate diol (24 g, Mw-3000) and cyclohexane (150 mb) were placed into a conical flask. The mixture was agitated thoroughly and then transferred into a Parr vessel (600 mb). The conical flask was rinsed with cyclohexane (150 mb) and the rinse transferred into the Panvessel. The hydrogenation catalyst (2.4 g, 3 wt.% Pd / CaCO3 catalyst) was added to the Parr vessel. The Parr vessel was sealed under a hydrogen atmosphere and heated at 75 °C until hydrogenation was determined to be complete.

[0125] Properties of the Virgin RR-PM Difunctional Diol were measured by H-NMR and are summarized below. PIG. 6 shows the 1H-NMR spectra of a, co-dihydroxy polyethylene, with IH-NMR of (TCE-d2, > 99.5 atom % D, 120 °C): 5: 3.66 (t, CH2-OH, a’); b); 1.61 - 1.24 (m, -CH2-. FIG. 7 shows the DSC data of a, co dihydroxy polyethylene showed a Tm and Tc of 118 °C and 96 °C, respectively. FIG. 8 shows the TGA of the difimctional diol in N2 atmosphere was found to be 452 °C.

[0126] Reaction of the difimctional oligomer with the difimctional linker (e.g., succinic acid) to form the RR-PM of the present invention was preformed using known polymer condensation methods. In general, the difimctional oligomer, the difimctional linker, and titanium tetra-isopropoxide (0.12 g, 1 wt. % of polymer) were introduced into the reactor and the reactor was then heated to 240 °C under stirring and in the presence of a nitrogen atmosphere. The reaction was held for 2.5 hrs at atmospheric pressure, then the nitrogen was discontinued to gradually reduce the pressure down to about 0.05 mbar and the temperature was raised to 220 °C to 260 °C. The reaction was held for 6 hrs until polycondensation was complete; the vacuum was released by bleeding in nitrogen and the polymer was collected.* * * *

[0127] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions, and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

CLAIMS1. A composition comprising:(a) a repeatedly recyclable polymer mimic (RR-PM) of a low-density polyethylene (LDPE) polymer, wherein the RR-PM is a reaction product of a difunctional oligomer and a difunctional linker that 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 low-density polyethylene (LDPE).

3. The composition of any one of claims 1 or 2, wherein the composition has a peak melting temperature (Tm) of 104 °C to 125 °C, preferably 114 °C to 120 °C, or more preferably 112.8 °C, a crystallinity temperature (Tc) of 88 °C to 100 °C, preferably 87 °C to 109 °C, or more preferably 95.8 °C, a glass transition peak temperature (Tg) of -112 °C to -108 °C, preferably -111 °C to -109 °C, or more preferably -110 °C, or a combination thereof.

4. The composition of anyone 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 wherein the difunctional oligomer has a degree of saturation of 98 % to 100%, the difunctional oligomer is a branched polyethylene having a carbon number of C40 to C2000, or a combination thereof.

5. The composition of any one of claims 1 or 2, wherein the RR-PM has a structure of:wherein n is an integer ranging from 2 to 13, Z is an aliphatic group, and X is a polyethylene comprising 40 to 2000 carbon atoms, preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms, wherein, the RR-PM has more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units, and the RR-PM has a density of 0.70 g / cm3to 0.99 g / cm3, and a molecular weight ranging from 20,000 g / mol to 6,000,000 g / mol.

6. The composition of any one of claims 1 or 2, wherein the composition comprises at least 0.001 wt.% to 3 wt.%, preferably 0.015 % to 0.15 %, of an article additive.

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

8. The composition of any one of claims 1 or 2, wherein the difunctional oligomer and the difunctional linkers of the liquefied article have a weight percentage that is at least 95 wt.% of the RR-PM.

9. A method of recycling 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, difunctional linkers, and the second polymer;(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 repeatedly recyclable polymer mimic (RR-PM).

10. The method of claim 9, wherein: the RR-PM from the article in step (a) is depolymerized prior to step (b) 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;the article in step (a) is liquefied by melting the article; or a combination therein; and forming a second article from the composition produced in step (c).

11. The method of any one of claims 9 or 10, wherein the method is repeated at least two times, preferably 2 to 500 times.

12. The method of any one of claim 9 or 10, further comprising adding athird polymer with the produced RR-PM to obtain the composition of any one of claims 1 to 8, the third polymer comprising LDPE and / or the second polymer and / or obtaining the article in step (a) from a consumer product made from a composition of any one of claims 1 to 8.

13. 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 polymer mimic (RR-PM) of a low-density polyethylene (LDPE) polymer, wherein the RR-PM is a reaction product of a difunctional oligomer and a difunctional linker that are both from a liquified article; and(b) a second polymer, preferably LDPE, wherein the weight ratio of (a) to (b) is 20:80 to 80:20.

14. A composite comprising the composition of any one of claims 1 or 2„ the composite comprising an optional filler having a surface in contact with the composition, wherein the filler is optionally dispersed in the composition, wherein the filler is a continuous fiber or discontinuous fibers, preferably the fiber is a glass fiber, an aramid fibers a polyester fiber, a polyamide fiber, a basalt fiber, or a steel fiber, or combination thereof.

15. A laminate comprising a first layer comprising the composition of any one of claims 1 or 2, or the composite of claim 14 and a second layer, preferably the second layer comprises the composition of any one of claims 1 or 2, or the composite of claim 14.

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