WO2024133403A1 - Mimétiques de polymères recyclables à plusieurs reprises (rr-pm) de polyéthylène à basse densité linéaire - Google Patents

Mimétiques de polymères recyclables à plusieurs reprises (rr-pm) de polyéthylène à basse densité linéaire Download PDF

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Publication number
WO2024133403A1
WO2024133403A1 PCT/EP2023/086860 EP2023086860W WO2024133403A1 WO 2024133403 A1 WO2024133403 A1 WO 2024133403A1 EP 2023086860 W EP2023086860 W EP 2023086860W WO 2024133403 A1 WO2024133403 A1 WO 2024133403A1
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Prior art keywords
article
composition
difunctional
fibers
oligomer
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PCT/EP2023/086860
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English (en)
Inventor
Sivadinarayana Chinta
Kaiwalya SABNIS
Ganesh Kannan
Lidia JASINSKA-WALC
Robbert Duchateau
Girish KORIPELLY
Alexander Stanislaus
Ravichander Narayanaswamy
Maria Soliman
Bart Albertus Hubertus ESSCHERT VAN DEN
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Sabic Global Technologies B.V.
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Publication of WO2024133403A1 publication Critical patent/WO2024133403A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention generally relates to repeatedly recyclable polymer mimics (RR- PM(s)) of linear low-density polyethylene (LLDPE) polymers.
  • Polyolefins have multiple industrial uses. Polyolefins such as polyethylene constitute the largest volume of synthetic plastic produced worldwide. Polyethylene such as linear low-density polyethylene (LLDPE) is used in wide variety of articles, such as films, sheets, foams, fibers, toys, bottles, containers, furniture, electronic parts, and plumbing materials.
  • LLDPE linear low-density polyethylene
  • One of the issues with the wide-spread use of LLDPE 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.
  • An alternative solution to discarding articles made with LLDPE 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
  • the mechanically recycled LLDPE can have reduced chemical and/or physical properties when compared with its native/virgin form. This damage oftentimes limits the amount of mechanically recycled LLDPE that can be used to re-produce new articles.
  • virgin LLDPE is often blended with the mechanically recycled LLDPE to create new articles.
  • the use of additional materials such as virgin LLDPE can be cost-inefficient and/or increase the carbon footprint of the resulting article.
  • An alternative solution to mechanically recycling articles made with LLDPE is to chemically recycle the LLDPE within the articles.
  • Typical chemical LLDPE recycling technologies subject the material to pyrolysis (cracking) and/or gasification reactions to chemically break down the LLDPE into various smaller hydrocarbon products (e.g., smaller alkanes, alkene, or dienes).
  • the chemical recycling process of LLDPE typically results in production of a fraction of ethylene, which can be used to make chemically recycled LLDPE.
  • 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.
  • the discovery relates to the use of a repeatedly recyclable polymer mimic (RR-PM) of a LLDPE, which, once made into an article, can repeatedly be recreated from the article, and reused to make additional articles.
  • the RR- PM can be the reaction product of a difunctional oligomer and a difunctional linker obtained by depolymerization of an article into a liquified article comprising mixtures of difunctional linkers and difunctional oligomers of the RR-PM.
  • the liquified article is obtained by, for example, melting and depolymerizing a previously manufactured and/or used article having the RR-PM.
  • Non-limiting examples of articles can include consumer goods, packaging products, dispensing bottles, wash bottles, tube, bags, electronic components, other molded articles, pharmaceutical containers, bottles, caps, closures, liners, trash bags, food packaging film and/or materials, laminations, pipes, hoses, fittings, etc.
  • the RR-PM of the present invention is repeatedly and directly recreated (e.g., 2 to 500 times or more) from an article made from the polymer at amounts that are substantially the same as present in the article being recycled. For example, at least 90 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, or 100 wt.
  • % of the RR-PM from the article being recycled is depolymerized into difunctional oligomers and difunctional linkers, repolymerized into recreated RR-PM, and reused in the newly produced article.
  • This high recycling efficiency can reduce or avoid the need to use additional materials (e.g., virgin RR-PM) to produce new articles.
  • the high recycling efficiency of the RR-PM can reduce or avoid having to use feed stock (e.g., virgin RR-PM feed stock) to produce additional article(s) from the recycled article(s).
  • feed stock e.g., virgin RR-PM feed stock
  • % of feed stock e.g., virgin RR-PM feed stock
  • the recreated RR- PM obtained from the article can have the same or substantially the same chemical and/or physical properties of the RR-PM present in the unrecycled article.
  • the RR-PM containing compositions, articles, and/or methods of the present invention provide for a recycling efficiency that can advantageously result in reduced costs of recycling articles, increased recycling efforts, and/or reduced amount of additional materials used to produce new articles. Still further, the recycling efficiency of the RR-PMs can result in a reduced carbon footprint for the produced articles.
  • a composition can include a repeatedly recyclable polymer mimic (RR-PM) of a linear low-density polyethylene (LLDPE) polymer and an article additive.
  • the RR-PM can be a reaction product of a difunctional oligomer and a difunctional linker that are both 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) and an additive.
  • 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%.
  • the difunctional oligomer of the RR-PM can have branched C40 to C2000 polyethylene.
  • the RR-PM oligomer has greater than 0 to 26 carbon branches with each carbon branch having 2 to 13 carbon atoms.
  • the difunctional oligomer can have a degree of branching of 22 to 30, preferably about 26.
  • the difunctional linker can have a carbon chain of 2 to 13 carbon atoms (C2-C13) and “F” of 2.0 ⁇ 0.3.
  • “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.
  • the carboxylic acid difunctionality is a combination of an acid and an ester.
  • the difunctional oligomer is a diol and the difunctional linker is a carboxylic acid.
  • the number average molecular weight (M n ) of the RR-PM can be 20,0000 to 1,000,000 g/mol.
  • the M n can be determined using gas permeation chromatography (GPC). More particularly, the M n can be determined as the polyethylene equivalent molecular weight by high temperature size exclusion chromatography performed at 160 °C in tri chlorobenzene using polyethylene standards.
  • a density of the RR- PM can be 0.910 g/cm 3 to 0.989 g/cm 3 .
  • the RR-PM can have a melt temperature (Tm) of 94 °C to 118 °C, 95 °C to 115 °C, or any value or range there between as measured by DSC at a heating rate of 10 °C per min.
  • the composition does not include any high- density polyethylene (HDPE), low density polyethylene (LDPE), polyolefin elastomer (POE), plastomer polyolefin (POP), and/or polypropylene (PP), or combinations thereof.
  • the composition can include at least 95 wt.%, preferably at least 98 wt. %, of the RR- PM and greater than 0 wt. to 2 wt.
  • 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.
  • the composition can include an article additive (e.g., an additive present in the article being liquified) in an amount ranging from more than 0 wt. % to less than 0.01 wt.%, based on the weight of the RR-PM.
  • 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 that includes 40 to 2000 carbon atoms, preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms and has from more than 0 to 26 carbon branches with each branch have a carbon chain length from C2 to C13.
  • the RR-PM can have more than 0 and less than 40 ester groups per 1000 backbone (CEE) carbon units.
  • a composition of the present invention can include: (a) a repeatedly recyclable- polymer mimic (RR-PM) of a linear low-density polyethylene (LLDPE) polymer that is a reaction product of a difunctional oligomer and a difunctional linker of a liquefied article comprising the difunctional oligomer and the difunctional linker; and (b) an article additive.
  • the difunctional oligomer and the difunctional linkers of the liquefied article can have a weight percentage that is at least 95 wt.% of the RR-PM.
  • the composition does not include any material selected from the group of high-density polyethylene (HDPE), low density polyethylene (LDPE), polyolefin elastomer (POE), plastomer polyolefin (POP) and polypropylene (PP), and combinations thereof.
  • the composition can include: (i) the RR-PM having a structure according to Formula I and (ii) an article additive.
  • n is an integer ranging from 2 to 13
  • Z is an aliphatic group
  • X is a polyethylene that can include 40 to 2000 carbon atoms preferably 60 to 1500 carbon atoms, or more preferably 80 to 1100 carbon atoms and can have from more than 0 to 26 carbon branches with a branching carbon chain length of C2 to Cl 3.
  • the RR-PM of Formula (I) has more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units.
  • a density of the Formula (I) RR-PM can be 0.910 g/cm 3 to 0.99 g/cm 3 .
  • a composite can include the RR-PM composition of the present invention.
  • the composite can include a plurality of fillers.
  • fillers include fibers, glass fibers, aramid fibers, polyester fibers, polyamide fibers basalt fibers, steel fibers, or combination thereof.
  • the fibers can be sized.
  • stacked polymeric compositions are described.
  • the stacked polymeric composition can include the RR-PM composition or composite of the present invention and a second layer.
  • the second layer can include the RR- PM composition or composite of the present invention.
  • the first and second layers can be coupled together via a coupling agent.
  • an article comprising a composition of the present invention are described.
  • the article can be recycled by the processes of the present invention and can be remade into another article (e.g., the article and the another article can be a cup, or the article can be a cup and the another article can be a plastic utensil).
  • 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.
  • 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.
  • depolymerization is 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.
  • 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.
  • the composition can be formed into an article.
  • the article can be used by consumers and then recycled to produce the composition of the present invention to continue the cycle.
  • the cycle can be repeated at least two times, preferably 2 to 500 times.
  • Also disclosed in the context of the present invention is a method of closed loop recycling that encompasses a combination of mechanical and chemical recycling events.
  • the method can include any one or any combination or all of the following steps: (1) obtaining an article comprising the RR-PM; (2) liquifying the article (e.g., melting the article) to obtain a liquified article composition; and/or (iii) forming a second or new article of manufacture from the liquified polymeric composition.
  • This mechanical recycling process can be performed without having to use virgin RR-PM or using minimal amounts of virgin RR-PM (e.g., 10, 5, 4, 3, 2, 1, or 0 wt. % of virgin RR-PM).
  • At least 90, 95, 96, 97, 98, 99, or 100 wt. % of the RR-PM from the article being liquified can be reused in the newly created article.
  • the article can include an article additive (e.g., greater than 0 wt.% to 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 composition of the present invention can be recycled multiple times and retain its mechanical and/or functional properties.
  • the recycled composition may include increasing article additive loadings for each round of recycling, which could affect the mechanical and/or functional properties due to increased article additive loadings.
  • the RR-PM can have similar functional properties to conventional LLDPE and/or to virgin RR-PM.
  • This provides a solution to the problems associated with recycling conventional LLDPE (e.g., articles made with conventional LLDPE can be made with the RR-PM of the present invention while having a high recycling efficiency).
  • the RR-PM 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 LLDPE.
  • composition comprising a polymer, wherein the polymer comprises moieties derived from any one of the difunctional oligomers and from any one of the difunctional linkers disclosed throughout the specification.
  • the composition can include an additive (e.g., any one of the additives disclosed throughout the specification).
  • the additive can be an article additive.
  • the composition can also include any one of the additional components, ingredients, features, and/or amounts of ingredients disclosed throughout this specification.
  • the composition can have structural and/or functional characteristics similar to virgin LLDPE.
  • composition comprising a polymer, wherein the polymer comprises moieties derived from any one of the difunctional oligomers and from any one of the difunctional linkers disclosed throughout the specification.
  • the composition can have an additive (e.g., any one of the additives disclosed throughout the specification).
  • the composition can also include any one of the additional components, ingredients, features, and/or amounts of ingredients disclosed throughout this specification.
  • Article Additive means an additive from an article being recycled.
  • 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.
  • “Repeatedly -Recyclable Polymer Mimic” or “RR-PM” ” means a polymer that is a mimic of linear low-density polyethylene (LLDPE).
  • the RR-PM is a reaction product of difunctional oligomer(s) and difunctional linker(s).
  • the difunctional linker(s) and the difunctional oligomer(s) are obtained from a liquefied article that includes the difunctional oligomer(s) and the difunctional linker(s).
  • the 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 difunctional linker(s).
  • the difunctional oligomer(s) and difunctional 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.
  • linker means an aliphatic group (e.g., “Z”) that can couple and decouple to a linear low density polyethylene oligomer (e.g., “X”).
  • “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.
  • “Use Cycle” indicates how many times an RR-PM 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).
  • the RR-PM is a “Virgin RR-PM”, and, therefore, the virgin RR-PM 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 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.
  • 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.
  • FIG. 2 provides a non-limiting example of a visually depiction of a Use Cycle of a RR-PM of the present invention.
  • branching refers the regular or random attachment of side chains to a polymer’s backbone chain.
  • degree of branching (DB)” of a group/oligomer/polymer refers to % of branched carbons in the backbone of the group/oligomer/polymer.
  • the following group having the formula of Formula (II) has a degree of branching of 20 to 30 %.
  • the branched carbons in the backbone of the group of Formula II is marked with a *.
  • R' in Formula II is a branching group, can be an alkyl group, and y is an integer and denotes number of repeat units.
  • 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.
  • 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.
  • the linear carbon chain can contain additional substitution.
  • 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.
  • wt.% 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.
  • 10 grams of component in 100 grams of the material is 10 wt.% of component.
  • 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.
  • compositions of the present invention can “comprise,” “consist(s) essentially of,” or “consist of’ particular groups, compositions, etc. disclosed throughout the specification.
  • a basic and novel characteristic of the present invention can include a RR-PM obtained from a liquified article that can be depolymerized into difunctional oligomers and difunctional linkers, repolymerized into RR-PM, and/or used to produce a new article.
  • the newly produced article can be substantially produced from the repolymerized RR-PM (e.g., at least 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 wt. % of the newly produced article can be from the RR-PM obtained from the liquified article).
  • the difunctional oligomer and the difunctional linkers of the liquefied article can have a weight percentage that is at least 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100 wt.% of the RR-PM.
  • FIG. 1 is an illustration of the system and method to make the composition of the present invention that includes a RR-PM.
  • FIG. 2 is an illustration of a closed loop Use Cycle of a RR-PM of the present invention.
  • FIG. 3 is an illustration of a stacked polymeric composition of the present invention that includes four fiber-reinforced composites of the present invention.
  • 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.
  • FIG. 5 is an illustration of the closed-loop recycling process of the present invention that include the RR-PM.
  • FIG. 6 shows the 'H-NMR of virgin RR-PM difunctional diol and RR-PM difunctional acid.
  • FIG. 7 is a graphical representation of the differential scanning calorimetry (DSC) data of virgin RR-PM of the present invention and conventional LLDPE.
  • FIG. 8 shows infrared spectra of virgin RR-PM of the present invention and conventional LLDPE.
  • FIG. 9 shows X-ray diffraction (XRD) patterns of virgin RR-PM and conventional LLDPE.
  • FIG. 10 shows a graphical illustrations of the viscosity characteristics of virgin RR- PM and conventional LLDPE.
  • FIGS. 11A and 11B show graphical illustrations of the dynamic mechanical thermal analysis (DMTA).
  • DMTA dynamic mechanical thermal analysis
  • the RR-PM of the present invention can be repeatedly and directly recreated (e.g., 2 to 500 times or more) from an article made from the RR-PM at an amount that is substantially the same as in the article. For example, at least 90 wt. %, 95 wt. %, 96 wt. %, 97 wt. %, 98 wt. %, 99 wt. %, or 100 wt.
  • % of the RR-PM from the article being recycled can be depolymerized, repolymerized into RR-PM, and re-used in the newly produced article.
  • This recycling efficiency of the RR-PM containing compositions and articles made therefrom can advantageously result in reduced costs of recycling articles, increased recycling efforts, and/or reduced amount of additional materials used to produce new articles. Additionally, the recycling efficiency can result in a reduced carbon footprint for the produced articles.
  • the RR-PM can have similar functional properties to conventional LLDPE and/or to virgin RR- PM.
  • the RR-PM can be used in such a manner that additional feed stock (e.g., virgin RR- PM) is not used or used in limited amounts (e.g., 5, 4, 3, 2, 1, or less wt. %) after multiple use cycles (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or more use cycles).
  • the composition can include a RR-PM of the present invention and an optional additive.
  • 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.
  • the composition does not include any high-density polyethylene (HDPE), low density polyethylene (LDPE), polyolefin elastomer (POE), plastomer polyolefin (POP), and/or polypropylene (PP), and/or combinations thereof.
  • HDPE high-density polyethylene
  • LDPE low density polyethylene
  • POE polyolefin elastomer
  • POP plastomer polyolefin
  • PP polypropylene
  • the RR-PM can include repeating units of a difunctional linker (Z) and a difunctional oligomer (X) obtained from a liquified article.
  • the number average molecular weight (M>) of the RR-PM can be 20,000 g/mol to 1,000,000 g/mol, 40,000 to 1,000,000 g/mol or 20,000 g/mol, 40,000 g/mol, 30,000 g/mol, 40,000 g/mol, 50,000 g/mol, 100,000 g/mol, 200,000 g/mol, 300,000 g/mol, 400,000 g/mol, 500,000 g/mol, 600,000 g/mol, 700,000 g/mol, 800,000 g/mol, 900,000 g/mol, 1,000,000 g/mol, or any range or value there between.
  • the Mn can be determined as the polyethylene equivalent molecular weight by high temperature size exclusion chromatography performed at 160 °C in tri chlorobenzene using polyethylene standards.
  • the RR-PM can have a melt temperature (T m ) of 94 °C to 118 °C, 95 °C to 115 °C, or 94 °C, 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, 105 °C, 106 °C, 107 °C, 108 °C, 109 °C, 110 °C, 111 °C, 112 °C, 113 °C, 114 °C, 115 °C, 116 °C, 117 °C, 118 °C, or any value or range there between as measured by DSC at a heating rate of 10 °C per
  • a density of the RR-PM can be 0.91 g/cm 3 to 0.989 g/cm 3 or 0.91 g/cm 3 , 0.91 g/cm 3 , 0.93 g/cm 3 , 0.94 g/cm 3 , 0.95 g/cm 3 , 0.96 g/cm 3 , 0.97 g/cm 3 , 0.98 g/cm 3 0.989 g/cm 3 or any range or value there between.
  • the polymer can have a poly dispersity index (PDI), of 1 to 5, or equal to any one of, at least any one of, or between any two of 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, and 5.
  • PDI poly dispersity index
  • 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.
  • Z can be a Cl to C13 aliphatic group.
  • 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.
  • 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 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. X can have from more than 0 to 26 carbon branches (e.g., 0, 1, 2, 3, 4,
  • Each carbon branch can have a carbon chain length of C3 to C13 (e.g., 3, 4, 5,
  • the RR-PM can have more than 0 and less than 40 ester groups per 1000 backbone (CH2) carbon units.
  • the RR-PM can have a branching index of 22 to 30, or 22, 23, 24, 25, 26, 27, 28, 29, 30, or any value or range there between.
  • the functional groups can contain hydrocarbon groups linking the functional group to the backbone of Z.
  • Z can vary randomly between the repeating units of Formula I.
  • the number of carbon atoms in the Z groups can vary randomly between the repeating units of Formula I.
  • Z does not vary between the repeating units of Formula I.
  • n can be 2 and Z can have the formula of Formula (1), and the polymer can contain repeating units of Formula Ic:
  • X can be an aliphatic group. X can contain at least 40 carbon atoms. In certain aspects, X can vary randomly between the repeating units of Formula I, 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.
  • 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.
  • X can include 60 to 1500 carbon atoms.
  • X can include 80 to 1100 carbon atoms.
  • X can be a branched hydrocarbon having a 0 to 26 branches with each branch having 3 to 13 carbon atoms.
  • the branched hydrocarbon can contain saturated Cl to C13 branches (e.g., on the hydrocarbon backbone).
  • the branched hydrocarbon can contain Cl to Cl 3 alkyl group branches.
  • X can be a polyolefin having the formula of Formula (III): can be an integer from 40 to 2,000 and denotes number of repeat units.
  • R can be -H or a Ci to Cio alkyl group, and varies independently (e.g., between -H and the Ci to C 10 alkyl group) in the repeating units -CHR-.
  • m can be equal to any one of, at least any one of, or between any two of 40 45, 50, 55, 60, 65, 70, 80, 90, 100, 150, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, and 2,000.
  • the -(CHR) m - group can have regular branching.
  • m can vary randomly between the repeating units of Formula II
  • X can optionally contain one or more side functional groups.
  • 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 %.
  • 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 linker can having the formula -R 2 ”, where R 1 and R 2 are each OH, CO2H, NH2, or a combination thereof, and n is 2 to 13 carbon atoms.
  • 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, R 1 and R 2 can be an amine (-NH2), an alcohol (-OH), a carboxylic acid (-COOH), or a combination thereof.
  • 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.
  • the difunctional linker can be oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, aconitic acid, isocitric acid, propane-1, 2, 3 -tricarboxylic acid, pentane- 1, 3, 5-tricarboxy lie acid, or any combinations thereof.
  • the difunctional oligomer can have a formula of ' 'n , (“R 3 -X-R 4 ”) where R 3 and R 4 are each OH, CO2H, NH2, or a combination thereof and n can be 40 to 2000.
  • 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,
  • 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.
  • X can be regular branched. Regular branching in the polyethylene backbone can provide the linear structure to the RR-PM.
  • the two functional groups, R 3 or R 4 can be an amine (-NH2), an alcohol (-OH), a carboxylic acid (-COOH), or a combination thereof.
  • the functionality “F” of the difunctional oligomer can be a statistical value of 2.0 ⁇ 0.3, or 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3 or any value or range there between. Functionality can be measured using known chemical analysis, for example, titration methods.
  • 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.
  • the compositions of the present invention can include at least one article additive.
  • the at least one article additive can be added when a RR-PM is made into an article.
  • Such additives can include catalysts and additive that are useful for making articles.
  • Nonlimiting examples of article additives can include, but are not limited to, an antioxidant, a metal deactivator, a processing aid, a UV stabilizer, a pigment, a phosphite, a phosphinate, a colorant, or mixtures thereof.
  • combinations of the article additives can be combined as an article package to be added to the composition.
  • the choice of additive packages may be driven by the specific type of article being made and its intended use. For use in pipes intended for use with chlorinated water, for instance, additive packages comprising certain types of antioxidants can lead to synergistic results. Other articles can preferably be made with specific types of additive packages.
  • Non-limiting examples of article antioxidant additives can include 3,3'3",5,5',5'- hexatert-butyl-alpha,alpha',alpha,"-(mesitylene-2,4,6-triyl )tri-p-cresol (CAS 1709-70-2) commercially known as Irganox 1330 (Ciba Specialty Chemicals) or Ethanox 330 (Albemarle Corporation); pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (CAS 6683-19-8) available as Irganox 1010 (Ciba Specialty Chemicals); octadecyl-3-(3.
  • 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 IrganoxTM MD 1024 and 2,2'-oxalyldiamidobis ethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (available as NaugardTM XL1), and mixtures thereof.
  • 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.
  • the RR-PM may not be substantially similar to the functional properties of virgin RR-PM or virgin LLDPE.
  • the amount of additives used to make an article can vary by application and can be from greater than 0 wt.% to 5 wt. %, or 0.00001 wt. %, 0.0001 wt. %, 0.001 wt. %, 0.01 wt. 0.05 wt. %, 0.06 wt. %, 0.07 wt. %, 0.08 wt. %, 0.09 wt. %, 0.1 wt. %, 0.2 wt. %, 0.3 wt.
  • 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.
  • the composition can include one or more optional additives.
  • optional additives can include a scratch-resistance agent, an antioxidant, a flame retardant, an UV absorber, a photochemical stabilizer, a filler such as glass and/or mineral filler, an optical brightener, a surfactant, a processing aid, a mold release agent, a pigment, flow modifiers, foaming agents or any combinations thereof.
  • 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 and optional additive.
  • An amount of 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.
  • 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.
  • the amount of the 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.
  • the composition include at least 0.01 % to 0.2 %, preferably 0.05 % to 0.15 %, of an article additive and 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, 99 wt.%, 100 wt.% of the RR-PM.
  • FIG. 1 illustrates a closed loop system and method of recycling the RR- LLDPE 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.
  • the article 108 is a plastic article.
  • Non-limiting examples of consumer goods can include a packaging product, a pharmaceutical container, a bottle, a cap, a closure, a liner, a trash bag, a food packaging film, a lamination, a pipe, a hose, a fitting, or a combination thereof.
  • the composition can contain a blend of the RR-PMs of varying molecular weight.
  • Plastic article 108 can be optionally cleaned of contaminants (e.g, inert materials) and shredded into smaller pieces prior to being fed to liquifi cation 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 optional additive.
  • 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.
  • the depolymerization can be performed at an inert atmosphere.
  • the depolymerization conditions can be 195 °C to 205 °C at 3.8 to 4.0 MPa.
  • 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-R 2 , where R 1 and R 2 are each OH, CO2H, NH2, or a combination thereof, and the difunctional linker R 3 -Z-R 4 , where R 3 and R 4 are each OH, CO2H, NH2, or a combination thereof.
  • the depolymerization method can include methanolysis of the composition under conditions suitable to obtain the difunctional oligomer (e.g, R'-X-R 2 .
  • Non-limiting examples of a catalyst used for methanolysis depolymerization can include a mineral acid, organic acid, organic base, and/or metallic compound.
  • Non-limiting examples of metallic compounds can include a metal complexed or bonded to a hydrocarbyl, an oxide, a chloride, a carboxylate, an alkoxide, an aryloxide, an amide, a salen ligan, a [3- ketiminato ligand, or a guanidinato ligan.
  • the metal can be Li, Na, K, Mg, Ca, Sc, Y, lanthanides, Ti, Zr, Zn, Mo, Mn, Al, Ga, Bi, Sb, or Sn.
  • the catalyst can be Ti(0iPr)4, Ti(0Bu)4, Al(OiPr)s, Sn(2-ethyl-hexanoate)2, MoOs, or any combinations thereof.
  • 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.
  • the difunctional oligomer(s) can be a solid and the difunctional linker(s) can be a liquid or vice versa.
  • the solid can be separated from the depolymerization composition using filtration, centrifugation, precipitation, or other known separation techniques.
  • the liquid component can be separated from the depolymerization composition using distillation methods.
  • both the difunctional oligomer and difunctional linker are both liquids or both solids and solid/solid or liquid/liquid separation/purification methods can be used to isolate the solids or liquids. Separation units can help to remove impurities and/or other unwanted items prior to repolymerization.
  • oligomers, and linkers from other LLDPE processes that are desired can be separated from the desired oligomers and linkers. For example, oligomers that are derived from PP, LDPE, HDPE, PoP, or PoE, or a combination thereof can be separated from the RR-PM difunctional oligomers.
  • Difunctional oligomer stream 112 and/or difunctional linker stream 114 can exit depolymerization unit 104 and enter polymerization unit 106. In some instances, difunctional oligomer stream 112 and difunctional linker stream 114 exit depolymerization unit 104 as a single stream. In some aspects, the article additive is included in oligomer stream 112 and/or linker stream 114. In some instances, depolymerization unit 104 and polymerization unit 106 are the same unit. In another instance, liquification unit 102, depolymerization unit 104, and polymerization unit 106 can be the same unit.
  • 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 114 can be repolymerized to form a recycled RR-PM.
  • 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.
  • the reaction can include esterification at 90 °C to 250 °C, and/or under inert atmosphere, followed by polycondensation at 90 °C to 250 °C, and/or under vacuum, e.g., at pressure below 0.0005 MPa, below 0.0001 MPa, below 0.00005 MPa.
  • the difunctional oligomers e.g., diol
  • the difunctional linker e.g, acid, ester, or anhydride
  • the polymerization 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.
  • the metal can be Li, Na, K, Mg, Ca, Sc, Y, lanthanides, Ti, Zr, Zn, Mo, Mn, Al, Ga, Bi, Sb, or Sn.
  • the catalyst can be Ti(OiPr)4, Ti(OBu)4, Al(OiPr)s, Sn(2-ethyl-hexanoate)2, MoOs, or any combinations thereof. In certain aspects, a combination of catalysts can be used.
  • 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)).
  • a difunctional linker e.g, HO2C-Z-CO2H, an ester, and/or cyclic anhydride thereof (e.g., of the acid of HO2C-Z-CO2H).
  • the difunctional oligomer can be repolymerized with i) a first diacid having the formula of HO2C- Z-CO2H (and/or an ester, and/or cyclic anhydride thereof) and/or ii) a second diacid having the formula of HO2C-Z’-CO2H (and/or an ester, and/or cyclic anhydride thereof), wherein Z is different than the Z', but both diacids are obtained from the depolymerization process.
  • 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.
  • 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.
  • the compound HO-X-OH can be polymerized with more than two acids selected from oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, aconitic acid, isocitric acid, propane- 1,2, 3 -tricarboxy lie acid, and pentane-l,3,5-tricarboxylic acid, and/or esters, and/or anhydride thereof obtained from a RR-PM recreated from an article comprising difunctional oligomers and difunctional linkers.
  • acids selected from oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, aconitic acid, isocitric acid, propane- 1,2, 3 -tricarboxy lie acid, and pent
  • RR-PM 116 can exit polymerization unit 106 and be sold, transported, or formed into a consumer product.
  • the article additive is included in RR-PM 116.
  • RR-PM 116 is formed into a pellet to be sold, transported, or converted into a consumer product.
  • Converting unit 118 can be onsite or offsite. Converting unit 118 can be a commercial manufacture of consumer goods and/or articles of manufacture.
  • RR-PM 116 can be formed into RR-PM article 120 that includes the RR-PMs of the present invention.
  • RR-PM 116 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.
  • RR-PM article 120 can be comprised in or in the form of a foam, a film, a layer, a sheet, a molded article, a welded article, a filament, a fiber, a wire, a cable, or a powder.
  • the composition is incorporated into a film.
  • the film may include at least one film layer that includes the composition.
  • an article additive can be combined with the RR-PM 116 prior to being sent to the converting unit 118.
  • the additive can be an article additive package that is typically used with the article to be produced.
  • 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.
  • 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.
  • RR-PM article 120 can contain a blend of the RR-PMs of varying molecular weight.
  • RR-PM article 120 can further include one or more additives.
  • the additives can be added in polymerization unit 106 and/or converting unit 118.
  • Non-limiting examples of additives can include, a scratch-resistance agent, an antioxidant, a flame retardant, an UV absorber, a photochemical stabilizer, a filler such as glass and/or mineral filler, an optical brightener, a surfactant, a processing aid, a mold release agent, a pigment, flow modifiers, foaming agents or any combinations thereof.
  • 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 122. After use, used RR-PM article 124 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.
  • compositions of the present invention that include the RR-PM 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).
  • 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.
  • 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
  • the RR-PM compositions can also be formed into films or sheets as well as components of laminate systems.
  • the sheet can be a foam sheet, paper sheet, or fabric sheet.
  • Articles include, for example, fibers, sheets, films, multilayer sheets, multilayer films, molded parts, extruded profiles, coated parts and foams, windows, luggage racks, wall panels, chair parts, lighting panels, diffusers, shades, partitions, lenses, skylights, lighting devices, reflectors, ductwork, cable trays, conduits, pipes, cable ties, wire coatings, electrical connectors, air handling devices, ventilators, louvers, insulation, bins, storage containers, doors, hinges, handles, sinks, mirror housing, mirrors, toilet seats, hangers, coat hooks, shelving, ladders, hand rails, steps, carts, trays, cookware, food service equipment, communications equipment and instrument panels.
  • 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.
  • FIG. 2 is an illustration of Use Cycle 200.
  • RR-PM n is shown, where n is an integer (e.g., 0 to 10000, or more).
  • an Articlen can be made from Block 202 RR-PM n . When n is 1, this can represent Use Cycle 1.
  • the Articlen from Block 204 made from RR- PMn can be liquefied by heating and depolymerization as described above to produce difunctional oligomer(s) and difunctional(s) linkers of Articlen.
  • the liquified Articlen of Block 206 e.g., the difunctional oligomer(s) and difunctional linker(s) of the present invention
  • the Article n +i can be produced from the RR-PMn+i of Block 208.
  • n is 2
  • the RR-PM has a Use Cycle rating of at least 2.
  • Block 212 the process can be continued, where Article n +i of Block 210 can be liquefied by heating and depolymerization as described above to produce difunctional oligomer(s) and difunctional(s) linkers.
  • the liquified Article n +i of Block 212 e.g., the difunctional oligomer(s) and difunctional linker(s) of the present invention
  • the RR-PM has a Use Cycle rating ranging from 2 to 1000.
  • the RR-PM has a Use Cycle rating ranging from 2 to 500.
  • the RR-PM has a Use Cycle rating ranging from 2 to 400. In another embodiment, the RR-PM has a Use Cycle rating ranging from 2 to 300. In another embodiment, the RR-PM has a Use Cycle rating ranging from 2 to 300. In another embodiment, the RR-PM has a Use Cycle rating ranging from 2 to 200. In another embodiment, the RR-PM has a Use Cycle rating ranging from 2 to 100. In some aspects, the Use Cycle rating can be greater than 1000 (e.g., 1500, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, or more).
  • the US Cycle rating can be 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, or more, or any range or number therein.
  • the Use Cycle ratings can be achieved without having to use additional feed stock (e.g., virgin RR-PM feed stock) or by using a limited amount of additional feed stock (5, 4, 3, 2, 1, 0.5, or 0 wt. % of virgin RR-PM feed stock).
  • additional feed stock e.g., virgin RR-PM feed stock
  • a limited amount of additional feed stock 5, 4, 3, 2, 1, 0.5, or 0 wt. % of virgin RR-PM feed stock.
  • 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.
  • 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.
  • the RR-PM compositions of the present invention can be included in composites.
  • Composites or compositions of the present invention 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.
  • RR-PM composites or compositions of the present invention can be formed into any structure.
  • structures include sandwich-type structures, multi-layered (stacked) composites and the like.
  • the composites or compositions of the present invention can be dimensioned and shaped according to respective applications.
  • Non-limiting examples of shapes include rectangular, triangular, square, polygonal (whether having sharp and/or rounded comers), circular, elliptical, or otherwise rounded, or can have an irregular shape or otherwise.
  • the overall thickness of the composites or compositions can be up to and even exceeding several millimeters.
  • Some embodiments of the present composites or compositions can include one or more openings, notches, and/or the like, which can facilitate incorporation of the composite into a structure.
  • Composites or compositions of the present invention can have any thickness.
  • the composite, composition, and/or stacked polymeric composition of the present invention can be decorated.
  • a surface of the composites or stacked polymeric compositions can be subjected to printing with ink.
  • an exposed surface of the composite, composition, 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.
  • each composite can be decorated.
  • 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.
  • 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).
  • an anti-microbial surface can be created by co-extrusion of film materials with silver or other germicides.
  • the cap layer can be made by screen-printing an aesthetic or functional ink layer. In most instances, these cap layers will be thermoformable.
  • the composites can be made using known panel consolidation techniques.
  • 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).
  • the composites and/or stacked polymeric compositions of the present invention can include at least 2 or 3, 4, 5, 6, 7, 8, 9, 10 or more RR-PM composites or compositions of the present invention having a thickness of about 0.1 to 10 mm, or 0.25 to 5 mm.
  • the core density can be reduced to a desired density by patterning the core thermoplastic layer.
  • a stack of RR-PM composites or compositions can be formed by heating and pressing more than one RR-PM composites or compositions together.
  • the composite stack can enter a first zone of a double belt press at a pressure of 5 to 15 N/cm 2 , 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.
  • the surface of one RR-PM composite or composition can be treated with a coupling agent prior to assembling the stack.
  • the coupling agent can be a RR-PoE or a RR-PoP composition.
  • 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/poly etherimides or a copolymer thereof, a polyethersulfone (PES), a polyurethane (PU), or a polyphenyl ether (PPO)Zstyrene blend, a PPO/polyamide blend, a PPE/polystyrene blend, a PPO/polypropylene blend a PPO-Si/polyamide blend, a PPO-Si/polystyrene blend, a PPO-Si/polypropylene blend, or any combination thereof.
  • PPO polyphenyl ether
  • Thermoplastic cores can be produced or are available from various commercial sources.
  • 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 DuPontTM (U.S.A.), Hexcel Corporation (U.S.A.), and the like.
  • 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.% of RR-PM, based on the total weight of the fiber-reinforced composite.
  • 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.
  • 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.
  • fillers (e.g, fibers) in the composite can be sized.
  • the sizing can include RR-PoP, RR-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.
  • 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.
  • the composites can be made by using known impregnation techniques.
  • 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 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).
  • the RR-PM 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.
  • 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.
  • a fiber-reinforced composite e.g, a ply or composition of the present invention can be used to make a stacked polymeric composition (e.g, a laminate).
  • 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.
  • 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.
  • each of the fiber-reinforced composites can be rectangular.
  • one or more fiber-reinforced composites or compositions of a stacked polymeric composition e.g, a laminate
  • a mixture of fiber-reinforced composites and unreinforced composites or compositions are used to make stacked polymeric compositions.
  • the stacked polymeric composition is made of only RR- PM composites or compositions of the present invention having fibers or sized fibers dispersed therein.
  • composite 300 can be a stacked polymeric composition (e.g, a laminate) and include at least two fiber-reinforced composites.
  • a stacked polymeric composition e.g, a laminate
  • 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 polymeric matrix having a plurality of fibers 310 dispersed therein.
  • Some embodiments of the present methods include producing a laminate (e.g., 300) at least by stacking two or more fiber-reinforced composites (e.g., including one or more of fiber-reinforced composites or composites in a 0/90 orientation).
  • RR-PM composites e.g., fiber-reinforced composites and/or non-fiber containing composites
  • 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.
  • 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.
  • Composites that include fibers (e.g, fibers 310) can have a pre-consolidation fiber volume fraction (Vf) that is greater than or substantially equal to any one of, or between any two of: 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90%.
  • Vf fiber volume fraction
  • one or more fiber-reinforced composites may not include fibers; such fiber-reinforced composite can, for example, include a sheet of thermoplastic polymer material such as, for example, a sheet of the RR-PM compositions of the present invention.
  • 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.
  • 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.
  • One or all of the fiber-reinforced composites can include fibers (e.g, fibers 310) dispersed within a matrix material or pressed into the polymer matrix material.
  • the laminates can be prepare using a double belt press with integrated contact heating and cooling supplied by, for example Meyer® (Schnfabrik, 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/cm 2 , 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.
  • a static heated press can be used.
  • each of the fiber-reinforced composites 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.
  • 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.
  • 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.
  • 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).
  • a fiber-reinforced composite can include a first set of fibers aligned in a first direction and a second set of fibers aligned in a second direction that is angularly disposed relative to the first direction, where the first set of fibers is woven with the second set of fibers.
  • a smallest angle between first direction and second direction can be greater than or substantially equal to any one of, or between any two of: 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 degrees.
  • the smallest angle between first direction and a length of a stack including such a fiber-reinforced composite can be greater than or substantially equal to any one of, or between any two of: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 degrees.
  • Some embodiments of the present stacks can include one or more polymeric composite, each formed from sections of fiber-reinforced composites material.
  • a unidirectional fiber-reinforced composite can be formed from sections of unidirectional fiber material that has been placed adjacent to one another.
  • sections of fiber-reinforced composites material can be placed adjacent to one another manually and/or by an automated material laying machine.
  • Some embodiments of the present stacked polymeric compositions 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.
  • 0-degree unidirectional fiber-reinforced composites e.g., plies
  • 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.
  • composites of the present invention 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.
  • each of the sub-stacks can include three fiber-reinforced composites.
  • 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 .
  • 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).
  • any suitable configuration e.g., balanced, symmetric, asymmetric, and/or the like.
  • Stacked polymeric compositions of the present invention can include coupling agents (e.g, tie layers) to adhere the composites together.
  • FIG. 4 illustrates stacked polymeric composition 400.
  • Stacked polymeric composition 400 can include fiber-reinforced composite layers 402 and 404 with tie layer 406.
  • Composite layers 402 and 404 can include fibers 408 dispersed in a RR-PM polymer matrix.
  • Non-limiting examples of coupling agents can include 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.
  • the stacked polymeric compositions and/or composites can be recycled as described throughout this specification.
  • the fibers can be removed after liquification of the RR-PM composite/stacked composition.
  • fibers and/or other fillers can be removed in liquefication unit 102 and/or in depolymerization unit 104.
  • HT-SEC Procedure The molecular weight and dispersity were determined by means of high temperature size exclusion chromatography (HT-SEC) performed at 150 °C in a HT- SEC -IR instrument equipped with a IR4 detector (PolymerChar, Valencia, Spain). Three Polymer Laboratories 13 pm PLgel Olexis columns constitute the set. 1 ,2-di chlorobenzene (o- DCB) was purchased from VWR and used as an eluent at flow rate of 1 mL*min-l. Molecular weights and corresponding dispersities were calculated from HT-SEC analysis with respect to narrow polystyrene standards (PSS, Mainz, Germany).
  • the purpose of these examples was to make a repeatedly recyclable-linear low- density polyethylene (RR-PM) polymer (a reaction product of a difunctional oligomer and a difunctional linker) from a liquefied article containing the difunctional oligomers and the difunctional linkers.
  • the purpose was also to (i) compare properties of the RR-PM with the properties of a virgin RR-PM that is made directly from a difunctional oligomer and a difunctional linker and (ii) whether an article made from a conventional process could be also used to make a repeatedly recyclable polymer.
  • FIGs. 2 and 5 show an overview of the closed loop process that makes possible, where RR-PM can made from articles that are liquefied multiple times.
  • Table 1 lists the materials used to make repeatedly recyclable oligomers and RR-PM from the oligomers.
  • 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 at this temperature for 3 hrs during which the depolymerization was completely occurred. After 3 hrs of depolymerization, the heating was stopped, and reactor was allowed to cool down to room temperature.
  • the reactor was disassembled, and the two-layer reaction mixture was processed.
  • the top layer was a methanol layer
  • 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., TiCh 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, TiCh and Ti(OH)4).
  • the difunctional oligomer (diol) (24.7 g) was recovered from the toluene layer and analyzed for purity by NMR.
  • the C20 to C2000 oligomer had carbon branching of more than 0 to 26 with a branching carbon chain length of 2 to 13 carbon atoms.
  • the diol oligomers was synthesized via Synthetic scheme B for a,co-dihydroxy polyethylene.
  • 1,3-butadiene solution (13.33 g, 36.97 mmol of 15 wt.% solution in n-hexane) was added to a Schlenk tube under argon atmosphere. Then /-BDMSOPrLi solution (1 mL, 0.5 mmol of 0.5 mol/L see above for analysis method) was added to the reaction mixture under stirring. After complete addition, the reaction mixture was heated to 50 °C and stirred at this temperature for 5 hours. After 5 hours, the reaction mixture was cooled to room temperature and ethylene oxide (15.6 mL, 12.5 mmol of 0.8mol/L in hexane) was added and allowed the reaction mixture to stir for another 2 h at room temperature.
  • reaction mixture was terminated by the addition of degassed (degassing done by freeze-pump-thaw method, see Appendix 2) methanol (1.5 mL) to form hydroxy end group in polybutadiene.
  • degassed degassing done by freeze-pump-thaw method, see Appendix 2
  • methanol 1.5 mL
  • the solution was concentrated and precipitated into an excess of methanol to obtain polybutadiene with one hydroxy end group as a white viscous liquid.
  • Step 2 Synthesis of dihydroxy terminated polybutadiene.
  • Reaction of the difunctional oligomer with the difunctional linker to form the RR- PM of the present invention was preformed using known polymer condensation methods.
  • the difunctional oligomer, the difunctional linker, and titanium tetra-isopropoxide (0.12 g, 1 wt. % of polymer) were introduced into the reactor and the reactor was then heated to 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.
  • FIG. 6 shows the 'H-NMR of virgin RR-PM difunctional diol and RR-PM difunctional acid. From the difunctional diol ’H-NMR it was determined that complete conversion of esterification and condensation of the oligomer and linker occurred to form a repeatedly recyclable LLDPE. From the succinic acid spectrum, the shift in the -CH2- peaks and ketone group of the ester functionality showed complete conversion. Compared to the conventional LLDPE, the virgin RR-PM showed a new peak at 3.7 ppm which was not present in conventional LLDPE and in the succinic acid NMR spectra, the protons of the -CH2- group linked to the oxygen in the ester group contributing from the linker are represented.
  • FIG. 7 shows the DSC data of conventional LLDPE 118NJ and virgin RR-PM showed a I'm and T c of 94.6 °C and 77.6 °C, respectively.
  • the virgin RR-PM showed a T m lower than conventional.
  • the lower T m was due to the ester groups in the virgin RR-PM.
  • Table 2 lists the data.
  • FIG. 8 shows infrared spectra of the RR-PM of the present invention and conventional LLDPE 118NJ.
  • the infrared spectroscopic characterization showed the finger printing regions of -CH2- for both conventional samples.
  • Two additional peaks at 1736 and 1157 cm' 1 which represents the carbonyl functional groups contributing from the linker ( succinic acid) for the RR-PM of the present invention.
  • FIG. 9 shows XRD patterns of virgin RR-PM and conventional LLDPE.
  • the XRD Peaks at 29 « 21.7° and 29 ⁇ 23.8° due to (110) and (200) reflections, are characteristics peaks of conventional LLDPE and virgin RR-PM.
  • Weak/broad shoulder band at « 19° represents semi-amorphous phase.
  • the amorphous phase in the RR-PM is higher hence the percentage crystallinity is lower than expected.
  • the percent crystallinity of the virgin RR-PM was 48% while conventional LLDPE crystallinity was 56%.
  • FIG. 10 shows a graphical illustration of the viscosity characteristics of virgin RR- PM and conventional LLDPE.
  • a change in complex viscosity with increase in shear rate (1/s) at lower shear rate the viscosity for virgin RR-PM was higher compared to conventional LLDPE and this observation is due to the narrow PDI of the virgin RR-PM.
  • Viscosity measurements were done at 190 °C which represents processing temperatures for recycling.
  • FIGS. 11A and 11B show dynamic thermal analysis (DMTA) of the virgin RR-PM and conventional LLDPE, which shows how the indicated properties of the two different types of polymers compare. Table 3 lists the GPC molecular weight data.
  • Example 3 An article made from virgin RR-PM made in Example 3 was extruded by adding an article additive( about 1000 ppm of Irganox 1010 and about 1000 ppm of IrgafosTM 168) at about 240 °C for a duration of 0.5 mins to 2 mins. The article was then liquefied by placing the article into a reactor along with methanol and heating the article and methanol to about 220 °C at an autogenous pressure of 39 bar until a mixture containing difunctional oligomers and difunctional linkers formed. The difunctional oligomers and the difunctional linkers were separated from the methanol mixture and reacted to produce a RR-PM composition as described above in Example 2.
  • Example 4 illustrates a RR-PM composition exhibiting a Use Cycle 1 rating.
  • Example 4 The virgin RR-PM composition obtained in Example 4 from the liquefied article was extruded into another article, in accordance with the procedure in Example 4. The article was then liquefied into a mixture containing difunctional oligomers and difunctional linkers and the difunctional oligomers and the difunctional linkers reacted to produce another RR-PM composition in accordance with the procedures described above. The new RR-PM composition was then tested for properties and compared to the properties of the virgin RR-PM.
  • Example 5 illustrates a RR-PM composition exhibiting a Use Cycle 2 rating.
  • Example 6
  • Example 5 The RR-PM obtained in Example 5 from the liquefied article was extruded into a different article, in accordance with the procedure described in Example 4. The article was then liquefied into a mixture containing difunctional oligomers and difunctional linkers. The difunctional oligomers and the difunctional linkers were reacted to produce yet another RR- PM composition in accordance with the procedures described above.
  • Example 6 illustrates a RR-PM composition exhibiting a Use Cycle 3 rating.
  • Example 7 illustrates a RR- PM composition exhibiting a Use Cycle 4 rating.
  • the results show that that the mass of the article was substantially similar to the mass of the RR-PM.
  • substantially all of the material of the article was used to make the RR-PM, thereby eliminating the need to use additional materials.
  • the difunctional oligomers and the difunctional linkers of the liquefied article had a wt. % that is at least 95% wt.% of the RR-PM Use Cycles 1-4.
  • Example 2 The purpose of this Example was to evaluate whether a conventionally made LLDPE could be repeatedly recyclable.
  • a conventional LLDPE (SABIC® 118NJ) extruded into an article using the procedure of Example 4.
  • the LLDPE article was processed and prepared for “liquification”.
  • the article was chopped into pellets and loaded into a reactor along with solvent.
  • the reactor was heated to about 220 °C for the liquefied and prepared article for liquification in presence of a solvent.
  • the polymer was in a molten phase at 220 °C and was inert (could not react) with methanol (solvent) in the reactor at reaction temperature hence could not be depolymerized.
  • the LLDPE polymer could not be depolymerized, it could not participate in any of the further processing methods, and it had a Use Cycle 1 rating. Once the molten LLDPE polymer was removed from the reactor it is solid again and has conventional defects which demonstrates difficulties in reprocessing. Hence cannot be “repeatedly recycled” for “closed loop recycling” hence has properties of single use applications.
  • the conventionally made LLDPE did not have a Use Cycle Rating of at least 2.
  • the conventional LLDPE was not able to be effectively liquefied by heating and depolymerization into difunctional oligomers and difunctional linkers and, as such, could not be polymerized into an LLDPE polymer. In other words, the conventional LLDPE had a single use utility.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Sont décrits une composition et des procédés de fabrication de la composition. La composition peut comprendre un mimétique de polymère (PM) recyclable à plusieurs reprises d'un polymère de polyéthylène à basse densité linéaire (LLDPE). Le RR-PM peut être un produit de réaction d'un oligomère difonctionnel et d'un lieur difonctionnel. L'oligomère difonctionnel et le lieur difonctionnel peuvent être obtenus à partir d'un article liquéfié.
PCT/EP2023/086860 2022-12-24 2023-12-20 Mimétiques de polymères recyclables à plusieurs reprises (rr-pm) de polyéthylène à basse densité linéaire WO2024133403A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5643998A (en) 1994-03-10 1997-07-01 Kabushiki Kaisha Toyota Chuo Kenkyusho Recyclable polymer, process for producing the same, method for recovering the same, and method for regenerating the same
WO2003054061A1 (fr) 2001-12-21 2003-07-03 Canon Kabushiki Kaisha Polymeres recyclables, leurs procedes de production, et procede de recyclage
WO2016142786A1 (fr) 2015-03-10 2016-09-15 Fibre Reinforced Thermoplastics B.V. Procédé de production de bandes renforcées de fibres unidirectionnelles
EP3907250A1 (fr) 2020-05-06 2021-11-10 Universitaet Konstanz Matériaux de type polyester or polycarbonate, leur solvolyse et fabrication d'éléments préfabriqués à partir de ceux-ci
WO2022214640A1 (fr) * 2021-04-08 2022-10-13 Sabic Global Technologies B.V. Polymères de polyester imitant une polyoléfine
WO2022214642A1 (fr) * 2021-04-08 2022-10-13 Sabic Global Technologies B.V. Polymères de polyester imitant une polyoléfine

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5643998A (en) 1994-03-10 1997-07-01 Kabushiki Kaisha Toyota Chuo Kenkyusho Recyclable polymer, process for producing the same, method for recovering the same, and method for regenerating the same
WO2003054061A1 (fr) 2001-12-21 2003-07-03 Canon Kabushiki Kaisha Polymeres recyclables, leurs procedes de production, et procede de recyclage
WO2016142786A1 (fr) 2015-03-10 2016-09-15 Fibre Reinforced Thermoplastics B.V. Procédé de production de bandes renforcées de fibres unidirectionnelles
EP3907250A1 (fr) 2020-05-06 2021-11-10 Universitaet Konstanz Matériaux de type polyester or polycarbonate, leur solvolyse et fabrication d'éléments préfabriqués à partir de ceux-ci
WO2022214640A1 (fr) * 2021-04-08 2022-10-13 Sabic Global Technologies B.V. Polymères de polyester imitant une polyoléfine
WO2022214642A1 (fr) * 2021-04-08 2022-10-13 Sabic Global Technologies B.V. Polymères de polyester imitant une polyoléfine

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HÄUSSLER MANUEL ET AL: "Closed-loop recycling of polyethylene-like materials", NATURE, vol. 590, no. 7846, 20 February 2021 (2021-02-20), pages 423 - 427, XP037372223, DOI: 10.1038/S41586-020-03149-9 *
MILLER ET AL., POLYMERS & POLYMER COMPOSITES, vol. 4, no. 002082 79-3, 1996

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