Polymer Recycle Process and Products

Abstract

Methods are provided for processing LDPE recyclates, including but not limited to polyethylene and polypropylene, and compositions therefrom. The LDPE recyclates can be thinning cracked to improve processing properties and / or devolatilized to remove waste by-products to produce processed LDPE recyclates. The processed LDPE recyclates can be compounded with pre-consumer polyolefins to produce blend compositions with acceptable or even improved processing properties. Such pre-consumer polyolefins can also be thinning cracked to further tailor the processing properties of such polymer blends. Extruders and / or combinations of extruder zones can be used in the same or different locations for thinning cracking and / or compounding of both the LDPE recyclates and / or pre-consumer polyolefins.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is filed under the Patent Cooperation Treaty, claiming priority to U.S. Provisional Patent Application No. 63 / 213,429, entitled "POLYMER RECYCLING PROCESS AND PRODUCTS," filed on June 22, 2021, and U.S. Provisional Patent Application No. 63 / 238,655, entitled "POLYMER RECYCLING PROCESS AND PRODUCTS," filed on August 30, 2021, the contents of which are incorporated herein by reference in their entireties.

[0002] The present disclosure relates to the use of extrusion processes to improve the processing characteristics of polyolefin recycles, either alone or in combination with other polyolefins. The present invention further relates to compositions produced by such processes. [Background technology]

[0003] Polyolefins, including polyethylene and polypropylene, can be used in many applications, including packaging of food and other cargo, electronic products, automotive parts, and various manufactured goods. Waste plastic materials can be obtained from various sources, including different recyclates of municipal plastic waste consisting of flexible packaging (cast films, blown films, BOPP films), rigid packaging, blown bottles, and injection molded containers. Usually, a separation step from other polymers such as PVC, PET, or PS results in two main polyolefin fractions, namely polyethylene (especially HDPE, LDPE, LLDPE) and polypropylene (homopolymer, random copolymer, heterophase copolymer).

[0004] The multicomponent properties of recycled polyolefins or polyolefin fractions may result in reduced mechanical and optical performance of articles or polyolefin formulations manufactured with a portion of the original LDPE replaced with recycled polymers. Unpredictable mechanical and / or optical properties may result from variability in one or more properties of recycled polyolefins, including, but not limited to, melt index, high load melt index, melt elasticity, complex viscosity, or combinations thereof. In addition, recycled polyolefins or polyolefin fractions may contain contamination with impurities or other components. Furthermore, the molecular weight, molecular weight distribution and / or comonomer content of recycled polyolefins or polyolefin fractions may limit the range of original LDPE into which recycled polyolefins can be incorporated. Another limitation to the use of recycled polyolefins may be the presence of unpleasant odors from volatile organic compounds that may have been absorbed into these polymers during use.

[0005] In the case of polyethylene, it may be desirable to separate polyethylene waste into fractions that are primarily HDPE, primarily MDPE, primarily LDPE, and primarily LLDPE. In the case of the LDPE fraction, the present disclosure provides a process for producing a polyolefin composition that includes recycled LDPE, such polyolefin composition having a useful combination of properties. Such a process can be very flexible and can be carried out using commonly used equipment and familiar techniques to produce a wide variety of products. Summary of the Invention

[0006] In general, the present disclosure relates to a method for processing polyolefin recycles, particularly low density polyethylene ("LDPE") recycles. Such processing includes performing in an extruder to convert the LDPE recycle to a LDPE recycle having a reduced weight average molecular weight. In some embodiments, the LDPE recycle is also subjected to devolatilization conditions to convert the LDPE recycle to a viscosity-thinning decomposed LDPE recycle having a reduced weight average molecular weight and reduced volatile organic compound ("VOC") content.

[0007] Viscosity reducing decomposition conditions include thermal tack reduction and / or peroxidative tack reduction. Thermal tack reduction includes sufficient temperature, pressure and mechanical shear to cause polymer chain rupture beyond polymer chain branching or crosslinking. Peroxidative tack reduction can occur by adding peroxide to the polymer melt in the extruder, followed by thermal decomposition of the peroxide to generate radicals that react with the polymer chains to break them. In some embodiments, tack reduction conditions include performing thermal tack reduction in the absence or substantially absence of oxygen at a temperature at least 180° C. above the melting point of the LDPE.

[0008] Devolatilization conditions can include reduction of VOCs in the polyolefin by a portion of the extruder having an intensive mixing arrangement and a devolatilization section to allow for removal of VOCs at high temperatures. Devolatilization conditions can be further enhanced by injection of gas into the extruder, distribution of gas in the polymer melt to recover VOC components, and extraction of the gas and recycled VOC components by venting and / or vacuum.

[0009] In some embodiments, the treated LDPE recycler can be pelletized as a product while exiting the extruder. In other embodiments, the treated LDPE recycler can be fed to a second extruder to be compounded or blended with the original LDPE. In yet other embodiments, the original LDPE can be a polyolefin powder product from the polymerization device, a pelletized polyolefin, or a polyolefin melt that is the product of a third extruder. In any of the embodiments of this paragraph, the original LDPE can be subjected to a viscosity-thinning cracking process before being added to the second reactor.

[0010] In some embodiments, the original LDPE is fed to a third extruder and the polymer melt forming the third extruder is co-fed with the treated LDPE recycle melt into a second extruder.

[0011] In some embodiments, there is provided a composition, the composition being a polymer blend comprising 5% to 90% by weight of LDPE recyclate and 10% to 95% by weight of original LDPE, all weight percentages being based on the combined weight of the polymer blend, and one or both of the LDPE recyclable material and the original LDPE have been subjected to viscosity thinning degradation. The viscosity thinning degradation may be thermal and / or peroxidative viscosity thinning degradation.

[0012] The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described below which form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and specific embodiments disclosed may be readily utilized as a basis for modifying or designing other membrane structures and / or processes for carrying out the same purposes of the present invention. Those skilled in the art will also realize that such equivalent structures do not depart from the spirit and scope of the invention as set forth in the appended claims. The novel features of the present invention, including its structure and method of manufacture, as well as other objects and advantages, will be better understood from the following description. [Brief description of the drawings]

[0013] The claimed subject matter can be understood by reference to the following description taken in conjunction with the accompanying drawings, where like reference numerals identify like elements and in which: [Figure 1] FIG. 1 is a simplified flow diagram of a process for obtaining treated LDPE recycler according to an embodiment of the present invention. [Diagram 2] FIG. 2 is a simplified flow diagram of a process for obtaining a blend of processed LDPE recycle and original LDPE using two extruders according to an embodiment of the present invention. [Diagram 3] FIG. 3 is a simplified flow diagram of a process for obtaining a blend of processed LDPE recycle and original LDPE using three extruders according to an embodiment of the present invention. [Figure 4] FIG. 4 is an overlay graph showing the effect of LDPE thinning decomposition on complex viscosity, in accordance with an embodiment of the present invention.

[0014] While the disclosed processes and compositions are susceptible to various modifications and alternative forms, the drawings show, by way of example, specific embodiments described in detail herein. It should be understood, however, that the description of specific embodiments herein is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Exemplary embodiments of the claimed subject matter below will now be disclosed. For purposes of clarity, some features of an actual implementation may not be described herein. It should be understood that in developing such an actual embodiment, many implementation-specific decisions must be made to achieve the developer's particular goals, including complying with system-related and business-related constraints that vary from implementation to implementation. Moreover, it should be understood that such development efforts, even if complex and time-consuming, would be routine for those of ordinary skill in the art having the benefit of this disclosure.

[0016] The words and phrases used herein should be understood and interpreted as having a meaning consistent with the understanding of those words and phrases by those of ordinary skill in the art. A special definition of a term or phrase, i.e., a definition that is different from the common and customary meaning as understood by those of ordinary skill in the art, is not intended to be implied by the consistent use of the term or phrase herein. To the extent that a term or phrase is intended to have a special meaning, i.e., a meaning other than the broadest meaning as understood by those of ordinary skill in the art, such special or specific definition will be expressly described in the definition method of the specification to provide a special or specific definition of the term or phrase. It should be noted that the singular forms "a," "an," and "the," as used herein and in the appended claims, include plural referents unless the context clearly dictates otherwise.

[0017] For example, the following description includes a non-exhaustive list of definitions of some specific terms used in this disclosure (other terms may be defined or clarified elsewhere herein). These definitions are intended to clarify the meaning of the terms used herein. It is believed that these terms are used in a manner consistent with their ordinary meaning, yet the definitions are provided here for clarity.

[0018] definition "Antioxidant," as used herein, means a compound that inhibits oxidation, a chemical reaction that can produce free radicals and chain reactions.

[0019] "Combined conditions," as used herein, means the temperature, pressure, and shear conditions implemented in an extruder to provide an intimate mixture of two or more polymers and, optionally, additives to produce a substantially homogeneous polymer product.

[0020] As used herein, "devolatilization conditions" means subjecting the polymer melt in the extruder to injection and withdrawal of sweep gas, addition of heat, physical mixing, pressure reduction by venting or applying vacuum, or combinations thereof. The devolatilization conditions implemented in the extruder are sufficient to reduce the VOCs of the polymer fed to the extruder at a predetermined rate and / or to a predetermined VOC target for the polymer exiting the extruder. Devolatilization conditions are directed to the reduction of VOCs in the polyolefin by a portion of the extruder having an intensive mixing arrangement and a devolatilization section to allow for the removal of VOCs at high temperatures. Devolatilization conditions can be further enhanced by injecting gas into the extruder, distributing the gas in the polymer melt to recover the VOC components, and extracting the gas and recovered VOC components by venting or vacuum.

[0021] "Devolatilized LDPE recycle" as used herein means the product obtained by subjecting LDPE recycle feedstock to the devolatilization conditions described herein.

[0022] "Extruder", as used herein in the context of "first extruder", "second extruder", and "third extruder", in some embodiments means separate extrusion apparatuses and in other embodiments means separate sections within a single extrusion apparatus. In some embodiments, the first extruder and the second extruder are separate machines. In some embodiments, the first extruder and the second extruder are separate sections within a single machine. In some embodiments, the second extruder and the third extruder are separate machines. In some embodiments, the second extruder and the third extruder are separate sections within a single machine. In some embodiments, the first extruder, the second extruder, and the third extruder are separate machines. In some embodiments, the first extruder, the second extruder, and the third extruder are separate sections within a single machine. As used herein, "extruder" includes any device or combination of devices capable of continuously processing one or more polyolefins under thinning, compounding, melting, or devolatilizing conditions, including, but not limited to, a Farrel continuous mixer (FCM™ mixer, available from Farrel Corporation, Ansonia, Conticut).

[0023] "HDPE" as used herein means a polyethylene produced by a suspension, solution, slurry, or gas phase polymerization process and has a density of 0.940 g / cm 3 ~0.970g / cm 3 It refers to ethylene homopolymers and ethylene copolymers having a density in the range of

[0024] "Feedstock LDPE recycle" as used herein means LDPE recycle after collection and sorting, but before being subjected to the processes disclosed herein.

[0025] "LDPE recycle" as used herein means post-consumer recycled ("PCR") LDPE and / or post-industrial recycled ("PIR") LDPE. Polyolefin recycle is derived from end products that have completed their life cycle as consumer goods, or from plastic scrap that would otherwise be disposed of as waste (e.g., polyethylene water bottles) or generated as waste from industrial processes. Post-consumer polyolefins include polyolefins collected in commercial and residential recycle programs, such as flexible packaging (cast film, blown film, BOPP film), rigid packaging, blow molded bottles, injection molded containers, etc. Typically, a separation step from other polymers such as PVC, PET, or PS results in two main polyolefin fractions: polyethylene (especially HDPE, LDPE, LLDPE) and polypropylene (homopolymer, random copolymer, heterophase copolymer). Polyethylene recycle can be further separated to recover the portion having LDPE as the predominant component. In addition to contamination from different polymers, LDPE recyclates frequently contain other impurities such as PMMA, PC, wood, paper, textiles, cellulose, food, and other organic waste, many of which cause unpleasant odors in the LDPE recyclates before and after typical processing.

[0026] "LDPE" as used herein means a polyethylene produced by high pressure free radical polymerization and has a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 It refers to ethylene homopolymers and ethylene copolymers having a density in the range of

[0027] "LLDPE" as used herein means any PE produced by a suspension, solution, slurry, or gas phase polymerization process and having a density of 0.910 g / cm 3 ~0.940g / cm 3 It means an ethylene copolymer having a density in the range of

[0028] "MDPE" as used herein means a polymer produced by a suspension, solution, slurry, or gas phase polymerization process and has a density of 0.925 g / cm 3 ~0.940g / cm 3 It means an ethylene copolymer having a density in the range of

[0029] "Melt conditions", as used herein, mean the temperature, pressure, and shear conditions, alone or in combination with each other, required to produce a polymer melt from a feed of polymer pellets or powder.

[0030] As used herein, "processed LDPE recycle" means the product obtained by subjecting LDPE recycle feedstock to viscosity-thinning cracking conditions or viscosity-thinning cracking conditions followed by devolatilization conditions, as described herein.

[0031] "Original LDPE" as used herein is a pre-consumed polyolefin. Pre-consumed polyolefins are polyolefin products obtained directly or indirectly from petrochemical feedstocks fed to a polymerization unit. Pre-consumed polyolefins may be subjected to post-polymerization processes such as, but not limited to, extrusion, pelletization, thinning cracking, and / or other processing completed before the product reaches the end-use consumer. In some embodiments, the original LDPE has a single heating history. In some embodiments, the original LDPE has two or more heating histories. In some embodiments, the original LDPE does not contain additives. In some embodiments, the original LDPE contains additives.

[0032] "Thinning degradation conditions", as used herein, refer to thermal thinning degradation and / or peroxidative thinning degradation. Thermal thinning degradation involves sufficient temperature, pressure, and / or mechanical shear to cause polymer chain scission, with branching or crosslinking of the polymer chains predominating. Peroxidative thinning degradation occurs when peroxide is added to the polymer melt in an extruder followed by thermal decomposition of the peroxide to form free radicals, which react with the polymer chains resulting in chain scission. As used herein, a thinning decomposed polymer will have a lower number average and weight average molecular weight, a narrower molecular weight distribution, a higher melt index, and a higher high-load melt index. In some embodiments, thinning degradation conditions consist of thermal thinning degradation at temperatures above 300°C, or in the range of 320°C to 400°C, in the absence or substantial absence of oxygen.

[0033] "Thinning degradation," as used herein, refers to the thermal and / or chemical treatment of a polymer to reduce the M of the LDPE so treated. n , M w , and MWD(M w / M n ), and the melt index I2 (ASTM D-1238, 2.16 kg @ 190 ° C) and high load melt index I 21 (ASTM D-1238, 21.6 kg @ 190°C). Application of high temperatures and / or addition of radical sources such as peroxides to polyolefin-based materials results in the degradation of the polymer chains and a decrease in the average molecular weight of the polymer. In parallel, the molecular weight distribution becomes narrower. When such methods are carried out intentionally to modify the properties of a polymer, these practices are commonly referred to as "thinning degradation".

[0034] As used herein, "viscosity-thinning decomposition LDPE recycle" refers to the product obtained by subjecting LDPE recycle feedstock to the viscosity-thinning decomposition conditions described herein.

[0035] Processing of LDPE recycled materials In FIG. 1, the flow diagram 100 includes a thinning cracking extruder 110 having a thinning cracking zone 115 and an optional devolatilization zone 120. LDPE recycle feedstock 125 is added to the thinning cracking extruder 110 proximate the inlet end of the extruder. The LDPE recycle is drawn through the extruder 110 by one or more rotating screw drives in the barrel of the thinning cracking extruder 110. The length of the thinning cracking extruder 110 is separated into one or more zones. Each zone can have one or more of a designated pitch on the screw drive, an inlet for injection of gas 130, 135, a vent or vacuum connection for withdrawal of gas 140, a means for adding or withdrawing heat, an inlet for injection of peroxide 145, and an inlet for injection of additives to impart preselected process conditions, including but not limited to pressure, temperature, and / or shear.

[0036] 1 shows an embodiment having a viscosity-thinning cracking zone 115 and an optional devolatilization zone 120. Other embodiments can have the viscosity-thinning cracking zone 115 alone without a devolatilization zone. The process conditions within the viscosity-thinning cracking extruder 110 can be further controlled by the rotational speed of the screw drive. The treated LDPE recycle 150 is withdrawn adjacent the discharge of the viscosity-thinning cracking extruder 110 for further processing or pelletization.

[0037] LDPE recycled raw material In some embodiments, the LDPE recycle feedstock is an ethylene homopolymer, a unit derived from ethylene, and a C3-C 12The LDPE returnable feedstock may be derived from a copolymer of units derived from one or more α-olefins, a copolymer of units derived from ethylene and units derived from one or more α-monoolefins containing polar groups, or a mixture thereof. The LDPE returnable feedstock may be derived as a portion of post-consumer recycled polyolefins and / or post-industrial recycled polyolefins, which consists predominantly of LDPE returnables, where "predominantly" means 80% by weight or more, 85% by weight or more, 90% by weight or less, or 95% by weight or more, based on the total weight of the LDPE recycle feedstock.

[0038] Such ethylene homopolymers can be produced in a high pressure free radical polymerization process, such as one or more tubular reactors, one or more autoclave reactors, or a combination thereof. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 It has a density in the range of

[0039] Such ethylene and C3-C 12 The copolymers of α-olefins can be produced in a high pressure free radical polymerization process, such as in one or more tubular reactors, one or more autoclave reactors, or a combination thereof. 12 The α-olefins include substituted or unsubstituted C3-C olefins such as propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecane, and their isomers. 12 Comonomers include, but are not limited to, alpha olefins. When present, comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm3 It has a density in the range of

[0040] Such copolymers of ethylene and one or more alpha monoolefins containing polar groups can be produced in a high pressure free radical polymerization process, such as one or more tubular reactors, one or more autoclave reactors, or a combination thereof. Such alpha monoolefins containing polar groups include, but are not limited to, methacrylic acid, esters, nitriles, and amides, such as acrylic acid, methacrylic acid, cyclohexyl methacrylate, methyl acrylate, acrylonitrile, acrylamide, or mixtures thereof. When present, the comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of up to 0.910 g / cm. 3 ~0.940g / cm 3 It has a density in the range of

[0041] LDPE recycle feedstock derived from LDPE as described above can be characterized as having the following: i) 0.910 g / cm 3 ~0.940g / cm 3 or 0.915g / cm 3 ~0.935g / cm 3 Density in the range of ii) a melt index (2.16 kg, 190°C) of 5.0 g / 10 min or less, 1.0 g / 10 min or less, 0.5 g / 10 min or less, 0.2 g / 10 min or less, or 0.1 g / 10 min or less; iii) a molecular weight distribution (M) of 4.0 or more, 8.0 or more, or 15 or more, and / or less than 35, less than 30, or less than 25; w / M n ), iv) a weight average molecular weight of 85,000 daltons or more, 120,000 daltons or more, 180,000 daltons or more, or 200,000 daltons or more, and / or 500,000 daltons or less, 400,000 daltons or less, 350,000 daltons or less, or 250,000 daltons or less, and v) Melt Elasticity ("ER") of 1.0 or greater, 1.4 or greater, or 2.0 or greater.

[0042] In some embodiments, in addition to the properties mentioned above, the LDPE recycle feedstock may be further characterized by having one or more of the following: vi) a first VOC content; vii) First high load melt index (I 21 , 21.6kg, 190℃), viii) First Melt Index Ratio (MIR, I 21 / I2), ix) a first long chain branching parameter (g') in the range of 0.40 to 0.75; x) the first total polydispersity ratio (PDR); xi) First complex viscosity ratio (

number

[0043] Viscosity reducing cracking extruder The LDPE recycle feedstock is fed to a first extruder and subjected to viscosity-thinning cracking conditions and optionally devolatilization conditions.

[0044] -Thinning decomposition The thinning decomposition conditions are implemented in the thinning decomposition zone of the first extruder and are tailored for LDPE. In some embodiments, the thinning decomposition conditions refer to thermal thinning decomposition and / or peroxidative thinning decomposition. In some embodiments, the thinning decomposition conditions consist of thermal thinning decomposition, the temperature of the thinning decomposition zone is 300°C or higher, and chain scission reactions are believed to prevail over long chain branching and / or crosslinking reactions. In some embodiments, the temperature of the thinning decomposition zone can range from 320°C to 500°C, 340°C to 480°C, or 360°C to 460°C. In some embodiments, instrumentation at the first extruder discharge includes rheology (I2, I 21 , viscosity, melt elasticity, complex viscosity ratio, etc.) are monitored directly or indirectly to measure and aid in controlling the thinning decomposition. In some embodiments where antioxidant addition is used in conjunction with the thinning decomposition, the antioxidant addition point is at a location on the first extruder after a substantial portion of the thinning decomposition reaction has taken place. In some embodiments, the thinning decomposition conditions consist of thermal thinning decomposition in the absence or substantial absence of oxygen, where substantial absence of oxygen means 1.0 wt.% or less, 0.10 wt.% or less, or 0.01 wt.% or less, based on the total weight of the polymer in the extruder. In some embodiments, the thinning decomposition extruder comprises one or more melt filters.

[0045] -Devolatilization Devolatilization conditions are optionally implemented in the first extruder to reduce the VOCs in the LDPE recycle feedstock by a portion of the extruder having an intimate mixing arrangement and a devolatilization section to allow for VOC reduction at elevated temperatures. Devolatilization conditions can be further enhanced by injecting a scavenging gas, such as, but not limited to, nitrogen, carbon dioxide, water, or combinations thereof, into the extruder, distributing the gas in the polymer melt to scavenge the VOC components, and extracting the gas and scavenged VOC components by venting and / or vacuum.

[0046] Processed LDPE Recycled Treated LDPE recyclerate is withdrawn from the discharge of a thinning cracking extruder, where "treated" means that the LDPE recyclerate feedstock has been subjected to thinning cracking conditions or thinning cracking conditions followed by devolatilization conditions. Treated LDPE recyclerate, as described above, can be characterized by having the following: i) a density, wherein the ratio of the density of the treated LDPE recycler to the density of the raw LDPE recycler is greater than or equal to 1.0; ii) a melt index, wherein the ratio of the melt index of the treated LDPE recycler to the melt index of the raw LDPE recycler is 5.0 or greater; and iii) a molecular weight distribution, wherein the ratio of the molecular weight distribution of the treated LDPE recyclate to the molecular weight distribution of the raw LDPE recyclate is within the range of 0.60 to 0.99 or 0.75 to 0.95; and iv) Weight average molecular weight (“M w2 "), wherein the ratio of the weight average molecular weight of the treated LDPE recycler to the weight average molecular weight of the raw LDPE recycler is within a range of 0.60 to 0.99 or 0.75 to 0.95. w2 ")and, v) Melt Elasticity ("ER"), wherein the ratio of the ER of the treated LDPE recycler to the ER of the raw LDPE recycler is in the range of 0.30 to 0.90.

[0047] In some embodiments, in addition to the properties mentioned above, the treated LDPE recyclate may be further characterized by having one or more of the following: vi) a VOC content, wherein the ratio of the VOC content of the treated LDPE recycler to the VOC content of the raw LDPE recycler is less than or equal to 0.9, 0.8, 0.7, 0.6, or 0.5, each alone or in combination with a lower limit of greater than or equal to 0.1; vii) High Load Melting Index (I 21 , 21.6 kg, 190°C), wherein the ratio of the high-load melt index of the treated LDPE recycler to the high-load melt index of the raw LDPE recycler is 2.0 or more. 21 , 21.6kg, 190℃) and viii) Melt Index Ratio (MIR, I 21 the melt index ratio (MIR,I / I2) of the treated LDPE recycler to the MIR of the raw LDPE recycler is within a range of 0.50 to 0.75; 21 / I2) and ix) a long chain branching parameter (g'), wherein the ratio of g' of the treated LDPE recycler to g' of the raw LDPE recycler is 1.0 or greater; and x) a total polydispersity ratio (PDR), wherein the ratio of the PDR of the treated LDPE recycler to the PDR of the raw LDPE recycler is 0.5 or less; and xi) Complex viscosity ratio (

number

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[0048] Blending Processed LDPE Recycled and Polyolefin Blend Components - Two Extruders Referring to Figure 2, a flow diagram 200 includes a thinning cracking extruder 210 and a compound extruder 255. The embodiment of the invention shown in Figure 2 includes a thinning cracking extruder 210 having a thinning cracking zone 215 and a devolatilization zone 220. LDPE recycle feedstock 225 is added to the thinning cracking extruder 210 proximate the inlet end of the extruder. The LDPE recycle feedstock 225 is drawn through the thinning cracking extruder 210 by one or more rotating screw drives within the barrel of the thinning cracking extruder 210. The length of the thinning cracking extruder 210 is separated into one or more zones. Each zone may have one or more of a specified thread pitch on the screw drive, an inlet for the injection of gases 230, 235, a vent or vacuum connection for the withdrawal of gas 240, a means for adding or withdrawing heat, an inlet for the injection of peroxide 245, and an inlet for the injection of additives to impart preselected process conditions including, but not limited to, pressure, temperature, and shear.

[0049] 2 shows an embodiment having both a viscosity-thinning cracking zone 215 and a devolatilization zone 220. Other embodiments can have either the viscosity-thinning cracking zone 215 or the devolatilization zone 220 independently without the other. The process conditions within the viscosity-thinning cracking extruder 210 can be further controlled by the rotational speed of the screw drive. The treated LDPE recycler 250 is withdrawn adjacent the discharge of the viscosity-thinning cracking extruder 210 for further processing.

[0050] The embodiment of FIG. 2 includes a second extruder 255 having a compounding region 260. The treated LDPE recycle 250 is added as a first blend component to the compounding extruder 255 near the extruder inlet end along with a polyolefin blend component 252 and subjected to compounding conditions. The polyolefin blend component 252 includes a parent polyolefin, a polyolefin recycle feedstock, a treated polyolefin recycle, or a combination thereof. In some embodiments, the parent polyolefin includes a parent LDPE, a parent LLDPE, a parent HDPE, a parent MDPE, a parent polypropylene, or a combination thereof. In some embodiments, the polyolefin recycle feedstock includes a LDPE recycle feedstock, a LLDPE recycle feedstock, a HDPE recycle feedstock, a MDPE recycle feedstock, a polypropylene recycle feedstock, or a combination thereof. In some embodiments, the treated polyolefin recycler comprises a second treated LDPE recycler, a treated LLDPE recycler, a treated HDPE recycler, a treated MDPE recycler, a treated polypropylene recycler, or a combination thereof. In some embodiments, the polyolefin blend component comprises an original LDPE, a LDPE recycler feedstock, a treated LDPE recycler, or a combination thereof. The mixture of LDPE recycler 250 and polyolefin blend component 252 is drawn through a compound extruder 255 by one or more rotating screw drives within the barrel of the extruder 255. One or more additional inlets proximate the inlet end of the extruder provide for the addition of antioxidants 265 and / or other components 270. The length of the compound extruder 255 can be separated into one or more zones. Each zone may have one or more of a specified thread pitch on the screw drive, a means for adding or withdrawing heat, an inlet for injection of additives, and a vent or vacuum connection for withdrawal of gas 275 to impart preselected process conditions including, but not limited to, pressure, temperature, and shear.The processed blend 280 of LDPE recycle 250 and polyolefin blend component 252 is removed near the exit of the compounding extruder 255 and used for further processing or pelletization.

[0051] In some embodiments, the polyolefin blend component may be a polyolefin powder product, pelletized polyolefin or polyolefin melt from the polymerization apparatus, which is the product removed from the third extruder. In some of these embodiments, the polymerization apparatus includes two, three or more polymerization reactors and / or two, three or more polymerization zones within the polymerization reactor. More specific polymerization apparatus embodiments include, but are not limited to, two or three gas-phase fluidized bed reactors in series, two or three slurry-phase reactors in series, and a gas-phase fluidized bed reactor in series with a multi-zone circulating reactor.

[0052] In some embodiments, the amount of a polyolefin blend component, which itself can include two or more polymers, is determined based on the logarithmic blend rule, where the blend components satisfy the following formula:

number

[0053] Blend Ingredients The first blend component is a processed LDPE recycle produced from a thinning decomposition extruder. The second blend component comprises an original polyolefin, a polyolefin recycle feedstock, a processed polyolefin recycle, or a combination thereof. In some embodiments, the original polyolefin comprises an original LDPE, an original LLDPE, an original HDPE, an original polypropylene, or a combination thereof. In some embodiments, the polyolefin recycle feedstock comprises an LDPE recycle feedstock, an LLDPE recycle feedstock, an HDPE recycle feedstock, a polypropylene recycle feedstock, or a combination thereof. In some embodiments, the processed polyolefin recycle comprises a second processed LDPE recycle, a processed LLDPE recycle, a processed HDPE recycle, a processed polypropylene recycle, or a combination thereof. In some embodiments, the polyolefin blend component comprises an original LDPE, an LDPE recycle feedstock, a processed LDPE recycle, or a combination thereof. When a processed LDPE recycler is blended with another processed LDPE recycler, the first LDPE recycler has at least one parameter that distinguishes it from the second processed LDPE recycler.

[0054] Original LDPE In some embodiments, the LDPE recycle feedstock is an ethylene homopolymer, a copolymer of units derived from ethylene, and a C3-C 12 The copolymers are selected from units derived from one or more alpha-olefins, copolymers of units derived from ethylene, and units derived from one or more alpha monoolefins containing a polar group, or mixtures thereof.

[0055] Such ethylene homopolymers can be produced in a high pressure free radical polymerization process, such as one or more tubular reactors, one or more autoclave reactors, or a combination thereof. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 It has a density in the range of

[0056] Such ethylene and C3-C 12 The copolymers of α-olefins can be produced in a high pressure free radical polymerization process, such as in one or more tubular reactors, one or more autoclave reactors, or a combination thereof. 12 The α-olefins include substituted or unsubstituted C3-C olefins such as propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecane, and their isomers. 12 Comonomers include, but are not limited to, alpha olefins. When present, comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 It has a density in the range of

[0057] Such copolymers of ethylene and one or more α-monoolefins containing polar groups can be produced during high pressure radical polymerization, for example in one or more tube reactors, one or more autoclave reactors, or a combination thereof. Such α-monoolefins containing polar groups include, but are not limited to, methacrylic acid, esters, nitriles, and amides, such as acrylic acid, methacrylic acid, methacrylic acid, cyclohexyl methacrylate, methyl acrylate, acrylonitrile, acrylamide, or mixtures thereof. When present, the comonomer can be present in an amount of up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of up to 0.910 g / cm. 3 ~0.940g / cm 3 It has a density in the range of

[0058] The original LDPE can be characterized as having the following: i) 0.910 g / cm 3 ~0.940g / cm 3 or 0.915g / cm 3 ~0.9 3 5g / cm 3 Density in the range of ii) a melt index (2.16 kg, 190°C) in the range of 1.0 g / 10 min to 100 g / 10 min, 2.0 g / 10 min to 80 g / 10 min, or 3.0 g / 10 min to 50 g / 10 min; iii) Molecular weight distribution (M w / M n ), iv) A weight average molecular weight of less than or equal to 250,000 daltons, less than or equal to 200,000 daltons, less than or equal to 150,000 daltons, or less than or equal to 100,000 daltons.

[0059] LDPE recycled raw material In some embodiments, the LDPE recycle feedstock is an ethylene homopolymer, a unit derived from ethylene, and a C3-C 12 The LDPE returnable feedstock may be derived from a copolymer of units derived from one or more α-olefins, a copolymer of units derived from ethylene and units derived from one or more α-monoolefins containing polar groups, or a mixture thereof. The LDPE returnable feedstock may be derived as a portion of post-consumer recycled polyolefins and / or post-industrial recycled polyolefins, which consists predominantly of LDPE returnables, where "predominantly" means 80% by weight or more, 85% by weight or more, 90% by weight or less, or 95% by weight or more, based on the total weight of the LDPE recycle feedstock.

[0060] Such ethylene homopolymers can be produced in a high pressure free radical polymerization process, such as one or more tubular reactors, one or more autoclave reactors, or a combination thereof. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 It has a density in the range of

[0061] Such ethylene and C3-C 12 The copolymers of α-olefins can be produced in a high pressure free radical polymerization process, such as in one or more tubular reactors, one or more autoclave reactors, or a combination thereof. 12 The α-olefins include substituted or unsubstituted C3-C olefins such as propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecane, and their isomers. 12Comonomers include, but are not limited to, alpha olefins. When present, comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 It has a density in the range of

[0062] Such copolymers of ethylene and one or more alpha monoolefins containing polar groups can be produced in a high pressure free radical polymerization process, such as one or more tubular reactors, one or more autoclave reactors, or a combination thereof. Such alpha monoolefins containing polar groups include, but are not limited to, methacrylic acid, esters, nitriles, and amides, such as acrylic acid, methacrylic acid, methacrylic acid, cyclohexyl methacrylate, methyl acrylate, acrylonitrile, acrylamide, or mixtures thereof. When present, the comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm. 3 ~0.940g / cm 3 It has a density in the range of

[0063] LDPE recycle feedstock derived from LDPE as described above can be characterized as having the following: i) 0.910 g / cm 3 ~0.940g / cm 3 or 0.915g / cm 3 ~0.935g / cm 3 With a density in the range of ii) a melt index (2.16 kg, 190°C) of 5.0 g / 10 min or less, 1.0 g / 10 min or less, 0.5 g / 10 min or less, 0.2 g / 10 min or less, or 0.1 g / 10 min or less; iii) a molecular weight distribution (M) greater than 4.0, greater than 8.0, or greater than 15, and / or less than 35, less than 30, or less than 25; w / M n )and, iv) a weight average molecular weight of 85,000 daltons or more, 120,000 daltons or more, 180,000 daltons or more, or 200,000 daltons or more, and / or 500,000 daltons or less, 400,000 daltons or less, 350,000 daltons or less, or 250,000 daltons or less, and v) Melt Elasticity ("ER") of 1.0 or greater, 1.4 or greater, or 2.0 or greater.

[0064] In some embodiments, in addition to the properties mentioned above, the LDPE recycle feedstock may be further characterized by having one or more of the following: vi) a first VOC content; vii) First high load melt index (I 21 , 21.6kg, 190℃, viii) First Melt Index Ratio (MIR, I 21 / I2), ix) a first long chain branching parameter (g') in the range of 0.40 to 0.75; x) the first total polydispersity ratio (PDR); xi) First complex viscosity ratio (

number

[0065] Processed LDPE Recycled Treated LDPE recyclerate is withdrawn from the discharge of a thinning cracking extruder, where "treated" means that the LDPE recyclerate feedstock has been subjected to thinning cracking conditions or thinning cracking conditions followed by devolatilization conditions. Treated LDPE recyclerate, as described above, can be characterized by having the following: i) a density, wherein the ratio of the density of the treated LDPE recycler to the density of the raw LDPE recycler is greater than or equal to 1.0; ii) a melt index, wherein the ratio of the melt index of the treated LDPE recycler to the melt index of the raw LDPE recycler is 5.0 or greater; and iii) a molecular weight distribution, in which the ratio of the molecular weight distribution of the treated LDPE recyclate to the molecular weight distribution of the raw LDPE recyclate is within the range of 0.60 to 0.99 or 0.75 to 0.95; iv) Weight average molecular weight (“M w2 "), wherein the ratio of the weight average molecular weight of the treated LDPE recycler to the weight average molecular weight of the raw LDPE recycler is within a range of 0.60 to 0.99 or 0.75 to 0.95. w2 ")and, v) Melt Elasticity ("ER"), wherein the ratio of the ER of the treated LDPE recycler to the ER of the raw LDPE recycler is in the range of 0.30 to 0.90.

[0066] In some embodiments, in addition to the properties mentioned above, the treated LDPE recyclate may be further characterized by having one or more of the following: vi) a VOC content, wherein the ratio of the VOC content of the treated LDPE recycle to the VOC content of the raw LDPE recycle is, each alone, less than or equal to 0.9, 0.8, 0.7, 0.6 or 0.5, or in combination with a lower limit of greater than or equal to 0.1; vii) High Load Melting Index (I21 , 21.6 kg, 190°C), wherein the ratio of the high-load melt index of the treated LDPE recycler to the high-load melt index of the raw LDPE recycler is 2.0 or greater; viii) Melt Index Ratio (MIR, I 21 the melt index ratio (MIR,I / I2), wherein the MIR of the treated LDPE recycler to the MIR of the raw LDPE recycler of the treated LDPE recycler is within a range of 0.50 to 0.75. 21 / I2) and ix) a long chain branching parameter (g'), wherein the ratio of g' of the treated LDPE recycle to that of the raw LDPE recycle is 1.0 or greater; and x) a total polydispersity ratio (PDR), wherein the ratio of the PDR of the treated LDPE recycler to the PDR of the raw LDPE recycler is 0.5 or less; and xi) Complex viscosity ratio (

number

number

number

number

[0067] Compound Extruder The treated LDPE recycle and polyolefin blend components are fed to a second extruder or mixer and the blend is subjected to compounding conditions. The compounding conditions are performed in a compounding zone of the second extruder or mixer and are tailored to the particular polyolefin and optional additive blend. Conditions of temperature, pressure, and shear are performed in the second extruder or mixer sufficient to provide intimate mixing of the treated LDPE recycle and the original LDPE, and optionally the additives, to produce a substantially homogenous polymer blend of the treated LDPE recycle and the original LDPE. In some embodiments, the compounding conditions include a temperature in the compounding zone of 300°C or less, 250°C or less, or 200°C or less. In some embodiments, the temperature in the compounding zone can range from 125°C to 195°C, 130°C to 180°C, or 135°C to 165°C.

[0068] Blends of processed LDPE recyclates and polyolefin blend components In some embodiments, the blend comprises 5%-90%, 10%-80%, 15%-70%, 20%-60%, or 25%-50% by weight of the treated LDPE recycle and 10%-95%, 20%-90%, 30%-85%, 40%-80%, or 50%-75% by weight of the polyolefin blend component, all weight percentages based on the combined weight of the polymer blend. In some embodiments, the original LDPE is degraded. Such degraded degradation of the original LDPE can be thermal degraded and / or peroxidic degraded. In some embodiments, such degraded conditions of the original LDPE comprise thermal degraded degradation at a temperature above the melting point of the LDPE, at or above 300°C, or in the range of 320°C to 400°C, in the absence or substantial absence of oxygen.

[0069] In some embodiments, the blend of the processed LDPE recycler and polyolefin blend component, in combination with or independent of the preceding blend ratios, comprises a bimodal polymer, and the processed LDPE recycler product has a weight average molecular weight ("M w3 "), and the polyolefin blend component has a weight average molecular weight ("M w4 ") and M w3 / M w4 is less than or equal to 0.9, 0.8, 0.7, 0.6, or 0.5, or alternatively is greater than or equal to 1.1, 1.25, 1.5, 1.75, 1.75, or 2.0.

[0070] Blending Processed LDPE Recycled with Polyolefin Blend Components - 3 Extruders Referring to Figure 3, a flow diagram 300 includes a thinning cracking extruder 310, a melt extruder 357, and a compound extruder 355. The embodiment of the invention shown in Figure 3 includes a thinning cracking extruder 310 having a thinning cracking zone 315 and a devolatilization zone 320. LDPE recycle feedstock 325 is added to the thinning cracking extruder 310 near the inlet end of the extruder. The LDPE recycle feedstock 325 is drawn through the thinning cracking extruder 310 by one or more rotating screw drives in the barrel of the thinning cracking extruder 310. The length of the thinning cracking extruder 310 is separated into one or more zones. Each zone may have one or more of a specified thread pitch on the screw drive, inlets for injection of gases 333, 335, vents or vacuum connections for withdrawal of gases 340, means for adding or withdrawing heat, inlets for injection of peroxide 345, and inlets for injection of additives to impart preselected process conditions including, but not limited to, pressure, temperature, and shear.

[0071] 3 shows an embodiment having both a thinning cracking zone 315 and a devolatilization zone 320. Other embodiments can have either the thinning cracking zone 315 or the devolatilization zone 320 independently without the other. The process conditions within the thinning cracking extruder 310 can be further controlled by the rotational speed of the screw drive. The treated LDPE recycle 350 is withdrawn adjacent the discharge of the thinning cracking extruder 310 for further processing.

[0072] The embodiment of FIG. 3 includes a second extruder 355 having a compounding zone 360 ​​and a third extruder 357 having a melt zone 362. A third blend component 383 is added to the melt extruder 357, optionally near the extruder inlet end, along with an antioxidant 365 and other components 370. The polyolefin blend component 352 includes a parent polyolefin, a polyolefin recycle feedstock, a processed polyolefin recycle, or a combination thereof. In some embodiments, the parent polyolefin includes a parent LDPE, a parent LLDPE, a parent HDPE, a parent MDPE, a parent polypropylene, or a combination thereof. In some embodiments, the polyolefin recycle feedstock includes a LDPE recycle feedstock, a LLDPE recycle feedstock, a HDPE recycle feedstock, a MDPE recycle feedstock, a polypropylene recycle feedstock, or a combination thereof. In some embodiments, the treated polyolefin recycler comprises a second treated LDPE recycler, a treated LLDPE recycler, a treated HDPE recycler, a treated MDPE recycler, a treated polypropylene recycler, or a combination thereof. In some embodiments, the polyolefin blend component comprises an original LDPE, a LDPE recycler feedstock, a treated LDPE recycler, or a combination thereof. The mixture of the third blend component 352 and optional antioxidant 365 and / or other components 370 is drawn through the melt extruder 357 by one or more rotating screw drives in the barrel of the melt extruder 357. The length of the melt extruder 357 can be separated into one or more zones. Each zone can have one or more of a set pitch on the screw drive, a means for the addition or withdrawal of heat, an inlet for injection of additives, and a vent or vacuum connection for the withdrawal of gas to impart preselected process conditions, including but not limited to pressure, temperature, and shear. The melt of polyolefin blend component 352 is withdrawn adjacent the discharge of melt extruder 357 for further processing or pelletization.

[0073] The processed LDPE recycle 350 is added to the compounding extruder 355 along with a melt of the polyolefin blend component 352 proximate the inlet end of the extruder. The mixture of the processed LDPE recycle 350 and the polyolefin blend component 352 is drawn through the compounding extruder 355 by one or more rotating screw drives in the barrel of the compounding extruder 355, subjecting the mixture to compounding conditions. The length of the compounding extruder 355 may be separated into one or more zones. Each zone may have one or more of a designated pitch on the screw drive, a means for the addition or withdrawal of heat, an inlet for injection of additives, and a vent and / or vacuum connection for withdrawal of gas 375 to impart preselected process conditions, including but not limited to pressure, temperature, and shear. A blend 380 of the processed LDPE recycle 350 and the melt of the polyolefin blend component 352 is removed near the outlet of the compounding extruder 355 and used for further processing or pelletization.

[0074] In some embodiments, the polyolefin blend component may be a polyolefin powder product from the polymerization apparatus, a pelletized polyolefin, or a polyolefin melt that is the product drawn from a third extruder. In some of these embodiments, the polymerization apparatus includes two, three, or more polymerization reactors and / or two, three, or more polymerization zones within the polymerization reactor. More specific polymerization apparatus embodiments include, but are not limited to, two or three gas-phase fluidized bed reactors in series, two or three slurry-phase reactors in series, and a gas-phase fluidized bed reactor in series with a multi-zone circulating reactor.

[0075] In some embodiments, the amount of a polyolefin blend component, which itself can include two or more polymers, is determined based on the logarithmic blend rule, where the blend components satisfy the following formula:

number

[0076] Blend Ingredients The first blend component is a processed LDPE recycle produced from a thinning decomposition extruder. The second blend component comprises an original polyolefin, a polyolefin recycle feedstock, a processed polyolefin recycle, or a combination thereof. In some embodiments, the original polyolefin comprises an original LDPE, an original LLDPE, an original HDPE, an original MDPE, an original polypropylene, or a combination thereof. In some embodiments, the polyolefin recycle feedstock comprises an LDPE recycle feedstock, an LLDPE recycle feedstock, an HDPE recycle feedstock, an MDPE recycle feedstock, a polypropylene recycle feedstock, or a combination thereof. In some embodiments, the processed polyolefin recycle comprises a second processed LDPE recycle, a processed LLDPE recycle, a processed HDPE recycle, a processed MDPE recycle, a processed polypropylene recycle, or a combination thereof. In some embodiments, the second blend component comprises original LDPE, LDPE recycle feedstock, processed LDPE recycle, or a combination thereof. When a processed LDPE recycle is blended with another processed LDPE recycle, the first LDPE recycle has at least one parameter that distinguishes it from the second processed LDPE recycle.

[0077] -Original LDPE In some embodiments, the LDPE recycle feedstock is an ethylene homopolymer, a unit derived from ethylene, and a C3-C 12The copolymer may be selected from a copolymer of units derived from one or more alpha-olefins, a copolymer of units derived from ethylene and units derived from one or more alpha monoolefins containing a polar group, or a mixture thereof.

[0078] Such ethylene homopolymers can be produced in a high pressure free radical polymerization process, such as one or more tubular reactors, one or more autoclave reactors, or a combination thereof. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 It has a density in the range of

[0079] Such ethylene and C3-C 12 The copolymers of α-olefins can be produced in a high pressure free radical polymerization process, such as in one or more tubular reactors, one or more autoclave reactors, or a combination thereof. 12 The α-olefins include substituted or unsubstituted C3-C olefins such as propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecane, and their isomers. 12 Comonomers include, but are not limited to, alpha olefins. When present, comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 It has a density in the range of

[0080] Such copolymers of ethylene and one or more alpha monoolefins containing polar groups can be produced in a high pressure free radical polymerization process, such as one or more tubular reactors, one or more autoclave reactors, or a combination thereof. Such alpha monoolefins containing polar groups include, but are not limited to, methacrylic acid, esters, nitriles, and amides, such as acrylic acid, methacrylic acid, methacrylic acid, cyclohexyl methacrylate, methyl acrylate, acrylonitrile, acrylamide, or mixtures thereof. When present, the comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm. 3 ~0.940g / cm 3 It has a density in the range of

[0081] The original LDPE can be characterized as having the following: i) 0.910 g / cm 3 ~0.940g / cm 3 or 0.915g / cm 3 ~0.935g / cm 3 With a density in the range of ii) a melt index (2.16 kg, 190°C) in the range of 1.0 g / 10 min to 100 g / 10 min, 2.0 g / 10 min to 80 g / 10 min, or 3.0 g / 10 min to 50 g / 10 min; iii) Molecular weight distribution (M w / M n )and, iv) A weight average molecular weight of less than or equal to 250,000 daltons, less than or equal to 200,000 daltons, less than or equal to 150,000 daltons, or less than or equal to 100,000 daltons.

[0082] -LDPE recycled raw material In some embodiments, the LDPE recycle feedstock is an ethylene homopolymer, a unit derived from ethylene, and a C3-C12 The LDPE returnable feedstock may be derived from a copolymer of units derived from one or more α-olefins, a copolymer of units derived from ethylene and units derived from one or more α-monoolefins containing polar groups, or a mixture thereof. The LDPE returnable feedstock may be derived as a portion of post-consumer recycled polyolefins and / or post-industrial recycled polyolefins, which consists predominantly of LDPE returnables, where "predominantly" means 80% by weight or more, 85% by weight or more, 90% by weight or less, or 95% by weight or more, based on the total weight of the LDPE recycle feedstock.

[0083] Such ethylene homopolymers can be produced in a high pressure free radical polymerization process, such as one or more tubular reactors, one or more autoclave reactors, or a combination thereof. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 It has a density in the range of

[0084] Such ethylene and C3-C 12 The copolymers of α-olefins can be produced in a high pressure free radical polymerization process, such as in one or more tubular reactors, one or more autoclave reactors, or a combination thereof. 12 The α-olefins include substituted or unsubstituted C3-C olefins such as propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecane, and their isomers. 12 Comonomers include, but are not limited to, alpha olefins. When present, comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm 3 ~0.940g / cm3 It has a density in the range of

[0085] Such copolymers of ethylene and one or more alpha monoolefins containing polar groups can be produced in a high pressure free radical polymerization process, such as one or more tubular reactors, one or more autoclave reactors, or a combination thereof. Such alpha monoolefins containing polar groups include, but are not limited to, methacrylic acid, esters, nitriles, and amides, such as acrylic acid, methacrylic acid, cyclohexyl methacrylate, methyl acrylate, acrylonitrile, acrylamide, or mixtures thereof. When present, the comonomers can be present in amounts up to 15 wt%, 10 wt%, or 5 wt%. Operating conditions for the high pressure process can include, but are not limited to, pressures ranging from 70 MPa to 700 MPa and temperatures ranging from 150°C to 500°C. Such homopolymers have a high degree of long chain branching and a viscosity of 0.910 g / cm. 3 ~0.940g / cm 3 It has a density in the range of

[0086] LDPE recycle feedstock derived from LDPE as described above can be characterized as having the following: i) 0.910 g / cm 3 ~0.940g / cm 3 or 0.915g / cm 3 ~0.935g / cm 3 Density in the range of ii) a melt index (2.16 kg, 190°C) of 5.0 g / 10 min or less, 1.0 g / 10 min or less, 0.5 g / 10 min or less, 0.2 g / 10 min or less, or 0.1 g / 10 min or less; iii) A molecular weight distribution (M) of greater than 4.0, greater than 8.0, or greater than 15, and / or less than 35, less than 30, or less than 25. w / M n ), iv) a weight average molecular weight of 85,000 daltons or more, 120,000 daltons or more, 180,000 daltons or more, or 200,000 daltons or more, and / or 500,000 daltons or less, 400,000 daltons or less, 350,000 daltons or less, or 250,000 daltons or less, and v) Melt Elasticity ("ER") of 1.0 or greater, 1.4 or greater, or 2.0 or greater.

[0087] In some embodiments, in addition to the properties mentioned above, the LDPE recycle feedstock may be further characterized by having one or more of the following: vi) a first VOC content; and vii) First high load melt index (I 21 , 21.6kg, 190℃) and viii) First Melt Index Ratio (MIR, I 21 / I2) and ix) a first long chain branching parameter (g') in the range of 0.40 to 0.75; x) a first overall polydispersity ratio (PDR); xi) First complex viscosity ratio (

number

[0088] -Processed LDPE recycle Treated LDPE recyclerate is withdrawn from the discharge of a thinning cracking extruder, where "treated" means that the LDPE recyclerate feedstock has been subjected to thinning cracking conditions or thinning cracking conditions followed by devolatilization conditions. Treated LDPE recyclerate, as described above, can be characterized by having the following: i) a density, wherein the ratio of the density of the treated LDPE recycler to the density of the raw LDPE recycler is greater than or equal to 1.0; ii) a melt index, wherein the ratio of the melt index of the treated LDPE recycler to the melt index of the raw LDPE recycler is 5.0 or greater; and iii) a molecular weight distribution, wherein the ratio of the molecular weight distribution of the treated LDPE recyclate to the molecular weight distribution of the raw LDPE recyclate is within the range of 0.60 to 0.99 or 0.75 to 0.95; iv) Weight average molecular weight (“M w2 "), wherein the ratio of the weight average molecular weight of the treated LDPE recycler to the weight average molecular weight of the raw LDPE recycler is within the range of 0.60 to 0.99 or 0.75 to 0.95. w2 ")and, v) Melt Elasticity (“ER”), wherein the ratio of the ER of the treated LDPE recycler to the ER of the raw LDPE recycler is in the range of 0.30 to 0.90.

[0089] In some embodiments, in addition to the properties mentioned above, the treated LDPE recyclate may be further characterized by having one or more of the following: vi) a VOC content, wherein the ratio of the VOC content of the treated LDPE recycle to the VOC content of the raw LDPE recycle is, each alone, less than or equal to 0.9, 0.8, 0.7, 0.6 or 0.5, or in combination with a lower limit of greater than or equal to 0.1; vii) High Load Melting Index (I 21 , 21.6 kg, 190°C), wherein the ratio of the high-load melt index of the treated LDPE recycler to the high-load melt index of the raw LDPE recycler is 2.0 or more. 21 , 21.6kg, 190℃) and viii) a total polydispersity ratio (PDR), wherein the ratio of the PDR of the treated LDPE recycler to the PDR of the raw LDPE recycler is 0.5 or less; and ix) a long chain branching parameter (g'), wherein the ratio of g' of the treated LDPE recycle to that of the raw LDPE recycle is 1.0 or greater; and x) a total polydispersity ratio (PDR), wherein the ratio of the PDR of the treated LDPE recycler to the PDR of the raw LDPE recycler is 0.5 or less; and xi) Complex viscosity ratio (

number

number

number

number

[0090] Melt Extruder The polyolefin blend components and optional antioxidants and / or other ingredients are fed to a third extruder or mixer and the blend is subjected to melting conditions. The melting conditions are implemented in a melting zone of the third extruder or mixer and are tailored to the particular polyolefin and optional additive mixture. Conditions of temperature, pressure, and shear are implemented in the second extruder or mixer sufficient to provide intimate mixing of the treated LDPE recycle and the original LDPE, and optionally the additives, to produce a substantially homogenous polymer blend of the treated LDPE recycle and the original LDPE. In some embodiments, the melting conditions include a temperature in the melting zone ranging from 130°C to 250°C or 150°C to 230°C.

[0091] Compound Extruder The treated LDPE recycle and polyolefin blend components are fed to a second extruder or mixer and the blend is subjected to compounding conditions. The compounding conditions are performed in a compounding zone of the second extruder or mixer and are tailored to the particular polyolefin and optional additive blend. Conditions of temperature, pressure, and shear are performed in the second extruder or mixer sufficient to provide intimate mixing of the treated LDPE recycle and the original LDPE, and optional additives, to produce a substantially homogenous polymer blend of the treated LDPE recycle and the original LDPE. In some embodiments, the compounding conditions include a temperature in the compounding zone of 300°C or less, 250°C or less, or 200°C or less. In some embodiments, the temperature in the compounding zone can range from 125°C to 195°C, 130°C to 180°C, or 135°C to 165°C.

[0092] Blends of processed LDPE recyclates and polyolefin blend components In some embodiments, the blend comprises 5%-90%, 10%-80%, 15%-70%, 20%-60%, or 25%-50% by weight of the treated LDPE recycle and 10%-95%, 20%-90%, 30%-85%, 40%-80%, or 50%-75% by weight of the polyolefin blend component, all weight percentages based on the combined weight of the polymer blend. In some embodiments, the original LDPE is degraded. Such degraded degradation of the original LDPE can be thermal degraded and / or peroxidic degraded. In some embodiments, such degraded conditions of the original LDPE comprise thermal degraded degradation at a temperature above the melting point of the LDPE, at or above 300°C, or in the range of 320°C to 400°C, in the absence or substantial absence of oxygen.

[0093] In some embodiments, the blend of the processed LDPE recycler and polyolefin blend component, in combination with or independent of the preceding blend ratios, comprises a bimodal polymer, and the processed LDPE recycler product has a weight average molecular weight ("M w3 "), and the polyolefin blend component has a weight average molecular weight ("M w4 ") and M w3 / M w4 is less than or equal to 0.9, 0.8, 0.7, 0.6, or 0.5, or alternatively is greater than or equal to 1.1, 1.25, 1.5, 1.75, 1.75, or 2.0.

[0094] Specific Embodiments In some embodiments, a method for processing low density polyethylene (LDPE) recycle includes providing a LDPE recycle feedstock, adding the LDPE recycle to a first extruder to produce a first LDPE recycle melt, and exposing the first LDPE recycle melt to viscosity-thinning cracking conditions to produce a second LDPE recycle melt. The LDPE recycle feedstock has a viscosity of 0.910 g / cm 3 ~0.940g / cm3 or 0.915g / cm 3 ~0.935g / cm 3 a first density in the range of 0.01 g / 10 min or less, 0.01 g / 10 min or less, 0.01 g / 10 min or less, 0.01 g / 10 min or less, 0.01 g / 10 min or less, 0.01 g / 10 min or less, 0.01 g / 10 min or less, 0.01 g / 10 min or less, 0.01 g / 10 min or less, 0.01 g / 10 min or less, 0.01 g / 10 min or less, w / M n a first weight average molecular weight ("M") of 85,000 daltons or more, 120,000 daltons or more, 180,000 daltons or more, or 200,000 daltons or more, and / or 500,000 daltons or less, 400,000 daltons or less, 350,000 daltons or less, or 250,000 daltons or less; w1 "); and a first melt elasticity ("ER") of 1.0 or greater, 1.4 or greater, or 2.0 or greater.

[0095] The second LDPE recycle melt has a second density, where the ratio of the second density to the first density is 1.0 or more; a second melt index, where the ratio of the second melt index to the first melt index is 5.0 or more; a second molecular weight distribution, where the ratio of the second molecular weight distribution to the first molecular weight distribution is within the range of 0.60 to 0.99 or 0.75 to 0.95; and a second weight average molecular weight ("M w2 "), where M w2 / M w1 a second melt elasticity, wherein a ratio of the second melt elasticity to the first melt elasticity is in the range of 0.30 to 0.90, and / or the second melt elasticity is less than 1.0.

[0096] In further embodiments, the method is further characterized by one or more of the following: The LDPE recycle feedstock comprises post-consumer recycle waste, post-industrial recycle waste, or a combination thereof; The thinning decomposition conditions comprise thermal thinning decomposition, which in some examples is carried out at a temperature of 300° C. or higher, or at a temperature in the range of 320° C. to 400° C. The first LDPE recycle melt is further subjected to devolatilization conditions to produce the second LDPE recycle melt, the LDPE recycle feedstock having a first volatile organic compound content, the first LDPE recycle melt having a second volatile organic compound content, and a ratio of the second volatile organic compound content to the first volatile organic compound content is 0.9 or less, and in some examples, the devolatilization conditions are Injecting and withdrawing a scavenge gas. In some examples, the scavenge gas may be nitrogen, carbon dioxide, water, or a combination thereof; a vent condition, a vacuum condition, or a combination thereof; The second LDPE recycle melt is passed through a melt filter; An antioxidant is added to the first extruder; the LDPE recycle feedstock has a first high-load melt index (21.6 kg, 190° C.) and the second LDPE recycle melt has a second high-load melt index, the ratio of the second high-load melt index to the first high-load melt index being 2.0 or greater; The LDPE recycle raw material has a first melt index ratio (I 21 / I2), the second LDPE recycle melt has a second melt index ratio, and the ratio of the second melt index ratio to the first melt index ratio is in the range of 0.50 to 0.75, the LDPE recycle feedstock has a first long chain branching parameter (g'), the second LDPE recycle melt has a second g', the ratio of the second g' to the first g' being 1.0 or greater, and / or the processed LDPE recycle has a g' in the range of 0.40 to 0.75; the LDPE recycle feedstock has an overall polydispersity scale ("PDR") in the range of 0.40 to 0.75, the second LDPE recycle melt has a second PDR, and a ratio of the second PDR to the first PDR is less than or equal to 0.5; The LDPE recycle raw material has a first complex viscosity ratio (

number

[0097] In some embodiments, the aforementioned method further comprises forming a LDPE recycle product by withdrawing the second LDPE recycle melt from the first extruder for further processing or pelletizing of the second LDPE recycle melt.

[0098] In further embodiments of the aforementioned method, the LDPE recycle product and the first polyolefin blend component are added to a second extruder and compounding conditions are performed in the second extruder to form a polyolefin product comprising a molten mixture of the treated LDPE recycle product and the first polyolefin blend component. In some embodiments, such compounding conditions include a temperature of 300° C. or less. In some embodiments, the first polyolefin blend component comprises original polyolefin, polyolefin recycle feedstock, treated polyolefin recycle, or a combination thereof. In still further embodiments, the original polyolefin comprises original LDPE, original LLDPE, original HDPE, original MDPE, original polypropylene, or combinations thereof, the polyolefin recycle feedstock comprises LDPE recycle feedstock, LLDPE recycle feedstock, HDPE recycle feedstock, MDPE recycle feedstock, polypropylene recycle feedstock, or combinations thereof, and the treated polyolefin recyclerate comprises a second treated LDPE recycle, a treated LLLDPE recycle, a treated HDPE recycle, a treated MDPE recycle, a treated polypropylene recycle, or combinations thereof. In some embodiments, the first polyolefin blend component comprises original LDPE, LDPE recycle feedstock, a treated LDPE recycle, or combinations thereof.

[0099] In further embodiments of the aforementioned method, the LDPE recycle product is added in an amount ranging from 5% to 90% by weight, or from 20% to 60% by weight, based on the combined weight of the LDPE recycle product and the first polyolefin blend component; and / or the LDPE recycle product has a third weight average molecular weight ("M w3 "), and the first polyolefin blend component has a fourth weight average molecular weight ("M w4 "), and w3 / M w3 teeth 、 It is either 0.8 or less, or 1.25 or more.

[0100] In further embodiments of the aforementioned method, the first polyolefin blend component is a first original LDPE comprising a polymer product prepared in a first polymerization apparatus, and in some examples, the polymer product is subjected to a viscosity thinning decomposition process after polymerization, and in some embodiments, the viscosity thinning decomposition process comprises thermal viscosity thinning decomposition, peroxide viscosity thinning decomposition, or a combination thereof.

[0101] In a further embodiment of the foregoing method, the first polyolefin blend component comprises a polyolefin powder prepared in a first polymerization apparatus.

[0102] In a further embodiment of the above method, an antioxidant is added to the second extruder.

[0103] In a further embodiment of the aforementioned method, the method further comprises adding a second polyolefin blend component to a third extruder, implementing melting conditions in the third extruder to produce a second polyolefin blend component melt, and withdrawing the second polyolefin blend component melt as the first polyolefin blend component.

[0104] In a further embodiment of the foregoing method, the second polyolefin blend component comprises original LDPE, LDPE recycle feedstock, processed LDPE recycle, or combinations thereof.

[0105] In further embodiments of the foregoing methods, the second polyolefin blend component is subjected to a viscosity thinning cracking process after polymerization, and in some instances the viscosity thinning cracking process comprises thermal viscosity thinning cracking.

[0106] In a further embodiment of the foregoing process, the second polyolefin blend component comprises polyethylene powder and / or polyethylene pellets prepared in a second polymerization equipment.

[0107] In a further embodiment of the aforementioned process, the first and / or second polymerization apparatus each comprises two or more polymerization reactors and / or two or more polymerization zones within the polymerization reactor.

[0108] In further embodiments of the aforementioned process, the first and / or second polymerization apparatus each comprise two or more gas-phase fluidized bed reactors in series, two or more slurry-phase reactors in series, or a gas-phase fluidized bed reactor in series with a multi-zone circulating reactor.

[0109] In a further embodiment of the above method, an antioxidant is added to the third extruder.

[0110] In some embodiments, the composition comprises a polymer blend of a first polymer and a second polymer. The first polymer is a first treated LDPE recycle and is present in an amount ranging from 5% to 90% by weight. The second polymer is a parent polyolefin, a raw polyolefin recycle, a treated polyolefin recycle, or a combination thereof and is present in an amount ranging from 10% to 95% by weight. All weight percentages are based on the total weight of the first and second polymers.

[0111] In further embodiments of the foregoing compositions, the original polyolefin comprises original LDPE, original LLDPE, original HDPE, original MDPE, original polypropylene, or combinations thereof; the polyolefin recycle feedstock comprises original LDPE recycle feedstock, original LLDPE recycle feedstock, original HDPE recycle feedstock, original MDPE recycle feedstock, original polypropylene recycle feedstock, or combinations thereof; and the treated polyolefin recyclerate comprises a second treated LDPE recycle, a treated LLDPE recycle, a treated HDPE recycle, a treated MDPE recycle, a treated polypropylene recycle, or combinations thereof.

[0112] In further embodiments of the foregoing compositions, the treated means is subjected to thermal thinning decomposition or thermal thinning decomposition and devolatilization.

[0113] In some embodiments, the blend comprises a viscosified decomposed LDPE having a first I2 and a parent LDPE, a raw LDPE recycle, a processed LDPE recycle, or a combination thereof having a second I2;

number

[0114] In another aspect, foams comprising treated LDPE recycles as disclosed herein can be produced via chemical foaming processes or via physical foaming processes. Physically blown polyolefin foams are generally produced with blowing agents such as isobutane, pentane, and cyclopentane. Generally, physically blown polyolefin foams have the advantage of producing higher expansion and therefore lower density compared to chemically blown polyolefin foams. In some embodiments, the treated LDPE recycles can be blended with up to 50 wt.% HDPE, MDPE, LLDPE, LDPE, or combinations thereof prior to blowing. The treated LDPE recycles, alone or in combination with such other polymers, provide compositions suitable for the production of non-crosslinked or crosslinked low density polyethylene foams, and provide compositions suitable for non-crosslinked low density polyethylene foam embodiments. In some embodiments, foam precursor compositions comprising treated LDPE recycles include nucleating agents to increase cell density and modify cell formation and growth dynamics. In some embodiments, foams comprising treated LDPE recycles can have a foam density of 15 kg / m 3 ~60kg / m 3Such foams may be used in protective packaging for electronics, furniture, fruit, glassware, toys, or any other article for which cushioning protection from shock and / or vibration is desired, among others. The compositions and / or foams may also be used in protective packaging for articles for which insulation from heat is desired. Foams comprising treated LDPE recycles may be further characterized by average cell size, open cell content (measured according to ASTM D6226-15), compressive strength (measured according to ASTM D3575-14, suffix D), and insulating K-factor (measured according to GBT3399-1982). In some embodiments, the foams are formed by physically and / or chemically blowing a composition comprising treated LDPE recycles and, optionally, up to 5% by weight, up to 10% by weight, up to 20% by weight, or up to 50% by weight of a parent polyolefin. In some embodiments, the parent polyolefin comprises parent LDPE, parent LLDPE, parent HDPE, parent MDPE, parent polypropylene, or a combination thereof.

[0115] The following examples are illustrative of the present invention. However, those skilled in the art will recognize many variations within the spirit of the present invention and the scope of the claims. In order to facilitate a better understanding of the present invention, the following are examples of preferred embodiments. The following embodiments should not be construed as limiting or defining the scope of the present invention. EXAMPLES

[0116] The following examples are included to illustrate preferred embodiments of the present invention. Those skilled in the art will appreciate that the techniques disclosed in the following embodiments represent techniques that the inventors have discovered to work well in embodiments of the present invention and can be considered to constitute preferred forms of embodiments of the present invention. However, those skilled in the art will appreciate, in light of this disclosure, that many changes can be made in the specific embodiments disclosed and still obtain the same or similar results without departing from the spirit and scope of the present invention.

[0117] The following examples use a commercially available LDPE composition having a low melt index as a proxy for the LDPE recycle feedstock. After processing, the degraded low melt index LDPE, either alone or in blends with other components as described herein, is compared to the higher melt index parent LDPE.

[0118] Test Method The density was measured according to ASTM D-4703 and ASTM D-1505 / ISO-1183.

[0119] High Load Melt Index ("I 21 ") was measured according to ASTM D-1238-F (190°C / 21.6 kg).

[0120] Shear rheological measurements were performed according to ASTM 4440-95a to characterize the dynamic viscoelastic properties (storage modulus G′, loss modulus G″ and complex viscosity η** as a function of oscillation frequency ω). A rotational rheometer (TA Instruments) is used for the rheological measurements. A 25 mm parallel plate fixture was utilized. Samples were compression molded into disks (diameter approximately 29 mm, thickness approximately 1.3 mm) using a hot press at 190 °C. Oscillatory frequency sweep experiments (from 398.1 rad / s to 0.0251 rad / s) were performed at 190 °C. ℃ The applied strain amplitude was about 10% and the operating gap was set at 1 mm. A nitrogen flow was applied to the sample chamber to minimize thermal oxidation during the measurements.

[0121] Melt Elasticity ("ER") is determined as described by R. Shroff and H. Mavridis, "New Measures of Polydispersity from Rheological Data on Polymer Melts", J. Applied Polymer Science 57 (1995)1605, as described in U.S. Patent Nos. 7,238,754, 6,171,993, and 5,534,472 (column 10, lines 20-30), the teachings of which are incorporated herein by reference. Thus, the storage modulus (G') and loss modulus (G") are measured. The nine lowest frequency points are used (five points in tenths of a frequency) and a linear equation is fitted by least squares regression to log G' vs. log G". Then, ER is calculated as ER=(1.781×10 -3 )×G', G''=5,000 dyn / cm 2 The same ER calculation program and equations were used for linear and long chain branched polyolefins.

[0122] PDR, or "total polydispersity measure", is a method of measuring the polydispersity of polymers by R. Shroff and H. Mavridis, "New Measures of Polydispersity from Rheological Data on Polymer Melts", J. Applied Polymer Science 57 (1995) 1605, Eq. 27, p. 1619, G* ref,1 =1.95*10 4 dyn / cm 2 and log 10 (G* ref,3 / G* ref,1 )=2. The same program and equations for the PDR calculations were used for both linear and long chain branched polyolefins.

[0123] complex viscosity

number

number

number

[0124] Melt index ("I2") was measured by ASTM D-1238-E (190°C / 2.16 kg).

[0125] Molecular weight distribution ("MWD") and molecular weight average (number average molecular weight M n , weight average molecular weight M w , and z average molecular weight M z ) is determined using high temperature polymer charge gel permeation chromatography ("GPC"), also known as size exclusion chromatography ("SEC"), equipped with a filter-based infrared detector IR5, a 4-capillary differential bridge viscometer, and a Wyatt 18 angle light scattering detector. w , M n, MWD and short chain branching (SCB) curves are reported, and the long chain branching index g' was measured at 145 °C using a combination of a viscometer and an infrared detector. Polymer classification was performed based on hydrodynamic size in 1,2,4-trichlorobenzene (TCB) using three Anchillen PLgel Olexis GPC columns at 145 °C, in which 300 ppm of the antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase. 16 mg of polymer was weighed into a 10 mL vial and sealed for GPC measurement. The dissolution process was obtained automatically (in 8 ml TCB) at 160 °C for 1 h with continuous shaking in an Agilent autosampler. 20 μL heptane is also injected into the vial as a flow marker during the dissolution process. After the dissolution process, 200 L of solution was injected into the GPC column. The GPC column was calibrated based on 12 monodisperse polystyrene (PS) standards (provided by PSS) ranging from 578 g / mol to 3,510,000 g / mol. Comonomer composition (or SCB distribution) was reported based on different calibration distributions obtained with a relatively narrow series of polyethylenes (Polymer Carbon provides polyethylenes with 1-hexene and 1-octene comonomers and internally synthesizes polyethylenes with 1-butene comonomer) with known values ​​of CH3 / 1000 total carbon measured using established solution NMR techniques. Data were analyzed using GPC-one software. The long chain branching parameter g' is determined by the following equation:

[0126]

number

[0127]

number

number

[0128] Volatile organic compounds ("VOCs") are measured by pyrolysis gas chromatography / mass spectrometry ("P-GC / MS") in parts per billion (ppb), parts per million (ppm), or micrograms per cubic meter (μg / m 3 ) is measured.

[0129] The zero shear viscosity η is determined using the Sabia equation fit of dynamic complex viscosity versus radian frequency as described in Shroff & Mavridis (1999) "A Long Chain Branching Index for Essentially Linear Polyethylenes", Macromolecules, 32, 8454-8464 (focusing on Appendix B), the disclosure of which is fully incorporated herein by reference in its entirety.

[0130] raw materials The raw materials used here are shown in Table 1.

[0131] Table 1 [Table 1] *190°C / 2.16kg **All materials available from LyondellBasell Industries NV Examples 1 to 3 Examples 1-3 in Table 2 show the results of a viscosity-thinning cracking of an LDPE resin. P1 is believed to be fairly representative of the LDPE recycle feedstock. Before treatment, P1 (an LDPE recycle feedstock proxy) had a viscosity of 0.923 g / cm 3 and a melt index I2 of 0.62 g / 10 min. The results of Example 1 in Table 2 show some other properties of P1.

[0132] Examples 2 and 3 were prepared by thinning cracking a portion of P1. Thinning cracking was performed by feeding P1 into a Werner and Pfleiderer ZSK40 twin screw extruder at a feed rate of 50 pounds per hour, a screw speed of 600 rpm, and a target temperature profile (from inlet to die) of 200 / 250 / 325 / 325 / 325 / 325 / 325 / 325 / 325°C. The extrudate was ground into granules. Different screw designs were used in Examples 2 and 3, and the energy input to the polymer in the extruder was increased in Example 3 compared to Example 2. The visbroken P1 of Example 2, which used the first extruder screw design, is labeled P1-vb1, and the visbroken P1 of Example 3, which used the second extruder screw design, is labeled P1-vb2 in Table 2.

[0133] Example 2 shows that the melt index I2 of P1 increases 6.3-fold by the thinning decomposition, while the density and long chain branching parameter g increase only nominally. Example 3 shows that the melt index I2 of P1 increases 7.7-fold by the thinning decomposition, while the long chain branching parameter g increases only nominally. The larger increase in melt index I2 of Example 3 compared to Example 2 is due to the specific energy input ("SPE") to the polymer of 0.499 kW.hr / kg for Example 3 versus 0.457 kW.hr / kg for Example 2.

[0134] Example 2 shows the high load melting index I 21 increased by 3.9 times due to the thinning decomposition, and the melt index ratio (I 213. The melt elasticity ("ER") is reduced by about a third for both Examples 2 and 3. The overall polydispersity ratio ("PDR") is reduced by more than half for both Examples 2 and 3.

[0135] Compared with P1, in Examples 2 and 3, the complex viscosity

number

number

number

number

[0136] In comparison with P1, in Examples 2 and 3, the number average molecular weight (M n ) decreased by 16% and 22%, respectively, and the weight average molecular weight (M w ) decreased by 26% and 27%, and the Z-average molecular weight (M z ) is reduced by 19% and 20%. In Examples 2 and 3, the molecular weight distribution (M w / M n ) decreased by 12% and 7%, and the molecular weight ratio (M z / M w ) will increase by 9% and 10%, respectively.

[0137] Table 2 [Table 2] vb = reduced viscosity decomposition The dynamic vibration data generated based on the analysis of the P1 and P1-vb samples is shown in Table 3 below. The data in Table 3 shows that the complex viscosity decreases as frequency increases for both P1 and P1-vb1. Table 3 further shows that the viscosity-thinning decomposition P1 results in a lower complex viscosity (η*) for P1-vb1 for all tested values ​​of frequency. In addition, the difference in complex viscosity between P1 and P1-vb1 decreases as frequency increases. Applicant believes this is due to the viscosity-thinning decomposition having a greater impact on the higher molecular weight chains in the LDPE, i.e., more chain scission, as well as a narrower MWD (M) for P1-vb1 compared to P1, although Applicant does not wish to be bound by any particular theory. w / M n ) is believed to show that the viscosity of the composite material is greater than that of the composite material. FIG. 4 shows a comparison of the curves generated for Example 1 and Example 2 based on the data in Table 3. The overlay plot shows the logarithm of the complex viscosity (η*) in poise as a function of the logarithm of the vibration frequency (radians / sec).

[0138] Table 3 [Table 3] For the sake of brevity, only certain ranges are expressly disclosed herein.However, in addition to the ranges listed, any lower limit can be combined with any upper limit to list a range that is not expressly listed, and a range from any lower limit can be combined with any other lower limit to list a range that is not expressly listed, and similarly, a range from any upper limit can be combined with any other upper limit to list a range that is not expressly listed.In addition, a range includes every point or individual value between its end points, even if it is not expressly listed.Therefore, every point or individual value can act as its own lower limit or upper limit in combination with any other point or individual value or any other lower limit or upper limit to list a range that is not expressly listed.

[0139] Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and modifications can be made herein without departing from the spirit and scope of the present invention as defined by the appended claims. Moreover, the scope of the present specification is not intended to be limited to the specific embodiments of the processes, machines, film structures, layer compositions, apparatus, methods, and / or steps described herein. As one skilled in the art can readily appreciate from the present disclosure, any currently existing or hereafter developed processes, machines, film structures, layer compositions, means, methods, and / or steps that function substantially the same as the corresponding embodiments described herein or achieve substantially the same results can be utilized in accordance with the present invention. Thus, the claims are intended to include these processes, machines, film structures, layer compositions, apparatus, methods, and / or steps.

Claims

1. A method for processing low-density polyethylene (LDPE) recycled, a. A step of providing an LDPE recyclable raw material having the following: i) 0.910g / cm ３ ~0.940g / cm ３ The first density in the range, ii) First melting index (I) of 5.0 g / 10 min or less ２ )and, iii) First molecular weight distribution greater than 4.0 (M ｗ / M ｎ )and, iv) First weight-average molecular weight of 85,000 Daltons or more ("M ｗ１ ")and, v) A first melt elasticity ("ER") of 1.0 or higher, b. The step of adding the LDPE recyclable raw material to the first extruder to produce a first LDPE recyclable melt, c. The first LDPE recyclate melt is subjected to viscosity reduction decomposition conditions to produce a second LDPE recyclate melt having the following: i) A second density wherein the ratio of the second density to the first density is 1.0 or greater, ii) A second melt index, wherein the ratio of the second melt index to the first melt index is 5.0 or greater, iii) A second molecular weight distribution wherein the ratio of the second molecular weight distribution to the first molecular weight distribution is in the range of 0.60 to 0.99, and iv) a second weight average molecular weight (“M ｗ２ ”), where M ｗ２ / M ｗ１ is in the range of 0.60 to 0.99, and the second weight average molecular weight v) A second melt elasticity, wherein the ratio of the second melt elasticity to the first melt elasticity is in the range of 0.30 to 0.90, and Includes, A method in which the first melting index and the second melting index are measured according to ASTM D-1238 under the conditions of 2.16 kg and 190°C.

2. The method according to claim 1, wherein the LDPE recyclable raw material includes post-consumer recyclable waste, post-industrialization recyclable waste, or a combination thereof.

3. The method according to claim 1, wherein the viscosity reduction decomposition conditions consist of thermal viscosity reduction decomposition.

4. The method according to claim 3, wherein the thermal deviscation is carried out at a temperature of 300°C or higher.

5. The steps include subjecting the first LDPE recyclable melt to devolving conditions to produce the second LDPE recyclable melt, and further comprising: The LDPE recyclable raw material has a first volatile organic compound content, The first LDPE recyclable melt has a second volatile organic compound content, The method according to claim 1, wherein the ratio of the content of the second volatile organic compound to the content of the first volatile organic compound is 0.9 or less.

6. The method according to claim 5, wherein the devolving conditions include injecting and withdrawing scavenging gas.

7. The above method is characterized by one or more of the following: i) The LDPE recyclable raw material has a first high-load melting index (I ２１ ) has, The second LDPE recyclable melt has a second high-load melting index, and the ratio of the second high-load melting index to the first high-load melting index is 2.0 or greater. ii) The LDPE recyclable raw material has a first melting index ratio (I ２１ / I ２ The second LDPE recyclable melt has a second melting index ratio, and the ratio of the second melting index ratio to the first melting index ratio is in the range of 0.50 to 0.

75. iii) The LDPE recyclable raw material has a first long-chain branching parameter (g') in the range of 0.40 to 0.75, the second LDPE recyclable melt has a second g', and the ratio of the second g' to the first g' is 1.0 or more. iv) The LDPE recyclate raw material has an overall polydispersity measure ("PDR"), the second LDPE recyclate melt has a second PDR, and the ratio of the second PDR to the first PDR is 0.5 or less. v) The LDPE recyclable raw material has a first composite viscosity ratio, the second LDE recyclable melt has a second composite viscosity ratio, the ratio of the second composite viscosity ratio to the first composite viscosity ratio is 0.40 or less, and / or the second composite viscosity ratio is 12 or less. vi) The LDPE recyclable raw material has a first intrinsic viscosity, the second LDPE recyclable melt has a second intrinsic viscosity, and the ratio of the second intrinsic viscosity to the first intrinsic viscosity is 0.85 or less. The method according to claim 1, wherein the first high-load melting index and the second high-load melting index are measured under the conditions of 2.16 kg and 190°C, based on ASTM D-1238.

8. The method according to claim 1, wherein an LDPE recyclate product is formed by drawing the second LDPE recyclate melt from the first extruder for further processing or pelletizing of the second LDPE recyclate melt.

9. The method according to claim 8, The steps include adding the LDPE recyclate product and the first polyolefin blend component to the second extruder, The method according to claim 8, further comprising the step of carrying out compounding conditions in the second extruder to form a polyolefin product comprising a molten blend mixture of the treated LDPE recycle product and the first polyolefin blend component.

10. The method according to claim 9, wherein the first polyolefin blend component comprises an original polyolefin, a polyolefin recyclable raw material, a treated polyolefin recyclable, or a combination thereof.

11. The method according to claim 9, wherein the LDPE recyclate product is added in an amount ranging from 5% to 90% by weight, based on the combined weight of the LDPE recyclate product and the first polyolefin blend component.

12. The method according to claim 9, wherein the compounding conditions include a temperature of 300°C or lower.

13. The step of adding a second polyolefin blend component to a third extruder, The third extruder comprises a step of influencing the melting conditions for generating the second polyolefin blend component melt, The method according to claim 9, further comprising the step of extracting a melt of the second polyolefin blend component as the first polyolefin blend component.

14. The method according to claim 13, wherein the second polyolefin blend component comprises original LDPE, LDPE recyclable raw material, processed LDPE recyclable, or a combination thereof.

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