Recyclable multilayered polymeric structure with thermal resistance and barrier properties and uses thereof

Abstract

The present disclosure pertains to recyclable multilayered polymeric structures comprising a number N of layers. Said recyclable multilayered polymeric structures comprise an outer surface layer N1, an inner surface layer N2, and optionally one or more layers between N1 and N2. Said recyclable multilayered polymeric structures comprise at least two different layers. The outer surface layer N1 is a barrier layer comprising a first polymer P1, P1 is polyethylene-based polymer with an ethylene content of at least about 50 mol% functionalized with polar groups and having an oxygen transmission rate (OTR) below 30 cc•20µm / m2•atm•day; a melting temperature above 160°C; a moisture resistance characterized by a water vapor transmission rate (WVTR) of less than 2 g•mm / m2•atm•day; and a density below 1.10 g / cm3. Said recyclable multilayered polymeric structures are for use in packaging applications, such as food packaging, building liners, geomembranes, pipes or containers for liquids.

Description

[0001] RECYCLABLE MULTILAYERED POLYMERIC STRUCTURE WITH THERMAL RESISTANCE AND BARRIER PROPERTIES AND USES THEREOF

[0002] TECHNICAL FIELD

[0003] The present disclosure relates to recyclable multilayered polymeric structures, focusing on their composition, manufacturing processes, and a range of applications, including for instance protection from high-oxygen and water-sensitive environments.

[0004] BACKGROUND

[0005] Historically, the plastics industry has relied on multi-material structures to meet diverse application requirements. These structures, comprising different polymer layers, each providing specific properties, can present challenges in recycling and sustainability. For example, materials such as Polyamides (PA) or Polyethylene Terephthalate (PET) are often used in food packaging but may be difficult to recycle.

[0006] The limitations associated with the use of materials such as Polyamides (PA) in certain applications can be also attributed to other factors. Firstly, there can be an issue of low compatibility between PA and Polyethylene (PE), which is also a commonly used material in various packaging applications. This incompatibility can present challenges in creating quality recycled materials. Secondly, PA requires higher melting and processing temperatures compared to PE. This disparity in thermal properties can complicate the manufacturing process but also increase energy consumption and operational costs, making PA less favorable for applications where PE is traditionally used.

[0007] PET / PE structures can also be used in packaging, but these structures may also be difficult to recycle.

[0008] Food packaging lines demand materials with high temperature resistance to maintain efficient operational speeds. Recently, Biaxially Oriented Polyethylene (BOPE) has emerged as an alternative, yet its adoption is hindered by high costs and operational constraints.

[0009] Another packaging property is the gas / aroma / chemical barrier properties that is required in various applications such as for extending the shelf life of food products and safely containing chemicals in packaging solutions. Common materials like Ethylene Vinyl Alcohol (EVOH) and Aluminum Oxide (AIOX) layers offer these properties but may not be conducive to recyclability.

[0010] Ethylene Vinyl Alcohol (EVOH) is widely utilized in the packaging industry. Despite its extensive use, EVOH's application as an outer layer in packaging is limited due to its high sensitivity to moisture. This sensitivity leads to EVOH's swelling in humid environments, compromising the integrity of the packaging. Additionally, handling EVOH as an outer layer poses challenges, particularly at high temperatures, where its tendency to become sticky complicates processing. Moreover, there can be limitations regarding the proportion of EVOH that can be included in products designed for recyclability. These constraints can restrict EVOH's use in various packaging applications, necessitating the exploration of alternative materials.

[0011] These limitations underscore the need for innovative material solutions that can bridge the compatibility gap between these commonly used polymers, facilitating the creation of more efficient and environmentally friendly recyclable packaging options.

[0012] Integrating all these polymers in a common multilayer structure may complicate the recycling process, contradicting the growing demand for environmentally friendly products. Currently, high barrier multilayer compositions are mostly not recyclable and fall under “single-use” plastics category. In the existing recyclable technologies, challenges may be encountered to provide high barrier packaging having high sealing temperatures, compared with conventional solutions. In addition, producing recyclable structures having double side treated print web film for several unique applications may be difficult. Providing high oxygen barrier resin with low moisture sensitivity in a way that its gas transmission rates stay more stable in various environments may also be complicated. In the currently known technologies, it may also be demanding to obtain recyclable high barrier structures that can withstand higher service temperature than PE.

[0013] Herein are disclosed multilayered polymeric structures that can address at least some of the current technologies’ drawbacks.

[0014] SUMMARY

[0015] In accordance with an aspect, there is provided a recyclable multilayered polymeric structure comprising a number N of layers with N > 2, wherein the recyclable multilayered polymeric structure comprises:

[0016] an outer surface layer N1 , which is a first barrier layer BL1 comprising a first polymer P1 comprising polar functional groups; and

[0017] an inner surface layer N2 comprising a non-polar polymer P or a second barrier layer BL2 comprising a second polymer P2 comprising polar functional groups; and optionally one or more layers between layer N1 and layer N2;

[0018] wherein at least two layers of the recyclable multilayered polymeric structure are different, and wherein the first polymer P1 comprising polar functional groups is a functionalized polyethylene-based polymer with an ethylene content of at least about 50 mol% and having:

[0019] an oxygen transmission rate (OTR) below about 30 cc*20pm / m2*atm*day at about 0% relative humidity (RH);

[0020] a melting temperature above 160°C;

[0021] a moisture resistance characterized by a water vapor transmission rate (WVTR) of less than about 2 g*mm / m2*atm*day; and

[0022] a density below about 1.10 g / cm3.

[0023] In an optional aspect, the recyclable multilayered polymeric structure as defined herein, is such that at least one of the barrier layers BL1 , BL2 and BL3 provide protection from pollutants, chemicals and / or gases.

[0024] In another optional aspect, at least one of the layers of the recyclable multilayered polymeric structure as defined herein, such as at least one of the barrier layers, e.g., at least the BL1 layer, provide protection from moisture.

[0025] In another optional aspect, the first barrier layer BL1 of the recyclable multilayered polymeric structure as defined herein is a gas barrier.

[0026] In another optional aspect, the first barrier layer BL1 of the recyclable multilayered polymeric structure as defined herein is an oxygen barrier.

[0027] According to another aspect, there is provided the use of the recyclable multilayered polymeric structure as defined herein in a packaging.

[0028] According to another aspect, there is provided the use of the recyclable multilayered polymeric structure as defined herein in a flexible packaging, a semi-rigid packaging or a rigid packaging. According to another aspect, there is provided the use of the recyclable multilayered polymeric structure as defined herein in food packaging.

[0029] According to another aspect, there is provided the use of the recyclable multilayered polymeric structure as defined herein in a liner, a pouch, a shrink bag or a bottle.

[0030] According to another aspect, there is provided the use of the recyclable multilayered polymeric structure as defined herein in building liners, geomembranes, pipes or containers for liquids. BRIEF DESCRIPTION OF THE FIGURES

[0031] Figure 1 represents a 3-layer polymeric structure according to one embodiment. Layer 100 is the outer surface layer N1 , layer 101 is a tie layer and layer 102 is the inner surface layer N2.

[0032] Figure 2 represents a 4-layer polymeric structure according to another embodiment. Layer 200 is the outer surface layer N1 , layer 201 is a tie layer, layer 202 is a polyolefin layer and layer 203 is the inner surface layer N2.

[0033] Figure 3 represents a 3-layer polymeric structure according to another embodiment. Layer 300 is the outer surface layer N1 , layer 301 is a tie layer and layer 302 is the inner surface layer N2.

[0034] Figure 4 represents an 8-layer polymeric structure according to another embodiment. Layer 400 is the outer surface layer N1 , layer 401 is a tie layer, layer 402 is a polyolefin layer, layer 403 is a polyolefin layer, layer 404 is tie layer, layer 405 is a barrier layer (e.g., BL3), layer 406 is a tie layer and layer 407 is the inner surface layer N2.

[0035] Figure 5 represents a 5-layer polymeric structure according to another embodiment. Layer 500 is the outer surface layer N1 , layer 501 is a tie layer, layer 502 is a polyolefin layer, layer 503 is a tie layer and layer 504 is the inner surface layer N2.

[0036] Figure 6 represents a 2-layer polymeric structure according to another embodiment. Layer 600 is the outer surface layer N1 and layer 601 is the inner surface layer N2.

[0037] Figure 7 represents a 5-layer polymeric structure according to another embodiment. Layer 700 is the outer surface layer N1 , layer 701 is a tie layer, layer 702 is a barrier layer (e.g., BL3), layer 703 is a tie layer and layer 704 is the inner surface layer N2.

[0038] DETAILED DESCRIPTION

[0039] All technical and scientific terms used herein have the same meaning as commonly understood by one ordinary skilled in the art to which the present technology pertains. For convenience, the meaning of certain terms and phrases used herein are provided below.

[0040] T o the extent the definitions of terms in the publications, patents, and patent applications incorporated herein by reference are contrary to the definitions set forth in this specification, the definitions in this specification control. The section headings used herein are for organizational purposes only, and are not to be construed as limiting the subject matter disclosed.

[0041] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. It should be noted that, the singular forms "a", "an", and "the" include plural forms as well, unless the content clearly dictates otherwise. Thus, for example, reference to a composition containing "a compound" also contemplates a mixture of two or more compounds. It should also be noted that the term "or" is generally employed in its sense including "and / or" unless the content clearly dictates otherwise. Furthermore, to the extent that the terms “including”, "includes", "having", "has", "with", or variants thereof are used in either the detailed description and / or the claims, such terms are intended to be inclusive in a manner similar to the term "comprising”. The term "about" means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, "about" can mean within 1 or more than 1 standard deviation, per the practice in the art. Alternatively, "about" can mean a range of up to 20%, preferably up to 10%, more preferably up to 5%, and more preferably still up to 1 % of a given value. Alternatively, particularly with respect to biological systems or processes, the term can mean within an order of magnitude, preferably within 5-fold, and more preferably within 2-fold, of a value. Where particular values are described in the application and claims, unless otherwise stated the term "about" meaning within an acceptable error range for the particular value should be assumed.

[0042] “ASTM D3985” used herein refers to ASTM D3985-17, Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film and Sheeting Using a Coulometric Sensor. “ASTM D638” used herein refers to ASTM D638-14, Standard Test Method for Tensile Properties of Plastics. “ASTM D792” refers to Standard Test Method for Density of Plastics. “ASTM D1238” refers to Standard Test Method for the determination of Melt Flow Index (MFI) and High Load Melt Index (HLMI) of Plastics. “ASTM D624” refers to Standard Test Method for the determination of the Heat Deflection Temperature (HDT) of Plastics. “ASTM D3418” refers to Standard Test Method for the determination of the Melt Temperature of Plastics. “ASTM F1249” refers to Standard Test Method for Water Vapor Transmission rate determination. “ASTM D570” refers to Standard Test Method for Water adsorption determination. “ASTM F88” refers to Standard Test Method for seal strength test for Plastics. “ASTM F3300” refers to Standard Test Method for abrasion resistance test for Plastics. “ASTM D6988” refers to Standard Guide for Determination of Thickness of Plastic Film Test Specimens. “ASTM D1922” refers to Standard Test Method for Propagation Tear Resistance of Plastic Film and Thin Sheeting by Pendulum Method. “ASTM D882” refers to Standard Test Method for Tensile Properties of Thin Plastic Sheeting. “ASTM D1709” refers to Standard Test Methods for Impact Resistance of Plastic Film by the Free-Falling Dart Method.

[0043] Recyclability of various plastics products are determined by different criteria worldwide. One of the most prominent organizations that has special protocol for determining the recyclability of plastics products is Association of Plastics Recyclers (APR) which publishes strict protocols for recyclability in PE recycling stream for North America. The present disclosure pertains to recyclable multilayered polymeric structures characterized by thermal resistance and barrier properties, and uses thereof. The recyclable multilayered polymeric structures described herein can balance high barrier capabilities with recyclability, and can thus address environmental concerns and regulatory demands for lower carbon footprint materials.

[0044] Recyclable multilayered polymeric structure

[0045] The recyclable multilayered polymeric structure of the present disclosure primarily comprises i) a first barrier layer comprising a first polymer P1 comprising polar functional groups, ii) a non-polar polymer P, or a second barrier layer comprising a second polymer P2 comprising polar functional groups, and iii) an optional adhesive or tie layer. This configuration is engineered to simplify the structure of multilayer products and overcome at least some of the limitations of traditional high barrier packaging materials, which often suffer from poor recyclability, over-engineering, and / or high production costs. The recyclable multilayered polymeric structure of the present disclosure comprises a number N of layers with N > 2, wherein the recyclable multilayered polymeric structure comprises:

[0046] - an outer surface layer N1 , which is a first barrier layer BL1 comprising a first polymer P1 comprising polar functional groups; and

[0047] - an inner surface layer N2 comprising a non-polar polymer P or a second barrier layer BL2 comprising a second polymer P2 comprising polar functional groups; and - optionally one or more layers between layer N1 and layer N2,

[0048] wherein at least two layers of the recyclable multilayered polymeric structure are different.

[0049] The term “outer surface” as used herein, refers to the surface of the recyclable multilayered polymeric structure, which is in contact with the exterior environment, such as air or water. Preferably, the exterior environment is air.

[0050] The term “inner surface” as used herein, refers to the surface of the recyclable multilayered polymeric structure, which is generally facing or is in contact with the interior environment. In some embodiments, the interior environment can be the inside of a packaging. In some embodiments, the inner surface can face or be in contact with any material / goods to be contained in and / or transported within an article made of the recyclable multilayered polymeric structure. In some embodiments, the inner surface faces or is in contact with a food product, water or chemical fluids. In some embodiments, the article can comprise a bag for containing goods, and the inner surface will be facing or be in contact with the goods. In other embodiments, the recyclable multilayered polymeric structure can be used as a film to protect goods for instance, and the inner surface will correspond to the surface of the film facing or being in contact with the goods to be protected from the outer environment. In other embodiments, the recyclable multilayered polymeric structure can be used to manufacture a pipe and the inner surface will be facing or be in contact with the material to be transported through the pipe. In some embodiments, the inner surface of the recyclable multilayered polymeric structure can itself be laminated to another material / film.

[0051] In some embodiments, the recyclable multilayered polymeric structure can comprise one or more layers between the layer N1 and the layer N2. In some embodiments, the recyclable multilayered polymeric structure can comprise one or more of a third barrier layer BL3, one or more of a tie layer, and / or one or more of a polyolefin layer, provided that when the recyclable multilayered polymeric structure comprises two or more third barrier layers BL3 and / or two or more tie layers then each one of the third barrier layers BL3 are not juxtaposed and each one of the tie layers are not juxtaposed. In some embodiments, the layer N1 is juxtaposed to one tie or adhesive layer. In some embodiments, the recyclable multilayered polymeric structure can comprise one or more of a third barrier layer BL3, one or more of a tie layer, and / or one or more of a polyolefin layer, provided that when the recyclable multilayered polymeric structure comprises two or more third barrier layers BL3 and / or two or more tie layers then each one of the third barrier layers BL3 are not juxtaposed and each one of the tie layers are not juxtaposed, and provided that the layer N1 is juxtaposed to one tie or adhesive layer. The third barrier layer BL3 can comprise a third polymer P3 which can comprise polar groups.

[0052] In the present description, polymers P1 , P2 and / or P3, which can comprise polar functional groups, can also be referred to as “polar polymer(s)”.

[0053] In some embodiments, the barrier layers comprising polar polymers P1 , P2 and P3, and the polyolefin layers, can qualify as incompatible layers depending on the olefinic content of said polar polymers. Incompatible layers cannot be juxtaposed, therefore a tie layer can be used in between two incompatible layers. In some embodiments, barrier layers BL1 , BL2 or BL3 can comprise olefinic moieties and the olefinic content of such barrier layers BL1 , BL2 or BL3 comprising respectively polar polymer(s) P1 , P2 and P3, can be less than 50 mol%, and the surface tension between the polar polymers and the non-polar polymers and / or the polyolefin layers can be such that a tie layer may be needed in between to provide suitable cohesion.

[0054] As used herein, the term “incompatible” refers to the inability of different polymers to mix, bond, or co-process effectively, resulting in phase separation or weakened mechanical properties after mixing (recycling).

[0055] In some embodiments, the recyclable multilayered polymeric structure can be free of a tie layer or an adhesive layer depending on the olefinic content of the polar polymers P1 , P2 and / or P3. When the olefinic content is at least 50 mol%, the level of surface tension between P1 , P2 and / or P3 and the non-polar polymer P and / or the polyolefin layers becomes so similar that a tie layer may not be needed.

[0056] In some embodiments, the recyclable multilayered polymeric structure can comprise a number N of layers with N > 2. In some embodiments, N is between 2 and 11 , N is between 2 and 10, N is between 2 and 9, or N is between 2 and 8. In some embodiments, N is 2, N is 3, N is 4, N is 5, N is 6, N is 7, N is 8, N is 9, N is 10, or N is 11.

[0057] In some embodiments, the recyclable multilayered polymeric structure can be such that N = 3 and one tie layer is used between the outer surface layer N1 and the inner surface layer N2.

[0058] In some embodiments, when N = 4, the recyclable multilayered polymeric structure can comprise: the layer N1 , the layer N2 which comprises the non-polar polymer P, and in between the layer N1 and the layer N2 successively, a barrier layer BL3 and a tie layer.

[0059] In some embodiments, when N = 4, the recyclable multilayered polymeric structure can comprise: the layer N1 , the layer N2 which comprises the non-polar polymer P, and in between the layer N1 and the layer N2 successively, a first tie layer and a first polyolefin layer.

[0060] In some embodiments, the recyclable multilayered polymeric structure can be such that N > 4 and one tie layer is intercalated between any incompatible layer present in the recyclable multilayered polymeric structure.

[0061] In some embodiments, when N = 5, the recyclable multilayered polymeric structure can comprise: the layer N1 , the layer N2 which comprises the second polymer P2, and in between the layer N1 and the layer N2 successively, a first tie layer, a first polyolefin layer and a second tie layer.

[0062] In some embodiment, when N = 5, the recyclable multilayered polymeric structure can comprise: the layer N1 , the layer N2 which comprises the non-polar polymer P, and in between the layer N1 and the layer N2 successively, a first tie layer, BL3 and a second tie layer.

[0063] In some embodiments, when N = 8, the recyclable multilayered polymeric structure can comprise: the layer N1 , the layer N2 which comprises the non-polar polymer P, and in between the layer N1 and the layer N2 successively, a first tie layer, a first polyolefin layer, a second polyolefin layer, a second tie layer, a third barrier layer BL3 and a third tie layer.

[0064] In another embodiment, at least one of the said layers is selected for providing at least one specific behaviour property to the structure.

[0065] In some embodiments, the layer N1 can be about 2 pm to about 20 pm thick. In some embodiments, the layer N2 can be about 8 pm to about 50 pm thick.

[0066] In some embodiments, a total thickness of the recyclable multilayered polymeric structure can be between about 10 pm and about 400 pm, between about 10 pm and about 300 pm, between about 10 pm and about 200 pm, or between about 10 pm and about 100 pm. In some embodiments, a total thickness of the recyclable multilayered polymeric structure can be between about 20 pm and about 120 pm. In some embodiments, a total thickness of the recyclable multilayered polymeric structure can be between about 25 pm and about 120 pm. In some embodiments, a total thickness of the recyclable multilayered polymeric structure can be between about 25 pm and about 80 pm. Possible layouts of the recyclable multilayered polymeric structure are represented in Figures 1 to 7. One will understand that other layouts can be contemplated. The recyclable multilayered polymeric structure 10 comprise an outer surface 10a which, in use, faces or is in contact with the outer environment 30 and an inner surface 10b, which in use, faces or is in contact with the inner environment 20. In use, the inner surface 10b will face or be in contact with any material / goods to be contained in and / or transported within an article made of the recyclable multilayered polymeric structure. In some embodiments, the article can comprise a bag for containing goods, and the inner surface 10b will face or be in contact with the goods, while the outer surface 10a will form the outer of the bag. In other embodiments, the recyclable multilayered polymeric structure can be used as a film to protect goods for instance, and the inner surface 10b will correspond to the surface of the film to face or to be in contact with the goods to be protected from the outer environment. In other embodiments, the recyclable multilayered polymeric structure can be used to manufacture a pipe and the inner surface 10b will face or be in contact with the material to be transported through the pipe. In some embodiments, the outer surface 10a of the recyclable multilayered polymeric structure will be in contact with air as the outer environment.

[0067] In some embodiments, the recyclable multilayered polymeric structure can be a 2-layer polymeric structure. In some embodiments, a recyclable 2-layer polymeric structure can be as represented in Figure 6. As shown in Figure 6, layer 600 is the outer surface layer N1 and layer 601 is the inner surface layer N2 of the recyclable multilayered polymeric structure. In some embodiments, layer 600 comprises the first polymer P1 and layer 601 comprises the non-polar polymer P. In some embodiments, layer 600 can comprise a Grinloop® product and layer 601 can comprise polyethylene. In some embodiments, the recyclable multilayered polymeric structure can be a 3-layer polymeric structure. In some embodiments, a recyclable 3-layer polymeric structure can be as represented in Figure 1. In Figure 1 , layer 100 is the outer surface layer N1 , layer 101 is a tie layer and layer 102 is the inner surface layer N2. In some embodiments, layer 100 comprises the first polymer P1 and layer 102 comprises the non-polar polymer P. In some embodiments, layer 100 comprises a Grinloop® product and layer 102 comprises a polyethylene. In some embodiments, a recyclable 3-layer polymeric structure can be as represented in Figure 3. In Figure 3, layer 300 is the outer surface layer N 1 , layer 301 is a tie layer and layer 302 is the inner surface layer N2. In some embodiments, layer 300 comprises the first polymer P1 and layer 302 comprises the second polymer P2. In some embodiments, layer 300 comprises a Grinloop® product and layer 302 comprises a second polymer P2. In some embodiments, the polymer P2 is EVOH, PA, PVA, a Grinloop® product or a mixture thereof.

[0068] In some embodiments, a recyclable 4-layer polymeric structure (not represented in the figures) can comprise successively an outer surface layer N1 comprising the first polymer P1 , a layer BL3 comprising a polymer P3 which can comprise polar groups, a tie layer, and an inner surface layer N2 comprising a non-polar polymer P. In some embodiments, such 4-layer polymeric structure can comprise a Grinloop® product in the outer surface layer N1 and the non-polar polymer P in the inner layer N2 can comprise a polyolefin, e.g., LDPE, a LLDPE or a mixture thereof. In some embodiments, the polymer P3 in the BL3 layer comprises EVOH, PA, PVA, a Grinloop® product or a mixture thereof. In some embodiments, the polymer P3 in the BL3 layer of such 4-layer structure, comprises EVOH. In some embodiments, the recyclable multilayered polymeric structure can be a 4-layer polymeric structure. In some embodiments, a recyclable 4-layer polymeric structure can be as represented in Figure 2. In Figure 2, layer 200 is the outer surface layer N1 , layer 201 is a tie layer, layer 202 is a polyolefin layer and layer 203 is the inner surface layer N2. In some embodiments, layer 200 comprises the first polymer P1 , layer 202 comprises a polyolefin layer and layer 203 comprises the non-polar polymer P. In some embodiments, layer 200 comprises a Grinloop® product, layer 202 comprises a polyethylene and layer 203 comprises a polyethylene, which is different than the polyethylene in layer 202. In some embodiments, the polyethylene in layer 202 can comprise a LDPE, a LLDPE or a mixture thereof, and the polyethylene in layer 203 can comprise a LLDPE. In some embodiments, the polyethylene in layer 202 can comprise a mixture of LDPE and LLDPE, and the polyethylene in layer 203 can comprise a LLDPE.

[0069] In some embodiments, the recyclable multilayered polymeric structure can be a 5-layer polymeric structure. In some embodiments, a recyclable 5-layer polymeric structure can be as represented in Figure 5. In some embodiments, layer 500 is the outer surface layer N1 , layer 501 is a tie layer, layer 502 is a polyolefin layer, layer 503 is a tie layer and layer 504 is the inner surface layer N2. In some embodiments, layer 500 comprises the first polymer P1 , layer 502 comprises a polyolefin layer and layer 504 comprises the second polymer P2. In some embodiments, layer 500 comprises a Grinloop® product, layer 502 comprises polyethylene and layer 504 comprises a Grinloop® product. In some embodiments, a recyclable 5-layer polymeric structure can be as represented in Figure 7. In Figure 7, layer 700 is the outer surface layer N1 , layer 701 is a tie layer, layer 702 is a third barrier layer BL3, layer 703 is a tie layer and layer 704 is the inner surface layer N2. In some embodiments, layer 700 comprises the first polymer P1 , layer 702 comprises a third polymer P3 and layer 704 comprises the non-polar polymer P. In some embodiments, layer 700 comprises a Grinloop® product, layer 702 comprises a third polymer P3 and layer 704 comprises polyethylene. In some embodiments, the polymer P3 is EVOH, PA or a mixture thereof. In some embodiments, the recyclable multilayered polymeric structure as represented in Figure 5 can be used for making pipes. In such structure, the polar polymers (i.e. , P1 and / or P3) can provide the chemical barrier while the polyethylene core can provide the vertebra for mechanical strength. In some embodiments, in a recyclable 5-layer polymeric structure, the central layer can comprise a third polymer P3 or a polyolefin for various applications. In some embodiments, the recyclable multilayered polymeric structure can be an 8-layer polymeric structure. In some embodiments, a recyclable 8-layer polymeric structure can be as represented in Figure 4. In some embodiments, layer 400 is the outer surface layer N1 , layer 401 is a tie layer, layer 402 is a polyolefin layer, layer 403 is a polyolefin layer, layer 404 is a tie layer, layer 405 is a third barrier layer BL3, layer 406 is a tie layer and layer 407 is the inner surface layer N2. In some embodiments, layer 400 comprises the first polymer P1 , layers 402 and 403 comprises polyolefin layers having different compositions, layer 405 comprises a third polymer P3, and layer 407 comprises the non-polar polymer P. In some embodiments, layer 400 comprises a Grinloop® product, layers 402 and 403 comprises polyethylene, layer 405 comprises a third polymer P3 and layer 407 comprises polyethylene. In some embodiments, the polymer P3 is EVOH, PA, PVA, a Grinloop® product or a mixture thereof.

[0070] In some embodiments, a barrier layer of the recyclable multilayered polymeric structure can have an oxygen barrier with transmission rates (OTR) below 40 cc*20pm / m2*atm*day at about 65% relative humidity (RH) and at about 23°C. In some embodiments, a barrier layer of the recyclable multilayered polymeric structure can have an OTR comprised between about 0.4 cc*20pm / m2*atm*day and about 36 cc*20pm / m2*atm*day at about 65% relative humidity (RH) and at about 23°C.

[0071] In some embodiments, the recyclable multilayered polymeric structure can have thermal resistance, and is capable of withstanding sealing temperatures up to 160°C. In some embodiments, the recyclable multilayered polymeric structure can have thermal resistance, and is capable of withstanding sealing temperatures between about 100°C and about 160°C.

[0072] In some embodiments, a barrier layer of the recyclable multilayered polymeric structure can have moisture resistance, with a Water Vapor Transmission Rate (WVTR) of less than about 5 g*mm / m2*atm*day at about 90% RH and at about 38°C. In some embodiments, a barrier layer of the recyclable multilayered polymeric structure can present a WVTR of less than about 2 g*mm / m2*atm*day, or less than about 1 g*mm / m2*atm*day, or comprised between about 0.4 g*mm / m2*atm*day and about 1 g*mm / m2*atm*day, at about 90% RH and at about 38°C.

[0073] In some embodiments, the recyclable multilayered polymeric structure can have density below 1000 kg / m3, aligning with recyclability requirements. In some embodiments, the recyclable multilayered polymeric structure can have density between about 920 kg / m3and about 990 kg / m3, aligning with recyclability requirements.

[0074] In some embodiments, at least one of the layers provide protection from moisture. In some embodiments, at least one of the layers provide protection from oxygen. In some embodiments, at least the outer layer provides protection from moisture and oxygen.

[0075] Barrier layer BL1 and first polymer P1

[0076] The recyclable multilayered polymeric structure comprises an outer layer N1 forming a first barrier layer BL1 , wherein the first barrier layer BL1 comprise a first polymer P1 which is a polar polymer, i.e., a polymer comprising polar functional groups. In some embodiments, the polymer P1 can be a polyethylene-based polymer functionalized with polar groups, characterized by a minimum ethylene content of at least about 50 mol%, thus ensuring recyclability of the final structure due to its affinity with polyethylene (PE).

[0077] In some embodiments, the first polymer P1 comprises sterically hindered polar functional groups. In some embodiments, the polar functional groups can be selected from the group consisting of carboxylic acids, alcohols, amides, anhydrides and esters.

[0078] The polar functional groups can provide the required polarity to the overall structure, as well as its oxygen and solvent resistivity, while the polyethylene portion can provide compatibility with PE. The controlled amount of the polar functional groups of the first polymer P1 can allow fine tuning of the properties of the resulting first barrier layer.

[0079] In some embodiments, the first polymer P1 has an oxygen transmission rate (OTR) below about 30 cc*20pm / m2*atm*day, below about 25 cc*20pm / m2*atm*day, below about 20 cc*20pm / m2*atm*day, below about 15 cc*20pm / m2*atm*day, below about 10 cc*20pm / m2*atm*day, or below about 8 cc*20pm / m2*atm*day at about 0% relative humidity (RH). In some embodiments, the OTR of the first polymer P1 is between about 0.01 cc*20pm / m2*atm*day and about 30 cc*20pm / m2*atm*day at about 0% RH. In some embodiments, the OTR of the first polymer P1 is between about 0.01 cc*20pm / m2*atm*day and about 20 cc*20pm / m2*atm*day at about 0% RH. In some embodiments, the OTR of the first polymer P1 is between about 0.01 cc*20pm / m2*atm*day and about 10 cc*20pm / m2*atm*day at about 0% RH. In some embodiments, the OTR of the first polymer P1 is between about 0.01 cc*20pm / m2*atm*day and about 8 cc*20pm / m2*atm*day at about 0% RH. In some embodiments, the first polymer P1 has a melting temperature above 160°C. In some embodiments, the first polymer P1 has a melting temperature between about 160°C and about 190°C. In some embodiments, the first polymer P1 has a melting temperature between about 160°C and about 180°C, or between about 160°C and about 170°C.

[0080] In some embodiments, the first polymer P1 has a moisture resistance characterized by a water vapor transmission rate (WVTR) of less than about 2 g*mm / m2*atm*day. In some embodiments, the first polymer P1 has a moisture resistance characterized by a water vapor transmission rate (WVTR) of less than about 1 g*mm / m2*atm*day. In some embodiments, the first polymer P1 has a moisture resistance characterized by a water vapor transmission rate (WVTR) between about 0.4 g*mm / m2*atm*day and about 1 g*mm / m2*atm*day.

[0081] In some embodiments, the first polymer P1 has a density below about 1.10 g / cm3. In some embodiments, the density of the first polymer P1 is between about 0.98 g / cm3and about 1.10 g / cm3. In some embodiments, the first polymer P1 can have the following characteristics:

[0082] i. An oxygen barrier with transmission rates below 30 cc*20pm / m2*atm*day at about 0% relative humidity (RH).

[0083] ii. High thermal resistance, capable of withstanding sealing temperatures between about 100°C and about 160°C, facilitating high-speed packaging processes.

[0084] iii. Moisture resistance, with a Water Vapor Transmission Rate (WVTR) of less than about 0.7 g*mm / m2*atm*day, ensuring stable performance in diverse environments.

[0085] iv. A density below 1.100 g / cm3, aligning with recyclability requirements.

[0086] In some embodiments, the first polymer P1 can withstand sealing temperatures between about 110°C and about 160°C, or between about 120°C and about 160°C, or between about 130°C and about 160°C, or between about 140°C and about 160°C, or between about 150°C and about 160°C.

[0087] In some embodiments, the first polymer P1 is compatible through recycling stream with polyolefins such as polyethylene. In other embodiments, the first polymer P1 is compatible through recycling stream with polyolefins such as polyethylene without the need for compatibilizers. In some embodiments, the first polymer P1 complies with the APR protocols for recyclability in the PE recycling stream.

[0088] As noted above, the first polymer P1 is comprised in the first barrier layer BL1 , which constitutes the outer surface layer N1 of the recyclable multilayered polymeric structure. In some embodiments, the first polymer P1 can be used in the outer layer and in the inner layer (when the inner layer comprises second polymer P2 and P2 is the same polymer as the first polymer P1). In some embodiments, the first barrier layer BL1 can provide protection from pollutants, chemicals and / or gases. In some embodiments, pollutants, chemicals and / or gases can comprise radon, CO2, O2, N2, CH4 and / or fuel or other chemical fluids.

[0089] In some embodiments, the first barrier layer BL1 can comprise from about 0.05 wt% to about 5 wt% of at least one additive such as heat stabilizers, process stabilizers, LIV stabilizers, or any other additive known in the art of polymeric structures.

[0090] In some embodiments, the first polymer P1 can provide protective properties from industrial pollutants or chemicals. Preferably, the pollutants or chemicals comprises radon, CO2, methane, and / or fuel. In some embodiments, the first polymer P1 can provide protective properties from gases such as O2, N2, CO2 and methane (CH4).

[0091] In some embodiments, the first polymer P1 can comprise a Grinloop® product. In some embodiments, the Grinloop® product can be Grinloop® GL-HO21 , Grinloop® GL-HP09, Grinloop® GL-MO74, or any combination thereof.

[0092] In some embodiments, the first barrier layer BL1 can comprise a Grinloop® product. In some embodiments, the Grinloop® product is Grinloop® GL-HO21 , Grinloop® GL-HP09, Grinloop® GL-MO74, or any combination thereof.

[0093] Grinloop® products are polymer resins compatible with polyolefins such as polyethylene, characterized by oxygen and moisture resistivity.

[0094] The molar ratio of olefinic portion to the different polar functional groups in GrinLoop® grades can determine the diffusion rate against various permeates and adhesion level of GrinLoop® to adjacent polyolefin layer.

[0095] Grinloop® GL-HO21 is a polyethylene-based polymer functionalized with polar functional groups wherein the molar ratio of olefinic portion to the different polar functional groups is of 1.44. In some embodiments, Grinloop® GL-HO21 processing can include blown-film and extrusion blow molding. Applications can include non-forming and rigid products used in various industries such as but not limited to packaging.

[0096] Grinloop® GL-HP09 is a polyethylene-based polymer functionalized with polar functional groups wherein the molar ratio of olefinic portion to the different polar functional groups is of 1.32. Applications can include non-forming and rigid products used in various industries such as but not limited to packaging. Grinloop® GL-MO74 is a polyethylene-based polymer functionalized with polar functional groups wherein the molar ratio of olefinic portion to the different polar functional groups is of 2.2. In some embodiments, Grinloop® GL-MO74 processing can include blown-film. Applications can include non-forming and rigid products used in various industries such as but not limited to packaging.

[0097] Barrier layers BL2 and BL3 and second and third polymers P2 and P3

[0098] In some embodiments, the inner layer N2 can be a barrier layer BL2 comprising the second polymer P2. In some embodiments, the third polymer P3 can be present in the one or more third barrier layer BL3.

[0099] In some embodiments, the second polymer P2 and the third polymer P3 can comprise polar functional groups, preferably independently selected from the group consisting of carboxylic acids, alcohols, amides, anhydrides and esters.

[0100] In some embodiments, the second polymer P2 can comprise an ethylene vinyl alcohol copolymer (EVOH), a polyamide (PA), a polyvinyl alcohol (PVA), a same polymer as the first polymer P1 , or any combination thereof.

[0101] In some embodiments, the one or more third polymer P3 independently can comprise EVOH, PA, PVA, an EVOH copolymer, a PA copolymer, a PVA copolymer, a same polymer as the first polymer P1 as defined herein, or any combination thereof.

[0102] In some embodiments, the second barrier layer BL2 can comprise the second polymer P2. In some embodiments, the second barrier layer BL2 can comprise a Grinloop® product, such as Grinloop® GL-HO21 , Grinloop® GL-HP09, Grinloop® GL-MO74, or any combination thereof.

[0103] In some embodiments, the one or more third barrier layers BL3 independently can comprise an EVOH copolymer-based film, a Grinloop® product such as Grinloop® GL-HO21 , Grinloop® GL-HP09, or Grinloop® GL-MO74, a silicon oxide polyolefin-based film, an aluminium oxide polyolefin-based film or any combination thereof.

[0104] Silicon oxide polyolefin-based film and aluminium oxide polyolefin-based film commonly used as coating layers can be used in the present in the present multilayered structure.

[0105] In some embodiments, the one or more third barrier layer BL3 can comprise a Grinloop® product, such as Grinloop® GL-HO21 , Grinloop®GL-HP09, Grinloop®GL-MO74, or any combination thereof. In some embodiments, the one or more third barrier layers BL3 can be independently less than about 10 pm. In some embodiments, the one or more third barrier layers BL3 can be independently about 1 pm to about 10 pm. In some embodiments, the one or more third barrier layers BL3 can be independently about 2 pm to about 5 pm.

[0106] In some embodiments, the second barrier layer BL2 can be less than about 10 pm. In some embodiments, the second barrier layer BL2 can be about 1 pm to about 10 pm. In some embodiments, the second barrier layer BL2 can be about 2 pm to about 5 pm.

[0107] In some embodiments, the third barrier layers BL3 can be less than about 10 pm thick. In some embodiments, the third barrier layers BL3 can be between about 0.01 pm and about 10 pm thick. In some embodiments, the coating layers can be between about 0.01 pm and about 0.2 pm thick. In some embodiments, at least one of BL1 , BL2 and BL3 can provide protection from pollutants, chemicals and / or gases. In some embodiments, pollutants, chemicals and / or gases can comprise radon, CO2, O2, N2, CH4 and / or fuel or other chemical fluids.

[0108] Tie layers

[0109] Tie layers can be polymer resins designed to provide adhesion between specific polymers in a given film manufacturing process.

[0110] In some embodiments, the one or more tie layers independently can comprise a non-polar polymer (e.g., polyethylene) combined with a maleic anhydride (MA)-grafted polyolefin (e.g., (MA)-grafted polyethylene). In some embodiments, the tie layers can comprise a blend of polyolefinic polymers. In some embodiments, the one or more tie layers can be independently about 2 pm to about 20 pm thick. In some embodiments, the one or more tie layers can be independently about 2 pm to about 15 pm thick. In some embodiments, the one or more tie layers can be independently about 2 pm to about 10 pm thick. In some embodiments, the one or more tie layers can be independently about 2 pm to about 8 pm thick.

[0111] Polyolefin layers and non-polar polymer P

[0112] In some embodiments, the inner surface N2 can comprise the non-polar polymer P. In some embodiments, the non-polar polymer P comprises a polyolefin.

[0113] In some embodiments, the one or more polyolefin layers can comprise polyethylene, an ethylenebased copolymer or a combination thereof.

[0114] In some embodiments, the non-polar polymer P can comprise polyethylene (PE) or polypropylene (PP). In some embodiments, the polyolefin can comprise a polyethylene homopolymer, a polyethylene-based copolymer, a polypropylene homopolymer, a polypropylene-based copolymer, or a combination thereof. In some embodiments, the polyethylene (PE) in the multilayered polymeric structure can have a density of about 0.910 to about 0.960 g / cm3. In some embodiments, the PE can be selected from the group consisting Linear Low Density PE (LLDPE), Low Density PE (LDPE), Medium Density PE (MDPE) and High Density PE (HDPE).

[0115] In some embodiments, the polyolefins as described herein can be post consumer recycled material (PCR) or post-industrial recycled material (PI R), thereby reducing the carbon footprint of the package. In some embodiments, the PE can be recycled PE.

[0116] In some embodiments, the inner surface N2 can comprise a LDPE, a LLDPE, an ethylene- 1 -octene copolymer, recycled PE or any combination thereof.

[0117] In some embodiments, the inner surface layer N2 can further comprise low seal initiation temperature polyolefins or Ethylene vinyl acetate (EVA).

[0118] In some embodiments, the inner layer N2 can comprise the non-polymer P when N = 2.

[0119] In some embodiments, the one or more polyolefin layers independently can comprise a LDPE, a LLDPE, an ethylene- 1 -octene copolymer, a recycled PE, or any combination thereof.

[0120] In some embodiments, the polyolefin layers can be between about 5 pm and about 75 pm thick, between about 5 pm and about 65 pm thick, between about 5 pm and about 55 pm thick or between about 5 pm and about 50 pm thick.

[0121] In some embodiments, primary and secondary antioxidants package and some other additives such as carbon black or TiC>2 can be added for process and long-term stabilisation or other properties. In some embodiments, primary antioxidants refer to compounds that directly scavenge and neutralize free radicals to prevent polymer degradation during processing. In some embodiments, secondary antioxidants refer to compounds that decompose hydroperoxides into stable, non-radical products, thus protecting polymers from oxidative degradation.

[0122] In some embodiments, the PE in all multilayered polymeric structure defined herein can be replaced with PP to direct final structures to PP recycling streams.

[0123] Additives

[0124] In some embodiments, any one of the layers of the recyclable multilayered polymeric structure independently can further comprise at least one additive.

[0125] In some embodiments, the at least one additive can be selected from the group consisting of heat stabilizers, antioxidants, process stabilizers, thermal stabilizers, UV stabilizers, oxygen scavenger, moisture absorber, and any combination thereof. In some embodiments, the at least one additive can be an antioxidant selected from pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), tris(2,4-di-tert-butylphenyl)phosphite, and a mixture thereof.

[0126] In some embodiments, the at least one additive can be selected from the group consisting of carbon black, TiC>2, Irganox® B 225 and any combination thereof.

[0127] In some embodiments, the first barrier layer BL1 can comprise from about 0.05 wt% to about 5 wt% of at least one additive such as heat stabilizers, process stabilizers, LIV stabilizers, or any other additive known in the art of polymeric structures.

[0128] In some embodiments, a compatibilizer can be added to at least one of the layers of the recyclable multilayered polymeric structure. In some embodiments, where a layer comprises polyamide (PA), a compatibilizer can be used in this layer. In some embodiments, where a layer comprises PA, the amount of PA can be up to about 10-12 wt% and this PA-containing layer can further comprise a compatibilizer. In some embodiments, where a layer comprises EVOH, this layer can comprise a compatibilizer or no compatibilizer. In some embodiments, where a layer comprises EVOH in an amount up to about 5 wt%, or EVOH in an amount below 5%, this layer does not comprise a compatibilizer. In some embodiments, where a layer comprises EVOH in an amount up to 10%, a compatibilizer can be added to the EVOH-containing layer.

[0129] In some embodiments, a stabilizer package, may be added to any layer comprises any combination of one or more of the following additives:

[0130] - LIV stabilizers functioning as free radical scavengers in Hindered Amine Light Stabilizer ("HALS") family (e.g., Chimmasorb 2020™ (BASF, Germany));

[0131] - antioxidants functioning as inhibitors of thermo-oxidative degradation at a broad temperature range for long-term thermal stabilizers in hindered phenolic family (e.g., Irganox 1010™ (BASF, Germany), which is a sterically hindered phenolic antioxidant);

[0132] - process or thermal stabilizers functioning as inhibitors of thermo-oxidative degradation during extrusion process in comprising a phosphite processing stabiliser (e.g., Irgafos 168™ (BASF, Germany));

[0133] - carbon black as UV absorber where the Carbon black is a furnace carbon black with particle size equal or below N660; and / or

[0134] - TiO2 with particle size of 100 nm and more.

[0135] In another embodiment, any of the recyclable multilayered polymeric structure can be used in combination with other materials to provide specific properties such as, but not limited to metallic layers, paper, nanomaterials, nanolayers or any other type of material to add at least one specific property to the structure.

[0136] Process of making the recyclable multilayered polymeric structure

[0137] In some embodiments, the process of making the recyclable multilayered polymeric structure can comprise co-extruding or co-laminating the N layers to form the multilayered structure. To produce the first layer, known process in the art can be used, such as Blown or Cast film process. Such structures are illustrated on Figures 1 to 5.

[0138] In some embodiments, one part of the layers can be co-extruded or co-laminated to form a first portion of the recyclable multilayered polymeric structure and a second part of the layers can be co-extruded or co-laminated to form a second portion of the recyclable multilayered polymeric structure. Then, in some embodiments, the first and second portions can be co-laminated to obtain the final recyclable multilayered polymeric structure. In some embodiments, in lamination process, an adhesive material such as a tie layer can be used to adhere two adjacent layers that are incompatible.

[0139] In coextrusion, the polymer layers can be brought together in the melt state.

[0140] In some embodiments, the recyclable multilayered polymeric structure can be a Recyclable-Barrier-Print-Web film, which can be laminated to any sealant film of any desired thickness / property.

[0141] In some embodiments, an all-PE sealant web can be used to laminate on a film made of the recyclable multilayered polymeric structure, leaving the first barrier layer BL1 as the outer layer. Using such a structure can fulfill the barrier requirements of majority of the applications in food packaging obviating the need to utilizing another barrier material in the core of the product. In addition to cost advantage, it can result in lower energy to produce and less complicated structure of the final product. In some embodiments, the recyclable multilayered polymeric structure can be used to produce containers for oil or other hydrocarbon or liquids containments via injection / blow molding processing method or any other method known in the art.

[0142] In some embodiments, the recyclable multilayered polymeric structure can be used to produce geomembranes liners of one or more layers for oil or other hydrocarbon or liquids primary or secondary containments via extrusion processing method (Blown film or Cast film operation) known in art.

[0143] In some embodiments, the recyclable multilayered polymeric structure can be laminated or coextruded with a sub-layer, the sub-layer being adapted to give the product a special property such as, but not limited to, electrical conductivity or printability. Recyclability

[0144] To be recyclable, the multilayered polymeric structures described herein should pass the various evaluation tests described in the protocol of recyclability for each market. Such protocol is designed by the Association of Plastic Recyclers (APR) in the US / Canada and Recyclass in Ell, that are well aware of the limitations and capabilities of their local recyclers.

[0145] In some embodiments, the multilayered polymeric structures described herein are recyclable in the PE stream.

[0146] In some embodiments, the multilayered polymeric structures described herein are recyclable in the PP stream.

[0147] Uses of the recyclable multilayered polymeric structure

[0148] In some embodiments, the one or more barrier layers of the recyclable multilayered polymeric structures is / are (a) gas barrier(s) and the recyclable multilayered polymeric structures can be used in the making of flexible, semi-rigid or rigid packaging, in particular for food packaging. Such packaging comprises liners, pouches, shrink bags or bottles, and the food products comprise oxygen and / or water sensitive material, such as meat products, diaries, vegetables, fruits, nuts, pet food, salad dressings or the like.

[0149] In some embodiments, the recyclable multilayered polymeric structure can be used in food packaging, where it can provide extended shelf-life for food products.

[0150] The high-temperature resistance of the polymer P1 present in the barrier layer BL1 (e.g., Grinloop® product) can enhance processing capabilities on food packaging lines. A prevalent challenge in recyclable flexible packaging products is the temperature limitations of Polyethylene (PE) when utilized as the skin layer. Currently, one of the most advanced products in this domain is Biaxially Oriented Polyethylene (BOPE) films. However, even BOPE's maximum operating temperature is capped at 130°C, which imposes constraints on the speed of packaging lines. In contrast, the polymer P1 can withstand operating temperature of 160°C — on par with Oriented Polypropylene (OPP) films — offering a substantial improvement in line speed and overall efficiency of packaging operations. This not only addresses a limitation in existing recyclable packaging materials but also allows for high-temperature resilience into sustainable packaging solutions.

[0151] Additionally, the polar functional groups of the polymer P1 can assist in elevating the surface's Dyne level for instance to 40-44, aligning it with that of polyester. Structures with barrier layer BL1 and therefore polymer P1 , as outer layers, possess the potential to be laminated without additional treatments, and will likely offer improved printability compared to polyolefins. In some embodiments, the recyclable multilayered polymeric structure can be used in containing industrial chemicals, addressing needs for sustainable and efficient barrier materials in various sectors. According to another embodiment, the one or more barrier layers can provide protective properties from industrial pollutants or chemicals, such as, but not limited to, radon, CO2, methane, and / or fuel. The recyclable multilayered polymeric structure can then be used in the making of building liners, geomembranes, pipes, or containers for non-polar liquid such as oils and / or other hydrocarbons. In another embodiment, the recyclable multilayered polymeric structure can provide protective properties from pollutants, chemicals and / or gases comprising radon, CO2, O2, N2, CH4 and / or fuel, or other chemical fluids such as agricultural fluids, hydrocarbon mixture, aromatic (Solvesso™ 150), cyclohexanone, N-methylpyrrolidone, Dowanol™ PM, propylene glycol, EL 400 Emulsion, and isododecyl benzene sulfonate.

[0152] In other embodiments, the recyclable multilayered polymeric structure can be used to form rigid and semi rigid containers containing non-polar liquids such as oils and / or other hydrocarbons.

[0153] In other embodiments, the recyclable multilayered polymeric structure can be used in thick films or sheets, known as liners or geomembranes, and also in pipes, resistant to gas permeations, oils and other hydrocarbons where neat polyolefin resins are not resistant enough.

[0154] In some embodiments, the thickness of the multilayered polymeric structure in rigid packaging or geomembranes can be between about 0.1 mm and about 5 mm.

[0155] In some embodiments, the recyclable multilayered polymeric structure can be a customized multilayer structure. By "customized", it is understood that the final structure can be adapted to the final use, which can be dictated by several conditions (geography, weather conditions, nature of the product intended to be contained, etc.).

[0156] In some embodiments, the recyclable multilayered polymeric structure can be used for cheese packaging. Cheese packaging presents unique challenges, requiring medium oxygen barrier properties to accommodate the specific needs of cheese products. During the aging period on store shelves, cheese generates CO2, necessitating packaging material that allows for the controlled release of this gas while maintaining appropriate barrier properties. Traditionally, Polyamide (PA) / Polyethylene (PE) films have been the solution of choice in such applications. However, with the increasing emphasis on recyclability, the use of PA is becoming less attractive. The recyclable multilayered polymeric structures described herein can meet the barrier performance needed for cheese packaging applications while also meeting recyclability standards. In some embodiments, a recyclable multilayered polymeric structure comprising a Grinloop® product such as Grinloop® GL-MO74, in the outer layer, can be used for preparing a cheese packaging. The present technology is further illustrated by the following examples, which should not be construed as further limiting.

[0157] EXAMPLES

[0158] Example 1

[0159] The barrier properties of three different grades of Grinloop® are presented in Table 1a.

[0160] Table 1a. OTR and water absorption properties of Grinloop® polymers (GL-HP09, GL-HO21 and GL-HO74). RH stand for Relative Humidity. Barrier

[0161]

[0162] GL-H021: Barrier properties are given for a monolayer blown film. Recyclability in PE stream is up to 30 wt% in a PE structure (approved by APR). Density is 1.04 g / cm3(ASTM D792). Melt temperature is 185 °C (ASTM D3418). Heat deflection temperature is 52 °C (ASTM D624). MFI (210 °C, 2160 g) is 0.85 g I 10 minutes (ASTM D1238) and HLMI (210 °C, 21600 g) is 38 g / 10 minutes (ASTM D1238).

[0163] GL-HO74: Barrier properties are given for a monolayer blown film. Recyclability in PE stream is up to 30 wt% in a PE structure (approved by APR). Density is 1.04 g / cm3(ASTM D792). Melt temperature is 185 °C (ASTM D3418). Heat deflection temperature is 50 °C (ASTM D624). MFI (210 °C, 2160 g) is 0.8 g / 10 minutes (ASTM D1238) and HLMI (210 °C, 21600 g) is 35 g / 10 minutes (ASTM D1238).

[0164] GL-HP09: Barrier properties are given for a monolayer blown film. Recyclability in PE stream is up to 30 wt% in a PE structure (approved by APR). Density is 1.05 g / cm3(ASTM D792). Melt temperature is 185 °C (ASTM D3418). Heat deflection temperature is 54 °C (ASTM D624). OTR for 35% RH and 23 °C is 0.03 Cc.20pm / m2.day.atm, OTR for 70% RH and 23 °C is 0.04 Cc.20pm / m2.day.atm, OTR for 88% RH and 23 °C is 0.12 Cc.20pm / m2.day.atm and OTR for 90% RH and 38 °C is 0.038 Cc.20pm / m2.day.atm. Mechanical properties of GL-HP09 are given in Table 1b. MFI (210 °C, 2160 g) is 0.9 g I 10 minutes (ASTM D1238) and HLMI (210 °C, 21600 g) is 39 g / 10 minutes (ASTM D1238). Table 1b. Mechanical properties of Grinloop® polymer GL-HP09.

[0165]

[0166] Example 2

[0167] Multilayered polymer structure. A multilayered polymer structure comprising 8 layers (MLPS-1) has been obtained via blown film coextrusion process (e.g., as represented in Figure 4), and its composition is shown in Table 2. The total thickness of MLPS-1 is 80 pm.

[0168] Table 2. Composition of the 8-layer polymeric structure (MLPS-1).

[0169]

[0170] The properties of this 8-layer polymeric structure (MLPS-1) are shown in Table 3.

[0171] Table 1. Properties of the 8-layer polymeric structure (MLPS-1).

[0172] <

[0173] <

[0174]

[0175] Packaging manufacture. This 8-layer polymeric structure (MLPS-1) underwent a trial on a packaging apparatus which utilizes rollstock film for crafting vertical form fill seal (VFFS) pouches. This 8-layer polymeric structure (MLPS-1) was processed on the packaging system with minimal alterations to the existing machine configurations. The food packaging process was achieved at an identical cycle rate comparable to that of the traditional products of the market. Moreover, these final packages successfully endured the seal strength test (ASTM F88) and abrasion resistance test (ASTM F3300), exhibiting no signs of failure.

[0176] Recyclability. A 8-layer polymeric structure (MLPS-1) containing 50% of recycled contents in its composition passed the guidance criteria for Film-To-Film recyclability tests of the Association of Plastic Recyclers (APR).

[0177] In this test the 8-layer polymeric structure (MLPS-1) is shredded, melted, mixed with PE and extruded to produce granules with 50% of PE and 50% of the recycled MLPS-1 product. During production of the pellets, no irregularity or significant change of pressure was observed.

[0178] From the 50 / 50 PE / MLPS-1 granules was obtained a film. No irregularities were observed during the production of the film. The physical, mechanical and thermal properties of the 50 / 50 film were compared to a control film obtained from 100% PE (Table 4). A decrease of no more than 17% was noted in the tensile, tear, and dart impact properties.

[0179] These results confirm the recyclability of the 8-layer polymeric structure MLPS-1 according to the APR protocol.

[0180] Table 4. Evaluation of blown film samples

[0181]

[0182]

[0183] Food packaging. Using MLPS-1, food packaging was produced and the shelf-life for the food products presented in table 5. The application is not limited to these products.

[0184] Table 2. Shelf-life of food products with MLPS-1 packaging.

[0185]

[0186] Example 3

[0187] Multilayered polymer structure. A 3-layer polymeric structure (MLPS-2) was produced (e.g., as represented in Figure 1) with the combination reported in Table 6. The total thickness of MLPS-2 is 25 pm.

[0188] Table 3. Composition of the 3-layer polymeric structure MLPS-2.

[0189]

[0190] The properties of this 3-layer polymeric structure MLPS-2 is shown in Table 7 below.

[0191] Table 4. Properties of the 3-layer polymeric structure MLPS-2.

[0192] <

[0193]

[0194] Recyclability. MLPS-2 meets the APR recognition program protocol recyclability criteria for PE film.

[0195] Food packaging. Using MLPS-2, food packaging was produced and the shelf-life for the food products presented in Table 8. The application is not limited to these food products.

[0196] Table 8. Shelf-life of food products in the 3-layer polymeric structure packaging.

[0197]

[0198] Example 4

[0199] Multilayered polymer structure. A 4-layer polymeric structure (MLPS-3) was produced with the combination reported in Table 9. The total thickness of MLPS-3 is 75 pm.

[0200] Table 9. Composition of the 4-layer polymeric structure (MLPS-3).

[0201]

[0202] MLPS-3 offers barrier properties which are comparable to those of Metalized Polyethylene Terephthalate (PET) at similar thickness levels (Table 10).

[0203] Table 10. OTR properties of MLPS-3 compared with conventional film.

[0204] < <

[0205]

[0206] Recyclability. The resulting multilayered polymeric structure is not only recyclable but also cost-effective to produce, owing to its streamlined and simple processing method. MLPS-3 meets the APR recognition program protocol recyclability criteria for PE film.

[0207] Food packaging. This multilayered polymer structure (MLPS-3) represents a sustainable replacement for food packaging applications called “Double Barrier” concept. It is an alternative to metallized PET for applications with long shelf-lives and high sensitivity to oxygen. One example is sauce tubes.

[0208] Example 5

[0209] Multilayered polymer structure. A 4-layer polymeric structure (MLPS-4) was produced (e.g., as represented in Figure 2) with the combination reported in Table 11. The total thickness of MLPS-4 is 62 pm.

[0210] Table 11. Composition of the 4-layer polymeric structure MLPS-4.

[0211]

[0212] MLPS-4 delivers barrier properties that match the performance of commonly used PA / PE films, even at equivalent thicknesses, as demonstrated in Table 12.

[0213] Table 12. OTR properties of MLPS-4 compared with conventional films

[0214] < <

[0215]

[0216] Recyclability. MLPS-4 meets the APR recognition program protocol recyclability criteria for PE film. The 4-layer polymeric structure MLPS-4 stands out for its recyclability and economic efficiency in production, attributed to a straightforward and efficient manufacturing process.

[0217] Although the invention has been illustrated and described with respect to one or more implementations, equivalent alterations and modifications will occur to others skilled in the art upon the reading and understanding of this specification. In addition, while a particular feature of the invention may have been disclosed with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular application.

[0218] Accordingly, it is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. Any publication, document, patent, patent application or publication referred to herein should be construed as incorporated by reference each in their entirety for all purposes.

Claims

CLAIMS1- A recyclable multilayered polymeric structure comprising a number N of layers with N > 2, wherein the recyclable multilayered polymeric structure comprises:an outer surface layer N1 , which is a first barrier layer BL1 comprising a first polymer P1 comprising polar functional groups; andan inner surface layer N2 comprising a non-polar polymer P or a second barrier layer BL2 comprising a second polymer P2 comprising polar functional groups; and optionally one or more layers between layer N1 and layer N2;wherein at least two layers of the recyclable multilayered polymeric structure are different, andwherein the first polymer P1 comprising polar functional groups is a functionalized polyethylene-based polymer with an ethylene content of at least about 50 mol% and having:an oxygen transmission rate (OTR) below about 30 cc*20pm / m2*atm*day at about 0% relative humidity (RH);a melting temperature above 160°C;a moisture resistance characterized by a water vapor transmission rate (WVTR) of less than about 2 g*mm / m2*atm*day; anda density below about 1.10 g / cm3.2- The recyclable multilayered polymeric structure of claim 1 , wherein N is between 2 and 11. 3- The recyclable multilayered polymeric structure of claim 1 or 2, wherein a total thickness of the recyclable multilayered polymeric structure is between about 10 pm and about 400 pm.4- The recyclable multilayered polymeric structure of claim 3, wherein the total thickness of the recyclable multilayered polymeric structure is between about 25 pm and about 120 pm.5- The recyclable multilayered polymeric structure of any one of claims 1 to 6, wherein the N layers are co-extruded or co-laminated to form the recyclable multilayered polymeric structure.6- The recyclable multilayered polymeric structure of any one of claims 1 to 7, wherein the polar functional groups of the first polymer P1 comprise sterically hindered polar groups.7- The recyclable multilayered polymeric structure of any one of claims 1 to 8, wherein the polar functional groups of the first polymer P1 and / or the second polymer P2 are selected from the group consisting of carboxylic acids, alcohols, amides, anhydrides and esters.8- The recyclable multilayered polymeric structure of any one of claims 1 to 9, wherein the firstpolymer P1 has an ethylene content between about 50 % and about 75 %.9- The recyclable multilayered polymeric structure of any one of claims 1 to 10, wherein the OTR of the first polymer P1 is between about 0.01 cc*20pm / m2*atm*day and about 30 cc*20pm / m2*atm*day at about 0% RH.10- The recyclable multilayered polymeric structure of any one of claims 1 to 10, wherein the OTR of the first polymer P1 is between about 0.01 cc*20 m / m2*atm*day and about 15 cc*20pm / m2*atm*day at about 0% RH.11- The recyclable multilayered polymeric structure of any one of claims 1 to 10, wherein the OTR of the first polymer P1 is between about 0.01 cc*20pm / m2*atm*day and about 10 cc*20pm / m2*atm*day at about 0% RH.12- The recyclable multilayered polymeric structure of any one of claims 1 to 11 , wherein the melting temperature of the first polymer P1 is between about 160°C and about 190°C.13- The recyclable multilayered polymeric structure of any one of claims 1 to 12, wherein the WVTR of the first polymer P1 below about 1 g*mm / m2*atm*day at about 90% RH and about 38°C, preferably between about 0.4 g*mm / m2*atm*day and about 1 g*mm / m2*atm*day.14- The recyclable multilayered polymeric structure of any one of claims 1 to 13, wherein the density of the first polymer P1 is between about 0.98 g / cm3and about 1.10 g / cm3.15- The recyclable multilayered polymeric structure of any one of claims 1 to 14, wherein the first barrier layer BL1 comprises a Grinloop® product, such as Grinloop® GL-HO21 , Grinloop® GL- HP09, Grinloop® GL-MO74, or any combination thereof.16- The recyclable multilayered polymeric structure of any one of claims 1 to 15, wherein the inner surface layer N2 comprises the second barrier layer BL2 comprising the second polymer P2.17- The recyclable multilayered polymeric structure of any one of claims 1 to 16, wherein the second polymer P2 comprises an ethylene vinyl alcohol copolymer (EVOH), a polyamide (PA), a polyvinyl alcohol (PVA), a same polymer as the first polymer P1 , or any combination thereof.18- The recyclable multilayered polymeric structure of any one of claims 1 to 17, wherein the second barrier layer BL2 comprises a Grinloop® product, such as Grinloop® GL-HO21, Grinloop® GL-HP09, Grinloop® GL-MO74, or any combination thereof.19- The recyclable multilayered polymeric structure of any one of claims 1 to 15, wherein the innersurface layer N2 comprises the non-polar polymer P.20- The recyclable multilayered polymeric structure of claim 19, wherein the non-polar polymer P comprises a polyolefin.21- The recyclable multilayered polymeric structure of claim 20, wherein the polyolefin is a polyethylene or a polypropylene.22- The recyclable multilayered polymeric structure of claim 20, wherein the polyolefin is an ethylene-based homopolymer or copolymer, a propylene-based homopolymer or copolymer, or a combination thereof.23- The recyclable multilayered polymeric structure of claim 21 , wherein the polyolefin is a polyethylene.24- The recyclable multilayered polymeric structure of claim 23, wherein the polyethylene is a Linear Low Density Polyethylene (LLDPE), a Low Density Polyethylene (LDPE), a Medium Density Polyethylene (MDPE), a High Density Polyethylene (HDPE), or a mixture thereof. 25- The recyclable multilayered polymeric structure of any one of claims 1 to 15, wherein the inner surface layer N2 further comprises low seal initiation temperature polyolefins or Ethylene vinyl acetate (EVA).26- The recyclable multilayered polymeric structure of any one of claims 19 to 25, wherein N = 2 and the layer N2 comprises the non-polar polymer P.27- The recyclable multilayered polymeric structure of any one of claims 1 to 25, wherein one or more layers are present between the layer N1 and the layer N2 and comprise(s) one or more of a third barrier layer BL3, one or more of a tie layer, and / or one or more of a polyolefin layer, provided that when the recyclable multilayered polymeric structure comprises two or more third barrier layers BL3 and / or two or more tie layers then each one of the tie layers are not juxtaposed, and provided that the layer N1 is optionally juxtaposed to one tie or adhesive layer, preferably the layer N1 is juxtaposed to one tie or adhesive layer.28- The recyclable multilayered polymeric structure of claim 27, wherein any of the first barrier layer BL1 , second barrier layer BL2, and / or third barrier layer BL3 are incompatible with any polyolefin layer.29- The recyclable multilayered polymeric structure of claim 27 or 28, wherein the one or more third barrier layer BL3 comprise a third polymer P3 comprising polar functional groups, preferablyindependently selected from the group consisting of carboxylic acids, alcohols, amides, anhydrides and esters.30- The recyclable multilayered polymeric structure of claim 29, wherein the third polymer P3 independently comprise EVOH, PA, PVA, an EVOH copolymer, a PA copolymer, a PVA copolymer, a same polymer as the first polymer P1 , or any combination thereof.31- The recyclable multilayered polymeric structure of any one of claims 27 to 30, wherein the one or more third barrier layers BL3 independently comprise an EVOH copolymer-based film, a Grinloop® product such as Grinloop® GL-HO21 , Grinloop® GL-HP09, or Grinloop® GL-MO74, a silicon oxide coated polyolefin-based film, an aluminium oxide coated polyolefin-based film or any combination thereof.32- The recyclable multilayered polymeric structure of any one of claims 27 to 31 , wherein the one or more third barrier layers BL3 are independently less than about 10 pm thick.33- The recyclable multilayered polymeric structure of any one of claims 27 to 32, wherein the one or more tie layers independently comprise a non-polar polymer (e.g., polyethylene) combined with a maleic anhydride (MA)-grafted polyolefin (e.g., (MA)-grafted polyethylene).34- The recyclable multilayered polymeric structure of any one of claims 27 to 32, wherein the one or more tie layers comprise a blend of polyolefinic polymers with functionalized polyolefins. 35- The recyclable multilayered polymeric structure of any one of claims 27 to 34, wherein the one or more tie layers are independently about 2 pm to about 20 pm thick.36- The recyclable multilayered polymeric structure of any one of claims 27 to 35, wherein the one or more polyolefin layers comprise polyethylene (PE) or an ethylene-based copolymer.37- The recyclable multilayered polymeric structure of claim 36, wherein the polyethylene is a Linear Low Density Polyethylene (LLDPE), a Low Density Polyethylene (LDPE), a Medium Density Polyethylene (MDPE), a High Density Polyethylene (HDPE), or a mixture thereof. 38- The recyclable multilayered polymeric structure of claim 36, wherein the one or more polyolefin layers independently comprise a LDPE, a LLDPE, a recycled PE, or any combination thereof.39- The recyclable multilayered polymeric structure of any one of claims 27 to 38, wherein the one or more polyolefin layers independently are about 5 pm to about 75 pm thick, preferably about 5 pm to about 65 pm thick, most preferably about 5 pm to about 55 pm thick.40- The recyclable multilayered polymeric structure of any one of claims 1 to 39, wherein any one of the layers of the recyclable multilayered polymeric structure independently further comprises at least one additive.41- The recyclable multilayered polymeric structure of claim 40, wherein the at least one additive is selected from the group consisting of heat stabilizers, antioxidants, process stabilizers, thermal stabilizers, LIV stabilizers, oxygen scavenger, moisture absorber, and any combination thereof.42- The recyclable multilayered polymeric structure of claim 40, wherein the at least one additive is selected from the group consisting of carbon black, TiC>2, Irganox® B 225 and any combination thereof.43- The recyclable multilayered polymeric structure of any one of claims 27 to 42, wherein N = 3 and one tie layer is used between the outer surface layer N1 and the inner surface layer N2.44- The recyclable multilayered polymeric structure of any one of claims 27 to 42, wherein N > 4 and one tie layer is intercalated between any incompatible layers present in the recyclable multilayered polymeric structure.45- The recyclable multilayered polymeric structure of claim 44, wherein N = 5 and comprising: the layer N1 , the layer N2 which comprises the second polymer P2, and in between the layer N1 and the layer N2 successively, a first tie layer, a first polyolefin layer and a second tie layer.46- The recyclable multilayered polymeric structure of claim 44, wherein N = 5 and comprising: the layer N1 , the layer N2 which comprises the non-polar polymer P, and in between the layer N1 and the layer N2 successively, a first tie layer, a third barrier layer BL3 and a second tie layer.47- The recyclable multilayered polymeric structure of any one of claims 27 to 42, wherein N = 4 and comprising: the layer N1 , the layer N2 which comprises the non-polar polymer P, and in between the layer N1 and the layer N2 successively, a first tie layer and a first polyolefin layer.48- The recyclable multilayered polymeric structure of any one of claims 27 to 42, wherein N = 8 and comprising: the layer N1 , the layer N2 which comprises the non-polar polymer P, and in between the layer N1 and the layer N2 successively, a first tie layer, a first polyolefin layer, a second polyolefin layer, a second tie layer, a third barrier layer BL3 and a third tie layer.49- The recyclable multilayered polymeric structure of any one of claims 1 to 48, wherein at least one of the barrier layers BL1 , BL2 and BL3 provide protection from pollutants, chemicals and / or gases.50- The recyclable multilayered polymeric structure of claim 49, wherein the pollutants, chemicals and / or gases comprise radon, CO2, O2, N2, CH4 and / or fuel or other chemical fluids.51- The recyclable multilayered polymeric structure of any one of claims 1 to 48, wherein at least one of the layers, such as at least one of the barrier layers, e.g., at least the BL1 layer, provide protection from moisture.52- The recyclable multilayered polymeric structure of any one of claims 1 to 48, wherein the first barrier layer BL1 is a gas barrier.53- The recyclable multilayered polymeric structure of claim 52, wherein the gas barrier is an oxygen barrier.54- Use of the recyclable multilayered polymeric structure of any one of claims 1 to 53 in a packaging.55- The use of claim 54, wherein the packaging is a flexible, a semi-rigid or a rigid packaging. 56- The use of claim 54 or 55, wherein the packaging is a food packaging.57- The use of claim 56, wherein the food packaging is a liner, a pouch, a shrink bag or a bottle.58- Use of the recyclable multilayered polymeric structure of any one of claims 1 to 53 in building liners, geomembranes, pipes or containers for liquids.59- The use of claim 58, wherein the liquid is an oil or a hydrocarbon.

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