Recycled polyolefin elastomer artificial leather

Abstract

A recycled polymer composition is provided, comprising polyolefin elastomer (POE) artificial leather and a compatibilizer comprising 3% to 10% by weight of the total weight of the recycled polymer composition. The POE artificial leather is post-consumer recycling (PCR), post-industrial recycling (PIR), or a combination of PCR and PIR. Furthermore, the POE artificial leather is formed of a laminated structure comprising a POE top layer, a fabric base layer, and a POE intermediate layer disposed between the POE top layer and the fabric base layer. The compatibilizer comprises a virgin ethylene-based polymer, wherein the virgin ethylene-based polymer is a polymerization product optionally copolymerized with one or more polar comonomers and / or grafted with ethylene. A method for producing the recycled polymer composition and articles containing the recycled polymer composition are also provided.

Description

Technical Field

[0001] The embodiments described herein generally relate to recycled polymer compositions, and more specifically to recycled polymer compositions derived from a combination of POE artificial leather and a compatibilizer, and articles derived from such recycled polymer compositions. Background Technology

[0002] Compared to competing synthetic leather products, polyolefin elastomer (POE)-based synthetic leather is considered an environmentally friendly and sustainable leather product, and its production is expected to increase. Compared to existing polyvinyl chloride (PVC) leather, POE leather is halogen-free and also free of phthalate plasticizers. Compared to another existing conventional polyurethane (PU) leather, POE leather manufacturing does not require solvents such as dimethylformamide (DMF). Therefore, POE leather production is more environmentally friendly, causing less pollution to water, air, and soil during the production process. Furthermore, from a performance perspective, POE exhibits excellent weather resistance and low-temperature flexibility, and does not experience hydrolysis or yellowing. POE leather also more easily meets the trend towards lightweight applications in luggage / bags, footwear, and automotive applications because POE has a significantly lower density than PVC (approximately 40%) and PU (approximately 25%). Therefore, it is believed that POE leather will likely replace PVC and PU leather in several applications, and its production will continue to increase. Summary of the Invention

[0003] However, due to the multi-layered structure of synthetic leather, which often exhibits poor recyclability due to the lack of compatibility between polar and non-polar polymers within the layers, separating multi-layered leather for recycling is difficult and expensive. Therefore, recycling POE synthetic leather requires consideration of recycling the entire multi-layered leather together. Consequently, a method for recycling the entire multi-layered structure of POE synthetic leather without separating and isolating the layers for further processing may be continuously needed. To meet these requirements, compatibilizers can be combined with POE synthetic leather during melt blending operations to provide compatibility between the polar and non-polar polymers in each layer.

[0004] According to at least one embodiment of this disclosure, a recycled polymer composition is provided. The recycled polymer composition comprises a polyolefin elastomer (POE) artificial leather containing POE and a compatibilizer comprising 3% to 10% by weight based on the total weight of the recycled polymer composition. Additionally, the POE artificial leather comprises a laminated structure consisting of a POE top layer, a fabric base layer, and a POE intermediate layer disposed between the POE top layer and the fabric base layer. The POE artificial leather may be a post-consumer recycled material (PCR), an industrial post-recycled material (PIR), or a combination of PCR and PIR materials. The compatibilizer comprises a virgin ethylene-based polymer, wherein the virgin ethylene-based polymer is optionally a polymerization product of copolymerization with one or more polar comonomers and / or grafted ethylene.

[0005] According to at least one embodiment of the present disclosure, a method for producing a recycled polymer composition is provided. The method may include milling POE artificial leather and melt-blending the milled POE artificial leather with a compatibilizer of 3% to 10% by weight based on the total weight of the melt blend composition to form a melt blend composition.

[0006] According to at least one embodiment of the present disclosure, an article comprising a recycled polymer composition is provided.

[0007] These and other embodiments are described in more detail below with reference to the accompanying drawings. Attached Figure Description

[0008] The following detailed description of specific embodiments of this disclosure is best understood in conjunction with the following drawings, in which similar reference numerals indicate similar structures and in the drawings: Figure 1 This is a schematic diagram of POE artificial leather according to one or more embodiments of this disclosure; Figure 2 This is a schematic diagram of a processing flow for producing a recycled polymer composition according to one or more embodiments of this disclosure; Figure 3A These are transmission electron micrographs of Comparative Example A; and Figure 3B This is a transmission electron micrograph of Embodiment 1 of the present invention according to one or more embodiments of this disclosure. Detailed Implementation

[0009] Specific embodiments of this application will now be described. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0010] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. Therefore, the general term polymer encompasses the term "homopolymer," which typically refers to a polymer prepared from only one type of monomer, and "copolymer," which refers to a polymer prepared from two or more different monomers. As used herein, the term "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. Therefore, the general term interpolymer includes copolymers or polymers prepared from more than two different types of monomers, such as terpolymers. As used herein, the term "elastomer" refers to a polymer that recovers its initial dimensions when deformed by external forces.

[0011] "Polyethylene" or "ethylene-based polymer" should mean a polymer containing more than 50 mol% of units derived from ethylene monomers. This includes ethylene-based homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylene-based polymers known in the art include, but are not limited to: low-density polyethylene (LDPE); linear low-density polyethylene (LLDPE); ultra-low-density polyethylene (ULDPE); very low-density polyethylene (VLDPE); single-point catalytic linear low-density polyethylene, including both linear low-density resins and substantially linear low-density resins (m-LLDPE); medium-density polyethylene (MDPE); and high-density polyethylene (HDPE). Ethylene copolymers can be produced using autoclaves or tubular reactors by methods well known in the polymer field. Copolymerization can be carried out in an autoclave as a continuous process, as disclosed in U.S. Patents 3,264,272; 4,351,931; 4,248,990; and 5,028,674 and International Patent Application WO99 / 25742.

[0012] "Multilayer article" means any structure having more than one layer. For example, a multilayer article may have three or more layers. A multilayer article can be described as having layers represented by letters. For example, a three-layer structure designated A / B / C may have a core layer B and two outer layers A and C. In other embodiments, a three-layer structure designated A / B / C may have a first layer A, a second layer B, and a third layer C. Similarly, a structure having two core layers B and C and two outer layers A and D may be designated A / B / C / D. As described in more detail below, a multilayer article may be a bottle.

[0013] The terms “pre-consumer recycled polymer” and “post-industrial recycled polymer” (“PIR”) refer to polymers, including blends of polymers recovered from pre-consumer materials as defined by ISO-14021. Therefore, the general term “pre-consumer recycled polymer” includes blends of polymers recovered from materials transferred from waste streams during the manufacturing process. The general term “pre-consumer recycled polymer” does not include the reuse of materials generated in the process and capable of being recovered in the same process in which they are generated, such as reprocessing, regrinding, or waste.

[0014] As used herein, the terms "post-consumer recycled resin" or "post-consumer recycled polymer" ("PCR") refer to polymeric materials recovered from materials previously used for consumer or industrial applications, as defined by ISO-14021, including blends of polymers. Therefore, the general term post-consumer recycled resin includes blends of polymers recovered from materials that are no longer usable for their intended purpose and are generated by household or commercial, industrial, and institutional facilities in their role as end-users of materials. The general term post-consumer recycled resin also includes blends of polymers recovered from returned materials from the distribution chain. PCR resins are typically collected from recycling programs and recycling plants. PCR resins may include one or more of polyethylene, polypropylene, polyester, poly(vinyl chloride), polystyrene, acrylonitrile butadiene styrene, polyamide, ethylene vinyl alcohol, ethylene vinyl acetate, or polyvinyl chloride. PCR resins may include one or more contaminants. Contaminants may be the result of the polymeric material being used prior to reuse. For example, contaminants may include paper, ink, food scraps, or other recycled materials other than polymers that may be generated from the recycling process.

[0015] PCR resins differ from virgin polymer materials. Virgin polymer materials do not include materials previously used in consumer or industrial applications. Like typical PCR resins, virgin polymer materials have not undergone, or have not otherwise undergone, heating or molding processes, except for polymer synthesis or granulation. PCR resins differ in their physical, chemical, and flow properties compared to virgin polymer resins, which can, in turn, present challenges in incorporating PCR resins into commercially applicable formulations.

[0016] Now, detailed reference will be made to embodiments of recycled polymer compositions comprising recycled polyolefin elastomer (POE) artificial leather. The recycled polymer composition comprises polyolefin elastomer artificial leather and a compatibilizer comprising 3% (wt.%) to 10% (wt.%) based on the total weight of the recycled polymer composition. Typically, the POE artificial leather comprises a laminated structure consisting of a POE top layer, a fabric base layer, and a POE intermediate layer disposed between the POE top layer and the fabric base layer. Additionally, the compatibilizer comprises a virgin ethylene-based polymer, wherein the virgin ethylene-based polymer is optionally a polymerization product of copolymerization with one or more polar comonomers and / or grafted ethylene.

[0017] The recycled polymer compositions have been generally described, and further details of the components that form the recycled polymer compositions are provided below.

[0018] Polyolefin elastomer (POE) artificial leather is a multilayered product containing a multi-layered laminated structure. (Reference) Figure 1 The POE artificial leather 10 is formed by stacking a POE top layer 20, a fabric base layer 30, and a POE intermediate layer 40. The POE intermediate layer 40 is disposed between the POE top layer 20 and the fabric base layer 30, thereby forming a laminated structure.

[0019] The POE top layer 20 of the POE artificial leather 10 provides the POE artificial leather 10 with mechanical strength, as well as flexibility and softness. As a layer disposed on or near the surface of the POE artificial leather 10, the POE top layer 20 provides the POE artificial leather 10 with tactile and sensory responsiveness.

[0020] The POE intermediate layer 40 of the POE artificial leather 10 provides increased thickness and softness to the POE artificial leather 10. As the central layer of the POE artificial leather 10, the POE intermediate layer 40 provides bulk and increased thickness to the POE artificial leather 10.

[0021] The POE top layer 20 contains a polyolefin elastomer. Similarly, the POE intermediate layer 40 contains a polyolefin elastomer. The "polyolefin elastomer" can be a polyethylene elastomer or a polypropylene elastomer. The POE top layer 20 and the POE intermediate layer 40 can contain the same or different polyolefin elastomers.

[0022] In one or more embodiments, the POE top layer 20, the POE intermediate layer 40, or both the POE top layer 20 and the POE intermediate layer 40 comprise a propylene-based polymer having a density of 0.850 g / cc to 0.900 g / cc. In other embodiments, the propylene-based polymer may have a density of about 0.850 g / cm³. 3 Approximately 0.895 g / cm³ 3 or approximately 0.850 g / cm³ 3Approximately 0.890 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.885 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.880 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.875 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.870 g / cm³ 3 or 0.855g / cm 3 Approximately 0.895 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.890 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.885 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.880 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.875 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.870 g / cm³ 3 or 0.860 g / cm 3 Approximately 0.895 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.890 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.885 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.880 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.875 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.870 g / cm³ 3 or approximately 0.865 g / cm³ 3 Approximately 0.869 g / cm³ 3 The density.

[0023] In one or more embodiments, the POE top layer 20, the POE intermediate layer 40, or both the POE top layer 20 and the POE intermediate layer 40 comprise a propylene-based polymer with a melt index (I2) of 0.5 g / 10 min to 32 g / 10 min when measured at 230 °C and 2.16 kg according to ASTM D1238. In some embodiments, the propylene-based polymer may have a content of about 0.2 g / 10 min to about 30.0 g / 10 min, about 0.2 g / 10 min to about 25.0 g / 10 min, about 0.2 g / 10 min to about 20.0 g / 10 min, about 0.2 g / 10 min to about 15.0 g / 10 min, about 0.2 g / 10 min to about 10.0 g / 10 min, about 1.0 g / 10 min to about 30.0 g / 10 min, about 1.0 g / 10 min to about 25.0 g / 10 min, or about 1.0 g / 10 min to about 20.0 g. Melt index of about 10 min, about 1.0 g / 10 min to about 15.0 g / 10 min, about 1.0 g / 10 min to about 10.0 g / 10 min, about 5.0 g / 10 min to about 30.0 g / 10 min, about 5.0 g / 10 min to about 25.0 g / 10 min, about 5.0 g / 10 min to about 20.0 g / 10 min, about 5.0 g / 10 min to about 15.0 g / 10 min, about 5.0 g / 10 min to about 10.0 g / 10 min, or about 6.0 g / 10 min to about 10.0 g / 10 min.

[0024] According to various embodiments, such propylene-based polymer having the disclosed properties may be present in POE artificial leather 10 at a maximum of 30 wt%, a maximum of 25 wt%, a maximum of 20 wt%, or a maximum of 18 wt%, wherein the lower limits are 0 wt%, 5 wt%, 8 wt%, 10 wt%, or 12 wt%.

[0025] In one or more embodiments, the POE top layer 20, the POE intermediate layer 40, or both the POE top layer 20 and the POE intermediate layer 40 comprise an olefin block copolymer having a density of 0.850 g / cc to 0.900 g / cc. In other embodiments, the olefin block copolymer may have a density of about 0.850 g / cm³. 3 Approximately 0.895 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.890 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.885 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.880 g / cm³3 or approximately 0.850 g / cm³ 3 Approximately 0.875 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.870 g / cm³ 3 or 0.855g / cm 3 Approximately 0.895 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.890 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.885 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.880 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.875 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.870 g / cm³ 3 or 0.860 g / cm 3 Approximately 0.895 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.890 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.885 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.880 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.875 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.870 g / cm³ 3 or approximately 0.865 g / cm³ 3 Approximately 0.870 g / cm³ 3 or approximately 0.865 g / cm³ 3 Approximately 0.869 g / cm³ 3 The density.

[0026] In one or more embodiments, the POE top layer 20, the POE intermediate layer 40, or both the POE top layer 20 and the POE intermediate layer 40 comprise an olefin block copolymer with a melt index (I2) of 0.5 g / 10 min to 32 g / 10 min when measured according to ASTM D1238 at 190°C and 2.16 kg. In some embodiments, the olefin block copolymer may have a melt index (I2) of about 0.2 g / 10 min to about 30.0 g / 10 min, about 0.2 g / 10 min to about 25.0 g / 10 min, about 0.2 g / 10 min to about 20.0 g / 10 min, about 0.2 g / 10 min to about 15.0 g / 10 min, about 0.2 g / 10 min to about 10.0 g / 10 min, about 0.2 g / 10 min to about 5.0 g / 10 min, or about 0.2 g / 10 min to about 1.0 g / 10 min. Melt index of 0 min, about 1.0 g / 10 min to about 30.0 g / 10 min, about 1.0 g / 10 min to about 25.0 g / 10 min, about 1.0 g / 10 min to about 20.0 g / 10 min, about 5.0 g / 10 min to about 30.0 g / 10 min, about 5.0 g / 10 min to about 25.0 g / 10 min, about 5.0 g / 10 min to about 20.0 g / 10 min, or about 10.0 g / 10 min to about 20.0 g / 10 min.

[0027] According to various embodiments, such olefin block copolymers having the disclosed properties may be present in POE artificial leather 10 at a maximum of 90 wt%, a maximum of 80 wt%, a maximum of 75 wt%, or a maximum of 70 wt%, wherein the lower limits are 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 25 wt%.

[0028] In one or more embodiments, the POE top layer 20, the POE intermediate layer 40, or both the POE top layer 20 and the POE intermediate layer 40 comprise an ethylene-octene copolymer having a density of 0.850 g / cc to 0.900 g / cc. In other embodiments, the ethylene-octene copolymer may have a density of about 0.850 g / cm³. 3 Approximately 0.895 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.890 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.885 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.880 g / cm³ 3 or approximately 0.850 g / cm³ 3 Approximately 0.875 g / cm³3 or approximately 0.850 g / cm³ 3 Approximately 0.870 g / cm³ 3 or 0.855g / cm 3 Approximately 0.895 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.890 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.885 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.880 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.875 g / cm³ 3 or approximately 0.855 g / cm³ 3 Approximately 0.870 g / cm³ 3 or 0.860 g / cm 3 Approximately 0.895 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.890 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.885 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.880 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.875 g / cm³ 3 or approximately 0.860 g / cm³ 3 Approximately 0.870 g / cm³ 3 or approximately 0.861 g / cm³ 3 Approximately 0.865 g / cm³ 3 The density.

[0029] In one or more embodiments, the POE top layer 20, the POE intermediate layer 40, or both the POE top layer 20 and the POE intermediate layer 40 comprise an ethylene-octene copolymer with a melt index (I2) of 0.1 g / 10 min to 2 g / 10 min when measured at 190 °C and 2.16 kg according to ASTM D1238. In some embodiments, the ethylene-octene copolymer may have a content of about 0.1 g / 10 min to about 1.8 g / 10 min, about 0.1 g / 10 min to about 1.6 g / 10 min, about 0.1 g / 10 min to about 1.4 g / 10 min, about 0.1 g / 10 min to about 1.2 g / 10 min, about 0.1 g / 10 min to about 1.0 g / 10 min, about 0.2 g / 10 min to about 2.0 g / 10 min, about 0.2 g / 10 min to about 1.8 g / 10 min, about 0.2 g / 10 min to about 1.6 g / 10 min, about 0.2 g / 10 min to about 1.4 g / 10 min, about 0.2 g / 10 min to about 1.2 g / 10 min, and about 0.2 g / 10 min. Melt index from about 0.3 g / 10 min to about 1.0 g / 10 min, from about 0.3 g / 10 min to about 2.0 g / 10 min, from about 0.3 g / 10 min to about 1.8 g / 10 min, from about 0.3 g / 10 min to about 1.6 g / 10 min, from about 0.3 g / 10 min to about 1.4 g / 10 min, from about 0.3 g / 10 min to about 1.2 g / 10 min, from about 0.3 g / 10 min to about 1.0 g / 10 min, from about 0.4 g / 10 min to about 2.0 g / 10 min, from about 0.4 g / 10 min to about 1.0 g / 10 min, from about 0.4 g / 10 min to about 0.8 g / 10 min, or from about 0.4 g / 10 min to about 0.6 g / 10 min.

[0030] According to various embodiments, such ethylene-octene copolymer having the disclosed properties may be present in POE artificial leather 10 in up to 30 wt%, up to 25 wt%, up to 20 wt% or up to 18 wt%, wherein the lower limit is 0 wt%, 5 wt%, 8 wt%, 10 wt% or 12 wt%.

[0031] In one or more embodiments, the POE interlayer 40 comprises a foamed polyolefin elastomer. The foamed polyolefin elastomer reduces the weight of the POE interlayer 40 while maintaining the desired thickness. The foamed polyolefin elastomer is prepared by adding a blowing agent to the polyolefin elastomer of the POE interlayer 40. As understood by those skilled in the art, a blowing agent is an agent that promotes foam formation during the manufacturing process. An example blowing agent is AC 9000 (azodicarbonamide), commercially available from Kum Yang Ltd. In one or more embodiments, no blowing agent is used, and the POE interlayer 40 comprises an unfoamed polyolefin elastomer.

[0032] The fabric base layer 30 of the POE artificial leather 10 provides strength to the POE artificial leather 10. The fabric base layer 30 is provided as an inner layer or backing layer of the POE artificial leather 10. In one or more embodiments, the fabric base layer 30 is a nonwoven or woven material. The nonwoven or woven material of the fabric base layer 30 provides strength in multiple directions. Additionally, in one or more embodiments, the fabric base layer 30 comprises polyethylene terephthalate (PET). Therefore, the POE artificial leather 10 comprises both a polyolefin elastomer and polyethylene terephthalate, as well as other components of each layer, which must be processed simultaneously to allow for batch recycling of the POE artificial leather 10.

[0033] In one or more embodiments, the POE synthetic leather includes a coating 60 disposed on a surface adjacent to the POE top layer 20. Specifically, the coating 60 can be considered as disposed on the POE top layer 20. The coating 60 provides the POE synthetic leather 10 with abrasion resistance, stain resistance, and desired tactile properties. Specifically, since the coating 60 provides the outer front surface of the POE synthetic leather 10, the coating 60 provides a surface resistant to abrasion (such as scratches, abrasions, and / or stains). Additionally, since the coating 60 provides the outer front surface of the POE synthetic leather 10, it becomes the surface that the user comes into contact with in articles made from the POE synthetic leather, and the coating 60 provides the desired tactile feel; in other words, the coating is not considered a surface with an unpleasant tactile feel, but more preferably a surface with a pleasant tactile feel.

[0034] In one or more embodiments, coating 60 comprises polyurethane, acrylate, or a combination thereof. Commercially available examples include WF-77-307 and XR-48-920 from Stahl, Waalwijk, Netherlands.

[0035] In one or more embodiments, the POE synthetic leather 10 may further include a primer layer 70 located between the POE top layer 20 and the coating 60. The primer layer 70 facilitates adhesion between the coating 60 and the POE top layer 20. Commercially available examples include HYPOD from The Dow Chemical Company, Midland, Michigan. ™ 1000 and toluene-free primer P339 and NUV primer P938 from NANPAO ResinsChemical Co., Ltd., Tainan City, Taiwan, China.

[0036] In one or more embodiments, the POE synthetic leather 10 includes one or more adhesive layers 50 that bond the various layers of the POE synthetic leather 10 together. Specifically, in one or more embodiments, the adhesive layer 50 may be disposed between the fiber base layer 30 and the POE intermediate layer 40. Commercially available examples include HYPOD from Dow Chemical Company, Midland, Michigan. ™ 1000, BYNEL ™ 22E757 and BYNEL ™ 21E533.

[0037] It should be understood that while the compositional details of a specific POE synthetic leather according to a selected embodiment of this disclosure are described in detail, the scope of POE synthetic leather that may be used under this disclosure should be interpreted broadly. Specifically, it is envisioned that various synthetic leathers comprising a polyolefin elastomer layer and a polyethylene terephthalate fabric can be processed and recycled to produce the recycled polymer compositions according to this disclosure.

[0038] The compatibilizer provided as a component of the recycled polymer composition comprises the original ethylene-based polymer. Additionally, the original ethylene-based polymer is a polymerization product of ethylene. In one or more embodiments, the original ethylene-based polymer is a polymerization product of ethylene copolymerized with one or more polar comonomers. The original ethylene-based polymer may additionally or alternatively be a polymerization product of ethylene grafted with one or more polar comonomers.

[0039] In one or more embodiments, the compatibilizer comprises a terpolymer of ethylene, alkyl acrylate, and glycidyl ester. In one or more embodiments where the compatibilizer comprises a terpolymer of ethylene, alkyl acrylate, and glycidyl ester, the alkyl acrylate comprises n-butyl acrylate, isobutyl acrylate, methyl acrylate, ethyl acrylate, or combinations thereof. Additionally, in one or more embodiments where the compatibilizer comprises a terpolymer of ethylene, alkyl acrylate, and glycidyl ester, the glycidyl ester comprises glycidyl methacrylate.

[0040] In one or more embodiments, as measured according to ASTM D792-91, the terpolymer of ethylene, alkyl acrylate, and glycidyl ester has a content of less than about 1,000 g / cm³. 3 ), or approximately 0.900 g / cm³ 3 Approximately 1.000 g / cm³ 3 The density is [not specified]. Other density ranges may be approximately 0.900 g / cm³. 3 To approximately 0.990 g / cm³ 3 Approximately 0.900 g / cm³ 3 Approximately 0.980 g / cm³ 3 Approximately 0.900 g / cm³ 3 Approximately 0.960 g / cm³ 3 Approximately 0.920 g / cm³ 3 Approximately 1.000 g / cm³ 3 Approximately 0.920 g / cm³ 3 Approximately 0.980 g / cm³ 3 Approximately 0.920 g / cm³ 3 Approximately 0.960 g / cm³ 3 or approximately 0.930 g / cm 3 Approximately 0.950 g / cm³ 3 .

[0041] In one or more embodiments, the terpolymer of ethylene, alkyl acrylate, and glycidyl ester may have a melt index (I2) of about 1 g / 10 min to about 50 g / 10 min, about 1 g / 10 min to about 30 g / 10 min, about 1 g / 10 min to about 20 g / 10 min, about 1 g / 10 min to about 15 g / 10 min, about 5 g / 10 min to about 30 g / 10 min, about 5 g / 10 min to about 20 g / 10 min, about 5 g / 10 min to about 18 g / 10 min, or about 10 g / 10 min to about 15 g / 10 min, as determined by ASTM method D1238 at 230 °C and 2.16 kg.

[0042] In one or more embodiments, the compatibilizer may be an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin elastomer. The anhydride and / or carboxylic acid-functionalized ethylene / α-olefin elastomer may be a base polymer having anhydride and / or carboxylic acid graft monomers grafted thereon.

[0043] In one or more embodiments, based on the total weight of the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin elastomer, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin elastomer comprises up to 10 wt%, up to 5 wt%, or 1 wt% to 4 wt% of anhydride and / or carboxylic acid-functionalized graft monomers. The weight percentage of the ethylene-based polymer is complementary to the amount of the anhydride and / or carboxylic acid-functionalized graft monomers, such that the sum of the weight percentages of the ethylene-based polymer and the anhydride and / or carboxylic acid-functionalized monomers is 100 wt%. Therefore, based on the total weight of the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin elastomer, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin elastomer comprises up to 90 wt%, up to 95 wt%, or 96 wt% to 99 wt% of the ethylene-based polymer.

[0044] In one embodiment, an anhydride and / or carboxylic acid graft monomers are grafted onto the polyolefin. Examples of anhydride grafted portions may include, but are not limited to, maleic anhydride, citrate anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic anhydride, bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic anhydride and 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic anhydride, o-octahydronaphthyl-2,3-dicarboxylic anhydride, 2-oxa-1,3-diketospiro(4.4)non-7-ene, bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride, norbornene-5-ene-2,3-dicarboxylic anhydride, nadic anhydride, methylnadic anhydride, and himic anhydride. (anhydride), methylhammic anhydride, and x-methyl-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic anhydride. In one embodiment, the anhydride graft portion comprises maleic anhydride.

[0045] In one or more embodiments, as measured according to ASTM D792-91, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin elastomer has a content of less than about 0.910 g / cm³. 3 or approximately 0.850 g / cm³ 3 Approximately 0.910 g / cm³ 3 The density is [not specified]. Other density ranges may be approximately 0.850 g / cm³. 3 To approximately 0.900 g / cm 3 Approximately 0.850 g / cm³3 Approximately 0.880 g / cm³ 3 Approximately 0.850 g / cm³ 3 Approximately 0.860 g / cm³ 3 Approximately 0.860 g / cm³ 3 Approximately 0.910 g / cm³ 3 Approximately 0.860 g / cm³ 3 Approximately 0.880 g / cm³ 3 Approximately 0.880 g / cm³ 3 Approximately 0.910 g / cm³ 3 or approximately 0.880 g / cm 3 To approximately 0.900 g / cm 3 .

[0046] In one or more embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin elastomer may have a melt index (I2) of about 1 g / 10 min to about 800 g / 10 min, about 1 g / 10 min to about 600 g / 10 min, about 1 g / 10 min to about 300 g / 10 min, about 1 g / 10 min to about 200 g / 10 min, about 1 g / 10 min to about 100 g / 10 min, or about 1 g / 10 min to about 50 g / 10 min, as determined by ASTM method D1238 at 230 °C and 2.16 kg.

[0047] Based on the total weight of the recycled polymer composition, the compatibilizer is present in the recycled polymer composition in the range of 3% to 10% by weight. This document includes and discloses any and all ranges from 3% to 10% by weight; for example, the compatibilizer may be present in the recycled polymer composition in the range of 5% to 10% by weight, 3% to 8% by weight, or 4% to 6% by weight.

[0048] In one or more embodiments, the recycled polymer composition comprises one or more additives. In one or more embodiments, the additives include one or more of inorganic fillers, antioxidants, pigments, and processing aids. Example inorganic fillers include calcium carbonate, magnesium silicate, calcium sulfate, mica, calcium silicate, barium sulfate, and kaolin. Antioxidants can be added to plastics to inhibit degradation caused by thermomechanical or thermo-oxidative conditions. Commonly used antioxidants include phenolic antioxidants, such as simple phenols, bisphenols, polyphenols, and thiobisphenols. Example pigments include masterbatches. Masterbatches are concentrated solid mixtures of pigments encapsulated in resin or wax, which allow for easier addition of pigments to the recycled polymer composition. Processing aids are materials added to improve the processability of the polymer compound. An exemplary processing aid is zinc stearate, which can be used as a release agent, heat stabilizer, and lubricant in plastic processing.

[0049] Another embodiment of this disclosure includes, in particular, a method for producing a recycled polymer composition. The production of the recycled polymer composition includes milling POE artificial leather and melt-blending the milled POE artificial leather with a compatibilizer to form a melt-blended composition.

[0050] refer to Figure 2 This disclosure provides processing steps for recycling POE-based synthetic leather according to one or more embodiments. Process 100 begins by supplying POE-based synthetic leather from various sources. POE-based synthetic leather 110 for recycling can be supplied directly from the production facility as unused and / or unsold POE-based synthetic leather 112. Similarly, POE-based synthetic leather 110 for recycling can be supplied as waste POE-based synthetic leather 114 generated during the manufacture of consumer products utilizing POE-based synthetic leather. For example, waste is generated as part of the manufacturing process during the production of golf bags containing synthetic leather or furniture upholstered in synthetic leather. Each of the unused and / or unsold POE-based synthetic leather 112 directly from the production facility and the waste POE-based synthetic leather 114 generated during the manufacture of consumer products is classified as post-industrial recycling (PIR). POE-based synthetic leather 110 for recycling can also be supplied to process 100 as consumer-recycled POE-based synthetic leather 116. The consumer-recycled POE synthetic leather 116 is classified as post-consumer recycling (PCR), meaning it is provided as part of a batch recycling stream generated by the public, rather than directly from a manufacturing or product production facility. The PIR stream provides more insight into the composition of the POE synthetic leather 110 used for recycling, but the PCR stream provides a larger pool of resources from which to extract, thus enhancing the overall recycling. The process 100 of this disclosure allows for the use of both the PIR and PCR streams, alone or in combination, to produce recycled polymer compositions.

[0051] Continue to refer to Figure 2In one or more embodiments, POE synthetic leather 110 for recycling is provided to a grinding step 130 having a system for grinding POE synthetic leather. For the purposes of this disclosure, “grinding POE synthetic leather” means reducing whole POE synthetic leather to smaller particle sizes. The mechanism by which POE synthetic leather is ground and reduced to smaller particles is not critical to the method of this disclosure and can be achieved using any method known to those skilled in the art. For example, POE synthetic leather can be sliced, shredded, cut, shredded, ground, or milled to reduce the POE synthetic leather to smaller particle sizes. The particle size of the ground POE synthetic leather is limited only by the melt kinetics of the POE synthetic leather and the melt blending process used to combine the ground POE synthetic leather with a compatibilizer. POE synthetic leather 110 for recycling is provided to the grinding step 130 as an unused POE synthetic leather stream 122, a waste POE synthetic leather stream 124, and / or a consumer recycled POE synthetic leather stream 126.

[0052] In the melt blending step 150, the milled POE artificial leather is combined with a compatibilizer. Specifically, the milled POE artificial leather from the milling step 130 is mixed with the compatibilizer supplied as a compatibilizer stream 140 to the melt blending step 150. Although Figure 2 The milled POE artificial leather and compatibilizer are shown to be supplied as separate streams to the melt blending step 150, but it will be readily understood that they can be combined and supplied as a single stream prior to the melt blending step 150.

[0053] The melt blending step 150 can be implemented using any polymer blending system known to those skilled in the art. According to various embodiments, the melt blending step 150 can utilize a twin-screw extruder, a single-screw extruder, or other conventional systems. In one or more specific embodiments, the melt blending step 150 utilizes a twin-screw extruder. The screw speed of the extruder can be in the range of 300 rpm to 600 rpm, and the feed rate can range from 5 kg / h to 20 kg / h. Additionally, in the melt blending step, the raw material can be heated to a temperature in the range of 240°C to 260°C for blending.

[0054] In one or more embodiments, a method for producing a recycled polymer composition includes granulating the melt-blended composition in a granulation step 160. Additionally, in one or more embodiments, the granules may be formed into articles made from the recycled polymer composition in a product manufacturing step 170. Articles made from the recycled polymer composition can be formed from the granules by any method known to those skilled in the art. These methods include, but are not limited to, molding, extrusion, blown film, cast film, and combinations thereof.

[0055] Another embodiment of this disclosure includes, in particular, articles produced from recycled polymer compositions. In some embodiments, the articles may be molded or manufactured articles. Articles may include injection-molded films, injection-molded articles, blown films, blown articles, molded articles, melt-spun fibers, or extruded articles.

[0056] When observed by transmission electron microscopy, embodiments of the recycled polymer composition and articles made from the recycled polymer composition may have PET particle sizes of less than 2 μm. In other embodiments, when observed by transmission electron microscopy, the recycled polymer composition and articles made from the recycled polymer composition may have PET particle sizes of less than 1.5 μm, 1.0 μm, 0.5 μm, or 0.3 μm. Without being bound by theory, it is believed that lower particle sizes indicate a higher level of compatibilization achieved by the recycled structure.

[0057] Test methods

[0058] The testing methods include the following: Gloss (60°) To test gloss, samples were prepared and measured according to ASTM D523-6 and reported in standard gloss units (%).

[0059] Flexural modulus (MPa)

[0060] To test the flexural modulus, samples were prepared and measured according to ASTM D790, and the results were reported in megapascals (MPa).

[0061] Tensile strength (MPa)

[0062] To test fracture stress, samples were prepared and measured according to ASTM D638, and the results were reported in megapascals (MPa).

[0063] Elongation (%)

[0064] To test elongation at break, samples were prepared and measured according to ASTM D638, and reported as a percentage of elongation (%).

[0065] Density (g / cm³) 3 )

[0066] To test density, samples were prepared according to ASTM D792, and ethylene was measured at 190°C and 2.16 kg, and propylene at 230°C and 2.16 kg, expressed in grams per cubic centimeter (g / cm³). 3 Report as a unit.

[0067] M

[0068] To test the melt index, samples were prepared and measured according to ASTM D1238 and reported in grams per 10 minutes (g / 10min).

[0069] Example

[0070] The following examples illustrate features of this disclosure but are not intended to limit its scope. The following experiments analyze the performance of embodiments of the recycled polymer compositions described herein.

[0071] POE artificial leather 1

[0072] The first representative POE synthetic leather was produced and named POE Synthetic Leather 1. POE Synthetic Leather 1 comprises a three-layer arrangement, consisting of a top POE layer, a middle POE layer, and a PET nonwoven fabric layer. The top POE layer has a thickness of approximately 0.1 mm and is composed of 80% Versify... ™ 3300 and 20% Infuse ™ The POE layer is formed from 9077. The intermediate POE layer has a thickness of approximately 0.2 mm and is formed from 100% Infuse 9107. The PET nonwoven fabric has a thickness of approximately 0.1 mm and is sourced from Xingda manufacturer. The main composition forming POE artificial leather 1 is approximately 17% by weight of Versify. ™ 3300, approximately 4% by weight of Infuse ™ 9077, approximately 66% by weight of Infuse ™ 9107 and approximately 13% by weight of PET.

[0073]

[0074] POE artificial leather 2

[0075] A second representative POE artificial leather was produced and named POE Artificial Leather 2. POE Artificial Leather 2 comprises a four-layer arrangement with a polyurethane coating, a top POE layer, a middle POE layer, and a PET woven fabric layer. The polyurethane coating has a thickness of approximately 0.05 mm and is formed by cross-linked polyurethane. Specifically, the coating is mixed with 4% PERMUTEX. ® XR-48-920 (Starr Company) crosslinking agent blend with PERMUTEX ® WF-77-307 (Starr Company). The top POE layer is approximately 0.15mm thick and is made of 65% Versify. ™ 3300 and 35% Infuse ™The POE layer is formed from 9077. The top POE layer further comprises 2 parts / 100 parts of a polyethylene-based color masterbatch (PHR). The middle POE layer has a thickness of approximately 0.25 mm and is formed from 50% Infuse 9807 and 50% Engage 8180. The middle POE layer also comprises 0.8 phr AC 9000 foaming agent, 0.4 phr ZnO, 0.2 phr CaSt, 0.2 phr talc, and 2 phr PE-based color masterbatch. The PET woven fabric has a thickness of approximately 0.4 mm and is sourced from Warren. The main composition forming POE artificial leather 2 is approximately 1% by weight polyurethane and approximately 15% by weight Versify. ™ 3300, approximately 8% by weight of Infuse ™ 9077, approximately 17% by weight of Infuse ™ 9807, approximately 17% by weight of Engage ™ 8108 and approximately 43% by weight of PET.

[0076]

[0077] To demonstrate the improvements provided according to this disclosure, POE artificial leather 1 and POE artificial leather 2 were processed into injection-molded specimens. To prepare the injection-molded specimens, the POE artificial leather was ground into small pieces. The ground POE artificial leather was fed into a ZSK 18ML twin-screw extruder, commercially available from Coperion GmbH, Stuttgart, Germany, at a set temperature of 240°C to 260°C to produce granules. For Comparative Example A, POE artificial leather 1 was processed without a compatibilizer. Similarly, for Comparative Example B, POE artificial leather 2 was processed without a compatibilizer. The ground POE artificial leather 1 was mixed with 5 phr of Elvaloy... ™ PTW and 0.2 phr Irganox ® B225 was supplied together with a twin-screw extruder to prepare Example 1 of the present invention. Similarly, by mixing milled POE artificial leather 2 with 5 phr of Elvaloy... ™ PTW (available commercially from Dow Chemical Company) and 0.2 phr of Irganox ® B225 (commercially available from BASF) was supplied together with a twin-screw extruder to prepare Example 2 of the present invention. The compositions of each of Comparative Example A, Comparative Example B, Example 1 of the present invention, and Example 2 of the present invention are provided in Table 3.

[0078]

[0079] The granulated products of Comparative Example A, Comparative Example B, Example 1 of the present invention, and Example 2 of the present invention were injection molded into specimens for performance testing. The injection temperature was 260°C to 280°C. The specimens were tested according to the test methods provided above. The test results are provided in Table 4.

[0080]

[0081] Figure 3A and Figure 3B Comparative Example A is shown. Figure 3A ) and Embodiment 1 of the present invention ( Figure 3B Micrograph of (as shown above). Figure 3A and Figure 3B As shown, Example 1 of the present invention has a smaller granularity compared to Comparative Example A. It is believed that the smaller granularity indicates that Example 1 of the present invention achieves a higher level of capacity expansion, which is consistent with the test data in Table 4.

[0082] It is obvious that modifications and variations are possible without departing from the scope of this disclosure as defined in the appended claims. More specifically, although some aspects of this disclosure are identified herein as preferred or particularly advantageous, it is considered that this disclosure is not necessarily limited to these aspects.

Claims

1. A recycled polymer composition comprising polyolefin elastomer (POE) artificial leather and a compatibilizer comprising 3% to 10% by weight based on the total weight of the recycled polymer composition, wherein: The POE artificial leather is a post-consumer recycled (PCR), industrial post-recycled (PIR), or a combination of PCR and PIR; The POE artificial leather comprises a laminated structure consisting of a POE top layer, a fabric base layer, and a POE intermediate layer disposed between the POE top layer and the fabric base layer; and The compatibilizer comprises a native ethylene-based polymer, wherein the native ethylene-based polymer is a polymerization product of ethylene optionally copolymerized with one or more polar comonomers and / or grafted with ethylene.

2. The recycled polymer composition of claim 1, wherein the POE interlayer comprises a foamed polyolefin elastomer.

3. The recycled polymer composition of claim 1, wherein the POE interlayer comprises an unfoamed polyolefin elastomer.

4. The recycled polymer composition according to any one of claims 1 to 3 further comprises a coating on the top layer of the POE, wherein the coating comprises polyurethane, acrylate, or a combination thereof.

5. The recycled polymer composition according to any one of claims 1 to 4, wherein the fabric base layer comprises polyethylene terephthalate.

6. The recycled polymer composition according to any one of claims 1 to 5, wherein the POE comprises a propylene-based polymer having a density of 0.850 g / cc to 0.900 g / cc and a melt flow rate of 0.5 g / 10 min to 32 g / 10 min as measured according to ASTM D1238 (230°C, 2.16 kg).

7. The recycled polymer composition according to any one of claims 1 to 6, wherein the POE comprises an olefin block copolymer having a density of 0.850 g / cc to 0.900 g / cc and a melt index (I2) of 0.1 g / 10 min to 32 g / 10 min as measured according to ASTM D1238 (190°C, 2.16 kg).

8. The recycled polymer composition according to any one of claims 1 to 7, wherein the compatibilizer comprises a terpolymer of ethylene, alkyl acrylate and glycidyl ester.

9. The recycled polymer composition of claim 8, wherein the alkyl acrylate comprises n-butyl acrylate, isobutyl acrylate, methyl acrylate, ethyl acrylate, or combinations thereof.

10. The recycled polymer composition according to claim 8 or 9, wherein the glycidyl ester comprises glycidyl methacrylate.

11. The recycled polymer composition according to any one of claims 1 to 10, wherein the recycled polymer composition comprises one or more of inorganic fillers, antioxidants, pigments, and processing aids.

12. An article comprising the recycled polymer composition according to any one of claims 1 to 11.

13. A method for producing the recycled polymer composition according to any one of claims 1 to 11, wherein the method comprises: Grind the POE artificial leather; as well as The milled POE artificial leather is melt-blended with a compatibilizer of 3% to 10% by weight based on the total weight of the melt blend composition to form the melt blend composition.

14. The method of claim 13, further comprising granulating the melt blend composition.

15. The method of claim 14, further comprising molding the granules into an article.

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