Multi-layer preform and container with polyethelene furanoate
By integrating PEF into a multi-layer preform for PET containers, the issues of reduced stretch ratio and haze in recycled PET are mitigated, resulting in improved mechanical properties and barrier performance without the use of nylon.
Patent Information
- Application Number
- PCT/US2024/060350
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-12-14
- Filing Date
- 2024-12-16
- Publication Date
- 2025-06-19
AI Technical Summary
Recycled PET containers face challenges such as reduced stretch ratio, increased haze, and mechanical weaknesses due to molecular weight degradation and thermal processes during recycling.
Incorporating polyethylene furanoate (PEF) into a multi-layer preform, particularly as a middle layer, to enhance the stretch ratio and barrier properties of PET containers, while maintaining recyclability and avoiding the use of nylon.
The addition of PEF helps maintain or improve the stretch ratio and optical clarity of PET containers, providing a recyclable and effective CO2 barrier without the need for nylon, thus addressing the limitations of recycled PET.
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Figure US2024060350_19062025_PF_FP_ABST
Abstract
Description
MULTI-LAYER PREFORM AND CONTAINER WITH POLYETHELENE FURANOATE CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 610,120, filed on Dec. 14, 2023, the entirety of which is incorporated herein by reference. TECHNICAL FIELD
[0002] The present disclosure generally relates to multi-layer preforms and containers that include polyethylene furanoate (PEF). BACKGROUND
[0003] Plastic containers are used to hold a variety of contents. Plastic containers may be comprised of various polymers and may include barriers.
[0004] However, it is known that with polymers, such as polyethylene terephthalate (PET), each recycling cycle involves mechanical and thermal processes – for example, grinding, remelting, and extrusion. Such process steps can expose the polymer (e.g., PET) to thermal and shear stresses, which can lead to chain scission and can reduce the molecular weight of the polymer, and which can decrease its intrinsic viscosity (IV). Further, the stretch ratio (extent to which PET can be elongated during biaxial stretching can depend, at least in part, on the polymer’s molecular weight and chain entanglement density. A lower molecular weight can result in reduced chain entanglements, which can in turn limit the polymer’s ability to be stretched without breaking. Consequently, a stretch ratio for a polymer material can decrease, at least slightly, with each recycling cycle.
[0005] Additionally, there can sometimes be an increase in haze associated with recycled polymer (e.g., PET) articles. Repeated heating and cooling cycles during the recycling process can lead to changes in the crystallinity of a polymer. Increased crystallinity or the presence of smaller, irregular crystals can scatter light more effectively, which can cause haze. Contaminants (such asforeign polymers or residual additives) introduced during the recycling process may not fully disperse in the PET matrix. These inclusions can scatter light and increase haze. Further, thermal degradation can produce low molecular weight byproducts or oligomers that disrupt the uniformity of the material. The optical clarity of PET relies on a uniform amorphous phase. Recycling can introduce inconsistencies in the amorphous phase due to, for example, uneven thermal history or molecular degradation, which can further contribute to haze.
[0006] With blow molding, a polymer such as PET is stretched and blown into a resultant shape. The process relies on the polymer’s stretch ratio and optical properties. When the stretch ratio is reduced due to molecular weight degradation, the material may not stretch uniformly, which can lead to mechanical weaknesses or variations in thickness. Similarly, increased haze could affect the aesthetic quality of transparent containers, which could make recycled (or overly recycled) PET less desirable for applications requiring high optical clarity, such as beverage bottles.
[0007] It can be desirable to address some or all of the above challenges.
[0008] It can further be desirable to provide a nylon-free, recyclable preform and / or container, such as a PET preform or container that among other things, imparts a barrier, for example, a CO2barrier. SUMMARY
[0009] Aspects and features of the present disclosure may address one or more challenges associated with the prior art. BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Further advantages, features and details of the disclosure result from the following description of embodiments as well as from the drawings.
[0011] While the claims are not limited to a specific illustration, an appreciation of various aspects may be gained through a discussion of various examples. The drawings are not necessarily to scale, and certain features may be exaggerated or hidden to better illustrate and explain an innovative aspect of an example. Further, the exemplary illustrations described herein are not exhaustive or otherwise limiting, and embodiments are not restricted to the precise form and configuration shown in the drawings or disclosed in the following detailed description. Exemplary illustrations are described in detail by referring to the drawings as follows:
[0012] FIG. 1 is a cross sectional elevation view generally illustrating an embodiment of a preform according to aspects or teachings of the present disclosure;
[0013] FIG. 2A is a side elevation view generally illustrating an embodiment of preform according to aspects or teachings of the present disclosure;
[0014] FIGS. 2B, 2C, and 2D are partial sectional views of portions of the preform shown in FIG. 2A;
[0015] FIG. 3 is an elevation view generally illustrating an embodiment of a container according to aspects or teachings of the present disclosure;
[0016] FIG. 4 is a perspective view generally illustrating an embodiment of a preform;
[0017] FIG. 5 is an elevation view generally illustrating an embodiment of a container formed from the preform of FIG. 4;
[0018] FIG. 6 is a perspective view generally illustrating an embodiment of a preform;
[0019] FIG. 7 is an elevation view generally illustrating an embodiment of a container formed from the preform of FIG. 4; and
[0020] FIGS. 8 and 9 generally illustrate views of embodiments of a preform and container similar to those illustrated in FIGS. 6 and 7, respectively, with identified zones. DETAILED DESCRIPTION
[0021] Polyethylene furanoate (PEF) is a bio-based polyester, and may be considered a bioplastic material. PEF is derived from renewable sources, including plant-based feedstocks, and is considered to be environmentally friendly, as it is both bio-based and biodegradable. Further, PEF can demonstrate good mechanical and thermal properties, and can provide excellent barrier properties for a number of applications.
[0022] Among other things, and as described herein, including with respect to certain non- limiting examples, the addition or inclusion of PEF to a compatible polymer (such as PET) for a preform, which may include post-consumer recycled content (such as recycled PET, or rPET) can be used to reduce or offset some or all of the typical reduction of stretch ratio associated with such polymer.
[0023] FIG. 1 generally illustrates an embodiment of a preform 10, which may be a monolayer or a multi-layer preform. For example and without limitation, an embodiment of a preform 10 may have an overall weight 28.3 grams and may have dimensions such as the following:D1 (dia.) 33mm D2 (dia.) 21.74 mm D3 (dia.) 25.65 mm D4 (dia.) 16.08 mm D5 (dia. tan pt.) 25 mm L1 (length) 88.53 mm L2 (length) 17 mm L3 (length) 59.11 mm T1 (wall thickness) 3.19 mm T2 (wall thickness) 4.45 mm The foregoing are examples of some possible dimensions associated with a preform. However, those of skill in the art will understand the disclosure is not limited to such specific dimensions, and other dimensions may be associated with various other embodiments.
[0024] A preform 10 may be formed, for example, via injection or compression molding. In embodiments, a preform may be formed by co-injection molding and may be formed by core biased injection.
[0025] FIG. 2A depicts an embodiment of a preform 10. The preform 10 may have different portions, including an upper portion or neck portion 12, some form of a transition portion 14, a sidewall portion 16, and a base portion 18. In some embodiments, the preform 10 may comprise multiple layers. With some embodiments, some portions of the container may include multiple layers, while other portions may not include multiple layers or may only include multiple layers in just a part of such portions (e.g., multiple layers extend only along part of a length of a portion, but not along an entire length of a portion).
[0026] FIGS. 2B, 2C, and 2D generally illustrate cross sections of the preform shown in FIG. 2A, taken at different portions of the preform 10. The layers may be provided via injection, e.g., co-injection, and may have the same or different thicknesses, viewed in cross-section. In the embodiment associated with FIGS. 2B, 2C, and 2D, the illustrated portions have three layers, which may generally be shown as an inner layer 20, a middle layer 22, and an outer layer 24. In some embodiment, middle layer 22 may be co-injected between the inner layer 20 and the outer layer 24. While FIG. 2C depicts just a portion of a base of a preform, such layers may extend across all or substantially the entire base portion of a preform. For some embodiments, a layer of PEF may extend substantially around the entire sidewall and base portion, and possibly also an upper / neck portion, of a preform and container formed therefrom. However, the disclosure is not limited to three layers and other embodiments may have less or more than three layers whichmay be in some or all portions. Further, the layers may have comparatively different thicknesses (which may further be varied or controlled along a length).
[0027] In some embodiments, an inner layer 20 and an outer layer 24 may comprise a first polymer, such as polyethylene terephthalate (PET), and a middle layer 22, which may comprise PEF. For some embodiments, a comparatively low amount of PEF will form the middle layer 22 but will be sufficient to provide a recyclable CO2barrier, which is adequate to serve as a functional substitute or replacement for a nylon barrier. That is, some embodiments may be devoid of a nylon or other barrier material. However, for some embodiments, a portion of the preform may include some amount of nylon and / or other material in at least some portions of a preform, which may serve as an additional barrier – such as a CO2barrier.
[0028] Additionally, with some embodiments, the injection of the PEF (PEF layer) is injected close to the core. In some embodiments, “close to the core” means that the PEF layer is relatively or comparatively closer to an inner side of the inner layer 20 (e.g., adjacent a core of a mold) than to an outer side of the outer layer. In some embodiments, “close to the core” may mean adjacent or nearly adjacent a core used to form a preform or within an inner 0.10 of the entire thickness of the preform. The injection of the PEF close to the core can, among other things, provide for improved stretch ratios associated with the preform and resulting container. In some embodiments, the overall stretch ratio associated with a resultant container may be about 6, about 7, about 9, about 12 or 12.5, or even about 15. Moreover, with some embodiments it may be desirable to add reheat to the PEF layer. Such an addition may improve color and, with a blowing process, it can be helpful to provide more heat in connection with PEF than with other polymers, such as PET.
[0029] In embodiments, the amount (volume or weight) of rPET included in the multi-layer preform (whether the inner layer, outer layer, or both) affects or modifies the stretch ratio of the multi-layer preform to the point that the multi-layer preform can have a stretch ratio (with PEF) that is the same or substantially equivalent to the stretch ratio of a multi-layer preform with substantially the same dimensions that does not include PEF.
[0030] FIG. 3 generally illustrates a container 100 that may be formed (e.g., via blow molding) from a preform, such as that shown in FIGS. 1 or 2A. For example and without limitation, a container 100 may be a 10 ounce (296 ml) container and may have dimensions such as the following:D6 (dia.) 33mm D7 (dia.) 26.16 mm D8 (dia.) 42 mm D9 (dia.) 63.5 mm L4 (length) 146.56 mm L5 (length) 17 mm L6 (length) 60.99 mm L7 (length) 22.86 mm The foregoing are examples of some possible dimensions associated with a container. However, those of skill in the art will understand the disclosure is not limited to such specific dimensions, and other dimensions may be associated with various other embodiments.
[0031] Attention is turned to a transformation in which a preform (e.g., exemplary preform 10 in FIG. 1) is formed into a container (e.g., exemplary container 100 in FIG. 3). With reference / comparison to other preform-to-container transformations, such as disclosed herein, the instant exemplary transformation (FIG. 1 to FIG. 3) may be characterized as a “low stretch” transformation. Such instant (low stretch) transformation may have, for example and without limitation, an axial orientation of 1.81, a hoop / radial orientation of 3.38 (3.90 with STEP), and a total orientation of 6.11 (7.07 with STEP).
[0032] Turning to FIGS. 4 and 5, embodiments of a preform 10 and a container 100, respectively, are shown. In such an embodiment, the container 100 may, for example, be about 15 grams and 330 ml. With reference / comparison to other preform-to-container transformations such as disclosed herein, the instant transformation (FIG. 4 to FIG. 5) may be characterized as a “medium stretch” transformation. Such instant (medium stretch) transformation may have, for example and without limitation, an axial orientation of 2.70, a hoop / radial orientation of 4.63, and a total orientation of 12.50.
[0033] Turning to FIGS. 6 and 7, embodiments of a preform 10 and a container 100, respectively, are shown. In such an embodiment, the container 100 may, for example, be about 18 grams and 500 ml.
[0034] With reference / comparison to other preform-to-container transformations such as disclosed herein, the instant transformation (FIG. 6 to FIG. 7) may be characterized as a “high stretch” transformation. For example and without limitation, with respect to FIG. 7, L8 (length) may be about 195.77 mm and L9 (length) may be about 3.23 mm. Such instant (high stretch)transformation may have, for example and without limitation, an axial orientation of 2.77, a hoop / radial orientation of 5.34, and a total orientation of 14.77.
[0035] In embodiments, the weight of the PEF content may be less than 10% of the overall weight of the associated preform or container. In some embodiments the weight of the PEF content may be less than 5% of the overall weight of the associated preform or container. In some embodiments, the weight of the PEF content may be about 2.5%. Further, with some embodiments, the weight of the PEF content may range between 0.5% and 2.5% of the overall weight of the associated preform or container, while with other embodiments, the weight of the PEF content may range between 2.5% and 5% of the overall weight of the associated preform or container.
[0036] FIGS. 8 and 9 generally illustrate views of embodiments of a preform 10 and container 100, respectively. The preform 10 and container 100 may be similar to those shown in FIGS. 6 and 7, but have PEF content limited to identified zones 40. With some embodiments, where a PEF layer is limited to one or more identified zones 40, less PEF material may be used, and / or may be used in portions of container walls that commonly have comparatively thinner walls (relative to other thicker wall portions). For some embodiments, it can be desirable to provide the PEF layer only in certain / smaller bands or zones - such as, for example and without limitation, as shown in FIGS. 8 and 9. The ability to provide PEF in portions or identified zones 40 of a container can, among other things, help to improve or optimize a barrier function, particularly in portions of a container in which the other polymer(s) (e.g., PET) is thinner or thinnest.
[0037] For example, with some embodiments (such as illustrated in FIG. 9), PEF (or a PEF layer) is not included in all or a significant portion of a base portion of a container. In some configurations / applications, the intentional omission of PEF in the base portion (i) may not significantly impact the barrier transmission associated with the container, (ii) may reduce the amount of PEF material (and associated cost), and / or (iii) may not have a practical detrimental impact in connection with certain testing (e.g., drop testing). In some embodiments / applications, keeping PEF material out of the base portion may be found to help avoid bursting in connection with bottle drops.
[0038] Various embodiments are described herein for various apparatuses, systems, and / or methods. Numerous specific details are set forth to provide a thorough understanding of the overallstructure, function, manufacture, and use of the embodiments as described in the specification and illustrated in the accompanying drawings. It will be understood by those skilled in the art, however, that the embodiments may be practiced without such specific details. In other instances, well-known operations, components, and elements have not been described in detail so as not to obscure the embodiments described in the specification. Those of ordinary skill in the art will understand that the embodiments described and illustrated herein are non-limiting examples, and thus it can be appreciated that the specific structural and functional details disclosed herein may be representative and do not necessarily limit the scope of the embodiments.
[0039] Reference throughout the specification to “various embodiments,” “with embodiments,” “in embodiments,” or “an embodiment,” or the like, means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, appearances of the phrases “in various embodiments,” “with embodiments,” “in embodiments,” or “an embodiment,” or the like, in places throughout the specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Thus, the particular features, structures, or characteristics illustrated or described in connection with one embodiment / example may be combined, in whole or in part, with the features, structures, functions, and / or characteristics of one or more other embodiments / examples without limitation given that such combination is not illogical or non-functional. Moreover, many modifications may be made to adapt a particular situation or material to the teachings of the present disclosure without departing from the scope thereof.
[0040] It should be understood that references to a single element are not necessarily so limited and may include one or more of such elements. Any directional references (e.g., plus, minus, upper, lower, upward, downward, left, right, leftward, rightward, top, bottom, above, below, vertical, horizontal, clockwise, and counterclockwise) are only used for identification purposes to aid the reader’s understanding of the present disclosure, and do not create limitations, particularly as to the position, orientation, or use of embodiments.
[0041] Joinder references (e.g., attached, coupled, connected, and the like) are to be construed broadly and may include intermediate members between a connection of elements and relative movement between elements. As such, joinder references do not necessarily imply that two elements are directly connected / coupled and in fixed relation to each other. The use of “e.g.” inthe specification is to be construed broadly and is used to provide non-limiting examples of embodiments of the disclosure, and the disclosure is not limited to such examples. Uses of “and” and “or” are to be construed broadly (e.g., to be treated as “and / or”). For example and without limitation, uses of “and” do not necessarily require all elements or features listed, and uses of “or” are intended to be inclusive unless such a construction would be illogical.
[0042] While examples of dimensions of certain components may be described herein, such dimensions are provided as non-limiting examples and the components may have other dimensions.
[0043] While processes, systems, and methods may be described herein in connection with one or more steps in a particular sequence, it should be understood that such methods may be practiced with the steps in a different order, with certain steps performed simultaneously, with additional steps, and / or with certain described steps omitted.
[0044] It is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative only and not limiting. Changes in detail or structure may be made without departing from the present disclosure.
Claims
Claims What is claimed is:
1. A multi-layer preform, comprising: a closed base portion; a sidewall portion extending upwardly from the closed base portion; and an upper portion extending upwardly from the sidewall portion; wherein at least a portion of the sidewall portion includes an inner layer and an outer layer each comprised of polyethylene terephthalate (PET); a polyethylene furanoate (PEF) layer that is comprised of polyethylene furanoate (PEF) and disposed between the inner layer and the outer layer; and at least one of the inner layer and the outer layer comprise post-consumer recycled PET (rPET).
2. The multi-layer preform of claim 1, wherein the PEF layer extends through the entire closed base portion.
3. The multi-layer preform of claim 1, wherein the preform includes at least four layers in one of the closed base portion and the sidewall portion.
4. The multi-layer preform of claim 1, wherein the inner layer, PEF layer, and outer layer all have different thicknesses.
5. The multi-layer preform of claim 1, wherein one or more of the inner layer, the PEF layer, and the outer layer have a thickness that varies along a length of the respective layer.
6. The multi-layer preform of claim 1, wherein a total weight of the PEF is less than 0.10 a total weight of the preform.
7. The multi-layer preform of claim 1, wherein a total weight of the PEF is less than 0.05 a total weight of the preform.
8. The multi-layer preform of claim 1, wherein a total weight of the PEF is about 0.025 a total weight of the preform.
9. The multi-layer preform of claim 1, wherein a total weight of the PEF ranges between 0.005 and 0.025 a total weight of the preform.
10. The multi-layer preform of claim 1, wherein a total weight of the PEF ranges between 0.025 and 0.05 a total weight of the preform.
11. The multi-layer preform of claim 1, wherein the PEF is derived from a plant-based feedstock.
12. The multi-layer preform of claim 1, wherein the preform 10 is formed via injection molding, co-injection molding, or compression molding.
13. The multi-layer preform of claim 1, wherein the preform has an overall weight of about 28.3 grams.
14. The multi-layer preform of claim 1, wherein a total amount of rPET included in the multi-layer preform affects or modifies a stretch ratio of the multi-layer preform with PEF so that the multi-layer preform with PEF has a stretch ratio that is the same or substantially equivalent to a stretch ratio of a multi-layer preform with substantially the same dimensions that does not include PEF.
15. A container formed from the multi-layer preform according to claim 1.
16. The container of claim 15, wherein an overall stretch ratio of the container is about 6.
17. The container of claim 15, wherein an overall stretch ratio of the container is about 7.
18. The container of claim 15, wherein an overall stretch ratio of the container is about 9.
19. The container of claim 15, wherein an overall stretch ratio of the container is about 12.
20. The container of claim 15, wherein an overall stretch ratio of the container is about 12.
5.
21. The container of claim 15, wherein an overall stretch ratio of the container is about 15.
22. The container of claim 15, wherein the preform-to-container transformation imparts an axial orientation of 1.81, a hoop / radial orientation of 3.38 (3.90 with STEP), and a total orientation of 6.11 (7.07 with STEP) in the container.
23. The container of claim 15, wherein the preform-to-container transformation imparts an axial orientation of 2.70, a hoop / radial orientation of 4.63, and a total orientation of 12.50 in the container.
24. The container of claim 15, wherein the preform-to-container transformation imparts an axial orientation of 2.77, a hoop / radial orientation of 5.34, and a total orientation of 14.
77.
25. A method of forming or using a multi-layer preform according to claim 1, including adding or directing reheat to the PEF layer.
Citation Information
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