Lightweight hot-fill container and method of manufacturing the same

Abstract

The present invention discloses a polymer composition comprising two or more polymers that can be used in preforms and containers for hot-fill beverages to increase the recycled content, shelf life of the contents, and hardness of the container. One polymer can be polyethylene terephthalate, and the second polymer can be polyethylene furanoate or polyethylene naphthalate. The polymers can be blended to form a cubic blend. A reheat agent can be used in the polymer composition. Methods for making preforms and bottles are also disclosed. The polymer composition can be made with increased recycled content without sacrificing the transparency of the material and can be used to make transparent preforms and bottles.

Description

Background Technology Technical Field

[0001] The described embodiments generally relate to polymer compositions for preforms and beverage containers. The polymer composition may have an increased recycling content and may increase the strength of the preforms and beverage containers. Summary of the Invention

[0002] Some embodiments relate to a bottle for hot-filled beverages comprising a polymer blend having a first polymer and a second polymer. The first polymer may be polyethylene terephthalate (PET), and the second polymer may be either polyethylene furanate (PEF) or polyethylene naphthalate (PAN). The bottle may include a shoulder portion and sidewalls. The PET may comprise at least 50% recycled PET. The polymer blend may be made from at least 50% recycled material. In some embodiments, the polymer blend may be made from at least 80% recycled material. The polymer blend may be 100% recyclable.

[0003] In any of the various embodiments disclosed herein, the second polymer is present in an amount of 5% to 15% by weight of the bottle. In any of the various embodiments disclosed herein, the second polymer is present in an amount of 5% to 10% by weight of the bottle. In any of the various embodiments disclosed herein, the second polymer is present in an amount of 7% by weight of the bottle.

[0004] In any of the various embodiments disclosed herein, the bottle is a single-layer bottle.

[0005] In any of the various embodiments disclosed herein, the bottle has a top load capacity of at least 20 pounds. In any of the various embodiments disclosed herein, the bottle has a top load capacity of at least 25 pounds.

[0006] In any of the various embodiments disclosed herein, the sidewall has a thickness of less than or equal to 0.015 inches.

[0007] In any of the various embodiments disclosed herein, the bottle volume shrinks by less than 3% during the hot filling process. In any of the various embodiments disclosed herein, the bottle volume shrinks by less than 2% during the hot filling process.

[0008] In any of the various embodiments disclosed herein, the second polymer is present in an amount of 7% by weight of the bottle, the second polymer is polyvinyl furanoate, and the bottle has a crystallinity of 25%.

[0009] In any of the various embodiments disclosed herein, the stiffness of the sidewall is at least 10% greater than that of the sidewall of a substantially identical container without the second polymer.

[0010] In any of the various embodiments disclosed herein, the bottle further comprises graphene in an amount ranging from 0.05% by weight to 5% by weight of the bottle.

[0011] Some embodiments relate to a preform for a beverage container, the preform comprising a polymer blend having a first polymer and a second polymer. The first polymer may be polyethylene terephthalate, and the second polymer may be one of polyethylene furanate or polyethylene naphthalate. The preform may include a reheat agent. The preform may be a single-layer blend. The presence percentage of the second polymer may be from 5% to 15% by weight of the preform. The first polymer may include at least 50% recycled material. The polymer blend may be fully recyclable.

[0012] In any of the various embodiments disclosed herein, the second polymer is present in a proportion of 5% to 10% by weight of the preform. In any of the various embodiments disclosed herein, the second polymer is present in a proportion of 7% by weight of the preform.

[0013] In any of the various embodiments disclosed herein, the second polymer is polyvinyl furanoate.

[0014] In any of the various embodiments disclosed herein, the second polymer is polyethylene naphthalate.

[0015] In any of the various embodiments disclosed herein, a preform may be used to form a bottle having a shoulder portion and a body portion. In any of the various embodiments disclosed herein, the bottle may have a top load capacity of at least 25 pounds.

[0016] Some embodiments relate to a method for manufacturing beverage containers for hot-fill processes. The method may include heating a preform and blowing gas into the preform to form a bottle. The preform may include a blend of a first polymer and a second polymer. The first polymer may be polyethylene terephthalate, and the second polymer may be one of polyethylene furanate or polyethylene naphthalate. The bottle may be transparent and fully recyclable.

[0017] In any of the various embodiments disclosed herein, the blend also includes a reheating agent.

[0018] In any of the various embodiments disclosed herein, the second polymer is present in a ratio of 5% to 15% by weight of the beverage container.

[0019] In any of the various embodiments disclosed herein, the second polymer is polyvinyl furanoate. In any of the various embodiments disclosed herein, the second polymer is polyethylene naphthalate.

[0020] In any of the various embodiments disclosed herein, the blend is made of at least 50% recycled material. In any of the various embodiments disclosed herein, the blend is made of at least 80% recycled material.

[0021] In any of the various embodiments disclosed herein, the method further includes filling the bottle with a beverage at a temperature of 85°C to 90°C and capping the bottle. In any of the various embodiments disclosed herein, the method further includes cooling the capped container.

[0022] Some embodiments relate to a method for preparing a preform, the method comprising blending a first polymer comprising polyethylene terephthalate and a second polymer comprising either polyethylene furanate or polyethylene naphthalate; extruding the blend to form a monolayer cubic blend; and molding the monolayer cubic blend to form a preform. In some embodiments, the preform comprises at least 50% recycled material.

[0023] In any of the various embodiments disclosed herein, the blending also includes a blending reheat agent.

[0024] In any of the various embodiments disclosed herein, the second polymer is polyvinyl furanoate.

[0025] In any of the various embodiments disclosed herein, the second polymer is polyethylene naphthalate. Attached Figure Description

[0026] Figure 1A and Figure 1B An exemplary hot-fill container according to some implementation schemes is shown.

[0027] Figure 2 Another exemplary hot-fill container is shown.

[0028] Figure 3 Exemplary preforms according to some embodiments are shown. Figure 1A and Figure 2 The container can be made from this preform.

[0029] Figure 4 Polymer blends according to some embodiments are shown. Figure 3 Preforms and Figure 1A and Figure 2The container can be made from this polymer blend.

[0030] Figure 5 This is a graph showing the effect of sidewall hardness on recycling content.

[0031] Figure 6 It is a flowchart of a process based on some implementation plans.

[0032] Figure 7 Biaxial tension of an exemplary sample of a container according to some embodiments is shown.

[0033] Figure 8 It is a graph of the normalized modulus of elasticity at various stretch ratios based on some implementation schemes.

[0034] Figure 9 It is a graph of the normalized elastic modulus at different temperatures. Detailed Implementation

[0035] Hot-fill containers are frequently used in the beverage industry for various applications, such as hot-filled juices, fruit drinks, vegetable drinks, energy drinks, and sports drinks. Hot-filling methods can reduce production time and extend the shelf life of beverages. However, after filling, the cooling of the contents of a hot-fill container creates a partial vacuum, which can place strain on the container and cause deformation. Therefore, hot-fill containers can have increased wall stiffness to resist this deformation. Higher wall stiffness is possible because the lower copolymer content in commercial hot-fill resins promotes higher crystallinity in the blow molding process. However, this increase in wall stiffness is also compensated for by greater wall thickness, resulting in containers that are undesirably heavier than carbonated soft drink or water containers.

[0036] Recycled PET (“rPET”) is commonly used in the manufacture of containers for carbonated soft drinks or water. Recycled PET containers can contain higher copolymer contents. However, hot-fill containers with rPET content may often have reduced crystallinity because the recycling content effectively increases the copolymer content, thereby suppressing crystallinity in the bottle walls. This can pose a challenge during hot filling, as the level of crystallinity helps ensure that the container maintains its shape as the filling temperature rises during the hot-fill process. If the crystallinity level is suppressed, the resulting container may not be as robust as desired, or may deform at the elevated temperatures required for hot filling. For example, the increased recycling content may undesirably reduce the stiffness or rigidity of the sidewalls. Therefore, containers with higher recycling content in the sidewalls—and correspondingly lower crystallinity—may be more prone to deformation.

[0037] Furthermore, some existing compositions used to add recycled content to hot-fill containers make the containers more prone to discoloration compared to virgin PET (i.e., non-recycled PET) containers. Other alternatives include laminated or multilayer preforms and containers, but these techniques can increase the required cost, complexity, weight, and material volume.

[0038] Therefore, there is a need for a hot-fill container with a high recycling content and full recyclability. Furthermore, there is a need for a hot-fill container with these recycling properties that does not deform during hot filling.

[0039] Using polymer compositions according to embodiments discussed herein, it is possible to increase the recycling content and reduce the weight of hot-fill containers relative to containers made solely of polyethylene terephthalate (“PET”), while maintaining container strength. Specifically, polymer blends comprising PET and a second polymer (e.g., polyethylene furanate (“PEF” or polyethylene naphthalate (“PEN”)) and / or additives (e.g., nanoclay, graphene, or boron nitride) can be used to produce lighter, fully recyclable hot-fill containers without sacrificing wall stiffness or transparency. Such containers may include reheating agents that allow for improved wall thickness uniformity. Furthermore, these containers can be manufactured on existing equipment used in hot-fill processes. In some embodiments, the polymer blend comprises PET and a second polymer (e.g., PEF or PEN). In some embodiments, the polymer blend comprises PET and a second compound (e.g., nanoclay, graphene, or boron nitride).

[0040] In some implementations, the hot-fill container (e.g., container 100 or container 200) is made of a polymer blend. Figure 1A and Figure 1B An exemplary hot-fill container 100 is shown. Figure 2 Another exemplary hot-fill container 200 is shown. Containers 100 and 200 can be manufactured using a blow molding process with preforms. Figure 3 An exemplary preform 50 is shown (e.g., container 100 or container 200 may be made from this exemplary preform). The preform 50 may be made from a polymer composition comprising two or more polymers (e.g., polymer blend 300), and therefore the resulting container (e.g., container 100 or container 200) formed from the preform 50 may have the same composition. The polymer blend 300 in... Figure 4The preform 50 may include a first polymer 310 and a second component 320. The preform 50 can be made by injection molding the polymer blend 300 to form the preform or by any other suitable means for preparing a preform from the polymer blend 300. In some embodiments, the preform is a monolayer blend of the polymer blend 300.

[0041] According to some embodiments, a polymer composition (e.g., polymer blend 300) is used to produce a preform (e.g., preform 50), and the preform can be used to form a hot-fill beverage container (e.g., container 100 or container 200).

[0042] Container 100 or container 200 may include a neck portion 110 that includes an opening for hot filling. This opening may have a diameter of at least 35 mm (e.g., at least 40 mm). In some embodiments, the opening has a diameter of 38 mm. In some embodiments, the opening has a diameter of 43 mm. This opening size is larger than that of a typical bottle for carbonated soft drinks (CSD) or water, which typically has an opening of about 28 mm. This larger opening size allows the hot-fill container to be filled without the filling equipment contacting the opening or the neck portion 110.

[0043] Compared to CSD or water bottles, container 100 or container 200 may also contain a lower comonomer content. For example, a typical CSD or water bottle has a comonomer content greater than 5 mol%. However, a higher comonomer content may slow down crystallization. Slower crystallization can be more detrimental to hot-fill bottles compared to CSD bottles because it reduces the rigidity of the bottle walls, and consequently reduces their ability to withstand reduced internal pressure (e.g., easy cooling after filling) without deformation. Therefore, container 100 or container 200 may be a hot-fill bottle with a comonomer content of less than or equal to 5 mol% (e.g., less than 5 mol% or less than 3 mol%). In some embodiments, the comonomer content of container 100 or container 200 is less than 5 mol%.

[0044] Container 100 or Container 200 may also include one or more vacuum panels 150 and / or one or more ribs 160 for accommodating pressure changes as the hot-filled contents cool. Typical CSD or water bottles do not include ribs or vacuum panels because such containers are not hot-filled and will have neutral or positive internal pressure. Container 100 or Container 200 may also include a flat bottom. In contrast, typical CSD or water bottles include feet on the bottom.

[0045] The polymer blend 300 may include two or more polymers blended together (e.g., a first polymer 310 and a second component 320). The first polymer 310 may be PET, and the second component 320 may be a polymer (e.g., polyethylene furanoate (“PEF”) or polyethylene naphthalate (“PEN”)) or another compound (e.g., nanoclay, graphene, or boron nitride). In some embodiments, the first polymer 310 is PET, and the second component 320 is PEF. In some embodiments, the first polymer 310 is PET, and the second component 320 is PEN. In some embodiments, the second component 320 includes both a polymer (e.g., PEF or PEN) and another compound (e.g., nanoclay, graphene, or boron nitride).

[0046] Compared to containers made solely of PET, the addition of a second component 320 (e.g., PEF or PEN) can increase the stiffness of the composition when used in beverage containers (e.g., hot-fill containers). The addition of the second component 320 can increase stiffness, for example, if the second polymer has a higher glass transition temperature (T0). g This is because the addition of a second polymer affects the overall stiffness of the polymer matrix. In some embodiments, the second component 320 is a polymer (e.g., PEF or PEN) and has a glass transition temperature of at least 90°C (e.g., at least 95°C, at least 100°C, at least 105°C, or at least 110°C). As discussed in more detail below, this can allow for the production of thinner and lighter bottles that maintain the same strength as conventional bottles (e.g., 100% PET bottles), or can allow for increased bottle strength without increasing bottle thickness or weight. This is illustrated in the following examples. In some embodiments, container 100 or container 200 may have a top load capacity of at least 20 pounds (e.g., at least 25 pounds or at least 30 pounds) and a wall thickness of less than or equal to 0.02 inches (e.g., less than or equal to 0.015 inches or less than or equal to 0.012 inches).

[0047] The amount of the second component 320 (e.g., PEF or PEN) in the blend may be, for example, from 0.05 wt% to 15 wt% of the polymer blend 300. In some embodiments, the amount of the second polymer is 5 wt% to 15 wt%, 6 wt% to 14 wt%, 7 wt% to 13 wt%, 8 wt% to 12 wt%, 9 wt% to 11 wt%, and all ranges and subranges (including endpoints) between the aforementioned values ​​having any two of the weight percentage values ​​listed above as endpoints. In some embodiments, the amount of the second polymer is 5 wt% to 10 wt% of the polymer blend 300. In some embodiments, the amount of the second polymer is 7 wt% of the polymer blend 300.

[0048] In some embodiments, the second component 320 comprises a polymer (e.g., PEF or PEN) present in an amount of 4% to 10% by weight (e.g., 7% by weight) of the polymer blend 300. In some embodiments, the second component comprises an additive (e.g., nanoclay, graphene, boron nitride) present in an amount of 0.05% to 5% by weight (e.g., 0.25% to 3% by weight, 0.5% to 1% by weight) of the polymer blend 300. In some embodiments, the second component comprises an additive present in an amount of 0.5% by weight of the polymer blend 300.

[0049] The first polymer 310 (e.g., PET) and the second component 320 (e.g., PEF or PEN) can be combined using any suitable method of polymer blending, including blending, mixing, or compounding the first and second polymers. In some embodiments, the first and second polymers are melt-blended to form a polymer composition. The mixture can be a cubic blend (also known as a black and white blend) formed by melt blending in an extruder. Figure 4 A cubic blend is shown, which includes a dispersed structural domain of a second component 320 (e.g., PEF or PEN) in a first polymer 310 (e.g., PET).

[0050] When compared to containers made solely of PET, the polymer compositions disclosed herein allow for a higher recycling content in hot-fill containers without compromising container strength or the clarity of the polymer composition. This is illustrated in Examples 6 and 7 below. As used herein, "recycling content" refers to the percentage of the finished bottle made from recycled material. In some embodiments, the hot-fill container (e.g., container 100 or container 200) may have a recycling content of at least 50% recycled material (e.g., at least 80% or at least 95% recycled material). In some embodiments, the hot-fill container is made of 100% recycled material.

[0051] Compared to 100% PET containers or other polymer-polymer blends (e.g., nylon-PET) containers, hot-fill containers (e.g., container 100 or container 200) made from the polymer compositions disclosed herein have many beneficial properties, including improved barrier properties, increased wall stiffness, and increased shelf life. Therefore, these polymer compositions can be used to increase shelf life compared to other polymer-polymer blends (e.g., nylon-PET). Furthermore, the shelf life of hot-fill containers can decrease with increasing recycling content.

[0052] Additionally, these polymer compositions can be used to increase wall stiffness relative to containers made solely of PET or containers containing other polymer-polymer blends (e.g., nylon-PET). These polymer compositions can be used to maintain wall stiffness and shelf life while reducing container weight and wall thickness. Polymer compositions can also be used to increase wall stiffness while simultaneously reducing container weight and wall thickness. Specifically, in some embodiments, adding a second polymer such as PEF or PEN reduces permeability while increasing wall stiffness compared to containers made solely of PET. This combination of PET and a second polymer (e.g., PEF or PEN) allows for several options in the production of hot-fill containers. In some embodiments, PEF or PEN is added to PET to produce bottles that will extend the shelf life of the contents and increase wall stiffness compared to containers made solely of PET. In some embodiments, containers containing PET and PEF or PEN (e.g., container 100 or container 200) can allow for weight reduction without a corresponding reduction in wall stiffness. This is illustrated in Examples 6 and 7, which show similar or increased wall stiffness (measured by axial and circumferential modulus of elasticity) compared to 100% PET containers. The modulus of elasticity measures the resistance of a material to elastic deformation when stress is applied. A higher modulus of elasticity corresponds to a harder and therefore more resistant material to deformation.

[0053] In some embodiments, the polymer composition (e.g., polymer blend 300) may allow a weight reduction of 1% to 20% (e.g., 3% to 18%, 5% to 15%, or 10% to 15%). In some embodiments, the polymer composition may allow a weight reduction of 10% to 15%. In some embodiments, the container (e.g., container 100 or container 200) may be 10% to 15% lighter than a substantially identical container without PEF or PEN (e.g., a container made only of PET). In some embodiments, the container (e.g., container 100 or container 200) may be 10% to 15% lighter but have the same or greater wall stiffness as a substantially identical container without PEF or PEN. For example, as shown in Example 6, bottle F (93% PET and 7% PEN) has similar or increased wall stiffness compared to bottle E (100% PET), but bottle F is 13% lighter than bottle E. Similarly, compared to bottle E (100% PET), bottle G (50% PET) has similar or increased wall stiffness, but bottle G is 12% lighter than bottle E.

[0054] Polymer blends used to extend shelf life may include nylon-PET blends. However, nylon-PET blends are not fully recyclable and tend to discolor after a relatively short period of time (e.g., 10 days or more). This discoloration can make the container less appealing to consumers. In some embodiments, the polymer composition (e.g., polymer blend 300) may be transparent and remain transparent for the shelf life of the contents of the hot-fill container.

[0055] Polymer blends according to some embodiments can be used in hot-fill containers for beverages (e.g., container 100 or container 200). The polymer compositions disclosed herein (e.g., polymer blend 300) can be used to produce any suitable beverage container (e.g., container 100 or container 200). In some embodiments, container 100 or container 200 is a hot-fill container. Container 100 and container 200 may each include a neck portion 110, a shoulder portion 120, a body portion 130, and a bottom portion 140. Container 100 or container 200 may have a height H extending from the top of the neck portion 110 to the bottom of the bottom portion 140. The shoulder portion 120 may include an upper shoulder portion 121 and a lower shoulder portion 122. The body portion 130 may include an upper body portion 131 and a lower body portion 132. Container 100 or container 200 can be molded from a preform (e.g., preform 50) made of polymer blend 300. In some implementations, container 100 or container 200 is a single-layer container.

[0056] Containers with increased recycling content are generally more prone to deformation compared to containers made of 100% PET. For example, a high recycling content may result in lower crystallinity of the container, which in turn reduces its strength. However, the addition of the second component 320 can increase the crystallinity of containers with increased recycling content. For example, the addition of the second component 320 can induce nucleation, which in turn increases crystallinity. In some embodiments, container 100 or container 200 made from the polymer compositions disclosed herein (e.g., polymer blend 300) has at least 25% (e.g., at least 27%, at least 30%, at least 31%, at least 32%, at least 33%, or at least 34%) crystallinity at any point on the container. In some embodiments, container 100 or container 200 has 25% crystallinity. Compared to a substantially identical container but without the second component 320, the crystallinity of container 100 or container 200 can be increased by 1% to 10% (e.g., 3% to 7%). In some implementations, heat treatment can promote thermal crystallization and increase wall rigidity to withstand deformation during the hot filling process.

[0057] As described below, the strength of a container can be assessed by measuring its top load capacity and its rigidity at various points. Figure 5A graph 500 is shown illustrating container rigidity against the percentage of recycled content. Line 510 shows a general relationship between the rigidity of a typical container and the percentage of recycled content. Generally, the rigidity of the container decreases as the percentage of recycled content increases. Line 520 conceptually illustrates a modified relationship between the rigidity of the container disclosed herein formed from polymer blend 300 and the percentage of recycled content. For the containers disclosed herein (e.g., container 100 or container 200 containing polymer blend 300), the container can maintain rigidity as the percentage of recycled content increases, as shown in Examples 6 and 7 below.

[0058] A measure of the strength of a beverage container is its top load capacity, which is a measure of how much downward force the container can withstand without buckling. A high top load capacity helps ensure that the container does not fail during filling, capping, transportation, or storage. The top load capacity of container 100 or container 200 may be greater than or equal to the top load capacity of a substantially identical container without a second polymer (e.g., PEF or PEN). For example, the top load capacity of container 100 or container 200 may be 10% to 30% (e.g., 15% to 25%) greater than the top load capacity of a substantially identical container without a second polymer (e.g., PEF or PEN). In some embodiments, container 100 or container 200 has a top load capacity of at least 20 pounds (e.g., at least 25 pounds or at least 30 pounds).

[0059] Another measure of the strength of a beverage container is its rigidity at various points. This is measured by applying force at a given location until the container irreversibly dents. Sidewall rigidity can be increased by adding the second component 320. For example, sidewall rigidity can increase by 10% to 30% (e.g., 15% to 25%) compared to a substantially identical container without the second component. One way to assess sidewall rigidity is by measuring sidewall deflection. Adding the second component 320 can allow for equal or greater sidewall rigidity at a lower container weight. Rigidity can be measured at various locations along the container. For example, in some embodiments, rigidity is measured at the upper shoulder portion 121, lower shoulder portion 122, upper body portion 131, lower body portion 132, and bottom portion 140. In some embodiments, the rigidity of container 100 or container 200 at the upper shoulder portion 121 is at least 15 pounds (e.g., at least 20 pounds or at least 25 pounds). In some embodiments, the rigidity of container 100 or container 200 at the lower shoulder portion 122 is at least 20 pounds (e.g., at least 25 pounds or at least 30 pounds). In some embodiments, the rigidity of container 100 or container 200 at the upper body portion 131 is at least 8 pounds (e.g., at least 10 pounds or at least 12 pounds). In some embodiments, the rigidity of container 100 or container 200 at the lower body portion 132 is at least 8 pounds (e.g., at least 9 pounds or at least 10 pounds). In some embodiments, the rigidity of container 100 or container 200 at the bottom portion 140 is at least 15 pounds (e.g., at least 18 pounds, at least 20 pounds, or at least 22 pounds).

[0060] The sidewall deflection test can also be used to assess stiffness or hardness. Adding the second component 320 increases the normalized sidewall deflection (lb / mm), which corresponds to the increased stiffness.

[0061] Another method to increase the wall rigidity of PET containers is to blend them with nanomaterials such as nanoclay, graphene, boron nitride, etc. Uniformly dispersed nanomaterials act as reinforcing agents and improve the mechanical properties of PET, including rigidity. Some nanomaterials, such as graphene, can also act as reheat agents and improve the thermal conductivity of PET preforms. In some embodiments, reheat agents are added to the polymer composition. In some embodiments, graphene is added as a reheat agent. In some embodiments, the addition of graphene improves the rigidity of the container.

[0062] When used, the reheating agent minimizes the temperature gradient within the wall of the preform during the blow molding process. During blow molding, the preform can be heated to a temperature above its glass transition temperature, allowing the preform to deform to take the shape of the mold. During this process, the preform rotates and is exposed to an infrared lamp. As the preform rotates, a temperature gradient forms between the outer and inner sides of the preform. Using a reheating agent minimizes this temperature gradient, resulting in the entire wall thickness being at a substantially uniform temperature. This allows more heat energy to be available, and more heat energy can be used to increase crystallinity during blow molding. In some embodiments, at least one point through the wall has no temperature gradient during blow molding (i.e., the entire wall thickness is at the same temperature).

[0063] Using a reheating agent in polymer blend 300 can lead to improvements in the mechanical properties of the container, as described above. Specifically, this combination allows for more uniform heat absorption, which in turn promotes optimal placement of the blend. For example, optimal placement of the blend can mean that the second polymer (e.g., PEF or PEN) is uniformly distributed within the first polymer (e.g., PET). Due to the improved thermal properties discussed above, optimal placement of the blend enables hot-fill containers to achieve increased rigidity and improved performance.

[0064] Reheating agents can improve various mechanical properties of PET, including flexural strength, flexural modulus, tensile strength, Young's modulus, and elongation at break. These improved mechanical properties may be due to the hardening and reinforcing effects of the reheating agent in PET. Additionally, the improved mechanical properties may be due to reinforcement-reinforcement interactions. Furthermore, reheating agents can improve thermal stability and electrical conductivity.

[0065] Figure 6 A flowchart of a process for manufacturing a hot-fill container (e.g., container 100 or container 200) according to some embodiments is shown. At step 600, two or more polymers are blended to form a polymer blend 300. In some embodiments, a reheating agent is blended with two or more polymers at step 600, forming a portion of the polymer blend 300. In some embodiments, the polymer blend 300 may be formed from a first polymer 310 (e.g., PET) and a second component 320 (e.g., PEF or PEN) as disclosed above (and optionally using a reheating agent). After preparing the polymer blend 300, at step 610, the polymer blend 300 may be formed into a preform (e.g., preform 50). In some embodiments, the polymer blend 300 is injection molded to form the preform 50. Then, at step 620, the preform may be blow-molded to form a container (e.g., in some embodiments, the preform 50 is blow-molded to form container 100 or container 200).

[0066] During blow molding, heat can be added to the bottle wall, which can increase the crystallinity of the polymer composition. In some embodiments, heat is added during blow molding until the crystallinity is at least 30% (e.g., at least 31%, at least 32%, at least 33%, or at least 34%) at any given point on the container. After blow molding, at step 630, the container can be filled. In some embodiments, a hot-fill process is used to fill container 100 or container 200. In some embodiments, the container is filled with a beverage at a temperature of 80°C to 100°C (e.g., 85°C to 95°C, 85°C to 90°C). In some embodiments, the container is filled with a beverage at a temperature greater than or equal to 85°C (e.g., greater than or equal to 90°C). After filling, at step 640, the container can be capped and the contents cooled.

[0067] The stability of the hot-fill containers disclosed herein during hot filling can be equal to or better than that of substantially identical containers without PEF or PEN (e.g., containers made solely of PET). Stability can be measured by how much the container shrinks during the hot-fill process. In some embodiments, the container volume shrinks by less than 3% (e.g., less than 2%) during the hot-fill process. The amount of shrinkage of container 100 or container 200 can also be less compared to substantially identical containers without a second polymer (e.g., PEF or PEN). For example, the shrinkage rate of container 100 or container 200 can be from 0.2% to 0.8% of the shrinkage rate of substantially identical containers without a second polymer.

[0068] The process for manufacturing the hot-fill containers disclosed herein can be integrated into existing hot-fill production facilities. In some embodiments, using the process for manufacturing the hot-fill containers disclosed herein, an existing hot-fill production line can produce at least 1,000 bottles per hour (e.g., at least 1,200 bottles per hour or at least 1,400 bottles per hour). In some embodiments, the processing speed is sufficient to produce 1,400 bottles per hour.

[0069] Example

[0070] Example 1

[0071] In one experiment, the segmental weights of four hot-fill bottles were measured. Segmental weight is the weight of different parts of the bottle. For example, the weight of each bottle was measured at the upper shoulder, upper rib, upper body panel, lower label panel, and bottom. These segments... Figure 1B and Figure 2The diagram shows an upper shoulder portion 121, a lower shoulder portion 122, an upper body portion 131, a lower body portion 132, and a bottom portion 140. Container 100 or container 200 can be molded from a preform (e.g., preform 50) made of polymer blend 300. In some embodiments, container 100 or container 200 is a single-layer container. Bottle A is a control bottle made of 100% PET and having a standard wall distribution; bottle B is a control bottle made of 100% PET and having a heavy bottom distribution; bottle C is a bottle made of PET and 70 ppm of reheat agent and having a standard wall distribution; and bottle D is a bottle made of PET and 70 ppm of reheat agent and having a heavy bottom distribution. As used herein, "heavy bottom distribution" means that the bottle is thicker at the bottom of the container compared to a container with a standard wall distribution. The weight of each segment is shown as a percentage of the total bottle weight in Table 1 below.

[0072] bottle Upper shoulder (%) Lower shoulder (%) Upper main body (%) Lower main body (%) bottom(%) A 38.5 10.9 16.0 14.0 20.6 B 37.8 10.3 15.4 13.9 22.7 C 38.3 11.4 15.8 14.2 20.3 D 37.3 10.8 15.3 14.0 22.5

[0073] Table 1

[0074] Another measure of material distribution is the thickness of the bottle at different points, as shown in Table 2 below.

[0075]

[0076] Table 2

[0077] As shown in Tables 1 and 2, compared with standard wall-distributed bottles A and C, containers B and D, which both have heavy bottom distribution, have higher weight and thickness at the bottom and lower weight and thickness at other parts of the container.

[0078] Example 2

[0079] In one experiment, the top load capacity of the bottles of Example 1 was measured. Table 3 shows the top load capacity of bottles A, B, C, and D.

[0080]

[0081]

[0082] Table 3

[0083] As shown in this embodiment, due to the more uniform distribution of the material, the bottles with reheating agent (bottles C and D) exhibit improved top load capacity compared to the corresponding bottles (bottles A and B) without reheating agent.

[0084] Example 3

[0085] In one experiment, the shrinkage rate of the bottle from Example 1 after hot filling was tested. The shrinkage rate was measured by the overall height and volume, as well as the height and volume at the shoulder, lower body, and upper body of the container. The results of these tests are shown in Table 4.

[0086]

[0087] Table 4

[0088] As shown in Table 4, bottles with reheat agent (bottles C and D) exhibit a smaller overall volume shrinkage rate compared to their corresponding bottles without reheat agent (bottles A and B). This indicates that bottles with reheat agent are more stable during hot filling than those without.

[0089] Example 4

[0090] In one experiment, the sidewall rigidity of the bottle from Example 1 was tested. Force was applied to various points on the bottle with a 0.5-inch deflection until the bottle no longer recovered from its dent. The results of these tests are shown in Table 5.

[0091] bottle Upper shoulder (lb) Lower shoulder (lb) Upper main body (lb) Lower main body (lb) Bottom (lb) A 19.41 25.47 12.24 9.18 18.37 B 18.51 24.23 11.80 8.85 20.46 C 23.95 26.09 13.06 10.15 20.87 D 19.65 23.10 10.97 10.79 22.51

[0092] Table 5

[0093] As shown in Table 5, bottles with reheating agent exhibit increased sidewall rigidity at almost every location along the bottle.

[0094] Example 5

[0095] In one experiment, the crystallinity of the bottle from Example 1 was tested at various points on the container.

[0096] Table 6 shows the crystallinity of the bottles at different points.

[0097] bottle Upper shoulder (%) Lower shoulder (%) Upper main body (%) Lower main body (%) bottom(%) A 33.91 33.78 33.91 34.22 33.40 B 34.18 33.81 34.32 34.63 33.71 C 33.54 33.51 34.22 33.30 32.93 D 34.35 32.62 34.15 33.07 32.22

[0098] Table 6

[0099] As these embodiments show, bottles manufactured according to some implementations can have improved top load capacity, improved stability during hot filling processes, and increased sidewall rigidity.

[0100] Example 6

[0101] In one experiment, the properties of different combinations of rPET and PET were evaluated for hot-fill containers. Bottles E through G were all 20-ounce containers of identical shape, differing only in material, sidewall thickness, and total weight. The composition of each evaluated bottle is shown in Table 7. The modulus of elasticity was measured at two locations on each bottle. The axial modulus was measured in the vertical direction at the body portion (e.g., body portion 130), and the circumferential modulus was measured in the horizontal direction at the shoulder portion (e.g., shoulder portion 120). A higher modulus of elasticity corresponds to a stiffer and therefore more resistant material to deformation. The axial and circumferential moduli are also shown in Table 7.

[0102]

[0103] Table 7

[0104] The performance of each bottle was measured by determining the sidewall deflection force. The sidewall deflection was measured when the bottles were hot-filled and capped. The normalized sidewall deflection force is shown in Table 8.

[0105] bottle Normalized sidewall deflection (lb / mm) E 20.1 F 20.0 G 21.7

[0106] Table 8

[0107] As shown in Tables 7 and 8, at least one of PEN or rPET can be added to PET to reduce the weight of the bottle without sacrificing its strength. For example, comparing bottle E and bottle F, adding PEN increases the axial modulus while only slightly reducing the circumferential modulus. Furthermore, as shown in Table 8, the normalized sidewall deflection of bottle F is similar to that of bottle E.

[0108] Adding 50% rPET yields similar results. For example, bottle G (50% rPET) has an axial modulus and circumferential modulus greater than or similar to that of bottle E (100% PET). When comparing bottle G (50% rPET) with bottle E (100% PET), the normalized sidewall deflection is higher with the inclusion of rPET.

[0109] Example 7

[0110] In one experiment, the properties of different combinations of rPET and PET were evaluated for hot-fill containers. Bottles H and I were both 18.5 oz containers with identical shapes, differing only in material, sidewall thickness, and total weight. The shapes of bottles H and I differed from those of bottles E through G in Examples 6. The compositions for each evaluated bottle are shown in Table 9. The modulus of elasticity was measured at two locations for each bottle. The axial modulus was measured in the vertical direction at the body portion (e.g., body portion 130), and the circumferential modulus was measured in the horizontal direction at the bottom portion (e.g., bottom portion 140). The axial and circumferential moduli are shown in Table 9.

[0111]

[0112] Table 9

[0113] The performance of each bottle was measured by determining the top load capacity and sidewall deflection force. The top load capacity was measured when the bottle was empty and ventilated (i.e., without a cap). The sidewall deflection was measured when the bottle was hot-filled and capped. The top load capacity and normalized sidewall deflection force are shown in Table 10.

[0114] bottle Top load capacity (lb) Normalized sidewall deflection (lb / mm) H 119.8 13.91 I 96.0 11.73

[0115] Table 10

[0116] As shown in Table 9, bottles with rPET and graphene exhibit increased axial and circumferential moduli.

[0117] Example 8

[0118] In one experiment, material samples used to manufacture bottles were biaxially stretched at various draw ratios and then annealed under constraint using a fixture. This was accomplished by heating the sample at a specified temperature for 15 seconds. A “2x2” draw ratio means that the sample is stretched in both the x and y directions, such that the stretched sample is twice the original length in both directions. Figure 7 Sample 700 under biaxial tension is shown. One material is 100% PET, and the other material is PET with graphene. Figure 8 and Figure 9 The results of this experiment are shown in the figure. Figure 8 The display shows that when various stretch ratios are applied in 1 second... -1 When stretched at a strain rate, samples containing PET with graphene consistently exhibit a higher normalized modulus of elasticity compared to 100% PET samples. Figure 9 The display shows that when stretched at a 3x3 ratio for 16 seconds... -1When stretched at a strain rate, the PET sample containing graphene exhibits a higher normalized elastic modulus compared to the 100% PET sample. Therefore, this experiment confirms that the elastic modulus can be increased by including graphene.

[0119] It should be understood that the Detailed Description section, and not the Summary of the Invention section and the Abstract of the Specification section, is intended to be used to interpret the claims. The Detailed Description section and the Abstract of the Specification section may provide one or more, but not all, exemplary embodiments of this disclosure as conceived by the inventors, and are therefore not intended to limit this disclosure and the appended claims in any way.

[0120] The present disclosure has been described above using functional building blocks that illustrate the implementation methods of specific functions and their relationships. For the sake of convenience, the boundaries of these functional building blocks are arbitrarily defined herein. Alternative boundaries may be defined as long as the specific functions and their relationships are properly performed.

[0121] The above description of specific embodiments will fully reveal the general nature of this disclosure, enabling others to easily modify and / or adapt these specific embodiments for various applications without departing from the overall conception of this disclosure by applying knowledge of the art, without excessive experimentation. Therefore, based on the teachings and guidance provided herein, such modifications and alterations are intended to be within the meaning and scope of equivalents of the disclosed embodiments. It should be understood that the wording or terminology used herein is for descriptive purposes and not for limiting purposes, and that the terminology or terminology of this specification should be interpreted by those skilled in the art in accordance with the teachings and guidance provided.

[0122] The breadth and scope of this disclosure should not be limited to any of the exemplary embodiments described above, but should be defined only by the claims and their equivalents.

Claims

1. A bottle for hot-filling beverages, the bottle comprising: Polymer blends comprising a first polymer and a second polymer, wherein: The first polymer is polyethylene terephthalate, and The second polymer is either polyethylene furanate or polyethylene naphthalate; shoulder area; and Side wall, At least 50% of the polyethylene terephthalate is recycled polyethylene terephthalate, and The second polymer is present in an amount of 5% to 15% by weight of the bottle.

2. The bottle according to claim 1, wherein the second polymer is present in an amount of 5% to 10% by weight of the bottle.

3. The bottle according to claim 2, wherein the second polymer is present in an amount of 7% by weight of the bottle.

4. The bottle of claim 1, wherein the polymer blend comprises at least 80% recycled material.

5. The bottle according to claim 1, wherein the bottle is a single-layer bottle.

6. The bottle of claim 1, wherein the bottle has a top load capacity of at least 20 pounds.

7. The bottle of claim 6, wherein the sidewall has a thickness of less than or equal to 0.015 inches.

8. The bottle of claim 1, wherein the volume of the bottle shrinks by less than 3% during the hot filling process.

9. The bottle according to claim 1, wherein the second polymer is present in an amount of 7% by weight of the bottle. The second polymer is polyvinyl furanate, and The bottle described therein has a crystallinity of at least 25%.

10. The bottle of claim 1, wherein the hardness of the sidewall is at least 10% greater than that of the sidewall of a substantially similar container but without the second polymer.

11. The bottle according to claim 1, wherein the bottle further comprises graphene in an amount of 0.05% to 5% by weight.

12. A preform for a beverage container, the preform comprising: A polymer blend comprising a first polymer and a second polymer, wherein the first polymer is polyethylene terephthalate and the second polymer is one of polyethylene furanate or polyethylene naphthalate. and Reheating agent, The polymer blend mentioned above is a monolayer blend. The second polymer is present in a proportion between 5% by weight and 15% by weight of the preform, and The first polymer comprises at least 50% recycled material.

13. The preform of claim 12, wherein the second polymer is present in a ratio of 5% by weight of the preform to 10% by weight of the preform.

14. The preform of claim 12, wherein the second polymer is present in a proportion of 7% by weight of the preform.

15. The preform of claim 12, wherein the second polymer is polyvinyl furanoate.

16. The preform of claim 12, wherein the second polymer is polyethylene naphthalate.

17. A bottle formed from a preform according to claim 12, wherein the bottle has a top load capacity of at least 25 pounds.

18. A method for manufacturing a beverage container for a hot-filling process, the method comprising: Heated preform, the preform comprising: A blend of a first polymer and a second polymer, wherein the first polymer is polyethylene terephthalate and the second polymer is one of polyethylene furanate or polyethylene naphthalate, wherein the blend comprises at least 50% recycled material; and Gas is blown into the preform to form a bottle.

19. The method of claim 18, wherein the blend further comprises a reheating agent.

20. The method of claim 18, wherein the second polymer is present in a ratio of 5% to 15% by weight of the beverage container.

21. The method of claim 18, wherein the blend comprises at least 80% recycled material.

22. The method according to claim 18, further comprising: The bottles are filled with beverages at a temperature of 85°C to 90°C; as well as The bottle is then capped.

23. A method for manufacturing a preform, the method comprising: The first polymer and the second polymer are blended, wherein the first polymer comprises polyethylene terephthalate and the second polymer comprises one of polyethylene furanate or polyethylene naphthalate. Extruding the blend to form a monolayer cubic blend; and Molding the single-layer cubic blend to form a preform, The preform contains at least 50% recycled material.

24. The method of claim 23, wherein the blend further comprises a blend reheat agent.

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