Multimodal Polyalkylene Terephthalate

Abstract

A method for forming a multimodal polyalkylene terephthalate (PAT) can include: providing a feed of low molecular weight (LMW) PAT, the LMW PAT having a low average molecular weight; providing a feed of high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight, the low average molecular weight being lower than the high average molecular weight; mixing the LMW PAT feed with the HMW PAT feed in a mixer to form multimodal PAT; and providing the multimodal PAT as an output. The multimodal PAT can include a low molecular weight (LMW) PAT with a low average molecular weight; and a high molecular weight (HMW) PAT with a high average molecular weight that is mixed with the LMW PAT to form the multimodal PAT, wherein the multimodal PAT lacks talc.

Description

[Technical field]

[0001] Inventor Mohammed Raheem Chris DeArmitt CROSS-REFERENCE TO RELATED APPLICATIONS This patent application claims priority to U.S. Provisional Application No. 62 / 942,659, filed December 2, 2019, which is hereby incorporated by specific reference in its entirety. [Background technology]

[0002] background Field

[0003] The present disclosure relates to compositions and methods for forming multimodal polyalkylene terephthalates having improved flowability, good mechanical properties and desirable optical properties. 2. Description of Related Art

[0004] Polyethylene terephthalate (PET) is a polymer that is prone to crystallization, which affects many properties of PET products, including clarity, stiffness, and strength. Commercially available PET has poor flowability due to its high molecular weight, making it impossible to produce thin-walled injection molded products with PET. Attempts to improve the flowability of PET have included particles that result in an opaque or smeared material.

[0005] There is a need for PET polymers that have better flow properties while retaining the good strength and bright optical properties of PET. PET is a polyalkylene terephthalate (PAT). [ka] Summary of the Invention

[0006] overview

[0007] In some embodiments, a method of forming a low molecular weight polyalkylene terephthalate (PAT) can include: providing a feed of high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight; providing a feed of decomposition molecules; reacting the HMW PAT with the decomposition molecules in a reactor; decomposing the HMW PAT with the decomposition molecules to a low molecular weight (LMW PAT) having a low average molecular weight lower than the high average molecular weight; and providing the LMW PAT as an output.

[0008] In some embodiments, a system for forming LMW PAT can include a feed line having a high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight; a feed line for cracked molecules; a reactor having the HMW PAT with the cracked molecules; and an output having a low molecular weight (LMW PAT) having a low average molecular weight lower than the high average molecular weight.

[0009] In some embodiments, a method of forming a multimodal polyalkylene terephthalate (PAT) can include: providing a feed of low molecular weight (LMW) PAT, the LMW PAT having a low average molecular weight; providing a feed of high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight, the low average molecular weight being lower than the high average molecular weight; mixing the feed of LMW PAT with the feed of HMW PAT in a mixer to form a multimodal PAT; and providing the multimodal PAT as an output. As used herein, "multimodal" or "blend" means that two or more compositions of different molecular weights of PAT are blended together to form a composition having a fraction with LMW PAT blended as well as a fraction with HMW PAT, such that the blended PAT is multimodal (e.g., has at least two different polymer composition molecular weights blended together). The blended PAT may be bimodal, trimodal, or otherwise multimodal, but may contain only a single distribution (e.g., a single chromatographic peak) populated by a fraction of LMW PAT blended with a fraction of HMW PAT, as well as other fractions with different molecular weights (e.g., additional LMW PAT, additional HMW PAT, or mid-range molecular weight PAT). The blend may be homogeneous or non-homogeneous. As a result, compositions with at least two different molecular weights are blended to form a multimodal PAT.

[0010] In some embodiments, a system for forming a multimodal PAT can include a feed of low molecular weight (LMW) PAT, the LMW PAT having a low average molecular weight; a feed of high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight, but the low average molecular weight is of a lower distribution than the high average molecular weight; a mixer having the LMW PAT and the HMW PAT; and an output having the multimodal PAT.

[0011] In some embodiments, the multimodal PAT may include: a low average molecular weight (LMW) PAT; and a high average molecular weight (HMW) PAT that is mixed with the LMW PAT to form the multimodal PAT, where the multimodal PAT is devoid of talc.

[0012] The foregoing summary is illustrative and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the drawings and the following detailed description. [Brief description of the drawings]

[0013] Brief description of the drawings The foregoing and following information as well as other features of the present disclosure will become more fully apparent from the following description and appended claims taken in conjunction with the accompanying drawings, in which: The present disclosure will be described with additional specificity and detail through the use of the accompanying drawings, with the understanding that these drawings depict only certain embodiments in accordance with the present disclosure and are therefore not to be considered limiting of its scope.

[0014] [Figure 1] FIG. 1 is a schematic diagram of a system for degrading HMW PET to LMW PET.

[0015] [Diagram 2] Figure 2 is a schematic diagram of a system for preparing multimodal PET from a mixture of LMW PET and HMW PET.

[0016] [Diagram 3] FIG. 3 is a schematic diagram of a system for preparing multimodal PET into different articles, possibly with additional optional components.

[0017] [Figure 4] FIG. 4 is a schematic diagram of an injection molding system for preparing PET alloys into injection molded articles.

[0018] [Diagram 5] FIG. 5A-FIG. 5 show the relationship of fluidity and strength to PET polymer chain length and for multimodal PET.

[0019] [Figure 6] Figure 6 shows the injection molding properties of different multimodal PET compositions. [Figure 7A] FIG. 7A shows the injection molding properties of the control PET. [Figure 7B] FIG. 7B shows the injection molding properties of multimodal PET.

[0020] The elements and components in the figures may be arranged in accordance with at least one of the embodiments described herein, and the arrangement may be modified by one of ordinary skill in the art in accordance with the disclosure provided herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Detailed Description In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, like symbols typically identify like components unless the context dictates otherwise. The exemplary embodiments described in the detailed description, drawings, and claims are not intended to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It is readily understood that aspects of the present disclosure, as generally described herein and illustrated in the figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are expressly contemplated herein.

[0022] In general, the present technology includes systems and methods for preparing multimodal PET, the multimodal PET comprising a first average molecular weight and a second average molecular weight. The first average molecular weight (e.g., a first average molecular weight having a standard distribution with a first intrinsic viscosity) comprises a lower average molecular weight compared to a higher second average molecular weight (e.g., a second average molecular weight having a standard distribution with a second intrinsic viscosity). Thus, the first mode is a low average molecular weight (e.g., a first low average molecular weight having a standard distribution with a first low intrinsic viscosity) and the second mode is a high average molecular weight (e.g., a second high average molecular weight having a standard distribution with a second high intrinsic viscosity). The first mode with a low average molecular weight is obtained by degrading a high average molecular weight PET composition with degrading molecules such as water, alcohols, diols, polyols (e.g., containing three or more hydroxyl groups). An example of a degrading molecule that can be used to degrade a high average molecular weight PET composition into a PET masterbatch with a first low average molecular weight is a low molecular weight polyol (not a polymer). The low average molecular weight PET masterbatch is then combined with a high average molecular weight PET composition having a second average molecular weight. The decomposition molecules can be characterized as molecules and are not minerals.

[0023] In some embodiments, multimodal PET can be replaced with any multimodal polyalkylene terephthalate (PAT). Thus, a reference to PET, unless specifically including PET, can refer generally to PAT, and a reference to PAT can include PET and other PAT. JPEG0007674353000002.jpg4396

[0024] In some embodiments, the technology includes systems and methods for preparing multimodal polyethylene terephthalate (PET) with two or more separate average molecular weights. Multimodal PET is formed using a system that prepares a first PET composition with a lower average molecular weight and combines the first PET composition with a second PET composition with a higher average molecular weight to produce a bimodal PET composition. Additional PET compositions with different molecular weights may also be added and blended. Thus, the system and method can produce a first PET composition (e.g., low molecular weight PET, or LMW PET) that is produced in a precise manner, and blend the LMW PET with a second PET (e.g., fresh PET, virgin PET, recycled PET, off-spec PET, or high molecular weight PET, or HMW PET) to form a multimodal PET composition that has better flow properties than PET while maintaining other desirable properties of PET, such as tensile strength and flexural yield strength, as well as favorable optical properties, such as transparent or substantially transparent (e.g., optically transparent and translucent hazy clear).

[0025] In some embodiments, when LMW PET is commercially available, it can be purchased and then combined with HMW PET to make the multimodal PET described herein. However, LMW PET has no significant use by itself because it has unfavorable mechanical properties. As a result, LMW PET is not commercially available. Therefore, the method can include preparing LMW PET from other PET (e.g., virgin, recycled, off-spec, etc.) as described herein to obtain LMW PET with high flow properties. LMW PET with high flow properties can be combined with HMW PET with low flow properties to make a multimodal PET with suitable flow properties as well as suitable mechanical properties. Thus, the method can be modified to include obtaining LMW PET instead of producing LMW PET as described herein.

[0026] Multimodal PET is preferred for its oxygen and moisture barrier properties, which allow the PET article to be a container for liquid storage such as beverages (e.g., soft drinks, water, beer, etc.). The high mechanical strength of multimodal PET may allow it to be used in tapes such as carriers for magnetic tapes or backings for pressure-sensitive adhesive tapes. The optically clear property allows PET to be used in products that, although hazy in some embodiments, customers are accustomed to having in clear plastics. Transparent PET is therefore suitable for a wider range of products than pure PET or other PET alloys (e.g., not transparent).

[0027] In some embodiments, multimodal PET can be modulated by the process and amount of decomposition molecules in LMW PET, and the relative amount of LMW PET and HMW PET bound to the multimodal PET. Multimodal PET can have variations in the amount of LMW PET and the amount of HMW PET that form the multimodal PET, and the relative amounts (e.g., LMW / HMW ratio) can be controlled for different physical properties. Multimodal PET can include low molecular weight PET (LMW PET) mixed with high molecular weight PET (HMW PET) to obtain faster or otherwise improved flow, so that multimodal PET can now be used in injection molding, such as for the production of thin-walled injection molded parts, and extrusion to form various extrudates, such as fibers and cylinders for pelletizing in a chopper.

[0028] In some embodiments, the improved systems and methods can now be used to produce multimodal PET that is manufactured in a precise manner, where LMW PET is then blended with virgin PET (e.g., HMW PET) to form a multimodal PET material with better mechanical properties.

[0029] Multimodal PET may be formed into an amorphous (transparent) article or a semi-crystalline article. Semi-crystalline materials can appear transparent. The absence of any particles (e.g., the absence of talc) can result in transparent and clear optical properties. Thus, the multimodal compositions of the present invention can be devoid of talc or other particulates in the polymer composition during manufacturing, injection molding, or other processes.

[0030] In one example, PET feedstock for either LMW PET or HMW PET can be prepared by any suitable process. For example, HMW PET can be reacted with decomposition molecules to form LMW PET. As is commonly known, the monomer bis(2-hydroxyethyl) terephthalate can be synthesized by esterification of terephthalic acid with ethylene glycol, with water as a by-product, or transesterification of ethylene glycol with dimethyl terephthalate (DMT), with methanol as a by-product. Polymerization is performed through a polycondensation reaction of the monomers (e.g., immediately following esterification / transesterification), with water as a by-product. PET feedstock can be prepared as described in US 2009 / 0212457, which is incorporated herein by specific reference in its entirety. PET feedstock can be in sheet, pellet, or other form, similar to liquid PET. PET feedstock can be processed to a liquid, flowable state for the methodology described herein.

[0031] In some embodiments, a method of forming LMW PET for use in preparing multimodal PET is provided. Such a method can be carried out using a PET system 100 as shown in FIG. 1. The PET system 100 for forming LMW PET can include a feed 120 of PET (PET feed); a feed of decomposition molecules 122 (e.g., a small molecule polyol feed); and a reactor 110 (e.g., a reactor mixer) coupled to an outlet of the PET feed 120 and coupled to an outlet of the decomposition molecules feed 122. The reactor 110 can react the PET with the decomposition molecules to form the LMW PET. The system 100 can also include an output of the LMW PET 102 operably coupled to an outlet of the reactor 110 to another process component 136. The process component 136 can be selected from vessels, pumps, flow paths, heaters, coolers, extruders, dies, pelletizers, mixers, and combinations thereof, as well as other art-known components for PET systems. As shown, system 100 can include a PET supply 120 having an inlet coupled to a PET supply 124 .

[0032] It should be appreciated that PET may be replaced by PAT or any other type of PAT in the method and system 100 and all of the methods and systems described herein and in all of the figures. That is, the system may be configured for use with any PAT, whereby the description of PET may also refer to PAT herein and for other methods and other systems provided herein. For example, PET system 100 may be PAT system 100, etc.

[0033] The system 100 can also include a decomposition molecule supply 122 having an inlet coupled to the decomposition molecule supply 126. The system 100 can include one or more of a PET reactor system 128; a PET recycling system 130; a PET conditioning system 132; or a PET reservoir 134. The PET reactor system 128 is configured to polymerize PET from PET precursor reagents. The PET recycling system 130 is configured to recycle PET from PET articles. The PET conditioning system 132 is configured to condition PET for reaction with the decomposition molecules, the conditioning being selected from one or more of heating, chopping PET pellets or sheets or other PET members, agitating, extruding, drying; off-gassing, or the like. The PET reservoir 134 contains liquid PET, which is molten PET.

[0034] The system 100 includes a reactor 110, which can be any reactor capable of reacting liquid PET and decomposition molecules in a batch or continuous manner. Any type of industrial reactor vessel can be used. In some embodiments, the reactor 110 also performs one or more of degassing, homogenizing, dispersing, or heating.

[0035] In some embodiments, the reactor 110 is configured as a mixer, such as a single screw mixer, a twin screw mixer, a continuous kneader (e.g., a B&P Littleford continuous kneader; a Buss Kneeder), a reciprocating screw mixer (e.g., a B&P Littleford TriVolution), a twin screw extruder (B&P Littleford), a continuous prout mixer (e.g., a B&P Littleford), or the like.

[0036] System 100 can include a PET reservoir 138. PET reservoir 138 can be of any type, and the LMW PET can be contained therein in any type (e.g., solid, liquid, pellets, etc.). However, the LMW PET can be pelletized or formed into any other storable format (e.g., molten liquid) prior to entering storage.

[0037] The system 100 may include an analysis system 140. The analysis system 140 includes one or more analytical devices capable of various analytical processes. For example, the analysis system 140 may be configured to determine the intrinsic viscosity of the molten LMW PET output 102. In another example, the analysis system 140 may be configured to determine the flow rate of the molten LMW PET output 102. In another example, the analysis system 140 may be configured to determine the melting point of the LMW PET output 102. In another example, the analysis system 140 may be configured to determine the crystallization temperature of the LMW PET output 102. In another example, the analysis system 140 may be configured to determine a differential scanning calorimetry profile of the LMW PET output 102. In another example, the analysis system 140 may be configured to determine the heat distortion temperature of the LMW PET output 102.

[0038] According to the system 100 for forming LMW PET, a method for forming LMW PET can be performed. Such a method can include providing a feed of PET 120 (PET feed, HMW PET), providing a feed of decomposition molecules 122 (decomposition molecule feed), reacting the feed of PET with the feed of decomposition molecules in a reactor 110 to decompose PET from high molecular weight to obtain low molecular weight PET (LMW PET), and providing LMW PET as an output 102. In some embodiments, the PET feed 120 is from a PET feed 124. In some embodiments, the decomposition molecule feed 122 is from a decomposition molecule supply 126.

[0039] In some embodiments, the PET supply 124 receives a PET supply from one or more of a PET reactor system 128, a PET recycle system 130, a PET conditioning system 132, or a PET reservoir 134. The PET reactor system 128 polymerizes PET from PET precursor reagents. The PET recycle system 130 recycles PET from PET articles. The PET conditioning system 132 conditions PET for mixing with talc, where the conditioning is selected from one or more of heating, cutting PET pellets or sheets or other PET pieces, stirring, extruding, drying, and off-gassing. The PET reservoir 134 of liquid PET, where the liquid PET is molten PET. The PET supply 124 includes HMW PET.

[0040] The method may also include providing the LMW PET output 102 to an output system 136. The output system 136 provides the LMW PET to storage 138 (e.g., in pellets) or to a multimodal PET system 200 or an analysis system 140. The method may include pelletizing the LMW PET output 102 in a pelletizer. The method may include analyzing the LMW PET output 102 in the analysis system 140, which may include determining an intrinsic viscosity of the molten LMW PET output 102, determining a flow rate of the molten LMW PET output 102, determining a melting point of the LMW PET output 102, determining a crystallization temperature of the LMW PET output 102, determining a differential scanning calorimetry profile of the LMW PET output 102, or determining a thermal warping temperature of the LMW PET output 102.

[0041] The multimodal PET system 200 is described in detail below. However, in some embodiments, the multimodal PET system 200 is configured to combine the LMW PET output 102 with a second feed of PET 220 (second PET feed, HMW PET) to produce a multimodal PET 202 having a combination of LMW PET and HMW PET in a single multimodal composition. This produces a composition having a multimodal distribution of two different average molecular weights of PET.

[0042] In some embodiments, the PET feed 120 is devoid of other polymers. In other embodiments, the decomposition molecule feed 122 is devoid of other polymers. However, the PET feed 120 and / or the decomposition molecule feed 122 may include other polymers, such as PAT or polycarbonate as defined herein. In some embodiments, the PET feed 120 consists essentially of (or consists of) PET. In some embodiments, the decomposition molecule feed 122 consists essentially of (or consists of) decomposition molecules (optionally with a carrier such as a solvent). In some embodiments, the PET feed 120 comprises molten PET.

[0043] In some embodiments, the PET feed 120 contains less than 5%, or less than 1%, or less than 0.1%, or traces of water, or is devoid of water. Thus, the method can include drying the PET feed 120 before reacting with the decomposition molecule feed 122. The method can also include drying (e.g., removing water) the decomposition molecule feed 122 before reacting with the PET feed 120. However, the decomposition molecule can be water, thereby including water in the decomposition molecule feed 122. In some aspects, the decomposition molecule is a low molecular weight polyol or alcohol, and water can be present, which can be tolerated.

[0044] In some embodiments, the method can include preparing PET. Thus, the method can include polymerizing PET from a polymerizable reagent.

[0045] In some embodiments, the LMW PET output 102 provided has an intrinsic viscosity of about 0.4 to about 0.6, or about 0.42 to about 0.55, or about 0.45 to about 0.52, or about 0.46 to about 0.5. In one example, the intrinsic viscosity of the LMW PET may be about 0.477, where the intrinsic viscosity may be provided as an indication of molecular weight. LMW PET has a lower intrinsic viscosity than feed or virgin PET or HMW PET.

[0046] The method of forming multimodal PET can be carried out in the system 200 of FIG. 2. The system 200 for forming multimodal PET can include a feed of HMW PET 220 (HMW PET feed), which can include any type of PET such as virgin PET, recycled PET, or other PET sources (e.g., with or without other polymers, additives, etc.), as long as it has a higher molecular weight compared to the LMW PET formed in the system 100. The system 200 can also include a feed of LMW PET (LMW PET feed), which can be the LMW PET output 102 obtained from the method used in the system 100 of FIG. 1. The system 200 can include a mixer 210 coupled to an outlet of the HMW PET feed 220 and coupled to an outlet of the LMW PET feed 222, which can mix to form a multimodal PET having an LMW distribution (e.g., a distribution of low average molecular weights and low molecular weights around the low average molecular weight) and an HMW distribution (e.g., a distribution of high average molecular weights and high molecular weights around the high average molecular weight). The system 200 can include a process component 236 operably coupled to an outlet of the mixer 210, the process component 236 being selected from a vessel, a pump, a flow line, a heater, a cooler, an extruder, a die, a pelletizer, and combinations thereof.

[0047] In some embodiments, the system 200 can include an HMW PET supply 220 having an inlet coupled to an HMW PET supply 224. The PET supply 224 can be of the same type as the PET supply 124 of the system 100 of FIG. 1. The system 200 can include a PET reactor system 128 configured to polymerize HMW PET from PET precursor reagents. The system 200 can include a PET recycling system 130 configured to recycle PET from PET articles resulting in HMW PET. The system 200 can include a PET conditioning system 132 configured to condition the HMW PET for blending with the LMW PET, where the conditioning can be selected from one or more of heating, cutting PET pellets or sheets or other PET members, stirring, extruding, drying, off-gassing, or other conditioning. The system 200 can include an HMW PET reservoir 134 of solid HMW PET pellets or liquid HMW PET, where the liquid HMW PET is molten PET. A heating system may also be included to heat the HMW PET to the appropriate temperature and liquefy the solid HMW PET pellets, where such a heating system may be included in any system component or flow path.

[0048] In some embodiments, system 200 can include an LMW PET supply 222 having an inlet coupled to an LMW PET supply 226. LMW PET supply 226 can include LMW PET output 102 and can be in solid pellet form or molten liquid form. In some aspects, LMW PET supply 226 includes LMW PET in a flowable form and / or includes a heater to heat the LMW PET to a flowable form (e.g., molten PET liquid). In some aspects, the LMW PET omits any particles (e.g., non-PET particles), for example, by omitting any talc particles, the LMW PET omits any particles (e.g., non-PET particles).

[0049] In some embodiments, mixer 210 is any mixer capable of mixing liquid HMW PET and LMW PET in a batch or continuous manner, such as a single screw mixer, a twin screw mixer, a continuous kneader (e.g., B&P Littleford continuous kneader; Buss Kneeder), a reciprocating screw mixer (e.g., B&P Littleford TriVolution), a twin screw extruder (B&P Littleford), a continuous prout mixer (e.g., B&P Littleford), or others. Mixer 210 is configured to perform one or more of the following: degassing, homogenizing, dispersing, or heating.

[0050] In some embodiments, the system 200 can include a storage 238. The storage 238 can include any form of multimodal PET, such as a heated liquid or a solid (e.g., a pelletized solid).

[0051] The system 200 can include an analysis system 240. The analysis system 240 includes one or more analysis devices capable of various analytical processes. For example, the analysis system 240 can be configured to determine the intrinsic viscosity of the molten multimodal PET output 202. In another example, the analysis system 240 can be configured to determine the flow rate of the molten multimodal PET output 202. In another example, the analysis system 240 can be configured to determine the melting point of the multimodal PET output 202. In another example, the analysis system 240 can be configured to determine the crystallization temperature of the multimodal PET output 202. In another example, the analysis system 240 can be configured to determine a differential scanning calorimetry profile of the multimodal PET output 202. In another example, the analysis system 240 can be configured to determine the heat distortion temperature of the multimodal PET output 202.

[0052] In some embodiments, the system 200 can include a manufacturing system 300 configured to convert the multimodal PET output 202 into a manufactured article 302. The manufacturing system 300 can include an optional component input feed 320. The optional component input feed 320 can be configured to provide the optional component to the multimodal PET. The optional component can be selected from fillers, TiO2, a second polymer, glass pellets, glass fibers, glass particles, sodium ionomer, sodium stearate, nucleating agents, polycarbonate, polybutylene terephthalate (PBT) or other polyalkylene terephthalates (PAT), or other components of the manufactured PET article 302. The optional component can be talc-free.

[0053] As shown in FIG. 3, the manufacturing system 300 may include one or more of a multimodal PET feed 301, one or more flow paths 308 containing flowable multimodal PET, a mixer 310, a heating system 312, an extruder system 316 producing a multimodal PET extrudate 317, a pump system 318, an injection molding system 322, and / or a cooling system 314.

[0054] In some embodiments, the optional ingredients (e.g., other than talc) may be provided to reactor 110 to be mixed into LMW PET output 102 or may be provided to mixer 210 to be mixed into multimodal PET output 202. Alternatively, the provided HMW PET 220 may include the optional ingredients, or the provided LMW PET 222 may be prepared to include the optional ingredients. Thus, the optional ingredients may be introduced into the PET at any stage in the processes described herein.

[0055] System 200 can have various modifications as described herein. In some embodiments, HMW PET feed 220 is devoid of another polymer. In some embodiments, LMW PET feed 222 is devoid of another polymer. In some embodiments, HMW PET feed 220 consists essentially of (or consists of) HMW PET. In some embodiments, LMW PET feed 222 consists essentially of (or consists of) LMW PET, optionally with trace amounts of water and a portion of decomposition molecules. In some embodiments, HMW PET feed 220 comprises molten HMW PET. In some embodiments, HMW PET feed 220 comprises less than 5%, or less than 1%, or less than 0.1%, or a trace amount of water, or no water. It should be appreciated that a portion of the decomposition molecules may be retained in the LMW PET and thereby may be present in the resulting multimodal PET.

[0056] In some embodiments, system 200 can include a dryer for drying HMW PET feed 220 prior to mixing with LMW PET feed 222. In some embodiments, system 200 can include a dryer for drying LMW PET feed 222 prior to mixing with HMW PET feed 220. Such a dryer can be included anywhere in system 200, or any suitable component can comprise a dryer. The dryer can facilitate removal of water to enhance processing and preparation of multimodal PET.

[0057] In some embodiments, the HMW PET feed 220 provided by the system 200 has an intrinsic viscosity of 0.55 or greater, such as about 0.6 to about 0.9, or about 0.625 to about 0.85, or about 0.65 to about 0.8, or about 0.7 to about 0.75, or about 0.76. In one example, the HMW PET feed comprises an intrinsic viscosity of about 0.786 to 0.79. A higher intrinsic viscosity indicates a higher molecular weight compared to LMW PET.

[0058] In some embodiments, the provided multimodal PET output 102 has an intrinsic viscosity of about 0.45 to about 0.7, or about 0.475 to about 0.6, or about 0.5 to about 0.58, or about 0.51 to about 0.56, or about 0.55. Exemplary ranges can be from 0.5 to 0.6 intrinsic viscosity. In one example, the multimodal PET output 102 has an intrinsic viscosity of about 0.518, or about 0.52, or about 0.55, where the intrinsic viscosity of the multimodal PET is between the intrinsic viscosities of LMW PET and HMW PET, thereby having a respective distribution.

[0059] In some embodiments, a method of forming multimodal PET can be implemented in a system 200 described herein. The method of forming multimodal PET can include providing a feed of HMW PET 220 (PET feed), providing a feed of LMW PET 222 (LMW PET feed), mixing the feed of HMW PET 220 with the feed of LMW PET 222 in a mixer 210 to form multimodal PET having a first distribution of LMW PET and a second distribution of HMW PET, and providing the multimodal PET as an output 202. In some embodiments, the HMW PET feed 220 is from a HMW PET feed 224 as described herein. In some embodiments, the LMW PET feed 122 is from a LMW PET feed 226 as described herein.

[0060] In some embodiments, the method can include the LMW PET supply 224 receiving an LMW PET feed from one or more of the PET reactor system 128; the PET recycling system 130; the PET conditioning system 132; or the PET reservoir 134. The PET reactor system 128 can polymerize PET from PET precursor reagents, which results in HMW PET. The PET recycling system 130 can recycle PET from PET articles. The PET conditioning system 132 can condition PET for mixing with the LMW PET, the conditioning being selected from one or more selected from heating, cutting PET pellets or sheets or other PET members, stirring, extruding, drying, and off-gassing. The PET reservoir 134 can hold PET in a solid state (e.g., pellets) or as liquid PET, which is molten PET. The LMW PET can be obtained as described herein, such as in FIG. 1.

[0061] In some embodiments, the multimodal PET output 202 is provided to a process component 236. The process component 236 provides the multimodal PET to a reservoir 238 or an analysis system 240 or a manufacturing system 300. The reservoir 238 may be adapted to hold the multimodal PET as a liquid or as pellets, such as by including a heater, whereby the output system 236 may include a pelletizer to pelletize the multimodal PET. In some embodiments, the analysis system 240 includes one or more analysis systems capable of performing one or more of the following analytical methods on the multimodal PET: determining an intrinsic viscosity of the molten multimodal PET output 202; determining a flow rate of the molten multimodal PET output 202; determining a melting point of the multimodal PET output 202; determining a crystallization temperature of the multimodal PET output 202; determining a differential scanning calorimetry profile of the multimodal PET output 202; or determining a heat distortion temperature of the multimodal PET output 202. In some embodiments, manufacturing system 300 operates to convert multimodal PET output 202 into an article of manufacture. In some embodiments, the article of manufacture may be multimodal PET pellets. In some embodiments, the article of manufacture may include other components that may be introduced into the PET alloy in system 300 or other systems, as described herein. Manufacturing system 300 is described in more detail herein.

[0062] In some embodiments, the method includes providing an HMW PET feed 220 that is devoid of another polymer. In some aspects, the method includes providing an LMW PET feed 222 that is devoid of another polymer. In some aspects, the method includes providing an HMW PET feed 220 that consists essentially of (or consists of) PET. In another aspect, the method can include providing an LMW PET feed 222 that consists essentially of (or consists of) PET, but may include some of the degraded molecules. In some aspects, the method includes providing the HMW PET feed 220 and / or the LMW PET feed 222 as molten PET. In some aspects, the method includes providing an HMW PET feed 220 and / or an LMW PET feed 222 that contains less than 5%, or less than 1%, or less than 0.1%, or trace amounts of water, or no water.

[0063] In some embodiments, the method can include drying the PET feed 220 prior to mixing with the LMW PET feed 222. In some aspects, the method can include drying the LMW PET feed 222 prior to mixing with the HMW PET feed 220.

[0064] In some embodiments, the method includes producing the multimodal PET output 102 to have an intrinsic viscosity of about 0.45 to about 0.7, or about 0.475 to about 0.6, or about 0.5 to about 0.55, or about 0.51 to about 0.53. In one example, the multimodal PET output 102 has an intrinsic viscosity of about 0.518 or about 0.52.

[0065] In some embodiments, the system 200 can include a manufacturing system 300 configured to convert the multimodal PET output 202 into a manufactured article 302. The manufacturing system 300 can include an optional component input feed 320. The optional ingredient input feed 320 can be configured to provide the optional ingredient to the multimodal PET. The optional ingredient can be selected from fillers, TiO2, a second polymer, glass pellets, glass fibers, glass particles, sodium ionomers, sodium stearate, nucleating agents, polycarbonates, polybutylene terephthalates (PBT) or other polyalkylene terephthalates (PAT), or other ingredients of the manufactured PET article 302. However, the system can specifically exclude any optional ingredient from the multimodal PET and can specifically exclude the use of any talc to manufacture the multimodal PET.

[0066] As shown in FIG. 3, manufacturing system 300 can include a multimodal PET feed 301, one or more flow paths 308 containing flowable multimodal PET, a mixer 310, a heating system 312 capable of heating any component of system 300, an extruder system 316 that produces multimodal PET extrudate 317 (which can also include, for example, a pelletizer that pelletizes multimodal PET extrudate 317), a pumping system 318 that can pump multimodal PET to any component in system 300, an injection molding system 322, and / or a cooling system 314 that can cool any component in the system.

[0067] High molecular weight PET chains (HMW PET) provide excellent strength to manufactured products, but have poor flowability during processing and cannot be used for injection molding. There is usually a trade-off between improved flowability and sacrificing strength. This multimodal PET provides good flowability and good strength. Bimodal PET (e.g., multimodal) can be considered to be bimodal PET or multimodal PET as shown in Figure 5C, but may or may not have two or more separate peaks. Blended PET can be considered to be bimodal or multimodal because it is formed from two or more different molecular weight PET compositions, such that the blended PET has at least two different molecular weights blended. However, multimodal PET may only show a single chromatographic peak, but is considered to be multimodal to define the multiple different molecular weight PET compositions that are blended by blending at least two PET compositions with different molecular weights. Figure 5A shows the average molecular weight distribution of normal PET (e.g., HMW PET), with low weights having good flowability but poor strength and high weights having good strength but poor flowability. FIG. 5B shows a lower average molecular weight distribution (e.g., LMW PET) where the smaller PET polymer has good flowability and poor strength. In FIG. 5B, the PET polymer chains have been shortened, such as by hydrolysis from decomposition molecules, to give good flowability, but the PET has poor strength because the short chains are not long enough to effectively entangle. FIG. 5C shows a bimodal PET (e.g., blended PET with two distinct peaks) with LMW PET, which has good flowability, and a portion that is normal HMW PET, where the low molecular weight portion contributes to the good flowability of the bimodal PET without significantly reducing strength. Additionally, multimodal PET can have more than one peak, but may only have one or two chromatographic peaks, depending on the distribution and amount. It is not the number of chromatographic peaks that defines the number of modes, but rather the number of different molecular weight PET compositions that define the number of modes (e.g., a composition of two or more different molecular weights is multimodal).By producing a low molecular weight, high flow LMW PET and then combining a small portion of the LMW PET with virgin, high molecular weight PET, and other molecular weight PET, it has been surprisingly found that the resulting multimodal PET material has very good flow while retaining excellent strength. The diagrams in Figures 5A-5C are for illustrative purposes. Multimodal PET may only show a single chromatographic peak, but may contain blends of two, three, four, or more different molecular weight PET compositions.

[0068] In some embodiments, HMW PET can include a polydispersity (e.g., Mw / Mn-polydispersity index) of about 1.55 to about 1.65, or about 1.575 to about 1.625, or about 1.585 to about 1.6, or about 1.595. In some embodiments, LMW PET can include a polydispersity (e.g., Mw / Mn-polydispersity index) of about 1.4 to about 1.5, or about 1.425 to about 1.475, or about 1.435 to about 1.455, or about 1.45. In some embodiments, multimodal PET (e.g., 30 / 70) can include a polydispersity (e.g., Mw / Mn-polydispersity index) of about 1.5 to about 1.575, or about 1.52 to about 1.55, or about 1.525 to about 1.54, or about 1.53.

[0069] Polydispersity can be used to quantify the width of the distribution curve for each respective composition, see Figures 5A-5C. Information regarding the width of the distribution curve provides information regarding the polymers in the composition. A polydispersity of 1 indicates that the polymers are all the same length, which is not preferred for this application. A polydispersity of 1.5 or greater for multimodal PET indicates the presence of both long chains from HMW PET and short chains from LMW PET. Data based in part on the proportions of both HMW PET and LMW PET in multimodal PET indicates that there is a larger portion of long chains and a smaller portion of small chains. The polydispersity results for multimodal PET indicate that the distribution of molecular weights is broadened, thereby broadening the distribution of different short and long polymer chains. Comparison of the different polydispersity values ​​indicates that multimodal PET has a broader distribution of small and long chains compared to a composition that has only a distribution from simple cleavage / hydrolysis of PET. Therefore, the polydispersity shows that having a distribution of LMW PET and a distribution of HMW PET can be improved to provide the benefits of each component of multimodal PET.

[0070] The bottom line is that if you cut PET in one go, you lose the long chains and it loses strength. This has been tried and tested for decades. Our invention allows us to leave most of the long chains intact, so it retains its strength.

[0071] In some embodiments, multimodal PET comprises a non-uniform distribution of LMW PET throughout HMW PET. In some instances, multimodal PET can be prepared without thoroughly mixing HMW PET and LMW PET together such that there are discrete regions of HMW PET and discrete regions of LMW PET. This is useful for facilitating processing of multimodal PET, such as injection molding, where the LMW PET lubricates the movement of the HMW PET.

[0072] Alternatively, multimodal PET contains LMW PET homogeneously dispersed throughout HMW PET. In some products where consistency and composition are important, it may make sense to have LMW PET homogeneously mixed throughout HMW PET.

[0073] In some embodiments, the multimodal PET contains less than 5%, or less than 1%, or less than 0.1%, or trace amounts of water, or no water.

[0074] In some embodiments, the multimodal PET has a HMW PET concentration of about 85% to about 55%, about 80% to about 60%, about 75% to about 63%, or about 70% to about 65%.

[0075] In some embodiments, the multimodal PET has an LMW PET concentration of about 15% to about 45%, about 20% to about 40%, about 25% to about 37%, or about 30% to about 35%.

[0076] In some embodiments, the multimodal PET has a melting temperature between about 240°C and about 255°C, or between about 245°C and about 250°C, or between 247°C and 249°C, or about 247.5°C.

[0077] In some embodiments, the multimodal PET has a viscosity of about 3-6 CC / (m 2 -day), ±25%, 20%, 15%, 10%, 5%, 2%, or 1% oxygen transmission rate.

[0078] In some embodiments, the multimodal PET has a crystallization temperature of between about 200°C and about 230°C, or between about 210°C and about 220°C, or about 212°C.

[0079] In some embodiments, the multimodal PET has a glass transition temperature of about 70°C to about 90°C, or about 75°C to about 85°C, or about 77°C to about 83°C, or about 79°C to about 80°C.

[0080] In some embodiments, the multimodal PET has a percent crystalline of about 21% to about 25%, or about 22% to about 24%, or about 23% to about 23.3%, or about 23.

[0081] In some embodiments, multimodal PET can be used for injection molding to form an article of manufacture. Thus, an injection molding system 400 can include a feed 420 of multimodal PET as shown in FIG. 4 to form an injection molded article of manufacture 402 including multimodal PET. The multimodal PET feed 420 can be liquid multimodal PET (e.g., molten multimodal PET). However, the injection molding system 400 can include a multimodal PET heater 424 that heats the multimodal PET feed 420 for flowability as liquid multimodal PET. The heater 424 can receive the multimodal PET as pellets 428, heated liquid multimodal PET 430, or as PET in any form 432. The heater 424 can feed the multimodal PET feed 420 to an extruder 410. Optionally, a dried and / or filtered multimodal PET pellet feed 422 can be fed to the extruder 410 from a multimodal PET drying and / or filtering device 426.

[0082] The multimodal PET can be processed in the injection molding system 400 through an in-line filtration system in the injection molding system. The multimodal PET pellets can be fed into the system 400 through a drying hopper, which then feeds into the inlet end of the plasticizing screw of the extruder 410. The plasticizing extrusion screw is enclosed in a barrel (i.e., the extruder 410) that is heated by a barrel heater. The helical (or other) flight of the screw conveys the multimodal PET along the working axis of the screw. Typically, the root diameter of the screw increases gradually along the working axis of the screw in a direction away from the inlet end. Once a desired amount of multimodal PET melt has accumulated in the extruder 410, it is transferred to a melt accumulator 440, which can include an injection plunger that functions to inject the molten multimodal PET into the mold cavity 438.

[0083] Melt filter 436, disposed in fluid communication between extruder 410 and melt accumulator 440, performs an in-line filtration step. The purpose of melt filter 436 is to filter impurities and other contaminants from the multimodal PET material being transferred from extruder 410 to melt accumulator 440. The specific embodiment of the melt filter is not particularly limited, and as an example, melt filter 436 can be implemented using off-the-shelf filters from Gneuss Inc. of Matthews, North Carolina (www.gneuss.com).

[0084] The in-line filtration step may be performed in a melt filter 436 having an inlet to allow the inflow of multimodal PET to be filtered and a filter outlet to allow the outflow of filtered multimodal PET. The melt filter 436 includes a filtering member disposed between the filter inlet and the filter outlet.

[0085] In some embodiments, the mold system can include a mold 439 having a mold cavity 438. The mold 439 receives the multimodal PET to fill the mold cavity 438. This is an advancement over prior PET, which was not adequately injected by such injection molding systems. Now, the mold cavity 438 can be completely filled with the multimodal PET without voids that would ruin the injection molded article. This allows the multimodal PET to be injection molded into the molded PET article 402.

[0086] The multimodal PET can have a PET including a first portion of a PET polymer having a first average molecular weight and a second portion of a PET polymer having a second average molecular weight, the first average molecular weight being less than the second average molecular weight. The multimodal PET can be devoid of talc in the PET. The multimodal PET completely fills the mold cavity 438 of the mold 439.

[0087] The systems and methods described herein provide a novel multimodal PET that can be used to prepare a number of PET products and can be used in a variety of processing techniques, such as injection molding, which allows the multimodal PET to be injected into a mold to form an article with a thin wall. Additionally, the multimodal PET allows for injection molding, as the cycle time from liquid multimodal PET to solid multimodal PET is significantly reduced compared to the cycle time for PET.

[0088] In the polyalkylene terephthalate (PAT) structure above, "n" may be any suitable integer, such as 1 (polymethylene terephthalate (PMT)), 2 (polyethylene terephthalate (PET)), 3 polypropylene terephthalate (PPT), 4 (polybutylene terephthalate (PBT)), or 5 polypentylene terephthalate (PPentT), etc. (e.g., n is 6, 7, 8, 9, 10, etc.). Thus, the methods and systems described herein can be adapted for use with any suitable polyalkylene. That is, PET may be replaced with any PAT. The PET of multimodal PET may be replaced with any PAT to form a multimodal PAT. Thus, although the systems and methods described herein are directed to PET, such systems and methods may include any suitable PAT, such as PBT.

[0089] In addition, various decomposition molecules can be used. As the decomposition molecule, water may be used, but alcohols are preferred, diols (e.g., two hydroxyl groups) can be used, and it has been found that polyols (e.g., three or more hydroxyl groups) may be preferred. An example of a low molecular weight polyol is trimethylolpropane, but other similar polyols can be used. Various low molecular weight sugar polyols can be used, such as xylitol, pentaerythritol, maltitol, sorbitol, isomalt, and glycerol. In some embodiments, thiols such as methanethiol, ethanethiol, 1-propanethiol, 2-propanethiol, and butanethiol can be used as the decomposition molecule. Examples of the decomposition molecule include dithiols such as geminal dithiol, 1,2-dithiol, 1,3-dithiol, and 1,4-dithiol. Examples of the decomposition molecule include amines such as methylamine, diethylamine, trimethylamine, ethylamine, and aniline. JPEG0007674353000003.jpg2364 Trimethylolpropane

[0090] As described, the method of forming LMW PET involves cleaving ester bonds in high molecular weight, bottle grade PET (HMW PET) to create low molecular weight, extra high flow PET (LMW PET). In one example, the process involves adding trimethylolpropane or other low molecular weight polyols (e.g., sugar polyols) or other decomposition molecules to the molten PET to cleave the bonds. The decomposition molecules can include other alcohols such as those described herein, water, water vapor, polyols, thiols, amines, etc. The decomposition molecules are molecules and not minerals, e.g., not talc, etc. The decomposition molecules can react as part of the decomposition molecules to form reaction products that can be attached to the PET polymer. In this way, LMW PET can include end groups that are reaction products of the decomposition molecules.

[0091] The decomposition molecules can be used at various concentrations to determine the amount of LMW and the low average molecular weight obtained. The amount of decomposition molecules relative to the amount of HMW PET can be used to obtain the desired amount of LMW with the desired low average molecular weight. If the amount of decomposition molecules is too low, the chains will not be decomposed sufficiently. If the amount of decomposition molecules is too high, low molecular weight material will result and smoke problems due to decomposition in the extruder may occur. It has been found that 0.25% to about 5% based on the total weight of the PET composition to be decomposed can provide the desired low average molecular weight. Here, the amount can vary, for example, 0.4% to about 4%, about 0.5% to about 3%, about 0.6% to about 2%, about 10% to about 10% based on the total weight of the PET composition. 0.The amount of degradant may be from about 7% to about 1%, or from about 0.75% to about 0.8%. The PET may be any HMW PET composition, such as a HMW PET composition having an intrinsic viscosity of about 0.6 to about 0.95, or from about 0.65 to about 0.9, or from about 0.7 to about 0.85, or from about 0.75 to about 0.78 to about 0.82, or from about 0.79 to 0.81. Standard HMW PET may be described as 0.8 IV PET and may have an intrinsic viscosity ranging from 0.78 to 0.82 IV within a margin of error. In one example, the degradant (e.g., trimethylolpropane) may be provided as 0.75% by weight of degradant in 0.8 IV standard bottle grade PET (HMW PET).

[0092] The mechanical properties of LMW PET are poor, especially in strength, due to the low molecular weight resulting in a low entanglement density, which is necessary for good strength. It was surprising and unexpected that LMW PET, having an intrinsic viscosity of about 0.48, can be used as described herein to obtain a flowable PET capable of injection molding, resulting in a multimodal PET having an intrinsic viscosity of about 0.5.

[0093] In some embodiments, the method can include diluting about 10-40% ultra-high flow low molecular weight polyol treated (i.e., trimethylolpropane treated) PET (e.g., LMW PET) into about 90-60% standard bottle grade PET (e.g., HMW PET). The optimal ratio is about 30-35% ultra-high flow PET (LMW) + 70-65% standard PET (HMW). This provides an optimal balance of flow and mechanical properties. Multimodal PET in these ranges retains excellent strength, stiffness, Tg, Tm, etc., as shown in the data provided herein. Multimodal PET has been shown to be usable for injection molded different parts, and the resulting parts are highly transparent, which is beneficial for use in many consumer packaging products.

[0094] In some embodiments, the HMW degraded or used in the multimodal PET mix can be bottle grade PET or recycled PET, as well as off-spec PET. For example, recycled PET has a somewhat lower IV and lower molecular weight than virgin HMW PET. The present invention starts with that somewhat degraded recycled PET and can further reduce the molecular weight by treatment with degrading molecules (e.g., trimethylolpropane). The starting characteristic of the HMW PET can determine the amount of degrading molecules and the amount of degrading used to obtain the LMW PET, or the amount of LMW PET mixed with the HMW PET to obtain the multimodal PET.

[0095] In some embodiments, small molecular weight polyols are the preferred decomposition molecules, carefully selected from many potential candidates. Small molecular weight polyols, such as sugar polyols, are desirably cheap, safe, food approved, kosher, temperature stable, colorless, high flash point, and safe for extrusion. Water can also be used as the decomposition molecule, but extremely small amounts of water are required and the dosage is difficult to control precisely. Water also evaporates quickly, making it difficult to react with PET. Amines are undesirable because they oxidize easily and turn yellow. Mercaptans have a strong odor. One attractive option is to inject steam into the PET melt to obtain the desired cleavage and resulting LMW PET.

[0096] In some embodiments, a method for forming a low molecular weight polyalkylene terephthalate (PAT) may include: providing a feed of high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight; providing a feed of decomposition molecules; reacting the HMW PAT with the decomposition molecules in a reactor; decomposing the HMW PAT with the decomposition molecules to a low molecular weight (LMW PAT) having a low average molecular weight lower than the high average molecular weight, and providing the LMW PAT as an output. In some embodiments, the decomposition molecules cleave the polymer chains of the HMW PAT into smaller polymer chains comprising reaction products of the HMW PAT and the decomposition molecules. In some embodiments, at least a portion of the decomposition molecules are unreacted and present in the LMW PAT. In some embodiments, the decomposition molecules are selected from water, alcohols, diols, polyols, thiols, dithiols, polythiols, amines, and combinations thereof. In some embodiments, the decomposition molecules are selected from the following: water in the form of steam; alcohols selected from methanol, ethanol, propanol, isopropanol, butanol, n-butanol, isobutanol, tertbutanol, or combinations thereof; diols selected from ethylene glycol, 1,4-butanediol, propylene-1,3-diol, beta propylene glycol, methanediol, propane-1,2-diol, alpha propylene glycol, or combinations thereof; polyols selected from xylitol, pentaerythritol, maltitol, sorbitol, isomalt, lactitol, mannitol, glycerol, trimethylolpropane, polyethylene glycol, or combinations thereof; thiols selected from methanethiol, ethanethiol, propanethiol, isopropanethiol, butanethiol, n-butanethiol, isobutanethiol, tertbutanethiol, or combinations thereof. a dithiol selected from methanedithiol, 1,1-ethanedithiol, and 1,1-cyclohexanedithiol, 1,3-propanedithiol, dithiothreitol, and combinations thereof; a polythiol selected from a polymer having a plurality of monomers having a thiol.Or an amine selected from methylamine, dimethylamine, trimethylamine, ethylamine, aniline, 4-methoxyaniline, N,N-dimethylaniline, 3-nitroaniline, 4-nitroaniline, 4-trifluoromethylaniline, and combinations thereof. In some embodiments, the decomposition molecule is not talc or other particles. In some embodiments, the LMW PAT does not include particles.

[0097] In some embodiments, the method can include characterizing the LMW PAT as having at least one of the following: an intrinsic viscosity of about 0.4 to about 0.6; a melting point of about 240° C. to about 247° C.; a glass transition temperature of about 70° C. to about 80° C.; or a degraded molecule at about 0.3% to about 0.5% by weight of the LMW PAT composition. In some embodiments, the degraded molecule is provided at about 0.25% to about 5% by weight of the total PAT composition to be degraded. In some embodiments, the HMW PAT has at least one of the following properties: an intrinsic viscosity of about 0.7 to about 0.85; a melting point of about 245° C. to about 255° C.; or a glass transition temperature of about 75° C. to about 85° C.

[0098] In some embodiments, the PAT supply receives a PAT supply from one or more of the following: a PAT reactor system, where the PAT reactor system polymerizes PAT from PAT precursor reagents; a PAT recycle system, where the PAT recycle system recycles PAT from a PAT article; a PAT conditioning system, where the PAT conditioning system conditions PAT for mixing with the talc, where the conditioning is selected from one or more of heating, cutting PAT pellets or sheets or other PAT material, stirring, extruding, drying, off-gassing, or a PAT reservoir, where the PAT reservoir has liquid PAT, where the liquid PAT is molten PAT.

[0099] In some embodiments, the LMW PAT output is provided to an output system that provides the LMW PAT to a repository or a multimodal PAT system or an analytical system. The analytical system includes one or more analytical systems that at least one of: determine an intrinsic viscosity of the LMW PAT output; determine a flow rate of the LMW PAT output; determine a melting point of the LMW PAT output; determine a crystallization temperature of the LMW PAT output; determine a differential scanning calorimetry profile of the LMW PAT output; or determine a heat distortion temperature of the LMW PAT output.

[0100] In some embodiments, the PAT feed is devoid of other polymers. In some aspects, the degraded molecules are devoid of particles and / or devoid of other polymers.

[0101] In some embodiments, the method can include drying the PAT feed before mixing with the decomposition molecules; and / or drying the decomposition molecules before mixing with the PET feed. In some embodiments, the method can include polymerizing the PAT from a polymerizable reagent. In some embodiments, the method can include mixing the PAT and the decomposition molecules in a mixer. Additionally, the method can include mixing in antistatic agents, antimicrobial agents, foaming agents, stabilizers, UV blockers, acetaldehyde scavengers, pigments, lubricants, and other typical additives for plastics.

[0102] In some embodiments, a system for carrying out a method of forming LMW PAT can be provided. Such a system can include a feed line having a high molecular weight (HMW) PAT, where the HMW PAT has a high average molecular weight; a feed line a for cracked molecules; a reactor having the HMW PAT together with the cracked molecules; and an output having a low molecular weight (LMW PAT) having a low average molecular weight lower than the high average molecular weight.

[0103] In some embodiments, a method of forming a multimodal polyalkylene terephthalate (PAT) can include: providing a feed of low molecular weight (LMW) PAT, the LMW PAT having a low average molecular weight; providing a feed of high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight, but the low average molecular weight is of a lower distribution than the high average molecular weight; mixing the feed of LMW PAT with the feed of HMW PAT in a mixer to form a multimodal PAT; and providing the multimodal PAT as an output. In some embodiments, the LMW PAT and / or the HMW PAT are devoid of talc or other particles. In some embodiments, the HMW PAT is recycled HMW PAT. In some embodiments, the LMW PAT has at least one of the following properties: an intrinsic viscosity of about 0.4 to about 0.6; a melting point of about 240° C. to about 247° C.; or a glass transition point of about 70° C. to about 80° C. In some embodiments, the HMW PAT has at least one of the following properties: an intrinsic viscosity of about 0.7 to about 0.85; a melting point of about 245°C to about 255°C; or a glass transition temperature of about 75°C to about 85°C. In some embodiments, the multimodal PAT comprises the LMW PAT at about 10% to about 50% by weight of the multimodal PAT composition. In some embodiments, the multimodal PAT comprises the LMW PAT at about 30% to about 35% by weight of the multimodal PAT composition. In some embodiments, the multimodal PAT has at least one of the following properties: an intrinsic viscosity of about 0.5 to about 0.75; a melting point of about 245°C to about 248°C; or a glass transition temperature of about 77°C to about 81°C. In some embodiments, the multimodal PAT has about 0.1% to about 0.3% by weight of degrading molecules, the degrading molecules being selected from water, alcohols, diols, polyols, thiols, dithiols, polythiols, amines, and combinations thereof.

[0104] In some embodiments, the mixing is performed in a mixer capable of mixing the PAT in batch or continuous form, such as a single screw mixer, a twin screw mixer, a continuous kneader, a reciprocating screw mixer, a twin screw extruder, a continuous plow mixer, or a combination thereof. In some embodiments, the mixer also performs one or more of degassing, homogenizing, dispersing, or heating. In some embodiments, the mixing in the mixer includes mixing in antistatic agents, antibacterial agents, foaming agents, stabilizers, UV blocking agents, acetaldehyde scavengers, pigments, lubricants, and other typical additives for plastics.

[0105] In some embodiments, the method includes providing the multimodal PAT output to an output system, which provides the multimodal PAT to storage or an analytical or manufacturing system. In some aspects, the analytical system includes one or more analytical systems capable of: determining the intrinsic viscosity of the molten multimodal PAT output; determining the flow rate of the molten multimodal PAT output; determining the melting point of the multimodal PAT output; determining the crystallization temperature of the multimodal PAT output; determining a differential scanning calorimetry profile of the multimodal PAT output; or determining the heat distortion shrinkage temperature of the multimodal PAT output. In some aspects, the method includes converting the multimodal PAT output into an article of manufacture, which includes converting the multimodal PAT output into an article of manufacture.

[0106] In some embodiments, the method may include drying the HMW PAT feed and / or the LMW PAT prior to mixing.

[0107] In some embodiments, a system for forming a multimodal PAT can include a feed of low molecular weight (LMW) PAT, the LMW PAT having a low average molecular weight; a feed of high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight, where the low average molecular weight is less distributed than the high average molecular weight; a mixer having the LMW PAT and the HMW PAT; and an output having the multimodal PAT. In some embodiments, the system can include an output operably coupled to an outlet of the mixer, the output being selected from a vessel, a pump, a flow line, a heater, a cooler, an extruder, a die, a pelletizer, a mixer, and combinations thereof. In some embodiments, the LMW PAT and / or the HMW PAT are devoid of talc or other particles.

[0108] In some embodiments, the system can be: a PAT reactor system that polymerizes HMW PAT from PAT precursor reagents; a PAT recycle system that recycles PAT from the PAT article; a PAT conditioning system that prepares HMW PAT for mixing with LMW PAT, where the conditioning can be selected from one or more of heating, chopping PAT pellets or sheets or other PAT material, mixing, extruding, drying; off-gassing; or a PAT reservoir of liquid PAT, where the liquid PAT includes dissolved PAT.

[0109] In some embodiments, the mixer is any mixer capable of mixing the liquid PAT in a batch or continuous manner, such as a single screw mixer, a twin screw mixer, a continuous kneader, a reciprocating screw mixer, a twin screw extruder, a continuous plow mixer, or a combination thereof. In some aspects, the mixer is configured to perform one or more of degassing, homogenizing, dispersing, or heating.

[0110] In some embodiments, the system may include a storage and / or analytical system; and / or a manufacturing system. In some aspects, the analytical system includes one or more analytical systems capable of: determining the intrinsic viscosity of the molten multimodal PAT output; determining the flow rate of the molten multimodal PAT output; determining the melting point of the multimodal PAT output; determining the crystallization temperature of the multimodal PAT output; determining the differential scanning calorimetry profile of the multimodal PAT output; or determining the heat distortion shrinkage temperature of the multimodal PAT output.

[0111] In some embodiments, the manufacturing system is configured to convert the multimodal PET output into manufactured articles, such as injection molding. In some aspects, the manufacturing system can include: an optional ingredient input feed configured to provide optional ingredients, the optional ingredients being selected from fillers, TiO2, second polymers, glass pellets, glass fibers, glass particles, sodium ionomers, sodium stearate; nucleating agents, antistatic agents, antimicrobial agents, foaming agents, stabilizers, UV blockers, acetaldehyde scavengers, pigments, lubricants and other typical additives for plastics, polycarbonates, polybutylene terephthalates (PBT) or other PATs (e.g., PET), or other components of the PAT article of manufacture. It is clear that the additives are added to the multimodal PAT and not to the LMW PAT or HMW PAT. In some embodiments, the manufacturing system includes one or more of a multimodal PAT feed; one or more flow paths containing flowable multimodal PAT; a mixer; a heating system; an extruder system producing a multimodal PAT extrudate; a pump system; an injection molding system; and / or a cooling system.

[0112] In some embodiments, the multimodal PAT composition can include: a low molecular weight (LMW) PAT having a low average molecular weight; a high average molecular weight (HMW) PAT mixed with the LMW PAT to form the multimodal PAT, where the multimodal PAT lacks talc. In some embodiments, the LMW PAT is present at about 10% to about 50% by weight of the multimodal PAT composition. In some embodiments, the multimodal PAT has at least one of the following properties: an intrinsic viscosity of about 0.5 to about 0.75; a melting point of about 245°C to about 248°C; or a glass transition point of about 77°C to about 81°C.

[0113] In some embodiments, the multimodal PET may have an intrinsic viscosity ratio of HMW PET to LMW PET, e.g., an IV ratio of 0.8:0.4 (HMW:LMW). However, other HMW:LMW IV ratios may be from 0.7:0.3 to about 0.9 to about 0.5, from about 0.75:0.35 to about 0.85:0.45; or from about 0.78 to about 0.43, or from about 0.79 to about 0.41. In other examples, the IV ratio may be about 0.8±0.025:0.4±0.025; 0.8±0.05:0.4±0.05, or 0.8±0.075:0.4±0.075.

[0114] In some embodiments, the LMW PAT has at least one of the following intrinsic viscosity characteristics: about 0.3 to about 0.6, about 0.35 to about 0.55, about 0.36 to about 0.5, about 0.37 to about 0.45, or about 0.38 to about 0.42.

[0115] In some embodiments, the multimodal PET can be configured for injection molding. The polymer composition for injection molding can include about 30% LMW PET and about 70% HMW PET (e.g., a resin having an intrinsic viscosity of about 0.8), resulting in about 0.225% sugar polyol in the polymer composition. However, it should be recognized that variations in the amounts of the components can also be suitable, such as ±10%, 5%, 2%, or 1%. experiment

[0116] LMW PET was first prepared from HMW PET to create a masterbatch of LMW PET, which was then mixed with HMW PET to form a multimodal PET with LMW and HMW distributions.

[0117] The data provided herein shows the properties of HMW PET (e.g., 0.81 IV PET), LMW PET, and multimodal PET (30% LMW PET + 70% HMW PET), as well as other multimodal PET. It should be recognized that values ​​can vary, such as 1%, 2.5%, 5%, 10%, 15%, or up to 25%. Also, values ​​for multimodal PET can change when the relative amounts of LMW and HMW PET are changed.

[0118] In these examples, the PET resin was fed 0.8IV. Approximately 0.75% glycerol was unloaded into the PET to produce a clear flow LMW PET masterbatch. Approximately 30% of the LMW PET masterbatch was then dry blended with 70% PET resin (e.g., 0.8IV). This resulted in 0.225% glycerol in the final recipe. Various ranges of glycerol were tested and the final multimodal PET was found to have approximately 0.15%, 0.188%, 0.263%, or 0.225% glycerol based on the total weight of the composition. 0.225% glycerol by weight (e.g., 30% LMW and 70% HMW) has the best combination of flow and mechanical properties. Mechanical tests were performed comparing the PET compositions. All tests indicate that the multimodal PET formulations can maintain beneficial strength properties along with improved flow that may be useful in injection molding. However, it should be appreciated that different degrading molecules may be used that can be retained in multimodal PET.

[0119] 3-point bending test

[0120] Testing was performed on an Instron 3366 unit with Bluehill Universal software applying the principles of ASTM D 790 "Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials, Procedure A". Sample size: 0.125 in. thick x 0.5 in. wide x 5.0 in. long, support span: 2 in., number of specimens per sample type. Five specimens were tested at each strain rate. The experiment included the following test conditions: Speed-0.05 in. / min, Span-2.0 in. The following results were obtained:

[0121] [Table 1]

[0122] [Table 2]

[0123] [Table 3]

[0124] Tensile Test

[0125] Testing was performed on an Instron 3366 unit with Bluehill Universal software applying the principles of ASTM D638 Tensile Properties of Plastics. A 10kN load cell was used. A long travel extensometer was used to measure strain values. For filled PET samples, a clip-on 2" gauge / 0.2" travel extensometer was used for better accuracy at low strain values. Crosshead speed: 2.0 in / min. Sample size: ASTM Type I Dogbone Specimen gauge length: 2.0 in. Number of specimens tested for each specimen type: 5 (minimum). Results are shown in the table below with the penultimate column being the average value for the column and the penultimate column being the standard deviation.

[0126] [Table 4]

[0127] [Table 5]

[0128] [Table 6]

[0129] Notched Izod Impact Test

[0130] Testing was performed on a Ceast Resil 25 Digital Pendulum Unit, Model 6545, in accordance with ASTM D256 "Standard Test Method for Izod Pendulum Impact Resistance of Plastics, Method A". Pendulum Capacity: 2.00 Joules Sample Size: Dimensional Notch Depth: 0.1 inch Number of specimens tested per specimen type: 5 (minimum). Test Temperature: The specimens were at room temperature 22C during testing. The results of the notched impact tests were obtained and are shown in the table below. The second to last column is the average value for the column and the third to last column is the standard deviation.

[0131] [Table 7]

[0132] [Table 8]

[0133] [Table 9]

[0134] Fracture classification definitions: C = complete break (break in which the specimen separates into two or more pieces); H = hinge break (incomplete break such that one portion of the specimen cannot be supported above horizontal when the other portion is held vertically); P = partial break (incomplete break that does not meet the definition of a hinge break but breaks more than 90% of the distance between the apex of the notch and the other side); and NB = no break (incomplete break where the break extends less than 90% of the distance between the apex of the notch and the other side). These definitions are the same for unnotched impact tests.

[0135] The results of the unnotched impact tests were obtained and are shown in the table below. The second to last column is the average value for the column and the third to last column is the standard deviation.

[0136] [Table 10]

[0137] [Table 11]

[0138] [Table 12]

[0139] Gardner Impact Test

[0140] Gardner impact testing was performed in accordance with ASTM D 5420 using a BYK Gardner impact tester (catalog number lG1120). The tester was bolted to a concrete floor. Geometry: GC, height increment: 1 inch, test temperature: 23°C. The failure mode was ductile failure, with the dart penetrating the sheet. The dart struck the sheet first. [Table 13]

[0141] Unreinforced (neat) PET and 30% LMW PET 70% HMW PET showed maximum values ​​on the Gardner impact tester at a load of 4 lbs and a maximum test height of 40 in. Failure types: a = crack on one side only (plaque can still hold water), b = crack through the entire thickness (water will likely penetrate the plaque), or c = brittle fracture (plaque is broken into several pieces after impact) d = ductile failure (plaque is penetrated with a blunt fracture).

[0142] Intrinsic Viscosity Test and Results

[0143] Intrinsic Viscosity: According to ASTM 4603-96. Solvent: Phenol / Tetrachloroethane (60 / 40 w / w). Temperature: 30°C. Concentration: 0.5 g / dL. [Table 14]

[0144] LMW / HMW multimodal PET ratio

[0145] The amount of LMW PET was varied to study the performance characteristics. The percentage samples were: 20% LMW PET and 80% HMW PET, 25% LMW PET and 75% HMW PET, 30% LMW PET and 70% HMW PET, and 35% LMW PET and 65% HMW PET. The data in Figure 6 shows that varying the LMW / HMW ratio between 20 / 80 and 35 / 65 also results in a multimodal PET that can be used for injection molding. A ratio of 30 / 70 was found to provide the optimum results.

[0146] Resin characterization and comparison

[0147] A HMW PET resin with an intrinsic viscosity of 0.81 (e.g., a 0.81 IV resin) was compared with a LMW PET masterbatch and multimodal PET (e.g., 30% LMW PET + 70% HMW PET resin), and the results are shown in the table below. [Table 15]

[0148] Intrinsic viscosity, melting point, and glass transition are provided to illustrate the differences between HMW PET, LMW PET, and multimodal PET, however, it should be recognized that variations in the ratio of LMW PET to HMW PET can cause variations in these values.

[0149] The data also show that LMW PET and multimodal PET have more COOH end groups compared to HMW PET, and multimodal PET has a higher percentage of crystallinity compared to HMW PET and LMW PET.

[0150] Thus, as evidenced by the Mn, Mw, and Mz, HMW PET has a higher molecular weight than LMW PET, and the molecular weight of multimodal PET is a combination of the molecular weights of HMW PET and LMW PET. Also, the polydispersity (e.g., Mw / Mn polydispersity index) of multimodal PET of 1.529 is in the appropriate range compared to the polydispersity of HMW PET of 1.596 and the polydispersity of LMW PET of 1.443. The polydispersity value of multimodal PET provides an advantage for using multimodal PET as described herein.

[0151] Regular PET has high strength but poor flow, which prevents it from being used in injection molded products, especially thin-walled products. Intentional random chain scission reduces the molecular weight, thereby improving flow, but at the expense of unacceptable strength loss. In this invention, we have created a molecular weight distribution that retains a large proportion of long chains while introducing very small chains to improve flow. The balance of flow and strength thus obtained is highly desirable, and has eluded PET manufacturers for decades. Thus, polydispersity provides a favorable combination of more long chains and smaller to short chains, improving flow while maintaining strength.

[0152] Therefore, by changing this ratio, the values ​​in the table are expected to change within the ranges of ±25%, 20%, 15%, 10%, 5%, 2%, and 1%.

[0153] injection molding

[0154] Injection molding experiments were performed with standard HMW PET with an intrinsic viscosity of 0.71 as the control and multimodal PET with an intrinsic viscosity of 0.56 as the test. These PET compositions were processed by injection molding under similar conditions as shown in Figures 7A (control) and 7B (Clearflow; multimodal PET). As can be seen, the multimodal PET uses a much lower switching press at 270 Bar, which is about half the 550 Bar of the control. Also, the hydraulic press for multimodal PET is a maximum of 27 Bar, which is much lower than the maximum of 55 Bar for the control. Thus, multimodal PET offers better injection molding due to better flowability, so that less injection pressure can be used. For example, it is believed that the hydraulic press with multimodal PET can be 45 Bar or less, about 40 Bar or less, about 35 Bar or less, about 30 Bar or less, about 25 Bar or less, about 20 Bar or less, or perhaps even lower due to optimized flowability. This shows that injection molding with multimodal PET is a significant advance over control PET. This lower injection pressure can be used to various advantages such as shorter cycle times, reduced wall thickness of the injection molding material, faster injection speeds, and other advancements. As a result, products using multimodal PET are mechanically equivalent to control PET, but have improved processability and injection moldability.

[0155] Bottles injection molded from multimodal PET are transparent and indistinguishable from control PET. Visually, therefore, multimodal PET can replace control PET. Bottle dimensions and bottle volumes were found to be substantially similar. Additionally, sidewall density and crystallinity were measured to be nearly the same for control PET and multimodal PET. Bottle material distribution was also found to be substantially similar between control PET and multimodal PET.

[0156] The bottle sidewall tensile data shows comparable results. The control PET sidewall tensile data modulus was 8.32 x 10 5 Sidewall tensile data for multimodal PET: Modulus of elasticity, in psi, is 8.33 x 10 5 The peak load for the control PET was 21.85 lbf, while that for the multimodal PET was 19.80, which is not significantly different from the control. The yield stress for the control and multimodal PET was 1.7 x 10 4 It was almost the same as psi.

[0157] Empty vent topload experiments show that multimodal PET is of sufficient quality for use as a bottle. At an empty vent topload of 20 inches per minute, the control PET had an initial peak of 15.09 lbf, a maximum load of 15.09 lbf, and a deflection load of 9.05 lbf, while the multimodal PET had an initial peak of 11.42 lbf, a maximum load of 12.44 lbf, and a deflection load of 11.47 lbf.

[0158] The fill cap top load experiment shows that the multimodal PET is of sufficient quality to be used as a bottle. At a fill cap top load of 0.5 inches per minute, the control PET had a first peak at 123 lbf, a maximum load at 123 lbf, and a deflection load of 50.51 lbf, while the multimodal PET had a first peak at 110 lbf, a maximum load at 110 lbf, and a deflection load of 51.10 lbf. Here, the data shows that the multimodal PET is an improvement.

[0159] The filled bottle sidewall stiffness intermediate label crush strength experiment shows that multimodal PET is of sufficient quality to be used as a bottle. The results of the filled bottle sidewall stiffness intermediate label crush strength experiment showed that the control PET had an initial peak of 3.22 lbf, a maximum load of 14.7 lbf, and a load at deflection of 14.62 lbf, while the multimodal PET had an initial peak of 3.67 lbf, a maximum load of 14.6 lbf, and a load at deflection of 14.53 lbf.

[0160] The color of the injection molded parts was compared. Both appear to be transparent. The data showed that the haze absorption was about 5.4 for the control PET and about 4.37 for the multimodal PET. A lower number means less haze or better transparency. Thus, the multimodal PET can provide better transparency or less haze compared to the control PET.

[0161] All chemical terms are defined as known in the art.

[0162] Those skilled in the art will appreciate that, for this and other processes and methods disclosed herein, the functions performed in the processes and methods may be performed in differing order. Moreover, the schematic steps and operations are provided only as examples, and some of the steps and operations may, in some cases, be combined into fewer steps and operations or expanded into additional steps and operations without detracting from the essence of the disclosed embodiments.

[0163] The present disclosure is not limited in terms of the specific embodiments described herein, but is intended as an illustration of various aspects. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope thereof. In addition to those enumerated herein, functionally equivalent methods and apparatuses within the scope of the present disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is understood that the present disclosure is not limited to specific methods, reagents, compounds compositions, or biological systems, which, of course, can vary. It is also to be understood that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to be limiting.

[0164] With respect to the use of virtually any plural and / or singular term herein, those of skill in the art can convert from plural to singular and / or from singular to plural as appropriate to the context and / or application. Various singular / plural permutations may be expressly set forth herein for clarity.

[0165] In general, those skilled in the art will understand that the terms used in this specification, and particularly in the appended claims (e.g., the body of the appended claims), are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," the term "including" should be interpreted as "including but not limited to," etc.). Those skilled in the art will further understand that where a particular number of introduced claims are intended, such intent will be expressly set forth in the claim, and in the absence of such recitation, no such intent exists. For example, to aid in understanding, the following appended claims include the use of the introductory phrases "at least one" and "one or more" to introduce the claim recitations. However, the use of such phrases should not be construed to mean that the introduction of a claim iteration with the indefinite article "a" or "an" limits any particular claim that includes such an introduced claim iteration to only those embodiments that include one such iteration, even if the same claim may be used in combination with indefinite articles such as "one or more" or "at least one" and "one" or "one" (e.g., "one" and / or "one" should be interpreted to mean "at least one" or "one or more"). Similarly, the use of definite articles used in the preamble of a claim may be used in combination with indefinite articles such as "one or more" or "at least one" (e.g., "one" and / or "one" should be interpreted to mean "at least one" or "one or more"). Moreover, even if a specific number of introduced claim iterations is explicitly recited, one of ordinary skill in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., a bare recitation of "two iterations" without other modifiers means at least two iterations, or two or more turns). Additionally, when a convention similar to "such as at least one of A, B, and C" is used, such structures are generally intended in the sense that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" would include, but is not limited to, a system having A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together).When a convention similar to "at least one of A, B, or C, etc." is used, such a configuration is generally intended in the sense that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, or C" would include, but is not limited to, systems having A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C, etc.). One of ordinary skill in the art would further appreciate that virtually any divisive word and / or phrase presenting two or more alternative terms, whether in the specification, claims, or drawings, should be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" would be understood to include the possibilities of "A" or "B" or "A and B."

[0166] Moreover, when features or aspects of the disclosure are described in terms of a Markush group, those skilled in the art will recognize that the disclosure is also described thereby in terms of any individual element or subgroup of elements of the Markush group.

[0167] As will be appreciated by those skilled in the art, for all purposes, including in terms of providing a written description, all ranges disclosed herein encompass any possible subranges and combinations of subranges thereof. Any recited range can be readily recognized as fully descriptive and allowing for the same range to be broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third, upper third, etc. As will also be appreciated by those skilled in the art, all language such as "up to," "at least," etc., refers to a range that includes the recited number and can then be broken down into subranges as described above. Finally, as will be appreciated by those skilled in the art, a range includes each individual member. Thus, for example, a group having 1 to 3 cells refers to a group having 1, 2, or 3 cells. Similarly, a group having 1 to 5 cells refers to a group having 1, 2, 3, 4, or 5 cells, etc.

[0168] From the foregoing, it will be understood that various embodiments of the present disclosure have been described herein for purposes of illustration, and that various changes may be made without departing from the scope and spirit of the present disclosure. Accordingly, the various embodiments disclosed herein are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

[0169] All documents mentioned herein are specifically incorporated herein by reference in their entirety. In relation to the present invention, the following is further disclosed: [1] 1. A method for forming a low molecular weight polyalkylene terephthalate (PAT), the method comprising: providing a feed of high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight; Providing a feed of degraded molecules; reacting the HMW PAT with a decomposition molecule in a reactor; Degrading the HMW PAT into low molecular weight (LMW PAT) degraded molecules having a low average molecular weight lower than the high average molecular weight; and Provide the LMW PAT as output. [2] The method of claim 1, wherein the decomposition molecule cleaves the polymer chains of the HMW PAT into smaller polymer chains comprising reaction products of the HMW PAT and the decomposition molecule. [3] The method according to [1], wherein at least a portion of the decomposition molecules is unreacted and present in the LMW PAT. [4] The method of claim 2, wherein the decomposition molecule is selected from water, alcohols, diols, polyols, thiols, dithiols, polythiols, amines, and combinations thereof. [5] The method according to [4], wherein the decomposition molecule is selected from the following: Water in vapor form; alcohols selected from methanol, ethanol, propanol, isopropanol, butanol, n-butanol, isobutanol, tert-butanol, or combinations thereof; a diol selected from ethylene glycol, 1,4-butanediol, propylene-1,3-diol, beta propylene glycol, methanediol, propane-1,2-diol, alpha propylene glycol, or combinations thereof; a polyol selected from xylitol, pentaerythritol, maltitol, sorbitol, isomalt, lactitol, mannitol, glycerol, trimethylolpropane, polyethylene glycol, or combinations thereof; thiols selected from methanethiol, ethanethiol, propanethiol, isopropanethiol, butanethiol, n-butanethiol, isobutanethiol, tertbutanethiol, or combinations thereof; dithiols selected from methanedithiol, 1,1-ethanedithiol, and 1,1-cyclohexanedithiol, 1,3-propanedithiol, dithiothreitol, and combinations thereof; A polythiol selected from a polymer having a plurality of thiol-bearing monomers; or Amines selected from methylamine, dimethylamine, trimethylamine, ethylamine, aniline, 4-methoxyaniline, N,N-dimethylaniline, 3-nitroaniline, 4-nitroaniline, 4-trifluoromethylaniline, and combinations thereof. [6] The method of [1], wherein the degraded molecules are not talc or other particles, whereby the LMW PAT is devoid of particles. [7] The method of claim 1, further comprising characterizing the LMW PAT as having at least one of the following: an intrinsic viscosity of about 0.4 dL / g to about 0.6 dL / g; A melting point of about 240°C to about 247°C; The glass transition temperature is about 70°C to about 80°C. [8] The method of [1], wherein the decomposition molecule is provided at about 0.25% by weight to about 5% by weight of the total PAT composition to be decomposed. [9] The method of claim 1, wherein the HMWPAT has at least one of the following characteristics: an intrinsic viscosity of about 0.7 dL / g to about 0.85 dL / g; A melting point of about 245°C to about 255°C; or The glass transition temperature is about 75°C to about 85°C.

[10] A system for carrying out the method according to [1], characterized in that it comprises: a feedline having a high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight; feed line for decomposition molecules; A reactor having a HMW PAT with cracked molecules; and Output having a low molecular weight polymer (LMW PAT) having a low average molecular weight lower than the high average molecular weight.

[11] 1. A method for forming a multimodal polyalkylene terephthalate (PAT), the method comprising: providing a feed of low molecular weight (LMW) PAT, the LMW PAT having a low average molecular weight; providing a feed of high molecular weight (HMW) PAT, the HMW PAT having a high average molecular weight, the low average molecular weight being lower than the high average molecular weight; mixing the LMW PAT feed with the HMW PAT feed in a mixer to form a multimodal PAT; and Providing a multimodal PAT as output.

[12] The method of claim 11, wherein the LMW PAT and / or HMW PAT does not contain talc or other particles.

[13] The method according to

[11] , wherein the HMW PAT is recycled HMW PAT.

[14] The method according to

[11] , further comprising: providing an LMW PAT having at least one of the following properties: an intrinsic viscosity of about 0.4 dL / g to about 0.6 dL / g; a melting point of about 240° C. to about 247° C.; or a glass transition temperature of about 70° C. to about 80° C.; and / or To provide a HMW PAT having at least one of the following properties: an intrinsic viscosity of about 0.7 dL / g to about 0.85 dL / g; a melting point of about 245°C to about 255°C; or a glass transition temperature of about 75°C to about 85°C.

[15] The method of claim 11, wherein the multimodal PAT comprises an LMW PAT in an amount of about 10% by weight to about 50% by weight of the multimodal PAT composition.

[16] The method of claim 15, wherein the multimodal PAT comprises an LMW PAT in an amount of about 30% to about 35% by weight of the multimodal PAT composition.

[17] The method according to

[11] , further comprising: To obtain a multimodal PAT having at least one of the following properties: an intrinsic viscosity of about 0.45 dL / g to about 0.65 dL / g; a melting point of about 245°C to about 248°C; or a glass transition temperature of about 77°C to about 81°C.

[18] The method of claim 11, wherein the multimodal PAT has about 0.1% by weight to about 0.3% by weight of decomposition molecules, and the decomposition molecules are selected from water, alcohols, diols, polyols, thiols, dithiols, polythiols, amines, and combinations thereof.

[19] A system for carrying out the method according to

[11] , characterized in that it comprises: Feed low molecular weight (LMW) PAT with low average molecular weight; A feed of high molecular weight (HMW) PAT having a high average molecular weight, wherein the low average molecular weight is lower than the high average molecular weight. A mixer having an LMW PAT and an HMW PAT; and Output with multimodal PAT.

[20] Multimodal Polyalkylene Terephthalates (PATs), including: Low molecular weight (LMW) PAT with low average molecular weight; High molecular weight (HMW) PAT with a high average molecular weight that is mixed with LMW PAT to form a multimodal PAT; Here, the multimodal PAT does not contain talc.

[21] The multimodal PAT according to

[20] , further comprising an LMW PAT in an amount of about 10% by weight to about 50% by weight of the multimodal PAT composition.

[22] The multimodal PAT according to

[21] , further comprising a multimodal PAT having at least one of the following characteristics: an intrinsic viscosity of about 0.45 dL / g to about 0.75 dL / g; A melting point of about 245°C to about 248°C; or The glass transition temperature is from about 77°C to about 81°C.

Claims

1. 1. A method for forming a multimodal polyalkylene terephthalate (PAT) composition, the method comprising: providing a first feed of high molecular weight (HMW) PAT, the HMW PAT having a first average molecular weight; providing a feed of decomposition molecules selected from alcohols, diols, polyols, thiols, dithiols, polythiols, amines, and combinations thereof; reacting the HMW PAT with a decomposition molecule in a reactor; degrading the HMW PAT with degradation molecules into low molecular weight (LMW PAT) having a second average molecular weight lower than said first average molecular weight; providing an intermediate composition having a decomposition molecule and a LMW PAT; providing a second feed of HMW PAT having a third average molecular weight, said second average molecular weight being lower than said third average molecular weight; mixing the intermediate composition with the second feed of HMW PAT in a mixer to form a multimodal PAT composition, the multimodal PAT composition having a HMW PAT having the third average molecular weight and a LMW PAT having the second average molecular weight; Providing as an output a multimodal PAT composition, the multimodal PAT composition comprising the degraded molecules.

2. 2. The method of claim 1, wherein the decomposition molecule is selected from: an alcohol selected from methanol, ethanol, propanol, isopropanol, butanol, n-butanol, isobutanol, tert-butanol, or combinations thereof; A diol selected from ethylene glycol, 1,4-butanediol, propylene-1,3-diol, beta propylene glycol, methanediol, propane-1,2-diol, alpha propylene glycol, or combinations thereof; A polyol selected from xylitol, pentaerythritol, maltitol, sorbitol, isomalt, lactitol, mannitol, glycerol, trimethylolpropane, polyethylene glycol, or combinations thereof; thiols selected from methanethiol, ethanethiol, propanethiol, isopropanethiol, butanethiol, n-butanethiol, isobutanethiol, tertbutanethiol, or combinations thereof; dithiols selected from methanedithiol, 1,1-ethanedithiol, and 1,1-cyclohexanedithiol, 1,3-propanedithiol, dithiothreitol, and combinations thereof; A polythiol selected from a polymer having multiple thiol-bearing monomers; or Amines selected from methylamine, dimethylamine, trimethylamine, ethylamine, aniline, 4-methoxyaniline, N,N-dimethylaniline, 3-nitroaniline, 4-nitroaniline, 4-trifluoromethylaniline, and combinations thereof.

3. The method of claim 1 , wherein the multimodal PAT composition is devoid of particles.

4. 10. The method of claim 1, further comprising characterizing the LMW PAT as having at least one of the following: an intrinsic viscosity of about 0.4 dL / g to about 0.6 dL / g; A melting point of about 240°C to about 247°C; The glass transition temperature is about 70°C to about 80°C.

5. The method of claim 1, wherein the degraded molecule is provided at about 0.25% to about 5% by weight of the total PAT to be degraded.

6. 2. The method of claim 1, wherein the HMW PAT of the first feed or the second feed has at least one of the following characteristics: an intrinsic viscosity of about 0.7 dL / g to about 0.85 dL / g; A melting point of about 245°C to about 255°C; or A glass transition temperature of about 75°C to about 85°C.

7. The method of claim 1 , wherein the multimodal PAT composition is talc-free.

8. 2. The method of claim 1, wherein the HM W PAT of the first feed or the second feed is recycled HM W PAT.

9. 13. The method of claim 1 further comprising: providing said LMW PAT having at least one of the following properties: an intrinsic viscosity of about 0.4 dL / g to about 0.6 dL / g; a melting point of about 240° C. to about 247° C.; or a glass transition temperature of about 70° C. to about 80° C.; and / or Providing an HM W PAT of the first feed or the second feed having at least one of the following properties: an intrinsic viscosity of about 0.7 dL / g to about 0.85 dL / g; a melting point of about 245°C to about 255°C; or a glass transition temperature of about 75°C to about 85°C.

10. The method of claim 1 , wherein the multimodal PAT composition comprises from about 10% to about 50% by weight of the multimodal PAT composition of the LMW PAT.

11. The method of claim 10, wherein the multimodal PAT composition comprises the LMW PAT at about 30% to about 35% by weight of the multimodal PAT composition.

12. 13. The method of claim 1 further comprising: Obtaining a multimodal PAT composition having at least one of the following properties: an intrinsic viscosity of about 0.45 dL / g to about 0.65 dL / g; a melting point of about 245°C to about 248°C; or a glass transition temperature of about 77°C to about 81°C.

13. The method of claim 1 , wherein the multimodal PAT composition has about 0.1% to about 0.3% by weight of degraded molecules.

14. Multimodal polyalkylene terephthalates (PATs), including: A low molecular weight (LMW) PAT having a first average molecular weight; and a high molecular weight (HMW) PAT of a second average molecular weight which is mixed with the LMW PAT to form a multimodal PAT; wherein the first average molecular weight is lower than the second average molecular weight; Here, the multimodal PAT comprises degrading molecules selected from alcohols, diols, polyols, thiols, dithiols, polythiols, amines, and combinations thereof, and is free of talc.

15. 15. The multimodal PAT of claim 14, further comprising said LMW PAT at about 10% to about 50% by weight of the multimodal PAT.

16. The multimodal PAT of claim 15 further comprising the multimodal PAT having at least one of the following characteristics: an intrinsic viscosity of about 0.45 dL / g to about 0.75 dL / g; A melting point of about 245°C to about 248°C; or A glass transition temperature of about 77°C to about 81°C.

17. The method of claim 1 , wherein the PAT is polyethylene terephthalate (PET).

18. The multimodal PAT composition comprises at least one of the following: A multimodal PAT composition having a polydispersity of about 1.5 to about 1.575; HMW PET having a polydispersity of about 1.55 to about 1.65; and LMW PET having a polydispersity of about 1.4 to about 1.5; 2. The method of claim 1, comprising:

19. The multimodal PAT composition has a viscosity of about 3 to 6 CC / (m ２ 2. The method of claim 1, wherein the oxygen transmission rate is within ±25% of the oxygen transmission rate (day 1).

20. The method of claim 1 , wherein the multimodal PAT composition has a crystallization temperature of about 200° C. to about 230° C.

21. The method of claim 1 , wherein the multimodal PAT composition has a crystalline fraction of about 21% to about 25%.

22. The method of claim 1, wherein the degraded molecule is provided at about 0.4% to about 4% by weight of the total PAT to be degraded.

23. The method of claim 1, wherein the degraded molecule is provided at about 0.5% to about 3% by weight of the total PAT to be degraded.

24. The method of claim 1, wherein the degraded molecule is provided at about 0.6% to about 2% by weight of the total PAT to be degraded.

25. The method of claim 1, wherein the degrading molecule is provided at about 0.7% to about 1% by weight of the total PAT to be degraded.

26. The method of claim 1, wherein the degraded molecule is provided at about 0.75% to about 0.8% by weight of the total PAT to be degraded.

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