Low color polyethylene furanoate from furan-2,5-dicarboxylic acid

Abstract

The Invention also relates to the manufacture of a composition comprising PEF (polyethylene furanoate). The Invention also relates to the manufacture of a composition Low Color PEF (polyethylene furanoate). New low colored PEF composition has been discovered. There is a need for technology to produce new polyesters, polyamides, plasticizers, and coatings from FDCA as part of a bio-based technology platform.

Description

LOW COLOR POLYETHYLENE FURANOATE FROM FURAN-2,5- DICARBOXYLIC ACIDFIELD OF THE INVENTION

[0001] The Invention also relates to the manufacture of a composition comprising PEF (polyethylene furanoate). The Invention also relates to the manufacture of a composition Low Color PEF (polyethylene furanoate). New low colored PEF composition has been discovered. There is a need for technology to produce new polyesters, polyamides, plasticizers, and coatings from FDCA as part of a bio-based technology platform.BACKGROUND OF THE INVENTION

[0002] Aromatic dicarboxylic acids, such as terephthalic acid and isophthalic acid, are used to produce a variety of polyester products. Important examples of which are poly (ethylene terephthalate) and its copolymers. These aromatic dicarboxylic acids are synthesized by the catalytic oxidation of the corresponding dialkyl aromatic compounds which are obtained from fossil fuels, which is disclosed in U.S. Patent Application 2006 / 0205977 A1), which is herein incorporated by reference to the extent it does not contradict the statements herein.

[0003] There is a growing interest in the use of renewable resources as feed stocks for the chemical industry mainly due to the progressive reduction of fossil reserves and their related environmental impacts. Furan-2,5-dicarboxylic acid (FDCA) is a versatile intermediate considered as a promising closest biobased alternative to terephthalic acid and isophthalic acid. Like aromatic diacids, FDCA can be condensed with diols such as ethylene glycol to make polyester resins similar to polyethylene terephthalate (PET) (Gandini, A.; Silvestre, A. J; Neto, C. P.; Sousa, A. F.; Gomes, M. J. Poly. Sci. A 2009, 47, 295.). Therefore, there is a need in the chemical industry for an efficient process to produce carboxylic acid compositions, especially FDCA. A highyield process (minimum of 90% FDCA yield) to produce a dry, purified FDCA product is provided herein.

[0004] The Invention also relates to the manufacture of a composition comprising PEF (polyethylene furanoate). The Invention also relates to the manufacture of a composition Low Color PEF (polyethylene furanoate). New low colored PEF composition has been discovered. There is a need for technology to produce new polyesters, polyamides, plasticizers, and coatings from FDCA as part of a bio-based technology platform.BRIEF DESCRIPTION OF THE DRAWINGS

[0005] Figure 1 illustrates different embodiments of the invention wherein a process to produce a dried purified carboxylic acid 710 is provided.

[0006] Figure 2 illustrates an embodiment of the invention, showing the GC chromatogram of the carboxylic acid composition 110 that has been dried.

[0007] Figure 3 illustrates an embodiment of the invention, showing a1H NMR of the carboxylic acid composition 110 that has been dried.

[0008] Figure 4 illustrates an embodiment of the invention, showing a13C{1H} NMR of the carboxylic acid composition 110 that has been dried.

[0009] Figure 5 illustrates an embodiment of the invention, showing absorbance versus wavelength (nm) for PEF samples made from commercial FDCA (example 4) and from in-house FDCA (example 6).DETAILED DESCRIPTION

[0010] It should be understood that the following is not intended to be an exclusive list of defined terms. Other definitions may be provided in the foregoing description, such as, for example, when accompanying the use of a defined term in context.

[0011] As used herein, the terms “a,” “an,” and “the” mean one or more.

[0012] As used herein, the term “and / or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. Forexample, if a composition is described as containing components A, B, and / or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

[0013] As used herein, the terms “comprising,” “comprises,” and “comprise” are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject

[0014] As used herein, the terms “having,” “has,” and “have” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above.

[0015] As used herein, the terms “including,” “includes,” and “include” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above.

[0016] The present description uses numerical ranges to quantify certain parameters relating to the invention. It should be understood that when numerical ranges are provided, such ranges are to be construed as providing literal support for claim limitations that only recite the lower value of the range as well as claim limitations that only recite the upper value of the range. For example, a disclosed numerical range of 10 to 100 provides literal support for a claim reciting “greater than 10” (with no upper bounds) and a claim reciting “less than 100” (with no lower bounds).

[0017] The present description uses specific numerical values to quantify certain parameters relating to the invention, where the specific numerical values are not expressly part of a numerical range. It should be understood that each specific numerical value provided herein is to be construed as providing literal support for a broad, intermediate, and narrow range. The broad range associated with each specific numerical value is the numerical value plus and minus 60 percent of the numerical value, rounded to two significant digits. The intermediate range associated with each specificnumerical value is the numerical value plus and minus 30 percent of the numerical value, rounded to two significant digits. The narrow range associated with each specific numerical value is the numerical value plus and minus 15 percent of the numerical value, rounded to two significant digits. For example, if the specification describes a specific temperature of 62 °F, such a description provides literal support for a broad numerical range of 25 °F to 99 °F (62 °F + / - 37 °F), an intermediate numerical range of 43 °F to 81 °F (62 °F + / - 19 °F), and a narrow numerical range of 53 °F to 71 °F (62 °F + / - 9 °F). These broad, intermediate, and narrow numerical ranges should be applied not only to the specific values, but should also be applied to differences between these specific values. Thus, if the specification describes a first pressure of 110 psia and a second pressure of 48 psia (a difference of 62 psi), the broad, intermediate, and narrow ranges for the pressure difference between these two streams would be 25 to 99 psi, 43 to 81 psi, and 53 to 71 psi, respectively.

[0018] In one embodiment of the invention, a process is provided to produce carboxylic acid composition and / or dry purified carboxylic acid 710 comprising furan-2,5-dicarboxylic acid (FDCA). Embodiments of the process are represented in Figure 1. The process comprises oxidizing at least one oxidizable compound in an oxidizable raw material stream 30 in the presence of an oxidizing gas stream 10, solvent stream 20, and at least one catalyst system. The oxidizable raw material stream 30 comprises at least one oxidizable compound suitable to produce a carboxylic acid composition 110 comprising FDCA. The amount of FDCA in the carboxylic acid composition 110 can range from greater than 10 by weight percent in the carboxylic acid composition 110, greater than 20 by weight percent in the carboxylic acid composition 110, greater than 30 by weight percent in the carboxylic acid composition 110. The carboxylic acid composition 110 comprises FDCA and solvent.

[0019] In another embodiment of the invention, the process comprises oxidizing at least one oxidizable compound in an oxidizable raw materialstream 30 in the presence of an oxidizing gas stream 10, solvent stream 20, and at least one catalyst system. The oxidizable raw material stream 30 comprises at least one oxidizable compound selected from the group consisting of 5-(hydroxymethyl)furfural (5-HMF), 5-HMF esters (5-R(CO)OCH2-furfural where R = alkyl, cycloalkyl and aryl), 5-HMF ethers (5-R’OCH2-furfural, where R’ = alkyl, cycloalkyl and aryl), 5-alkyl furfurals (5-R”-furfural, where R” = alkyl, cycloalkyl and aryl), mixed feedstocks of 5-HMF and 5-HMF esters, mixed feedstocks of 5-HMF and 5-HMF ethers, mixed feedstocks of 5-HMF and 5-alkyl furfurals to generate a carboxylic acid composition comprising FDCA. The process can optionally include removing impurities from the carboxylic acid composition 110 in a liquid displacement zone 225 to form a low impurity slurry stream 210. The low impurity slurry stream 210 can be further treated in a secondary oxidation zone 335 to produce a secondary oxidation slurry stream 310 which can be routed to a crystallization zone 425 to form a crystallized slurry stream 410. The crystallized slurry stream 410 is cooled in a cooling zone 430 and the cooled crystallized slurry stream 510 can be routed to a solid-liquid separation zone 625 to generate a purified wet cake stream 610 comprising FDCA that is dried in a drying zone 725 to generate a dried, purified carboxylic acid 710 comprising purified FDCA.

[0020] In one embodiment of the invention, a process is provided to produce a dried, purified carboxylic acid 710 comprising dried, purified furan-2,5-dicarboxylic acid (FDCA) and comprises the following steps.

[0021] Step (a) comprises oxidizing at least one oxidizable compound in an oxidizable raw material stream 30 in the presence of an oxidizing gas stream 10, solvent stream 20, and at least one catalyst system in a primary oxidation zone 125 which comprises at least one primary oxidizer reactor to produce a carboxylic acid composition 110 comprising furan-2,5-dicarboxylic(FDCA); wherein the oxidizable raw material stream 30 comprises at least one oxidizable compound selected from the group consisting of 5- (hydroxymethyl)furfural (5-HMF), 5-HMF esters (5-R(CO)OCH2-furfural whereR = alkyl, cycloalkyl and aryl), 5-HMF ethers (5-R'OCH2-furfural, where R’ = alkyl, cycloalkyl and aryl), 5-alkyl furfurals (5-R”-furfural, where R” = alkyl, cycloalkyl and aryl), mixed feedstocks of 5-HMF and 5-HMF esters, mixed feedstocks of 5-HMF and 5-HMF ethers, and mixed feedstocks of 5-HMF and 5-alkyl furfurals. Structures for the various oxidizable raw material compounds are outlined below:Preferred 5-HMF Derivative FeedsO5-methoxymethylfurfural 5-formoxy methy If u rf u ral 5-methyifurfurai o5-ethoxymethy!furfural 5-acetoxymethylfurfural5-propoxymethyifurfural 5-propionoxymethylfurfuralO5-butoxymethylfurfural 5-butyroxymethytfurfuralThe 5-HMF or its derivatives are oxidized with elemental O2 in a multi-step reactions, eqs 1 and 2, to form FDCA with 5-formyl furan-2-carboxyic acid (FFCA) as a key intermediate.5-HMF FFCA 0 0 0 0H'^'XJT^OH + 1 / 202 (2)FFCA FDCA

[0022] In one embodiment of this invention, streams routed to the primary oxidation zone 125 comprises an oxidizing gas stream 10 comprising oxygen and a solvent stream 20 comprising solvent, an oxidizable raw material stream 30, and a catalyst system. Oxidizable raw material stream 30 comprises a continuous liquid phase. In another embodiment of the invention, the oxidizable raw material stream 30, the oxidizing gas stream 10, the solvent stream 20 and the catalyst system can be fed to the primary oxidization zone 125 as separate and individual streams or combined in any combination prior to entering the primary oxidation zone 125 wherein said feed streams may enter at a single location or in multiple locations in the primary oxidization zone 125.

[0023] The carboxylic acid composition 110 comprises FDCA and FFCA. In another embodiment the FFCA in the carboxylic acid composition 110 ranges from about 0.1 wt% (weight percent) to about 4 wt% or 0.1 wt% to about 0.5 wt%, or 0.1wt% to about 1wt%. In another embodiment of the invention the carboxylic acid composition 110 comprises FDCA and FFCA and at least one of 2,5-diformylfuran in an amount ranging from 0 wt% to about 0.2 wt%, levulinic acid in an amount ranging from 0 wt% to 0.5 wt%, succinic acid in an amount ranging from 0 wt% to 0.5 wt% and acetoxy acetic acid in an amount ranging from 0 wt% to 0.5 wt%.

[0024] In another embodiment of the invention the carboxylic acid composition 110 comprises FDCA, FFCA and EFCA. In other embodiment of the invention the EFCA in the carboxylic acid composition 110 in an range from about 0.05 wt% to 4 wt%, or about 1 wt% to 2 wt%.

[0025] The catalyst system comprises at least one catalyst suitable for oxidation. Any catalyst known in the art capable of oxidizing the oxidizable compound can be utilized. Example of suitable catalysts comprise at least one selected from, but are not limited to, cobalt, bromine, and manganese compounds, which are soluble in the selected oxidation solvent, in another embodiment of the invention, the catalyst system comprises cobalt, manganese, and bromine wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 10 to about 400 and the weight ratio of cobalt to bromine is from about 0.7 to about 3.5.

[0026] The oxidizing gas stream comprises oxygen. Examples include, but are not limited to, air and purified oxygen. The amount of oxygen in the primary oxidation zone ranges from about 5 mole % to 45 mole %, 5 mole % to 60 mole % 5 mole % to 80 mole %.

[0027] Suitable solvents include water and the aliphatic solvents. In an embodiment of the invention, the solvents are aliphatic carboxylic acids which include, but are not limited to, aqueous solutions of C2 to Ce monocarboxylic acids, e.g., acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, tri methylacetic acid, caprioic acid, and mixtures thereof. In another embodiment of the invention, the solvent is volatile under the oxidation reaction conditions to allow it to be taken as an off-gas from the oxidation reactor. In yet another embodiment of the invention the solvent selected is also one in which the catalyst composition is soluble under the reaction conditions.

[0028] The most common solvent used for the oxidation is an aqueous acetic acid solution, typically having a concentration of 80 to 99 wt. %. In especially preferred embodiments, the solvent comprises a mixture of water and acetic acid which has a water content of 0% to about 15% by weight. Additionally, a portion of the solvent feed to the primary oxidation reactor may be obtained from a recycle stream obtained by displacing about 80 to 90% of the mother liquor taken from the crude reaction mixture stream dischargedfrom the primary oxidation reactor with fresh, wet acetic acid containing about 0 to 15% water.

[0029] Suitable solvents include, but are not limited to, aliphatic monocarboxylic acids, preferably containing 2 to 6 carbon atoms and mixtures thereof and mixtures of these compounds with water. Examples of aliphatic mono-carboxylic acids, include, but are not limited to acetic acid.

[0030] Generally, the oxidation temperature can vary from about 100°C to about 220°C, from about 100°C to about 200°C, from about 100°C to about 180°C, from about 100°C to about 170°C, from about 100°C to about 160°C, from about 100°C to about 150°C, from about 110°C to about 220°C, from about 110°C to about 220°C, from about 110°C to about 190°C, from about 100°C to about 180°C, from about 110°C to about 170°C, from about 110°C to about 160°C, from about 110°C to about 150°C, from about 120°C to about 200°C, from about 120°C to about 180°C, from about 120°C to about 170°C, from about 120°C to about 160°C, and from about 120°C to about 150°C.

[0031] In another embodiment of the invention, a process is provided to produce furan-2,5-dicarboxylic acid (FDCA) in high yields by liquid phase oxidation that minimizes solvent and starting material loss through carbon burn. The process comprises oxidizing at least one oxidizable compound in an oxidizable raw material stream 30 in the presence of an oxidizing gas stream 10, solvent stream 20, and at least one catalyst system in a primary oxidation zone 125; wherein the oxidizable compound is at least one selected from the group consisting of H(C=O)-R-(C=O)H, HOH2C-R-(C=O)H, and 5- (hydroxymethyl)furfural (5-HMF). The oxidizable compound can be oxidized in a solvent comprising acetic acid with or without the presence of water with oxygen in the presence of a catalyst system comprising cobalt, manganese, and bromine, wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 10 to about 400 and the weight ratio of cobalt to bromine is from about 0.7 to about 3.5. Such a catalyst system with improved Co: Mn ratio can lead to high yield of FDCA. In this process, the oxidation temperature can vary from about 100°C to about 220°C, or another rangefrom about 110°C to about 160°C, which can minimize carbon burn. The cobalt concentration of the catalyst can range from about 1000 ppm to about 6000 ppm, and the amount of manganese from about 2 ppm to about 600 ppm, and the amount of bromine from about 300 ppm to about 4500 ppm with respect to the total weight of the liquid in the reaction medium of the primary oxidation zone 125. As used herein, process temperature is the temperature of the reaction mixture within the primary oxidation zone where liquid is present as the continuous phase. The primary oxidizer reactor will typically be characterized by a lower section where gas bubbles are dispersed in a continuous liquid phase. Solids can also be present in the lower section. In the upper section of the primary oxidizer, gas is in the continuous phase and entrained liquid drops can also be present.

[0032] In various embodiments of the invention, the catalyst compositions employed in the processes of the invention comprise cobalt atoms, manganese atoms, and bromine atoms, supplied by any suitable means, as further described below. The catalyst composition is typically soluble in the solvent under reaction conditions, or it is soluble in the reactants fed to the oxidation zone. Preferably, the catalyst composition is soluble in the solvent at 40° C. and 1 atm, and is soluble in the solvent under the reaction conditions.

[0033] The cobalt atoms may be provided in ionic form as inorganic cobalt salts, such as cobalt bromide, cobalt nitrate, or cobalt chloride, or organic cobalt compounds such as cobalt salts of aliphatic or aromatic acids having 2-22 carbon atoms, including cobalt acetate, cobalt octanoate, cobalt benzoate, cobalt acetylacetonate, and cobalt naphthalate.

[0034] The oxidation state of cobalt when added as a compound to the reaction mixture is not limited, and includes both the +2 and +3 oxidation states.

[0035] The manganese atoms may be provided as one or more inorganic manganese salts, such as manganese borates, manganese halides, manganese nitrates, or organometallic manganese compounds such as the manganese salts of lower aliphatic carboxylic acids, including manganeseacetate, and manganese salts of beta-diketonates, including manganese acetylacetonate.

[0036] The bromine component may be added as elemental bromine, in combined form, or as an anion. Suitable sources of bromine include hydrobromic acid, sodium bromide, ammonium bromide, potassium bromide, and tetrabromoethane. Hydrobromic acid, or sodium bromide may be preferred bromine sources.

[0037] In another embodiment of the invention, a process is provided for producing furan-2,5-dicarboxylic acid (FDCA) in high yields by liquid phase oxidation that minimizes solvent and starting material loss through carbon burn. The process comprises oxidizing at least one oxidizable compound in an oxidizable raw material stream 30 in the presence of an oxidizing gas stream 10, solvent stream 20, and at least one catalyst system in a primary oxidation zone 125; wherein the oxidizable compound is selected from the group consisting of 5-(acetoxymethyl)furfural (5-AMF), 5- (ethoxymethyl)furfural (5-EMF), 5-methyl furfural (5-MF); wherein the solvent stream 20 comprises acetic acid with or without the presence of water; wherein the catalyst system comprising cobalt, manganese and bromine, wherein the weight ratio of cobalt to manganese in the reaction mixture ranges from about 10 to about 400 and the weight ratio of cobalt to bromine is from about 0.7 to about 3.5. The catalyst system with improved Co: Mn ratio can lead to high yield of FDCA. In this process, the oxidation temperature can vary from about 100 °C to about 220 °C, or from about 110 °C to about 160 °C to minimize carbon burn. The cobalt concentration in the catalyst system can range from about 500 ppm to about 6000 ppm, and the amount of manganese from about 2 ppm to about 600 ppm and the amount of bromine from about 300 ppm to about 4500 ppm with respect to the total weight of the liquid in the reaction medium. Mixed feedstocks of 5-AMF and 5-HMF or 5-EMF and 5-HMF or 5-MF and 5-HMF or 5-AMF, 5-EMF, and 5-HMF, with varying ratios of the components can be used and similar results can be obtained.

[0038] In another embodiment of the Invention, a process is provided for producing furan-2,5-dicarboxylic acid (FDCA) in high yields by liquid phase oxidation that minimizes solvent and starting material loss through carbon bum. The process comprises oxidizing at least one oxidizable compound in an oxidizable raw material stream 30 in the presence of an oxidizing gas stream 10, solvent stream 20, and at least one catalyst system in a primary oxidation zone 125; wherein said oxidizable compound is 5- (hydroxymethyl)furfural (5-HMF); wherein said solvent stream comprises acetic acid with or without the presence of water; wherein said catalyst system comprising cobalt, manganese and bromine, wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 10 to about 400. In this process, the temperature can vary from about 100°C to about 220°C, from about 105°C to about 180°C, and from about 110°C to about 160°C. The cobalt concentration of the catalyst system can range from about 1000 ppm to about 6000 ppm, and the amount of manganese can range from about 2 ppm to about 600 ppm, and the amount of bromine can range from about 300 ppm to about 4500 ppm with respect to the total weight of the liquid in the reaction medium.

[0039] In another embodiment of the invention, the process comprises oxidizing at least one oxidizable compound in an oxidizable raw material stream 30 in the presence of an oxidizing gas stream 10, solvent stream 20, and at least one catalyst system in a primary oxidation zone 125; wherein said oxidizable compound is 5-(hydroxymethyl)furfural (5-HMF); wherein said solvent stream comprises a saturated organic acid having from 2-6 carbon atoms with or without the presence of water at a temperature of 100°C to 220°C to produce a dicarboxylic acid composition; wherein the primary oxidation zone 125 comprises at least one primary oxidation reactor and wherein the catalyst system comprises cobalt in a range from about 500 ppm by weight to about 6000 ppm by weight with respect to the weight of the liquid in the reaction medium, manganese in an amount ranging from about 2 ppm by weight to about 600 ppm by weight with respect to the weight of the liquidin the reaction medium and bromine in an amount ranging from about 300 ppm by weight to about 4500 ppm by weight with respect to the weight of the liquid in the reaction medium.

[0040] In another embodiment of the invention, when the oxidizable raw material stream 30 comprises 5-HMF, then the cobalt to manganese ratio by weight is at ieast 10: 1, 15: 1, 20: 1, 25: 1, 30: 1, 40: 1, 50: 1, 60: 1, or 400 to 1.

[0041] In another embodiment of the invention, when the oxidizable material stream 30 comprises at least one oxidizable compound selected from the group consisting of 5-HMF esters (5-R(CO)OCH2-furfural where R = alkyl, cycloalkyl and aryl), 5-HMF ethers (5-R’OCH2-furfural, where R’ = alkyl, cycloalkyl and aryl), 5-alkyl furfurals (5-R”-furfural, where R” = alkyl, cycloalkyl and aryl), mixed feedstocks of 5-HMF and 5-HMF esters, mixed feedstocks of 5-HMF and 5-HMF ethers, and mixed feed-stocks of 5-HMF and 5-alkyl furfurals, the cobalt to manganese ratio by weight of the catalyst system is at least 1:1, 10:1, 20:1, 50:1, 100:1, or 400:1.

[0042] In another embodiment of this invention, furan-2,5-dicarboxylic acid (FDCA) can be obtained by liquid phase oxidation of 5-(hydroxymethyl)furfural (5-HMF), 5-(acetoxymethyl)furfural (5-AMF) and 5-(ethoxymethyl)furfural (5- EMF) with molecular oxygen using Co / Mn / Br catalyst system in acetic acid solvent After the oxidation of 5-HMF / 5-AMF / 5-EMF in presence of acetic acid, the FDCA precipitates out of solution. After filtration, washing with acetic acid and then with water, and drying, solids were obtained with a minimum of 90%, 92%, 94%, 96% FDCA content by weight.

[0043] In another embodiment of the invention, FDCA is obtained by liquid phase oxidation of 5-HMF, 5-AMF and 5-EMF with molecular oxygen using Co / Mn / Br catalyst system in acetic acid solvent. After the oxidation of 5- HMF / 5-AMF / 5-EMF in acetic acid, the FDCA precipitates out of solution. After filtration, washing with acetic acid and then with water, and drying, solids were obtained with a minimum of 96% FDCA content and a maximum b* of 15, 16, 17, 18, 19, or 20.

[0044] The b* is one of the three-color attributes measured on a spectroscopic reflectance-based instrument. The color can be measured by any device known in the art. A Hunter Ultrascan XE instrument is typically the measuring device. Positive readings signify the degree of yellow (or absorbance of blue), while negative readings signify the degree of blue (or absorbance of yellow).

[0045] In another embodiment of the invention, a process is provided for producing furan-2,5-dicarboxylic acid (FDCA) in minimum yields of 80% or 85% or 90% or greater by liquid phase oxidation that minimizes solvent and starting material loss through carbon bum. As used herein, yield is defined as mass of FDCA obtained divided by the theoretical amount of FDCA that should be produced based on the amount of raw material use. For example, if one mole or 126.11 grams of 5-HMF are oxidized, it would theoretically generate one mole or 156.01 grams of FDCA. If for example, the actual amount of FDCA formed is only 150 grams, the yield for this reaction is calculated to be = (150 / 156.01) times 100, which equals a yield of 96%. The same calculation applies for oxidation reaction conducted using 5-HMF derivatives or mixed feeds.

[0046] In another embodiment of this invention, a process is provided comprising oxidizing at least one oxidizable compound in an oxidizable raw material stream 30 in the presence of an oxidizing gas stream 10, solvent stream 20, and at least one catalyst system in a primary oxidation zone 125; wherein said oxidizable compound is selected from the group consisting of H(C=O)-R-(C=O)H, HOH2C-R-(C=O)H, 5-(hydroxymethyl)furfural (5-HMF); wherein said solvent stream comprises acetic acid with or without the presence of water; wherein said catalyst system comprises cobalt, manganese and bromine, wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 10 to about 400 and the weight ratio of cobalt to bromine is from about 0.7 to about 3.5. Such a catalyst system with improved Co: Mn and Co: Br ratio can lead to high yield of FDCA (minimum of 90%), decrease in the formation of impurities (measured by b*) causing colorin the downstream polymerization process while keeping the amount of CO and CO2 in the off-gas at a minimum.

[0047] The temperature in the primary oxidation zone can range from about 100 °C to about 220°C, and can range from about 110°C to about 160 °C or can range from about 105°C to about 180°C or about 100°C to about 200°C, or about 100°C to about 190°C. One advantage of the disclosed primary oxidation conditions is low carbon bum as illustrated in Table 1. Oxidizer off gas stream 120 is routed to the oxidizer off gas treatment zone 825 to generate an inert gas stream 810, liquid stream 820 comprising water, and a recovered solvent stream 830 comprising condensed solvent. In one embodiment, at least a portion of recovered solvent stream 830 is routed to wash fed stream 620 and the combined stream is routed to the solid-liquid separation zone 625 for the purpose of washing the solids present in the solid-liquid separation zone 625. In one embodiment, the inert gas stream 810 can be vented to the atmosphere. In another embodiment, at least a portion of the inert gas stream 810 can be used as an inert gas in the process for inerting vessels and or used for conveying gas for solids in the process.

[0048] In another embodiment of the invention, the composition of the liquid phase within the primary oxidizer can have a pH from about -4.0 to about 1.0 or the feedstock pH is from about -1.8 to about 1.0, or the feedstock pH is from about -1.5 to about 1.0.

[0049] It should be understood that steps (b)- (g) are optional and only one possible embodiment of a process to purified the carboxylic acid composition.

[0050] Step (b) comprises routing the crude carboxylic composition 110 and fresh solvent stream 220 to a liquid displacement zone 225 to produce a displaced mother liquor stream 230 and low impurity slurry stream 210 comprising FDCA. The displaced mother liquor stream 230 comprises solvent and soluble matter dissolved in the solvent comprising dissolved impurities and dissolved catalyst. In various embodiments of the invention, from about 5% to about 99%, from about 30% to about 90%, and most preferably fromabout 50 to about 85% of mother liquor present in the carboxylic acid composition 110 is displaced in the liquid displacement zone 225 resulting in dissolved matter comprising impurities present in the displaced mother liquor not going forward in the process. Sufficient fresh solvent is fed to the liquid displacement zone 225 that becomes mixed with solids present resulting in a low impurity slurry stream 210 being pumpable with weight % solids ranging from 1% to 50%, 10% to 40%, and preferably the weight % solids in stream 210 will range from 25% to 38%.

[0051] The liquid displacement zone may be a single unit operation or multiple unit operations. In one embodiment of the invention, the liquid displacement zone 225 may be any solid-liquid separation device capable of generating an isolated wet cake from a feed slurry and then mixing the isolated wet cake with fresh solvent in a separate mixing device to generate the low impurity slurry stream 210. Examples of suitable solid-liquid separation devices include, but are not limited to, a continuous pressure drum filter, solid bowl centrifuges including, but not limited to, decanter and disc stack centrifuges, and batch pressure filters including, but not limited to, candle and leaf filters. The preferred solid-liquid separation device for this application is a continuous pressure drum filter. The solid-liquid separator is operated at temperatures between about 30 degrees C. to about 200 degrees C., preferably 80 degrees C. to about 170. degree. C. The solid-liquid separator in the liquid displacement zone 225 may be operated in continuous or batch mode, although it will be appreciated that for commercial processes, the continuous mode is preferred. Alternatively, a portion of the mother liquor in stream 110 is displaced with fresh liquor stream 220 in a single device to form the low impurity slurry stream 210 without forming an isolated wet cake.

[0052] In one embodiment, from 5% to 100% by weight of the displaced mother liquor stream 230 is routed to a purge zone 235 wherein a portion of the impurities present in stream 230 are isolated and exit the process as purge stream 920, wherein a portion is 5% by weight or greater. Recovered solvent stream 910 comprises solvent and catalyst isolated from stream 230and is recycled to the process. In one embodiment, recovered solvent stream 910 is recycled to the primary oxidation zone 125 and contains greater than 30% of the catalyst that entered the purge zone 235 in stream 230. In another embodiment, stream 910 is recycled to the primary oxidation zone 125 and contains greater than 50 weight %, contains greater than 70 weight %, and preferably greater than 90 weight % of the catalyst that enters the purge zone 235 in stream 230 on a continuous or batch basis.

[0053] In another embodiment of this invention, a portion up to 100% of the carboxylic acid composition 110 may be routed directly to a secondary oxidation zone 335 without being subjected to the liquid displacement zone 225. In another embodiment of the invention, up to 100% of the feed to the purge zone 235 may be a mother liquor stream 630 generated in a solid-liquid separation zone 625 which also produces the purified wet cake stream 610.

[0054] In yet another embodiment, up to 100% of the feed to the purge zone 235 may be mother liquor generated in a secondary liquid displacement zone located at some location downstream of the secondary oxidation zone 325. A secondary liquid displacement zone is not shown in Figure 1, and it comprises equipment like that described for the liquid displacement zone 225 located after the primary oxidation zone 125, and must be located after the secondary oxidation zone 335.

[0055] Step (c) comprises oxidizing the low impurity slurry stream 210 in a secondary oxidation zone 335 to form a purified slurry stream 310. In one embodiment of the invention, the low impurity slurry stream 210 is routed to a secondary oxidation zone 335 where it is heated to between about 115 degrees C. and about 220 degrees C., and preferably between about 120 degrees C. to about 200 degrees C. and further oxidized with an oxidizing gas, such as air, fed by line 320 to produce a purified slurry stream 310. The secondary oxidation zone comprises at least one oxidation reactor vessel. In one embodiment, the secondary oxidation zone can be one or more oxidation vessels. When the carboxylic acid in low impurity slurry stream 210 is FDCA, the secondary oxidation zone is operated at a temperature ranging from about115 degrees C. to about 220 degrees C., preferably between about 120 degrees C. to about 200 degrees C., and stream 210 is further oxidized with an oxidizing gas stream fed by iine 320 to produce a purified slurry stream 310.

[0056] Generally, oxidation in the secondary oxidation zone 335 is at a higher temperature than the oxidation in the primary oxidation zone 125 to enhance the impurity removal. In one embodiment, the secondary oxidation zone 335 is operated at about 30°C, 20°C, and preferably 10°C higher temperature than the oxidation temperature in the primary oxidation zone 125 to enhance the impurity removal. The secondary oxidation zone 335 can be heated directly with solvent vapor, or steam via stream 320 or indirectly by any means known in the art.

[0057] Additional purification of the low impurity slurry stream 210 is accomplished in the secondary oxidation zone by a mechanism involving recrystallization or crystal growth and oxidation of impurities and intermediates including FFCA. One of the functions of the secondary oxidation zone is to convert FFCA to FDCA. FFCA is considered monofunctional relative to a polyester condensation reaction because it contains only one carboxylic acid. FFCA is present in the carboxylic acid composition stream 110 and the low impurity slurry stream 210. FFCA is generated in the primary oxidation zone 125 because the reaction of 5-HMF to FFCA can be about eight times faster than the reaction of FFCA to the desired di-functional product FDCA. Additional air or molecular oxygen may be fed in stream 320 to the secondary oxidation zone 335 in an amount necessary to oxidize a substantial portion of the partially oxidized products such as FFCA in the stream 210 to the corresponding carboxylic acid FDCA. Generally, at least 70% by weight of the FFCA present in the low impurity slurry stream 210 is converted to FDCA in the secondary oxidation zone 335. Preferably, at least 80% by weight of the FFCA present in the low impurity slurry stream 210 is converted to FDCA in the secondary oxidation zone 335, and most preferably, at least 90% by weight of the FFCA present in the low impurity slurry stream210 is converted to FDCA in the secondary oxidation zone 335. Significant concentrations of monofunctional molecules like FFCA in the dried, purified FDCA product are particularly detrimental to polymerization processes as they may act as chain terminators during the polyester condensation reaction.

[0058] The amount of oxygen fed in the secondary oxidation zone 335 in controlled to limit the burning of organic molecules to CO2. The amount of oxygen in stream 330 is monitored and used to control the amount of oxygen fed in stream 320. Another function of the secondary oxidation zone 335 is to dissolve and recrystallize solids present in the low impurity slurry stream 210 fed to the secondary oxidation zone. At least 10% by weight, 25% by weight, 50% by weight, and preferably at least 85% by weight of solid impurities and oxidation by-products in stream 210 feed to the secondary oxidation zone 335 go into solution as the FDCA particles are dissolved and re-crystallized in the secondary oxidation zone 335. Off gas from the secondary oxidation zone is withdrawn via line 330 and fed to a recovery system where the solvent is removed from the off gas comprising volatile organic compounds (VOCs). VOCs including methyl bromide may be treated, for example by incineration in a catalytic oxidation unit. The purified slurry stream 310 generated in the secondary oxidation zone is routed to the crystallization zone 425.

[0059] Step (d) comprises crystallizing the secondary oxidation slurry 310 in a crystallization zone 425 to form a crystallized slurry stream 410. Generally, the crystallization zone 425 comprises at least one crystallizer. Vapor from the crystallization zone can be condensed in at least one condenser and returned to the crystallization zone 425 or routed away from crystallization zone 425. Optionally, the liquid from the condenser or vapor product from the crystallization zone can be recycled, or it can be withdrawn or sent to an energy recovery device. In addition, the crystallizer off gas is removed via line 420 and can be routed to a recovery system where the solvent is removed, and crystallizer off gas comprising VOCs may be treated, for example, by incineration in a catalytic oxidation unit. When the carboxylic acid is FDCA, the purified slurry stream 310 from the secondary oxidationzone 335 is fed to a crystallization zone 425 comprising at least one crystallizer where it is cooled to a temperature between about 40. degrees C. to about 175 degrees C. to form a crystallized slurry stream 410, preferably to a temperature between about 50 degrees C. to about 170 degrees C., and most preferably from about 60 degrees C. to about 165 degrees C.

[0060] The crystallized slurry stream 410 is then routed to a cooling zone 430 to generate a cooled crystallized slurry stream 510. The cooling of the crystallized slurry stream 410 can be accomplished by any means known in the art. Typically, the cooling zone 430 comprises a flash tank. The temperature of stream 510 can range from 35°C to 160°C, 45°C to 120°C, and preferably from 55°C to 95°C.

[0061] In another embodiment, a portion of up to 100% of the secondary oxidation slurry stream 310 is routed directly to the cooling zone 425, thus the portion is not subjected to a crystallization zone 430. In yet another embodiment, a portion of up to 100% of the crystallized slurry stream 410 is routed directly to a secondary liquid displacement zone which is not illustrated in Figure 1. Up to 100% of the slurry effluent comprising FDCA from a secondary liquid displacement zone can be routed to the solid-liquid separation zone 625 and or routed directly to the cooling zone 430. The function of the secondary liquid displacement zone is to displace a portion of solvent in the crystallized slurry stream 410 with fresh solvent and / or water wherein a portion must be greater than 5 weight percent. The secondary liquid displacement zone is separate and distinct from the liquid displacement zone 225 located after the primary oxidation zone 125. The same type of equipment may be used for both the primary and secondary liquid displacement zones. In yet another embodiment, crystallized slurry stream 410 can be routed directly to the solid-liquid separation zone 625 without being first processed in the cooling zone 430.

[0062] Step (e) comprises isolating, washing, and dewatering solids present in the cooled, crystallized slurry stream 510 in the solid-liquid separation zone 625. These functions may be accomplished in a single solid-liquid separation device or multiple solid-liquid separation devices. The solid¬ liquid separation zone 625 comprises at least one solid-liquid separation device capable of separating solids and liquids, washing solids with a wash solvent stream 620, and reducing the % moisture in the washed solids to less than 30 weight %, less than 25 weight %, less than 20 weight%, less than 15 weight %, and preferably less than 10 weight %.

[0063] Equipment suitable for the solid liquid separation zone 625 can typically be comprised of, but not limited to, the following types of devices: centrifuges, cyclones, rotary drum filter, belt filters, pressure leaf filters, candle filters, etc. The preferred solid liquid separation device for the solid liquid separation zone 625 is a rotary pressure drum filter. The temperature of the cooled, crystallized slurry steam 510 which is routed to the solid-liquid separation zone 625 can range from 50°C to 140°C, 70°C to 120°C, and is preferably from 75°C to 95°C. The wash solvent stream 620 comprises a liquid suitable for displacing and washing mother liquor from the solids.

[0064] In one embodiment of the invention, a suitable wash solvent comprises acetic acid and water. In another embodiment, a suitable solvent comprises water up to 100% water. The temperature of the wash solvent can range from 20°C to 135°C, 40°C and 110°C, and preferably from 50°C to 90°C. The amount of wash solvent used is defined as the wash ratio and equals the mass of wash divided by the mass of solids on a batch or continuous basis. The wash ratio can range from about 0.3 to about 5, about 0.4 to about 4, and preferably from about 0.5 to 3.

[0065] After solids are washed in the solid liquid separation zone, they are dewatered. Dewatering involves reducing the mass of moisture present with the solids to less than 30% by weight, less than 25% by weight, less than 20% by weight, less than 15% by weight, and most preferably less than 10% by weight resulting in the generation of a purified wet cake stream 610. In one embodiment, dewatering is accomplished in a filter by passing a gas stream through the solids to displace free liquid after the solids have been washed with a wash solvent. In another embodiment, dewatering is achieved bycentrifugal forces in a perforated bowl or solid bowl centrifuge. Stream 630 generated in the solid-liquid separation zone 625 is a mother liquor stream comprising oxidation solvent, catalyst, and some impurities and oxidation byproducts. In one embodiment, a portion of stream 630 is routed to a purge zone 235 and a portion is routed back to the primary oxidation zone 125 wherein a portion is at least 5 weight %. Wash liquor stream 640 is also generated in the solid-liquid separation zone 625 and comprises a portion of the mother liquor present in stream 510 and wash solvent wherein the ratio of mother liquor mass to wash solvent mass is less than 3 and preferably less than 2.

[0066] Step (f) comprises drying the purified wet cake stream 610 in a drying zone 725 to generate a dry purified carboxylic acid 710 and a vapor stream 720. In one embodiment, vapor stream 720 comprises wash solvent vapor. In another embodiment, vapor stream 720 comprises oxidation solvent and wash solvent. The drying zone 725 comprises at least one dryer and can be accomplished by any means known in the art that is capable of evaporating at least 10% of the volatiles remaining in the purified wet cake stream 610 to produce the dried, purified carboxylic acid 710 comprising purified FDCA and a vapor stream 720. For example, indirect contact dryers include, but are not limited to, a rotary steam tube dryer, a Single Shaft Porcupine RTM dryer, and a Bepex Solidaire TM dryer. Direct contact dryers include, but are not limited to, a fluid bed dryer and drying in a convey line can be used for drying to produce stream 710. The dried, purified carboxylic acid 710 comprising purified FDCA can be a carboxylic acid composition with less than 8% moisture, preferably less than 5% moisture, and more preferably less than 1% moisture, and even more preferably less than 0.5%, and yet more preferably less than 0.1%. In another embodiment of this invention, if the liquid portion of the purified wet cake stream 610 comprises water and contains less than 0.1 weight % acetic acid, less than 500 ppm wt acetic acid, and preferably less than 200 ppm wt, the stream 610 can be fed directly to a polymerization zone without first being dried.

[0067] In one embodiment of the invention, a vacuum system can be utilized to draw vapor stream 720 from the drying zone 725. If a vacuum system is used in this fashion, the pressure of stream 720 at the dryer outlet can range from about 760 mmHg to about 400 mmHg, from about 760 mmHg to about 600 mmHg, from about 760 mmHg to about 700 mmHg, from about 760 mmHg to about 720 mmHg, and from about 760 mmHg to about 740 mmHg wherein pressure is measured in mmHg above absolute vacuum. The contents of the conduit between solid-liquid separation zone 625 and drying zone 725 utilized to transfer the purified wet cake stream 610 comprises wet cake stream and gas wherein gas is the continuous phase. The pressure at the exit of the solid liquid separation zone 625 can be close to that of the pressure where vapor stream 720 exits the drying zone 725, wherein close is defined as within 2 psig, within 0.8 psig, and preferably within 0.4 psig.

[0068] In an embodiment of the invention, the dried, purified carboxylic acid 710 has a b* less than about 9.0. In another embodiment of the invention, the b* color of the dried, purified carboxylic acid 710 is less than about 6.0. In another embodiment of the invention, the b* color of the dried, purified carboxylic acid 710 is less than about 5.0. In another embodiment of the invention, the b* color of the dried, purified carboxylic acid 710 is less than about 4.0. In another embodiment of the invention, the b* color of the dried, purified carboxylic acid 710 is less than about 3. The b* color is one of the three-color attributes measured on a spectroscopic reflectance-based instrument. A Hunter Ultrascan XE instrument in reflectance mode is typically the measuring device. Positive readings signify the degree of yellow (or absorbance of blue), while negative readings signify the degree of blue (or absorbance of yellow).

[0069] It should be appreciated that the process zones previously described can be utilized in any other logical order to produce the dried, purified carboxylic acid 710. It should also be appreciated that when the process zones are reordered that the process conditions may change. It is also understood that all percent values are weight percents.

[0070] Optionally a dried, purified carboxylic acid 710 can be obtained by hydrogenating crude carboxylic acid. The oxidation solvent in the crude carboxylic acid composition 110 is desirably replaced at least in part with a hydrogenation solvent to avoid producing a large amount of undesirable by¬ products of the oxidation solvent during hydrogenation. The hydrogenation solvent composition is different than the oxidation solvent composition. The hydrogenation solvent composition desirably comprises a solvent which dissolves at least a portion of the FDCA solids under conditions used in the hydrogenation reaction zone and which does not itself convert to other products which must be separated in any appreciable amount, e.g., more than 20% conversion of the types of products requiring removal. Suitable hydrogenation solvent compositions include water and steam. Desirably, the hydrogenation solvent composition comprises at least 80 wt.% water, or at least 90 wt.% water, or at least 95 wt.% water, or at least 99 wt.% water, or at least 100 wt.% water.

[0071] In another embodiment of the invention, FDCA could be polymerized; wherein the polymerization reaction occurs in at least one reactor previously used in a polyester reaction. The process is applicable for any polyester. Such polyesters comprise at least one dicarboxylic acid residue and at least one glycol residue. More specifically, suitable dicarboxylic acids include aromatic dicarboxylic acids preferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferably having 4 to 12 carbon atoms, or cycloaliphatic dicarboxylic acids preferably having 8 to 12 carbon atoms. Examples of dicarboxylic acids comprise terephthalic acid, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, dipheny-3,4’-dicarboxylic acid, 2,2,-dimethyl-1,3-propandiol, dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, mixtures thereof, and the like.

[0072] Suitable diols comprise cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 2 to 20 carbon atoms.Examples of such diols comprise ethylene glycol (EG), diethylene glycol, triethylene glycol, 1,4 -cyclohexane-dimethanol, propane-1, 3-diol, butane-1,4-diol, pentane- 1,5-diol, hexane-1,6-diol, neopentylglycol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(1,4), 2,2,4-trimethylpentane-diol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropane-diol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1, 1,3,3-tetramethyl-cyclobutane, 2, 2, 4, 4 tetramethylcyclobutanediol, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, 2,2-bis-(4-hydroxypropoxyphenyl)-propane, isosorbide, hydroquinone, BDS-(2,2-(sulfonylbis)4,1-phenyleneoxy))bis(ethanol), mixtures thereof, and the like. Polyesters may be prepared from one or more of the above type diols.

[0073] Any polyester plant or process known in the art could be utilized.

[0074] In another embodiment of the invention, a polymer comprising PEF could be produced through polymerization wherein the polymerization occurs in at least one reactor previously used in a PET (polyethylene terephthalate) plant. Any PET plant or process known in the art could be utilized. A variety of PET processes have been developed. For example, PET produced with ethylene glycol (“EG”) vapor as reactants is disclosed in U. S. Patent Nos.2,829,153 and 2,905,707. Multiple stirred pots have been disclosed to gain additional control of the reaction (U. S. Patent No. 4,110,316 and WO 98 / 10007). U. S. Patent No. 3,054,776 discloses the use of lower pressure drops between reactors, while U. S. Patent No. 3,385,881 discloses multiple reactor stages within one reactor shell. These designs were improved to solve problems with entrainment or plugging, heat integration, heat transfer, reaction time, the number of reactors, etc., as described in U. S. Patent Nos.3,118,843; 3,582,244; 3,600,137; 3,644,096; 3,689,461; 3,819,585; 4,235,844; 4,230,818; and 4,289,895. All of the patents enclosed in this paragraph are herein incorporated by reference.

[0075] For certain embodiments of the invention, the PEF polymer may exhibit any of the following inherent viscosities as determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C: greaterthan 0.50, greater than 0.55, greater than 0.60, greater than 0.65, greater than 0.70, 0.35 to less than 0.70 dL / g; 0.35 to 0.68 dL / g; 0.35 to less than 0.68 dL / g; 0.35 to 0.65 dL / g.; 0.40 to 0.70 dL / g; 0.40 to less than 0.70 dL / g; 0.40 to 0.68 dL / g; 0.40 to less than 0.68 dL / g; 0.40 to 0.65 dL / g.; 0.45 to less than 0.70 dL / g; 0.45 to 0.68 dL / g; 0.45 to less than 0.68 dL / g; 0.45 to 0.65 dL / g; 0.50 to less than 0.70 dL / g; 0.50 to 0.68 dL / g; 0.50 to less than 0.68 dL / g; 0.50 to 0.67 dL / g; 0.50 to 0.66 dL / g;0.50 to 0.65 dL / g; 0.55 to less than 0.70 dL / g; 0.55 to 0.68 dL / g; 0.55 to less than 0.68 dL / g; 0.55 to 0.65 dL / g; 0.58 to less than 0.70 dL / g; 0.58 to 0.68 dL / g; 0.58 to less than 0.68 dL / g; or 0.58 to 0.65 dL / g.

[0076] For embodiments of the invention where the inherent viscosity of the PEF polymer of the invention ranges from 0.35 to 0.85 or higher dL / g, the PEF polymer may also exhibit any of the following inherent viscosities as determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C: 0.35 to less than 0.85 dL / g; 0.4 to 0.8 dL / g; or 0.5 to 0.8 dl / g.

[0077] For embodiments of the invention where the absorbance of PEF polymer as a 5 mg / mL solution in a dichloromethane:hexafluroisoporopanol 8:2 at 400 nm is below 0.50; below 0.40; below 0.30; below 0.20; below 0.10; below 0.090; below 0.080, below 0.070; below 0.060; 0.05; below 0.045; below 0.04; below 0.035; below 0.03; below 0.025; below 0.0.2; below 0.015; below 0.01; below 0.005.

[0078] In one embodiment, the average molecular weight (as determined by GPC based on polystyrenes standards) of PEF polymer is greater than 10,000; greater than 15,000; greater than 20,000; greater than 25,000; greater than 30,000; greater than 35,000; greater than 40,000; greater than 45,000; greater than 50,000; greater than 55,000; greater than 60,000; greater than 65,000; greater than 70,000; greater than 75,000; greater than 80,000; greater than 90,000; greater than 100,000.

[0079] In one embodiment, the average molecular weight (as determined by GPC based on polystyrenes standards) of PEF polymer is 10,000 to100,000; 20,000 to 100,000; 30,000 to 100,000; 40,000 to 100,000; 10,000 to 90,000; 20,000 to 90,000; 30,000 to 90,000; 30,000 to 90,000; 40,000 to 90.000; 50,000 to 90,000.

[0080] In one embodiment, the polydispersity of PEF polymer (as determined by GPC based on polystyrenes standards) is 1 to 6; 1 to 5; 1 to 4; 1 to 3; 2 to 6; 2 to 5; 2 to 4; 2 to 3; 3 to 6; 3 to 5.

[0081] In one embodiment, the PEF polymer of the invention, with or without toners, can have color values L*, a* and b* which can be determined using a Hunter Lab Ultrascan Spectra Colorimeter manufactured by Hunter Associates Lab Inc., Reston, Va. The color determinations are averages of values measured on either pellets of the polyesters or plaques or other items injection molded or extruded from them. They are determined by the L*a*b* color system of the CIE (International Commission on Illumination) (translated), wherein L* represents the lightness coordinate, a* represents the red / green coordinate, and b* represents the yellow / blue coordinate. In certain embodiments, the b* values for the polyesters useful in the invention can be from -10 to less than 10 and the L* values can be from 50 to 90. In other embodiments, the b* values for the polyesters useful in the invention can be present in one of the following ranges: from -10 to 9; -10 to 8; -10 to 7; -10 to 6; -10 to 5; -10 to 4; -10 to 3; -10 to 2; from -5 to 9; -5 to 8; -5 to 7; -5 to 6; -5 to 5; -5 to 4; -5 to 3; -5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to 3; and 1 to 2. In other embodiments, the L* value for the polyesters useful in the invention can be present in one of the following ranges: 50 to 60; 50 to 70; 50 to 80; 50 to 90; 60 to 70; 60 to 80; 60 to 90; 70 to 80; 80 to 90.

[0082] Suitable catalysts for use in the processes of the invention to make the PEF polymer include titanium, tin, antimony, and zinc.

[0083] In another embodiment, suitable catalysts for use in the processes of the invention to make the PEF polymer include at least one titanium compound. The PEF compositions of the invention may also comprise at least one of the titanium compounds useful in the processes of the invention. Othercatalysts could possibly be used in the invention optionally in combination with the at least one titanium compound. Other catalysts may include, but are not limited to, those based on tin, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compounds, and an aluminum compound with lithium hydroxide or sodium hydroxide.

[0084] In one embodiment, the catalyst can be a combination of at least one tin compound and at least one titanium compound. Catalyst amounts can range from 10 ppm to 20,000 ppm or 10 to 10,000 ppm, or 10 to 5000 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or 10 to 250 ppm based on the catalyst metal and based on the weight of the final polymer.

[0085] The polymerization process can be carried out in either a batch or continuous process. In one embodiment, the catalyst is a titanium compound. In one embodiment, the catalyst is solely a titanium compound. In one embodiment, the titanium compound can be used in either the esterification reaction or the polycondensation reaction or both reactions. In another embodiment, the catalyst is solely a titanium compound used in the esterification reaction. Generally, in one embodiment, the titanium compound catalyst is used in amounts of from about 0.005% to about 0.2% based on the weight of the dicarboxylic acid or dicarboxylic acid ester. Generally, in one embodiment, less than about 700 ppm elemental titanium, less than 600 ppm elemental titanium, less than 500 ppm elemental titanium, less than 400 titanium, less than 300 ppm elemental titanium, less than 200 ppm elemental titanium, less than 150 ppm elemental titanium, less than 125 ppm elemental titanium, less than 100 ppm elemental titanium, less than 75 ppm elemental titanium, less than 50 ppm elemental titanium, less than based on PEF polymer weight should be present as residue in the PEF polymer based on the total weight of the PEF polymer.

[0086] When titanium is added to the PEF polymer compositions and / or process of making the PEF polymer of the invention, it is added to the process of making the PEF polymer in the form of a titanium compound. The amount of the titanium compound added to the PEF polymer composition of theinvention and / or processes of the invention can be measured in the form of titanium atoms present in the final polyester, for example, by weight measured in ppm.

[0087] In another embodiment, the catalyst is solely a titanium compound used in the esterification reaction in the amount of 10 ppm to 20,000 ppm or 10 to 10,000 ppm, or 10 to 5000 ppm or 10 to 4500 ppm or 10 to 4000 ppm or 10 to 3500 ppm or 10 to 3000 ppm or 10 to 2500 ppm or 10 to 2000 ppm or 10 to 1500 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or 10 to 250 ppm or 15 ppm to 20,000 ppm or 15 to 10,000 ppm, or 15 to 5000 ppm or 15 to 4500 ppm or 15 to 4000 ppm or 15 to 3500 ppm or 15 to 3000 ppm or 15 to 2500 ppm or 15 to 2000 ppm or 15 to 1500 ppm or 15 to 1000 ppm or 15 to 500 ppm or 15 to 400 ppm or 15 to 300 ppm or 15 to 250 ppm or 20 ppm to 20,000 ppm or 20 to 10,000 ppm, or 20 to 5000 ppm or 20 to 4500 ppm or 20 to 4000 ppm or 20 to 3500 ppm or 20 to 3000 ppm or 20 to 2500 ppm or 20 to 2000 ppm or 20 to 1500 ppm or 20 to 1000 ppm or 20 to 500 ppm, or 20 to 300 ppm or 20 to 250 ppm 25 ppm to 20,000 ppm or 25 to 10,000 ppm, or 25 to 5000 ppm or 25 to 4500 ppm or 25 to 4000 ppm or 25 to 3500 ppm or 25 to 3000 ppm or 25 to 2500 ppm or 25 to 2000 ppm or 25 to 1500 ppm or 25 to 1000 ppm or 25 to 500 ppm, or 25 to 400 ppm, or 25 to 300 ppm or 25 to 250 ppm or 30 ppm to 20,000 ppm or 30 to 10,000 ppm, or 30 to 5000 ppm or 30 to 4500 ppm or 30 to 4000 ppm or 30 to 3500 ppm or 30 to 3000 ppm or 30 to 2500 ppm or 30 to 2000 ppm or 30 to 1500 ppm pr 30 to 1000 ppm or 30 to 500 ppm, or 30 to 300 ppm or 30 to 250 ppm or 35 ppm to 20,000 ppm or 35 to 10,000 ppm, or 35 to 5000 ppm or 35 to 4500 ppm or 35 to 4000 ppm or 35 to 3500 ppm or 35 to 3000 ppm or 35 to 2500 ppm or 35 to 2000 ppm or 35 to 1500 ppm or 35 to 1000 ppm or 35 to 500 ppm, or 35 to 300 ppm or 35 to 250 ppm or 40 ppm to 20,000 ppm or 40 to 10,000 ppm, or 40 to 5000 ppm or 40 to 4500 ppm or 40 to 4000 ppm or 40 to 3500 ppm or 40 to 3000 ppm or 40 to 2500 ppm or 40 to 2000 ppm or 40 to 1500 ppm or 40 to 1000 ppm or 40 to 500 ppm, or 40 to 300 ppm or 40 to 250 ppm or 40 to 200 ppm or 45 ppm to 20,000 ppm or 45 to 10,000 ppm, or 45 to5000 ppm or 45 to 4500 ppm or 45 to 4000 ppm or 45 to 3500 ppm or 45 to 3000 ppm or 45 to 2500 ppm or 45 to 2000 ppm or 45 to 1500 ppm or 45 to 1000 ppm or 45 to 500 ppm, or 45 to 300 ppm or 45 to 250 ppm or 50 ppm to 20,000 ppm or 50 to 10,000 ppm, or 50 to 5000 ppm or 50 to 4500 ppm or 50 to 4000 ppm or 50 to 3500 ppm or 50 to 3000 ppm or 50 to 2500 ppm or 50 to 2000 ppm or 50 to 1500 ppm or 50 to 1000 ppm or 50 to 500 ppm, or 50 to 300 ppm or 50 to 250 ppm or 50 to 200 ppm or 50 to 150 ppm 50 to 125 ppm based on the weight of the final PEF polymer, as measured in the form of titanium atoms in the final PEF polymer.Examples:

[0088] This invention can be further iliustrated by the following examples of embodiments thereof, although it will be understood that these examples are included merely for the purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.FDCA synthesis

[0089] In Examples 1a-3d, glacial acetic acid and the catalyst components in concentrations described in Tables 1, 2 and 3 were transferred to a 300 mL titanium autoclave equipped with a high pressure condenser, a baffle and an Isco pump. Cobalt, manganese, and ionic bromine were provided as cobalt (II) acetate tetrahydrate, manganese (II) acetate and sodium bromide and / or aqueous hydrobromic acid, respectively. The autoclave was pressurized with approximately 50 psig of nitrogen and the homogeneous mixture was heated to the desired temperature in a closed system (i.e., with no gas flow) with stirring. At reaction temperature, an air flow of 1500 seem was introduced at the bottom of the solution and the reaction pressure was adjusted to the desired pressure. A solution of 5-HMF / 5-AMF / 5-EMF in acetic acid was fed to the mixture at a rate of 0.833 mL / min via a high pressure Isco pump (this is t=0 for the reaction time). After 30 seconds from the start of substrate feeding, 1.0 g of peracetic acid in 5.0 mL of acetic acid was introduced using a blow-case to start the reaction. The feed was stopped after 1 h and the reaction continued for an additional hour at the same conditions of air flow, temperature, and pressure. After the reaction time was completed, the air flow was stopped and the autoclave was cooled to room temperature and depressurized. The heterogeneous mixture was filtered to isolate the crude FDCA. The mass of the filtrate was recorded. The crude FDCA was washed with 60 mL of acetic acid two times and then twice with 100 mL of DI water. The washed crude FDCA was oven dried at 110 °C under vacuum overnight and then weighed. The solid and the filtrate were analyzed by Gas Chromatography using BSTFA derivatization method.

[0090] The Off-gas was analyzed for CO and CO2 by ND-IR (ABB, Advanced Optima) and O2 by a paramagnetism detection system (Servomex, 1440 Model).Analytical

[0091] Gas Chromatographic Method Process samples were analyzed using a Shimadzu gas chromatograph Model 2010 (or equivalent) equipped with a split / heated injector (300°C) and a flame ionization detector (300°C). A capillary column (60 meter x 0.32 mm ID) coated with (6% cyanopropylphenyl)-methylpolysiloxane at 1.0 pm film thickness (such as DB-1301 or equivalent) was employed. Helium was used as the carrier gas with an initial column head pressure of 29.5 psi and an initial column flow of 3.93 mL / minute while the carrier gas linear velocity of 45 cm / second was maintained constant throughout the entire oven temperature program. The column temperature was programmed as follows: The initial oven temperature was set at 80 °C and was held for 6 minutes, the oven was ramped up to 150 °C at 4°C / minute and was held at 150 °C for 0 minute, the oven was ramped up to 240 °C at 10°C / minute and was held at 240 °C for 5 minutes, then the oven was ramped up to 290 °C at 10°C / minute and was held at 290 °C for 17.5 minutes (the total run time was 60 mins). 1.0-µl of the prepared sample solution was injected with a split ratio of 40:1. EZ-Chrom Elitechromatography data system software was used for data acquisition and data processing. The sample preparation was done by weighing 0.1 g (accurate to 0.1 mg) of sample in a GC vial and adding 200.0 µl ISTD solution (1% by volume of decane in pyridine) and 1000 µl of BSTFA (A / , O-bis(trimethylsilyl) trifluoroacetamide) with 1% TMSCI (trimethylchlorosilane) to the GC vial. The content was heated at 80 °C for 30 minutes to ensure complete derivatization.1.0-µl of this prepared sample solution was injected for GC analysis.Color measurement.

[0092] 1) Assemble the Carver Press die as instructed in the directions — place the die on the base and place the bottom 40 mm cylinder polished side face-up.

[0093] 2) Place a 40 mm plastic cup (Chemplex Plasticup, 39.7 x 6.4 mm) into the die.

[0094] 3) Fill the cup with the sample to be analyzed. The exact amount of sample added is not important.

[0095] 4) Place the top 40 mm cylinder polished side face-down on the sample.

[0096] 5) Insert the plunger into the die. No “tilt” should be exhibited in the assembled die.

[0097] 6) Place the die into the Carver Press, making sure that it is near the center of the lower platen. Close the safety door.

[0098] 7) Raise the die until the upper platen makes contact with the plunger. Apply > 20,000 lbs pressure. Then allow the die to remain under pressure for approximately 3 minutes (exact time not critical).

[0099] 8) Release the pressure and lower the lower platen holding the die.

[0100] 9) Disassemble the die and remove the cup. Place the cup into a labeled plastic bag (Nasco Whirl-Pak 4 oz).

[0101] 10) Using a HunterLab Colorquest XE colorimeter, create the following method (Hunterlab EasyQuest QC software, version 3.6.2 or later)Mode: RSIN-LAV (Reflectance Specular Included-Large Area View) Measurements:CIE L* a* b*CIE X Y Z

[0102] 11) Standardize the instrument as prompted by the software using the light trap accessory and the certified white tile accessory pressed against the reflectance port.

[0103] 12) Run a green tile standard using the certified white tile and compare the CIE X, Y, and Z values obtained against the certified values of the tile. The values obtained should be ± 0.15 units on each scale of the stated values.

[0104] 13) Analyze the sample in the bag by pressing it against the reflectance port and obtaining the spectrum and L*, a*, b* values. Obtain duplicate readings and average the values for the report.Interpretation of Results:

[0105] During the oxidation of 5-HMF to FDCA the alcohol site (ArCH₂OH) was converted into carboxylic acid (ArCOOH) mainly via aldehyde (ArCHO), eq 3. Examples 1a, and 1b (Table-1) which use catalyst systems consisting of cobalt, manganese and aqueous hydrobromic acid source produced about 90 % yield of FDCA with > 98 % purity of crude FDCA solid and with a b* of about 6. The crude FDCA solid also contains 5-Formylfuran-2-carboxylic acid (FFCA), only the hydroxylmethyl groups are oxidized to carboxylic acid groups, due to incomplete oxidation.Co / Mn / Br, AcOH, O2, heat 5- HMF FDCA FFCA

[0106] Oxidation of 5-AMF, which contains an oxidizable ester and aldehydes moieties, produced FDCA, FFCA, and acetic acid, eq 4. Examples 2a to 2b (Table-2) demonstrate that a minimum of 99% purity FDCA solid with a b* of about 7 or less can be achieved using cobalt, manganese and aqueous hydrobromic acid catalyst system.5-AMF

[0107] Oxidation of 5-EMF, which contains an oxidizable ether and aldehyde moieties, produced FDCA, FFCA, 5-(ethoxycarbonyl)furan-2-carboxylic acid (EFCA) and acetic acid, eq 5. Examples 3a to 3d (Table-3) show that a minimum of 96% purity FDCA solid with a b* of about 6 or less can be achieved using cobalt, manganese and aqueous hydrobromic acid catalyst system.EFCA

[0108] It is very important to note that in a continuous process under the same conditions as described in this invention report (which was conducted as a batch process) even higher purity of crude FDCA is expected due to efficient mixing, relatively low concentrations of reactive intermediates, and other reasons familiar to those skilled in the art.Table 1. Results from semi-batch reactions performed as described above using 5-HMF feed.*Solid Composition Mn conc Br conc Temp yield of FDCA yield of FFCAExample Co conc (ppm) (ppm) (ppm) (°C) (%) (%) FDCA FFCA b* 1a 2000 93.3 3000 132 89.4 0.58 99.20 0.81 5.8451b 2000 93.3 3000 132 88.6 0.8 98.67 0.77 6.175 *P = 130 psig.Table 2. Results from semi-batch reactions performed as described above using 5-AMF feed.*SoSd Qorrpesftson Wkiconc &conc Tertp yddofFDGA yiddcifFFCA Scarce a>conc(pfM (EWi (ppn} (”C) (%) (%) FDCA FFCA b**P= 130 psig.Table 3. Results from semi-batch reactions performed as described above using EMF feed.*Solid Composition Co conc Mn conc Br conc Temp yield of FDCA yield of FFCA yield of EFCAExample (ppm) (ppm) (ppm) (°C) (%) (%) (%) FDCA FFCA EFCA b**P = 130 psig.

[0109] It is very important to note that in a continuous process under the same conditions as described in this invention report (which was conducted as a batch process) with different feed stock even higher yields of crude FDCA is expected due to efficient mixing, relatively low concentrations of reactive intermediates, and other reasons familiar to those skilled in the art.

[0110] Commercial FDCA was obtained from Satachem and used as received. In-house FDCA was prepared following the procedure described in US 9,249,118 B2.General procedure:

[0111] In examples 4 to 10, approximately 15.8 grams (0.10 mol) furan-2,5-dicarboxylic acid (FDCA), 18.6 grams (0.30 mol) ethylene glycol and Ti catalyst (50 to 100 ppm) were charged to a clean 100 mL round bottom flask equipped with a stainless-steel stirrer and nitrogen inlet. The titanium catalyst was added as a 1.0 wt% Ti solution made up of titanium (IV) isopropoxide in n-butanol. The flask and contents were attached to glassware conducive to condensation type polymerizations equipped with ice traps, vacuum, and nitrogen for removal of volatile byproducts. After glassware assembly, the contents were vacuum purged two times under nitrogen and then partially submerged in a molten metal bath at 200°C. The contents were heated under a nitrogen sweep of 0.4 SCFH (standard cubic feet / hour). As the solids melted, the stir speed was ramped to 150 rpm over a 10-minute time period. The contents were esterified at 200 - 210°C for 3 hrs. After esterification, the temperature was ramped to a finisher temperature of 250°C over a 20-minute period and held for 10 minutes. The internal pressure was then reduced from atmospheric to 0.50 Torr over a 30-minute period as the stirring was reduced from 150 to 100 rpm. The reaction proceeded at 250°C and 0.5 Torr for 2 hours. Stir speed was reduced as the polymer melt viscosity increased. The above description is a general example of how polymerizations were conducted. In some instances, the finisher temperature, finisher time, stirring profile and Ti concentration were changed to see the effects on polymer properties. Finished polymers were cryogenically ground and pulverized. Samples were submitted for IV, UV-VIS, GPC, and ICP analysis to determine their inherent Viscosity (Ih. V), absorbance, molecular weight distribution, and catalyst level. The results are given in Table 4. Absorbance comparison forPEF made from commercial FDCA sample (example 4) vs PEF made from in¬ house sample (example 6) is given in Figure 5.Table 4. PEF synthesis using commercial and in-house FDCA.FinisherExample FDCA source Tl charge3ICP Ih V A GPC GPC time(PPm) (ppm Ti) (hr) (dL / g) (400 nm) EL 4 Commercial 50 56 2 0.547 0.065 55726 3.514 5 Commercial 100 110 2 0.711 0.111 81406 4.358 6 In-house 50 52 2 0.514 0.011 48804 3.249 7 In-house 50 50 3 0.589 0.017 59592 3.573 8 In-house 20 55 2 0.583 0.016 59891 3.56 9 In-house 100 105 2 0.636 0.019 66329 3.8110 In-house 100 103 2.5 0.681 0.022 74108 3.927a*Ti(IV) isopropoxide.Figure 5: Absorbance versus wavelength (nm) for PEF samples made from commercial FDCA (example 4) and in-house FDCA (example 6).Analytical techniques:Absorbance measurement:

[0112] Samples of the 2,5-furandicarboxylate polymers were received and solutions at 0.05 g / mL concentrations in 20 % hexafluoroisopropanol / 80 % dichloromethane (v / v) solutions were prepared. The UV / Visible spectra of these were collected on a PerkinElmer Lambda 1050 dual-beam UV / Visible / NIR spectrophotometer with a photomultiplier tube detector and a 150 mm diameter integrating sphere accessory (0 / 8 degree geometry). The following parameters were used:Scan Range: 700 nm - 350 nmScan Speed: 266.75 nm / minPhotomultiplier Tube Detector Slit Width: 5 nm Photomultiplier Tube Response: 0.20 secondsData Spacing: 1 nm

[0113] 20 % hexafluoroisopropanol / 80 % dichloromethane was used in the reference cell position. A 20 % hexafluoroisopropanol / 80 % dichloromethane blank in the sample position was run with every sample set analysis.

[0114] The raw sample spectra were normalized by any small deviations from an ideal sample concentration of 5.00 mg / mL.

[0115] The integrating sphere accessory was used to minimize the effect of any haze in the samples. Even then, spectral intensity shifts (baselines < 0 absorbance) were observed for some higher-haze samples. In such cases, the normalized (for weight) sample absorbance values at 400 nm were corrected for by subtracting out the 20 % hexafluoroisopropanol / 80 % dichloromethane blank value at 700 nm to crudely minimize the effect of haze. This subtraction elevated the raw sample values at 400 nm to higher values so would be a conservative method (i.e., it could result in absorbance values higher than the true values) to report the absorbance.GPC measurement:

[0116] Gel Permeation Chromatography (GPC) measurements were performed using an Agilent 1260 series HPLC system equipped with an Agilent PLgel mixed 5 micron guard (7.5 X 50mm) and an Agilent PLgel 5 micron Mixed-C (7.5 X 300mm) columns. The instrument consists of a degasser, autosampler with an injection volume of 10 microliters and a variable wavelength detector with UV detection at 255nm. Dichloromethane: Hexafluoroisopropanol 95:5 solvent mixture was used as eluent. The sample was prepared by weighing 5 to 7 milligrams in 10 milliliters of the azeotrope of Dichloromethane: Hexafluoroisopropanol a 69:31 mixture which has Toluene added at 3 milliliters per liter. The Toluene is used as a flowrate marker. Calculation of molecular weight was based on polystyrene standards and carried out by Agilent GPC / SEC software Version A.02.01 Build 9.34851 {12}.

[0117] Inherent viscosity: The inherent viscosity of the polyesters was determined in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at25°C.CLAIMS NOT LIMITED TO DISCLOSED EMBODIMENTS

[0118] The preferred forms of the invention described above are to be used as illustration only, and should not be used in a limiting sense to interpret the scope of the present invention. Modifications to the exemplary embodiments, set forth above, could be readily made by those skilled in the art without departing from the spirit of the present invention.

[0119] The inventors hereby state their intent to rely on the Doctrine of Equivalents to determine and assess the reasonably fair scope of the present invention as it pertains to any apparatus not materially departing from but outside the literal scope of the invention as set forth in the following claims.

Claims

We claim:

1. A process to produce PEF comprising,(a) Oxidizing 5-HMF and its derivatives to produce crude FDCA having a b* of less than 16; wherein the crude FDCA comprises at least 80% FDCA;(b) Separating the crude FCDA to remove the oxidation solvent to yield a solvent stream and crude FDCA;(c) Optionally recycling the solvent stream;(d) Optionally hydrogenating of the crude FDCA to produce hydrogenated FDCA;(e) Recrystallization of the hydrogenated FDCA;(f) Separation of a portion of the hydrogenated FDCA to produce a purified FDCA; wherein the purified FDCA comprises at least 95% FDCA;(g) Polymerizing FDCA to produce PEF having an Inherent Viscosity greater than 0.50 dL / g and an absorbance less than 0.1.

2. A PEF process of claim 1 wherein the PEF has an absorbance of less than 0.07, or less than.05.

3. A PEF process of claim 1 wherein the PEF has a molecular weight 10,000 to 200,000.

4. A PEF process of claim 1 wherein the molecular weight 40,000 to 100,000.

5. A PEF process of claim 1 wherein the molecular weight 50,000 to 90,000.

6. A process of claim 1 wherein the molecular weight 30,000 to 90,000.

7. A PEF process of claim 1 wherein the PEF has a Polydispersity 1 to 6.

8. A PEF process of claim 1 wherein the Polydispersity 1 to 5.

9. A PEF process of claim 1 wherein the Polydispersity 2 to 5.

10. A PEF process of claim 1 wherein the Titanium concentration of less than about 200 ppm.

11. A PEF process of claim 1 wherein the Titanium concentration of less than about 175 ppm.

12. A PEF process of claim 1 wherein the Titanium concentration of less than about 125 ppm or less than 50 ppm or less than 25 ppm.

13. A PEF process of claim 1 wherein Titanium concentration ranges from 0.01 to 200 ppm.

14. A PEF composition comprising PEF with absorbance less than 0.1, Inherent Viscosity greater than 0.50 dL / g, Molecular Weight (MW) 10,000 to 200,000.

15. A PEF composition according to claim 14 wherein the absorbance is less than 0.07, less than 0.05.

16. The PEF composition of claim 14 wherein MW 20,000 - 100,000.

17. The PEF composition of claim 14 wherein PD = 2.0 to 6.0.

18. The PEF composition of claim 14 wherein MW 40,000 - 90,000.

19. The PEF composition of claim 14 wherein PD 2.5 to 4.5.

20. The PEF composition of claim 14 wherein MW 60,000 to 80,000.

21. The PEF composition of claim 14 wherein a titanium concentration of less than about 200 ppm.

22. The PEF composition of claim 14 wherein a titanium concentration of less than about 125 ppm.

23. The PEF composition of claim 14 wherein a titanium concentration of less than about 75ppm.

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