High performance material as nutrient of the future

Abstract

The present invention relates to a method for producing biodegradable polyester articles comprising monomers of ethylene glycol, terephthalic acid, dimethylgluturate, sodium dimethyl 5-sulfoisophthalate in specific ratios that permit the resultant articles to be degradable in marine and soil environments with no toxic products from degradation such that polyester breakdown products can be nutrients for microbes. The invention further relates biodegradable polyester articles obtained from said process.

Description

HIGH PERFORMANCE MATERIAL AS NUTRIENT OF THE FUTURECROSS-REFERENCE TO RELATED APPLICATIONThe present application claims the benefit of priority of EP Patent Application No. EP24197599 filed 30 August 2024, the content of which is hereby incorporated by reference in its entirety for all purposes.TECHNICAL FIELD

[0001] The present invention relates to a method for producing a biodegradable polyester article with highly desirable properties. Said method includes the production of intermediate articles such as granules (chips, pellets, powder), further intermediates (fibers, yarns, filaments, sheets, foils) and further finished articles such as a hollow molding (bottle, flask, tube, hollow frame for garments), an injection molded article (buttons, clasps, fasteners etc.) or a printed article (3D and 2D printed articles) and yet even further articles such as textiles inclusive of products therefrom (a net, a floor covering, a fabric or a garment).BACKGROUND

[0002] Plastics enter nature as waste or microparticles through abrasion or washing. In the case of PET, the parts end up in the water or soil as fragments. In the case of textiles, for example, tens of thousands of tons of clothing are dumped in the Atacama Desert in Chile, with an ever-increasing proportion of polyester. Polyester is a cost-effective fiber that hardly degrades in nature. Conventional polyester has residues of catalysts in the plastic such as antimony oxide (150-300 ppm / kg) or flame retardants and other problematic ingredients. In the environment, these ingredients dissolve out of the material and also enter the food chain.

[0003] The present invention contains a comprehensive solution. This material is a PET polyester replacement and is free of problematic substances and has more positive properties such as flame retardancy, hydrophilicity, elasticity, rapid degradability, soft feel in polymerization without downstream processing and the fact that the material is safe for the biological cycle and can be easily depolymerized so that the raw materials are not lost. In nature, the new material does not have a less harmful effect, but rather a positive impact and a good footprint essentially becoming nutrients for microorganisms through the act of degradation without the threat of toxins.

[0004] The release of particles through abrasion or washing means that sooner or later these parts end up in the world's oceans. From there they very quickly enter the food chain. The solution of the invention enables the product to be recycled. In the biological cycle, the product becomes a nutrient without problematic substances entering the environment and inthe technical cycle, the material can be broken down with little energy and returned to production as an equivalent raw material to make it new.

[0005] The microparticles in the water cycle break down quickly and become nutrients for phytoplankton (biological cycle). This new material must not have any disadvantages in terms of performance compared to existing PET polyester. The inventors have invested extensive research in equipping the material with properties that are improved in conventional materials by problematic additives or subsequent processes.

[0006] The invention enables the performance compared to conventional polyester PET with less energy to result in a product that has more positive properties and qualities than conventional products that are of great ecological concern. Subsequent extensions to the properties of today's PET polyester are in most cases associated with additional processes (energy consumption) and / or additives that are ecologically questionable or worsen the performance of the material and cause costs.

[0007] Since ecology is a key driver of the present invention, care was taken to use a significant proportion of chemically recycled PET in the feedstock. Since, for example, the chemical structure of terephthalic acid is identical in virgin TPA and cTPA, but the crystalline form is not, adjustments had to be made to the process. The invention can also be manufactured with virgin feedstock. In the medium term, when the feedstock is available, the invention will be manufactured from the PET polyester waste of civilization. Chemical recycling of PET is state of the art, but is not yet available in large quantities in pure form. Feedstock from mechanical recycling cannot be used because contamination and contamination cannot be avoided in this process. For example, residues of catalysts such as antimony remain in the material with the known processes, which is unacceptable in terms of potential harm to both environmental and physical health for the present aims.

[0008] The invention was built using state-of-the-art ingredients. Using an exclusion process, it was determined that there would be no negative impact on the environment and living beings, but that there would also be positive effects for the environment if the product were released into the environment, and that there would be no reduction in the quality and lifespan of the product. Biological degradation may only begin when the product enters the environment in the form of small fragments or has been in the environment for a longer period of time. Hardwood was used as the inspiration for degradation. If broken down into small chips, hardwood degrades quickly, but as a large product it can take a few years. One of the decisive factors in this attribute is that nothing escapes during degradation that is a problem for the environment and living beings.

[0009] An important factor in polycondensation is the choice of catalyst, which in the desired solution must not be based on heavy metals or semi-metals (such as antimony dioxide). An experimental investigation was carried out to select a catalyst that could be easily removedfrom the invention during polycondensation with almost no residue. The catalyst is based on aluminum but can also be made with an enzymatic catalyst. Dyes such as titanium dioxide, which are permitted in the food industry, were also replaced in the invention because various studies have also described them as being mutagenic. The invention can also be made with titanium dioxide but is best made with the colorant listed in the description. No changes to the properties and performance of the invention were found other than the possible improvements to mutagenic effects.

[0010] Particular attention was paid to the durability of the products from the invention. In comparison to biodegradable materials, such as natural materials, the invention has the property that biological degradation or simple depolymerization does not negatively affect the service life, quality such as color fastness, or care options. The material from the invention can be used in any area where conventional PET polyester is used without any qualitative disadvantages. In addition, the invention offers the above-mentioned added values and properties without additional finishing processes, which can only be achieved with conventional PET polyester with significantly greater effort and often ecologically questionable additives or processes.SUMMARY

[0011] The goals and objectives of the invention were accomplished by the methods and products having the features of the independent claims. Specifically, the performance of the new material compared to conventional PET polyester are: o the new material already has hydrophilic properties after polycondensation, which conventional PET cannot demonstrate without downstream processes o the new material is flame-retardant after polycondensation, without additional equipment or additives o the new material is quickly biodegradable after polycondensation, without the addition of oxidants in a subsequent compounding process. o the material can be dyed at a significantly lower temperature, particularly as a fiber / yarn or textile surface, and the structure of the new material means that the use of dye (pigment, dispersion) can be kept lower than with conventional PET polyester. o the chemical structure of the new material means that, particularly when dyed at a lower temperature, the product can have a more pleasant and softer feel without the addition of additives (plasticizers). A significant change in the feel is clearly noticeable in textiles, films and thin-walled injection-molded parts o after the life cycle, the material can be depolymerized more quickly and easily than conventional PET polyester through solvolysis without the addition of additional energy and can be reused as a raw material with a high degree of purity o after the biological degradation of fragments or entire products made from the new material, not only CO2 and water are in the environment, but also nutrients, especially for phytoplankton.

[0012] In a first aspect, the present invention relates to a process for producing a biodegradable polyester article comprising:(I) providing a slurry comprising a source of terephthalic acid monomer, a source of ethylene glycol monomer, a source of monomer according to structure (i):, wherein X is in the range of from 2 to 18, wherein R is a C1 to C6 hydrocarbon or H, and a source of monomer according to structure (ii):hydrocarbon or H, and an aluminum salt catalyst; wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of ethylene glycol monomer (EG) in the range of from 1 : 1 .2 to 1 : 1.6 (calculated as moles of (TA) I moles of (EG)); wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (i) (strj) in the range of from 1 : 0.04 to 1 : 0.12 (calculated as moles of (TA) I moles of (strj)) ; wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (ii) (strji) in the range of from 2000 : 1 to 650 : 1 (calculated as moles of (TA) I moles of (strji)); wherein the aluminum salt catalyst (Al-cat) is present in a molar amount relative to the source of monomer of terephthalic acid (TA) (calculated as moles of Al present in the aluminum salt catalyst I moles of TA monomer * 100 mol.-%) is in the range of from 0.01 mol.-% to 0.0001 mol.-%;(1.1) reacting the slurry provided according to (I) in a first esterification;(1.2) obtaining a first composition comprising bis(2-hydroxyethyl)terephthalate (BHET);(II) adding one or more further components to the first composition obtained according to(1.2) to obtain a mixture;(11.1) reacting the mixture obtained according to (II) in a second esterification;(11.2) obtaining a second composition from (11.1) comprising pre-polymers (pre-condensed polyester) comprising independently at each occurrence monomers of bis(2- hydroxyethyl)terephthalate (BHET), monomers according to structure (i) and / or monomers according to structure (ii);(III) heating the second composition obtained according to (II.2) comprising;(111.1) purging with nitrogen while heating the second composition to a temperature in the range of from 160 °C to 190 °C;(111.2) after reaching the temperature according to (111.1), heating the second composition with the nitrogen purge to a temperature in the range of from 240 °C to 290 °C for a duration in the range of from 3.5 hours to 6 hours;(111.3) the composition is transferred to a further reactor after heating according to (III.2);(IV) heating the transferred composition in a reactor according to (III.3) to a temperature in the range of from 210 °C to 290 °C for a duration of from 4 hours to 7 hours at an absolute pressure in the range of 10 to 30 pascal; and followed by cooling to a temperature in the range of 15 °C to 30 °C while simultaneously purging with nitrogen;(V) obtaining a third composition from (IV) comprising a polyester copolymer comprising PET monomers terephthalate and ethylene glycol interspersed independently from one another at each occurrence monomers of bis(2-hydroxyethyl)terephthalate (BHET), monomers of structure (i) and monomers of structure (ii);(VI) transferring the composition comprising the polyester copolymer obtained according to (V) to any one of a granulator, a spinning system, an extrusion molding system, an injection molding system or a printing system;(VII) obtaining a biodegradable polyester article.

[0013] A second aspect relates a biodegradable polyester article obtained according to any one of the process claims.BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The invention will be better understood with reference to the detailed description when considered in conjunction with the non-limiting examples and the drawings, in which:

[0015] Figure 1 shows the % marine biodegradation of Ex. 1 over a period of 99 days according to ASTM D6691 vs a reference polymer of cellulose. #

[0016] Figure 2 is a plot of viscosity vs the shear rate of Ex. 1 at temperatures of 240 °C, 230 °C and 220 °C.DETAILED DESCRIPTION

[0017] As set out above, in a first aspect the present invention relates to In a first aspect, the present invention relates to a process for producing a biodegradable polyester article comprising:(I) providing a slurry comprising a source of terephthalic acid monomer, a source of ethylene glycol monomer, a source of monomer according to structure (i):, wherein X is in the range of from 2 to 18, wherein R is a C1 to C6 hydrocarbon or H, and a source of monomer according to structure (ii):hydrocarbon or H, and an aluminum salt catalyst; wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of ethylene glycol monomer (EG) in the range of from 1 : 1.2 to 1 : 1.6 (calculated as moles of (TA) I moles of (EG)); wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (i) (strj) in the range of from 1 : 0.04 to 1 : 0.12 (calculated as moles of (TA) I moles of (strj)); wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (ii) (strji) in the range of from 2000 : 1 to 650 : 1 (calculated as moles of (TA) I moles of (strji)) ; wherein the aluminum salt catalyst (Al-cat) is present in a molar amount relative to the source of monomer of terephthalic acid (TA) (calculated as moles of Al present in the aluminum salt catalyst I moles of TA monomer * 100 mol.-%) is in the range of from 0.01 mol.-% to 0.0001 mol.-%;(1.1) reacting the slurry provided according to (I) in a first esterification;(1.2) obtaining a first composition comprising bis(2-hydroxyethyl)terephthalate (BHET);(II) adding one or more further components to the first composition obtained according to(1.2) to obtain a mixture;(11.1) reacting the mixture obtained according to (II) in a second esterification;(11.2) obtaining a second composition from (11.1) comprising pre-polymers (pre-condensed polyester) comprising independently at each occurrence monomers of bis(2- hydroxyethyl)terephthalate (BHET), monomers according to structure (i) and / or monomers according to structure (ii);(III) heating the second composition obtained according to (II.2) comprising;(111.1) purging with nitrogen while heating the second composition to a temperature in the range of from 160 °C to 190 °C;(111.2) after reaching the temperature according to (III .1), heating the second composition with the nitrogen purge to a temperature in the range of from 240 °C to 290 °C for a duration in the range of from 3.5 hours to 6 hours;(111.3) the composition is transferred to a further reactor after heating according to (III.2);(IV) heating the transferred composition in a reactor according to (III.3) to a temperature in the range of from 210 °C to 290 °C for a duration of from 4 hours to 7 hours at an absolute pressure in the range of 10 to 30 pascal; and followed by cooling to a temperature in the range of 15 °C to 30 °C while simultaneously purging with nitrogen;(V) obtaining a third composition from (IV) comprising a polyester copolymer comprising PET monomers terephthalate and ethylene glycol interspersed independently from one another at each occurrence monomers of bis(2-hydroxyethyl)terephthalate (BHET), monomers of structure (i) and monomers of structure (ii);(VI) transferring the composition comprising the polyester copolymer obtained according to (V) to any one of a granulator, a spinning system, an extrusion molding system, an injection molding system or a printing system;(VII) obtaining a biodegradable polyester article.

[0018] Concerning the form of the biodegradable polyester article, said article can be made as a replacement for any article made from conventional PET. Generally, it is preferred that the biodegradable polyester article is in the form of a textile, a fiber, a filament, a yarn, a chip, a granule, a film, a foil, a sheet, a hollow molding, an injection molded article or a printed article. It is preferred that the biodegradable polyester article is in the form of a textile, a fiber, a yarn, a chip, a granule, an injection molded article or a printed article, preferably a textile, a fiber, a yarn, a chip, a granule or an injection molded article, more preferably a textile, a fiber, a yarn, a chip or a granule. In some embodiments the biodegradable polyester article is in the form of a granule. However, a chip or a pellet is equivalent to said granule and both forms are also preferred as intermediate forms that can be further processed into other biodegradable polyester articles according to the present disclosure. Likewise, it is preferred that the biodegradable polyester article is in the form of a fiber, a filament or a yarn since these articles can also be used to make further articles according to the present disclosure. In other general embodiments, the biodegradable polyester article is in the form of a textile. In related more specific embodiments, the biodegradable polyester textile is in the form of a net, a floor covering, a fabric or a garment. In specific embodiments, the biodegradable polyester article is in the form of a fiber. In specific embodiments, the biodegradable polyester article is in the form of a yarn. In some embodiments, the biodegradable polyester article is in the form of a fabric. In more specific embodiments the biodegradable polyester article is in the form of a fabric for garment production, preferably for quick dry garments. In some embodiments, the biodegradable polyester article is in the form of a net. In more specific embodiments wherein the biodegradable polyester article is in the form of a net, it is preferred that the net is for use in anchoring and / or mooring, preferably for use in anchoring and / or mooring for marine wind turbine towers. In specific embodiments, the biodegradable polyester article is in the form of a garment. In embodiments related to textiles according tothe present disclosure, it is preferred that the textile is a fire-resistant fabric according to DIN 4102-1. In some general embodiments, the biodegradable polyester article is in the form of a foil, a film, a sheet, a hollow molding, an injection molded article or a printed article.In specific embodiments, the biodegradable polyester article is in the form of a film. In specific embodiments, the biodegradable polyester article is in the form of a foil.In specific embodiments, the biodegradable polyester article is in the form of a hollow molding. In specific embodiments, the biodegradable polyester article is in the form of an injection molded article. In specific embodiments, the biodegradable polyester article is in the form of a printed article, preferably a 3D or a 2D printed article, more preferably a 3D printed article. In specific embodiments, the biodegradable polyester article is in the form of a 3D printed article.

[0019] With respect to the degradability of the polyester articles according to the present disclosure, it is preferred that the biodegradable polyester article is a marine biodegradable polyester article, a soil biodegradable polyester article or both a marine biodegradable polyester article and a soil biodegradable polyester article. It is further noted that being biodegradable does not preclude chemical degradation and that polyester articles according to the present disclosure can also be rapidly degraded to useful intermediates for recycling by chemical means. However, it is preferred that the biodegradable polyester article is a marine biodegradable polyester article, preferably according to ASTM D6691. This reflects the observation that all plastics will eventual form microparticles and that microplastics derived from biodegradable articles can be recycled environmentally as nutrients. Likewise, it is preferred that the biodegradable polyester article is a soil biodegradable polyester article, preferably according to ASTM D5988 or ISO 17556, more preferably ASTM D5988. In more specific embodiments, it is preferred that the biodegradable polyester article has a biological degradability in the range of from 80 wt.-% to 100 wt.-% (calculated as the final weight I the initial weight x 100%), preferably in the range of from 90 wt.-% to 99.9 wt.-%, more preferably in the range of from 92 wt.-% to 99 wt.-%, optionally determined according to ASTM D6691 or ASTM D5988. It is further preferred that the biodegradable polyester article is biodegradable in the range of from 80 wt.-% to 100 wt.-% within N days and N is in the range of 1 to 99 days (calculated as the final weight measured on the Nthday / the initial weight x 100%), preferably in the range of from 90 wt.-% to 99.9 wt.-% within N days and N is in the range of 50 to 99 days (calculated as the final weight measured on the Nthday / the initial weight x 100%), more preferably in the range of from 92 wt.-% to 99 wt.-% within N days and N is in the range of 70 to 99 days (calculated as the final weight measured on the Nthday / the initial weight x 100%), optionally determined according to ASTM D6691 or ASTM D5988.

[0020] Regarding terephthalic acid monomer source, it is preferred that according to (I) the terephthalic acid monomer source is either terephthalic acid or a C1 to C6 diester of terephthalic acid, preferably is terephthalic acid. Preferably in general embodiments, according to (I) the terephthalic acid monomer source is virgin grade terephthalic acid, recycled terephthalic acid or a mixture of virgin grade terephthalic acid and recycledterephthalic acid. In some embodiments, according to (I) the terephthalic acid monomer source is virgin grade terephthalic acid. In other embodiments, according to (I) the terephthalic acid monomer source is recycled terephthalic acid. In some embodiments, according to (I) the terephthalic acid monomer source is a mixture of virgin grade terephthalic acid and recycled terephthalic acid. In detailed embodiments, according to (I) the terephthalic acid monomer source is a mixture of virgin grade terephthalic acid and recycled terephthalic acid and the weight ratio of virgin grade terephthalic acid to recycled terephthalic acid is in the range of 10 : 1 to 1:2, preferably in the range of from 9 : 1 to 1 :1 , more preferably in the range of from 5 : 1 to 2: 1.

[0021] With respect to the source of ethylene glycol monomer, it is preferred that according to (I) the ethylene glycol monomer source is ethylene glycol, preferably being recycled ethylene glycol, virgin ethylene or ethylene glycol from a biological process. In some embodiments, according to (I) the source of monomer according to structure (i) is recycled or virgin grade, preferably is recycled dimethyl gluturate.

[0022] Concerning the further monomer source according to structure (i), it is preferred in general embodiments that according to (I) the source of monomer according to structure (i) is recycled or virgin grade, preferably is recycled dimethyl gluturate or virgin grade dimethyl gluturate. Preferably, according to (I) the source of monomer according to structure (i):the range of from 2 to 12, more preferably in the range of 2 to 6, more preferably being 2 or 3; wherein R is a C1 to C6 hydrocarbon, preferably is a C1 to C3 hydrocarbon, more preferably is methyl or ethyl, more preferably is methyl. In more specific embodiments, it is preferred that according to (I) the source of monomer according to structure (i) comprise, preferably consist of, dimethyl glutarate, preferably according to structure (i-a):

[0023] Regarding the further monomer source according to structure (ii), it is preferred in general embodiments that according to (I) the source of monomer according to structure (ii) is either recycled or virgin grade, preferably is recycled sodium dimethyl 5-sulfoisophthalate or virgin grade sodium dimethyl 5-sulfoisophthalate. Preferably, according to (I) the source ofmonomer according to structure (ii):s a cation, preferably M is an alkaline metal or an alkaline earth metal, more preferably M is Li, Na, K, Mg or Ca, more preferably M is Na; wherein R’ is a C1 to C6 hydrocarbon, preferably is a C1 to C3 hydrocarbon, more preferably is methyl or ethyl, more preferably is methyl. It is further preferred that according to (I) the source of monomer according to structure (ii) comprise, preferably consist of, sodium dimethyl 5-sulfoisophthalate, preferably according to structure (ii-a):

[0024] With respect to the catalyst, catalysts useful to the invention have been investigated in US7144614B2 which is incorporated by reference in its’ entirety. It is preferred that according to (I) the aluminum salt catalyst is according to structure (iii):wherein R1is selected from the group consisting of C5 to C20 aromatics,M is selected from the group consisting of Li, Na, K, Be, Mg, Ca, Sr, Ba, Mn, Ni, Cu and Zn, R2is a C1 to C20 hydrocarbon, R3is a C1 to C20 hydrocarbon, Y+Z is 4 and Y is in the range of 1 to 3. In more specific embodiments related to said catalyst structure (iii), it is preferred that structure (iii) is according to structure (iii-a):(iii-a), whereinM is selected from the group consisting of Li, Na, K, Be, Mg, Ca, Sr, Ba, Mn, Ni, Cu, and Zn, R2is a C1 to C20 hydrocarbon, R3is a C1 to 020 hydrocarbon, R4is a 01 to 020 hydrocarbon, OH, Cl, F, NO2 or H, R5is a 01 to C20 hydrocarbon, OH, Cl, F, NO2 or H, Y+Z is 4 and Y is in the range of 1 to 3, preferably wherein the phosphorous comprising ligand comprised by (iii-a) is monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (CAS Nr. 66165-37-5). In some embodiments, M is selected from the group consisting of Li, Na, K, Mg, Ca, Mn, Ni, Cu, and Zn, preferably selected from the group consisting of Li, Na, K, Mg, Ca, and Zn, more preferably selected from the group consisting of Li, Na, K, Mg, and Ca, more preferably selected from the group consisting of Li, Na and Ca, more preferably is Li, Na or Ca. In some embodiments, R2is a C1 to C8 hydrocarbon, preferably R2is a C1 to C6 hydrocarbon, preferably R2is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl and iso-butyl, more preferably R2is methyl, ethyl, n-propyl or isopropyl, more preferably R2is methyl or ethyl. In some embodiments, R3is a C1 to C18 hydrocarbon, preferably R3is a C1 to C12 hydrocarbon comprising a 1,3-dicarbonyl or a straight chain hydrocarbon, preferably R3is selected from the group consisting of acetylacetonoate, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl and iso-butyl, more preferably R3is acetylacetonoate, methyl, ethyl, n-propyl or isopropyl, more preferably R3is acetylacetonoate, methyl or ethyl. In some embodiments, R4is a C1 to C6 hydrocarbon, OH, Cl, F, NO2 or H, preferably is a C1 to C5 hydrocarbon, OH, Cl, F, NO2 or H, more preferably is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl or iso-butyl, more preferably is H, methyl, ethyl, isopropyl, or t-butyl, more preferably is H, methyl or t-butyl. In some embodiments, R5is a C1 to C5 hydrocarbon, OH, Cl, F, NO2 or H, preferably is a C1 to C3 hydrocarbon, OH, Cl, F, NO2 or H, more preferably is a OH, NO2 or H, more preferably is a OH or H. In some embodiments, according to (I) Y+Z is 4 and Y is 2 or 3.

[0025] In more detailed embodiments, it is preferred that according to (I) the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of ethylene glycol monomer (EG) in the range of from 1: 1.3 to 1 : 1.5, preferably in the range of from 1: 1.38 to 1 : 1.47, (calculated as moles of (TA) / moles of (EG)).

[0026] I In more detailed embodiments, it is preferred that according to (I) the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (i) (strj) in the range of from 1: 0.06 to 1 : 0.10 (calculatedas moles of (TA) / moles of (strj)).

[0027] I In more detailed embodiments, it is preferred that according to (I) the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (ii) (strji) in the range of from 1500 : 1 to 700 : 1 (calculated as moles of (TA) I moles of (strji)) , preferably in the range of from 1000 : 1 to 800 : 1 (calculated as moles of (TA) I moles of (strji)).

[0028] I In more detailed embodiments, it is preferred that according to (I) the aluminum salt catalyst (Al-cat) is present in a molar amount relative to the source of monomer of terephthalic acid (TA) (calculated as moles of Al present in the aluminum salt catalyst I moles of TA monomer * 100 mol.-%) is in the range of from 0.01 mol.-% to 0.001 mol.-%.

[0029] With regards to conditions for the first esterification and second esterification, it is noted that US8614280B2 provides conditions and reactors useful to said steps and the document is incorporated by reference in its entirety. It is preferred that according to (1.1) the first esterification is carried out at a temperature in a range of from 180 °C to 260 °C, preferably of from 220 °C to 250 °C. It is preferred that according to (1.1) the first esterification has a pressure in the range of from 0.6 bar to 1.2 bar, preferably of from 0.8 bar to 1.1 bar. Preferably, according to (1.1) the first esterification is carried out for a duration of from 0.5 hour to 2.5 hours, preferably in the range of from 1 hour to 2 hours.

[0030] It is preferred that according to (1.2) the first composition comprises bis(2- hydroxyethyl)terephthalate (BHET) in a range of from 70 wt.-% to 100 wt.-% (calculated as the weight of BHET I the total weight of all components present x 100%), preferably in a range of from 80 wt.-% to 99 wt.-%, more preferably in a range of from 90 wt.-% to 98 wt.-%.

[0031] Regarding other steps comprised within (I), it is preferred that (I) further comprises(1.3) removing unreacted ethylene glycol and recycling the ethylene glycol after purification by distillation to the slurry provided in (I).Regarding other steps comprised within (I), it is preferred that (I) further comprises(1.4) removing water from the first esterification to a waste treatment system.

[0032] With respect to (II), according to (II) the one or more further components comprise a fluorescent tracer dye. It is further preferred that the fluorescent tracer dye is a Particle- Fingerprint Fluorescence Tracer model TrackByStars® obtained from (Polysecure).Preferably, the fluorescent tracer dye is added in an amount of less than 0.001 wt.-% relative to the terephthalate monomers (calculated as weight tracer dye / total weight of terephthalate monomers x 100%), preferably less than 0.0001 wt.-%, more preferably in the range of from than 0.001 wt.-% to than 0.000001 wt.-%, more preferably in the range of from 0.0001 wt.-%to than 0.000001 wt.-%. Preferably, the fluorescent tracer dye is invisible to normal visual inspection.

[0033] Concerning other further components, it is preferred that according to (II) the one or more further components comprise a delusterant. In detailed embodiments, the delusterant is present in an amount in the range of from 0.1 wt.-% to 2.0 wt.-% relative to the terephthalate monomers (calculated as weight delusterant I total weight of terephthalate monomers x 100%), preferably in an amount in the range of from 0.2 wt.-% to 1.4 wt.-%, more preferably in an amount in the range of from 0.3 wt.-% to 0.9 wt.-%, more preferably in an amount in the range of from 0.4 wt.-% to 0.8 wt.-%. Generally, the delusterant is free of titanium dioxide. In detailed embodiments, the delusterant has an elemental formula of (CaO)a(Al2O3)b(CaSC>4)c(H2O)d and a is in the range of from 1 to 5, b is in the range of from 0.1 to 2, c is in the range of from 2 to 5 and d is in the range of from 20 to 40, preferably a is in the range of from 2 to 4, b is in the range of from 1 to 2, c is in the range of from 3 to 4 and d is in the range of from 25 to 35. In other detailed embodiments, the delusterant has an elemental formula of (CaO)a(Al2O3)b(CaSO4)c(H2O)d and a, b, c and d are all whole integers, a is in the range of from 1 to 5, b is 1 or 2, c is in the range of from 2 to 5 and d is in the range of from 20 to 40, preferably a is in the range of from 2 to 4, b is 1 or 2, c is in the range of from 3 to 4 and d is in the range of from 25 to 35.

[0034] It is preferred that according to (II) the one or more further components comprise a dye. Preferably, the dye is for textiles. It is further preferred that said the textile is a fabric or garment. Preferably the dye is biodegradable and non-toxic. It is preferred that the dye is a natural dye.

[0035] It is preferred that according to (II) the one or more further components comprise one or more of selected from the group consisting of lubricants, flame retardants, fillers, weather stabilizers, plasticizers and combinations of two or more thereof. In addition, the aluminum catalyst according to (I) may also be adjusted or added according to (II). It is also preferred that the aluminum salt catalyst according to (I) is only first added according to (II) as one or more further components. It is further preferred that according to (II) the one or more further components is biodegradable, preferably marine biodegradable or soil biodegradable, more preferably marine biodegradable according to ASTM D6691 or soil biodegradable according to ASTM D5988. It is further preferred that according to (II) the one or more further components is non-toxic.

[0036] Concerning the physical parameters of the second esterification according to (11.1), it is preferred that the second esterification is carried out at a temperature in a range of from 230 °C to 270 °C, preferably of from 240 °C to 260 °C. It is also preferred that according to (11.1) the second esterification has an initial pressure in the range of from 0.1 bar to 0.5 bar, preferably of from 0.2 bar to 0.4 bar. It is also preferred that according to (11.1) the second esterification has a final pressure in the range of from 0.001 bar to 0.1 bar, preferably of from0.005 bar to 0.02 bar. Preferably, according to (11.1) the second esterification is carried out for a duration in the range of from 0.5 hour to 3 hours, preferably in the range of from 1 hour to 2 hours. In detailed embodiments, the initial pressure of the second esterification is measured at T=0 and the ending pressure of the second esterification is measured at T=final, T is the time of the second esterification and the total sum of T is equal to the duration of the second esterification.

[0037] It is preferred that (II) further comprises(11.3) removing unreacted ethylene glycol and recycling the ethylene glycol after purification by distillation to the slurry provided in (I).

[0038] It is preferred that (II) further comprises(11.4) removing water from the second esterification to a waste treatment system.

[0039] Concerning additional procedures for (I), (II) or both, it is preferred that (I) and / or (II) further comprise(1.5) and / or (11.5) cooling the esterification, preferably cooling to a temperature in the range of from 15 °C to 45 °C, preferably in the range of from 20 °C to 30 °C.It is also preferred that (I) and / or (II) further comprise(1.6) and / or (11.6) purging the esterification with nitrogen, preferably to atmospheric pressure.Preferably, cooling is simultaneous with purging the esterification with nitrogen. Also preferred is cooling and / or purging is conducted for a duration of 0.5 hours to 2 hours.

[0040] With respect to the products obtained from the second esterification, it is preferred that the second composition obtained according to (II.2) has an intrinsic viscosity in the range of from 0.18 dl / g to 0.58 dl / g, preferably in the range of from 0.30 dl / g to 0.50 dl / g, optionally measured according to DIN EN ISO 1628-1.

[0041] Regarding the physical parameters according to (111.1), it is preferred that according to (111.1) purging with nitrogen while heating the second composition to a temperature in the range of from 165 °C to 185 °C. It is also preferred that according to (III.2), heating the second composition with the nitrogen purge to a temperature in the range of from 260 °C to 290 °C for a duration in the range of from 3.5 hours to 5 hours. Preferably, according to (111.3), the reactor is a vacuum reactor.

[0042] Embodiments related to injection molded articles or printed articles according to the invention may require filler. For example, it was found that bra-wire comprising a tuberequired calcium carbonate to maintain structural integrity when washing at 70 °C. Likewise, a cup made according to the injection molded article required calcium carbonate to be able to maintain structure when washing at higher dishwasher temperatures. Accordingly, it is preferred that according to (III.3), if the biodegradable polyester article is an injected molded article or a printed article, calcium carbonate, preferably calcium carbonate obtained from renewable bio-source, more preferably calcium carbonate obtained from mussel shells, is added to the reactor. It is further preferred that the calcium carbonate is added in an amount relative to the amount of terephthalic acid monomer (TA) in the range of from 0.1 wt.-% to 10 wt.-% (calculated as weight of CaCCh I weight of terephthalic acid monomer (TA) x 100%), preferably in the range of from 1 wt.-% to 8 wt.-%, more preferably in the range of from 2 wt.- % to 6 wt.-%. The calcium carbonate is 85 wt.-% to 98 wt.-% CaCO3 and the remainder are bio-polymers from shells. It is further preferred that the calcium carbonate is in the form of a powder.

[0043] If color stabilizers are desired, it is preferred that according to (III.3), a color stabilizer is added to the reactor. It is also preferred that the color stabilizer is adenosyl cobalamine (Coenzyme B12, CAS 13870-90-1). Alternatively, the color stabilizer is phosphorous acid, triphenylphosphite, triphenylphosphate, sodium hypophosphite or sodium phosphite. The color stabilizer is preferably added in an amount relative to the amount of terephthalic acid monomer (TA) in the range of from 0.001 wt.-% to 4 wt.-%, preferably 0.01 wt.-% to 3.5 wt.- %, more preferably 0.1 wt.-% to 3.0 wt.-%, (calculated as weight of the color stabilizer I weight of terephthalic acid monomer (TA) x 100%).

[0044] With respect to the physical conditions for (IV), it is preferred that according to (IV) heating comprises heating to an initial temperature (Tp)initialin the range of from 270 °C to 290 °C for an initial time (T)initialin the range of from 5 to 15 minutes followed by cooling to a reaction temperature (Tp)lxnin the range of from 210 °C to 260 °C and maintaining heating at (Tp)ranfor a reaction time (T)lxnin the range of from 3.5 hours to 6.5 hours. It is also preferred that the reaction temperature (Tp)lxnis in the range of from 230 °C to 250 °C and maintaining heating at (Tp)lxnfor a reaction time (T)lxnin the range of from 4.5 hours to 6.5 hours. Preferably, according to (IV), during heating or maintaining heat, the absolute pressure is in the range of 10 to 20 pascal. It is preferred that according to (IV), during cooling to a temperature in the range of 15 °C to 30 °C the reaction is purged with nitrogen until the vacuum has been released and atmospheric pressure is reached. Preferably, according to (IV), during heating and / or cooling the reactor is mixed.

[0045] Regarding the characteristics of the third composition according to (V), it is preferred that the third composition obtained according to (V) has an intrinsic viscosity in the range of from 0.65 dl / g to 1.1 dl / g, preferably in the range of from 0.67 dl / g to 0.9 dl / g, more preferably in the range of from 0.67 dl / g to 0.8 dl / g, preferably in the range of from 0.68 dl / g to 0.75 dl / g, optionally measured according to DIN EN ISO 1628-1. It is also known that the intrinsic viscosity can be advantageously controlled to higher or lower values by controllingcrystallization temperatures or by altering monomer ratios, higher values being advantageous for articles that require more strength such as pressurized flasks (carbonated beverage flasks for instance). Preferably, the third composition obtained according to (V) has a number average molecular weight MN in the range of from 7,000 g / mol to 40,000 g / mol, preferably in the range of from 10,000 g / mol to 25,000 g / mol, more preferably determined by gel permeation chromatography optionally using a polystyrene standard, preferably under chromatography conditions under 60 °C. In some applications, such as those that require increased strength such as pressurized flasks or strong fibers, it is advantageous to have higher average molecular weight MN and the skilled person would adjust the foregoing range to be in the range of from 20,000 g / mol to 40,000 g / mol, preferably in the range of from 25,000 g / mol to 37,000 g / mol, more preferably in the range of from 27,000 g / mol to 35,000 g / mol. It is also preferred that the third composition obtained according to (V) has a glass transition temperature in the range of from 40 °C to 50 °C, preferably in the in the range of from 42 °C to 48 °C, measured with DSC according to ASTM D3418. Preferably, the third composition obtained according to (V) has a melting point temperature in the range of from 190 °C to 210 °C, preferably in the in the range of from 195 °C to 205 °C, measured with DSC according to ASTM D3418. It is preferred that the third composition obtained according to (V) has a crystallization temperature in the range of from 120 °C to 160 °C, preferably in the in the range of from 130 °C to 150 °C, measured with DSC according to ASTM D3418. Preferably, the third composition obtained according to (V) has a density in the range of from 1.28 g / ml to 1.42 g / ml, preferably in the in the range of from 195 °C to 205 °C, measured according to ASTM D1505.

[0046] According to (VI), it is preferred that the transferring of the composition comprising the polyester copolymer obtained according to (V) is to a granulator, a spinning system or an extrusion molding system. Preferably, according to (VI) the transferring of the composition comprising the polyester copolymer obtained according to (V) is to a granulator. It is further preferred that the granulator is an extruder, preferably a twin-screw extruder type. The granules are preferably extruded at a temperature in the range of from 200 °C to 290 °C, preferably in the range of from 210 °C to 260 °C, more preferably in the range of from 220 °C to 250 °C. The granules are preferably cooled immediately after extrusion, preferably by water cooling. Polybutylene succinate (PBS) is preferably added relative to the amount of terephthalic acid monomer (TA) in the range of from 0.1 wt.-% to 10 wt.-%, preferably of from 1 wt.-% to 8 wt.-%, more preferably of from 2 wt.-% to 7 wt.-%, (calculated as weight of PBS I weight of terephthalic acid monomer (TA) x 100%). Preferably, the granules are in the form of pellets or chips. It is also preferred that the granules are extruded with a nitrogen atmosphere.

[0047] According to (VI) the transferring of the composition comprising the polyester copolymer obtained according to (V) is also preferably to a spinning system. Preferably, fibers are extruded from the spinning system at a temperature in the range of from 200 °C to 260 °C, preferably in the range of from 210 °C to 250 °C, more preferably in the range of from 230 °C to 245 °C. It is preferred that the spinning oil is free of phthalates, MCDP,glycidol and B(E)TX aromatics. It is also preferred that the fiber or yarn obtained from the spinning system or a textile therefrom is further dyed at a temperature below 130 °C, preferably below 120 °C. Preferably, the fiber or yarn obtained from the spinning system or a textile therefrom is further dyed at a temperature in the range of from 90 °C to 125 °C, preferably in the range of from 95 °C to 120 °C, more preferably in the range of from 100 °C to 115 °C, more preferably in the range of from 105 °C to 115 °C. It is also preferred that the fiber or yarn obtained from the spinning system or textile therefrom is further dyed for a duration in the range of from 30 min to 240 min, preferably of from 45 min to 180 min, more preferably of from 60 min to 120 min. Preferably, the fiber, yarn or textile is dyed comprising- soaking the fiber in a solution of dye at a temperature in the range of from 50 °C to 70°C for a duration in the range of 10 min to 30 min followed by-heating to a temperature in the range of from 90 °C to 125 °C, preferably in the range of from 95 °C to 120 °C, more preferably in the range of from 100 °C to 115 °C, more preferably in the range of from 105 °C to 115 °C for a duration in the range of from 30 min to 240 min, preferably of from 45 min to 180 min, more preferably of from 60 min to 120 min, followed by- cooling to a temperature in the range of from 60 °C to 75 °C, removing the fiber from the dye solution and washing the fiber in water at a temperature in the range of 8 °C to 12 °C, followed by- soaking the fiber in a solution of dye at a temperature in the range of from 30 °C to 50°C for a duration in the range of 5 min to 10 min, followed by-heating to a temperature in the range of from 70 °C to 90 °C, for a duration in the range of from 15 min to 45 min, followed by- cooling to a temperature in the range of from 50 °C to 70 °C, removing the fiber from the dye solution and washing the fiber in water at a temperature in the range of 8 °C to 12 °C, followed by- soaking the fiber in water at a temperature in the range of from 40 °C to 50°C for a duration in the range of 5 min to 10 min, followed by- removing the fiber from the dye solution and washing the fiber in water at a temperature in the range of 8 °C to 12 °C, followed by- soaking the fiber in water at a temperature in the range of from 30 °C to 40°C for a duration in the range of 5 min to 10 min, followed by- removing the fiber from the dye solution and washing the fiber in water at a temperature inthe range of 8 °C to 12 °C.

[0048] A textile or textile intermediate is preferably fashioned from fiber or yarn by weaving, knitting or spinning systems preferably according to the present disclosure.

[0049] In general embodiments, it is preferred that according to (VI) the transferring of the composition comprising the polyester copolymer obtained according to (V) is to an extrusion molding system. In some embodiments, it is preferred that foil or sheets are extruded at a temperature in the range of from 200 °C to 260 °C, preferably in the range of from 210 °C to 250 °C, more preferably in the range of from 230 °C to 245 °C. Preferably, sheets are extruded. Films are also preferably extruded. Foils are also preferably extruded. It is also preferred in some embodiments that the third composition obtained according to (V) has been granulated in a granulator prior to measurement of any of the properties relating to the material of items 99 to 104. It is also preferred that the third composition obtained according to (V) has been granulated in a granulator, preferably according to any one of items 105 to 112, prior to transfer to a further process. Preferably, the further process is a spinning system, an extrusion molding system, an injection molding system or a printing system.

[0050] After granulation, the material is preferably dried in a vacuum oven prior to entering the further process. The drying is preferably conducted at a temperature in the range of from 80 °C to 120 °C, preferably of from 90 °C to 110 °C. Preferably, the drying is conducted for a duration in the range of from 4 hours to 12 hours, preferably 5 hours to 10 hours. The drying is conducted with a flow rate of air preferably in the range of from 25 L / min to 35 L / min. Preferably, the drying is conducted in air having a water content of 50 to 100 part per million by mass. Dry can be of importance in environments having high humidity when the polymer has been heated and it has been found that undried materials can in some conditions depolymerize. Accordingly, the vacuum drying may be conducted for longer or shorter periods depending on storage environment and local conditions. Thus, the skill person may also conduct the drying with a purged nitrogen vacuum system that may further operate under a protective nitrogen purge. Explicitly the duration of the drying may be adjusted by the skilled person with the knowledge that polyester articles according to the present disclosure show higher tendency to depolymerize in the presence of heat and water that may be dealt with by simply adjusting the time or atmosphere. Thus, combinable with the foregoing embodiments relating to drying, it is preferred that the drying is conducted for a duration in the range of from 1 to 48 hours, preferably in the range of from 4 to 24 hours, more preferably in the range of from 8 hours to 20 hours, more preferably 10 to 18 hours, and / or preferably 4 hours to 12 hours, preferably 5 hours to 10 hours. Concerning the pressure of the drying, it is preferred that the pressure under vacuum drying is maintained in the range of from 1.332 Pa to 1332 Pa, preferably of from 6.666 Pa to 66.66 Pa, more preferably of from 10.00 Pa to 16.66 Pa. Furthermore, the drying is preferably conducted in an atmosphere having a water content of 50 to 100 part per million by mass.

[0051] In general embodiments according to the present disclosure, it is preferred that thebiodegradable polyester article is free of antimony, preferably according to ISO 17294- 2:2016 wherein the water sample was prepared by digestion of granules according to ASTM D6691.

[0052] In general embodiments, it is also preferred that the biodegradable polyester article is free of titanium, preferably determined by elemental analysis.

[0053] In general embodiments according to the present disclosure, it is preferred that the biodegradable polyester article is free of heavy metal and fluorine according to EN 13432.

[0054] In general embodiments according to the present disclosure, it is preferred that the biodegradable polyester article is free of volatile organic compounds (VOC) according to EN 13432, preferably wherein the article is greater than 99 wt.-% dry mater (calculated as dry matter / total weight x 100%) according to EN 13432.

[0055] In general embodiments according to the present disclosure, it is preferred that the biodegradable polyester article is non-toxic according to OECD 202.

[0056] The present disclosure also features a further aspect of a biodegradable polyester article obtained according to any one of the claims.

[0057] It is noted that as used herein, the singular forms “a”, “an”, and “the”, include plural references unless the context clearly indicates otherwise. Thus, for example, reference to “a reagent” includes one or more of such different reagents and reference to “the method” includes reference to equivalent steps and methods known to those of ordinary skill in the art that could be modified or substituted for the methods described herein.

[0058] Unless otherwise indicated, the term "at least" preceding a series of elements is to be understood to refer to every element in the series. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the present invention.

[0059] The term "and / or" wherever used herein includes the meaning of "and", "or" and "all or any other combination of the elements connected by said term".

[0060] The term “less than” or in turn “greater than” does not include the concrete number. For example, “less than 20” means less than the number indicated. Similarly, “greater than” means greater than the indicated number, e.g., greater than 80 % means greater than the indicated number of 80 %.

[0061] Throughout this specification and the claims which follow, unless the context requires otherwise, the word “comprise”, and variations such as “comprises” and “comprising”, will beunderstood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integer or step. When used herein the term “comprising” can be substituted with the term “containing” or “including” or sometimes when used herein with the term “having”.

[0062] When used herein, “consisting of" excludes any element, step, or ingredient not specified in the claim element. When used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each instance herein any of the terms "comprising", "consisting essentially of" and "consisting of' may be replaced with either of the other two terms.

[0063] When used herein, the term "about" is understood to mean that there can be variation in the respective value or range (such as pH, concentration, percentage, molarity, time etc.) that can be up to 5 %, up to 10 % of the given value. For example, if a formulation comprises about 5 mg / ml of a compound, this is understood to mean that a formulation can have between 4.5 and 5.5 mg / ml.

[0064] It should be understood that this invention is not limited to the particular methodology, protocols, material, reagents, and substances, etc., described herein and as such can vary. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention, which is defined solely by the claims.

[0065] All publications cited throughout the text of this specification (including all patents, patent application, scientific publications, instructions, etc.), whether supra or infra, are hereby incorporated by reference in their entirety. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention. To the extent the material incorporated by reference contradicts or is inconsistent with this specification, the specification will supersede any such material.

[0066] The content of all documents and patent documents cited herein is incorporated by reference in their entirety.

[0067] A better understanding of the present invention and of its advantages will be provided by the following examples, offered for illustrative purposes only. The examples are not intended to limit the scope of the present invention in any way.EXAMPLES

[0068] Example 1. Preparation of chip (granule)The following were used for preparation of intermediate granulated chips in accordance with the invention:A master batch (slurry) containing 61.62 wt.-% terephthalic acid CAS 100-21-0, 5.18 wt.-% dimethylglutarate CAS 1119-40-0, 0.12 wt.-% sodium dimethyl 5-sulfoisophthalate CAS 3965-55-7 and 32.78 wt.-% ethylene glycol CAS 107-21-1 , were reacted in an initial a two stage esterification using conditions and reactors according to US8614280B2 examples. An aluminum salt catalyst was added analogous to the examples of US7144614B2 during the two stage esterification as well as 50 ppb fluorescent particles as a tracker / marker and 0.3 wt.-% delusterant having molecular formula (CaO)a(Al2O3)b(CaSO4)c(H2O)d. The obtained prepolymers were then heated to 175 °C with nitrogen purge followed by heating at 280 °C for 4.5 hours, the composition was then briefly (5 min) heated to 285 °C under nitrogen purge followed by transfer to a vacuum reactor for a 6-hour period at 240 °C at 100 milli-torr (13.33 Pa). The vacuum was released under nitrogen and the resultant composition cooled to 22 °C that was then granulated and extruded with a hopper and middle temperature set at 250 °C and the die was set to 240 °C, the residue was collected as chips.

[0069] Thermal propertiesThe obtained resin had an intrinsic viscosity of 0.7 dL / g measured by DIN EN ISO 1628-1, a glass transition temperature of 45 °C measured by DSC ASTM D3418, a melting point of 238 °C measured by DSC ASTM D3418, a density of 1.35 g / mL measured according to ASTM1505, a crystallization temperature of 140 °C measured by DSC ASTM D3418 and a thermal decomposition temperature of 363 °C.

[0070] Marine BiodegradabilityThe resin was further determined to be have 93% Biodegradability in seawater at 30 ± 2 °C according to ASTM D6691. Biodegradability is carried on according to ASTM D6691 - 17 official method at 30 ± 2 °C. The test started on April 27th 2023 and ended on August 04th 2023 (for the plateau phase)Information on seawater and reference material (cellulose)The natural seawater was collected at Boccale, Livorno (43.475029 N, 10.329790 E) on April 27th 2023. The seawater was added with inorganic nutrients (0.5 g / l NH4CI and 0.1 g / l of KH2PO4). The pre-incubation of the inoculum has been performed for 5 hours at 30°C.The reference material is microcrystalline cellulose, average dimension of the particles is 20 pm, produced by ALDRICH, distributed by SIGMA ALDRICH SRL, Code number 310697- 500G, Lot number MKCL 9441.The samples of both the reference cellulose and the tested resin were degraded at constant 30 °C over 99 days with 3 samples per each reference and test compounds. The resultswere then averaged after subtracting background CO2 emission and the results are presented in Figure 1.The tested material complies with the requirements of the biodegradability degree in marine environment, providing:• average absolute biodegradation degree 93,7% ± 2,0% after 99 days,• average relative biodegradation degree 95,2% ± 2,2% after 99 days,• lag phase duration is lower than 1 day.The residual percentage of not-detected CO2 could be due to the experimental uncertainty and measurements during the overall test duration.The resultant solutions were then used for analysis of elements.

[0071] Environmental safety (toxicity) according to OECD 202The evaluation of the acute toxicity of the aquatic biodegradation residuals by means of invertebrate Daphnia magna is in line with OECD 202 - Daphnia sp., Acute Immobilization Test (2004). Toxicity was evaluated by means of Daphnia magna, a freshwater crustacean, of which the newborns obtained from dormant forms (ephippia) are used. The ephippia are supplied by MicroBioTests Inc. (Belgium) and commercialized by Ecotox (Italy).The chemical characteristics of Standard Freshwater (SFW) are:64.75 mg / L NaHCO3294 mg / L CaCI2-2H2O 123.25 mg / L MgSO4-7H2O5.75 mg / L CaCI2The Standard Freshwater was prepared according to ISO 6341 and OECD 202. Microbial inoculum was obtained from activated sludge coming from a sewage-treatment plant (Consorzio Aquapur - Porcari) treating domestic and industrial wastewater. Sludge was filtered over a 75 pm sieve and decanted for 10 minutes; resulting supernatant was removed and replaced with an equal volume of SFW.The test material was added in a 0.1% concentration to Standard Freshwater that was spiked with a microbial inoculum. The composition of the control series and the test series is:The material was incubated in the dark at a constant temperature of 30 ± 2°C for a period established according to the following rules related to the progress of the biodegradability test in sea water:• 3 months if during this period the biodegradation in sea water has reached 60%;• if biodegradation in seawater has reached 90% in less than 3 months, the stabilization period is identical to that required for the biodegradation process to reach 90%;• in all other cases the maximum period is 6 months.During the incubation period the content of the reactors was periodically stirred (at least 3 times a week) in order to promote oxygenation. Samples were incubated for 70 days, since during this incubation period sample reached 90% biodegradation in sea water.Daphnia magna ephippia are sexual eggs protected by a chitinous capsule that can be stored at 2-8°C for long periods without losing their viability. When the ephippia are placed in specific environmental conditions and triggers, they hatch in about 3 days originating neonates which can be immediately used for the assessment of toxicity tests.Three days before the beginning of the test, ephippia are plenty washed with tap water in a plastic sieve, placed in a hatching petri dish containing freshwater and incubated at 20 ± 2°C in the presence of a light source. Ephippia hatch on day 3 and the resulting neonates must be employed within 24 hours to perform the toxicity tests.The toxicity tests are performed in a polycarbonate multiwell test plate composed of 6 rinsing wells and 24 wells for the test series. The rinsing wells prevent dilution in the multiwell cups during the transfer of the test organisms from the hatching petri dish to the test plate. Solutions and test organisms are placed in the test wells and kept there in a static system, without any renewal of the test solutions.In order to increase the statistical significance, the tests were performed in triplicate.For the execution of the test:• 10 ml of the different series (SFW, Control and Test series) are added to the rinsing well and to the 4 test wells;• at least 20 actively swimming neonates are transferred with a micro-pipet from the hatching petri dish into each rinsing well;• 5 neonates are transferred from the rinsing well into the 4 wells of each test series;• the multiwell plate is covered with a parafabric strip and incubated at 20 ± 2°C in darkness for 48 hours;• after 24 and 48 hours the number of dead and immobilized neonates is recorded;• at the beginning and the end of the test pH and dissolved oxygen values are recorded.OECD 202 defines “Immobilisation” as: those animals that are not able to swim within 15 seconds, after gentle agitation of the test vessel are considered to be immobilized (even if they can still move their antennae). The pH was measured with a pH meter mod. Seven Easy (Mettler Toledo). Dissolved oxygen is measured with an optical probe mod. Intellical LDO101(Hach Lange). The results are expressed in mg / l.For test validity:• in control SFW series at least 90% of test organisms must survive and remain mobile for the duration of the test. In other words, test is not valid if more than 10% of the control organisms are immobilized during the 48-h test period;• the dissolved oxygen (DO) concentration at the end of the test should be > 3 mg / l in control and test vessels.The number of the mobile Daphnia nauplii after 24 hours and 48 hours:Percentage mobility of Daphnia neonates after 24- and 48-hour expositionThe pH and dissolved O2 values at the initial time of the testThe pH and dissolved O2 values at the initial time of the testThe Daphnia neonates in the standard freshwater (SFW) showed an average mobility of 100% after 48 hours, which means that the pass level of 90% mobility was reached.Dissolved oxygen in control and test vessels at the end of the test was higher than 3 mg / l. Based on these data, the test can be considered valid.The requirement prescribes that at least 90% of the tested organisms should remain mobile at the end of the test (48 hours). In the sample series mobility of the Daphnia neonates was observed as 96.7% after 24 hours and 91.7% after 48 hours. From these results it can be concluded that the addition of 0.1% sample to a chemically defined (mineral) aqueous medium that was spiked with micro-organisms, does not exert a negative effect on the mobility of Daphnia magna after a 70-day incubation period at 30°C. Therefore, the ecotoxicity of the material is non-toxic according to OECD 202 standard.

[0072] Antimony testing EN ISO 17294-2:2016A sample of the solution of marine biodegraded material from above was analyzed according to EN ISO 17294-2:2016 and it was determined that had 1.62 micrograms of antimony per liter of tested solution with a standard deviation of 0.34. The value is within the range of antimony found in sea water.

[0073] Heavy metal and fluorine testing EN 13432A sample of the solution of marine biodegraded material from above was analyzed according to EN 13432. The results are below.

[0074] Example 2: Preparation of a fiber by melt spinningMelt spinning: The spinning oil used must be a product that is free of phthalates, MCDP, glycidol, B(E)TX aromatics, as residues remain in the yarns or enter the water cycle when washed out. Takemoto oil TX-221 was used for the spinning. The copolymer must be dried very well before melting. The drying time is significantly longer than with conventional PET- polyester chips before melting. Alternatively, if the copolymer is fed directly into the melt spinning system, drying is not necessary.A conventional melt spinning system can be used for fibers or filaments. The invention was tested on systems from Fournee and separately from Sulzer. The material is more elastic than conventional PET polyester. During stretching, the godets must rotate faster and generate more tension than with conventional material. The temperature on the godets should be set 15 degrees Celsius lower than with conventional PET polyester. In order to obtain an optimal fiber / filament and to run the spinning system or injection at a high, normal speed, the melt should be <250 degrees Celsius, it must be below the point used for conventional PET polyester.Granulate according to Ex. 1 was transferred to a melt spinning system after drying and a fiber having a diameter of 161 ±3 pm was made.The fiber was then woven into a fabric and tested alongside the resin of Ex. 1 and found to have very similar properties with regards to biodegradation, non-toxicity and to be similarly free of the elements as noted above for Example 1.

[0075] Example 3: Fabric flammability testingThe fiber of example 2 was loosely woven into a fabric and tested for flammability according to DIN EN ISO 4589-2. The fibers were loose, prepared as padding for testing and preconditioned according to DIN EN ISO 139 (20 °C, 65 % hum.), the conditions in a test chamber were room temperature (21 °C) with a relative humidity of 41.3%. A gas flow of 18L / min corresponding to a flow rate of 3-4 cm / sec was used.The LOI value (determined to be 26% O2 in the present case) indicates the oxygen content at which the sample just bums under the test conditions. Below this oxygen concentration, the sample did not bum under the test conditions. This type of test is typically intended for woven, knitted or other specimens. In the present order, however, it was fibers, which made an adapted sample preparation necessary. About 0.4 g of the fiber material was taken for each test and a fiber bundle measuring about 4 x 4 cm was formed from it. This bundle of fibers was clamped about halfway between two glass slides for confirmation. This assembly was then mounted in the standard test sample frame (140 mm x 50 mm) approximately 2 cm below the top edge. The sample preparation took place under the climatic conditions mentioned above. The prepared samples were hermetically sealed in a PE bag and onlyremoved individually directly before the respective test, so that the influence of the climate in the test room was as small as possible. The flame hit the fiber bundle at an angle from the side 0 - 6 mm below the upper edge of the fiber bundle and was tracked when the material began to melt. The test result is valid under the conditions of this test. Furthermore, the polyester fabric has a slightly better LOI value than an average wool (25.2 % O2) and is far superior in comparison with conventional polyester (20.2 % O2).The same material was also tested under the German flammability standard DIN4102-1 and successfully passed the examination for building material B1.

[0076] Example 4: Properties of yarn and fabricsA yarn was produced similar to example 2 and further tested according to DIN EN ISO 139:2011-10. Results: Ex. 4 yarn: 0.39% I Reference yarn of PET: 0.5%. The values confirm that presently disclosed yarn has a lower moisture absorption comparted to conventional PET yarns, although it has hydrophilic properties (high water absorption). This indicates excellent material moisture management and is advantageous for quick-drying applications, e.g. sportswear or underwear.The result has been verified by making a fabric with said yarn and testing under standardized test according to AATCC 201: Pro Dry - evaporation rate (acc. AATCC 201):- Ex. 4 unfinished: 1.8 ml / h- PES unfinished: 0.8 ml / hThe fabric accordingly is more quickly dried than a conventional PES material.As noted above, said fabric was also tested for hydrophilicity against a conventional PET reference fabric in the following tests:(1) DIN 53823 Ex. 4 Fabric: 75.0%, Reference PET Fabric: 24.3%.(2) ISO 9073-6 (4) Ex. 4 Fabric: 2s, Reference PET Fabric: <120s(3) Contact angle Ex. 4 Fabric: immediately soaking, Reference PET Fabric: 125.

[0077] Fabrics according to the invention have also surprisingly been successfully dyed at 100 °C in aqueous solutions. Fabrics based on the presently disclosed materials can be dyed at substantially lower temperatures. PET-based fabrics require 130°C when dyeing, fabrics based on the inventive materials require only 100°C, without any compromise on quality or color-fastness.Respective energy savings have been calculated according to laboratory scale. Deviation of laboratory to industry difference and have been assumed accordingly.For a regular dyeing process, energy consumption can be analyzed in 3 process stages. The table below shows the comparison of energy use between conventional PET and the presently disclosed material, where the main energy saving potential is given through a lower temperature in phase 1. This has positive effects on both following phases.

[0078] Example 5: Preparation and properties of a tensile barThe example was prepared according to example 1 except 2.5 wt.% powdered calcium carbonate obtained from mussels (calculated relative to total weight of the composition) was added in addition to the vacuum reactor. The resultant chips were dried at 80 to 100 °C for 6 to 8 hours under an air flow of 28 L / min with air having 50 to 100 ppm water. The chips were then extruded as a test bar. The bar was tested for Heat Deflection Temperature (HDT) according to ASTM D648 and found to have an HDT at 66PSI of 46 °C. The bar was furthertested under notched Izod tests according to ASTM D256-97 (result of 27 J / M or 0.5 ft-lbs / in) and unnotched Izod ASTM D4812 (result of no break).Example 6: Barrier filmA barrier film having a thickness of 25 pm was made from chips according to Ex. 1 with the exception that delusterant and the fluorescent dye were not added. The resultant film was subsequently tested for water vapor transmission rate on a Mocon Permatran W Water Vapor Transmission tester and found to have a water transmission rate of 3 (g mm) / (m2day atm) (8 (g mil) / (100 in2day atm)). The film was further tested according to ASTM D3985 and found to have an O2 transmission rate of 2.2 (mL mm) / (m2day atm) ( 5 (mL mil) / ( 100 in2day atm).Example 7: SheetA sheet having a thickness of 250 pm was made from chips according to Ex. 1 with the exception that delusterant and the fluorescent dye were not added. The sheet was subsequently tested for gloss according to ASTM D2457 and found to have a gloss of 102 at 200angle and 100 at a 450angle, haze was measured at 1.66 % according to ASTM D1003. The tensile strength MD was found to be 65 MPa and tensile strength TD was found to be 53 MPa both measured according to ASTM D882. The tensile modulus MD was found to be 2172 MPa and tensile modulus TD was found to be 1751 MPa both measured according to ASTM D882. Spencer impact was determined to be 4.1 J / mm according to ASTM D3420 and the tearing resistance was determined to be 17 N / mm according to ASTM D1922.Example 8: Cups and bottlesChips were prepared according to example 1 with the exception that neither pigments nor delusterant were added. The condensation product was allowed to crystalize between 180 and 240 °C and condense further to achieve viscosities according to or slightly higher than Ex. 1 (in the range of 0.7 to 1.0). It is noted that copolymers according to the present disclosure crystalize more slowly than conventional pet. It is also noted that the viscosity and crystallinity of the resultant polymer can also be increased by decreasing the amount of dimethylglutarate (glutaric acid dimethyl ester). The resultant granulate / chips were carefully dried in a vacuum oven for 16 hours at 100 milli-torr (13.33 Pa) pressure and a temperature in the range of 90°C to 100°C until a water content below 50 ppm (weight) was achieved determined by either thermogravimetric analysis (TGA) or Karl Fischer titration, preferably by Karl Fischer titration. The dried chips / granulate was then used to form bottles via injection molding and stretch-blow molding) and drinking cups (via film extrusion and thermoforming) were manufactured. The obtained copolymer-based flasks and cups had exceptional claritywhen compared to conventional PET products by simple visual inspection and no negative flavors.Example 9: Comparative depolymerization experimentsA set of depolymerization experiments was conducted in order to evaluate the reactivity and the potential recyclability of the biodegradable polyester articles according to the present disclosure.Copolymer fibers and chips according to example 1 were prepared. A comparative fiber quality PET reference material was purchased having an average molecular weight of approximately 20,000 and a density of approximately 1.38 g / ml. Both fibers and chips of the copolymer and reference PET material were prepared. Fibers had a diameter of 250 micrometers.General procedure: A polymer sample was dried in a vacuum oven at 100 milli-torr (13.33 Pa) pressure and 90°C for 16 hours followed by cooling and release under a dry nitrogen atmosphere. 15 grams of said dried polymer was added to a suitable flask equipped with a stir bar and a thermometer. A 2M aqueous sodium hydroxide solution was added with stirring to the flask comprising the polymer with rapid stirring (100 mL, calculated for a slight excess of hydroxide assuming 254 g / mol per diester monomer). The reaction progress was visually monitored for complete dissolution of the polymer while simultaneously measuring the temperature. The results are summarized below for both fiber and chip samples. Initial temperature was measured immediately (21 °C for all samples) and final temperatures are taken at the time for complete dissolution. The reaction was stirred overnight and partially concentrated to 50 mL, cooled to 4 °C for 24 hours and then filtered to remove the precipitate which was dried by pulling vacuum on the filtrate followed by weighing of the dried recovered white precipitated sodium diacid mixtures. Results are presented below.(1) Time to complete dissolution by visual inspection(2) Dry weight of the obtained filtered precipitate (predominantly sodium salt of terephthalic acid)In view of the results above, it is clear that polyester articles according to the present invention show increased reactivity towards hydrolysis while providing higher return of thediacids. Accordingly, polyester articles according to the present have potentially improved recyclability relative to conventional PET.Example 10: Further comparative experimentsExperiments without nitrogen purgeExperiment 1 was repeated without nitrogen purging at each one of the indicated purging steps. Each time a nitrogen purge was omitted resulted in lower molecular weights, lower viscosities, increased oligomers and in the cases involving heating above 250 °C, extensive depolymerization.Experiments without drying chipsAttempts to produce either fibers by spinning or molded products by injection molding from stored chips resulted in either weak fibers or brittle molded products if the chips were not vacuum dried at 90 °C to 100 °C for 16 hours at 100 milli-torr (13.33 Pa) prior use. If the chips were immediately used after production (i.e. not stored), drying was unnecessary in the presence of a nitrogen purge when moving the material from reactor to granulator or granulator to a spinning or molding system.Overheating during spinningAttempts to heat the material above 255 °C during spinning led to increased fiber breakage, likely due to weakening from depolymerization in the presence of water vapor when exiting the spinner.Example 11 : Temperature nuclei free (TNF)Chips according were prepared according to Ex 1 , vacuum dried at either 90 °C or 100 °C in a vacuum oven at 100 milli-torr (13.33 Pa) for 16 hours, vented under a dry passive nitrogen atmosphere resulting in a material with the following properties:A series of DSC measurements under an inert atmosphere of dry nitrogen were conducted on a sample dried at 100 °C by heating a sample of the above material to a preset temperature (Thoid) above the Tmtemperature, holding the DSC sample at that temperature for 2 minutes followed by controlled cooling whilst observing the sample for crystallization. The sample was then reheated to a new temperature set higher than the previous setting followed by controlled cooling and observation with respect to crystallization, the peak of the observed crystallization is listed below in relation to the set hold temperature. The most relevant results for the above Ex. 1 are given as follows:As can be seen by the results, changes in the relative amounts of crystallized nuclei do not appear to be especially persistent when the sample is heated to 250 °C or above. This result being relevant for spinning fibers or creating moldings from a polyester article according to the present disclosure.Example 12 Melt spinning conditions for improving tenacityMaterial was prepared according to Ex 1 and had the properties as listed above in Ex. 11. The material was dried as detailed above in Ex. 11 immediately prior to spinning experiments.A FET spinning-drawing-winding machine (M93) was used with settings specific for each material. An extruder with screw 032 mm and compression ratios of 2.0 and 3.25 were used along with a gear pump with a capacity of 3 cc / rev. The height of the spin line was set at 4500 mm. The spinneret had 48 orifices being 250 microns in diameter and 400 microns in length (L / R of 1.6). The extruder was maintained to have an inlet temperature of 245 °C and an outlet temperature of 250 °C, the melt temperature was maintained at about 245 °C and the spinneret was maintained between 251 °C to 250 °C and a screw speed of either 10 rpm or 8.9 rpm. Melt pump speed was maintained either at 5 rpm or 9 rpm with a pressure of 17 to 48 bar depending on the sample. The drawing ratio, defined as the ratio of the take-up speed of the fiber to the extrusion speed of the molten polymer from the spinneret was varied from 3.0 to 5.0.The linear density of spun yarns was determined with a Zweigle type L232 wrap reel machine and an analytical balance. 50 meters of yarn per sample was collected with a pretension of 5 mN / tex (n=3). Tensile properties were determined according to ASTM D2256 / D885 using an Instron Tensile Ester model 5564. The tensile tester was equipped with a 1 kN load cell and pneumatic yarn grips. A crosshead speed of 250 mm / min and gauge length of 250 mm was used. Each sample was measured 5 times with a pretension of 5 mN / tex and a yarn twist of 60 TPM, values below are reported as averages.Example 13Material was prepared according to Ex. 1 accept the ratio of dimethylglutarate (Comp. 1) and sodium dimethyl 5-sulfoisophthalate (Comp. 2) was varied. Test fabrics were woven having identical thread count and the fabrics were exposed to dye in a dye bath at 115 °C for 1 hr. After fixing, cooling and drying the color and feel performance was noted as follows.The invention is further characterized by the following items:1. A process for producing a biodegradable polyester article comprising:(I) providing a slurry comprising a source of terephthalic acid monomer, a source of ethylene glycol monomer, a source of monomer according to structure (i):, wherein X is in the range of from 2 to 18, wherein R is a C1 to C6 hydrocarbon or H, and a source of monomer according to structure (ii):d R’ is a C1 to C6 hydrocarbon or H, and an aluminum salt catalyst; wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of ethylene glycol monomer (EG) in the range of from 1 : 1.2 to 1 : 1.6 (calculated as moles of (TA) I moles of (EG)); wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (i) (strj) in the range of from 1 : 0.04 to 1 : 0.12 (calculated as moles of (TA) I moles of (str_i)); wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (ii) (strji) in the range of from 2000 : 1 to 650 : 1 (calculated as moles of (TA) I moles of (strji)) ; wherein the aluminum salt catalyst (Al-cat) is present in a molar amount relative to the source of monomer of terephthalic acid (TA) (calculated as moles of Al present in the aluminum salt catalyst I moles of TA monomer * 100 mol.-%) is in the range of from 0.01 mol.-% to 0.0001 mol.-%;(1.1) reacting the slurry provided according to (I) in a first esterification;(1.2) obtaining a first composition comprising bis(2-hydroxyethyl)terephthalate (BHET);(II) adding one or more further components to the first composition obtained according to (1.2) to obtain a mixture;(11.1) reacting the mixture obtained according to (II) in a second esterification;(11.2) obtaining a second composition from (11.1) comprising pre-polymers (precondensed polyester) comprising independently at each occurrence monomers of bis(2-hydroxyethyl)terephthalate (BHET), monomers according to structure (i) and / or monomers according to structure (ii);(Ill) heating the second composition obtained according to (II.2) comprising;(111.1) purging with nitrogen while heating the second composition to a temperature in the range of from 160 °C to 190 °C;(111.2) after reaching the temperature according to (III .1), heating the second composition with the nitrogen purge to a temperature in the range of from 240 °C to 290 °C for a duration in the range of from 3.5 hours to 6 hours;(111.3) the composition is transferred to a further reactor after heating according to (HI.2);(IV) heating the transferred composition in a reactor according to (III.3) to a temperature in the range of from 210 °C to 290 °C for a duration of from 4 hours to 7 hours at an absolute pressure in the range of 10 to 30 pascal; and followed by cooling to a temperature in the range of 15 °C to 30 °C while simultaneously purging with nitrogen;(V) obtaining a third composition from (IV) comprising a polyester copolymer comprising PET monomers terephthalate and ethylene glycol interspersed independently from one another at each occurrence monomers of bis(2- hydroxyethyl)terephthalate (BHET), monomers of structure (i) and monomers of structure (ii);(VI) transferring the composition comprising the polyester copolymer obtained according to (V) to any one of a granulator, a spinning system, an extrusion molding system, an injection molding system or a printing system;(VII) obtaining a biodegradable polyester article. The process of item 1 , wherein the biodegradable polyester article is in the form of a textile, a fiber, a filament, a yarn, a chip, a granule, a film, a foil, a sheet, a hollow molding, an injection molded article or a printed article. The process of item 1 or 2, wherein the biodegradable polyester article is in the form of a textile, a fiber, a yarn, a granule, an injection molded article or a printed article, preferably a textile, a fiber, a yarn, a granule or an injection molded article, more preferably a textile, a fiber, a yarn or a granule. The process of any one of the preceding items, wherein the biodegradable polyester article is in the form of a granule. The process of any one of the preceding items, wherein the biodegradable polyester article is in the form of a fiber.The process of any one of the preceding items, wherein the biodegradable polyester article is in the form of a yarn. The process of any one of the preceding items, wherein the biodegradable polyester article is in the form of a textile. The process of item 7, wherein the biodegradable polyester textile is in the form of a net, a floor covering, a fabric or a garment. The process of item 7 or 8, wherein the biodegradable polyester article is in the form of a net The process of item 9, wherein the net is for use in anchoring and / or mooring, preferably for use in anchoring and / or mooring for marine wind turbine towers. The process of any one of the items 7 to 10, wherein the textile is a fabric for garment production. The process of any one of the items 7 to 11 , wherein the textile is a fire-resistant fabric according to DIN 4102-1. The process of any one of the preceding items, wherein the biodegradable polyester article is in the form of a foil, a film, a sheet, a hollow molding, an injection molded article or a printed article. The process of any one of the preceding items, wherein the biodegradable polyester article is in the form of a film or a foil. The process of any one of the preceding items, wherein the biodegradable polyester article is in the form of a hollow molding. The process of any one of the preceding items, wherein the biodegradable polyester article is in the form of an injection molded article. The process of any one of the preceding items, wherein the biodegradable polyester article is in the form of a printed article, preferably a 3D or a 2D printed article, more preferably a 3D printed article. The process of any one of the preceding items, wherein the biodegradable polyester article is a marine biodegradable polyester article, a soil biodegradable polyester article or both a marine biodegradable polyester article and a soil biodegradable polyester article. The process of any one of the preceding items, wherein the biodegradable polyester article is a marine biodegradable polyester article, preferably according to ASTM D6691.The process of any one of the preceding items, wherein the biodegradable polyester article is a soil biodegradable polyester article, preferably according to ASTM D5988 or ISO 17556, more preferably ASTM D5988. The process of any one of the preceding items, wherein the biodegradable polyester article has a biological degradability in the range of from 80 wt.-% to 100 wt.-% (calculated as the final weight I the initial weight x 100%), preferably in the range of from 90 wt.-% to 99.9 wt.-%, more preferably in the range of from 92 wt.-% to 99 wt.-%, optionally determined according to ASTM D6691 or ASTM D5988. The process of item 21 , wherein the biodegradable polyester article is biodegradable in the range of from 80 wt.-% to 100 wt.-% within N days and N is in the range of 1 to 99 days (calculated as the final weight measured on the Nthday / the initial weight x 100%), preferably in the range of from 90 wt.-% to 99.9 wt.-% within N days and N is in the range of 50 to 99 days (calculated as the final weight measured on the Nthday / the initial weight x 100%), more preferably in the range of from 92 wt.-% to 99 wt.-% within N days and N is in the range of 70 to 99 days (calculated as the final weight measured on the Nthday / the initial weight x 100%), optionally determined according to ASTM D6691 or ASTM D5988. The process of any one of the preceding items, wherein according to (I) the terephthalic acid monomer source is either terephthalic acid or a C1 to C6 diester of terephthalic acid, preferably is terephthalic acid. The process of any one of the preceding items, wherein according to (I) the terephthalic acid monomer source is virgin grade terephthalic acid, recycled terephthalic acid or a mixture of virgin grade terephthalic acid and recycled terephthalic acid. The process of any one of the preceding items, wherein according to (I) the terephthalic acid monomer source is virgin grade terephthalic acid. The process of any one of the preceding items, wherein according to (I) the terephthalic acid monomer source is recycled terephthalic acid. The process of any one of the preceding items, wherein according to (I) the terephthalic acid monomer source is a mixture of virgin grade terephthalic acid and recycled terephthalic acid. The process of any one of the preceding items, wherein according to (I) the terephthalic acid monomer source is a mixture of virgin grade terephthalic acid and recycled terephthalic acid and the weight ratio of virgin grade terephthalic acid to recycled terephthalic acid is in the range of 10 : 1 to 1 :2, preferably in the range of from 9 : 1 to 1 :1 , more preferably in the range of from 5 : 1 to 2:1.The process of any one of the preceding items, wherein according to (I) the ethylene glycol monomer source is ethylene glycol, preferably being recycled ethylene glycol, virgin ethylene or ethylene glycol from a biological process. The process of any one of the preceding items, wherein according to (I) the source of monomer according to structure (i) is recycled or virgin grade, preferably is recycled dimethyl gluturate or virgin grade dimethyl gluturate. The process of any one of the preceding items, wherein according to (I) the source of monomer according to structure (i):the range of from 2 to 12, more preferably in the range of 2 to 6, more preferably being 2 or 3; wherein R is a C1 to C6 hydrocarbon, preferably is a C1 to C3 hydrocarbon, more preferably is methyl or ethyl, more preferably is methyl. The process of any one of the preceding items, wherein according to (I) the source of monomer according to structure (i) comprise, preferably consist of, dimethylglutarate, preferably according to structure (i-a):The process of any one of the preceding items, wherein according to (I) the source of monomer according to structure (ii) is either recycled or virgin grade, preferably is recycled sodium dimethyl 5-sulfoisophthalate or virgin grade sodium dimethyl 5- sulfoisophthalate. The process of any one of the preceding items, wherein according to (I) the source of monomer according to structure (ii):up consisting of S(O)OM, S(0)20M, and C(O)OM, more preferably is more preferably is S(0)20M and M is a cation, preferably M is an alkaline metal or an alkaline earth metal, more preferably M is Li, Na, K, Mg or Ca, more preferably M is Na; wherein R’ is a C1 to C6 hydrocarbon, preferably is a C1 to C3 hydrocarbon, more preferably is methyl or ethyl, more preferably is methyl. The process of any one of the preceding items, wherein according to (I) the source of monomer according to structure (ii) comprise, preferably consist of, sodium dimethyl 5- sulfoisophthalate, preferably according to structure (ii-a):The process of any one of the preceding items, wherein according to (I) the aluminum salt catalyst is according to structure (iii):wherein R1is selected from the group consisting of C5 to C20 aromatics,M is selected from the group consisting of Li, Na, K, Be, Mg, Ca, Sr, Ba, Mn, Ni, Cu and Zn, R2is a C1 to C20 hydrocarbon, R3is a C1 to C20 hydrocarbon, Y+Z is 4 and Y is in the range of 1 to 3.The process of item 36, wherein structure (iii) is according to structure (iii-a):(iii-a), whereinM is selected from the group consisting of Li, Na, K, Be, Mg, Ca, Sr, Ba, Mn, Ni, Cu, and Zn, R2is a C1 to C20 hydrocarbon, R3is a C1 to C20 hydrocarbon, R4is a C1 to C20 hydrocarbon, OH, Cl, F, NO2 or H, R5is a C1 to C20 hydrocarbon, OH, Cl, F, NO2 or H, Y+Z is 4 and Y is in the range of 1 to 3, preferably wherein the phosphorous comprising ligand comprised by (iii-a) is monoethyl 3,5-di-tert-butyl-4- hydroxybenzylphosphonate (CAS Nr. 66165-37-5). The process of item 36 or 37, wherein M is selected from the group consisting of Li, Na, K, Mg, Ca, Mn, Ni, Cu, and Zn, preferably selected from the group consisting of Li, Na, K, Mg, Ca, and Zn, more preferably selected from the group consisting of Li, Na, K, Mg, and Ca, more preferably selected from the group consisting of Li, Na and Ca, more preferably is Li, Na or Ca. The process of any one of items 36 to 38, wherein R2is a C1 to C8 hydrocarbon, preferably R2is a C1 to C6 hydrocarbon, preferably R2is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl and iso-butyl, more preferably R2is methyl, ethyl, n-propyl or isopropyl, more preferably R2is methyl or ethyl. The process of any one of items 36 to 39, wherein R3is a C1 to C18 hydrocarbon, preferably R3is a C1 to C12 hydrocarbon comprising a 1 ,3-dicarbonyl or a straight chain hydrocarbon, preferably R3is selected from the group consisting of acetylacetonoate, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl and iso-butyl, more preferably R3is acetylacetonoate, methyl, ethyl, n-propyl or isopropyl, more preferably R3is acetylacetonoate, methyl or ethyl. The process of any one of items 37 to 40, wherein R4is a C1 to C6 hydrocarbon, OH, Cl, F, NO2 or H, preferably is a C1 to C5 hydrocarbon, OH, Cl, F, NO2 or H, more preferably is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl or iso-butyl, more preferably is H, methyl, ethyl, isopropyl, or t-butyl, more preferably is H, methyl or t- butyl.The process of any one of items 37 to 41 , wherein R5is a C1 to C5 hydrocarbon, OH, Cl, F, NO2 or H, preferably is a C1 to C3 hydrocarbon, OH, Cl, F, NO2 or H, more preferably is a OH, NO2 or H, more preferably is a OH or H. The process of any one of items 36 to 42, wherein according to (I) Y+Z is 4 and Y is 2 or 3. The process of any one of the preceding items, wherein according to (I) the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of ethylene glycol monomer (EG) in the range of from 1 : 1.3 to 1 : 1.5, preferably in the range of from 1 : 1.38 to 1 : 1.47, (calculated as moles of (TA) I moles of (EG)). The process of any one of the preceding items, wherein according to (I) the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (i) (strj) in the range of from 1 : 0.06 to 1 : 0.10 (calculated as moles of (TA) I moles of (strj)). The process of any one of the preceding items, wherein according to (I) the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (ii) (strji) in the range of from 1500 : 1 to 700 : 1 (calculated as moles of (TA) I moles of (str_ii)), preferably in the range of from 1000 : 1 to 800 : 1 (calculated as moles of (TA) I moles of (strji)). The process of any one of the preceding items, wherein according to (I) the aluminum salt catalyst (Al-cat) is present in a molar amount relative to the source of monomer of terephthalic acid (TA) (calculated as moles of Al present in the aluminum salt catalyst I moles of TA monomer * 100 mol.-%) is in the range of from 0.01 mol.-% to 0.001 mol.- %. The process of any one of the preceding items, wherein according to (1.1) the first esterification is carried out at a temperature in a range of from 180 °C to 260 °C, preferably of from 220 °C to 250 °C. The process of any one of the preceding items, wherein according to (1.1) the first esterification has a pressure in the range of from 0.6 bar to 1.2 bar, preferably of from 0.8 bar to 1.1 bar. The process of any one of the preceding items, wherein according to (1.1) the first esterification is carried out for a duration of from 0.5 hour to 2.5 hours, preferably in the range of from 1 hour to 2 hours. The process of any one of the preceding items, wherein according to (1.2) the first composition comprises bis(2-hydroxyethyl)terephthalate (BHET) in a range of from 70 wt.-% to 100 wt.-% (calculated as the weight of BHET I the total weight of all components present x 100%), preferably in a range of from 80 wt.-% to 99 wt.-%, more preferably in a range of from 90 wt.-% to 98 wt.-%.The process of any one of the preceding items, wherein (I) further comprises(1.3) removing unreacted ethylene glycol and recycling the ethylene glycol after purification by distillation to the slurry provided in (I). The process of any one of the preceding items, wherein (I) further comprises(1.4) removing water from the first esterification to a waste treatment system. The process of any one of the preceding items, wherein according to (II) the one or more further components comprise a fluorescent tracer dye. The process of item 54, wherein the fluorescent tracer dye is a Particle-Fingerprint Fluorescence Tracer model TrackByStars® obtained from (Polysecure). The process of item 54 or 55, wherein the fluorescent tracer dye is added in an amount of less than 0.001 wt.-% relative to the terephthalate monomers (calculated as weight tracer dye / total weight of terephthalate monomers x 100%), preferably less than 0.0001 wt.-%, more preferably in the range of from than 0.001 wt.-% to than 0.000001 wt.-%, more preferably in the range of from 0.0001 wt.-% to than 0.000001 wt.-%. The process of any one of items 54 to 56, wherein the fluorescent tracer dye is invisible to normal visual inspection. The process of any one of the preceding items, wherein according to (II) the one or more further components comprise a delusterant. The process of item 58, wherein the delusterant is present in an amount in the range of from 0.1 wt.-% to 2.0 wt.-% relative to the terephthalate monomers (calculated as weight delusterant I total weight of terephthalate monomers x 100%), preferably in an amount in the range of from 0.2 wt.-% to 1 .4 wt.-%, more preferably in an amount in the range of from 0.3 wt.-% to 0.9 wt.-%, more preferably in an amount in the range of from 0.4 wt.-% to 0.8 wt.-%. The process of item 58 or 59, wherein the delusterant is free of titanium dioxide. The process of any one of items 58 to 60, wherein the delusterant has an elemental formula of (CaO)a(Al2O3)b(CaSO4)c(H2O)d and a is in the range of from 1 to 5, b is in the range of from 0.1 to 2, c is in the range of from 2 to 5 and d is in the range of from 20 to 40, preferably a is in the range of from 2 to 4, b is in the range of from 1 to 2, c is in the range of from 3 to 4 and d is in the range of from 25 to 35. The process of any one of items 58 to 60, wherein the delusterant has an elemental formula of (CaO)a(Al2O3)b(CaSO4)c(H2O)d and a, b, c and d are all whole integers, a is in the range of from 1 to 5, b is 1 or 2, c is in the range of from 2 to 5 and d is in therange of from 20 to 40, preferably a is in the range of from 2 to 4, b is 1 or 2, c is in the range of from 3 to 4 and d is in the range of from 25 to 35. The process of anyone of the preceding items, wherein according to (II) the one or more further components comprise a dye. The process of item 63, wherein the dye is for textiles. The process of item 64, wherein the textile is a fabric or garment. The process of any one of items 63 to 65, wherein the dye is biodegradable and nontoxic. The process of any one of items 63 to 66, wherein the dye is a natural dye. The process of anyone of the preceding items, wherein according to (II) the one or more further components comprise one or more of selected from the group consisting of lubricants, flame retardants, fillers, weather stabilizers, plasticizers and combinations of two or more thereof; ; preferably and / or wherein the aluminum salt catalyst according to (I) may also be adjusted or added according to (II), preferably wherein the aluminum salt catalyst according to (I) is only first added according to (II) as one or more further components. The process of any one of the preceding items, wherein according to (II) the one or more further components is biodegradable, preferably marine biodegradable or soil biodegradable, more preferably marine biodegradable according to ASTM D6691 or soil biodegradable according to ASTM D5988. The process of any one of the preceding items, wherein according to (II) the one or more further components is non-toxic. The process of any one of the preceding items, wherein according to (11.1) the second esterification is carried out at a temperature in a range of from 230 °C to 270 °C, preferably of from 240 °C to 260 °C. The process of any one of the preceding items, wherein according to (11.1) the second esterification has an initial pressure in the range of from 0.1 bar to 0.5 bar, preferably of from 0.2 bar to 0.4 bar. The process of any one of the preceding items, wherein according to (11.1) the second esterification has a final pressure in the range of from 0.001 bar to 0.1 bar, preferably of from 0.005 bar to 0.02 bar. The process of any one of the preceding items, wherein according to (11.1) the second esterification is carried out for a duration in the range of from 0.5 hour to 3 hours, preferably in the range of from 1 hour to 2 hours.The process of any one of items 71 to 74, wherein the initial pressure of the second esterification is measured at T=0 and the ending pressure of the second esterification is measured at T=final, T is the time of the second esterification and the total sum of T is equal to the duration of the second esterification. The process of any one of the preceding items, wherein (II) further comprises(11.3) removing unreacted ethylene glycol and recycling the ethylene glycol after purification by distillation to the slurry provided in (I). The process of any one of the preceding items, wherein (II) further comprises(11.4) removing water from the second esterification to a waste treatment system. The process of any one of the preceding items, wherein (I) and / or (II) further comprise(1.5) and / or (11.5) cooling the esterification, preferably cooling to a temperature in the range of from 15 °C to 45 °C, preferably in the range of from 20 °C to 30 °C. The process of any one of the preceding items, wherein (I) and / or (II) further comprise(1.6) and / or (11.6) purging the esterification with nitrogen, preferably to atmospheric pressure. The process of item 78 or item 79, wherein cooling is simultaneous with purging the esterification with nitrogen. The process of any one of items 78 to 80, wherein cooling and / or purging is conducted for a duration of 0.5 hours to 2 hours. The process of any one of the preceding items, wherein the second composition obtained according to (II.2) has an intrinsic viscosity in the range of from 0.18 dl / g to 0.58 dl / g, preferably in the range of from 0.30 dl / g to 0.50 dl / g, optionally measured according to DIN EN ISO 1628-1. The process of any one of the preceding items, wherein according to (111.1) purging with nitrogen while heating the second composition to a temperature in the range of from 165 °C to 185 °C. The process of any one of the preceding items, wherein according to (III.2), heating the second composition with the nitrogen purge to a temperature in the range of from 260 °C to 290 °C for a duration in the range of from 3.5 hours to 5 hours. The process of any one of the preceding items, wherein according to (III.3), the reactor is a vacuum reactor.The process of any one of the preceding items, wherein according to (III.3), if the biodegradable polyester article is an injected molded article or a printed article, calcium carbonate, preferably calcium carbonate obtained from renewable bio-source, more preferably calcium carbonate obtained from mussel shells, is added to the reactor. The process of item 86, wherein the calcium carbonate is added in an amount relative to the amount of terephthalic acid monomer (TA) in the range of from 0.1 wt.-% to 10 wt.-% (calculated as weight of CaCCh I weight of terephthalic acid monomer (TA) x 100%), preferably in the range of from 1 wt.-% to 8 wt.-%, more preferably in the range of from 2 wt.-% to 6 wt.-%. The process of item 86 or 87, wherein the calcium carbonate is 85 wt.-% to 98 wt.-% CaCCh and the remainder are bio-polymers from shells. The process of item 86 or 87, wherein the calcium carbonate is in the form of a powder. The process of any one of the preceding items, wherein according to (III.3), a color stabilizer is added to the reactor. The process of item 90, wherein the color stabilizer is adenosyl cobalamine (Coenzyme B12, CAS 13870-90-1). The process of item 90 or 91 , wherein the color stabilizer is phosphorous acid, triphenylphosphite, triphenylphosphate, sodium hypophosphite or sodium phosphite. The process of any one items 90 to 91 , wherein the color stabilizer is added in an amount relative to the amount of terephthalic acid monomer (TA) in the range of from 0.001 wt.-% to 4 wt.-%, preferably 0.01 wt.-% to 3.5 wt.-%, more preferably 0.1 wt.-% to 3.0 wt.-%, (calculated as weight of the color stabilizer I weight of terephthalic acid monomer (TA) x 100%). The process of any one of the preceding items, wherein according to (IV) heating comprises heating to an initial temperature (Tp)initialin the range of from 270 °C to 290 °C for an initial time (T)initialin the range of from 5 to 15 minutes followed by cooling to a reaction temperature (Tp)lxnin the range of from 210 °C to 260 °C and maintaining heating at (Tp)lxnfor a reaction time (T)lxnin the range of from 3.5 hours to 6.5 hours. The process of item 94, wherein the reaction temperature (Tp)lxnis in the range of from 230 °C to 250 °C and maintaining heating at (Tp)lxnfor a reaction time (T)lxnin the range of from 4.5 hours to 6.5 hours. The process of any one of the preceding items, wherein according to (IV), during heating or maintaining heat, the absolute pressure is in the range of 10 to 20 pascal.The process of any one of the preceding items, wherein according to (IV), during cooling to a temperature in the range of 15 °C to 30 °C the reaction is purged with nitrogen until the vacuum has been released and atmospheric pressure is reached. The process of any one of the preceding items, wherein according to (IV), during heating and / or cooling the reactor is mixed. The process of any one of the preceding items, wherein the third composition obtained according to (V) has an intrinsic viscosity in the range of from 0.65 dl / g to 1.1 dl / g, preferably in the range of from 0.67 dl / g to 0.9 dl / g, more preferably in the range of from 0.67 dl / g to 0.8 dl / g, more preferably in the range of from 0.68 dl / g to 0.75 dl / g, optionally measured according to DIN EN ISO 1628-1. The process of any one of the preceding items, wherein the third composition obtained according to (V) has a number average molecular weight MN in the range of from 7,000 g / mol to 40,000 g / mol, preferably in the range of from 10,000 g / mol to 25,000 g / mol, more preferably determined by gel permeation chromatography optionally using a polystyrene standard, preferably under chromatography conditions under 60 °C. The process of any one of the preceding items, wherein the third composition obtained according to (V) has a glass transition temperature in the range of from 40 °C to 50 °C, preferably in the in the range of from 42 °C to 48 °C, measured with DSC according to ASTM D3418. The process of any one of the preceding items, wherein the third composition obtained according to (V) has a melting point temperature in the range of from 190 °C to 210 °C, preferably in the in the range of from 195 °C to 205 °C, measured with DSC according to ASTM D3418. The process of any one of the preceding items, wherein the third composition obtained according to (V) has a crystallization temperature in the range of from 120 °C to 160 °C, preferably in the in the range of from 130 °C to 150 °C, measured with DSC according to ASTM D3418. The process of any one of the preceding items, wherein the third composition obtained according to (V) has a density in the range of from 1.28 g / ml to 1.42 g / ml, measured according to ASTM D1505. The process of any one of the preceding items, wherein according to (VI) the transferring of the composition comprising the polyester copolymer obtained according to (V) is to a granulator, a spinning system or an extrusion molding system. The process of any one of the preceding items, wherein according to (VI) the transferring of the composition comprising the polyester copolymer obtained according to (V) is to a granulator.The process of item 106, wherein the granulator is an extruder, preferably a twin-screw extruder type. The process of item 106 or 107, wherein the granules are extruded at a temperature in the range of from 200 °C to 290 °C, preferably in the range of from 210 °C to 260 °C, more preferably in the range of from 220 °C to 250 °C. The process of any one of items 106 to 108, wherein the granules are cooled immediately after extrusion, preferably by water cooling. The process of any one of items 106 to 109, wherein polybutylene succinate (PBS) is added relative to the amount of terephthalic acid monomer (TA) in the range of from 0.1 wt.-% to 10 wt.-%, preferably of from 1 wt.-% to 8 wt.-%, more preferably of from 2 wt.-% to 7 wt.-%, (calculated as weight of PBS I weight of terephthalic acid monomer (TA) x 100%). The process of any one of items 106 to 110, wherein the granules are in the form of pellets or chips, preferably chips. The process of any one of items 106 to 110, wherein the granules are extruded with a nitrogen atmosphere. The process of any one of the preceding items, wherein according to (VI) the transferring of the composition comprising the polyester copolymer obtained according to (V) is to a spinning system. The process of item 113, wherein fibers are extruded from the spinning system at a temperature in the range of from 200 °C to 260 °C, preferably in the range of from 210 °C to 250 °C, more preferably in the range of from 230 °C to 245 °C. The process of item 113 or 114, wherein the spinning oil is free of phthalates, MCDP, glycidol and B(E)TX aromatics. The process of any one of items 113 to 115, wherein the fiber or yarn obtained from the spinning system or a textile therefrom is further dyed at a temperature below 130 °C, preferably below 120 °C. The process of any one of items 113 to 116, wherein the fiber or yarn obtained from the spinning system or the textile therefrom is further dyed at a temperature in the range of from 90 °C to 125 °C, preferably in the range of from 95 °C to 120 °C, more preferably in the range of from 100 °C to 115 °C, more preferably in the range of from 105 °C to 115 °C. The process of any one of items 113 to 117, wherein the fiber or yarn obtained from the spinning system or the textile therefrom is further dyed for a duration in the range offrom 30 min to 240 min, preferably of from 45 min to 180 min, more preferably of from 60 min to 120 min. The process of any one of items 113 to 117, wherein the fiber, yarn or textile is dyed comprising- soaking the fiber in a solution of dye at a temperature in the range of from 50 °C to 70°C for a duration in the range of 10 min to 30 min followed by-heating to a temperature in the range of from 90 °C to 125 °C, preferably in the range of from 95 °C to 120 °C, more preferably in the range of from 100 °C to 115 °C, more preferably in the range of from 105 °C to 115 °C for a duration in the range of from 30 min to 240 min, preferably of from 45 min to 180 min, more preferably of from 60 min to 120 min, followed by- cooling to a temperature in the range of from 60 °C to 75 °C, removing the fiber from the dye solution and washing the fiber in water at a temperature in the range of 8 °C to 12 °C, followed by- soaking the fiber in a solution of dye at a temperature in the range of from 30 °C to 50°C for a duration in the range of 5 min to 10 min, followed by-heating to a temperature in the range of from 70 °C to 90 °C, for a duration in the range of from 15 min to 45 min, followed by- cooling to a temperature in the range of from 50 °C to 70 °C, removing the fiber from the dye solution and washing the fiber in water at a temperature in the range of 8 °C to 12 °C, followed by- soaking the fiber in water at a temperature in the range of from 40 °C to 50°C for a duration in the range of 5 min to 10 min, followed by- removing the fiber from the dye solution and washing the fiber in water at a temperature in the range of 8 °C to 12 °C, followed by- soaking the fiber in water at a temperature in the range of from 30 °C to 40°C for a duration in the range of 5 min to 10 min, followed by- removing the fiber from the dye solution and washing the fiber in water at a temperature in the range of 8 °C to 12 °C. The process of any one of the preceding items, wherein a textile or textile intermediate is fashioned from fiber or yarn by weaving, knitting or spinning systems.The process of any one of the preceding items, wherein according to (VI) the transferring of the composition comprising the polyester copolymer obtained according to (V) is to an extrusion molding system. The process of item 121, wherein foil or sheets are extruded at a temperature in the range of from 200 °C to 260 °C, preferably in the range of from 210 °C to 250 °C, more preferably in the range of from 230 °C to 245 °C. The process of item 121 or 122, wherein sheets are extruded. The process of any one of items 121 to 123, wherein films or foils are extruded. The process of any one of items 121 to 124, wherein the extruded product is then molded. The process of item 125, wherein the molding is vacuum molding or injection molding. The process of any of the preceding items, wherein the third composition obtained according to (V) has been granulated in a granulator prior to measurement of any of the properties relating to the material of items 99 to 104. The process of any of the preceding items, wherein the third composition obtained according to (V) has been granulated in a granulator, preferably according to any one of items 105 to 112, prior to transfer to a further process. The process of item 128, wherein the further process is a spinning system, an extrusion molding system, an injection molding system or a printing system. The process of any one of the preceding items, wherein after granulation the material is dried in a vacuum oven prior to entering the further process, preferably wherein the pressure under vacuum drying is maintained in the range of from 1.332 Pa to 1332 Pa, preferably of from 6.666 Pa to 66.66 Pa, more preferably of from 10.00 Pa to 16.66 Pa. The process of item 130, wherein the drying is conducted at a temperature in the range of from 80 °C to 120 °C, preferably of from 90 °C to 110 °C. The process of item 130 or 131 , wherein the drying is conducted for a duration in the range of from 1 to 48 hours, preferably in the range of from 4 to 24 hours, more preferably in the range of from 8 hours to 20 hours, more preferably 10 to 18 hours, and / or preferably 4 hours to 12 hours, preferably 5 hours to 10 hours. The process of any one of items 130 to 132, wherein the drying is conducted with a flow rate of air in the range of from 25 L / min to 35 L / min. The process of any one of items 130 to 133, wherein the drying is conducted in an atmosphere having a water content of 50 to 100 part per million by mass.The process of any one of items 130 to 134, wherein the drying is conducted in air having a water content of 50 to 100 part per million by mass. The process of item 134 or 135, wherein the atmosphere, preferably air, is nitrogen. The process of any of the preceding items, wherein the biodegradable polyester article is free of antimony, preferably according to ISO 17294-2:2016 wherein the water sample was prepared by digestion of granules according to ASTM D6691. The process of any of the preceding items, wherein the biodegradable polyester article is free of titanium, preferably determined by elemental analysis. The process of any of the preceding items, wherein the biodegradable polyester article is free of heavy metal and fluorine according to EN 13432. The process of any of the preceding items, wherein the biodegradable polyester article is free of volatile organic compounds (VOC) according to EN 13432, preferably wherein the article is greater than 99 wt.-% dry mater (calculated as dry matter / total weight x 100%) according to EN 13432. The process of any of the preceding items, wherein the biodegradable polyester article is non-toxic according to OECD 202. The process of any one of the preceding items, wherein the process is conducted under nitrogen, preferably having a water content according to any one of the preceding items, more preferably item 134. he process of any one of the preceding items, wherein according to (VI) the transferring of the composition comprising the polyester copolymer obtained according to (V) is to a spinning system having a draw ratio in the range of 3.0 to 5.0, preferably in the range of 4.0 to 5.0. The process of any one of the preceding items, preferably item 143, wherein a yarn is obtained having a tenacity greater than 3.8 g / Den, preferably having a tenacity in the range of 3.0 to 6.0 g / Den, more preferably having a tenacity in the range of 4.0 to 5.5 g / Den determined according to ASTM D2256 / D885. The process of any one of the preceding items, wherein no diethylene glycol is purposively added. 146. The process of any one of the preceding items, wherein the third composition obtained according to (V), preferably the biodegradable polyester article, has a Temperature Nuclei Free (TNF) of 247 °C or greater, more preferably having a Temperature Nuclei Free (TNF) in the range of 247 °C to 260 °C, more preferably in the range of 250 °C to 255°C. A biodegradable polyester article obtained according to any one of the preceding process items.148. A biodegradable polyester article, having subject-matter according to any one of the preceding items.ReferencesUS7144614B2 (aluminum salt catalyst)US8614280B2 (initial conditions)

Claims

1. Claims1. A process for producing a biodegradable polyester article comprising:(I) providing a slurry comprising a source of terephthalic acid monomer, a source of ethylene glycol monomer, wherein the ethylene glycol monomer source is ethylene glycol, a source of monomer according to structure (i):wherein X is in the range of from 2 to 18, wherein R is a C1 to C6 hydrocarbon or H, and a source of monomer according to structure (ii):d R’ is a C1 to C6 hydrocarbon or H, and an aluminum salt catalyst; wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of ethylene glycol monomer (EG) in the range of from 1 : 1.2 to 1 : 1.6 (calculated as moles of (TA) I moles of (EG)); wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (i) (strj) in the range of from 1 : 0.04 to 1 : 0.12 (calculated as moles of (TA) I moles of (str_i)); wherein the slurry has a molar ratio of the source of terephthalic acid monomer (TA) relative to the source of monomer according to structure (ii) (strji) in the range of from 2000 : 1 to 650 : 1 (calculated as moles of (TA) / moles of (strji)) ;wherein the aluminum salt catalyst (Al-cat) is present in a molar amount relative to the source of monomer of terephthalic acid (TA) (calculated as moles of Al present in the aluminum salt catalyst I moles of TA monomer * 100 mol.-%) is in the range of from 0.01 mol.-% to 0.0001 mol.-%;(1.1) reacting the slurry provided according to (I) in a first esterification;(1.2) obtaining a first composition comprising bis(2-hydroxyethyl)terephthalate (BHET);(II) adding one or more further components to the first composition obtained according to (1.2) to obtain a mixture;(11.1) reacting the mixture obtained according to (II) in a second esterification;(11.2) obtaining a second composition from (11.1) comprising pre-polymers (precondensed polyester) comprising independently at each occurrence monomers of bis(2-hydroxyethyl)terephthalate (BHET), monomers according to structure (i) and / or monomers according to structure (ii);(III) heating the second composition obtained according to (II.2) comprising;(111.1) purging with nitrogen while heating the second composition to a temperature in the range of from 160 °C to 190 °C;(111.2) after reaching the temperature according to (III .1), heating the second composition with the nitrogen purge to a temperature in the range of from 240 °C to 290 °C for a duration in the range of from 3.5 hours to 6 hours;(111.3) the composition is transferred to a further reactor after heating according to (HI.2);(IV) heating the transferred composition in a reactor according to (III.3) to a temperature in the range of from 210 °C to 290 °C for a duration of from 4 hours to 7 hours at an absolute pressure in the range of 10 to 30 pascal; and followed by cooling to a temperature in the range of 15 °C to 30 °C while simultaneously purging with nitrogen;(V) obtaining a third composition from (IV) comprising a polyester copolymer comprising PET monomers terephthalate and ethylene glycol interspersed independently from one another at each occurrence monomers of bis(2- hydroxyethyl)terephthalate (BHET), monomers of structure (i) and monomers ofstructure (ii);(VI) transferring the composition comprising the polyester copolymer obtained according to (V) to any one of a granulator, a spinning system, an extrusion molding system, an injection molding system or a printing system;(VII) obtaining a biodegradable polyester article.

2. The process of claim 1, wherein the biodegradable polyester article is in the form of a textile, a fiber, a filament, a yarn, a chip, a granule, a film, a foil, a sheet, a hollow molding, an injection molded article or a printed article.

3. The process of any one of the preceding claims, wherein the biodegradable polyester article is in the form of a textile, preferably wherein the biodegradable polyester textile is in the form of a net, a floor covering, a fabric or a garment.

4. The process of claim 2 or 3, wherein the textile is a fire-resistant fabric according to DIN 4102-1.

5. The process of any one of the preceding claims, wherein the biodegradable polyester article is a marine biodegradable polyester article according to ASTM D6691.

6. The process of any one of the preceding claims, wherein the biodegradable polyester article is a soil biodegradable polyester article according to ASTM D5988 or ISO 17556, more preferably ASTM D5988.

7. The process of any one of the preceding claims, wherein the biodegradable polyester article has a biological degradability in the range of from 80 wt.-% to 100 wt.-% (calculated as the final weight I the initial weight x 100%), preferably in the range of from 90 wt.-% to 99.9 wt.-%, more preferably in the range of from 92 wt.-% to 99 wt.-%, determined according to ASTM D6691 or ASTM D5988.

8. The process of any one of the preceding claims, wherein according to (I) the terephthalic acid monomer source is either terephthalic acid or a C1 to C6 diester of terephthalic acid, preferably is terephthalic acid.

9. The process of any one of the preceding claims, wherein according to (I) the terephthalic acid monomer source is a mixture of virgin grade terephthalic acid and recycled terephthalic acid and the weight ratio of virgin grade terephthalic acid to recycled terephthalic acid is in the range of 10 : 1 to 1 :2, preferably in the range of from 9 : 1 to 1:1 , more preferably in the range of from 5 : 1 to 2:1.

10. The process of any one of the preceding claims, wherein according to (I) the source of monomer according to structure (i) comprise, preferably consist of, dimethyl glutarate,preferably according to structure (i-a):11 . The process of any one of the preceding claims, wherein according to (I) the source of monomer according to structure (ii) comprise, preferably consist of, sodium dimethyl 5- sulfoisophthalate, preferably according to structure (ii-a):

12. The process of any one of the preceding claims, wherein according to (I) the aluminum salt catalyst is according to structure (iii):wherein R1is selected from the group consisting of C5 to C20 aromatics,M is selected from the group consisting of Li, Na, K, Be, Mg, Ca, Sr, Ba, Mn, Ni, Cu and Zn, R2is a C1 to C20 hydrocarbon, R3is a C1 to C20 hydrocarbon, Y+Z is 4 and Y is in the range of 1 to 3.

13. The process of any of the preceding claims, wherein the biodegradable polyester article is free of any combination of:- antimony, according to ISO 17294-2:2016 wherein the water sample was prepared by digestion of granules according to ASTM D6691 ;- titanium, determined by elemental analysis;- heavy metal and fluorine according to EN 13432; and / or- volatile organic compounds (VOC) according to EN 13432, preferably wherein the article is greater than 99 wt.-% dry mater (calculated as dry matter / total weight x 100%) according to EN 13432.

14. The process of any of the preceding claims, wherein the biodegradable polyester article is non-toxic according to OECD 202.

15. The process of any one of the preceding claims, wherein the third composition obtained according to (V) has been granulated in a granulator prior to transfer to a further process.

16. The process of any one of the preceding claims, wherein after granulation the material is dried in a vacuum oven prior to entering the further process.

17. The process of claim 16, wherein the pressure under vacuum drying is maintained in the range of from 1.332 Pa to 1332 Pa, preferably of from 6.666 Pa to 66.66 Pa, more preferably of from 10.00 Pa to 16.66 Pa.

18. The process of claim 16 or 17, wherein the drying is conducted at a temperature in the range of from 80 °C to 120 °C, preferably of from 90 °C to 110 °C.

19. The process of any one of the preceding claims, wherein no diethylene glycol is purposively added.

20. The process of any one of the preceding claims, wherein the third composition obtained according to (V), preferably the biodegradable polyester article, has a Temperature Nuclei Free (TNF) of 247 °C or greater, more preferably having a Temperature Nuclei Free (TNF) in the range of 247 °C to 260 °C, more preferably in the range of 250 °C to 255°C.

21. A biodegradable polyester article obtained according to any one of the preceding process claims; wherein the biodegradable polyester article is free of one or more of the following:- antimony according to ISO 17294-2:2016 wherein the water sample was prepared by digestion of granules according to ASTM D6691;- titanium determined by elemental analysis;- heavy metal and fluorine according to EN 13432; and / or- volatile organic compounds (VOC) according to EN 13432, preferably wherein the article is greater than 99 wt.-% dry mater (calculated as dry matter / total weight x 100%) according to EN 13432.

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