Continuous production of biodegradable polyesters

Abstract

A method for spinning biodegradable polyester copolymer filaments is disclosed. A biodegradable polyester copolymer melt is formed by polymerizing terephthalic acid, ethylene glycol, a caprolactone monomer, calcium carbonate, and polybutylene succinate to form the biodegradable polyester copolymer melt. The biodegradable polyester copolymer melt can be spun into biodegradable polyester copolymer filaments.

Description

Technical Field

[0001] The present invention generally relates to polymer compositions that are suitable for textiles and are biodegradable. Background Art

[0002] Textiles are of vital importance to human culture and have been manufactured and used by humans for thousands of years. The earliest known textiles are woven from natural fibers such as flax, wool, silk and cotton. Recently, textile fibers, yarns and fabrics have also been industrially produced by polymers such as polyester, nylon olefins, other thermoplastic polymers and combinations thereof. Many modern polymers can be made into almost endless various attractive, durable and waterproof shapes and products. In many cases, these synthetic fibers or yarns (depending on required technology and final product) can be mixed with natural fibers to obtain the final product with the characteristics of required natural materials and synthetic materials.

[0003] While durability and water resistance are desirable, these same properties can cause secondary environmental problems. Textiles produced from polymer fibers do not naturally biodegrade in the same manner as natural fibers and can remain in landfills and water (e.g., lakes, oceans) for hundreds of years or more.

[0004] The biodegradable fibers available at present further have various problems in their manufacture. Usually, in order to form biodegradable polymers, a masterbatch method is used to form biodegradable polymers in the case of an extruder process. However, masterbatch is expensive and requires additional compounding, drying and crystallization steps. In addition, the polycaprolactone (Mw is 6400, a known biodegradable polymer) in pellet form is very suitable for the masterbatch method, but it is more difficult to be used in a continuous polymerization process.

[0005]

[0006] Therefore, there is a need for biodegradable polymers suitable for forming textiles having desirable properties similar to traditional textiles, which can be formed via continuous production (ie, continuous polymerization) rather than masterbatch production. Summary of the invention

[0006] In one aspect, a method for spinning biodegradable polyester copolymer filaments is provided. The method comprises polymerizing terephthalic acid, ethylene glycol, caprolactone monomers, calcium carbonate and polybutylene succinate to form a biodegradable polyester copolymer melt. The biodegradable polyester copolymer melt is then spun into biodegradable polyester copolymer filaments.

[0007] In another aspect, a biodegradable textile composition is disclosed that includes terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate.

[0008] In yet another aspect, a biodegradable polyester copolymer filament comprising terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate is disclosed. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The foregoing and other advantages of the present invention will become apparent upon review of the following detailed description of non-limiting examples of embodiments and the accompanying drawings, in which:

[0010] Figure 1 is a table of additive components and associated levels in overhead and vacuum.

[0011] Figure 2 Shown are the results of a standard test method for determining the anaerobic biodegradation of plastic materials under high solids anaerobic digestion conditions, evaluating the materials of the present disclosure at 296 days.

[0012] Figure 3 Shown are the results of a standard test method for determining the anaerobic biodegradation of plastic materials under high solids anaerobic digestion conditions, evaluating the materials of the present disclosure at 298 days.

[0013] Figure 4 Shown are the results of a standard test method for determining the anaerobic biodegradation of plastic materials under high solids anaerobic digestion conditions, evaluating the material of the present disclosure at 305 days.

[0014] Figure 5 is a graph of the biodegradation of materials of the present disclosure compared to positive and negative controls from 0-305 days.

[0015] Figure 6 is a graph of the biodegradation of the material of the present disclosure compared to a negative control from 0-305 days.

[0016] Figure 7 is a table showing the amounts of components of the polyester fibers of the present disclosure. DETAILED DESCRIPTION

[0017] As described herein, the present disclosure describes fibers that have desirable properties similar to conventional fibers that are biodegradable and that can be formed via continuous production rather than masterbatch production. More specifically, biodegradable polyester (polyethylene terephthalate or PET) fibers are disclosed.

[0018] The present invention will now be described more fully with reference to the accompanying drawings, in which some, but not all, embodiments of the invention are shown. The present invention may be implemented in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. As used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise.

[0019] As used herein, the term "biodegradable" means that when given the appropriate natural conditions and the presence of microorganisms, a material will decay or decompose into its essential components and mix with the soil on a significantly faster scale than non-biodegradable materials.

[0020] As used herein, in the context of synthetic fibers and their manufacture, the term "intrinsic viscosity" is used to describe a property that is proportional to the average molecular weight of a polymer. The intrinsic viscosity is calculated based on the viscosity of a polymer solution (in a solvent) extrapolated to zero concentration.

[0021] In the field of textiles, the term "texturing" is widely and specifically used. In the broadest sense, texturing is used as a synonym to refer to the following steps, in which synthetic filaments, staple fibers or yarns are mechanically treated, heat treated or both to have a larger volume than untreated filaments, staple fibers or yarns. In a narrow sense, the term texturing is used to refer to the processing of looping and curling. This meaning is usually clear in the context. As used herein, the term "texture" is used in a broad sense to include all possibilities of producing a desired effect in filaments, staple fibers or yarns.

[0022] When "between" is used to indicate a numerical range, the range is inclusive of the numbers used. For example, "between about 10% and about 13%" includes both 10% and 13% and all numbers between 10% and 13%.

[0023] As used herein, "percent" or "%" refers to weight percent unless otherwise specified. In addition, unless otherwise specified, concentrations and ratios refer to the concentration or ratio in the finished copolymer.

[0024] Thus, biodegradable polyester (polyethylene terephthalate) fibers are described. Typically, to form biodegradable polymers, a masterbatch approach is used in the case of an extruder process. However, masterbatches are expensive, require additional compounding, drying and crystallization steps, and are therefore rarely employed, and biodegradable fibers are not widely available at an affordable price point. Continuous polymerization processes are more economical for the synthesis of polyesters, however, polycaprolactone (Mw of 6400, a known biodegradable polymer) is in pellet form and is well suited for the masterbatch approach but not for the continuous polymerization process.

[0025] To overcome these difficulties, the present disclosure introduces caprolactone monomer (clear liquid) into polyester in a continuous polymerization process. Caprolactone monomer is a precursor of polycaprolactone that is biodegradable in natural environments and imparts other desirable properties to the fiber, such as dye enhancement. Compared to the masterbatch method that limits production throughput to about 2,000 pounds per hour, the use of caprolactone monomer on a conventional continuous polymerization line results in high production at low cost, with output exceeding 30,000 pounds per hour, or sometimes about 40,000 pounds per hour or even 60,000 to 90,000 pounds per hour.

[0026] Furthermore, the caprolactone monomer is almost completely consumed or nearly completely consumed (eg, a value of less than 200 ppm).

[0027] In order to produce the biodegradable polymer of the present disclosure, terephthalic acid (or purified terephthalic acid or PTA) and ethylene glycol (or monoethylene glycol or MEG) are reacted in a heated esterification reaction to produce monomers and oligomers of terephthalic acid and ethylene glycol and water as a byproduct. The esterification reaction can be carried out in one or more containers, and two containers are used in some embodiments, each container is an esterifier (estifier). Pressure gradient is generally used to drive a continuous polymerization process. In addition, a pump can be used to drive the process. In order to enable the esterification reaction to be substantially completed, water and MEG are continuously removed. The monomers and oligomers formed via esterification are subsequently polymerized via polycondensation catalysis to form polyethylene terephthalate (or PET) polyester. The polycondensation reaction can be carried out in one or more containers, and each container is a polymerizer. In some embodiments, two containers are used, a low polymerizer under low vacuum and a high polymerizer under high vacuum, as known in the art.

[0028] During the above esterification and polycondensation reaction, caprolactone monomer and calcium carbonate (CaCO 3). In some embodiments, the caprolactone monomer and calcium carbonate can be added directly to a container containing the condensation product, such as an oligomer. In some embodiments, the caprolactone monomer and calcium carbonate can be added to a transfer line between the esterifier and the polymerizer. In a subsequent step, polybutylene succinate (PBS) is added. The reaction is typically carried out at about 280°C (e.g., between about 270°C and 295°C). The caprolactone monomer is introduced into a polyester fiber together with the PBS and calcium carbonate to form a biodegradable polyester material. The resulting fiber comprising polycaprolactone, PBS and calcium carbonate is digested by microorganisms to break down the polymer chains and allow the fiber to biodegrade.

[0029] The polymerization of terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate can include polymerizing about 83% to about 86% terephthalic acid by weight of the biodegradable polyester copolymer melt. About 13% to about 16% ethylene glycol by weight of the biodegradable polyester copolymer melt can be used. About 0.3% to about 2.5% caprolactone monomer by weight of the biodegradable polyester copolymer melt can be used. About 0.01% to about 0.03% calcium carbonate by weight of the biodegradable polyester copolymer melt can be used. About 0.05% to about 0.25% polybutylene succinate by weight of the biodegradable polyester copolymer melt can be used, and points therebetween.

[0030] Those of ordinary skill in the art recognize that other types of additives may be introduced into the polymers of the present invention. As non-limiting examples, anatase titanium dioxide, one or more fluorescent whitening agents, and blue pigments may be added. Such additives include, but are not limited to, matting agents, preform heat-up rate enhancers, friction reducing additives, UV absorbers, inert particulate additives (e.g., clay or silica), colorants, pigments, antioxidants, branching agents, oxygen barriers, carbon dioxide barriers, oxygen scavengers, flame retardants, crystallization control agents, acetaldehyde reducing agents, impact modifiers, catalyst deactivators, melt strength enhancers, antistatic agents, lubricants, chain extenders, nucleating agents, solvents, fillers, and plasticizers.

[0031] In embodiments where 83-86% terephthalic acid is disclosed, the concentration of terephthalic acid may be between about 83% and about 83.1%, between about 83% and about 83.2%, between about 83% and about 83.3%, between about 83% and about 83.4%, between about 83% and about 83.5%, between about 83% and about 83.6%, between about 83% and about 83.7%, between about 83% and about 83.8%, between about 83% and about 83.9%, between about 83% and about 84%, between about 83% and about 84. between about 83% and about 84.1%, between about 83% and about 84.2%, between about 83% and about 84.3%, between about 83% and about 84.4%, between about 83% and about 84.6%, between about 83% and about 84.7%, between about 83% and about 84.8%, between about 83% and about 84.9%, between about 83% and about 85%, between about 84% and about 85%, between about 84% and about 85.1%, between about 84% and about 85.2%, between about 84% and about 85. 3%, between about 84% and about 85.4%, between about 84% and about 85.6%, between about 84% and about 85.7%, between about 84% and about 85.8%, between about 84% and about 85.9%, between about 84% and about 86%, between about 85.9% and about 86%, between about 85.8% and about 86%, between about 85.7% and about 86%, between about 85.6% and about 86%, between about 85.5% and about 86%, between about 85.4% and about 86%, between about Between 85.3% and about 86%, between about 85.2% and about 86%, between about 85.1% and about 86%, between about 85% and about 86%, between about 84.9% and about 86%, between about 84.8% and about 86%, between about 84.7% and about 86%, between about 84.6% and about 86%, between about 84.3% and about 86%, between about 84.2% and about 86%, between about 84.1% and about 86%, and / or between about 84% and about 86%, and points therebetween.

[0032] In embodiments where 13-16% ethylene glycol is disclosed, the concentration of ethylene glycol can be between about 13% and about 13.1% ethylene glycol, between about 13% and about 13.2%, between about 13% and about 13.3%, between about 13% and about 13.4%, between about 13% and about 13.5%, between about 13% and about 13.6%, between about 13% and about 13.7%, between about 13% and about 13.8%, between about 13% and about 13.9%, between about 13% and about 14%, between about 13% and about 14.1%, between about 13% and about 14.2%, between about 13% and about 14.3%, between about 13% and about 14.4%, between about 13% and about 14.5%, between about 13% and about 14.6%, between about 13% and about 14.7%, between about 13% and about 14.8%, between about 13% and about 14.9%, between about 13% and about 15.1%, between about 13% and about 15.2%, between about 13% and about 15.3%, between about 13% and about 15.4%, between about 13% and about 15.5%, between about 13% and about 15.6%, between about 13% and about 15.7%, between about 13% and about 15.8%, between about 13% and about 15.9%, between about 13% and about 16%. between about 13% and about 14.4%, between about 13% and about 14.5%, between about 13% and about 14.6%, between about 13% and about 14.7%, between about 13% and about 14.8%, between about 13% and about 14.9%, between about 13% and about 15%, between about 13% and about 15.1%, between about 13% and about 15.2%, between about 13% and about 15.3%, between about 13% and about 15.4%, between about 13% and about 15.5%, between about 13% and about 15.6%, between about 13% and about 15.7%, between about 13% and about 15.8%, between about 13% and about 15.9 ... .9%, between about 13% and about 16%, between about 13.1% and about 16%, between about 13.2% and about 16%, between about 13.3% and about 16%, between about 13.4% and about 16%, between about 13.5% and about 16%, between about 13.6% and about 16%, between about 13.7% and about 16%, between about 13.8% and about 16%, between about 13.9% and about 16%, between about 14% and about 16%, between about 14.1% and about 16%, between about 14.2% and about 16%, between about 14.3% and about 16%, between about 14.4% and about 16%, between about 14.6% and about 16%, between about 14.7% and about 16%, between about 14.8% and about 16%, between about 14.9 ... .5% and about 16%, between about 14.6% and about 16%, between about 14.7% and about 16%, between about 14.8% and about 16%, between about 14.9% and about 16%, between about 15% and about 16%, between about 15.1% and about 16%, between about 15.2% and about 16%, between about 15.3% and about 16%, between about 15.4% and about 16%, between about 15.5% and about 16%, between about 15.6% and about 16%, between about 15.7% and about 16%, between about 15.8% and about 16%, and / or between about 15.9% and about 16%, and points therebetween.

[0033] In embodiments where 0.3-2.5% caprolactone monomer is disclosed, the concentration of the caprolactone monomer may be between about 0.3% and about 0.4%, between about 0.3% and about 0.4%, between about 0.3% and about 0.6%, between about 0.3% and about 0.7%, between about 0.3% and about 0.8%, between about 0.3% and about 0.9%, between about 0.3% and about 1.0%, between about 0.3% and about 1.1%, between about 0.3% and about 1.2%. , between about 0.3% and about 1.3%, between about 0.3% and about 1.4%, between about 0.3% and about 1.5%, between about 0.3% and about 1.6%, between about 0.3% and about 1.7%, between about 0.3% and about 1.8%, between about 0.3% and about 1.9%, between about 0.3% and about 2.0%, between about 0.3% and about 2.1%, between about 0.3% and about 2.2%, between about 0.3% and about 2.3%, between about 0.3% and about %, between about 0.3% and about 2.5%, between about 0.4% and about 2.5%, between about 0.5% and about 2.5%, between about 0.6% and about 2.5%, between about 0.7% and about 2.5%, between about 0.8% and about 2.5%, between about 0.9% and about 2.5%, between about 1.0% and about 2.5%, between about 1.1% and about 2.5%, between about 1.2% and about 2.5%, between about 1.3% and about 2.5%, between about Between 1.4% and about 2.5%, between about 1.5% and about 2.5%, between about 1.6% and about 2.5%, between about 1.7% and about 2.5%, between about 1.8% and about 2.5%, between about 1.9% and about 2.5%, between about 2.0% and about 2.5%, between about 2.1% and about 2.5%, between about 2.2% and about 2.5%, between about 2.3% and about 2.5% and / or between about 2.4% and about 2.5%, and points therebetween.

[0034] In embodiments where 0.01-0.03% calcium carbonate is disclosed, the concentration of calcium carbonate may be between about 0.01% and about 0.02%, or about 0.02% to about 0.03%, and points therebetween.

[0035] In embodiments where 0.05-0.25% polybutylene succinate is disclosed, the concentration of polybutylene succinate may be between about 0.05% and about 0.06%, between about 0.05% and about 0.07%, between about 0.05% and about 0.08%, between about 0.05% and about 0.09%, between about 0.05% and about 0.1%, between about 0.05% and about 0.11%, between about 0.05% and about 0.12%, between about 0.05% and about 0.13%, between about 0.05% and about 0.14%, between about 0.05% and about 0.15%, between about 0.05% and about 0.16%, between about 0.05% and about 0.17%, between about 0.05% and about 0.18%, between about 0.05% and about 0.19%, between about 0.05% and about 0.110%, between about 0.05% and about 0.12%, between about 0.05% and about 0.13%, between about 0.05% and about 0.14%. %, between about 0.05% and about 0.14%, between about 0.05% and about 0.15%, between about 0.05% and about 0.16%, between about 0.05% and about 0.17%, between about 0.05% and about 0.18%, between about 0.05% and about 0.19%, between about 0.05% and about 0.20%, between about 0.05% and about 0.21%, between about 0.05% and about 0.22%, between about 0.05% and about 0.23%, between about 0.05% and about 0.24%, between about 0.05% and about 0.25%, between about 0.05% and about 0.26%, between about 0.05% and about 0.27%, between about 0.05% and about 0.28%, between about 0.05% and about 0.29%, between about 0.05% and about 0.30%, between about 0.05% and about 0.31%, between about 0.05% and about 0.32%, between about 0.05% and about 0.33%, between about 0.05% and about 0.34%, between about 0.05% and about 0.35%, between about 0.05% and about 0.36%, between about 0.05% and about 0.37%, between about 0.05% and about 0.38%, between about 0.05% and about 0.39%, between about 0.05% and about 0. between about 0.24%, between about 0.05% and about 0.25%, between about 0.24% and about 0.25%, between about 0.23% and about 0.25%, between about 0.22% and about 0.25%, between about 0.21% and about 0.25%, between about 0.20% and about 0.25%, between about 0.19% and about 0.25%, between about 0.18% and about 0.25%, between about 0.17% and about 0.25%, between about 0.16% and about 0.25%, Between about 0.15% and about 0.25%, between about 0.14% and about 0.25%, between about 0.13% and about 0.25%, between about 0.12% and about 0.25%, between about 0.11% and about 0.25%, between about 0.1% and about 0.25%, between about 0.09% and about 0.25%, between about 0.08% and about 0.25%, between about 0.07% and about 0.25%, and / or between about 0.06% and about 0.25%, and points therebetween.

[0036] The polymerization is continued until the desired molar weight of the polyester terephthalate is reached. The residence time in the polymerization vessel and the feed rates of ethylene glycol and terephthalic acid into the continuous process are determined in part based on the target molecular weight of the polyester. Since the molecular weight can be determined by the intrinsic viscosity of the polymer melt, the intrinsic viscosity of the polymer melt is often used to determine polymerization conditions, such as temperature, pressure, feed rates of reactants, and residence time in the polymerization vessel.

[0037] After the polycondensation stage is complete, the polymer melt can be filtered and extruded. After extrusion, the polyethylene terephthalate is quenched, for example, by a water spray, to solidify the polyester. The solidified polyethylene terephthalate can be cut into sheets for storage and handling purposes.

[0038] In some embodiments, the polyester produced by this process is spun into filaments using conventional techniques known in the art.

[0039] In some embodiments, the polyesters produced by this process can be blow molded into packaging and other products.

[0040] In some embodiments, the filaments produced by the method are textured and cut into staple fibers.Texturing is well known in the art and will not be described in further detail except to point out that the compositions of the present invention so far produce filaments that can be textured using conventional steps (e.g., heat setting while in a twisted position).

[0041] In some embodiments, staple fibers produced by the method are spun into yarn.

[0042] In some embodiments, staple fibers may be laid down in a nonwoven batting.

[0043] In some embodiments, staple fibers are spun with cotton or rayon to form a blended yarn. The yarn can then be used to form a fabric that can be used to make textiles such as clothing. The fabric can be woven or knitted, and such fabrics are used to make textiles and clothing. Similarly, nonwoven batting can be used to form fabrics or textiles to make clothing, etc.

[0044] The resulting fibers, filaments, fabrics, containers, etc. are biodegradable in landfill environments, marine environments, sewage sludge, and in seawater and fresh water and other natural and non-natural environments containing microorganisms. The time scale of biodegradation in the exemplary embodiment is comparable to the time scale of biodegradation of natural fibers. In some embodiments, the degradation of fibers or fabrics of the present disclosure is substantially or mostly completed in 3-4 years. In some or other embodiments, the degradation of fibers or fabrics of the present disclosure is substantially or mostly completed in less than 3 years.

[0045] Now turning to the attached figure, Figure 1 is a table of additive components and relative levels in air and vacuum. Six experiments are shown, with additives added at various steps in the polyester synthesis process (including upfront, before esterification), and Capa added in esterification, while polybutylene succinate (PBS) and calcium carbonate (CaCO) were added later. 3 ).

[0046] Figure 2An ASTM D5511 study, which is a standard test method for determining the anaerobic biodegradation of plastic materials under high solids anaerobic digestion conditions, is shown, evaluating samples of the present disclosure at 296 days. Cellulose was used as a positive control for the adjusted biodegradation percentages under the assumption that the cellulose would fully biodegrade. The negative control was polypropylene. All values ​​have been proportionally adjusted relative to cellulose degradation.

[0047] Figure 3 An ASTM D5511 study of samples at 298 days is shown. Again, cellulose was used as a positive control.

[0048] Figure 4 An ASTM D5511 study of samples at 305 days is shown, with cellulose as a positive control.

[0049] Figure 5 is a graph of biodegradation plotted to 305 days, with the positive control showing maximum degradation (top line), and the negative control showing no degradation (bottom line). As shown, the degradation of an embodiment of the present disclosure (plaque crystallization grind, no mold 3 minute hold time at 270°C) shows increasing biodegradation over time (middle line).

[0050] Figure 6 is a graph of biodegradation plotted to 305 days comparing the degradation of an embodiment of the present disclosure (top line) to a negative control (polypropylene, bottom line). The compositions of the present disclosure show increasing biodegradation over time.

[0051] Figure 7 is a table showing the amounts of components of the polyester fibers of the present disclosure.

[0052] Example

[0053] The following non-limiting examples are provided to illustrate the present disclosure.

[0054] Example 1

[0055] In this example, 1000 g portions of biodegradable polyethylene terephthalate are continuously produced. The 1000 g portions are formed by adding about 850 g of terephthalic acid and a stoichiometric amount of ethylene glycol to an esterifier; adding about 100 ppm of calcium carbonate; adding between about 0.5 wt % and 1 wt % of caprolactone monomer; and finally adding about 0.1 wt % of polybutylene succinate.

[0056] Example 2

[0057] In this example, a precursor composition for a biodegradable polyester is present in an oligomerizer. The composition comprises an ester condensation product of terephthalic acid and a stoichiometric amount of ethylene glycol; between about 0.5 wt % and 1 wt % caprolactone monomer; about 100 ppm by weight of calcium carbonate; and about 0.1 wt % of polybutylene succinate.

[0058] Therefore, the present disclosure is well suited to achieve the objects and advantages mentioned and those inherent therein. The specific embodiments disclosed above are illustrative only, as the present disclosure may be modified and implemented in different but equivalent manners, which will be apparent to those of ordinary skill in the art and to those who benefit from the teachings herein. In addition, except as described in the appended claims, it is not intended to limit the details of the construction or design shown herein. Therefore, it is apparent that the specific illustrative embodiments disclosed above may be changed, combined or modified and all such variations are considered to be within the scope and spirit of the present disclosure. The embodiments disclosed illustratively herein may be appropriately implemented in the absence of any element not specifically disclosed herein and / or any optional element disclosed herein.

Claims

1. A method for spinning biodegradable polyester copolymer filaments, the method comprising: polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate to form a biodegradable polyester copolymer melt; and The biodegradable polyester copolymer is melt-spun into the biodegradable polyester copolymer filament.

2. The method of claim 1, wherein polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate and polybutylene succinate to form a biodegradable polyester copolymer melt is carried out on a continuous polymerization line.

3. The process of claim 1, wherein polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate and polybutylene succinate to form a biodegradable polyester copolymer melt is carried out on a batch reactor.

4. The method of any one of the preceding claims, wherein polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing from about 83% to about 86% terephthalic acid by weight of the biodegradable polyester copolymer melt.

5. The method of any one of the preceding claims, wherein polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing from about 13% to about 16% ethylene glycol by weight of the biodegradable polyester copolymer melt.

6. The method of any one of the preceding claims, wherein polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing from about 0.3% to about 2.5% caprolactone monomer by weight of the biodegradable polyester copolymer melt.

7. The method of any one of the preceding claims, wherein polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing from about 0.01% to about 0.03% calcium carbonate by weight of the biodegradable polyester copolymer melt.

8. The method of any one of the preceding claims, wherein polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing from about 0.05% to about 0.25% polybutylene succinate by weight of the biodegradable polyester copolymer melt.

9. The method of any one of the preceding claims, wherein terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate are polymerized at a temperature of about 270°C to about 295°C.

10. A method of forming a textured biodegradable polyester copolymer filament, the method comprising texturizing a biodegradable polyester copolymer filament produced by the method of any one of the preceding claims to form the textured biodegradable polyester copolymer filament.

11. A method of forming textured biodegradable polyester copolymer staple fibers, the method comprising cutting the textured biodegradable polyester copolymer filaments of claim 10 to form textured biodegradable polyester copolymer staple fibers.

12. A method of forming a textured biodegradable polyester sheet, the method comprising pelletizing the textured biodegradable polyester copolymer of claim 10 to form a textured biodegradable polyester sheet.

13. A method of forming a textured biodegradable polyester container, the method comprising blow molding the textured biodegradable polyester copolymer of claim 10 to form a textured biodegradable polyester container.

14. A method of forming a textured biodegradable polyester wrap, the method comprising blow molding the textured biodegradable polyester copolymer of claim 10 to form a textured biodegradable polyester wrap.

15. A method of forming a textured biodegradable polyester copolymer yarn, the method comprising spinning the textured biodegradable polyester copolymer staple fiber of claim 11 to form the yarn.

16. A method of forming a textured biodegradable polyester copolymer blended yarn, the method comprising spinning the textured biodegradable polyester copolymer staple fiber of claim 11 with one or more of cotton fiber and rayon fiber to form a blended yarn.

17. A method of forming a fabric from the textured biodegradable polyester copolymer staple fibers of claim 11.

18. The method of claim 17, wherein forming the fabric comprises knitting the textured biodegradable polyester copolymer staple fibers to form the fabric.

19. The method of claim 17, wherein forming the fabric comprises weaving the textured biodegradable polyester copolymer staple fibers to form the fabric.

20. The method of claim 17, wherein forming the fabric comprises laying down a nonwoven batting.

21. A method of forming a garment from the fabric of any one of claims 17-20.

22. A method of forming a fabric from the biodegradable polyester copolymer filaments of any one of claims 1 to 9.

23. A biodegradable textile composition comprising: Terephthalic acid; Ethylene glycol; Caprolactone monomer; calcium carbonate; and Polybutylene succinate.

24. The biodegradable textile composition according to claim 23, wherein the biodegradable textile composition comprises about 83 wt% to about 86 wt% terephthalic acid.

25. The biodegradable textile composition according to claim 23 or 24, wherein the biodegradable textile composition comprises about 13 wt% to about 16 wt% ethylene glycol.

26. The biodegradable textile composition according to any one of claims 23-25, wherein the biodegradable textile composition comprises from about 0.3 wt% to about 2.5 wt% of the caprolactone monomer.

27. The biodegradable textile composition according to any one of claims 23-26, wherein the biodegradable textile composition comprises from about 0.01 wt% to about 0.03 wt% calcium carbonate.

28. The biodegradable textile composition according to any one of claims 22 to 26, wherein the biodegradable textile composition comprises from about 0.05 wt% to about 0.25 wt% of polybutylene succinate.

29. A biodegradable polyester copolymer filament made from the biodegradable textile composition of any one of claims 23-28.

30. A textured biodegradable polyester copolymer filament made from the biodegradable polyester copolymer filament of claim 29.

31. A textured biodegradable polyester copolymer staple fiber made from the textured biodegradable polyester copolymer filament of claim 29.

32. A fabric made from the textured biodegradable polyester copolymer staple fibers of claim 31.

33. The fabric of claim 32, wherein the fabric is a woven fabric.

34. The fabric of claim 32, wherein the fabric is a knitted fabric.

35. The fabric of claim 32, wherein the fabric is a nonwoven batting.

36. A garment made from the fabric of any one of claims 33-35.

37. A fabric made of the biodegradable polyester copolymer filaments of claim 29.

38. A garment made from the fabric of claim 37.

39. A biodegradable polyester copolymer filament comprising: Terephthalic acid; Ethylene glycol; Caprolactone monomer; calcium carbonate; and Polybutylene succinate.

40. The biodegradable polyester copolymer filament of claim 39, wherein the biodegradable polyester copolymer filament comprises from about 83 wt% to about 86 wt% terephthalic acid.

41. The biodegradable polyester copolymer filament of claim 39 or 40, wherein the biodegradable polyester copolymer filament comprises from about 13 wt% to about 16 wt% ethylene glycol.

42. The biodegradable polyester copolymer filament according to any one of claims 39-41, wherein the biodegradable polyester copolymer filament comprises from about 0.3 wt% to about 2.5 wt% caprolactone monomer.

43. The biodegradable polyester copolymer filament according to any one of claims 39-42, wherein the biodegradable polyester copolymer filament comprises from about 0.01 wt% to about 0.03 wt% calcium carbonate.

44. The biodegradable polyester copolymer filament of any one of claims 39-43, wherein the biodegradable polyester copolymer filament comprises from about 0.05 wt% to about 0.25 wt% polybutylene succinate.

45. A textured biodegradable polyester copolymer filament made from the biodegradable polyester copolymer filament of any one of claims 39-44.

46. ​​A textured biodegradable polyester copolymer staple fiber made from the textured biodegradable polyester copolymer filament of claim 45.

47. A fabric made from the textured biodegradable polyester copolymer staple fibers of claim 46.

48. The fabric of claim 47, wherein the fabric is a woven fabric.

49. The fabric of claim 47, wherein the fabric is a knitted fabric.

50. A garment made from the fabric of any one of claims 47-49.

51. A fabric made from the biodegradable polyester copolymer filaments of any one of claims 39-44.

52. A garment made from the fabric of claim 51.

53. A plurality of biodegradable staple fibers cut from the textured biodegradable polyester copolymer filaments of claim 45.

Images