Continuous production of biodegradable polyester

Abstract

A method for spinning biodegradable polyester copolymer filaments is disclosed. The biodegradable polyester copolymer melt is formed by polymerizing terephthalic acid, ethylene glycol, 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 invention disclosed herein relates generally to polymeric compositions that are suitable for textiles and that are biodegradable. [Background technology]

[0002] Textiles are fundamental to human culture and have been made and used by humans for thousands of years. The oldest known textiles were woven from natural fibers such as flax, wool, silk, and cotton. More recently, textile fibers, yarns, and fabrics have been industrially produced from polymers such as polyester, nylon, olefin, other thermoplastic polymers, and combinations thereof. Many of the modern polymers can be made into an almost limitless variety of shapes and products that are attractive, durable, and water resistant. Often, these synthetic fibers or yarns (depending on the desired technology and end product) can be blended with natural fibers to obtain an end product that has the desired characteristics of both the natural and synthetic materials.

[0003]

[0003] Although durability and water resistance are desirable, these same properties can lead to secondary environmental problems: Textiles made from polymeric fibers do not naturally biodegrade in the same manner as natural fibers and can persist in landfills and water (e.g., lakes and oceans) for hundreds of years or more.

[0004]

[0004] Currently available biodegradable fibers also have various problems in their production. Typically, a masterbatch approach is used in an extrusion process to form a biodegradable polymer. However, masterbatches are expensive and require additional mixing, drying, and crystallization steps. Furthermore, polycaprolactone (Mw 6400), a known biodegradable polymer in pellet form, is suitable for the masterbatch approach, but is more difficult to use in a continuous polymerization process. Summary of the Invention [Problem to be solved by the invention]

[0005]

[0005] Thus, there is a need for biodegradable polymers suitable for forming textiles having desirable properties similar to conventional textiles that can be formed via continuous production (i.e., continuous polymerization) rather than masterbatch production. [Means for solving the problem]

[0006] In one aspect, a method for spinning biodegradable polyester copolymer filaments is provided. The method includes 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 another aspect, a biodegradable polyester copolymer filament is disclosed that includes terephthalic acid, ethylene glycol, caprolactone monomers, calcium carbonate, and polybutylene succinate.

[0009] The foregoing and other advantages of the present invention will become apparent from a consideration of the following detailed description and drawings of non-limiting examples of embodiments. [Brief description of the drawings]

[0010] [Figure 1]

[0010] is a table of additive components and associated levels in the overhead and vacuum. [Diagram 2]

[0011] 1 is a table showing the results of evaluation of materials of the present disclosure at 296 days in the Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High Solids Anaerobic Digestion Conditions. [Diagram 3]

[0012] 1 is a table showing the results of evaluation of materials of the present disclosure at 298 days in the Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High Solids Anaerobic Digestion Conditions. [Figure 4]

[0013] 1 is a table showing the results of evaluation of materials of the present disclosure at 305 days in the Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High Solids Anaerobic Digestion Conditions. [Diagram 5]

[0014] 1 is a graph of the biodegradation of materials of the present disclosure compared to positive and negative controls from 0 to 305 days. [Figure 6]

[0015] 1 is a graph of biodegradation of materials of the present disclosure compared to a negative control from 0 to 305 days. [Figure 7]

[0016] 1 is a table showing the amounts of components of polyester fibers of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011]

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

[0012]

[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 present invention are shown. The present invention may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein, but rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0013]

[0019] As used herein, the term "biodegradable" refers to a material that, given the appropriate natural conditions and the presence of microorganisms, will degrade, i.e., break down into its basic components and become integrated into the earth, on a scale significantly faster than non-biodegradable materials.

[0014]

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

[0015]

[0021] In textile technology, the term "texturing" is used in both broad and narrow senses. In the broadest sense, texturing is used synonymously to refer to a process in which synthetic filaments, staple fibers, or yarns are mechanically and / or thermally treated to have a greater volume than untreated filaments, staple fibers, or yarns. In a narrower sense, the term texturing is used to refer to a process that produces loops and curls; the meaning is largely clear from the context. As used herein, the term "texture" is used broadly to encompass all possibilities for producing a desired effect on a filament, staple fiber, or yarn.

[0016]

[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%, as well as all numbers between 10% and 13%.

[0017]

[0023] As used herein, "percent" or "%" means percent by weight unless otherwise specified. Additionally, concentrations and percentages refer to the concentration or percentage in the finished copolymer unless otherwise specified.

[0018]

[0024] Thus, biodegradable polyester (polyethylene terephthalate) fibers are described. Generally, a masterbatch approach is used with an extruder process to form biodegradable polymers. However, the high cost of masterbatches and the need for additional mixing, drying, and crystallization steps make them less likely to be adopted, and biodegradable fibers are not widely available at affordable prices. A continuous polymerization process is more economical for the synthesis of polyesters, but polycaprolactone (Mw 6400), a known biodegradable polymer, is in pellet form and is suitable for the masterbatch approach but not for use in a continuous polymerization process.

[0019]

[0025] To overcome these difficulties, the present disclosure incorporates caprolactone monomer, a clear liquid, into polyester in a continuous polymerization process. Caprolactone monomer is a precursor to polycaprolactone, is biodegradable in the natural environment, and imparts other desirable properties to the fiber, such as dye enhancement. The use of caprolactone monomer in a conventional continuous polymerization line allows for high throughput at low cost, with production rates exceeding 30,000 pounds per hour, in some cases 40,000 pounds per hour, and even 60,000 to 90,000 pounds per hour, compared to the masterbatch approach, which limits production rates to about 2,000 pounds per hour.

[0020]

[0026] Additionally, the caprolactone monomer is nearly or nearly completely consumed (eg, values ​​below 200 ppm).

[0027] To produce the biodegradable polymers 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 by-product. The esterification reaction can be carried out in one or more vessels, and in some embodiments, two vessels, each an esterification reactor (estifier), are used. A pressure gradient is conventionally used to drive the continuous polymerization process. Additionally, pumps may be used to drive the process. Water and MEG are continuously removed to drive the esterification reaction to substantial completion. The monomers and oligomers formed by esterification are then catalytically polymerized by polycondensation to form polyethylene terephthalate (or PET) polyester. The polycondensation reaction can be carried out in one or more vessels, each a polymerizer. In some embodiments, two vessels are used, a low polymerizer under low vacuum and a high polymerizer under high vacuum, as is known in the art.

[0021]

[0028] Caprolactone monomer and calcium carbonate (CaCO3) are added during the esterification and polycondensation reactions described above. In some embodiments, the caprolactone monomer and calcium carbonate may be added directly to a vessel containing the condensation product, for example, an oligomerizer. In some embodiments, the caprolactone monomer and calcium carbonate may be added to a transfer line between the esterification reactor and the polymerizer. In a subsequent step, polybutylene succinate (PBS) is added. The reaction typically proceeds at about 280°C (e.g., between about 270°C and 295°C). The caprolactone monomer is incorporated into the polyester fiber along with the PBS and calcium carbonate to form a biodegradable polyester material. Microorganisms digest the resulting fiber containing polycaprolactone, PBS, and calcium carbonate to break down the polymer chains and biodegrade the fiber.

[0022]

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

[0023]

[0030] Those skilled in the art will recognize that other types of additives can be incorporated into the polymer of the present invention. Non-limiting examples include anatase titanium dioxide, one or more optical brighteners, and blue pigments. 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 barrier agents, carbon dioxide barrier agents, 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.

[0024]

[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 84.1%, 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 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 any points therebetween.

[0025]

[0032] In embodiments where 13-16% ethylene glycol is disclosed, the concentration of ethylene glycol may be between about 13% and about 13.1%, 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%, 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 13.1% 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 14.5% and about 16% The range may be 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 any points therebetween.

[0026]

[0033] In embodiments where 0.3-2.5% caprolactone monomer is disclosed, the concentration of 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 0.5%, between about 0.5% and about 1.6%, between about 0.5% and about 1.8%, between about 0.5% and about 1.9%, between about 0.5% and about 2.0%, between about 0.5% and about 2.5 ... between 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 2. between about 0.4%, 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 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 any points therebetween.

[0027]

[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 between about 0.02% and about 0.03%, and points therebetween.

[0028]

[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 0.19%, 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 0.3 .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 0.20%, 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%, .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 any points therebetween.

[0029]

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

[0030]

[0037] After the polycondensation step is complete, the polymer melt can be filtered and extruded. After extrusion, the polyethylene terephthalate is quenched to solidify the polyester, such as by spraying with water. The solidified polyethylene terephthalate can be cut into chips for storage and handling.

[0031]

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

[0039] In some embodiments, the polyester produced by the present method can be blow molded into packaging or other products.

[0032]

[0040] In some embodiments, the filaments produced by this method are textured and cut into staple fibers. Texturing is well understood in the art and will not be described in particular detail at this time other than to point out that the compositions of the present invention result in filaments that can be textured (e.g., heat set while in the twisted position) using conventional processes.

[0033]

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

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

[0034]

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

[0035]

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

[0036]

[0045] Turning now to the figures, Figure 1 is a table of additive components and associated levels in overhead and vacuum. Six trials are shown, with additives added at various stages of the polyester synthesis process, including Capa, which is added upfront, pre-esterification, and during esterification, with polybutylene succinate (PBS) and calcium carbonate (CaCO3) added at later stages.

[0037]

[0046] Figure 2 shows the ASTM D5511 test, a standard test method for determining the anaerobic biodegradation of plastic materials under high solids anaerobic digestion conditions, evaluating the samples of the present disclosure at 296 days. Cellulose is used as a positive control for purposes of adjusted biodegradation rates, under the assumption that cellulose will completely biodegrade. The negative control is polypropylene. All values ​​are adjusted proportionally to cellulose degradation.

[0038]

[0047] Figure 3 shows the ASTM D5511 testing on the 298 day old sample, where again cellulose was used as a positive control.

[0048] FIG. 4 shows the ASTM D5511 testing on the 305 day old samples with cellulose as a positive control.

[0039]

[0049] 5 is a chart of biodegradation plotted out to 305 days, with the positive control showing the greatest degradation (top line) and the negative control showing no degradation (bottom line). As shown, the degradation of one embodiment of the present disclosure, a crushed crystalline plaque held without a mold at 270° C. for 3 minutes, shows increasing biodegradation over time (middle line).

[0040]

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

[0041]

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

[0052] EXAMPLES

[0042]

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

[0054]

[0043] Example 1

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

[0044]

[0056]

[0045] Example 2

[0057] In this example, a biodegradable polyester precursor composition is present in a low polymerization vessel, the composition comprising an ester condensation product of terephthalic acid and a stoichiometric amount of ethylene glycol, about 0.5-1 wt. % caprolactone monomer, about 100 ppm by weight calcium carbonate, and about 0.1 wt. % polybutylene succinate.

[0046]

[0058] Thus, the present disclosure is well adapted to achieve the objects and advantages mentioned, as well as those inherent therein. The specific embodiments described above are merely illustrative, as the disclosure may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Moreover, no limitations are intended to the details of construction or design shown herein, other than as set forth in the following claims. Thus, it is apparent that the specific exemplary embodiments disclosed above may be altered, combined or modified, and all such variations are deemed to be within the scope and spirit of the present disclosure. The embodiments illustratively disclosed herein may suitably be practiced in the absence of any element not specifically disclosed herein and / or any optional element disclosed herein.

Claims

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

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

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

4. 4. The method according to any one of claims 1 to 3, wherein the step of polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing about 83% to about 86% terephthalic acid by weight of the biodegradable polyester copolymer melt.

5. 5. The method of any one of claims 1 to 4, wherein the step of polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing with about 13% to about 16% ethylene glycol by weight of the biodegradable polyester copolymer melt.

6. 6. The method according to any one of claims 1 to 5, wherein the step of polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing about 0.3% to about 2.5% caprolactone monomer by weight of the biodegradable polyester copolymer melt.

7. 7. The method of any one of claims 1 to 6, wherein the step of polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing with about 0.01% to about 0.03% calcium carbonate by weight of the biodegradable polyester copolymer melt.

8. 8. The method of any one of claims 1 to 7, wherein the step of polymerizing terephthalic acid, ethylene glycol, caprolactone monomer, calcium carbonate, and polybutylene succinate comprises polymerizing about 0.05% to about 0.25% polybutylene succinate by weight of the biodegradable polyester copolymer melt.

9. 9. The method of any one of claims 1 to 8, wherein terephthalic acid, ethylene glycol, caprolactone monomers, calcium carbonate, and polybutylene succinate are polymerized at a temperature of about 270°C to about 295°C.

10. 10. A method of forming a textured biodegradable polyester copolymer filament, comprising texturing the biodegradable polyester copolymer filament produced by the method of any one of claims 1 to 9 to form the textured biodegradable polyester copolymer filament.

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

12. 11. A method of forming a textured biodegradable polyester chip, comprising granulating the textured biodegradable polyester copolymer of claim 10 to form a textured biodegradable polyester chip.

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

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

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

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

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

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

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

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

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

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

23. terephthalic acid, Ethylene glycol, Caprolactone monomer, Calcium carbonate, and Polybutylene succinate, A biodegradable textile composition comprising:

24. 24. The biodegradable textile composition of claim 23 comprising about 83 wt% to about 86 wt% terephthalic acid.

25. 25. The biodegradable textile composition of claim 23 or 24, comprising about 13 wt% to about 16 wt% ethylene glycol.

26. 26. The biodegradable textile composition of any one of claims 23 to 25, comprising from about 0.3 wt% to about 2.5 wt% caprolactone monomer.

27. 27. The biodegradable textile composition of any one of claims 23 to 26, comprising about 0.01 wt% to about 0.03 wt% calcium carbonate.

28. 27. The biodegradable textile composition of any one of claims 22 to 26, comprising about 0.05 wt% to about 0.25 wt% polybutylene succinate.

29. 29. Biodegradable polyester copolymer filaments made from the biodegradable textile composition according to any one of claims 23 to 28.

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

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

32. 32. A fabric made from the textured biodegradable polyester copolymer staple fiber 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 knit.

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

36. An article of clothing made from the fabric of any one of claims 33 to 35.

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

38. 38. An article of apparel made from the fabric of claim 37.

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

40. 40. The biodegradable polyester copolymer filament of claim 39, comprising about 83 wt% to about 86 wt% terephthalic acid.

41. 41. The biodegradable polyester copolymer filament according to claim 39 or 40, comprising about 13 wt% to about 16 wt% ethylene glycol.

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

43. 43. The biodegradable polyester copolymer filament according to any one of claims 39 to 42, comprising about 0.01 wt% to about 0.03 wt% calcium carbonate.

44. 44. The biodegradable polyester copolymer filament according to any one of claims 39 to 43, comprising about 0.05 wt% to about 0.25 wt% polybutylene succinate.

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

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

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

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

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

50. 50. An article of apparel made from the fabric of any one of claims 47 to 49.

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

52. 52. An article of apparel made from the fabric of claim 51.

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

Images