Polyester Polymer Nanocomposite

Abstract

Embodiments of the present disclosure include a polymer-polysaccharide nanocomposite resin composition and a method for producing the same, which comprises preparing a dispersion containing polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid monomers, and polycondensing the alkanediol monomers and alkanedioic acid monomers in the dispersion to produce the polymer-polysaccharide nanocomposite resin. Embodiments of the present disclosure also include a polybutylene succinate nanocomposite composition and a method for producing the same, which comprises dispersing cellulose nanocrystals in 1,4 butanediol (BDO) to form a cellulose-BDO dispersion, and esterifying the cellulose-BDO dispersion with succinic anhydride to form a plurality of polybutylene succinate oligomers. The polybutylene succinate oligomers are condensed to form the polybutylene succinate nanocomposite.

Description

[Background technology]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 62 / 863,029, filed June 18, 2019, the disclosure of which is incorporated by reference in its entirety.

[0002] introduction Polybutylene succinate (PBS) is typically synthesized by the esterification reaction between 1,4 butanediol and succinic acid, followed by condensation of the oligomeric product to form PBS. A common method for increasing the molecular weight of PBS is to add a chain extender such as a carbonate or diisocyanate.

[0003] One of the by-products of PBS production is tetrahydrofuran (THF), a hazardous waste product formed when 1,4 butanediol is cyclized. Diisocyanate chain extenders are a non-renewable resource, potentially toxic, and require additional processing steps before they can be used.

[0004] There remains a need for methods for producing polymer-polysaccharide nanocomposite resins that utilize renewable feedstocks and improve the properties of the resulting products while reducing the amount of waste produced. Summary of the Invention

[0005] Embodiments of the present disclosure include a polyester polymer-polysaccharide nanocomposite resin composition and a method for producing the same, which comprises preparing a dispersion containing polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid monomers, and polycondensing the alkanediol monomers and alkanedioic acid monomers in the dispersion to produce the polymer-polysaccharide nanocomposite resin. Embodiments of the present disclosure also include a polybutylene succinate nanocomposite composition and a method for producing the same, which comprises dispersing cellulose nanocrystals in 1,4 butanediol (BDO) to form a cellulose-BDO dispersion, and esterifying the cellulose-BDO dispersion with succinic anhydride to form a plurality of polybutylene succinate oligomers. The polybutylene succinate oligomers are condensed to form the polybutylene succinate nanocomposite.

[0006] In another embodiment, the method includes adding cellulose nanocrystals to 1,4 butanediol to form a cellulose-BDO mixture, and then sonicating the cellulose-BDO mixture to disperse the cellulose nanocrystals in the 1,4 butanediol to form a cellulose-BDO dispersion. A succinate derivative is esterified in the cellulose-BDO dispersion to form a plurality of polybutylene succinate oligomers. The polybutylene succinate oligomers are condensed to form a polybutylene succinate nanocomposite.

[0007] Another embodiment of the method includes adding cellulose nanocrystals to 1,4 butanediol to form a cellulose-BDO mixture and sonicating the cellulose-BDO mixture to disperse the cellulose nanocrystals in the 1,4 butanediol to form a cellulose-BDO dispersion. The cellulose-BDO dispersion and succinate anhydride are esterified to form polybutylene succinate oligomers, which are then condensed to form a polybutylene succinate nanocomposite. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 10 is a plot of dynamic viscosity versus temperature for a polybutylene succinate nanocomposite synthesized from cellulose nanocrystals dispersed in 1,4 butanediol using a homogenizer and esterified with epoxidized linseed oil. [Figure 2] 1 is a particle size distribution plot of polymer fibers containing material as shown in Example 13. [Figure 3] Particle size distribution plot of cellulose nanocrystals dispersed in 1,4 butanediol at 60% sonication amplitude. [Figure 4] Particle size distribution plot of cellulose nanocrystals dispersed in 1,4 butanediol at 80% sonication amplitude. [Figure 5] FIG. 10 is a particle size distribution plot of cellulose nanocrystals dispersed in 1,4 butanediol at 100% sonication amplitude. [Figure 6] FIG. 10 is a particle size distribution plot of cellulose nanocrystals dispersed in 1,4 butanediol at a homogenizer speed of 10,000 rpm for 1 minute. [Figure 7] 1 is a particle size distribution plot of cellulose nanocrystals dispersed in 1,4 butanediol at a homogenizer speed of 13,333 rpm for 1 minute. [Figure 8] 16 is a particle size distribution plot of cellulose nanocrystals dispersed in 1,4 butanediol at a homogenizer speed of 16,666 rpm for 1 minute. DETAILED DESCRIPTION OF THE INVENTION

[0009] The foregoing and other aspects of the present invention will be described in more detail with reference to the descriptions and methodologies provided herein. It is understood that the present invention may be embodied in 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 be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

[0010] The terms used in the description of the present specification are for the purpose of describing particular embodiments only and are not intended to limit the present invention. When used in describing embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. Also, as used herein, "and / or" refers to and includes any and all possible combinations of one or more of the associated listed items.

[0011] When referring to a measurable value such as the amount of a compound, dosage, time, temperature, etc., the term "about" as used herein is meant to encompass variations of 20%, 10%, 5%, 1%, 0.5%, or even 0.1% of the specified amount. Unless otherwise defined, all terms, including technical and scientific terms, used in the description have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0012] As used herein, the terms "comprise," "comprises," "comprising," "include," "includes," and "including" specify the presence of stated features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof.

[0013] As used herein, the term "consisting essentially of" (and grammatical variations thereof) as applied to the compositions and methods of the present invention means that the composition / method may contain additional components so long as the additional components do not substantially alter the composition / method. The term "substantially alter" as applied to a composition / method refers to an increase or decrease in the effectiveness of the composition / method by at least about 20% or more.

[0014] All patents, patent applications, and publications referenced herein are incorporated by reference in their entirety. In the event of a conflict of terminology, the present specification will control.

[0015] Embodiments of the present disclosure include a polymer-polysaccharide nanocomposite resin composition and a method for producing the same, which comprises preparing a dispersion containing polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid monomers, and polycondensing the alkanediol monomers and alkanedioic acid monomers in the dispersion to produce the polymer-polysaccharide nanocomposite resin. Embodiments of the present disclosure also include a polybutylene succinate nanocomposite composition and a method for producing the same, which comprises dispersing cellulose nanocrystals in 1,4 butanediol (BDO) to form a cellulose-BDO dispersion, and esterifying the cellulose-BDO dispersion with succinic anhydride to form a plurality of polybutylene succinate oligomers. The polybutylene succinate oligomers are condensed to form the polybutylene succinate nanocomposite.

[0016] Polyester polymer-polysaccharide nanocomposite resin An embodiment of the present disclosure includes a polyester polymer-polysaccharide nanocomposite resin composition.

[0017] A nanocomposite, as used herein in its conventional sense, generally consists of multiple nanoscale materials or nanoscale materials incorporated into a bulk material. Nanocomposites can be multiphase solid materials in which one of the phases is one-, two-, or three-dimensional, or structures with repeating nanoscale distances between the different phases that make up the material. Thus, nanocomposites can include nanoparticles entrained in a polymer matrix.

[0018] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin comprises increased modulus and strength due to the addition of the nanocomposite to provide reinforcing fibers.

[0019] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin may act to toughen the base polymer resin, thereby enhancing one or more mechanical properties of the base resin. Non-limiting properties that may be improved by incorporating polysaccharide nanoparticles into the base polyester polymer resin may be selected from at least one of reduced modulus of elasticity, tensile yield stress, hoop stress rating, flexural modulus, UV resistance, and gas permeability. Thus, the present disclosure allows for measurable enhancement of performance without significant loss of other desirable properties, such as tensile strength, ultimate elongation, melt index, thermal stability, impact strength, slow crack growth resistance, and rapid crack propagation resistance.

[0020] In some embodiments, polyester polymer-polysaccharide nanocomposite resins provide at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, at least 7%, at least 8%, at least 9%, or at least 10% improved yield stress compared to the base polymer alone, i.e., a composition lacking polysaccharide nanoparticles. In some embodiments, polyester polymer-polysaccharide nanocomposite resins provide at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% improved yield stress compared to the base polymer alone. In some embodiments, polyester polymer-polysaccharide nanocomposite resins provide up to 200%, e.g., up to 100%, improved yield stress compared to the base polymer alone. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin provides an improved yield stress in the range of 10% to 15%, 15% to 20%, 20% to 25%, 25% to 30%, 30% to 35%, 35% to 40%, 40% to 45%, or 45% to 50% compared to the base polymer alone.

[0021] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a tensile strength in the range of about 10 MPa to about 60 MPa. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a tensile strength in the range of about 10 MPa to about 15 MPa, about 15 MPa to about 20 MPa, about 20 MPa to about 25 MPa, about 25 MPa to about 30 MPa, about 30 MPa to about 35 MPa, about 35 MPa to about 40 MPa, about 40 MPa to about 45 MPa, about 45 MPa to about 50 MPa, about 50 MPa to about 55 MPa, about 55 MPa to about 60 MPa, about 60 MPa to about 65 MPa, or about 65 MPa to about 70 MPa. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a tensile strength of about 10 MPa or more, about 15 MPa or more, about 15 MPa or more, about 20 MPa or more, about 20 MPa or more, about 25 MPa or more, about 25 MPa or more, about 30 MPa or more, about 30 MPa to about 35 MPa or more, about 35 MPa or more, 40 MPa or more, about 45 MPa or more, about 45 MPa or more, about 50 MPa or more, about 50 MPa or more, about 55 MPa or more, about 55 MPa or more, about 60 MPa or more, about 65 MPa or more, or about 70 MPa or more. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a tensile strength in the range of about 20 MPa to about 35 MPa. In some embodiments, the polymer-polysaccharide nanocomposite resin has a tensile strength in the range of about 20 MPa to about 40 MPa. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a tensile strength in the range of about 20 MPa to about 60 MPa. In some embodiments, the polymer-polysaccharide nanocomposite resin has a tensile strength ranging from about 20 MPa to about 70 MPa. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a tensile strength ranging from about 10 MPa to about 70 MPa.

[0022] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a stiffness modulus in the range of 250 MPa to about 450 MPa. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a modulus or stiffness in the range of 300 MPa to 400 MPa. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a modulus or stiffness of 300 MPa or greater, 305 MPa or greater, 310 MPa or greater, 315 MPa or greater, 320 MPa or greater, 330 MPa or greater, 340 MPa or greater, 350 MPa or greater, 360 MPa or greater, 370 MPa or greater, 380 MPa or greater, 390 MPa or greater, or 400 MPa or greater.

[0023] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has an elastic modulus in the range of 0.10 GPa to about 1.0 GPa. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has an elastic modulus in the range of 0.20 GPa to about 0.5 GPa. In some embodiments, the polymer-polysaccharide nanocomposite resin has an elastic modulus in the range of 0.20 GPa to about 0.4 GPa. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has an elastic modulus of 0.10 GPa or greater, 0.15 GPa or greater, 0.20 GPa or greater, 0.25 GPa or greater, 0.30 GPa or greater, 0.35 GPa or greater, 0.40 GPa or greater, 0.45 GPa or greater, or 0.50 GPa or greater.

[0024] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a tensile strain (εu) percentage ranging from 10% to about 300%. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a tensile strain (εu) percentage ranging from 20% to 200%. The polyester polymer-polysaccharide nanocomposite resin can have a tensile strain (εu) percentage of 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 100% or more, 110% or more, 120% or more, 130% or more, 140% or more, 150% or more, 160% or more, 170% or more, 180% or more, 190% or more, 200% or more, 210% or more, 220% or more, 230% or more, 240% or more, 250% or more, 260% or more, 270% or more, 280% or more, 290% or more, or 300% or more.

[0025] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has an intrinsic viscosity in the range of about 0.10 to about 1.50 dL / g. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has an intrinsic viscosity in the range of about 0.20 to about 0.50 dL / g. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has an intrinsic viscosity of about 0.10 dL / g or greater, 0.15 dL / g or greater, 0.20 dL / g or greater, 0.25 dL / g or greater, 0.30 dL / g or greater, 0.35 dL / g or greater, 0.40 dL / g or greater, 0.45 dL / g or greater, 0.50 dL / g or greater, 0.55 dL / g or greater, 0.60 dL / g or greater, 0.65 dL / g or greater, 0.70 dL / g or greater. g or greater, 0.75 dL / g or greater, 0.80 dL / g or greater, 0.85 dL / g or greater, 0.90 dL / g or greater, 0.95 dL / g or greater, 1.0 dL / g or greater, 1.10 dL / g or greater, 1.15 dL / g or greater, 1.20 dL / g or greater, 1.25 dL / g or greater, 1.30 dL / g or greater, 1.35 dL / g or greater, 1.40 dL / g or greater, 1.45 dL / g or greater, or 1.50 dL / g or greater.

[0026] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a relative viscosity in the range of about 3 to about 150. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a relative viscosity in the range of about 3 to about 5, about 5 to about 7, about 7 to about 10, about 10 to about 15, about 15 to about 20, about 20 to about 25, about 25 to about 30, about 30 to about 35, about 35 to about 40, about 40 to about 45, about 45 to about 50, about 50 to about 55, about 55 to about 60, about 60 to about 65, about 65 to about 70, or about 70 to about 75. , about 75 to about 80, about 80 to about 85, about 85 to about 90, about 90 to about 95, about 95 to about 100, about 100 to about 105, about 105 to about 110, about 110 to about 115, about 115 to about 120, about 120 to about 125, about 125 to about 130, about 130 to about 135, about 135 to about 140, about 140 to about 145, or about 145 to about 150.

[0027] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a melt viscosity ranging from about 500 to about 15,000 cP. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a melt viscosity ranging from about 500 to about 10,000 cP. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a melt viscosity ranging from about 500 to about 1,000 cP. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a melt viscosity ranging from about 800 to about 10,000 cP. In some embodiments, the polyester polymer-polysaccharide nanocomposite resin has a melt viscosity in the range of about 500 to about 1,000 cP, about 1,000 cP to about 1,500 cP, about 1,500 cP to about 2,000 cP, about 2,000 cP to about 2,500 cP, about 2,500 cP to about 3,000 cP, about 3,000 cP to about 3,500 cP, about 4,000 cP, about 4,000 cP to about 4,500 cP, about 4,500 cP to about 5,000 cP, about 5,000 cP to about 7,000 cP, about 7,000 cP to about 10,000 cP, or about 10,000 cP to about 15,000 cP. In some cases, the melt temperature at which the melt viscosity is measured is from about 115°C to about 230°C.

[0028] Polysaccharide nanoparticles Aspects of the present disclosure include polyester polymer-polysaccharide nanocomposite resins that include polysaccharide nanoparticles.

[0029] Polysaccharides are composed of multiple sugar units linked together by glycosidic linkages and have several unique characteristics that distinguish them from other biopolymer families. The polysaccharide materials that find use in the subject nanocomposites can be nanoparticles, i.e., nanostructured forms of the polysaccharide of interest. In some cases, the nanoparticles are crystalline and can be referred to as nanocrystals.

[0030] The polyester polymer-polysaccharide resin can be derived from polysaccharide nanoparticles. In some embodiments, the polyester polymer-polysaccharide resin is derived from polysaccharide nanocrystals and one or more monomers. In some embodiments, the one or more monomers include alkanediol monomers and alkanedioic acid monomers.

[0031] In some embodiments, the polysaccharide nanocrystals are derived from heparin, chitosan, chitin, hyaluronan, starch, cellulose, alginate, pectin, guar, starch / chitosan, chitosan / heparin, chitosan / hyaluronan, hyaluronan / heparin, or cellulose, as well as chitin whiskers and platelet-like starch. In some embodiments, the polysaccharide nanocrystals are derived from cellulose, starch, or chitin.

[0032] In some embodiments, the polysaccharide nanocrystals are derived from cellulose. In some embodiments, the polysaccharide nanocrystals are derived from starch. In some embodiments, the polysaccharide nanocrystals are derived from chitin.

[0033] In some embodiments, the polysaccharide nanocrystals can be spheres, rods, disks, or any other shape. In some embodiments, the nanocrystals can have a low size distribution. In some embodiments, the nanocrystals can have a high size distribution.

[0034] cellulose nanoparticles Polysaccharide nanoparticles that find use in the nanocomposites of the present disclosure can be composed of or derived from cellulose. In some embodiments, the polysaccharide nanocrystals are derived from cellulose. The terms cellulose nanoparticles and nanocellulose are used interchangeably herein. Nanocellulose refers to nanostructured cellulose, which can include nanofibers or non-fibrils, nanocrystals, or other nano-sized structures. Cellulose is a polysaccharide (formula: CH 10 O5) n ) and composed of linear chains of β(1→4)-linked D-glucose units (e.g., n is 100-100,000, such as 500-10,000). In some embodiments, the polysaccharide nanocrystals are cellulose nanocrystals. The terms cellulose nanocrystals and nanocellulose crystals (NCC) are used interchangeably herein. An exemplary formula for unmodified cellulose is shown below:

[0035] [ka]

[0036] In some embodiments, cellulose nanocrystals, as a subset of cellulose nanoparticles, are highly ordered nanoscale crystals that remain after treatment to remove disordered amorphous regions from nanofibrils (the next member of the cellulose hierarchy).

[0037] In some embodiments, cellulose nanocrystals are crystals derived from cellulose fibers by chemical treatment, such as acid hydrolysis. In some embodiments, cellulose nanocrystals are derived from acid-hydrolyzed cellulose from cellulosic biomass via an acid hydrolysis technique similar to that first described by Ranby, BG (Ranby, BG (1951) Discussion of the Faraday Society, 11, 158-164). Nanocellulose crystals (NCC) produced via sulfuric acid treatment and neutralized with base (in this case, NaOH) contain a large amount of sodium sulfate substituents, which affect their dispersibility in hydrophilic media.

[0038] It is understood that the NCCs found for use in the subject nanocomposites can be unmodified or modified, for example, by incorporating one or more substituents to replace or derivatize one or more of the three hydroxyl groups of one or more of the glucopyranose repeat units. In some cases, the NCCs are sulfated (-OSOH). During sulfuric acid hydrolysis of cellulose, starch, or chitin, sulfate groups cover the surface of the nanocrystals. If hydrochloric acid is used instead, sulfate groups (or other substituents) can be later attached to the nanocrystal surface by an esterification reaction with sulfuric acid. After HCl or HBr hydrolysis, the NCCs can be unmodified. Further modification steps can be performed to add substituents, such as amine-containing groups to provide surface cationization. After H3PO4 hydrolysis, the NCCs can be modified with phosphate (-OPO3H2). In some cases, after HCl / HBr hydrolysis and subsequent TEMPO-oxidation, the -CH2OH hydroxyl can be converted to a carboxylic acid.

[0039] Exemplary modifying units that can be incorporated into the glucopyranose repeat units at the surface of the NCC are shown below, where R is any convenient substituent, such as alkyl or substituted alkyl, alkanoyl or substituted alkanoyl, and the like.

[0040] [ka]

[0041] In some embodiments, the cellulose nanocrystals are derived from acid-hydrolyzed cellulose from source wood, cotton, bacteria, or algae. In some cases, sulfuric acid is used in the acid treatment of the cellulose. NCCs of interest that find use in the subject methods and compositions include those described by George et al. ("Cellulose nanocrystals: synthesis, functional properties, and applications," Nanotechnol Sci Appl. 2015;8:45-54), the disclosure of which is incorporated by reference.

[0042] In some embodiments, NCC generally toughens polybutylene succinate. In some embodiments, additives such as epoxy derivatives or epoxidized oils also toughen polybutylene succinate, but also soften PBS. In some embodiments, using a combination of NCC and epoxidized oil makes the material tough, but it also softens slightly.

[0043] In some embodiments, the acid hydrolyzed cellulose is obtained from naturally occurring cellulose fibers. In some embodiments, the acid hydrolyzed cellulose is obtained, for example, from plant biomass, vascular plants, cotton plants, wood pulp, jute, hemp, corn, frass, rice, wheat straw, or sisal. In some embodiments, the cellulose is obtained from plant biomass, including, but not limited to, trees, grasses, cotton, sisal, bamboo, and ramie.

[0044] In some embodiments, cellulose nanocrystals can be found as structural components of urochordates (sea creatures similar to sea cucumbers) and are produced naturally by the bacterium Acetobacter xylinum.

[0045] In some embodiments, the cellulose nanocrystals have average dimensions of about 1-80 nm in width and about 25-1000 nm in length. In some embodiments, the cellulose nanocrystals have average dimensions of about 1-100 nm in width and about 25-3000 nm in length. In some embodiments, the cellulose nanocrystals have average dimensions of about 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, 80 nm or more, 85 nm or more, 90 nm or more, 95 nm or more, or 100 nm or more in width and about 25 nm or more, 50 nm or more, 100 nm or more in length. and having an average length dimension of 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 500 nm or more, 550 nm or more, 600 nm or more, 650 nm or more, 700 nm or more, 800 nm or more, 850 nm or more, 900 nm or more, 950 nm or more, 1000 nm or more, 1500 nm or more, 2000 nm or more, 2500 nm or more, or 3000 nm or more.

[0046] In some embodiments, the cellulose nanocrystals have average dimensions of about 3-50 nm width and about 100-1000 nm length.

[0047] In some embodiments, the cellulose nanocrystals have an average aspect ratio (length / diameter) that is 10 or greater, e.g., 20 or greater, 30 or greater, 40 or greater, 50 or greater, 60 or greater, 70 or greater, 80 or greater, 90 or greater, 100 or greater, 150 or greater, 200 or greater, or even greater. In some embodiments, the cellulose nanocrystals have an average aspect ratio (length / diameter) that is 10 to 200, e.g., 20 to 200, 50 to 200, or 100 to 200.

[0048] In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 1 d.nm to about 400 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 1 d.nm to about 50 d.nm, from about 50 d.nm to about 100 d.nm, from about 100 d.nm to about 150 d.nm, from about 150 d.nm to about 200 d.nm, from 200 d.nm to about 250 d.nm, from 250 d.nm to about 300 d.nm, from 300 d.nm to about 350 d.nm, or from 350 d.nm to about 400 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 1 d.nm to about 20 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 10 d.nm to about 100 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 10 d.nm to about 30 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 100 d.nm to about 200 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from 1 d.nm or more, 2 d.nm or more, 4 d.nm or more, 6 d.nm or more, 8 d.nm or more, 10 d.nm or more, 12 d.nm or more, 14 d.nm or more, 16 d.nm or more, 18 d.nm or more, 20 d.nm or more, 22 d.nm or more, 24 d.nm or more, 26 d.nm or more, 28 d.nm or more, 30 d.nm or more, 32 d.nm or more, 34 d.nm or more, 36 d.nm or more, 38 d.nm or more, 40 d.nm or more, 42 d.nm or more, 44 d.nm or more, 46 d.nm or more, 48 d.nm or more, 50 d.nm or more. and having a particle size distribution of 0.05 d.nm or more, 52 d.nm or more, 54 d.nm or more, 56 d.nm or more, 58 d.nm or more, 60 d.nm or more, 62 d.nm or more, 64 d.nm or more, 66 d.nm or more, 68 d.nm or more, 70 d.nm or more, 72 d.nm or more, 74 d.nm or more, 76 d.nm or more, 78 d.nm or more, 80 d.nm or more, 82 d.nm or more, 84 d.nm or more, 86 d.nm or more, 88 d.nm or more, 90 d.nm or more, 92 d.nm or more, 94 d.nm or more, 96 d.nm or more, 98 d.nm or more, or 100 d.nm or more.In some embodiments, the nanocrystals in the dispersion have a diameter of 100 d.nm or greater, 125 d.nm or greater, 150 d.nm or greater, 175 d.nm or greater, 200 d.nm or greater, 225 d.nm or greater, 250 d.nm or greater, 275 d.nm or greater, 300 d.nm or greater, 325 d.nm or greater, 350 d.nm or greater, 400 d.nm or greater, 425 d.nm or greater, 500 d.nm or greater, 525 d.nm or greater, 550 d.nm or greater, 575 d.nm and having a particle size distribution of ≥ 600 d.nm, ≥ 625 d.nm, ≥ 650 d.nm, ≥ 675 d.nm, ≥ 700 d.nm, ≥ 725 d.nm, ≥ 750 d.nm, ≥ 775 d.nm, ≥ 800 d.nm, ≥ 825 d.nm, ≥ 850 d.nm, ≥ 875 d.nm, ≥ 900 d.nm, ≥ 925 d.nm, ≥ 950 d.nm, ≥ 975 d.nm, or ≥ 1000 d.nm.

[0049] In some embodiments, increasing the length of the cellulose nanocrystals increases the potential load distribution throughout the polymer. In some embodiments, the orientation of the cellulose nanocrystals within the polymer increases the interfacial contact between adjacent cellulose nanocrystals in the axial orientation, which may increase the ultimate tensile strength. In some embodiments, the transverse orientation

[0050] The morphology (e.g., length, aspect ratio, length polydispersity) and surface charge of cellulose nanocrystals vary greatly based on synthesis conditions. In some embodiments, acid hydrolysis is used to decompose cellulose microfibrils by digesting the amorphous regions connecting the cellulose nanocrystals. In some embodiments, processing typically requires heating, agitation, rinsing, filtration, dialysis, and ultrasonication, with the parameters of each step having a direct effect on the morphology and / or surface chemistry of the cellulose nanocrystals. In some embodiments, the end result of cellulose nanocrystal processing involves the production of a suspension of liquid crystalline cellulose nanocrystals, which form either a nematic or chiral nematic mesophase (e.g., depending on the length, aspect ratio, length polydispersity, surface charge, nanocrystalline cellulose (NCC) concentration, and electrolyte concentration of the cellulose nanocrystals).

[0051] In some embodiments, cellulose nanocrystals enhance one or more mechanical properties of the polymer base resin. Non-limiting properties that can be improved by incorporating cellulose nanoparticles into the base polymer resin can be selected from at least one of the following: elastic modulus, tensile yield stress, hoop stress rating, flexural modulus, UV resistance, and reduced gas permeability. Thus, the present disclosure allows for measurable performance enhancement without significant loss of other desirable properties, such as tensile strength, ultimate elongation, melt index, thermal stability, impact strength, slow crack growth resistance, and rapid crack propagation resistance.

[0052] Aspects of the subject disclosure include the preparation of nanocomposites in which polymer chains can be grafted to polysaccharide nanoparticles, such as cellulose nanocrystals, for example, via ester linkages to the hydroxyl groups of the polysaccharide.

[0053] Polyester Polymer The nanocomposites of the present disclosure are based on polyester polymers. The term polyester polymer refers to a polymer comprising multiple repeating units linked via ester linkages. In some embodiments, the ester linkages are formed between an aliphatic diol comonomer and an aliphatic diacid comonomer. The polyester polymers of the nanocomposites of interest can be biodegradable. The exact components of the polyester polymer can be selected to provide desired properties for the resulting nanocomposite.

[0054] The term "unit" refers to a structural subunit of a polymer. The term unit is meant to include monomers, comonomers, coblocks, segments, repeat units, and the like. A "repeating unit" is a subunit of a polymer defined by the minimum number of distinct structural features required for the unit to be considered a monomer, such that when the unit is repeated n times, the resulting structure represents a polymer or block thereof. In some cases, a polymer may contain two or more different repeating units; for example, if the polymer is a multiblock polymer, each block may define a distinct repeating unit. In some cases, a repeating unit of a polymer contains a single monomer group. In certain instances, a repeating unit of a polymer contains two or more monomer groups, i.e., two, three, four or more comonomer groups, etc.

[0055] The term "comonomer" or "comonomer group" refers to a structural unit of a polymer that may itself be part of a repeat unit of the polymer. In some embodiments, the polyester polymer comprises a block copolymer composed of blocks of polymerized monomers. In such cases, the block copolymer may be described as having distinct repeat units, each corresponding to a distinct coblock of the polymer. In some cases, the polymer is a diblock copolymer, containing two different coblocks. In such cases, the polymer may be described as comprising coblocks, and each coblock may be composed of one, two, three or more comonomers, etc.

[0056] In some embodiments, the nanocomposite comprises a polyester polymer comprising a repeating unit of formula (I):

[0057] [ka]

[0058] During the ceremony, L 1 and L 2 are each independently a linking group 2 to 12 atoms in length; p is 1 to 100,000; Each * independently represents H, OH, alkyl, alkoxy, alkanoyl, aroyl, heteroaroyl, aryloxy, heteroaryloxy, capping group, copolymer segment, repeat unit, comonomer, grafted polysaccharide nanoparticle, linker, crosslinker, or epoxidized oil, epoxy derivative, or fatty acid.

[0059] L 1 and L 2 can be any convenient divalent linking group having a chain length of 2 to 12 atoms, e.g., 2, 3, 4, 5, 6, 8, 10, or 12 carbon atoms, and the linker can be linear, branched, or cyclic. In certain cases, 1, 2, 3, 4, or 5 or more carbon atoms in the linking group backbone can be optionally substituted with sulfur, nitrogen, or oxygen heteroatoms. The bonds between the backbone atoms can be saturated or unsaturated (e.g., alkenyl), and in some cases, one, two, or up to three unsaturated bonds are present in the linker backbone. The linker can include one or more substituents, e.g., with alkyl, aryl, or alkenyl groups. Linkers may include, but are not limited to, polyethylene glycol; ether, thioether, tertiary amine, alkenyl, alkyl (which may be linear or branched), such as methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, 1,1-dimethylethyl (t-butyl), and the like. In some embodiments of Formula (I), L 1 and L 2are each independently selected from alkyl, substituted alkyl, alkenyl, and substituted alkenyl.

[0060] "Alkyl" refers to a divalent aliphatic hydrocarbyl group (e.g., alkyl or alkenyl), either straight-chained or branched, and preferably having 2 to 12, more preferably 2 to 6, carbon atoms, optionally interrupted with one or more groups selected from -O-, -NR10-, NRC(O)-, -C(O)NR10-, and the like. This term includes, by way of example, methylene (CH2), ethylene (CH2CH2), n-propylene (CH2CH2CH2), iso-propylene (CH2CH(CH3)), (C(CH3)2CH2CH2), (C(CH3)2CH2C(O)), (C(CH3)2CH2C(O)NH), (CH(CH3)CH2-), and the like. "Substituted alkylene" refers to an alkylene group having one to three hydrogens replaced with a substituent.

[0061] In some embodiments of Formula (I), p is 2 to 100,000. In some embodiments of Formula (I), p is 5 to 100,000. In some embodiments of Formula (I), p is 10 to 100,000. In some embodiments of Formula (I), p is 100 to 100,000. In some embodiments of Formula (I), p is 1000 to 100,000.

[0062] In some embodiments of Formula (I), p is 2 to 10,000. In some embodiments of Formula (I), p is 5 to 10,000. In some embodiments of Formula (I), p is 10 to 10,000. In some embodiments of Formula (I), p is 100 to 10,000. In some embodiments of Formula (I), p is 1,000 to 10,000. In some embodiments of Formula (I), p is 2 to 1,000. In some embodiments of Formula (II), p is 5 to 1,000. In some embodiments of Formula (I), p is 10 to 1,000. In some embodiments of Formula (I), p is 100 to 1,000.

[0063] Any convenient polymer, and / or its monomer precursor, can be adapted for incorporation into the subject preparation methods to provide nanocomposite compositions with desirable physical properties (e.g., tensile strength, etc., as described herein). Polymers of interest, and their monomer precursors, that can be adapted for use in the subject preparation methods and nanocomposite compositions include, but are not limited to, the polymers and monomers described by Zheng et al. (Ind. Eng. Chem. Res. 2013, 52, 6147-6155), Tserki et al. (Polymer Degradation and Stability, Volume 91, Issue 2, February 2006, 367-376), US2019 / 0194400, and US9,796,849, the disclosures of which are incorporated herein by reference in their entireties.

[0064] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin is derived from a mixture comprising polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid monomers. Aspects of the subject disclosure include the preparation of nanocomposites via polymerization reactions in which polysaccharide nanoparticles, such as cellulose nanocrystals, are present during polymerization to allow for the grafting of polymer chains to the polysaccharide, for example, via ester linkages to hydroxyl groups on the polysaccharide.

[0065] In some embodiments, the polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid agent monomers are polycondensed in the dispersion to produce a polyester polymer-polysaccharide nanocomposite resin.

[0066] In some embodiments, the polyester polymer of the polymer-polysaccharide nanocomposite resin is an aliphatic polyester polymer. In some cases, the polyester polymer is biodegradable. In some embodiments, the polymer comprises a polybutylene succinate homopolymer or copolymer. In some embodiments, the polymer comprises poly(butylene succinate-co-butylene adipate).

[0067] The polyester polymer may include one or more additional comonomers incorporated into the polymer to provide certain desired properties.

[0068] In some embodiments, the aliphatic polyester polymer may comprise segments of specific aliphatic polyester polymers selected from, but not limited to, polylactide (PLA) (e.g., poly(lactic acid)), polyglycolide (PGA) (e.g., polyglycolic acid), poly(ε-caprolactone) (PCL), poly(γ-valerolactone) (PVL), and copolymer poly(lactic-co-glycolic acid) (PLGA).

[0069] PLA is a biodegradable and hydrophobic polymer synthesized from lactic acid.

[0070] PCL is a semi-crystalline polyester, typically with a melting temperature of about 55-60°C.

[0071] PGA is a highly crystalline polymer, typically with a melting point above 200°C and a glass transition temperature of about 35-40°C.

[0072] PLGA can be fabricated with different ratios of its monomers, lactide and glycolide, allowing for tunable degradation and release rates.

[0073] In some embodiments, the nanocomposite comprises a polyester polymer comprising a repeating unit of formula (II):

[0074] [ka]

[0075] During the ceremony, n is 1 to 11; m is 1 to 11; p is 1 to 100,000; Each * independently represents H, OH, alkyl, alkoxy, alkanoyl, aroyl, heteroaroyl, aryloxy, heteroaryloxy, capping group, copolymer segment, repeat unit, comonomer, grafted polysaccharide nanoparticle, linker, crosslinker, or epoxidized oil, epoxy derivative, or fatty acid.

[0076] In some embodiments of Formula (II), n is 1-5 and m is 1-5.

[0077] In some embodiments of Formula (II), n is 1. In some embodiments of Formula (II), n is 2. In some embodiments of Formula (II), n is 3. In some embodiments of Formula (II), n is 4. In some embodiments of Formula (II), n is 5.

[0078] In some embodiments of Formula (II), m is 2 to 5. In some embodiments of Formula (II), m is 2. In some embodiments of Formula (II), m is 3. In some embodiments of Formula (II), m is 4. In some embodiments of Formula (II), m is 5.

[0079] In some embodiments of Formula (II), n is 1 and m is 3.

[0080] In some embodiments of Formula (II), p is 2 to 100,000. In some embodiments of Formula (II), p is 5 to 100,000. In some embodiments of Formula (II), p is 10 to 100,000. In some embodiments of Formula (II), p is 100 to 100,000. In some embodiments of Formula (II), p is 1000 to 100,000.

[0081] In some embodiments of Formula (II), p is 2 to 10,000. In some embodiments of Formula (II), p is 5 to 10,000. In some embodiments of Formula (II), p is 10 to 10,000. In some embodiments of Formula (II), p is 100 to 10,000. In some embodiments of Formula (II), p is 1000 to 10,000.

[0082] In some embodiments of Formula (II), p is 2 to 1,000. In some embodiments of Formula (II), p is 5 to 1,000. In some embodiments of Formula (II), p is 10 to 1,000. In some embodiments of Formula (II), p is 100 to 1,000.

[0083] In some embodiments of Formulas (I)-(II), at least one * represents a grafted polysaccharide nanoparticle. In some embodiments of Formulas (I)-(II), at least one * represents a grafted cellulose nanoparticle. In some embodiments of Formulas (I)-(II), at least one * represents a grafted cellulose nanocrystal.

[0084] In some embodiments of Formulas (I)-(II), at least one * represents a capping group. A capping group is a group containing a compatible functional group suitable for attachment to the hydroxy or carboxylic acid end of a polymer segment. Exemplary capping groups include an alkanoyl group, which forms an ester linkage to the hydroxy end, and an alkoxy group, which forms an ester linkage to the carboxylic acid end. A variety of chemical linkages and capping groups can be utilized. In some embodiments of Formulas (I)-(II), at least one * represents a linkage to an epoxidized oil, epoxy derivative, or fatty acid. The epoxidized oil may have one or more epoxide groups suitable for coupling to a reactive group on a polyester polymer, such as a carboxylic acid end group to form an ester linkage to the epoxidized oil, or a hydroxyl end group to form an ether linkage. When the epoxidized oil has two or more epoxide-reactive groups, it can provide crosslinking between two or more polyester polymers. In some cases, a fatty acid can be used to cap the polyester polymer via an ester linkage to the hydroxyl end group.

[0085] In some embodiments of Formulas (I)-(II), at least one * represents a comonomer, copolymer segment, or repeat unit (e.g., as described herein), such that the polyester polymer is a copolymer (e.g., as described herein), it being understood that such a copolymer may be a random copolymer or a block copolymer.

[0086] In some embodiments, the polyester polymer-polysaccharide nanocomposite resin comprises a diol monomer HO-L 2 -OH-based polymer repeat units, wherein L 2 is as defined in formula (I). 2 is alkyl or substituted alkyl. 2 is alkenyl or substituted alkenyl.

[0087] Alkanediol Monomers In some aspects, the polyester polymer-polysaccharide nanocomposite resin comprises polymer repeat units based on alkanediol monomers. Alkanediol monomers refer to linear or branched alkyl groups (e.g., HO-alkyl-OH) with terminal hydroxyl groups. The alkanediol monomers can have C2-C12 chains connecting the terminal hydroxyl groups. The alkanediol monomers can be unsubstituted or substituted with one or more substituents. In some embodiments, the alkyl groups contain 1-10 carbon atoms. In certain embodiments, the alkyl groups contain 1-6 carbon atoms, such as 1-4 carbon atoms. The term includes, by way of example, linear and branched hydrocarbyl groups such as ethyl (CH3CH2), n-propyl (CH3CH2CH2-), isopropyl ((CH3)2CH-), n-butyl (CH3CH2CH2CH2), isobutyl ((CH3)2CHCH2), sec-butyl ((CH3)(CH3CH2)CH-), t-butyl ((CH3)3C-), n-pentyl (CH3CH2CH2CH2CH2-), and neopentyl ((CH3)3CCH2-).

[0088] The term "substituted alkyl" refers to an alkyl group, as defined herein, wherein one or more carbon atoms in the alkyl chain are optionally O-, N-, S-, -S(O)n- (where n is 0-2), -NR- (where R is hydrogen or alkyl), and includes alkoxy, substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, acyl, acylamino, acyloxy, amino, aminoacyl, aminoacyloxy, oxyaminoacyl, azido, cyano, halogen, hydroxyl, oxo, thioketo, carboxyl, carboxylalkyl, thioaryloxy, thioheteroaryloxy, thioheterocyclooxy, thioheterocyclooxy, thioaryl ... and substituted with a heteroatom having one to five substituents selected from the group consisting of thiol, thiol, thioalkoxy, substituted thioalkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro, -SO-alkyl, -SO-aryl, -SO-heteroaryl, -SO2-alkyl, -SO2-aryl, SO2-heteroaryl, and -NRaRb, where Ra and Rb may be the same or different and are selected from hydrogen, optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl, and heterocyclic.

[0089] In some embodiments, the alkanediol monomer is selected from 1,4-butanediol monomer, 1,2-ethanediol monomer, 1,3-propanediol monomer, 1,5-pentanediol monomer, or 1,6-hexanediol monomer.

[0090] In some embodiments, the alkanediol monomer comprises one or more diols for forming a polyester composite. Non-limiting examples of other suitable diols include, but are not limited to, ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 1,4-cyclohexanedimethanol, hydroquinone, 1,5-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)-2,2-propane, and combinations thereof.

[0091] In some embodiments, the alkanediol monomer 1,4-butanediol. In some embodiments, the alkanediol monomer is 1,2-ethanediol. In some embodiments, the alkanediol monomer is 1,3-propanediol.

[0092] In some embodiments, one or more additional components may be added along with one or more other diols or may be substituted for 1,4-butanediol to form a polyester composite.

[0093] Non-limiting examples of other suitable diols include, but are not limited to, ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 1,4-cyclohexanedimethanol, hydroquinone, 1,5-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)-2,2-propane, and combinations thereof.

[0094] In some embodiments, polyethers having hydroxyl end groups can be used in combination with the diols of the present disclosure. In some embodiments, the polyethers having hydroxyl end groups typically have a carbon number of 4 or more, with a lower limit of 10 or more, and typically 1,000 or less, 200 or less, or even 100 or less. Non-limiting examples of polyethers having hydroxyl end groups include, but are not limited to, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-1,6-hexamethylene glycol, and the like. Copolymer polyethers of polyethylene glycol and polypropylene glycol can also be used.

[0095] Alkanedioic Acid Agent Monomer The polyester polymer-polysaccharide nanocomposite comprises a polymer repeat unit based on a diacid monomer (e.g., a compound of the formula HO2C-L 1 -CO2, or a derivative or equivalent thereof, wherein L 1 is as defined in formula (I). The polyester polymer-polysaccharide nanocomposite includes polymer repeat units based on alkanedioic acid monomers. Alkanedioic acid monomers refer to linear or branched alkyl groups having terminal hydroxyl groups. Alkanedioic acid monomers can have C2-C12 alkyl chains connecting terminal carboxylic acid or ester groups, or equivalent functional groups. Alkanedioic acid monomers can be unsubstituted or substituted with one or more substituents. In some embodiments, the alkyl group contains 1 to 10 carbon atoms. In certain embodiments, the alkyl group contains 1 to 6 carbon atoms, such as 1 to 4 carbon atoms. It is understood that the diacid group of the monomer is typically provided in a derivative form suitable for polymerization with a hydroxyl-containing comonomer. In some embodiments, when the alkanedioic acid monomer is provided in the form of an ester or cyclic anhydride, the monomer is capable of transesterification with a hydroxyl-containing monomer, such as an alkanediol monomer.

[0096] In some embodiments, the alkanedioic acid agent monomer is selected from succinic acid, monoalkyl succinates, dialkyl succinates (e.g., dimethyl or diethyl succinate), succinic anhydride, adipic acid, monoalkyl adipates, dialkyl adipates (e.g., dimethyl or diethyl adipate), and adipic anhydride.

[0097] In some embodiments, the alkanedioic acid monomer is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, and their cyclic acid anhydride equivalents. In certain embodiments, the succinate derivative is substituted with or added to one or more additional components. In some embodiments, these one or more additional components include one or more dicarboxylic acids or dicarboxylic acid anhydrides. Non-limiting examples include, but are not limited to, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, and their cyclic acid anhydride equivalents.

[0098] In some embodiments, the polyester polymer comprises repeat units based on an aliphatic diacid comonomer (e.g., as described herein). In certain embodiments, the aliphatic diacid comonomer is fumaric acid.

[0099] Polybutylene succinate or fumarate polymers and copolymers In some embodiments, the polyester polymer-polysaccharide nanocomposite resin comprises polysaccharide nanocrystals, alkanediol monomers, and diacid agent monomers.

[0100] In some embodiments, the alkanediol monomer is a 1,4-butanediol monomer. In some embodiments, the alkanedioic acid agent monomer is a succinic acid agent monomer. In some embodiments, the alkanedioic acid agent monomer is succinic anhydride.

[0101] Aliphatic homopolyesters and copolyesters can be prepared from 1,4 butanediol and succinic acid monomers (e.g., succinic anhydride or the dimethyl ester of succinic acid), and optionally one or more other comonomers (e.g., as described herein), by a two-step process of transesterification and polycondensation. Similarly, alkenyl diacid monomers such as fumaric acid monomers, e.g., maleic anhydride, can be utilized with 1,4-butanediol monomers to produce polybutylene fumarate (PBF) homopolymers or copolymers for use in the subject nanocomposites.

[0102] In some embodiments, a mixture comprising polysaccharide nanocrystals, 1,4-butanediol monomers, and succinic acid agent monomers (optionally in the presence of one or more additional comonomers) is polycondensed in a dispersion to produce a polymer-polysaccharide nanocomposite resin.

[0103] In some embodiments, the polymer of the polymer-polysaccharide nanocomposite resin is a polybutylene succinate (PBS) homopolymer or copolymer.

[0104] In some embodiments, the polymer of the polymer-polysaccharide nanocomposite resin is a polybutylene succinate copolymer.

[0105] In some embodiments, the polybutylene succinate copolymer is butylene fumarate or a polymer blend of PBS and polybutylene fumarate (PBF). In some embodiments, the polybutylene succinate copolymer is represented by formula (III):

[0106] [ka]

[0107] wherein p, q, and r independently range from 1 to 100,000, and each * independently represents H, OH, alkyl, alkoxy, alkanoyl, aroyl, heteroaroyl, aryloxy, heteroaryloxy, capping group, copolymer segment, repeat unit, comonomer, grafted polysaccharide nanoparticle, linker, crosslinker, or epoxidized oil, epoxy derivative, or fatty acid.

[0108] In some embodiments of Formula (III), p and q are independently 2 to 100,000. In some embodiments of Formula (III), p and q are independently 5 to 100,000. In some embodiments of Formula (III), p and q are independently 10 to 100,000. In some embodiments of Formula (III), p and q are independently 100 to 100,000. In some embodiments of Formula (III), p and q are independently 1000 to 100,000.

[0109] In some embodiments of Formula (III), p and q are independently 2 to 10,000. In some embodiments of Formula (III), p and q are independently 5 to 10,000. In some embodiments of Formula (III), p and q are independently 10 to 10,000. In some embodiments of Formula (III), p and q are independently 100 to 10,000. In some embodiments of Formula (III), p and q are independently 1,000 to 10,000. In some embodiments of Formula (III), p and q are independently 2 to 1,000. In some embodiments of Formula (III), p and q are independently 5 to 1,000. In some embodiments of Formula (III), p and q are independently 10 to 1,000. In some embodiments of Formula (III), p and q are independently 100 to 1,000.

[0110] In some embodiments of Formula (III), r is 1 to 10,000. In some embodiments of Formula (III), r is 1 to 1,000. In some embodiments of Formula (III), r is 1 to 100. In some embodiments of Formula (III), r is 1 to 10.

[0111] It is understood that the polybutylene succinate copolymer can include any convenient arrangement of comonomers, such as a coblock or random arrangement. In some embodiments, the polybutylene succinate copolymer is represented by formula (IV):

[0112] [ka]

[0113] where x, y, and z represent the mol % of the comonomer in the polymer.

[0114] In some embodiments, x, y, and z are each independently 1 to 50 mol%. In some cases, y is x + z. In some embodiments, x > z. In some embodiments, z > x.

[0115] In some embodiments, the polybutylene succinate copolymer has an average MW of between 10 kDa and 100 kDa, such as between 10 kDa and 50 kDa or between 20 kDa and 40 kDa.

[0116] In some embodiments, adding a fumarate moiety broadens the crystalline melt temperature of PBS by up to 10-15°C. For example, PBS has a melt temperature of approximately 115°C, which can hinder melt processability in yarn / fabric production and yarn / fabric applications. Pure PBF has a melt temperature of approximately 139°C. In some embodiments, PBF, when blended with succinate-derived polyesters, acts as a polymer nucleating agent, enhancing the crystallization rate.

[0117] In some embodiments, the polybutylene succinate copolymer is diethylene glycol succinate. In some embodiments, diethylene glycol (DEG) can be replaced with triethylene glycol, 1,3 propanediol, sorbitol, or xylitol. In some embodiments, the introduction of a hydrophilic backbone creates a better substrate for certain bacteria and fungi to adhere to, allowing aerobic / anaerobic degradation processes to occur. In some embodiments, the introduction of an asymmetric backbone reduces crystallinity and improves biodegradability. PBS's hydrophobicity and high crystallinity limit its ease of degradation in certain aquatic and terrestrial environments.

[0118] In some embodiments, the polybutylene succinate copolymer is polypropylene oxide succinate. The incorporation of poly(1,3 propylene oxide) polyol allows for the formation of phase-separated soft segments in the copolymer, creating a thermoplastic polyester elastomer (TPPE). The molecular weight of the polyol can range from 500 to 2700 g / mol. In some embodiments, polytetramethylene oxide (PTMO) or polyethylene glycol (PEG) polyols of similar molecular weight can also be used. In some embodiments, fumaric acid can be included in the copolymer. In some embodiments, fumaric acid can be introduced to increase crystallinity and induce better phase separation of the hard (PBS) and soft (PPOS) segments.

[0119] In some embodiments, the polybutylene succinate copolymer is phenylethylene succinate. In some embodiments, tyrosol can be substituted with homovanillyl alcohol, coniferyl alcohol, or vanillyl alcohol. For example, the introduction of naturally occurring aryl hydroxy acids increases the strength and durability of polybutylene succinate.

[0120] In some embodiments, the polybutylene succinate copolymer is butylene coumarate. In some embodiments, p-coumaric acid is replaced with ferulic acid, phloretic acid, syringic acid, sinapic acid, or caffeic acid. For example, the introduction of hydroxycinnamic acid derivatives increases the strength and melting point of PBS.

[0121] Succinic Acid Monomer In some embodiments, the alkanedioic acid agent monomer is a succinic acid agent monomer or a derivative thereof. In some embodiments, the alkanedioic acid agent monomer is a succinic acid agent monomer. In some embodiments, the succinic acid agent is succinic anhydride.

[0122] In some embodiments, the succinic agent monomer includes, but is not limited to, a succinic agent selected from succinic acid, a monoalkyl succinate, a dialkyl succinate (e.g., dimethyl succinate or diethyl succinate), or succinic anhydride.

[0123] In some embodiments, the succinic acid agent is a succinate derivative. In some embodiments, the succinate derivative is succinate anhydride. In some embodiments, succinate anhydride increases the rate of esterification with 1,4 butanediol and also reduces the amount of harmful THF produced during the esterification step. However, other suitable, non-limiting examples of succinate derivatives can include succinic acid or succinate esters.

[0124] additives In some embodiments, the polymer-polysaccharide nanocomposite resin comprises one or more additional monomers and / or capping agents.

[0125] In some embodiments, the polymer-polysaccharide nanocomposite comprises one or more additional monomers, such as, but not limited to, comonomers, epoxy derivatives, oils, pigments, crosslinkers, and the like.

[0126] In some embodiments, the one or more additional monomers include an additional alkanediol monomer and / or an additional diacid agent monomer.

[0127] In some embodiments, the additional alkanediol monomers include, but are not limited to, 1,4-butanediol monomers, 1,2-ethanediol monomers, 1,3-propanediol monomers, 1,5-pentanediol monomers, or 1,6-hexanediol monomers.

[0128] In some embodiments, additional diacid agent monomers include, but are not limited to, succinic acid, monoalkyl succinates, dialkyl succinates (e.g., dimethyl or diethyl succinate), succinic anhydride, adipic acid, monoalkyl adipates, dialkyl adipates (e.g., dimethyl or diethyl adipate), and adipic anhydride.

[0129] In some embodiments, the additional alkanedioic acid agent monomer comprises adipic anhydride.

[0130] In some embodiments, the one or more additional components may include a hydrophobic agent. In some embodiments, the hydrophobic agent is an oil. In some embodiments, the hydrophobic agent is an elastomeric material. In some embodiments, the hydrophobic agent is epoxidized soybean oil or an elastomeric material.

[0131] In some embodiments, the one or more additional components include, but are not limited to, agents to provide additional water and oxygen barrier properties. Non-limiting exemplary water and oxygen barrier agents include candelilla wax, beeswax, and other waxes. In some embodiments, such barrier agents are derived from renewable sources.

[0132] In some embodiments, one or more additional components are non-covalent plasticizers. Plasticizers are additives used to impart flexibility to polymer blends and improve their processability. Any known non-covalent plasticizer can be included as one or more additional components.

[0133] In some embodiments, the one or more additional components include a polishing agent that provides an aesthetically pleasing sheen to the finished product. Non-limiting exemplary polishing agents include shea butter and nut oils such as Brazil nut oil. In some embodiments, the polishing agent is derived from a renewable source.

[0134] In some embodiments, the one or more additional components include, but are not limited to, impact modifiers, antioxidants, antibacterial agents, antifungal agents, antistatic agents, fillers, heat stabilizers, UV stabilizers, dyes, fillers, crystallization promoters, and coupling agents.

[0135] Non-limiting examples of antioxidants include hindered phenol antioxidants such as p-tert-butylhydroxytoluene and p-tert-butylhydroxyanisole, sulfur antioxidants such as distearyl thiodipropionate and dilauryl thiodipropionate, and the like; heat stabilizers include triphenyl phosphite, trilauryl phosphite, tris-nonylphenyl phosphite, and the like; UV stabilizers include p-tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone, and the like; lubricants include calcium stearate, zinc stearate, barium stearate, sodium palmitate, and the like; and antistatic agents include N,N-bis(hydroxyethyl methyl acrylate). Flame retardants include hexabromocyclododecane, tris-(2,3-dichloropropyl)phosphate, pentabromophenyl allyl ether, etc.; antiblocking agents include combinations of inorganic fillers such as silica and oleamide; inorganic fillers or nucleating agents include calcium carbonate, silica, titanium oxide, talc, mica, barium sulfate, alumina, a mixture of NaHCO3 and citric acid, etc.; crystallization accelerators include polyethylene terephthalate, poly-transcyclohexanedimethanol terephthalate, etc.; organic fillers include wood powder, rice husks, recycled paper such as newspaper, starch (including modified materials such as alpha-starch), cellulose, etc.

[0136] In some embodiments, polyethers having hydroxyl end groups can be used in combination with the diols disclosed in the present disclosure. The carbon number of the hydroxyl end group polyether is typically 4 or more, preferably 10 or more, with a lower limit of 1,000 or less, preferably 200 or less, and more preferably 100 or less. Non-limiting examples of polyethers having hydroxyl end groups include, but are not limited to, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-1,6-hexamethylene glycol, and the like. Copolymer polyethers of polyethylene glycol and polypropylene glycol can also be used.

[0137] In some embodiments, the one or more additional monomers comprise one or more dicarboxylic acids or dicarboxylic anhydrides. Non-limiting examples may include, but are not limited to, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, and their cyclic anhydride equivalents.

[0138] In some embodiments, the one or more additional monomers include an epoxidized oil, an epoxy derivative, or a fatty acid. In some embodiments, the epoxidized oil, epoxy derivative, or fatty acid can be esterified. In some embodiments, the epoxy derivative or epoxidized oil is added at the end of the reaction. For example, in some embodiments, the epoxy derivative or epoxidized product can be added after repressurizing the vessel just before cooling and discharging the polymer. In some embodiments, the NCC, expoxy derivative, and / or epoxidized oil can be added upfront with the alkanediol monomer and / or alkanedioic acid monomer. For example, in some embodiments, the NCC can be added in the form of a dispersion at the beginning of the reaction. In some embodiments, the epoxy derivative or epoxidized oil is added at the end of the esterification process just before the catalyst is added and polycondensation is performed. In some examples, the catalyst is added after the epoxy derivative or epoxidized oil is allowed to react for 5 minutes. The high-shear disperser method follows the same process as the ultrasonication method in terms of time and power consumption, but instead uses the equipment described at https: / / www(dot)mixers(dot)com / products / high-speed-dispersers / .

[0139] In some embodiments, one or more additional monomers are epoxidized oils. In some embodiments, one or more additional monomers are epoxidized derivatives. In some embodiments, epoxidized oils or epoxy derivatives include but are not limited to epoxidized linseed oil, lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, tung oil, tall oil, calendula, rapeseed oil, peanut oil, sesame oil, grapeseed oil, olive oil, jojoba oil, dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil, corn oil, rapeseed oil, orange oil, and mixtures thereof.

[0140] In some embodiments, the one or more additional monomers comprise a catalyst.

[0141] Non-limiting exemplary catalysts include titanium or zirconium compounds, such as titanium lactate or zirconium butoxide. Generally, compounds containing at least one metal element from Groups 1 to 14 of the periodic table can be used as esterification catalysts. Specific examples of metal elements include scandium, yttrium, samarium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium. Among these, scandium, yttrium, titanium, zirconium, vanadium, molybdenum, tungsten, zinc, iron, and germanium are preferred, with titanium, zirconium, tungsten, iron, and germanium being particularly preferred. Furthermore, to reduce the concentration of polyester ends, which affect the thermal stability of polyesters, metal elements from Groups 3 to 6 of the periodic table that exhibit Lewis acidity are preferred. Specific examples include scandium, titanium, zirconium, vanadium, molybdenum, and tungsten. Titanium and zirconium are particularly preferred from the viewpoint of availability, and titanium is more preferred from the viewpoint of reaction activity.

[0142] In some embodiments, the catalyst comprises inorganic compounds such as oxides, halides, and the like of the aforementioned metals and mixtures thereof, as well as compounds containing organic groups such as carboxylates, alkoxy salts, organic sulfonates, or β-diketonate salts, each containing such a metal element.

[0143] In some embodiments, the method includes a compound that is liquid or soluble in the ester oligomer or polyester during polymerization. In some embodiments, a liquid or soluble compound in the ester oligomer or polyester is added because the polymerization rate is higher when the catalyst is in a molten or dissolved state during polymerization.

[0144] In some embodiments, the catalyst is a titanium compound. In some embodiments, the titanium compound is a tetraalkyl titanate and its hydrolyzates. Non-limiting examples include, but are not limited to, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetrabenzyl titanate, and mixed titanates thereof, and their hydrolyzates.

[0145] In some embodiments, the catalyst comprises titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, titanium(diisopropoxide)acetylacetonate, titanium bis(ammonium lactate)dihydroxide, titanium bis(ethylacetoacetate)diisopropoxide, titanium(triethanolaminate)isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolaminate, butyl titanate dimer, etc. In some embodiments, the method further comprises adding a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the extended periodic table (IUPAC Recommendations for Nomenclature of Inorganic Chemistry 2005) (hereinafter sometimes referred to as "Group 2 metal compound of the extended periodic table"), a phosphate ester compound, and a titanium compound.

[0146] In some embodiments, a catalyst selected from tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, titanium bis(ammonium lactate) dihydroxide, polyhydroxytitanium stearate, titanium lactate, or butyl titanate dimer is mixed with an alcohol, a Group 2 metal compound of the extended periodic table, and a phosphate ester compound, and a liquid material obtained by adding a titanium compound is added.

[0147] In some embodiments, the catalyst is selected from tetra-n-butyl titanate, titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, polyhydroxytitanium stearate, titanium lactate, or butyl titanate dimer, and is added to a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the extended form of the periodic table, and a phosphate ester compound, and adding a titanium compound.

[0148] In some embodiments, the catalyst is selected from tetra-n-butyl titanate, polyhydroxytitanium stearate, titanium(oxy)acetylacetonate, and titanium tetraacetylacetonate, and is added to a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the long form periodic table, and a phosphate ester compound, and adding a titanium compound.

[0149] Non-limiting examples of zirconium compounds as catalysts include, but are not limited to, zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy)stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate, and mixtures thereof.

[0150] In some embodiments, the catalyst is selected from zirconyl diacetate, zirconium tris(butoxy)stearate, zirconium tetraacetate, zirconium acetate hydroxide, ammonium zirconium oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, and zirconium tetra-t-butoxide, zirconyl diacetate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy)stearate, ammonium zirconium oxalate, zirconium tetra-n-propoxide, and zirconium tetra-n-butoxide. In some embodiments, the catalyst is selected from zirconium tris(butoxy)stearate. In some embodiments, colorless polyesters with a high degree of polymerization are easily obtained using zirconium tris(butoxy)stearate.

[0151] In some embodiments, the catalyst is a germanium compound. Non-limiting examples of germanium compounds include, but are not limited to, inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. From the viewpoint of cost and availability, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferred, with germanium oxide being particularly preferred.

[0152] In some embodiments, the catalyst is an inorganic chloride. Non-limiting examples of inorganic chlorides include ferric chloride, inorganic oxides such as iron oxide, organic iron complexes such as ferrocene, and the like. In some embodiments, the catalyst is an inorganic oxide.

[0153] In some embodiments, the catalyst is a metal-containing compound. Non-limiting examples of metal-containing compounds include, but are not limited to, scandium compounds such as scandium carbonate, scandium acetate, scandium chloride, and scandium acetylacetonate; yttrium compounds such as yttrium carbonate, yttrium chloride, yttrium acetate, and yttrium acetylacetonate; vanadium compounds such as vanadium chloride, vanadium trichloride oxide, vanadium acetylacetonate, and vanadium acetylacetonate oxide; molybdenum compounds such as molybdenum chloride and molybdenum acetate; tungsten compounds such as tungsten chloride, tungsten acetate, and tungstic acid; lanthanide compounds such as cerium chloride, samarium chloride, and ytterbium chloride.

[0154] method Aspects of the present disclosure include methods for producing polyester polymer-polysaccharide nanocomposite resins.

[0155] In some embodiments, the method comprises preparing a dispersion comprising polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid agent monomers.

[0156] In some embodiments, the method further comprises polycondensing the alkanediol monomers and the alkanedioic acid agent monomers in the dispersion to produce a polymer-polysaccharide nanocomposite resin.

[0157] Preparation of dispersion An embodiment of the method includes preparing a dispersion including polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid agent monomers.

[0158] In some embodiments, preparing the dispersion comprises dispersing polysaccharide nanocrystals in a solution comprising one or both of an alkanediol monomer and an alkanedioic acid agent monomer.

[0159] In some embodiments, the dispersing comprises contacting the polysaccharide nanocrystals in a solution, hi some embodiments, the solution comprises one or both of an alkanediol monomer and an alkanedioic acid agent monomer.

[0160] In some embodiments, the solution comprises an alkanediol monomer and an alkanedioic acid agent monomer. In some embodiments, the solution consists of an alkanediol monomer and an alkanedioic acid agent monomer.

[0161] In some embodiments, the solution further comprises a non-aqueous solvent. In some embodiments, the solution further comprises a non-aqueous organic solvent.

[0162] In some embodiments, the solution further comprises water, hi some embodiments, the water is deionized water.

[0163] In some embodiments, dispersing the polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid agent monomers comprises contacting cellulose nanocrystals with a solution comprising polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid agent monomers to form a mixture, and sonicating the mixture to uniformly disperse the polysaccharide nanocrystals in the solution to form a dispersion.

[0164] For example, polysaccharide nanocrystals are added to and dispersed in alkanediol monomers and / or alkanedioic acid agents.

[0165] In some embodiments, the method includes charging an alkanediol monomer and / or an alkanedioic acid agent to a reaction vessel to form a reactant mixture. In some embodiments, the method includes stirring the reactants with a nitrogen gas flow in the range of 100 to 250 rpm (e.g., 100 rpm or more, 150 rpm or more, 200 rpm or more, or 250 rpm or more) until a homogeneous slurry is formed.

[0166] In some embodiments, the method further comprises contacting the polysaccharide nanocrystals with a homogeneous slurry.

[0167] In some embodiments, the method further comprises increasing the temperature of the slurry. In some embodiments, the temperature is increased to at least 100° C., at least 125° C., at least 150° C., at least 175° C., at least 200° C., at least 225° C., at least 250° C., or at least 275° C. In some embodiments, the temperature is increased for at least about 10 minutes, at least about 20 minutes, at least about 30 minutes, at least about 40 minutes, at least about 50 minutes, at least about 60 minutes, at least about 70 minutes, at least about 80 minutes, at least about 90 minutes, at least about 100 minutes, at least about 110 minutes, at least about 120 minutes, at least about 130 minutes, at least about 140 minutes, or at least about 150 minutes.

[0168] In some embodiments, as the temperature is increased, water and THF are formed. In some embodiments, the method further comprises removing water and THF from the reactor via a distillation apparatus.

[0169] In some embodiments, the polysaccharide nanocrystals are dispersed in the alkanediol monomer by sonicating the polysaccharide-alkanediol mixture. In some embodiments, dispersing the polysaccharide-alkanediol mixture involves sonicating the mixture, as opposed to other mechanical means, such as stirring, to eliminate or substantially eliminate settling. In some embodiments, a polysaccharide-alkanediol mixture with a higher dispersion value (smaller polysaccharide nanocrystal particle size) ultimately produces a polysaccharide nanocomposite with more desirable properties, including increased transparency, processability, and toughness. However, other embodiments of the method may include using mechanical means to disperse the polysaccharide nanocrystals, such as a homogenizer for high-shear dispersion.

[0170] In some embodiments, the polysaccharide nanocrystals are dispersed in the alkanediol monomer using a homogenizer.

[0171] In some embodiments, polysaccharide nanocrystals are dispersed prior to esterification. For example, a polysaccharide-alkanediol dispersion can be obtained by dispersing polysaccharide nanocrystals in an alkanediol monomer prior to esterification. Furthermore, the quality of the dispersion can be verified before further processing, and the dispersion can be adjusted until the desired level is achieved. The quality of the dispersion can be verified by measuring the quality of the dispersion before the reaction occurs. For example, in processing, an aliquot of the BDO / NCC dispersion can be taken and confirmed to meet requirements. More data can be collected regarding the level of dispersion prior to the reaction (e.g., more than 50% of the material has dimensions <100 nm) to evaluate how it affects the properties of the final polymer, which may include the NCC gel size of the final polymer.

[0172] In some embodiments, the polysaccharide nanocrystals are dispersed in the alkanedioic acid agent by sonicating the polysaccharide-alkanedioic acid agent mixture. In some embodiments, dispersing the polysaccharide-alkanedioic acid agent mixture involves sonicating the mixture, as opposed to other mechanical means, such as stirring, to eliminate or substantially eliminate settling. In some embodiments, a polysaccharide-alkanedioic acid agent mixture with a higher dispersion value (smaller polysaccharide nanocrystal particle size) ultimately produces a polysaccharide nanocomposite with more desirable properties, including increased transparency, processability, and toughness. However, other embodiments of the method may include using mechanical means to disperse the polysaccharide nanocrystals, such as a homogenizer for high-shear dispersion.

[0173] In some embodiments, the polysaccharide nanocrystals are dispersed in the alkanedioic acid agent using a homogenizer.

[0174] In some embodiments, the polysaccharide nanocrystals are dispersed in the alkanedioic acid agent by sonicating the polysaccharide-alkanedioic acid agent mixture. In some embodiments, dispersing the polysaccharide-alkanedioic acid agent mixture involves sonicating the mixture, as opposed to other mechanical means, such as stirring, to eliminate or substantially eliminate settling. In some embodiments, a polysaccharide-alkanedioic acid agent mixture with a higher dispersion value (smaller polysaccharide nanocrystal particle size) ultimately produces a polysaccharide nanocomposite with more desirable properties, including increased transparency, processability, and toughness. However, other embodiments of the method may include using mechanical means to disperse the polysaccharide nanocrystals, such as a homogenizer for high-shear dispersion.

[0175] In some embodiments, the polysaccharide nanocrystals are dispersed in the alkanedioic acid agent using a homogenizer.

[0176] In some embodiments, the polysaccharide nanocrystals are dispersed using a high shear disperser.

[0177] In some embodiments, the method comprises contacting the polysaccharide-alkanediol monomer dispersion with an alkanedioic acid agent monomer, hi some embodiments, the polysaccharide-alkanediol monomer mixture is added to the alkanedioic acid agent monomer as a slurry.

[0178] In some embodiments, sonicating the mixture is carried out under conditions sufficient to produce a dispersion in which there is no visible settling.

[0179] In some embodiments, the method comprises contacting the polysaccharide-alkanediol monomer dispersion with an alkanedioic acid agent monomer, hi some embodiments, the polysaccharide-alkanediol monomer mixture is added to the alkanedioic acid agent monomer as a slurry.

[0180] In some embodiments, sonicating the mixture is carried out under conditions sufficient to produce a dispersion in which there is no visible settling.

[0181] In some embodiments, polysaccharide nanocrystals are dispersed in the alkanediol monomer and the alkanedioic acid agent by sonicating the polysaccharide-alkanediol-alkanedioic acid agent mixture. In some embodiments, dispersing the polysaccharide-alkanediol-alkanedioic acid agent mixture involves sonicating the mixture, as opposed to other mechanical means, such as stirring, to eliminate or substantially eliminate settling. In some embodiments, polysaccharide-alkanediol-alkanedioic acid agent mixtures with higher dispersion values ​​(smaller polysaccharide nanocrystal particle sizes) ultimately yield polysaccharide nanocomposites with more desirable properties, including increased transparency, processability, and toughness. However, other embodiments of the method may include using mechanical means to disperse the polysaccharide nanocrystals, such as a homogenizer for high-shear dispersion.

[0182] In some embodiments, the polysaccharide nanocrystals are dispersed in the alkanediol monomer-alkanedioic acid agent mixture using a homogenizer.

[0183] In some embodiments, the polysaccharide nanocrystals are dispersed prior to esterification. For example, a polysaccharide-alkanediol-alkanedioctyl agent dispersion can be obtained by dispersing polysaccharide nanocrystals in an alkanediol monomer-alkanedioctyl agent prior to esterification. Furthermore, the quality of the dispersion can be verified before further production, and the dispersion can be adjusted until the desired level is achieved.

[0184] In some embodiments, sonicating the mixture comprises sonicating for a duration of about 5 minutes or greater. In some embodiments, sonicating the mixture comprises sonicating for a duration of about 5 minutes or greater (e.g., at at least 60% of the amplitude of the maximum output of the sonicator). In some embodiments, sonicating the mixture comprises sonicating for a duration of about 5 minutes or greater (e.g., at at least 80% of the amplitude of the maximum output of the sonicator). In some embodiments, sonicating the mixture comprises sonicating for a duration of about 5 minutes or greater (e.g., at at least 100% of the amplitude of the maximum output of the sonicator).

[0185] In some embodiments, sonicating the mixture comprises sonicating for a duration of about 6 minutes or more, 7 minutes or more, 8 minutes or more, 9 minutes or more, 10 minutes or more, 11 minutes or more, 12 minutes or more, 13 minutes or more, 14 minutes or more, or 15 minutes or more.

[0186] Dispersion components In some embodiments, the dispersion comprises polysaccharide nanocrystals and one or more monomers, hi some embodiments, the one or more monomers comprise alkanediol monomers and alkanedioic acid monomers.

[0187] In some embodiments, the polysaccharide nanocrystals are derived from heparin, chitosan, chitin, hyaluronan, starch, cellulose, alginate, pectin, guar, starch / chitosan, chitosan / heparin, chitosan / hyaluronan, hyaluronan / heparin, or cellulose, as well as chitin whiskers and platelet-like starch. In some embodiments, the polysaccharide nanocrystals are derived from cellulose, starch, or chitin.

[0188] In some embodiments, the polysaccharide nanocrystals are derived from cellulose. In some embodiments, the polysaccharide nanocrystals are derived from starch. In some embodiments, the polysaccharide nanocrystals are derived from chitin.

[0189] In some embodiments, the polysaccharide nanocrystals can be spheres, rods, disks, or any other shape. In some embodiments, the nanocrystals can have a narrow size distribution. In some embodiments, the nanocrystals can have a broad size distribution.

[0190] In some embodiments, the polysaccharide nanocrystals are derived from cellulose. In some embodiments, the polysaccharide nanocrystals are cellulose nanocrystals.

[0191] In some embodiments, cellulose nanocrystals are crystals derived from cellulose fibers by chemical treatment, such as acid hydrolysis. In some embodiments, cellulose nanocrystals are derived from acid-hydrolyzed cellulose from cellulosic biomass via an acid hydrolysis technique similar to that originally described by Ranby, BG (Ranby, BG (1951) Discussion of the Faraday Society, 11, 158-164). NCC produced via sulfuric acid and neutralized with a base (in this case, NaOH) contains a large amount of sodium sulfate groups, which affects its dispersibility in hydrophilic media.

[0192] In some embodiments, the acid hydrolyzed cellulose is obtained from naturally occurring cellulose fibers. In some embodiments, the acid hydrolyzed cellulose is obtained, for example, from plant biomass, vascular plants, cotton plants, wood pulp, jute, hemp, corn, frass, rice, wheat straw, or sisal. In some embodiments, the cellulose is obtained from plant biomass, including, but not limited to, trees, grasses, cotton, sisal, bamboo, and ramie.

[0193] In some embodiments, cellulose nanocrystals can be found as structural components of urochordates (sea creatures similar to sea cucumbers) and are produced naturally by the bacterium Acetobacter xylinum.

[0194] In some embodiments, the cellulose nanocrystals have average dimensions of about 1-80 nm in width and about 25-1000 nm in length. In some embodiments, the cellulose nanocrystals have average dimensions of about 1-100 nm in width and about 25-3000 nm in length. In some embodiments, the cellulose nanocrystals have average dimensions of about 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, 80 nm or more, 85 nm or more, 90 nm or more, 95 nm or more, or 100 nm or more in width and about 25 nm or more, 50 nm or more, 100 nm or more in length. and having an average length dimension of 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 500 nm or more, 550 nm or more, 600 nm or more, 650 nm or more, 700 nm or more, 800 nm or more, 850 nm or more, 900 nm or more, 950 nm or more, 1000 nm or more, 1500 nm or more, 2000 nm or more, 2500 nm or more, or 3000 nm or more.

[0195] In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 1 d.nm to about 400 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 1 d.nm to about 50 d.nm, from about 50 d.nm to about 100 d.nm, from about 100 d.nm to about 150 d.nm, from about 150 d.nm to about 200 d.nm, from 200 d.nm to about 250 d.nm, from 250 d.nm to about 300 d.nm, from 300 d.nm to about 350 d.nm, or from 350 d.nm to about 400 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 1 d.nm to about 20 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 10 d.nm to about 100 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 10 d.nm to about 30 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from about 100 d.nm to about 200 d.nm. In some embodiments, the nanocrystals in the dispersion have a particle size distribution ranging from 1 d.nm or more, 2 d.nm or more, 4 d.nm or more, 6 d.nm or more, 8 d.nm or more, 10 d.nm or more, 12 d.nm or more, 14 d.nm or more, 16 d.nm or more, 18 d.nm or more, 20 d.nm or more, 22 d.nm or more, 24 d.nm or more, 26 d.nm or more, 28 d.nm or more, 30 d.nm or more, 32 d.nm or more, 34 d.nm or more, 36 d.nm or more, 38 d.nm or more, 40 d.nm or more, 42 d.nm or more, 44 d.nm or more, 46 d.nm or more, 48 d.nm or more, 50 d.nm or more. and having a particle size distribution of 0.05 d.nm or more, 52 d.nm or more, 54 d.nm or more, 56 d.nm or more, 58 d.nm or more, 60 d.nm or more, 62 d.nm or more, 64 d.nm or more, 66 d.nm or more, 68 d.nm or more, 70 d.nm or more, 72 d.nm or more, 74 d.nm or more, 76 d.nm or more, 78 d.nm or more, 80 d.nm or more, 82 d.nm or more, 84 d.nm or more, 86 d.nm or more, 88 d.nm or more, 90 d.nm or more, 92 d.nm or more, 94 d.nm or more, 96 d.nm or more, 98 d.nm or more, or 100 d.nm or more.In some embodiments, the nanocrystals in the dispersion have a diameter of 100 d.nm or greater, 125 d.nm or greater, 150 d.nm or greater, 175 d.nm or greater, 200 d.nm or greater, 225 d.nm or greater, 250 d.nm or greater, 275 d.nm or greater, 300 d.nm or greater, 325 d.nm or greater, 350 d.nm or greater, 400 d.nm or greater, 425 d.nm or greater, 500 d.nm or greater, 525 d.nm or greater, 550 d.nm or greater, 575 d.nm and having a particle size distribution of ≥ 600 d.nm, ≥ 625 d.nm, ≥ 650 d.nm, ≥ 675 d.nm, ≥ 700 d.nm, ≥ 725 d.nm, ≥ 750 d.nm, ≥ 775 d.nm, ≥ 800 d.nm, ≥ 825 d.nm, ≥ 850 d.nm, ≥ 875 d.nm, ≥ 900 d.nm, ≥ 925 d.nm, ≥ 950 d.nm, ≥ 975 d.nm, or ≥ 1000 d.nm.

[0196] In some embodiments, increasing the length of the cellulose nanocrystals increases the potential load distribution throughout the polymer. In some embodiments, the orientation of the cellulose nanocrystals within the polymer increases the interfacial contact between adjacent cellulose nanocrystals in the axial orientation, which may increase the ultimate tensile strength. In some embodiments, the transverse orientation

[0197] The morphology (e.g., length, aspect ratio, length polydispersity) and surface charge of cellulose nanocrystals vary greatly based on synthesis conditions.

[0198] In some embodiments, acid hydrolysis is used to decompose cellulose microfibrils by digesting the amorphous regions connecting the cellulose nanocrystals. In some embodiments, processing typically requires heating, agitation, rinsing, filtration, dialysis, and ultrasonication, with the parameters of each step having a direct effect on the morphology and / or surface chemistry of the cellulose nanocrystals. In some embodiments, the end result of cellulose nanocrystal processing involves the production of a suspension of liquid crystalline cellulose nanocrystals, which form either a nematic or chiral nematic mesophase (e.g., depending on the cellulose nanocrystal length, aspect ratio, length polydispersity, surface charge, cellulose nanocrystal concentration, and electrolyte concentration).

[0199] In some embodiments, the polymer of the polymer-polysaccharide nanocomposite resin comprises an aliphatic polyester polymer, which may include, but is not limited to, an aliphatic polyester polymer selected from polylactide (PLA) (e.g., poly(lactic acid)), polyglycolide (PGA) (e.g., polyglycolic acid), poly(ε-caprolactone) (PCL), poly(γ-valerolactone) (PVL), and copolymer poly(lactic-co-glycolic acid) (PLGA).

[0200] In some embodiments, the polymer of the polymer-polysaccharide nanocomposite resin includes a polybutylene succinate homopolymer or a polybutylene succinate copolymer (eg, a polybutylene succinate adipate copolymer).

[0201] In some embodiments, the dispersion comprises an alkanediol monomer.

[0202] In some embodiments, alkanediol monomers include, but are not limited to, 1,4-butanediol monomers, 1,2-ethanediol monomers, 1,3-propanediol monomers, 1,5-pentanediol monomers, or 1,6-hexanediol monomers.

[0203] In some embodiments, the alkanediol monomer comprises one or more diols for forming a polyester composite. Non-limiting examples of other suitable diols include, but are not limited to, ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 1,4-cyclohexanedimethanol, hydroquinone, 1,5-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)-2,2-propane, and combinations thereof.

[0204] In some embodiments, the alkanediol monomer 1,4-butanediol. In some embodiments, the alkanediol monomer is 1,2-ethanediol. In some embodiments, the alkanediol monomer is 1,3-propanediol.

[0205] In some embodiments, the dispersion comprises an alkanedioic acid agent monomer, including, but not limited to, an alkanedioic acid agent monomer selected from succinic acid, monoalkyl succinates, dialkyl succinates (e.g., dimethyl or diethyl succinate), succinic anhydride, adipic acid, monoalkyl adipates, dialkyl adipates (e.g., dimethyl or diethyl adipate), and adipic anhydride.

[0206] In some embodiments, the alkanedioic acid agent monomer is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, and their cyclic anhydride equivalents.

[0207] In certain embodiments, the alkanediol monomer is a 1,4-butanediol monomer. In certain embodiments, the alkanedioic acid agent monomer is a succinic acid agent monomer. In certain embodiments, the alkanedioic acid agent monomer is succinic anhydride.

[0208] In some embodiments, the dispersing comprises contacting cellulose nanocrystals, 1,4-butanediol monomers, and succinic acid agent monomers to produce a cellulose mixture.

[0209] In some embodiments, the alkanedioic acid agent monomer is a succinic acid agent monomer or a derivative thereof. In some embodiments, the alkanedioic acid agent monomer is a succinic acid agent monomer. In some embodiments, the succinic acid agent is succinic anhydride.

[0210] In some embodiments, the succinic agent monomer includes, but is not limited to, a succinic agent selected from succinic acid, a monoalkyl succinate, a dialkyl succinate (e.g., dimethyl succinate or diethyl succinate), or succinic anhydride.

[0211] In some embodiments, the succinic acid agent is a succinate derivative. In some embodiments, the succinate derivative is succinate anhydride. In some embodiments, succinate anhydride increases the rate of esterification with 1,4 butanediol and also reduces the amount of harmful THF produced during the esterification step. However, other suitable, non-limiting examples of succinate derivatives can include succinic acid or succinate esters.

[0212] In some embodiments, the dispersion includes one or more additional monomers.

[0213] In some embodiments, the one or more additional monomers include, but are not limited to, comonomers, epoxy derivatives, oils, pigments, crosslinkers, and the like.

[0214] In some embodiments, the one or more additional monomers include an additional alkanediol monomer and / or an additional alkanedioic acid agent monomer.

[0215] In some embodiments, the additional alkanediol monomers include, but are not limited to, alkanediol monomers and / or additional alkanedioic acid monomers, including, but not limited to, 1,4-butanediol monomer, 1,2-ethanediol monomer, 1,3-propanediol monomer, 1,5-pentanediol monomer, or 1,6-hexanediol monomer.

[0216] In some embodiments, diacid agent monomers include, but are not limited to, alkanedioic acid agent monomers selected from succinic acid, monoalkyl succinates, dialkyl succinates (e.g., dimethyl or diethyl succinate), succinic anhydride, adipic acid, monoalkyl adipates, dialkyl adipates (e.g., dimethyl or diethyl adipate), and adipic anhydride.

[0217] In some embodiments, the additional alkanedioic acid agent monomer comprises adipic anhydride. In some embodiments, the additional alkanedioic acid agent monomer comprises fumaric acid, or an ester or anhydride thereof.

[0218] In some embodiments, one or more additional components may include a hydrophobic agent. In some embodiments, the hydrophobic agent is an oil. In some embodiments, the hydrophobic agent is an elastomeric material. In some embodiments, the hydrophobic agent is epoxidized soybean oil or an elastomeric material. The hydrophobic agent may be utilized as an end-capping agent for the polyester polymer in the composition, for example, linked via an ether, ester, or carbamate linkage.

[0219] In some embodiments, the one or more additional components include, but are not limited to, agents to provide additional water and oxygen barrier properties. Non-limiting exemplary water and oxygen barrier agents include candelilla wax, beeswax, and other waxes. In some embodiments, such barrier agents are derived from renewable resources.

[0220] In some embodiments, the one or more additional monomers comprise a polishing agent that provides an aesthetically pleasing sheen to the finished product. Non-limiting exemplary polishing agents include shea butter and nut oils such as Brazil nut oil. In some embodiments, the polishing agent is derived from a renewable resource.

[0221] In some embodiments, the one or more additional monomers include, but are not limited to, impact modifiers, antioxidants, antibacterial agents, antifungal agents, antistatic agents, fillers, heat stabilizers, UV stabilizers, dyes, fillers, crystallization promoters, and coupling agents.

[0222] Non-limiting examples of antioxidants include hindered phenol antioxidants such as p-tert-butylhydroxytoluene and p-tert-butylhydroxyanisole, sulfur antioxidants such as distearyl thiodipropionate and dilauryl thiodipropionate, and the like; heat stabilizers include triphenyl phosphite, trilauryl phosphite, tris-nonylphenyl phosphite, and the like; UV stabilizers include p-tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone, and the like; lubricants include calcium stearate, zinc stearate, barium stearate, sodium palmitate, and the like; and antistatic agents include N,N-bis(hydroxyethyl methyl acrylate). Flame retardants include hexabromocyclododecane, tris-(2,3-dichloropropyl)phosphate, pentabromophenyl allyl ether, etc.; antiblocking agents include combinations of inorganic fillers such as silica and oleamide; inorganic fillers or nucleating agents include calcium carbonate, silica, titanium oxide, talc, mica, barium sulfate, alumina, a mixture of NaHCO3 and citric acid, etc.; crystallization accelerators include polyethylene terephthalate, poly-transcyclohexanedimethanol terephthalate, etc.; organic fillers include wood powder, rice husks, recycled paper such as newspaper, starch (including modified materials such as alpha-starch), cellulose, etc.

[0223] In some embodiments, polyethers having hydroxyl end groups can be used in combination with the diols disclosed in the present disclosure. The carbon number of the hydroxyl end group polyether is typically 4 or more, preferably 10 or more, with a lower limit of 1,000 or less, preferably 200 or less, and more preferably 100 or less. Non-limiting examples of polyethers having hydroxyl end groups include, but are not limited to, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly-1,6-hexamethylene glycol, and the like. Copolymer polyethers of polyethylene glycol and polypropylene glycol can also be used.

[0224] In some embodiments, the one or more additional monomers comprise one or more dicarboxylic acids or dicarboxylic anhydrides. Non-limiting examples may include, but are not limited to, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, and their cyclic anhydride equivalents.

[0225] In some embodiments, the one or more additional monomers comprise an epoxidized oil, an epoxy derivative, or a fatty acid. In some embodiments, the epoxidized oil, an epoxy derivative, or a fatty acid can be esterified.

[0226] In some embodiments, the one or more additional monomers include an epoxidized oil, an epoxy derivative, or a fatty acid. In some embodiments, the epoxidized oil, the epoxy derivative, or the fatty acid can be esterified. In some embodiments, the epoxy derivative or the epoxidized oil is added at the end of the reaction. For example, in some embodiments, the method includes adding the epoxy derivative or the epoxidized product after repressurizing the vessel just before cooling and discharging the polymer. In some embodiments, the method includes adding an NCC, an epoxy derivative, and / or an epoxidized oil, which may be added in advance with the alkanediol monomer and / or the alkanedioic acid monomer. For example, in some embodiments, the method includes adding the NCC in the form of a dispersion at the beginning of the reaction. In some embodiments, the method includes adding the epoxy derivative or the epoxidized oil at the end of the esterification process just before the catalyst is added and polycondensation is performed. In some examples, the catalyst is added after the epoxy derivative or the epoxidized oil is allowed to react for 5 minutes. The high shear disperser method follows the same process as the ultrasonication method in terms of time and power consumption, but instead uses the equipment described at https: / / www(dot)mixers(dot)com / products / high-speed-dispersers / .

[0227] In some embodiments, one or more additional monomers are epoxidized oils. In some embodiments, one or more additional monomers are epoxidized derivatives. In some embodiments, epoxidized oils or epoxy derivatives include but are not limited to epoxidized linseed oil, lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, tung oil, tall oil, calendula, rapeseed oil, peanut oil, sesame oil, grapeseed oil, olive oil, jojoba oil, dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil, corn oil, rapeseed oil, orange oil, and mixtures thereof.

[0228] In some embodiments, the one or more additional monomers comprise a catalyst.

[0229] Non-limiting exemplary catalysts include titanium or zirconium compounds, such as titanium lactate or zirconium butoxide. Generally, compounds containing at least one metal element from Groups 1 to 14 of the periodic table can be used as esterification catalysts. Specific examples of metal elements include scandium, yttrium, samarium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium. Among these, scandium, yttrium, titanium, zirconium, vanadium, molybdenum, tungsten, zinc, iron, and germanium are preferred, with titanium, zirconium, tungsten, iron, and germanium being particularly preferred. Furthermore, to reduce the concentration of polyester ends, which affect the thermal stability of polyesters, metal elements from Groups 3 to 6 of the periodic table that exhibit Lewis acidity are preferred. Specific examples include scandium, titanium, zirconium, vanadium, molybdenum, and tungsten. Titanium and zirconium are particularly preferred from the viewpoint of availability, and titanium is more preferred from the viewpoint of reaction activity.

[0230] In some embodiments, the catalyst comprises inorganic compounds such as oxides, halides, and the like of the aforementioned metals and mixtures thereof, as well as compounds containing organic groups such as carboxylates, alkoxy salts, organic sulfonates, or β-diketonate salts, each containing such a metal element.

[0231] In some embodiments, the method includes a compound that is liquid or soluble in the ester oligomer or polyester during polymerization. In some embodiments, a liquid or soluble compound in the ester oligomer or polyester is added because the polymerization rate is higher when the catalyst is in a molten or dissolved state during polymerization.

[0232] In some embodiments, the catalyst is a titanium compound. In some embodiments, the titanium compound is a tetraalkyl titanate and its hydrolyzates. Non-limiting examples include, but are not limited to, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetrabenzyl titanate, and mixed titanates thereof, and their hydrolyzates.

[0233] In some embodiments, the catalyst comprises titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, titanium(diisopropoxide)acetylacetonate, titanium bis(ammonium lactate)dihydroxide, titanium bis(ethylacetoacetate)diisopropoxide, titanium(triethanolaminate)isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolaminate, butyl titanate dimer, etc. In some embodiments, the method further comprises adding a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the extended periodic table (IUPAC Recommendations for Nomenclature of Inorganic Chemistry 2005) (hereinafter sometimes referred to as "Group 2 metal compound of the extended periodic table"), a phosphate ester compound, and a titanium compound.

[0234] In some embodiments, a catalyst selected from tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, titanium bis(ammonium lactate) dihydroxide, polyhydroxytitanium stearate, titanium lactate, or butyl titanate dimer is mixed with an alcohol, a Group 2 metal compound of the extended periodic table, and a phosphate ester compound, and a liquid material obtained by adding a titanium compound is added.

[0235] In some embodiments, the catalyst is selected from tetra-n-butyl titanate, titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, polyhydroxytitanium stearate, titanium lactate, or butyl titanate dimer, and is added to a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the extended form of the periodic table, and a phosphate ester compound, and adding a titanium compound.

[0236] In some embodiments, the catalyst is selected from tetra-n-butyl titanate, polyhydroxytitanium stearate, titanium(oxy)acetylacetonate, and titanium tetraacetylacetonate, and is added to a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the long form periodic table, and a phosphate ester compound, and adding a titanium compound.

[0237] Non-limiting examples of zirconium compounds as catalysts include, but are not limited to, zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy)stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate, and mixtures thereof.

[0238] In some embodiments, the catalyst is selected from zirconyl diacetate, zirconium tris(butoxy)stearate, zirconium tetraacetate, zirconium acetate hydroxide, ammonium zirconium oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, and zirconium tetra-t-butoxide, zirconyl diacetate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy)stearate, ammonium zirconium oxalate, zirconium tetra-n-propoxide, and zirconium tetra-n-butoxide. In some embodiments, the catalyst is selected from zirconium tris(butoxy)stearate. In some embodiments, colorless polyesters with a high degree of polymerization are easily obtained using zirconium tris(butoxy)stearate.

[0239] In some embodiments, the catalyst is a germanium compound. Non-limiting examples of germanium compounds include, but are not limited to, inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. From the viewpoint of cost and availability, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferred, with germanium oxide being particularly preferred.

[0240] In some embodiments, the catalyst is an inorganic chloride. Non-limiting examples of inorganic chlorides include ferric chloride, inorganic oxides such as iron oxide, organic iron complexes such as ferrocene, and the like. In some embodiments, the catalyst is an inorganic oxide.

[0241] In some embodiments, the catalyst is a metal-containing compound. Non-limiting examples of metal-containing compounds include, but are not limited to, scandium compounds such as scandium carbonate, scandium acetate, scandium chloride, and scandium acetylacetonate; yttrium compounds such as yttrium carbonate, yttrium chloride, yttrium acetate, and yttrium acetylacetonate; vanadium compounds such as vanadium chloride, vanadium trichloride oxide, vanadium acetylacetonate, and vanadium acetylacetonate oxide; molybdenum compounds such as molybdenum chloride and molybdenum acetate; tungsten compounds such as tungsten chloride, tungsten acetate, and tungstic acid; lanthanide compounds such as cerium chloride, samarium chloride, and ytterbium chloride.

[0242] Polycondensation An embodiment of the method includes polycondensing alkanediol monomers and alkanedioic acid agent monomers in a dispersion to produce a polymer-polysaccharide nanocomposite resin.

[0243] In some embodiments, polycondensing comprises esterifying the alkanediol monomers and the alkanedioic acid monomers to form a plurality of oligomers, hi some embodiments, polycondensing further comprises condensing the plurality of oligomers to produce a high MW polymer (e.g., as described herein) in the polymer-polysaccharide nanocomposite resin.

[0244] In some embodiments, the oligomers have an average MW of 500 Da or more, up to 10,000 Da. In some embodiments, the oligomers have an average MW of 1000-10,000 Da.

[0245] In some embodiments, the oligomer has the formula (IIa):

[0246] [ka]

[0247] During the ceremony, n is 1 to 11; m is 1 to 11; p is 1 to 100; Each * independently represents H, OH, a copolymer segment, a repeat unit, a comonomer, or a grafted polysaccharide nanoparticle.

[0248] In some embodiments of Formula (IIa), p is 1-50, for example, 5-50, 10-50, 10-40, or 20-40.

[0249] In some embodiments, the oligomer is a PBS or PBF homopolymer. In some embodiments, the oligomer is a PBS or PBF copolymer. In some embodiments, the oligomer is represented by formula (IIIa):

[0250] [ka]

[0251] During the ceremony, p is 0 to 50; q is 0 or 50, where p+q>0; r is 1 to 50; Each * independently represents H, OH, copolymer segment, repeat unit, comonomer, or grafted polysaccharide nanoparticle. The oligomer may have a total of up to about 50 repeat units. In some cases, the oligomer has an average MW of 1000 to 10,000 Da.

[0252] In some embodiments of Formula (IIIa), (p+q)r is < 50. In some embodiments of Formula (IIIa), r is 1 to 50, e.g., 5 to 50, 10 to 50, 10 to 40, or 20 to 40.

[0253] In some embodiments, the plurality of oligomers and high MW polymers each comprise butylene succinate repeat units. In some embodiments, the oligomers and high MW polymers each comprise multiple butylene succinate repeat units. In some embodiments, the oligomers and high MW polymers each comprise blocks or segments of polybutylene succinate.

[0254] In some embodiments, the polymer of the polymer-polysaccharide nanocomposite resin is a polybutylene succinate homopolymer or a polybutylene succinate copolymer (eg, polybutylene succinate adipate copolymer).

[0255] In some embodiments, the polycondensing further comprises condensing the oligomer or polymer with an epoxidized oil. In such embodiments, the dispersion comprises an epoxidized oil.

[0256] In some embodiments, polycondensing further comprises condensing the nanocomposite resin with an epoxy derivative (e.g., an esterifiable epoxidized oil or fatty acid).

[0257] The present disclosure includes nanocomposite synthetic precursor compositions comprising a mixture of a plurality of oligomers (e.g., as described herein), cellulose nanocrystals, and optionally one or more reagents or solvents (e.g., as described herein) suitable for polycondensation.

[0258] Esterification An embodiment of this method involves esterifying an alkanediol monomer and an alkanedioic acid monomer to form multiple oligomers. Esterification of epoxy derivatives into polybutylene succinate nanocomposites increases durability, increases melt viscosity, and reduces the concentration of acid end groups in the polybutylene succinate nanocomposite, making it easier to process and more stable against thermal and hydrolytic effects. The resulting polybutylene succinate nanocomposite is biodegradable and primarily composed of ester bonds, with two to three ether linkages introduced with one of the reactants.

[0259] In some embodiments, polycondensing further comprises esterifying the epoxidized oil or epoxy derivative (e.g., the epoxidized oil or epoxy derivative as an additional component).

[0260] In some embodiments, the one or more additional monomers include an epoxidized oil, an epoxy derivative, or a fatty acid. In some embodiments, the epoxidized oil, the epoxy derivative, or the fatty acid can be esterified. In some embodiments, the epoxy derivative or the epoxidized oil is added at the end of the esterification process, just before the catalyst is added and polycondensation is performed. In some examples, the catalyst is added after the epoxy derivative or the epoxidized oil is allowed to react for 5 minutes. The high-shear disperser method follows the same process as the ultrasonic treatment method in terms of time and power consumption, but instead uses the equipment described at https: / / www(dot)mixers(dot)com / products / high-speed-dispersers / .

[0261] In some embodiments, one or more additional monomers are epoxidized oils. In some embodiments, one or more additional monomers are epoxidized derivatives. In some embodiments, epoxidized oils or epoxy derivatives include but are not limited to epoxidized linseed oil, lard, beef tallow, fish oil, coffee oil, soybean oil, safflower oil, tung oil, tall oil, calendula, rapeseed oil, peanut oil, sesame oil, grapeseed oil, olive oil, jojoba oil, dehydrated castor oil, tallow oil, sunflower oil, cottonseed oil, corn oil, rapeseed oil, orange oil, and mixtures thereof.

[0262] In some embodiments, the esterification is carried out under vacuum or inert gas conditions. For example, the esterification reaction can be carried out in a reaction vessel using nitrogen gas. The esterification can be carried out at approximately ambient pressure or at a slightly higher pressure with an optional inert gas. The slurry can be heated to a temperature of about 100°C or higher, about 105°C or higher, about 110°C or higher, about 120°C or higher, about 130°C or higher, about 140°C or higher, or about 150°C or higher to initiate the reaction.

[0263] In some embodiments, the esterification may be carried out in the vapor phase.

[0264] In some embodiments, the esterification comprises heating the dispersion to an initial temperature of 100°C to 140°C (e.g., the esterification is initiated at 110°C ± 10°C, 110°C ± 5°C, or about 110°C). In some embodiments, the esterification comprises heating the dispersion to an initial temperature of about 100°C or higher, about 105°C or higher, about 110°C or higher, about 120°C or higher, about 130°C or higher, about 140°C or higher, or about 150°C or higher.

[0265] In some embodiments, the esterification further comprises heating the dispersion to a second temperature of 200°C to 250°C (e.g., 225°C ± 15°C, or about 225°C) after the reaction temperature exceeds 140°C. In some embodiments, the esterification further comprises heating the dispersion to a second temperature of 200°C or higher, 225°C or higher, 230°C or higher, 235°C or higher, 240°C or higher, 245°C or higher, or 250°C or higher after the reaction temperature exceeds 140°C. In some embodiments, the esterification further comprises heating the dispersion to a second temperature of 200°C ± 15°C, 215°C ± 15°C, 230°C ± 15°C, 245°C ± 15°C, or 250°C ± 15°C after the reaction temperature exceeds 140°C.

[0266] catalyst In some embodiments, the polycondensing is carried out in the presence of a catalyst. In some embodiments, the rate of the reaction can be further increased by adding a catalyst. In some embodiments, the polycondensing further comprises adding a catalyst (e.g., a catalyst added to the dispersion or during polycondensation).

[0267] When using a metal compound as an esterification catalyst, the lower limit of the amount of catalyst added, in terms of the amount of metal relative to the polyester formed, is generally 0.1 ppm by mass or more, preferably 0.5 ppm by mass or more, and more preferably 1 ppm by mass or more, while the upper limit is generally 3,000 ppm by mass or less, preferably 2,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, and particularly preferably 500 ppm by mass or less. Using too much catalyst is economically disadvantageous. Furthermore, the polyester may have a high terminal carboxyl group concentration. Therefore, there is concern that the increased terminal carboxyl group concentration and residual catalyst concentration may reduce the thermal stability and hydrolysis resistance of the polyester. Conversely, using too little catalyst reduces polymerization activity, which subsequently induces thermal decomposition of the polyester during polyester production. As a result, the yield of polyesters exhibiting practically useful physical properties is low.

[0268] The timing of adding the catalyst to the reaction system is not particularly limited. In some embodiments, the catalyst is added before the esterification reaction step. In some embodiments, the catalyst may be added when charging the raw materials. In some embodiments, the catalyst is added after the esterification reaction step.

[0269] Non-limiting exemplary catalysts include titanium or zirconium compounds, such as titanium lactate or zirconium butoxide. Generally, compounds containing at least one metal element from Groups 1 to 14 of the periodic table can be used as esterification catalysts. Specific examples of metal elements include scandium, yttrium, samarium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium. Among these, scandium, yttrium, titanium, zirconium, vanadium, molybdenum, tungsten, zinc, iron, and germanium are preferred, with titanium, zirconium, tungsten, iron, and germanium being particularly preferred. Furthermore, to reduce the concentration of polyester ends, which affect the thermal stability of polyesters, metal elements from Groups 3 to 6 of the periodic table that exhibit Lewis acidity are preferred. Specific examples include scandium, titanium, zirconium, vanadium, molybdenum, and tungsten. Titanium and zirconium are particularly preferred from the viewpoint of availability, and titanium is more preferred from the viewpoint of reaction activity.

[0270] In some embodiments, the catalyst comprises inorganic compounds such as oxides, halides, and the like of the aforementioned metals and mixtures thereof, as well as compounds containing organic groups such as carboxylates, alkoxy salts, organic sulfonates, or β-diketonate salts, each containing such a metal element.

[0271] In some embodiments, the method includes a compound that is liquid or soluble in the ester oligomer or polyester during polymerization. In some embodiments, a liquid or soluble compound in the ester oligomer or polyester is added because the polymerization rate is higher when the catalyst is in a molten or dissolved state during polymerization.

[0272] In some embodiments, the esterification is carried out in the absence of a solvent. In some embodiments, the esterification is carried out in the presence of a solvent. In some embodiments, a small amount of solvent can be used to dissolve the catalyst. Non-limiting examples of solvents for use in dissolving the catalyst include alcohols such as methanol, ethanol, isopropanol, and butanol; the aforementioned diols such as ethylene glycol, butanediol, and pentanediol; ethers such as diethyl ether and tetrahydrofuran; nitriles such as acetonitrile; hydrocarbon compounds such as heptane and toluene; water; and mixtures thereof. Regarding the amount used, the solvent is generally used so that the catalyst concentration is 0.0001% by weight or more and 99% by weight or less.

[0273] In some embodiments, the catalyst is a titanium compound. In some embodiments, the titanium compound is a tetraalkyl titanate and its hydrolyzates. Non-limiting examples include, but are not limited to, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetrabenzyl titanate, and mixed titanates thereof, and their hydrolyzates.

[0274] In some embodiments, the catalyst comprises titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, titanium(diisopropoxide)acetylacetonate, titanium bis(ammonium lactate)dihydroxide, titanium bis(ethylacetoacetate)diisopropoxide, titanium(triethanolaminate)isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolaminate, butyl titanate dimer, etc. In some embodiments, the method further comprises adding a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the extended periodic table (IUPAC Recommendations for Nomenclature of Inorganic Chemistry 2005) (hereinafter sometimes referred to as "Group 2 metal compound of the extended periodic table"), a phosphate ester compound, and a titanium compound.

[0275] In some embodiments, the method includes adding a catalyst selected from tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium(oxy)acetylacetonate, titanium tetraacetylacetonate, titanium bis(ammonium lactate) dihydroxide, polyhydroxytitanium stearate, titanium lactate, or butyl titanate dimer, and adding a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the long form of the periodic table, and a phosphate ester compound, and adding a titanium compound.

[0276] In some embodiments, the method includes adding a catalyst selected from tetra-n-butyl titanate, titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, polyhydroxytitanium stearate, titanium lactate, or butyl titanate dimer, and adding a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the extended form of the periodic table, and a phosphate ester compound, and adding a titanium compound.

[0277] In some embodiments, the method includes adding a catalyst selected from tetra-n-butyl titanate, polyhydroxy titanium stearate, titanium(oxy)acetylacetonate, and titanium tetraacetylacetonate, and adding a liquid material obtained by mixing an alcohol, a Group 2 metal compound of the long form of the periodic table, and a phosphate ester compound, and adding a titanium compound.

[0278] Non-limiting examples of zirconium compounds as catalysts include, but are not limited to, zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy)stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate, and mixtures thereof.

[0279] In some embodiments, the catalyst is selected from zirconyl diacetate, zirconium tris(butoxy)stearate, zirconium tetraacetate, zirconium acetate hydroxide, ammonium zirconium oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, and zirconium tetra-t-butoxide, zirconyl diacetate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy)stearate, ammonium zirconium oxalate, zirconium tetra-n-propoxide, and zirconium tetra-n-butoxide. In some embodiments, the catalyst is selected from zirconium tris(butoxy)stearate. In some embodiments, colorless polyesters with a high degree of polymerization are easily obtained using zirconium tris(butoxy)stearate.

[0280] In some embodiments, the catalyst is a germanium compound. Non-limiting examples of germanium compounds include, but are not limited to, inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. From the viewpoint of cost and availability, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferred, with germanium oxide being particularly preferred.

[0281] In some embodiments, the catalyst is an inorganic chloride. Non-limiting examples of inorganic chlorides include ferric chloride, inorganic oxides such as iron oxide, organic iron complexes such as ferrocene, and the like. In some embodiments, the catalyst is an inorganic oxide.

[0282] In some embodiments, the catalyst is a metal-containing compound. Non-limiting examples of metal-containing compounds include, but are not limited to, scandium compounds such as scandium carbonate, scandium acetate, scandium chloride, and scandium acetylacetonate; yttrium compounds such as yttrium carbonate, yttrium chloride, yttrium acetate, and yttrium acetylacetonate; vanadium compounds such as vanadium chloride, vanadium trichloride oxide, vanadium acetylacetonate, and vanadium acetylacetonate oxide; molybdenum compounds such as molybdenum chloride and molybdenum acetate; tungsten compounds such as tungsten chloride, tungsten acetate, and tungstic acid; lanthanide compounds such as cerium chloride, samarium chloride, and ytterbium chloride.

[0283] condensation Aspects of the present disclosure include esterifying alkanediol monomers and alkanedioic acid agent monomers to form multiple oligomers and condensing the multiple oligomers to produce high MW polymers in the polymer-polysaccharide nanocomposite resin.

[0284] In some embodiments, condensing the plurality of oligomers is carried out in a reaction vessel under reduced pressure. In some embodiments, the pressure of the vessel may be reduced during condensation. In some embodiments, the condensing is carried out at a pressure of about 500 mTorr. In some embodiments, the condensing is carried out at a pressure of about 400 mTorr. In some embodiments, the condensation is carried out at a pressure of about 300 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 700 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 710 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 720 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 730 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 740 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 750 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 760 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 770 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr.

[0285] In some embodiments, the method includes pressurizing the reaction vessel at an initial pressure, heating the reaction vessel, and subsequently reducing the initial pressure to a lower pressure.

[0286] In some embodiments, the pressure may be reduced from an initial pressure of about 780 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 790 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr. In some embodiments, the pressure may be reduced from an initial pressure of about 800 Torr (i.e., atmospheric pressure) to a final pressure of about 500 mTorr.

[0287] After esterification, the reaction vessel can be heated to about 225° C. to condense multiple oligomers to produce high MW polymers in the polymer-polysaccharide nanocomposite resin.

[0288] In some embodiments, the temperature of the vessel may be gradually increased as the reaction proceeds, hi some embodiments, the temperature may be increased to about 200°C or greater, 210°C or greater, 220°C or greater, 230°C or greater, 240°C or greater, or 250°C or greater.

[0289] In some embodiments, the method includes adding an epoxy derivative or epoxidized oil at the end of the reaction. For example, in some embodiments, the epoxy derivative or epoxidized oil can be added after repressurizing the vessel just before cooling and discharging the polymer.

[0290] Post-polymerization additives In some embodiments, the method includes adding one or more additional components after polymerization of the nanocomposite.

[0291] Use of polymer-polysaccharide nanocomposite resins in the fabrication of yarns / fibers Aspects of the present disclosure include articles comprising nanocomposite resins produced by the methods described herein.

[0292] In some embodiments, articles are manufactured from the nanocomposite resins using any known method, non-limiting examples of which include, but are not limited to, injection molding, blow molding, compression molding, extrusion, and melt spinning.

[0293] In some embodiments, the article is a molded article molded at a mold temperature of In some embodiments, the article is a yard or a fiber.

[0294] In some embodiments, the polysaccharide-polymer nanocomposite resin (e.g., polybutylene succinate nanocomposite) produced by the present method can then be formed into an article of manufacture. For example, in some embodiments, the present process can include thermoforming, extruding, injection molding, or blow molding the composition in molten form.

[0295] In some embodiments, an injection molding process includes any molding process in which a polymer melt, or a monomer or oligomer solution, is forced under pressure into a mold, for example, using a ram injector or reciprocating screw, where it is shaped and cured. A blow molding process can include any method in which an extrudable polymer composition can be shaped using a fluid and then cured to form a product. Blow molding processes can include extrusion blow molding, injection blow molding, and injection stretch blow molding, as appropriate. Non-limiting examples of extrusion molding methods include those in which an extrudable polymer composition is extruded through a die under pressure and cured to form a final product, such as a film or fiber.

[0296] In some embodiments, a single-screw or twin-screw extruder can be used, the selection of which and the amount of each component will vary depending on the extruder and are within the skill of those in the art. Other molding methods can include gas foam molding, bead foam molding, T-dye film molding, stretch blow molding, blown film molding, and sheet molding.

[0297] In some embodiments, the resulting shaped article is a container. As used herein, the term "container" includes, but is not limited to, any article, receptacle, or vessel utilized to store, dispense, package, portion, or transport various types of products or objects, including, but not limited to, food and beverage products. Non-limiting examples of such containers include, but are not limited to, boxes, cups, "clamshells," jars, bottles, plates, bowls, trays, cartons, cases, crates, cereal boxes, frozen food boxes, milk cartons, beverage carriers, plates, egg cartons, lids, straws, envelopes, stacks, bags, baggies, or other types of holders. Storage products and other products used in combination with the container are also intended to be included within the term "container."

[0298] In some embodiments, the molded article is a storage product that is a closure. As used herein, the term "closure" includes, but is not limited to, any storage product such as a cap, lid, liner, divider, wrapper, film, cushioning material, and any other product used to package, store, transport, portion, serve, or dispense an object in a container. Non-limiting examples of closures include, but are not limited to, screw caps, snap-on caps, tamper-resistant, tamper-evident, and child-resistant stoppers or caps.

[0299] The following examples are merely illustrative of the present invention and are not limiting thereof. [Example]

[0300] Example 1 Pure PBS made from succinic acid and butanediol 113.55 g of 1,4-butanediol (BDO) and 141.71 g of succinic acid (SA) are charged to a 1 L glass reactor. The reactants are stirred at 150 rpm with a N2 flow until a homogeneous slurry is formed. The temperature is then increased to 225 °C over approximately 100 minutes, with the reaction mixture continuously stirred. During this increase, water and THF are formed and removed from the reactor via a distillation apparatus. When the reaction reaches 225 °C, 600 μL of catalyst is added (80 wt% zirconium butoxide (ZBO) in 1-butanol, 470 ppm Zr total), and the pressure in the vessel is gradually reduced over approximately 1.5 hours to a final pressure of approximately 500 mTorr. The temperature is then increased to 230 °C, and the polycondensation reaction is allowed to proceed for 3 hours from this point. The vessel is repressurized and cooled to 110 °C, after which the polymer is removed. The reaction takes about 6 hours in total and produces a beige, semi-crystalline polymer.

[0301] Example 2 PBS with 0.1 wt% nanocrystalline cellulose (SA+BDO method) 112.26 g of 1,4-butanediol (BDO) and 140.09 g of succinic acid (SA) are charged to a 1 L glass reactor. The reactants are stirred at 150 rpm with a N2 flow until a uniform slurry is formed. 5.4 mL of a 4.8 wt% nanocrystalline cellulose (NCC) dispersion in DI water is added to the slurry to reach a total NCC concentration of approximately 0.1 wt%. The temperature is then increased to 225 °C over approximately 2 hours while the reaction mixture is continuously stirred. During this increase, water and THF are formed and removed from the reactor via a distillation apparatus. When the reaction reaches 225 °C, a certain amount of catalyst is added (80 wt% zirconium butoxide (ZBO) in 1-butanol, 470 ppm Zr total), and the pressure in the vessel is gradually reduced over approximately 2 hours to a final pressure of approximately 500 mTorr. The temperature is increased to 230°C, at which point the polycondensation reaction is allowed to proceed for 1 hour. The vessel is repressurized and cooled to 110°C before the polymer is removed. The reaction takes approximately 5 hours in total and produces a beige semi-crystalline polymer.

[0302] Example 3 PBS with 0.4 wt% ELO (SA+BDO method) 113.55 g of 1,4-butanediol (BDO) and 141.71 g of succinic acid (SA) are charged to a 1 L glass reactor. The reactants are stirred at 150 rpm with a N2 stream until a uniform slurry is formed. The temperature is then increased to 225 °C over approximately 2 hours, with the reaction mixture continuously stirred. During this increase, water and THF are formed and removed from the reactor via a distillation apparatus. When the reaction reaches 225 °C, 600 μL of catalyst is added (80 wt% zirconium butoxide (ZBO) in 1-butanol, 470 ppm [Zr] total), and the pressure in the vessel is gradually reduced over approximately 1.5 hours to a final pressure of approximately 500 mTorr. The temperature is then increased to 230 °C, and the polycondensation reaction proceeds for 2 hours from this point. The vessel is repressurized and 1.03 g of epoxidized linseed oil (ELO) is added to the melt and allowed to react for 15 minutes. The vessel is then cooled to 110°C and the polymer is removed. The reaction takes approximately 7 hours in total and produces a beige semi-crystalline polymer.

[0303] Example 4 PBS with 0.1 wt% NCC + 0.4 wt% ELO (SA + BDO method) 97.79 g of 1,4-butanediol (BDO) and 122.05 g of succinic acid (SA) are charged to a 1 L glass reaction vessel. The reactants are stirred at 150 rpm with a N2 flow until a uniform slurry is formed. 4.7 mL of a 4.8 wt% NCC dispersion in DI water is added to the slurry to achieve a total NCC concentration of approximately 0.1 wt%. The temperature is then increased to 225 °C over approximately 2 h while the reaction mixture is continuously stirred. During this increase, water and THF are formed and removed from the reactor via a distillation apparatus. When the reaction reaches 225 °C, 600 μL of catalyst is added (80 wt% zirconium butoxide (ZBO) in 1-butanol, 470 ppm Zr total), and the pressure in the vessel is gradually reduced over approximately 1 h to a final pressure of approximately 500 mTorr. The temperature is increased to 230°C, at which point the polycondensation reaction is allowed to proceed for 1 hour. The vessel is repressurized, and 0.89 g of ELO is added to the melt and allowed to react for 15 minutes. The vessel is then cooled to 110°C, after which the polymer is removed. The reaction takes a total of approximately 4.5 hours, producing a beige, semi-crystalline polymer.

[0304] Example 5 PBS with 1 wt% NCC (SA+BDO method) 97.79 g of 1,4-butanediol (BDO) and 122.05 g of succinic acid (SA) are charged to a 1 L glass reactor. The reactants are stirred at 150 rpm with a N2 flow until a uniform slurry is formed. 46.64 mL of a 4.8 wt% NCC dispersion in DI water is added to the slurry to achieve a total NCC concentration of approximately 1 wt%. The temperature is then increased to 225 °C over approximately 2 hours while the reaction mixture is continuously stirred. During this increase, water and THF are formed and removed from the reactor via a distillation apparatus. The reaction is a dark brown color. When the reaction reaches 225 °C, a certain amount of catalyst is added (80 wt% zirconium butoxide (ZBO) in 1-butanol, 470 ppm Zr total), and the pressure in the vessel is gradually reduced over approximately 2 hours to a final pressure of approximately 500 mTorr. The temperature is increased to 230°C, at which point the polycondensation reaction is allowed to proceed for approximately 15 minutes, but is quickly stopped due to the high viscosity of the polymer. The vessel is repressurized and cooled to 110°C, after which the polymer is removed. The reaction takes a total of approximately 4.5 hours, producing a dark brown, brittle polymer.

[0305] Example 6 PBS with 0.1 wt% NCC + 0.4 wt% ELO succinic anhydride + BDO 115.35 g of BDO and 128.09 g of succinic anhydride (SAn) are charged to a 1 L reaction vessel. The reaction is stirred at 150 rpm with a N2 flow until a uniform slurry is formed. 23.95 g of a 1 wt % dispersion of BDO and NCC is added to the reaction vessel, and the reaction temperature is increased to 110°C over 30 minutes. As the reaction reaches 110°C, an endotherm occurs, measured via a thermocouple probe. Shortly after a large exotherm occurs, the temperature rises to a maximum of approximately 135°C. The temperature is then increased to 225°C over 1 hour. During this increase, water is formed and removed from the reactor. When the reaction reaches 225°C, 575uL of catalyst is added (80 wt% zirconium butoxide (ZBO) in 1-butanol, 470 ppm [Zr] total), and the pressure in the vessel is gradually reduced over approximately 1 hour to a final pressure of approximately 500 mTorr. The temperature is then increased to 230°C. From this point, the reaction proceeds for 1 hour, but may stop. The vessel is repressurized, and 1g of ELO is added to the mixture and allowed to react for approximately 15 minutes. The reaction takes approximately 3.5 hours and produces a material with a very tough and high melt viscosity that lends itself to processing.

[0306] Example 7 PBS with 0.1 wt% NCC + 0.4 wt% ELO succinic anhydride + BDO 491.31 g of BDO and 513.36 g of succinic anhydride (SAn) are charged to a 2 L reactor. The reactants are stirred at 190 rpm with N2 flow until a uniform slurry is formed. 114.11 g of a 1 wt % BDO and NCC dispersion is added to the reactor, and the reaction temperature is increased to 225 °C over 110 minutes. As the reaction reaches 130 °C, a mild endotherm occurs, measured via a thermocouple probe. Shortly after the exotherm occurs, the temperature increases to a maximum of approximately 155 °C, stabilizes there, and continues to increase to 225 °C. During this increase, water is formed and removed from the reactor. When the reaction reaches 225 °C, 2.45 g of catalyst is added (80 wt % zirconium butoxide (ZBO) in 1-butanol, 470 ppm [Zr] total), and the pressure in the vessel is gradually reduced over approximately 1 hour to a final pressure of approximately 500 mTorr. The temperature is then increased to 230°C. From this point, the reaction proceeds for 30 minutes, with the stirring speed gradually reduced to 50 rpm as the viscosity of the melt increases. The vessel is repressurized, and 4g of ELO is added to the mixture and allowed to react for approximately 15 minutes. Next, 0.6g of a 50% by weight solution of phytic acid in DI water is added as a heat stabilizer and decolorizer. The reaction takes approximately 4 hours and produces a very tough, high melt viscosity material that lends itself to processing.

[0307] Example 8(A): PBS Benchmark Example 9(B): PBS Epoxide Capping Example 10(C): PBS NCC Stretching Example 11(D): PBS NCC stretched, epoxide capped Example 12(E): PBS 10x NCC stretch, epoxide capped Example 13(F): NCC extension via PBS SAn, epoxide capping Example 14(G): PBS NCC + Epoxide Stretching, Sonication Method Example 15(H): PBS NCC + Epoxide stretching, high shear dispersion method As noted above, the term "capping" is defined herein as a reactant (in this case, ELO) being added at the end of the reaction. In Examples 9, 11, 12, and 13, this means that the ELO was added after repressurizing the vessel just prior to cooling and discharging the polymer. The term "stretching" is defined as the reactants (NCC, ELO) being added upfront along with BDO and SA or SAn. In Examples 11, 12, and 13, the NCC is added in the form of a dispersion at the beginning of the reaction. In Examples 14 and 15, the ELO is added at the end of the esterification process just prior to adding the catalyst and polycondensation. In these examples, the ELO is allowed to react for 5 minutes before adding the catalyst.

[0308] The high shear disperser method follows the same process as the ultrasonication method in terms of time and power consumption, but instead uses the equipment described at https: / / www(dot)mixers(dot)com / products / high-speed-dispersers / .

[0309] Sonication of Cellulose-BDO Mixtures The cellulose-BDO mixture was prepared by either: i) preparing a 1 wt% solution of NCC in 1,4 butanediol by combining approximately 20 g of reactants in a 40 mL scintillation vial, or ii) adding approximately 20 g of a 4.8 wt% dispersion of NCC in DI water (provided by CelluForce) to a 40 mL scintillation vial. Pulse-sonicate the cellulose-BDO mixture at 60% amplitude for a total of 5 minutes using a Qsonica Q55 ultrasonic homogenizer (available from Qsonica LLC) with a stainless steel probe tip (55 W). The complete cellulose-BDO dispersion was added to the slurry under mixing and N2.

[0310] Tensile strength test of PBS nanocomposite Tensile strength testing for PBS nanocomposites is performed according to ASTM D882-18: Standard Test Method for Tensile Properties of Thin Plastic Sheets. Briefly, the material is placed in a 20,000 lbs hot press at 145°C for 15 minutes. The thickness of the sheet is controlled to approximately 1 mm using spacers. The sample is then cut into 50 mm x 10 mm strips, and a gauge length of approximately 30 mm is used for testing. The sample is kept at 20°C with a moisture content of approximately 65% ​​for either 24 or 72 hours. The sample is placed in Instron mechanical grips and subjected to a crosshead speed of 6 mm / min. The sample thickness is measured as the average thickness at five different points along the gauge length.

[0311] Table 1 lists the tensile strengths of Examples 4-6 based on samples held at 20°C at 65% moisture content. Table 2 lists the tensile strengths of Examples 8-13 at a strain rate of 50 mm / min based on samples held at 20°C for 24 hours at 65% moisture content, and Table 3 lists the tensile strengths based on samples held for 72 hours. Table 4 lists the tensile strengths of Examples 11-13 at a strain rate of 6 mm / min and 24 hours of conditioning, and Table 5 lists the tensile strengths based on 72 hours of conditioning. Table 6 lists the tensile strength of polymer fibers composed of PBS formed in Example 13 at a strain rate of 150 mm / min and 24 hours of conditioning, and Table 7 lists the tensile strengths at a strain rate of 55 mm / min with 24 hours of conditioning.

[0312] [Table 1]

[0313] [Table 2]

[0314] [Table 3]

[0315] [Table 4]

[0316] [Table 5]

[0317] [Table 6]

[0318] [Table 7]

[0319] The tensile strength data demonstrate that the PBS nanocomposites synthesized using the methods disclosed herein are comparable to benchmark PBS synthesized using conventional means known in the prior art, and in some cases, the PBS nanocomposites exhibit improved properties over the benchmark PBS.

[0320] Intrinsic viscosity test of PBS nanocomposite Intrinsic viscosity testing was performed according to ASTM D445 and D2515 test methods. Briefly, 4 g of material was dissolved in 100 mL of chloroform in a volumetric flask for 2 days. The polymer solution was then filtered through a glass core funnel and diluted to different concentrations before being placed in a CANNON-FENSKE viscometer (available from Cannon Instrument Company, State College, PA). Before each measurement, the entire viscometer was placed in a water bath at approximately 25°C for 10 minutes. Each polymer solution was loaded into the device, and the time it took for the solution to pass between the two red lines was measured. The intrinsic viscosity was calculated as the intersection point between the plots of relative viscosity and specific viscosity at zero concentration.

[0321] Table 8 lists the viscosity values ​​for Examples 1-6, and Table 9 lists the viscosity values ​​for Examples 8-15. Higher viscosity values ​​are associated with higher molecular weight polymers and higher quality materials. Dispersing NCC in BDO prior to esterification results in higher viscosity PBS nanocomposites, as shown in Example 15. Esterification with succinic anhydride also increases the intrinsic viscosity of PBS nanocomposites compared to esterification with succinic acid (see Examples 6 and 13).

[0322] [Table 8]

[0323] [Table 9]

[0324] Acid value of Example 15 The acid value of Example 15 is determined according to ASTM D7409 standard. Briefly, approximately 0.6 g of sample is dissolved in a chloroform / methanol solution. Phenolphthalein is added to the solution, and titration is performed using a Metrohm photometric titrator with 0.1 N KOH in ethanol. The acid value of Example 15 is approximately 0.9 mg KOH / g, which corresponds to approximately 16 carboxylic acid end group equivalents per metric ton.

[0325] Dynamic Viscosity Dynamic viscosity values ​​are determined using a Brookfield HAHB viscometer. Figure 1 provides a plot illustrating the relationship between viscosity and temperature for Example 15. Dynamic viscosity values ​​are determined using a Brookfield AMETEK rotational viscometer with a #27 spindle and a thermostat. A small amount of polymer was placed in a sample container, and the temperature was increased to 230°C to induce melting. Viscosity measurements were recorded stepwise as the sample temperature decreased over time. Data collection was stopped when the temperature approached the melting temperature of the polymer.

[0326] Differential scanning calorimetry (DSC) The sample is placed in a TA Instruments Q2000 equilibrated at 30°C for 1 minute under a stream of nitrogen gas. In the first cycle, the calorimeter is ramped to 140°C at 10°C / min. The sample is then held isothermally for 3 minutes. In the second cycle, the calorimeter is ramped to -60°C at 20°C / min. A 2-minute isothermal hold concludes the second cycle. A final cycle is performed, ramping the calorimeter to 380°C at 10°C / min.

[0327] Thermogravimetric analysis (TGA) The sample is equilibrated under a stream of nitrogen gas for 1 minute at 30° C. The oven is heated to 600° C. at 10° C. / min.

[0328] [Table 10]

[0329] Thermal analysis of Examples 8 to 15 Table 10 provides a comparison of a number of thermal properties of each PBS nanocomposite: 1) Glass transition temperature (T g ), 2) Crystal melting temperature (T m ), 3) Low temperature crystallization temperature (T c ), 4) decomposition temperature at 5% mass loss (T 5% ), and 5) percent crystallization (X c ). Most of the properties are substantially comparable among the various PBS nanocomposites. The cold crystallization temperature increases for PBS nanocomposites that are NCC-stretched and esterified with epoxidized linseed oil. The polymer produced from Example 13 was subjected to a basic melt-spinning procedure using a twin-screw extruder feeding a spinneret block with 19 circular holes. The barrel temperature and spinneret were both set at 190°C, and the barrel pressure was maintained at 500 psi. Under non-isothermal conditions, the fibers were collected on a rotating drum without any drawing procedure. At this temperature, the polymer begins to nucleate and grow crystalline domains. In some cases, a higher T c This aids in the dimensional stability of the polymer.

[0330] 1H-NMR The polymers and compositions can be characterized by 1H NMR.

[0331] [Table 11]

[0332] The number average molecular weights of Examples 8-13 are provided in Table 11. The addition of succinic anhydride resulted in a higher M compared to the PBS nanocomposite esterified with succinic acid. n is provided.

[0333] Particle Size Analysis The polymer fibers produced from Example 13 are dissolved in chloroform at a concentration of 100 ppm. The solution is homogenized and then subjected to particle size analysis using a Malvern Nano ZS Zetasizer. The absorbance of the fibers is set to zero, and the refractive index of the sample is set to 1.49 (the value for PBS). The experiment is performed five times.

[0334] [Table 12]

[0335] Table 12 and Figure 2 show the particle size distribution of the dissolved polymer fibers. The majority of the polymer fiber particles have an average diameter of about 10-30 nm.

[0336] Particle size analysis of NCC dispersed using ultrasonic treatment Nanocrystalline cellulose is slowly added to 1,4 butanediol at a ratio of 1:10 (w / w) while stirring. The solution is continuously stirred and mixed to obtain a thick white liquid without lumps. Samples are dispersed at different amplitudes (60%, 80%, and 100%) at a frequency of 1 Hz. For each amplitude, samples are collected for 1, 3, and 5 minutes of sonication. Each sample is diluted with 5% (w / v) distilled water. Particle size analysis of the samples is performed using a Malvern Nano ZS Zetasizer. The absorbance of NCC is set to 0.001 and the refractive index is set to 1.58. The absorbance of water is set to zero and the refractive index is set to 1.33. The experiment is repeated five times for every nine runs to confirm reproducibility and improve the precision of the gel size and polydispersity index.

[0337] [Table 13]

[0338] Figures 3-5 and Table 13 compare particle size distribution data across different sonication time points and amplitudes. Particle size correlates with the degree of NCC dispersion in BDO, with smaller particle sizes indicating increased NCC dispersion. Increasing sonication amplitude generally increases the level of NCC dispersion (as indicated by a larger distribution of small particle sizes), especially for shorter sonication times. The difference in sonication values ​​decreases as the duration increases. Similarly, longer sonication durations result in greater NCC dispersion.

[0339] Particle size analysis of NCC dispersed using homogenization Nanocrystalline cellulose was slowly added to 1,4 butanediol at a ratio of 1:10 (w / w) while stirring. The solution was continuously stirred and mixed to obtain a thick, white liquid without any lumps. The sample was dispersed at three different homogenizer speeds ranging from 10,000 rpm to 16,667 rpm. For each speed setting, samples were collected at 1, 3, and 5 minutes of homogenization. Each sample was diluted with 5% (w / v) distilled water. Particle size analysis of the samples was performed using a Malvern Nano ZS Zetasizer. The absorbance of Ncc was set to 0.001 and the refractive index was set to 1.58. The absorbance of water was set to zero and the refractive index was set to 1.33. Experiments were repeated five times for every nine runs to confirm reproducibility and improve the precision of the gel size and polydispersity index.

[0340] [Table 14]

[0341] Figures 6-8 and Table 14 compare particle size distribution data across different homogenization times and speeds. Higher speeds correspond to higher shear levels, and particle size correlates with the degree of NCC dispersion in BDO, with smaller particle sizes indicating increased NCC dispersion. As seen in Table 14, high homogenization speeds are required to effectively disperse NCC. Speeds of 13,330 and 10,000 rpm result in a higher distribution of medium and large particle sizes.

[0342] While the present approach has been illustrated and described herein with reference to preferred embodiments and specific examples thereof, it will be readily apparent to those skilled in the art that other embodiments and examples may perform similar functions and / or achieve similar results, and all such equivalent embodiments and examples are within the spirit and scope of the present approach.

Claims

1. 1. A method for producing a polymer-polysaccharide nanocomposite resin, comprising: preparing a dispersion comprising polysaccharide nanocrystals, alkanediol monomers, and alkanedioic acid agent monomers; and polycondensing the alkanediol monomers and the alkanedioic acid monomers in the dispersion to produce a polymer-polysaccharide nanocomposite resin, wherein the polycondensation step further comprises treating the resin with a capping agent or capping group, wherein the capping agent is an epoxidized oil or an epoxy derivative.

2. 10. The method of claim 1, wherein the polysaccharide nanocrystals are derived from cellulose, heparin, chitosan, hyaluronan, alginate, pectin, guar, starch, or chitin.

3. The method of claim 1 , wherein the polysaccharide nanocrystals are cellulose nanocrystals.

4. 4. The method of claim 3, wherein the cellulose nanocrystals are derived from acid hydrolyzed cellulose from wood, cotton, bacteria, or algae.

5. 5. The method of claim 3 or 4, wherein the cellulose nanocrystals have average dimensions of about 3-50 nm in width and about 100-1000 nm in length.

6. The method of any one of claims 1 to 5, wherein the alkanediol monomer is selected from 1,4-butanediol, 1,3-propanediol, and 1,2-ethanediol.

7. The method of claim 6, wherein the alkanediol monomer is 1,4-butanediol.

8. 8. The method of any one of claims 1 to 7, wherein the alkanedioic acid agent monomer is selected from succinic acid, monoalkyl succinates, dialkyl succinates (e.g., dimethyl or diethyl succinate), succinic anhydride, adipic acid, monoalkyl adipates, dialkyl adipates (e.g., dimethyl or diethyl adipate), and adipic anhydride.

9. 9. The method of claim 8, wherein the alkanedioic acid agent monomer is succinic anhydride.

10. the method is for producing a polybutylene succinate-cellulose nanocomposite resin; preparing a dispersion comprising cellulose nanocrystals, 1,4-butanediol monomers, and succinic acid agent monomers; and polycondensing the 1,4-butanediol monomer and the succinic acid agent monomer in the dispersion to produce a polybutylene succinate-cellulose nanocomposite resin.

11. 11. The method of claim 10, wherein the cellulose nanocrystals are derived from acid hydrolyzed cellulose from wood, cotton, bacteria, or algae.

12. 12. The method of claim 10 or 11, wherein the cellulose nanocrystals have average dimensions of about 3-50 nm in width and about 100-1000 nm in length.

13. 13. The method of any one of claims 10 to 12, wherein the succinic agent monomer is selected from succinic acid, monoalkyl succinates, dialkyl succinates (e.g., dimethyl succinate or diethyl succinate), and succinic anhydride.

14. The method of claim 13, wherein the succinic acid agent monomer is succinic anhydride.

15. The method of any one of claims 1 to 14, wherein the dispersion further comprises one or more additional monomers.

16. The polycondensation esterifying the alkanediol monomers and the alkanedioic acid agent monomers to form a plurality of oligomers; and c) condensing the plurality of oligomers to produce a high MW polymer in the polymer-polysaccharide nanocomposite resin.

17. 17. The method of claim 16, wherein the plurality of oligomers and the high MW polymer each comprise butylene succinate repeat units.

18. The method of any one of claims 1 to 17, wherein the polymer of the polymer-polysaccharide nanocomposite resin is a polybutylene succinate homopolymer or a polybutylene succinate copolymer.

19. 19. The method of any one of claims 1 to 18, wherein preparing the dispersion comprises dispersing cellulose nanocrystals in a solution comprising one or both of the alkanediol monomer and the alkanedioic acid agent monomer.

20. 20. The method of claim 19, wherein the solution consists of the alkanediol monomer and the alkanedioic acid agent monomer.

21. 21. The method of claim 19 or 20, wherein the solution further comprises a non-aqueous organic solvent.

22. 21. The method of claim 19 or 20, wherein the solution further comprises water.

23. The dispersing step comprises: contacting the cellulose nanocrystals with a solution comprising 1,4-butanediol (BDO) and succinic anhydride to produce a cellulose mixture; and sonicating the cellulose mixture to uniformly disperse the cellulose nanocrystals in the solution to form the dispersion.

24. 24. The method of claim 23, wherein said sonicating said cellulose mixture is carried out under conditions sufficient to produce a dispersion in the absence of visible sedimentation.

25. 25. The method of claim 23 or 24, wherein said sonicating the cellulose mixture comprises sonicating for a duration of about 5 minutes or more.

26. 10. The method of claim 1, wherein the epoxidized oil is epoxidized linseed oil.

27. 2. The method of claim 1, wherein the epoxidized oil is selected from epoxidized linseed oil, epoxidized lard, epoxidized beef tallow, epoxidized fish oil, epoxidized coffee oil, epoxidized soybean oil, epoxidized safflower oil, epoxidized tung oil, epoxidized tall oil, epoxidized calendula, epoxidized rapeseed oil, epoxidized peanut oil, epoxidized sesame oil, epoxidized grapeseed oil, epoxidized olive oil, epoxidized jojoba oil, epoxidized dehydrated castor oil, epoxidized tallow oil, epoxidized sunflower oil, epoxidized cottonseed oil, epoxidized corn oil, epoxidized rapeseed oil, epoxidized orange oil, and mixtures thereof.

28. 17. The method of claim 16, wherein the esterifying further comprises heating the dispersion to a second temperature of from 200°C to 250°C after the reaction temperature exceeds 140°C.

29. The method of any one of claims 1 to 28, wherein the polycondensing is carried out in the presence of a catalyst.

30. 30. The method of claim 29, wherein the catalyst is zirconium butoxide.

31. 18. The method of claim 16 or 17, wherein said condensing said plurality of oligomers is carried out in a reaction vessel under reduced pressure.

32. 32. The method of claim 31, wherein the condensing of the plurality of oligomers is carried out at a reaction temperature of 200°C to 250°C.

33. 33. The method of claim 31 or 32, wherein the condensing is carried out at a pressure of about 500 mTorr.

34. 20. The method of claim 19, wherein preparing the dispersion further comprises stirring in a homogenizer operating at 10,000 rpm to 16,667 rpm.

35. 35. The method of claim 19 or 34, wherein preparing the dispersion further comprises heating and filtering the dispersion.

36. The method of claim 4, wherein the acid used in the acid hydrolysis is sulfuric acid, hydrochloric acid, hydrobromic acid, or phosphoric acid.

37. The method of claim 4, wherein the cellulose nanocrystals are produced by hydrolysis with hydrochloric acid and / or hydrobromic acid and subsequent TEMPO-oxidation.

38. The cellulose nanocrystals have the following formula: 【Chemical 1】 The method of claim 4, wherein the glucopyranose repeating unit is:

39. The cellulose nanocrystals have the following formula: 【Chemistry 2】 39. The method of claim 38, wherein the glucopyranose repeating unit is:

40. The cellulose nanocrystals have the following formula: 【Chemistry 3】 38. The method of claim 37, wherein the glucopyranose repeating unit is:

41. A nanocomposite resin produced according to any one of claims 1 to 40.

42. 42. An article comprising the nanocomposite resin of claim 41.

43. 43. The article of claim 42, wherein the article is made from the nanocomposite resin using a process selected from injection molding, blow molding, compression molding, extrusion, and melt spinning.

44. 44. The article of claim 43, wherein the article is a molded article.

45. The article of any one of claims 42 to 44, wherein the article is a yarn or fiber.

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