Alginate-based polymers and products and their manufacture

Abstract

A polymer comprising alginate, products including such a polymer and methods of making the same are provided, wherein the alginate is ionically crosslinked with a multivalent cation bridged hetero-substituted dicarboxylate salt.

Description

[0001] priority

[0002] This application claims priority to U.S. Provisional Application No. 63 / 067,988, filed August 20, 2020, and U.S. Provisional Application No. 63 / 171,812, filed April 7, 2021, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] This application provides alginate-based polymers and products, such as fibers. Alginate-based fibers can be used to produce textiles and serve as a compostable alternative to petrochemical-based polymers, with a wide range of applications in industries such as footwear, apparel, accessories, packaging, and furniture. Background Technology

[0004] Industry seeks "cradle-to-grave" solutions for many products, such as textiles, where products can be made from renewable resources and then recycled or otherwise disposed of with little or no environmental impact. Attempts have been made to utilize natural products such as alginate; however, previous efforts have been unsatisfactory because these products either lack sufficient performance properties or use ingredients or solvents that contribute to adverse environmental impacts. Summary of the Invention

[0005] The products provided typically possess and retain excellent properties such as elasticity, resilience, and toughness, making them well-suited for many applications, including textile fibers. For example, the fibers (including filaments and staple fibers), yarns (fiber bundles), and other textile products (e.g., fabrics, such as woven and nonwoven fabrics) disclosed herein exhibit unexpectedly excellent mechanical integrity and can be used in a range of industries, significantly reducing the environmental damage caused by the textile industry.

[0006] These products can be made using alginate derived from kelp, thus being considered plant-based and reducing the need for harmful raw materials. Kelp is a type of seaweed or macroalgae that grows in the cold coastal waters of the world. Kelp is one of the fastest-growing and most rapidly replenishing organisms on Earth. Kelp is grown without the use of harmful fertilizers and pesticides, arable land, or freshwater irrigation. During its growth, kelp effectively absorbs carbon / CO2 and filters pollutants from the surrounding waters. Kelp cultivation can help rebuild economic and ecological communities affected by overfishing and pollution by providing new sources of income and improving marine habitats. It has been reported that kelp absorbs 20 times more carbon per acre than terrestrial forests, so products made from kelp are likely to be carbon neutral or carbon negative.

[0007] These products are ideally suited for current and future industrial applications and possess properties that make them well-suited to replacing products currently used in many industries, particularly the textile industry. For example, fibers can be spun and processed using existing wet spinning equipment and chemicals that are safer for workers and the environment. Compared to other alginate products, these products exhibit superior properties including, for example, tensile strength (toughness), breaking strength, elasticity, elongation, resilience, wet strength, modulus, and toughness; they are compatible with the mechanical properties of rayon and are biodegradable. The processability and efficiency of fiber manufacturing are improved. Alginate-based products can readily absorb pigments and dyes using conventional methods.

[0008] These products are biodegradable and compostable, and can generally be broken down by fungi and bacteria. They are also biodegradable in seawater and will not harm aquatic life even if consumed.

[0009] One advantage of this disclosure is that water can be used as a solvent in the manufacture of the product. For example, in wet spinning, water can be used in the dope and coagulation bath, while many other wet spinning processes use solvents derived from petroleum or caustic alkali solutions. From an environmental, processing, safety, and cost perspective, using water as a solvent is advantageous.

[0010] A polymer comprising an alginate is provided, wherein the alginate is crosslinked with a heterosubstituted dicarboxylate ion bridged by a polyvalent cation, wherein the dicarboxylate is present in an amount of at least about 0.05 molar equivalents relative to the alginate carboxylate.

[0011] A polymer comprising an alginate is also provided, wherein the alginate is crosslinked with a heterosubstituted dicarboxylate ion bridged by a multivalent cation, wherein the polymer is prepared by a method comprising reacting the alginate with at least about 1% by weight of at least one heterosubstituted dicarboxylate based on the weight of the alginate.

[0012] In some embodiments, the method includes reacting an alginate with at least 2.5%, at least 5%, at least 7.5%, and at least 10% by weight of at least one heterosubstituted dicarboxylate.

[0013] In some embodiments, the method includes reacting an alginate with at least one heterosubstituted dicarboxylate in amounts of up to about 125%, up to about 100%, and up to about 75% by weight of the alginate.

[0014] In some embodiments, the dicarboxylate bridge is C3-C. 20 Heterosubstituted aliphatic dicarboxylate.

[0015] In some embodiments, the heterosubstituted dicarboxylate is C3-C12 Heterosubstituted dicarboxylate.

[0016] In some embodiments, the polymer is prepared by a method comprising the following steps: (a) mixing: (i) at least one monovalent cationic alginate; (ii) at least one heterosubstituted dicarboxylate; and (iii) at least one polyvalent cationic crosslinking agent; and (b) reacting them to form a polymer.

[0017] A method for preparing the polymer is provided, comprising: (a) mixing: (i) at least one monovalent cationic alginate; (ii) at least one heterosubstituted dicarboxylate; and (iii) at least one polyvalent cationic crosslinking agent; and (b) reacting them to form a polymer.

[0018] In some embodiments, the method includes first mixing at least one monovalent cationic alginate with at least one heterosubstituted dicarboxylate to form a mixture, and then mixing the mixture with at least one polyvalent cationic crosslinking agent to form a polymer.

[0019] A method for preparing a molded article from said polymer is also provided, comprising: (a) molding the polymer to form a molded article. The molded article includes fibers, films, and granules. In some embodiments, the molded article is a fiber. In some embodiments, forming the fiber (molded article) includes air-gap wet spinning.

[0020] A method for preparing molded articles is provided, comprising: reacting at least one monovalent cationic alginate with at least one C3-C... 20 A heterosubstituted dicarboxylate and at least one polyvalent cationic crosslinker are mixed and reacted with optional one or more additives to form a molded article comprising a polymer containing crosslinked alginate. In some embodiments, the molded article is a fiber. In some embodiments, molding includes wet spinning.

[0021] A method for preparing a molded article from the above-described polymer is also provided, comprising: molding the polymer to form a molded article. In some embodiments, the molded article is a fiber. In some embodiments, the molded article is a film. In some embodiments, the molded article is a fabric.

[0022] A method for preparing fibers via wet spinning is also provided, comprising:

[0023] a. A stock solution for preparing at least one monovalent metal alginate and at least one heterosubstituted dicarboxylate in a solvent;

[0024] b. The solution is extruded through a spinneret to form fibers;

[0025] c. Stretching the fibers through at least one coagulation bath containing a solvent and at least one multivalent cationic crosslinking agent; and

[0026] d. Dried fibers.

[0027] In some embodiments, the alginate is selected from the group consisting of sodium alginate, potassium alginate, and ammonium alginate.

[0028] In some embodiments, the alginate has a molecular weight of about 10,000 g / mol to about 500,000 g / mol.

[0029] In some embodiments, alginate has a G / M ratio of about 1 to about 2.5.

[0030] In some embodiments, the heterosubstituted dicarboxylate is a heterosubstituted sodium dicarboxylate, a heterosubstituted potassium dicarboxylate, a heterosubstituted lithium dicarboxylate, or a heterosubstituted ammonium dicarboxylate.

[0031] In some embodiments, the stock solution comprises about 0.5% to about 50% by weight of monovalent metal alginate based on the weight of the stock solution.

[0032] In some embodiments, the stock solution is prepared using at least one heterosubstituted dicarboxylate at about 1% to about 125% by weight of the alginate.

[0033] In some embodiments, the multivalent cationic crosslinking agent has a cation selected from the group consisting of calcium, copper, iron, aluminum, zinc, magnesium, barium, chromium, cobalt, nickel, manganese, and mixtures thereof.

[0034] In some embodiments, the coagulation bath contains at least one polyvalent cationic crosslinking agent in a solvent at a concentration of about 0.02 to about 2 mol / L.

[0035] In some embodiments, the solvent of the stock solution is water. In some embodiments, the solvent of the coagulation bath is water. In some embodiments, the solvent of both the stock solution and the coagulation bath is water.

[0036] In addition, fabrics made from the fiber are provided. In some embodiments, the fabric is a knitted fabric. In some embodiments, the fabric is a woven fabric. In some embodiments, the fabric is a nonwoven fabric.

[0037] In some embodiments, the heterosubstituted dicarboxylic acid salt is a hydroxylated dicarboxylic acid salt. In some embodiments, the heterosubstituted dicarboxylic acid salt is derived from a dicarboxylic acid selected from the group consisting of hydroxymalonic acid, malic acid, tartaric acid, citramalic acid, hydroxyglutaric acid, dihydroxyglutaric acid, hydroxyadipic acid, and saccharic acid.

[0038] In some embodiments, the heterosubstituted dicarboxylate is an amino-substituted dicarboxylate. In some embodiments, the amino-substituted dicarboxylate is derived from a dicarboxylate selected from the group consisting of aspartic acid and glutamic acid.

[0039] In some embodiments, the heterosubstituted dicarboxylic acid salt is a halogen-substituted dicarboxylic acid salt. In some embodiments, the halogen-substituted dicarboxylic acid salt is derived from a dicarboxylic acid selected from the group consisting of chloromalonic acid, bromomalonic acid, chlorosuccinic acid, bromosuccinic acid, dibromosuccinic acid, and bromoglutaric acid.

[0040] In some embodiments, the heterosubstituted dicarboxylate is a ketone-substituted dicarboxylate. In some embodiments, the ketone-substituted dicarboxylate is derived from oxaloacetic acid.

[0041] In some embodiments, the heterosubstituted dicarboxylic acid salt is derived from a dicarboxylic acid selected from the group consisting of malic acid, tartaric acid, oxaloacetic acid, chlorosuccinic acid, glutamic acid, and aspartic acid.

[0042] In some embodiments, the heterosubstituted dicarboxylate is monosubstituted.

[0043] In some embodiments, the heterosubstituted dicarboxylate is polysubstituted.

[0044] In some embodiments, the heterosubstituted dicarboxylate is a heterosubstituted sodium dicarboxylate, a heterosubstituted potassium dicarboxylate, a heterosubstituted lithium dicarboxylate, or a heterosubstituted ammonium dicarboxylate.

[0045] In some embodiments, it includes at least one monovalent cationic alginate and at least one C3-C 20 A mixture of heterosubstituted dicarboxylate salts is wet-spun into a bath containing at least one polyvalent cationic crosslinking agent.

[0046] In some embodiments, the polymer or fiber manufacturing method further includes:

[0047] (1) Mixing:

[0048] (a) at least one C3-C 20 Heterosubstituted dicarboxylic acids; and

[0049] (b) at least one base; and

[0050] (2) React them to form heterosubstituted dicarboxylate salts.

[0051] A membrane made of the polymer and a method for manufacturing the membrane are provided.

[0052] A foam made from the said polymer and a method for manufacturing the foam are provided.

[0053] A granular particle or pellet made from the polymer is provided. In some embodiments, a method for manufacturing the granular particle or pellet using a water bath or spray method is included.

[0054] In some embodiments, in the products or methods disclosed herein, the linear heterosubstituted dicarboxylic acid used to prepare the dicarboxylic acid salt can be described by the following formula, wherein y and z total 1-18; y is 1-18, z is 0-17; X is OR1, NR2R3, halogen (e.g., Cl and Br) and =O; R1, R2 and R3 can be the same or different and are selected from C1-C8 straight-chain, branched or cyclic alkyl or hydrogen.

[0055]

[0056] Those skilled in the art will readily recognize the corresponding dicarboxylate. In some embodiments, y and z are independently 1-6, y is 1-4, and z is 0-3.

[0057] Additional features and advantages of this disclosure will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practice of this disclosure. The objects and other advantages of this disclosure will be realized and obtained by means of the elements and combinations particularly pointed out in the specification and claims.

[0058] The foregoing general description and the following detailed description are exemplary and illustrative, intended only to provide further explanation of this disclosure, and do not limit the scope of the subject matter covered by the claims. Detailed Implementation

[0059] The details shown herein are merely examples, intended only for the purpose of illustrative discussion of various embodiments of this disclosure, and to provide what is considered the most useful and readily understood description of the principles and concepts of the disclosed subject matter. In this regard, no attempt is made to show the details of the disclosed subject matter in more detail than is necessary for a basic understanding of this disclosure, which enables those skilled in the art to understand how the various forms of this disclosure can be implemented in practice.

[0060] The following disclosure relates to more detailed embodiments. However, the disclosed subject matter may be implemented in different forms and should not be construed as limiting oneself to the embodiments set forth herein. Although similar or equivalent methods and materials to those described herein may be used in practice or testing of this disclosure, suitable methods and materials are described herein.

[0061] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. The specialized terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used in the specification and claims, the singular forms “a,” “an,” and “the” are intended to also include the plural forms unless the context clearly indicates otherwise. Furthermore, the phrases “at least one” and “one or more” are intended to be interchangeable, and their use is not intended to limit the scope of any described or claimed feature preceded by “a,” “an,” and “the” to the singular form.

[0062] All publications, patent applications, patents, and other documents mentioned herein are incorporated herein by reference in their entirety. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. In case of any conflict, this specification (including definitions) shall prevail.

[0063] Unless otherwise stated, all figures used in the specification and claims to indicate quantities of ingredients, reaction conditions, etc., should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters listed in the specification and claims are approximate values ​​that may vary depending on the desired characteristics sought to be obtained in a particular embodiment. At least, and without attempt to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter should be interpreted according to the number of significant figures and common rounding methods. When the term "about" is used to describe an endpoint of a numerical value or range, this disclosure should be understood to include the specific numerical value or endpoint referred to.

[0064] Although the numerical ranges and parameters describing the broad scope of the disclosed subject matter are approximations, the numerical values ​​illustrated in the specific examples are reported as precisely as possible. However, any numerical value inherently contains a certain degree of error, which is necessarily caused by the standard deviation found in the method of obtaining that value. Every numerical range given throughout the specification includes every narrower numerical range falling within such a broader range, as if such a narrower numerical range were explicitly stated herein.

[0065] When content, concentration, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and lower values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value and any lower or preferred value, regardless of whether the range is disclosed individually. In the case of ranges of numerical values ​​listed herein, unless otherwise stated, the range is intended to include its endpoints, as well as all integers and fractions within that range. This does not mean that the scope of this disclosure is limited to the specific values ​​listed when the range is defined.

[0066] Unless otherwise stated, all percentage measurements in this application are based on 100% of the weight of a given sample and are measured by weight. Therefore, for example, 30% represents 30 parts by weight out of every 100 parts by weight of the sample. Unless otherwise stated, all percentages, parts, proportions, etc., are by weight.

[0067] This disclosure includes a large number and many components contemplated for inclusion in the disclosed compositions. It should be understood that while the inventors explicitly contemplate including these components, they also explicitly contemplate excluding them. Therefore, all components disclosed herein are also explicitly contemplated for exclusion.

[0068] Unless otherwise specified, trademarks are shown in capital letters.

[0069] As used herein, the terms “comprising,” “including,” “containing,” “characterized by,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, “or” refers to inclusive or rather than exclusive or. For example, conditions A or B satisfy any of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0070] The transitional phrase "composed of..." excludes any element, step, or ingredient not specified in the claim, thereby closing the claim to exclude materials other than those listed, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the elements set forth in that clause; other elements are not excluded from the entire claim.

[0071] The transitional phrase "consistently composed of..." limits the scope of the claim to specific materials or steps, as well as those materials or steps that do not substantially affect the essential and novel features of the claimed invention. Claims "consistently composed of..." fall between closed claims drafted in the "consistent with..." format and fully open claims drafted in the "comprising..." format.

[0072] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that such description should be interpreted as also using the terms “substantially consisting of” or “consisting of” to describe such an invention.

[0073] This disclosure relates to polymers having an alginate “backbone” and their manufacture and use, wherein the alginate is crosslinked with a heterosubstituted dicarboxylate ion bridged by a polyvalent cation (the term “backbone” is used in this specification only to refer to the fact that the polymer component is essentially an alginate or derived from an alginate. It is not intended to imply that the entire polymer component must be an alginate, as alginate is well known in the art). The heterosubstituted dicarboxylate is essentially a divalent anion of the heterosubstituted dicarboxylate. Salts are generally preferred because they are water-soluble and work well in many applications, such as wet spinning of fibers. Without wishing to be bound by any particular operational theory, it is believed that a polyvalent cation (e.g., calcium or other cation) from the crosslinking agent replaces the sodium or other metal counterion of the dicarboxylate and attaches the heterosubstituted dicarboxylate to the anion of the carboxylate group of the alginate. In some embodiments, the polymers of this disclosure may be characterized as crystalline, semi-crystalline, or amorphous.

[0074] Other attempts have been made to manufacture alginate fibers, but none have utilized the concepts disclosed in this application. For example, CN 101033564A describes the preparation of calcium alginate fibers by wet spinning using calcium chloride crosslinking agents. These fibers do not possess sufficient properties for commercial use. Other literature, such as US 7,270,654, discloses the use of alginate in the manufacture of molded articles, but none of these documents teach that the products possess properties suitable for industrial applications and have minimal or no subsequent environmental impact.

[0075] WO 2020 / 118080 A1 relates to alginate compositions comprising sodium alginate, methylcellulose and a polyol plasticizer (glycerol), and their use in the wet spinning of fibers, fabrics and films.

[0076] The polymers disclosed herein are made of (a) an alginate backbone, (b) a heterosubstituted dicarboxylate, and (c) a polyvalent cation. The relative proportions of each typically depend on the molecular weight or chain length of the dicarboxylate used, and the valence and weight of the polyvalent cation used. While embodiments may include only one type of alginate, heterosubstituted dicarboxylate, or polyvalent cation, more than one type of each component may be included, such that, for example, a mixture of one or more of alginate, dicarboxylate, and polyvalent cation may be used.

[0077] In the polymers disclosed herein, the dicarboxylate is present in an amount of at least about 0.05 molar equivalent relative to the alginate carboxylate. It should be understood herein that the alginate polymer has carboxylates along the chain, and reference is made to the number of dicarboxylates per carboxylate in the alginate chain.

[0078] In some embodiments, the dicarboxylate bridge is present in amounts of at least about 0.1 and at least about 0.2 molar equivalents relative to the alginate carboxylate content. In some embodiments, the dicarboxylate bridge is present in amounts of at most about 1.0, at most about 0.5, and at most about 0.75 molar equivalents relative to the alginate carboxylate content.

[0079] In some embodiments, the alginate backbone may comprise at least about 20% by weight of polymer, or at least about 50% by weight, 60% by weight, 70% by weight, 80% by weight, 90% by weight, 92.5% by weight, or 95% by weight of polymer. In some embodiments, the alginate backbone may comprise up to about 97.5% by weight of polymer. In some embodiments, the alginate backbone may comprise up to about 95% by weight of polymer.

[0080] In some embodiments, the heterosubstituted dicarboxylate may contain at least about 1% by weight of the polymer, or at least about 2.5%, 5%, 10%, 20%, 30%, 40%, or 50% by weight of the polymer.

[0081] Starting materials

[0082] The polymer can be prepared from: at least one monovalent cationic alginate; at least one C3-C 20 Heterosubstituted dicarboxylate; and at least one polyvalent cationic crosslinking agent.

[0083] Alginate

[0084] The polymers disclosed herein have an alginate backbone. Any suitable cationic alginate can be used to prepare the polymers of this disclosure. The polymers of this disclosure can be prepared using at least one alginate derived from one or more alginates having a monovalent cation. Examples include, but are not limited to, sodium, potassium, and ammonium salts. In some embodiments, the polymer is prepared using sodium alginate.

[0085] Naturally occurring alginates are polysaccharides composed of linear copolymers of β-(1–4)-linked d-mannuronic acid units (M-units) and β-(1–4)-linked l-guluronic acid units (G-units) linked via glycosidic bonds. These units can be found in homopolymer blocks (MM or GG) or random copolymer blocks (GM) within the polymer chain. Alginates are typically described by the ratio of their G-units to M-units, or G / M ratio. The G / M ratio can vary over a wide range, but is typically between 3:1 and 1:3. Alginates used in this disclosure can be naturally derived (e.g., extracted from kelp) or prepared by biotechnological methods. This disclosure is not limited to the source of alginates.

[0086] The alginates used in this disclosure may have their original, i.e., "natural" structure, or may be chemically modified, such as propylene glycol alginate. Such modification is acceptable as long as it does not unacceptably interfere with the basic concepts of this disclosure.

[0087] Algates with any suitable G / M ratio can be used. The G / M ratio is determined by high-performance anion exchange-pulse amperometric chromatography (HPAE-PAC).

[0088] In some embodiments, the G / M ratio is at least about 0.5. In some embodiments, the G / M ratio is at least about 1. In some embodiments, the G / M ratio is at least about 1.5, and the G / M ratio may be at most about 2.5. In some embodiments, the G / M ratio may be at most about 2. A desired alginate has a G / M ratio of about 1.8. (Those skilled in the art will readily recognize that ratios can be described using a single number, so a G / M ratio of 0.5 is the same as 0.5 / 1, and a G / M ratio of 2 is the same as a ratio of 2 / 1).

[0089] Algates can be described by their molecular weight and / or viscosity. In this paper, alginates are described relative to each of molecular weight and viscosity. As used herein, for optimal efficiency and accuracy, molecular weight is measured by multi-angle light scattering (MALS). This method yields a weight-average molecular weight (Mi). w (Note: The molecular weight of any alginate mentioned in this article refers to M.) w Molecular weight directly affects the viscosity measured in solution. High viscosity is usually caused by a high average molecular weight. To measure viscosity directly, a 1% by weight aqueous solution is typically maintained at 20°C and the viscosity is obtained using a Brookfield viscometer. Those skilled in the art will readily recognize that the presented viscosity is not precisely related to the described molecular weight, and one or both of these properties can be used to select an alginate for a given application.

[0090] In some embodiments, the alginate may have a molecular weight of at least about 10,000 g / mol, at least about 15,000 g / mol, at least about 50,000 g / mol, or at least about 90,000 g / mol. In some embodiments, the alginate has a molecular weight of at most about 500,000 g / mol, at most about 325,000 g / mol, or at most about 250,000 g / mol. In terms of viscosity, the alginate may have a viscosity of at least about 15 cP, at least about 20 cP, at least about 25 cP, at least about 30 cP, at least about 35 cP, or at least about 40 cP. The alginate may have a viscosity of at most about 1000 cP, at most about 900 cP, at most about 800 cP, at most about 700 cP, at most about 600 cP, at most about 500 cP, at most about 400 cP, or at most about 325 cP.

[0091] In some embodiments, the alginate may have a high molecular weight and a high G / M ratio. In these embodiments, the alginate may have a molecular weight of about 200,000 to about 500,000 g / mol or a viscosity of about 150 cP to about 1,000 cP, and a G / M ratio of about 1.5 to about 2.5. In some embodiments, the alginate may have a molecular weight of about 200,000 to about 500,000 g / mol or a viscosity of about 150 cP to about 1,000 cP, and a G / M ratio of about 1.5 to about 2.0.

[0092] In some embodiments, it may have a high molecular weight and a low G / M ratio. In these embodiments, the alginate may have a molecular weight of about 200,000 to about 500,000 g / mol or a viscosity of about 150 cP to about 1,000 cP, and a G / M ratio of about 0.5 to about 0.75.

[0093] In some embodiments, the alginate may have a low molecular weight and a high G / M ratio. In these embodiments, the alginate may have a molecular weight of about 30,000 to about 200,000 g / mol or a viscosity of about 20 cP to about 150 cP, and a G / M ratio of about 1.5 to about 2.5. In some embodiments, the alginate may have a molecular weight of about 30,000 to about 200,000 g / mol or a viscosity of about 20 cP to about 150 cP, and a G / M ratio of about 1.5 to about 2.0.

[0094] In some embodiments, it may have a low molecular weight and a low G / M ratio. In these embodiments, the alginate may have a molecular weight of about 30,000 to about 200,000 g / mol or a viscosity of about 20 cP to about 150 cP, and a G / M ratio of about 0.5 to about 0.75.

[0095] In some embodiments, a moderate G / M ratio may be present. In embodiments where a moderate G / M ratio exists, a G / M ratio of about 0.75 to about 1.5 may be specified.

[0096] Examples of alginates used in the practices of this disclosure are commercially available. Examples include, for example: alginate IL-6G (Kimica, Tokyo, Japan); alginate I-3G-80 (Kimica); alginate I-8 (Kimica); 3541 (Algaia, Paris, France); 7041 (Algaia, Paris, France); S1600N (Algaia); S20NS (Algaia); ProNova SLM 100 (International Flavors & Fragrances NovaMatrix, Sanverka, Norway); ProNova SLG 20 (International Flavors & Fragrances); Sodium alginate (Sigma Aldrich, St. Louis, Missouri). In wet spinning, the use of low molecular weight and high G / M ratios (such as alginate IL-6G) is preferred for processability.

[0097] dicarboxylic acid salt

[0098] The polymers disclosed herein are crosslinked with dicarboxylate ions bridged by polyvalent cations. The term "dicarboxylate" refers to a mono- or poly-substituted dicarboxylate. Those skilled in the art will readily recognize that dicarboxylates possess positive counterions associated with their carboxyl groups.

[0099] The dicarboxylate bridge is derived from any available heterosubstituted dicarboxylate. In some embodiments, the main carbon chain contains only carbon atoms. “Heterosubstituted” means that there are substituents containing atoms other than carbon or hydrogen atoms attached to the main carbon chain or cyclic group. For the avoidance of doubt, substituents also include hydrocarbon substituents, such as alkyl (e.g., methyl) or aryl.

[0100] In some embodiments, the heterosubstituted dicarboxylate bridge is C3-C. 20 Heterosubstituted dicarboxylate bridges, and from C3-C 20 C3-C obtained from heterosubstituted dicarboxylic acids 20 It is derived from heterosubstituted dicarboxylate.

[0101] Dicarboxylate salts can be monosubstituted or polysubstituted, meaning they can have one or more substituents. If polysubstituted, the dicarboxylate salt can have two or more substituents, at least one of which should be a hetero-containing substituent. In some embodiments, the dicarboxylate salt has one substituent, and that substituent is a hetero-containing substituent. In some embodiments, the dicarboxylate salt has two or more substituents, which are hetero-containing substituents. In some embodiments, the dicarboxylate salt has two substituents, which are hetero-containing substituents. In some embodiments, the dicarboxylate salt has two substituents, one of which is a hetero-containing substituent, and the other substituent contains only carbon and hydrogen atoms.

[0102] Dicarboxylate or dicarboxylic acid may comprise a straight-chain, branched-chain, or alicyclic hydrocarbon chain. In some embodiments, straight-chain or branched hydrocarbons are referred to. In some embodiments, a straight-chain hydrocarbon is selected.

[0103] In this document, when referring to bridges, salts, and acids, this relevance will be readily apparent to those skilled in the art. For example, examples include those from C3-C... 12 C3-C obtained from heterosubstituted dicarboxylic acids 12 Heterosubstituted dicarboxylate. In the following discussion, when referring to the characteristics of a bridge, salt, or acid, those skilled in the art should also understand that the description covers the corresponding bridge, salt, or acid.

[0104] Examples of heterosubstituted dicarboxylic acids that can be used in this disclosure include, but are not limited to, malic acid, tartaric acid, oxaloacetic acid, chlorosuccinic acid, glutamic acid, and aspartic acid.

[0105] In some embodiments, the heterosubstituted dicarboxylic acid is a hydroxylated dicarboxylic acid. Examples include hydroxymalonic acid, malic acid, tartaric acid, citric acid, hydroxyglutaric acid, dihydroxyglutaric acid, hydroxyadipic acid, and gluconic acid (also known as gluconic acid).

[0106] In some embodiments, the heterosubstituted dicarboxylic acid is an amino-substituted dicarboxylic acid. Examples are aspartic acid and glutamic acid.

[0107] In some embodiments, the heterosubstituted dicarboxylic acid is a halogen-substituted dicarboxylic acid. Examples are chloromalonic acid, bromomalonic acid, chlorosuccinic acid, bromosuccinic acid, dibromosuccinic acid, and bromoglutaric acid.

[0108] In some embodiments, the heterosubstituted dicarboxylic acid is a ketone-substituted dicarboxylic acid. An example is oxaloacetic acid.

[0109] The specific examples of dicarboxylic acids listed above are for reference only, and this disclosure is not limited to these examples.

[0110] In some embodiments, the linear heterosubstituted dicarboxylic acid used to prepare the dicarboxylate can be described by the following formula, where X is OR1, NR2R3, a halogen (e.g., Cl and Br), and =O:

[0111]

[0112] Those skilled in the art will readily recognize that the diagram illustrates the presence of two potential types of carbon groups, thus groups y and z can be arranged in any order along the chain when group z is present. Furthermore, those skilled in the art will readily recognize the corresponding dicarboxylate salts.

[0113] In some embodiments, y and z total 1-18, y is 1-18, and z is 0-17.

[0114] In some embodiments, y and z are independently 1-6, y is 1-4, and z is 0-3.

[0115] In some embodiments, y and z are independently 1-4. In some embodiments, y is 2. In some embodiments, y is 1.

[0116] Those skilled in the art will readily recognize the z and y values ​​of the above-mentioned dicarboxylic acids and their corresponding dicarboxylic acid salts.

[0117] In some embodiments, X is OR1, and each R1 may be the same or different, and is selected from C1-C8 straight-chain, branched or cyclic alkyl groups or hydrogen. In some embodiments, X is OR1, and each R1 may be the same or different, and is selected from C1-C4 straight-chain or branched alkyl groups or hydrogen. In some embodiments, OR1 is a hydroxyl group.

[0118] In some embodiments, X is NR2R3, and each R2 and R3 may be the same or different, and is selected from C1-C8 straight-chain, branched or cyclic alkyl groups or hydrogen. In some embodiments, X is NR2R3, and each R2 and R3 may be the same or different, and is selected from C1-C4 straight-chain or branched alkyl groups or hydrogen. In some embodiments, NR2R3 is NH2.

[0119] In some embodiments, X is OR1 and X is NR2R3, and R1, R2, and R3 may be the same or different, selected from C1-C8 straight-chain, branched, or cyclic alkyl groups or hydrogen. In some embodiments, R1, R2, and R3 may be the same or different, selected from C1-C4 straight-chain or branched alkyl groups or hydrogen. In some embodiments, R1, R2, and R3 may be the same or different, selected from C1-C4 straight-chain alkyl groups.

[0120] In some embodiments, X is a halogen. In some embodiments, X is Cl. In some embodiments, X is Br.

[0121] In some embodiments, X is =O (i.e., a ketone substituent or an oxygen atom linked by two bonds).

[0122] A mixture of one or more dicarboxylic acids may be used in any embodiment, while in other cases using only one dicarboxylic acid may be preferred. In some embodiments, the mixture consists of a heterosubstituted dicarboxylic acid or a specific type of heterosubstituted dicarboxylic acid, such as an aliphatic dicarboxylic acid salt containing only monohydroxy or polyhydroxy substituted salts. In some embodiments, the mixture consists of a heterosubstituted dicarboxylic acid and one or more unsubstituted dicarboxylic acid salts.

[0123] When "aliphatic" dicarboxylate or dicarboxylic acid is referred to, it means a dicarboxylate or dicarboxylic acid having a straight-chain, branched-chain, or alicyclic hydrocarbon chain. In some embodiments, it refers to a straight-chain or branched hydrocarbon. In some embodiments, a straight-chain hydrocarbon is selected.

[0124] In some embodiments, the unsubstituted dicarboxylate is aliphatic and the carbon chain is saturated. For example, in these embodiments, the dicarboxylate is derived from a saturated aliphatic dicarboxylic acid selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, and tetradecanoic acid. In some embodiments, the dicarboxylate is derived from an unsubstituted aliphatic dicarboxylic acid selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, and mixtures thereof. In some embodiments, the dicarboxylate is derived from a saturated aliphatic dicarboxylic acid selected from the group consisting of succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, and mixtures thereof. In some embodiments, the saturated aliphatic dicarboxylate is derived from a dicarboxylic acid selected from the group consisting of succinic acid, azelaic acid, sebacic acid, and mixtures thereof. In some embodiments, the unsubstituted aliphatic dicarboxylic acid is sebacic acid. In some embodiments, the dicarboxylic acid is adipic acid. In some embodiments, the dicarboxylic acid is glutaric acid. In some embodiments, the dicarboxylic acid is succinic acid.

[0125] In some embodiments, the unsubstituted dicarboxylic acid is aliphatic and the carbon chain is unsaturated. Examples of unsaturated aliphatic dicarboxylic acids that can be used in this disclosure include, but are not limited to, maleic acid and fumaric acid.

[0126] Dicarboxylate salts can be formed by reacting dicarboxylic acids with a base. These dicarboxylate salts are commercially available or can be readily prepared. In some embodiments, these dicarboxylate salts are prepared and isolated in a separate reaction prior to use. Alternatively, these dicarboxylate salts can be prepared by sequential addition.

[0127] Examples of dicarboxylate salts include, but are not limited to, sodium dicarboxylate, potassium dicarboxylate, lithium dicarboxylate, or ammonium dicarboxylate. In some embodiments, sodium dicarboxylate is used. In some embodiments, potassium dicarboxylate is used. Mixtures of dicarboxylate salts may be used.

[0128] For applications involving the dissolution of dicarboxylic acids or salts in solvents such as water, solubility is important and may require the use of cosolvents or alternative monovalent counterions to ensure sufficient solubility of higher molecular weight dicarboxylic acids.

[0129] Any suitable base can be used to prepare dicarboxylate. For wet spinning, it may be desirable to use a salt that is soluble in a solvent (most commonly water). In some embodiments, the base is selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, and mixtures thereof. In some embodiments, the base is sodium hydroxide. In some embodiments, the base is potassium hydroxide.

[0130] The preparation of dicarboxylic acids is well known in the art and can be carried out using any technique (including conventional techniques) by means of solutions or solids. For example, sodium hydroxide can be purchased in solution or solid form and then reacted with dicarboxylic acids. Caustic base solutions, such as a 50% sodium hydroxide solution in water, are readily available. Caustic bases can also be purchased as solids.

[0131] Crosslinking agent

[0132] In the polymers disclosed herein, the alginate backbone is crosslinked with dicarboxylate ions bridged by polyvalent cations. That is, at least one polyvalent cation crosslinking agent attaches the dicarboxylate to the alginate backbone via ionic bonds.

[0133] Direct ionic crosslinking can also be achieved via multivalent cations. Of course, this depends on stoichiometry and can be used to adjust the properties of the polymer and the resulting product.

[0134] Examples of polyvalent cations are calcium, copper, iron, aluminum, zinc, magnesium, barium, chromium, cobalt, nickel, manganese, and mixtures thereof. Crosslinked polyvalent cations may be selected from calcium, copper, iron, aluminum, zinc, cobalt, barium, and mixtures thereof. In some embodiments, the crosslinked cation is selected from calcium, copper, iron, aluminum, and zinc, and mixtures thereof. In some embodiments, the crosslinked cation is selected from calcium, copper, aluminum, and mixtures thereof. In one specific embodiment, the crosslinked cation is calcium.

[0135] Any suitable cationic crosslinking agent that is sufficiently soluble in a certain amount of water or other solvent system (e.g., glycerol) used to carry out the reaction can work. Examples of crosslinking agents include, for example, calcium chloride, barium chloride, aluminum chloride, copper chloride, copper sulfate, aluminum sulfate, ferric sulfate, and zinc sulfate. More specific crosslinking agents are calcium chloride, barium chloride, calcium bicarbonate, copper sulfate, aluminum sulfate, ferric sulfate, and zinc sulfate. A specific crosslinking agent is calcium chloride.

[0136] Cellulose

[0137] Cellulose can be added to polymers, as described in WO 2020 / 118080 A1. Examples of suitable celluloses include methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, other cellulose derivatives, or combinations thereof. In many embodiments, cellulose may not be used.

[0138] additive

[0139] Polymers and products made from such polymers may contain one or more additives, examples of which are known in the art, and additives may be used in amounts suitable for the desired properties, typically those described in the art. Examples of these types of additives are well known in the art and include pigments, dyes, brighteners or other colorants, optical brighteners, stabilizers (e.g., flame retardants / fire retardants, light stabilizers, heat stabilizers, antioxidants), plasticizers, matting agents (e.g., TiO2, CaCO3, silica), viscosity modifiers, surfactants, antimicrobial agents, antistatic agents, lubricants, processing aids, slip agents, antiblocking agents, mold release agents, fillers, and other components of additives known in the art. (Some additives, such as TiO2, can satisfy more than one of these purposes.) It is readily apparent that additives can be added to various process steps using a variety of techniques.

[0140] Polymers and Products

[0141] The products disclosed herein are well-suited for current and future industrial applications and possess properties that make them ideal replacements for products currently used in many industries, particularly the textile industry. The products of this disclosure possess and retain excellent properties such as elasticity, resilience, and toughness, making them well-suited for many applications, including textile fibers and membranes. For example, the fibers (including filaments and staple fibers), yarns (fiber bundles), and other textile products (e.g., fabrics, such as woven and nonwoven fabrics) of this disclosure exhibit unexpectedly excellent mechanical integrity and can be used in a range of industries, significantly reducing the environmental damage caused by the textile industry.

[0142] Various types of fibers, including filaments and staple fibers, can be manufactured using this disclosure. These terms are used in their general commercial sense. In this document, "filament" is generally used to refer to continuous fibers on a spinning machine.

[0143] "Staple fiber" is used to refer to short fibers or cut filaments. For example, staple fibers used in nonwoven fabrics may have a length of at least about 1 inch. In some embodiments, the length is at least about 1.25 inches or even longer. Depending on the application, the length may be up to about 6 inches or longer. In some embodiments, the length is up to about 4 inches. In some embodiments, the length is up to about 2 inches.

[0144] The embodiments primarily or exclusively use the polymers of this disclosure (with additives), sometimes referred to in the art as single-component fibers or configurations. However, other embodiments may include the polymers of this disclosure as well as other polymers. That is, the polymers of this disclosure can be used in multi-component (e.g., bicomponent) configurations, including conventional sheath / core and side-by-side multi-component configurations and multi-component (e.g., bicomponent) configurations. When multiple polymers are present (including one or more alginates as shown), any suitable combination of said multiple polymers, including multi-component and multi-component configurations, can be employed. The type and proportion of polymers used can be readily determined by those skilled in the art without extensive experimentation. For example, these embodiments may include very small amounts to large amounts of the polymers of this disclosure. Thus, in some embodiments, at least about 5%, at least about 10%, at least about 15%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 75%, at least about 85%, at least about 90%, and at least about 95% of the polymer may be included, all percentages being by weight of the fiber.

[0145] Yarn (also known as "bundle") preferably consists of many short fibers or filaments.

[0146] The size and shape of the fibers vary depending on the application and can range from as low as 0.1 denier (dpf) or less to as high as 300 dpf or greater. For many textile applications, depending on the end use, the fibers of this disclosure have a denier (dpf) of at least about 0.1, at least about 0.5, and at most about 30, at most about 10, at most about 5, more preferably at most about 3. These sizes are for illustrative purposes, and those skilled in the art will recognize the sizes required for various purposes.

[0147] This disclosure can also be used to prepare monofilaments. Monofilaments are typically from about 10 dpf to about 300 dpf. Monofilaments, monofilament yarns, and their uses are well known in the art.

[0148] The fibers (short fibers or filaments) can be of any shape, including, for example, circular, substantially circular, elliptical, or having other shapes such as grooved, substantially flat, dogbone, octagonal, triangular, sunburst (also known as sol), fan-shaped elliptical, trefoil, tetra-channel (also known as quatra-channel), fan-shaped ribbon, ribbon, starburst, snowman, etc. They can be solid, hollow, or multiple hollow. In some embodiments, the fiber is a solid filament that is circular or substantially circular. In some embodiments, the fiber is a solid filament that is flat or substantially flat. In some embodiments, the fiber is a ribbon or fan-shaped ribbon filament.

[0149] This disclosure includes fabrics made of fibers, including knitted fabrics, woven fabrics, nonwoven fabrics, and other types of fabrics. Woven or knitted fabrics can be made from, but are not limited to, monofilaments, multifilaments, and staple yarns. Nonwoven fabrics are typically made from short fibers through wet spinning, air-jet spinning, or carding processes, or directly formed using electrospinning or solution blowing processes. Fabrics may include blends with other types of fibers or filaments, including spinning alginate fibers together with other natural and synthetic fibers and coating existing yarns with alginate hydrogels or filaments.

[0150] This disclosure includes all types of textile end uses, such as clothing (like garments or fabrics for footwear) or short fibers and filaments in technical textiles such as carpets, automotive interiors, and wall coverings.

[0151] Yarns and fabrics include blends of fibers (staple fibers and filaments), such as those made from cotton, animal materials (e.g., wool and chitosan), regenerated cellulose (e.g., viscose and dissolving fibers), compostable polymers (e.g., polylactic acid (PLA) and polyhydroxybutyrate (PHA)), hemp (e.g., flax and hemp), and protein-based materials (e.g., silk). Blends may also include synthetic fibers (staple fibers and filaments), such as polyaramids (e.g., ...). and ), nylon (e.g., nylon 6, nylon 6,6, nylon 6,10, nylon 5,6 and nylon 6,12), polyester (e.g., polyethylene terephthalate (PET), polypropylene terephthalate (PTT)). Polybutylene terephthalate (PBT) (tetramethyl terephthalate) and polypropylene. Those skilled in the art will readily recognize the desired dimensions and other properties of these fibers. For example, blends of filaments and staple fibers may comprise at least about 10 wt%, at least about 25 wt%, at least about 30 wt%, at least about 40 wt%, at least about 45 wt%, at least about 50 wt%, at least about 55 wt%, at least about 60 wt%, at least about 75 wt%, and at least about 90 wt% of the filaments or staple fibers of this disclosure, and filaments or staple fibers of other commercially available polymers with filaments of at least about 0.5 dpf, at least about 1 dpf, at least about 2 dpf, at least about 3 dpf, at least about 5 dpf, and at least about 10 dpf or greater, depending on the application. In some embodiments, the fibers or filaments are up to at least about 10 dpf and up to at least 5 dpf.

[0152] The yarn and fabric may contain small amounts (e.g., at least about 1 wt%, at least about 2 wt%, at least about 3 wt%, at least about 4 wt%, at least about 5 wt%, and up to about 10 wt% or up to about 5 wt%) of elastic filaments, and may be supplemented with short fibers (e.g., spandex, elastic fibers, or sheath-core and side-by-side PET / PTT, PET / PBT, and PTT / PBT bicomponent fibers) with appropriate dimensions and tensile properties to obtain the desired fiber and fabric properties. The drawn filaments and fibers may have dimensions of at least about 0.5 dpf, at least about 1 dpf, at least about 2 dpf, at least about 3 dpf, and at least about 5 dpf. In some embodiments, the filaments and fibers have dimensions of up to about 10 dpf and up to about 5 dpf.

[0153] This disclosure also includes polymer films, foams, granules, and hydrogels. Films are prepared by conventional methods, including but not limited to spin coating, spin casting, solvent casting, and single-layer or multi-layer co-extrusion. Foams can be prepared by conventional methods, including but not limited to open-cell (continuous distribution) and closed-cell methods.

[0154] Granular particles or microspheres can be prepared using water bath (e.g., cutting in a water bath) or spray processes. Examples of granular particles include, but are not limited to, microspheres or microcapsules used for the delivery of agricultural products (e.g., pesticides such as insecticides, fungicides, and herbicides, as well as other types of agricultural products), drug delivery, spraying odors, or encapsulating powders of laundry and dishwashing detergents. Granular particles can also be used to encapsulate cells or bacteria.

[0155] It is readily apparent that many other products can be prepared using the polymers disclosed herein through conventional methods.

[0156] A method for preparing a polymer is provided, comprising: (a) mixing: (i) at least one monovalent cationic alginate; (ii) at least one C3-C 20 (iii) a heterosubstituted dicarboxylate; and (b) at least one polyvalent cationic crosslinking agent; and react them to form a polymer.

[0157] In some embodiments, it includes first reacting at least one monovalent cationic alginate with at least one C3-C 20 The heterosubstituted dicarboxylate is mixed to form a mixture, which is then mixed with at least one polyvalent cationic crosslinker to form a polymer.

[0158] Furthermore, a method for preparing a molded article from a polymer is provided, comprising molding the polymer to form a molded article. In some embodiments, the molded article is a fiber. In some embodiments, the molded article is a film. In some embodiments, the molded article is a fabric.

[0159] In some embodiments, the method includes mixing an alginate and a heterosubstituted dicarboxylate, followed by molding, and then adding a crosslinking agent.

[0160] In some embodiments, the method includes reacting an alginate with at least 2.5%, at least 5%, at least 7.5%, and at least 10% of a heterosubstituted dicarboxylate based on the weight of the alginate. In some embodiments, the method includes reacting an alginate with at most 125%, at most 100%, and at most 75% of a heterosubstituted dicarboxylate based on the weight of the alginate.

[0161] In some embodiments, a stock solution is used. In these embodiments, the stock solution comprises (a) from about 0.5% to about 50% by weight of a monovalent metal alginate, (b) from about 1% to about 125% by weight of at least one heterosubstituted dicarboxylate, and the remainder being predominantly or substantially water. The weight of the monovalent metal alginate may be at least about 1% by weight, or at least about 2% by weight, or at least about 4% by weight. The weight of the monovalent metal alginate may be at most about 40%, or at most about 25%, or at most about 18%.

[0162] In some embodiments, the method is carried out in a bath containing at least one polyvalent cationic crosslinking agent in a solvent at a concentration of about 0.02 to about 2 mol / L and about 0.05 to about 1.5 mol / L. In some embodiments, the solvent is water.

[0163] wet spinning

[0164] In some embodiments, this disclosure relates to fibers (e.g., continuous filaments and staple fibers), yarns (e.g., staple fiber yarns) and other textile products (e.g., fabrics, such as woven fabrics and nonwoven fabrics), such as wet-spun fibers, yarns, and textile products. One advantage of fibers, yarns, and other textile products is that they can be manufactured using existing industrial equipment.

[0165] A manufacturing method includes wet spinning. A specific wet spinning process includes the following steps: preparing at least one monovalent cationic alginate and at least one C3-C in a solvent. 20 The process involves: a dicarboxylate stock solution; extrusion of the stock solution through a spinneret to form fibers; stretching the fibers through a coagulation bath containing a solvent and at least one polyvalent cationic crosslinking agent; and drying the fibers. One or more coagulation baths may be used.

[0166] Those skilled in the art will readily recognize the advantages of using water as a solvent. This is advantageous from environmental, processing, safety, and cost perspectives. One advantage of this disclosure is that, in some embodiments, the solvent in the stock solution and the coagulation bath is water.

[0167] The temperatures of the stock solution and the baths can vary and can be the same or different. Because the preferred solvent includes water, the temperature will typically be above 0°C and below 100°C. Since multiple baths can be used, the temperatures within these baths can also be varied to achieve the desired effect.

[0168] The stock solution may include common additives, such as, but not limited to, light and heat stabilizers, pigments and dyes, antimicrobial agents, matting agents, fillers, flame retardants, plasticizers, viscosity modifiers, processing aids, and other components of additives known in the art.

[0169] The coagulation bath may include other components, such as, but not limited to, non-crosslinked ions (e.g., sodium and potassium), dyes, surfactants, anti-blocking agents, slip agents, and flame retardants.

[0170] In some embodiments, a free dicarboxylic acid and a base are mixed in a solvent to form a dicarboxylic acid salt, and then an alginate is added.

[0171] In some embodiments, the method further includes a washing step after stretching and before drying. In some embodiments, stretching is performed in one or more stretching steps.

[0172] In some embodiments, the method further includes cutting the fibers into short fibers.

[0173] In some embodiments, the method further includes winding the fibers into a continuous filament.

[0174] Stretching can be performed in one or more stretching steps.

[0175] In some embodiments, the method further includes deforming the filament. In some embodiments, the method further includes curling.

[0176] In some embodiments, the method further includes applying a spinning finishing agent. Examples of spinning finishing agents are known in the art.

[0177] In some embodiments, the stock solution comprises (a) from about 0.5% to about 50% by weight of a monovalent metal alginate, (b) from about 1% to about 125% by weight of the alginate in the stock solution, and the remainder being predominantly or substantially water. The monovalent metal alginate may be at least about 1% by weight, or at least about 2% by weight, or at least about 4% by weight. The monovalent metal alginate may be up to about 40%, or up to about 25%, or up to about 18% by weight. The heterosubstituted dicarboxylate may be at least about 2.5%, at least about 5%, or at least about 7.5%, or at least about 10% by weight of the alginate in the stock solution. The heterosubstituted dicarboxylate may be up to about 100% or up to about 75% by weight of the alginate in the stock solution.

[0178] The coagulation bath may contain at least one polyvalent cationic crosslinking agent at a concentration of at least about 0.02 mol / L, at least about 0.05 mol / L, or at least about 0.075 mol / L. The coagulation bath may contain at most one polyvalent cationic crosslinking agent at a concentration of at most about 2 mol / L, at most about 1.5 mol / L, or at most about 0.75 mol / L.

[0179] Crosslinking occurs in one or more coagulation baths. Therefore, the method can be carried out using one or more coagulation baths arranged independently or in series, and optionally may include the use of countercurrent to improve curing efficiency. For sufficient crosslinking to occur, the fibers may remain in one or more coagulation baths for at least about 2 seconds, or at least 5 seconds. The fibers may remain in one or more coagulation baths for up to about 20 seconds, or up to about 15 seconds.

[0180] Various finishing agents, such as spinning finishing agents and / or overfinishing agents, can be applied as needed to provide antistatic properties, lubricity, and / or other properties that may be required when processing the fibers of this disclosure into specific articles.

[0181] This disclosure also includes a method for coloring alginate-based fibers, yarns, or textiles, including conventional dip-dyeing or solution dyeing, wherein a colorant is added to a solution. A variety of dyes and pigments can be used to color the alginate-based fibers, yarns, or textiles of this application without affecting the inherent chemical or mechanical properties of the alginate-based fibers, yarns, or textiles, including natural, non-toxic, or biosynthetic dyes or pigments.

[0182] Example

[0183] Example 1

[0184] A sodium malate solution was prepared by dissolving 0.54 parts by weight of malic acid and 8.0 parts by volume of 1.0M sodium hydroxide aqueous solution in approximately 65 parts of water. Then, 7 parts by weight of low molecular weight high-G sodium alginate (ALGIN) were added to the solution. TMIL-6G (Kimica, Tokyo, Japan) and 20 parts by weight of distilled water were mixed and stirred until all alginate was dissolved. After removing entrained air, the solution was filtered through a 3 μm filter and extruded through a 150 μm spinneret at a rate of 0.14 g / hole / min. The fibers were drawn through a 1-meter coagulation bath containing 0.12 M CaCl2 at a rate of 6.0 m / min. They were then drawn through a distilled water bath at a rate of 8.1 m / min to remove residual calcium salts and heated on guide rollers. The fibers were collected on a spool at a rate of 8.5 m / min. After drying overnight at room temperature, the filaments were placed at 20 ± 2 °C and 65 ± 3% relative humidity, and the denier and tensile properties were determined. The results (average of 10 replicates per sample) are shown in Table 1.

[0185] Example 2

[0186] Example X was repeated using a sodium tartrate solution. The sodium tartrate solution was prepared by dissolving 0.91 parts by weight of sodium tartrate dihydrate in approximately 70 parts by weight of water. The results (average of 10 replicates for each sample) are shown in Table 1.

[0187] Example 3

[0188] Example X was repeated using a sodium / potassium gluconate solution. The sodium / potassium gluconate solution was prepared by dissolving 1.07 parts by weight of the mixed sodium / potassium gluconate in approximately 70 parts by weight of water. The results (average of 10 replicates for each sample) are shown in Table 1.

[0189] Table 1

[0190]

[0191] Example 4

[0192] The following examples were conducted using each dicarboxylic acid described in Table 2 to produce 10 denier (g / 9000m) filaments. A sodium dicarboxylic acid solution was prepared by dissolving 0.58 parts by weight of the dicarboxylic acid in 85 parts by volume of a 0.09M sodium hydroxide aqueous solution under stirring until completely dissolved. Five parts by weight of alginate (e.g., high molecular weight high-G sodium alginate, ALGIN) were added to the solution. TMI-3G-80) and 9.5 parts distilled water were added and stirred until all alginate was dissolved. After removing entrained air, the solution was filtered through a 3 μm filter and extruded through a 150 μm spinneret at a rate of 0.14 g / hole / min. The fibers were drawn through a 1-meter coagulation bath containing 0.12 M CaCl2 at a rate of 6.0 m / min. They were then drawn through a distilled water bath at a rate of 8.1 m / min to remove residual calcium salts and heated on guide rollers. The fibers were collected on a spool at a rate of 8.4 m / min. After drying overnight at room temperature, the filaments were placed at 20 ± 2 °C and 65 ± 3% relative humidity, and the denier was determined and tensile properties were measured (ASTM 2256).

[0193] Some filaments are curled and cut to produce short fibers of the following lengths: 1 inch, 1.25 inches, 2 inches, 4 inches, and 6 inches.

[0194] Table 2

[0195] Dicarboxylic acid A tartaric acid B Citric acid C malic acid D Hydroxyglutaric acid E Aspartic acid F glutamic acid G Bromosuccinic acid H Dihydroxyglutaric acid I Hydroxyhexanic acid J Sugar dicarboxylic acid L Oxaloacetic acid M Chloromalonic acid N Bromomalonic acid O Chlorosilicate R Bromosuccinic acid S Dibromosuccinic acid T Bromoglutaric acid

[0196] Example 5

[0197] Example 3 was repeated using the alginates listed in Table 3 to produce 10 denier filaments. Some of the filaments were crimped and cut to obtain short fibers of the following lengths: 1 inch, 1.25 inches, 2 inches, 4 inches, and 6 inches.

[0198] Table 3

[0199] Alginate molecular weight Alginate G ratio Alginate A high medium sodium B high Low sodium C medium high sodium D medium medium sodium E medium Low sodium F Low high sodium G Low medium sodium H Low Low sodium

[0200] Example 6

[0201] Examples 4 and 5 were repeated using the alginates listed in Table 4 to produce 10 denier filaments. Some of the filaments were crimped and cut to obtain short fibers of the following lengths: 1 inch, 1.25 inches, 2 inches, 4 inches, and 6 inches.

[0202] Table 4

[0203] Alginate molecular weight Alginate G ratio Alginate A high high ammonium B high medium ammonium C high Low ammonium D medium high ammonium E medium medium ammonium F medium Low ammonium G Low high ammonium H Low medium ammonium I Low Low ammonium J high high Potassium K high medium Potassium L high Low Potassium M medium high Potassium N medium medium Potassium O medium Low Potassium P Low high Potassium Q Low medium Potassium R Low Low Potassium

[0204] Example 7

[0205] 2-denier filaments were prepared using the dicarboxylic acids described in Table 2, as described below. A sodium dicarboxylic acid solution was prepared by adding 1 part solid NaOH to 225 parts distilled water. 1.6 parts dicarboxylic acid were added to the solution and mixed until dissolved. A spinning solution was prepared by slowly adding 15 parts alginate to the sodium dicarboxylic acid solution while mixing. Once dissolved, another 150 parts distilled water were added to obtain a spinning solution containing 5% sodium alginate by weight. After removing entrained air, the solution was filtered through a filter bag and extruded through a 60 μm 400-hole spinneret at a speed of 4 m / min. The fibers were drawn through a coagulation bath containing 0.12 M CaCl2 at a speed of 4 m / min or 12 m / min. The fibers were then washed in deionized water and treated with a fabric softener (neutral, Unilever London, UK) to prevent melting during drying. The fibers were then dried at 80°C for 45 minutes. Drying is carried out using filaments collected on a spool (under tension) or using filaments cut from the spool (without tension).

[0206] Some filaments are curled and cut to produce short fibers of the following lengths: 1 inch, 1.25 inches, 2 inches, 4 inches, and 6 inches.

[0207] Example 8

[0208] Example 7 was repeated using the alginate described in Examples 5 and 6 to produce 2 denier filaments. Some of the filaments were crimped and cut to obtain short fibers of the following lengths: 1 inch, 1.25 inches, 2 inches, 4 inches, and 6 inches.

[0209] Example 9

[0210] Examples 4-8 were repeated using the following bases instead of sodium hydroxide: potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, and lithium bicarbonate.

[0211] Example 10

[0212] Examples 4-9 were repeated using the following cationic crosslinking agents: barium chloride, aluminum chloride, copper chloride, copper sulfate, aluminum sulfate, ferric sulfate, and zinc sulfate.

[0213] Example 11

[0214] The following are used to prepare short fiber yarns: (a) 10 wt%, 25 wt%, 30 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 75 wt%, 90 wt%, and 100 wt% of short fibers made from the fibers of Examples 4-10, and (b) the remaining commercially available fractions, which are (i) 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, 5 dpf, and 10 dpf short fibers (having a length corresponding to the length of the short fibers of this disclosure) of synthetic and semi-synthetic polymers listed in Table 5 or (ii) natural fibers listed in Table 5.

[0215] Table 5

[0216]

[0217]

[0218] Example 12

[0219] The yarns were prepared using the following: (a) 10 wt%, 25 wt%, 30 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 75 wt%, 90 wt%, and 100 wt% of continuous filaments made from the fibers of Examples 1-10, and (b) the remaining commercially available fractions, which were (i) 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, 5 dpf, and 10 dpf continuous fibers of synthetic and semi-synthetic polymers listed in Table 6, or (ii) continuous silk fibers.

[0220] Table 6

[0221]

[0222] Example 13

[0223] Fabrics were prepared using the following: (a) 10 wt%, 25 wt%, 30 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 75 wt%, 90 wt%, and 100 wt% of continuous filament yarns of Examples 1-10, and (b) the remainder, which are commercially available yarns of suitable sizes of the materials listed in Table 7.

[0224] Example 14

[0225] Fabrics were prepared using the following: (a) 10 wt%, 25 wt%, 30 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 75 wt%, 90 wt%, and 100 wt% of the short fiber yarns of Examples 4-10, and (b) the remainder, which are yarns of suitable sizes of commercially available fibers of the materials described in Table 7.

[0226] Table 7

[0227]

[0228] Example 15

[0229] Example 11 was repeated using the 0.5dpf, 1dpf, 3dpf and 5dpf short fibers of this disclosure and the commercially available fibers described in Example 11.

[0230] Example 16

[0231] Example 12 was repeated using the 0.5dpf, 1dpf, 3dpf and 5dpf continuous filaments of this disclosure and the commercially available fibers described in Example 12.

[0232] Example 17

[0233] Examples 12 and 16 were repeated using 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, and 10 wt% spandex (elastic fiber) continuous filaments having suitable dimensions (e.g., 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, and 5 dpf measured in a relaxed state before stretching) and tensile properties for desired yarn and fabric properties.

[0234] Example 18

[0235] Examples 11 and 15 were repeated using 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, and 10 wt% of side-by-side or sheath / core type short fibers of polyethylene terephthalate / polypropylene terephthalate, the short fibers having suitable dimensions (e.g., 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, and 5 dpf) and tensile properties for desired yarn and fabric properties.

[0236] Example 19

[0237] Examples 12 and 16 were repeated using 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, and 10 wt% of polyethylene terephthalate / polypropylene terephthalate side-by-side or sheath / core continuous filaments having suitable dimensions (e.g., 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, and 5 dpf) and tensile properties for desired yarn and fabric properties.

[0238] Example 20

[0239] Examples 11 and 15 were repeated using 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, and 10 wt% of polyethylene terephthalate / polybutylene terephthalate (PET / PBT) side-by-side or sheath / core staple fibers, the staple fibers having suitable dimensions (e.g., 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, and 5 dpf) and tensile properties for the desired yarn properties.

[0240] Example 21

[0241] Examples 12 and 16 were repeated using 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, and 10 wt% of PET / PBT side-by-side or sheath / core continuous filaments having suitable dimensions (e.g., 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, and 5 dpf) and tensile properties for desired fabric properties.

[0242] Example 22

[0243] Examples 12 and 16 were repeated using 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, and 10 wt% melt-spun thermoplastic elastomer continuous filaments having suitable dimensions (e.g., 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, 5 dpf, and 10 dpf) and tensile properties for desired yarn and fabric properties.

[0244] Example 23

[0245] Yarn blends were prepared using the yarns prepared in Examples 11, 12, 15, and 16 and commercially available yarns containing the materials listed in Table 5. Additionally, yarns were prepared using a third yarn, which was (a) a continuous spandex (elastic fiber) filament having suitable dimensions (e.g., 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, and 5 dpf) and tensile properties measured before stretching; (b) polyethylene terephthalate / polypropylene terephthalate side-by-side or sheath / core staple fibers having suitable dimensions (e.g., 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, and 5 dpf) and tensile properties for the desired performance; and (c) suitable dimensions (e.g., 0.5 dpf, 1 dpf, 2 dpf, 3 dpf, 5 dpf) for the desired performance. (d) polyethylene terephthalate / polypropylene terephthalate side-by-side or sheath / core continuous filaments with suitable dimensions (e.g., 0.5dpf, 1dpf, 2dpf, 3dpf, and 5dpf) and tensile properties, and (e) polyethylene terephthalate / polybutylene terephthalate (PET / PBT) side-by-side or sheath / core staple fibers with suitable dimensions (e.g., 0.5dpf, 1dpf, 2dpf, 3dpf, and 5dpf) and tensile properties for desired performance. The fabric is made from each of these yarns.

[0246] The following measurement techniques are used in the examples.

[0247] Daniil

[0248] Denier is a unit of linear density, which is the weight in grams per 9000 meters of fiber. Denier is determined using two different methods. For monofilaments, measuring denier involves collecting fibers of known length, placing them in a climate chamber (22±3°C and 65±5%) for at least 24 hours, and then measuring their weight. For multifilaments, single-strand denier is measured using VIBROSKOP / VIBRODYN from Lenzing Technik (Austria).

[0249] Tensile measurement

[0250] For single filaments, tensile measurements were performed using an EXPERT 7600 from ADMET (Norwood, Massachusetts, USA) at a clamping speed of 50.8 mm / min and a clamping distance of 164 mm on fibers placed at 20 ± 2 °C and 65 ± 3% relative humidity for at least 12 hours (ASTM 2256). For single filaments, tensile measurements were performed using a VIBROSKOP / VIBRODYN from Lenzing Technik (Austria) at a clamping speed of 20 mm / min and a clamping distance of 20 mm on fibers placed at 20 ± 2 °C and 65 ± 3% relative humidity (EN ISO 5079).

[0251] Other embodiments of this disclosure will be apparent to those skilled in the art in light of this specification and the practice of the disclosure herein. This specification and embodiments are intended to be considered exemplary only, and the true scope and spirit of this disclosure are indicated by the appended claims and their equivalents.

Claims

1. A method for preparing polymer fibers by wet spinning, comprising: a. A stock solution containing at least one monovalent metal alginate selected from the group consisting of sodium alginate, potassium alginate, and ammonium alginate, and at least one C3-C6 hydroxyl or amino-substituted aliphatic dicarboxylic acid salt dissolved in a solvent; wherein the at least one C3-C6 hydroxyl or amino-substituted aliphatic dicarboxylic acid salt is derived from a dicarboxylic acid selected from the group consisting of glutamic acid, malic acid, tartaric acid, and sucralose. b. The solution is extruded through a spinneret to form fibers; c. The fiber is stretched through at least one coagulation bath containing a solvent and at least one polyvalent cationic crosslinking agent, wherein the polyvalent cationic crosslinking agent has cations selected from the group consisting of calcium, copper, iron, aluminum, zinc, barium, and mixtures thereof; and d. Dry the fibers; Wherein, the solvent of the stock solution is water, and the solvent of the coagulation bath is water; The alginate has a molecular weight of 10,000 g / mol to 250,000 g / mol and a viscosity of 15 cP to 400 cP.

2. The method of claim 1, wherein: b. The alginate has a G / M ratio of 1 to 2.5; d. The stock solution contains 0.5% to 50% by weight of the monovalent metal alginate, based on the weight of the stock solution; e. The stock solution is prepared using 1% to 125% of the weight of the alginate as a percentage of at least one C3-C6 hydroxyl or amino-substituted aliphatic dicarboxylate; f. The multivalent cationic crosslinking agent has cations selected from the group consisting of calcium, copper, aluminum, and mixtures thereof; and g. The coagulation bath contains 0.02 to 2 mol / L of the at least one polyvalent cationic crosslinking agent in the solvent.

3. The method as described in claim 1, wherein, The polymer comprises an alginate crosslinked with a C3-C6 hydroxy- or amino-substituted aliphatic dicarboxylate ions bridged by polyvalent cations, wherein (a) the dicarboxylate is present in an amount of 0.05 to 1.0 molar equivalent relative to the alginate carboxylate content; and (b) cations of calcium, copper, iron, aluminum, zinc, or barium attach the at least one C3-C6 hydroxy- or amino-substituted aliphatic dicarboxylate to the anion of the carboxylate group of the alginate.

4. The method of claim 1, wherein, (a) A calcium, copper or aluminum cation attaches at least one C3-C6 hydroxyl or amino-substituted aliphatic dicarboxylate to the anion of the carboxylate group of the alginate.

5. The method of claim 1, wherein, The polymer comprises an alginate, which is crosslinked with aliphatic dicarboxylate ions that are bridged by multivalent cations and substituted with C3-C6 hydroxyl or amino groups. The polymer is prepared by reacting an alginate selected from the group consisting of sodium alginate, potassium alginate, and ammonium alginate, at least 1% by weight of the at least one C3-C6 hydroxyl or amino-substituted aliphatic dicarboxylate, with at least one polyvalent cationic crosslinking agent, wherein the polyvalent cationic crosslinking agent has a cation selected from the group consisting of calcium, copper, aluminum, and mixtures thereof.

6. The method according to any one of claims 3-5, wherein, The dicarboxylate is present in a concentration of 0.1 to 0.75 molar equivalents relative to the alginate carboxylate, and The polymer is prepared by reacting an alginate with at least one C3-C6 hydroxyl or amino-substituted aliphatic dicarboxylate at a weight of 5% to 75% based on the weight of the alginate.

7. The method according to any one of claims 3-5, wherein, The polymer is prepared by the following steps: a. Mixed: i. At least one monovalent cationic alginate selected from the group consisting of sodium alginate, potassium alginate and ammonium alginate; ii. At least one C3-C6 hydroxyl- or amino-substituted aliphatic dicarboxylic acid sodium salt, potassium dicarboxylic acid, lithium dicarboxylic acid, or ammonium dicarboxylic acid; and iii. At least one multivalent cationic crosslinking agent, wherein the multivalent cationic crosslinking agent has a cation selected from the group consisting of calcium, copper, aluminum, and mixtures thereof; and b. React them to form a polymer.

8. The method according to any one of claims 3-5, wherein, The dicarboxylic acid is glutamic acid.

9. The method according to any one of claims 3-5, wherein, The dicarboxylic acid mentioned is malic acid.

10. The method according to any one of claims 3-5, wherein, The dicarboxylic acid is tartaric acid.

11. The method according to any one of claims 3-5, wherein, The dicarboxylic acid is sucralose.

12. A fiber, wherein, The fiber is prepared by the method described in any one of claims 1-11.

13. A fabric, wherein, The fabric is prepared from fibers produced by the method described in any one of claims 1-11.

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