Production method for the production of polyacrylate fiber, polyacrylate fiber or filament obtained therefrom and use thereof

Abstract

This invention belongs to the textile field and relates to creating an efficient process by optimizing the reaction environment conditions and parameters for the manufacture of polyacrylate fibers, the aforementioned polyacrylate fibers as raw materials for manufacturing textiles with a variety of different functions, and the industrial applicability of the aforementioned process.

Description

Technical Field

[0001] This invention provides a method developed and optimized for manufacturing polyacrylate fibers from acrylic fibers in the related technical field. The invention relates to the optimization of reaction conditions and parameters in existing processes for manufacturing polyacrylate fiber products. In the polyacrylate manufacturing process of this invention, by finding ideal reaction conditions and parameters, production capacity can be increased, recycling costs (energy consumption) can be reduced, and efficiency can be improved. Furthermore, due to the improvements in the manufacturing process of this invention, environmentally friendly and sustainable polyacrylate fibers can be obtained during the manufacturing of polyacrylate fibers by reducing water consumption, reducing the carbon footprint, and minimizing the generation of by-product waste.

[0002] This invention belongs primarily to the textile field and relates to creating an efficient process by optimizing the reaction environment conditions and parameters for the manufacture of polyacrylate fibers, using polyacrylate fibers as a raw material for manufacturing textiles with various functions, and the industrial applicability of the aforementioned process. Prior Technology

[0003] Acrylic fibers of various thicknesses and cross-sectional shapes are obtained from solutions containing 85% or more acrylonitrile monomers by weight, using wet / dry processes known in this technology. Additional methods or chemicals can be developed to improve their chemophysical properties and performance, resulting in acrylic fiber products suitable for consumer needs and application areas during the applied process steps. Acrylic fibers are a commonly used type of fiber in the field of technology because they can be washed like synthetic fibers without retaining their shape, are mothproof, oil-proof, and chemical-proof, can be colored, and possess high light and heat fastness properties similar to synthetic fibers.

[0004] Due to its composition, polyacrylate fibers possess heat resistance and flame retardancy, a low thermal conductivity, high thermal insulation and moisture absorption properties, and high odor absorption due to their chemical resistance to acids and alkalis, pH buffer solutions, and acidic cationic and reactive coating systems. Because of these characteristics, polyacrylate fibers are a commonly used fiber in related technical fields. Polyacrylate fibers are obtained from acrylic fibers by methods known in this art. The manufacturing method includes the following process steps: - Chemical cross-linking reaction of acrylic fibers; The use of polyamine functional chemicals as crosslinking agents in this process requires high safety and method control because these chemicals have corrosive chemical effects, are carcinogenic, cause skin itching, sensitizing effects, environmental water toxicity, and are highly reducing, explosive, and flammable. - The nitrile groups within the fiber undergo a hydrolysis reaction with alkali metal salts; As is well known, this process step is basically a two-step process, namely a connection and elimination reaction mechanism. Related technical fields have found that in this process step, the conversion of nitrile groups, -CONH₂, and -COO-M⁺ does not occur with 100% efficiency, and this negative situation affects method parameters and conditions, thereby impacting product quality. - To allow the obtained fibers to undergo a neutralization reaction; Due to the application of the preceding process steps, a carboxylate salt with strong basic characteristics was obtained. To ensure the neutralization process discussed is carried out efficiently, it is necessary to optimize the selection of the most suitable acid and the process step conditions. - Perform a multivalent metal complex formation process as the final process step; In this process step, the key is to select an appropriate metal-organic / inorganic salt solvent, determine the process step conditions that will provide the required ionization amount, and determine the parameters of the coordination bonds that form the chelate complex of metal ions.

[0005] In this technology, polyacrylate fibers are manufactured through the application of the four independent reactions described above. The process used to manufacture these polyacrylate fibers is a discontinuous and inefficient method due to its long reaction times, complex reaction mechanisms, and precise manufacturing steps. These negative aspects result in high manufacturing costs, time, energy, and water losses for polyacrylate fibers. A manufacturing method that replaces all these negative processes with an efficient and continuous industrial manufacturing process, eliminating existing disadvantages, has become a necessary requirement in the relevant technical field.

[0006] WO 2008 / 128660 A1 relates to a method for manufacturing fire-retardant polyacrylate fibers that are low in toxicity, emit smoke, and have uniform dyeing properties. The manufacturing method includes the following process steps; - A hydrazine solution with a concentration of 15% by weight is used as a crosslinking agent for acrylic fibers, and this crosslinking process is carried out at 105°C for 5 hours. The next step involves neutralization with a 5% sodium hydroxide solution (by weight), performed at 100°C for 2 hours. - Subsequently, a neutralization process was carried out using a 5% by weight sulfuric acid solution at 60°C for 1 hour. - The final process step is combined with a solution treated by a mixture of zinc acetate and acetic acid, and this process step is carried out at 100°C for 1 hour.

[0007] In this invention, highly complex and controllable process steps are employed to obtain polyacrylate fibers with desired properties, and these process steps have relatively long reaction times. In this invention, a time period of at least 9 hours is required to obtain polyacrylate fibers. Obviously, a manufacturing method with such a long reaction time requires high energy, labor, and water demands, resulting in high costs and high controllability requirements in polyacrylate fiber manufacturing.

[0008] The invention with patent number EP 1788145 A1 relates to a fiber with high flame retardancy and moisture absorption properties, and specifically to its manufacture. The following process steps are used to obtain the fiber with these properties: - The fiber is crosslinked using a hydrazine solution, wherein the crosslinking solution contains 30% hydrazine solution by weight, and this process is carried out at 98°C for 3 hours. - For the hydrolysis process, a 3% sodium hydroxide solution by weight is used. This process is carried out at 92°C for a period of 5 hours. - The neutralization process uses a 6% nitric acid solution by weight. This process is carried out at 60°C for a period of 2 hours. - For the misalignment process, a magnesium nitrate solution with a concentration of 15% by weight is used. This process step is carried out at a temperature of 60°C for 2 hours.

[0009] In order to manufacture fibers with the properties required by this invention, it is necessary to apply the above-described reaction process steps at a specified temperature and composition for at least 12 hours.

[0010] Invention EP 1026309 A2 relates to obtaining fibers that can be used as raw materials or fillers in clothing, interior decoration, transportation, and construction, possessing flame-retardant properties. These fibers are obtained using the following method steps: - The fiber is crosslinked using a hydrazine solution, wherein the crosslinking agent solution contains 35% by weight of hydrazine solution, and the process is carried out at 120°C for 2 hours. - The hydrolysis process uses a 32% sodium hydroxide solution by weight. This process is carried out at 120°C for 0.5 hours. - The neutralization process uses a 5.8% nitric acid solution by weight. This process is carried out at 65°C for 2 hours. - For the misalignment process, a zinc sulfate solution with a concentration of 13% by weight is used. This process step is carried out at a temperature of 120°C for a period of 20 minutes. In order to manufacture fibers with the properties required by this invention, it is necessary to apply the reaction process steps at a specified temperature and composition for at least 5 hours.

[0011] The manufacturing of polyacrylate fibers using known methods in this technology involves process steps lasting 5-24 hours. This extended manufacturing time results in high energy, water, and chemical consumption, low efficiency, high workload, and excessive personnel requirements. Therefore, research and development of a more environmentally friendly manufacturing process for polyacrylate fibers, along with reduced unit manufacturing costs, is urgently needed. Summary of the Invention

[0012] This invention provides a method in which process steps for manufacturing polyacrylate fibers are optimized and improved to eliminate known negative impacts in the relevant art and to provide additional advantages to the art. The invention aims to obtain a more environmentally friendly, high-throughput, controllable, and continuous industrial process for manufacturing polyacrylate fibers.

[0013] The method of manufacturing polyacrylate fibers according to the present invention will provide technical solutions and advantages for related technical fields: - To produce a higher quantity of polyacrylate fibers per unit time. - Reduce energy consumption, - Reduce the need for personnel. - Reduce water and chemical inputs and consumption. - Reduce the carbon footprint during manufacturing. - Provides continuous industrial processes, - Use chemicals that pose less harm to health, safety and the environment

[0014] In view of all these benefits, the present invention provides a method for manufacturing polyacrylate fibers in a lower cost and more environmentally friendly manner.

[0015] This invention proposes a method for manufacturing polyacrylate fibers, wherein the reaction time is shortened by optimizing the reaction medium and parameters known in the art for manufacturing polyacrylate fibers. Simple Explanation of the Diagram

[0016] none. Implementation

[0017] The subject of this invention is a method developed for manufacturing polyacrylate fibers, with optimized parameters, and is explained by way of examples which are not intended to be limiting but are merely for better understanding of the subject matter.

[0018] In this invention, the optimized process is applied to all process steps in the manufacture of high-efficiency polyacrylate fibers, thereby eliminating existing disadvantages, and the optimized process is applied to all process steps. Therefore, the manufacturing method of this invention includes the following process steps: Process step i: Crosslinking of acrylic fibers using at least one crosslinking agent; Process step ii involves hydrolyzing the acrylic fibers that have undergone the cross-linking process with at least one alkali metal salt; Process step iii: Following process step ii, the fiber undergoes a neutralization reaction with at least one acid. Process step iv: The fiber obtained as a result of the neutralization process forms a complex with at least one metal salt.

[0019] In step i) of the manufacturing method of the present invention, it is ensured that the nitrile group (-CN) of the polymer forming acrylic fibers crosslinks with the functional groups in the crosslinking chemical compound, and that the fiber form and properties are maintained in subsequent reaction stages.

[0020] In step i) of the manufacturing method of the present invention, a hydrazine compound can be used as a crosslinking agent.

[0021] As is known in the art, hydrazine chemicals have environmental and biological disadvantages. Due to these known disadvantages, in the manufacturing method of the present invention, chemical compounds having at least two, or at least three, four, five, or more than five amine functional groups can also be used as crosslinking agents.

[0022] The crosslinking agent may include at least one amine functional group. The crosslinking agent may be tertiary in structure, limited by containing at least two amine groups or at least two amine groups having at least two or more than three, four, five, or more than five amine chemical functional groups. Each amine group may have a primary, secondary, or tertiary chemical structure, or at least two amine groups having at least two primary or secondary structures. Other chemical structures may include more than two secondary amine groups, or three, four, or five, and two or more amine groups, each of which is primary or secondary. The polyamine has a functional 2HN-R-NH₂ structure; R may be alkyl or aryl, or may include more than one heteroaryl group. In some chemical structures, the alkyl, aryl, or heteroalkyl group may be straight-chain, branched, cyclic, or have more than one of these structures. The R group is an ether, diether, or polyether (((CH2CH2)O)n(CH2CH2) where n = 1, 2, 3, 4, 5, or greater than 5; polyether ((CH2CR2)S)O(CH2CH2) where n = 1, 2, 3, 4, 5, or greater than 5; or polyamine (CH2CH2)NX)n(CH2CH2), where each X is independently H, alkyl, aryl, or another suitable group and n = 1, 2, 3, 4, 5, or greater than 5. The R group can be a dye with a chemical group that absorbs light in the visible light range (400-700 nm) to impart the desired color to the fiber. The R group can also be selected from flame retardants or flame-retardant phosphorus chemical functional groups. These can be groups containing trialkylphosphine, trialkyl phosphite, trialkyl phosphate, trialkylphosphonate, trialkylphosphamide, hexaalkylcyclotriphosphine, or other phosphorus groups.

[0023] The method for manufacturing polyacrylate of the present invention may include a chemical compound having the following formula as a crosslinking agent: -NH₂-(CH₂)n-NH₂, where n is one of the values ​​0, 2, 4, 6, or 8. -NH₂-(CH₂)ₙ-NH₂-(CH₂)ₙ-NH₂-(CH₂)ₙ-NH₂, where n is one of the values ​​0, 2, 4, 6, or 8. -NH₂-(CH₂)nN-(-(CH₂)n-NH₂))(CH₂)n-NH₂, where n is one of the values ​​0, 2, 4, 6, or 8. -NH 2-(CH 2) nR-(CH 2) n-NH-(CH 2) n-NH 2, where n is one of the values ​​0, 2, 4, 6, and 8, and R includes one of the groups CH and C.

[0024] In the manufacturing method of the present invention, at least one crosslinking agent containing an amine functional group can be used as a crosslinking agent.

[0025] In the manufacturing method of this invention, various chemical compounds can be used as crosslinking agents. At least one of the crosslinking agents that can be used in this invention is a chemical compound containing an amine group.

[0026] In this invention, a crosslinking agent is preferably used, and the crosslinking agent contains at least one amine group in its bulk.

[0027] In a preferred embodiment of the present invention, the crosslinking agent used in manufacturing step i) contains more than one amine functional group. The crosslinking agent may contain 2, 3, 4 or 5 amine groups.

[0028] The most specific embodiment of the present invention may include a mixture of at least one of the following compounds in a certain proportion: hydrazine, hexamethylenediamine, diethylenetriamine, tetraethylenetriamine, tetraethylenepentamine, bis-hexamethylenediamine, and tris(2-aminoethyl)amine, or all of them as crosslinking agents.

[0029] The crosslinking method in process step i) is carried out under reflux conditions at a boiling temperature. The temperature of the process under discussion is between 100°C and 110°C. The preferred process temperature is one of 100°C, 105°C, 106°C, 107°C, 108°C, 109°C, and 110°C.

[0030] Process step i) is one of the crosslinking: acrylic fiber ratios by weight of 1:1, 1:25, 1:50, 1:100, 1:200, or 1:300.

[0031] The crosslinking agent in step i) is used to form a solution in at least one solvent. The amine group capable of solvent crosslinking can be an organic solvent. The solvent contains at least one of the following organic solvents: water, methanol, ethanol, isopropanol, acetone, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide. Water is preferably used as the solvent, and at least one organic solvent is preferably present in the water. Preferably, at least one organic solvent is present in a concentration ranging from 10% to 50% by weight. In the preferred embodiment, only water is present as the solvent. The crosslinking agent used in step i) is preferably contained in the solvent in a concentration ranging from 20% to 60% by weight. Preferably, the crosslinking agent:solvent ratio is in the range of 35% to 50%.

[0032] The mixing process (i) is preferably performed during the process step. The mixing is preferably in the range of 100 to 500 rpm. The mixing process is preferably in the range of 200 to 400 rpm.

[0033] In process step i) of this invention, the crosslinking ratio of acrylic fibers is 4.6% (w / w) by weight. This value is considered to be the value achieved in the prior art through necessary crosslinking. In this invention, the crosslinking ratio achieved in process step i) is at least 4.6% (w / w) of acrylic fibers by weight.

[0034] In the optimization and development approach, the reaction time of process step i) is in the range of 10 to 45 minutes.

[0035] The reaction time of process step i) is preferably within the range of 15 to 30 minutes, while optimization and process development are carried out simultaneously.

[0036] As is known in the art, in process step ii), due to process step i), the uncrosslinked polymer nitrile groups (-CN) of the remaining acrylic fibers formed are converted into nitrile CONH2 and COOM functional groups in the presence of alkali metals through a two-stage adhesion and elimination reaction. Process step ii) is carried out under reflux conditions. Preferably, process step ii) is carried out at a temperature in the range of 100 to 110°C. The temperature of process step ii) is preferably one of 100°C, 105°C, 106°C, 107°C, 108°C, 109°C, and 110°C.

[0037] The reaction mentioned in process step ii) is preferably carried out by mixing using at least one mixer. The mixing is preferably carried out in the range of 200 to 400 rpm.

[0038] At least one of the alkali metal salt compounds mentioned in process step ii) is calcium hydroxide, magnesium hydroxide, sodium hydroxide, calcium nitrate, magnesium nitrate, potassium nitrate, and sodium nitrate.

[0039] The alkali metal salt used in process step ii) is in at least one solvent in the range of 8% to 20% by weight. At least one of water, methanol, ethanol, isopropanol, and other solvents may be used as solvents mentioned herein. Water is used as the solvent, and preferably, at least one organic solvent may be present in the water. Preferably, process step ii) includes at least one solvent dissolved in water in a value in the range of 10% to 50% by weight.

[0040] In the preferred embodiment, water is used as a solvent in process step ii).

[0041] Process step ii) is preferably performed within a timeframe of 10 to 30 minutes.

[0042] In step ii), the amount of alkali metal salt in the fiber is 1:1, 1:10, 1:25, 1:50, or 1:100 by weight.

[0043] Preferably, at least one acid is used in the neutralization process of step iii). Preferably, the pH of the acid to be used is expected to be in the range of 1 to 5. Preferably, the pH of the acid to be used is expected to be 3 or below. If preferred, the acids may be a mixture. At least one of the acid mixtures is an organic acid. Preferably, the organic acid in the acid mixture is at least 50% by weight.

[0044] At least one of the following groups—propionic acid, acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, and benzoic acid—is used as the neutralizing acid in process step iii).

[0045] Preferably, acid is used as the acid in process step iii) and during the process.

[0046] In step iii) of the process, the concentration of the acid preferably used is in the range of 10%-20% by weight.

[0047] In process steps and process iii), the acrylic fiber:acid ratio is in the range of 1:1 to 1:150.

[0048] The neutralization process is carried out at a temperature range of 40°C to 60°C. Preferably, the neutralization process is carried out at a temperature of 45°C, 50°C, 55°C, and 60°C.

[0049] Chlorides, acetates, sulfates, phosphates, and carbonates of metals with ionic values ​​of +2 or +3 and included in the 4th and 5th periods of the periodic table may be used as metal salts in process step iv). Preferably, salts of more than one metal may be used as metal salts.

[0050] At least one of the chloride, acetate or carbonate of a transition metal with a preferred ion value of (+2) is used as the metal salt in process step iv).

[0051] Preferably, a zinc chloride, acetate, bromide, or carbonate is used as the metal salt in process step iv).

[0052] In process step iv), the amount of metal salt used is in the range of 8% to 20% by weight.

[0053] In process step iv), the ratio of acrylic fiber to metal salt is in the range of 1:1 to 1:150.

[0054] In this invention, process step iv) is performed at a temperature range of 90 to 100°C.

[0055] In this invention, process step iv) is performed within a range of 15 to 30 minutes.

[0056] Because of the manufacturing process steps mentioned in this invention, the manufacturing of polyacrylate fibers can be carried out in a time period between 60 minutes and 120 minutes.

[0057] In this invention, the term "filament bundle" refers to a fiber form of infinitely long filaments.

[0058] Current polyacrylate manufacturing utilizes a complex, continuous process involving reactor-boiler steps. This process is discontinuous, inefficient in terms of production volume and method, costly, and extremely time-consuming (the available manufacturing process steps in this technology range from 6 to 36 hours). Furthermore, the waste and byproducts are not intended for reuse. Another innovative aspect of this invention involves optimization of the manufacturing process, resulting in manufacturing within a progressively continuous bath system. Therefore, this invention, based on optimized parameters for polyacrylate fiber manufacturing, develops a process and manufacturing technology by modifying the tow belt to operate continuously within a progressively continuous bath system, providing a technical solution and advantages for related technical fields.

[0059] Due to the manufacturing process of polyacrylate fibers according to this invention, the following additives have emerged in related technical fields: ● Provides continuous industrial manufacturing processes. ● Long-term, large-scale production of polyacrylate fibers, ● Use chemicals that pose less harm to health, safety, and the environment. ● Reduce energy consumption, ● Reduce the need for personnel. ● Reduce water and chemical inputs and consumption. ● Reduce the carbon footprint during manufacturing.

[0060] In this technology, the manufacture of polyacrylate requires approximately 5 hours to complete the longest process step, which involves sequentially performing complex crosslinking, hydrolysis, neutralization, and metal bonding processes in a reactor-boiler system with a discontinuous batch process system, while the shortest process step requires approximately 1 hour. Therefore, in current manufacturing methods in this technical field, it is not possible to carry out continuous manufacturing for 1 to 5 hours in a bathroom.

[0061] If step i) of the process takes approximately 5 hours, the manufacturing method in this technology requires a bath designed to continuously manufacture 300 m of fiber at an input speed of 1 m / min. The investment cost of such a bath configuration is industrially impractical. In this invention, the complex crosslinking, hydrolysis, neutralization, and metallization processes involved in the sequential formation of polyacrylate fibers can be performed as continuous manufacturing of fiber bundles in a series of continuous bath systems. In the manufacturing process of this invention, the optimization of each continuous chemical process step was studied to obtain a shorter process time, and suitable bath size, bundle quantity, and fiber extraction rate for sustainable manufacturing were considered. In this way, the manufacturing process of polyacrylate fibers can be ensured to be manufactured on an industrial scale.

[0062] Similar to WO 2008 / 128660 A1 and EP1026309 A2 patents, the polyacrylate manufacturing process in this technology has a relatively long processing time, averaging around 9 hours. Through the optimized and improved polyacrylate manufacturing method of this invention, the process time is shortened to 1 hour, achieving industrial manufacturing capability. Unlike the manufacturing method in this technology, the process of this invention can produce 9 tons of fiber instead of 1 ton of fiber, and their duration and consumption are also different. Because of the manufacturing process of this invention, a highly efficient manufacturing method is proposed, the process manufacturing time is shortened, a continuous manufacturing method is developed to replace discontinuous manufacturing, and energy consumption and cycle costs are low.

[0063] In current manufacturing methods, boiler coating is produced at a flote ratio of 1:4 to 1:6 for approximately 9 hours, and for producing 1 ton of fiber, each step uses approximately 5 tons of water, resulting in a total water consumption of 25 tons. Furthermore, including the washing step, this figure approaches 30 tons. Unfortunately, this amount of water used in current manufacturing methods cannot be recycled and is treated as waste. In this invention, in a continuous manufacturing system, water is theoretically not consumed except for moisture from the fiber bundles and a certain amount of water lost through process losses and leaks. Manufacturing is carried out by adding chemicals as needed. In current manufacturing methods, it can be seen that using this invention, polyacrylate fibers with a water consumption of 30 tons can be produced with a water consumption of only 1-2 tons.

[0064] [surface] [1.] Technical properties of polyacrylate fibers obtained by the manufacturing method of the present invention [parameter] [WO 2008 / 128660A1] [EP1026309A2] [This invention] [Fiber content] [(kg)] 1000 1000 1000 Crosslinking process Water (kg) 4817 5452 200 Temperature (°C) 105 120 107 Time (min) 300 120 15 Hydrolysis process Water (kg) 5383 5258 200 Temperature (°C) 100 120 105 Time (min) 120 30 15 neutralization operate Water (kg) 5383 5130 200 Temperature (°C) 60 65 60 Time (min) 60 10 15 Chelation operate Water (kg) 5187 4743 400 Temperature (°C) 100 120 94 Time (min) 60 20 15

[0065] In the polyacrylate fiber manufacturing method of the present invention, the carbon footprint of the process is also improved due to the reduction of water consumption, the reduction of energy consumption and the increase of manufacturing capacity.

[0066] When the current manufacturing method is compared with the manufacturing method of the present invention, there are improvements in many aspects such as manufacturing cost, duration, and carbon footprint.

[0067] The polymer forming the fiber is an acrylonitrile polymer, which may contain monomer units in the polymer chemical structure (CR 1R 2-CR 3CN) and also nitrile functional monomer units. Here, structures R 1, R 2, and R 3 may be H, alkyl (methyl, ethyl, propyl), or aryl (phenyl). However, R 1 and R 2 may both be H, and R 3 may be methyl and H. These polymer chemical structures (methyl) may be acrylate, alkyl vinyl ether, or other types of comonomer units, or may be polyacrylonitrile and polymethacrylonitrile, acrylonitrile-vinyl ester copolymers, and acrylonitrile polymer mixtures formed therefrom. If the acrylonitrile polymer is a copolymer, such as a copolymer (terpolymer, block copolymer), then the above chemical structure (CR 1R 2-CR 3CN) has at least about 50% or more, or even 60%, 70%, 80%, or 90% or even 100% monomer units.

[0068] The fibers developed using the manufacturing technology of this invention can be in the form of short fibers (e.g., about 1 mm to about 1 cm in length) or long fibers (e.g., about 1 cm to about 1 m or longer). Simultaneously, the fiber diameter can be between approximately 0.7 and 50 tex. If the diameter of the fine fibers in the fiber is <3 tex, they can facilitate the penetration of chemicals into the fiber and polymer during crosslinking, hydrolysis, neutralization, and metal complex bonding. If the diameter of the coarse fibers in the fiber is >7 tex, the chemical reactions can occur unevenly throughout the fiber. However, the small size of the fiber pore structure, the crystalline structure and degree of the polymer forming the fiber, and the orientation of the polymer chains may facilitate or hinder the penetration of chemical processes occurring at various stages, depending on their extent. In fact, a core-shell structure can be formed by polymer modification near the outer layer of the fiber. In such cases, it is obtained by modifying the properties of the obtained fiber and the outer layer of the fiber, and the modified fiber can provide flame retardancy and heat resistance, antifungal or antibacterial properties, low heat transfer coefficient, high heat insulation and moisture absorption properties, pH balance buffering properties, and resistance to acids and alkalis.

[0069] Polyacrylate fibers can be obtained from the pores, yarns, filaments, woven-nonwoven fabrics, and mixtures of at least one, two, or more acrylic fibers, such as from various forms of short fibers, tows, tops, and bumps. Furthermore, in acrylic textile applications, fabrics can be garments, such as socks, underwear, or shirts; blankets, such as fire blankets; curtains; fiber mats; cushions; and carpets.

[0070] Polyacrylate fibers can be manufactured starting from acrylic fibers, prepared using appropriate heat, light, stabilizers, antibacterial agents, antiviral agents, deodorizing agents, biocidal additives, conductive reinforcing agents, antioxidants, pigments, plasticizers, and some additives that provide antifungal properties. These additives can be used to produce polyacrylate products by known methods, for example, by dissolving the polymer in a solvent, combining the solution with the additives, and manufacturing fibers using a wet gravity process. The resulting fibers are obtained from polyacrylate fibers using the manufacturing techniques detailed in this invention. The obtained polyacrylate can be in the form of fibers, yarns, or fabrics. The resulting products can be used in many applications in the textile industry, such as protective clothing, public transportation textiles, filtration, fire blankets, interior decoration, apparel (socks, underwear), and outdoor and indoor textile applications.

[0071] Polyacrylate fibers can be prepared by mixing with one or more of the following in a metal complexation step: heat, light, stabilizers, antibacterial agents, antiviral agents, deodorants, biocidal additives, conductive enhancers, antioxidants, pigments, plasticizers, and some antifungal additives. This is the final step in known methods, and the fibers can be manufactured by heat treatment drying or fixing. These additives can be used to produce polyacrylate products by known methods, by dissolving the additives in a suitable solvent, combining the solution with the additives, or by manufacturing fibers using wet-jetting techniques. The resulting polyacrylate can be in the form of fibers, yarns, or fabrics. Protective clothing, public transportation textiles, filters, fire blankets, interior decoration, apparel (socks, underwear), and outdoor and indoor textiles can be obtained from the obtained polyacrylate fibers.

[0072] Additional chemical compounds may be used during the manufacture of the polyacrylate fibers of the present invention to increase the chemical and physical properties of the desired polyacrylate fibers, such as non-flammability, strength and moisture content.

[0073] As is known from the invention in patent number JP 5056358, dyeing methods for polyacrylate fibers can be carried out using cationic dyeing systems because they possess carboxylates and carboxylic acid chemical functional groups. However, after such methods, polyacrylate fibers do not provide the desired technical properties in terms of color fastness and industrial applications. The inventors have determined that polyacrylate fibers, reagents, and pigment dyeing systems can exhibit excellent performance in terms of applicability and color fastness.

[0074] The scope of protection of this invention is defined in the appended claims and is not limited to what is interpreted in this embodiment for sampling purposes. Clearly, those skilled in the art can demonstrate similar embodiments based on the foregoing facts without departing from the subject matter of this invention. [test]

[0075] For the manufacture of polyacrylate fibers, the known process steps in this technology are applied. These process steps are provided below: Process step i. Crosslinking acrylic fibers using at least one crosslinking agent. Process step ii. The acrylic fibers subjected to the cross-linking method undergo a hydrolysis reaction with at least one alkali metal salt. Process step iii. Following process step ii, the fiber undergoes a neutralization reaction with at least one acid. Process step iv. The fiber obtained as a result of the neutralization process forms a complex with at least one metal salt.

[0076] These process steps were tested using the development and optimization processes described in this invention. The results obtained are shared under this heading.

[0077] In the test, hydrazine solution was used as a crosslinking agent in process step i).

[0078] Fiber crosslinking was performed using hydrazine chemicals, and the concentration NIR spectra on the fibers were analyzed after application to both solution and fiber. For analysis in solution, 0-80% reference solutions of known concentrations were prepared, and spectral calibration was performed. The correlation of the prepared calibration was R² = 98. To analyze the crosslinked hydrazine on the fiber surface, solutions of known concentrations of 0-80% were prepared and applied individually at 107°C for 180 minutes. The resulting fibers were dried and analyzed using NIR spectra, and calibration plots were prepared within the reliability range (R² > 97%). [Study on the crosslinking ratio of hydrazine-fiber]

[0079] In these tests, 30 g of acrylic fibers were prepared by crosslinking with a hydrazine solution at a concentration of 15% by weight in a mixed medium at 107°C and 200 rpm for different time periods specified in the table. After each process step, the fibers were washed with fiber water to remove chemical residues and dried overnight in an incubator at 60°C.

[0080] As can be seen in detail from Table 2, through nitrogen elemental analysis and weight calculation, 4.6% hydrazine was found to be attached to the fiber when it was taken out within 180 minutes.

[0081] [surface] [2.] Study on the crosslinking ratio of hydrazine-fiber [test] [Mixed Speed] [(rpm)] [temperature] [(°C)] [Hydrazine concentration] [(%) [Hydrazine time] [(min.)] [Corrosion agent concentration] [(%) [Fiber Properties] 1 200 107 15 10 3 Fiber dissolution. 2 200 107 15 20 3 3 200 107 15 30 3 4 200 107 15 45 3 5 200 107 15 60 3 6 200 107 15 90 3 The fibers swell into a gel state. It disperses during washing, and its form remains dispersed. 7 200 107 15 120 3 8 200 107 15 135 3 9 200 107 15 180 3 The fibers retain their shape and exhibit mechanical strength. 10 200 107 15 240 3 11 200 107 15 480 3 *Reaction completion was calculated using reaction efficiency methods such as NIR, elemental analysis, and gravimetric analysis. [Process steps for crosslinking hydrazine solution for acrylic fibers]

[0082] To investigate the relationship between hydrazine concentration and reaction time in acrylic fibers, 30 g of acrylic fibers were processed at the concentrations specified in Table 2 at 107°C and 200 rpm in a mixed medium. After each process step, the fibers were washed with water to remove chemical residues and dried overnight in an oven at 60°C. The amount of crosslinking on the fiber surface was then analyzed within the calibration range prepared by NIR spectroscopy. Based on the fact that the hydrazine solution formed 4.6% (w / w) crosslinking on the fibers, the required time is given in Table 3.

[0083] [surface] [3.] Study on the conditions and parameters of crosslinking reaction of hydrazine solution [test] [Mixed Speed] [(rpm)] [temperature] [(°C)] [Hydrazine concentration] [(%) [Reaction Duration] [(min)] 1 200 107 5 1080 2 200 107 10 340 3 200 107 15 180 4 200 107 20 135 5 200 107 25 110 6 200 107 30 65 7 200 107 35 37 8 200 107 40 25 9 200 107 45 20 10 200 107 50 15 11 200 107 60 12 12 200 107 70 10 13 200 107 80 8 *Reaction completion was calculated using reaction efficiency methods such as NIR, elemental analysis, and gravimetric analysis.

[0084] In testing studies, it has been determined that acrylic fibers cannot provide the required physical properties when the concentration of the crosslinking agent in the solution is 60% or higher by weight.

[0085] [surface] [4.] Study on the cross-linking reaction conditions and parameters of DMA solution [test] [Mixed Speed] [(rpm)] [temperature] [(°C)] [HMDA] [concentration] [(%) [Reaction Duration] [(min)] 1 200 107 5 360 2 200 107 10 300 3 200 107 15 240 4 200 107 20 200 5 200 107 25 180 6 200 107 30 168 7 200 107 35 155 8 200 107 40 135 9 200 107 45 95 10 200 107 50 80 11 200 107 60 80 12 200 107 70 80 13 200 107 80 80 *Reaction completion was calculated using reaction efficiency methods such as NIR, elemental analysis, and gravimetric analysis. [To cause the acrylic fibers that have undergone the cross-linking process to undergo a hydrolysis reaction with at least one alkali metal salt]

[0086] Hydrolysis was performed on 30.5 g of cross-linked fibers (4.6% by weight) at a concentration specified in Table 5 using sodium hydroxide (an alkaline metal salt) at 105°C and 200 rpm in a mixed medium. The hydrolysis mechanism was carried out in two stages: the first stage was understood by a dark red color change, and the second stage was determined by the complete light yellow color of the fibers. The completion of this stage of the reaction was detected by the time it took to complete the two-color transition. After each process step, the obtained fibers were washed with warm water to remove chemical residues and dried overnight in an incubator at 60°C.

[0087] [surface] [5.] Study on the conditions and parameters of sodium hydroxide solution hydrolysis reaction [test] [Mixed Speed] [(rpm)] [temperature] [(°C)] [Solution] [pH] [Sodium hydroxide concentration] [(%) [Reaction Duration] [(min)] 1 200 105 13.8-14.5 1 230 2 200 105 13.8-14.5 2 185 3 200 105 13.8-14.5 3 135 4 200 105 13.8-14.5 4 87 5 200 105 13.8-14.5 5 59 6 200 105 13.8-14.5 6 45 7 200 105 13.8-14.5 8 36 8 200 105 13.8-14.5 10 22 9 200 105 13.8-14.5 12 15-16 10 200 105 13.8-14.5 16 12-14 11 200 105 13.8-14.5 20 9-10 12 200 105 13.8-14.5 30 6-8 The completion of the reaction is determined by the completion of two stages of color change.

[0088] In testing studies, it has been determined that acrylic fibers cannot provide the required physical properties when the concentration of alkali metal salts in the solution is 30% or higher by weight. [Reacts with at least one acid in a neutralization reaction]

[0089] Acetic acid neutralization of polyacrylate derived from acrylic fibers was performed at 56°C and 200 rpm in a mixed medium, using the weak organic acid acetic acid at the concentrations specified in Table 6. Fiber neutralization was determined by monitoring the peaks of COONa chemical functional groups across a broad wavelength range of 2900–3600 cm⁻¹ using FT-IR spectroscopy. The obtained fibers were washed with water to remove acidic chemical residues and dried overnight at 60°C, with the results analyzed by FT-IR. Table 6 provides the acetic acid concentrations used for neutralization at different time points.

[0090] [surface] [6.] Neutralization conditions and parameters for the neutralization reaction in acetic acid solution [test] [Mixed Speed] [(rpm)] [temperature] [(°C)] [Solution] [pH] [Acetic acid] [(%) [Reaction Duration] [(min)] 1 200 56 3.2-3.8 1 200 2 200 56 3.2-3.8 2 110 3 200 56 3.2-3.8 3 90 4 200 56 3.2-3.8 5 60 5 200 56 3.2-3.8 6 48 6 200 56 3.2-3.8 8 36 7 200 56 3.2-3.8 10 30 8 200 56 3.2-3.8 12 26 9 200 56 3.2-3.8 15 20 10 200 56 3.2-3.8 20 15 11 200 56 3.2-3.8 30 12-14 12 200 56 3.2-3.8 50 10-12 * FT-Ir spectroscopy, COONa peak detected at wavelengths of 2900-3600 cm⁻¹.

[0091] In testing studies, it has been determined that acrylic fibers cannot provide the required physical properties when the concentration of acid in the solution is 30% or higher by weight. [The obtained fibers are bonded to at least one metal salt]

[0092] Polycarboxylate fibers with carboxylic acid chemical groups were prepared by neutralizing sodium polyacrylate fibers, and polyvalent fibers could be obtained by binding metal ions. In this process, at a temperature of 60°C and a mixing ratio of 200 rpm, acid was added to increase the concentration of water and ionization as a suitable solvent for the metal-organic-inorganic salt. Zinc ions were bound to the polymer with chelate complex coordination bonds at the zinc concentration specified in Table 7, and the solution was adjusted to the pH range of 4.5-5 in the presence of a weak acid at different times. The obtained fibers were washed with water to ensure that excess zinc ions and acetate residues were not removed from the fibers by washing, and the fibers were tested by drying in an incubator at 60°C.

[0093] [surface] [7.] Conditions and parameters for the miscibility reaction of zinc acetate solution [test] [Mixed Speed] [(rpm)] [temperature] [(°C)] [Solution] [pH] [Zinc] [(%) [Reaction Duration] [(min)] 1 200 60 4.5-4.8 1 220 2 200 60 4.5-4.8 2 130 3 200 60 4.5-4.8 3 95 4 200 60 4.5-4.8 5 68 5 200 60 4.5-4.8 6 48 6 200 60 4.5-4.8 8 36 7 200 60 4.5-4.8 10 30 8 200 60 4.5-4.8 15 20 9 200 60 4.5-4.8 20 15 10 200 60 4.5-4.8 30 10

[0094] In testing studies, it has been determined that acrylic fibers cannot provide the required physical properties when the concentration of metal salt in the solution is 30% or higher by weight.

[0095] [surface] [8.] Technical properties of polyacrylate fibers obtained by the manufacturing method of the present invention

[0096] [LOI] [Moisture] [(%) [density] [(g / cm3)] [strength] [(cN / )] [Fentex] [)] 32-35 >10% 1.4-1.6 12-35

[0097] When the manufacturing process described in this invention involves continuous chemical treatment with chemical solutions of fiber bundles at speeds of 10 m / min and 0.01 m / min in a continuous sequential bath system, the polyacrylate fiber has a physical property of 12-35 cN / tex strength in the range of 0.7-45 tex fiber thickness.

[0098] However, polyacrylate fibers may have low thermal conductivity, moisture retention of 10% or higher, and flame retardancy in the range of 30-40% LOI. In acrylic textile applications derived from at least one, two, or more mixtures of cotton, cellulose, polyester, nylon, fibers, yarns, fabrics, garments, socks or underwear or tops, blankets and fire blankets, curtains, fiber mats, cushions, and carpets, polyacrylate fibers and filament yarns are available.

[0099] none.

Claims

1. A method for manufacturing polyacrylate fibers from acrylic textiles, the method comprising the following steps: i) crosslinking acrylic fibers with at least one crosslinking agent; wherein the at least one crosslinking agent is hydrazine, a compound containing at least two amine functional groups, or a mixture thereof; wherein the at least one crosslinking agent is present in at least one solution at a concentration of 35% to 50% by weight; wherein step i) is carried out at a temperature in the range of 100°C to 110°C; and wherein the weight ratio of acrylic fibers to crosslinking agent is in the range of 1:1 to 1:300; ii) hydrolyzing the crosslinked acrylic fibers obtained in step i) with at least one alkali metal salt; wherein the at least one alkali metal salt is present in the solution at a concentration in the range of 8% to 20% by weight; wherein step ii) is carried out at a temperature in the range of 100°C to 110°C; and wherein the weight ratio of acrylic fibers to alkali metal salt is in the range of 1:1 to 1:100; iii) neutralizing the fibers obtained in step ii) with at least one acid; At least one of the aforementioned acids is present in the aforementioned solution in an amount ranging from 10% to 20% by weight; wherein process step iii) is carried out at a temperature ranging from 40°C to 60°C; wherein the weight ratio of acrylic fiber to acid is in the range of 1:1 to 1:150; and wherein the aforementioned acid is an acid with a pH of 3 or lower; and iv) forming a complex with at least one metal salt using the fiber obtained in process step iii); wherein the aforementioned at least one metal salt is present in the aforementioned solution in an amount ranging from 8% to 20% by weight; wherein process step iv) is carried out at a temperature ranging from 90°C to 100°C; and wherein the weight ratio of acrylic fiber to metal salt is in the range of 1:1 to 1:

150.

2. The manufacturing method as described in claim 1, wherein each of the aforementioned process steps i-iv) is carried out in a separate bath or reactor, or wherein the aforementioned process step i) is carried out in a separate bath or reactor and the aforementioned process steps ii), iii), and iv) are carried out sequentially in separate baths or reactors.

3. The manufacturing method as described in claim 1, wherein the aforementioned process steps i)-iv) are carried out continuously and sequentially in separate baths or reactors.

4. The manufacturing method described in any one of claims 1 to 3, wherein when the aforementioned process steps are performed continuously, the speed of the filament bundle is in the range of 0.01 m / min to 10 m / min.

5. The manufacturing method described in any one of claims 1 to 3, wherein the aforementioned acrylic fiber is subjected to one or more washing processes before, after or during one or more of the aforementioned process steps i)-iv).

6. The manufacturing method as described in claim 5, wherein the water and solvent mixture used in the aforementioned washing process has a temperature of 20°C, 30°C, 40°C, 50°C, 60°C and 80°C.

7. The manufacturing method as described in any one of claims 1 to 3, wherein in the aforementioned process step i), the aforementioned at least one crosslinking agent is selected from the group consisting of: - NH2-(CH2)n-NH2, wherein n is 0, 2, 4, 6 or 8; - NH2-(CH2)n-NH-(CH2)n-NH-(CH2)n-NH2, wherein n is 0, 2, 4, 6 or 8; - NH2-(CH2)nN-(-(CH2)n-NH2))(CH2)n-NH2, wherein n is 0, 2, 4, 6 or 8; - NH2-(CH2)nR-(CH2)n-NH-(CH2)n-NH2, wherein n is 0, 2, 4, 6 or 8, and R is CH or C.

8. The manufacturing method as described in claim 7, wherein the aforementioned at least one crosslinking agent is selected from the group consisting of: hydrazine, hexamethylenediamine, diethylenetriamine, tetraethylenetriamine, tetraethylenepentamine, bis-hexamethylenediamine, and tris(2-aminoethyl)amine.

9. The manufacturing method as described in claim 8, wherein the aforementioned at least one crosslinking agent is dissolved in at least one solvent selected from the group consisting of water, methanol, ethanol and isopropanol.

10. The manufacturing method as described in claim 9, wherein water is used as the aforementioned solvent, and the concentration of the aforementioned at least one crosslinking agent in the aforementioned water is in the range of 35% to 50% by weight.

11. The manufacturing method described in any of claims 1 to 3, wherein the aforementioned process step i) lasts for 15 to 30 minutes.

12. The manufacturing method described in any of claims 1 to 3, wherein the temperature of the aforementioned process step i) is one of 100°C, 105°C, 106°C, 107°C, 108°C, 109°C or 110°C.

13. The manufacturing method as described in claim 1, wherein in the aforementioned process step ii), at least one of the aforementioned alkali metal salt compounds, namely calcium hydroxide, magnesium hydroxide, sodium hydroxide, calcium nitrate, magnesium nitrate, potassium nitrate, and sodium nitrate, is used.

14. The manufacturing method as described in claim 1, wherein the solvent used in the aforementioned process step ii) is at least one of water, methanol, ethanol or isopropanol.

15. The manufacturing method as described in claim 1, wherein the aforementioned process step ii) is performed for 15 to 30 minutes.

16. The manufacturing method as described in claim 1, wherein at least one of the aforementioned acids used in the aforementioned process step iii) is selected from propionic acid, acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid or benzoic acid.

17. The manufacturing method as described in claim 1, wherein the aforementioned process step iii) is performed at a temperature of 45°C, 50°C, 55°C or 60°C.

18. The manufacturing method as described in claim 1, wherein the aforementioned process step iii) is performed for 15 to 30 minutes.

19. The manufacturing method as described in claim 1, wherein in the aforementioned process step iv), at least one of the chloride, bromide, acetate or carbonate of the metal with an ion value of (+2) or (+3) of the aforementioned metal salt system is used.

20. The manufacturing method as described in claim 19, wherein the aforementioned metal salt is a zinc-containing chloride, acetate, bromide, or carbonate.

21. The manufacturing method as described in claim 1, wherein the aforementioned process step iv) is performed for a period of 15 to 30 minutes.

22. The manufacturing method described in any one of claims 1 to 3, wherein the textile is treated by at least one of cationic and nonionic chemical auxiliaries, antistatic agents, lubricants and / or softening components obtained by applying the aforementioned process steps.

23. A polyacrylate fiber or filament suitable for textile applications, obtained by the manufacturing method described in any one of claims 1 to 22, wherein the polyacrylate fiber or filament has a strength of 12 cN / tex or greater, a thickness in the range of 0.7 to 45 tex, a length in the range of 25 to 150 mm, an LOI value in the range of 30% to 40%, and a moisture retention of 10% or greater.

24. The polyacrylate fiber or filament as described in claim 23, wherein the strength of the aforementioned polyacrylate fiber or filament is in the range of 18 to 35 cN / tex.

25. The polyacrylate fiber or filament as described in claim 23 or 24, wherein the aforementioned polyacrylate fiber or filament has antibacterial, antiviral, antifungal and deodorizing properties, and wherein the aforementioned polyacrylate fiber or filament can be used alone or in a fiber mixture comprising at least one of cotton, cellulose, polyester and nylon, and is suitable for fabrics, clothing, socks, underwear, tops, blankets, fire blankets, curtains, fiber mats, cushions or carpets.

26. The polyacrylate fiber or filament as described in claim 23 or 24, wherein the aforementioned polyacrylate fiber or filament is capable of absorbing moisture and water vapor and has heat-generating properties, and wherein the aforementioned polyacrylate fiber or filament can be used alone or in a fiber mixture comprising at least one of cotton, cellulose, polyester and nylon for the manufacture of yarn, fabric, garment, socks, underwear or garment.

27. Use of a polyacrylate fiber or filament as described in any one of claims 23 to 25, whether used alone or in a blend of fibers comprising at least one of cotton, cellulose, polyester, and nylon, for the manufacture of yarn, fabrics, clothing, socks, underwear, garments, blankets, fire blankets, curtains, fiber wicker, mats, or carpets.