CN119663473A - Preparation method of melt-spun anion polyamide fiber - Google Patents
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Abstract
The invention relates to the field of polyamide fibers, and provides a preparation method of a melt-directly-spun negative ion polyamide fiber, aiming at the problem of poor dispersibility of a negative ion generator in polyamide slices, comprising the following steps of (1) blending a polymerization monomer and an auxiliary agent, and sequentially carrying out prepolymerization and final polymerization; the auxiliary agent comprises a ring-opening agent, a blocking agent, a stabilizing agent and an anion generator treated by a compatibilizer modifier, wherein (2) the monomer is removed by one or two of a disc evaporator and a cage evaporator at the same time of or after the final polymerization reaction to obtain a melt after the removal of monomers, and (3) the melt after the removal of monomers is directly pelletized to obtain slices or directly spun to obtain the anion polyamide fiber. The negative ion generator is kept in a melt state all the time, which is favorable for the stability of surface modification and the high efficiency of functions, thus not only improving the product performance, but also improving the production efficiency.
Description
Technical Field
The invention relates to the field of polyamide fibers, in particular to a preparation method of a melt-spun anion polyamide fiber.
Background
The polyamide fiber (nylon) has excellent physical properties, high breaking strength, high wear resistance, good hygroscopicity, excellent elastic recovery rate and fatigue resistance, and good dyeing property, and is widely applied to the clothing field. In recent years, with social progress and continuous improvement of living standard of people, the demands of the masses on clothes are not simple and comfortable, warm-keeping and attractive, and more people begin to pursue health-preserving and health-care functions. Based on this demand, anion functional fibers have been developed. The anion fiber fabric can accelerate the emission of anions in the air in the human body movement process, and 82% of anions of the human body are absorbed through skin, and the skin is in direct contact with the anion fiber fabric, so that the health care function of the anion fabric can be exerted. The anion fabric not only can sterilize and disinfect, but also can promote blood circulation and metabolism, relieve muscle and joint pain and regulate a nervous system. Therefore, research and development of the fiber fabric with the function of releasing anions have important practical significance.
The anion generator represented by Qizhi stone is a kind of cyclic silicate mineral and contains multiple microelements such as magnesium, iron, tin, manganese, sodium, cobalt, silicon, fluorine, etc. The crystal structure belongs to a three-party or hexagonal crystal system, and the special crystal structure enables the crystal structure to form a piezoelectric effect and a pyroelectric effect under the external temperature and pressure change or spontaneous polarization effect, and charges are generated on the surface to ionize air molecules, so that anions are formed. At present, some research results have been accumulated on the anion fiber, and the patent 'an anion polyamide fiber and a manufacturing method (200710012497.9) thereof' discloses a preparation method of the anion polyamide fiber, which comprises the steps of preparing anion master batch after surface treatment of an anion generator and preparing the anion polyamide fiber by slicing and melt spinning. Although the method enhances the dispersion of the anion generator in the matrix of the master batch to a certain extent, the strong shearing action of the screw rod easily damages the effect of surface treatment in the process of melt blending spinning of the master batch and polyamide chips, so that the inorganic salt particles are agglomerated again, the stability and the anion function of spinning are damaged and weakened, and the processing steps of the method are complicated. Therefore, other modification methods need to be proposed while simplifying the process flow.
Disclosure of Invention
In order to overcome the problem of poor dispersibility of the negative ion generating agent in polyamide chips, the invention provides the preparation method of the melt-spun negative ion polyamide fiber, and the negative ion generating agent is always maintained in a melt state, so that the stability of surface modification and the high efficiency of functions of the negative ion generating agent are facilitated, the product performance is improved, and the production efficiency is also improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A method for preparing melt-spun anion polyamide fiber, which comprises the following steps:
(1) Blending a polymerization monomer and an auxiliary agent, and sequentially carrying out prepolymerization and final polymerization, wherein the auxiliary agent comprises a ring-opening agent, a blocking agent, a stabilizer and a negative ion generator treated by a compatibilizer modifier;
(2) At the same time of the final polymerization reaction or after the final polymerization reaction is finished, removing the monomer by using one or two combination of a disc evaporator and a cage evaporator to obtain a melt after the removal of the monomer;
(3) And directly granulating the melt after the singulation to obtain slices or directly spinning to obtain the anion polyamide fiber.
The method comprises the steps of preparing raw materials, and blending a polymerization monomer and various assistants. And (3) carrying out prepolymerization after uniformly stirring the raw materials to obtain the polyamide oligomer. And then heating the prepolymer for final polymerization, and carrying out polycondensation reaction between short chains to further increase the molecular weight, and obtaining the polyamide melt with high molecular weight after the final polymerization reaction is finished. The invention is characterized in that after the final coalescence, a disc evaporator or a cage evaporator is selected, and residual micromolecular substances in the polyamide melt are removed under specific process conditions, so that the liquid phase extraction of the polyamide is realized, the melt reaches the spinning standard, and the process can be controlled accurately. And then conveying the obtained melt after the removal of the single to a spinning box, and directly carrying out melt spinning and forming to obtain the anion polyamide fiber. The traditional polyamide 6 can only adopt an indirect spinning process, and the existing production flow is that the slice is extracted, dried and then melted for indirect spinning. After the step (3) of the process, other functional components can be added into the melt before the melt enters the spinning system.
Preferably, the polyamide is polyamide 6, polyamide 56, polyamide 610, polyamide 6-66 copolymer or polyamide 6-10 copolymer.
Preferably, the ring-opening agent in the step (1) is deionized water, the addition amount is 1-4wt% of the polymerized monomer, the end-capping agent is one or more of acetic acid, benzoic acid, terephthalic acid, decanediamine, oxalic acid and homologs thereof, the addition amount is 0.2-0.6wt% of the polymerized monomer, the stabilizer is one or more of SEED, salicylic acid, benzophenone benzotriazole, calcium carbonate and talcum powder, the addition amount is 0.1-0.5wt% of the polymerized monomer, and the addition amount of the negative ion generator treated by the compatibilizer modifier is 1-5wt% of the polymerized monomer.
Preferably, the anion generator in the step (1) is one or more of Qiyang stone, tourmaline, opal and Qiyang stone, the particle size is 100-300nm, and the compatibilizer modifier is one or more of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane and 3-isocyanic acid propyl triethoxysilane.
Preferably, the mass of the compatibilizing modifier is 0.02-2 times that of the negative ion generator.
Preferably, the treatment method of the anion generator in the step (1) comprises the steps of dispersing the anion generator in absolute ethyl alcohol, adjusting pH to be acidic, adding a compatibilizer modifier, uniformly dispersing, centrifuging, collecting a solid phase, and drying to obtain the functionalized modified anion generator.
Preferably, the pH is 3-5, the centrifugation is carried out at 3000-10000rpm for 3-10min, the centrifugation is repeated for 3-5 times, and the drying is carried out at 50-80 ℃ for 6-12h.
As a further preferable method, the anion generator is treated by adding inorganic salt anion generator into absolute ethyl alcohol to form suspension with concentration of 1-5wt%, adjusting pH to 3-5 with one or more of hydrochloric acid, glacial acetic acid and sulfuric acid, adding compatibilizer modifier with mass of 0.1-2% of that of the suspension, and magnetically stirring at 300-800rpm for 5-12h to uniformly disperse the anion generator in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotating speed is 3000-10000rpm for 3-10min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 3-5 times. Collecting the bottom sediment obtained by the last centrifugation, and drying in vacuum at 50-80 ℃ for 6-12h to obtain the functionalized modified anion generator.
Preferably, the pre-polymerization in the step (1) is carried out at the temperature of 190-260 ℃ and the absolute pressure of 0.1-3MPa for 2-10 hours.
Preferably, the final polymerization in step (1) is carried out at a temperature of 220-280 ℃ and an absolute pressure of 0.05-100kPa for 2-10 hours.
Preferably, the conditions of the step (2) of the deallocation are that the temperature is 240-280 ℃, the absolute pressure is 0.05-10kPa, the time is 0.1-4 hours, and the number average molecular weight of the melt after the deallocation is 25000-45000.
Therefore, the invention has the beneficial effects that:
(1) The method has the advantages of simple process, strong flexibility and wide application range, and the obtained melt after the removal of the single can be directly granulated to obtain functional slices, and can also be directly spun to obtain functional fibers.
(2) The newly added single removing section after the final polymerization section can replace the existing extraction step, reduce the content of small molecules, directly spin the melt, greatly simplify the process flow and greatly reduce the energy consumption.
(3) The negative ion generator is always maintained in a melt state, which is beneficial to the stability of surface modification and the high efficiency of functions. Not only improves the product performance, but also improves the production efficiency, simplifies the process flow, is beneficial to reducing the production cost, reduces the carbon emission and promotes the sustainable development of society and economy.
Detailed Description
The technical scheme of the invention is further described through specific embodiments.
In the present invention, unless otherwise specified, the materials and equipment used are commercially available or are commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified. Unless otherwise indicated, parts are parts by weight, temperatures are expressed in degrees Celsius or at ambient temperature and pressure is absolute. There are numerous variations and combinations of reaction conditions (e.g., component concentrations, solvents needed, solvent mixtures, temperatures, pressures, and other reaction ranges) that can be used to optimize the purity and yield of the product obtained by the process, with only reasonable routine experimentation to optimize such process conditions.
A method for preparing melt-spun anion polyamide fiber, which comprises the following steps:
(1) The preparation of the compatibilizer modifier treated anion generator comprises the steps of adding inorganic salt anion generator into absolute ethyl alcohol to form suspension with the concentration of 1-5wt%, adjusting the pH value to 3-5 by one or more of hydrochloric acid, glacial acetic acid and sulfuric acid, adding the compatibilizer modifier accounting for 0.1-2% of the mass of the suspension, and magnetically stirring at 300-800rpm for 5-12h to uniformly disperse the anion generator in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotating speed is 3000-10000rpm for 3-10min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 3-5 times. Collecting the bottom sediment obtained by the last centrifugation, and drying in vacuum at 50-80 ℃ for 6-12h to obtain the functionalized modified anion generator.
The anion generator is one or more of Qiyang stone, tourmaline, opal and Qiyang stone, and has particle diameter of 100-300nm. The compatibilizer modifier is one or more of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane and 3-isocyanatopropyl triethoxysilane. The mass of the compatibilizing modifier is 0.02-2 times of that of the negative ion generator.
(2) Compounding, namely blending the polymerized monomer and the auxiliary agent.
The polymerized monomer is polyamide 6, polyamide 56 or polyamide 6-66 copolymer, and is selected from caprolactam, pentanediamine, hexanediamine and adipic acid.
The auxiliary agent comprises a ring-opening agent, a blocking agent, a stabilizing agent and a negative ion generator treated by the compatibilizing modifier in the step (1). The ring-opening agent is deionized water, the addition amount is 1-4wt% of the polymerized monomer, the end-capping agent is one or more of acetic acid, benzoic acid, terephthalic acid, decanediamine, oxalic acid and homologs thereof, the addition amount is 0.2-0.6wt% of the polymerized monomer, the stabilizer is one or more of SEED, salicylic acid, benzophenone benzotriazole, calcium carbonate and talcum powder, the addition amount is 0.1-0.5wt% of the polymerized monomer, and the addition amount of the negative ion generator treated by the compatibilizer modifier is 1-5wt% of the polymerized monomer.
(3) And (3) performing polycondensation reaction, namely sequentially performing prepolymerization and final polymerization reaction.
The prepolymerization condition is that the temperature is 190-260 ℃, the absolute pressure is 0.1-3MPa, the time is 2-10h, and the number average molecular weight of the prepolymerized melt is 5000-15000.
The final polymerization condition is that the temperature is 220-280 ℃, the absolute pressure is 0.05-100kPa, the time is 2-10 hours, and the number average molecular weight of the final polymerization melt is 15000-30000.
(4) And (3) monomer removal treatment, namely removing the monomers by using one or two combinations of a disc evaporator and a cage evaporator at the same time of the final polymerization reaction or after the final polymerization reaction to obtain a melt after the monomer removal.
The conditions of the deallocation are that the temperature is 240-280 ℃, the absolute pressure is 0.05-10kPa, the time is 0.1-4 hours, and the number average molecular weight of the melt after the deallocation is 25000-45000.
(5) And directly granulating the melt after the singulation to obtain slices or directly spinning to obtain the anion polyamide fiber.
Example 1
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) Preparing a compatibilizer modifier treated anion generator, namely adding 5g of Qixite nano particles with the particle size of 200nm into 100mL of absolute ethyl alcohol to form a suspension, adjusting the pH to 3.5 by hydrochloric acid, adding 1mL of 3-aminopropyl trimethoxy silane, and magnetically stirring at 800rpm for 12 hours to uniformly disperse Qixite in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotating speed is 5000rpm for 5min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 3 times. And collecting bottom sediment obtained by the last centrifugation, and drying the sediment in vacuum at 80 ℃ for 12 hours to obtain the silane functionalized Qizhongshi nano particles.
(2) Compounding 100kg caprolactam, 2kg deionized water, 0.4kg PTA, 0.2kg SEED and 1kg silane functionalized Qiyte were blended and stirred at 80℃for 2h.
(3) The polycondensation reaction is to perform the prepolymerization reaction, raise the temperature of the raw materials to 240 ℃, control the absolute pressure to 0.2MPa, react for 5 hours, then perform the final polymerization reaction, raise the temperature of the prepolymer to 260 ℃, control the pressure to 100kPa, and react for 5 hours.
(4) Removing monomers from final polymer by disc evaporator, controlling temperature at 260 deg.C, absolute pressure at 0.1kPa, reacting for 2h, and number average molecular weight of melt after removing monomers 25000-45000.
(5) And (3) spinning, namely directly conveying the melt after the removal of the single to a spinning system for spinning, wherein the spinning temperature is 260 ℃, and obtaining the functionalized anion polyamide 6 fiber.
Example 2
The difference from example 1 is that the silane-functionalized Qiyaku of step (2) has a mass of 5kg.
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) Preparing a compatibilizer modifier treated anion generator, namely adding 5g of Qixite nano particles with the particle size of 200nm into 100mL of absolute ethyl alcohol to form a suspension, adjusting the pH to 3.5 by hydrochloric acid, adding 1mL of 3-aminopropyl trimethoxy silane, and magnetically stirring at 800rpm for 12 hours to uniformly disperse Qixite in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotating speed is 5000rpm for 5min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 3 times. And collecting bottom sediment obtained by the last centrifugation, and drying the sediment in vacuum at 80 ℃ for 12 hours to obtain the silane functionalized Qizhongshi nano particles.
(2) Compounding 100kg caprolactam, 2kg deionized water, 0.4kg PTA, 0.2kg SEED and 5kg silane functionalized Qiyte were blended and stirred at 80℃for 2h.
(3) The polycondensation reaction is to perform the prepolymerization reaction, raise the temperature of the raw materials to 240 ℃, control the absolute pressure to 0.2MPa, react for 5 hours, then perform the final polymerization reaction, raise the temperature of the prepolymer to 260 ℃, control the pressure to 100kPa, and react for 5 hours.
(4) Removing monomers from final polymer by disc evaporator, controlling temperature at 260 deg.C, absolute pressure at 0.1kPa, reacting for 2h, and number average molecular weight of melt after removing monomers 25000-45000.
(5) And (3) spinning, namely directly conveying the melt after the removal of the single to a spinning system for spinning, wherein the spinning temperature is 260 ℃, and obtaining the functionalized anion polyamide 6 fiber.
Comparative example 1
The difference from example 1 is that step (2) does not add silane functionalized qibing stone.
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) Compounding 100kg caprolactam, 2kg deionized water, 0.4kg PTA and 0.2kg SEED were blended and stirred at 80℃for 2h.
(2) The polycondensation reaction is to perform the prepolymerization reaction, raise the temperature of the raw materials to 240 ℃, control the absolute pressure to 0.2MPa, react for 5 hours, then perform the final polymerization reaction, raise the temperature of the prepolymer to 260 ℃, control the pressure to 100kPa, and react for 5 hours.
(3) Removing monomers from final polymer by disc evaporator, controlling temperature at 260 deg.C, absolute pressure at 0.1kPa, reacting for 2h, and number average molecular weight of melt after removing monomers 25000-45000.
(4) And (3) spinning, namely directly conveying the melt after the removal of the single to a spinning system for spinning, wherein the spinning temperature is 260 ℃, and obtaining the functionalized anion polyamide 6 fiber.
Comparative example 2
The difference from example 1 is that the silane-functionalized Qiyaku of step (2) has a mass of 0.3kg, which is less than the preferred range of 1-5wt%.
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) Preparing a compatibilizer modifier treated anion generator, namely adding 5g of Qixite nano particles with the particle size of 200nm into 100mL of absolute ethyl alcohol to form a suspension, adjusting the pH to 3.5 by hydrochloric acid, adding 1mL of 3-aminopropyl trimethoxy silane, and magnetically stirring at 800rpm for 12 hours to uniformly disperse Qixite in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotating speed is 5000rpm for 5min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 3 times. And collecting bottom sediment obtained by the last centrifugation, and drying the sediment in vacuum at 80 ℃ for 12 hours to obtain the silane functionalized Qizhongshi nano particles.
(2) Compounding 100kg caprolactam, 2kg deionized water, 0.4kg PTA, 0.2kg SEED and 0.3kg silane functionalized Qiyte were blended and stirred at 80℃for 2h.
(3) The polycondensation reaction is to perform the prepolymerization reaction, raise the temperature of the raw materials to 240 ℃, control the absolute pressure to 0.2MPa, react for 5 hours, then perform the final polymerization reaction, raise the temperature of the prepolymer to 260 ℃, control the pressure to 100kPa, and react for 5 hours.
(4) Removing monomers from final polymer by disc evaporator, controlling temperature at 260 deg.C, absolute pressure at 0.1kPa, reacting for 2h, and number average molecular weight of melt after removing monomers 25000-45000.
(5) And (3) spinning, namely directly conveying the melt after the removal of the single to a spinning system for spinning, wherein the spinning temperature is 260 ℃, and obtaining the functionalized anion polyamide 6 fiber.
Comparative example 3
The difference from example 1 is that the silane-functionalized Qiyaku of step (2) has a mass of 8kg, which is in excess of the preferred range of 1 to 5% by weight.
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) Preparing a compatibilizer modifier treated anion generator, namely adding 5g of Qixite nano particles with the particle size of 200nm into 100mL of absolute ethyl alcohol to form a suspension, adjusting the pH to 3.5 by hydrochloric acid, adding 1mL of 3-aminopropyl trimethoxy silane, and magnetically stirring at 800rpm for 12 hours to uniformly disperse Qixite in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotating speed is 5000rpm for 5min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 3 times. And collecting bottom sediment obtained by the last centrifugation, and drying the sediment in vacuum at 80 ℃ for 12 hours to obtain the silane functionalized Qizhongshi nano particles.
(2) Compounding 100kg caprolactam, 2kg deionized water, 0.4kg PTA, 0.2kg SEED and 8kg silane functionalized Qiyte were blended and stirred at 80℃for 2h.
(3) The polycondensation reaction is to perform the prepolymerization reaction, raise the temperature of the raw materials to 240 ℃, control the absolute pressure to 0.2MPa, react for 5 hours, then perform the final polymerization reaction, raise the temperature of the prepolymer to 260 ℃, control the pressure to 100kPa, and react for 5 hours.
(4) Removing monomers from final polymer by disc evaporator, controlling temperature at 260 deg.C, absolute pressure at 0.1kPa, reacting for 2h, and number average molecular weight of melt after removing monomers 25000-45000.
(5) And (3) spinning, namely directly conveying the melt after the removal of the single to a spinning system for spinning, wherein the spinning temperature is 260 ℃, and obtaining the functionalized anion polyamide 6 fiber.
Example 3
The difference from example 2 is that the anion generator in step (1) is tourmaline and the compatibilizer modifier is 3-isocyanatopropyl triethoxysilane.
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) Preparing a compatibilizer modifier treated anion generator, namely adding 5g of tourmaline nano particles with the particle size of 200nm into 100mL of absolute ethyl alcohol to form suspension, adjusting the pH to 3.5 by hydrochloric acid, adding 1mL of 3-isocyanatopropyl triethoxysilane, and magnetically stirring at 800rpm for 12 hours to uniformly disperse the tourmaline in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotating speed is 5000rpm for 5min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 3 times. Collecting the bottom sediment obtained by the last centrifugation, and vacuum drying at 80 ℃ for 12 hours to obtain the silane functionalized tourmaline nano particles.
(2) Compounding 100kg caprolactam, 2kg deionized water, 0.4kg PTA, 0.2kg SEED and 1kg silane functional tourmaline were blended and stirred at 80 ℃ for 2 hours.
(3) The polycondensation reaction is to perform the prepolymerization reaction, raise the temperature of the raw materials to 240 ℃, control the absolute pressure to 0.2MPa, react for 5 hours, then perform the final polymerization reaction, raise the temperature of the prepolymer to 260 ℃, control the pressure to 100kPa, and react for 5 hours.
(4) Removing monomers from final polymer by disc evaporator, controlling temperature at 260 deg.C, absolute pressure at 0.1kPa, reacting for 2h, and number average molecular weight of melt after removing monomers 25000-45000.
(5) And (3) spinning, namely directly conveying the melt after the removal of the single to a spinning system for spinning, wherein the spinning temperature is 260 ℃, and obtaining the functionalized anion polyamide 6 fiber.
Example 4
The difference from example 2 is that the negative ion generator in step (1) is opal and the compatibilizer modifier is 3-aminopropyl triethoxysilane.
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) Preparing a negative ion generator treated by the compatibilizer modifier, namely adding 5g of opal nano particles with the particle size of 200nm into 100mL of absolute ethyl alcohol to form a suspension, adjusting the pH to 3.5 by hydrochloric acid, adding 1mL of 3-aminopropyl triethoxysilane, and magnetically stirring at 800rpm for 12 hours to uniformly disperse the opal in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotating speed is 5000rpm for 5min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 3 times. And collecting bottom sediment obtained by the last centrifugation, and drying the sediment in vacuum at 80 ℃ for 12 hours to obtain the silane functionalized opal nano particles.
(2) The ingredients were blended 100kg caprolactam, 2kg deionized water, 0.4kg PTA, 0.2kg SEED and 1kg silane functionalized opal and stirred at 80℃for 2h.
(3) The polycondensation reaction is to perform the prepolymerization reaction, raise the temperature of the raw materials to 240 ℃, control the absolute pressure to 0.2MPa, react for 5 hours, then perform the final polymerization reaction, raise the temperature of the prepolymer to 260 ℃, control the pressure to 100kPa, and react for 5 hours.
(4) Removing monomers from final polymer by disc evaporator, controlling temperature at 260 deg.C, absolute pressure at 0.1kPa, reacting for 2h, and number average molecular weight of melt after removing monomers 25000-45000.
(5) And (3) spinning, namely directly conveying the melt after the removal of the single to a spinning system for spinning, wherein the spinning temperature is 260 ℃, and obtaining the functionalized anion polyamide 6 fiber.
Example 5
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) As in example 1.
(2) Compounding, namely blending 55kg of adipic acid and 45kg of pentanediamine with 0.3L of water respectively, and stirring for 1h to dissolve. Mixing adipic acid and hexamethylenediamine solution, continuously stirring for 1h, fully cooling, filtering, performing true drying at 60 ℃ for 5h to obtain polyamide 56 salt, and adding 0.4kg of PTA, 0.2kg of SEED and 5kg of silane functionalized Qiyaku for blending to obtain a polymerization raw material.
(3) The polycondensation reaction is to perform the prepolymerization reaction, heat the raw materials to 220 ℃, control the absolute pressure to 1.5MPa, react for 3 hours, then perform the final polymerization reaction, heat the prepolymer to 260 ℃, control the pressure to 10kPa, and react for 3 hours.
(4) Removing monomers from final polymer by disc evaporator, controlling the temperature to 270 deg.C, absolute pressure to 0.1kPa, reacting for 0.1h, and obtaining melt with number average molecular weight 25000-45000.
(5) And (3) spinning, namely directly conveying the melt after the removal of the single to a spinning system for spinning, wherein the spinning temperature is 255 ℃, and obtaining the functionalized anion polyamide 56 fiber.
Example 6
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) As in example 1.
(2) Blending 80kg of caprolactam and 20kg of polyamide 66 salt, adding 10kg of water, 0.4kg of PTA, 0.2kg of SEED and 5kg of silane functionalized Qiyaku, and blending to obtain a polymerization raw material.
(3) The polycondensation reaction is to perform the prepolymerization reaction, raise the temperature of the raw materials to 200 ℃, control the absolute pressure to 1.5MPa, react for 3 hours, and then perform the final polymerization reaction, raise the temperature of the prepolymer to 270 ℃, control the pressure to 10kPa, and react for 3 hours.
(4) Removing monomers from final polymer by disc evaporator, controlling the temperature to 280 deg.C, absolute pressure to 0.1kPa, reacting for 0.5h, and obtaining melt with number average molecular weight 25000-45000.
(5) And (3) spinning, namely directly conveying the melt after the removal of the monomers to a spinning system for spinning, wherein the spinning temperature is 280 ℃, and obtaining the functionalized anion polyamide 6-66 copolymer fiber.
Example 7
The difference from example 1 is that the final polymerization and the dealkylation are carried out simultaneously, the temperature is raised to 260 ℃ after the end of the pre-polymerization, the pressure is controlled to be 0.1kPa, the reaction is carried out for 7 hours, and the number average molecular weight of the melt after the final polymerization and the dealkylation is 15000-30000.
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) Preparing a compatibilizer modifier treated anion generator, namely adding 5g of Qixite nano particles with the particle size of 200nm into 100mL of absolute ethyl alcohol to form a suspension, adjusting the pH to 3.5 by hydrochloric acid, adding 1mL of 3-aminopropyl trimethoxy silane, and magnetically stirring at 800rpm for 12 hours to uniformly disperse Qixite in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotating speed is 5000rpm for 5min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 3 times. And collecting bottom sediment obtained by the last centrifugation, and drying the sediment in vacuum at 80 ℃ for 12 hours to obtain the silane functionalized Qizhongshi nano particles.
(2) Compounding 100kg caprolactam, 2kg deionized water, 0.4kg PTA, 0.2kg SEED and 1kg silane functionalized Qiyte were blended and stirred at 80℃for 2h.
(3) The prepolymerization reaction is carried out firstly, the temperature of the raw materials is raised to 240 ℃, the absolute pressure is controlled to be 0.2MPa, and the prepolymer is obtained after the reaction for 5 hours.
(4) Polycondensation and deallocation, namely heating the prepolymer to 260 ℃, controlling the pressure to 0.1kPa, reacting for 7 hours, and finally polymerizing and deallocation, wherein the number average molecular weight of the melt after the deallocation is 15000-30000.
(5) And (3) spinning, namely directly conveying the melt after the removal of the single to a spinning system for spinning, wherein the spinning temperature is 260 ℃, and obtaining the functionalized anion polyamide 6 fiber.
Example 8
A preparation method of a melt-spun anion polyamide fiber comprises the following steps:
(1) Preparing a compatibilizer modifier treated anion generator, namely adding 3g of Qixite nano particles with the particle size of 200nm into 100mL of absolute ethyl alcohol to form a suspension, adjusting the pH to 5 by hydrochloric acid, adding 2mL of 3-aminopropyl trimethoxysilane, and magnetically stirring at 500rpm for 8 hours to uniformly disperse Qixite in the mixed solution. And (3) after stirring, carrying out centrifugal washing on the mixed solution, wherein the centrifugal rotation speed is 10000rpm for 3min, pouring out supernatant after centrifugation, taking out bottom sediment, adding absolute ethyl alcohol, continuously carrying out centrifugal washing, and repeating the steps for 4 times. And collecting bottom sediment obtained by the last centrifugation, and vacuum drying at 60 ℃ for 10 hours to obtain the silane functionalized Qizhongshi nano particles.
(2) The ingredients were 100kg caprolactam, 4kg deionized water, 0.6kg acetic acid, 0.2kg talc and 1kg silane functionalized Qiyaku blended and stirred at 80℃for 2h.
(3) The polycondensation reaction comprises the steps of pre-polymerizing, heating raw materials to 260 ℃, controlling the absolute pressure to 3MPa, reacting for 2 hours, controlling the number average molecular weight of the pre-polymerized melt to 15000, then final polymerizing, heating the pre-polymer to 280 ℃, controlling the pressure to 80kPa, reacting for 2 hours, and controlling the number average molecular weight of the final polymerized melt to 30000.
(4) The process of removing monomers includes removing monomers from final polymer by combination of disc evaporator and cage evaporator, controlling temp. to 240 deg.C, absolute pressure to 0.05kPa, reacting for 0.1h, and obtaining melt with number average molecular weight of 45000.
(5) Spinning, namely directly granulating the melt after the single removal to obtain slices.
Comparative example 4
The difference from example 1 is that the step (4) of the singulation process is not performed. As a result, the fiber is difficult to form during spinning and cannot be spun.
Performance testing
The fibers obtained in each of the above examples and comparative examples were subjected to performance testing using GB/T14344-2008. The results are shown in the following table.
Table 1 fiber index for each example and comparative example
From the table above, it can be seen that:
(1) From examples 2,3 and 4, various options and combinations of the negative ion generating agent and the modifying agent are known. From examples 2, 5, and 6, the polyamide melt direct spinning process according to the present invention is applicable to a variety of polyamide materials, including but not limited to polyamide 6, polyamide 56, and polyamide 6-66 copolymers. As is clear from examples 1 and 7, the dealkylation treatment may be performed after the completion of the final polymerization or may be performed simultaneously with the final polymerization.
(2) As is clear from comparative example 1, example 1 and example 2, under the same polymerization conditions, the amount of negative ions generated by the fiber is the lowest, only 1090 negative ions per cm 3, and the amount of negative ions generated by the fiber is obviously improved from 1wt% to 5wt% along with the addition of the functional negative ion generating agent, which means that the functional negative ion generating agent has a direct effect on the amount of negative ions generated by the fiber and has no obvious effect on the relative molecular mass and strength of the fiber within the range.
(3) As is clear from comparative example 2 and example 1, the amount of the functionalized anion generator added was low and the anion generating effect of the fiber was poor under the same conditions. As is clear from comparative example 3 and example 1, when the addition amount of the functionalized anion generator exceeds the range, the strength of the fiber is significantly reduced because the introduction of the inorganic auxiliary agent damages the orientation of the molecular weight to some extent, and the crystallinity of the polymer is affected, resulting in a reduction in strength, indicating that the excessively high addition amount of the functionalized anion generator adversely affects the performance of the direct spinning fiber. However, when the addition amount of the functional negative ion generating agent exceeds the range, the method can be adopted, and melt after the removal of the monomers is not input into a spinning system, so that the functional master batch is obtained.
(4) As is clear from comparative example 4 and example 1, under the same conditions, the melt which is not subjected to the removal of the monomers is not spun directly after being fed into the spinning system, and the fiber is difficult to form, because the removed melt contains about 8wt% of caprolactam monomer, and the existence of the caprolactam monomer causes stress concentration of the melt during the fiber forming, so that the monofilament is broken. Therefore, the monomer removal system plays a vital role in the direct spinning process of the polyamide melt.
The present invention is not limited to the preferred embodiments, and the present invention is described above in any way, but is not limited to the preferred embodiments, and any person skilled in the art will appreciate that the present invention is not limited to the embodiments described above, while the above disclosure is directed to various equivalent embodiments, which are capable of being modified or varied in several ways, any simple modification, equivalent changes and variation of the above embodiments according to the technical principles of the present invention will still fall within the scope of the present invention.
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