CN116180268B - Diclofenac sodium modified terylene large biological fiber and preparation method thereof - Google Patents
Diclofenac sodium modified terylene large biological fiber and preparation method thereof Download PDFInfo
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Abstract
The invention provides a diclofenac sodium modified large polyester biological fiber and a preparation method thereof, belonging to the field of large polyester biological fibers. The preparation method of the diclofenac sodium modified terylene large biological fiber comprises the following steps: preparing a carrier, activating the carrier, loading, forming, preparing functional master batch, melt spinning and post-treating. The preparation method of the diclofenac sodium modified terylene large biological fiber can avoid the influence of the diclofenac sodium by high temperature environment, organic solvent and the like, effectively reduce the loss of the diclofenac sodium and has stable modification effect on terylene fibers; meanwhile, the combination of the diclofenac sodium and the polyester fiber is firm, the loss rate is low, and the long-acting slow release performance of the diclofenac sodium modified polyester large biological fiber is good; can ensure the physical properties of the polyester fiber while realizing effective modification of the polyester fiber.
Description
Technical Field
The invention relates to the field of large terylene biological fibers, in particular to a sodium diclofenac modified large terylene biological fiber and a preparation method thereof.
Background
Polyester fiber, also called polyester fiber, is a synthetic fiber obtained by spinning polyester formed by polycondensation of organic dibasic acid and dihydric alcohol, and is an important variety in synthetic fibers. The polyester fiber has a series of excellent properties such as high breaking strength and elastic modulus, moderate rebound resilience, excellent heat setting effect, good heat resistance and light resistance and the like. The melting point of the polyester fiber is about 255 ℃, the glass transition temperature is about 70 ℃, the shape of the fabric is stable, and the fabric is not easy to deform after washing.
Meanwhile, the polyester fiber has good resistance (such as organic solvent resistance, soap resistance, detergent resistance, bleaching liquid resistance, oxidant resistance and the like) and good corrosion resistance, so the polyester fiber has wide application space. In addition, with the rapid development of the petroleum industry, the method provides more abundant and cheap raw materials for the production of the polyester fibers, and in addition, the development of chemical, mechanical, electronic self-control and other technologies in recent years, the short-cut, continuous, automatic and high-speed processes of the polyester fibers are gradually realized in the processes of raw material production, fiber forming, post-processing and finishing and the like. At present, polyester fibers become synthetic fibers with the highest development speed and highest yield.
With the development of organic synthesis, polymer science and polyester fiber industry, various functional polyester fibers with different characteristics have been developed in the prior art. Such as polybutylene terephthalate fiber with high elasticity, wholly aromatic polyester fiber with high strength and modulus, etc. The large biological polyester fiber, i.e. large biological functional polyester fiber, is prepared by adding a certain amount of functional material capable of acting on human body or other organisms into polymer of high polyester polymer, so as to modify the polyester fiber, thereby endowing the polyester fiber with one or more functions. In recent years, the variety of the biological functional polyester fiber at home and abroad is various, and the biological functional polyester fiber is continuously promoted to be new, and has wide application prospect. Therefore, the functional polyester fiber becomes the development focus of the future polyester fiber field, and has important significance for the research and development of the functional polyester fiber.
In the prior art, a large number of plant active substances (such as plant extracts and the like) are adopted, and the corresponding functions are realized on the polyester fibers by modifying the polyester fibers through specific functions of the plant active substances such as antibiosis, antivirus, anti-mite, antioxidation, antiallergic and the like. However, until the date of application, technical information for modifying polyester fibers by using diclofenac sodium has not been disclosed yet. The diclofenac sodium is a phenylacetic acid non-steroidal anti-inflammatory drug (NSAIDs), and has antipyretic, analgesic and anti-inflammatory effects, and the action intensity of the diclofenac sodium exceeds that of indomethacin, naproxen and other traditional non-steroidal anti-inflammatory drugs. The selectivity of diclofenac sodium for the membrane-bound protein COX-2 is similar to celecoxib.
Diclofenac sodium blocks the conversion of arachidonic acid to prostaglandins by inhibiting the activity of Cyclooxygenase (COXs); it can also promote the combination of arachidonic acid and triglyceride, reduce the concentration of free arachidonic acid in cells, thereby indirectly inhibiting the synthesis of leukotriene, and further realizing the effects of easing pain, resisting inflammation and relieving fever. In the prior art, diclofenac sodium is suitable for treating non-articular soft tissue rheumatalgia, such as shoulder pain, tenosynovitis, bursitis and myalgia; can also be used for treating acute mild and moderate pain, such as postoperative pain, postoperative pain or postoperative pain after strain, dysmenorrhea, toothache, and headache. Auxiliary treatment of severe infectious painful inflammation (such as pharyngeal tonsillitis and otitis) of otorhinolaryngology. In addition, diclofenac sodium has an antipyretic effect on fever in adults and children. However, diclofenac sodium has great side effects on intestines and stomach, and is obvious in gastrointestinal discomfort after oral administration.
In order to avoid the irritation of the diclofenac sodium to intestines and stomach and expand the performance and application range of the large polyester biological fiber, the inventor hopes to develop and obtain the large diclofenac sodium modified polyester biological fiber, and the effective exertion and long-acting slow release of the diclofenac sodium effect on the polyester fiber are realized through the functional modification of the diclofenac sodium to the polyester fiber. Meanwhile, the modified large terylene biological fiber can be prepared into downstream products such as medical patches, defervescence patches, bandages, underwear and the like, and the aim of improving the pertinence of the corresponding symptoms is realized through the transdermal absorption of the slow release diclofenac sodium of the modified large terylene biological fiber, so that the direct stimulation of the diclofenac sodium to intestines and stomach is avoided. However, the inventor finds that, in the process of using sodium diclofenac for modifying polyester fibers, since the process steps of high-temperature melting, high-temperature drawing, oiling and the like are required in the process of preparing the polyester fibers, the sodium diclofenac is easily affected by factors such as a high-temperature melting environment, an organic solvent, an auxiliary agent, extrusion or drawing, and the like, the loss rate of the sodium diclofenac is higher, the modifying effect is unstable, and the effective modification of the polyester fibers cannot be realized. Meanwhile, the combination of the diclofenac sodium and the polyester fiber is not tight enough, and the long-acting slow release effect can not be realized due to high loss rate after water washing or frequent friction. The inventors have found that, after the diclofenac sodium related ingredient is added to the polyester fiber, the physical properties of the polyester fiber are affected, and the physical indexes such as breaking strength, breaking elongation and the like of the polyester fiber are reduced to a certain extent.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the diclofenac sodium modified large polyester biological fiber and the preparation method thereof, which can prevent the diclofenac sodium from being influenced by high-temperature environment, organic solvent and the like in the preparation process of the polyester fiber, effectively reduce the loss of the diclofenac sodium, stabilize the modification effect of the polyester fiber and realize the effective modification of the polyester fiber; meanwhile, the combination of the diclofenac sodium and the polyester fiber is firm, the loss rate is low, and the long-acting slow release performance of the diclofenac sodium modified polyester large biological fiber is good; and ensuring the physical properties of the polyester fiber while realizing effective modification of the polyester fiber.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the diclofenac sodium modified terylene large biological fiber comprises the following steps: preparing a carrier, activating the carrier, loading, forming, preparing functional master batch, melt spinning and post-treating.
The carrier preparation, namely adding sodium alginate into deionized water with the weight of 100-120 times of that of the carrier, and stirring for 3-6 hours at normal temperature to obtain sodium alginate solution; dripping sodium alginate solution into 8-10 times of calcium chloride solution under the stirring condition of 300-400rpm, continuously stirring for 8-10h after dripping, standing for 1-2h, and filtering to obtain sodium alginate gel; putting sodium alginate gel into a freeze dryer, freeze-drying at 60-55 ℃ below zero for 40-50h, transferring into a tube furnace, heating to 850-950 ℃ at a heating rate of 3-6 ℃/min under the protection of nitrogen, preserving heat for 1-2h, and naturally cooling to normal temperature to obtain carbide; adding carbide into hydrochloric acid solution with 6-9 times of volume, standing for 8-10h, filtering, washing with absolute ethanol and deionized water, and drying at 75-85deg.C for 5-8h to obtain nanometer mesoporous carrier.
The carrier is prepared, and the concentration of the calcium chloride solution is 0.1-0.12mol/L;
the concentration of the hydrochloric acid solution is 0.8-1mol/L;
the specific surface area of the nano mesoporous carrier is 379-406m 2 Per gram, pore volume is 1.24-1.35mL/g.
The carrier is activated, the nano mesoporous carrier is placed in a tube furnace, and is heated to 200-220 ℃ at a heating rate of 1-3 ℃/min under the protection of nitrogen, and is kept for 2-4 hours and naturally cooled to normal temperature; putting into 8-10 times volume of activating solution, heating to 40-50 ℃, preserving heat, stirring for 2-3h, centrifugally separating, washing by absolute ethyl alcohol and deionized water in sequence, and drying at 75-85 ℃ for 5-8h to obtain the activating carrier.
In the carrier activation, an activating solution is prepared by adding a silane coupling agent KH-580 into an ethanol solution and uniformly dispersing;
the volume concentration of the ethanol solution is 88-92%;
the weight ratio of the silane coupling agent KH-580 to the ethanol solution is 2.4-3:100.
And (3) loading, namely, under the condition of stirring in a light-shielding environment, putting the activated carrier into a loading liquid with the weight being 90-100 times that of the activated carrier, heating to 35-40 ℃, preserving heat, stirring at 40-60rpm, adsorbing for 36-48h, washing with deionized water with the volume being 16-20 times that of the activated carrier, and drying by air blast at 50-60 ℃ for 6-8h to obtain the loaded carrier, namely, the activated carrier loaded with diclofenac sodium.
In the loading, the loading liquid is an absolute ethanol solution of diclofenac sodium; the concentration of diclofenac sodium in the loading solution is 10-12g/L.
The forming is carried out, the loaded material is put into a sodium alginate solution with the weight of 90-100 times, and the dispersion is uniform, thus preparing a loaded material dispersion liquid; under the stirring condition of 150-200rpm, dripping the dispersed load into the calcium chloride solution at the dripping rate of 4-6mL/min, continuously stirring for 30-60min after dripping, standing for 1-2h, and filtering to obtain a solid; washing solid with 10-12 times volume of deionized water for 1-2 times, pre-freezing at-6deg.C-4deg.C for 5-7 hr, transferring into freeze dryer, and lyophilizing at-60deg.C-55deg.C for 12-16 hr to obtain active ingredient.
In the forming, the concentration of the sodium alginate solution is 0.9-1.1wt%;
the concentration of the calcium chloride solution is 0.1-0.12mol/L.
The preparation method comprises the steps of uniformly mixing polyester chips, active ingredients, polytrimethylene terephthalate, calcium stearate and antioxidant TNP, transferring into a double-screw extruder, and performing melt extrusion and granulation to obtain the functional master batch.
In the preparation of the functional master batch, the weight ratio of polyester chips, active ingredients, polytrimethylene terephthalate, calcium stearate and antioxidant TNP is 50-60:16-18:6-8:3-4:0.8-1.
The melt spinning is carried out by putting polyester chips, functional master batch and amino silicone oil into a double-screw extruder, and melt extruding to obtain mixed melt; filtering and metering the mixed melt, introducing the mixed melt into a spinning machine, controlling the spinning temperature to 285-290 ℃, controlling the speed of side blowing cooling air to be 0.4-0.5m/s, and spinning at the spinning speed of 3200-3600m/min at the temperature of 20-22 ℃ to obtain the fiber.
In the melt spinning, the weight ratio of the polyester chips to the functional master batch to the amino silicone oil is 100:8-10:1-1.5.
And (3) carrying out primary drafting, oiling and secondary drafting on the fiber obtained by melt spinning after the post-treatment, and winding to obtain the diclofenac sodium modified terylene large biological fiber.
In the post-treatment, the primary drafting temperature is 180-190 ℃ and the drafting multiple is 3.5-4.2 times; the secondary drafting temperature is 110-120 deg.c and drafting doubling speed is 1.6-2.1 times.
The diclofenac sodium modified terylene large biological fiber is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the diclofenac sodium modified terylene large biological fiber, a specific carrier preparation step is adopted to prepare a nano mesoporous carrier by adopting sodium alginate; after the nano mesoporous carrier is subjected to activation treatment, the nano mesoporous carrier is used for loading sodium diclofenac contained in a loading liquid in a loading step, so that a loaded object is obtained; the load is molded to obtain active ingredients, and then the active ingredients are used for preparing functional master batches; then melt spinning the functional master batch and polyester chips; the method can avoid the influence of high-temperature melting environment, organic solvent, auxiliary agent and the like in the preparation process of the polyester, effectively reduce the loss of the diclofenac sodium and has stable modification effect on the polyester fiber; meanwhile, the combination of the diclofenac sodium and the polyester fiber is firm, the loss rate is low, and the long-acting slow release performance of the diclofenac sodium modified polyester large biological fiber is good; can ensure the physical properties of the polyester fiber while realizing effective modification of the polyester fiber.
(2) The preparation method of the diclofenac sodium modified large polyester biological fiber can effectively ensure the physical properties of the polyester fiber while realizing the effective modification of the polyester fiber; according to detection, the breaking strength of the diclofenac sodium modified terylene large biological fiber is 5.8-6.2cN/dtex, the breaking elongation is 20-23%, the breaking elongation CV value is 8.3-8.9%, the dry heat shrinkage rate at 180 ℃ is 2.7-3.3%, and the defect content is 2.9-3.8mg/100g.
(3) The diclofenac sodium modified large polyester biological fiber has good modification effect on polyester fibers, and can fully and effectively exert the effect of the diclofenac sodium; experiments prove that the traditional Chinese medicine composition can effectively eliminate or obviously relieve soft tissue rheumatic pain of patients suffering from non-articular soft tissue rheumatic pain, has no recurrence or aggravation during application, and has the obvious efficiency and the effective rate of 100 percent; at the same time, no recurrence or exacerbation of soft tissue rheumatalgia occurred within 7 days of discontinuation.
(4) According to the diclofenac sodium modified large polyester biological fiber, the combination of the diclofenac sodium and the large polyester fiber is firm, and after the test and the continuous washing for 10 times, the content reduction rate of the diclofenac sodium in the diclofenac sodium modified large polyester biological fiber is 5.1-5.6%, so that the realization of the long-acting slow release performance of the diclofenac sodium modified large polyester biological fiber can be ensured.
(5) According to the diclofenac sodium modified large polyester biological fiber, the combination of the diclofenac sodium and the large polyester fiber is firm, and after the test, the continuous friction is carried out for 100 times, the content reduction rate of the diclofenac sodium in the diclofenac sodium modified large polyester biological fiber is 3.7-4.2%, so that the realization of the long-acting slow release performance of the diclofenac sodium modified large polyester biological fiber is further ensured.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
The preparation method of the diclofenac sodium modified terylene large biological fiber specifically comprises the following steps:
1. carrier preparation
Adding sodium alginate into deionized water with the weight being 100 times that of the sodium alginate, and stirring for 3 hours at normal temperature to obtain sodium alginate solution; dropwise adding the sodium alginate solution into a calcium chloride solution with the volume of 8 times under the stirring condition of 300rpm, continuously stirring for 8 hours after the dropwise adding is completed, standing for 1 hour, and filtering to obtain sodium alginate gel; putting sodium alginate gel into a freeze dryer, freeze-drying at-60 ℃ for 40 hours, transferring into a tube furnace, heating to 850 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, preserving heat for 1 hour, and naturally cooling to normal temperature to obtain carbide; adding carbide into hydrochloric acid solution with 6 times of volume, standing for 8 hours, filtering, washing by absolute ethyl alcohol and deionized water in sequence, and drying at 75 ℃ for 5 hours to prepare the nano mesoporous carrier.
Wherein the concentration of the calcium chloride solution is 0.1mol/L.
The concentration of the hydrochloric acid solution was 0.8mol/L.
The specific surface area of the nano mesoporous carrier is 379m 2 Per gram, pore volume was 1.24mL/g.
2. Carrier activation
Placing the nano mesoporous carrier in a tube furnace, heating to 200 ℃ at a heating rate of 1 ℃/min under the protection of nitrogen, preserving heat for 2 hours, and naturally cooling to normal temperature; putting the mixture into 8 times of volume of activating solution, heating to 40 ℃, preserving heat and stirring for 2 hours, centrifugally separating, washing by adopting absolute ethyl alcohol and deionized water in sequence, and drying at 75 ℃ for 5 hours to prepare the activating carrier.
Wherein the activating solution is prepared by adding a silane coupling agent KH-580 into an ethanol solution and uniformly dispersing.
The volume concentration of the ethanol solution was 88%.
The weight ratio of the silane coupling agent KH-580 to the ethanol solution is 2.4:100.
3. Load(s)
In a light-shielding environment, under the stirring condition, the activated carrier is put into a load liquid with the weight being 90 times that of the activated carrier, the temperature is raised to 35 ℃, the temperature is kept, the stirring and the adsorption are carried out for 36 hours at 40rpm, the activated carrier is washed by adopting 16 times of deionized water, and the activated carrier loaded with the diclofenac sodium is prepared after the activated carrier is dried for 6 hours by blowing at 50 ℃.
Wherein the loading liquid is an absolute ethanol solution of diclofenac sodium; the concentration of diclofenac sodium in the loading solution is 10g/L.
4. Shaping
Putting the load into a sodium alginate solution with the weight being 90 times that of the load, and uniformly dispersing to prepare a load dispersion liquid; under the stirring condition of 150rpm, dripping the load dispersion liquid into the calcium chloride solution at the dripping rate of 4mL/min, continuously stirring for 30min after the dripping is finished, standing for 1h, and filtering to obtain a solid; washing the solid with 10 times of deionized water for 1 time, pre-freezing the solid at-6deg.C for 5h, transferring into a freeze dryer, and lyophilizing at-60deg.C for 12h to obtain active ingredient.
Wherein the concentration of the sodium alginate solution is 0.9wt%.
The concentration of the calcium chloride solution is 0.1mol/L.
5. Preparation of functional masterbatch
The polyester chips, the active ingredients, the polytrimethylene terephthalate, the calcium stearate and the antioxidant TNP are uniformly mixed and transferred into a double-screw extruder to be subjected to melt extrusion and granulation to prepare the functional master batch.
Wherein the weight ratio of the polyester chips to the active ingredients to the polytrimethylene terephthalate to the calcium stearate to the antioxidant TNP is 50:16:6:3:0.8.
6. Melt spinning
Putting polyester chips, functional master batches and amino silicone oil into a double-screw extruder, and carrying out melt extrusion to obtain a mixed melt; filtering and metering the mixed melt, introducing the mixed melt into a spinning machine, controlling the spinning temperature to be 285 ℃, controlling the speed of side blowing cooling air to be 0.4m/s, and spinning at the spinning speed of 3200m/min at the side blowing cooling air temperature of 20 ℃ to obtain the fiber.
Wherein the weight ratio of the polyester chips to the functional master batch to the amino silicone oil is 100:8:1.
7. Post-treatment
The fiber obtained by melt spinning is subjected to primary drafting, oiling and secondary drafting and winding to obtain the diclofenac sodium modified terylene large biological fiber in the example 1.
Wherein, the primary drafting temperature is 180 ℃ and the drafting multiple is 3.5 times;
the secondary drawing temperature is 110 ℃, and the drawing doubling speed is 1.6 times.
Example 2
The preparation method of the diclofenac sodium modified terylene large biological fiber specifically comprises the following steps:
1. carrier preparation
Adding sodium alginate into deionized water with the weight being 110 times that of the sodium alginate, and stirring for 5 hours at normal temperature to obtain sodium alginate solution; dropwise adding the sodium alginate solution into a calcium chloride solution with the volume being 9 times of that of the sodium alginate solution under the stirring condition of 350rpm, continuously stirring for 9 hours after the dropwise adding is finished, standing for 1.5 hours, and filtering to obtain sodium alginate gel; putting sodium alginate gel into a freeze dryer, freeze-drying at-58 ℃ for 45h, transferring into a tube furnace, heating to 900 ℃ at a heating rate of 4.5 ℃/min under the protection of nitrogen, preserving heat for 1.5h, and naturally cooling to normal temperature to obtain carbide; adding carbide into hydrochloric acid solution with 8 times of volume, standing for 9 hours, filtering, washing by absolute ethyl alcohol and deionized water in sequence, and drying at 80 ℃ for 7 hours to prepare the nano mesoporous carrier.
Wherein the concentration of the calcium chloride solution is 0.11mol/L.
The concentration of the hydrochloric acid solution was 0.9mol/L.
The specific surface area of the nano mesoporous carrier is 406m 2 Per gram, pore volume was 1.35mL/g.
2. Carrier activation
Placing the nano mesoporous carrier in a tube furnace, heating to 210 ℃ at a heating rate of 2 ℃/min under the protection of nitrogen, preserving heat for 3 hours, and naturally cooling to normal temperature; putting into activating solution with the volume of 9 times, heating to 45 ℃, preserving heat, stirring for 2.5 hours, centrifugally separating, washing by absolute ethyl alcohol and deionized water in sequence, and drying at 80 ℃ for 7 hours to obtain the activating carrier.
Wherein the activating solution is prepared by adding a silane coupling agent KH-580 into an ethanol solution and uniformly dispersing.
The volume concentration of the ethanol solution was 90%.
The weight ratio of the silane coupling agent KH-580 to the ethanol solution is 2.8:100.
3. Load(s)
And (3) in a light-shielding environment, under the stirring condition, putting the activated carrier into a load liquid with the weight being 95 times that of the activated carrier, heating to 37 ℃, preserving heat, stirring and adsorbing for 42 hours at 50rpm, washing with 18 times of deionized water, and drying for 7 hours at 55 ℃ by blowing to obtain the loaded carrier, namely the activated carrier loaded with the diclofenac sodium.
Wherein the loading liquid is an absolute ethanol solution of diclofenac sodium; the concentration of diclofenac sodium in the loading solution is 11g/L.
4. Shaping
Adding the load into sodium alginate solution with the weight being 95 times that of the load, and uniformly dispersing to prepare load dispersion liquid; under the stirring condition of 180rpm, dripping the load dispersion liquid into the calcium chloride solution at the dripping rate of 5mL/min, continuously stirring for 50min after the dripping is finished, standing for 1.5h, and filtering to obtain a solid; washing the solid with 11 times of deionized water for 2 times, pre-freezing at-5deg.C for 6 hr, transferring into a freeze dryer, and lyophilizing at-60deg.C for 14 hr to obtain active ingredient.
Wherein the concentration of the sodium alginate solution is 1wt%.
The concentration of the calcium chloride solution is 0.11mol/L.
5. Preparation of functional masterbatch
The polyester chips, the active ingredients, the polytrimethylene terephthalate, the calcium stearate and the antioxidant TNP are uniformly mixed and transferred into a double-screw extruder to be subjected to melt extrusion and granulation to prepare the functional master batch.
Wherein the weight ratio of polyester chips, active ingredients, polytrimethylene terephthalate, calcium stearate and antioxidant TNP is 55:17:7:3.5:0.9.
6. Melt spinning
Putting polyester chips, functional master batches and amino silicone oil into a double-screw extruder, and carrying out melt extrusion to obtain a mixed melt; filtering and metering the mixed melt, introducing the mixed melt into a spinning machine, controlling the spinning temperature to be 287 ℃, controlling the speed of side-blowing cooling air to be 0.45m/s, controlling the temperature of side-blowing cooling air to be 21 ℃, and spinning at 3450m/min to obtain the fiber.
Wherein the weight ratio of the polyester chips to the functional master batch to the amino silicone oil is 100:9:1.2.
7. Post-treatment
The fiber obtained by melt spinning is subjected to primary drafting, oiling and secondary drafting and winding to obtain the diclofenac sodium modified terylene large biological fiber in example 2.
Wherein, the primary drafting temperature is 185 ℃ and the drafting multiple is 3.9 times;
the secondary drawing temperature is 115 ℃, and the drawing doubling speed is 2.0 times.
Example 3
The preparation method of the diclofenac sodium modified terylene large biological fiber specifically comprises the following steps:
1. carrier preparation
Adding sodium alginate into deionized water with the weight of 120 times of that of the sodium alginate, and stirring for 6 hours at normal temperature to obtain sodium alginate solution; dropwise adding the sodium alginate solution into a 10-time volume of calcium chloride solution under the stirring condition of 400rpm, continuously stirring for 10 hours after the dropwise adding is completed, standing for 2 hours, and filtering to obtain sodium alginate gel; putting sodium alginate gel into a freeze dryer, freeze-drying at-55 ℃ for 50 hours, transferring into a tube furnace, heating to 950 ℃ at a heating rate of 6 ℃/min under a nitrogen protection environment, preserving heat for 2 hours, and naturally cooling to normal temperature to obtain carbide; adding carbide into hydrochloric acid solution with the volume of 9 times, standing for 10 hours, filtering, washing by adopting absolute ethyl alcohol and deionized water in sequence, and drying at 85 ℃ for 8 hours to prepare the nano mesoporous carrier.
Wherein the concentration of the calcium chloride solution is 0.12mol/L.
The concentration of the hydrochloric acid solution was 1mol/L.
The specific surface area of the nano mesoporous carrier is 393m 2 Per gram, pore volume was 1.31mL/g.
2. Carrier activation
Placing the nano mesoporous carrier in a tube furnace, heating to 220 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, preserving heat for 4 hours, and naturally cooling to normal temperature; putting the mixture into an activating solution with the volume of 10 times, heating to 50 ℃, preserving heat and stirring for 3 hours, centrifugally separating, washing by adopting absolute ethyl alcohol and deionized water in sequence, and drying at 85 ℃ for 8 hours to prepare the activating carrier.
Wherein the activating solution is prepared by adding a silane coupling agent KH-580 into an ethanol solution and uniformly dispersing.
The volume concentration of the ethanol solution was 92%.
The weight ratio of the silane coupling agent KH-580 to the ethanol solution is 3:100.
3. Load(s)
And (3) under the condition of light shielding and stirring, putting the activated carrier into a loading liquid with the weight being 100 times that of the activated carrier, heating to 40 ℃, preserving heat, stirring and adsorbing for 48 hours at 60rpm, washing with deionized water with the volume being 20 times that of the activated carrier, and drying for 8 hours at 60 ℃ by blowing to obtain the loaded carrier, namely the activated carrier loaded with the diclofenac sodium.
Wherein the loading liquid is an absolute ethanol solution of diclofenac sodium; the concentration of diclofenac sodium in the loading solution is 12g/L.
4. Shaping
Adding the load into a sodium alginate solution with the weight being 100 times that of the load, and uniformly dispersing to prepare a load dispersion liquid; under the stirring condition of 200rpm, dripping the load dispersion liquid into the calcium chloride solution at the dripping rate of 6mL/min, continuously stirring for 60min after the dripping is finished, standing for 2h, and filtering to obtain a solid; washing the solid with deionized water of 12 times volume for 2 times, pre-freezing the solid at-4deg.C for 7 hr, transferring into a freeze dryer, and lyophilizing at-55deg.C for 16 hr to obtain active ingredient.
Wherein the concentration of the sodium alginate solution is 1.1wt%.
The concentration of the calcium chloride solution is 0.12mol/L.
5. Preparation of functional masterbatch
The polyester chips, the active ingredients, the polytrimethylene terephthalate, the calcium stearate and the antioxidant TNP are uniformly mixed and transferred into a double-screw extruder to be subjected to melt extrusion and granulation to prepare the functional master batch.
Wherein the weight ratio of polyester chips, active ingredients, polytrimethylene terephthalate, calcium stearate and antioxidant TNP is 60:18:8:4:1.
6. Melt spinning
Putting polyester chips, functional master batches and amino silicone oil into a double-screw extruder, and carrying out melt extrusion to obtain a mixed melt; filtering and metering the mixed melt, introducing the mixed melt into a spinning machine, controlling the spinning temperature to be 290 ℃, controlling the speed of side blowing cooling air to be 0.5m/s, controlling the temperature of side blowing cooling air to be 22 ℃, and spinning at 3600m/min to obtain the fiber.
Wherein the weight ratio of the polyester chips to the functional master batch to the amino silicone oil is 100:10:1.5.
7. Post-treatment
The fiber obtained by melt spinning is subjected to primary drafting, oiling and secondary drafting and winding to obtain the diclofenac sodium modified terylene large biological fiber of the example 3.
Wherein, the primary drafting temperature is 190 ℃ and the drafting multiple is 4.2 times;
the secondary drawing temperature is 120 ℃, and the drawing doubling speed is 2.1 times.
Comparative example 1
The preparation method of the diclofenac sodium modified terylene large biological fiber in the embodiment 2 is characterized in that: 1) Omitting the carrier activation step, and directly using the nano mesoporous carrier prepared in the previous step in the loading step; 2) And omitting the forming step, and directly using the load prepared in the loading step in the step of preparing the functional master batch.
The diclofenac sodium modified terylene large biological fiber prepared in examples 1-3 and comparative example 1 is tested for breaking strength, breaking elongation CV value, 180 ℃ dry heat shrinkage and defect content.
The specific detection results are as follows:
the diclofenac sodium modified terylene large biological fibers of examples 1-3 and comparative example 1 are blended with spandex to prepare test bandages, and the content of the diclofenac sodium modified terylene large biological fibers in each test bandage is controlled to be 90 percent, and the content of the spandex is controlled to be 10 percent.
80 volunteers aged 40-60 years with non-articular soft tissue rheumatalgia were selected and the number of men and women in the volunteers was controlled to be half. The 80 volunteers were randomly divided into 4 groups and each half of men and women within each group was controlled. Wherein, groups 1-3 correspond to the application of the test bandages of examples 1-3, and groups 4 correspond to the application of the test bandage of comparative example 1, respectively. The specific application method is to clean the skin of the soft tissue rheumatalgia area every day, fix the test bandage to the soft tissue rheumatalgia area, keep 10 hours every day, and apply for 28 days continuously. Investigation of the application effect (effective, ineffective) of each test bandage, and statistics of the corresponding number of people; and the number of soft tissue rheumatal recurrence or exacerbation persons in the active and effective volunteers was counted during the administration period and for 7 days after discontinuation of the administration.
Wherein, the drug has the obvious effects of effectively eliminating soft tissue rheumatalgia and no recurrence during the application period.
Effectively, the rheumatic pain of the soft tissue is obviously relieved, and the pain is not aggravated during the application period.
The ineffectiveness is that there is no significant difference in soft tissue rheumatalgia compared to the test bandages not applied.
The specific test results are as follows:
further, the diclofenac sodium modified terylene large biological fibers of the examples 1-3 and the comparative example 1 are respectively spun into terylene fabrics, cut into 20 cm-20 cm water washing samples, and the content of the diclofenac sodium in the water washing samples before water washing is detected; then placing the water washing sample in a washing machine, taking washing for 30min as water washing, continuously washing for 10 times, and detecting the content of diclofenac sodium in the water washing sample after water washing; the reduction rate of the diclofenac sodium content (i.e. the water washing loss rate) after 10 times of water washing is calculated.
Wherein, the reduction rate of the sodium diclofenac content after 10 times of water washing is = [ (the sodium diclofenac content in the water washing sample before water washing-the sodium diclofenac content in the water washing sample after water washing)/the sodium diclofenac content in the water washing sample before water washing ]. 100%. The specific test results are as follows:
further, the diclofenac sodium modified terylene large biological fibers of the examples 1-3 and the comparative example 1 are respectively spun into fabrics, cut into friction samples of 20cm x 5cm, and the content of the diclofenac sodium in each friction sample before friction treatment is detected; and then placing each friction sample on a friction platform of a friction testing machine, and controlling the load of the friction testing machine to be 6N, the friction times to be 100 times, the friction distance to be 100mm and the friction speed to be 10 times/min under the condition that the relative humidity is 65% at the room temperature of 25 ℃ to carry out friction treatment. After the friction treatment is finished, detecting the content of diclofenac sodium in each friction sample; the reduction rate (i.e., the friction loss rate) of the diclofenac sodium content after 100 times of friction was calculated.
Wherein, the reduction rate of the diclofenac sodium content after rubbing 100 times = [ (the diclofenac sodium content in the rubbing sample before rubbing treatment-the diclofenac sodium content in the rubbing sample after rubbing treatment)/the diclofenac sodium content in the rubbing sample before rubbing treatment ] ×100%.
The specific test results are as follows:
it can be seen that the diclofenac sodium modified terylene large biological fiber in the embodiment 1-3 of the invention adopts sodium alginate to prepare nano mesoporous carrier through a specific carrier preparation step; after the nano mesoporous carrier is subjected to activation treatment, the nano mesoporous carrier is used for loading sodium diclofenac contained in a loading liquid in a loading step, so that a loaded object is obtained; the load is molded to obtain active ingredients, and then the active ingredients are used for preparing functional master batches; then melt spinning the functional master batch and polyester chips; the method can avoid the influence of high-temperature melting environment, organic solvent, auxiliary agent and the like in the preparation process of the polyester, effectively reduce the loss of the diclofenac sodium and has stable modification effect on the polyester fiber; meanwhile, the combination of the diclofenac sodium and the polyester fiber is firm, the loss rate is low, and the long-acting slow release performance of the diclofenac sodium modified polyester large biological fiber is good; can ensure the physical properties of the polyester fiber while realizing effective modification of the polyester fiber.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the diclofenac sodium modified terylene large biological fiber is characterized by comprising the following steps: preparing a carrier, activating the carrier, loading, forming, preparing functional master batches, melt spinning and post-processing;
the carrier preparation, namely adding sodium alginate into deionized water with the weight of 100-120 times of that of the carrier, and stirring for 3-6 hours at normal temperature to obtain sodium alginate solution; dropwise adding the sodium alginate solution into the calcium chloride solution under the stirring condition, continuously stirring for 8-10h after the dropwise adding is completed, standing for 1-2h, and filtering to obtain sodium alginate gel; after freeze-drying sodium alginate gel, heating to 850-950 ℃ at a heating rate of 3-6 ℃/min under the protection of nitrogen, preserving heat for 1-2h, and naturally cooling to normal temperature to obtain carbide; adding carbide into hydrochloric acid solution, standing for 8-10h, filtering, washing with absolute ethyl alcohol and deionized water in sequence, and drying to obtain nano mesoporous carrier;
the concentration of the calcium chloride solution is 0.1-0.12mol/L;
the concentration of the hydrochloric acid solution is 0.8-1mol/L;
the specific surface area of the nano mesoporous carrier is 379-406m 2 Per gram, pore volume of 1.24-1.35mL/g;
the carrier is activated, the nano mesoporous carrier is placed in a closed environment, and is heated to 200-220 ℃ at a heating rate of 1-3 ℃/min under the protection of nitrogen, and is kept for 2-4 hours and naturally cooled to normal temperature; putting the mixture into an activating solution with the volume of 8-10 times, heating to 40-50 ℃, preserving heat, stirring for 2-3 hours, centrifugally separating, washing by adopting absolute ethyl alcohol and deionized water in sequence, and drying to obtain an activating carrier;
in the carrier activation, an activating solution is an ethanol solution of a silane coupling agent KH-580; the weight ratio of the silane coupling agent KH-580 to the ethanol solution is 2.4-3:100;
the volume concentration of the ethanol solution is 88-92%;
the loading is carried out, under the condition of stirring, the activated carrier is put into the loading liquid, stirred and adsorbed for 36-48 hours, filtered out, washed by deionized water and dried to prepare the loading substance;
in the loading, the loading liquid is an absolute ethanol solution of diclofenac sodium; the concentration of diclofenac sodium in the loading solution is 10-12g/L;
the forming is carried out, the loaded material is put into a sodium alginate solution with the weight of 90-100 times, and the dispersion is uniform, thus preparing a loaded material dispersion liquid; under the stirring condition, dripping the load dispersion liquid into the calcium chloride solution at the dripping rate of 4-6mL/min, continuously stirring for 30-60min after the dripping is finished, standing for 1-2h, and filtering to obtain a solid; washing the solid with deionized water, and lyophilizing to obtain active ingredient;
the concentration of the sodium alginate solution is 0.9-1.1wt%;
the concentration of the calcium chloride solution is 0.1-0.12mol/L.
2. The preparation method of the diclofenac sodium modified terylene large biological fiber according to claim 1, which is characterized in that the preparation of the functional master batch is characterized in that terylene polyester chips, active ingredients, polytrimethylene terephthalate, calcium stearate and antioxidant TNP are uniformly mixed, and the functional master batch is prepared by melt extrusion and granulation;
the melt spinning is carried out by mixing polyester chips, functional master batch and amino silicone oil, melt extruding, filtering, metering and spinning to obtain fiber;
and after the post-treatment, the fiber is subjected to primary drafting, oiling, secondary drafting and winding to obtain the diclofenac sodium modified terylene large biological fiber.
3. The method for preparing the diclofenac sodium modified terylene large biological fiber according to claim 1, wherein the loading is carried out by putting the activated carrier into a loading liquid with 90-100 times of weight under the condition of stirring in a light-proof environment, heating to 35-40 ℃, preserving heat, stirring and adsorbing for 36-48h, filtering, washing with deionized water, and drying.
4. The preparation method of the diclofenac sodium modified terylene large biological fiber according to claim 2, which is characterized in that in the preparation of the functional master batch, the weight ratio of terylene polyester chips, active ingredients, polytrimethylene terephthalate, calcium stearate and antioxidant TNP is 50-60:16-18:6-8:3-4:0.8-1;
in the melt spinning, the spinning temperature is 285-290 ℃, the side blowing cooling air speed is 0.4-0.5m/s, the side blowing cooling air temperature is 20-22 ℃, and the spinning speed is 3200-3600m/min;
the weight ratio of the polyester chips to the functional master batch to the amino silicone oil is 100:8-10:1-1.5.
5. The method for preparing the diclofenac sodium modified terylene large biological fiber according to claim 2, wherein in the post treatment, the primary drafting temperature is 180-190 ℃ and the drafting multiple is 3.5-4.2 times;
the secondary drafting temperature is 110-120 deg.c and drafting doubling speed is 1.6-2.1 times.
6. A diclofenac sodium modified terylene large biological fiber, which is characterized in that the fiber is prepared by the preparation method of any one of claims 1 to 5.
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