CN116145275B - Diclofenac sodium modified viscose large biological fiber and preparation method thereof - Google Patents
Diclofenac sodium modified viscose large biological fiber and preparation method thereof Download PDFInfo
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- CN116145275B CN116145275B CN202310422764.9A CN202310422764A CN116145275B CN 116145275 B CN116145275 B CN 116145275B CN 202310422764 A CN202310422764 A CN 202310422764A CN 116145275 B CN116145275 B CN 116145275B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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Abstract
The invention provides a diclofenac sodium modified viscose large biological fiber and a preparation method thereof, belonging to the field of viscose large biological fiber. The preparation method of the diclofenac sodium modified viscose large biological fiber comprises the following steps: preparing a porous carrier, modifying the porous carrier, preparing an active ingredient, preparing spinning solution and spinning. The preparation method of the diclofenac sodium modified viscose large biological fiber can effectively avoid the failure caused by the influence of factors such as the added auxiliary agent, coagulation bath components, process conditions and the like in the modification and preparation process of the viscose fiber, has good modification effect on the viscose fiber, and can realize the full and effective exertion of the effect of the diclofenac sodium; meanwhile, the combination of the diclofenac sodium and the viscose fiber is firm, the washing loss rate is low, and the long-acting slow release performance of the diclofenac sodium modified viscose large biological fiber is good.
Description
Technical Field
The invention relates to the field of viscose large biological fibers, in particular to a diclofenac sodium modified viscose large biological fiber and a preparation method thereof.
Background
The viscose fiber is also called viscose fiber for short, which is a regenerated cellulose fiber prepared by taking natural fibers such as wood fiber, cotton linter and the like as raw materials, preparing soluble cellulose xanthate through the procedures of alkalization, aging, sulfonation and the like, dissolving the soluble cellulose xanthate in dilute alkali solution to prepare viscose, and spinning the viscose as spinning stock solution through a wet spinning process. The viscose fiber has the advantages of strong hygroscopicity, strong air permeability, comfortable wearing, smoothness, coolness, static resistance, easy dyeing, good spinnability and the like, and is widely applied to the fields of clothing, home textile, non-woven fabrics and the like.
The viscose large biological fiber, namely the large biological functional viscose fiber, is prepared by adding a certain amount of functional materials which can act on human bodies or other organisms into a polymer of viscose high polymer, and processing the polymer by a special technology, thereby endowing the viscose fiber with one or more functions. In recent years, various domestic and foreign biological functional fibers are developed, a large space is provided for the development of functional products, market consumption is also increased, and the fiber has wide application prospects in the fields of construction, traffic, water conservancy, agriculture, fishery, medical and health, even the fields of electronics, communication, national defense and the like. Thus, functional viscose fibers have become an important development point in the future viscose fiber field, and functional fiber materials are paid attention to industry and welcome in the market by virtue of their specificity, differentiation and functional pertinence.
In the prior art, a large number of plant active substances (such as plant extracts and the like) are disclosed, and the viscose is modified by specific functions of the plant active substances, such as antibiosis, antivirus, antioxidation, antiallergic and the like, so that corresponding functions are realized on the viscose. However, until the date of application, no technical information has been disclosed for modifying viscose fibers using sodium diclofenac. 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.
In order to expand the performance and application range of the viscose large biological fiber, the inventor hopes to develop and obtain the diclofenac sodium modified viscose large biological fiber, and the effective exertion and long-acting slow release of the diclofenac sodium effect on the viscose fiber are realized through the functional modification of the diclofenac sodium on the viscose fiber. Meanwhile, the modified viscose large biological fiber can be prepared into downstream products such as medical patches, defervescence patches, bandages, underwear and the like, and the targeted improvement of corresponding diseases is realized through the transdermal absorption of the modified viscose large biological fiber slow-release diclofenac sodium. However, the inventor finds that the sodium diclofenac is easy to be influenced and disabled by factors such as the added viscose auxiliary agent, the viscose coagulation bath component, the viscose stock solution, the technological conditions required by the viscose preparation and the like in the modification and preparation processes of the viscose in the modification process of the viscose, and the modification effect on the viscose is not ideal, so that the full and effective play of the effect of the sodium diclofenac cannot be realized. Meanwhile, the bonding of the diclofenac sodium and the viscose is weak, so that the long-acting slow release effect is difficult to realize, and the loss rate of the diclofenac sodium is high after the viscose is washed with water, so that the due long-acting performance cannot be maintained.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the diclofenac sodium modified viscose large biological fiber and the preparation method thereof, which can effectively avoid the failure caused by the influence of factors such as added auxiliary agents, coagulation bath components, process conditions and the like in the modification and preparation processes of the viscose fiber, has good modification effect on the viscose fiber and can realize the full and effective exertion of the effect of the diclofenac sodium; meanwhile, the combination of the diclofenac sodium and the viscose fiber is firm, the washing loss rate is low, and the long-acting slow release performance of the diclofenac sodium modified viscose large biological fiber is good.
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 viscose large biological fiber comprises the following steps: preparing a porous carrier, modifying the porous carrier, preparing an active ingredient, preparing spinning solution and spinning.
The preparation of the porous carrier comprises the steps of adding hexadecyl trimethyl ammonium bromide and polyethylene glycol PEG-6000 into deionized water at 35-40 ℃, stirring for 30-60min, continuously adding mesitylene, and stirring for 30-60 min; adding water glass at a feeding rate of 1-1.5g/min, and continuously stirring for 1.5-3.5h after the water glass feeding is completed; adjusting the pH value to 10-10.5 by adopting a hydrochloric acid solution with the concentration of 2-2.5mol/L, and keeping the temperature and standing for 12-16h; then transferring into a reactor, heating to 105-110 ℃, preserving heat and crystallizing for 20-30h; filtering out crystal grains, washing with deionized water with volume of 12-16 times, drying at 80-90deg.C for 18-22h, and roasting at 350-400deg.C for 4-7h to obtain porous carrier.
In the preparation of the porous carrier, the weight ratio of hexadecyl trimethyl ammonium bromide to polyethylene glycol PEG-6000 to mesitylene to water glass to deionized water is 1.5-2:0.08-0.1:0.8-1:9-11:70-80;
the water glass contains 26-28wt% of SiO 2 8.7 to 9.5 weight percent of Na 2 O；
The porous carrier has a specific surface area of 917-1005m 2 And/g, pore diameter is 3.4-3.8nm.
The porous carrier is modified, the porous carrier is put into ethanol solution with the weight of 35-45 times of that of the porous carrier, and the porous carrier is uniformly dispersed by ultrasonic; under the stirring condition, simultaneously dripping a silane coupling agent KH-550 and a silane coupling agent KH-580 at the dripping rate of 2-3mL/min, and regulating the pH value to 4.5-5 by adopting acetic acid after the dripping is completed; stirring and heating to 50-60 ℃ under the protection of nitrogen and in the dark, preserving heat, and stirring and refluxing for 5-8h; centrifuging to separate solid, washing with 8-10 times of absolute ethyl alcohol, washing with 18-20 times of deionized water, and drying at 45-55deg.C to obtain modified porous carrier.
In the modification of the porous carrier, the volume concentration of the ethanol solution is 88-92%;
the weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-580 to the ethanol solution is 0.7-0.8:2.2-2.5:100.
The preparation method comprises the steps of preparing an active ingredient, under the condition of avoiding light, putting a modified porous carrier into 90-100 times of loading liquid by weight, heating to 30-35 ℃, stirring and adsorbing for 20-30 hours at 50-80rpm, washing with 12-15 times of deionized water by volume, and then carrying out heat preservation and drying at 45-55 ℃ until the moisture content is 1-3wt% under the condition of vacuum degree of 0.01-0.03MPa, so as to obtain the active ingredient, namely the modified porous carrier loaded with diclofenac sodium.
In the preparation of the active ingredient, the loading liquid is an aqueous solution of diclofenac sodium, and the concentration of the diclofenac sodium is 4-6mg/mL.
The preparation method comprises the steps of preparing spinning solution, adding active ingredients into 80-90 times of deionized water by weight, and uniformly stirring to prepare active ingredient solution; then adding the active component liquid, a silane coupling agent KH-792, sodium alginate and sodium carboxymethyl cellulose into the spinning solution, uniformly mixing, and filtering, defoaming and ripening to obtain the spinning solution.
In the preparation of the spinning solution, the weight ratio of the active component solution to the silane coupling agent KH-792 to the sodium alginate to the sodium carboxymethyl cellulose to the spinning solution is 12-16:0.8-1:0.5-0.7:0.4-0.5:90-95;
in the spinning solution, the content of alpha-fiber is 9.1-9.3%, the content of total alkali is 2.8-3.2%, and the viscosity is 35-40s.
The spinning is carried out by introducing spinning solution into a spinning machine, spinning treatment is carried out at a spinning speed of 16-18m/min, spinning is carried out into a coagulating bath with a temperature of 40-45 ℃, and after spinning solidification, the diclofenac sodium modified viscose large biological fiber is prepared through desulfurization, water washing, oiling and drying.
In the spinning, the content of each component in the coagulating bath is as follows: 60-70g/L of sulfuric acid, 120-130g/L of sodium sulfate, 22-26g/L of zinc sulfate and 7-9g/L of calcium chloride.
The diclofenac sodium modified viscose 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 viscose large biological fiber, a porous carrier is prepared by adopting specific raw materials and a process method, and the porous carrier is modified; the modified porous carrier is used for preparing active ingredients, the diclofenac sodium in the loading liquid is effectively adsorbed, and the prepared active ingredients are used for preparing spinning liquid; the method can effectively avoid the failure caused by the influence of factors such as added auxiliary agents, coagulation bath components, process conditions and the like in the modification and preparation processes of the viscose fiber, has good modification effect on the viscose fiber, can realize the full and effective exertion of the effect of the diclofenac sodium, and further expands the performance and application range of the viscose large biological fiber; meanwhile, the combination of the diclofenac sodium and the viscose fiber is firm, the washing loss rate is low, and the long-acting slow release performance of the diclofenac sodium modified viscose large biological fiber is good.
(2) The diclofenac sodium modified viscose large biological fiber has good modification effect on viscose fiber, can fully and effectively exert the effect of the diclofenac sodium, can effectively eliminate or obviously relieve the rheumatic pain of the soft tissue aiming at patients suffering from the rheumatic pain of the non-articular soft tissue, has no recurrence or aggravation during the application period, and has the obvious efficiency up to 100 percent; and no recurrence or exacerbation of soft tissue rheumatalgia occurred within 7 days of discontinuation.
(3) According to the diclofenac sodium modified viscose large biological fiber, the combination of the diclofenac sodium and the viscose 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 viscose large biological fiber is 4.6-5.1%, so that the realization of the long-acting slow release performance of the diclofenac sodium modified viscose large biological fiber can be ensured.
(4) According to the diclofenac sodium modified viscose large biological fiber, the combination of the diclofenac sodium and the viscose fiber is firm, the long-term stability is good, and the test shows that after the diclofenac sodium modified viscose large biological fiber is stood for 30 days in an illumination environment at the temperature of 35 ℃, the content reduction rate of the diclofenac sodium is 5.2-5.8%, so that the realization of the long-term slow release performance of the diclofenac sodium modified viscose large biological fiber is further ensured.
(5) According to detection, the diclofenac sodium modified viscose large biological fiber has the dry breaking strength of 3.09-3.19cN/dtex, the wet breaking strength of 1.60-1.70cN/dtex, the constant elongation load of 2.99-3.08cN, the whiteness of 54.8-55.1%, the moisture regain of 12.0-12.5% and the defect content of 1.3-1.4mg/100g, and can ensure the physical properties of the viscose fiber while realizing the effective modification of the diclofenac sodium on the viscose fiber.
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 viscose large biological fiber specifically comprises the following steps:
1. preparation of porous support
Adding hexadecyl trimethyl ammonium bromide and polyethylene glycol PEG-6000 into deionized water at 35 ℃, stirring for 30min, continuously adding mesitylene, and stirring for 30 min; adding water glass at a feeding rate of 1g/min, and continuously stirring for 1.5h after the water glass feeding is finished; adjusting the pH value to 10 by adopting a hydrochloric acid solution with the concentration of 2mol/L, and keeping the temperature and standing for 12 hours; then transferring into a reactor, heating to 105 ℃, preserving heat and crystallizing for 20h; filtering out crystal grains, washing with deionized water with the volume of 12 times, drying at 80 ℃ for 18h, and roasting at 450 ℃ for 4h to obtain the porous carrier.
Wherein, the weight ratio of cetyl trimethyl ammonium bromide to polyethylene glycol PEG-6000 to mesitylene to water glass to deionized water is 1.5:0.08:0.8:9:70.
The water glass contains 26 weight percent of SiO 2 8.7wt% Na 2 O。
The porous carrier has a specific surface area of 917m 2 And/g, pore size of 3.4nm.
2. Porous support modification
Putting the porous carrier into an ethanol solution with the weight being 35 times of that of the porous carrier, and uniformly dispersing the porous carrier by ultrasonic waves; under the stirring condition, simultaneously dripping a silane coupling agent KH-550 and a silane coupling agent KH-580 at a dripping rate of 2mL/min, and regulating the pH value to 4.5 by adopting acetic acid after the dripping is completed; stirring and heating to 50 ℃ under the protection of nitrogen and in a dark condition, preserving heat, and stirring and refluxing for 5 hours; and (3) centrifugally separating out solid, washing by using 8 times of absolute ethyl alcohol, washing by using 18 times of deionized water, and drying at the temperature of 45 ℃ to prepare the modified porous carrier.
Wherein the volume concentration of the ethanol solution is 88%.
The weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-580 to the ethanol solution is 0.7:2.2:100.
3. Preparation of the active ingredient
Under the condition of avoiding light, putting the modified porous carrier into 90 weight parts of loading liquid, heating to 30 ℃, stirring and adsorbing for 20 hours at 50rpm, washing with 12 volumes of deionized water, and then drying at 45 ℃ under the condition of vacuum degree of 0.01MPa until the water content is 1 weight percent to obtain the active ingredient, namely the modified porous carrier loaded with diclofenac sodium.
Wherein the loading solution is an aqueous solution of diclofenac sodium, and the concentration of the diclofenac sodium is 4mg/mL.
4. Preparation of spinning solution
Adding the active ingredients into 80 times of deionized water in parts by weight, and uniformly stirring to obtain an active ingredient liquid; then adding the active component liquid, a silane coupling agent KH-792, sodium alginate and sodium carboxymethyl cellulose into the spinning solution, uniformly mixing, and filtering, defoaming and ripening to obtain the spinning solution.
Wherein the weight ratio of the active component liquid to the silane coupling agent KH-792 to the sodium alginate to the sodium carboxymethyl cellulose to the spinning solution is 12:0.8:0.5:0.4:90.
In the spinning solution, the content of alpha-fiber is 9.1%, the total alkali content is 2.8% and the viscosity is 35s.
5. Spinning process
Introducing the spinning solution into a spinning machine, spinning at a spinning speed of 16m/min, spinning into a coagulating bath at a temperature of 40 ℃, and after spinning solidification, carrying out desulfurization, water washing, oiling and drying to obtain the diclofenac sodium modified viscose large biological fiber in example 1.
Wherein, the content of each component in the coagulating bath is as follows: 60g/L of sulfuric acid, 120g/L of sodium sulfate, 22g/L of zinc sulfate and 7g/L of calcium chloride.
Example 2
The preparation method of the diclofenac sodium modified viscose large biological fiber specifically comprises the following steps:
1. preparation of porous support
Adding hexadecyl trimethyl ammonium bromide and polyethylene glycol PEG-6000 into deionized water at 38 ℃, stirring for 50min, continuously adding mesitylene, and stirring for 50 min; adding water glass at a feeding rate of 1.2g/min, and continuously stirring for 2.5h after the water glass feeding is finished; adjusting the pH value to 10.2 by adopting a hydrochloric acid solution with the concentration of 2.2mol/L, and keeping the temperature and standing for 14h; then transferring into a reactor, heating to 108 ℃, preserving heat and crystallizing for 25h; filtering out crystal grains, washing with 15 times of deionized water, drying at 85 ℃ for 20h, and roasting at 480 ℃ for 6h to obtain the porous carrier.
Wherein, the weight ratio of cetyl trimethyl ammonium bromide to polyethylene glycol PEG-6000 to mesitylene to water glass to deionized water is 1.7:0.09:0.9:10:75.
The water glass contains 27 weight percent of SiO 2 9.1wt% Na 2 O。
The porous carrier has a specific surface area of 1005m 2 And/g, pore size of 3.8nm.
2. Porous support modification
Putting the porous carrier into an ethanol solution with the weight of 40 times of that of the porous carrier, and uniformly dispersing the porous carrier by ultrasonic waves; under the stirring condition, simultaneously dripping a silane coupling agent KH-550 and a silane coupling agent KH-580 at a dripping rate of 2.5mL/min, and regulating the pH value to 4.6 by adopting acetic acid after the dripping is completed; stirring and heating to 55 ℃ under the protection of nitrogen and in a dark condition, preserving heat, and stirring and refluxing for 6.5h; and (3) centrifugally separating out solid, washing by using 9 times of absolute ethyl alcohol, washing by using 19 times of deionized water, and drying at 50 ℃ to prepare the modified porous carrier.
Wherein the volume concentration of the ethanol solution is 90%.
The weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-580 to the ethanol solution is 0.75:2.4:100.
3. Preparation of the active ingredient
Under the condition of avoiding light, putting the modified porous carrier into 95 times of load liquid by weight, heating to 32 ℃, stirring and adsorbing for 25 hours at 75rpm, washing with 14 times of deionized water by volume, and then drying at 50 ℃ under the condition of vacuum degree of 0.02MPa until the moisture content is 2wt%, thereby obtaining the active ingredient, namely the modified porous carrier loaded with diclofenac sodium.
Wherein the loading solution is an aqueous solution of diclofenac sodium, and the concentration of the diclofenac sodium is 5mg/mL.
4. Preparation of spinning solution
Adding the active ingredients into 85 times of deionized water in parts by weight, and uniformly stirring to obtain an active ingredient liquid; then adding the active component liquid, a silane coupling agent KH-792, sodium alginate and sodium carboxymethyl cellulose into the spinning solution, uniformly mixing, and filtering, defoaming and ripening to obtain the spinning solution.
Wherein the weight ratio of the active component liquid to the silane coupling agent KH-792 to the sodium alginate to the sodium carboxymethylcellulose to the spinning stock solution is 14:0.9:0.6:0.45:92.
In the spinning solution, the content of alpha-fiber is 9.2%, the total alkali content is 3% and the viscosity is 37s.
5. Spinning process
Introducing the spinning solution into a spinning machine, spinning at a spinning speed of 17m/min, spinning into a coagulating bath at a temperature of 42 ℃, and after spinning solidification, desulfurizing, washing, oiling and drying to obtain the diclofenac sodium modified viscose large biological fiber of the embodiment 2.
Wherein, the content of each component in the coagulating bath is as follows: 65g/L of sulfuric acid, 125g/L of sodium sulfate, 24g/L of zinc sulfate and 8g/L of calcium chloride.
Example 3
The preparation method of the diclofenac sodium modified viscose large biological fiber specifically comprises the following steps:
1. preparation of porous support
Adding hexadecyl trimethyl ammonium bromide and polyethylene glycol PEG-6000 into deionized water at 40 ℃, stirring for 60min, continuously adding mesitylene, and stirring for 60 min; adding water glass at a feeding rate of 1.5g/min, and continuously stirring for 3.5h after the water glass feeding is finished; adjusting the pH value to 10.5 by adopting a hydrochloric acid solution with the concentration of 2.5mol/L, and keeping the temperature and standing for 16h; then transferring into a reactor, heating to 110 ℃, preserving heat and crystallizing for 30 hours; the grains are filtered out, washed by deionized water with 16 times of volume, dried at 90 ℃ for 22 hours and baked at 500 ℃ for 7 hours, and the porous carrier is prepared.
Wherein, the weight ratio of cetyl trimethyl ammonium bromide to polyethylene glycol PEG-6000 to mesitylene to water glass to deionized water is 2:0.1:1:11:80.
The water glass contains 28 weight percent of SiO 2 9.5wt% Na 2 O。
The porous carrier has a specific surface area of 984m 2 And/g, pore size of 3.5nm.
2. Porous support modification
Putting the porous carrier into 45 times of ethanol solution in weight portion, and uniformly dispersing by ultrasonic waves; under the stirring condition, simultaneously dripping a silane coupling agent KH-550 and a silane coupling agent KH-580 at a dripping rate of 3mL/min, and regulating the pH value to 5 by adopting acetic acid after the dripping is completed; stirring and heating to 60 ℃ under the protection of nitrogen and in a dark condition, preserving heat, and stirring and refluxing for 8 hours; and (3) centrifugally separating out solid, washing by using 10 times of absolute ethyl alcohol, washing by using 20 times of deionized water, and drying at the temperature of 55 ℃ to prepare the modified porous carrier.
Wherein the volume concentration of the ethanol solution is 92%.
The weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-580 to the ethanol solution is 0.8:2.5:100.
3. Preparation of the active ingredient
Under the condition of avoiding light, the modified porous carrier is put into 100 weight portions of loading liquid, heated to 35 ℃, stirred and adsorbed for 30 hours at 80rpm, washed by 15 volumes of deionized water, and then dried at 55 ℃ under the condition of vacuum degree of 0.03MPa until the moisture content is 3 weight percent, so as to obtain the active ingredient, namely the modified porous carrier loaded with diclofenac sodium.
Wherein the loading solution is an aqueous solution of diclofenac sodium, and the concentration of the diclofenac sodium is 6mg/mL.
4. Preparation of spinning solution
Adding the active ingredients into 90 times of deionized water in parts by weight, and uniformly stirring to obtain an active ingredient liquid; then adding the active component liquid, a silane coupling agent KH-792, sodium alginate and sodium carboxymethyl cellulose into the spinning solution, uniformly mixing, and filtering, defoaming and ripening to obtain the spinning solution.
Wherein the weight ratio of the active component liquid to the silane coupling agent KH-792 to the sodium alginate to the sodium carboxymethyl cellulose to the spinning solution is 16:1:0.7:0.5:95.
In the spinning solution, the content of alpha-fiber is 9.3%, the total alkali content is 3.2% and the viscosity is 40s.
5. Spinning process
Introducing the spinning solution into a spinning machine, spinning at a spinning speed of 18m/min, spinning into a coagulating bath at a temperature of 45 ℃, and after spinning solidification, carrying out desulfurization, water washing, oiling and drying to obtain the diclofenac sodium modified viscose large biological fiber of the embodiment 3.
Wherein, the content of each component in the coagulating bath is as follows: 70g/L of sulfuric acid, 130g/L of sodium sulfate, 26g/L of zinc sulfate and 9g/L of calcium chloride.
Comparative example 1
The preparation method of the diclofenac sodium modified viscose large biological fiber adopting the embodiment 2 is characterized in that: 1) In the step of preparing the porous carrier, polyethylene glycol PEG-6000 and mesitylene are omitted; 2) The porous support modification step was omitted.
Comparative example 2
The preparation method of the diclofenac sodium modified viscose large biological fiber adopting the embodiment 2 is characterized in that: the steps of preparing the porous carrier and modifying the porous carrier are omitted, and the MCM-41 molecular sieve sold in the market is adopted for preparing the active ingredient.
Wherein the specific surface area of the commercial MCM-41 molecular sieve is 1000m 2 And/g, pore size of 3.6nm.
The diclofenac sodium modified viscose large biological fibers of examples 1-3 and comparative examples 1-2 were made into test bandages, and the content of the diclofenac sodium modified viscose large biological fibers in each test bandage was controlled to be 65%.
100 volunteers, aged 40-60 years, with non-articular soft tissue rheumatalgia and no allergy to diclofenac sodium, were selected, and the number of men and women in the volunteers was controlled to be half. 100 volunteers were randomized into 5 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 4-5 correspond to the application of the test bandages of comparative examples 1-2, 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 viscose large biological fibers of the examples 1-3 and the comparative examples 1-2 are respectively spun into viscose 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 viscose large biological fibers of the examples 1-3 and the comparative examples 1-2 are respectively spun into fabrics, cut into stability samples of 20cm x 20cm, and the content of the diclofenac sodium in each sample before the stability treatment is detected; then placing the stability samples in an illumination environment, standing for 30 days at 35 ℃, and detecting the content of diclofenac sodium in each sample after the stability treatment; and calculating the reduction rate of the diclofenac sodium content after standing for 30 days.
Wherein, the reduction rate of the diclofenac sodium content after standing for 30 days = [ (the diclofenac sodium content in the sample before the stabilization treatment-the diclofenac sodium content in the sample after the stabilization treatment)/the diclofenac sodium content in the sample before the stabilization treatment ] ×100%.
The specific test results are as follows:
further, the dry breaking strength, wet breaking strength, elongation load, whiteness, moisture regain and defect content of the diclofenac sodium-modified viscose large biological fibers prepared in examples 1 to 3 and comparative examples 1 to 2 were examined. The whiteness is detected by using a DatacolorSF600 color measuring and matching instrument under the condition that the temperature is 20 ℃ and the relative humidity is 65%. The moisture regain was measured using a Y802k eight basket oven with constant temperature, an electronic balance (accuracy 0.001 g), at a temperature of 20℃and a relative humidity of 65%.
The specific detection results are as follows:
it can be seen that the diclofenac sodium modified viscose large biological fiber of the embodiment 1-3 of the invention prepares a porous carrier by adopting specific raw materials and a process method, and carries out modification treatment on the porous carrier; the modified porous carrier is used for preparing active ingredients, the diclofenac sodium in the loading liquid is effectively adsorbed, and the prepared active ingredients are used for preparing spinning liquid; the method can effectively avoid the failure caused by the influence of factors such as added auxiliary agents, coagulation bath components, process conditions and the like in the modification and preparation processes of the viscose, has good modification effect on the viscose, and can realize the full and effective exertion of the effect of the diclofenac sodium; meanwhile, the combination of the diclofenac sodium and the viscose fiber is firm, the washing loss rate is low, and the long-acting slow release performance of the diclofenac sodium modified viscose large biological fiber is good.
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 (9)
1. The preparation method of the diclofenac sodium modified viscose large biological fiber is characterized by comprising the following steps of: preparing a porous carrier, modifying the porous carrier, preparing an active ingredient, preparing a spinning solution and spinning;
the preparation of the porous carrier comprises the steps of adding hexadecyl trimethyl ammonium bromide and polyethylene glycol PEG-6000 into deionized water at 35-40 ℃, stirring, continuously adding mesitylene, and uniformly stirring; adding water glass, and continuously stirring for 1.5-3.5h after the water glass is added; regulating pH value to 10-10.5, keeping temperature and standing for 12-16h; then transferring into a reactor, heating to 105-110 ℃, preserving heat and crystallizing for 20-30h; filtering out crystal grains, washing with deionized water, drying, and roasting to obtain porous carrier;
the porous carrier is modified, the porous carrier is put into ethanol solution with the weight of 35-45 times of that of the porous carrier, and the porous carrier is uniformly dispersed; under the stirring condition, simultaneously dripping a silane coupling agent KH-550 and a silane coupling agent KH-580, and adjusting the pH value to 4.5-5 after the dripping is completed; stirring and heating to 50-60 ℃ under the protection of nitrogen and in the dark, preserving heat, and stirring and refluxing for 5-8h; centrifuging to separate out solid, washing the solid with absolute ethyl alcohol and deionized water, and drying to obtain a modified porous carrier;
the preparation of the active ingredient comprises the steps of adding a modified porous carrier into 90-100 times of load liquid in parts by weight, heating to 30-35 ℃, stirring and adsorbing for 20-30 hours, washing with deionized water, and vacuum drying until the water content is 1-3wt% to obtain the active ingredient;
in the preparation of the active ingredient, the loading liquid is an aqueous solution of diclofenac sodium;
the preparation method comprises the steps of preparing spinning solution, adding active ingredients into 80-90 times of deionized water by weight, and uniformly stirring to prepare active ingredient solution; then adding the active component liquid, a silane coupling agent KH-792, sodium alginate and sodium carboxymethyl cellulose into the spinning solution, uniformly mixing, and filtering, defoaming and ripening to obtain a spinning solution;
and spinning the fiber by adopting a spinning solution to perform spinning treatment to obtain the diclofenac sodium modified viscose large biological fiber.
2. The method for preparing the diclofenac sodium modified viscose large biological fiber according to claim 1, wherein in the preparation of the porous carrier, the feeding rate of the water glass is 1-1.5g/min;
the water glass contains 26-28wt% of SiO 2 8.7 to 9.5 weight percent of Na 2 O。
3. The preparation method of the diclofenac sodium modified viscose large biological fiber according to claim 1, wherein in the preparation of the porous carrier, the weight ratio of cetyl trimethyl ammonium bromide to polyethylene glycol PEG-6000 to mesitylene to water glass to deionized water is 1.5-2:0.08-0.1:0.8-1:9-11:70-80;
the specific surface area of the porous carrier is 917-1005m 2 And/g, pore diameter is 3.4-3.8nm.
4. The method for preparing the diclofenac sodium modified viscose large biological fiber according to claim 1, wherein in the modification of the porous carrier, the dripping rate of the silane coupling agent KH-550 is 2-3mL/min;
the dropping rate of the silane coupling agent KH-580 is 2-3mL/min.
5. The method for preparing the diclofenac sodium modified viscose macrobiological fiber according to claim 1, wherein in the modification of the porous carrier, the volume concentration of the ethanol solution is 88-92%;
the weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-580 to the ethanol solution is 0.7-0.8:2.2-2.5:100.
6. The method for preparing the diclofenac sodium modified viscose large biological fiber according to claim 1, wherein the concentration of the diclofenac sodium in the loading solution in the preparation of the active ingredient is 4-6mg/mL.
7. The preparation method of the diclofenac sodium modified viscose large biological fiber according to claim 1, wherein in the preparation of the spinning solution, the weight ratio of the active ingredient solution to the silane coupling agent KH-792 to the sodium alginate to the sodium carboxymethylcellulose to the spinning solution is 12-16:0.8-1:0.5-0.7:0.4-0.5:90-95;
in the spinning solution, the content of alpha-fiber is 9.1-9.3%, the total alkali content is 2.8-3.2%, and the viscosity is 35-40s.
8. The method for preparing the diclofenac sodium modified viscose large biological fiber according to claim 1, which is characterized in that spinning is carried out by introducing spinning solution into a spinning machine, spinning at a spinning speed of 16-18m/min, spinning into a coagulating bath at a temperature of 40-45 ℃, desulfurizing, washing, oiling and drying after spinning solidification, thus obtaining the diclofenac sodium modified viscose large biological fiber;
in the spinning, the content of each component in the coagulating bath is as follows: 60-70g/L of sulfuric acid, 120-130g/L of sodium sulfate, 22-26g/L of zinc sulfate and 7-9g/L of calcium chloride.
9. A diclofenac sodium modified viscose macrobiological fiber, characterized in that it is produced by the preparation method according to any one of claims 1-8.
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