Based on supercritical CO2Processing method for making cellulose fibre possess anti-inflammatory function by fluid technology
Technical Field
The invention relates to a supercritical fluid technologyA process for making cellulose fibres functional, more particularly a process based on supercritical CO2A process for imparting anti-inflammatory properties to cellulosic fibers by fluid technology.
Background
In recent years, with the increasing quality of life, the demands of people on clothes are more and more diversified, for example, from the first cold protection and warm keeping to the later beautiful fashion, and meanwhile, the demands of consumers on the comfort and the functionality of the clothes are gradually increased. The existing functional clothes mainly lean on the functions of water resistance, ultraviolet resistance, ventilation, static resistance, moisture absorption, quick drying, quick perspiration, sun protection, mosquito prevention and the like, the research and development on the beauty functional clothes are relatively few, and the skin care products and the textiles are combined to develop the characteristic beauty textiles, such as the textiles with the functions of moisture preservation, coolness, antibiosis, anti-inflammation, weight reduction, insect expelling and the like, and the beauty functional clothes can be used for daily wearing of people and can greatly meet the psychological and physiological requirements of consumers.
The existing development of the fabric with aesthetic property generally adopts chemical finishing methods including coating co-extrusion method, composite finishing method, complexation method and the like (Handbook of Medical Textiles, 2011,153), all of which involve chemical reactions, have few kinds of functional substances which can be reliably applied (mainly limited to hydrophilic processing and the like), and have relatively complex finishing process and single function, and cannot form a durable and controllable slow-release effect. In contrast, the microcapsule technology is adopted to control release, and the functional drugs can be prepared in various types, but the functional drugs are required to be wrapped by the encapsulation material, various physical and chemical reactions are involved, the requirements on wall materials, core materials and particle sizes are required (knitting industry, 2017(09):5-7), the capsule takes the wall thickness as a main component, the relative content of the functional content is very small, and the resin is bonded on the fiber product, so that the hand feeling of the textile is influenced. Therefore, there is a need for a new method for preparing a cosmetic textile that overcomes the above-mentioned problems of the prior art.
Combining the current green and pollution-free concept, if the beauty textile can be produced in a more environment-friendly and simple way, the beauty textile can be promotedA better development of the field. The supercritical fluid technology is a recognized green and environment-friendly technology, namely supercritical CO2The fluid has low polarity, good wettability, no toxicity and no combustion, the critical pressure is 7.383MPa, the critical temperature is 31.06 ℃ (Textile Research Journal,1994,64(7), 371-. In addition, for the clothing textiles, the textiles processed by natural Materials have better wearing comfort (Applied Composite Materials,2000,7(5),415 and 420), and the development of the beauty textiles by taking the cellulose fibers as the base Materials is more in line with the current environmental protection and comfort concept.
Supercritical CO2The fluid is successfully applied to a plurality of fields of food sanitation, chemical materials, medical pharmacy, environmental protection and the like, and has good effect.
Supercritical CO2Use of a fluid in textile processing, for cellulosic fibre materials, using supercritical CO2The fluid can carry a large amount of functional substances (powder or fluid) to permeate into the microstructure of the fiber material, and the swelling performance of the fiber material can be utilized to accept the supercritical CO2The functional substance is applied and retained by the characteristics of fluid temperature and pressure control, and the functional substance is screened to ensure that the functional substance and the fiber material have proper compatibility, so that the release rate of the functional substance in the fiber serving as a carrier is regulated, and the fiber modified by; and is insensitive to practical efficiency in terms of application position and uniformity of application amount, and is more than supercritical CO2Fluid staining is easier. Furthermore, supercritical CO2The fluid technology can take the cellulose fiber as a macro-capsule, and directly load the functional substance into the macro-capsule without adding other auxiliary materials.
Supercritical CO which is currently known2The fluid extraction, dyeing, drug loading and other technologies can adopt supercritical CO2Fluid technology preparation functionThe chemical fiber provides reference for hardware equipment guarantee, technology transfer and use and scientific theory.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The functionality of the cosmetic cellulose fiber has various categories, such as antibiosis, antioxidation, slimming, whitening, anti-inflammation, anti-wrinkle, insect expelling, moisture retention, coolness, cancer resistance and the like.
Therefore, the invention provides a supercritical CO-based catalyst2A process for the fluid technology of imparting anti-inflammatory properties to cellulosic fibres, characterized in that it comprises the following steps:
1) pre-swelling or pre-treating the cellulose fibers;
2) addition of adjuvants to increase the anti-inflammatory drug in supercritical CO2Solubility in fluids, for poorly soluble supercritical CO2The hydrophilic anti-inflammatory drug is dissolved in supercritical CO indirectly by supercritical microemulsion/reverse micelle method2In a fluid;
3) adding antiinflammatory agent into the tank of high-pressure equipment, removing air, and introducing CO2Raising the pressure in the container to 8-30 MPa at 32-120 ℃ to obtain supercritical CO2A fluid, thereby soaking the cellulose fibers in the supercritical fluid;
4) the anti-inflammatory agent is dissolved in supercritical CO2The fluid enters the pre-swollen cellulose fibers and carries the supercritical CO2There is continuous relative motion between fluid and the cellulose fibre, and the anti-inflammatory drug stays in the amorphous area inside the cellulose fibre after the pressure relief, forming the drug-loaded cellulose fibre that can slowly release.
In one embodiment of the present invention, the cellulose fiber includes natural cellulose fiber and regenerated cellulose fiber, the natural cellulose fiber includes cotton fiber and hemp fiber (including ramie fiber, hemp fiber, flax fiber, apocynum venetum fiber, etc.), the regenerated cellulose fiber uses natural cellulose (cotton, hemp, bamboo, tree, shrub, etc.) as raw material, does not change its chemical structure, only changes the physical structure of the natural cellulose, thereby producing regenerated cellulose fiber with better performance, including viscose fiber, high wet modulus viscose fiber (viscose fiber, etc.) and solvent spinning regenerated cellulose fiber (Lyocell fiber, tencel fiber, etc.).
In another embodiment of the invention, for some cellulose fibers, supercritical CO2The fluid is difficult to swell and permeate, so that the drug loading of the fiber is low, and therefore, the cellulose fiber enters supercritical CO2The fluid device is preceded by a pre-swelling treatment to increase the amorphous regions of the cellulose fibers. The methods of pre-swelling are as follows:
1) preparing an N-methylmorpholine-N-oxide (NMMO) aqueous solution with the mass fraction of 30-80%, immersing cellulose fibers in the aqueous solution with the bath ratio of 1: 15-1: 35, setting the temperature to be 60-90 ℃ and the time to be 10-80 min;
2) preparing NaOH aqueous solution with the concentration of 10% -20%, immersing cellulose fibers in the NaOH aqueous solution at the bath ratio of 1: 25-1: 40, setting the temperature to be-10-20 ℃, and keeping the time for 10-80 min;
3) preparing a water-containing ionic liquid 1-butyl-3-methylimidazole chloride salt solution with the water content of 2% -5%, immersing cellulose fibers in the solution at the bath ratio of 1: 25-1: 40, setting the temperature to be 60-120 ℃, and keeping the time to be 10-80 min.
All three of the above methods can pre-swell the cellulose fiber, NMMO/H2The pollution of the O solvent is low, the solubility of the cellulose fiber is high, and the recovery rate of the solvent is high; NaOH/H2The O solvent has wider source and low price, and can effectively remove natural impurities such as pectin, wax and the like on the cellulose fiber and foreign impurities such as sizing agent, grease and the like; the ionic liquid is a novel cellulose fiber solvent, has the advantages of low melting point, high thermal stability, low vapor pressure, strong designability and the like, and different swelling agents can be selected according to specific needs in practical application.
In another embodiment of the present invention, the pretreatment of the cellulose fibers further comprises live grafting. When the interaction between the anti-inflammatory drug and the cellulose fiber is poor, some active groups need to be introduced, so that the interaction force between the anti-inflammatory drug and the cellulose fiber is increased, and the drug loading capacity is increased. In addition, when the anti-inflammatory drug interacts well with the cellulose fiber, but higher drug loading is desired, living grafting can be performed to further increase the drug loading. The active grafting is specifically that cellulose fibers are cleaned, dried, balanced and weighed, added into a reactor, added with water with corresponding mass, the ratio of the cellulose fibers to the water is 1: 1.5-1: 5.0, introduced with nitrogen for protection, and added with an initiator Na2SO3/K2S2O8The amount is 1.0-4.0%. And (3) reacting for 20-40 min, adding a 2-acrylic acid amino-2-methyl propanesulfonic Acid (AMPS) monomer, wherein the ratio of the monomer to the cellulose fiber is 0.8: 1-2.0: 1, reacting for 1.0-6.0H, at the temperature of 30-60 ℃, cooling, filtering, washing with water, washing with acetone and ether, and drying to obtain the cellulose fiber/AMPS graft copolymer. The active grafting of cellulose is carried out by grafting more polar groups or groups with stronger polarity while keeping most of physicochemical characteristics, such as basic shape of fiber, so that the cellulose has better interaction force with the drug, the drug loading is increased, and the slow release performance is improved.
In another embodiment of the invention, the adjuvants are methanol, ethanol and acetone. The method of the supercritical microemulsion/reverse micelle is specifically to use sodium bis (2-ethylhexyl) sulfosuccinate (AOT), ethanol, water and supercritical CO2The method comprises the steps of preparing a supercritical microemulsion formed by a fluid, wherein AOT is a main surfactant, ethanol is a cosurfactant, preparing 10-90% ethanol solution by using water, and then preparing 0.01-0.1 mol/L AOT/ethanol solution, wherein the bath ratio ranges from 1:25 to 1:50, and the method expands the selection range of medicines.
In another embodiment of the present invention, the anti-inflammatory agent may be selected from the group consisting of tea polyphenols, indolacetic acid, perillyl alcohol, cysteine, gallic acid, methionine, lichenin, panthenol, licorice flavonoids, cinchona acid, arginine, lactucaSugar, melatonin or isoleucine. Anti-inflammatory drug derived from CO2The molecular and cellulose fiber structures themselves are screened from the viewpoints of polarity, molecular weight, specific groups, and the like. The screened anti-inflammatory drug can improve the effect of the anti-inflammatory drug in supercritical CO2The treatment efficiency in the fluid is shortened, the time is shortened, the drug loading is increased, and a more excellent slow release effect is formed. In terms of polarity, it should contain a part of polar groups and a part of non-polar groups, so as to maintain the anti-inflammatory drug in supercritical CO2The fluid has certain solubility and can maintain certain interaction force with the cellulose fibers; in terms of molecular weight, substances with a smaller molecular weight between 30 and 600 should be selected; for specific groups, the CO-philic may be chosen2A group of (a), such as a carbonyl group C (C ═ O) -), an ether bond (C-O-C), an ester group (C- (CO) -O-C), a carbon-sulfur bond (C ═ S), and the like; the cellulose fiber contains a large amount of polar group hydroxyl (-OH), and optional polar group amino (-NH)2) Imino (-NH-), hydroxyl (-OH), carboxyl (-COOH), etc.
In another embodiment of the present invention, the anti-inflammatory agent is added in an amount of 1% to 15% by mass of the cellulose fiber.
In another embodiment of the invention, supercritical CO2The fluid high-pressure equipment is internally provided with a special medicine groove and contains a camera for taking a picture, and the camera can be used for monitoring the state of the anti-inflammatory medicine in the fluid and observing the change of the anti-inflammatory medicine in the system more intuitively.
In another embodiment of the present invention, where the anti-inflammatory agent has poor accessibility to the cellulose fiber, the anti-inflammatory agent does not readily penetrate into the interior of the cellulose fiber, and the rate of steady-state pressure application to add the anti-inflammatory agent is slow, the method may further comprise applying supercritical CO via a pressure pump2The method comprises the following steps of (1) applying pulse pressure to fluid, specifically, enabling cellulose fibers to be in a supercritical fluid for 10-40min, wherein the temperature is 60-120 ℃, and the pressure is 8-15 MPa; then, the pressure is increased to 15-30 MPa at the speed of 0.5-1.0 MPa/min; and stopping heating after the experiment is finished, and reducing the pressure at the speed of 1.0-4.0 MPa/min until the experiment is finished. This step can increase the amount of the functional substance in the cellulose as a carrierInfiltration capacity inside the fiber. According to the diffusion quantification, the penetration of the functional substance in the fiber is also influenced by the concentration gradient, so that high concentration can be realized locally, and the penetration of the functional substance and the improvement of the drug-loading rate are facilitated. Because the functional substance is formed by supercritical CO when the pressure is increased2The fluid carries deeper structural levels that can penetrate into the fiber, and the saturation that can be accommodated decreases as the pressure decreases, resulting in an increase in the local concentration gradient of the functional substance at the microstructure inside the fiber, and also contributing to an increase in the accessibility and penetration of the functional substance into the fiber. Compared with constant pressure control, the pulse pressure can improve the drug loading rate by 1-10%, and the slow release time can be prolonged by 720-20000 min.
The invention is processed by supercritical CO2The fluid technology can effectively carry the anti-inflammatory drugs into the surface and the interior of the cellulose fiber, and the supercritical CO2The swelling action of the fluid can further enlarge the amorphous region of the cellulose fibers and increase the effective volume, so that more anti-inflammatory drugs enter the cellulose fibers; finally, the cellulose fiber is used as a drug-loading giant capsule and has good slow release effect. Compared with the prior method that the anti-inflammatory drug is wrapped by the microcapsule (cyclodextrin and chitosan) and then is bonded with the fiber in a bond mode, the method has better hand feeling.
Drawings
Fig. 1a and 1b show the release amount of tea polyphenol, which is an anti-inflammatory drug, of example 1 and comparative example 1, respectively, as a function of time.
Fig. 2a and 2b show the release of the anti-inflammatory drug indole acetic acid of example 2 and comparative example 2, respectively, as a function of time.
Fig. 3a and 3b show the time-dependent release profiles of perillyl alcohol, the anti-inflammatory drugs of example 3 and comparative example 3, respectively.
Fig. 4a and 4b show the anti-inflammatory drugs of example 4 and comparative example 4, respectively, and the release amount of gallic acid is plotted with time.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1: supercritical CO2Method for loading anti-inflammatory drug tea polyphenol to viscose fiber by fluid
Firstly, washing viscose fabric with ethanol and deionized water, drying and balancing for 24H, weighing tea polyphenol according to 7.5% of the weight of the viscose fabric, preparing 20% ethanol solution with water, preparing 0.04mol/L AOT/ethanol solution, and putting the solution into a clean container to prepare microemulsion.
The prepared microemulsion is put into a medicine groove of high-pressure equipment, and then the viscose fabric is put into the medicine groove. Using a cooling tank to feed CO2Gas CO flowing out of steel cylinder2Cooling to form liquid, setting the pressure of the high-pressure equipment at 19MPa and the temperature at 60 ℃, and cooling to form CO2Converting into supercritical fluid, soaking and balancing for 4.5H, and finishing the experiment to obtain the viscose fiber loaded with tea polyphenol. The drug loading of the viscose fiber is 6.8 percent.
In order to analyze the sustained release performance of the viscose fiber loaded with tea polyphenol, two pieces of supercritical CO with the size of 4.5cm multiplied by 4.5cm are cut2The fluid treated viscose fabric is put into 150ml of 0.9% physiological saline stored in a beaker, stirred at the speed of 65rpm at 37 ℃, and the change curve of the release amount of the tea polyphenol with time measured by an ultraviolet spectrophotometry calibration method is shown in figure 1a, which shows that the tea polyphenol can be continuously released in the physiological saline for a long time, and in the actual use, the tea polyphenol can be released to the skin of a human body when trace sweat exists on the surface of the skin of the human body, but the tea polyphenol can not be released in a dry state.
Comparative example 1: the tea polyphenol is directly put into a medicine groove of high-pressure equipment without a microemulsion mode, other conditions are completely the same as the method of the embodiment 1, the medicine-loading rate of the finally obtained viscose fiber is 3.8%, and a slow-release curve is shown in figure 1 b.
Comparison of example 1 with comparative example 1 shows that the microemulsion method can increase drug loading and prolong sustained release time.
Example 2: supercritical CO2Method for loading anti-inflammatory drug indoleacetic acid to fibrilia by fluid
Weighing a proper amount of fibrilia, preparing a water-containing ionic liquid 1-butyl-3-methylimidazole chloride salt solution with the water content of 2%, immersing the fibrilia fiber in the solution at the bath ratio of 1:25, setting the temperature to be 65 ℃, standing for 30min, and taking out the fibrilia after the end.
Cleaning the pre-swelled fibrilia with ethanol and deionized water, drying and balancing for 24H, weighing indoleacetic acid according to 8.5% of the weight of the fibrilia, preparing 40% ethanol solution with water, preparing 0.06mol/L AOT/ethanol solution, and putting the solution into a clean container to prepare the microemulsion.
The prepared microemulsion is put into a medicine groove of high-pressure equipment, and then the fibrilia is put into the medicine groove. And (3) cooling the gas carbon dioxide flowing out of the carbon dioxide steel cylinder into liquid by using a cooling tank, setting the pressure of a high-pressure device to be 18Mpa, setting the temperature to be 90 ℃, changing the carbon dioxide into a supercritical fluid, and soaking and balancing for 1.5H, and then finishing the experiment to obtain the fibrilia loaded with the indoleacetic acid. The drug loading of the fibrilia is 4.6%.
In order to analyze the slow release performance of the fibrilia loaded with the indoleacetic acid, two supercritical CO blocks with the sizes of 4.5cmx4.5cm are cut2The fluid-treated linen fabric was placed in 150ml of 0.9% physiological saline in a beaker, and the release of indole acetic acid was observed as a time-dependent curve, with the slow release curve shown in fig. 2 a.
Comparative example 2: the fibrilia is not subjected to the pre-swelling treatment of the aqueous ionic liquid, and other conditions are completely the same as the method in the example 2, so that the obtained fibrilia drug-loading rate is 1.8%, and the slow-release curve is shown in fig. 2 b.
Comparison of example 2 with comparative example 2 shows that pre-swelling can increase drug loading and prolong the time of sustained release.
Example 3: supercritical CO2Method for loading anti-inflammatory drug perillyl alcohol into modal fiber by fluid
Firstly, cleaning a proper amount of modal fabric with ethanol and deionized water, drying and balancing for 24H, weighing perilla alcohol according to the weight of 7.5% of the modal fabric, putting the weighed perilla alcohol into a medicine tank of high-pressure equipment, adding acetone of which the weight is 0.1% of the modal fabric, and then putting the modal fabric. The gaseous carbon dioxide discharged from the carbon dioxide cylinder is cooled to liquid by a cooling tank.
Setting the pressure of a high-pressure device at 12Mpa and 35 ℃, converting carbon dioxide into supercritical fluid, soaking and balancing for 25min, and increasing the pressure to 26MPa at the speed of 0.6 MPa/min; after the completion of the experiment, the heating was stopped, and the pressure was decreased at a rate of 1.0MPa/min, thereby obtaining the anti-inflammatory perillyl alcohol-loaded modal fiber. The drug loading of the modal fiber was 7.0%.
In order to analyze the sustained release performance of the perillyl alcohol-loaded modal fiber, two 4.5 cmx4.5cm-sized supercritical CO blocks were cut2The fluid-treated modal fabric was placed in 150ml of 0.9% physiological saline in a beaker, and the release of perillyl alcohol was observed as a time-dependent curve, with the slow release curve shown in FIG. 3 a.
Comparative example 3: the pressure was set to a constant value and maintained at 26Mpa, the total impregnation time was identical to the above experimental time, i.e., 60min, and the other conditions were exactly the same as the method of example 3, and the final drug loading of the modal fiber was 4.3%, and the sustained release profile is shown in fig. 3 b.
A comparison between example 3 and comparative example 3 shows that the pulse pressurization can increase the drug loading amount and prolong the sustained-release time.
Example 4: supercritical CO2Method for loading anti-inflammatory drug and gallic acid into cotton fiber by fluid
Weighing an appropriate amount of cotton fiber, cleaning, drying, balancing, weighing, adding into a reactor, adding water with corresponding mass, wherein the ratio of cotton fiber to water is 1:1.8, introducing nitrogen for protection, and adding initiator Na2SO3/K2S2O8The dosage is 2.0%. Reacting for 35min, adding 2-acrylic acid amino-2-methyl propanesulfonic Acid (AMPS) monomer, wherein the ratio of the monomer to cotton fiber is 1.2:1, reacting for 3.5H at 40 ℃, cooling, filtering, washing with water, washing with acetone and ether, and drying to obtain the cotton fiber/AMPS graft copolymer.
Washing the copolymer with ethanol and deionized water, drying, balancing for 24H, weighing gallic acid according to 8.2% of the weight of the copolymer, placing the gallic acid into a medicine tank of a high-pressure device, and then placing the copolymer. Cooling the gas carbon dioxide flowing out of the carbon dioxide steel cylinder into liquid by using a cooling tank, setting the pressure of a high-pressure device to be 22Mpa and the temperature to be 90 ℃, converting the carbon dioxide into supercritical fluid, soaking and balancing for 1.5H, and finishing the experiment to obtain the copolymer loaded with the gallic acid. The drug loading of the copolymer was 5.1%.
To analyze the sustained release properties of the copolymer loaded with gallic acid, two 4.5cmx4.5cm sized blocks of supercritical CO were clipped2The fluid-treated copolymer was placed in 150ml of 0.9% physiological saline in a beaker, and the release of gallic acid was observed as a time-dependent curve, and the sustained-release curve was shown in FIG. 4 a.
Comparative example 4: the cotton fiber was not grafted, and the other conditions were completely the same as in example 4, and the drug loading of the finally obtained cotton fiber was 1.6%, and the sustained release curve is shown in fig. 4 b.
Comparison of example 4 and comparative example 4 shows that the graft treatment can increase the drug loading and prolong the sustained-release time.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.