CN108729217A - One kind being based on supercritical CO2Fluid technique makes processing method of the cellulose fibre with whitening function - Google Patents
One kind being based on supercritical CO2Fluid technique makes processing method of the cellulose fibre with whitening function Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/228—Cyclic esters, e.g. lactones
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- Medicinal Preparation (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention relates to one kind being based on supercritical CO2Fluid technique makes processing method of the cellulose fibre with whitening function comprising：1) pre-swollen or pretreatment are carried out to cellulose fibre；2) addition auxiliary agent is to increase whitening medicaments in supercritical CO2Solubility in fluid, for being not readily dissolved in supercritical CO2Hydrophilic class whitening medicaments so that it is dissolved in supercritical CO indirectly using the method for overcritical microemulsion/reverse micelle2In；3) whitening medicaments are added in the drug slot of high-tension apparatus, exclude air, is passed through CO2, at 32~120 DEG C, container inner pressure is risen into 8~30MPa, obtains supercritical CO2Fluid, to which cellulose fibre is immersed in supercritical CO2In；4) whitening medicaments are by being dissolved in supercritical CO2Enter the cellulose fibre being swollen in advance in fluid, and carries medicine supercritical CO2There is ongoing relative motion between cellulose fibre, whitening medicaments rest on inside cellulose fibre in unformed area after pressure release, form the drug-loading fibre cellulose fiber that can be sustained.
Description
Technical field
The present invention relates to one kind to make cellulose fibre have functional processing method based on supercritical fluid technique, more
Body it is related to a kind of based on supercritical CO2Fluid technique makes processing method of the cellulose fibre with whitening function.
Background technology
In recent years, with the continuous rising of people's quality of the life, demand of the people to clothes is also more and more diversified, such as
By initial warming finally beautiful and stylish, while consumer also gradually increases the comfort of clothes with functional requirements
Add.Existing functional clothing is mainly biased to waterproof, UV resistance, ventilative, antistatic, hydroscopic fast-drying, rapid perspiration, sun-proof, anti-
The functions such as mosquito, and it is relatively on the low side for the research and development of esthetics function clothes, and skin care item and textile are combined and are developed
The esthetics textile of characteristic, such as with moisturizing, nice and cool, antibacterial, anti-inflammatory, weight reducing, whitening function textile, be used for people
Everyday general purpose, it will meet the psychology and psychological need of consumer significantly.
The existing exploitation about esthetics textile includes generally coating co-extrusion platen press using chemical finishing method, compound
Finishing method, complexometry etc. (Handbook of Medical Textiles, 2011,153), these methods all refer to chemical anti-
It answers, the functional materials type that can reliably apply is less (being limited primarily to the processing such as hydrophiling), and arrangement process is relative complex, work(
Can be single, lasting and controllable slow release effect cannot be formed.In contrast the controllable release of microcapsules technology is used, and can be made
Standby functional drug type is more, but it needs to wrap up functional drug wherein by coating material, is related to therebetween various
Physics, chemical reaction, wall material, core material, grain size are all required (《Hosiery industry》, 2017 (09):5-7), and the composition of capsule
Using wall thickness as main component, the relative amount of functional content is seldom, and by resin-bonding on fibre, can influence
The feel of textile.Therefore, it is necessary to a kind of new methods to prepare esthetics textile, to overcome above-mentioned exist in the prior art
The problem of.
In conjunction with current green, pollution-free theory, if esthetics weaving can be produced in such a way that one kind is more environmentally-friendly, simple
Product, it will this field is promoted preferably to develop.Supercritical fluid technique is a kind of generally acknowledged green, green technology, overcritical
CO2Fluid polarity is low, wellability is good, nontoxic, non-ignitable, and critical pressure 7.383MPa, critical-temperature are 31.06 DEG C of (Textile
Research Journal, 1994,64 (7), 371-374) it, with the mobility as gas and the Portability as liquid, can be incited somebody to action
Small-molecule substance (such as dyestuff, drug) is applied in polymer (Green Chemistry, 2008,10 (10), 1061-1067),
Water and organic solvent is replaced to use as environmental-friendly solvent.For taking textile, processed by natural material
Made of textile have better wearing comfort (Applied Composite Materials, 2000,7 (5), 415-
420) and esthetics textile is developed as base material using cellulose fibre and more meets environmentally friendly, comfortable theory instantly.
Supercritical CO2Fluid oneself be successfully applied to multiple necks such as food hygiene, chemical materials, medical treatment and pharmacy, environmental protection
Domain, and obtain good effect.
Supercritical CO2Application of the fluid in terms of textile processing utilizes supercritical CO for cellulosic fibre material2Stream
Physical efficiency carries in the microstructure of larger amount of functional materials (powder or fluid) infiltrated fiber material, and utilizes its undulation degree
The swelling behavior of material is subjected to supercritical CO2Fluid temperature (F.T.), the characteristic of pressure control apply and retain functional materials, and lead to
Screening functional materials are crossed, make have compatibility appropriate between functional materials and fibrous material, thus regulatory function substance
The rate discharged in the fiber as carrier has simple and convenient processing method, may modify more kinds of fibers, applied amount and sustained release speed
The advantage that rate is adjustable；And it is insensitive to actual efficacy in terms of the uniformity of application position and applied amount, than supercritical CO2
Fluid dyeing is more prone to.In addition, supercritical CO2Fluid technique can be using cellulose fibre as huge capsule, directly will be functional
Substance is loaded into wherein, it is not necessary that other auxiliary materials are added.
The supercritical CO grasped at present2The technologies such as fluid extraction, dyeing, load medicine can be using supercritical CO2Fluid skill
Art prepares the reference that functional fiber provides hardware device guarantee, technique transfers use and scientific theory.
The information for being disclosed in the background of invention technology segment is merely intended to deepen the reason of the general background technology to the present invention
Solution, and it is known to those skilled in the art existing to be not construed as recognizing or imply that the information is constituted in any form
Technology.
Invention content
Esthetics cellulose fibre it is functional there are many classification, as antibacterial, anti-oxidant, weight reducing, whitening, it is anti-inflammatory, crease-resistant,
Expelling parasite, moisturizing, nice and cool, anticancer etc., present invention is generally directed to the processing methods of whitening fiber cellulose fiber.
Therefore, the present invention provides a kind of based on supercritical CO2Fluid technique makes cellulose fibre have adding for whitening function
Work method, which is characterized in that the described method comprises the following steps：
1) pre-swollen or pretreatment are carried out to cellulose fibre；
2) addition auxiliary agent is to increase whitening medicaments in supercritical CO2Solubility in fluid, it is overcritical for being not readily dissolved in
CO2The hydrophilic class whitening medicaments of fluid make it be dissolved in supercritical CO indirectly using the method for overcritical microemulsion/reverse micelle2Fluid
In；
3) whitening medicaments are added in the drug slot of high-tension apparatus, exclude air, is passed through CO2, will at 32~120 DEG C
Container inner pressure rises to 8~30MPa, obtains supercritical CO2Fluid, to which cellulose fibre is immersed in supercritical CO2Fluid
In；
4) whitening medicaments are by being dissolved in supercritical CO2Enter the cellulose fibre being swollen in advance in fluid, and carries medicine
Supercritical CO2There is ongoing relative motion between fluid and cellulose fibre, whitening medicaments rest on cellulose after pressure release
In the unformed area of fibrous inside, the drug-loading fibre cellulose fiber that can be sustained is formed.
In one embodiment of the invention, the cellulose fibre includes native cellulose fibre and regenerated cellulose
Fiber, native cellulose fibre include that (including ramee, hemp, flax fiber, bluish dogbane are fine for cotton fiber and flaxen fiber
Dimension etc.), regenerated celulose fibre is not change its chemistry with native cellulose (cotton, fiber crops, bamboo, tree, shrub etc.) for raw material
Structure only changes the physical arrangement of native cellulose, to manufacture the better regenerated celulose fibre of performance, including it is viscous
Glue fiber, koplon (viscose rayon etc.) and solvent spin regenerated celulose fibre, and (Lyocell fiber, tencel are fine
Dimension etc.).
In another embodiment of the present invention, for some fibre cellulose fiber, supercritical CO2Fluid is difficult to it molten
Swollen and infiltration, causes fiber drugloading rate low, therefore enter supercritical CO in cellulose fibre2Before fluid device, first to its into
Row pre-swollen processing, with the amorphous region of this increased fiber cellulose fiber.The preswollen method has following several：
1) N-methylmorpholine-N- oxides (NMMO) aqueous solution is prepared, mass fraction is 30~80%, by cellulose fibre
It is immersed, bath raio ranging from 1:15~1:35,60~90 DEG C of set temperature, 10~80min of time；
2) NaOH aqueous solutions are prepared, cellulose fibre is immersed by concentration 10%~20%, bath raio ranging from 1:25~
1:40, -10 DEG C of set temperature~20 DEG C, 10~80min of time；
3) aqueous ionic liquid 1-butyl-3-methyl imidazolium chloride solution is prepared, moisture content is 2%~5%, by fiber
Cellulose fiber is immersed, bath raio ranging from 1:25~1:40,60 DEG C~120 DEG C of set temperature, 10~80min of time.
Three of the above mode can carry out pre-swollen, NMMO/H to cellulose fibre2O solvent contaminations are low, cellulose fiber
It is high to tie up solubility height, solvent recovering rate；NaOH/H2O solvent sources are more extensive, cheap, can effectively remove cellulose
Pectin, wax on fiber, etc. natural impuritys, the exogenous impurities such as slurry, grease；And ionic liquid is a kind of novel cellulose
Fiber solvent has the advantages such as low melting point, high thermal stability, low-steam pressure, designability be strong, can be according to specific in practical application
It needs to select different swellers.
In another embodiment of the present invention, the pretreatment of cellulose fibre further includes active grafting.When whitening class
Interaction between drug and cellulose fibre is poor, needs to introduce some active groups, increases whitening medicaments and fibre with this
The interaction force of cellulose fiber, to increase drugloading rate.In addition, when whitening medicaments and cellulose fibre interaction are preferable,
But when needing to obtain higher drugloading rate, activity grafting can be carried out and further increase drugloading rate.The activity, which is grafted, is specially
Cellulose fibre dries balance weighing after cleaning, and is added in reactor, adds the water of corrresponding quality, cellulose fibre and water
Ratio range is 1:1.5~1:5.0, lead to nitrogen protection, initiator Na is added2SO3/K2S2O8, dosage is 1.0~4.0%.Reaction
2- acrylic acid amido -2- methyl propane sulfonic acids (AMPS) monomer is added after 20~40min, the ratio range with cellulose fibre is
0.8:1~2.0:1,1.0~6.0H of reaction time, 30~60 DEG C of temperature terminates postcooling, filtering, washing, acetone are washed, ether
It washes, is drying to obtain cellulose fibre/AMPS graft copolymers.Active grafting is carried out to cellulose, should retain most of object
Physical chemistry characteristic is grafted more multiple polar group or the stronger group of polarity such as the basic configuration of fiber, to have more preferably with drug
Interaction force, increase drugloading rate, promoted sustained release performance.
In another embodiment of the present invention, the auxiliary agent is methanol, ethyl alcohol and acetone.The overcritical micro emulsion/
The method of reverse micelle is specifically with succinic acid two (2- ethylhexyls) ester sodium sulfonate (AOT), ethyl alcohol, water and supercritical CO2Fluid
The overcritical microemulsion formed, AOT is primary surfactant, and ethyl alcohol is cosurfactant, wherein preparing 10~90% with water
Ethanol solution, then prepare 0.01mol/L~0.1mol/L AOT/ ethanol solutions, bath raio ranging from 1:25~1:50, the method
Expand the range of choice of drug.
In another embodiment of the present invention, whitening medicaments can be selected from the bright peaceful alkali of resveratrol, fructus piperis longi, pantolactone or
The drugs such as tetrahydrochysene methylpyrimidine carboxylic acid.Whitening medicaments are from CO2Molecule and this body structure of cellulose fibre are from polarity, molecular weight, spy
Determine group angularly to be screened.It can be improved in supercritical CO by the above-mentioned whitening medicaments after screening2Place in fluid
Efficiency is managed, the time is shortened, increases drugloading rate, forms more excellent slow release effect.For polarity, segment polarity base should be contained
Group and part non-polar group, the drug that can stay pale in this way is in supercritical CO2Fluid has certain dissolubility, and can maintain
Certain interaction force between cellulose fibre；For molecular weight, molecular weight should be selected smaller between 30-600
Substance；For special groups, parent CO may be selected2Group, such as carbonyl C (C=O) -), ehter bond (C-O-C), ester group (C-
(CO)-O-C), carbon-sulfur bond (C=S) etc.；Cellulose fibre contains a large amount of polar group hydroxyl (- OH), and polar group may be selected
Amino (- NH2), imino group (- NH-), hydroxyl (- OH), carboxyl (- COOH) etc..
In another embodiment of the present invention, the addition of the whitening medicaments is the 1% of cellulose fibre quality
To 15%.
In another embodiment of the present invention, the addition of the auxiliary agent be cellulose fibre quality 0.02% to
0.2%.
In another embodiment of the present invention, supercritical CO2It is equipped with special drug slot in fluid high-pressure equipment, and contains
There is photographing camera, which can be used for monitoring the state of whitening medicaments in a fluid, more intuitively observes whitening medicaments and is being
Variation in system.
In another embodiment of the present invention, whitening medicaments are poor to the accessibility of cellulose fibre, whitening medicaments
Be not easily penetrated into inside cellulose fibre, stable state pressure addition whitening medicaments rate it is slow when, the method can also be further
Including by compression pump to supercritical CO2Fluid applies the step of pulse, is specially in first cellulose fibre super
Critical CO210~40min in fluid, temperature is 60~120 DEG C at this time, and pressure is 8~15MPa；Then pressure with 0.5~
The speed of 1.0MPa/min rises to 15~30MPa；After stop heating, pressure is declined with the speed of 1.0~4.0MPa/min,
Until terminating to test.The step can improve functional materials to the infiltration capacity inside the cellulose fibre as carrier.Root
Quantitative according to diffusion, functional materials are also influenced by concentration gradient in intrastitial infiltration, can locally realized high concentration, are being conducive to
The infiltration of functional materials and the raising of drugloading rate.Because when pressure improves, functional materials are by supercritical CO2Fluid carries
The deeper layer of structure of fiber can be penetrated into, open ended saturation degree declines when dropping under stress, causes in fibrous inside
Microstructure at functional materials local concentration gradients improve, be also beneficial to improve functional materials to fiber can and
Degree and infiltration capacity.It being controlled compared to constant pressure, drugloading rate can be improved 1~10% by pulse pressure, and slow-release time can extend 720~
20000min。
The present invention is through supercritical CO2Fluid can effectively carry whitening medicaments into fiber surface and inside, and overcritical
CO2The swelling action of fluid can further expand the amorphous region of fiber, increase effective volume so that more whitening medicaments enter
Into cellulose fibre；Final cellulose fibre has good slow release effect as the huge capsule of medicine is carried.And with current micro- glue
Capsule (cyclodextrin, chitosan) wraps up whitening medicaments again compared with fiber is bonded by way of associative key, and feeling is better.
Description of the drawings
The burst size of the whitening medicaments resveratrol of embodiment 1 and comparative example 1 is shown respectively at any time in Fig. 1 a and Fig. 1 b
Between the curve that changes.
Fig. 2 a and Fig. 2 b be shown respectively the burst size of the bright peaceful alkali of whitening medicaments fructus piperis longi of embodiment 2 and comparative example 2 with
The curve of time change.
The burst size of the whitening medicaments pantolactone of embodiment 3 and comparative example 3 is shown respectively at any time in Fig. 3 a and Fig. 3 b
The curve of variation.
Releasing for the whitening medicaments tetrahydrochysene methylpyrimidine carboxylic acid of embodiment 4 and comparative example 4 is shown respectively in Fig. 4 a and Fig. 4 b
The curve high-volume changed over time.
Specific implementation mode
With reference to embodiment, the specific embodiment of the present invention is further described.Following embodiment is only used for more
Add and clearly demonstrate technical scheme of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1：Supercritical CO2Fluid load whitening medicaments resveratrol to viscose rayon method
After first cleaning viscose fabric ethyl alcohol, deionized water, drying balance 24H weighs, by viscose fabric weight
8.5%, which weighs resveratrol, is put into the drug slot of high-tension apparatus, and the methanol of viscose fabric weight 0.1% is added, and places into viscous
Glue fabric.With cooling bath by CO2The gas CO of steel cylinder outflow2It is cooled to liquid.
High-tension apparatus pressure is set as 12Mpa, 100 DEG C of temperature first, and carbon dioxide becomes supercritical fluid, dipping balance
After 25min, pressure rises to 30MPa with the speed of 0.5MPa/min；After stop heating, pressure is with the speed of 1.0MPa/min
Decline, until terminating to test, obtaining load has the viscose rayon of whitening medicaments resveratrol.Viscose rayon drugloading rate is 6.4%.
In order to analyze the sustained release performance that load has the viscose rayon of resveratrol, two pieces of 4.5cm × 4.5cm sizes of clip
Through supercritical CO2The viscose fabric of fluid processing, is put into the physiological saline for depositing in the 150ml in beaker a concentration of 0.9%,
It is stirred with the rate of 95rpm at 37 DEG C, the change of the burst size of resveratrol at any time is measured with uv-spectrophotometric standardization
Change curve is as shown in Figure 1a, and showing can be long lasting for release, in actual use, in human skin surface in physiological saline
Resveratrol can be discharged into human skin by having when micro sweat, and will not be released in drying regime resveratrol.
Comparative example 1：Pressure is set as steady state value, is maintained at 30Mpa, total dip time and above-mentioned experimental period one
It causes to be 91min, other conditions are identical with the method for embodiment 1, and it is 4.6% to finally obtain viscose rayon drugloading rate, sustained release
Curve is as shown in Figure 1 b.
By the comparison of embodiment 1 and comparative example 1, show that pulse-pressure can increase drugloading rate, when extending sustained release
Between.
Embodiment 2：Supercritical CO2The bright peaceful alkali of fluid load whitening medicaments fructus piperis longi to cotton fiber method
Appropriate cotton fiber is weighed, it is solution to prepare aqueous ionic liquid 1-butyl-3-methyl imidazolium villaumite, and moisture content is
2.5%, cotton cellulose fiber is immersed, bath raio ranging from 1:28,80 DEG C of set temperature, time 45min.
After cotton fiber ethyl alcohol, deionized water clean after drying balance 24H weigh, according to cotton fiber weight 8.5%
It weighs the bright peaceful alkali of fructus piperis longi to be put into the drug slot of high-tension apparatus, and the ethyl alcohol of cotton fabric weight 0.06% is added, place into cotton fiber.
The atmospheric carbon dioxide that carbon dioxide steel cylinder flows out is cooled to liquid with cooling bath, high-tension apparatus pressure is set as 21Mpa, temperature
50 DEG C of degree, carbon dioxide become supercritical fluid, and after dipping balances 3.5H, experiment terminates, and obtaining load has the bright peaceful alkali of fructus piperis longi
Cotton fiber.Cotton fiber drugloading rate is 4.3%.
In order to analyze the sustained release performance that load has the cotton fiber of the bright peaceful alkali of fructus piperis longi, two pieces of 4.5cmx4.5cm sizes of clip
Through supercritical CO2The cotton fabric of fluid processing, is put into the physiological saline for depositing in the 150ml in beaker a concentration of 0.9%,
It is stirred with the rate of 75rpm at 37 DEG C, observes the burst size versus time curve of the bright peaceful alkali of fructus piperis longi, elution profiles such as Fig. 2 a
It is shown.
Comparative example 2：Cotton fiber is handled without the pre-swollen of aqueous ionic liquid, and other conditions are complete with the above method
Exactly the same, it is 1.2% to finally obtain cotton fiber drugloading rate, and elution profiles are as shown in Figure 2 b.
By the comparison of embodiment 2 and comparative example 2, shows that pre-swollen can increase drugloading rate, extend slow-release time.
Embodiment 3：Supercritical CO2Fluid load whitening medicaments pantolactone to tencel fiber method
After taking appropriate Tencel fabric ethyl alcohol, deionized water to clean first, drying balance 24H weighs, according to Tencel fabric
Weight 9.5% weighs pantolactone, is put into the drug slot of high-tension apparatus, and the ethyl alcohol of Tencel fabric weight 0.12% is added, then puts
Enter Tencel fabric.The atmospheric carbon dioxide that carbon dioxide steel cylinder flows out is cooled to liquid with cooling bath.
High-tension apparatus pressure is set as 12Mpa, 100 DEG C of temperature first, and carbon dioxide becomes supercritical fluid, dipping balance
After 25min, pressure rises to 30MPa with the speed of 1.0MPa/min；After stop heating, pressure is with the speed of 1.0MPa/min
Decline, until terminating to test, obtaining load has whitening medicaments pantolactone to tencel fiber.Tencel fiber drugloading rate is 7.8%.
In order to analyze the sustained release performance that load has the tencel fiber of pantolactone, the warp of two pieces of 4.5cmx4.5cm sizes of clip
Supercritical CO2The Tencel fabric of fluid processing, is put into the physiological saline for depositing in the 150ml in beaker a concentration of 0.9%, sees
The burst size versus time curve of pantolactone is examined, elution profiles are as shown in Figure 3a.
Comparative example 3：Pressure is set as steady state value, is maintained at 30Mpa, total dip time and above-mentioned experimental period one
It causes to be 91min, other conditions are identical with the method for embodiment 3, and it is 4.8% to finally obtain tencel fiber drugloading rate, sustained release
Curve is as shown in Figure 3b.
By the comparison of embodiment 3 and comparative example 3, show that pulse-pressure can increase drugloading rate, when extending sustained release
Between.
Embodiment 4：Supercritical CO2Fluid load whitening medicaments tetrahydrochysene methylpyrimidine carboxylic acid to Modal fibre method
It weighs after appropriate Modal fibre is cleaned and dries balance weighing, be added in reactor, add the water of corrresponding quality,
The ratio range of Modal fibre and water is 1:4.0, lead to nitrogen protection, initiator Na is added2SO3/K2S2O8, dosage 2.8%.
2- acrylic acid amido -2- methyl propane sulfonic acids (AMPS) monomer is added after reacting 40min, the ratio range with cotton fiber is 1.5:
1, reaction time 5.5H, 40 DEG C of temperature, end postcooling, filtering, washing, acetone is washed, ether is washed, and is drying to obtain Modal fibre
Dimension/AMPS graft copolymers.
After copolymer fibre ethyl alcohol, deionized water clean after drying balance 24H weigh, according to copolymer weight
9.0% weighs tetrahydrochysene methylpyrimidine carboxylic acid, 40% ethanol solution is prepared with water, then to prepare 0.08mol/L AOT/ ethyl alcohol molten
Liquid is put into clean container and is configured to microemulsion.
Prepared microemulsion is put into the drug slot of high-tension apparatus, copolymer is placed into.With cooling bath by carbon dioxide
The atmospheric carbon dioxide of steel cylinder outflow is cooled to liquid, and high-tension apparatus pressure is set as 28Mpa, temperature 70 C, and carbon dioxide becomes
For supercritical fluid, after dipping balances 2.0H, experiment terminates, and obtaining load has the copolymer of tetrahydrochysene methylpyrimidine carboxylic acid.Copolymerization
Object drugloading rate is 7.8%.
In order to analyze the sustained release performance that load has the copolymer of tetrahydrochysene methylpyrimidine carboxylic acid, two pieces of 4.5cmx4.5cm of clip
Size through supercritical CO2The copolymer of fluid processing, is put into the physiology salt of the 150ml deposited in beaker a concentration of 0.9%
In water, is stirred with the rate of 65rpm at 37 DEG C, observe the burst size versus time curve of theanine, elution profiles are such as
Shown in Fig. 4 a
Contrast experiment：Modal fibre is handled without grafting, and other conditions are identical with the method for embodiment 4, finally
It is 4.6% to obtain Modal fibre drugloading rate, and elution profiles are as shown in Figure 4 b.
By the comparison of embodiment 4 and comparative example 4, show that grafting processing can increase drugloading rate, when extending sustained release
Between.
The above is only a preferred embodiment of the present invention, it is noted that for the general technical staff of the art
For, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. one kind being based on supercritical CO2Fluid technique makes processing method of the cellulose fibre with whitening function, which is characterized in that
It the described method comprises the following steps：
1) pre-swollen or pretreatment are carried out to cellulose fibre；
2) addition auxiliary agent is to increase whitening medicaments in supercritical CO2Solubility in fluid, for being not readily dissolved in supercritical CO2Stream
The hydrophilic class whitening medicaments of body make it be dissolved in supercritical CO indirectly using the method for overcritical microemulsion/reverse micelle2In fluid；
3) whitening medicaments are added in the drug slot of high-tension apparatus, exclude air, is passed through CO2, will be in container at 32~120 DEG C
Pressure rises to 8~30MPa, obtains supercritical CO2Fluid, to which cellulose fibre is immersed in supercritical CO2In fluid；
4) whitening medicaments are by being dissolved in supercritical CO2Enter the cellulose fibre being swollen in advance in fluid, and it is overcritical to carry medicine
CO2There is ongoing relative motion between fluid and cellulose fibre, whitening medicaments rest in cellulose fibre after pressure release
In the unformed area in portion, the drug-loading fibre cellulose fiber that can be sustained is formed.
2. according to claim 1 be based on supercritical CO2Fluid technique makes processing side of the cellulose fibre with whitening function
Method, which is characterized in that the cellulose fibre includes native cellulose fibre and regenerated celulose fibre, the native cellulose
Fiber includes cotton fiber and flaxen fiber, and the regenerated celulose fibre includes viscose rayon, koplon and solvent
Spin regenerated celulose fibre.
3. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for whitening function
Work method, which is characterized in that the preswollen method has following several：
1) N-methylmorpholine-N- oxide water solutions are prepared, mass fraction is 30~80%, and cellulose fibre is immersed,
Bath raio ranging from 1:15~1:35,60~90 DEG C of set temperature, 10~80min of time；
2) NaOH aqueous solutions are prepared, cellulose fibre is immersed by concentration 10%~20%, bath raio ranging from 1:25~1:
40, -10 DEG C of set temperature~20 DEG C, 10~80min of time；
3) aqueous ionic liquid 1-butyl-3-methyl imidazolium chloride solution is prepared, moisture content is 2%~5%, by cellulose fiber
Dimension is immersed, bath raio ranging from 1:25~1:40,60 DEG C~120 DEG C of set temperature, 10~80min of time.
4. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for whitening function
Work method, which is characterized in that the pretreatment includes carrying out active grafting to cellulose fibre.
5. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for whitening function
Work method, which is characterized in that the auxiliary agent is methanol, ethyl alcohol and acetone.
6. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for whitening function
Work method, which is characterized in that the method for the overcritical microemulsion/reverse micelle is with succinic acid two (2- ethylhexyls) ester sodium sulfonate
AOT, ethyl alcohol, water and supercritical CO2The overcritical microemulsion that fluid is formed, AOT are primary surfactant, and ethyl alcohol is that surface is helped to live
Property agent then prepare 0.01mol/L~0.1mol/L AOT/ ethanol solutions wherein preparing 10~90% ethanol solution with water, bathe
Than ranging from 1:25~1:50.
7. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for whitening function
Work method, which is characterized in that whitening medicaments are selected from resveratrol, the bright peaceful alkali of fructus piperis longi, pantolactone or tetrahydrochysene methylpyrimidine carboxylic acid.
8. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for whitening function
Work method, which is characterized in that the addition of the whitening medicaments is the 1% to 15% of cellulose fibre quality.
9. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for whitening function
Work method, which is characterized in that supercritical CO2It is equipped with drug slot in fluid high-pressure equipment, and contains photographing camera, the camera is for supervising
It surveys whitening medicaments state in a fluid and observes the variation of whitening medicaments in systems.
10. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for whitening function
Work method, which is characterized in that the method is still further comprised through compression pump to supercritical CO2Fluid applies pulse
Step.
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