CN109023960A - One kind being based on supercritical CO2Fluid technique makes processing method of the cellulose fibre with crease-resistant function - Google Patents
One kind being based on supercritical CO2Fluid technique makes processing method of the cellulose fibre with crease-resistant 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
- 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
- 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
- D06M13/144—Alcohols; Metal alcoholates
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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
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts 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
- 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
- D06M13/325—Amines
- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
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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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds 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
- D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents 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
- 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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- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
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Abstract
The present invention relates to one kind to be based on supercritical CO2Fluid technique makes processing method of the cellulose fibre with crease-resistant function comprising: 1) pre-swollen or pretreatment is carried out to cellulose fibre；2) auxiliary agent is added to increase crease-resistant drug in supercritical CO2Solubility in fluid, for being not readily dissolved in supercritical CO2The crease-resistant drug of hydrophilic class so that it is dissolved in supercritical CO indirectly using the method for overcritical microemulsion/reverse micelle2In；3) crease-resistant drug is added in the drug slot of high-tension apparatus, excludes air, is passed through CO2, at 32~120 DEG C, container inner pressure is risen into 8~30MPa, obtains supercritical CO2Fluid, so that cellulose fibre is immersed in supercritical CO2In；4) crease-resistant drug is 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, crease-resistant drag residence in unformed area, forms the drug-loading fibre cellulose fiber that can be sustained inside the cellulose fibre after pressure release.
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 crease-resistant function.
Background technique
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, crease-resistant function textile, be used for people
Everyday general purpose, it will meet the psychology and psychological need of consumer significantly.
It includes coating co-extrusion platen press that the existing exploitation about esthetics textile, which generally uses 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, function
Can be single, lasting and controllable slow release effect cannot be formed.In contrast it using the controllable release of microcapsules technology, and can make
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 all require (" hosiery industry ", 2017 (09): 5-7) wall material, core material, partial size, and the composition of capsule
Using wall thickness as main component, the relative amount of functional content is seldom, and will affect on fibre by resin-bonding
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, environmental protection 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 substrate 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 larger amount of functional materials (powder or fluid) and penetrates into the microstructure of fibrous 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 easier.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 for using supercritical CO2Fluid skill
Art prepares functional fiber and provides the reference of 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 to general background technique of the 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.
Summary of the invention
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 crease-resistant cellulose fibre.
Therefore, the present invention provides a kind of based on supercritical CO2Fluid technique makes cellulose fibre have adding for crease-resistant 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) auxiliary agent is added to increase crease-resistant drug in supercritical CO2Solubility in fluid, it is overcritical for being not readily dissolved in
CO2The crease-resistant drug of hydrophilic class of fluid makes it be dissolved in supercritical CO indirectly using the method for overcritical microemulsion/reverse micelle2Fluid
In；
3) crease-resistant drug is added in the drug slot of high-tension apparatus, excludes air, is passed through CO2, will at 32~120 DEG C
Container inner pressure rises to 8~30MPa, obtains supercritical CO2Fluid, so that cellulose fibre is immersed in supercritical CO2Fluid
In；
4) crease-resistant drug is 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, crease-resistant drag residence is in 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 structure of native cellulose, to manufacture the better regenerated celulose fibre of performance, including 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- oxide (NMMO) aqueous solution is prepared, mass fraction is 30~80%, by cellulose fibre
Be immersed, bath raio range be 1:15~1:35,60~90 DEG C of set temperature, 10~80min of time；
2) prepare NaOH aqueous solution, cellulose fibre is immersed by concentration 10%~20%, bath raio range be 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 range be 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 contamination is low, cellulose fiber
It is high to tie up solubility height, solvent recovering rate；NaOH/H2O solvent source is 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 crease-resistant class
Interaction between drug and cellulose fibre is poor, needs to introduce some active groups, increases crease-resistant drug and fibre with this
The interaction force of cellulose fiber, to increase drugloading rate.In addition, when crease-resistant drug 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, leads to nitrogen protection, and initiator Na is added2SO3/K2S2O8, dosage is 1.0~4.0%.Reaction
2- acrylic acid amido -2- methyl propane sulfonic acid (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, after cooling, filtering, washing, acetone wash, ether
It washes, is drying to obtain cellulose fibre/AMPS graft copolymer.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, to have more preferably with drug such as the basic configuration of fiber
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- ethylhexyl) 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 solution, bath raio range is 1:25~1:50, the method
Expand the range of choice of drug.
In another embodiment of the present invention, crease-resistant drug can be selected from galacturonic acid, alanine, theanine, core
The drugs such as acid or xanthorrhizol.Crease-resistant drug is from CO2Molecule and this body structure of cellulose fibre are from polarity, molecular weight, special groups
Angularly screened.It can be improved it in supercritical CO by the above-mentioned crease-resistant drug after screening2Treatment effeciency in fluid,
Shorten the time, increases drugloading rate, form more excellent slow release effect.For polarity, segment polarity group and portion should be contained
Divide non-polar group, is both able to maintain crease-resistant drug in this way in supercritical CO2Fluid has certain dissolubility, and can maintain and fiber
Certain interaction force between cellulose fiber；For molecular weight, the smaller substance between 30-600 of molecular weight should be selected；
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), may be selected polar group amino (-
NH2), imino group (- NH-), hydroxyl (- OH), carboxyl (- COOH) etc..
In another embodiment of the present invention, the additional amount of the crease-resistant drug is the 1% of cellulose fibre quality
To 15%.
In another embodiment of the present invention, the additional amount 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 crease-resistant drug in a fluid, more intuitively observes crease-resistant drug and is being
Variation in system.
In another embodiment of the present invention, crease-resistant drug is poor to the accessibility of cellulose fibre, crease-resistant drug
Be not easily penetrated into inside cellulose fibre, stable state pressure add crease-resistant drug rate it is slow when, the method can also be further
Including passing through pressure 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.Functional materials can be improved to the infiltration capacity inside the cellulose fibre as carrier in the step.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 functional materials are by supercritical CO when pressure improves2Fluid carries
The deeper layer of structure of fiber can be penetrated into, open ended saturation degree decline, causes in fibrous inside when dropping under stress
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 crease-resistant drug into fiber surface and inside, and overcritical
CO2The swelling action of fluid can further expansion fiber amorphous region, increase effective volume, so that more crease-resistant drug enters
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 crease-resistant drug again compared with fiber is bonded by way of associative key, and feeling is better.
Detailed description of the invention
Fig. 1 a and Fig. 1 b be shown respectively the burst size of the crease-resistant drug galacturonic acid of embodiment 1 and comparative example 1 with
The curve of time change.
The burst size of the crease-resistant drug alanine of embodiment 2 and comparative example 2 is shown respectively at any time in Fig. 2 a and Fig. 2 b
The curve of variation.
The burst size of the crease-resistant drug xanthorrhizol 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.
The burst size of the crease-resistant drug theanine of embodiment 4 and comparative example 4 is shown respectively at any time in Fig. 4 a and Fig. 4 b
The curve of variation.
Specific embodiment
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 solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1: supercritical CO2The crease-resistant drug galacturonic acid of fluid load to viscose rayon method
After viscose fabric ethyl alcohol, deionized water are cleaned first, drying balance 24H weighing, by viscose fabric weight
10% weighs galacturonic acid, and 30% ethanol solution is prepared with water, then prepares 0.05mol/LAOT/ ethanol solution, is put into dry
Net container is configured to microemulsion.
Prepared microemulsion is put into the drug slot of high-tension apparatus, viscose fabric is placed into.With cooling bath by CO2Steel cylinder
The gas CO of outflow2It is cooled to liquid, high-tension apparatus pressure is set as 27MPa, temperature 45 C, CO2It is changed into supercritical fluid,
After dipping balance 3.5H, experiment terminates, and obtains the viscose rayon that load has galacturonic acid.Viscose rayon drugloading rate is 8.2%.
In order to analyze the sustained release performance that load has the viscose rayon of galacturonic acid, two pieces of 4.5cm × 4.5cm sizes of clip
Through supercritical CO2The viscose fabric of fluid processing is put into the physiological saline that the 150ml concentration deposited in beaker is 0.9%
In, it is stirred at 37 DEG C with the rate of 50rpm, measures the burst size of galacturonic acid at any time with uv-spectrophotometric standardization
Change curve it is as shown in Figure 1a, showing can be long lasting for release, in actual use, in human skin in physiological saline
Surface has galacturonic acid can be discharged into human skin when micro sweat, and will not discharge in drying regime galacturonic acid
Out.
Comparative example 1: galacturonic acid is directly placed into the drug slot of high-tension apparatus, not by way of microemulsion,
Other conditions are identical with the method for embodiment 1, and finally obtaining viscose rayon drugloading rate is 4.6%, elution profiles such as Fig. 1 b
It is shown.
Through embodiment 1 compared with comparative example 1, show that the method for microemulsion can increase drugloading rate, extends slow
Release the time.
Embodiment 2: supercritical CO2The crease-resistant drug alanine of fluid load to flaxen fiber method
Appropriate flaxen fiber is weighed, by the bath raio of 1:30, is dipped into 70min in the NaOH aqueous solution that concentration is 14%, water-bath
10 DEG C of temperature, after, take out flaxen fiber.
After flaxen fiber ethyl alcohol, deionized water clean after drying balance 24H weighing, according to flaxen fiber weight 9.5%
Alanine is weighed, 50% ethanol solution is prepared with water, then prepares 0.08mol/L AOT/ ethanol solution, is put into clean container
It is configured to microemulsion.
Prepared microemulsion is put into the drug slot of high-tension apparatus, flaxen fiber 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 29Mpa, and 40 DEG C of temperature, carbon dioxide becomes
For supercritical fluid, after dipping balances 2.5H, experiment terminates, and obtains the flaxen fiber that load has alanine.Flaxen fiber drugloading rate is
4.8%.
In order to analyze the sustained release performance that load has the flaxen fiber of alanine, the warp of two pieces of 4.5cmx4.5cm sizes of clip is super
Critical CO2The linen of fluid processing is put into the physiological saline that the 150ml concentration deposited in beaker is 0.9%, at 37 DEG C
Under stirred with the rate of 65rpm, observe the burst size versus time curve of alanine, elution profiles are as shown in Figure 2 a.
Comparative example 2: flaxen fiber is handled without the pre-swollen of NaOH aqueous solution, the method for other conditions and embodiment 2
Identical, finally obtaining flaxen fiber drugloading rate is 1.9%, and elution profiles are as shown in Figure 2 b.
Through embodiment 2 compared with comparative example 2, shows that pre-swollen can increase drugloading rate, extend slow-release time.
Embodiment 3: supercritical CO2The crease-resistant drug xanthorrhizol of fluid load to Modal fibre method
After taking appropriate modal fabric ethyl alcohol, deionized water to clean first, drying balance 24H weighing, according to Mo Daer
Fabric weight 7.0% weighs xanthorrhizol, is put into the drug slot of high-tension apparatus, and the first of modal fabric weight 0.12% is added
Alcohol places into modal 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 10Mpa first, and 90 DEG C of temperature, carbon dioxide becomes supercritical fluid, dipping balance
After 10min, pressure rises to 25MPa with the speed of 0.8MPa/min；After stop heating, pressure is with the speed of 1.8MPa/min
Decline obtains the Modal fibre that load has crease-resistant drug xanthorrhizol until terminating to test.Modal fibre drugloading rate is
6.2%.
In order to analyze the sustained release performance that load has the Modal fibre of xanthorrhizol, two pieces of 4.5cmx4.5cm sizes of clip
Through supercritical CO2The modal fabric of fluid processing is put into the physiological saline that the 150ml concentration deposited in beaker is 0.9%
In, it is stirred at 37 DEG C with the rate of 95rpm, observes the burst size versus time curve of xanthorrhizol, elution profiles are as schemed
Shown in 3a.
Comparative example 3: being set as steady state value for pressure, is maintained at 25Mpa, total dip time and above-mentioned experimental period one
It causes to be 43min, other conditions are identical with the method for embodiment 3, and finally obtaining Modal fibre drugloading rate is 2.9%, delay
It is as shown in Figure 3b to release curve.
Through embodiment 3 compared with comparative example 3, show that pulse-pressure can increase drugloading rate, when extending sustained release
Between.
Embodiment 4: supercritical CO2The crease-resistant drug theanine of fluid load to cotton fiber method
It weighs after appropriate cotton fiber is cleaned and dries balance weighing, be added in reactor, add the water of corrresponding quality, viscose glue
The ratio range of fiber and water is 1:2.5, leads to nitrogen protection, and initiator Na is added2SO3/K2S2O8, dosage 2.0%.Reaction
2- acrylic acid amido -2- methyl propane sulfonic acid (AMPS) monomer is added after 30min, the ratio range with cotton fiber is 1.3:1, instead
4.5H between seasonable, 35 DEG C of temperature, after cooling, filtering, washing, acetone is washed, ether is washed, be drying to obtain cotton fiber/AMPS and connect
Graft copolymer.
After copolymer fibre ethyl alcohol, deionized water clean after drying balance 24H weighing, according to copolymer weight
8.5% weighs theanine, and 45% ethanol solution is prepared with water, then prepares 0.07mol/L AOT/ ethanol solution, is put into clean
Container be 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 30Mpa, temperature 45 C, and carbon dioxide becomes
For supercritical fluid, after dipping balances 2.0H, experiment terminates, and obtains the copolymer that load has theanine.Copolymer drugloading rate is
5.0%.
In order to analyze the sustained release performance that load has the copolymer of theanine, the warp of two pieces of 4.5cmx4.5cm sizes of clip is super
Critical CO2The copolymer of fluid processing is put into the physiological saline that the 150ml concentration deposited in beaker is 0.9%, at 37 DEG C
Under stirred with the rate of 65rpm, observe the burst size versus time curve of theanine, elution profiles are as shown in fig. 4 a
Comparative example 4: cotton fiber is handled without grafting, and other conditions are identical with the method for embodiment 4, final
It is 2.3% to cotton fiber drugloading rate, elution profiles are as shown in Figure 4 b.
Through embodiment 4 compared with 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 is based on supercritical CO2Fluid technique makes processing method of the cellulose fibre with crease-resistant 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) auxiliary agent is added to increase crease-resistant drug in supercritical CO2Solubility in fluid, for being not readily dissolved in supercritical CO2Stream
The crease-resistant drug of hydrophilic class of body makes it be dissolved in supercritical CO indirectly using the method for overcritical microemulsion/reverse micelle2In fluid；
3) crease-resistant drug is added in the drug slot of high-tension apparatus, excludes air, is passed through CO2, will be in container at 32~120 DEG C
Pressure rises to 8~30MPa, obtains supercritical CO2Fluid, so that cellulose fibre is immersed in supercritical CO2In fluid；
4) crease-resistant drug is 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, crease-resistant drag residence is 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 crease-resistant 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 crease-resistant function
Work method, which is characterized in that the preswollen method has following several:
1) N-methylmorpholine-N- oxide water solution is prepared, mass fraction is 30~80%, cellulose fibre is immersed,
Bath raio range be 1:15~1:35,60~90 DEG C of set temperature, 10~80min of time；
2) NaOH aqueous solution is prepared, cellulose fibre is immersed by concentration 10%~20%, and bath raio range is 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 range be 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 crease-resistant function
Work method, which is characterized in that the pretreatment includes that active grafting is carried out to cellulose fibre.
5. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for crease-resistant 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 crease-resistant function
Work method, which is characterized in that the method for the overcritical microemulsion/reverse micelle is with succinic acid two (2- ethylhexyl) ester sodium sulfonate
AOT, ethyl alcohol, water and supercritical CO2The overcritical microemulsion that fluid is formed, AOT are primary surfactant, and ethyl alcohol is to help surface living
Property agent wherein preparing 10~90% ethanol solution with water then prepare 0.01mol/L~0.1mol/L AOT/ ethanol solution, bathe
It is 1:25~1:50 than range.
7. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for crease-resistant function
Work method, which is characterized in that crease-resistant drug is selected from galacturonic acid, alanine, theanine, nucleic acid or xanthorrhizol.
8. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for crease-resistant function
Work method, which is characterized in that the additional amount of the crease-resistant drug 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 crease-resistant 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 crease-resistant drug state in a fluid and observes the variation of crease-resistant drug in systems.
10. according to claim 1 or 2 be based on supercritical CO2Fluid technique makes cellulose fibre have adding for crease-resistant function
Work method, which is characterized in that the method is still further comprised through pressure pump to supercritical CO2Fluid applies pulse
Step.
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