A kind of aquogel type alginate fibre and preparation method thereof
Technical field
The present invention relates to a kind of aquogel type alginate fibre and preparation method thereof, belong to textile science technical field.
Background technology
Alginate fibre is that the polysaccharide of extraction is as raw material in natural seaweed, and water miscible metal salt solution is coagulating bath, a kind of novel high-performance fiber obtained by wet spinning production technology.Use the medical dressing that alginate fibre is made, it is possible to absorbing wound exudate, form gelinite in wound surface, accelerate wound surface hemostasis, intercept bacterial invasion, promote wound healing;And, the adhesion that this layer of gelinite is possible to prevent between wound and fiber, it is very easy to remove, reduces the secondary injury of wound;It addition, the biocompatibility of alginate fibre is the most excellent, life-time service will not cause the ill symptomses such as wound location skin sensitivity or anaphylaxis.At present, seaweed fiber medical dressing is widely used.Sargassum have accumulated mineral abundant in ocean, and containing compositions such as carbohydrate, aminoacid, fatty and various vitamin, can be with the metabolism of active cell, there is antiinflammatory, antipruritic function, so alginate fibre has effect of natural curing, moisturizing, beauty treatment to human body skin, treating skin disease is also had specific use simultaneously, is highly suitable for making the hydrogel facial film of beauty and skin care.
China Patent Publication No. is CN1986921A, invention entitled algae fiber gel spinning preparing process, that application discloses and sodium alginate is dissolved in the aqueous solution of sodium hydroxide, and add a certain amount of hypochlorous acid and salt etc. and be configured to spinning solution, with containing water, the solution of lower alcohol is the first coagulating bath, containing lower alcohol, hydrogen chloride and calcium chloride water are the second gelation, use the method that gel spinning technique prepares alginate fibre, but owing to program spinning solution adding hypochlorous acid and salt, it is easily caused spinning head blocking, and the mechanical property of the fiber prepared is poor.China Patent Publication No. is CN101033564A, the invention entitled common and preparation method of functional calcium alginate fiber and purposes, this application case discloses adds suitable functional material in sodium alginate aqueous solution and is configured to spinning solution, with calcium chloride water as coagulating bath, use the method that wet spinning prepares calcium alginate fibre, but the alginic acid fibre prepared by the program meet in the case of water can not gelation, limit it in the application as hydrogel facial film field.China Patent Publication No. is CN104338173A, the production method of invention entitled a kind of quick imbibition gelatinised sea algae bleeding-stopping dressing and purposes, this application case discloses and textile or the bonded fabric product of calcium alginate fibre is first soaked in the alcohol-water solution containing univalent metal salt, remove remaining solution after a period of time, complete immersion treatment;Immerse the solution that alcohol mixes with water afterwards, remaining solution is removed after a period of time, complete rinsing to process, again drying, cut, pack, prepared finished product of sterilizing, but the preparation method of the quick imbibition gelatinised sea algae bleeding-stopping dressing that the method is prepared is complicated, the preparation technology time is longer, relatively costly, and gel effect is less desirable.
China Patent Publication No. is CN 103774281A, publication date is on May 7th, 2014, the preparation technology of invention entitled a kind of alginate fibre spinning that keeps healthy, this application case disclose sodium alginate is dissolved in containing sodium hydroxide, sodium hypochlorite aqueous solution in, it is extruded in coagulating bath by spinning screw, again the alginate fibre of first one-step forming is carried out ion exchange, drawing-off obtains the method for alginate fibre, but water met by the alginic acid fibre that the method is prepared can not occur gelation, it is impossible to be used for making hydrogel facial film.
At present, use the alginate fibre prepared of document public technology, in distilled water can not gelation, limit the alginate fibre application in hydrogel facial film field.And, use alginate fibre prepared by document public technology, even if in the wound fluid containing sodium ion, its gelation time is the longest, the time needing more than at least 30 minutes just can complete absorb sepage or pus and blood and change into gel, for acute bleed profusely or sepage wound cleaning and nursing for, be still difficult to meet requirement.
Summary of the invention
Problem for above-mentioned existence, it is an object of the invention to provide a kind of alginate fibre that can meet water PhastGel, mainly by sodium alginate is configured to spinning solution, spinning solution is extruded from spinneret through dosing pump, as-spun fibre is obtained through calcium chloride the first coagulating bath, the as-spun fibre sodium hydroxide ethanol solution in the second bath again, sodium ion and the calcium ion generation exchange reaction in as-spun fibre, adjust the content of calcium ion in fiber, gradually form aquogel type alginate fibre, the most again through second time drawing-off, washing bath washs, drawing-off for the third time, it is dried and winding, obtain aquogel type alginate fibre.The aquogel type alginate fibre prepared can be used for making medical sanitary dressing and beauty skin-care face mask, and fracture strength and pliability are excellent, production technology is simple, aquogel type alginate fibre of low cost and preparation method thereof, to achieve these goals, its technical solution is:
A kind of aquogel type alginate fibre, in aquogel type alginate fibre, the content of calcium ion is 0.02~0.1 mg/g fiber, and line density is 1.0~1.5 dtex, and fracture strength is 1.2~2.0 cN/dtex, liquid absorption to distilled water is 10~20 g/g fibers, meets water and i.e. forms gelinite.
The preparation method of a kind of aquogel type alginate fibre, the preparation method of aquogel type alginate fibre comprises the steps:
A weighs sodium alginate according to 5%~the 10% of distilled water quality, and it is added to mechanical agitation dissolving 2~5 h in distilled water, then standing and defoaming 24~36 h, or vacuumizing and defoaming 12~24 h, obtain spinning solution, the molecular weight of described sodium alginate is 300000~500000, and M/G value is 1.5~2.5.
The molecular structure of sodium alginate is made up of mannuronic acid (being called for short M unit) and two kinds of construction units of guluronic acid (being called for short G unit), and two kinds of alduronic acid ratios in the molecule and the change of order, the physicochemical properties that can cause sodium alginate are different.Wherein G unit can form chelate structure with calcium ion, and M unit and calcium ion do not occur any effect.The present invention select M/G value between 1.5~2.5 sodium alginate be raw material, guarantee alginate fibre quick shaping in the coagulating bath of calcium chloride water, in fiber, the content of calcium ion controls, in suitable scope, to be designed from source to the molecular structure of aquogel type alginate fibre simultaneously.
B weighs calcium chloride according to 1%~the 5% of distilled water quality, and is added to mechanical agitation dissolving 10~20 min in distilled water, obtains the first coagulating bath.
C is according to 5%~20% weighing sodium hydroxide of dehydrated alcohol quality, and is added to mechanical agitation dissolving 30~60 min in dehydrated alcohol, obtains the second gelation.
The present invention uses two-step method to prepare hydrogel alginate fibre, first step solidification uses calcium chloride water, first the shaping of alginate fibre is ensured, second step uses the ethanol solution of sodium hydroxide, by sodium ion and the calcium ion generation exchange reaction in shaped fibers, adjust the content of calcium ion in fiber, gradually form aquogel type alginate fibre.Meanwhile, the solvent of second coagulating bath uses dehydrated alcohol, and dehydrated alcohol can be enable the hydrogel alginate fibre of shaping to keep fibre morphology by the hydrone contained in extraction removing as-spun fibre, and ensured dried fiber adhesion, the most also silk.
The spinning solution that step a is prepared by d filters, then extrudes from spinneret after dosing pump, enters in the first coagulating bath that step b prepares, first solidification temperature is 40~60 DEG C, setting time is 1~2 min, obtains as-spun fibre, and the aperture of described spinneret is 0.03~0.05 mm.
By reducing the content of calcium ion in fiber, aquogel type alginate fibre can be obtained, but the too low meeting of calcium ion content causes the decline of fibrous mechanical property, to the acupuncture of fiber, weave, the Downstream processing such as cut and bring difficulty.The present invention is by the spinneret selecting aperture to be 0.03~0.05 mm, reduce the diameter of shaped fibers, be conducive to the abundant solidification of fiber, and by controlling temperature and the setting time of fiber of coagulating bath, ensure that fiber can carry out effective drawing-off while fully solidification, form highly oriented Fiber super-molecular structure, thus obtain the aquogel type alginate fibre matrix of high intensity.
The as-spun fibre that step d is obtained by e introduces in the second gelation that step c prepares after first time drawing-off, the drafting multiple of drawing-off for the first time is 2~4 times, second solidification temperature is 40~60 DEG C, setting time is 1~3 min, again through second time drawing-off, washing bath washs, drawing-off for the third time, it is dried and winding, obtain aquogel type alginate fibre, the drafting multiple of the second time drawing-off of described fiber is 1.0~1.5 times, the drafting multiple of drawing-off for the third time is 1.0~2.0 times, the washing bath of described fiber is dehydrated alcohol, wash time is 3~5 min, the baking temperature of described fiber is 60~80 DEG C, drying time is 3~5 min.
Owing to the spinning liquid of alginate fibre containing substantial amounts of hydrone, aquogel type alginate fibre runs into hydrone and gelation i.e. occurs, so dried aquogel type alginate fibre is very easy to the adhesion between fiber, causes feel to harden, and affect the following process of fiber.The preparation method of subject hydrogel type alginate fibre, first used dehydrated alcohol that the hydrogel alginate fibre after shaping is washed before fiber drying, by the hydrone contained in extraction removing fiber while washing, and by controlling baking temperature and drying time, the adhesion preventing aquogel type alginate fibre is hardened, to ensure being smoothed out of fiber following process.
Owing to have employed technique scheme, the Advantageous Effects of the present invention a kind of aquogel type alginate fibre and preparation method thereof is:
The preparation method of 1 subject hydrogel type alginate fibre, by structure control and the design of coagulation bath composition of raw material, adjusts the metal ion content in alginate fibre molecular structure, it is thus achieved that aquogel type alginate fibre.The preparation method of the present invention is simple, and technological process is short, and production cost is relatively low, expands the application of alginate fibre, it is achieved that alginate fibre is general health care dressing and beauty skin-care face mask field.
The preparation method of 2 subject hydrogel type alginate fibres, use dehydrated alcohol that the hydrogel alginate fibre after shaping is washed, by the hydrone contained in extraction removing fiber while washing, and by controlling baking temperature and drying time, the adhesion preventing aquogel type alginate fibre is hardened, and does not affect the following process of fiber.
The preparation method of 3 subject hydrogel type alginate fibres, in reducing alginate fibre molecular structure while metal ion content, control by techniques such as spinning head aperture, solidification temperature, setting time and drafting multiples, improve intensity and the pliability of hydrogel alginate fibre, thus meet acupuncture, weave, cut etc. the requirement of fiber Downstream processing, on existing Industry Foundation, quickly can form complete industrial chain.
Detailed description of the invention
Below in conjunction with specific embodiment, the preparation method of the aquogel type alginate fibre of the present invention is described in further detail:
Embodiment 1
Weighing 100 grams of distilled water successively and 5 gram-molecular weights are 300000, M/G value is the sodium alginate of 1.5, adds in distilled water by the sodium alginate weighed while stirring, and mechanical agitation 2 h, then standing and defoaming 24 h, obtains spinning solution;Weighing 5000 grams of distilled water and 50 grams of calcium chloride successively, add in distilled water by the calcium chloride weighed while stirring, mechanical agitation dissolves 10 min, obtains the first coagulating bath;Weighing 5000 grams of dehydrated alcohol and 250 grams of sodium hydroxide successively, add in dehydrated alcohol by the sodium hydroxide weighed while stirring, mechanical agitation dissolves 30 min, obtains the second gelation;Being filtered by spinning solution, then be the spinneret extrusion of 0.03 mm from aperture after dosing pump, enter in the first coagulating bath, solidification temperature is 40 DEG C, and setting time is 2 min, obtains as-spun fibre;Introduce after as-spun fibre is carried out 2 times of drawing-offs for the first time in the second gelation, solidification temperature is 40 DEG C, setting time is 3 min, introduce after carrying out the drawing-off of 1.5 times of second time again in dehydrated alcohol bath and wash, wash time is 3 min, then 2.0 times of three drawing-offs are carried out, in the drying baker of 60 DEG C, after dried 5 min, winding receives silk, the content obtaining calcium ion is 0.02 mg/g fiber, line density is 1.0 dtex, fracture strength is 1.2 cN/dtex, the aquogel type alginate fibre that liquid absorption is 20 g/g fibers to distilled water.
Embodiment 2
Weighing 100 grams of distilled water successively and 10 gram-molecular weights are 500000, M/G value is the sodium alginate of 2.5, adds in distilled water by the sodium alginate weighed while stirring, and mechanical agitation 5 h, then standing and defoaming 36 h, obtains spinning solution;Weighing 5000 grams of distilled water and 250 grams of calcium chloride successively, add in distilled water by the calcium chloride weighed while stirring, mechanical agitation dissolves 20 min, obtains the first coagulating bath;Weighing 5000 grams of dehydrated alcohol and 1000 grams of sodium hydroxide successively, add in dehydrated alcohol by the sodium hydroxide weighed while stirring, mechanical agitation dissolves 60 min, obtains the second gelation;Being filtered by spinning solution, then be the spinneret extrusion of 0.05 mm from aperture after dosing pump, enter in the first coagulating bath, solidification temperature is 60 DEG C, and setting time is 1 min, obtains as-spun fibre;As-spun fibre is carried out 4 times of drawing-offs, then introduce in the second gelation, solidification temperature is 60 DEG C, setting time is 1 min, introduce after carrying out 1.0 times of secondary drawing-offs again in dehydrated alcohol bath and wash, wash time is 5 min, then 1.0 times of three drawing-offs are carried out, in the drying baker of 80 DEG C, after dried 3 min, winding receives silk, the content obtaining calcium ion is 0.1 mg/g fiber, line density is 1.5 dtex, and fracture strength is 2.0 cN/dtex, the aquogel type alginate fibre that liquid absorption is 10 g/g fibers to distilled water.
Embodiment 3
Weighing 100 grams of distilled water successively and 8 gram-molecular weights are 400000, M/G value is the sodium alginate of 2.0, adds in distilled water by the sodium alginate weighed while stirring, and mechanical agitation 4 h, then vacuumizing and defoaming 24 h, obtains spinning solution;Weighing 5000 grams of distilled water and 150 grams of calcium chloride successively, add in distilled water by the calcium chloride weighed while stirring, mechanical agitation dissolves 18 min, obtains the first coagulating bath;Weighing 5000 grams of dehydrated alcohol and 500 grams of sodium hydroxide successively, add in dehydrated alcohol by the sodium hydroxide weighed while stirring, mechanical agitation dissolves 50 min, obtains the second gelation;Being filtered by spinning solution, then be the spinneret extrusion of 0.04 mm from aperture after dosing pump, enter in the first coagulating bath, solidification temperature is 50 DEG C, and setting time is 1.5 min, obtains as-spun fibre;As-spun fibre is carried out 3 times of drawing-offs, then introduce in the second gelation, solidification temperature is 50 DEG C, setting time is 1.5 min, introduce after carrying out 1.2 times of secondary drawing-offs again in dehydrated alcohol bath and wash, wash time is 4 min, then 1.8 times of three drawing-offs are carried out, in the drying baker of 70 DEG C, after dried 4 min, winding receives silk, the content obtaining calcium ion is 0.08 mg/g fiber, line density is 1.3 dtex, and fracture strength is 1.8 cN/dtex, the aquogel type alginate fibre that liquid absorption is 12 g/g fibers to distilled water.
Embodiment 4
Weighing 100 grams of distilled water successively and 6 gram-molecular weights are 400000, M/G value is the sodium alginate of 1.8, adds in distilled water by the sodium alginate weighed while stirring, and mechanical agitation 3 h, then vacuumizing and defoaming 12 h, obtains spinning solution;Weighing 5000 grams of distilled water and 100 grams of calcium chloride successively, add in distilled water by the calcium chloride weighed while stirring, mechanical agitation dissolves 15 min, obtains the first coagulating bath;Weighing 5000 grams of dehydrated alcohol and 400 grams of sodium hydroxide successively, add in dehydrated alcohol by the sodium hydroxide weighed while stirring, mechanical agitation dissolves 40 min, obtains the second gelation;Being filtered by spinning solution, then be the spinneret extrusion of 0.03 mm from aperture after dosing pump, enter in the first coagulating bath, solidification temperature is 45 DEG C, and setting time is 1.5 min, obtains as-spun fibre;As-spun fibre is carried out 2.5 times of drawing-offs, then introduce in the second gelation, solidification temperature is 45 DEG C, setting time is 2.5 min, introduce after carrying out 1.3 times of secondary drawing-offs again in dehydrated alcohol bath and wash, wash time is 4 min, then 1.6 times of three drawing-offs are carried out, in the drying baker of 65 DEG C, after dried 5 min, winding receives silk, the content obtaining calcium ion is 0.06 mg/g fiber, line density is 1.2 dtex, and fracture strength is 1.6 cN/dtex, the aquogel type alginate fibre that liquid absorption is 16 g/g fibers to distilled water.
Embodiment 5
Weighing 100 grams of distilled water successively and 7 gram-molecular weights are 300000, M/G value is the sodium alginate of 2.0, adds in distilled water by the sodium alginate weighed while stirring, and mechanical agitation 3 h, then vacuumizing and defoaming 20 h, obtains spinning solution;Weighing 5000 grams of distilled water and 150 grams of calcium chloride successively, add in distilled water by the calcium chloride weighed while stirring, mechanical agitation dissolves 15 min, obtains the first coagulating bath;Weighing 5000 grams of dehydrated alcohol and 300 grams of sodium hydroxide successively, add in dehydrated alcohol by the sodium hydroxide weighed while stirring, mechanical agitation dissolves 40 min, obtains the second gelation;Being filtered by spinning solution, then be the spinneret extrusion of 0.05 mm from aperture after dosing pump, enter in the first coagulating bath, solidification temperature is 50 DEG C, and setting time is 1 min, obtains as-spun fibre;As-spun fibre is carried out 3 times of drawing-offs, then introduce in the second gelation, solidification temperature is 50 DEG C, setting time is 2 min, introduce after carrying out 1.2 times of secondary drawing-offs again in dehydrated alcohol bath and wash, wash time is 5 min, then 1.5 times of three drawing-offs are carried out, in the drying baker of 75 DEG C, after dried 4 min, winding receives silk, the content obtaining calcium ion is 0.05 mg/g fiber, line density is 1.3 dtex, and fracture strength is 1.5 cN/dtex, the aquogel type alginate fibre that liquid absorption is 18 g/g fibers to distilled water.
Embodiment 6
Weighing 100 grams of distilled water successively and 9 gram-molecular weights are 450000, M/G value is the sodium alginate of 2.5, adds in distilled water by the sodium alginate weighed while stirring, and mechanical agitation 4 h, then standing and defoaming 20 h, obtains spinning solution;Weighing 5000 grams of distilled water and 200 grams of calcium chloride successively, add in distilled water by the calcium chloride weighed while stirring, mechanical agitation dissolves 20 min, obtains the first coagulating bath;Weighing 5000 grams of dehydrated alcohol and 500 grams of sodium hydroxide successively, add in dehydrated alcohol by the sodium hydroxide weighed while stirring, mechanical agitation dissolves 50 min, obtains the second gelation;Being filtered by spinning solution, then be the spinneret extrusion of 0.05 mm from aperture after dosing pump, enter in the first coagulating bath, solidification temperature is 50 DEG C, and setting time is 1 min, obtains as-spun fibre;As-spun fibre is carried out 3 times of drawing-offs, then introduce in the second gelation, solidification temperature is 50 DEG C, setting time is 2 min, introduce after carrying out 1.1 times of secondary drawing-offs again in dehydrated alcohol bath and wash, wash time is 4 min, then 1.3 times of three drawing-offs are carried out, in the drying baker of 75 DEG C, after dried 4 min, winding receives silk, the content obtaining calcium ion is 0.03 mg/g fiber, line density is 1.4 dtex, and fracture strength is 1.3 cN/dtex, the aquogel type alginate fibre that liquid absorption is 19 g/g fibers to distilled water.
The line density of embodiment 1,2,3,4,5,6 gained aquogel type alginate fibre and fracture strength, calcium ion content in fiber, be shown in Table 1 to the liquid absorption of distilled water.The method of testing of properties is as follows:
The mensuration of calcium ion content: weigh 0.2 g alginate fibre sample in crucible, be placed in Muffle furnace, through 800 DEG C, carbonization treatment 3 h, after being cooled to room temperature, add 2 mL HNO3, heating slightly makes it dissolve, and then constant volume in 50 mL volumetric flasks uses Atomic Absorption Spectrometer to record the content of calcium ion on alginate fibre.
The mensuration of liquid absorption: weigh 0.1 g alginate fibre sample, be placed in the distilled water of 50 mL and soak 30 min;By fiber centrifuge dehydration 15 min after water suction, centrifuge speed is 2000 r/min, weighs, and quality is designated as M1;Then being placed in by fiber in 105 DEG C of baking ovens and dry to constant weight, weigh, quality is designated as M2.The liquid absorption N=(M of fiber1—M2)/M2。
With reference to the line density of " GB/T 14335-2008 man-made staple fibres dimension line density test method " test fiber, with reference to the fracture strength of " GB/T 14337-2008 man-made staple fibres Wella stretches method for testing performance " test fiber.
The properties of table 1 aquogel type alginate fibre