CN1387590A - Method and device for producing cellulose fibres and cellulose filament yarns - Google Patents

Method and device for producing cellulose fibres and cellulose filament yarns Download PDF

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Publication number
CN1387590A
CN1387590A CN00815429A CN00815429A CN1387590A CN 1387590 A CN1387590 A CN 1387590A CN 00815429 A CN00815429 A CN 00815429A CN 00815429 A CN00815429 A CN 00815429A CN 1387590 A CN1387590 A CN 1387590A
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cellulose
spinning
solution
coagulating bath
spinning head
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CN1155746C (en
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C·米歇尔斯
B·科萨
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Thueringisches Institut fuer Textil und Kunststoff Forschung eV
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Thueringisches Institut fuer Textil und Kunststoff Forschung eV
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods

Abstract

The invention relates to a method for producing cellulose fibres or filaments from cellulose according to the dry-wet extrusion process, using aqueous amine oxides as the solvent. According to said method a) cellulose with a cuoxam-DP in the region of between 250 and 3000 is dispersed in an aqueous amine oxide, b) the dispersion obtained is converted at a high temperature by dehydration and shearing into a homogenous solution with a zero shear viscosity in the region of between 600 and 6000 Pa.s at 85 DEG C, c) the solution is fed to at least one spinneret, d) the solution in each spinneret is formed into at least one capillary and the capillary or capillaries of each spinneret are drawn through a non-precipitative medium and are subsequently guided through a spinning bath where the cellulose fibres are precipitated and e) at the end of the spinning bath section, the cellulose fibres are separated from the currents of the spinning bath by deviation and the threads are drawn off. The method is characterised in that the dispersion in step b) is converted into a solution with a relaxation time of between 0.3 and 50 s at 85 DEG C and that the solution in step c) is passed through a flow chamber, common to the spinnerets, in which the residence time of the solution is at least equal to its relaxation time at the spinning temperature.

Description

The method and apparatus of preparation cellulose fiber peacekeeping cellulose filament yarn
The present invention relates to by with aqueous amine oxide, said particularly N-oxidation-N-methylmorpholine make the method for cellulose fibre or long filament by cellulose as the dry-wet extrusion of solvent, it comprises the steps: a) to be that cellulose or the cellulose mixtures of 250-3000 is dispersed in the aqueous amine oxide, said with cuoxam-DP, b) at high temperature, the homogeneous solution that under dehydration and the condition sheared the dispersion of gained to be changed into 85 ℃ of zero-shear viscosities be 600-6000Pa.s, c) described solution is transported at least one spinning head, d) solution in each spinning head is configured as at least one thread (Kapilare), thread in each spinning head is pulled through noncoagulating medium, then under the condition that cellulose fibre solidifies by the coagulating bath section, e) end in the coagulating bath section makes cellulose tow depart from coagulating bath stream, and draw tow, the relaxation time is the 0.3-50 solution of second when it is characterized in that dispersion in the step b) changes into 85 ℃, with solution in the step c) by the inflow chamber shared with spinning head, this solution equals the relaxation time of described solution under this spinning temperature at least in the time of staying of described inflow chamber.The invention still further relates to by aqueous amine oxide, said is made the equipment of cellulose fibre or long filament as the dry-wet extrusion of solvent by cellulose, it comprises spinneret sub-assembly with spinnerets and spinning head, have the coagulating bath of two grooves that connect with the coagulating bath pump, in spinning head and described two grooves above space and at least one draw-off godet between the coagulating bath surface in groove.
United States Patent (USP) 5246221 and 4416698 has been described cellulose dissolution in aqueous tertiary amine oxide, under small shearing, this solution is configured as dynamic analysis of spinning, under very little draw speed, this solution thread is pulled through a big space, the spinning bath coagulated fibre element of and amine oxide moisture by is pulled through draw-off godet with cellulose tow then.Also proposed the problem of cellulose tow adhesion in the space in the above-mentioned document, and suggestion is by the moistened surface of a roll with cellulose tow.
Inter-adhesive in the space for fear of cellulose tow, DD-A 218121 suggestions add polyalkylene ether at spinning solution.
United States Patent (USP) 5417909 has been described a kind of method.This method under high shearing, solution is shaped in spinning capillary, in the solution thread is pulled through under the high draw speed space of a weak point, solidify fine accurate plainly, make tow send a spinning funnel to form current-sharing then.This short space has prevented adhesion, can be with 3K/mm 2Thread density carry out spinning.
WO 96/20300 has described two kinds of relations: the relation that one side is produced with reeling off raw silk from cocoons interelement distance by distance between two dynamic analysis of spinning and spinning head, the relation that produces by the space on the other hand, and require a kind ofly to draw the equipment of cellulose fibre with＜45 degree.The final claimed a kind of equipment that to swing boundling parts (bundelungelement) that has in EP-A 0832995.This equipment can guarantee under the little situation in space that the angle between perpendicular bisector is no more than 20 ° on the long filament and spinning head farthest.
In order to improve thread density, EP-A 0584318 and 0671492 requires method of in the space tow being dried or the equipment that feeds cold air.Advise among the EP 795052 that the air that will contain a certain amount of moisture is used for cooling.The claimed a kind of method and apparatus of in the space, drying of WO94/28218.The final requirement of WO96/21758 dried in two districts.
The purpose of all method and apparatus all is in order to obtain good spinning reliability for high thread density when carrying out spinning with enough big space and big as far as possible spinning head.During the plain long filament of spinning fibre, low more to the requirement of thread density, but that the restriction of spinning head accuracy causes the requirement of the speed of drawing is high more.
In all methods, long filament is non-contactly by the space, make the length in cellulose cooling and surface solidification and space all very important by blowing humid air in the space.Distance that tow must pass through in spinning bath and consequent frictional force are never considered.Therefore, the swing of boundling parts has also obviously enlarged the spinning bath distance in the angle among the EP-A 0832995 between the minimizing long filament.Blowing humid air in the space makes the cellulose partial coagulation make the orientation significant difficulties.Only make tow pass through to have considered this situation in the United States Patent (USP) 5417909 of coagulating bath of co-flow with spinning funnel.Yet tow/spinning bath frictional force obviously increases with the increase of above-mentioned distance and tow speed, and the result causes the reduction of fibre machinery performance.Therefore, once attempt reducing the speed of drawing during spinning fibre and came this situation of balance.When spinning filament yarn, in order to operate under height is drawn speed, a 0.5-8 centimetre of coagulating bath section that flows along the tow direction is used in suggestion in the United States Patent (USP) 5868985.When being 18 centimetres in the space, this structure is only applicable to the very little simple spinning of thread density, is only applicable to singly spin according to embodiment.
Described method and apparatus when task of the present invention provides this paper and begins.Can and draw the filament yarn of spinning fibre and multifilament spinning mechanical fiber excellent performance under the condition of speed in high thread density, spinning reliability with equipment in this way.Particularly should improve the uniformity and the homogeneity of the volume thread that passes through each spinning head than existing method.In addition, above-mentioned target should be blown the situation of extruding thread without cold air etc. and is issued in the space.Other advantage can draw from following description.
Described the inventive method was solved when these tasks can begin with this paper, be that dispersion in the step b) is the 0.3-50 solution of second in the relaxation time when changing into 85 ℃, cross the shared inflow chamber of spinning head with the flow of solution in the step c), this solution equals the relaxation time of described solution under this spinning temperature at least in the time of staying of described inflow chamber.Preferred 85 ℃ of relaxation times are 1-5 second.
The spinning solution of cellulose in aqueous amine oxide, said has very outstanding viscoplasticity, thereby stored carrying and the necessary elastic energy of shaping spinning solution in slinning cabinet of a great deal of, and can resile after ambient pressure is eliminated in the relaxation time.The time of staying that is flowing in the chamber when spinning solution surpasses relaxation time λ m, can carry out relaxation completely, therefore has zero-shear viscosity above each spinning head, and near pressure makes identical volume flow by each spinning head.
Described the method (Ch.Michels, Das Papier, (1998) 1,3-8 pages or leaves) of determining the relaxation time by the rheological data of cellulose solution in the literature in detail.In fact there is the solution relaxation time spectrum that shows that molecular weight cellulose distributes.Fig. 1 has represented the relaxation time spectrum of four kinds of different cellulose solutions, i.e. the suitable frequency H* of relaxation time λ.Relaxation time λ m is the relaxation time that relative frequency maximum place occurs.
In the embodiment of the inventive method, cellulose or cellulose mixtures are carried out the enzyme preliminary treatment.Can reduce the inhomogeneities that some molecular weight cellulose distributes by this kind of enzyme preliminary treatment.For example the bimodal distribution of pine sulfite cellulose can be transformed into Unimodal Distribution.
In yet another embodiment of the present invention, for the preparation cellulose mixtures can be earlier that the cellulose of 600-3000 is dispersed in the water with cuoxam-DP, add the cellulose that cuoxam-DP is 250-600 then, disperse equally, wet pressing divides dried up back as the cellulose mixtures in the step a).The maximum in relaxation time can be improved by the cellulosic component of sneaking into high molecular, thereby gap length can be enlarged.Hereinafter will be for a more detailed description to this.
The thread of extruding should be passed through noncoagulating medium separately and abreast, again by the coagulating bath section of length less than 20 centimetres.In this case, spinning head the and hereinafter thread guide that elaborates should be arranged to such an extent that make long filament substantially parallel and mutual non-contiguously by short coagulating bath section, and avoid the friction between long filament and the coagulating bath significantly.The coagulating bath section is better less than 5 centimetres.The consumption of coagulating bath is less, is 1.5-7 liter/spinning head.Above-mentioned coagulating bath recycles when solidifying and carry tow.
The step a) cellulose tow should be with the angle deviating coagulating bath stream of β＞10 °, and draw with the tow tension that is 5cN/tex to the maximum.Above-mentioned tow separated with departing from the coagulating bath of stratiform precipitation of β angle, drew by drawing dish under above-mentioned tow tension, and was adjusted to the required speed v a that draws.The tow of drawing can be separately as filament yarn wash, avivage and drying, perhaps be merged into multistrand yarn by thread guide, washing, cutting and as fiber wash, increase gentle post processing and drying.
Described present device was solved when above-mentioned task also began by this paper, had promptly disposed a shared inflow chamber above the spinnerets with a row or multi-row or group spinning head, and its volume satisfies following relation:
V 〉=v Lλ m(I) V represents to flow into the volume of chamber in the formula, with centimetre 3Meter; v LThe expression cellulose solution volume flow, with centimetre 3/ second meter; λ mThe relaxation time at the frequency maximum place of the relaxation spectrum of expression spinning solution is in second.Relaxation time λ mIt is the distinctive value of solution.Be described asking for this value in one section of " experimental implementation " on the article of above-mentioned Ch.Michels, particularly 3-4 page or leaf.Description in the document clearly is attached in the application's the disclosure.Under the situation of determining inflow chamber volume, the uniformity of delivering to the volume flow of the spinning solution in two or more above-mentioned spinning heads through a Spinning pumps reaches optimum value.
Another characteristics of described present device were the width in space and the relaxation time of spinning solution to satisfy following relation when this paper began:
A 〉=[5+16 λ m 0.6] e 0.002V a(II) a represents gap length in the formula, in millimeter, and λ mIn relaxation time at frequency maximum place of the relaxation time spectrum of expression spinning solution, in second, va represents the speed of drawing, in rice/minute.By the above-mentioned relation formula as can be known, at relaxation time λ mAnd having following relation between gap length, gap length can be with relaxation time λ mIncrease and enlarge, and can not reduce the thread density in the spinning head or draw speed, perhaps influence the spinning reliability.Therefore, give regularly when pore diameter, the space enlarges with the increase in relaxation time, and in other words, obtaining the required gap length of high fiber quality under the condition of high spinning reliability can be regulated by the relaxation time of solution.
Preferably, the size of spinning head, gap length and coagulating bath section satisfies following relation: x ≥ a + w w · 4 D - - - ( III ) X represents two distances between adjacent spinneret hole in the formula, and a represents gap length, and w represents the length of coagulating bath section, and D represents the diameter of spinneret hole.The further explanation of above-mentioned each value is provided by Fig. 6.
In the preferred implementation of present device, better use the thread guide of making by pottery in last coagulating tank bottom.This thread guide is the perforation of above-mentioned trench bottom.The tow that solidifies leaves coagulating tank by these perforation with coagulating bath stream.Thread guide makes coagulating bath divide streamed outflow with stratiform.Like this can be independently and promptly obtain each tow.Spinning head should have identical arrangement with thread guide.Tow can be mutually non-contiguously by the coagulating bath section, and almost abreast around by on draw-off godet or the pull roll.The in a row suitable or grouping arrangement of thread guide.On spinnerets, diameter is about 12.5 or 20 millimeters spinning cap and is in line (being suitable for long filament) or multirow (being suitable for fiber), makes the long filament injection stream be in line, and can be almost abreast with long filament on pull roll or draw-off godet.During spinning, for example on 90 or 250 square millimeters/each spinning cap, should dispose and be no less than 360 or 1020 pores.Therefore, pore density is no less than 4/ millimeter 2
Spinning head should have a hat cone, and the shared spinning head area of spinning capillary is equal to or less than the inlet area of thread guide.The tow of Xing Chenging can be parallel to each other basically and mutually non-contiguously by coagulating bath like this.
The diameter of thread guide inlet face and exit face than E/e better 〉=1, and the exit corner angle are removed.This thread guide is used on the manufacturing fiber.Its general gross thickness that surpasses bottom land at least.The height h of above-mentioned thread guide is the 2-20 millimeter.
In another embodiment, ratio h/e＜1 of the height of described thread guide and exit face interior diameter, the corner angle at entrance and exit place all are removed.This thread guide is used to make filament yarn, the general 2-5 millimeter of its height h.The inlet diameter E of this thread guide or affiliated bottom plate hole is generally the 12-20 millimeter.Diameter e on this thread guide exit face is generally the 4-10 millimeter.The surface texture of this thread guide has the characteristic that produces minimized friction between its surface and tow that passes through and coagulating bath.The corner angle that grind off also can be used for this purpose.
Last coagulating tank better has introducing port.The preposition surge chamber of this groove.Surge chamber for example can comprise that a flow sections that filler is housed and one do not have the promptly empty flow sections of filler.In the sort buffer chamber, the coagulating bath of circulation pumping is slowed to basically enters coagulating tank with stratiform.
Last coagulating tank should have the adjustable overfall of at least one overflow height.Can change the coagulating bath section by move overfall in vertical direction.Particularly when just spinning, can produce other advantage like this.
The relative position of last coagulating tank and spinneret sub-assembly also better can be regulated in vertical direction.Here also can change gap length by mobile overfall in vertical direction.
In addition, can also be at the draw-off godet below horizontal or vertical direction adjusted is arranged on coagulating tank.Deflection angle β between the coagulating bath stream that so especially can change tow and flow down.
Referring now to drawings and Examples method and apparatus of the present invention is described in more detail.
Fig. 1 is the curve map of the relaxation time spectrum of four kinds of different cellulose solutions;
Fig. 2 is a schematic diagram of implementing the equipment of the inventive method.
Fig. 3 is the schematic plan of equipment shown in Figure 2.
Fig. 4 is a kind of axial, cross-sectional view of embodiment that is applicable to the thread guide of spinning fibre.
Fig. 5 is the axial, cross-sectional view of another kind of embodiment that is applicable to the thread guide of spinning filament yarn.
Fig. 6 is the geometric diagram of spinning process, is used for explaining each physical dimension of relational expression (III).
Fig. 1 represents the relative frequency H* of four kinds of cellulose solutions being formed by different celluloses and the relation in relaxation time in moisture N-oxidation-N-methylmorpholine.Their details can be referring to the form among Fig. 1, wherein λ mThe relaxation time at expression frequency maximum place is in second; DP represents the degree of polymerization (cuoxam), and η e represents the zero-shear viscosity of solution, in Pa.s; C represents the cellulose concentration of solution, in %.The given relaxation time λ relevant in relational expression (I) and (II) with gap length mIt is the relaxation time that relative frequency maximum place occurs.Solution p9915102 contains cellulose mixtures, and wherein (Cuoxam-DP 470 with relaxation time of pine sulfite cellulose for the cellulosic component by being blended into high molecular; λ m=1.6 seconds) bring up to λ m=2.1 seconds.
Fig. 2 represents to comprise the spinning equipment of coagulating tank 1, following coagulating tank 2 and spinneret sub-assembly 3.Spinneret sub-assembly 3 comprises supporting plate, inflow chamber (Anstromkammer) 5 and a plurality of spinning head 6 that has filter 4.Spinning head has an interstitial distance at the port of export from coagulating bath surface 7.The bottom 10 of last coagulating tank 1 strengthens, and corresponding to a plurality of thread guides 11 of the alignment arrangements of spinning head 6.Tow 12 is discharged coagulating tank 1 with coagulating bath stream by above-mentioned thread guide.
Configuration can be vertically and the draw-off godet 13 that moves horizontally below coagulating tank 1.Draw-off godet makes tow and the coagulating bath on all thread guides 11 flow β angle of 14 deflections, and rolls under suitable tension force.Coagulating bath stream 14 flows to down in the coagulating tank 2, and passes through on pipeline 16 pumped back in the coagulating tank 1 with pump 15.This shows that the coagulating bath section w that tow 12 passes through is till the position of this tow and coagulating bath stream 14 thread guides that separate 11 lower ends.Pipeline 16 leads to earlier in the surge chamber 18 of part with the filler filling.Coagulating bath liquid is postponed and is come out to flow in the coagulating tank 1 by hole 19 then towards the chamber.
As seen, the thread guide in the bottom land 10 is that dislocation is arranged from the vertical view of Fig. 3, and with tow 12 side by side on draw-off godet 13.
Fig. 4 represents to be used to make the thread guide 11 of fibre bundle, and it is made by pottery.As shown in the figure, the interior cross section streamwise of this thread guide narrows down gradually.The thread guide that is used to make filament yarn shown in Figure 5 is like this equally.The preferred version that does not draw the corner angle of thread guide 11 are removed in these accompanying drawings.Behind thread guide, tow at once with the coagulating bath flow point from.
Fig. 6 schematically shows the physical dimension that is comprised in the relational expression (III).Label 6 ' expression aperture is two spinneret hole of D in the accompanying drawing.D represents the center distance of spinneret hole 6 ' port of export pore.X represents two distances between pore, the center distance when d ' expression enters spinning bath between thread.P be fibre bundle and coagulating bath flow point from point.β is the deflection angle of separating.β * is the angle (very little) between two adjacent filaments in the coagulating bath.
Embodiment 1
(Cuoxam-DP 580 with 0.49 kilogram of pretreated pine sulfite cellulose of enzyme in a stirred vessel, dried content is 44.9%) be suspended among the 2.6 kilograms of NMMO (dried content 65.0%) that contain 0.44 gram stabilizing agent, then at the water of shearing, distill under the condition of 90 ℃ and 500-25 millibar 0.93 kilogram.The cellulose solution that forms consist of 10% cellulose, 78.5%NMMO and 11.5% water.This solution does not contain the visible particle of microscopically.The laser diffraction grading analysis is (referring to B.Kosa; Ch.MichelsChemical Fibers International 49[1999] the 50-54 page or leaf) confirm that the granule content of diameter＜9 micron is 19ppm.The zero-shear viscosity of this solution is 3450Pas, and the relaxation time is 4.1 seconds.(1.2ml/U, under effect 25.8Upm), spinning solution is transported in the inflow chamber of filament yarn spinner with the speed of 31 ml/min at a Spinning pumps.This spinner has two hat spinning heads side by side.The diameter of spinning head is 12.5 millimeters, and it is 130 microns spinning capillary (L/D ≌ 1) that 30 diameters are respectively arranged.Spinning solution is 4.3 λ in the time of staying that flows into the chamber mThe diameter that flows into the chamber is 5.4 centimetres, highly is 0.4 centimetre.Spinning solution under the shearing condition of 39000l/s in spinneret, be configured as tow, with the ratio of the draw speed of 200l/s and 12.9 space by 35 millimeters long, making cellulose then highly is being to solidify in 3.5 centimetres the vertical coagulating bath, tow is passed be contained in (the e=5 millimeter of thread guide as shown in Figure 5 of spinning tank bottom (E=13 millimeter), the h=4 millimeter), with 40 ° angle deviatings almost with the coagulating bath thread of laminar flow, the parallel draw-off godet that is transported under the tow tension of 2.5cN/tex, speed with 500 meters/minute is drawn, and washs under the tow tension of≤1.25cN/tex at last, dry, increase soft coiling.
The following parameter characterization of the filament yarn of gained:
Fineness 40dtex (30)
Tensile strength 43.7cN/tex
The coefficient of variation 2.3%
Extension at break 8.5%
Tubercle fracture strength 34.1cN/tex
Wu Site (inertia) 0.1%
Embodiment 2
Under shearing with a water conservancy diversion blender (Leitstrahlmischer) in 0.18 kilogram of Baumwoll-Linters cellulose (Cuoxam-DP 1907) being smashed dispersion with 1: 20 ratio of water.In order to obtain uniform suspension, continuing slowly to add 4.20 kilograms of pine sulfite celluloses (Cuoxam-DP 450) under the stirring.Depress in suction and to isolate cellulose mixtures.
In a stirred vessel, add above-mentioned cellulose mixtures and 30.42 kilograms of NMMO (dried content is 84%), add NaOH its pH value is adjusted to 11.2.Under high temperature, vacuum and shearing condition, distill 7.69 kilograms water.At this moment, this suspension is transformed into clear solution.It consist of 13.0% cellulose, 75.9%NMMO and 11.1% water, zero-shear viscosity is 3850Pas, the relaxation time is 3.1 seconds.(4.8ml/U, under effect 32.7Upm), spinning solution is transported in the inflow chamber of filament yarn spinner with the speed of 157 ml/min at a Spinning pumps.This spinner has 4 hat spinning heads side by side.The diameter of spinning head is 20 millimeters, and it is 120 microns spinning capillary (L/D ~ 1) that 90 diameters are respectively arranged.Spinning solution is 2.3 λ in the time of staying that flows into the chamber mFlow into the chamber and be of a size of 13.0 * 4.0 * 0.35 centimetre.Spinning solution under the shearing condition of 42900l/s in spinneret, be configured as tow, with the ratio of the draw speed of 245l/s and 11.7 space by 28 millimeters long, making cellulose then highly is being to solidify in 4.0 centimetres the vertical coagulating bath, tow is passed be contained in 2 thread guide (e=7 millimeters as shown in Figure 5 of spinning tank bottom (E=18 millimeter), the h=4 millimeter), angle deviating coagulating bath thread with 50 °, the parallel draw-off godet that is transported under the tow tension of ~ 3cN/tex, speed with 450 meters/minute is drawn, and washs under the tow tension of≤1.5cN/tex at last, dry, increase soft coiling.
The following parameter characterization of the filament yarn of gained:
Fineness 150dtex (90)
Tensile strength 41.7cN/tex
The coefficient of variation 3.2%
Extension at break 9.1%
Tubercle fracture strength 28.9cN/tex
Wu Site (inertia) 0.1%
Embodiment 3
With 7.66 kilograms/hour enzyme activations and stable pine sulfite cellulose (Cuoxam-DP480, dried content is 50.0%) and N-oxidation-N-methylmorpholine (NMMO of 29.0 kilograms/hour, dried content is 84.0%) join continuously among CO-ROTATING-PROCESSOR 25 CONTI (LIST AG ARISDORF) of a heating, be dispersed into uniform suspension.With a measuring pump above-mentioned suspension is sent into DISKOTHEM B 63 CONTI (LIST AG ARISDORF) type dissolvers, in the content temperature is that 90 ℃ and vacuum are that the speed with 4.7 kilograms/hour distills water under 20 millibars the condition, produces the uniform fiber cellulose solution of 27.0l/h.It consist of 12.0% cellulose, 76.3%NMMO and 11.7% water, zero-shear viscosity is 3100Pas, 85 ℃ of relaxation times are 1.9 seconds.
(9.6ml/U, under effect 47Upm), spinning solution passes through the spinning head filter with the speed of 451 ml/min and 85 ℃ content temperature, through being of a size of 9.2 * 6.2 * 0.8=45.6 centimetre at a Spinning pumps 3Inflow chamber (time of staying ≌ 3 λ m), entering 13 spinning caps of lining up 3 row, it is 100 microns spinning capillary that each spinning cap respectively has 350 diameters.Spinning solution is clamp-oned 4550 slinning cabinets under the shear rate of 16850l/s, be configured as tow, with the ratio of the draw speed of 90l/s and 9.5 space by 20 millimeters long, making cellulose then is to solidify in 6.0 centimetres the coagulating bath in that the coagulating bath section is arranged, angle deviating stratiform coagulating bath thread with 35 °, draw with 120 meters/minute speed with draw-off godet, be transported to post processing and drying at last.
Use 13 as shown in Figure 4 ceramic filar guide based in spinning tank bottom.The homotaxy of spinneret cap on the arrangement of these thread guides and the spinnerets.They are of a size of: the E=13 millimeter; E=9 millimeter and h=20 millimeter.
The following parameter characterization of the silvalin of gained:
Fineness dtex 1.3
Dry tensile strength cN/tex 43.5
Wet tensile (strength) cN/tex 36.5
Dried extension at break % 14.5
Wet extension at break % 15.1
Hook joint ultimate strength degree cN/tex 15.6
Staple fiber ppd millimeter 38
Embodiment 4
In a turbine blender in 0.23 kilogram of high molecular pine sulfite cellulose (Cuoxam-DP 1100) being smashed with 1: 16 ratio of water.In order to obtain uniform suspension, 4.45 kilograms of Cuoxam-DP of the small quantities of adding of branch are 480 pine sulfite cellulose, continue to stir.From water, isolate the plain mixture of uniform fibers with net belt type equipment, obtain 9.36 kilograms of dried content and be 50% cellulose.(dried content is 84% with above-mentioned cellulose mixtures and 35.9 kilograms of NMMO in one hour, also contain 10 gram stabilizing agents) add among CO-ROTATING-PROCESSOR 25 CONTI (LIST AGARISDORF) of a heating in batches, be dispersed into uniform suspension, distill 2.26 kg water simultaneously.43.0 kilograms/hour suspension is sent in DICKOTHEM B 63 CONTI (LIST AGARISDORF) the type kneading machine of a heating with a measuring pump, in the content temperature is that 93 ℃ and vacuum are that the speed with 4.0 kilograms/hour distills water under 22 millibars the condition, produces 39 kilograms/hour uniform fiber cellulose solution.It consist of 12.0% cellulose, 77.3%NMMO and 10.7% water.The zero-shear viscosity of this solution is 3750Pas, and the relaxation time is 2.1 seconds.Solidifying the cellulosic Cuoxam-DP that from this solution is 506.
A Spinning pumps (9.6ml/U, under effect 47Upm), spinning solution with the content temperature of the speed of 547 ml/min and 85 ℃ by the spinning head filter, through being of a size of inflow chamber (time of staying ≌ 2.4 λ of 9.2 * 6.2 * 0.8=45.6 centimetres 3 m), entering 5 spinning caps of lining up 2 row, it is 80 microns spinning capillary that each spinning cap respectively has 1020 diameters.Spinning solution is clamp-oned 5100 slinning cabinets under the shear rate of 13770l/s, be configured as tow, with the ratio of the draw speed of 67l/s and 8.8 space by 22 millimeters long, making cellulose then is to solidify in 5.0 centimetres the coagulating bath in that the coagulating bath section is arranged, and with 30 ° angle deviating stratiform coagulating baths stream, draws with 100 meters/minute speed, be merged into multistrand yarn, washing cuts into silvalin, carries out post processing and drying.
At the thread guide as shown in Figure 5 that has 5 to line up 2 row at spinning tank.They are of a size of: the E=20 millimeter; E=10 millimeter and h=20 millimeter.
The coagulating bath (6-8 ℃) of cooling is carried out with a membrane pump in the conveying between the spinning tank up and down, and speed is about 35 liters/minute.
The following parameter characterization of the silvalin of gained:
Fineness dtex 1.7
Dry tensile strength cN/tex 42.8
Wet tensile (strength) cN/tex 35.9
Dried extension at break % 15.5
Wet extension at break % 15.9
Hook joint is broken powerful cN/tex 15.1
Staple fiber ppd millimeter 38

Claims (17)

  1. By with aqueous amine oxide, said particularly N-oxidation-N-methylmorpholine make the method for cellulose fibre or long filament as the dry-wet extrusion of solvent by cellulose, it comprises the steps:
    A) be that cellulose or the cellulose mixtures of 250-3000 is dispersed in the aqueous amine oxide, said with cuoxam-DP,
    B) homogeneous solution that under the condition of high temperature, dehydration and shearing the dispersion of gained to be changed into 85 ℃ of zero-shear viscosities be 600-6000Pa.s,
    C) described solution is transported at least one spinning head,
    D) solution in each spinning head is configured as at least one thread, and the thread in each spinning head is pulled through noncoagulating medium, then under the condition that cellulose fibre solidifies by coagulating bath,
    E) end in the coagulating bath section makes cellulose tow depart from coagulating bath stream, and draws tow,
    The relaxation time is the 0.3-50 solution of second when it is characterized in that dispersion in the step b) changes into 85 ℃, cross the shared inflow chamber of spinning head with the flow of solution in the step c), this solution equals the relaxation time of described solution under this spinning temperature at least in the time of staying of described inflow chamber.
  2. 2. the method for claim 1 is characterized in that cellulose or cellulose mixtures are carried out the enzyme preliminary treatment.
  3. 3. method as claimed in claim 1 or 2, when it is characterized in that preparing cellulose mixtures, the cellulose that with cuoxam-DP is 600-3000 earlier is dispersed in the water, add the cellulose that cuoxam-DP is 250-600 then, and disperse, wet pressing divides dried up back as the cellulose mixtures in the step a).
  4. 4. as each described method among the claim 1-3, it is characterized in that described thread is passed through noncoagulating medium separately and abreast, then by the coagulating bath section of length less than 20 centimetres.
  5. 5. as each described method among the claim 1-4, it is characterized in that cellulose tow in the step e) with the angle deviating coagulating bath stream of β＞10 °, and draw with the tow tension that is 5cN/tex to the maximum.
  6. 6. by the equipment of the dry-wet extrusion that aqueous amine oxide, said is used as solvent by cellulose manufacturing cellulose fibre or long filament, it comprises:
    Spinneret sub-assembly (3) with spinnerets and spinning head (6),
    Coagulating bath in two grooves (1,2) that connect with coagulating bath pump (15),
    Space (a) between the coagulating bath surface (7) in the top groove in spinning head (6) and described two grooves (1,2),
    Draw-off godet (13)
    It is characterized in that disposed a shared inflow chamber (5) in the spinnerets top with a row or multi-row or group spinning head (6), its volume satisfies following relation:
    V 〉=v Lλ m(I) V represents to flow into the volume of chamber in the formula, with centimetre 3Meter; v LThe expression cellulose solution volume flow, with centimetre 3/ second meter; λ mThe relaxation time at the frequency maximum place of the relaxation spectrum of expression spinning solution.
  7. 7. by the equipment of the dry-wet extrusion that aqueous amine oxide, said is used as solvent by cellulose manufacturing cellulose fibre or long filament, it comprises:
    Spinneret sub-assembly (3) with spinnerets and spinning head (6),
    Have two coagulating baths with the groove (1,2) of coagulating bath pump (15) connection,
    Space (a) between the coagulating bath surface (7) in the top groove in spinning head (6) and described two grooves (1,2),
    Draw-off godet (13)
    It is characterized in that the width of space (a) and the relaxation time of spinning solution are satisfied following relation:
    A 〉=[5+16 λ m 0.6] e 0.002v a(II) a represents gap length in the formula, in millimeter, and λ mIn relaxation time at frequency maximum place of the relaxation spectrum of expression spinning solution, va represents the speed of drawing, in rice/minute.
  8. 8. as claim 6 or 7 described equipment, it is characterized in that the size of spinning head (6), gap length (a) and coagulating bath section (w) satisfies following relation: x ≥ a + w w · 4 D - - - ( III ) X represents the distance between two adjacent spinneret hole (6 ') in the formula, and a represents gap length, and w represents the length of coagulating bath section, and D represents the diameter of spinneret hole.
  9. 9. as each described equipment among the claim 6-8, it is characterized in that, use the thread guide of making by pottery (11) in the bottom (10) of last coagulating tank (1).
  10. 10. equipment as claimed in claim 9 is characterized in that, described thread guide (11) branch or group are arranged.
  11. 11., it is characterized in that spinning head (6) has hat cone as claim 9 or 10 described equipment, and the shared spinning head area of spinning capillary is equal to or less than the inlet area of thread guide (11).
  12. 12., it is characterized in that the inlet face of described thread guide (11) and the diameter of exit face are than E/e 〉=1 as each described equipment among the claim 9-11, the outlet corner angle are removed.
  13. 13. as each described equipment among the claim 9-11, it is characterized in that, ratio h/e＜1 of the height of described thread guide (11) and exit face interior diameter, the corner angle at entrance and exit place all are removed.
  14. 14., it is characterized in that last coagulating tank (1) has this inflow entrance front buffer chamber (18) of inflow entrance (19) as each described equipment among the claim 6-13.
  15. 15., it is characterized in that last coagulating tank (1) has at least one overfall (9) as each described equipment among the claim 6-14, its spout hole height can be regulated.
  16. 16., it is characterized in that last coagulating tank (1) can vertical adjusting with respect to the position of spinneret sub-assembly (3) as each described equipment among the claim 6-15.
  17. 17., it is characterized in that the draw-off godet (13) that is arranged on below the coagulating tank (1) can be vertically and/or the level adjusting as each described equipment among the claim 6-16.
CNB008154295A 1999-11-10 2000-10-28 Method and device for producing cellulose fibres and cellulose filament yarns Expired - Fee Related CN1155746C (en)

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CN101142346B (en) * 2005-03-15 2010-06-16 株式会社晓星 A cellulose multi-filament
CN103492621A (en) * 2011-03-08 2014-01-01 赛佩荷兰服务有限公司 Method for spinning anionically modified cellulose and fibres made using the method
CN109457312A (en) * 2018-10-26 2019-03-12 德蓝水技术股份有限公司 Hollow-fibre membrane spinning machine
CN110872732A (en) * 2018-08-30 2020-03-10 奥若泰克股份有限公司 Method and device for spinning filaments by deflection
CN111155183A (en) * 2019-12-31 2020-05-15 中国纺织科学研究院有限公司 Continuous preparation method of cellulose fiber

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CN101142346B (en) * 2005-03-15 2010-06-16 株式会社晓星 A cellulose multi-filament
CN103492621A (en) * 2011-03-08 2014-01-01 赛佩荷兰服务有限公司 Method for spinning anionically modified cellulose and fibres made using the method
CN103492621B (en) * 2011-03-08 2015-04-29 赛佩荷兰服务有限公司 Method for spinning anionically modified cellulose and fibres made using the method
CN110872732A (en) * 2018-08-30 2020-03-10 奥若泰克股份有限公司 Method and device for spinning filaments by deflection
CN110872732B (en) * 2018-08-30 2022-02-15 奥若泰克股份有限公司 Method and device for spinning filaments by deflection
CN109457312A (en) * 2018-10-26 2019-03-12 德蓝水技术股份有限公司 Hollow-fibre membrane spinning machine
CN111155183A (en) * 2019-12-31 2020-05-15 中国纺织科学研究院有限公司 Continuous preparation method of cellulose fiber

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WO2001034885A3 (en) 2002-02-14
ATE261008T1 (en) 2004-03-15
KR20020049045A (en) 2002-06-24
AU2500701A (en) 2001-06-06
EP1232298B1 (en) 2004-03-03
KR100652153B1 (en) 2006-11-29
DE19954152C2 (en) 2001-08-09
CN1155746C (en) 2004-06-30

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