EP0900292B1 - Verfahren zur herstellung cellulosischer formkörper - Google Patents

Verfahren zur herstellung cellulosischer formkörper Download PDF

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Publication number
EP0900292B1
EP0900292B1 EP97920723A EP97920723A EP0900292B1 EP 0900292 B1 EP0900292 B1 EP 0900292B1 EP 97920723 A EP97920723 A EP 97920723A EP 97920723 A EP97920723 A EP 97920723A EP 0900292 B1 EP0900292 B1 EP 0900292B1
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EP
European Patent Office
Prior art keywords
area
conical
diameter
process according
nozzle channel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97920723A
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German (de)
English (en)
French (fr)
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EP0900292A1 (de
Inventor
Günter FRISCHMANN
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Akzo Nobel NV
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Akzo Nobel NV
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    • 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
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • 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

Definitions

  • the present invention relates to a method for manufacturing a cellulosic shaped body in which a cellulose and solution containing tertiary amine N-oxides by a Nozzle containing at least one nozzle channel with an inflow area, an outflow area and a nozzle channel outlet, extruded, then passed through an air gap, possibly stretched in this and finally in a coagulation bath is coagulated, the at least one nozzle channel a conical facing the inflow area Area with decreasing towards the nozzle channel outlet Has diameter.
  • Solutions of cellulose as a high polymer material in tertiary Amine N-oxides also have viscous properties elastic properties.
  • the flow behavior of such solutions is determined by the totality of these properties, the so-called viscoelastic properties influenced.
  • This has to Consequence that e.g. in the flow of such solutions Nozzles after the solution has emerged from the nozzles to expand the jet comes, i.e. the diameter of the one leaving the nozzle channel Solution jet is larger than the exit diameter of the nozzle channel.
  • the extent of the beam expansion is e.g. through the throughput through the nozzle or the shape of the nozzle channel influenced.
  • Threads by extrusion of the above Cellulose solutions through nozzles must be used to achieve a desired small diameter of the finished thread of the thread to be stretched to the maximum thread diameter in the range the beam expansion to the final thread diameter to get.
  • Such stretching leads to orientation of the cellulose molecules in the thread.
  • a too high orientation however, has an adverse effect in the sense of insufficient stretching of the finished threads. Small strains are in most Cases undesirable.
  • EP-A-494 852 describes a process for producing cellulosic Molded articles, in particular cellulosic threads, in which a cellulosic amine N-oxide solution through a nozzle pressed, then passed through an air gap in this if necessary, stretched and finally coagulated in a precipitation bath becomes.
  • the nozzles used according to this document are long-channel nozzles that are preferred in one Embodiment a channel length of about 1500 microns and a minimum Have a diameter of at most 70 ⁇ m.
  • the channel contour this nozzle is designed so that on the outlet side a cylindrical area with a length of at least 1/4, preferably 1/3 of the total length of the nozzle channel is present, which is conical towards the entry side expanded.
  • Nozzles with such a long cylindrical area the exit side, connected to those specified in EP-A-494 852 small diameters, have the disadvantage that even at relatively low cellulosic throughputs Solutions through the nozzle flow instabilities occur. Thereby can when using these nozzles - also taking into account by the design and length of the nozzle channel conditioned high pressure build-up - high process speeds cannot be realized. Furthermore, it is also a safe one and accurate manufacture of such nozzles difficult.
  • DE-A-44 09 609 describes a process for spinning cellulose fibers and filament yarns from solutions of cellulose in water-containing amine-N-oxides after a dry-wet extrusion process by extruding the solutions through nozzle channels disclosed, in which the solution after leaving the nozzle channels e.g. passed through an air gap, stretched there and then coagulated in a precipitation bath.
  • the nozzle channels with a total length between 200 ⁇ m to 800 ⁇ m on the entry side a first cylindrical area, the towards the exit side into a second cylindrical one Area with a smaller diameter that is between 40 ⁇ m and 100 ⁇ m is, and a length of between 40 ⁇ m and 180 ⁇ m passes. Is located between the first and the second cylindrical area there is a conical transition area.
  • the short duct nozzles constructed in this way according to DE-A-44 09 609 have compared to the long-channel nozzles of EP-A-494 852 a smaller one Pressure build up and can because of the short length of the Outlet channel with a small diameter made easier become.
  • the nozzles according to DE-A-44 09 609 also have the disadvantage that relative to the design of the nozzle channel Flow instabilities occur early and thus high process speeds can also not be realized.
  • DE-A-39 23 139 describes a method for gel spinning ultra high molecular weight Polyethylene described in the nozzle with Nozzle channels are used, the cross section of which is trumpet-shaped, funnel-shaped or pseudo-hyperbolic to the exit side gets smaller.
  • the channels of these nozzles can too have a funnel-shaped opening part that is conical which can then either be abrupt or after a transition into passes a conical shape, in which the cone one has a more acute opening angle than the cone of the inlet part.
  • the according DE-A-39 23 139 polyethylene solutions used have concentrations up to a maximum of 6% by weight and are therefore low concentrated. This is for a gel spinning process as in DE-A-39 23 139 described, typically required for the polymer molecules are dispersed and thereby in the spinning process achieve a pronounced orientation and stretching of the molecules can be.
  • the concentrations of Cellulose solutions according to the present invention in the range of at least 10% by weight. Different rheological behavior but also draws different demands on the Execution of the nozzles by themselves through which the respective spinning solutions be extruded.
  • the at least one nozzle channel has a second conical area facing the outflow area with a decreasing diameter in the direction of the nozzle channel exit, that the first conical area is connected to the second conical area by a rounded area, that the first conical region has a larger opening angle than the second conical region and that the second conical region has a length-to-diameter (L / D) ratio, based on the diameter D of the nozzle channel outlet, of between 1 and 15.
  • "Rounded" in the sense of the present invention means an embodiment of the transition from the first to the second conical region which has no edges, kinks or other discontinuities, ie that the transition between the conical regions takes place in the form of a continuous curve. As a rule, the above-mentioned transition area will open tangentially into the adjacent conical areas.
  • the second conical Range of used in the method according to the invention Nozzles advantageously an opening angle ⁇ between 3 ° and 20 °, particularly advantageous an opening angle ⁇ between 6 ° and 12 °.
  • Excellent experience are made with nozzles whose second tapered area has an opening angle ⁇ of 8 ° or 10 °.
  • double the opening angle of the conical areas the angle between the nozzle channel axis and the cone wall to understand.
  • nozzles with a diameter D of the nozzle channel outlet to be used in the range between 20 ⁇ m and 300 ⁇ m.
  • This area of the nozzle channel lies for those used in the method according to the invention Nozzles in front of the second conical area and includes a the first conical area and the area that the first conical area with the second conical area Area connects.
  • the onset of flow instabilities further to higher throughputs through the nozzle can be moved if according to a preferred embodiment of the process the first conical area of the used Nozzles with an opening angle ⁇ of less than 120 ° is executed, but this opening angle ⁇ always the Condition larger than the opening angle ⁇ of the second conical Area to be fulfilled.
  • the opening angle ⁇ of the first conical Range 40 ° to 60 ° larger than that of the second conical Area is.
  • Opening angles ⁇ of the first conical are particularly preferred Range between 40 ° and 90 °. Angle ⁇ with 50 °, 60 ° and 75 ° turned out to be particularly cheap.
  • this connection executed as a rounded area, where Different embodiments of the rounding are possible. However, it is preferred that the rounded area has a circular arc contour has, which is substantially tangential to the adjacent conical areas. In one too preferred embodiment, the rounded region has a hyperbolic contour that is essentially tangential in the adjacent conical area merges.
  • the nozzles used in the method according to the invention therefore show with regard to the onset of flow instabilities an improved property profile and lead due to the In addition, the contour of the nozzle channel is comparatively small Pressure build-up at high throughputs. As a result, a significant increase by means of the method according to the invention achieve the process speed.
  • the cylindrical outflow region mentioned advantageously has a diameter that is equal to the smallest Diameter of the adjacent conical area.
  • the cylindrical Outflow area a length 1 between 2 ⁇ m and 40 ⁇ m, in one particularly preferred embodiment a length 1 between 5 ⁇ m and 20 ⁇ m. Excellent experiences have been made with use of nozzles with a length 1 of the cylindrical outflow area made of 10 ⁇ m.
  • the total length of the nozzle channel in the process according to the invention used nozzles from entering the first conical
  • the range up to the nozzle channel outlet is advantageously in the range between 1000 ⁇ m and 4000 ⁇ m.
  • Figure 1 in the inventive method from a nozzle 1 with a plurality of nozzle channels a variety of Individual filaments 2 spun.
  • the freshly spun filaments 2 pass through an air gap of height H before entering one Immerse the precipitation bath 3 in which they are coagulated.
  • the coagulated Filaments are combined into a yarn 5, which is drawn off via a deflection element 4 immersed in the precipitation bath.
  • the finished precipitated yarn 5 is by means of a deflector 6 for further processing.
  • Figure 2 shows a longitudinal section through the nozzle channel 7 a Nozzle 1 according to the present invention.
  • the nozzle channel 7 opens in the nozzle channel outlet 8 and has the diameter D there on.
  • the nozzle duct has a first one in its inflow region conical region 9, which exits in the direction of the nozzle channel a second conical region 10 with the Length L follows and over with the first conical area a rounded area 11 is connected.
  • the diameter of the first conical region 9 as well as that of the second conical area 10 takes towards the nozzle channel exit 8 from.
  • the opening angle ⁇ of the first conical The area is larger than the opening angle ⁇ of the second conical area.
  • the nozzles used in the examples below were regarding the maximum possible throughput before insertion judged by flow instabilities, in direct relation stands for the maximum possible process speeds.
  • the solution jet leaving the nozzles became irregular observed.
  • the throughput through the nozzles at the first appearance of irregularities in the blasting surface was assumed to be the maximum mass flow.
  • NMMO N-methyl-morpholine-N-oxide
  • concentration information and the viscosity of the solution are given as the amount of complex viscosity at one temperature of 90 ° C and a frequency of 1 Hz, are in the tab. 1 listed.
  • the solution was passed through a nozzle according to the invention with a extruded single nozzle channel that a first, inlet-side, conical area with an opening angle ⁇ of 60 ° and a second, conical area on the outlet side with an opening angle ⁇ of 8 ° and its transition a rounded, from the first to the second conical area, had an essentially hyperbolic contour.
  • the solution was extruded through a die whose Nozzle channel also a first, the inflow area of the nozzle channel facing and a second, the outflow area of the nozzle channel facing conical area, at which, however, is the transition from the first to the second conical Area was sharp-edged (comparison nozzle 1).
  • the details for the geometry of the nozzle channels can be found in Tab. 2.
  • a cellulose solution in water-containing NMMO was used of the pulp V65 (from Buckeye) (For concentration details and viscosity, see Tab. 1). This cellulose solution was at a nozzle temperature of 95 ° C by the extruded the same nozzles as in Example 1 or in the comparative example C1. The results are again in Tab. 2 Find.
  • the outlet area of the comparison nozzle 2 was cylindrical with a length L of 2000 microns and a diameter D of 200 microns. The transition from the entry side conical area in the cylindrical outlet area was rounded off with an essentially hyperbolic Contour.
  • Example 4 the solution was passed through a nozzle according to the invention with a diameter of the nozzle channel outlet of 100 ⁇ m extruded at a die temperature of 95 ° C.
  • the other geometrical Sizes of this nozzle according to the invention are in the table 3 to find.
  • the same cellulose solution was used, on the one hand, according to the comparative example 4 through a nozzle with a sharp-edged transition extruded between the first and second conical areas.
  • the solution according to the comparative example 5 extruded through a nozzle, which instead of the second, the nozzle outlet conical region facing a cylindrical Area with a diameter D of 100 microns and one Has length L of 500 microns and their transition from that of the inflow area the conical area facing the nozzle in the cylindrical area was executed with sharp edges.
  • the remaining geometric sizes of those in these comparative examples nozzles used match those of the example 4 used nozzle according to the invention, as in Table 3 can be seen.
  • Example 5 The same cellulose solution as in Example 4 was used.
  • the in Example 5 and Comparative Examples C 6 and C 7 nozzles used corresponded to those in Example 4 and the comparative examples C 4 and C 5 with the exceptions that the diameter the nozzle channel exit was 130 ⁇ m and the L / D ratio of the conical or cylindrical exit area 6 was.
  • the geometric sizes are in Table 3 listed.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP97920723A 1996-04-29 1997-04-19 Verfahren zur herstellung cellulosischer formkörper Expired - Lifetime EP0900292B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19617079 1996-04-29
DE19617079 1996-04-29
PCT/EP1997/001986 WO1997041284A1 (de) 1996-04-29 1997-04-19 Verfahren zur herstellung cellulosischer formkörper

Publications (2)

Publication Number Publication Date
EP0900292A1 EP0900292A1 (de) 1999-03-10
EP0900292B1 true EP0900292B1 (de) 1999-11-17

Family

ID=7792766

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97920723A Expired - Lifetime EP0900292B1 (de) 1996-04-29 1997-04-19 Verfahren zur herstellung cellulosischer formkörper

Country Status (8)

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EP (1) EP0900292B1 (id)
JP (1) JP2000512695A (id)
AT (1) ATE186758T1 (id)
AU (1) AU2700197A (id)
DE (1) DE59700734D1 (id)
ID (1) ID17252A (id)
TW (1) TW360720B (id)
WO (1) WO1997041284A1 (id)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT1180121E (pt) 1999-05-17 2004-03-31 Conjuchem Inc Peptidos insulinotropicos de longa duracao
GB0226574D0 (en) * 2002-11-14 2002-12-18 Spinox Ltd Apparatus and method for forming materials
CN103014982A (zh) * 2012-12-25 2013-04-03 常熟市碧溪新区明月缝制设备厂 网络喷嘴结构
CN103266360A (zh) * 2013-05-31 2013-08-28 吉铨精密机械(苏州)有限公司 一种丝股铸带头的喷丝板
CN114457431A (zh) * 2020-11-10 2022-05-10 中国石油化工股份有限公司 一种高纺速干喷湿纺制备聚丙烯腈基碳纤维原丝方法
CN114318557A (zh) * 2021-12-20 2022-04-12 晋江市永信达织造制衣有限公司 一种用于涤纶工业丝的纺丝组件及加工方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL87168C (id) * 1951-11-08
BE521689A (id) * 1952-07-25 1900-01-01
US3210451A (en) * 1960-12-01 1965-10-05 Celanese Corp Spinnerettes
AT395863B (de) * 1991-01-09 1993-03-25 Chemiefaser Lenzing Ag Verfahren zur herstellung eines cellulosischen formkoerpers
US5296185A (en) * 1992-12-03 1994-03-22 The Dow Chemical Company Method for spinning a polybenzazole fiber
US5652001A (en) * 1993-05-24 1997-07-29 Courtaulds Fibres Limited Spinnerette
JP3185506B2 (ja) * 1993-12-27 2001-07-11 東レ株式会社 ポリエステル溶融紡糸用口金
DE4409609A1 (de) * 1994-03-21 1994-10-13 Thueringisches Inst Textil Verfahren zum Erspinnen von Cellulosefasern und -filamentgarnen

Also Published As

Publication number Publication date
WO1997041284A1 (de) 1997-11-06
EP0900292A1 (de) 1999-03-10
JP2000512695A (ja) 2000-09-26
ATE186758T1 (de) 1999-12-15
TW360720B (en) 1999-06-11
AU2700197A (en) 1997-11-19
ID17252A (id) 1997-12-11
DE59700734D1 (de) 1999-12-23

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