SI9111976A - Procedure for preparing cellulose forms - Google Patents

Procedure for preparing cellulose forms Download PDF

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SI9111976A
SI9111976A SI9111976A SI9111976A SI9111976A SI 9111976 A SI9111976 A SI 9111976A SI 9111976 A SI9111976 A SI 9111976A SI 9111976 A SI9111976 A SI 9111976A SI 9111976 A SI9111976 A SI 9111976A
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velocity
cellulose
air gap
stretch
spinning
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SI9111976A
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Slovenian (sl)
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Raimund Jurkovic
Heinrich Firgo
Dieter Eichinger
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Chemiefaser Lenzing Ag
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Priority claimed from AT0003191A external-priority patent/AT395862B/en
Application filed by Chemiefaser Lenzing Ag filed Critical Chemiefaser Lenzing Ag
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Abstract

Za pripravo celuloznega oblikovanca stisnemo celulozno raztopino amonoksida skozi šobo ali skozi režo, nato vodimo skozi zračno režo in končno koaguliramo v obarjalni kopeli. V smislu izuma ne raztegujemo v zračni reži, t.j. razmerje odvajalne hitrosti proti hitrosti izstopa iz luknic je največ 1; šele koagulirano celulozo raztegnemo ali globoko vlečemo.To prepare the pulp mold, press cellulose ammonia solution through the nozzle or through slot, then run through the air gap and finally coagulate in a precipitate bath. According to the invention no stretch in the air gap, i.e. laxative ratio the velocity against the exit velocity of the holes is not more than 1; only coagulate the pulp or pull it deep.

Description

Postopek za pripravo celuloznega oblikovancaProcess for the preparation of a cellulose mold

Predloženi izum se nanaša na postopek za pripravo celoluloznega oblikovanca, pri katerem celulozno raztopino aminoksida stisnemo skozi šobo ali režo, nato vodimo skozi zračno režo in končno koaguliramo v obarjalni kopeli.The present invention relates to a process for the preparation of a cellulosic mold, in which a cellulose solution of amino acid is squeezed through a nozzle or slot, then guided through an air gap and finally coagulated in a precipitation bath.

Znano je, da lahko vlakna z dobrimi uporabnimi lastnostmi iz visokih polimerov dobijo le takrat, če lahko dosežejo vlakneno strukturo (Ullmann, 5. naklada Vol. A10, 456). Med drugim je za to potrebno, da v vlaknu dosežejo mikroorientirana območja v polimerih, npr. fibride. To orientiranje določi postopek priprave in temelji na fizikalnih ali fizikalno-kemičnih procesih. V mnogih primerih raztegovanje povzroči to orientiranje.It is known that fibers with good usable properties from high polymers can only be obtained if they can reach the fiber structure (Ullmann, 5th edition Vol. A10, 456). Among other things, it is necessary for the fiber to reach microorientated regions in the polymers, e.g. fibride. This orientation is determined by the preparation process and is based on physical or physico-chemical processes. In many cases, stretching causes this orientation.

Za dosežene lastnosti vlaken je odločilno, v kateri stopnji postopka in v katerih pogojih poteče to raztegovanje. Pri talilnem predenju raztegujejo vlakna v toplem plastičnem stanju, ko so molekule še gibljive. Raztopljene polimere lahko predejo suhe ali mokre. Pri suhem predenju poteče raztegovanje med izhajanjem oz. uparjan1 jem topila; v obarjalno kopel ekstrudirane niti raztegujejo med koaguliranjem. Postopki te vrste so znani in so obširno opisani. V vseh teh primerih pa je važno, da prehod od tekočega stanja (neodvisno od tega, ali gre za talino ali raztopino) v trdno stanje poteče tako, da lahko med nastankom niti dosežejo tudi orientiranje polimernih verig ali verižnih paketov (tj. fibridi, fibrili, itd.).For the fiber properties achieved, it is crucial at what stage of the process and under what conditions this stretching expires. In melting spinning, the fibers stretch in a warm plastic state when the molecules are still moving. Dissolved polymers can pass dry or wet. In the case of dry spinning, the elongation during the spinning process takes place. evaporate solvents; extruded filaments into the precipitate bath during coagulation. Methods of this type are known and are extensively described. In all these cases, however, it is important that the transition from the liquid state (whether melt or solution) to the solid state expires so that the orientation of the polymer chains or chain packages (i.e., fibrids, fibrils) can also be achieved during the formation of the threads. , etc.).

Obstaja več možnosti, da bi preprečili hitro uparjanje topila iz vlakna med suhim predenjem.There are several options to prevent the rapid evaporation of solvent from the fiber during dry spinning.

Problematiko zelo hitre koagulacije polimera pri mokrem predenju (kot npr. v primeru celuloznih raztopin aminoksida) pa so lahko doslej reševali le s kombinacijo suhega in mokrega predenja.However, the problem of very rapid coagulation of the polymer in wet spinning (such as in the case of cellulose solutions of amine oxide) has so far been solved only by a combination of dry and wet spinning.

Tako je znano, da vnesejo raztopine polimerov preko zračne reže v koagulacijski medij. V EP-A-295 672 je opisana priprava aramidnih vlaken, ki jih vnesejo preko zračne reže v ne-koagulirni medij, raztegnejo in nato koagulirajo.Thus, polymer solutions are known to be introduced through the air gap into the coagulation medium. EP-A-295 672 describes the preparation of aramid fibers which are introduced through an air gap into a non-coagulating medium, stretched and then coagulated.

Predmet DD-PS 218 121 je predenje celuloze v aminoksidih preko zračne reže, pri čemer so predvideni ukrepi, ki preprečujejo zlepljenje.The object of DD-PS 218 121 is the spinning of cellulose in amino acids through an air gap, and measures are provided to prevent adhesion.

Po US-PS 4 501 886 predejo raztopino celuloznega triacetata s pomočjo zračne reže.According to US-PS 4 501 886, a cellulose triacetate solution is obtained by means of an air gap.

V US-PS 3 414 645 je prav tako opisana priprava aromatskih poliamidov iz raztopin v postopku predenja suho-mokro.US-PS 3 414 645 also describes the preparation of aromatic polyamides from solutions in the dry-wet spinning process.

Pri vseh teh postopkih dosežejo v zračni reži določeno orientiranje, kajti samo iztekanje židke raztopine skozi majno odprtino navzdol vsili na osnovi težnosti delcem raztopine orientiranje. To orientiranje zaradi težnosti se lahko še zviša, če sta ekstrudirna hitrost polimerne raztopine in odvajalna hitrost niti tako naravnani, da dosežejo raztegovanje.In all of these processes, a certain orientation is achieved in the air gap, since only the leakage of the liquid solution through a small opening downwards forces the particles of the solution to orient themselves. This orientation due to gravity may be further enhanced if the extrusion velocity of the polymer solution and the discharge velocity are not even adjusted to achieve stretching.

Postopek te vrste je opisan v AT-PS 387 792 (oz. temu ekvivalentnim US-PS 4 246 221 in 4 416 698). Oblikujejo raztopino celuloze v NMMO (NMMO = N-metilmorfolin-N-oksid) in vodi, raztegnejo v zračni reži in nato oborijo. Raztegovanje izvedejo pri raztegovalnem razmerju najmanj 3.A process of this type is described in AT-PS 387 792 (or equivalent US-PS 4 246 221 and 4 416 698). They form a cellulose solution in NMMO (NMMO = N-methylmorpholine-N-oxide) and water, stretch it in an air gap and then precipitate. They shall be stretched at a stretching ratio of at least 3.

Hiba tega postopka je pomanjkljiva fleksibilnost, ki lahko spremeni lastnosti oblikovanca. Potrebno je minimalno predilno-raztezalno razmerje, da dosežejo ustrezne tekstilne podatke. Pri zelo majhnem raztegu se dajo doseči le izredno skromne tekstilne lastnosti vlaken, t.j. da se npr. pri izdelavi vlaken doseže izredno majhno trgalno delo (to je produkt iz trdnosti vlaken in raztezka vlaken). Nadaljnja hiba je, da je učinek t.i. resonace odvajalne/izstopne hitrosti (prim. Navard, Haudin, Spinning of a Cellulose N-Methylmorpholine-N-oxide solution, Polymer Process Engineering, 3(3), 291 (1985)), ki vodi do neenakomernih premerov vlaken, tem večja, čim večji je predilno-raztezalno razmerje. Končno je tudi pomanjlkljivo, da lahko pride do oblikovanja praktično le v zračni reži. Naknadno oblikovanje je mogoče le zelo s težavo. Zaradi tega je širina traku možnih produktov seveda omejena. Zaželen bi bil naknadni vpliv na lastnosti produktov, s čimer bi ta postopek pridobil bistveno fleksibilnost.The downside of this process is the lack of flexibility that can alter the properties of the designer. A minimum spinning-elongation ratio is required to obtain adequate textile data. Only very modest textile properties can be achieved at very low elongation, i.e. that e.g. achieves very little tear-off work in the manufacture of fibers (that is, the product of fiber strength and elongation). A further disadvantage is that the effect of t.i. resonance of discharge / exit velocity (cf. Navard, Haudin, Spinning of a Cellulose N-Methylmorpholine-N-oxide solution, Polymer Process Engineering, 3 (3), 291 (1985)), leading to uneven fiber diameters, the greater the spinning-elongation ratio. Finally, it is also minor that design can be practically only in the air gap. Subsequent design can only be very difficult. As a result, the bandwidth of possible products is, of course, limited. Subsequent impact on product properties would be desirable, giving this process substantial flexibility.

Naloga predloženega izuma je, da bi odstranili te hibe.It is an object of the present invention to eliminate these defects.

To nalogo rešimo s postokom uvodoma navedene vrste v smislu izuma tako, da je razmerje odvajalne hitrosti proti hitrosti izstopa iz luknjic največ 1 in da oblikovanec po koagulaciji raztegnemo ali globoko vlečemo.This task is accomplished by postoccupying the species of the invention according to the invention, such that the ratio of the discharge velocity to the exit velocity of the holes is at most 1 and that the coagulation is stretched or deeply drawn after coagulation.

V smislu izuma je torej odvajalna hitrost manjša (ali največ enaka) hitrosti izstopa iz predelne mase iz luknjic, tako da ne more priti do raztegovanja; s tem ostane celuloza do koagulacije v obarjalni kopeli v relativno neorientiranem stanju. To je ugodno, kajti čim manjše je orientiranje pred oz. pri koaguliranju, tem večja je možnost vpliva na lastnosti kasneje. Zaradi majhnega orientiranja ima koagulirana (oborjena) celuloza elastičnost, ki skoraj spominja na gumo. V smislu izuma lahko sedaj to celulozo raztegnemo oz. globoko vlečemo, da dosežemo želene lastnosti. S tem dosežemo želeno fleksibilnost.According to the invention, therefore, the discharge velocity is less (or at most equal to) the velocity of the exit of the mass from the holes, so that no stretching can occur; thus, the cellulose remains coagulated in the precipitation bath in a relatively undirected state. This is advantageous, since the orientation towards the front or rear is as small as possible. when coagulated, the greater the chance of affecting the properties later. Due to the low orientation, the coagulated (precipitated) cellulose has an elasticity that almost resembles rubber. According to the invention, this pulp can now be stretched or stretched. we pull deeply to achieve the desired properties. This achieves the desired flexibility.

Nadaljnja prednost obstoji v tem, da zaradi nič več prisotnega raztegovanja lahko izdelamo zračno režo skoraj poljubno kratko, tako da celo takrat, če imajo predilne šobe zelo visoko gostoto luknjic, ne obstoji nevarnost, da bi se sosednje niti zlepile. Ker lahko pri industrijski proizvodnji odločilno povečamo produktivnost z zvišanjem gostote luknjic, je tudi to bistvena prednost predloženega izuma.A further advantage is that, due to the more extensible presence, the air gap can be made almost arbitrarily short, so that even if the spinning nozzles have a very high hole density, there is no risk of contiguity or sticking. Since productivity can be decisively increased in industrial production by increasing the density of holes, this is also an essential advantage of the present invention.

Izum bliže pojasnjujejo naslednji primeri.The invention is further explained by the following examples.

PRIMER 1EXAMPLE 1

Priprava vlakna pri razmerju odvajalne hitrosti proti hitrosti izstopa iz luknjic pod 1 (primerjalni poskus) %-no celulozno NMMO raztopino (celičnina tipov Viskokraft firme ICP, 10 % vode, 77 % NMMO, 0,1 % oksalne kisline kot stabilizatorja) stisnemo skozi šobo s 100 luknjicami (premer luknjic vsakokrat 130 μτη). Izriv je 16,5 g/min; iz tega dobljena izrivna hitrost je 10,35 m/min. 100 niti vodimo skozi 8 mm dolgo zračno režo in nato s hitrostjo 6 m/min vodimo skozi 15 cm dolgo predilno kopel (temperatura: 2°C, koncentracija NMMO: 5 %). Razmerje odvajalne proti izstopni hitrosti znaša torej 0,58.Preparation of the fiber at the ratio of the discharge velocity to the exit velocity of the holes below 1 (comparative experiment)% cellulose NMMO solution (cellulose of ICP Viscocraft types, 10% water, 77% NMMO, 0.1% oxalic acid as stabilizer) is squeezed through the nozzle with 100 holes (holes each 130 μτη each). The displacement is 16.5 g / min; the ejection velocity obtained is 10.35 m / min. 100 strands were run through an 8 mm long air gap and then run at a speed of 6 m / min through a 15 cm long spin bath (temperature: 2 ° C, NMMO concentration: 5%). The ratio of the discharge to the exit velocity is therefore 0.58.

Iz tega dobljeno vlakno ima trdnost 11,8 cN/tex pri raztezku 77,5 %. Vrednost za raztezek je zelo visoka; to dokazuje, da se celuloza nahaja v relativno neurejenem stanju.The fiber obtained has a strength of 11.8 cN / tex in elongation of 77.5%. The stretch value is very high; this proves that the pulp is in a relatively disordered state.

PRIMER 2EXAMPLE 2

Raztegovanje vlaken po koagulaciji na zrakuStretching of fibers after coagulation in air

Pri tem poskusu delamo kot v primeru 1. V tem primeru pa vlakno po predilni kopeli, t.j. po koaguliranju, navijemo na galeto s 6 m/min in snopič niti vodimo preko druge galete s hitrostjo 13 m/min. Raztegovanje znaša torej 117 %. (Ob raztegovanju vlakna v % je mišljeno v okviru te prijave (končna dolžina - začetna dolžina)/začetna dolžina.100). Iz tega dobljena vlakna imajo trdnost 22,4 cN/tex pri raztezku 15,3 %).In this experiment, we act as in Example 1. In this case, however, the fiber is after a spinning bath, i.e. after coagulation, wind on the galette at 6 m / min and thread the bundle through another galette at a speed of 13 m / min. The stretch is therefore 117%. (By stretching the fiber in% is meant under this application (final length - initial length) / initial length.100). The resulting fibers have a strength of 22.4 cN / tex in elongation of 15.3%).

PRIMER 3EXAMPLE 3

Raztegovanje vlaken po koagulaciji v vodiStretching of fibers after coagulation in water

Pri tem vlakno vodimo spet kot v primeru 1 skozi predilno kopel s 6 m/min (odvajalna/izstopna hitrost: 0,58) in nato skozi 80 cm dolgo raztegovalno kopel z vodo (temperatura: 77°C). Druga galeta obratuje z dvema različnima hitrostima v. Dobljena vlakna imajo naslednje lastnosti:The fiber is then run again as in Example 1 through a spinning bath of 6 m / min (discharge / exit velocity: 0.58) and then through an 80 cm long stretch bath with water (temperature: 77 ° C). The second galette operates at two different speeds in. The fibers obtained have the following characteristics:

v v raztegovanje stretching Titer Titer trdnost kond. raztezek kond. the strength of the cond. elongation of the cond. m/min m / min % % dtex dtex cN/tex cN / tex % % 14 14 133 133 32,4 32,4 19,7 19.7 17,5 17.5 21 21 250 250 10,3 10.3 22,3 22.3 9,2 9.2

PRIMER 4EXAMPLE 4

Priprava vlakna pri razmerju odvajalne hitrosti proti hitrosti izstopa iz luknjic nad 1 (primerjalni poskus) %-no celuzlozno NMMO-raztopino (celičnina tipov Visokraft firme ICP, 10 % vode, 77 % NMMO, 0,1 % oksalne kisline kot stabilizatorja) stisnemo skozi šobo s 100 luknjicami (premer luknjic vsakokrat 70 μ,ιη). Transportna količina je 5,1 g/min, kar ustreza izstopni hitrosti 11,1 m/min. Odvajalna hitrost prve galete je 33,3 m/min, t.j. razmerje odvajalne proti izstopni hitrosti je 3,0. S hitrostjo galete 1 vodimo niti skozi predilno kopel, katere temperatura znaša 33°C in katere koncentracija NMMO 10 %. Naslednja raztegovalna kopel ima temperaturo 79°C in koncentracijo NMMO 9 %. Druga galeta po raztegovalni kopeli ima odvajalno hitrost 46,9 m/min, t.j. raztegovanje znaša 41 %.Preparation of the fiber at the ratio of the discharge rate to the exit velocity of the holes above 1 (comparative experiment)% cellulose NMMO solution (cellulose of ICP Visokraft types, 10% water, 77% NMMO, 0.1% oxalic acid as stabilizer) 100-hole nozzle (hole diameter 70 µ each, ιη). The transport quantity is 5.1 g / min, which corresponds to an exit velocity of 11.1 m / min. The discharge velocity of the first galette is 33.3 m / min, i.e. the laxative to outlet velocity ratio is 3.0. At the speed of galette 1, the filaments are guided through a spinning bath whose temperature is 33 ° C and whose NMMO concentration is 10%. The next stretch bath has a temperature of 79 ° C and a NMMO concentration of 9%. The second stretch bath has a discharge velocity of 46.9 m / min, i.e. stretching is 41%.

Tekstilne lastnosti dobljenih vlaken so:The textile properties of the fibers obtained are:

Titer: 3,5 dtexTiter: 3.5 dtex

Trdnost kondicionirano: 25 cN/texCondition strength: 25 cN / tex

Raztezek kondicionirano: 8,8 %.Elongation conditioned: 8.8%.

Vlakna so pri razmerju odvajalne hitrosti proti hitrosti izstopa iz luknjic nad 1 načelno tudi še raztegljiva, vendar ne več v tisti meri, kot je dokumentirano v primerih 2 do 4.The fibers are, in principle, still extensible at the ratio of the discharge velocity to the exit velocity of holes above 1, but not to the extent described in Examples 2 to 4.

PRIMER 5EXAMPLE 5

Priprava folije %-no celulozno NMMO raztopino (celičnina tipov Buckeye V5 firme Procter & Gamble, 12 % vode, 79 % NMMO, 0,1 % oksalne kisline kot stabilizatorja) stisnemo skozi zarezno šobo (reža 50 μηπ; dolžina: 30 mm). Izriv znaša 21,3 g/min, kar ustreza izstopni hitrosti 11,7 m/min. Ekstrudirano raztopino odvajamo skozi 7 mm dolgo zračno režo in nato skozi 15 cm dolgo predilno kopel (temperatura: 24°C; koncentracija: NMMO 20 %) s pomočjo prve galete s hitrostjo 6 m/min. Razmerje odvajalne proti izstopni hitrosti znaša torej 0,51. V isti delovni stopnji vodimo folijo skozi 80 cm dolgo raztegovalno kopel (temperatura: 90°C; koncentracija: 20 %) in raztegnemo z drugo galeto (hitrost: 11 m/min). Raztegovanje znaša torej 83 %. Lastnosti izprane in posušene folije so: debelina: 10 μm; trdnost: 200 N/mm2; raztezek: 6,5 %.Preparation of the foil% cellulose NMMO solution (cellulose of Buckeye V5 types from Procter & Gamble, 12% water, 79% NMMO, 0.1% oxalic acid as stabilizer) was squeezed through a notch nozzle (50 μηπ slot; length: 30 mm). The displacement is 21.3 g / min, which corresponds to an output velocity of 11.7 m / min. The extruded solution is discharged through a 7 mm long air gap and then through a 15 cm long spin bath (temperature: 24 ° C; concentration: NMMO 20%) using the first galette at a speed of 6 m / min. The ratio of the discharge to the exit velocity is therefore 0.51. In the same working step, run the film through an 80 cm long stretch bath (temperature: 90 ° C; concentration: 20%) and stretch with another galette (speed: 11 m / min). The stretch is therefore 83%. The properties of the washed and dried foil are: thickness: 10 μm; strength: 200 N / mm 2 ; elongation: 6.5%.

PRIMER 6EXAMPLE 6

Priprava oblikovancaDesigning the designer

Pripravimo folijo kot v primeru 5, vendar je ne raztegnemo, t.j. po prvi galeti folijo odvzamemo. V neraztegnejem stanju jo globoko vlečemo s stekleno palčko 3 mm, izperemo in posušimo, s čimer dobimo stabilen oblikovanec.Prepare the foil as in Example 5, but do not stretch it, i.e. remove the foil after the first galette. In a non-stretchable state, it is deeply drawn with a 3 mm glass rod, washed and dried to give a stable mold.

Claims (1)

Postopek za pripravo celuloznega oblikovanca, pri katerem celulozno raztopino aminoksida stisnemo skozi šobo ali režo, nato vodimo skozi zračno režo in končno koaguliramo v obarjalni kopeli, označen s tem, da je razmerje odvajalne hitrosti proti hitrosti izstopa iz luknjic največ 1 in da oblikovanec po koagulaciji raztegnemo ali globo povlečemo.A process for the preparation of a cellulose mold, in which a cellulose solution of amino acid is squeezed through a nozzle or slot, is then guided through an air gap and finally coagulated in a precipitation bath, characterized in that the ratio of the discharge velocity to the velocity of the holes exits at most 1 and that the mold after coagulation stretch or fine drag.
SI9111976A 1991-01-09 1991-12-23 Procedure for preparing cellulose forms SI9111976A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0003191A AT395862B (en) 1991-01-09 1991-01-09 METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY
YU197691A YU47786B (en) 1991-01-09 1991-12-23 PROCEDURE FOR PREPARING A DESIGNED CELLULOSE ARTICLE

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SI9111976A true SI9111976A (en) 1994-12-31

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