CA2040844A1 - Method of making an aqueous solution of cellulose - Google Patents
Method of making an aqueous solution of celluloseInfo
- Publication number
- CA2040844A1 CA2040844A1 CA002040844A CA2040844A CA2040844A1 CA 2040844 A1 CA2040844 A1 CA 2040844A1 CA 002040844 A CA002040844 A CA 002040844A CA 2040844 A CA2040844 A CA 2040844A CA 2040844 A1 CA2040844 A1 CA 2040844A1
- Authority
- CA
- Canada
- Prior art keywords
- cellulose
- water
- ccell
- ch2o
- weight
- 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.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Abstract
ABSTRACT OF THE DISCLOSURE
A system of cellulose in N-methylmorpholine-N-oxide and water is subjected to mixing at shear rates of 400 to 3000 sec-1, preferably 500 to 800 sec-1 and the following conditions are maintained (cCell representing the mass proporion of cellulose and cH2O representing the mass proportion of water):
and cCell ? 0.58 - 2.23 cH2O. (IV).
ef-
A system of cellulose in N-methylmorpholine-N-oxide and water is subjected to mixing at shear rates of 400 to 3000 sec-1, preferably 500 to 800 sec-1 and the following conditions are maintained (cCell representing the mass proporion of cellulose and cH2O representing the mass proportion of water):
and cCell ? 0.58 - 2.23 cH2O. (IV).
ef-
Description
7~23 N~ 20 40 84 4 I~OD 0~ 15A~:NG AN AQUEOUS SO~U~ION ~F OE~WI~6E
SPECIFICATION
our pres~nt lnv~n~ion rel~tes to a ~ethod of preparin~ a ~olut~on o~ ~ellulos~ in N-~thyl~orphol~no-N-Gxids an~ ~ter $n ~hich th- three Gomponentc ~r m~x-d to~ether. The invention also r~l4tes to a solution oX cellulo~e oontaining the N-methyl~or-pholine-oxido and wat~r. Such ~olution~ can b~ u-ed wherever the ~or~atlon of c-llulo~- articles by precipitation ~rom ~olution is to be ef~c~ed.
B~kp~ou~ Q~ ~h~ I~ven~gn A process rOr ~a~ing a ~olut~on of oellulo6~ in N-~-thylmo~phol~ne-N-oxide tNN~0~ ha$ been d~scribed in ~.s~ patent 4,196,282. ~o deter~lne th- ~aximum c~llul~e ~onoentration experi~ontAlly ~ccordln~ to thl~ p~tent, the three-co~ponent ~y-tem ~orc~ a ho~e~ogQneou- ~lxture w~ich, by the ~levation o ~e~pera-turo, stlrring and eYaporatlon o~ w~ter~ i8 converted ~o a ho~ogenaou~ ~inning ma3~ ~o~ ~hlch ~ellulose ~ber~ can b~ spun.
78~3 HR 2040844 ~ t ha~ be~n ~ound that the ~aximu~ c:ellulo6e concentration drop~ an th~ watqr pr~portion ino~ea6e~ ~hat mean~ that, for a g~ n cellulose concentra~ion, there i~ a maximum p~rmiBsible w~ter concontration. I~ the wat~ concentrat~on drops becau~e of 5 ovRporation o~ water, the cellulo~e will go completely into ~olution. Th- mas~ or weight proportions under th~e conditlon0 stAbl~h ~or A given w~ter propo~tion the associated maxi~u~
c~llulo~e proportion.
A~ ~ con8egu~nce OS ~nany test ~eries, the following 10 r~latio~s~hip was ostabli~hed in that patent between th~ mass proport$on or oonc~ntr~t i on oS cellulo~e tcc~ n~ the ~a-6 ~roportion or conc:entration of th~ water (cH2O):
ccell ~ 0. 3469-1. 695 ~20 ~I) Cc~ll S 0-3469~ 695 c~20 1 0.0081 h.65+0.1tlOO c~2o-12.76)~
~h-~Q two inequaliti~ are represen~ed in F~G. S of th~
afore~erl~on-d pAt~nt ~n whlch cur~ A corre~ond~ to the inequality II and the cunre ~ to ths ~negu~ y 1.
I~ th~ ~nequ~ y I i~ ~ulfllled tin thi~ ca6~ the in~uality TI i~ toDlAtically ~o ful~illQ~), t~e celluloc- csn di~ol~e reli~ly in N~S0 ~nd ~aterO 11~ o~ly the isl~qu~lity I le ~ul~illed ~nd the $rlequal~ty I i~ not ~ulfLlled, th~r~ s~ghlficant ~robabil~ty, but n~rth-le~ no a~uranco, of co~plete ~olul~iliza-tlon og th~ c-llulo~ h- c~tod u.s. patent al~o ~ives lo~lrer li~its ~or t~ water ~nd ~ellulo~e contant ~curve6 c ~nd ~ in ~IC. 5~.
Should the water cont~nt Pall exce si~ely, ~ olution can cry~tallize out by ~hoar lnduction av~n ~t very hlgh temperatures.
8uah ~ ~olution cannot b~ procass~d further even by a ~ub~e~auenS incr~as- in the t-m~era~ure.
7823 l~a 2040844 In ~ddition, at low w~t~r contents, th~ ~xture falls in~o t$mp~r~ture and c:onc~ntratior. ran~e which lies close to the ~ecompo~tlon and explosive llmit of the NM~50-cellulose system.
D~f~er~nt~al scannirg calori~etry ~DSC~ ~neasure~ent3 show the ~egins~ing of thQ decomposition to b2 ju~t 61ightl~ above 170'C. To malce ~ dis~olution proe~s~ r~l~a~le, howevQr, ~t lIlU5t ~e cer'cain that t;h~ opQrating te~pQraturo is as fsr as possible from ~e temperature at whioh d~co~po8ition wlll be initiate~
In th- d~olul:ion o~ cellulo~ in NMMo and wat~r, the water ha~ ~av~ral funotions. On~ o~ lt- ad~antages i8 that in a ~ixture of N~SO ~nd w~ter, more c~llulose can be dissolved th~n ~n pure NMMO.
Thu8 an extru~lon of the solution, for example, for th~ spinning of colluloo- flla~nent, i~ po~lble~ me water content, however, ~hould not bo too l~ h ~lnc- elevatlon of the w;lter content re~ult~ in line~r reduotlon o~ th- ~ximurd pos5ible cellulos~ concentration.
When the 801uti~n ~ ~xtruded and ~n ~g~eous N~O ~olution for~s tb- ~r~ciplt~ting b~ , the pre¢ipitating~ b~th can b~
concentr~tod in a r~circulatlng ~ste~, cl~ned and ~herea~t~r r-cycl~d to th~ cellulo~e-~ssolvln~ st~3p or ~tage.
The over~ll e~ici~ncy ~nd ~nv~ronment~l ~oundnes~ o~ the procoss ~epsn~s upon the xt-nt to which thore is ~n NMqO ~nd wat~r r~rculatlon. F~thermor~, ~t ~s Advantageou~ ~o replace th~ very co~tly solvent )~SO wlth wat~r ~n th~ sp~nning mass and to thereby ro~uo~ t~o pro~ co~t dlrec~ly. I~ oolution~ wit~ a high w~ter cont~nt ~r- oxtrudQd~ ~aving~ ln respe¢t to th~ precipitatlng ba~h can ~l~o be mado.
7~23 lSR
It i~, ther~fo~e, th~2 principal ob~ect of the preserlt invention to provid~ ~n i~p2~0ved ~et~od for preparing a solut~ on of c~llulo~ in ~MMO and water which has ~n increased wa~er content, in which 'che ~a~oty of the proce~ ~nd the te~nperature o~ decompo~it~ on ar~ ~ncr~a~ed ~nd which con~Qnr~s the exp~5sive ~olvent and pr~c~pitating agent which ~ust bo regenerated.
Anoth-r ob~act of thl~ invention 1~ to provtde ~n improved method of ~ olvlng cellulo-- in ~0 and wa~er where~y drawback~ of oarlier ~y~tem~ ~xoe ~voided.
~tlll nother ob~ect ~ ~ to provide an improved cellUlos2-NMM0--water o~ut~on.
o ob~-ct~ and oth~r6 which will beco~e appar~nt hereinaft-r are atta$n~d, in ~ccordance wi'ch th~ ~resent invent~on, in ~ proc~ or ma~c~n~ a solution of c~llulo~e in ~ and water ~hi~h co~prl~e~ ttl- ~tep~ o~s (~1) for~ing A m~xtur- of water, cellulo~ ~nd ~-mothyl~orphol lne-N-oxld~;
~b~ 6ub~ecting the ~ix~ure to ~ixing wit~ ~ ~hear rate oS 400 to 3000 ~ and to~ controlllng th- concentxation by weight cCell o~
c~llulo~ and th- concent~tion by weight o~ wator ¢~zO ~o that it ~ti~fie~ the rel~tion:
C~ 0~346g v 1.695 ~0- (III) 78a3 MP.
Advant~geously, ~he shear rate is 500 to 800 5 ~. It h~s ~een found, 6urpri ingly, th t siqnificantly more oellulose can ~e dissolved w$th a given water concentration when the mixture i5 ~ub~octed to th~ high 6hear ra~es ~;e~ forth. Thi~ phenomenon has 5 been $ound to depend ~ar ~nore upon the 6hear ra~ce than upon the ~tirs~ing en~rgy which al~o is quit~ surprising.
Tho ~0 which i~ introduced into th~ ~ixture can b~ eithex t~,hnic~l grad~ N~10 or 2~MO which has ~e~n recycled ln the manner des~ri~d a~ve.
I~ hll- b~en found to b~ ~dvant~geou~ to ~a1ntain a t~p~rature, dur~ng tha mix,tng ~ the shear rat~s des~x~bed above, of 70 ~o 120-C, p~f-rably ~bou'c ~09~. A~ the~e te~pornture~ the cellulo~e dissolve~ espac~lly well ~nd the operatinsl tempexatur4 is ~u~iciently ~ar remov-~ from thQ deco~position te~era~UrQ o~ the 5 N~Q~0 .
an~ageou~ly, one o~ tho component~ o~ 'che Dllxture or the ~xtur~ it~el~ conta$n~ or ha~ ~dded thoreto 0 to 19~ ~y w~ight of a or. Th- ~t~blliz~r c~n be ~elected ~rom ehe group whi~h con~i~t- o~ g~llic ac$d and gallic ~cld estQr~, pyro~a~echln, ellagic 20 Acid, yyrog~llol, ox~llc acid, phosphoric ~cid a3~d Bodiu~ hexameta-pho~phat-.
axtn~u~o cellulo~ concentra~ion wh~ch c~n be achlov~d~
~coordlng to ~- ~nventlon correspond~ 'co the ir,equality:
cce~ 0 58-2 ~3 CH20 tIV) Tho ~olution o~ tnq in~rention thu~ conta~n~ cellulose, N2~0 ~n~ water with th~ ma~ proportion of cellulo~Q cc"ll and the ~a~s proportlon o~ wat-r (c~20) corresponding to 'che ~ollowing r ~tion~:
_ 5 _ 782~ )IR
C--ll 1.695 ~2 + 0.00~1 ~,/1.6510.1(100 cH o-12 j~2 (V~
cCell ~ 0-5B - 2-23 ~H O (1~) For the inequal~y IV, w- have d~veloped a theoretic 1 explanation ~lthou~h we dG not wi~h te bQ bound by thi~ th~ory. The t~ory 18 ~ev~loped wlth rQfer~nce to the acco~parlying dr~w~ng.
!rho ~bovQ ~nd other ob~ ects, featur~ and ~dvant~ges of the p~ nt imrent~on will b-com- mor~ readily apparent ~rom the following dewription, 2~ r-nc- ~e$ng ~ade to ~he acco~panying dr~wlng in whi~h:
FIG. 1 i~ A g~ph d$agranm~nçl the ~ax~um col~ility o~
c~lluloo- JlR ~eporld~nce upon a water ~ontent:
F~C. 2 is ~ binary d~agr~m for the f~y8te~ O~H~O; and ~`I6. 3 $~ ~n X-~y ~tructur~l ~nalysio of cellotetro~e and ~n~y~ro N~QSO~
~çc$~1c,_~rip~Qn It ~ known th~t th~ ~yotem NM~O/watsr has not ~ ~n~le eutectic bu'c two utec~ic~ (s~- FIG. 2).
To di-~olve the cellulo~o, it h~s been po~ le heret~fora to 2~ u~- only th- eutectio which oorresponded to the ~onohydrate ~
Surprl-ingly we hav~ discov~r~d that ~y oporat1ng a~ th~ h~ghe~ 6hear ra~o~ Or th~ inv~rltion, i'c ~ pos-lble to utilize the secot~d e-~tecti~
which corre~pond~ to 2C~ w~tor and 7~% N~SO. ~he D~lt~n~ point of ut~ctlc is 36-C. It corr~spond to a ~olar ratio o~ ~ mol N~MO
t~ Z.3 ~ol ~ tor ~th~ Nl*10-2.3-hydrat-i or the ~ihydrate ~H).
-- 6 ~
7823 ~ X04084~
Th6 N~O ~.3 hyd~at~ is parl:icularly advantageous ~ecause in o~n~tion of 'ch~ olution, wa~er molecule~ are exl:nanged Wit~
cellulose-o~ ~olecules~
In an X-ray ~truc ur 1 analysis of cellotetrose and anhydro N~qO ~AP), (FIG. 3), it i~ four~d tha~ only one glu~o~e unit i~
bound. IS. Maia, E.R.: Peguy, A.,: Perez, S.: Cellulose organic ~olution~. T. Th~ ~ruotur~ o~ ~nhydrou~ 50 ~nd N~O ~onohydrate Act~ Cry~t~llogr., S~ct.B ~9Bl, B37(10), 1858-62, J~n 1, lg~l.) With th- ~ormation of the NMM0-2.3-hydrat~ ln ~he liqu~d phase ~) with replac~m~nt o~ th~ wa~r molRcule by Cell-OH, solut~on~ with ~uPstantlally high~ water con~ent t~an i~ the cace $n the 6y~te~s de~crib-d ~n the U.S. pat~nt 4,196,2~2, can be atta~ned.
In th~ ~olution, the ~ree NMMO i5 in th~ for~ o~ NMMO (Z to 2.3~-bonding) (c~ th- ~utectic mixture in FIG. 2~ ~nd ~2ch ~nhydro ~luco~e un~t o~ the celluloRe ~ bound to anhydro NMMO. ~he m~xi~u~
po~ Yat~r concentration in an NNMO-c~llulos~-wat~r ~olu~on can b- d t~m~lned ~y th~ bln~ry dl~gra~ ~FIG. 2). ~er~ ~t a cellulo~
con¢entr~tion ~ 0~:
CHzO~ Z6~ - n.2~.
~h- m~x~mu~A c~llulo~- concent~a~ion (water-rre~ ~olutlon) is ~ ren ~rom F~ ~ upon a bonding of each anhydro glucosa un~
to 4 ~axi~u~ o~ 1 N~So, 1.~. a ~olecul~ ~at~o ~so: anhydro gluclose ~ount~ to 1.
~CC-ll/ ~ Anhyar ~lucog~ ~ o/JQ5 ~ o) ~ 1 (¢1~ell/l62)/ ~ 7) ~ 1 2040~344 78Z3 M~
~CC-ll/CNM~o) ' ~62/1~7 - ~.38 Cc~ 1.38 * cNMM0 ~--11 CNMMo 100% G
From the~e two equations it ~an be seen tA~t:
5 ~MO ~I 42~; ccæl}, e 58%
Fro~ thi~ one c~n obtaln by linea~ int~rpolation the r~ght-hand ~ou~dary ~C) of the ~olubilit~ range in FI~. 1 as:
C~ell ' O.S8 - 2-23 ~ cH~o or, tr~n~or~ed as:
~H20 ' 0-26 - 0.448 * CC 11 ln addl~lons ~N~Mo ~ 1 - CH20 CCell CSt~b~1izer ~n ~C. 1, two boundary concentrations hove been qi~en by the ~o~o-c~t~d U.~. pat~nt 4,196,2~2, na~ely, c~rve6 A and B o~ ~IG. 5 ~5 the~or and nloo d~s$gn~t~d ~s A ~nd B. In FIG. 1, ~urther points ~r- ~n~c~t-d ~h~h corr~-pond to the ~xa~le~ d~.~cus~d below. ~n the ~xa~pl-~, th- d~t~mination o~ th~ cellulose content io ~ect~d gr~motrically by the pre~p1tat~on o~ the ~ellulose with ~t~r. In t~- rlltrat~, the NMMo ~onc~ntratlon ~8 poten~io~e~rically qet~r-~n-d. ~he deter~n~ion o~ the water conc~n ration i~ e~fec~ed a~t~r ~roc~ptt~ n o~ th~ ce~lulose with ~ethanol in tho ~ltr~te by ~ean~ o~ the ~arl-Fiwher r~a~on~.
Tbe cellulo~--D~ i- determined by cal~ulating the numerieal ~verAg~ and d-t~rmin~ng the l~miting vi~co~ity coefficie~ in ~ccordance wit~ the cuen ~otho~ ~TAPPI T230). Mea~urement~ were made in th~ oscillatlon modo t~ ~ angular v~locity~.
Classification of the solution:
Optically: u~der the ~icroscope.
Vl~cosi~Qtrically: By m~ans o~ a ~otational viscosimeter of the firm HAAXE, type ~V20 ystem plate-2-pla~e (PQI, gap: lmm, m-asuring temp-rature: 95'C, oscillation mode3.
Tn ~ 3 liter kn~ader, Typ~: Werner ~ Pfl~iderer, LU~ S III-l, the ~o~ponent~ cellulo~e, N~MO ~recry~tali2ed ~rom acetone) ~ate~ and GPE (gallic acld propyl e~ter) ~3 ~ta~ili2er is knR~ded fro~ 15 to 115 ~inute~ t 70-C to 120'C (~ble 1) unt~l a transparent solution 18 ~or~ed ~6 ~t~r~in-d by m~cro~co~e exa~ination. The ex~c~
p~r~tor~ o~ the t~0t ~n~ th~ re~ult~ ~re ~ccumul~ed in Tabla 1.
Exa~pl~ nd 21 lie in the known ranqes out~ide the inv~ntion.
; 5h~y h~vo be~n lncorpor~ted ~o lnd~cate that the u~e of a st~bilizer $~ ~d~Antageou~ ln all ca~4 to rQ~uce cellulose decompo~tion~ The hlgh~ tho st~bilizer co~centrAt~on, the less the cellulosa d-co~po-itlon tDP)~
Examples 13, 14 and 20 are out~de the progno~ticat~d solutlon r~ng- ~nd show no dlssolut~on of the cellulose. In Example 17 there ~r- m~ny und~-~ol~ed ~bor fragment~ ln the solu~ion.
q~bl e 1 2040844 _ ,_ -_ _ __ . _ Viscoslty __ Cell. N~o r~ o GPE ~per-tu~e 'rrea~rnent ~ 0~31 ;xample (~ ~x~ ~) ~x) ~ ~c) ~uratioh ~ DP
. ~1n~ ," i~ IP~
~..... .~ ~ - _. __ _ _~. _ , _,~
1 s,e 13,~ 76,8 0,0~ 18- a7 20- ss 2,93.10~ ~0 2 1~ ,0 13,~ 72,7 O,o~ ~7~103 2S~ 85 ~ 0~ ~50 S 3 ~5,3 ~Z" 7~,6 0,02 96-lOS 15- 60 6,06.10~ ~70 ~ ~,9 IJ,S ~ 0,02 97~0~ 15- 60 s,oQ.lo~ ~0 S 13,9 1~,~ 69.8 0.02 ~9-10- ~5- 60 7,~0.10~ S10 15,2 IS,J Cs,S 0,02 ~oo-lo~ 60 I,o~. 10~ 550 7 15,0 1~,5 66,5 0.08 ~00-10~ 55 1,29. ~o~ Sgo ~ 1-,~ ~2,1 69.6' 0~02 ~ 07 20- 8S ~,10.10~ J20 . g ~Z,O 1~,~ 65,2 0,02 99-lOS ~o- 60 9,08.10~ 3~0 ~,2 ~2,~ 66,~ 0,02 89-lQs 20- 6~ 9,38.10~ ~0 11 20,t 12.6 ~6,7 O~oz 9a~05 15- co I,~o.10~ Z~O
12 21,7 11,1 67,2 o.oa llo ~s- zo J,02.JO' ~lO
1~ . 20,0 1~,~ ~2.S O,Ot 107-~12 90 3.36. JO~ 33~
1~ 20,0 2~,0 S3,0 O,OB IOS IIS 115 1,61. lol 220 ~ ~2,~ 11,0 66,2 0.02 ~3-~13 20- 0 1,3~. iO~ 220 IC ~3,2 9,g ~,3 0,02 llO~119 IS- 10 Z.t3. 10~ aoo lt a~,~ ~t,~ S9,z 0,02 110-120 ~5- 70 9,~5.10~ ~90 ~8 Z~,J ~,7 1~,0 0,0~ t~O-~20 ~S~ 70 1,50.10~ 190 1~ ~0,~ ~ ~ 0C02 tl~ O ~- 90 1 nea~ 200 ~,0 I~,S ~,S 0,0~ ~5~0 1~- 90neas~P~ble ~ olut~o Z~ ~,~ 1~,~ ~7,~ ~ 95- 98 aO-~300 ~,85.10~ 390 .... . . _ __ ., , . . .. - .,._... ~ --J
~ St~rt o~ dl~aolY~ End of dis~olv~n~
~) M~a~in~ Per~tur~: lO5-C
78~3 ~R
In ~ one lit~r stirr~d vessel a suspension of 60% aqueous N~M0 ~olutlon, ~llulo5e and 0.01~ GPE as stabilizer, water is ~i~tilled o~f in va~uum ~-~e ~abl~ 2). T~e solution f~r~tlon is followed by 5 means of the increa~e in visco ity (power required by the 6tirrer) or und~r the mi~roscope. Th~ xact test parameters and ~esults ~r~
g~ven in T~le ~.
Clari~ic~t~on: 1st lin-: Beginning of 601ution ~onm~tio~
~Rise ~n vi~c05ity):
~ime - 07 by that Gt~g~ a p~edet~r-~ined amount of w te~ has ~lr~ady evapor~ted - ~ee compo~itlon.
2nd lin~: Ti~e ~ven at thc end of the ~olutlon proce~s.
~blc 2 Ex~plO Ti~ Starter a~ount~ t0~ D~st. Solutlon Compo~t~on _ CQll H~ ~ ~o ~ NM
C~llulo~o: BucXeye V5 22 0 30 ~0 ~86 676 166 4.44% 23.67~ 71.8~%
30 143 486 653 1~3 4.55% 21.70% 73.75~
23 0 42 1~8 480 690 156 ~.0g% 24.35% 69.56%
42 140 480 662 1~4 ~.34~ 21.15~ 72.5~%
2~ 0 54 162 477 6g3 29~ 7.79% 23.38% 68.83~
2S S4 1~5 477 656 333 8.23~ 1~.05% 72.72%
~crap Pap-r 0 30 160 486 676 166 4.44% 23.67% 71.8~%
30 143 4R~ 6S9 183 4.55% 21.70~ 73.75 2~ 0 ~2 168 ~80 6g0 156 6.09% 24~3S~ 69.56 42 140 480 fi62 184 6~34% 21.15~ ?2.51%
~ Avlc-ll 27 0 90 115 390 595 149 15.1~ 19.3~ 65.6%
90 92 3~0 S73 12Z ~5.7 lG.l~ 68.2 7823 11~
In a 5 li~er ~irred vessel ~ suspensio~ oo~posed of a 60%
ous N~O 601ution, ~elluloss (~uck~ye V5 cellulose) and GPE, w~t~r iB ~istilled o~f under Yacuuro~ After about 3 hours, 3, Ooo g S of a Bolution o~ the ~ollowing oomposltion ls obtained:
9 . O .% e~llulo~e ~2uckeye ys) 18.3 % water 73 . ~ O
O . 02~ GPE
~ Th~ solut~on tempe~tur~ w~ 94 to ~G'C. ~h~ compl~x viscoslty o~
~h~ ~p~nn~ng mas3 ~t 9~-C ~RV20, o~cillation w~ith an ang~lar v~loc~ty w - 0.31 6ec~l~: 550 Pa.
8h~r rate: S00 ~ec -1 olution i~ pressed ~t a rat~ of 10 ~/min through a 100 hole sp~ ret ~rlt~ ori~c-- having a diametQr o~ '30 ~U~D lnto air whero it i~ ~t~etcl~ed nd th~n 1~ coagulated in a precipltat~n5r bath to ~or~ r~.
In a S l~t~r st~rr~ v~ l wa~er ~3 distilled of und~r ~ rrom a ~uep~n~ion o~ a 60% agu~ou~ N~o ~olution, o~llulo8~
~nd GPE. A~ter ab~ut 5 hour~, 3,000 g o so~ution of the followlng co~pssitlon wa~ ob a~n~:
1s.s % cellulo~ tAv~cell, DP ~ 170) 1~.4 ~ wat~r 69.7 % ~o 0.02~ GP~
!~!he ~olution tempe~tur- wa~ 9J, to 96-C. The complex v~sco~ity o~
th- ~pln m~ at 35~c ~RV20, o~oillation at w ~ 0,3~ ~c 1):
2g3 Pa.-.
~0 Shear rat- 500 ~ec -1~
20408~4 7823 nR
Thi~ zolution was pressed at 10 gJ~in through a 100 hole spinnere~ ~ith 130 /um ori~ices, stre~ched in ~ 2cm air gap ~nd coagulat-d in a precipitating bath. The resulting ~ibers had the ~ollowing c~aracteristi~s:
Av~cell ~it-r ~dtex) 4.8 ~ber t~nacity (conditioned) ~cN/tex) 23 F~b~r elongation (conditioned) (%) B.2 102276 g o~ a be-ch ~ulf~t~ collulose tsolids or dry conten~
94~, DP 750,~ 0%) ~nd 0.02% GPE n~ sta~ilizer i~ su~pend~d in 2~13~ g o~ 60~ ~qu~ous NMMO ~olution ~nd tho su6p~n~1On i5 d~tilled at ~OO-C ~nd a ~acuum of 50 to 300 ~bar until ~415 g of water ~re di~till-d of~. Th ~olutlon wa~ e~aluated by vi~co~i~y and ~nder a 15-ml~roscope~ me ~ar r~ was 370 sec~l. ThQ 601uti~n tl~e w~s th- tia~ ln total from dis~illlng of the water to ~ho ~or~a~ion off th- ~olut~ on~
Param t-r~ o~ th- sp~nnlng ~olut~on;
C~llulos~ ~ ~.95 ~ter ~ 15.4 NMMO ~ 74~65 801utlon t~m~ ~hours, rainute~ 5~25 Complox vi8oo8it~ 0~ th- spin ma~ at 95'C
(R~20, o~clllation at w - 0.31 sec 1~ 1680 P~.s ~plnnlng p~r~-ter~:
s~lnnin~ t~p~rature (~) 75 gplnneret o~ c- number 589 Orl~ic- dl~meter 150 Alr gap ~D~) g 7823 ~R
Quarltity ~orc~d through spinneret ~gJmin) 103 Strotchln~ 8 . 2$
Take-up ~peed ~m/min) 6 F~bex characteristi~s:
T~ter ~dtox) 3 . o r1ber tonac:~ ty ~conditioned) 34 . 6 Flb~r elongat~on ~condit~onQd) (%) 9.6 ~x~p;L~a31 ~ T~ts w~h Fi~ ~gS~
A ~ extruder ~ro~ the BUSS Company (~ype HS-00~0: 0.5 m2 air, s~o~r rAé~ ~bout 3,000 ~c 1, g~p ~ 1.5 ~lan) fro~ g~ritzerl~r~d is u8e~ ~o ext~:ud~ a olutlor~. The ~olution i5 fo~ned by evaporating water rro~ a slurry o~ a 609~ a~ueou~ ~MM0 ~olution ~nd c~llulo~R. The wat~r iK eva~orat-d in vacuum (100 ~nbar) until the eoaposltion qiv~n ~-low ~ red.
SP-Q~ of tha ~otor: 4 50 RPM
Exa~ple ~11 wat~r Cellulose Heat Vi~cosity*
~ % temp. C ~d~0.31 sec~l Pa.
318.39 2~.64 ~uckeye VS 170 1670 32~.95 15.7 Buckeye Y5 185 2360 3314.6 13.13 ~uckeye V5 210 9860 34 8 16 Beec:h X20 1970 Cellulose DP~750 ~90%
~Vls~o~lty ~ ~ompl~x vi~co~lty ~easured at an ~n~ r ~elocity o~
0.31 ~c ~ ~n o~cillation ~od~ on ~ ~AAX~S RV20 at ~5'C.
20~0844 7823 )IR
The ~ne~n residenc- tim~ ~f the cellulose was about 4 D~nut-~. Fro~ ~ rheological point of view the product was a solution. rn ~ome cases i~ was ~omewhat cloudy, indicating the pr~l~ence of undissolved componen~s.
In theso exampl~, u~i~g DSC measure~nent~ on NMMo ~onohydrate and ¢ellulwic ~olutlons, the deoompo~ition ~emperatures wero deterPIin-d. ~ro~ thQs~ ~x~pl~, only Example ~0 i~ in the r~nge o~
th- ln~vent~on, thQ r-~a~nlng examples being comp~rati~re. Th~
re~ult~ ~r ~hown in T~ble 3. The ter~ "beqin" rafer6 to the lnitlatlon te~peratur~ o~ d~co~posit$on. ~he ter~ "aaxi~" r~fer~
to th- to~p~rature ~t wt~ich th~ exothermicity pa~e~ lts maximu~.
nand" re~er~ to th- to~pera~ure a~ which ~he exo~her~i~ity u~d8 .
T~bl~ 3 T~Jlperature C
J;xa~ple Cell. . ~0 Water ~Qg~ n ~ax~ mu~ En~
35~N~o.x20) - 87.7 13.3 197 ~33 2~0 2~ 36 9 77 . S13 . 5 190 225 236 37 10 78 . 012 . 0 184 212 230 38 23 72.0 5.0 164 205 218 39 23 66 . O11 . O 1'~ 217 230 C-llu~ose ir. 601ution reduce~ th~ initia~ decomposition t~era~ure (co~pare with ~xample 36). At ~olutions with higher water concontratlon wlth oor~pond~ng ¢ellulo~e ~oncentrat~on~, hlgher inltial t~p~rature~ ~r~ a~hiev~.
SPECIFICATION
our pres~nt lnv~n~ion rel~tes to a ~ethod of preparin~ a ~olut~on o~ ~ellulos~ in N-~thyl~orphol~no-N-Gxids an~ ~ter $n ~hich th- three Gomponentc ~r m~x-d to~ether. The invention also r~l4tes to a solution oX cellulo~e oontaining the N-methyl~or-pholine-oxido and wat~r. Such ~olution~ can b~ u-ed wherever the ~or~atlon of c-llulo~- articles by precipitation ~rom ~olution is to be ef~c~ed.
B~kp~ou~ Q~ ~h~ I~ven~gn A process rOr ~a~ing a ~olut~on of oellulo6~ in N-~-thylmo~phol~ne-N-oxide tNN~0~ ha$ been d~scribed in ~.s~ patent 4,196,282. ~o deter~lne th- ~aximum c~llul~e ~onoentration experi~ontAlly ~ccordln~ to thl~ p~tent, the three-co~ponent ~y-tem ~orc~ a ho~e~ogQneou- ~lxture w~ich, by the ~levation o ~e~pera-turo, stlrring and eYaporatlon o~ w~ter~ i8 converted ~o a ho~ogenaou~ ~inning ma3~ ~o~ ~hlch ~ellulose ~ber~ can b~ spun.
78~3 HR 2040844 ~ t ha~ be~n ~ound that the ~aximu~ c:ellulo6e concentration drop~ an th~ watqr pr~portion ino~ea6e~ ~hat mean~ that, for a g~ n cellulose concentra~ion, there i~ a maximum p~rmiBsible w~ter concontration. I~ the wat~ concentrat~on drops becau~e of 5 ovRporation o~ water, the cellulo~e will go completely into ~olution. Th- mas~ or weight proportions under th~e conditlon0 stAbl~h ~or A given w~ter propo~tion the associated maxi~u~
c~llulo~e proportion.
A~ ~ con8egu~nce OS ~nany test ~eries, the following 10 r~latio~s~hip was ostabli~hed in that patent between th~ mass proport$on or oonc~ntr~t i on oS cellulo~e tcc~ n~ the ~a-6 ~roportion or conc:entration of th~ water (cH2O):
ccell ~ 0. 3469-1. 695 ~20 ~I) Cc~ll S 0-3469~ 695 c~20 1 0.0081 h.65+0.1tlOO c~2o-12.76)~
~h-~Q two inequaliti~ are represen~ed in F~G. S of th~
afore~erl~on-d pAt~nt ~n whlch cur~ A corre~ond~ to the inequality II and the cunre ~ to ths ~negu~ y 1.
I~ th~ ~nequ~ y I i~ ~ulfllled tin thi~ ca6~ the in~uality TI i~ toDlAtically ~o ful~illQ~), t~e celluloc- csn di~ol~e reli~ly in N~S0 ~nd ~aterO 11~ o~ly the isl~qu~lity I le ~ul~illed ~nd the $rlequal~ty I i~ not ~ulfLlled, th~r~ s~ghlficant ~robabil~ty, but n~rth-le~ no a~uranco, of co~plete ~olul~iliza-tlon og th~ c-llulo~ h- c~tod u.s. patent al~o ~ives lo~lrer li~its ~or t~ water ~nd ~ellulo~e contant ~curve6 c ~nd ~ in ~IC. 5~.
Should the water cont~nt Pall exce si~ely, ~ olution can cry~tallize out by ~hoar lnduction av~n ~t very hlgh temperatures.
8uah ~ ~olution cannot b~ procass~d further even by a ~ub~e~auenS incr~as- in the t-m~era~ure.
7823 l~a 2040844 In ~ddition, at low w~t~r contents, th~ ~xture falls in~o t$mp~r~ture and c:onc~ntratior. ran~e which lies close to the ~ecompo~tlon and explosive llmit of the NM~50-cellulose system.
D~f~er~nt~al scannirg calori~etry ~DSC~ ~neasure~ent3 show the ~egins~ing of thQ decomposition to b2 ju~t 61ightl~ above 170'C. To malce ~ dis~olution proe~s~ r~l~a~le, howevQr, ~t lIlU5t ~e cer'cain that t;h~ opQrating te~pQraturo is as fsr as possible from ~e temperature at whioh d~co~po8ition wlll be initiate~
In th- d~olul:ion o~ cellulo~ in NMMo and wat~r, the water ha~ ~av~ral funotions. On~ o~ lt- ad~antages i8 that in a ~ixture of N~SO ~nd w~ter, more c~llulose can be dissolved th~n ~n pure NMMO.
Thu8 an extru~lon of the solution, for example, for th~ spinning of colluloo- flla~nent, i~ po~lble~ me water content, however, ~hould not bo too l~ h ~lnc- elevatlon of the w;lter content re~ult~ in line~r reduotlon o~ th- ~ximurd pos5ible cellulos~ concentration.
When the 801uti~n ~ ~xtruded and ~n ~g~eous N~O ~olution for~s tb- ~r~ciplt~ting b~ , the pre¢ipitating~ b~th can b~
concentr~tod in a r~circulatlng ~ste~, cl~ned and ~herea~t~r r-cycl~d to th~ cellulo~e-~ssolvln~ st~3p or ~tage.
The over~ll e~ici~ncy ~nd ~nv~ronment~l ~oundnes~ o~ the procoss ~epsn~s upon the xt-nt to which thore is ~n NMqO ~nd wat~r r~rculatlon. F~thermor~, ~t ~s Advantageou~ ~o replace th~ very co~tly solvent )~SO wlth wat~r ~n th~ sp~nning mass and to thereby ro~uo~ t~o pro~ co~t dlrec~ly. I~ oolution~ wit~ a high w~ter cont~nt ~r- oxtrudQd~ ~aving~ ln respe¢t to th~ precipitatlng ba~h can ~l~o be mado.
7~23 lSR
It i~, ther~fo~e, th~2 principal ob~ect of the preserlt invention to provid~ ~n i~p2~0ved ~et~od for preparing a solut~ on of c~llulo~ in ~MMO and water which has ~n increased wa~er content, in which 'che ~a~oty of the proce~ ~nd the te~nperature o~ decompo~it~ on ar~ ~ncr~a~ed ~nd which con~Qnr~s the exp~5sive ~olvent and pr~c~pitating agent which ~ust bo regenerated.
Anoth-r ob~act of thl~ invention 1~ to provtde ~n improved method of ~ olvlng cellulo-- in ~0 and wa~er where~y drawback~ of oarlier ~y~tem~ ~xoe ~voided.
~tlll nother ob~ect ~ ~ to provide an improved cellUlos2-NMM0--water o~ut~on.
o ob~-ct~ and oth~r6 which will beco~e appar~nt hereinaft-r are atta$n~d, in ~ccordance wi'ch th~ ~resent invent~on, in ~ proc~ or ma~c~n~ a solution of c~llulo~e in ~ and water ~hi~h co~prl~e~ ttl- ~tep~ o~s (~1) for~ing A m~xtur- of water, cellulo~ ~nd ~-mothyl~orphol lne-N-oxld~;
~b~ 6ub~ecting the ~ix~ure to ~ixing wit~ ~ ~hear rate oS 400 to 3000 ~ and to~ controlllng th- concentxation by weight cCell o~
c~llulo~ and th- concent~tion by weight o~ wator ¢~zO ~o that it ~ti~fie~ the rel~tion:
C~ 0~346g v 1.695 ~0- (III) 78a3 MP.
Advant~geously, ~he shear rate is 500 to 800 5 ~. It h~s ~een found, 6urpri ingly, th t siqnificantly more oellulose can ~e dissolved w$th a given water concentration when the mixture i5 ~ub~octed to th~ high 6hear ra~es ~;e~ forth. Thi~ phenomenon has 5 been $ound to depend ~ar ~nore upon the 6hear ra~ce than upon the ~tirs~ing en~rgy which al~o is quit~ surprising.
Tho ~0 which i~ introduced into th~ ~ixture can b~ eithex t~,hnic~l grad~ N~10 or 2~MO which has ~e~n recycled ln the manner des~ri~d a~ve.
I~ hll- b~en found to b~ ~dvant~geou~ to ~a1ntain a t~p~rature, dur~ng tha mix,tng ~ the shear rat~s des~x~bed above, of 70 ~o 120-C, p~f-rably ~bou'c ~09~. A~ the~e te~pornture~ the cellulo~e dissolve~ espac~lly well ~nd the operatinsl tempexatur4 is ~u~iciently ~ar remov-~ from thQ deco~position te~era~UrQ o~ the 5 N~Q~0 .
an~ageou~ly, one o~ tho component~ o~ 'che Dllxture or the ~xtur~ it~el~ conta$n~ or ha~ ~dded thoreto 0 to 19~ ~y w~ight of a or. Th- ~t~blliz~r c~n be ~elected ~rom ehe group whi~h con~i~t- o~ g~llic ac$d and gallic ~cld estQr~, pyro~a~echln, ellagic 20 Acid, yyrog~llol, ox~llc acid, phosphoric ~cid a3~d Bodiu~ hexameta-pho~phat-.
axtn~u~o cellulo~ concentra~ion wh~ch c~n be achlov~d~
~coordlng to ~- ~nventlon correspond~ 'co the ir,equality:
cce~ 0 58-2 ~3 CH20 tIV) Tho ~olution o~ tnq in~rention thu~ conta~n~ cellulose, N2~0 ~n~ water with th~ ma~ proportion of cellulo~Q cc"ll and the ~a~s proportlon o~ wat-r (c~20) corresponding to 'che ~ollowing r ~tion~:
_ 5 _ 782~ )IR
C--ll 1.695 ~2 + 0.00~1 ~,/1.6510.1(100 cH o-12 j~2 (V~
cCell ~ 0-5B - 2-23 ~H O (1~) For the inequal~y IV, w- have d~veloped a theoretic 1 explanation ~lthou~h we dG not wi~h te bQ bound by thi~ th~ory. The t~ory 18 ~ev~loped wlth rQfer~nce to the acco~parlying dr~w~ng.
!rho ~bovQ ~nd other ob~ ects, featur~ and ~dvant~ges of the p~ nt imrent~on will b-com- mor~ readily apparent ~rom the following dewription, 2~ r-nc- ~e$ng ~ade to ~he acco~panying dr~wlng in whi~h:
FIG. 1 i~ A g~ph d$agranm~nçl the ~ax~um col~ility o~
c~lluloo- JlR ~eporld~nce upon a water ~ontent:
F~C. 2 is ~ binary d~agr~m for the f~y8te~ O~H~O; and ~`I6. 3 $~ ~n X-~y ~tructur~l ~nalysio of cellotetro~e and ~n~y~ro N~QSO~
~çc$~1c,_~rip~Qn It ~ known th~t th~ ~yotem NM~O/watsr has not ~ ~n~le eutectic bu'c two utec~ic~ (s~- FIG. 2).
To di-~olve the cellulo~o, it h~s been po~ le heret~fora to 2~ u~- only th- eutectio which oorresponded to the ~onohydrate ~
Surprl-ingly we hav~ discov~r~d that ~y oporat1ng a~ th~ h~ghe~ 6hear ra~o~ Or th~ inv~rltion, i'c ~ pos-lble to utilize the secot~d e-~tecti~
which corre~pond~ to 2C~ w~tor and 7~% N~SO. ~he D~lt~n~ point of ut~ctlc is 36-C. It corr~spond to a ~olar ratio o~ ~ mol N~MO
t~ Z.3 ~ol ~ tor ~th~ Nl*10-2.3-hydrat-i or the ~ihydrate ~H).
-- 6 ~
7823 ~ X04084~
Th6 N~O ~.3 hyd~at~ is parl:icularly advantageous ~ecause in o~n~tion of 'ch~ olution, wa~er molecule~ are exl:nanged Wit~
cellulose-o~ ~olecules~
In an X-ray ~truc ur 1 analysis of cellotetrose and anhydro N~qO ~AP), (FIG. 3), it i~ four~d tha~ only one glu~o~e unit i~
bound. IS. Maia, E.R.: Peguy, A.,: Perez, S.: Cellulose organic ~olution~. T. Th~ ~ruotur~ o~ ~nhydrou~ 50 ~nd N~O ~onohydrate Act~ Cry~t~llogr., S~ct.B ~9Bl, B37(10), 1858-62, J~n 1, lg~l.) With th- ~ormation of the NMM0-2.3-hydrat~ ln ~he liqu~d phase ~) with replac~m~nt o~ th~ wa~r molRcule by Cell-OH, solut~on~ with ~uPstantlally high~ water con~ent t~an i~ the cace $n the 6y~te~s de~crib-d ~n the U.S. pat~nt 4,196,2~2, can be atta~ned.
In th~ ~olution, the ~ree NMMO i5 in th~ for~ o~ NMMO (Z to 2.3~-bonding) (c~ th- ~utectic mixture in FIG. 2~ ~nd ~2ch ~nhydro ~luco~e un~t o~ the celluloRe ~ bound to anhydro NMMO. ~he m~xi~u~
po~ Yat~r concentration in an NNMO-c~llulos~-wat~r ~olu~on can b- d t~m~lned ~y th~ bln~ry dl~gra~ ~FIG. 2). ~er~ ~t a cellulo~
con¢entr~tion ~ 0~:
CHzO~ Z6~ - n.2~.
~h- m~x~mu~A c~llulo~- concent~a~ion (water-rre~ ~olutlon) is ~ ren ~rom F~ ~ upon a bonding of each anhydro glucosa un~
to 4 ~axi~u~ o~ 1 N~So, 1.~. a ~olecul~ ~at~o ~so: anhydro gluclose ~ount~ to 1.
~CC-ll/ ~ Anhyar ~lucog~ ~ o/JQ5 ~ o) ~ 1 (¢1~ell/l62)/ ~ 7) ~ 1 2040~344 78Z3 M~
~CC-ll/CNM~o) ' ~62/1~7 - ~.38 Cc~ 1.38 * cNMM0 ~--11 CNMMo 100% G
From the~e two equations it ~an be seen tA~t:
5 ~MO ~I 42~; ccæl}, e 58%
Fro~ thi~ one c~n obtaln by linea~ int~rpolation the r~ght-hand ~ou~dary ~C) of the ~olubilit~ range in FI~. 1 as:
C~ell ' O.S8 - 2-23 ~ cH~o or, tr~n~or~ed as:
~H20 ' 0-26 - 0.448 * CC 11 ln addl~lons ~N~Mo ~ 1 - CH20 CCell CSt~b~1izer ~n ~C. 1, two boundary concentrations hove been qi~en by the ~o~o-c~t~d U.~. pat~nt 4,196,2~2, na~ely, c~rve6 A and B o~ ~IG. 5 ~5 the~or and nloo d~s$gn~t~d ~s A ~nd B. In FIG. 1, ~urther points ~r- ~n~c~t-d ~h~h corr~-pond to the ~xa~le~ d~.~cus~d below. ~n the ~xa~pl-~, th- d~t~mination o~ th~ cellulose content io ~ect~d gr~motrically by the pre~p1tat~on o~ the ~ellulose with ~t~r. In t~- rlltrat~, the NMMo ~onc~ntratlon ~8 poten~io~e~rically qet~r-~n-d. ~he deter~n~ion o~ the water conc~n ration i~ e~fec~ed a~t~r ~roc~ptt~ n o~ th~ ce~lulose with ~ethanol in tho ~ltr~te by ~ean~ o~ the ~arl-Fiwher r~a~on~.
Tbe cellulo~--D~ i- determined by cal~ulating the numerieal ~verAg~ and d-t~rmin~ng the l~miting vi~co~ity coefficie~ in ~ccordance wit~ the cuen ~otho~ ~TAPPI T230). Mea~urement~ were made in th~ oscillatlon modo t~ ~ angular v~locity~.
Classification of the solution:
Optically: u~der the ~icroscope.
Vl~cosi~Qtrically: By m~ans o~ a ~otational viscosimeter of the firm HAAXE, type ~V20 ystem plate-2-pla~e (PQI, gap: lmm, m-asuring temp-rature: 95'C, oscillation mode3.
Tn ~ 3 liter kn~ader, Typ~: Werner ~ Pfl~iderer, LU~ S III-l, the ~o~ponent~ cellulo~e, N~MO ~recry~tali2ed ~rom acetone) ~ate~ and GPE (gallic acld propyl e~ter) ~3 ~ta~ili2er is knR~ded fro~ 15 to 115 ~inute~ t 70-C to 120'C (~ble 1) unt~l a transparent solution 18 ~or~ed ~6 ~t~r~in-d by m~cro~co~e exa~ination. The ex~c~
p~r~tor~ o~ the t~0t ~n~ th~ re~ult~ ~re ~ccumul~ed in Tabla 1.
Exa~pl~ nd 21 lie in the known ranqes out~ide the inv~ntion.
; 5h~y h~vo be~n lncorpor~ted ~o lnd~cate that the u~e of a st~bilizer $~ ~d~Antageou~ ln all ca~4 to rQ~uce cellulose decompo~tion~ The hlgh~ tho st~bilizer co~centrAt~on, the less the cellulosa d-co~po-itlon tDP)~
Examples 13, 14 and 20 are out~de the progno~ticat~d solutlon r~ng- ~nd show no dlssolut~on of the cellulose. In Example 17 there ~r- m~ny und~-~ol~ed ~bor fragment~ ln the solu~ion.
q~bl e 1 2040844 _ ,_ -_ _ __ . _ Viscoslty __ Cell. N~o r~ o GPE ~per-tu~e 'rrea~rnent ~ 0~31 ;xample (~ ~x~ ~) ~x) ~ ~c) ~uratioh ~ DP
. ~1n~ ," i~ IP~
~..... .~ ~ - _. __ _ _~. _ , _,~
1 s,e 13,~ 76,8 0,0~ 18- a7 20- ss 2,93.10~ ~0 2 1~ ,0 13,~ 72,7 O,o~ ~7~103 2S~ 85 ~ 0~ ~50 S 3 ~5,3 ~Z" 7~,6 0,02 96-lOS 15- 60 6,06.10~ ~70 ~ ~,9 IJ,S ~ 0,02 97~0~ 15- 60 s,oQ.lo~ ~0 S 13,9 1~,~ 69.8 0.02 ~9-10- ~5- 60 7,~0.10~ S10 15,2 IS,J Cs,S 0,02 ~oo-lo~ 60 I,o~. 10~ 550 7 15,0 1~,5 66,5 0.08 ~00-10~ 55 1,29. ~o~ Sgo ~ 1-,~ ~2,1 69.6' 0~02 ~ 07 20- 8S ~,10.10~ J20 . g ~Z,O 1~,~ 65,2 0,02 99-lOS ~o- 60 9,08.10~ 3~0 ~,2 ~2,~ 66,~ 0,02 89-lQs 20- 6~ 9,38.10~ ~0 11 20,t 12.6 ~6,7 O~oz 9a~05 15- co I,~o.10~ Z~O
12 21,7 11,1 67,2 o.oa llo ~s- zo J,02.JO' ~lO
1~ . 20,0 1~,~ ~2.S O,Ot 107-~12 90 3.36. JO~ 33~
1~ 20,0 2~,0 S3,0 O,OB IOS IIS 115 1,61. lol 220 ~ ~2,~ 11,0 66,2 0.02 ~3-~13 20- 0 1,3~. iO~ 220 IC ~3,2 9,g ~,3 0,02 llO~119 IS- 10 Z.t3. 10~ aoo lt a~,~ ~t,~ S9,z 0,02 110-120 ~5- 70 9,~5.10~ ~90 ~8 Z~,J ~,7 1~,0 0,0~ t~O-~20 ~S~ 70 1,50.10~ 190 1~ ~0,~ ~ ~ 0C02 tl~ O ~- 90 1 nea~ 200 ~,0 I~,S ~,S 0,0~ ~5~0 1~- 90neas~P~ble ~ olut~o Z~ ~,~ 1~,~ ~7,~ ~ 95- 98 aO-~300 ~,85.10~ 390 .... . . _ __ ., , . . .. - .,._... ~ --J
~ St~rt o~ dl~aolY~ End of dis~olv~n~
~) M~a~in~ Per~tur~: lO5-C
78~3 ~R
In ~ one lit~r stirr~d vessel a suspension of 60% aqueous N~M0 ~olutlon, ~llulo5e and 0.01~ GPE as stabilizer, water is ~i~tilled o~f in va~uum ~-~e ~abl~ 2). T~e solution f~r~tlon is followed by 5 means of the increa~e in visco ity (power required by the 6tirrer) or und~r the mi~roscope. Th~ xact test parameters and ~esults ~r~
g~ven in T~le ~.
Clari~ic~t~on: 1st lin-: Beginning of 601ution ~onm~tio~
~Rise ~n vi~c05ity):
~ime - 07 by that Gt~g~ a p~edet~r-~ined amount of w te~ has ~lr~ady evapor~ted - ~ee compo~itlon.
2nd lin~: Ti~e ~ven at thc end of the ~olutlon proce~s.
~blc 2 Ex~plO Ti~ Starter a~ount~ t0~ D~st. Solutlon Compo~t~on _ CQll H~ ~ ~o ~ NM
C~llulo~o: BucXeye V5 22 0 30 ~0 ~86 676 166 4.44% 23.67~ 71.8~%
30 143 486 653 1~3 4.55% 21.70% 73.75~
23 0 42 1~8 480 690 156 ~.0g% 24.35% 69.56%
42 140 480 662 1~4 ~.34~ 21.15~ 72.5~%
2~ 0 54 162 477 6g3 29~ 7.79% 23.38% 68.83~
2S S4 1~5 477 656 333 8.23~ 1~.05% 72.72%
~crap Pap-r 0 30 160 486 676 166 4.44% 23.67% 71.8~%
30 143 4R~ 6S9 183 4.55% 21.70~ 73.75 2~ 0 ~2 168 ~80 6g0 156 6.09% 24~3S~ 69.56 42 140 480 fi62 184 6~34% 21.15~ ?2.51%
~ Avlc-ll 27 0 90 115 390 595 149 15.1~ 19.3~ 65.6%
90 92 3~0 S73 12Z ~5.7 lG.l~ 68.2 7823 11~
In a 5 li~er ~irred vessel ~ suspensio~ oo~posed of a 60%
ous N~O 601ution, ~elluloss (~uck~ye V5 cellulose) and GPE, w~t~r iB ~istilled o~f under Yacuuro~ After about 3 hours, 3, Ooo g S of a Bolution o~ the ~ollowing oomposltion ls obtained:
9 . O .% e~llulo~e ~2uckeye ys) 18.3 % water 73 . ~ O
O . 02~ GPE
~ Th~ solut~on tempe~tur~ w~ 94 to ~G'C. ~h~ compl~x viscoslty o~
~h~ ~p~nn~ng mas3 ~t 9~-C ~RV20, o~cillation w~ith an ang~lar v~loc~ty w - 0.31 6ec~l~: 550 Pa.
8h~r rate: S00 ~ec -1 olution i~ pressed ~t a rat~ of 10 ~/min through a 100 hole sp~ ret ~rlt~ ori~c-- having a diametQr o~ '30 ~U~D lnto air whero it i~ ~t~etcl~ed nd th~n 1~ coagulated in a precipltat~n5r bath to ~or~ r~.
In a S l~t~r st~rr~ v~ l wa~er ~3 distilled of und~r ~ rrom a ~uep~n~ion o~ a 60% agu~ou~ N~o ~olution, o~llulo8~
~nd GPE. A~ter ab~ut 5 hour~, 3,000 g o so~ution of the followlng co~pssitlon wa~ ob a~n~:
1s.s % cellulo~ tAv~cell, DP ~ 170) 1~.4 ~ wat~r 69.7 % ~o 0.02~ GP~
!~!he ~olution tempe~tur- wa~ 9J, to 96-C. The complex v~sco~ity o~
th- ~pln m~ at 35~c ~RV20, o~oillation at w ~ 0,3~ ~c 1):
2g3 Pa.-.
~0 Shear rat- 500 ~ec -1~
20408~4 7823 nR
Thi~ zolution was pressed at 10 gJ~in through a 100 hole spinnere~ ~ith 130 /um ori~ices, stre~ched in ~ 2cm air gap ~nd coagulat-d in a precipitating bath. The resulting ~ibers had the ~ollowing c~aracteristi~s:
Av~cell ~it-r ~dtex) 4.8 ~ber t~nacity (conditioned) ~cN/tex) 23 F~b~r elongation (conditioned) (%) B.2 102276 g o~ a be-ch ~ulf~t~ collulose tsolids or dry conten~
94~, DP 750,~ 0%) ~nd 0.02% GPE n~ sta~ilizer i~ su~pend~d in 2~13~ g o~ 60~ ~qu~ous NMMO ~olution ~nd tho su6p~n~1On i5 d~tilled at ~OO-C ~nd a ~acuum of 50 to 300 ~bar until ~415 g of water ~re di~till-d of~. Th ~olutlon wa~ e~aluated by vi~co~i~y and ~nder a 15-ml~roscope~ me ~ar r~ was 370 sec~l. ThQ 601uti~n tl~e w~s th- tia~ ln total from dis~illlng of the water to ~ho ~or~a~ion off th- ~olut~ on~
Param t-r~ o~ th- sp~nnlng ~olut~on;
C~llulos~ ~ ~.95 ~ter ~ 15.4 NMMO ~ 74~65 801utlon t~m~ ~hours, rainute~ 5~25 Complox vi8oo8it~ 0~ th- spin ma~ at 95'C
(R~20, o~clllation at w - 0.31 sec 1~ 1680 P~.s ~plnnlng p~r~-ter~:
s~lnnin~ t~p~rature (~) 75 gplnneret o~ c- number 589 Orl~ic- dl~meter 150 Alr gap ~D~) g 7823 ~R
Quarltity ~orc~d through spinneret ~gJmin) 103 Strotchln~ 8 . 2$
Take-up ~peed ~m/min) 6 F~bex characteristi~s:
T~ter ~dtox) 3 . o r1ber tonac:~ ty ~conditioned) 34 . 6 Flb~r elongat~on ~condit~onQd) (%) 9.6 ~x~p;L~a31 ~ T~ts w~h Fi~ ~gS~
A ~ extruder ~ro~ the BUSS Company (~ype HS-00~0: 0.5 m2 air, s~o~r rAé~ ~bout 3,000 ~c 1, g~p ~ 1.5 ~lan) fro~ g~ritzerl~r~d is u8e~ ~o ext~:ud~ a olutlor~. The ~olution i5 fo~ned by evaporating water rro~ a slurry o~ a 609~ a~ueou~ ~MM0 ~olution ~nd c~llulo~R. The wat~r iK eva~orat-d in vacuum (100 ~nbar) until the eoaposltion qiv~n ~-low ~ red.
SP-Q~ of tha ~otor: 4 50 RPM
Exa~ple ~11 wat~r Cellulose Heat Vi~cosity*
~ % temp. C ~d~0.31 sec~l Pa.
318.39 2~.64 ~uckeye VS 170 1670 32~.95 15.7 Buckeye Y5 185 2360 3314.6 13.13 ~uckeye V5 210 9860 34 8 16 Beec:h X20 1970 Cellulose DP~750 ~90%
~Vls~o~lty ~ ~ompl~x vi~co~lty ~easured at an ~n~ r ~elocity o~
0.31 ~c ~ ~n o~cillation ~od~ on ~ ~AAX~S RV20 at ~5'C.
20~0844 7823 )IR
The ~ne~n residenc- tim~ ~f the cellulose was about 4 D~nut-~. Fro~ ~ rheological point of view the product was a solution. rn ~ome cases i~ was ~omewhat cloudy, indicating the pr~l~ence of undissolved componen~s.
In theso exampl~, u~i~g DSC measure~nent~ on NMMo ~onohydrate and ¢ellulwic ~olutlons, the deoompo~ition ~emperatures wero deterPIin-d. ~ro~ thQs~ ~x~pl~, only Example ~0 i~ in the r~nge o~
th- ln~vent~on, thQ r-~a~nlng examples being comp~rati~re. Th~
re~ult~ ~r ~hown in T~ble 3. The ter~ "beqin" rafer6 to the lnitlatlon te~peratur~ o~ d~co~posit$on. ~he ter~ "aaxi~" r~fer~
to th- to~p~rature ~t wt~ich th~ exothermicity pa~e~ lts maximu~.
nand" re~er~ to th- to~pera~ure a~ which ~he exo~her~i~ity u~d8 .
T~bl~ 3 T~Jlperature C
J;xa~ple Cell. . ~0 Water ~Qg~ n ~ax~ mu~ En~
35~N~o.x20) - 87.7 13.3 197 ~33 2~0 2~ 36 9 77 . S13 . 5 190 225 236 37 10 78 . 012 . 0 184 212 230 38 23 72.0 5.0 164 205 218 39 23 66 . O11 . O 1'~ 217 230 C-llu~ose ir. 601ution reduce~ th~ initia~ decomposition t~era~ure (co~pare with ~xample 36). At ~olutions with higher water concontratlon wlth oor~pond~ng ¢ellulo~e ~oncentrat~on~, hlgher inltial t~p~rature~ ~r~ a~hiev~.
Claims (7)
1. A method of making a solution of cellulose in N-methylmorpholine-N-oxide and water, comprising the steps of:
(a) forming a mixture of water, cellulose and N-methylmorpholine-N-oxide;
(b) subjecting said mixture to mixing with a shear rate of 400 to 3000 s-1: and (c) controlling the concentration by weight cCell of cellulose and the concentration by weight of water cH2O so that it satisfies the relation:
cCell > 0.3469 - 1.695 cH2O. (III)
(a) forming a mixture of water, cellulose and N-methylmorpholine-N-oxide;
(b) subjecting said mixture to mixing with a shear rate of 400 to 3000 s-1: and (c) controlling the concentration by weight cCell of cellulose and the concentration by weight of water cH2O so that it satisfies the relation:
cCell > 0.3469 - 1.695 cH2O. (III)
2. The method defined in claim 1 wherein said shear rate during mixing is maintained at 500 to 800 s-1.
3. The method defined in claim 1 wherein said mixing at said shear rate is carried out at a temperature of 70° to 120°C.
4. The method defined in claim 3 wherein said temperature is about 100°C.
5. The method defined in claim 1, further comprising the step of introducing into said mixture up to 1% by weight of at least one stabilizer selected from the group which consists of gallic acid and gallic acid esters, pyrocatechin, ellagic acid, pyrogallol, oxalic acid, phosphoric acid and sodium hexametaphosphate.
6. The method defined in claim 1 wherein the relation with respect to which the concentration by weight cCell of cellulose and the concentration by weight of water cH2O are controlled is:
cCell ? 0.58 - 2.23 cH2O. (IV)
cCell ? 0.58 - 2.23 cH2O. (IV)
7. A cellulose solution which consists essentially of cellulose, N-methylmorpholine-N-oxided and water and wherein the concentration by weight cCell of cellulose and the concentration by weight of water cH2O satisfy the relations:
and ccell ? 0.58 - 2.23 cH2O.
and ccell ? 0.58 - 2.23 cH2O.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0092690A ATA92690A (en) | 1990-04-20 | 1990-04-20 | METHOD FOR PRODUCING A SOLUTION OF CELLULOSE IN N-METHYLMORPHOLIN-N-OXIDE AND WATER |
| AT926/90 | 1990-04-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2040844A1 true CA2040844A1 (en) | 1991-10-21 |
Family
ID=3503033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002040844A Abandoned CA2040844A1 (en) | 1990-04-20 | 1991-04-19 | Method of making an aqueous solution of cellulose |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0452610A3 (en) |
| JP (1) | JPH05156084A (en) |
| AT (1) | ATA92690A (en) |
| BG (1) | BG60069A3 (en) |
| CA (1) | CA2040844A1 (en) |
| ES (1) | ES2029970T1 (en) |
| FI (1) | FI911916A (en) |
| GR (1) | GR910300144T1 (en) |
| HU (1) | HUT58775A (en) |
| IE (1) | IE911316A1 (en) |
| NO (1) | NO911463L (en) |
| PL (1) | PL289950A1 (en) |
| PT (1) | PT97394A (en) |
| RO (1) | RO107664B1 (en) |
| ZA (1) | ZA912710B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626810A (en) * | 1993-10-19 | 1997-05-06 | Lenzing Aktiengesellschaft | Process for the preparation of cellulose solutions |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT395863B (en) * | 1991-01-09 | 1993-03-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY |
| DE4244609C2 (en) * | 1992-12-31 | 1996-07-11 | Thueringisches Inst Textil | Stable molding and spinning mass |
| AT399348B (en) * | 1993-05-05 | 1995-04-25 | Chemiefaser Lenzing Ag | FORM- OR SPIDING MASS CONTAINING CELLULOSE AND USE OF CERTAIN SUBSTANCES FOR YOUR STABILIZATION |
| US5413631A (en) * | 1993-05-24 | 1995-05-09 | Courtaulds (Holding) Limited | Formation of a cellulose-based premix |
| AT399519B (en) * | 1993-09-14 | 1995-05-26 | Chemiefaser Lenzing Ag | FORM- OR SPINNING CONTAINER CONTAINING CELLULOSE AND METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES |
| DE4439149C2 (en) * | 1994-11-03 | 1997-07-31 | Thueringisches Inst Textil | Process for the preparation of a homogeneous cellulose solution |
| DE4441468C2 (en) * | 1994-11-22 | 2000-02-10 | Ostthueringische Materialpruef | Process for the production of a homogeneous solution of cellulose in water-containing N-methylmorpholine-N-oxide |
| DE19730090A1 (en) | 1997-07-14 | 1999-01-21 | Wolff Walsrode Ag | Novel cellulose ethers and processes for their production |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144080A (en) * | 1977-07-26 | 1979-03-13 | Akzona Incorporated | Process for making amine oxide solution of cellulose |
| US4196282A (en) * | 1977-11-25 | 1980-04-01 | Akzona Incorporated | Process for making a shapeable cellulose and shaped cellulose products |
| DE3367232D1 (en) * | 1982-06-08 | 1986-12-04 | Courtaulds Plc | Polymer solutions |
| DD226573A1 (en) * | 1984-09-24 | 1985-08-28 | Schwarza Chemiefaser | METHOD FOR PRODUCING HOMOGENEOUS, CONCENTRATED POLYMER SOLUTIONS |
-
1990
- 1990-04-20 AT AT0092690A patent/ATA92690A/en unknown
- 1990-12-18 ES ES199090890335T patent/ES2029970T1/en active Pending
- 1990-12-18 EP EP19900890335 patent/EP0452610A3/en not_active Withdrawn
-
1991
- 1991-04-11 ZA ZA912710A patent/ZA912710B/en unknown
- 1991-04-15 NO NO91911463A patent/NO911463L/en unknown
- 1991-04-16 JP JP3083807A patent/JPH05156084A/en active Pending
- 1991-04-16 BG BG94271A patent/BG60069A3/en unknown
- 1991-04-18 PT PT97394A patent/PT97394A/en not_active Application Discontinuation
- 1991-04-18 RO RO147381A patent/RO107664B1/en unknown
- 1991-04-19 CA CA002040844A patent/CA2040844A1/en not_active Abandoned
- 1991-04-19 HU HU911304A patent/HUT58775A/en unknown
- 1991-04-19 IE IE131691A patent/IE911316A1/en unknown
- 1991-04-19 FI FI911916A patent/FI911916A/en not_active Application Discontinuation
- 1991-04-19 PL PL28995091A patent/PL289950A1/en unknown
-
1992
- 1992-06-30 GR GR91300144T patent/GR910300144T1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626810A (en) * | 1993-10-19 | 1997-05-06 | Lenzing Aktiengesellschaft | Process for the preparation of cellulose solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| GR910300144T1 (en) | 1992-06-30 |
| JPH05156084A (en) | 1993-06-22 |
| HUT58775A (en) | 1992-03-30 |
| ATA92690A (en) | 1992-06-15 |
| ES2029970T1 (en) | 1992-10-16 |
| BG60069A3 (en) | 1993-09-15 |
| PL289950A1 (en) | 1991-10-21 |
| ZA912710B (en) | 1992-01-29 |
| HU911304D0 (en) | 1991-10-28 |
| FI911916A (en) | 1991-10-21 |
| PT97394A (en) | 1992-01-31 |
| NO911463D0 (en) | 1991-04-15 |
| NO911463L (en) | 1991-10-21 |
| RO107664B1 (en) | 1993-12-30 |
| IE911316A1 (en) | 1991-10-23 |
| EP0452610A3 (en) | 1992-01-08 |
| FI911916A0 (en) | 1991-04-19 |
| EP0452610A2 (en) | 1991-10-23 |
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