Note: Descriptions are shown in the official language in which they were submitted.
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.
2U40844
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$n~d, in ~ccordance wi'ch th~ ~resent invent~on,
in ~ proc~ or ma~c~n~ a solution of c~llulo~e in ~ and water
~hi~h co~prl~e~ ttl- ~tep~ o~s
(~1) for~ing A m~xtur- of water, cellulo~ ~nd
~-mothyl~orphol lne-N-oxld~;
~b~ 6ub~ecting the ~ix~ure to ~ixing wit~ ~ ~hear rate
oS 400 to 3000 ~ and
to~ controlllng th- concentxation by weight cCell o~
c~llulo~ and th- concent~tion by weight o~ wator ¢~zO ~o that
it ~ti~fie~ the rel~tion:
C~ 0~346g v 1.695 ~0- (III)
- 4 -
2040844
78a3 MP.
Advant~geously, ~he shear rate is 500 to 800 5 ~. It h~s
~een found, 6urpri ingly, th t siqnificantly more oellulose can ~e
dissolved w$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$d and gallic ~cld estQr~, pyro~a~echln, ellagic
20 Acid, yyrog~llol, ox~llc acid, phosphoric ~cid a3~d Bodiu~ hexameta-
pho~phat-.
axtn~u~o cellulo~ concentra~ion wh~ch c~n be achlov~d~
~coordlng to ~- ~nventlon correspond~ 'co the ir,equality:
cce~ 0 58-2 ~3 CH20 tIV)
Tho ~olution o~ tnq in~rention thu~ conta~n~ cellulose, N2~0
~n~ water with th~ ma~ proportion of cellulo~Q cc"ll and the ~a~s
proportlon o~ wat-r (c~20) corresponding to 'che ~ollowing
r ~tion~:
_ 5 _
2040844
782~ )IR
C--ll 1.695 ~2 + 0.00~1 ~,/1.6510.1(100 cH o-12 j~2 (V~
cCell ~ 0-5B - 2-23 ~H O (1~)
For the inequal~y IV, w- have d~veloped a theoretic 1
explanation ~lthou~h we dG not wi~h te bQ bound by thi~ th~ory. The
t~ory 18 ~ev~loped wlth rQfer~nce to the acco~parlying dr~w~ng.
!rho ~bovQ ~nd other ob~ ects, featur~ and ~dvant~ges of the
p~ nt imrent~on will b-com- mor~ readily apparent ~rom the
following dewription, 2~ r-nc- ~e$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 $n the 6y~te~s
de~crib-d ~n the U.S. pat~nt 4,196,2~2, can be atta~ned.
In th~ ~olution, the ~ree NMMO i5 in th~ for~ o~ NMMO (Z to
2.3~-bonding) (c~ th- ~utectic mixture in FIG. 2~ ~nd ~2ch ~nhydro
~luco~e un~t o~ the celluloRe ~ bound to anhydro NMMO. ~he m~xi~u~
po~ Yat~r concentration in an NNMO-c~llulos~-wat~r ~olu~on can
b- d t~m~lned ~y th~ bln~ry dl~gra~ ~FIG. 2). ~er~ ~t a cellulo~
con¢entr~tion ~ 0~:
CHzO~ Z6~ - n.2~.
~h- m~x~mu~A c~llulo~- concent~a~ion (water-rre~ ~olutlon) is
~ ren ~rom F~ ~ upon a bonding of each anhydro glucosa un~
to 4 ~axi~u~ o~ 1 N~So, 1.~. a ~olecul~ ~at~o ~so: anhydro gluclose
~ount~ to 1.
~CC-ll/ ~ Anhyar ~lucog~ ~ o/JQ5 ~ o) ~ 1
(¢1~ell/l62)/ ~ 7) ~ 1
-- 7 --
2040~344
78Z3 M~
~CC-ll/CNM~o) ' ~62/1~7 - ~.38
Cc~ 1.38 * cNMM0
~--11 CNMMo 100% G
From the~e two equations it ~an be seen tA~t:
5 ~MO ~I 42~; ccæl}, e 58%
Fro~ thi~ one c~n obtaln by linea~ int~rpolation the r~ght-hand
~ou~dary ~C) of the ~olubilit~ range in FI~. 1 as:
C~ell ' O.S8 - 2-23 ~ cH~o
or, tr~n~or~ed as:
~H20 ' 0-26 - 0.448 * CC 11
ln addl~lons
~N~Mo ~ 1 - CH20 CCell CSt~b~1izer
~n ~C. 1, two boundary concentrations hove been qi~en by the
~o~o-c~t~d U.~. pat~nt 4,196,2~2, na~ely, c~rve6 A and B o~ ~IG. 5
~5 the~or and nloo d~s$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~.
- 8 -
7823 MR 2040844
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.
7823 MR
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
-- 10 -
2040844
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
2040844
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~
-- 12 --
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
- 13 -
2040844
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.
-- 14 --
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~.
- 15 -
