Heft 57 LENZINGER BERICHTE Mai 1984

Regenerated Cellulose Fibers From Cellu- ques. But there were many Problems to tackle to resch
this goal. Two of the major ones were,
lose Carbamate Solutions
- how to control the degree of polymerization of the
cellulose to get a derivative with suitable Solution
characteristics, and
- how to get an even distribution of carbamate groups
Kurt Ekman, Vidar Eklund, Jan Fors, Jouko 1. Huttunen, along the cellulose chain in the heterogeneous reaction.
Leo Mandell, Johan-Fredrik Selin and Olli T. Turunen,
The first Problem had the additional restraint that we
Neste Oy, Research Centre, Kulloo, Finnland
wanted the process to be continuous, and dry. Irradiation
with accelerated electrons provided the answer. Table 1
Shows the DP of cellulose sheets as a function of the
electron beam treatment.
Cellulose reacts with urea to form a stable derivative, cellulose
carbamate. The derivate is soluble in aqueous sodium hydroxide.
The resulting Solution is extruded into a precipitation bath to form Table 1: Electron beam irradiation of cellulose effect on DP
cellulose carbamate filaments, which tan be hydrolysed to re-
generated cellulose fibers. The fibers have properties compar-
able with those of viscose or modal fibers. DOSE DF
(Mrad)
Cellulose reagiert mit Harnstoff zu stabilen Derivaten, Cellulose-
Carbonate. Diese sind in wäßriger NaOH löslich. Die daraus er- 00 800
haltene Lösung wird in ein Fäilbad extrudiert, wobei Cellulose- 05 L95
carbamatfasern entstehen, die zu Celluloseregeneratfasern hy- 10 LOO
drolysiert werden können. Die Fasern weisen Eigenschaften auf, 1 5 320
die mit Viskose- oder Modaifasern vergleichbar sind. 20 270
30 2LO
--

In Order to get the urea evenly distributed in the ceilulose

we have to impregnate it with an appropriate Solution.
Solutions of urea in water or alkaline media are proposed
in the literature, but they do not give satisfactory results4.5.
Introduction The reaction products have poor solubility properties,
obviously because the urea mainly gets into the amorphous
Cellulose is a renewable raw material. Manmade cellulosic Parts of the cellulose. Liquid ammonia is, on the other
fibers have many good properties that synthetic fibers hand. known to open up and Change the crystal structure
lack. Today we often use both together to obtain the best of cellulose6~‘. Liquid ammonia near its boiling Point also
possible properties. dissolves enough urea so that with one impregnation we
Cellulose is difficult to dissolve or to use in homogeneous get the required amount of urea into the ceilulose.
reactions. The only commercial direct dissolving System
After impregnation the ammonia is evaporated, and the
is the cuprammonium fiber process. The high tost of cellulose-urea mixture is brought to reaction by heating
topper and the difficulties in its economical recircula- to a temperature above 130%. Depending on the tempera-
tion are serious limitations to its use’. ture and urea content of the cellulose the reaction time
Much work has been put into Surveys of organic solvent varies from a few minutes to some hours. After the reaction
Systems for cellulose. Although many are promising, the cellulose is washed with hot water to remove unreacted
none of these Systems has yet been applied commercial- urea and byproducts. The dried carbamate is stable, mak-
ly2 3. The tost of solvents and their economical recircula- ing subsequent handling and use easy.
tion are serious problems.
Today the most important man-made cellulosic fibers
Product Characterization
are made by the viscose process. In this System cellulose Very little information about the Synthesis and structure
is dissolved as a Chemical derivative in aqueous caustic of cellulose carbamate tan be found in the literature, and
solutiqns. The process has many advantages, but it has even less on the properties and potential applications4a8.g.
many serious environmental Problems, too. Therefore some words on its characterization are appro-
This Paper describes another cellulose derivative soluble priate. The reaction product we obtain contains chemicaf-
in aqueous alkaline solutions, which tan be processed ly bound nitrogen, which tan be removed by alkaline hy-
like cellulose xanthate, but without many of the Problems drolysis. From figure 1 it tan be seen how the nitrogen
of the latter. content of the cellulose increases with reaction time and
temperature. A nitrogen content of about 2% is easity
achieved, and that is sufficient to give the cellulose the
Synthesis desirable solubility properties; this corresponds to a de-
A few years ago we found that cellulose reacts with urea gree of Substitution of about 0.25.
to yield a product that is soluble in sodium hydroxide. Figure 2 Shows the IR-spectrum of cellulose carbamate
We got’cellulose carbamate. This solubility in aqueous with a carbonyl peak at 1715 cm-‘. There is a good cor-
Systems made us use the carbamate as the raw-material relation between the increase in the carbonyl peak and
for a fiber produced by conventional wet-spinning techni- the nitrogen content.

38
 Mai 1984 LENZINGER BERICHTE Heft 57

degrees. The spin bath tan be either acidic, or alcoholic.

Table 2 Shows some properties of fibers prepared either
way.
Wet modulus is defined as 20 times the value for the wet
stress at 5% elongation.

<’ 65 ‘C
Table 2: Regenerated cellulosic fibres from cellulose carbamate
acid precipitation

,*

Acid System Alcohol System

Property Stretch Stretch
50% 75% 100% 100% 133%

Titre (dtex) 1.8 1.7 1.9 4.0 4.0

Tenacity (cN/dtex)
- conditioned 2.0 2.5 3.0 1.8 2.0
- wet 1.1 1.5 1.7 0.7 0.8

Wet modulus 6 8 12 7 9

Elongation (%)
1 2 3 4 h - conditioned 20 17 15 8 9
TIME - wet 19 16 12 13 IO

Fig. 1: Increase in nitrogen content of cellulose carbamate

(AGU : UREA 1:l) as a function of time and temperature

In the above examples the carbamate groups were al-

ready removed from the cellulose by treatment with alkali,
in table 3 the effect on the fibers of this hydrolytic treat-
ment is shown. The most profound changes concern the
alkali solubility of the fibers; with decreasing content of
carbamate groups the solubility decreases. But from the
table it is seen that we get beneficial effects on the wet
tenacity and elongation as weil.

Table 3: Effect of after - treatment at 95% on fibers from

cellulose carbamate

c Fig. 2: IR Spectra of unreacted (A) and reacted (B) cellulose

Spinning and Fiber Properties

The cellulose carbamate tan be dissolved in 8% sodium
hydroxide to a content of 7 to 10%. The dissolution
best done at temperatures around or below OS. The solu-
tion is clear,but with a light yellowish color. lt is easily
filtered and deaerated. As the carbamate groups hydro-
lyze in alkaline media, the solutions should be handl-
ed at low temperatures. Hut even at + 5°C the hydrolysis
is slow enough to allow storage for up to 24 hours.
From these solutions fibers have been spun on a small
scale experimental apparatus. We have usually worked
with Spinnerets having 300 orifices with a diameter of
50 or 80 v , but lately we have scaled up to Spinnerets
with 2000 orifices. The working distance in the spin bath
is mostly 30 cm. The Speed of the first reel tan be varied
between 12 and 40 mlmin, and the fiber bundles may be
stretched, in air or in a separate stretch bath, to various
is
Discussion
We have here a new way to produce a stable, easily dis-
solved, derivative of cellulose. The stability of the in-
termediate makes a large scale production possible with
improved economy. The Synthesis of the cellulose carba-
mate tan be made into a continuous process, with virtual-
ly no harmful emissions. Ammonia is handled and emitted
in the process, but it tan be collected and recovered or
burned. The wast water still contains urea and biuret,
which tan both be recirculated to the process.

39
Heft 57 LENZINGER BERICHTE Mai 1984

The main advantages of the fiber spinning process is 3) Dube, M., RH. Blackwell: Precipitation and Crystall-
seen in the fact that it so closely resembles the viscose ization of Cellulose from Amine Oxide Solutions,
process - roughly the same solvents, precipitation baths Tappi International Dissolving and Specialty Pulps
and technology tan be used, and only minor modifications Conference, Boston (1983)
are needed. But here, too, the big plus is in the absence Hill, J.W., R.A. Jacobson; Chemical Process, U.S. ,
4)
of harmful and toxic emissions. Pat. 2.134.825 (NOV. 1,193a)
The production costs should be very competitive, too. 5) Segal, L., F.V. Eggerton: Some Aspects of the Re-
The fibers tan be produced ata tost roughly the same as action between Urea and Cellulose; Text.Res.J.,
for the viscose process. Raw material costs are lower, 31,460 (1961)
but the Overall energy requirement is somewhat higher. Lewin, M., L.G. Roldan: The Effect of Liquid Ammonia
6)
This part of the process is not yet optimized, however. in the Structure and Morphology of Cotton Cellulose;
Although this Paperdeals only with the fiber application J.Polym.Sci., 36,213 (1971)
of cellulose carbamate, we have here a versatile derivative 7) Cheek, L., H. Struszczyk: The Effect of Anhydrous
with potential applications in many areas. Liquid Ammonia and Sodium Hydroxide on Viscose
Fabric; Cellul.Chem.Technol., 14,893 (1980)
8) Hebeish, A., A.Waly, E. El-Alfy, N. Abou-Zeid, A.T.
El-Aref and M.H. El-Rafie: Behaviour of Chemically
References Modified Cellulose Towards Dyeing; V. Dyeing of
1) Hathaway, J.L.: Cellulosic Fibers Made from Cupram- Methylolated Cellulose Carbamate with Different
monium, in Man-Made Fibers. Volume 2; Classes of Dyestuffs; Cellul.Chem.Technol., 13, 327
Mark, H.F., S.M. Atlas and E. Cernia, eds., Intersci. (1979)
Pulishers, New York(1968) 9) Khalil, M.I., E. El-Alfy, M.H. EI.Rafie and A. Hebeish:
2) Turbak, A.F.: Newer Cellulose Solvent Systems; Tappi Graft Polymerization of Methyl Methacrylate of Cellu-
International Dissolving and Specialty Pulps Con- lose Carbamate and Modified Cottons Derived from
ference, Boston (1983) it; Cellul.Chem.Technol., 16,465(1982)

40