EP3728332A1 - Verfahren zur herstellung von cellulosecarbamat, cellulosecarbamat sowie hieraus hergestellte formkörper - Google Patents
Verfahren zur herstellung von cellulosecarbamat, cellulosecarbamat sowie hieraus hergestellte formkörperInfo
- Publication number
- EP3728332A1 EP3728332A1 EP17829196.9A EP17829196A EP3728332A1 EP 3728332 A1 EP3728332 A1 EP 3728332A1 EP 17829196 A EP17829196 A EP 17829196A EP 3728332 A1 EP3728332 A1 EP 3728332A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cellulose
- hours
- reaction
- temperatures
- carbamate
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
Definitions
- the invention relates to a process for the preparation of cellulose carbamate by reacting cellulose and urea at elevated temperature in an organic reaction medium.
- the products resulting from this process are distinguished by a good solubility in sodium hydroxide solution and are particularly suitable for the production of shaped cellulose articles, for example regenerated cellulose fibers, films and beads.
- Cellulose carbamate is usually made by heating a homogeneous as possible NEN mixture of cellulose and urea at temperatures above 130 ° C ago. This reaction can be carried out either in the absence of a liquid reaction medium or in the presence of an inert organic liquid as a slurry process. The reaction without liquid reaction medium is to the effect of part, that the heat transfer are bad, which is local to Studentshit tongues and thus inhomogeneous process temperature control. This results in an uneven substitution pattern of the carbamate moieties within the cellulose, severely adversely affecting product quality in terms of solubility behavior.
- a disadvantage of the known slurry process is that due to the Verwen tion of a high excess of inert organic reaction medium based on the cellulose and considering a guaranteed mixing of the system, the material space yield is lower than Ver drive, which without inert, organic reaction medium be performed.
- the use of an inert, organic reaction medium means increased work-up expenditure with regard to the separation of the cellulose carbamate as end product.
- the use of xylene as an inert organic reaction medium is most commonly used (e.g., US 5,906,926, WO 2004/046198).
- the published in the patent literature excess of xylene based on the weight of the cellulose is from 23 to 17 times, under the specification as a product in sodium hydroxide solution, completely soluble, to obtain cellulose acetate.
- the present invention thus relates to a process for the preparation of cellulose carbamate, in which a) activation of cellulose, b) addition of an inert organic reaction medium in a mass ratio of 10: 1 to 0.1: 1 (reaction medium: cellulose) and urea in in any order, and c) reaction of the reaction mixture under mechanical agitation at reaction temperatures of more than 100 ° C.
- the present invention makes it possible to produce cellulose carbamate with significantly reduced use of an inert organic reaction medium.
- an inert organic reaction medium instead of an increased proportion of reaction medium in this case resorted to mechanical agitation.
- the reaction is carried out in reactor systems which ensure intensive mixing at high substance density (eg kneader).
- high substance density eg kneader
- the amount of inert, organic reaction medium could be significantly reduced thereby, without reducing the product quality.
- This has a particularly positive effect on the downstream processing of the products obtained. Since considerably less reaction medium is present, the separation of the products from the reaction medium is much less energy-intensive and therefore more economical.
- the yield of material in the process according to the invention is higher than in the processes known from the prior art which use more reaction medium.
- the reduced proportion of the reaction medium has a positive effect on the Stoffrau mausbeute.
- the products obtained are also completely soluble in aqueous sodium hydroxide solution.
- the pro- Duct qualities are repro ducible at any time with the method according to the invention.
- the invention described herein relates to an improved process for the preparation of cellulose carbamate with significantly reduced use of an inert, organic reaction medium.
- an inert, organic reaction medium In comparison to the described United drive (US 5,906,926, WO 2004/046198) can be produced under simple reaction and Aufarbeitungsbedin conditions in sodium hydroxide-soluble cellulose carbamates.
- solutions of the cellulose carbamates thus produced show significantly lower viscosity-corrected filter values, which suggests a verbes serten solution state, whereby a higher spin safety is ensured.
- the improved procedure makes it possible to realize narrower polydispersities of the cellulose carbamates produced and to produce narrow molar mass distributions as are the state of the art in the industrial production of cellulosic staple fibers.
- the mass ratio of the inert organic reaction medium to cellulose is 7.5: 1 to 0.5: 1, preferably 6: 1 to 1: 1, more preferably 5: 1 to 2: 1, particularly preferably 4.5 : 1 to 3: 1.
- the mechanical agitation of the reaction mixture is carried out in a kneader.
- the reaction mixture is preferably reacted over a period of from 10 minutes to 48 hours, preferably from 20 minutes to 24 hours, more preferably from 30 minutes to 8 hours, and / or at temperatures of from 75.degree. C. to 220.degree. C., preferably from 90.degree 200 ° C, more preferably from 100 ° C to 180 ° C.
- the activation of the cellulose takes place in a preferred embodiment by conversion into alkali cellulose using a 5 to 50% by weight, preferably 7.5 to 30% by weight, particularly preferably 10 to 20% by weight aqueous alkali metal hydroxide solution, especially sodium hydroxide, at temperatures from 0 ° C to 90 ° C, preferably 10 to 60 ° C, and / or over a period of 5 minutes and 48 hours, preferably 10 minutes and 24 hours, more preferably 10 minutes and 10 hours.
- aqueous alkali metal hydroxide solution especially sodium hydroxide
- the activation can also be carried out mechanically, hydrothermally and / or enzymatically.
- the alkali cellulose obtained during activation is ripened, especially at temperatures of from 0 ° C. to 120 ° C., preferably from 10 ° C. to 100 ° C., more preferably from 20 ° C to 60 ° C, and / or over a period of 10 minutes to 48 hours, preferably from 12 hours to 24 hours.
- the alkali metal cellulose can be washed out to an alkali content of ⁇ 5% by weight with water.
- a further advantage is that the urea after addition over a period of 5 minutes to 48 hours, preferably 10 minutes to 24 hours and / or at temperatures of 0 ° C to 90 ° C, preferably 10 ° C to 80 ° C, especially preferably from 15 ° C to 70 ° C is intercalated into the cellulose.
- the urea is used in egg nem ratio of 0.05: 1 to 3: 1, preferably 0.5 to 2: 1, based on the anhydroglucose unit of the cellulose.
- step c) a partial Ent train of water from the reaction mixture is carried out, in particular under ge ambient pressure compared to reduced pressure and / or at temperatures of 20 to 100 ° C.
- the cellulose carbamate can be separated from the liquid phase, optionally washed with water and then dried.
- the inert organic reaction medium is selected from the group consisting of toluene, o-xylene, p-xylene, tetralin, decalin, cumene and mixtures thereof.
- the DP CUOx (measured according to SCAN-CM 15:99) of the cellulose used is 500 to 150, preferably 400 to 200, particularly preferably 350 to 250.
- An exemplary, in particular preferred method sequence according to the invention provides for the following steps:
- a process for the preparation of cellulose carbamate in an organic reac tion medium with the following reaction steps a) activation of the pulp by a. Treatment with 10-20% aqueous sodium hydroxide solution for 10 minutes to 10 hours at temperatures of 10.degree. C. to 60.degree
- the present invention also relates to a cellulose carbamate which can be prepared according to the method of the invention described above.
- the cellulose carbamate according to the invention is characterized by a viscosity-corrected filter value (k r ), determined according to leaflet 1116 B / 68, 1968, from the association of pulp and paper chemists and engineers, from 2000 to 15000.
- k r viscosity-corrected filter value
- the DP cuo x (measured according to SCAN-CM 15:99) of the cellulose carbamate is in this case preferably from 200 to 500, preferably 230 to 400.
- the polydispersity index (PDI), determined by means of GPC-MALLS after saponification with subsequent tricarbanilination of the cellulose carbamates, of the cellulose carbamate according to the invention is from 1.5 to 5.0, preferably 2.0 to 4.0.
- the present invention also relates to moldings comprising or consisting of the previously described inventive cellulose cellulose.
- the shaped bodies are in the form of fibers, films or beads. The present invention will be explained in more detail with reference to the following embodiments, but without limiting the invention thereto.
- the reaction mixture was subsequently separated from xylene and washed several times with distilled water.
- the air-dried cellulose carbamate had a nitrogen content of 2.89% and a DP Cu0 x of 313 and was completely soluble in 9% sodium hydroxide solution.
- the viscosity-corrected filter value (kr) of this solution was 12473.
- the molecular weight determination by GPC after saponification gives a polydispersity index (PDI) of 3 , 7th
- the activation of the pulp was carried out analogously to the ge Georgia in Example 1 th procedure and gave a washed out alkali cellulose with a residual alkali content of 1.3% and a cellulose content of 30.2%.
- the DP of the washed out alkali cellulose was DP Cu0 x: 335.
- the reaction mixture was subsequently separated from xylene and washed several times with distilled water.
- the air-dried cellulose carbamate had a nitrogen content of 2.91% and a DP Cu0x of 266 and was completely soluble in 9% sodium hydroxide solution.
- the viscosity-corrected filter value (kr) of this solution was 2341.
- the molecular weight determination by GPC after saponification gives a polydispersity index (PDI) of 2 ; 2.
- Pulp plates of a prehydrolysis kraft pulp (DP Cu0x : 611) were pre- ripened for 35 h at 35 ° C. and then washed almost free of alkali (as described in Ex. 1). The residual alkali content was 1.23% and the cellulose content 30.3%, wherein the cellulose has a DP Cu0x : 323.
- 100 g of urea were added and this was intercalated in a 51 kneader with 2 Sigmaschaufeln for 2 h.
- vacuum 100 mbar
- adjusted flow temperature was within 2 h, the water contained in the reaction mixture separated till.
- 2.41 o-xylene were added to the reaction mixture (ratio CelkXyl 1: 5). The reaction temperature was set to 136 ° C and the reaction was carried out for 2 hours.
- the reaction mixture was subsequently separated from xylene and washed several times with distilled water.
- the air-dried cellulose carbamate had a nitrogen content of 2.43% and a DP Cu0x of 248 and was completely soluble in 9% sodium hydroxide solution.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2017/083977 WO2019120529A1 (de) | 2017-12-21 | 2017-12-21 | Verfahren zur herstellung von cellulosecarbamat, cellulosecarbamat sowie hieraus hergestellte formkörper |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3728332A1 true EP3728332A1 (de) | 2020-10-28 |
Family
ID=60972209
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17829196.9A Pending EP3728332A1 (de) | 2017-12-21 | 2017-12-21 | Verfahren zur herstellung von cellulosecarbamat, cellulosecarbamat sowie hieraus hergestellte formkörper |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP3728332A1 (de) |
WO (1) | WO2019120529A1 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI129395B (en) | 2020-04-06 | 2022-01-31 | Andritz Oy | PROCESS FOR THE PREPARATION OF CELLULOSACARBAMATE |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5378827A (en) | 1992-12-16 | 1995-01-03 | Zimmer Aktiengesellschaft | Process for the production of cellulose carbamate |
DE19715617A1 (de) | 1997-04-15 | 1998-10-22 | Zimmer Ag | Verfahren für die modifizierte Herstellung von Cellulosecarbamat |
DE19835688A1 (de) * | 1998-08-07 | 2000-02-10 | Piesteritz Stickstoff | Verfahren zur Herstellung von Cellulosecarbamat |
DE10223171A1 (de) * | 2002-05-24 | 2003-12-11 | Zimmer Ag | Verfahren zur Herstellung von Cellulosecarbamat |
DE10253672B3 (de) | 2002-11-18 | 2004-02-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung von Cellulosecarbamat in einem inerten organischen, mit Wasser nicht mischbaren Lösungsmittel |
-
2017
- 2017-12-21 WO PCT/EP2017/083977 patent/WO2019120529A1/de unknown
- 2017-12-21 EP EP17829196.9A patent/EP3728332A1/de active Pending
Also Published As
Publication number | Publication date |
---|---|
WO2019120529A1 (de) | 2019-06-27 |
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Owner name: FRAUNHOFER-GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V. |