DD229708A1 - METHOD FOR PRODUCING STABLE POLYMER SOLUTIONS - Google Patents
METHOD FOR PRODUCING STABLE POLYMER SOLUTIONS Download PDFInfo
- Publication number
- DD229708A1 DD229708A1 DD27073284A DD27073284A DD229708A1 DD 229708 A1 DD229708 A1 DD 229708A1 DD 27073284 A DD27073284 A DD 27073284A DD 27073284 A DD27073284 A DD 27073284A DD 229708 A1 DD229708 A1 DD 229708A1
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- mmno
- cellulose
- polymer solutions
- water
- mass
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001913 cellulose Substances 0.000 claims abstract description 16
- 229920002678 cellulose Polymers 0.000 claims abstract description 16
- 150000002989 phenols Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940005740 hexametaphosphate Drugs 0.000 claims abstract description 6
- 239000008240 homogeneous mixture Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 11
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 8
- IVNPXOUPZCTJAK-UHFFFAOYSA-N 4-methylmorpholin-4-ium;hydroxide Chemical compound O.CN1CCOCC1 IVNPXOUPZCTJAK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 2
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Die Erfindung dient zur Herstellung von Polymerloesungen aus Cellulose, N-Methylmorpholin-N-oxid (MMNO) und Wasser fuer die Erzeugung von Folien und Faserstoffen. Ziel und Aufgabe bestehen in der Herstellung solcher Polymerloesungen, die gegen thermooxydativen Abbau weitgehend stabil sind. Erfindungsgemaess enthaelt die zu extrudierende homogene Mischung aus Cellulose, MMNO und Wasser gleichzeitig 0,2-0,2 Masse-% substituiertes Phenol/substituierte Phenole, z. B. 2.6 Di-tert.-butyl-p-Kresol, oder die gleiche Menge einer Mischung eines solchen Phenols/solcher Phenole mit Alkalihexametaphosphat.The invention is for the preparation of polymer solutions of cellulose, N-methylmorpholine-N-oxide (MMNO) and water for the production of films and fibers. The aim and the object are to produce such polymer solutions which are largely stable against thermo-oxidative degradation. According to the invention, the homogeneous mixture of cellulose, MMNO and water to be extruded contains at the same time 0.2-0.2% by weight of substituted phenol / substituted phenols, e.g. B. 2.6 di-tert-butyl-p-cresol, or the same amount of a mixture of such phenol / phenols with alkali metal hexametaphosphate.
Description
Verfahren zur Herstellung von stabilen PolymerlösungenProcess for the preparation of stable polymer solutions
Oie Erfindung betrifft ein Verfahren zur Herstellung von Polymerlösungen aus Cellulose, N-Methylmorpholin-N-oxid (MMNO) und Wasser und dient in der Chemiefaserund Plastindustrie zur Erzeugung von Faserstoffen und Folien.The invention relates to a process for the preparation of polymer solutions of cellulose, N-methylmorpholine-N-oxide (MMNO) and water and is used in the chemical and plastics industry for the production of fibers and films.
Es ist bekannt, Cellulose in Schmelzen oder wässrigen Lösungen von MMNO zu dispergieren und die homogene Suspension in Extrudern oder Vakuumrührgefäßen bei erhöhter Temperatur in klare Lösungen umzuwandeln. (FR-PS 2 398 788; SU-PS 994 587;- Loubinoux, D. u.a., L* Industrie Textile 1140 (1984) 1 S. 25 - 26)It is known to disperse cellulose in melts or aqueous solutions of MMNO and to convert the homogeneous suspension in extruders or Vakuumrührgefäßen at elevated temperature into clear solutions. (FR-PS 2 398 788; SU-PS 994 587; - Loubinoux, D. et al., L * Industrie Textile 1140 (1984) 1 p. 25 - 26)
Suspensionen bzw. Lösungen aus Cellulose, MMNO und Wasser werden bei Temperaturen oberhalb 70 0C deutlich thermooxydativ geschädigt. Der Wirkungsmechanismus ist für Cellulose und MMNO unterschiedlich. Meßbares Ergebnis sind die Abnahme des Polymerisationsgrades der Cellulose und der MMNO-Konzentration, eine Ver-Suspensions or solutions of cellulose, MMNO and water are significantly damaged at temperatures above 70 0 C thermooxydatively. The mechanism of action differs for cellulose and MMNO. The measurable result is the decrease in the degree of polymerization of the cellulose and the MMNO concentration, a
färbung der Lösung sowie eine Zunahme des Methylmorpholingehaltes.coloring of the solution and an increase in Methylmorpholingehaltes.
Es ist bekannt, den mit dem Löse- und Verarbeitungsprozeß oberhalb 70 0C verbundenen Abbau der Cellulose und des MMNO in der Suspension durch Zusatz von Phosphorsäuren, Phosphaten und Phosphorsäurekomplexen mit Metallionen zu inhibieren. (WO-PS 83/04415)It is known to inhibit the degradation associated with the dissolution and processing process above 70 0 C of cellulose and MMNO in the suspension by the addition of phosphoric acids, phosphates and phosphoric acid complexes with metal ions. (WO-PS 83/04415)
Diese Verfahren haben den Nachteil, daß der Abbau des MMNO in der Cellulose/MMNO-Mischung während des Löse- und Verarbeitungsprozesses gar nicht oder nur unzureichend inhibiert wird· Das gilt insbesondere für Ver· arbeitungstemperaturen oberhalb 100 0C.These methods have the advantage that the degradation of the MMNO in the cellulose / MMNO mixture during the dissolving and processing process is not or only insufficiently inhibits the disadvantage · This is particularly true Ver · processing temperatures above 100 0 C.
Das Ziel der Erfindung besteht in einem Verfahren zur Herstellung von Polymerlösungen aus Cellulose, MMNO und Wasser mit erhöhter Stabilität gegen thermooxydativen Abbau.The object of the invention is a process for the preparation of polymer solutions of cellulose, MMNO and water with increased stability against thermooxidative degradation.
Die Aufgabe der Erfindung besteht in der Erarbeitung eines Verfahrens zur Stabilisierung von Polymerlösungen aus Cellulose, MMNO und Wasser gegen thermooxydativen Abbau beim Löse- und Verarbeitungsprozeß.The object of the invention is the development of a method for the stabilization of polymer solutions of cellulose, MMNO and water against thermo-oxidative degradation in the dissolution and processing process.
Erfindungsgemäß wird das erreicht durch Zusatz von 0,2 - 2,0 Masse% substituiertem Phenol/substituierten Phenolen, vorzugsweise 2.6 Di-tert.-butyl-p-Kresol, oder einer Mischung aus substituiertem Phenol/substituierten Phenolen und Alkalihexametaphosphat zu einer homogenen Mischung aus 5-30 Massel Cellulose undAccording to the invention, this is achieved by adding 0.2-2.0% by weight of substituted phenol / substituted phenols, preferably 2,6-di-tert-butyl-p-cresol, or a mixture of substituted phenol / substituted phenols and alkali metal hexametaphosphate to form a homogeneous mixture from 5-30 mass of cellulose and
95 - 70 Massed MMNO mit 4-18 Massel Wassergehalt vor der Extrusion.95 - 70 Massed MMNO with 4-18 wt. Water content before extrusion.
Die Erfindung soll nachstehend an Beispielen erläutert werden..Dabei wird die stabilisierende Wirkung von Zusätzen vorteilhaft durch den Inhibierungsgrad I in % ausgedrückt:The invention will be explained below by way of examples. The stabilizing effect of additives is advantageously expressed by the degree of inhibition I in % :
100100
a = MMNO-Gehalt der Ausgangsmischunga = MMNO content of the starting mixture
b = MMNO-Gehalt der getemperten Mischung ohne Stabilisatorzusatzb = MMNO content of the tempered mixture without stabilizer addition
c = MMNO-Gehalt der getemperten Mischung mit Stabilisatorzusatzc = MMNO content of the tempered mixture with stabilizer addition
Seispiel 1Example 1
Eine homogene Mischung aus 20 Massel Cellulose, 68,5 bzw. 67,6 Masse% MMNO, 10,5 bzw. 10,4 Masse% Wasser und 1,0 bzw. 2 Masse% Stabilisator wird bei 100 bzw. 120 0C während 1 h getempertA homogeneous mixture of 20 mass% cellulose, 68.5 or 67.6 mass% MMNO, 10.5 and 10.4 mass% water and 1.0 and 2 mass% stabilizer is at 100 or 120 0 C during 1 h tempered
Die Ergebnisse enthält folgende Tabelle: The results include the following table:
Stabilisatorzusatz ' MMNO-Inhibierungs-Stabilizer additive 'MMNO inhibition
grad % grad %
100 0C 120 0C100 0 C 120 0 C
ohne 0 0without 0 0
2 Massel Na-hexametaphosphat 21 62 mass of Na-hexametaphosphate 21 6
1 Masse% 2.6 Di-tert.-butyl-p-1 mass% 2.6 di-tert-butyl-p-
Kresol 29 15Cresol 29 15
2 Masse% 2.6 Di-tert.-butyl-p-2% by weight 2.6 di-tert-butyl-p-
Kresol 59 10Cresol 59 10
1 Masse% einer Mischung von 30/70 Teilen aus Na-hexametaphosphat1 mass% of a mixture of 30/70 parts of Na-hexametaphosphate
und Di-tert.-butyl-p-Kresol 74 54 1 Massel einer Mischung von 70/30 Teilen aus Na-hexametaphosphatand di-tert-butyl-p-cresol 74 54 1 wt of a mixture of 70/30 parts of Na-hexametaphosphate
und Di-tert.-butyl-p-Kresol 46 46and di-tert-butyl-p-cresol 46 46
In einem beheizbarew Rührgefäß werden 8,0 kg einer 70 masse%igen wässrigen MMNO-Lösung, die gleichzeitig 0,3 Massel Na-hexametaphosphat und 0,7 Massel 2.6 Di-tert.-butyl-p-Kresol enthält, vorgelegt und auf 50 0C erwärmt. In diese Lösung trägt man 100 g Blattzellstoff (DP = 754) mit 6 Masse% Feuchte ein, läßt 10 Minuten quellen und rührt weitere 15 Minuten. Durch Zentrifugieren wird das Flottenverhältnis von 1 : 80 auf 1 : 3,72 reduziert, der Wassergehalt durch Vakuumtrocknung von 23,5 auf 13 Masse% herabgesetzt. Durch Extrusion in einem Doppelschneckenextruder mit Entgasungszone bei Temperaturen zwischen 80 und 110 0C entsteht eine klare Lösung.8.0 kg of a 70% by weight aqueous MMNO solution, which simultaneously contains 0.3% by weight of sodium hexametaphosphate and 0.7% by weight of 2,6-di-tert-butyl-p-cresol, are placed in a heatable stirred vessel and brought to 50.degree 0 C heated. 100 g of leaf pulp (DP = 754) with 6% by weight of moisture are introduced into this solution, allowed to swell for 10 minutes and stirred for a further 15 minutes. The liquor ratio is reduced from 1: 80 to 1: 3.72 by centrifuging, the water content is reduced by vacuum drying from 23.5 to 13% by mass. By extrusion in a twin-screw extruder with degassing zone at temperatures between 80 and 110 0 C, a clear solution.
Der MMNO-Inhibierungsgrad beträgt 65 %, der Cellulose~ Abbau, ausgedrückt in DP-Einheiten, 100, ohne Stabilisierungszusatz bei einer Parallelprobe 300.The MMNO inhibition degree is 65 %, the cellulose degradation, expressed in DP units, 100, without stabilization additive in a parallel sample 300.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD27073284A DD229708A1 (en) | 1984-12-13 | 1984-12-13 | METHOD FOR PRODUCING STABLE POLYMER SOLUTIONS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD27073284A DD229708A1 (en) | 1984-12-13 | 1984-12-13 | METHOD FOR PRODUCING STABLE POLYMER SOLUTIONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD229708A1 true DD229708A1 (en) | 1985-11-13 |
Family
ID=5563260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD27073284A DD229708A1 (en) | 1984-12-13 | 1984-12-13 | METHOD FOR PRODUCING STABLE POLYMER SOLUTIONS |
Country Status (1)
| Country | Link |
|---|---|
| DD (1) | DD229708A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4244609A1 (en) * | 1992-12-31 | 1994-07-07 | Thueringisches Inst Textil | Stable molding and spinning mass |
| AT399519B (en) * | 1993-09-14 | 1995-05-26 | Chemiefaser Lenzing Ag | FORM- OR SPINNING CONTAINER CONTAINING CELLULOSE AND METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES |
| WO1995023827A1 (en) * | 1994-03-01 | 1995-09-08 | Lenzing Aktiengesellschaft | Process for producing cellulose shaped bodies |
| WO2001064775A1 (en) * | 2000-02-28 | 2001-09-07 | Thüringisches Institut für Textil-und Kunststoff-Forschung E.V. | Method for producing a cellulose solution in an aqueous amine oxide, said solution having an increased thermal stability |
-
1984
- 1984-12-13 DD DD27073284A patent/DD229708A1/en not_active IP Right Cessation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4244609A1 (en) * | 1992-12-31 | 1994-07-07 | Thueringisches Inst Textil | Stable molding and spinning mass |
| AT399519B (en) * | 1993-09-14 | 1995-05-26 | Chemiefaser Lenzing Ag | FORM- OR SPINNING CONTAINER CONTAINING CELLULOSE AND METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES |
| US5556452A (en) * | 1993-09-14 | 1996-09-17 | Lenzing Aktiengesellschaft | Moulding materials and spinning materials containing cellulose |
| WO1995023827A1 (en) * | 1994-03-01 | 1995-09-08 | Lenzing Aktiengesellschaft | Process for producing cellulose shaped bodies |
| GB2291834A (en) * | 1994-03-01 | 1996-02-07 | Chemiefaser Lenzing Ag | Process for producing cellulose shaped bodies |
| US5628941A (en) * | 1994-03-01 | 1997-05-13 | Lenzing Aktiengesellschaft | Process for the production of cellulose moulded bodies |
| GB2291834B (en) * | 1994-03-01 | 1998-01-07 | Chemiefaser Lenzing Ag | Process for the production of cellulose moulded bodies |
| CN1085994C (en) * | 1994-03-01 | 2002-06-05 | 连津格股份公司 | Process for producing cellulose shaped bodies and aqueous regenerating solutions of tertiary amine oxides |
| WO2001064775A1 (en) * | 2000-02-28 | 2001-09-07 | Thüringisches Institut für Textil-und Kunststoff-Forschung E.V. | Method for producing a cellulose solution in an aqueous amine oxide, said solution having an increased thermal stability |
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| EP | Request for examination under paragraph 12(1) filed | ||
| RPI | Change in the person, name or address of the patentee (searches according to art. 11 and 12 extension act) | ||
| WP12 | As result of examination under paragraph 12 erstrg. patent revoked |