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DE19700902A1 - Activated lignin intermediates for lignin polymers preparation - Google Patents

Activated lignin intermediates for lignin polymers preparation

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Publication number
DE19700902A1
DE19700902A1 DE1997100902 DE19700902A DE19700902A1 DE 19700902 A1 DE19700902 A1 DE 19700902A1 DE 1997100902 DE1997100902 DE 1997100902 DE 19700902 A DE19700902 A DE 19700902A DE 19700902 A1 DE19700902 A1 DE 19700902A1
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Germany
Prior art keywords
lignin
intermediate product
enzyme treatment
lignin derivatives
oxygen
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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.)
Withdrawn
Application number
DE1997100902
Other languages
German (de)
Inventor
Aloys Prof Dr Huettermann
Annette Dr Braun-Luellemann
Andrzej Dr Majcherzcyk
Sonja Noetzold
Alireza Dr Kharazipour
Juergen Prof Dr Huettermann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stockhausen GmbH and Co KG
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Individual
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Individual filed Critical Individual
Priority to DE1997100902 priority Critical patent/DE19700902A1/en
Priority to EP98905265A priority patent/EP0963399B1/en
Priority to DE19880043T priority patent/DE19880043D2/en
Priority to CN98801827A priority patent/CN1243524A/en
Priority to BR9807535A priority patent/BR9807535A/en
Priority to JP53354798A priority patent/JP2001512500A/en
Priority to CA002277784A priority patent/CA2277784A1/en
Priority to PCT/DE1998/000254 priority patent/WO1998031728A1/en
Priority to AU60896/98A priority patent/AU735443B2/en
Priority to DE59811199T priority patent/DE59811199D1/en
Priority to AT98905265T priority patent/ATE264358T1/en
Priority to PL98334681A priority patent/PL334681A1/en
Priority to US09/341,487 priority patent/US6410674B2/en
Publication of DE19700902A1 publication Critical patent/DE19700902A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D197/00—Coating compositions based on lignin-containing materials
    • C09D197/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/22—Preparation of oxygen-containing organic compounds containing a hydroxy group aromatic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D21H21/20—Wet strength agents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Biochemistry (AREA)
  • Zoology (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Paper (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

An intermediate product for the preparation of polymers from lignin derivatives obtained from the cellulose industry is prepared by treating the lignin derivative with a phenol-oxidising enzyme in the presence of an oxidising agent. The lignin derivatives are subjected to enzyme treatment for more than 3 hours in the presence of air, or enzyme treatment is carried out for 10 minutes or longer whilst passing air or oxygen through the reaction medium. A chemical oxidising agent is used in combination with the enzyme treatment.The use of these products for the preparation of polymers from lignin derivatives obtained from the cellulose industry is also claimed.

Description

Die vorliegende Erfindung betrifft ein Zwischenprodukt für die Herstellung von Polymerisaten aus Ligninderivaten, die bei der Zellstoffproduktion anfallen, sowie die Verwendung dieser Zwischenprodukte bei der Herstellung von Beschichtungsmitteln für die Herstellung von wasserfesten Papieren und Pappen.The present invention relates to an intermediate product for the manufacture of Polymers made from lignin derivatives that arise during pulp production, as well as the Use of these intermediates in the manufacture of coating agents for the production of waterproof paper and cardboard.

In der DE 37 992 C2 ist ein Verfahren zur Herstellung eines Bindemittels für Holzwerkstoffe unter Verwendung von phenolischen Stoffen, insbesondere Ligninsulphonat, beschrieben, bei dem zwecks Aktivierung der phenolische Stoff mit Enzymen versetzt wird, die Phenole nach einem Radikalmechanismus oxidativ polymerisieren, wobei der phenolische Stoff in ein aktives Bindemittel umgeformt wird. Es war zwar bekannt, daß diese Reaktion in Gegenwart von Sauerstoff, z. B. Luftsauerstoff, abläuft, aber bisher war ein solches aktiviertes Bindemittel nicht längere Zeit oder durch intensives Belüften mit Sauerstoff umgesetzt worden.In DE 37 992 C2 is a method for producing a binder for Wood-based materials using phenolic substances, in particular Lignosulphonate, described, in which the phenolic substance with the purpose of activation Enzymes are added, the phenols oxidatively according to a radical mechanism polymerize, whereby the phenolic substance is transformed into an active binder. Although it was known that this reaction in the presence of oxygen, e.g. B. Atmospheric oxygen, but so far such an activated binder has not been prolonged Time or by intensive ventilation with oxygen.

Überraschenderweise wurde gefunden, daß aus der Zellstoffindustrie stammende Ligninderivate, wie beispielsweise Kraftlignin oder Ligninsulfonat, bei intensiver oder langandauernder Umsetzung mit Sauerstoff, Luft oder anderen chemischen Oxidationsmitteln ein besonders reaktionsfähiges Ligninprodukt als Zwischenprodukt bildet. Dieses kann isoliert und längere Zeit gelagert werden und reagiert mit weiteren, nicht aktivierten Ligninderivaten zu einem hochmolekularen Polymerisat weiter. Das Zwischenprodukt kann dadurch charakterisiert werden, daß das Material mit Laccase umgesetzt wird. Es weist nach dieser Reaktion ein typisches ESR-Spektrum mit einem Signal für Phenoxyradikale im Bereich von ca. 3400 Gauss auf, welches aber als typisches Radikalsignal auf Dauer nicht beständig erhalten bleibt. Überraschenderweise bleibt aber die erhöhte Reaktivität des Zwischenprodukts auch nach langen Zeiträumen, wie beispielsweise nach Monaten, noch erhalten. Das heißt, daß dieses aktivierte Zwischenprodukt beim Umsatz mit phenoloxidierenden Enzymen erheblich aktiver ist als nicht vorbehandelte Ligninderivate und demgemäß das typische ESR-Spektrum in wesentlich höherer Intensität ausbildet als nicht derart vorbehandelte Ligninderivate.Surprisingly, it has been found that originating from the pulp industry Lignin derivatives, such as Kraft lignin or lignosulfonate, for intensive or long-term reaction with oxygen, air or other chemical Oxidizing agents a particularly reactive lignin product as an intermediate product forms. This can be isolated and stored for a long time and reacts with other, non-activated lignin derivatives to a high molecular weight polymer. That Intermediate product can be characterized in that the material contains laccase is implemented. After this reaction it exhibits a typical ESR spectrum with a Signal for phenoxy radicals in the range of approx. 3400 Gauss, but which as typical radical signal is not permanently maintained in the long term. Surprisingly but the increased reactivity of the intermediate remains even after long periods of time, such as after months, still received. That is, this activated Intermediate product in the conversion with phenol-oxidizing enzymes is considerably more active than untreated lignin derivatives and accordingly the typical ESR spectrum in forms significantly higher intensity than lignin derivatives that have not been pretreated in this way.

Die Intensität des Signals des aktivierten Zwischenprodukts beträgt zumindest mehr als das Fünffache des Signals des als Ausgangsprodukt dienenden Ligninderivats. Das Signal wird beispielsweise unter folgenden Bedingungen gemessen:
77°K; 9,5 Ghz, ESR-Dämpfung 20 dB, Mod.-Freq. 100 Mhz; Mod. Amplitude 4,0 Gauss.The intensity of the signal of the activated intermediate product is at least more than five times the signal of the lignin derivative serving as the starting product. For example, the signal is measured under the following conditions:
77 ° K; 9.5 Ghz, ESR attenuation 20 dB, Mod.-Freq. 100 Mhz; Mod. Amplitude 4.0 Gauss.

Das aktivierte Zwischenprodukt kann erhalten werden, indem technische Lignine, wie beispielsweise Ligninsulfonat, Kraftlignin, Organosolvlignin, Acetosolvlignin, ASAM- Lignin, die bei der Zellstoffproduktion anfallen, längere Zeit in Gegenwart von phenoloxidierenden Enzymen mit Luft oder Sauerstoff behandelt werden. Bereits nach einem Zeitraum von beispielsweise ca. drei Stunden, insbesondere aber nach zwanzig Stunden, ist eine Erhöhung des Phenoxyradikal-Signals festzustellen. Beim Durchleiten von Luft oder Sauerstoff unter Druck tritt das erhöhte Signal bereits nach wesentlich kürzerer Zeit auf, beispielsweise nach ca. 30 min.The activated intermediate can be obtained by engineering lignins such as for example lignin sulfonate, kraft lignin, organosolvlignin, acetosolvlignin, ASAM- Lignin from pulp production in the presence of for a long time phenol oxidizing enzymes can be treated with air or oxygen. Already after a period of, for example, about three hours, but especially after twenty Hours, an increase in the phenoxy radical signal can be observed. When passing through of air or oxygen under pressure, the increased signal occurs significantly shorter time, for example after about 30 minutes.

Auch mit chemischen Oxidationsmitteln läßt sich das Zwischenprodukt gewinnen. Hierzu können beispielsweise in der Ligninchemie übliche dienen, wie Kaliumpermanganat, Bichromate oder Ozon.The intermediate product can also be obtained with chemical oxidizing agents. For this can be used, for example, in lignin chemistry, such as potassium permanganate, Bichromates or ozone.

Die enzymatische Bildung des aktivierten Zwischenprodukts ist nur in Gegenwart größerer Mengen Sauerstoff möglich. Da sich bei Zimmertemperatur in Wasser nur 9 mg/l Sauerstoff lösen, wird die Bildung des Zwischenprodukts nur durch erhöhte Zufuhr von Sauerstoff, entweder durch Belüften oder durch Zugabe von Oxidationsmitteln, begünstigt. Auch wenn sich das Sauerstoff-Gleichgewicht über einen längeren Zeitraum einstellt, kann nach einiger Zeit genügend Sauerstoff auf das Ligninderivat eingewirkt haben.The enzymatic formation of the activated intermediate is only in the presence larger amounts of oxygen possible. Since only 9 mg / l Dissolving oxygen, the formation of the intermediate is only possible through increased intake of oxygen, either by venting or by adding oxidizing agents, favored. Even if the oxygen balance changes over a long period of time adjusts, enough oxygen can act on the lignin derivative after a while to have.

Das aktivierte Zwischenprodukt reagiert in Gegenwart von phenoloxidierenden Enzymen beispielsweise mit nichtaktivierten Ligninderivaten, wie sie beispielsweise aus der Zellstoffproduktion gewonnen werden können, unter Ausbildung von polymeren Ligninprodukten, wobei die erhaltenen Molgewichte wesentlich höher sind als jene, die bei der Einwirkung von phenoloxidierenden Enzymen auf Ligninderivate ohne die Gegenwart aktivierter Ligninderivate erhalten werden.The activated intermediate reacts in the presence of phenol oxidizing agents Enzymes, for example with non-activated lignin derivatives, such as those from pulp production can be obtained with the formation of polymers Lignin products, the molecular weights obtained being much higher than those obtained in the action of phenol oxidizing enzymes on lignin derivatives without the Presence of activated lignin derivatives can be obtained.

Sie liegen im allgemeinen mindestens um das Doppelte höher.They are generally at least twice as high.

Die bei der Polymerisation von Ligninderivaten in Gegenwart der aktiven Zwischenprodukte erhaltenen Ligninpolymere lassen sich für die Herstellung von hochaktiven Beschichtungsmitteln für die Herstellung von wasserfesten Papieren und Pappen verwenden.The polymerization of lignin derivatives in the presence of the active Lignin polymers obtained from intermediates can be used for the production of highly active coating agents for the production of waterproof papers and Use cardboard.

Das aktivierte Lignin weist gegenüber dem als Ausgangsmaterial verwendeten Lignin ein ESR-Spektrum mit wesentlich erhöhter Intensität des Phenoxyradikal-Signals auf. Dies wird durch die Fig. 1 und 2 dargestellt. Fig. 1 zeigt ein ESR-Spektrum von 1% Ligninsulfonat mit Zusatz von Laccase (4 U/ml) nach 30minütlicher Inkubation ohne Sauerstoffbehandlung. Fig. 2 zeigt das entsprechende Spektrum von Ligninsulfonat, das 20 Stunden unter erhöhter Sauerstoffzufuhr mit Laccase inkubiert und anschließend autoklaviert und drei Monate gelagert wurde. Nach erneuter Inkubation mit Laccase (4 U/ml, 30 min. Inkubation ohne Sauerstoffbehandlung) zeigt der Vergleich des stärksten Signals bei ca. 3400 Gauss mit den Hintergrundsignalen, daß gegenüber der Fig. 1 die Intensität des Phenoxyradikal-Signals um mindestens das Fünffache verstärkt wurde. The activated lignin has an ESR spectrum with a significantly higher intensity of the phenoxy radical signal than the lignin used as the starting material. This is illustrated by FIGS. 1 and 2. Fig. 1 shows an ESR spectrum of 1% lignin sulfonate by addition of laccase (4 U / ml) to 30minütlicher incubation without oxygen treatment. Fig. 2 shows the corresponding spectrum of lignin, the 20 hours under an increased oxygen supply incubated with laccase and then autoclaved and three months was stored. After another incubation with laccase (4 U / ml, 30 min. Incubation without oxygen treatment), the comparison of the strongest signal at approx. 3400 Gauss with the background signals shows that the intensity of the phenoxy radical signal is at least five times stronger than in FIG. 1 became.

Die Erfindung wird nachfolgend anhand der Beispiele näher erläutert:The invention is explained in more detail below with the aid of the examples:

Beispiel 1example 1

20 g Ligninsulfonat werden in 80 ml McIlvaine-Puffer, pH 5,5 gelöst und mit 800 U/ml Laccase versetzt. Die Lösung wird in einem 500 ml Erlenmeyerkolben bei 37°C im Wasserbad für 20 Stunden geschüttelt. Die Lösung wird anschließend autoklaviert. Das erhaltene Ligninsulfonat wird zwei Monate gelagert. Nach erneuter Inkubation mit Laccase (4 U/ml, 30 min. Inkubation ohne Sauerstoffbehandlung) hat es das ESR- Spektrum gemäß Fig. 2.20 g of lignosulfonate are dissolved in 80 ml of McIlvaine buffer, pH 5.5, and 800 U / ml of laccase are added. The solution is shaken in a 500 ml Erlenmeyer flask at 37 ° C. in a water bath for 20 hours. The solution is then autoclaved. The lignosulfonate obtained is stored for two months. After another incubation with laccase (4 U / ml, 30 min. Incubation without oxygen treatment), it has the ESR spectrum according to FIG. 2.

Beispiel 2Example 2

Aktiviertes Ligninsulfonat nach Beispiel 1 wird im Verhältnis 1 : 10 mit Kraftlignin versetzt und mit einer Konzentration von 100 mg/10 ml in Puffer suspendiert und im verschlossenen Reagenzglas, ohne besondere Sauerstoffbehandlung, mit Laccase (500 U/ml) für 6 h inkubiert. Parallel dazu wurden entsprechende Kontrollversuche mit nichtaktiviertem Lignin und Inkubationen ohne Laccase durchgeführt. Die Lignine wurden anschließend isoliert und die Molekulargewichtsverteilung in der HPLC gemessen.Activated lignosulfonate according to Example 1 is mixed with Kraft lignin in a ratio of 1:10 added and suspended at a concentration of 100 mg / 10 ml in buffer and im sealed test tube, without special oxygen treatment, with laccase (500 U / ml) incubated for 6 h. Corresponding control tests were carried out in parallel with this non-activated lignin and incubations without laccase. The lignins were then isolated and the molecular weight distribution in the HPLC measured.

Dabei wurden die folgenden Molekulargewichte ermittelt:
The following molecular weights were determined:

nichtaktiviertes Kraftligninunactivated kraft lignin 5.400 g/Mol5,400 g / mole nichtaktiviertes Kraftlignin inkubiert mit Laccaseunactivated Kraft lignin incubated with laccase 6.300 g/Mol6,300 g / mole nichtaktiviertes Kraftlignin plus aktiviertes Lignin ohne Laccaseunactivated kraft lignin plus activated lignin without laccase 6.000 g/Mol6,000 g / mole nichtaktiviertes Kraftlignin plus aktiviertes Lignin inkubiert mit Laccaseunactivated kraft lignin plus activated lignin incubated with laccase 11.000 g/Mol11,000 g / mole

Beispiel 3Example 3

Eine Ligninsuspension bestehend aus:
A lignin suspension consisting of:

80 ml McIlvain Puffer pH 4,5
16,5 g Kraftlignin
4 g Ligninsulfonat
80 ml McIlvain buffer pH 4.5
16.5 grams of kraft lignin
4 g of lignin sulfonate

wurden mit konzentrierter Laccase auf eine Endkonzentration von 800 U/ml eingestellt und mit Preßluft für 3 h belüftet und gerührt. Nach 3 h wurde die Lösung mit einer Laccaselösung (800 U/ml in Puffer pH 4,5) im Verhältnis 1+4 verdünnt und beidseitig auf Filterpapier aufgebracht.were adjusted to a final concentration of 800 U / ml with concentrated laccase and aerated and stirred with compressed air for 3 h. After 3 h the solution was with a Laccase solution (800 U / ml in buffer pH 4.5) diluted in a ratio of 1 + 4 and on both sides applied to filter paper.

Die behandelten Papiere wurden über Nacht an der Luft getrocknet. Die Papiere hatten einen Beschichtungsgrad von 9% atro Lignin bezogen auf atro Papier.The treated papers were air dried overnight. The papers had a degree of coating of 9% dry lignin based on dry paper.

Um den Bindungsgrad des Lignins an die Papierfaser zu bestimmen, wurden die beschichteten Papiere in Wasser und 0,1 M NaOH inkubiert. Gleichzeitig wurde die Wasseraufnahme bestimmt.In order to determine the degree of binding of the lignin to the paper fiber, the coated papers are incubated in water and 0.1 M NaOH. At the same time, the Determined water absorption.

Eine dreistündige Inkubation in Wasser bewirkte eine Herauslösung des aufgetragenen Lignins um 3% (w/w) der aufgetragenen Menge, eine gleich lange Inkubation in 0,1 N NaOH löste 31% (w/w) des Lignins von der Papieroberfläche ab.A three hour incubation in water resulted in a dissolution of the applied Lignins by 3% (w / w) of the amount applied, an incubation of the same length in 0.1 N NaOH detached 31% (w / w) of the lignin from the paper surface.

Die beschichteten Papiere hatten im Vergleich zu den unbeschichteten Kontrollen eine um 30 niedrigere Wasseraufnahme. Die Wasserreißfestigkeit war deutlich verbessert: während das unbehandelte Papier sich in einzelne Fasern auflöste, war das beschichtete Papier noch völlig intakt.The coated papers had a compared to the uncoated controls 30 lower water absorption. The water tear resistance was significantly improved: while the untreated paper dissolved into individual fibers, that was coated Paper still completely intact.

Beispiel 4Example 4

Nach dem in Beispiel 3 angegebenen Verfahren beschichtetes Papier wurde im Hochvakuum mit Gold besputtert und in einem Raster-Elektronenmikroskop untersucht. According to the procedure given in Example 3, coated paper was im Sputtered with gold in a high vacuum and examined in a scanning electron microscope.

Fig. 3 läßt eine innige Verbindung zwischen der Beschichtung und der Papierfaser erkennen, ohne daß dabei eine Übergangszone sichtbar wird. Dies zeigt, daß die Beschichtung auf eine echte kovalente Bindung zwischen dem Lignin und der Faser zurückzuführen ist. Fig. 3 may be an intimate bond between the coating and the paper fiber recognize, without causing a transition zone is visible. This shows that the coating is due to a true covalent bond between the lignin and the fiber.

Claims (8)

1. Zwischenprodukt für die Herstellung von Polymerisaten aus Ligninderivaten aus der Zellstoffindustrie, hergestellt durch Behandlung der Ligninderivate mit phenoloxidierenden Enzymen in Gegenwart von Oxidationsmitteln, dadurch gekennzeichnet, daß die Ligninderivate
  • a) länger als 3 Std. in Anwesenheit von Luft der Enzymbehandlung unterworfen, oder
  • b) länger als 10 min unter Durchleitung von Luft oder Sauerstoff der Enzymbehandlung unterworfen, oder
  • c) durch Behandlung mit chemischen Oxidationsmitteln oxidiert werden.
1. Intermediate product for the production of polymers from lignin derivatives from the pulp industry, produced by treating the lignin derivatives with phenol-oxidizing enzymes in the presence of oxidizing agents, characterized in that the lignin derivatives
  • a) subjected to the enzyme treatment in the presence of air for more than 3 hours, or
  • b) subjected to the enzyme treatment for longer than 10 min while air or oxygen is passed through, or
  • c) are oxidized by treatment with chemical oxidizing agents.
 2. Zwischenprodukt nach Anspruch 1, dadurch gekennzeichnet, daß die Ligninderivate Kraftlignin oder Ligninsulfonat sind.2. Intermediate product according to claim 1, characterized in that the lignin derivatives Kraft lignin or lignin sulfonate are. 3. Zwischenprodukt nach Anspruch 1, dadurch gekennzeichnet, daß die phenoloxidierenden Enzyme Phenoloxidase, Laccase oder dergleichen sind.3. Intermediate product according to claim 1, characterized in that the phenol oxidizing enzymes are phenol oxidase, laccase, or the like. 4. Zwischenprodukt nach Anspruch 1, dadurch gekennzeichnet, daß die Enzymbehandlung nach Stufe a) länger als 15 Stunden durchgeführt wird.4. Intermediate product according to claim 1, characterized in that the Enzyme treatment according to stage a) is carried out for more than 15 hours. 5. Zwischenprodukt nach Anspruch 1, dadurch gekennzeichnet, daß die Enzymbehandlung nach Stufe b) länger als 30 min. durchgeführt wird.5. Intermediate product according to claim 1, characterized in that the Enzyme treatment according to step b) is carried out for longer than 30 minutes. 6. Zwischenprodukt nach Anspruch 1, dadurch gekennzeichnet, daß bei der Enzymbehandlung nach Stufe b) Druckluft oder Sauerstoff unter Druck eingeleitet wird.6. Intermediate product according to claim 1, characterized in that the Enzyme treatment after stage b) compressed air or oxygen is introduced under pressure. 7. Verwendung des Zwischenprodukts der Ansprüche 1 bis 6 zur Herstellung von Polymerisaten von Ligninderivaten aus der Zellstoffindustrie.7. Use of the intermediate of claims 1 to 6 for the preparation of Polymers of lignin derivatives from the pulp industry. 8. Verwendung nach Anspruch 7 zur Herstellung von Beschichtungsmitteln für Papiere und Pappen.8. Use according to claim 7 for the production of coating compositions for papers and cardboard.
DE1997100902 1997-01-14 1997-01-14 Activated lignin intermediates for lignin polymers preparation Withdrawn DE19700902A1 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
DE1997100902 DE19700902A1 (en) 1997-01-14 1997-01-14 Activated lignin intermediates for lignin polymers preparation
EP98905265A EP0963399B1 (en) 1997-01-14 1998-01-14 Intermediate for the production of lignin polymers and their use in the production of reagents for the production of composite materials from plant fibers, waterproof papers and cardboards as well as duroplastics from lignin derivatives
DE19880043T DE19880043D2 (en) 1997-01-14 1998-01-14 Intermediate product for the production of lignin polymers and its use for the production of reagents for the production of composites from vegetable fibers, waterproof papers and cardboards as well as thermosets from lignin derivatives
CN98801827A CN1243524A (en) 1997-01-14 1998-01-14 Intermediate products for the preparation of lignin polymerization products and their use in the manufacture of composite materials from plant fibers, waterproof paper and cardboard, and as reagents for the manufacture of thermosetting plastics from lignin derivatives
BR9807535A BR9807535A (en) 1997-01-14 1998-01-14 Intermediate product for the production of lignin polymers and its use for obtaining reagents for the production of composite materials from vegetable fibers, water-resistant paper and cardboard, as well as hard plastics from lignin derivatives.
JP53354798A JP2001512500A (en) 1997-01-14 1998-01-14 Use of said intermediate product for producing a lignin polymer and a reagent for producing a composite comprising vegetable fibers, water-resistant paper and cardboard and a duroplastic comprising a lignin derivative
CA002277784A CA2277784A1 (en) 1997-01-14 1998-01-14 Intermediate for the production of lignin polymers and their use in the production of reagents for the production of composite materials from plant fibers, waterproof papers and cardboards as well as duroplastics from lignin derivatives
PCT/DE1998/000254 WO1998031728A1 (en) 1997-01-14 1998-01-14 Intermediate for the production of lignin polymers and their use in the production of reagents for the production of composite materials from plant fibers, waterproof papers and cardboards as well as duroplastics from lignin derivatives
AU60896/98A AU735443B2 (en) 1997-01-14 1998-01-14 Intermediate for the production of lignin polymers and their use in the production of reagents for the production of composite materials from plant fibers, waterproof papers and cardboards as well as duroplastics from lignin derivatives
DE59811199T DE59811199D1 (en) 1997-01-14 1998-01-14 INTERMEDIATE PRODUCT FOR THE PRODUCTION OF LIGNIN POLYMERISATS AND THE USE THEREOF FOR THE PRODUCTION OF REAGENTS FOR THE PRODUCTION OF COMPOSITES FROM VEGETABLE FIBERS, WATERPROOF PAPERS AND PAPERBOARDS AND DUROPLASTIVES FROM LIGNIN
AT98905265T ATE264358T1 (en) 1997-01-14 1998-01-14 INTERMEDIATE PRODUCT FOR THE PRODUCTION OF LIGNIN POLYMERS AND THE USE THEREOF FOR THE PRODUCTION OF REAGENTS FOR THE PRODUCTION OF COMPOSITE MATERIALS FROM VEGETABLE FIBERS, WATERPROOF PAPERS AND PAPERBOARD AND THERMOSETS FROM LIGNIN DERIVATIVES
PL98334681A PL334681A1 (en) 1997-01-14 1998-01-14 Intermediate product for obtaining lignin polymers as well as application thereof in obtaining the reagents for use in production of plant fibre laminates, water-proof paperrs and cardboards as well as hardenable materials obtained from lignin
US09/341,487 US6410674B2 (en) 1997-01-14 1998-01-19 Intermediate product for manufacturing ligain polymers and it's use in manufacturing reagents for making composite materials from plant fibers, waterproof papers and cardboards, and thermosetting plastics from derivatives

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DE1997100902 DE19700902A1 (en) 1997-01-14 1997-01-14 Activated lignin intermediates for lignin polymers preparation

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DE19700902A1 true DE19700902A1 (en) 1998-07-16

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19852082C1 (en) * 1998-11-11 2000-06-15 Fraunhofer Ges Forschung Composite extruded section, especially for window frames, comprises an outer synthetic polymer part round an inner extrudable lignin part
WO2012126709A1 (en) 2011-03-24 2012-09-27 Annikki Gmbh Method for producing lignin derivatives

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19852082C1 (en) * 1998-11-11 2000-06-15 Fraunhofer Ges Forschung Composite extruded section, especially for window frames, comprises an outer synthetic polymer part round an inner extrudable lignin part
EP1039087A1 (en) 1998-11-11 2000-09-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Composite profile for window frames
DE19852082C5 (en) * 1998-11-11 2006-01-19 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Composite profile, in particular for window frames
WO2012126709A1 (en) 2011-03-24 2012-09-27 Annikki Gmbh Method for producing lignin derivatives
EP2522690A1 (en) 2011-03-24 2012-11-14 Annikki GmbH Method for manufacturing lignin derivatives
US9206292B2 (en) 2011-03-24 2015-12-08 Annikki Gmbh Method for producing lignin derivatives

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8181 Inventor (new situation)

Free format text: HUETTERMANN, ALOYS, PROF. DR., 37075 GOETTINGEN, DE BRAUN-LUELLEMANN, ANNETTE, DR., 37120 BOVENDEN,DE MAJCHERZCYK, ANDRZEJ, DR., 37077 GOETTINGEN, DE NOETZOLD, SONJA, 37077 GOETTINGEN, DE KHARAZIPOUR, ALIREZA, DR., 37079 GOETTINGEN, DE HUETTERMANN, JUERGEN, PROF. DR., 66424 HOMBURG, DE

8127 New person/name/address of the applicant

Owner name: STOCKHAUSEN GMBH & CO. KG, 47805 KREFELD, DE

8143 Lapsed due to claiming internal priority