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EP2408847A1 - Procédé de fabrication de produits de dégradation de la lignine chimiquement modifiés - Google Patents

Procédé de fabrication de produits de dégradation de la lignine chimiquement modifiés

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Publication number
EP2408847A1
EP2408847A1 EP10709238A EP10709238A EP2408847A1 EP 2408847 A1 EP2408847 A1 EP 2408847A1 EP 10709238 A EP10709238 A EP 10709238A EP 10709238 A EP10709238 A EP 10709238A EP 2408847 A1 EP2408847 A1 EP 2408847A1
Authority
EP
European Patent Office
Prior art keywords
lignin
acid
degradation
molecular weight
chemically modified
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.)
Withdrawn
Application number
EP10709238A
Other languages
German (de)
English (en)
Inventor
Norman Blank
Irene Schober
Philipp Rudolf Von Rohr
Tobias Voitl
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
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.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Priority to EP10709238A priority Critical patent/EP2408847A1/fr
Publication of EP2408847A1 publication Critical patent/EP2408847A1/fr
Withdrawn legal-status Critical Current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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants

Definitions

  • the invention relates to a process for the preparation of chemically modified lignin degradation products, their use as dispersants, and to a composition comprising a chemically modified lignin degradation product and a hydraulic binder.
  • Lignin besides cellulose, is the most abundant material in living nature and is a major constituent of plants having the function of imparting rigidity to the cell scaffold.
  • the lignin content can vary from plant to plant.
  • the chemical structure of lignin also has plant-specific differences.
  • the macromolecule lignin is composed of different proportions of the monomers coniferyl alcohol, sinapyl alcohol and cumaryl alcohol, with the proportion of coniferyl alcohol dominating in many cases (especially in softwoods).
  • lignin as a raw material are described in the literature.
  • a frequently used approach is the gasification of biomass at high temperatures (800-1000 0 C) with air and / or water vapor to synthesis gas (CO, H 2, CO 2 and CH 4). From this synthesis gas various basic chemicals, such as methanol, ether, formic acid and higher molecular weight hydrocarbons (by Fischer-Tropsch synthesis), can be prepared in further stages.
  • WO 2008/106811 describes a process for the direct production of molecules with a minimum molecular weight of 78 g / mol from lignin.
  • lignin, lignin derivatives, lignin fragments and / or lignin-containing substances or mixtures in the presence of at least one
  • Polyoxometalat degraded to the desired products. Not to the
  • Target products converted lignin fragments or lignin are oxidized by means of oxygen to carbon dioxide and water or for energy
  • Lignins or lignosulfonates can be widely used.
  • US Pat. No. 6,313,055 and DE 101 16 849 A1 disclose lignosulfonates as dispersants or condenser for hydraulic binders.
  • the low molecular weight molecules are not made available for any other use.
  • the object of the present invention is to provide a simple and safe method for the chemical utilization of lignin, lignin derivatives, lignin fragments and / or lignin-containing substances or mixtures.
  • chemically modified lignin degradation products are prepared from a lignin-containing starting material.
  • the method according to the invention comprises the following steps:
  • step (c) the chemical modification of the high-molecular-weight lignin degradation products according to step (c) takes place only after the steps (a) and (b).
  • the inventive method allows a chemical recovery of high molecular lignin degradation products and thus offers a more technologically valuable and useful alternative to the previously known methods for oxidation or energy by burning.
  • the chemically modified Ligninabbau area are for example extremely well as dispersants, for example for cementitious systems, as complexing agents for polyvalent metal cations, as a phenol component in binders or resins, or as flocculants, thickeners, components or auxiliaries for coatings, paints, adhesives or resins.
  • the method according to the invention thus makes possible a very useful and meaningful utilization of the renewable raw material lignin.
  • the degradation of lignin can increase the number of chemically modifiable functional groups in the degraded high-molecular-weight lignin molecules.
  • the chemically modified lignin degradation products obtained according to the invention have no or very low levels of low molecular weight lignin degradation products or chemically modified low molecular weight lignin degradation products due to step b.
  • the presence of such, in particular phenolic, low molecular weight lignin degradation products or chemically modified low molecular weight lignin degradation products is particularly undesirable because they may be toxicologically disadvantageous on the one hand or because, especially when used in curable materials, such as concrete or mortar, washed out after or during curing or can be dissolved out, whereby the properties, in particular the environmental compatibility, of these cured materials is unfavorably influenced.
  • the low molecular weight lignin degradation products separated off in step (b), for example vanilin, can be used in other ways.
  • lignin describes a whole class of substances. This is known to the person skilled in the art.
  • chemically modified lignin degradation products can be obtained from all lignin types, regardless of origin and pretreatment. It is also possible to have a aimed at pretreatment of the lignin used, for example, to modify the solubility in organic or inorganic solvent. Furthermore, it is also possible to use an already partially decomposed lignin.
  • Degradation takes place by cleavage of bonds in the lignin backbone, which reduces the molecular weight of the lignin and thus leads to degradation products which, depending on the molecular weight, are low molecular weight or high molecular weight lignin degradation products within the meaning of this document.
  • the degradation according to step (a) of the process according to the invention is carried out in the presence of at least one polyoxometalate.
  • polyoxometalates In contrast to the conventional methods for the degradation of lignins, which are usually based on purely chemophysical methods (high temperature and pressure), based on simple acid- or base-catalyzed hydrolysis, here Polyoxometallate allow the selective cleavage of bonds and thus the degradation of lignin already at comparatively low temperatures.
  • polyoxometalates as catalysts for the degradation of lignin, lignin derivatives, lignin fragments, lignin-containing substances and mixtures is described in WO 2008/106811, the disclosure of which is expressly incorporated herein by reference.
  • Polyoxometalates of molybdenum and phosphorus have been found to be particularly suitable. Most preferred phosphomolybdic acid (H3PM012O40 as representable), which is also referred to by the skilled person as 12-Phosphomolybdänchure. Polyoxometalates are preferably used in step (a) in an amount of 0.01-50 g, preferably 0.1-10 g, per 1 g of starting material.
  • the degradation according to step (a) is carried out in the presence of at least one acid, in particular in the presence of an acid having a pK a i of less than 3, preferably less than 2.5.
  • an acid provides a simple and cost effective alternative to the polyoxometalate catalysts.
  • Advantageous in the use of such acids is that the acids can be readily neutralized and without adversely affecting the chemical modification in step (c) without separation. On the contrary, it can also be advantageous that these acids even support or catalyze the chemical modification. Most acids are also less expensive than the polyoxometalates.
  • inorganic and organic acids for example HCl, H 2 SO 4 , H 2 SO 3 , HNO 3 , HNO 2 , H 3 PO 4 , H 3 PO 3 , sulfonic acids, in particular benzenesulfonic acid, methanesulfonic acid or trifluoroacetic acid , Trichloroacetic acid.
  • step (a) such acid (s) may also be used in combination with polyoxometalate (s).
  • step (a) provides a starting material selected from the group consisting of lignin, lignin derivatives,
  • the pH can be in the range of 0.5 to 6 or be set, preferably in a range of 1 to 3.
  • an optimal implementation of the lignin-containing starting material used to the low and high molecular weight can be in the range of 0.5 to 6 or be set, preferably in a range of 1 to 3.
  • the degradation of the lignin-containing starting material is carried out at a temperature of 20 to 300 0 C, in particular at a temperature of 100 to 200 0 C.
  • the degradation of lignin can be carried out at an overpressure of 0 to 200 bar, preferably at an overpressure of 0 to 50 bar.
  • the degradation takes place in the presence of N 2 , air or O 2 , preferably O 2 .
  • the degradation of lignin in step (a) can also take place in a continuous process instead of in a batchwise, batchwise process.
  • This has the particular advantage of lower labor and cleaning costs and therefore represents a cost reduction of the degradation process and is particularly preferred for industrial, large-volume lignin degradation or chemical modification of Ligninabbau employment particularly.
  • the advantageously used polyoxometalates are continuously separated from the reaction mixture and recycled to the process.
  • the degradation according to step (a) is carried out in the presence of at least one compound which prevents recombination of degradation products.
  • at least one compound which prevents recombination of degradation products are radical scavengers.
  • Radical scavengers serve in the context of this invention to scavenge the radicals formed during the degradation of lignin and thus to prevent repolymerization reactions. In particular, so should the Yield of the desired chemically modified lignin degradation products can be increased.
  • the degradation is carried out in the presence of a radical scavenger which is selected from the group consisting of alcohols, preferably methanol or ethanol; organic radical scavengers, preferably methanol or ethanol; organic radical scavengers, preferably methanol or ethanol; organic radical scavengers, preferably methanol or ethanol; organic radical scavengers, preferably methanol or ethanol; organic radical scavenger which is selected from the group consisting of alcohols, preferably methanol or ethanol; organic radical scavenger which is selected from the group consisting of alcohols, preferably methanol or ethanol; organic radical scavengers, preferably methanol or ethanol; organic radical scavengers, preferably methanol or ethanol; organic radical scavengers, preferably methanol or ethanol; organic radical scavengers, preferably methanol or ethanol; organic radical scavengers, preferably methanol or
  • Acids preferably ascorbic acid; Phenols, preferably butylhydroxytoluene; and stabilized free radicals, preferably nitroxyl radicals.
  • Another embodiment provides to convert lignin-containing starting material in the presence of two liquid phases.
  • two liquid phases which are only partly or immiscible, are in contact with each other.
  • the two liquid phases have a substantially different polarity. Due to different solubilities of polyoxometalate (s) or acid, of lignin and of lignin degradation products in the selected liquid phases, a partial or complete separation of the components can take place.
  • the low molecular weight Ligninabbau area can be separated from the reaction medium before they react further in subsequent reactions.
  • the degradation of the lignin in the presence of two liquid phases is also carried out in the presence of a radical scavenger.
  • the liquid medium used in step (a) is water, optionally in combination with an alcohol.
  • an alcoholic radical scavenger is used in the degradation, in particular methanol and / or ethanol, wherein the volume ratio of water to alcoholic radical scavenger is particularly preferably in the range from 1:10 to 10: 1.
  • the at least substantial separation of the low molecular weight Ligninabbau area can, for example, by distillation or extraction or precipitation or filtration or ultrafiltration. Extraction and ultrafiltration by means of membrane, which typically has a cut-off of 100 daltons or 1000 daltons, have proven particularly suitable. In addition, it is also possible, in addition to the low molecular weight lignin degradation products also separate any other components, eg. As solvents or excess reagents.
  • the separation of the low molecular weight lignin degradation products in step (b) is such that the proportion of the sum of low molecular weight lignin degradation products and chemically modified low molecular lignin degradation products less than 20 wt .-%, in particular in the chemically modified Ligninabbau furnace after step (c) less than 10 wt%, preferably less than 5 wt%, most preferably less than 1 wt%.
  • step (b) the separation of the low molecular weight constituents, which have only one benzene ring (referred to in this context as "monomers") corresponding to a molecular weight Mw of the low molecular weight degradation products of less than 200 g / mol, advantageously takes place as completely as possible the amount of monomers present in the reaction mixture after step (a) is separated off by means of step (b) to more than 90% by weight, in particular more than 95% by weight, preferably more than 97% by weight the high molecular weight fraction after step (b) less than 5 wt .-%, in particular less than 2 wt .-%, preferably less than 1 wt .-% of monomers.
  • step (b) it is basically possible to carry out step (b) during step (a), i. that the separation of the low-molecular
  • Lignin degradation products at least partially during the degradation of the Starting material can be carried out, for example by extraction in one operation (reactive extraction) or by separation (filtration) via a membrane in a membrane reactor.
  • the phenolic products separated as low-molecular-weight lignin degradation products can be used for a different purpose, for example as starting materials for the preparation of organic compounds.
  • the chemical properties of the high molecular weight lignin degradation products can be determined such that the modified products are suitable for the desired use.
  • the high-molecular lignin degradation products can be chemically modified, for example, by etherification, esterification, alkoxylation, sulfonation or graft polymerization.
  • the chemical modification of the high molecular weight lignin degradation products comprises a reaction selected from the group consisting of addition, condensation and graft polymerization.
  • the high molecular weight lignin degradation products contain after step (b) in particular chemically modifiable groups which are selected from the group consisting of aliphatic alcohol groups, aromatic alcohol groups (phenolic groups), carboxylic acid groups and carbonyl groups. In addition, they may possibly emerge as radicals from step (b). In particular, such groups are the chemical modification in step (c) accessible.
  • Modification of the high-molecular lignin degradation products by reaction with at least one reactant which is selected from the group consisting of alcohols, carboxylic acids, hydroxycarboxylic acids, amino acids, acid chlorides, acid anhydrides, sulfonic acids, hydroxysulfonic acids, aminosulfonic acids, sulfamic acid, esters, lactones, lactams, alkyl halides, epoxides , Amines, hydroxylamines, sulfuric acid, oleum, Chlorosulfonic acid, adducts of SO3 such as DMF or pyridine, and olefinically unsaturated compounds.
  • reactant which is selected from the group consisting of alcohols, carboxylic acids, hydroxycarboxylic acids, amino acids, acid chlorides, acid anhydrides, sulfonic acids, hydroxysulfonic acids, aminosulfonic acids, sulfamic acid, esters, lactones, lactam
  • Phenolic and non-phenolic alcohol groups in the high-molecular-weight lignin decomposition products can be reacted with ethylene oxide, propylene oxide or butylene oxide or mixtures thereof, for example, under conditions customary for alkoxylations.
  • ethylene oxide, propylene oxide or butylene oxide or mixtures thereof for example, under conditions customary for alkoxylations.
  • polyalkylene oxide chains of different lengths and compositions can be applied to the degraded lignin molecule.
  • the following chemical groups can be introduced by means of alkoxylation:
  • the radical L linked via a dashed bond is intended in each case to represent the polymer backbone of a high-molecular-weight lignin degradation product before and after the chemical modification. It goes without saying that it is certainly also possible to append a number of - even different - of the functionalities shown to such a polymer backbone.
  • Phenolic and non-phenolic alcohol groups in the high molecular weight lignin degradation products can be further added to epoxides such as epoxidized fatty acids, glycidyl methacrylate or epoxidized maleic acid.
  • epoxides such as epoxidized fatty acids, glycidyl methacrylate or epoxidized maleic acid.
  • the following chemical modified groups can be obtained by addition to epoxides:
  • suitable compounds are (meth) acrylic acid, (meth) acrylates, (meth) acrylamides, (meth) acrylonitrile, vinylsulfonic acid or vinylphosphonic acid.
  • Further possible compounds are maleic acid, crotonic acid or itaconic acid or their mono- or diesters and -amides and also the monoamide of maleic acid with sulphanilic acid.
  • Phenolic and non-phenolic alcohol groups in the high molecular weight lignin degradation products can be esterified with mono- or dicarboxylic acids or their anhydrides or acid chlorides, or transesterified with simple carboxylic acid esters.
  • mono- or dicarboxylic acids or their anhydrides or acid chlorides or transesterified with simple carboxylic acid esters.
  • these are acetic acid, maleic acid, fumaric acid, phthalic acid or Fatty acids such as lauric acid or oleic acid, their anhydrides, acid chlorides or simple esters.
  • the following chemical modified groups can be obtained by esterification:
  • Aromatic nuclei with aromatic alcohol groups i.e., phenolic rings
  • formaldehyde i.e., formaldehyde
  • formaldehyde or other aldehydes and amines or polyamines leads to Mannich bases.
  • Alanine has been shown to be particularly suitable amine. These can be further functionalized as needed.
  • the following chemical modified groups can be obtained:
  • Examples of such reactions are the esterification or amidation with ⁇ -alkoxy- ⁇ -hydroxy-polyalkylene glycols or ⁇ -alkoxy- ⁇ -amino-polyalkylene glycols, preferably ⁇ -methoxy- ⁇ -hydroxy-polyethylene glycols, ⁇ -alkoxy- ⁇ - amino-polyethylene glycols or ⁇ -alkoxy- ⁇ -amino-poly (ethylene / propylene glycols), or the esterification with fatty alcohols such as lauryl alcohol or oleyl alcohol.
  • Aldehyde or keto groups in the high molecular weight lignin degradation products can be converted with sulfite to the corresponding hydroxy sulfonic acids.
  • the following chemical modified groups can be obtained from aldehyde groups:
  • the high molecular weight lignin degradation products can be reacted in a radical graft polymerization with at least one olefinically unsaturated compound.
  • the at least one olefinically unsaturated compound is preferably selected from the group consisting of alkenes, dienes, olefinically unsaturated acids, olefinically unsaturated esters, olefinically unsaturated acid anhydrides, olefinically unsaturated amides, olefinically unsaturated ethers and olefinically unsaturated alcohols, preferably selected from the group consisting of acids or anhydrides or esters or amides of acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid, vinyl ethers, vinylsulfonic acids, vinyl esters, allyl alcohol and allyl ether.
  • such olefinically unsaturated compounds are (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid or itaconic acid, their esters, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid , the half-amide of maleic acid and sulphanilic acid, polyalkylene glycol (meth) acrylates or maleic acid-polyalkylene glycol mono- or maleic acid polyalkylene glycol diesters or amides, styrene, styrenesulfonic acid, vinyl acetate, N-vinylpyrrolidone, vinylpolyalkylene glycols, vinylsulfonic acid, vinylphosphonic acid or allyl polyalkylene glycols.
  • graft (co) polymerizations are generally carried out with a suitable initiator and, if necessary, molecular weight regulators and / or reducing agents.
  • initiators are peroxides such as hydrogen peroxide or dibenzoyl peroxide (DBPO), persulfates such as sodium, potassium or ammonium persulfate, hydroperoxides such as cumene hydroperoxide or azo compounds such as aziosobutyronitrile (AiBN).
  • DBPO dibenzoyl peroxide
  • persulfates such as sodium, potassium or ammonium persulfate
  • hydroperoxides such as cumene hydroperoxide or azo compounds such as aziosobutyronitrile (AiBN).
  • Suitable regulators are, for example, allyl compounds, alcohols, aldehydes, sulfur compounds, e.g.
  • Mercaptans such as thioacetic acid, mercaptopropionic acid, dodecyl mercaptan
  • suitable reducing agents are, for example, alkali metal sulfites or alkali hydrogen sulfites, alkali phosphites, ascorbic acid, thiosulfates or Rongalit or transition metals, for example.
  • Fe (II) salts are, for example, alkali metal sulfites or alkali hydrogen sulfites, alkali phosphites, ascorbic acid, thiosulfates or Rongalit or transition metals, for example.
  • the graft polymerization is preferably carried out with H 2 O 2 together with Fe (II) sulfate and Rongalit or with alkali persulfate and alkali metal sulfite.
  • the polymerization is preferably carried out in an organic solvent. In this case, it is advisable to use initiator systems that are soluble in organic solvents such as AiBN or DBPO.
  • Aromatic nuclei especially phenolic rings, in the high molecular weight
  • Lignin degradation products can be used, for example, with oleum or sulfuric acid be sulfonated or sulfomethylated with formaldehyde and sulfite.
  • oleum or sulfuric acid be sulfonated or sulfomethylated with formaldehyde and sulfite.
  • chemical modified groups can be obtained:
  • a high-molecular-weight lignin degradation product can be alkoxylated in a first step and, in a second step, the resulting and the remaining alcohol groups can be esterified.
  • amino groups are introduced, which are reacted with epoxides in a second step.
  • it is sulfonated in a first step on the aromatic and in a second step, the alcohol groups reacted with alkylene oxide.
  • more than one functional group can be implemented simultaneously, e.g. the alkoxylation can be carried out simultaneously on the aromatic and on the aliphatic alcohol group.
  • the weight average molecular weight M w of the high molecular lignin degradation products after step (a) is less than 80% of the molecular weight of the starting material used in step (a), preferably less than 60%.
  • the degradation which takes place in step (a) advantageously leads to a very marked reduction in the molecular weight and thus to a strong degradation of the lignin.
  • the present invention further relates to the use of a chemically modified lignin degradation product prepared by a process according to the invention as a dispersant.
  • the chemically modified lignin degradation products may also be used as complexing agents for polyvalent metal cations, as a phenolic component in binders or resins, or as flocculants, thickeners, component or auxiliaries for coatings, paints, adhesives or resins.
  • the present invention further relates to a composition comprising at least one chemically modified lignin degradation product prepared by a process according to the invention and at least one hydraulic binder.
  • hydraulic binder As a “hydraulic binder”, this document basically refers to all hydraulically setting substances known to the skilled worker, in particular the hydraulic binders are cements, such as Portland cements or high-alumina cements and their mixtures with fly ash, silica fume, slags, slag sands
  • hydraulic binders are also understood as meaning the hydraulically setting substances gypsum, in the form of anhydrite or hemihydrate, or calcined lime. Cement is preferred as the hydraulically setting binder.
  • the composition may have other ingredients in addition to hydraulic binder and chemically modified Ligninabbaueck.
  • Such other ingredients include additives such as sand, gravel, stones, quartz, chalk, Kalksteinfiller and customary additives such as Betonver hypossiger, such as lignosulfonates, sulfonated naphthalene-formaldehyde condensates, sulfonated melamine-formaldehyde condensates or polycarboxylate, accelerators, corrosion inhibitors, retarders, Schwlashduzierer Defoamer or pore-forming agent.
  • additives such as sand, gravel, stones, quartz, chalk, Kalksteinfiller and customary additives such as Betonver hypossiger, such as lignosulfonates, sulfonated naphthalene-formaldehyde condensates, sulfonated melamine-formaldehyde condensates or polycarboxylate, accelerators, corrosion inhibitors, retarders, Schwrimzierer Defoamer or pore-forming agent
  • compositions cure as a result of the reaction of the hydraulic binder with water under the influence of water.
  • such compositions may be used as mortar or concrete compositions.
  • the chemically modified Ligninabbau area also have a liquefying effect on hydraulic binders, or on compositions containing hydraulic binders.
  • a hydraulic binder or a composition comprising a hydraulic binder has a more fluid consistency or increased flow behavior than the corresponding hydraulic binder or the composition comprising the hydraulic binder, without chemically modified lignin degradation products with the same amount of water.
  • the chemically modified lignin degradation products reduce the water requirement of a hydraulic binder, or a composition comprising the hydraulic binder, in order to achieve a specific flow behavior.
  • the flow, or the flow behavior is typically determined by the so-called slump size, measured according to EN 1015-3.
  • the chemically modified Ligninabbau effort described in the context of this invention in particular have a higher liquefaction effect for hydraulic binders, compared both with the corresponding chemically modified Ligninabbau arean where the low molecular weight Ligninabbau excursi have not been separated before the chemical modification, as well as with the corresponding chemically modified lignins, which were not subjected to lignin degradation before the chemical modification ,
  • the higher liquefaction effect of the chemically modified Ligninabbau area disclosed in the invention in hydraulic binders affects in improved processing properties, or in a lower water demand for the achievement of a specific processing consistency, which shows experience shows higher mechanical properties of the cured hydraulic system.
  • Lignin 1 Indulin® AT, an unmodified Kraft lignin from MeadWestvaco (USA), available for example from Staerkle & Nagler AG, Zollikon, Switzerland • Lignin 2: weakly sulphonated spruce kraft lignin supplied by Sigma Aldrich, Switzerland
  • Example 1 Lignin 1 / Extraction via extraction. A mixture of 80 ml of methanol and 20 ml of water was added as
  • Reaction solution prepared.
  • the pH of the solution was adjusted to pH 1.10 by addition of a few drops of concentrated sulfuric acid with simultaneous measurement with a Polilyte HT120 sensor (Hamilton Bonaduz AG, CH-Bonaduz).
  • the solution was then transferred to a 400 ml autoclave (Premex Reactor AG, CH-Lengnau) equipped with a gassing stirrer. Before closing the reactor, 1 g of lignin 1 was added. The mixture was then charged three times with 11 bar of oxygen and then vented again to displace the initial air in the reactor. Finally, the reactor 11 was filled bar oxygen, and the mixture was heated at a stirrer speed of 1000 rev / min at a rate of 8 K / min to 170 0 C.
  • the mixture was kept at 170 ° C. for 20 minutes and then cooled to below 30 ° C. within 60 minutes. Thereafter, the reactor was depressurized, opened and the liquid reaction mixture (including the resulting solid) removed. In order to recover the degraded lignin as completely as possible from the reactor, the interior of the reactor was freed from solid deposits, the reactor was rinsed with a little water and the wash water added to the reaction mixture. This reaction mixture is referred to below as RG1.
  • Ex-CI chloroform extracts
  • Ex-WI contained virtually no lignin degradation products.
  • the solid S1 was predried on a rotary evaporator and finally freeze-dried and designated as a separated high-molecular lignin degradation product AHLA1.
  • Example 2 was carried out in an analogous manner to Example 1, except that instead of the lignin 1 lignin 2 was used.
  • the corresponding reaction mixture is hereinafter referred to as RG2, the solid as S2, the chloroform extract as Ex-C2 and the aqueous phase as Ex-W2. Since the aqueous phase Ex-W2 still contained lignin degradation products, in Example 2 the solid S2 was combined with aqueous phase Ex-W2, mixed, pre-dried on a rotary evaporator and finally freeze-dried and the separated high-molecular lignin degradation product designated AHLA2.
  • Example 3 Lignin 2 (larger autoclave) / separation via ultrafiltration
  • Example 3 was carried out in an analogous manner to Example 1, except that instead of the lignin 1 lignin 2 was used and a larger amount of lignin was used.
  • the corresponding reaction mixture is hereinafter referred to as RG3.
  • This reaction mixture was adjusted to pH 10.7 with NaOH and concentrated on a rotary evaporator and then freeze-dried.
  • the majority of the low molecular weight decomposition products and the salts were separated by ultrafiltration with a 1000 Dalton membrane. In ultrafiltration, the solution is stirred in each case The ultrafiltration cell (300 ml volume) was separated at a pressure of about 4 bar via a membrane with a specified exclusion limit (for example 1000 daltons here).
  • the phase passed through the membrane is referred to as filtrate, the remaining phase is referred to as residue.
  • the filtrate obtained here was designated as filtrate F3.
  • the residue was concentrated on a rotary evaporator and freeze-dried. 1.3 g of a powder having an organic carbon content of 48.0% (determined by TOC measurement) were obtained. This residue is the separated high molecular weight lignin degradation product and is referred to as AHLA3.
  • H3PM012O40 phosphomolybdic acid, No. 31426, Sigma-Aldrich, CH Buchs
  • the pH of the solution was then determined to be 1.13 with a Polylite HT120 sensor (Hamilton Bonaduz AG, CH-Bonaduz).
  • the solution was then transferred to a 400 ml autoclave (Premex Reactor AG, CH-Lengnau) equipped with a gassing stirrer. Before closing the reactor, 1 g of lignin 2 was added.
  • the mixture was then charged three times with 11 bar of oxygen and then vented again to displace the initial air in the reactor. Finally, the reactor 11 was filled bar oxygen, and the mixture was heated at a stirrer speed of 1000 rev / min at a rate of 8 K / min to 170 0 C. The mixture was kept for 20 minutes at 170 0 C and then cooled within 60 min to below 30 ° C. Thereafter, the reactor was depressurized, opened and the liquid reaction mixture (including small amounts of solid) removed. Around To remove the degraded lignin as completely as possible from the reactor, the interior of the reactor was freed from solid deposits, the reactor rinsed with a little water and the wash water added to the reaction mixture. This reaction mixture is referred to below as RG4.
  • AHLAI was almost completely dissolved in 10 ml of dry DMSO and 0.22 g of sulfamic acid added.
  • the reaction mixture was stirred at 80 ° C. for 17 hours. After cooling to room temperature, the reaction mixture was poured onto 300 ml of ethanol in which 1.3 g of NaOH had been dissolved.
  • the resulting precipitate was filtered off and washed with ethanol.
  • the after 2 days in the refrigerator from the filtrate further precipitated precipitate was also filtered off and combined with the first and dried.
  • the solid was dissolved in water, the pH was adjusted to about 12 using NaOH, and the solution was ultrafiltered through a 1000 Dalton membrane to remove most of the inorganic salts.
  • the residue was freeze-dried giving 0.7 g of a brown powder, which was designated B1.
  • the TOC measurement of the dried residue gave 50.2% organic carbon.
  • the reaction mixture RG1 was concentrated on a rotary evaporator and freeze-dried.
  • the 3.68 g solids contain 2.0 g of degraded lignin. This was dissolved in 40 ml of dry DMSO. After the addition of 0.44 g of sulfamic acid, the reaction mixture for 3 hours at 80 0 C was stirred. After cooling, it was poured onto 600 ml of ethanol in which 2.0 g of NaOH were dissolved and the resulting precipitate was filtered off and washed with ethanol. The precipitate which precipitated from the filtrate after standing for 2 days in the refrigerator was also filtered off and combined with the first. The solid was dissolved in a little water, freeze-dried to give 3.9 g of powder, designated Ref.RGI. The TOC measurement gave 20.4% organic carbon.
  • the reaction mixture RG3 was adjusted to pH 10 with NaOH, concentrated on a rotary evaporator and freeze-dried. 5.9 g of this powder with an organic carbon content of 28.7% (determined by TOC measurement) (corresponds to 3.4 g degraded lignin) were dissolved in 15 ml of water and 1.7 g of DL-alanine was added and also dissolved. The pH of the solution was adjusted to 9-10 by adding NaOH. After the addition of 1.5 ml of a 36% formaldehyde solution was heated with stirring for 16 hours under nitrogen to 85 ° C and it was obtained a Mannich base. The reaction conversion of alanine was 28%, as calculated from the decrease of the alanine peak in HPLC.
  • the reaction mixture RG4 was brought to pH 10-10.5 with NaOH, concentrated by rotary evaporation and freeze-dried. 12.4 g of a powder were isolated.
  • the TOC measurement has an organic carbon content of 3.6%.
  • 12.3 g (corresponds to approx. 0.9 g mined Lignin) were mixed with 11.9 ml of water and partially dissolved.
  • 0.48 g of DL-alanine was added and the pH of the solution was adjusted to 9-10 by addition of 250 mg of NaOH.
  • 0.42 ml of a 36% formaldehyde solution was added and the mixture was stirred under nitrogen at 85 ° C for 16 hours to obtain a Mannich base.
  • the weight average molecular weight M w was determined via SEC (Size Exclusion Chromatography). The SEC analysis was carried out on a HPLC system (Alliance 2695, Waters) equipped with a column cascade from Polymer Standards Service GmbH (MCX 10 ⁇ m 1000A, MCX 10 ⁇ m 100000A + precolumn) and a UV detector (320 nm). As solvent and solvent for lignin and lignin degradation products, 0.01 molar aqueous sodium hydroxide solution was used. The calibration was carried out by means of 9 narrow polymer standards of sulfonated polystyrene in the molecular weight range 1'020'0OO Da to 3'420 Da. The weight average molecular weight was thus determined relative to sulfonated polystyrene.
  • the measured absorption signal of the UV detector (320 nm) was normalized in the chromatograms to the highest peak (corresponds to the unit (AU) 1). Plotted as X-axis is the elution volume (V e ) or the corresponding molecular weight M w (g / mol).
  • FIG. 1 shows the comparison of the SEC chromatograms of lignin 1 with the reaction mixture RG1.
  • FIG. 2 shows the comparison of the SEC chromatograms of lignin 2 with the reaction mixture RG2.
  • FIG. 3 shows the comparison of the SEC chromatograms of lignin 2 with the reaction mixture RG3.
  • FIG. 4 shows the comparison of the SEC chromatograms of lignin 2 with the reaction mixture RG4. From the shift in the maximum molecular weight in the respective reaction mixture, it can be seen that a considerable reduction in the molecular weight has taken place during the degradation.
  • FIG. 5 shows by way of example the comparison of the SEC chromatograms of the chloroform extracts Ex-CI with the separated high-molecular lignin degradation product AHLA1 in Example 1.
  • FIG. 6 shows the comparison of the SEC chromatograms of the filtrate F3 and the separated high-molecular lignin degradation product AHLA3 of the reaction mixture RG3 separated by ultrafiltration in Example 3.
  • FIG. 7 shows the comparison in Example 3 of the SEC chromatograms of the reaction mixture RG3 and of the high molecular weight lignin decomposition product AHLA3 separated by ultrafiltration from the reaction mixture RG3.
  • the normalized SEC chromatograms as shown in FIG. 7 were used.
  • the separation efficiency AE was calculated therefrom according to the following formula:
  • Example 3 is 98%.
  • the separated mono-, di- and trimers appear in the SEC chromatogram of the filtrate F3 (permeate).
  • small amounts of degradation products larger than trimers are detectable in F3.
  • the largest components found in the filtrate F3 have a molecular weight in the order of the cut-off of the membrane of 1000 daltons.
  • the amounts of lignin or chemically modified degraded lignin indicated in Table 1 were weighed into the mixing water and dissolved in a 250 ml mixing vessel.
  • 200 g of a mixture of 3 Swiss CEM I 42.5 cements (1: 1: 1 by weight) were sprinkled in each case.
  • the cement paste thus formed was well mixed with a 2 cm diameter propeller stirrer at 2000 rpm for 2 minutes.
  • An open measuring cylinder 50 mm diameter, 51 mm height standing on a clean glass plate with a diameter of 30 cm was filled flat with the cement paste. The measuring cylinder is lifted so that the cement paste can flow out.
  • the diameter of the cement paste cake formed is measured to an accuracy of 1 mm and recorded as flow grade ⁇ "FM2m ⁇ n").
  • the cement paste is filled back into the mixing vessel after the measurement and the measurement is repeated after 30 or 60 minutes from the addition of the mixing water the cement paste was mixed again for 15 seconds, and noted as a flow of the material after 30 minutes (“FM 30 mm") or 60 minutes (“FM 60 mm").
  • results show that the examples which are based on chemically modified lignin degradation products B1, B2, B3 or B4 according to the invention have a significantly improved flow behavior than the comparative examples with the corresponding chemically modified degradation products not separated from the low molecular weight degradation products, or the chemical modified undegraded lignins.
  • Example Ex2 shows that with the additive B2 according to the invention, a comparable fluidity can already be achieved with just one third of the dosage as in the comparative additives Ref. 2 or Ref. R2G2 ,

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Abstract

La présente invention concerne un procédé de fabrication de produits de dégradation de la lignine, chimiquement modifiés. Ce procédé consiste à prendre un matériau de départ contenant de la lignine et à le mettre en présence d'un milieu liquide dans des conditions acides pour le dégrader en des produits de dégradation de lignine de faible poids moléculaire et de haut poids moléculaire, puis au moins à en séparer les produits de dégradation de lignine de faible poids moléculaire de façon à obtenir une fraction de haut poids moléculaire. Ensuite, on convertit en produits de dégradation de lignine chimiquement modifiés les produits de dégradation de lignine de haut poids moléculaire contenus dans la fraction de haut poids moléculaire. Les produits de dégradation de lignine chimiquement modifiés ainsi obtenus conviendront, notamment, comme dispersants, constructeurs de complexes, floculants phénolés, épaississants ou auxiliaires pour systèmes cimentiques, revêtements, peintures ou colles.
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