EP2183322A2 - Procédé pour produire des matériaux fibreux - Google Patents

Procédé pour produire des matériaux fibreux

Info

Publication number
EP2183322A2
EP2183322A2 EP08787363A EP08787363A EP2183322A2 EP 2183322 A2 EP2183322 A2 EP 2183322A2 EP 08787363 A EP08787363 A EP 08787363A EP 08787363 A EP08787363 A EP 08787363A EP 2183322 A2 EP2183322 A2 EP 2183322A2
Authority
EP
European Patent Office
Prior art keywords
fiber materials
binder
binders
polyamine
hydrolytic
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Withdrawn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
EP08787363A
Other languages
German (de)
English (en)
Inventor
Stephan WEINKÖTZ
Tilo Habicher
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP08787363A priority Critical patent/EP2183322A2/fr
Publication of EP2183322A2 publication Critical patent/EP2183322A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof

Definitions

  • the invention relates to a process for the production of fiber materials in which at least one hydrolytic protein mixture and at least one polyamine- or polyimine-containing binder or any mixture of these binders is used for the production of the fiber materials.
  • the invention further relates to the use of at least one hydrolytically active protein mixture and at least one polyamine or polyimine-containing binder or any mixture of these binders alone or in combination with at least one other binder or at least one excipient or at least one other binder and at least one excipient Production of fiber materials.
  • the invention also relates to fiber materials, which by means of a method in which at least one hydrolytic protein mixture and at least one polyamine binder or at least one polyimine binder or at least one polyamine-containing or polyimine-containing binder or any mixture of these binders used for the production of the fiber materials was, are available.
  • Fiber materials are materials that are made up of small units of cellulosic plant material. These small units are referred to as pulp and can be made from numerous cellulosic fibers, or lignocellulosic materials. Using high pressure, heat or binders, the pulp is formed into new materials, called fiber materials, and reconnected. If the pulp is pressed in the production of the fiber materials, so different fiber materials can be produced with different densities depending on the pressure used.
  • the fiber materials are generally referred to as insulation boards, at a density of about 350 to about 800 kg / m 3 is usually called medium-hard fiberboard, at a density of about 650 to about 900 kg / m 3 in general of MDF fibreboard (medium-density fiberboard) and a density of about 800 to about 1200 kg / m 3 is achieved, so it is generally spoken of HDF (high-density fiberboard) fiber-boards).
  • medium-hard fiberboard at a density of about 650 to about 900 kg / m 3 in general of MDF fibreboard (medium-density fiberboard) and a density of about 800 to about 1200 kg / m 3 is achieved, so it is generally spoken of HDF (high-density fiberboard) fiber-boards).
  • the production of fiber materials usually proceeds in a multi-stage process.
  • the pulp is obtained by thermo-mechanical defibration of wood chips. This is followed by a drying and Beleim suits, the gluing can be done before or after drying. Then the pulp becomes too a nonwoven (nonwoven fabric) scattered and formed in a press under the influence of pressure and temperature to a fiber material.
  • the pressing tool plate-shaped or multi-dimensionally shaped fiber materials are manufactured. This can be done, for example, by preforming the fiber material and subsequently shaping it into double-belt presses or with multi-dimensionally shaped pressing tools to form the finished fiber materials.
  • the fiber materials are used for example in the automotive, construction, packaging or furniture industry.
  • the fibrous materials can be used here as wall and floor elements for interior work, for example as interior linings or floor laminate, as a furniture element.
  • Fiber materials with low density are preferably used as insulation boards on or in buildings.
  • Another field of application of fiber materials are molded parts, which are used, for example, in motor vehicle applications.
  • Motor vehicles are all vehicles that can move by machine power. These are, for example, automobiles, aircraft, rail vehicles or self-propelled construction machines, such as excavators, caterpillars or cranes.
  • binders for example, synthetic resins such as diisocyanates or urea, phenol or melamine-Fomaldehyd resins can be used. If formaldehyde-containing binders are used, formaldehyde can be released into the ambient air and lead to health impairments, especially in enclosed spaces. It is therefore attempted to reduce the proportion of formaldehyde-containing binders in fiber materials or to completely replace the formaldehyde-containing binders.
  • EP 1 192 223 B1 discloses polyamines and polyamine-containing aminoplast resins as binders for producing fiberboards.
  • the document DE 43 08 089 A1 describes the use of an agent for the production of binders for wood bonding, which is a polyamine, a sugar and one or more components from the group formed by dicarboxylic acid derivatives, aldehydes having two or more carbon atoms and epoxides , contain.
  • oxidases in particular phenol oxidases, can promote the recombination of lignin in the fiber materials and thus develop a binding effect.
  • EP 1 184 144 A2 uses hydrolytic enzymes such as hemicellulases or cellulases in order to positively influence the fiber structure of wood fibers and to produce fiber materials without or with a reduced proportion of synthetic binders.
  • hydrolytic enzymes can be used for the production of formaldehyde-free binders.
  • DE 43 40 518 A1 describes that potato pulp, if it has been treated with pectinases, hydrolases or cellulases, has a binding effect in fibrous materials.
  • the object was to develop a combination of a hydrolytic protein mixture with one or more binders, which can be used in the smallest possible amounts and still leads to fiber materials with acceptable quality properties. Furthermore, the object, at least one property of fibrous materials, such as the transverse tensile strength, the bending strength, the bending modulus, the 24-h thickness swelling, the water absorption or the amount of extractable formaldehyde through the use of hydrolytic protein mixtures turned out in combination with one or more binders or in combination with one or more binders and one or more excipients.
  • hydrolytic protein mixtures in combination with at least one polyamine- or polyimine-containing binder or any mixture of these binders. It has been found that hydrolytic protein mixtures in combination with one or more polyamine- or polyimine-containing binders or in combination with one or more other binders and one or more auxiliaries, not only the required amount of the required hydrolytic protein mixture and the required amount But also reduces the transverse tensile strength or the bending strength or the bending modulus or the 24-h thickness swelling or water absorption or the amount of extractable formaldehyde. In general, a combination of these properties is improved. Fiber materials are usually made of fiber.
  • Pulp in turn can be obtained from lignocellulose-containing materials by thermo-mechanical pulping or by chemical pulping according to, for example, sulfite, sulfate or organosolv processes or by the Mason steam explosion process.
  • the thermo-mechanical digestion is usually carried out in a defibrillator or a refiner.
  • lignocellulosic materials which usually consist of woodchip chips sawdust or other materials with more or less large accumulations of cellulose fibers or lignocellulose.
  • Other materials include waste wood, rape straw, flax, hemp, grain straw, coconut fibers, bamboo, rice straw or bagasse. They can be used alone or in mixtures. Under old wood here are understood all wood materials that have already been used in the form of timber, furniture, pallets, fiber materials or the like.
  • the pulp is brought into contact or mixed with one or more hydrolytically active protein mixtures, the binder (s) and any auxiliaries needed. This can be done individually or in mixtures and at one or more times. Preferably, hydrolytic protein mixtures having different properties or compositions are used at different times.
  • the type and amount of binder and excipients required in each case depends on the requirements and quality standards which the manufactured fiber material has to meet.
  • the pulp is treated with the hydrolytic protein mixture, the binder or the binders and the auxiliary or excipients, a distinction is made between the wet, semi-dry and dry processes.
  • the treated pulp should not exceed a nonwoven moisture content of 25% by weight.
  • Nonwoven moisture is a measure of the moisture content of the pulp and refers to the total weight of the wet pulp.
  • the fleece moisture can be determined by means of thermogravimetry, for example with an IR moisture meter, or by determining the difference in mass between moist pulp and the pulp dried to constant mass.
  • the hydrolytically acting protein mixtures used in the process according to the invention can be brought into contact with the pulp in a variety of ways, for example by spraying, dipping or impregnating, or mixed with the pulp. Due to the smaller amount of liquid, spraying is preferred in the dry process. For the wet or semi-dry process, the hydrolytic protein mixtures can also be brought into contact with the pulp by means of dipping or impregnation.
  • the hydrolytic protein mixtures used in the process according to the invention have a xylanase or AZO-CMC activity. Preferably, they have a xylanase and an AZO-CMC activity.
  • the xylanase or the AZO CMC activity or both can each be based on the activity of individual enzymes or on different enzymes or isoenzymes of the same or similar activity. These enzymes or isoenzymes may be present in a hydrolytic protein mixture at different concentrations.
  • All proteins and enzymes mentioned in the patent specification may be of viral, microbial, plant or animal origin. In particular, they may be microbial, for example prokaryotic or fungal origin.
  • Xylanase activity is caused by xylanases.
  • Xylanases are hemicelluloses which can hydrolyze polysaccharides from 1,4- ⁇ -glycosidically linked D-xylanopyranoses with short, differently composed side groups (so-called xylans). They have a large structural diversity and are formed by numerous organisms. Depending on the nature of the respective xylanase, they may have endo- or exo-activity or endo- and exo-activity.
  • Xylanases are typically divided into three groups, each containing xylanases with predominantly or exclusively endo-1,4- ⁇ -D-xylanase, or predominantly or exclusively endo-1,3- ⁇ -xylanase or predominantly or exclusively xylan. 1, 4- ⁇ -xylosidase activity.
  • the xylanase activity can be assisted or synergistically promoted by enzymes which can deacetylate acetylxylane.
  • the activity should be in the range of 100 to 30,000 U / ml. It is preferably in the range of 10,000 to 21,000 U / ml and more preferably in the range of 17,000 to 21,000 U / ml.
  • the AZO CMC activity is mainly caused by a subset of cellulases.
  • Cellulases are enzymes that can break down cellulose.
  • Cellulases are typically classified into four groups, each comprising enzymes with predominantly or exclusively endo-1,4- ⁇ -glucanase, predominantly or exclusively exo-cellobiohydrolase, predominantly or exclusively cellobiase or predominantly or exclusively exo-glucohydrolase activity have.
  • AZO CMC activity is mainly mediated by enzymes with predominantly or exclusively endo-1, 4-beta
  • Glucanase activity which are therefore also referred to as endo-cellulases.
  • the AZO CMC activity can be determined by means of CM-cellulose, in particular CM-cellulose 4M, at a pH of 4.5 and a temperature of 40 ° C.
  • the activity should be in a range of 50 to 700 U / ml. It is preferably in the range from 100 to 500 U / ml and particularly preferably in the range from 300 to 450 U / ml.
  • hydrolytic protein mixtures further activities can be determined.
  • various substrates can be used.
  • the activity is usually determined in the form of International Units (IU).
  • IU International Units
  • One international unit corresponds to a substrate turnover of 1 ⁇ mol per minute.
  • 1 IU of filter paper activity (FPA) corresponds to the formation of 1 ⁇ mol of glucose, with filter paper as the substrate.
  • the hydrolytic protein mixtures contain further enzymes which can deacetylate acetylxylane or other enzymes with exo-cellobiohydrolase activity or other enzymes with cellobiase activity or other enzymes with phenoloxidase activity, for example laccase activity, or other enzymes with peroxidase activity.
  • the hydrolytic protein mixtures preferably contain further enzymes for two or more of these activities.
  • the protein mixtures contain enzymes for xylanase, AZO CMC, laccase, and peroxidase activity.
  • Phenol oxidases are enzymes that can convert mono-, oligo- or polyphenols into the corresponding quinones with the participation of oxygen.
  • a particularly important group of phenol oxidases are laccases, the laccase activity is usually determined with syringaldehydazine or ABTS.
  • Peroxidases are enzymes that catalyze the oxidation of various substrates with hydrogen peroxide (H2O2) as the oxidant. They can be detected by the ABTS test.
  • H2O2 hydrogen peroxide
  • the hydrolytic protein mixtures used in the process according to the invention may contain proteins with binding activity. These are proteins which can bind components of plant cell walls, for example lignocellulose, cellulose, hemin cellulose or comparable materials, or their
  • Such proteins are lectins, albumins or keratins.
  • binding proteins can also be added to the pulp before, after, or during use of the hydrolytic protein mixtures.
  • the hydrolytic protein mixtures used in the process according to the invention are generally obtained from microbial culture supernatants.
  • the term culture supernatant includes all components of a microbial culture other than the cultured organism. They are usually liquid and can be separated from the cultured organism by processes such as filtration or centrifugation.
  • these may be combined with other culture supernatants or protein fractions, fractionated, purified, concentrated or treated by further conventional techniques. Corresponding techniques are known to the person skilled in the art.
  • the protein mixtures can be wholly or partly obtained by the digestion of organisms. These organisms are usually of a microbial nature, but can in principle come from all organisms rich.
  • the hydrolytic protein mixtures may be completely or partially dissolved in a solvent, present as a solid with a more or less large amount of liquid or dried. In dried form, the hydrolytic protein mixtures may have been brought as a powder, granules or in a more or less specific form. Such forms are for example tablets or pellets.
  • bacterial or fungal organisms As a source of the hydrolytic protein mixtures, or for the microbial cultures particularly bacterial or fungal organisms are suitable, which can feed on lignocellulosic substrates, such as brown or white fungi. Suitable enzymes also occur, for example, in insects, such as the clothes moth, or in mollusks or in prokaryotic or eukaryotic cell types of the intestinal flora of other organisms, for example the intestinal flora of insects or ruminants.
  • the term microbial cultures should therefore also include cell cultures of plant origin or cultures of cells of invertebrate animals. Examples of such cultures are cultures of unicellular or multicellular algae, protozoa, cell cultures of multicellular plants or insect cell cultures.
  • Bacillus, Streptomyces, or Ce lumonasart can be used as bacterial organisms.
  • Bacillus subtilis Bacillus pumilus, Bacillus coagulans, Bacillus stearothermophilus or Streptomyces lividans.
  • yeasts such as Aureobasidium pullulans, Cryptococcus albidus or Trichosporon cutaneum, or filamentous fungi such as Trichoderma, Trichothetium, Aspergillus or Penicillium species can be used.
  • these are Trichoderma reesei, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Aspergillus terreus, Aspergillus japonicus, Aspergillus fumigatus, Trichothecium roseum, Thermosascus aurantiacus, Penicillium simplicissimus, Penicillium verruculosum or Penicillium janthinellum.
  • Trichoderma reesei Trichoderma harzianum, Trichoderma viride, Aspergillus niger, Aspergillus terreus, Bacillus pumilus, Bacillus coagulans or Bacillus subtilis are preferably used. Trichoderma reesei is particularly preferably used.
  • Cells or organisms used for the microbial cultures may be derived from naturally occurring strains, crosses, mutants or recombinant forms.
  • the genome of these strains or varieties, cross-products, mutants or recombinant forms may occur completely or partially in haplo-, die- or polyploider form.
  • the hydrolytic protein mixtures used in the process according to the invention generally originate from a culture supernatant of a pure microbial culture, i. from a microbial culture that contains only one type of organism.
  • the hydrolytic protein mixtures can also be obtained from culture supernatants of mixed cultures, i. from cultures of two or more species of organisms or mixtures of two or more culture supernatants or mixtures of two or more proteins or protein mixtures of two or more culture supernatants.
  • Culture supernatants are considered to be different culture supernatants when derived from microbiological cultures of organisms of various species. Or were obtained from culture supernatants of organisms of the same biological species, which differ in the particular strain used or the variety, the cross-product, the mutant or the recombinant form or in the culture conditions used.
  • Culture conditions include all parameters in which microbial cultures can differ and which have an influence on the composition of the culture supernatant.
  • parameters may be mentioned the composition of the culture medium, the pH, the incubation temperature, the culture time, the culture density or the change of one or more such parameters as well as the time sequence of these changes.
  • proteins from different culture supernatants can be mixed before or after their addition to the pulp. This can be effected, for example, by adding hydrolytic protein mixtures from different culture supernatants in liquid or solid form at different times to the pulp.
  • the incubation conditions and the Incubation time can be adjusted.
  • the incubation period can last for example from a few minutes to a few days.
  • Incubation conditions such as pH, temperature, concentration of the hydrolytic protein mixture or the concentration of salts, can vary and be adapted to the respective production conditions.
  • the optimal incubation conditions can be determined by routine experimentation. For example, favorable incubation conditions for hydrolytic protein mixtures of Trichoderma reesei in the range of 20 to 65 0 C. Preferred is a temperature in the range of 40 to 55 0 C and particularly preferably in the range of 45 to 55 0 C. Most preferred is a temperature of 50 0 C.
  • the pH is usually in the range of 3 to 7, preferably in a range from 4.5 to 6.0 and particularly preferably in a range of 4.5 to 5.0.
  • hydrolytic protein mixture or the hydrolytic protein mixtures are used according to the invention in combination with at least one polyamine-containing or polyimine-containing binder.
  • polyamine-containing or polyimine-containing binder are preferred.
  • the polyamine-containing or polyimine-containing binders can either contain only polyamines or only polyimines or any desired mixture of these.
  • the proportion of the polyamines or of the polyimines can be up to 100% by weight, based on the total weight of the polyamine-containing or polyimine-containing binders.
  • the polyamine-containing or polyimine-containing binders may contain amide, amine, acid, ester, halogen, acetal, hemiacetal, aminal, hemiaminal, carbamate or imine groups or a mixture of these. They preferably contain amine, amide, ester or acetal groups or a mixture of at least two of these groups. Most preferably, they contain only amine groups.
  • polyethyleneimines are preferred.
  • Polyethyleneimines are polymers of ethyleneimine obtained by polymerizing ethyleneimine in an aqueous medium in the presence of small amounts of acids or acid-forming compounds such as halogenated hydrocarbons, e.g. Chloroform, carbon tetrachloride, tetrachloroethane or ethyl chloride, or condensation products of epichlorohydrin and amino group containing compounds such as mono- and polyamines e.g. Dimethylamine, diethylamine, ethylenediamine, diethylenetriamine and triethylenetetramine or ammonia.
  • acids or acid-forming compounds such as halogenated hydrocarbons, e.g. Chloroform, carbon tetrachloride, tetrachloroethane or ethyl chloride, or condensation products of epichlorohydrin and amino group containing compounds such as mono- and polyamines e.g. Dimethylamine, diethylamine, ethylenediamine, diethylenetri
  • This group of cationic polymers also includes graft polymers of ethyleneimine on compounds which have a primary or secondary amino group, for example polyamidoamines of dicarboxylic acids and polyamines.
  • the with ethyleneimine grafted polyamidoamines may optionally be reacted with bifunctional crosslinkers, for example with epichlorohydrin or bis-chlorohydrin ethers of polyalkylene glycols.
  • Water-soluble, crosslinked, partially amidated polyethyleneimines are known from WO-A-94/12560. They are obtainable by reaction of polyethyleneimines with monobasic carboxylic acids or their esters, anhydrides, acid chlorides or acid amides to form amides and reaction of the amidated polyethyleneimines with crosslinkers containing at least two functional groups.
  • the average molecular weights M w of the polyethyleneimines in question usually have a broad molecular weight distribution and an average molecular weight (M w ) of, for example, 129 to 2 million g / mol, preferably 430 to 1 million g / mol, more preferably within a range of 1 000 to 500 000 g / mol. In another embodiment, they are in a range of 800 to 100,000 g / mol.
  • M w average molecular weight of the polyethyleneimines in question usually have a broad molecular weight distribution and an average molecular weight (M w ) of, for example, 129 to 2 million g / mol, preferably 430 to 1 million g / mol, more preferably within a range of 1 000 to 500 000 g / mol. In another embodiment, they are in a range of 800 to 100,000 g / mol.
  • the molecular weight can be determined by light scattering.
  • the polyethyleneimines are partially amidated with monobasic carboxylic acids, so that, for example, 0.1 to 90, preferably 1 to 50%, of the amidable nitrogen atoms in the polyethyleneimines is present as the amide group.
  • Suitable crosslinkers containing at least two functional double bonds are epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols.
  • halogen-free crosslinkers are used.
  • the polyethyleneimines can be quaternized polyethylenimines.
  • the homopolymers are prepared, for example, by polymerizing ethyleneimine in aqueous solution in the presence of acids, Lewis acids or alkylating agents such as methyl chloride, ethyl chloride, propyl chloride, ethylene chloride, chloroform or tetrachlorethylene.
  • the quaternization of the polyethyleneimines can be carried out, for example, with alkyl halides, such as methyl chloride, ethyl chloride, hexyl chloride, benzyl chloride or lauryl chloride, and with, for example, dimethyl sulfate.
  • alkyl halides such as methyl chloride, ethyl chloride, hexyl chloride, benzyl chloride or lauryl chloride
  • dimethyl sulfate alkyl halides
  • Other suitable polyethyleneimines are Strecker reaction modified polyethyleneimines, e.g. the reaction products of polyethyleneimines with formaldehyde and sodium cyanide with hydrolysis of the resulting nitriles to the corresponding carboxylic acids. These products may optionally be reacted with a crosslinker containing at least two functional groups (see above).
  • phosphonomethyl Of Polyethylenimine and alkoxylated polyethyleneimines for example, by reacting polyethyleneimine with ethylene oxide and / or propylene oxide and are described in WO 97/25367.
  • the phosphonomethylated and the alkoxylated polyethyleneimines may optionally be reacted with a crosslinker containing at least two functional groups (see above).
  • Polyamine-containing binders preferably comprise an aliphatic polyamine having at least three functional groups selected from the group of primary and secondary amino groups and which apart from tertiary amino groups is substantially free of other functional groups.
  • Polyamines can be made from polyvinylamides.
  • Polyvinylamides are known, cf. US-A-4,421,602, US-A-5,334,287, EP-A-216,387, US-A-5,981,689, WO-A-00/63295, US-A-6,121,409 and US-A-6, 132.558. They are prepared by hydrolysis of open-chain N-vinylcarboxylic acid amide units containing polymers. These polymers are e.g. obtainable by polymerizing N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide and N-vinylpropionamide. The monomers mentioned can be polymerized either alone or together with other monomers. Preference is given to N-vinylformamide.
  • polyvinylamines preference is given to homopolymers of N-vinylformamide or of copolymers obtained by copolymerizing N-vinylformamide with vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, methyl acrylate, ethyl acrylate and / or methyl methacrylate and subsequent hydrolysis of the homo- or copolymers with the formation of vinylamine units from the copolymerized N-vinylformamide units, the degree of hydrolysis being, for example, 1 to 100 mol%, preferably 25 to 100 mol%, particularly preferably 50 to 100 mol% and particularly preferably 70 to 100 mol% ,
  • the hydrolysis of the above-described polymers is carried out by known methods by the action of acids (eg mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, carboxylic acids such as formic acid or acetic acid, or sulfonic acids or Phsophonkla), bases or enzymes, such as in DE-A 31 28 478 and U SA-6, 132,558.
  • acids eg mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, carboxylic acids such as formic acid or acetic acid, or sulfonic acids or Phsophonklaren
  • bases or enzymes such as in DE-A 31 28 478 and U SA-6, 132,558.
  • the degree of hydrolysis of the homopolymers is synonymous with the content of the polymers of vinylamine units.
  • hydrolysis of the ester groups to form vinyl alcohol units may occur. This is especially the case if the hydrolysis of the copolymers in the presence of sodium hydroxide is carried out. lye performs.
  • Polymerized acrylonitrile is also chemically altered upon hydrolysis. This produces, for example, amide groups or carboxyl groups.
  • the homopolymers and copolymers containing vinylamine units may optionally contain up to 20 mol% of amidine units which are formed, for example, by reaction of formic acid with two adjacent amino groups or by intramolecular reaction of an amino group with an adjacent amide group, for example of copolymerized N-vinylformamide.
  • the average molecular weights M w of the polymers containing vinylamine units are, for example, 500 to 10 million, preferably 750 to 5 million and particularly preferably 1 000 to 2 million g / mol (determined by light scattering).
  • the average molar masses are from 5000 to 200 000 g / mol or 600 to 1 million g / mol.
  • This molar mass range corresponds for example to K values of 30 to 150, preferably 60 to 100 (determined according to H. Fikentscher in 5% aqueous Saline at 25 ° C., a pH of 7 and a polymer concentration of 0.5% by weight).
  • the polymers containing vinylamine units have for example a charge density (determined at pH 7) of 0 to 18 meq / g, preferably of 5 to 18 meq / g and especially of 10 to 16 meq / g.
  • the polymers containing vinylamine units are preferably used in salt-free form.
  • Salt-free aqueous solutions of polymers comprising vinylamine units can be prepared, for example, from the above-described salt-containing polymer solutions by means of ultrafiltration on suitable membranes at separation limits of, for example, 1,000 to 500,000 daltons, preferably 10,000 to 300,000 daltons.
  • Suitable comonomers are monoethylenically unsaturated monomers.
  • examples of these are vinyl esters of saturated carboxylic acids of 1 to 6 carbon atoms such as vinyl formate, vinyl acetate, N-vinyl pyrrolidone, vinyl propionate and vinyl butyrate and vinyl ethers such as C1 to C6 alkyl vinyl ethers, e.g. Methyl or ethyl vinyl ether.
  • Suitable comonomers are esters of alcohols having, for example, 1 to 6 carbon atoms, amides and nitriles of ethylenically unsaturated C3 to C6 carboxylic acids, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate and dimethyl maleate, acrylamide and methacrylamide, and acrylonitrile and methacrylonitrile.
  • comonomers are derived from glycols or polyalkylene glycols, wherein in each case only one OH group is esterified, e.g. hydroxyethyl acrylate,
  • esters of ethylenically unsaturated carboxylic acids with amino alcohols such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate and diethylamino-butyl acrylate.
  • the basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or sulfonic acids or in quaternized form.
  • Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
  • Suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids having alkyl radicals of 1 to 6 carbon atoms, e.g. N-methylacryloamide, N, N-dimethylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide and tert-butylacrylamide and basic (meth) acrylamides, such as e.g.
  • N-vinylcaprolactam acrylonitrile, methacrylonitrile
  • N-vinylimidazole and substituted N-vinylimidazoles such as e.g. N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as N-vinylimidazoline, N-vinyl-2-methylimidazo-Nn and N-vinyl-2-ethylimidazoline.
  • N-vinylimidazoles and N-vinylimidazolines are also used, except in the form of the free bases, in neutralized or quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride. Also suitable are diallyldialkylammonium halides, e.g. Diallyl dimethyl ammonium chloride.
  • the polymerization of the monomers is usually carried out in the presence of radical-forming polymerization initiators.
  • the homopolymers and copolymers can be obtained by all known processes, for example by solution polymerization in water, alcohols, ethers or dimethylformamide or in mixtures of various solvents, by precipitation polymerization, reverse suspension polymerization (polymerizing an emulsion of a monomeric aqueous solution) Phase in an oil phase) and polymerizing a water-in-water emulsion, for example, in which one dissolves or emulsifies an aqueous monomer solution in an aqueous phase and to form an aqueous dispersion of a water-soluble polymers, as described, for example, in WO 00/27893.
  • the homopolymers and copolymers which contain copolymerized N-vinylcarboxamide units are partially or completely hydrolyzed as described.
  • Derivatives of polymers containing vinylamine units can also be used as polyamine-containing binders. It is thus possible, for example, to prepare a multiplicity of suitable derivatives from aminotization, alkylation, sulfonamide formation, urea formation, thiourea formation, carbamate formation, acylation, carboxymation, phosphonomethylation or Michael addition of the amino groups of the polymer from the polymers containing vinylamine units.
  • the polymers containing vinylamine units also include hydrolyzed graft polymers of, for example, N-vinylformamide on polyalkylene glycols, polyvinyl acetate, polyvinyl alcohol, polyvinylformamides, polysaccharides such as starch, oligosaccharides or monosaccharides.
  • the graft polymers can be obtained by free-radically polymerizing, for example, N-vinylformamide in aqueous medium in the presence of at least one of the stated grafting bases together with copolymerizable other monomers and then hydrolyzing the grafted vinylformamide units in a known manner to give vinylamine units.
  • hydrolytic protein mixtures and polyamine-containing or polyimine-containing binders can be combined with one or more other binders.
  • polyamine-containing or polyimine-containing binders are used alone.
  • Possible other binders may be: urea, phenol or melamine-urea-formaldehyde resins or alkyd, epoxy, unsaturated polyester, polyurethane, ketone, isocyanate, polyamide, polyester or diisocyanate resins.
  • urea-formaldehyde resins and melamine-urea-formaldehyde resins are advantageous. Preference is given to urea-formaldehyde resins. For example, those sold under the trade names of BASF Aktiengesellschaft such as Kaurit® 347, Kaurit® 403 or Kauramin® 620. Among the melamine-urea
  • Formaldehyde resins are those with more than 20 wt .-% melamine, based on the total weight of the melamine-urea-formaldehyde resin, preferred. If urea, phenol or melamine-urea-formaldehyde resins are used in combination with hydrolytic protein mixtures, a combination of from 3 to 15% by weight of binder and from 0.1 to 10% by weight of hydrolytically active protein mixture is advantageous , Preference is given to a combination of 5 to 12% by weight of binder and 0.1 to 5% by weight of hydrolytically active protein mixture. Particularly preferred is a combination of 5 to 8 wt .-% binder and 0.3 to 3 wt% hydrolytic protein mixture.
  • polyamine-containing or polyimine-containing binders are used in combination with hydrolytic protein mixtures, a combination of 0.3 to 10% by weight polyamine-containing or polyimine-containing binder and from 0.1 to 10% by weight hydrolytic protein mixture is advantageous; Combination of 0.5 to 6% by weight of polyamine-containing or polyimine-containing binder and of 0.1 to 5% by weight of hydrolytic protein mixture. Particularly preferred is a combination of 0.8 to 4% by weight polyamine-containing or polyimine-containing binder and from 0.3 to 3% by weight hydrolytic protein mixture.
  • sugars, dicarboxylic acid derivatives, aldehydes having two or more carbon atoms or epoxides or mixtures of these can be used. This can be done by adding one or more sugars, one or more dicarboxylic acid derivatives or one or more aldehydes having two or more carbon atoms or one or more epoxides, individually or in admixture with the binders, to the pulp.
  • Monosaccharides as well as di- or polysaccharides can be used as sugar.
  • sugars are: hydrolyzates of starch, sucrose or glucose.
  • Suitable dicarboxylic acid derivatives are dicarboxylic acid derivatives of alkyl or aryldicarboxylic acids.
  • the term dicarboxylic acid derivatives are to be understood as meaning both the free dicarboxylic acids and the corresponding anhydrides or esters.
  • Suitable dicarboxylic acids are, for example, maleic acids, fumaric acid, phthalic acid and glutaric acid. Succinic anhydride, maleic anhydride and phthalic anhydride are advantageous.
  • aldehydes having two or more carbon atoms aldehydes having two to six carbon atoms are preferred.
  • Preferred aldehydes having two or more carbon atoms are propanal, butanal, pentanal, and most preferably 2-methoxyacetaldehyde.
  • Particularly suitable epoxides are epoxides having from 2 to 10 carbon atoms. These are in particular propylene oxide, isobutene oxide, butene oxide, cyclohexene oxide and styrene oxide.
  • the binder or binders are usually used in an amount of 3 to 20 wt .-%, based on the total weight of the respective fiber material and measured as the total weight of all binders used, in the inventive method.
  • the required amount of the binder depends strongly on the type of binder or the combination of binder and other binders.
  • polyvinylamines or polyethyleneimines usually in a range of 0.05 to 5 wt .-%, and preferably in a range of 0.1 to 2 wt .-% based on the total weight of the respective pulp used.
  • the quantities used may also differ from the stated amounts.
  • auxiliaries can be added to the fiber.
  • auxiliaries all substances are referred to, which are not binders, hydrolytic protein mixtures or pulp and improve the properties, in particular quality properties, of the fiber materials, based on the respective intended use of the fiber material.
  • Adjuvants may be, for example: water repellents, salts, water glass, biocides, dyes, fire retardants, surfactants, stabilizers or formaldehyde scavengers.
  • hydrophobing agents for example, paraffin waxes, paraffin emulsions, oils or silicones can be used. Preference is given to paraffin waxes or paraffin emulsions, particular preference being given to paraffin emulsions.
  • biocides are fungicides or insecticides.
  • examples of biocides are Na benzoate, boron, fluorine and arsenic compounds, copper salts, quaternary ammonium compounds or chromates.
  • Formaldehyde also has biocidal activity and could therefore function in this capacity
  • Paraffin is usually used in a proportion of 0.01 to 3 wt .-%, based on the total weight of the fiber material. It is preferably used in a proportion of 0.1 to 2 wt .-%. It is particularly preferably used in a proportion of 0.3 to 1.5% by weight. Most preferably with a proportion of 0.5 to 1 wt .-%. In one embodiment, it is used in an amount of 1% by weight, based in each case on the total weight of the pulp.
  • the adjuvants may be added together or separately from the binders or the hydrolytic protein mixture (s) or any of these.
  • the preferred procedure depends on the nature of the excipient and the process used to produce the fiber materials and is known to the person skilled in the art. The expert can find hints in DIN 68800-3 or in M. Dunky, P. Niemz, wood materials and glues, Springer Verlag, 2002, for example on pages 436 to 444.
  • paraffin may be added together or separately with one or more binders.
  • paraffin is added separately from the binder (s).
  • the dried with the hydrolytic protein mixture, the one or more binders and any necessary excipients, brought into contact or blended pulp is, prior to pressing in current or belt dryers at temperatures between 30 and 150 0 C, preferably between 40 and 90 0 C and under Influence of heat and pressure compressed.
  • temperatures between 30 and 150 0 C, preferably between 40 and 90 0 C and under Influence of heat and pressure compressed care must be taken that the temperatures used do not lead to inactivation of the respective enzymes.
  • the dry gluing of the blow-line gluing is preferred.
  • the hydrolytic protein mixture in combination with the binder (s) and / or the auxiliaries which may be required is applied to the pulp after the drying process.
  • the particular maximum temperature depends on the type of enzymes contained in the hydrolytic protein mixtures. The maximum usable temperature should result in no or only a slight inactivation of the enzymatic activity. In case high temperatures are used, hydrolytic protein mixtures with a high temperature optimum should be used. These are usually found in thermophilic or hyperthermophilic organisms. An example of such an organism is Pyrococcus horikoshii.
  • all methods which are suitable for destroying or temporarily blocking enzymatic activity are suitable for terminating the incubation period; these are, for example, heat inactivation, addition of inhibitors or a change in the pH.
  • the preferred method depends on the properties of the hydrolytic protein mixture used and the conditions of production.
  • the hot pressing can be done by the usual methods. These methods are known to the person skilled in the art. Further information can be found, for example, in M. Dunky, P. Niemz, Holzwerkstoffe und Leime, Springer Verlag, 2002, pages 91 to 158.
  • the density of the fiber materials produced can be in the range of 100 to 1200 kg / m 3 .
  • MDF boards or molded articles preferably have a density of 650 to 900 kg / m 3
  • insulating boards preferably have a density in the range of 200 to 400 kg / m 3 .
  • the quality of fiber materials is therefore determined by means of various measurement methods, each describing different quality properties of the fiber materials.
  • quality properties are, for example, the water vapor permeability according to DIN EN ISO 12572, the lift-off strength of the surface according to DIN EN 31 1, the shear strength parallel to the slab level according to DIN 52371, the tensile strength perpendicular to the slab level according to DIN EN 319, the screw pull-out resistance according to DIN EN 320, the moisture content according to DIN 52351, the water absorption according to DIN EN 317, the bending strength according to DIN EN 310, the bending modulus according to DIN EN 310, the 24-h thickness swelling according to DIN EN 317, the transverse tensile strength according to DIN EN 319 or the Amount of extractable formaldehyde according to DIN EN 120.
  • one or more of the following quality properties is improved: The, the water absorption according to DIN EN 317, the bending strength according to DIN EN 310, the bending modulus according to DIN EN 310, the 24-h thickness swelling according to DIN EN 317, transverse tensile strength to DIN EN 319 and the amount of extractable formaldehyde according to DIN EN 120. Most preferably, the transverse tensile strength is improved according to DIN EN 319.
  • the invention will be elucidated by the following non-limiting examples.
  • hydrolytic protein mixture prepared by Novozym from a microbial culture of Trichoderma reesii was used with the following properties: 334 g / l protein content, 355.8 U / ml AZO CMC activity, 13404 IU / ml xylanase activity
  • Example 1 (combination of hydrolytic protein mixtures with polyethyleneimine binders):
  • a pulp was used. This pulp was made from pine wood chips shredded at 170 ° C. and a 0.2 mm grinding gap. The pulp moisture was, after an intermediate drying in the tubular dryer, 3.3% by weight, based on the total mass of the hydrogen.
  • changing types of binders and hydrolytic protein mixtures were added to this fibrous material.
  • the hydrolytic protein mixtures and the binder were mixed first and then added to the pulp.
  • the polyethylenimine used consisted of a cationic, dendritically branched, unmodified homopolymer having a molecular weight (M w ) of 5000 measured by light scattering.
  • U / ml means units / ml
  • IU / ml means international units / ml, each determined according to the IUPAC rules for the determination of the respective enzyme activity.
  • the percentages by weight relate to the total weight of the pulp in the absolutely dry state (atro).
  • the mixture with the pulp was carried out in each variant by means of a Beleimtrommel in a dry process. To adjust the fiber moisture, these were provided with about 8 wt .-% buffer. After mixing, the pulp was sprinkled by hand to a nonwoven. The nonwoven moisture was in all variants between 8 to 10 wt .-%, based on the total mass of the web.
  • the web was transferred to a hot press and pressed into 4 mm thin fibrous materials measuring 20 ⁇ 20 cm. The hot pressing was carried out at a temperature of 180 0 C and 90 seconds press time (22 seconds per mm). After hot pressing, the plates were air conditioned for 24 hours.
  • the starting material used was spruce wood pulp which had been equilibrated for 24 hours at 25 ° C. and 65% relative humidity. From this pulp 1000 g were purged with gaseous nitrogen. After one minute, depending on the experimental variant, binder or hydrolytic protein mixture or both introduced at a constant flow rate of 20 ml / minute.
  • the hydrolytic protein mixture used had a protein content of 71.4 g / l, an AZO CMC activity of 141, 62 U / ml, a filter paper activity of 29.21 IU / ml, a xylanase activity of 2032.84 IU / ml and a content reduced sugar of 9.84 g / ⁇ .
  • the hydrolytic protein mixture was introduced first. After this, after a further 10 minutes reaction time, the particular binder used was added. After a mixing time of one minute, the contained mixture was incubated for an additional hour. Subsequently, the mixture was placed in a hot technical press of 30 ⁇ 30 cm and molded at a temperature of 180 ° C. for 60 seconds and a force of 10 kN. This resulted in fiber materials with a thickness of 4.0 mm and a density of 800 kg / m 3 . The fiber materials were stored at room temperature for 16 hours before their quality properties were measured.
  • the polyvinylamine vinylformamide used was prepared from and had a degree of hydrolysis of 95 and a K-value of 45.
  • the K value was determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 0 C, a pH value of 7 and a polymer concentration of 0.5 wt .-% determined.

Landscapes

  • Chemical & Material Sciences (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)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un procédé pour produire des matériaux fibreux, selon lequel on utilise, pour la fabrication des matériaux fibreux, au moins un mélange de protéines présentant une action hydrolytique et au moins un liant renfermant de la polyamine ou de la polyimine ou un mélange quelconque de ces liants. L'invention concerne en outre l'utilisation d'au moins un mélange de protéines présentant une action hydrolytique et d'au moins un liant renfermant de la polyamine ou de la polyimine ou d'un mélange quelconque de ses liants, seul ou en combinaison avec au moins un autre liant ou au moins un auxiliaire ou au moins un autre liant et au moins un auxiliaire pour la production de matériaux fibreux. L'invention concerne également des matériaux fibreux pouvant être obtenus au moyen dudit procédé, selon lequel on utilise, pour la production des matériaux fibreux, au moins un mélange de protéines présentant une action hydrolytique et au moins un liant de polyamine ou au moins un liant de polyimine ou au moins un liant renfermant de la polyamine ou de la polyimine ou un mélange quelconque de ces liants.
EP08787363A 2007-08-24 2008-08-21 Procédé pour produire des matériaux fibreux Withdrawn EP2183322A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08787363A EP2183322A2 (fr) 2007-08-24 2008-08-21 Procédé pour produire des matériaux fibreux

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07114909 2007-08-24
EP08787363A EP2183322A2 (fr) 2007-08-24 2008-08-21 Procédé pour produire des matériaux fibreux
PCT/EP2008/060916 WO2009027297A2 (fr) 2007-08-24 2008-08-21 Procédé pour produire des matériaux fibreux

Publications (1)

Publication Number Publication Date
EP2183322A2 true EP2183322A2 (fr) 2010-05-12

Family

ID=40351800

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08787363A Withdrawn EP2183322A2 (fr) 2007-08-24 2008-08-21 Procédé pour produire des matériaux fibreux

Country Status (4)

Country Link
US (1) US20110065842A1 (fr)
EP (1) EP2183322A2 (fr)
CA (1) CA2695693A1 (fr)
WO (1) WO2009027297A2 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2172333A1 (fr) * 2008-09-19 2010-04-07 Basf Se Corps de formage à teneur en lignocellulose multicouche à émission en formaldéhyde réduite
ES2377912T5 (es) 2009-09-03 2020-07-21 SWISS KRONO Tec AG Agente protector de la madera de actividad fungicida para uso en tableros de fibra de madera
US8623501B2 (en) * 2010-03-04 2014-01-07 Basf Se Lignocellulose materials having good mechanical properties
US8920923B2 (en) * 2010-03-04 2014-12-30 Basf Se Lignocellulose materials having good mechanical properties
AU2011285710B2 (en) * 2010-08-03 2015-07-16 Basf Se Tackifiers for composite articles
WO2013003675A2 (fr) * 2011-06-30 2013-01-03 Hercules Incorporated Additif adhésif
CN102634221B (zh) * 2012-04-28 2014-03-12 广东省石油化工研究院 一种以回收abs树脂为基体的木塑复合材料及其制备方法
CN109049234B (zh) * 2018-08-13 2021-06-11 安吉艾格赛思生物科技有限公司 一种农林废弃物资源化高效处理技术工艺
US20230082241A1 (en) * 2020-02-04 2023-03-16 Cargill, Incorporated Carbohydrate-based adhesives
WO2024006761A1 (fr) 2022-06-29 2024-01-04 Cargill, Incorporated Adhésif comprenant du poly(acétate de vinyle) et un mélange de glucose et de fructose

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3128478A1 (de) * 1981-07-18 1983-02-03 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von linearen, basischen polymerisaten
DE3534273A1 (de) * 1985-09-26 1987-04-02 Basf Ag Verfahren zur herstellung von vinylamin-einheiten enthaltenden wasserloeslichen copolymerisaten und deren verwendung als nass- und trockenverfestigungsmittel fuer papier
DE4127733A1 (de) * 1991-08-22 1993-02-25 Basf Ag Pfropfpolymerisate aus saccharidstrukturen enthaltenden naturstoffen oder deren derivaten und ethylenisch ungesaettigten verbindungen und ihre verwendung
CA2093581C (fr) * 1992-04-09 2004-06-22 Alireza Kharazipour Procede d'agglomeration des particules de bois permettant de faconner des formes diverses
DE4240110A1 (de) * 1992-11-28 1994-06-01 Basf Ag Kondensationsprodukte von Polyalkylenpolyaminen, Verfahren zu ihrer Herstellung und ihre Verwendung bei der Herstellung von Papier
US5981689A (en) * 1997-11-19 1999-11-09 Amcol International Corporation Poly(vinylamine)-based superabsorbent gels and method of manufacturing the same
US6087448A (en) * 1997-11-19 2000-07-11 Amcol International Corporation Solid superabsorbent material containing a poly(vinylguanidine) and an acidic water-absorbing resin
US6059967A (en) * 1998-05-20 2000-05-09 Big Iron Drilling Ltd. Distributor device for water conditioner backflush apparatus
DE19851024A1 (de) * 1998-11-05 2000-05-11 Basf Ag Wäßrige Dispersionen von wasserlöslichen Polymerisaten von N-Vinylcarbonsäureamiden, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19930525A1 (de) * 1999-07-01 2001-01-04 Basf Ag Faserplatten aus Polyaminen oder Polyamin-haltigen Aminoplastharzen als Bindemittel
DE10043662A1 (de) * 2000-08-30 2001-02-22 Saechsisches Inst Fuer Angewan Verfahren zur enzymatischen Aktivierung von lignocellulosen Faserstoffen zur Herstellung von Werkstoffen
US7252735B2 (en) * 2002-05-13 2007-08-07 State Of Oregon Acting By And Through The Oregon State Board Of Higher Education On Behalf Of Oregon State University Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives
PT1740670E (pt) * 2004-04-20 2012-07-12 Oregon State Adesivos lignocelulósicos livres de formaldeído e compósitos feitos dos adesivos
TW200813181A (en) * 2006-06-01 2008-03-16 Akzo Nobel Coatings Int Bv Adhesive system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009027297A2 *

Also Published As

Publication number Publication date
CA2695693A1 (fr) 2009-03-05
WO2009027297A2 (fr) 2009-03-05
WO2009027297A3 (fr) 2009-04-23
US20110065842A1 (en) 2011-03-17

Similar Documents

Publication Publication Date Title
EP2183322A2 (fr) Procédé pour produire des matériaux fibreux
EP2225076B2 (fr) Liant pour matériaux à base de copeaux et/ou de fibres de bois, procédé de fabrication de ce liant et élément moulé
DE851162C (de) Verfahren zum Impraegnieren von Cellulosefasermaterialien mit organischen Impraegnierungsmitteln
EP2315875B1 (fr) Procédé pour améliorer la résistance à sec du papier, du carton-pâte et du carton
EP2242797B1 (fr) Liants exempts de formaldéhyde utilisés pour produire des matériaux ligneux
Nasir et al. Fabricating eco-friendly binderless fiberboard from laccase-treated rubber wood fiber.
DE1176990B (de) Verfahren zur Erhoehung der Trockenfestigkeit von Faserstoffbahnen
EP0565109B1 (fr) Procédé pour coller des fragments de bois
EP1184144B1 (fr) Procédé pour l'activation enzymatique de matériaux en fibres à base de lignocellulose pour la fabrication de produits
CN102504562A (zh) 一种阻燃抑烟型烟梗粉基木塑复合材料及其制备方法
EP2334871A1 (fr) Procédé de fabrication de papier et de carton par utilisation d'endo-bêta-1,4-glucanases en tant qu'agent d'égouttage
EP1399623B1 (fr) Apprets pour papier conferant une resistance a l'humidite
EP1819876B1 (fr) Agent d'encollage pour papier
KR102005082B1 (ko) 친환경 중밀도 섬유판의 제조방법 및 이로부터 제조된 친환경 중밀도 섬유판
EP1511779B1 (fr) Polymeres contenant des unites vinylamine ou ethylenimine modifiees de facon hydrophobe, procede de fabrication et utilisation en tant qu'agent de retention
DE10164659C2 (de) Bindemittelfreier Faserdämmstoff und Verfahren zu dessen Herstellung
EP2974841A1 (fr) Procede de fabrication d'un panneau de fibres
DE4305411C2 (de) Verfahren zur Herstellung von bindemittelfreien Formkörpern
DE102006057566B4 (de) Verfahren zur Herstellung eines emissionsreduzierten lignozellulosen Rohstoffes bzw. Werkstoffs, Bauteils oder Produkts
CH704766A1 (de) Verfahren zur Herstellung einer cellulosehaltigen Masse zur Herstellung eines Verbundmaterials.
EP0613906B1 (fr) Article moulé, en particulier en forme de panneau de fibres
AT501049A4 (de) Verfahren zur acylierung eines insbesondere cellulose und/oder hemicellulose und/oder lignin aufweisenden materials und damit erhältliches material
EP3455042B1 (fr) Panneau de fibres à résistance accrue contre toute attaque fongique et son procédé de fabrication
EP3268190B1 (fr) Procédé de fabrication d'un matériau à base de particules de bois et durcisseur employé dans ledit matériau pour aminoplaste
EP3733366B1 (fr) Liant destiné à la fabrication de matériaux dérivé du bois

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100324

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140301