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WO2008119398A1 - Corps moulés constitués d'une matière contenant de la cellulose - Google Patents

Corps moulés constitués d'une matière contenant de la cellulose Download PDF

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Publication number
WO2008119398A1
WO2008119398A1 PCT/EP2007/063274 EP2007063274W WO2008119398A1 WO 2008119398 A1 WO2008119398 A1 WO 2008119398A1 EP 2007063274 W EP2007063274 W EP 2007063274W WO 2008119398 A1 WO2008119398 A1 WO 2008119398A1
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WO
WIPO (PCT)
Prior art keywords
oil
weight
component
shaped body
binder
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.)
Ceased
Application number
PCT/EP2007/063274
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German (de)
English (en)
Inventor
Lothar Thiele
Hans-Peter Kohlstadt
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
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Publication of WO2008119398A1 publication Critical patent/WO2008119398A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/60—Compositions for foaming; Foamed or intumescent adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers

Definitions

  • the invention relates to moldings of cellulosic materials and 2K polyurethane compositions which have a low density. Furthermore, 2K PU binders for producing such shaped bodies are described.
  • Moldings of wood materials are known. This wood powder, fibers or shavings are glued together with different binders. These moldings may be plates or blocks or have other shapes. Such moldings are known, for example, as chipboard or MDF boards. It is customary to bond together the cellulose-containing materials to be bonded with phenolic, urea or melamine resin binders. It is also known to bond such moldings with polyurethane systems.
  • moldings have a stable surface. Furthermore, the mechanical properties of such shaped bodies, such as transverse tensile and flexural strength, dimensional stability or freedom from migrations or vapors are to be ensured. A general interest is that such moldings have a low density. This should be made of such moldings use body, such as furniture parts, easy and manageable. A deterioration of a mechanical property should not be given.
  • polymer wood moldings which consist of wood particles or cellulose particles and 2-component polyurethane binder. These moldings contain more than 10 parts by weight of PU binder per 100 parts of wood components.
  • the preparation is carried out under the autogenous pressure of the reaction mixture. This consists of polyether polyols, low molecular weight polyols such as glycerol, as well as catalysts and MDI as crosslinking component.
  • the pressure required in the manufacturing process becomes produced by CO 2 formation with the moisture of the wood particles and with the added water.
  • the PU compositions described there consist of low molecular weight polyethers, low molecular weight polyols, such as glycerol or dipropylene glycol, and of carboxylic acids. These carboxylic acids should react with isocyanates and thereby form CO 2 , which lead to foaming of the binder. Furthermore, water from residual moisture of the wood particles is used in the reaction, this being between 5 and 20% by weight of the wood particles.
  • EP 1131386 is known.
  • stone composite panels are described. These consist of a mineral shaped body, are molded on the polyurethane foams.
  • this polyurethane foams up to 80% fillers, such as stone dust, sand, chalk, wood chips, wood flour or foam glass can be added. Due to the high density heavy moldings are obtained with a high density. These are not comparable with conventional polymer wood moldings.
  • binders isocyanates are described with polyols, as foaming agents fatty acids or small amounts of water.
  • WO 02/45960 is known.
  • composite body of mineral moldings and polyurethane foams are described.
  • heavy moldings are obtained. These are produced by foaming the PU binder with introduced carboxylic acids or water and filling the appropriate shape by the autogenous pressure. It is described that up to 80% of stone powder, chalk or wood flour can be added to this PU binder if necessary.
  • An application of such compositions on wooden body with low density are not described.
  • the object is that molded bodies based on cellulose-containing materials are produced together with 2K polyurethane compositions which have a low density. Regardless of the low density of these moldings are to show an improved swelling behavior against moisture and have sufficient mechanical stability and have a stable surface.
  • the invention is achieved by a molding according to claim 1.
  • Another object of the invention are the suitable polyurethane compositions which give such moldings.
  • the cellulosic material used in the moldings are vegetable fibers, for example cotton, jute, flax, hemp, bast, sisal, ramie, cosco fibers, yucca fibers or manila, paper and pulp yarns.
  • woodponds can span or powdered wood particles are used. These can be made of hard or softwood.
  • flax and hemp shives, straw particles, bamboo shavings, nut shells, cork schnitzel or bagasse may be included. It may also be crushed wood-containing waste from the chipboard or furniture industry.
  • the particles are present in the form of wood chips, wood flour or other cellulose-containing materials in particle sizes of not more than 5 mm thick, 50 mm wide and 100 mm long, in particular as chips or fibers of different sizes.
  • the moisture of the cellulose-containing materials for producing the shaped bodies according to the invention can be up to 20% by weight. This may optionally be increased by moistening or lowered by drying at elevated temperature. By the reaction with the isocyanates, the water content of the finished form body is reduced.
  • the shaped articles according to the invention may additionally contain, for example, wires, cables, wire nets, rods or the like as inserts or reinforcing agents.
  • the shaped articles according to the invention contain a foamed, crosslinked polyurethane composition for binding the cellulose-containing constituents.
  • This composition is formed by crosslinking a 2K PU composition.
  • a necessary component is a polyisocyanate component.
  • Polyisocyanates which are suitable for this component are the known polyfunctional isocyanates having on average 2 to 6, preferably 4 to and in particular 2 or 3 isocyanate groups per molecule.
  • the usable polyisocyanates may be aromatic, cycloaliphatic or aliphatic isocyanates.
  • aromatic polyisocyanates are the isomers of toluene diisocyanate (TDI) isomerically pure or as a mixture, naphthalene-1, 5-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), diphenylmethane-2,4'-diisocyanate, mixtures , Xylylen diisocyanate (XDI), 4,4'-diphenyl-dimethyl methane diisocyanate, di- and tetraalkyl diphenylmethane diisocyanates, 4,4'-di- benzyl diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate.
  • TDI toluene diisocyanate
  • MDI diphenylmethane-4,4'-diisocyanate
  • MDI diphenylmethane-2,4'-diiso
  • Suitable cycloaliphatic polyisocyanates are the hydrogenation products of the abovementioned aromatic diisocyanates, for example 4,4'-dicyclohexylmethane diisocyanate (Hi 2 MDI), 1-isocyanatomethyl-3-isocyanato-1,5,5-thmethylcyclohexane (isophorone diisocyanate) , IPDI), cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate (H 6 XDI), 1-methyl-2,4-diisocyanato-cyclohexane, tetramethylxylene diisocyanate (m-TMXDI, p-TMXDI) and dimer fatty acid diisocyanate ,
  • aliphatic polyisocyanates are tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hex
  • aliphatic and cycloaliphatic isocyanates their isocyanurates or biurets, in particular those of HDI or IPDI, are also to be used.
  • aromatic isocyanates are preferred, preferably the diphenylmethane diisocyanate, either in the form of pure isomers, as mixtures of isomers and the so-called crude MDI.
  • low molecular weight NCO-containing reaction products of MDI or TDI can be used with low molecular weight diols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol or polyethylene glycol.
  • Another component of the 2-component PU composition according to the invention is a polyol component, which consists of a mixture of different polyols and other additives and additives.
  • the PU binder contains oleochemical polyols.
  • Oleochemical polyols are understood to mean polyols based on natural oils and fats, e.g. the reaction products of epoxidized fatty substances with mono-, di- or polyfunctional alcohols or glycerol esters of long-chain fatty acids which are at least partially substituted by hydroxyl groups.
  • epoxidized triglycerides ie epoxidized fatty acid glycine esters in which the ring opening has been carried out to obtain the ester bonds.
  • epoxidized triglycerides are suitable which have 2 to 10 percent by weight of epoxide oxygen.
  • Such products can be prepared by epoxidation of the double bonds from a range of fats and oils, e.g. Beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil and sunflower oil.
  • Particularly preferred epoxidized triglycerides are epoxidized soybean oil and epoxidized linseed oil.
  • alcohols for the ring opening of the epoxidized triglycerides can methanol, ethanol, propanol, isopropanol, butanol, hexanol, 2-ethylhexanol, fatty alcohols having 6 to 22 carbon atoms, cyclohexanol, benzyl alcohol, 1, 2-ethanol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol.
  • ring-opening reaction of epoxidized fatty acid esters or triglycerides with an alcohol may optionally be followed by transesterification with itself or other post-added triglycerides.
  • oleochemical polyols are e.g. described in the German patent application DE-A 41 28 649.
  • oleochemical polyols are ring-opening and transesterification products of epoxidized fatty acid esters of lower alcohols, ie of epoxidized fatty acid methyl, ethyl, propyl or butyl esters.
  • the preparation of such products can be carried out by known epoxidation or ring-opening methods, wherein the transesterification can be carried out during or after the ring-opening step by removing the lower alcohol from the reaction equilibrium.
  • oleochemical polyols include the reaction products of epoxidized fatty alcohols with C 2 -Cs alcohols having the functionality of 1 to 10, in particular 2 to 4.
  • oleochemical polyols which are accessible via transesterification of di- or polyfunctional alcohols with triglycerides, such as palm oil, peanut oil, rapeseed oil or sunflower oil. It is likewise possible to use polyols which, according to the teaching of DE-A 41 24 665, by the transesterification of polymerized glycerol with the The above-mentioned triglycerides are available. Resin-modified oleochemical polyols can also be used.
  • the oleochemical polyols suitable according to the invention may have hydroxyl numbers of from 50 to 400, preferably from 100 to 250, mg KOH / g of solids. These polyols generally have an average functionality between 2.5 to 5.
  • castor oil or dimerdiols as oleochemical polyols and those polyester polyols obtained by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride Derivatives are prepared to alkyl ester polyols having 1 to 12 carbon atoms in the alkyl radical.
  • the PU composition according to the invention may additionally contain further polyols, in particular the known polyhydroxy polyethers of the molecular weight range from 250 to 20,000 g / mol, in particular below 15,000 g / mol, preferably from 400 to 10,000 g / mol, with 2 to 10 OH groups per molecule, in particular with 2 to 4 OH groups.
  • Such polyhydroxypolyethers are obtained in a conventional manner by alkoxylation of suitable starter molecules, for.
  • suitable starter molecules for.
  • Suitable alkoxylating agents are in particular propylene oxide and possibly also ethylene oxide.
  • the liquid polyether compounds are useful with two or three hydroxyl groups per molecule, e.g. di- and / or trifunctional polypropylene glycols in the molecular weight range from 250 to 10,000 g / mol, preferably in the range from 400 to 6000 g / mol. It is possible to use random and / or block copolymers of ethylene oxide and propylene oxide.
  • polystyrene resins are the poly-tetramethylene glycols, for example by the acidic polymerization of tetrahydrofuran
  • the molecular weight range of the polytetra methylene glycols is between 250 and 6000 g / mol, preferably in the range from 400 to 4000 g / mol.
  • the inventively suitable polyol mixture should contain 25 to 90 wt .-% of oleochemical polyols, in particular 35 to 70 wt .-%. Furthermore, the amount of polyether polyols should be between 1 and 50% by weight, in particular between 5 and 35% by weight, based in each case on the polyol component.
  • a particular embodiment works with a mixture of polyether polyols, in particular a difunctional and a trifunctional polyether polyol.
  • low molecular weight polyhydroxyl compounds may still be present.
  • the molecular weight should be between 60 to 250 g / mol.
  • These may be polyols having 2 to 6 OH groups, for example glycol, butanediol, hexanediol, octanediol, glycerol, pentaerythritol, trimethylolpropane or sugar alcohols. These ingredients increase the urethane group concentration of the polymer and affect the hardness of the crosslinked adhesive.
  • composition according to the invention must furthermore contain carboxylic acids. These react with the isocyanates in the presence of catalysts with elimination of carbon dioxide.
  • Carboxylic acids are acids which contain one or more, preferably one carboxyl groups and preferably 6 to 100 carbon atoms. The carboxyl groups are connected to saturated or unsaturated alkyl radicals which have a linear, branched or cyclic structure or with aromatic radicals. These may contain other heteroatoms such as ether, ester, halogen and hydroxy groups.
  • carboxyl-terminated polyesters and polyethers and dimer and trimer fatty acids can be used. Also suitable are partial esters of the acids which contain more than one carboxyl group.
  • esters and partial esters of diols and triols, tetrols, Pentols, sugars and carbohydrates with carboxylic acids having more than one carboxyl group are also known to be suitable.
  • the compounds mentioned can be used in mixtures, preference being given to liquid products or liquid mixtures, as well as compounds which are easy to process with the other constituents into liquid mixtures.
  • composition according to the invention in the polyol component may still contain solution-promoting amino compounds. These compounds effect solubilization between the ingredients without adversely affecting foaming.
  • Suitable amines are aliphatic or aromatic di- or triamines having primary and / or secondary amino groups, in particular also heterocyclic amines.
  • the amines must contain at least 3, but preferably 6 carbon atoms.
  • the amines may also have a hydroxy function. The amount should be between 0.1 to 5 wt .-%.
  • Suitable amines are, for example, Ethylenediamine, 1, 2- and 1, 3-propylenediamine, hexamethylenediamine, 1, 4- and 1, 6-toluenediamine, 4,4'-diphenylmethanediamine and diethylenetriamine. It is also possible to use hydroxy-functional polyamines, e.g. N- (2-aminoethyl) ethanolamine can be used. Also suitable are piperazine and aminoalkyl- or hydroxyalkyl-substituted piperazines, in particular also aminoethylpiperazine. The mixing ratio of the abovementioned amines to the carboxylic acids should be 1: 0.3 to 1: 100.
  • the reaction mixture still contains water.
  • the water reacts under CO 2 formation with the isocyanate groups.
  • the water can be added separately or it is included in the polyol component.
  • the amount of water is important to a sufficient hardness and To achieve strength of the molding.
  • the water content of the polyol component can be between 0 and 10 wt .-%, preferably it is between 0.3 and 5 wt .-%.
  • the equivalent ratio between carboxylic acid and water should be between 1: 0.5 and 200. In particular, the ratio should be 1: 0.9 to 1:20. Both components cause CO 2 cleavage from the isocyanates. If the amount of water chosen too high, the swelling behavior of the finished, crosslinked moldings is poor, ie the stability to moisture of cellulose-based moldings is reduced. If the content of carboxylic acids is too high, the stability to moisture is also reduced. Overall, the content of the mixture of carboxylic acid and water should be between 1 and 30% by weight, preferably between 2 and 20% by weight, based on the polyol component
  • compositions according to the invention contain from 1 to 25% by weight of drying and / or semi-drying oils, in particular from 2.5 to 20% by weight.
  • Drying or semi-drying oils are, for example, esters of glycerol with unsaturated fatty acids, for example more than 20% linoleic acid or linolenic acid.
  • drying or semi-drying oils are cottonseed oil, thistle oil, wood oil, hemp oil, linseed oil, poppy oil, oiticica oil, perilla oil, rapeseed oil, soybean oil, safflower oil, sunflower oil or walnut oil.
  • liquid tall oils or turpentine oils are suitable. These are generally natural products, but they can be modified by chemical reactions.
  • the iodine value of the drying or semi-drying oils should be between 100 to 250. Preference is given to using drying oils, such as linseed oil, wood oil, oiticica oil, poppy seed oil or perilla oil, if appropriate also as mixtures.
  • the added oils generally increase the flexibility of the crosslinked adhesive. Another advantage of the drying oils is to be found in an influence on the water absorption of the adhesive or the bonded substrate. Furthermore, the viscosity by addition of low viscosity drying and / or semi-drying oils are influenced. If such oils are present, it is expedient if necessary to add drying catalysts, in particular the known metal-containing catalysts. It may contain metal catalysts, so-called siccatives, such as Mn, Zr, Fe or co-octoate. Such products are known to the person skilled in the art.
  • compositions according to the invention usually react with one another at room temperature. However, heating may also take place for an accelerated reaction. However, it is preferred that the mixture contains catalysts.
  • organometallic compounds or tert. Be amines examples of organometallic compounds are stannous salts of carboxylic acids, strong bases such as alkali hydroxides, alcoholates and phenolates, e.g.
  • Di-n-octyl-tin-mercaptide dibutyltin, dilaurate, tin-diethyl-hexoate; Tin oxides and sulfides and thiolates such as bis (th-butyl tin oxide), dioctyl tin dodecyl thiolate, tributyl tin (thioglycolic acid 2-ethyl hexoate), or dibutyl and dioctyl tin bis (thioethylene glycol 2-ethylhexanoate).
  • Tin oxides and sulfides and thiolates such as bis (th-butyl tin oxide), dioctyl tin dodecyl thiolate, tributyl tin (thioglycolic acid 2-ethyl hexoate), or dibutyl and dioctyl tin bis (thioethylene glycol 2-ethyl
  • tertiary amines are also suitable as a catalyst.
  • aliphatic tertiary amines in particular having a cyclic structure.
  • tertiary amines are those which additionally bear reactive groups relative to the isocyanates, in particular hydroxyl and / or amino groups.
  • the catalysts may also be in oligomerized or polymethylated form, e.g. as N-methylated polyethyleneimine.
  • the CO 2 cleavage from the isocyanate-carboxylic acid reaction is to take place intensified, it is expedient to use amino-substituted pyridines and / or N- to use substituted imidazoles as additional catalysts.
  • Particularly suitable are 1-methylimidiazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 1-phenylimidazole, 1, 2,4,5-tetramethylimidazole, 1 (3-aminopropyl) imidazole, N-dodecyl-2-methylimidazole , Pyrimidazole, 4-dimethylamino-pyhdine, 4-pyrrolidinopyridine, 4-morpholino-pyridine and 4-methylpyridine.
  • the amount of catalysts should be from 0.1 to 2 wt .-%.
  • the polyol component is prepared by known methods.
  • the 2K PU composition of the present invention is prepared by mixing. This should be mixed immediately after production with the cellulose-containing solids. Another procedure is to mix the particulates with the polyol component. Thereafter, this mixture is added to the isocyanate component and mixed. Due to the proportion of drying oils, the viscosity of the composition is reduced, so that a good miscibility is ensured. Methods and machines for the production of moldings are known to the person skilled in the art.
  • the amount of polyisocyanates is chosen so that an NCO: OH ratio of 1: 1 to 3.5: 1 is obtained. In general, it is preferred if there is an excess of isocyanate groups, i. the ratio should be over 1, 2: 1.
  • the amount of cellulosic materials should be between 99 to 85 wt .-%, the amount of 2-component polyurethane composition 1 to 15 wt .-%.
  • the shaped bodies according to the invention are produced in a manner known per se.
  • the cellulose-containing materials, in particular wood chips or fibers, are homogeneously mixed with a mixture of the 2-component PU binder.
  • the resulting mixture is processed in single or twin belt presses into plates or in special shapes to form bodies. Under pressure and at elevated temperature, for example at 80 to 230 0 C, the mixtures are crosslinked and transferred to the cured molding.
  • These shaped bodies have a density of less than 1 g / cm 2 , for example between 0.25 to 0.70 g / cm 3 .
  • the shaped bodies according to the invention are mechanically stable. They can be well made in different shapes or cut into different shapes. They have a low density, but can be provided with fasteners such as screws, etc., without any breakage of the moldings is observed. Despite the low density, they have a high screw pullout strength.
  • these moldings show only low swellability with water, that is, the increase in thickness is less than 1%.
  • Known hydrophobization processes by coating the wood chips with paraffin are not necessary. Thereby, a simplification of the manufacturing process can be achieved.
  • An advantage of the 2-component polyurethane binder according to the invention is that the OH components are easy to prepare. The known incompatibilities of polyols, organic carboxylic acids and water are avoided. These OH components are storage stable. The homogeneous composition produces homogeneous moldings which have a uniform distribution of binder and cellulose-containing materials.
  • the selected mixing ratio of carboxylic acid and water to polyol ensures that the ratio of crosslinking of the 2-component PU binder to foam formation is adjusted so that connection and homogeneous bonding of the individual cellulose particles is possible. An additional hydrophobing of the cellulose particles is not necessary.
  • the invention will be explained in more detail by embodiments.
  • Adhesive content 8% in top layer, 6% in middle layer (based on dry wood)
  • Hydrophobization 1% hydrophobing wax Sasol 730 (paraffin wax)
  • polyol component and optionally the hydrophobing wax are to be mixed.
  • the chips are then mixed with the polyol and then with the isocyanate component in a free-fall cascade drum. Thereafter, the mixture is in a
  • Example 1 Example 2
  • Example 3 Example 4 Density: 475 480 465 480 480 475 470 480 Kg / m 3
  • the transverse tensile strengths of the plates produced are 0.3 MPa.
  • the comparative experiments show that a mixture of short-chain di- and trifunctional polyols with a chain extender or a polyol mixture with castor oil or a high proportion of the foaming agent cause a still to be improved water swelling.
  • the swelling can be reduced by adding a hydrophobing wax.
  • Example 4 of the invention the addition of the drying oil leads to a reduction of the swelling. It is no longer necessary to add hydrophobing wax.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Forests & Forestry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des corps moulés constitués d'une matière contenant de la cellulose et de liants polyuréthanne à 2 composants réticulés, composés de 99 à 85 % en poids de la matière contenant de la cellulose avec 1 à 15 % en poids d'un liant polyuréthanne à 2 composants (PU 2C), le liant PU 2C contenant 25 à 90 % en poids de polyols oléochimiques avec une fonctionnalité allant de 2,5 à 5; 1 à 50 % en poids de polyéther-polyols bi- à quadrifonctionnels, ayant un poids moléculaire situé entre 250 et 20 000 g/mole; 0,1 à 5 % en poids de di- ou triamines aliphatiques ou aromatiques ayant des groupes amino primaires et/ou secondaires; 1 à 30 % en poids d'un mélange d'eau et d'un acide carboxylique en C<SUB>2</SUB> à C<SUB>100 </SUB>; 1 à 25 % en poids d'huiles siccatives et / ou semi-siccatives, ainsi que le cas échéant d'autres additifs, les constituants s'additionnant pour atteindre 100 %, et au moins un polyisocyanate aromatique à rapport NCO/OH allant de 1/1 à 3,5/1.
PCT/EP2007/063274 2007-03-30 2007-12-04 Corps moulés constitués d'une matière contenant de la cellulose Ceased WO2008119398A1 (fr)

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DE102007015802A DE102007015802A1 (de) 2007-03-30 2007-03-30 Formkörper aus cellulosehaltigen Materialien
DE102007015802.7 2007-03-30

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EP2421706A4 (fr) * 2009-01-27 2013-03-20 Momentive Specialty Chemicals Res Belgium Sa Compositions de triglycéride utiles pour préparer des panneaux composites et applications associées
CN108164744A (zh) * 2017-12-27 2018-06-15 武汉大学 一种弹性纤维素气凝胶及其疏水性纤维素气凝胶的制备方法
CN113574084A (zh) * 2019-03-15 2021-10-29 巴斯夫欧洲公司 木质纤维素复合制品

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CN111516079B (zh) * 2020-05-06 2021-10-15 安徽科林新材料科技有限公司 一种棉杆刨花板的加工工艺

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EP0672698A1 (fr) * 1994-03-17 1995-09-20 Bayer Ag Procédé de préparation de polyuréthanes et/ou polyuréthaneurées éventuellement cellulaires
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EP2421706A4 (fr) * 2009-01-27 2013-03-20 Momentive Specialty Chemicals Res Belgium Sa Compositions de triglycéride utiles pour préparer des panneaux composites et applications associées
CN108164744A (zh) * 2017-12-27 2018-06-15 武汉大学 一种弹性纤维素气凝胶及其疏水性纤维素气凝胶的制备方法
CN113574084A (zh) * 2019-03-15 2021-10-29 巴斯夫欧洲公司 木质纤维素复合制品
CN113574084B (zh) * 2019-03-15 2024-04-23 巴斯夫欧洲公司 木质纤维素复合制品

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