EP3080202A1 - Produit en matériau dérivé du bois ou produit en matériau composite renforcé par des fibres naturelles et utilisation d'une résine aminique ou amidique sans formaldéhyde pour leur production - Google Patents

Produit en matériau dérivé du bois ou produit en matériau composite renforcé par des fibres naturelles et utilisation d'une résine aminique ou amidique sans formaldéhyde pour leur production

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Publication number
EP3080202A1
EP3080202A1 EP13821795.5A EP13821795A EP3080202A1 EP 3080202 A1 EP3080202 A1 EP 3080202A1 EP 13821795 A EP13821795 A EP 13821795A EP 3080202 A1 EP3080202 A1 EP 3080202A1
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EP
European Patent Office
Prior art keywords
amide
formaldehyde
product
wood
resin
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.)
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Application number
EP13821795.5A
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German (de)
English (en)
Inventor
Brigitte Dix
Frank BÖRNER
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP3080202A1 publication Critical patent/EP3080202A1/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Withdrawn legal-status Critical Current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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/262—Alkali metal carbonates

Definitions

  • the invention relates to a wood-based product or natural fiber composite product comprising at least one lignocellulose and / or cellulose containing material which has been provided with a formaldehyde-free amino or amide resin based on carbohydrate aldehydes and cured or crosslinked in the desired form.
  • Natural fiber composites, or natural fiber reinforced plastics are composites of a polymer or a matrix (thermosets, thermoplastics or combinations) and natural fibers and / or synthetic fibers.
  • Natural fiber-reinforced composite materials or plastics have considerable market potential in vehicle construction (passenger cars, commercial vehicles, rail-bound vehicles), boat building, furniture and interior fittings. In the German automotive industry, the production of large-area natural fiber-reinforced plastics for the interior takes place more than 90% after the compression molding process. About 60% of these natural fiber molded parts have a duroplastic matrix.
  • Thermosets include the aminoplasts (e.g., urea and melamine-formaldehyde resins), phenolic resins (e.g., phenol-formaldehyde resins), epoxy resins, polyacrylates, polyurethanes, and other crosslinked polymers.
  • aminoplasts e.g., urea and melamine-formaldehyde resins
  • phenolic resins e.g., phenol-formaldehyde resins
  • epoxy resins e.g., polyacrylates, polyurethanes, and other crosslinked polymers.
  • Wood-based materials are mainly used in the construction and furniture industry.
  • wood-based materials are used in vehicle construction and as packaging material.
  • the wood materials include e.g. Plywood, particleboard and fiberboard, scrimber, wood-polymer materials (WPC), engineered wood products such as Oriented Strand Boards (OSB), Laminated Veneer Lumber (LVL), Veneer Strip Lumber (Parallel Strand Lumber [PSL]), carrier systems, I-beams and honeycomb panels with a core made of paper, aluminum etc. and a cover layer, eg made of plywood or fiberboard.
  • the starting material for lignocellulose wood materials or composite materials are particles of wood, annual and perennial plants, secondary residues such as waste wood, waste paper, production residues and lignocellulose-containing residues from agriculture, eg straw or hemp shives.
  • the particles are usually assembled by means of an adhesive or a polymer (matrix) to form a composite material.
  • the composites usually contain additives such as water repellents, flame retardants, curing accelerators, adhesion promoters, formaldehyde scavengers, dyes and surface-active substances to obtain certain properties of the material.
  • UF resin urea-formaldehyde resin
  • UF resins Inside, more than 90% of Holzwerk fabrics are bound with UF resin.
  • UF resins also have disadvantages such as increased brittleness, limited moisture resistance and formaldehyde emission.
  • mUF or MUF resins melamine
  • resin combinations for example UF resin and polymeric diphenylmethane-4,4'-diisocyanate [PMDI]
  • PF resins alkaline-curing phenol-formaldehyde resins
  • MUF resins MUF resins
  • adhesives based on polymeric diisocyanate (PMDI) are used.
  • the PF resins release formaldehyde in small amounts.
  • wood-based materials with mixed resins of various reaction components containing phenol eg MUPF resins
  • PMDI is formaldehyde-free and suitable for the bonding of particles, but not without modification for surface bonding.
  • MF resins formaldehyde-free and suitable for the bonding of particles, but not without modification for surface bonding.
  • MF resins formaldehyde-free and suitable for the bonding of particles, but not without modification for surface bonding.
  • RF resins resorcinol
  • tannin (TF resins) mixed resins with additional components for use in composites are possible.
  • Melamine-formaldehyde resins are widely used as impregnating resins for decorative paper coating of wood-based
  • Adhesives based on renewable raw materials such. Lignins, tannins, polysaccharides, e.g. Starch, fatty acids, proteins have so far not been able to assert themselves for reasons of both technology and availability; to a lesser extent, they are useful as extenders for synthetic resins (e.g., tannin or lignin in phenol-formaldehyde resin, soy protein in combination with polyamidoamine-epichlorohydrin resin [PAE resin]).
  • synthetic resins e.g., tannin or lignin in phenol-formaldehyde resin, soy protein in combination with polyamidoamine-epichlorohydrin resin [PAE resin]
  • Cement-bonded chipboard according to DIN EN 634-2 consist of about 60% by volume of wood chips and about 40% by volume of cement and additives.
  • the composite of the wood chips takes place by the setting of the mineral substance components.
  • particleboard and fiberboard containing gypsum or magnesite as an inorganic component.
  • Another inorganic binder for chipboard and fiberboard is waterglass, which are sodium and potassium silicates or their aqueous solutions.
  • Laminate flooring elements consist of at least four layers, a chipboard support, a high-density (HDF) or medium-density fiberboard (MDF), as well as a room-side coating of the panels, usually consisting of several layers of high-grade paper impregnated with a transparent melamine resin are. Furthermore, there is a so-called Gegenzugpapier back. For the impregnation of decorative paper is often cost reasons in a two-stage Process urea-formaldehyde resin (UF resin) and then used melamine-formaldehyde resin. The surface film (protective function) is usually melamine-formaldehyde resin.
  • the adhesives may contribute directly (formaldehyde-containing adhesives) and / or indirectly through interaction between the adhesive and the lignocellulose to emit formaldehyde and other volatile organic compounds (VOCs).
  • VOCs volatile organic compounds
  • the wood-based materials currently contain predominantly formaldehyde-containing adhesives.
  • Formaldehyde-free adhesives which are already used or can be used in composite materials are, for example, polymeric diphenylmethane-4,4'-diisocyanate (PMDI), polyurethanes, EPI adhesives, adhesives based on polyamides, polyacrylamides, polyethylene, polyesters, polyvi nylacetates, epoxides, organofunctional silanes, cyclic urea, renewable raw materials such as starch, protein, lignin, fatty acids, latex or other biopolymers and inorganic binders.
  • PMDI polymeric diphenylmethane-4,4'-diisocyanate
  • EPI adhesives adhesives based on polyamides, polyacrylamides, polyethylene, polyesters, polyvi nylacetates, epoxides, organofunctional silanes, cyclic urea
  • renewable raw materials such as starch, protein, lignin, fatty acids, latex or other biopol
  • PMDI The disadvantage of PMDI is the high price, the necessary use of emulsifiers or special dosing and gluing techniques as well as release agents, the need for higher occupational safety measures as well as a limited amount Availability.
  • One-component polyurethanes often have a high viscosity, must be diluted with organic solvents and subjected to high temperatures for curing.
  • 2-component polyurethanes require a complex working behavior due to two components and have a very short service life. Overall, the cost is high and there is the safety risk of unbound isocyanate monomers.
  • the safety risk is due to unpolymerized acrylamide, which is toxic.
  • Polyvinyl acetates have a thermoplastic behavior and are sensitive to creep of the bondline. The curing can only take place at relatively low temperatures, so that PVAC can be used only in the cover layer or in thin plates.
  • Epoxies require resin and hardener, which must be present in an exact mixing ratio; moreover, the polyaddition is highly exothermic, so that there is a risk of fire.
  • the service life is very short, epoxies are irritating, environmentally hazardous, so that a special protective equipment is required during handling.
  • the adhesive is not recyclable, the applications are limited.
  • silanvernetzten polymer adhesives or organofunctional silanes are difficult because of the viscoelastic property.
  • Renewable raw materials have varying properties with mostly low reactivity. Availability is not always guaranteed, the costs are comparatively high and ready-to-use forms of delivery are rare.
  • the object of the invention was to develop wood-based products with formaldehyde-free amino resins, in which the production conditions and the mechanical and hygric material properties correspond as far as possible to the materials bound with formaldehyde-containing aminoplast resin.
  • aldehydes are in principle available for the production of formaldehyde-free amino resins, such as, for example, acetaldehyde, propionaldehyde, acrolein, crotonaldehyde, glyoxal, furfuraldehyde, etc.
  • Adam, 1988: Melaminharze. In: Kunststoff-Handbuch 10: Duroplaste, ed .: Woeb - cken, W, Adam, W. ISBN-3-446- 4418-8).
  • Formaldehyde-free resins as adhesives for wood-based materials or decorative papers based on urea or cyclic urea (ethyleneurea) are listed in some patents.
  • US-A-4,395,504 discloses a formaldehyde-free binder for making particleboard from a cyclic urea, e.g. Ethylene urea and glyoxal in a molar ratio of 1, 1 .... 1, 5: 1 described.
  • US-A-4,906,727 discloses a urea-aldehyde condensate for surface coatings obtained by reacting urea or certain alkylene ureas with certain aldehydes (including formaldehyde).
  • US-A-4,220,751 discloses a resin for surface coatings of urea or urea derivatives and certain monoaldehydes (e.g., alkyl, aryl-aldehyde).
  • DE 691 03 847 T2 describes the preparation and use of ethylene-urea / glutaraldehyde resin or urea / ethyleneurea / glutaraldehyde resin in wood-based materials.
  • the molar ratio of ethyleneurea to glutaraldehyde can vary between 0.3 and 3.5. With this resin, a catalyst is not required to achieve the appropriate cure and bond strength.
  • US-A-4,906,726 describes resins for surface coatings of two components, on the one hand a mixture of polyaldehydes (glyoxal or glutaraldehyde or derivatives thereof) and a water-dispersible component (eg epoxy resin emulsion, synthetic latex) and on the other hand, a reaction product of eg urea Formaldehyde ether monomer, a polyamine and calcium, strontium or barium oxide or hydroxide.
  • glyoxal Due to the structure are in principle similar high crosslinking densities as expected in the previously known, formaldehyde-based melamine resins. Reactions of glyoxal with melamine, however, already lead to a cross-linked product upon addition, since up to 3 molecules of aldehyde can attach to one molecule of melamine under similar reaction conditions. Dialdehyde-based resins, which by themselves promise high network density with melamine, are not storable and unsuitable for commercial use in relevant applications.
  • the literature discusses the possibility of unilaterally providing glyoxal with protective groups, for example in DE 103 22 107 B4. However, the introduction of such protective groups is expensive and only partially conceivable for commercial products for the production of wood-based materials.
  • Formaldehyde-free urea and melamine adhesives based on dimethoxyethanal (DME) were used for laboratory particle board (Despres A., Pizzi, A., Vu C, Delmotte L. 2010: Colourless formaldehyde-free urea resin adhesives for wood panels Eur. J. Wood Prod. 68: 13-20, Properzi M., Wieland, S., Pichelin, F., Pizzi, A., Vu C. 2009: Dimethoxyethanal-derived resins for wood based panels : Processing of the International Panel Products Symposium 2009, 16-18 September 2009, La Cite Internationale de Congres Nanes, France, ISBN: 978-1-184220-118-3).
  • Dimethoxyethanal is a derivative of glyoxal that is colorless and non-volatile.
  • DME dimethyl methacrylate
  • urea urea
  • melamine melamine
  • precursors of amino resin were prepared.
  • crosslinking reaction of urea with DME was present, it was too slow to meet the requirements for adhesives for wood-based materials.
  • Crosslinking was improved by adding 14% to 20% polymeric diisocyanate (PMDI).
  • PMDI polymeric diisocyanate
  • melamine-DME precursors in admixture of 5% to 16.5% PMDI, 26.5% latex or 16.5% PMDI and 5% glyoxylic acid (based on melamine-DME + latex) as an adhesive for Chipboard used.
  • the manufacturing conditions for the plates were 8% ... 9% adhesive, 20 s / mm ... 43 s / mm plate thickness press time, 193 ° C press temperature.
  • a sufficient transverse tensile strength was only achieved with very long process times of 34 s / mm, which are not acceptable for the industry.
  • urea resins based on glyoxal e.g. for crease-resistant finishing of textiles, described in DE 30 41 580 T2.
  • urea resins based on formaldehyde This particularly concerns discolorations and problems with the stability of the resins.
  • protective groups are frequently used here in order to limit the reactivity (Despres A., Pizzi, A., Vu C, Delmotte L. 2010: Colourless formaldehyde-free urea resin adhesives for wood panels. Eur. J. Wood Prod. 68: 13-20).
  • dialdehydes such as glyoxal
  • amine or amide is already attached during the addition of the dialdehyde.
  • water-soluble formaldehyde-free polycondensation products based on aminotriazines, glyoxylic acid and an amino compound are known as additives for aqueous suspensions based on inorganic binders from DE 196 27 531 B4.
  • this object is achieved by a wood-based product or natural fiber composite product having the features of the main claim and the use of a formaldehyde-free amino, amido or phenolic resin for producing a wood-based product or natural fiber composite product, prepared by a process in which a hydroxy-monoaldehyde with a Amine or amide or an aromatic hydroxy compound is reacted.
  • a formaldehyde-free amino, amido or phenolic resin for producing a wood-based product or natural fiber composite product, prepared by a process in which a hydroxy-monoaldehyde with a Amine or amide or an aromatic hydroxy compound is reacted.
  • Advantageous embodiments and further developments of the invention are disclosed in the subclaims, the descriptions and the tables.
  • Glycolaldehyde and / or glyceraldehyde can be used as the aldehydic component.
  • Glycolaldehyde is only offered as a dimer by various fine chemical traders (for example Sigma Aldrich GmbH) due to its production at a comparatively high purchase price in the trade.
  • This dimer can also be used for amino resin synthesis by base-catalyzed ring opening.
  • the wood-based product or natural fiber composite product of at least one lignocellulosic and / or cellulose-containing material which is provided with an adhesive and cured in the desired shape or is wet, provides that the adhesive consists of an aldehyde component (glycaldehyde and / or glyceraldehyde with possibly additional aldehyde components) and an amine, amide and / or phenol component.
  • an aldehyde component glycocaldehyde and / or glyceraldehyde with possibly additional aldehyde components
  • Natural fiber composites, or natural fiber reinforced plastics are composites of a polymer or a matrix (thermosets, thermoplastics or combinations) and natural fibers and / or synthetic fibers correspondingly for products containing natural fiber composites, or n have ature fiber reinforced plastics, ie for natural fiber composite products. Natural fiber composites may also be formed as plates or moldings.
  • the present invention relates to a formaldehyde-free resin obtainable by reacting a hydroxy-monoaldehyde with an amine or an amide or an aromatic hydroxy compound.
  • the resin has free aldehyde groups.
  • the solids content of the resin can be varied over a wide range.
  • the solids content is at least 40% by weight.
  • the concentration or the solids content of the resin is in the range of 40 to 80% by weight or 55 to 70% by weight.
  • the resin of the invention shows good storage stability even at high solids content. Stabilizing additives are not required.
  • the resin does not contain a polymeric additive.
  • the wood-based product or natural fiber composite product may be formed in one or more layers or as a multilayer composite material, wherein the amino or amide resin is used in at least one layer.
  • the formaldehyde-free amino or amide resin can be used as a decor or surface coating or for fixing a decorative layer or a wear protection layer. This makes it possible to glue decors, such as decorative films or decor papers or cover a decor.
  • the formaldehyde-free amino or amide resins can also be used after the printing of decors as wear protection layer, optionally with the addition of wear protection components, such as corundum.
  • the wood-base product or natural-fiber composite product may also contain, in addition to lignocellulose-containing or cellulose-containing fractions, materials which are not made from renewable raw materials, for example polystyrenes, polyurethane foams, plastics, synthetic fibers, aramids or intumescent elements.
  • the wood-based product or natural fiber composite product may also be configured as a single-layer or multi-layer, with multilayer wood products or natural fiber composite products also layers of non-cellulosic or non-lignocellulose-containing materials may be provided, so that a total of a composite material from the wood-based product or natural fiber Composite product and the other materials results.
  • the design as a composite material increases the possible uses of the end product.
  • a variant of the invention provides that the amino or amide resin is used as the sole adhesive. As a result, the use of formaldehyde is ruled out.
  • formaldehyde-free amino or amide resin it is provided that a combination with formaldehyde-containing or formaldehyde-free other organic adhesives is used.
  • formaldehyde-containing adhesives z.
  • urea, melamine, phenol or resorcinol formaldehyde resins are used.
  • fomaldehyde-containing adhesives based on renewable raw materials such as lignin, tannin, protein, starch, fatty acids, latex or mixtures thereof can be used.
  • the formaldehyde-free organic adhesives may be e.g.
  • PMDI polymeric diisocyanate
  • EPI emulsion polymer isocyanate
  • polyurethane epoxy resin
  • polyvinyl acetate polyvinyl acetate
  • silane crosslinked polymers and adhesives based on renewable raw materials or mixtures thereof may be formed.
  • the amino or amide resin can be used in combination with a nem inorganic binder such as gypsum, magnisite, cement and / or water glass, the aminoplast resin thus having at least one inorganic binder.
  • a nem inorganic binder such as gypsum, magnisite, cement and / or water glass
  • the formaldehyde-free amino or amide resin can be used in solid, liquid, foamed or intumescent form.
  • Functional additives such as water repellents, flame retardants, curing accelerators, adhesion promoters, formaldehyde scavengers, dyes and / or surface-active substances may be added to the wood-base product or natural-fiber composite material product.
  • the invention also relates to the use of a formaldehyde-free resin for producing a wood-based product or natural fiber composite product as described above, prepared by a process in which a hydroxy-monoaldehyde is reacted with an amine or amide or an aromatic hydroxy compound.
  • a hydroxy-monoaldehyde is understood as meaning an organic compound which has an aldehyde group and also one or more hydroxyl groups.
  • a hydroxy monoaldehyde may also be referred to as carbohydrate aldehyde or sugar aldehyde. It is preferably in the hydroxy-monoaldehyde by a hydroxy monoaldehyde having 2-3 carbon atoms (hereinafter also referred to as hydroxy-C 2-3- monoaldehyde hereinafter).
  • Suitable hydroxy C 2-3 monoaldehydes are, in particular, glycolaldehyde or glyceraldehyde or a mixture of these aldehydes.
  • Hydroxy monoaldehydes in particular hydroxy-C 2 -3 monoaldehydes, such as glycolaldehyde or glyceraldehyde, can be prepared by conventional synthesis methods known to the person skilled in the art or are commercially available.
  • Glycolaldehyde for example, is commercially available as a dimer, but at a relatively high purchase price. This dimer can be used by basic catalyzed ring opening for resin synthesis.
  • Hydroxy-C2-3 monoaldehydes such as glycolaldehyde or glyceraldehyde
  • formaldehyde or a source of formaldehyde eg paraformaldehyde
  • carbonyl umpolung carbonyl umpolung
  • a polarity reversal is a chemical reaction in which a compound containing a functional group is modified with the aim of reversing its polarity.
  • Such a catalytic Umpolungsrecision of formaldehyde for the preparation of hydroxy-C2-3-monoaldehydes is described for example in DE 42 12 264.
  • this hydroxy-C, 2- 3-monoaldehyde, particularly glycol aldehyde and / or glyceraldehyde, preferably in a catalytic umpolung which comprises the following steps: (i) providing a reaction solution containing an organic solvent, formaldehyde and / or paraformaldehyde, and a catalyst, (ii) heating the reaction solution to form the hydroxy-2- C 3- monoaldehyde,
  • step (iii) contacting the reaction solution with an aqueous phase. Once the reaction solution is in contact with the aqueous phase in step (iii) is brought, it is preferred that no heating of the reaction solution by an external heat source takes place more.
  • the aqueous phase with which the reaction solution is contacted may have a temperature of 30 ° C or less.
  • the aqueous phase may also be frozen water (i.e., ice).
  • the reaction solution By bringing the reaction solution into contact with the aqueous phase after the formation of the hydroxy C2-3 monoaldehyde, the further reaction to hydroxyaldehydes having 4 or more carbon atoms can be suppressed.
  • the hydroxy-C go 2- 3- monoaldehydes such as glycolaldehyde and / or glyceraldehyde in step (iii) in the aqueous phase, while the Umpolungskatalysator remains in the organic solvent.
  • the umpolung catalyst would still be sufficiently catalytically active at room temperature to catalyze a further reaction to products with 4 or more carbon atoms. This spatial separation of umpolung catalyst and hydroxy-C 2 -3 monoaldehyde thus helps to prevent further reaction to products with 4 or more carbon atoms.
  • the contacting of the reaction solution with the aqueous phase may be carried out in a conventional manner, e.g. in that the reaction solution is poured onto the aqueous phase (or vice versa).
  • the reaction solution in steps (i) and (ii) is preferably a single-phase reaction solution.
  • the water content of the reaction solution is relatively low (e.g., less than 10% by volume or less than 5% by volume based on the volume of the organic solvent (s)) or the reaction solution is even anhydrous.
  • the term "single-phase reaction solution" in this preferred embodiment excludes the presence of a separate aqueous phase for steps (i) and (ii).
  • a suitable organic solvent can be made by a person skilled in the art readily make on the basis of his general expertise. Both protic and aprotic organic solvents can be used. In a preferred embodiment, an aprotic solvent or a mixture of aprotic solvents is used. Suitable organic solvents may, for. For example, alcohols such as Ci -4 alcohols, acetic sigklareethylester, pyridine, acetone, cyclic ethers (1, 4-dioxane / TH F) and non-cyclic ether (e.g., as dipropyl ether, dibutyl ether, diglyme) can be mentioned.
  • alcohols such as Ci -4 alcohols, acetic sigkladreethylester, pyridine, acetone, cyclic ethers (1, 4-dioxane / TH F) and non-cyclic ether (e.g., as dipropyl ether, dibutyl ether, diglyme)
  • Suitable Umpolungskatalysatoren are described for example in DE 42 12 264 A1.
  • Preferred catalysts for the reversal reaction of formaldehyde are, for example, mesoionic triazolium or tetrazolium compounds.
  • nitro n (1,4-diphenyl-4H- [1,2,4] triazol-3-yl) -phenylamine) is used as the catalyst.
  • Commercially available paraformaldehyde may contain formic acid. Since the umpolung catalyst could be deactivated in the presence of an acid, the addition of a base is preferably carried out in step (i) and / or step (ii). Their basicity should preferably not be too strong, otherwise a Cannizzaro reaction may occur.
  • suitable bases for example, carbonates, tert. Amines, or anion exchangers are called.
  • a higher reaction rate can be realized compared to a two-phase reaction medium (phase transfer reaction).
  • phase transfer reaction As soon as the hydroxy-C 2 -C 3 monoaldehyde has formed in this single-phase reaction medium, the further conversion to hydroxyphenyls of 4 or more carbon atoms can be prevented by bringing into contact with an aqueous phase in step (iii) , As already mentioned above, the hydroxy-C go 2- 3-monoaldehydes such Glycolal- dehyd and / or glyceraldehyde because of their good solubility in water in step (iii) in the aqueous phase.
  • the starting amine or parent amide may, for example, have 2-3 amine or amide groups (i.e., diamines or diamides or triamines and triamides, respectively). In the context of the present invention, however, it is also possible to use amines or amides having more than 3 amine or amide groups.
  • amine or amide for example, there is an amino triazine, urea, a urea derivative, thiourea, a thiourea derivative, imino urea (ie Guanidine), an imino urea derivative, a cyanamide, a diaminoalkane, a diaminoalkane, a polyacrylamide or a mixture of these compounds.
  • imino urea ie Guanidine
  • imino urea derivative ie Guanidine
  • an imino urea derivative a cyanamide, a diaminoalkane, a diaminoalkane, a polyacrylamide or a mixture of these compounds.
  • vegetable / animal amines / amides such as proteins, gelatin can be used.
  • Suitable aminotriazines are in particular amino, 3,5-triazines such as melamine, acetoguanamine and benzoguanamine.
  • suitable urea derivatives there may be mentioned, for example, alkylated ureas such as methyl urea or cyclic ureas such as acetylene diurea or ethylene urea.
  • Suitable thiourea derivatives include, for example, cyclic thioureas such as ethylene thiourea.
  • suitable imino urea derivatives include cyclic imino ureas.
  • cyanamide for example, dicyandiamide or cyanamide may be mentioned.
  • suitable diaminoalkanes are diamino- C8 -alkanes. Diamido-C 1-8 -alkanes, for example, may be mentioned as suitable diamidoalkanes.
  • Suitable aromatic hydroxy compounds are, for example, phenol or phenol compounds having at least two hydroxyl groups.
  • phenol compounds having at least two hydroxyl groups for example, catechol, resorcinol, hydroquinone, phloroglucinol, hydroxyhydroquinone, pyrogallol or a mixture of at least two of these phenolic compounds may be mentioned. If the resin synthesis is carried out with an amine or amide, the molar ratio of the hydroxy-monoaldehyde to the amine groups of the amine or the amide groups of the amide can be varied over a wide range.
  • the molar ratio of the hydroxy monoaldehyde to the amine groups of the amine or amide groups of the amide is preferably in the range of 0.5 / 3 to 3/3, more preferably 1, 5/3 to 2.5 / 3 or 1, 8/3 to 2.2 / 3.
  • the amine or amide has, for example, 2 amine or amide groups
  • the molar ratio of the hydroxy-monoaldehyde to the aromatic hydroxy compound can be varied over a wide range.
  • the molar ratio of the hydroxy monoaldehyde to the aromatic hydroxy compound is preferably in the range of 0.5 / 1 to 1/3, more preferably 1/1 to 1/2.
  • the molar ratio of the hydroxy monoaldehyde to the aromatic hydroxy compound is preferably in the range of 0.5 / 1 to 1/4, more preferably 1/1 to 1/2.
  • each amine group of the starting amine or each amide group of the starting amide or for phenols it is possible in principle for each amine group of the starting amine or each amide group of the starting amide or for phenols to be any ring position of the aromatic ring which is ortho or para to the OH group (hereinafter also referred to as reactive ring positions the aromatic hydroxy compound) reacted with at least one monoaldehyde.
  • reactive ring positions the aromatic hydroxy compound the aromatic hydroxy compound
  • the product obtained from the reaction of the hydroxy-monoaldehyde with the amine, the amide or the aromatic hydroxy compound can then be reacted with a further aldehyde, preferably a dialdehyde or a trialdehyde.
  • a further aldehyde preferably a dialdehyde or a trialdehyde.
  • the monoaldehyde may be added in molar excess, based on the number of amine amines or amide groups of the amide or the molar amount of the aromatic hydroxy compound.
  • Suitable solvents for the reaction of the hydroxy-monoaldehyde with the amine, the amide or the aromatic hydroxy compound are known in principle to the person skilled in the art.
  • an aqueous solvent is used.
  • hydrogen bond-breaking polar solvents can be used.
  • Suitable reaction conditions (such as reaction temperature and pH) for the reaction of the hydroxy-monoaldehyde with the amine, the amide or the hydroxyaromatic compound are generally known to the person skilled in the art.
  • the reaction temperature may be, for example, in the range of 20 ° C to 100 ° C, more preferably in the range of 40 to 65 ° C.
  • the pH may vary over a wide range.
  • the pH may be, for example, in the range of 6 to 10, more preferably 7 to 8.5.
  • oligomers are formed with very short sequences. These resins can be readily stabilized even at high solids levels (e.g., 60% by weight) (i.e., high storage stability). The addition of stabilizing additives is not required.
  • the resin of the invention may, for example, have a solids content of at least 40% by weight or even at least 55% by weight.
  • the resin can be free of polymeric additives.
  • this is from the implementation of the hydro- xy-Monoaldehyds with the amine, the amide or the aromatic hydroxy compound product then reacted with another aldehyde, wherein the aldehyde is a dialdehyde, a trialdehyde, a monoaldehyde such as glyoxylic acid, or a mixture of at least two of these aldehydes.
  • storage-stable resins can also be prepared with dialdehydes or trialdehydes when the amine or amide or the aromatic hydroxy compound is first reacted with the hydroxy-monoaldehyde.
  • the aldehyde group reacts with the nitrogen of the amine or amide group or with a reactive ring position (i.e., a position of the aromatic ring ortho or para to the OH group) of the hydroxy aromatic compound.
  • a reactive protecting group "attached to the amine or amine group (ie, a group which initially prevents undesired premature crosslinking in a subsequent reaction with a di- or trialdehyde, but otherwise has a reactive group later to provide the desired crosslinking or curing support a networked material).
  • the dialdehyde or trialdehyde is added, it can initially react only with N atoms or those reactive positions of the aromatic ring which have not yet been blocked with a protective group in the first step.
  • the dialdehyde or trialdehyde in the second step can partially replace the protective groups derived from the hydroxy-monoaldehyde.
  • the resin has free aldehyde groups.
  • the presence of free aldehyde groups can increase the reactivity in setting appropriate conditions and thus assist in the preparation of a final crosslinked product.
  • Dialdehydes or trialdehydes which can be reacted with amines or amides or aromatic hydroxy compounds are known per se to a person skilled in the art.
  • glyoxal or a dialdehyde of the formula OHC- (CH 2 ) i- 3- CHO ie malonaldehyde, succindialdehyde, glutaraldehyde
  • a suitable trialdehyde for example, 2,4,6-tris (p-formylphenoxy) - 1,3,5-triazine can be mentioned.
  • dialdehyde or trialdehyde it is possible for the dialdehyde or trialdehyde to be added to the product from the first step, which is preferably present in an aqueous solution.
  • the product from the first step for example in the form of an aqueous solution
  • it is preferred that one component of the other component is continuously metered. While in the first case is added slowly enough, so that in the reaction medium during the reaction is always a low concentration of unreacted dialdehyde or trialdehyde, is rapidly dosed in the case of good water-soluble products to stabilize the resin by cooling after the reaction.
  • the product from the first step is preferably not isolated, but used in the form of the aqueous solution in which it was prepared in the first step, for the reaction with the dialdehyde or trialdehyde in the second step.
  • the amount of dialdehyde or trialdehyde added in the second step can be varied over a wide range.
  • the molar ratio of the dialdehyde or trialdehyde to the amine groups or amide groups is preferably in the range from 0, 1/3 to 5/3, more preferably 0.5 / 3 to 3 / 3 or 0.8 / 3 to 2.2 / 3.
  • the starting amine or starting amine 2 Aminverted. Amide groups the molar ratio of the dialdehyde or trialdehyde to the amine groups or amide groups is preferably in the range of 0.1 / 3.9 to 3.9 / 0.1, more preferably 0.3 / 1, 7 to 1, 7 / 0.3, more preferably 0.5 / 1.5 to 1, 5 / 0.5.
  • the molar ratio of the dialdehyde or trialdehyde added in the second step to the hydroxy monoaldehyde added in the first step can be in the range from 1 / 0.01 to 1/3 or 1 / 0.2 to 1/2 or even 1 / 0.5 to 1/1, 5 are. If the amine or amide has three amine or amide groups, the molar ratio of the dialdehyde or trialdehyde added in the second step to the hydroxy-monoaldehyde added in the first step can be, for example, in the range from 1 / 0.01 to 1/5 or 1, 5 / 0.2 to 1, 5/2 or even 2 / 0.3 to 2/1.
  • reaction conditions such as reaction temperature and pH
  • reaction temperature and pH Suitable reaction conditions for the reaction of an amine or amide or an aromatic hydroxy compound with the dialdehyde or trialdehyde are known in the art.
  • the reaction temperature in the second step may be, for example, in the range of 20 ° C to 100 ° C, more preferably 40 ° C to 65 ° C.
  • the pH may be, for example, in the range of 6 to 10, more preferably 7 to 8.5.
  • oligomers can be formed with very short sequences and the resins can also be stabilized without problems even at high solids contents (eg 60% by weight) , Also with the well-soluble compounds such as urea or Guanidine the reaction products remain so low viscous by the derived from the hydroxy-monoaldehyde reactive protecting group that stabilization is very possible even at high solids content.
  • the resin is characterized by having free aldehyde groups which increase the reactivity in setting suitable conditions and thus assist in the production of a crosslinked final product.
  • the reactivity of the resin is also increased by the presence of the reactive protecting group.
  • the produced resins can be stabilized, for example by
  • Cooling e.g., to a temperature below 30 ° C, more preferably below 25 ° C
  • Cooling e.g., to a temperature below 30 ° C, more preferably below 25 ° C
  • Adjust the pH to a value in the range of 7.0-9.0, more preferably 7.5-8.5.
  • nitrone is almost insoluble in water, after phase separation (ethyl acetate / water), the nitrone can be recovered from the ethyl acetate by concentration.
  • the ethyl acetate phase is shaken out repeatedly with 100 g of water each time.
  • the weight of the combined aqueous phases is 2304 g, and the content of aldehyde products (glycolaldehyde and glyceraldehyde) is about 49%.
  • Single-layer chipboard was produced from spruce shavings under the following conditions:
  • Adhesive content 12% solid resin based on atro wood
  • Paraffin dispersion 1 Paraffin dispersion 1, 5% (solid based on atro wood)

Abstract

L'invention concerne un produit en matériau dérivé du bois ou un produit en matériau composite renforcé par des fibres naturelles réalisé dans au moins un matériau lignocellulosique et/ou contenant de la cellulose qui est pourvu d'une résine aminique ou amidique sans formaldéhyde à base d'aldéhydes d'hydrate de carbone et est durci ou réticulé dans la forme souhaitée, la colle étant conçue en tant que résine aminique ou amidique d'aldéhydes d'hydrate de carbone comme l'aldéhyde glycol et/ou glycérine, sans formaldéhyde. L'invention concerne également l'utilisation d'une telle colle pour la production d'un produit en matériau dérivé du bois ou un produit en matériau composite renforcé par des fibres naturelles.
EP13821795.5A 2013-12-12 2013-12-12 Produit en matériau dérivé du bois ou produit en matériau composite renforcé par des fibres naturelles et utilisation d'une résine aminique ou amidique sans formaldéhyde pour leur production Withdrawn EP3080202A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2013/003753 WO2015086035A1 (fr) 2013-12-12 2013-12-12 Produit en matériau dérivé du bois ou produit en matériau composite renforcé par des fibres naturelles et utilisation d'une résine aminique ou amidique sans formaldéhyde pour leur production

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EP3080202A1 true EP3080202A1 (fr) 2016-10-19

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PT3219756T (pt) * 2016-03-17 2018-10-19 Sestec Sp Z O O Aglutinante para madeira isento de formaldeído
US11459495B2 (en) 2017-09-20 2022-10-04 Sestec Innovations Sp. Z O.O. Binder for cellulose-containing materials
DE102017218627A1 (de) 2017-10-18 2019-04-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Lack mit Formaldehyd-freiem Vernetzer

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GB1578290A (en) * 1977-05-06 1980-11-05 Ici Ltd Amino-resin compositions in the form of fibres
SU1257079A1 (ru) * 1984-07-12 1986-09-15 Всесоюзный Научно-Исследовательский Институт Деревообрабатывающей Промышленности Композици дл древесностружечных плит
CN101298520B (zh) * 2008-06-30 2010-08-18 北京林业大学 脲醛树脂添加剂、其制备方法及脲醛树脂粘合剂

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