EP3080204A1 - Produit en matériau dérivé du bois ou produit en matériau composite renforcé par des fibres naturelles et utilisation d'une résine aminique et amidique sans formaldéhyde sur la base d'ester d'acide glyoxylique 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 et amidique sans formaldéhyde sur la base d'ester d'acide glyoxylique pour leur production

Info

Publication number
EP3080204A1
EP3080204A1 EP13814038.9A EP13814038A EP3080204A1 EP 3080204 A1 EP3080204 A1 EP 3080204A1 EP 13814038 A EP13814038 A EP 13814038A EP 3080204 A1 EP3080204 A1 EP 3080204A1
Authority
EP
European Patent Office
Prior art keywords
amide
resin
formaldehyde
wood
natural fiber
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Withdrawn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
EP13814038.9A
Other languages
German (de)
English (en)
Inventor
Brigitte Dix
Frank BÖRNER
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.)
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Publication of EP3080204A1 publication Critical patent/EP3080204A1/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Withdrawn legal-status Critical Current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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • 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
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • 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
    • B27N7/00—After-treatment, e.g. reducing swelling or shrinkage, surfacing; Protecting the edges of boards against access of humidity
    • B27N7/005—Coating boards, e.g. with a finishing or decorating layer

Definitions

  • the invention relates to a wood-based product or natural fiber composite product comprising at least one lignocellulosic and / or cellulose-containing material which has been provided with an adhesive or a polymer or a matrix and cured or crosslinked in the desired form, and the use of a formaldehyde-free amino or amide resin based on glyoxylic acid ester for the production of such a material.
  • Other aldehydes which can be processed with the aldehyde component can be glyoxylic acid, glycolaldehyde, glyoxal, furfural or glutaraldehyde.
  • imino resins can also be used.
  • 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. In addition, wood-based materials are used in vehicle construction and as packaging material.
  • the wood materials include e.g. Plywood, particleboard and fibreboard, scrims, wood-polymer materials (WPC), engineered wood products such as Oriented Strand Boards (OSB), Laminated Veneer Lumber (LVL), Veneer Strip Wood (Parallel Strand Lumber [PSL]), carrier
  • the starting material for lignocellulose composites and possibly natural fiber composites are particles of wood, annual and perennial plants, secondary residues such as waste wood, waste paper, production residues and lignocellulose-containing residues from agriculture, e.g. Used straw or hemp shives.
  • the particles are usually joined by means of an adhesive to a wood material or with a polymer (duroplastic or thermoplastic) to form a natural fiber 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.
  • Amino resins and amide resins are relatively low molecular weight, curable materials obtained by reacting carbonyl compounds (especially aldehydes such as formaldehyde) with compounds having NH groups. Subsequent crosslinking (i.e., curing) of the amino or amide resin yields a thermoset.
  • aldehyde component is preferably due to its high reactivity and low raw material price formaldehyde used. Resin synthesis often involves an excess of aldehyde to aid in the reactions between the two components. The residual contents of formaldehyde are correspondingly high. Formaldehyde can also be released by hydrolysis of the polycondensates.
  • UF resin urea-formaldehyde resin
  • UF resins Inside, more than 90% of the wood materials are bound with UF resin.
  • UF resins in addition to many positive properties such as There are also disadvantages such as increased brittleness, limited moisture resistance and formaldehyde emission.
  • UF resins eg with Me-Iamin (mUF or MUF resins) or the use of resin combinations (eg UF resin and polymeric diphenylmethane-4,4'-diisocyanate [PMDI] ) required.
  • Me-Iamin mUF or MUF resins
  • PMDI polymeric diphenylmethane-4,4'-diisocyanate
  • 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 materials with mixed resins of various reaction components containing phenol e.g., MUPF resins
  • PMDI is formaldehyde-free and suitable for the bonding of particles, but not without modification for surface bonding.
  • MF resins formaldehyde with melamine
  • RF resins resorcinol
  • TF resins tannin
  • Melamine-formaldehyde resins are widely used as impregnating resins for decorative paper coating of wood-based materials.
  • Adhesives based on renewable raw materials such as e.g. 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.
  • chipboard and fibreboard the gypsum or magnesite as inorganic Component included.
  • 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, typically consisting of several layers of high-grade paper impregnated with a transparent melamine resin. Furthermore, there is a so-called Gegenzugpapier back. For cost-effectiveness, urea-formaldehyde resin (UF resin) and then melamine-formaldehyde resin are often used in a two-stage process for the impregnation of decorative paper. 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.
  • the formaldehyde release of wood-based materials and products made from them is currently regulated by law in Germany to a compensation concentration of max.
  • Formaldehyde has been classified by the European Union in the regulation on the classification, packaging and labeling of hazardous substances from category 3 (substances with possible carcinogenic effects) to category 2 (substances that are considered to be carcinogenic) (EU Directives, 2004 / 73 / EC 2004, EU Regulation No. 1272/2008).
  • Formaldehyde-free adhesives which are already used or can be used in composite materials include, for example, polymeric diphenylmethane-4,4'-diisocyanate (PMDI), polyurethanes, EPI adhesives, adhesives based on polyamides, polyacrylamides, polyethylene, polyesters, polyvinyl acetates, epoxides organo-functional 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, polyvinyl acetates, epoxides organo-functional silanes, cyclic urea, renewable raw materials such as starch, protein, lignin, fatty acids, latex or other biopoly
  • PMDI The disadvantage of PMDI is the high price, the necessary use of emulsifiers or special dosing and gluing techniques and release agents, the need for higher occupational safety measures and limited availability.
  • One-component polyurethanes are often highly viscous, need to be diluted with organic solvents, and exposed 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 costs are high and there is the security 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. Curing can only take place at relatively low temperatures, so that PVAC can only be used in the cover layer or in thin plates.
  • Epoxies require resin and hardener, which must be present in an exact Trustsver ratio, also the polyaddition is highly exothermic, so that a fire hazard is given. The service life is very short, epoxies are irritating, environmentally hazardous, so that a special protective equipment when handling is lent.
  • 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 possible to the materials bound with formaldehyde-containing aminoplast resin.
  • aldehydes are available in principle for the preparation of formaldehyde-free aminoplast resins, such as, for example, Acetaldehyde, propionaldehyde, acrolein, crotonaldehyde, glutaraldehyde, glyoxal, furfuraldehyde, etc.
  • 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.
  • DE 691 03 847 T2 describes the preparation and use of ethyleneurea / glutaraldehyde resin or urea / ethyleneurea / glutaraldehyde resin in wood-based materials.
  • the molar ratio of ethylene urea 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 (e.g., epoxy resin emulsion, synthetic latex) and on the other hand a reaction product of e.g. Urea-formaldehyde ether monomer, a polyamine and calcium, strontium or barium oxide or hydroxide.
  • polyaldehydes glycoxal or glutaraldehyde or derivatives thereof
  • a water-dispersible component e.g., epoxy resin emulsion, synthetic latex
  • reaction product e.g. Urea-formaldehyde ether monomer, a polyamine and calcium, strontium or barium oxide or hydroxide.
  • glyoxal Due to the structure, similarly high crosslinking densities are to be expected as in the previously known formaldehyde-based melamine resins. Reactions of glyoxal with melamine, however, lead to a cross-linked product during the 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 protecting groups, e.g. 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 dimethoxyglyoxal also referred to as dimethoxyethanal [DME]
  • dimethoxyglyoxal also referred to as dimethoxyethanal [DME]
  • DME dimethoxyethanal
  • Dimethoxyethanal is a derivative of glyoxal that is colorless and non-volatile.
  • urea resins based on glyoxal e.g. for crease-resistant finishing of textiles, described in DE 30 41 580 12.
  • 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 Wood Prod. 68: 13-20).
  • DE 41 40 899 A1 describes a condensation product of a mixture of, for example, melamine or urea, glyoxylic acid and glyoxal, which is likewise used as tanning agent.
  • part of the glyoxal is oxidized to glyoxylic acid.
  • This mixture is reacted with melamine.
  • the problem with this approach is that the melamine must be brought into solution during the addition of the aldehydes and glyoxal can already build oligomeric units in this phase. Such resins are correspondingly difficult to stabilize.
  • Pure glyoxylic acid-based amino resins also provide stable resins, but carry a high salt load since, prior to synthesis, they need to be neutralized to the amino resins with a base to cure. These salts easily absorb water and lead to increased swellability of the end products when used in wood-based materials. However, since the acid group forms water-insoluble salts with calcium ions, such systems are used as a concrete consolidator and flow aid in the construction industry (e.g., US-A-2008/108732, DE 2004050395 A1, US-A-5750634, US-A-5891983).
  • 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.
  • the object of the present invention is to provide a wood-based product or natural fiber composite product which contains a formaldehyde-free adhesive with high reactivity and sufficient storage stability and which meets the requirements of use in terms of mechanical and hygric properties and emissions of volatile organic compounds.
  • 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 formaldehyde-free amino and amide resins based on glyoxylic esters as the aldehyde component.
  • Advantageous embodiments and further developments of the invention are disclosed in the subclaims, the description and the tables.
  • 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 or crosslinked in the desired form, provides that the adhesive is a formaldehyde-free amino or amido resin based on glyoxylic esters as aldehyde Component is formed.
  • Natural fiber composites, or natural fiber reinforced plastics (NFK) are composites of a polymer or a matrix (thermosets, Thermoplastics or combinations) and natural fibers and / or synthetic fibers. If the following is spoken of a wood-based product, the statements apply accordingly to products that have natural fiber composites, or natural fiber reinforced plastics, ie for natural fiber composite products. Natural fiber composites may also be formed as plates or shaped bodies.
  • these resins can be reacted with glyoxal.
  • the glyoxylic acid esters serve as a protective group of the amide functions.
  • resins are then produced which have a high free aldehyde content and therefore increase the reactivity by addition reactions. Resins could be synthesized whose reactivity to urea resins was comparable or even higher.
  • amino resins based on glyoxylic acid esters offer the advantage over prior art amino resins that the hydrophobicity of the resins can be adjusted by the type of ester. Since no glyoxylic acid is used, these resins bring no salt load in the end products compared to the Glyoxylklareharzen.
  • Another advantage of using glyoxylic acid esters is that a small amount of glyoxylic acid is released upon curing by hydrolysis. This can act as a catalyst, so that no further catalysts must be added during curing.
  • Another advantageous aspect of these resins is that by adjusting the hydrophobicity, a reduction of the thickness swelling of the end products can be achieved.
  • the wood-based product or natural fiber composite product may be single-layered or multi-layered or formed as a multi-layer 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-resistant 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-based product or natural fiber composite product may also contain materials which are not made from renewable raw materials, for example polystyrenes, polyurethane foams, plastics, synthetic fibers, aramids or intumescent elements, in addition to ligno-cellulosic or cellulose-containing components.
  • materials which are not made from renewable raw materials for example polystyrenes, polyurethane foams, plastics, synthetic fibers, aramids or intumescent elements, in addition to ligno-cellulosic or cellulose-containing components.
  • Wood, annual and perennial crops as well as residual and recycling materials, such as paper are used.
  • the wood-based product or natural fiber composite product may also be designed as a single-layer or multi-layer, wherein layers of non-cellulose-containing or non-lignocellulose-containing materials can be provided in multilayer wood-based products or natural fiber composite products, so that a total of a composite material from the wood-based product or natural fiber composite product and the other materials.
  • 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 Formaldehyd cluster is excluded.
  • 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 based on a reactive protective group and a dialdehyde is used as a network former in combination with an inorganic binder such as gypsum, magnisite, cement and / or water glass, the amino or amide resin so at least one inorganic Binder has.
  • an inorganic binder such as gypsum, magnisite, cement and / or water glass
  • the formaldehyde-free amino or amide resin based on a reactive protective group and a dialdehyde as a network former 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 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 glyoxylic acid ester is reacted with an amine, an amide or an aromatic hydroxy compound.
  • Glyoxylic acid ester based resins offer the advantage, compared to known resins, that the hydrophobicity of the resins can be adjusted by the type of ester. Since glyoxylic acid is either not or optionally used only in minor amounts, bring these resins in comparison to the Glyoxylklareharzen no or only a very low salt load in the final products.
  • Another advantage of using glyoxylic acid esters is that a small amount of glyoxylic acid is released upon curing by hydrolysis. This can act as a catalyst, so that no further catalysts must be added during curing.
  • the reactivity of the resins based on glyoxalic acid esters is comparable to that of UF resins, making them more reactive than the classic formaldehyde-based melamine resins.
  • the glyoxylic acid ester is preferably a glyoxylic acid alkyl ester, in particular a glyoxylic acid C -4 -alkyl ester.
  • a glyoxylic acid alkyl ester in particular a glyoxylic acid C -4 -alkyl ester.
  • methyl glyoxylate, ethyl glyoxylate, propyl glyoxylate, glyoxylic acid isopropyl or Glyoxylklarebutylester or mixtures thereof may be mentioned.
  • Glyoxylic acid esters can be prepared by conventional synthesis methods known to those skilled in the art or are commercially available.
  • glyoxylic acid esters can be obtained by esterification of the glyoxylic acid with an alcohol. If the esterification does not proceed quantitatively, glyoxylic acid is present in addition to the glyoxylic acid ester.
  • the amine, amide or aromatic hydroxy compound which is reacted with the glyoxylic acid ester to produce a formaldehyde-free resin may be those usually used for the production of resins.
  • the starting amine or Struktur desipramine can for example 2-3 amine or
  • Amide groups i.e., diamines or diamide or triamine or triamide.
  • amines or amides having more than 3 amine or amide groups for example polyamide, polyacrylamide.
  • amine or amide there are, for example, an amino triazine, urea, a urea derivative, thiourea, a thiourea derivative, imino urea (i.e., guanidine), an imino urea derivative, a cyanamide, a diaminoalkane, a diamidoalkane, a polyacrylamide, or a mixture of these compounds.
  • imino urea i.e., guanidine
  • imino urea derivative i.e., guanidine
  • imino urea derivative i.e., guanidine
  • imino urea derivative i.e., guanidine
  • an imino urea derivative i.e., guanidine
  • an imino urea derivative i.e., guanidine
  • an imino urea derivative i.e., guanidine
  • Suitable aminotriazines are in particular amino-1, 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 for example, cyclic imino ureas can be mentioned.
  • a suitable cyanamide for example, dicyandiamide or cyanamide may be mentioned.
  • Suitable diaminoalkanes for example diamino-Ci-s-alkanes may be mentioned.
  • suitable diamido alkanes for example diamido Ci -8 are called alkanes.
  • Suitable aromatic hydroxy compounds are, for example, phenol (i.e., only one hydroxy group) or phenolic compounds having at least two hydroxy groups.
  • phenol i.e., only one hydroxy group
  • phenolic compounds having at least two hydroxy groups For example, catechol, resorcinol, hydroquinone, phloroglucinol, hydroxyhydroquinone, pyrogallol or a mixture of at least two of these phenol compounds may be mentioned as preferred phenolic compounds.
  • the molar ratio of the glyoxylic ester 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 glyoxylic ester 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 molar ratio of the glyoxylic acid ester to the amine groups of the amine or the amide groups of the amide is preferably in the range from 0.2 / 2 to 2/2, more preferably 0.3 / 2 to 1, 5/2, more preferably 0.5 / 2 to 1, 5/2.
  • the molar ratio of the glyoxylic ester to the hydroxy aromatic compound can be varied over a wide range.
  • the molar ratio of the glyoxylic acid ester 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 glyoxylic acid ester 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 each ring position of the aromatic ring ortho or para to the OH group (hereinafter also referred to as reactive ring positions of the aromatic hydroxy compound) reacts with at least one glyoxylic acid ester.
  • at least one amine group of the amine or an amide group of the amide or a reactive ring position of the aromatic hydroxy compound is not reacted with the glyoxylic acid ester.
  • the product obtained from the reaction of the glyoxylic ester 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 glyoxylic acid ester with the amine, the amide or the aromatic hydroxy compound, free amine or amide groups or reactive ring positions are still present, they would be directly accessible for reaction with the dialdehyde or trialdehyde in a subsequent reaction step. Suitable process conditions to ensure this are known to those skilled in the art.
  • the glyoxylic acid ester can be added in molar deficiency based on the number of amine groups of the amine or amide groups of the amide or reactive ring positions of the hydroxyaromatic compound.
  • Suitable solvents for the reaction of the glyoxylic acid ester 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.
  • reaction conditions such as reaction temperature and pH
  • reaction temperature and pH Suitable reaction conditions for the reaction of the glyoxylic acid ester with the amine, amide or hydroxy aromatic compound are known in the art.
  • the reaction temperature may be, for example, in the range of 20 ° C to 00 ° 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 product obtained from the reaction of the glyoxylic acid ester with the amine, the amide or the aromatic hydroxy compound is subsequently reacted with a further aldehyde, wherein the aldehyde is preferably a dialdehyde, a trialdehyde, glyoxylic acid, glycolaldehyde or furfural or a mixture of at least two of these aldehydes.
  • the aldehyde is preferably a dialdehyde, a trialdehyde, glyoxylic acid, glycolaldehyde or furfural 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 glyoxylic acid ester.
  • 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 which is ortho or para to the OH group) of the hydroxy aromatic compound.
  • an aldehyde for example, to an amine or amide according to the reaction equation -NHR + OHC- NR-CH (OH) - the aldehyde group is converted into a hemiacetal group and this hemiacetal group is a reactive group that can be used for a later crosslinking reaction becomes a "reactive protecting group" in this first reaction step attached to the amine or amide group (ie, a group on the one hand in a subsequent reaction with a di- or trialdehyde initially prevents unwanted premature crosslinking, but on the other hand has a reactive group, which later support the desired crosslinking or curing to a crosslinked material can).
  • a reactive protecting group ie, a group on the one hand in a subsequent reaction with a di- or trialdehyde initially prevents unwanted premature crosslinking, but on the other hand has a reactive group, which later support the desired crosslinking or curing to a crosslinked material can.
  • one or more amine groups of the amine or amide groups of the amide or one or more positions of the aromatic phenol ring are initially blocked by a reactive protective group derived from the glyoxylic acid ester. If, in a further step, the dialdehyde or trialdehyde is added, it can initially react only with N atoms or reactive positions of the aromatic ring which have not yet been blocked with a protective group in the first step. In addition, since the reaction of the glyoxylic acid ester with the amine or amide is an equilibrium reaction in the first step, the dialdehyde or trialdehyde in the second step can partially replace the protective groups derived from the glyoxylic acid ester.
  • 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 the person skilled in the art.
  • glyoxal or a dialdehyde of the formula OHC- (CH 2 ) i-3-CHO ie malonaldehyde, succinic dialdehyde, glutaraldehyde
  • OHC- (CH 2 ) i-3-CHO ie malonaldehyde, succinic dialdehyde, glutaraldehyde
  • 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 molar ratio of the dialdehyde or trialdehyde to the amine groups or amide groups is preferably in the range from 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 glyoxylic acid ester added in the first step can be, for example, in the range from 1 / 0.01 to 1/3 or 1/0, 2 to 1/2 or 1 / 0.5 to 1/1, 5 are. If the amine or amide has three amine or amide groups, then the molar ratio of the dialdehyde or trialdehyde added in the second step to the glyoxylic acid ester added in the first step can be 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.
  • the molar ratio of the dialdehyde or trialdehyde to the aromatic hydroxy compound is preferably in the range of 1 / 0.1 to 1 / 2.5, more preferably 1 / 0.1 to 1/1, 5.
  • the molar ratio of the dialdehyde or trialdehyde to the aromatic hydroxy compound is preferably in the range of 1 / 0.1 to 1 / 3.5, more preferably 1 / 0.1 to 1/2.
  • 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) , Even in the case of readily soluble compounds such as urea or guanidine, the reaction products remain so low in viscosity due to the reactive protective group derived from the glyoxylic ester that stabilization is very well possible even at high solids contents.
  • 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
  • the present invention relates to a method for
  • Suitable conditions for the crosslinking of a resin for the production of a crosslinked material are basically known to the person skilled in the art.
  • another advantage of using glyoxylic acid esters is that a small amount of glyoxylic acid is liberated by hydrolysis during curing. This can act as a catalyst, so that no further catalysts must be added during curing.
  • no external catalyst is supplied to the curing resin obtained by the process of the present invention.
  • thermosets Crosslinked materials are also referred to as thermosets.
  • urea or polyamide or polyacrylamide (preferably in each case in the form of a solution) is therefore added to the formaldehyde-free resin before and / or during the crosslinking.
  • the addition of the amide is carried out in an amount such that the number of free primary amide groups is less than the number of free aldehyde groups.
  • the present invention relates to a formaldehyde-free resin obtainable by the above-described process, that is, by reacting a glyoxylic acid ester 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 present invention relates to a crosslinked material obtainable from the above-described resin.
  • the crosslinked material is obtained by curing the resin appropriately, i. is subjected to crosslinking.
  • foams or foamed materials or also fibers can be mentioned.
  • a further advantage of products based on the glyoxylic acid ester resins is that the partial hydrolysis of the ester groups can generate acidic and thus fungicidally active surfaces.
  • this acidic surface can catalyze the resin system because the condensation catalyst (acid) is permanently present in the final products.
  • the condensation catalyst (acid) is permanently present in the final products.
  • a self-healing effect can therefore be achieved by renewed condensation even at room temperature.
  • Example 2 This gives 496 g of a solution of glyoxylic acid and ethyl glyoxylate, which was used in Example 3 or 4 directly for resin synthesis.
  • Example 2
  • Example 7 For the resin synthesis in Example 7, the isopropanol of the organic phase was distilled off after the phase separation. The product was overcoated with 100 g of water to bring melamine into the aqueous phase in the synthesis of the resin (see Example 7).
  • the viscosity curve was determined as a function of the temperature. This is shown in FIG.
  • the resin had a pH of 6.3.
  • No catalyst was added in the form of an acid. Curing started at a temperature of 92 ° C.
  • the resin contains free aldehyde groups and has a high storage stability at room temperature.
  • the free aldehyde groups in the curing of these resins 0 in addition to the condensation and an addition reaction allows, which increases the reactivity.
  • Resin Synthesis 4 Glvoxylic Acid Ester / Glivoxylic Acid / Glvoxal Resins Based on Melamine (Ester from Example 2) After neutralization, 53.95 g (0.428 mol) of melamine were added to the ester from Example 2 and stirred at 60 ° C. for 30 min. touched. Then 31.3 g of glyoxal were added. After 12min. a clear resin was obtained, which was cooled down to room temperature in a water bath.
  • the resin contains free aldehyde groups and has a high storage stability at room temperature.
  • the free aldehyde groups in the curing of these resins in addition to the condensation and an addition reaction allows, which increases the reactivity.
  • the concentrated organic phase from Example 2 was neutralized after addition with 100 g of water with potassium carbonate solution and admixed with 8.46 g (0.067 mol) of melamine. After stirring for 1.5 h at 56 ° C., a highly viscous resin was obtained.
  • Example 8 Particleboard with a formaldehyde-free amino resin based on
  • the glue resin was prepared as described in Example 1:
  • Chips spruce chips (sieve fraction: 0.6> x ⁇ 5 mm)
  • Adhesive melamine-glyoxylic acid / glyoxylic acid ester resin
  • Adhesive content 12% (solid resin based on atro wood)
  • Curing accelerator 2.5% ammonium sulfate: (solid / solid resin)
  • Paraffin dispersion 1, 5% (solid based on atro wood)
  • Table 2 Formaldehyde release (bottle and test chamber method) of chipboard with a melamine-glyoxylic acid / glyoxylic acid ester resin

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

L'invention concerne un produit en matériau dérivé du bois ou un produit en matériau composite renforcé par des fibres naturelles, qui est constitué d'au moins un matériau lignocellulosique et/ou contenant de la cellulose qui est pourvu d'une colle puis est durci ou réticulé dans la forme souhaitée, la colle étant conçue comme résine aminique ou amidique sans formaldéhyde à base d'ester glyoxylique en tant que composant aldéhyde. L'invention concerne également l'utilisation d'une telle colle pour la production d'un produit en matériau dérivé du bois ou d'un produit en matériau composite renforcé par des fibres naturelles.
EP13814038.9A 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 et amidique sans formaldéhyde sur la base d'ester d'acide glyoxylique pour leur production Withdrawn EP3080204A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2013/003752 WO2015086034A1 (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 et amidique sans formaldéhyde sur la base d'ester d'acide glyoxylique pour leur production

Publications (1)

Publication Number Publication Date
EP3080204A1 true EP3080204A1 (fr) 2016-10-19

Family

ID=49883050

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13814038.9A Withdrawn EP3080204A1 (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 et amidique sans formaldéhyde sur la base d'ester d'acide glyoxylique pour leur production

Country Status (2)

Country Link
EP (1) EP3080204A1 (fr)
WO (1) WO2015086034A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3684573B8 (fr) * 2017-09-20 2025-08-13 Sestec Innovations Sp. Z O.O. Agent liant pour matériaux cellulosiques

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2102741A5 (fr) * 1970-08-19 1972-04-07 Commissariat Energie Atomique
US4906726A (en) * 1989-03-13 1990-03-06 Adhesive Coatings Co. Water-based coating compositions containing hydroxides and oxides of calcium, strontium and barium
DE3935879A1 (de) * 1989-10-27 1991-05-02 Basf Ag Verfahren zum alleingerben von bloessen und zum nachgerben von chromleder
DE19627531B4 (de) * 1996-07-09 2006-11-02 Construction Research & Technology Gmbh Wasserlösliche formaldehydfreie Polykondensationsprodukte auf Basis von Amino-s-triazinen
DE10322107B4 (de) * 2003-03-26 2005-09-08 Ami-Agrolinz Melamine International Gmbh Aminotriazin-Kondensationsprodukt, Verwendung eines Aminotriazin-Kondensationsproduktes und Verfahren zur Herstellung des Aminotriazin-Kondensationsproduktes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2015086034A1 *

Also Published As

Publication number Publication date
WO2015086034A1 (fr) 2015-06-18

Similar Documents

Publication Publication Date Title
AT389881B (de) Verfahren zur herstellung von span-oder faserplatten und verwendung eines fluessigen konzentrates zu ihrer herstellung
EP2346682B1 (fr) Corps moulés multicouches contenant de la lignocellulose, à faible émission de formaldéhyde
FI71085B (fi) Foerfarande foer framstaellning av en spaonskiva samt foer utfoerande av foerfarandet avsedd limloesning
WO2008068180A1 (fr) Mélange liant contenant des polymères hyperramifiés ou des résines aminoplastes contenant des polymères hyperramifiés
US20100279137A1 (en) Novel hybrid binder with natural compounds for low emission products
EP2614117B1 (fr) Corps moulés multicouches contenant de la lignocellulose, à faible émission de formaldéhyde
EP3684573B1 (fr) Agent liant pour matériaux cellulosiques
EP3080202A1 (fr) 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
EP3067402B1 (fr) Composition de liant et son utilisation dans des panneaux en dérivé de bois
EP0341569B1 (fr) Procédé de préparation émettant une quantité réduite de formaldéhyde, de matériaux composites
EP0699510B1 (fr) Procédé pour baisser le relâchement de formaldehyde de produits à base de lignocellulose
EP2510032A1 (fr) Colle stabilisée, hautement réactive, à base de polyisocyanate
DE102013014641B4 (de) Holzwerkstoffprodukt oder Naturfaser-Verbundwerkstoffprodukt und Verwendung eines formaldehydfreien Aminoplastharzes zu deren Herstellung
WO2015086034A1 (fr) Produit en matériau dérivé du bois ou produit en matériau composite renforcé par des fibres naturelles et utilisation d'une résine aminique et amidique sans formaldéhyde sur la base d'ester d'acide glyoxylique pour leur production
EP1266730B1 (fr) Procédé de fabrication des panneaux de fibres résistant à l'humidité
DE69810574T2 (de) Phenol-Melamin-Harnstoff-Formaldehyd-Copolymerharzmischungen, Verfahren zu ihrer Herstellung und Härtungskatalysatoren
EP3733368B1 (fr) Liant destiné à la fabrication de matériaux dérivé du bois
EP3733366B1 (fr) Liant destiné à la fabrication de matériaux dérivé du bois
WO2009080748A1 (fr) Dérivés de glyoxal en tant que liants et agents de réticulation
EP3511353A1 (fr) Composition de liant sans formaldéhyde pour plaques contenant de la lignocellulose et son procédé de fabrication
EP0740673B1 (fr) Liant pour la production de pieces moulees contenant de la lignocellulose
WO2008129056A1 (fr) Matériaux de bois à base de liants contenant des polyamines
EP0254040B1 (fr) Durcisseur pour aminoplastes, son utilisation dans l'encollage de surfaces de bois et procédé d'encollage de surfaces de bois
WO2024046878A2 (fr) Procédé de fabrication d'un panneau en matériau dérivé du bois pourvu d'un agent ignifuge
DE102004025442A1 (de) Aminoplastharz für die Herstellung von Bindemitteln

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: 20160311

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: BA ME

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: 20180703