WO2011042610A1 - Bioadhésif et planche de bois - Google Patents

Bioadhésif et planche de bois Download PDF

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Publication number
WO2011042610A1
WO2011042610A1 PCT/FI2010/050784 FI2010050784W WO2011042610A1 WO 2011042610 A1 WO2011042610 A1 WO 2011042610A1 FI 2010050784 W FI2010050784 W FI 2010050784W WO 2011042610 A1 WO2011042610 A1 WO 2011042610A1
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WO
WIPO (PCT)
Prior art keywords
bio
acid
adhesive
binder material
veneers
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PCT/FI2010/050784
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English (en)
Inventor
Samantha Kiljunen
Gatja Tiusanen
Esa Lappalainen
Sanna Lehtinen
Ulf Hotanen
Original Assignee
Upm-Kymmene Wood Oy
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Application filed by Upm-Kymmene Wood Oy filed Critical Upm-Kymmene Wood Oy
Publication of WO2011042610A1 publication Critical patent/WO2011042610A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
    • C09J105/02—Dextran; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J197/00—Adhesives based on lignin-containing materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J197/00—Adhesives based on lignin-containing materials
    • C09J197/005—Lignin

Definitions

  • the invention relates to a bio-adhesive as defined in the preamble of claim 1 and a wood board as defined in the preamble of claim 14.
  • EPO752027 discloses esterfication of lignin.
  • the lignin is utilised from kraft black liquor.
  • CN101157833 discloses a starch-based adhesive polymerised with polyisocyanate .
  • 2007149589 discloses an adhesive of tannin-furfuryl alcohol catalyzed by acid.
  • a cross-linking of chitosan and lignin with polycarboxylic acids is known. Also, known is the depolymerisation step to reduce the molecules molecular weight.
  • the objective of the invention is to disclose a new type of a bio-adhesive for gluing veneers of a wood board. Further, the objective of the invention is to disclose a new type of a wood board wherein the veneers are glued together with the bio- adhesive .
  • a bio-adhesive and a wood board according to the invention are characterized by what is presented in the claims.
  • the invention is based on a bio-adhesive for gluing veneers of a wood board.
  • the bio-adhesive is formed by reaction, selected from the group of esterification, condensation and their combinations, of natural based binder material containing active groups, typically hydroxyl or amine groups, with a reactant having suitable reactive groups capable of forming bonds with -OH and/or -NH 2 groups of the binder material.
  • the bio-adhesive is formed by esterification reaction of natural based binder material containing active -OH and/or -NH 2 groups with a reactant having reactive groups capable of forming bonds, e.g.
  • the bio-adhesive can also be formed by condensation reaction of natural based binder material containing active -OH and/or -NH 2 groups with a reactant having reactive groups capable of forming bonds, e.g. ether, amine or carbon-carbon bonds, with -OH and/or -NH 2 groups of the binder material.
  • a reactant having reactive groups capable of forming bonds, e.g. ether, amine or carbon-carbon bonds, with -OH and/or -NH 2 groups of the binder material.
  • the reactive groups of the reactant can form ester, ether, amine, amide and/or carbon-carbon bonds with -OH groups of the natural based binder material and the wood of the veneer.
  • the reactive groups of the reactant can form ester, ether, amine, amide and/or carbon-carbon bonds with -NH 2 groups of the natural based binder material and the wood of the veneer.
  • the binder material can be treated or modified, and/or different reactants can be added to the binder material.
  • the bio-adhesive consists mainly of a binder material and a reactant which is able to transform a liquid or soft binder to cured material.
  • the binder material is formed of natural based bio-material.
  • binder material can be also binder polymer.
  • the invention is specifically based on the adhesive system comprising a natural based binder material, e.g. tannin, lignin, cellulose, hemicellulose, chitosan or the like, possessing active hydroxyl or amine groups and a polycarboxylic acid or other material capable of forming bonds with the natural based material.
  • a natural based binder material e.g. tannin, lignin, cellulose, hemicellulose, chitosan or the like, possessing active hydroxyl or amine groups and a polycarboxylic acid or other material capable of forming bonds with the natural based material.
  • the invention also is based on the method of producing plywood or wood board using the said adhesive.
  • the esterification for the forming a binder material out of the biomass creates a bio- adhesive with unique properties.
  • a veneer refers to any veneer of a wood board.
  • the wood board can be a wood panel product, plywood product, composite product, beam, pressed panel product or the like, formed of a number of layers, preferably veneer layers, and principally of wood-based materials, in which the layers are laid one upon the other and glued together.
  • the veneer can be formed of any material, e.g. wood-based material, fiber material, composite material or the like.
  • the veneer refers to any layer of the wood board.
  • the veneer is a thin layer of the wood board. The thicknesses of the veneer layers can vary.
  • bio-adhesive it can be added additional reactants.
  • the reactant is selected from the group: polycarboxylic acids and anhydrides, e.g. propionic anhydride, butyric anhydride and acetic anhydride, amino acids, hydroxycarboxylic acids, isocyanates, e.g. di- and poly-isocyanates and thio-isocyanates, aldehydes with nitric acids, fatty acids, their derivates and their combinations.
  • polycarboxylic acids or polymeric carboxylic acids possess acid groups.
  • Anhydrides comprise acid groups with water already removed. Isocyanates form a nitrogen containing esters.
  • the reactant is a cross-linking agent and is able to combine chemically fragments of the binder material and the cross-linking agent forms cross-linking bonds with -OH and/or -N3 ⁇ 4 groups.
  • the cross- linking agent forms ester, ether or carbon-carbon cross-linking bonds.
  • the cross- linking agent has carboxyl groups and the carboxyl groups of the cross-linking agent being reactive with -OH and/or -N3 ⁇ 4 groups of the binder material and the wood of the veneers.
  • the carboxyl groups are reactive via a two step process, where there is, in step one a formation of a cyclic anhydride from the acid. This intermediate then reacts by ring opening and forming ester bonds with -OH and/or -NH 2 groups.
  • condensation reactions between the hydroxyl groups of the cross-linking agent and the binder material occur during the curing and/or cross- linking.
  • the cross- linking agent is polycarboxylic acid.
  • polycarboxylic acid has three or more reactive groups where at least two of them are carboxylic acids in order to cross-link by reaction with hydroxyl groups of the binder material.
  • the reactant is selected from the group: 1,2,3,4- butanetetracarboxylic acid, citric acid, maleic acid, succinic acid, itaconic acid, trans-aconitic acid, cis-aconitic acid, tricarballylic acid, talloid fatty acid and suberin fatty acid and their oligomers, glucosamine, polyethylene glycol, polypropylene glycol, polyglycols, proteins, sugars, polyvinyl alcohol, polyalkylene oxides, polyalkylene alcohols, oligomers or polymers of glycerol, glyoxal, furfuryl alcohol and aldehyde, pentaerythritol , phloroglucinol , eugenol, resorcinols, 1, 2-benzenedicarboxylic acid and anhydride, 1 , 3-benzenedicarboxylic acid, 1,4- benzenedicarboxylic acid, 1
  • reactants containing only two acid groups are able to assist in the polymer growth but unable to form side chains by grafting.
  • ester and amide bonds also ether and carbon-carbon bonds can be formed but for these alternative cross-linking agents and often a catalyst is required.
  • Alternative reactants can be aldehydes, e.g.
  • acetaldehyde and benzaldehyde with a nitric acid or furfuryl aldehydes, furfuryl alcohol, monolignols, p-coumaryl alcohol, coniferyl alcohol, sinapyl alcohol, dimethylamine ethanal, suberin fatty acids, ⁇ -caprolactam, glycerol, glyoxal, derivatives of lignin and products of pyrolysis and degradation/depolymerization of lignin.
  • the above materials can be used as reactants, cross-linking agents or polymerisation chemicals instead of or in combination with ester bond forming chemicals, such as polycarboxylic acids and anhydrides.
  • a reactant is also formed of bio-material .
  • the binder material is selected from the group: tannin, chitosan, starch, cellulose, lignin, hemicellulose, alginic acid, pectins, hyaluronic acid, chitin, glucosamine copolymers, polyglycols, proteins, sugars, e.g. sorbitol, xylitol, sucrose, glucose or fructose, polyvinyl alcohol, hydroxyl or amine containing polymers, polyalkylene oxides, polyalkylene alcohols, fatty acid oligomers and polymers, oligomers or polymers of glycerol, and their derivates and their combinations.
  • any binder material containing hydroxyl or amine groups capable of reacting with the reactant to form an ester bond are suitable.
  • the binder material is selected from lignin, tannin and their combinations.
  • polyethylene glycol, polyglycols, polyvinyl alcohol, polyalkylene oxides, polyalkylene alcohols and/or oligomers or polymers of glycerol can be used as reactants to modify the binder material .
  • Chitosan is a naturally occurring polysaccharide and is cationic in nature composed of mainly (1,4) linked 2-amino-2-deoxy- p-D-glucan and soluble in acidic solutions but insoluble in alkaline solutions. Both the amino groups in the chitosan molecule are pH sensitive. Chitosan is a derivative from shells and possesses a primary amine group on its polysaccharide ring which may be grafted onto wood by incorporation of a bi-functional cross-linking agent.
  • Cellulose is also a polysaccharide and will therefore form cross-links in similar manner as chitosan .
  • bio-adhesive is impregnated into the wood cell wall of the veneer so that the reactive groups or the carboxyl groups of the reactant form, via a two step process, ester bonds with -OH groups of the wood and the binder material in the wood cell wall for improving dimensional stability of the wood board.
  • the binder material also possesses an amine group, e.g. chitosan
  • the binder material is depolymerized for reducing the molecular weight of the material to monomers and oligomers and at the same time activating or increasing the reactivity of the binder material prior to the reaction, e.g. polymerization, cross-linking, esterification or condensation or their combination.
  • the formed monomers and oligomers are polymerized again.
  • the activating of the binder material can occur prior to or during the polymerization of the oligomers.
  • the binder material is too big molecularly to create a bio-adhesive that both penetrates into the wood and also creates the glue-line; therefore the binder material has to be depolymerized.
  • the binder material can be impregnated to wood without further processing but larger molecules need to be depolymerized first. When the binder material is reduced in molecular weight they are more soluble in water and they have improved biological activities.
  • the binder material is depolymerized by oxidation.
  • the oxidation is carried out with hydrogen peroxide, hydrogen peroxide and sodium nitrite (NaN0 2 ) , hydrogen peroxide and sodium nitrate (NaN0 3 ) or other hydrogen peroxide combinations.
  • the depolymerization method is selected from the group; acid hydrolysis, alkaline hydrolysis, enzymatic treatment and physical methods. Physical methods can include radiation and pyrolysis.
  • the depolymerization techniques can be combined with the isolation techniques.
  • the binder material is isolated prior to the reaction, e.g. esterification or condensation or their combination. In one embodiment the binder material is isolated by precipitation. In one embodiment the binder material is isolated by precipitation and ultrafiltration in the case of lignin. The invention is not limited to these techniques only.
  • Chitosan is the N-deactylated form of chitin and is derived from chitin by deacetylation .
  • Lignin can be isolated from black liquor as described below. However, the final isolated product may still contain hemicellulose and other materials.
  • Black liquor from the Kraft pulping process is good source for lignin.
  • Black liquor is an alkaline aqueous solution of lignin residues, hemicellulose, and inorganic chemicals used in the process. In the pulping process where the black liquor components originate both from softwood and hardwood different wood species can be used in various proportions.
  • the black liquor can be taken from several points of the process cycle. Dry content of black liquor at evaporation plant used for lignin precipitation is normally 25 - 30 wt% and the weak black liquor approximately 15 wt% .
  • Lignin can be isolated from black liquor by precipitation. Precipitation of lignin is a generally well-known technique. Lignin starts usually to precipitate when pH declines under 11 - 12.
  • Precipitation of lignin can be performed using for example sodium bisulphite, sulphuric acid or CC>2-gas.
  • Lignin fractions with different properties are achieved by precipitating to different pH levels or to several sequential pH levels. These lignin fractions differ from each other by molecular weight distribution, e.g. Mw and Mn, polydispersity, hemicellulose and extractive contents.
  • Mw and Mn molecular weight distribution
  • the molar mass of the lignin precipitated in the high pH is higher that the lignin precipitated at the low pH.
  • the molecular weight distribution of the lignin fraction precipitated at a low pH level is wider than at a high pH level. Therefore each of the separated lignin fractions has properties that make it optimal for specific gluing applications.
  • the purity of the lignin fractions vary according to the number and efficiency of the acidic washing stages and filtration steps used after precipitation. An acidic washing step purifies the lignin from in
  • Ultrafiltration using membrane or several membranes with different cut-off values is effective technique to isolate and fractionate lignin straight from black liquor or to fractionate already precipitated lignin.
  • the membrane material, filtration temperature and pressure, and diafiltration steps are critical factors to achieve satisfactory flow level and concentration during the ultrafiltration.
  • the most critical factor in obtaining the lignin fractions with optimal molar mass and molecular weight distribution in perspective of adhesive applications is the cut-off values of used membranes.
  • the molar mass of lignin fractionated with ultrafiltration is also connected to activity and reactivity of lignin.
  • the lignin fraction with small molar mass is more reactive than the lignin fraction with high molar mass and with a more polymeric structure. Both of these fractions have its purpose in the bio-adhesive applications.
  • the lignin isolation process is selected and performed according to properties wanted for the lignin fraction or fractions.
  • the combination of the both techniques described above can also be used to achieve the optimal lignin fraction or fractions for further modification and bio-adhesive applications.
  • the de-polymerization process can remove the brown colour. This is advantageous from the point of view of using the material as an adhesive.
  • the binder material is reacted and/or polymerized/cross-linked with the reactant with or without a catalyst.
  • the reactant contains a catalyst or catalysts.
  • the bio-adhesive contains a catalyst or catalysts.
  • the bio-adhesive is typically containing a binder material, a reactant and catalyst or catalysts which aids in activating, modifying or curing of the binder material.
  • Catalysts can be used to treat binder material chemically, i.e. to manipulate it by polymerization, depolymerization, activation, modification etc.
  • the catalyst is selected from the group: sodium hypophosphite monohydrate (SHP) , sodium hypophosphite (NaH 2 PC>2) , sodium phosphate (NaH 2 P0 4 ) , sodium phosphinate monohydrate (NaH 2 PC>2 H 2 0) , titanium dioxide, triethylamine , acid catalysts, e.g. citric acid, and other neutral catalysts and their combinations.
  • the amount of the catalyst is 2 - 5 %.
  • the catalysts used are heat sensitive and therefore for example cross-linking will not occur until a certain temperature is reached. Therefore at room temperature there will not be any cross-linking so that diffusion into the cell wall of the chemicals is not hindered.
  • the cross-linking occurs at temperatures 120 - 130 °C, preferably time is from 12 minutes to 12 hours, which are typical temperatures and times used during the gluing process in the production of wood board.
  • temperatures 120 - 130 °C preferably time is from 12 minutes to 12 hours, which are typical temperatures and times used during the gluing process in the production of wood board.
  • the cross-linking is carried out in connection with wood board manufacturing. In one embodiment the cross-linking is carried out after the wood board manufacturing, e.g. at the end of the production line. In one embodiment the curing of the adhesive and the cross-linking in the cell wall is performed by radiation treatment, e.g. by E-beam, microwave or X-ray treatment.
  • the bio- adhesive contains at least one additive selected from the group: extenders, fillers, property modification agents, reactivity increasing agents, viscosity enhancers, surfactants, other additives or their combinations.
  • the bio-adhesive contains dyes, pigments, biocides, fire retardants and/or fluorescent particles to create functional and pigmented adhesives.
  • the bio-adhesive contains extenders.
  • the bio- adhesive contains at least one or more of the following: wheat flour, rye flour, barley flour, oatmeal, wood flour, such as hard wood, soft wood and mixtures of them, different types of native and modified starches based on rice, potato, maize and tapioca, proteins, chitosan, such as feather flour, shrimp flour, clamshell flour and bone meal, casein, gelatine, carbohydrates and their combinations.
  • the bio-adhesive contains at least one or more of the following additives and/or catalysts: different types of thickening agents, ethanol, methanol and other alcohols C 1 -C5, a 2 C0 3 , K 2 C0 3 , CaCC>3 , NaOH, KOH, NH 4 OH, amines, amides, anilines, melamine, urea, thiourea, acetone, formic acid, amino acids, silanes, Na 2 S0 4 , Na 2 S 2 0 7 , NH 4 C1 and other ammonium salts, sulphate-ammonium ions, and carbonate ions, and their derivates and their combinations.
  • the above mentioned catalysts can also act like additives and tackifiers .
  • the bio-adhesive contains phenol formaldehyde resin partially substituted with bio-phenolic derivates, e.g. from bio-oil, or the bioresin containing aliphatic or aromatic polymers as the major component. Resin curing is possible by heat, E-beam and X-ray treatment for deeper penetration.
  • the binder material is dissolved in a polar solvent prior to the reaction, e.g. esterification, condensation or their combination .
  • the binder material is polymerized with cross-linking agents and catalyst or with catalyst to the reactive form.
  • there are alkaline process conditions during the reaction selected from condensation, esterification and their combination.
  • the bio-adhesive contains 10 - 80 wt% binder material, 5 - 50 wt% solvent and 5 - 50 wt% other chemicals like reactants and additives.
  • the invention is based on a wood board which is formed from a number of veneers in such manner that the veneers are laid one above the other and combined by means of glue.
  • the veneers are glued by the bio-adhesive which is formed by reaction, selected from the group of esterification, condensation and their combinations, of natural based binder material containing active groups with a reactant having reactive groups capable of forming ester, ether, amine, amide or carbon-carbon bonds with -OH and/or - ⁇ 3 ⁇ 4 groups of the binder material and the veneers.
  • the bio- adhesive is applied between the veneers in a liquid form, a film form or a solid form and the veneers are joined together by means of pressing and heat.
  • the bio- adhesive is applied between the veneers and the veneers are joined together by a cold press at room temperature .
  • the veneers of the wood board are impregnated with the bio- adhesive by a hot-cold thermal process.
  • Each veneer can be impregnated wholly or partly.
  • the veneer can be pre- treated prior to the manufacturing wood board.
  • the veneer can be treated by drying, heat-treatment, rewetting, corona treatment, UV/IR treatment, microwave treatment and/or by means of coupling agent or primer or by their combinations.
  • the veneer is in green state.
  • the whole wood board can be treated with the chemicals to create a dimensionally stable wood board.
  • the bio-adhesive can be dosed to the veneers by the following methods: roller application, stripe application, spray application, foam extrusion, curtain application, dipping or their combination.
  • Spreading amounts of the bio-adhesive is from 80 g/m 2 to 270 g/m 2 depending on process parameters for example the application method, wood species and thickness and quality of the veneers and structure of the wood panel.
  • the adhesive can be applied in the form of powder, film, dispersion, colloid, liquid., aerosol or foam.
  • the adhesive film can be formed by extrusion of the binder material and cross- linking agent. The film is then applied to the veneers and the adhesion is initiated by heat with or without a catalyst.
  • the cross-linking is carried out in connection with the wood board manufacturing, e.g. in a gluing of the veneers and/or in a hot- pressing.
  • the hot-pressing can be carried out at temperatures 120 - 170 °C for curing the glue and cross-linking in cell wall.
  • Curing of the bio-adhesive can be done by cold press, hot press, IR or UV light depending on application method, the form of adhesive, the formulation of adhesive and the structure of the panel. Curing process can also include some or all of curing methods. Curing time can be from 3 min to several hours depending on process parameters and the structure of the wood panel. Typically curing is done by hot pressing at 100 - 170 °C and in cold press at room temperature. Curing time depends on the thickness of the panel, typically 5 - 15 min by hot press and several hours by cold press.
  • the manufacturing wood board can be carried out using apparatuses known per se. Laying the veneers one upon the other, joining them together by glue and other typical steps can be performed in any manner known per se in the art.
  • the wood board according to the invention may be used in different embodiments.
  • the bio-adhesive of the invention is easy to prepare. Thanks to the invention, it is possible to provide many different veneer and wood board modifications. This invention produces the wood board with dimensional stability.
  • the bio-adhesive is nontoxic and therefore creates a non toxic glue-line in a plywood or a wood board production.
  • bio-adhesive and the wood board in accordance with the invention are suitable for various applications .
  • Fig. 1 shows a mechanism of a formation of ester bonds in polymerization and cross-linking
  • Fig. 2 shows a mechanism of a succinylation or maleation of chitosan
  • Fig. 3 shows a mechanism of a condensation of polyglycols .
  • binder material was selected and isolated.
  • the binder material was lignin.
  • the binder material was de-polymerized by oxidation with H2O2.
  • a cross-linking agent and a catalyst were selected.
  • the cross-linking agent was polycarboxylic acid and the catalyst was SHP (sodium hypophosphite monohydrate) . Said adhesive components were combined together.
  • the formed bio-adhesive was applied onto the veneers and the veneers were joined together by the bio-adhesive for forming a plywood.
  • the veneers were pressed together by a hot-pressing at temperature between 120 - 170 °C or by a cold-pressing at room temperature.
  • the bio-adhesive was cured by cross-linking for forming ester bonds.
  • the bio-adhesive compositions contained 10 - 80 wt% lignin, 5 - 50 wt% solvent and 5 - 50 wt% polycarboxylic acid and catalyst.
  • bio-adhesive compositions of the invention are suitable glues to be used for gluing the veneers together and for the manufacturing of plywood.
  • bio-binder according to the invention was formed by the ester polymerization of chitosan .
  • the bio-binder was prepared in a 250 ml flask reactor with mechanical stirring. 20 g of citric acid was dissolved in 150 g of water. 20 g of chitosan or chitosan oligosaccharide was added with stirring. The temperature was increased from 20 to 100 °C in 30 min. The mixture was refluxed for 60 minutes. Excess water was evaporated in rotavapor. The yield was a water solution and a gel like polymeric material.
  • the glue mixture was made by blending polymeric material (65 parts per wt) , water (20 parts per wt) and a starch powder, e.g. potato starch Emsol, (15 parts per wt) .
  • Birch plywood panels with light brown glue seams were produced by using trivial industrial production parameters.
  • the prepress tack was good.
  • the wood failure value of 80 % was measured under dry conditions.
  • bio-binder according to the invention was formed by the ester polymerization of polyglycol .
  • the bio-binder was prepared in a 250 ml flask reactor with magnetic stirring. 15 g of citric acid was added and dissolved in 150 g of water. 10 g of polyglykol (PEG 200) was added. The mixture was refluxed for 90 minutes. The temperature was cooled down and excess water was removed by rotavapor. The yield was a viscous colorless sticky liquid which can be used as a cold press adhesive material as such or by blending a similar glue mixture than in Example 2.
  • bio-binder according to the invention was formed by lignin activation.
  • the bio-binder was prepared in a 250 ml flask reactor with magnetic stirring. 10 g of Kraft lignin was dissolved in 100 g of water solution. The slurry solution was adjusted to acidic by sulphuric acid and was stirred at room temperature for 15 min. 0.2 g of iron sulphate (FeS0 4 ) and a surfactant were added to decrease the surface tension if needed. The mixture was stirred at RT for 15 min. 3 ml of hydrogen peroxide (H 2 C>2 , 30 % solution) was added at room temperature in 200 microliters portions and the mixture was stirred for 5 minutes.
  • H 2 C>2 , 30 % solution hydrogen peroxide
  • bio-binder according to the invention was formed by lignin activation.
  • the bio-binder was prepared in a 250 ml flask reactor with magnetic stirring. 10 g of Kraft lignin was dissolved in 100 g of water solution. The slurry solution was adjusted to medium alkalic by sodium hydroxide solution and was stirred at room temperature for 15 min. 2 ml of hydrogen peroxide (H 2 0 2 , 30 % solution) was added at room temperature in 200 microliters portions and the mixture was stirred for 5 minutes. 1.0 g of polyglycol (1,1,1- tris (hydroxymethyl) propane, THMP) was added and the temperature was raised to 100 °C with stirring. Then the temperature was cooled down after 1 h cooking.
  • H 2 0 2 , 30 % solution hydrogen peroxide
  • the glue mixture was made by blending 80 parts per wt of the binder solution and 20 parts per wt of a suitable starch extender. Plywood gluing with the glue mix indicated a sufficient penetration into the veneer and a satisfactory wood failure.
  • a bio-adhesive and a wood board according to the invention are suitable in its different embodiments for different types of applications.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Veneer Processing And Manufacture Of Plywood (AREA)

Abstract

L'invention concerne un bioadhésif obtenu par une réaction sélectionnée dans le groupe formé par l'estérification, la condensation et des combinaisons de celles-ci, d'un liant naturel contenant des groupes actifs avec un réactif contenant des groupes réactifs aptes à former des liaisons avec les groupes -OH et/ou les groupes -NH2 du liant. La présente invention concerne également une planche de bois dans laquelle les placages sont collés par ledit bioadhésif.
PCT/FI2010/050784 2009-10-08 2010-10-08 Bioadhésif et planche de bois WO2011042610A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20096036A FI20096036A0 (fi) 2009-10-08 2009-10-08 Bioliima ja puulevy
FI20096036 2009-10-08

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WO2011042610A1 true WO2011042610A1 (fr) 2011-04-14

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ITMI20111897A1 (it) * 2011-10-19 2013-04-20 Milano Politecnico Resina legante per nontessuti, in particolare per la produzione di supporti per membrane bituminose, procedura per la sua preparazione e nontessuto ottenuto con l'uso della resina suddetta.
CN103272570A (zh) * 2013-06-14 2013-09-04 湖北省潜江市华山水产食品有限公司 一种半纤维素/壳聚糖/纳米TiO2杂化材料的制备方法及应用
WO2013163245A1 (fr) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Produits composites faits avec des compositions de liant comprenant des tanins et des composés aldéhydiques multifonctionnels
WO2013163242A1 (fr) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Produits composites constitués de compositions liantes catalysées à l'acide de lewis comprenant des acides tanniques et des aldéhydes multifonctions
WO2014022666A1 (fr) * 2012-08-01 2014-02-06 Cornell University Compositions de résine réticulée d'amidon natif et cireux et procédés pour leur fabrication
GB2524462A (en) * 2014-01-08 2015-09-30 Xiaobin Zhao Algal Bio-adhesives: Compositions, Process for Manufacturing, Formulations and Uses
CN107158453A (zh) * 2017-06-02 2017-09-15 武汉纺织大学 一种透明质酸组织粘合剂的制备方法
CN107629728A (zh) * 2017-10-17 2018-01-26 高昕文 一种标签胶专用复合淀粉胶黏剂的制备方法
US10428254B2 (en) 2014-01-08 2019-10-01 Cambond Limited Bio-adhesives
CN110452635A (zh) * 2019-08-28 2019-11-15 贵州大学 一种环保型单宁-壳聚糖基胶粘剂
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EP3633005A1 (fr) * 2018-10-05 2020-04-08 Aarhus Universitet Composition adhésive aqueuse pour matériaux lignocellulosiques tels que du bois et procédé de production
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WO2021197624A1 (fr) * 2020-04-03 2021-10-07 Rockwool International A/S Liant à l'état solide
CN113652047A (zh) * 2021-09-23 2021-11-16 浙江科技学院 木质素纳米颗粒/聚乙烯醇/壳聚糖三元复合材料及其制备方法和应用
CN113717656A (zh) * 2013-12-20 2021-11-30 新西兰森林研究机构有限公司 黏着剂
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CN114347193A (zh) * 2022-01-22 2022-04-15 漳州市桥头木业有限公司 一种胶合板及其生产工艺
EP3169741B1 (fr) 2014-07-17 2022-11-02 Knauf Insulation SPRL Compositions liant améliorées et leurs utilisations
CN115449329A (zh) * 2022-09-22 2022-12-09 广西科学院 一种木质素改性胶黏剂的方法
CN115466590A (zh) * 2022-09-22 2022-12-13 广西科学院 一种利用微波-酸解淀粉改性异氰酸酯胶的方法
WO2023070800A1 (fr) * 2021-10-28 2023-05-04 周霞 Procédé de production d'un adhésif de bois monoester d'anhydride cyclique d'origine biologique à l'aide d'une matière première en poudre d'origine biologique
CN116218416A (zh) * 2023-02-20 2023-06-06 西南林业大学 一种改性壳聚糖基木材胶黏剂及其制备方法和应用
CN116289312A (zh) * 2023-04-26 2023-06-23 上海昶法新材料有限公司 一种生物基表面施胶剂及其制备方法
US11690332B2 (en) 2020-04-03 2023-07-04 Rockwool A/S Method of growing plants
RU2802891C2 (ru) * 2018-10-05 2023-09-05 Роквул Интернэшнл А/С Водная клеевая композиция для лигноцеллюлозных материалов, таких как древесина, и способ ее получения
DE102022121145A1 (de) 2022-08-22 2024-02-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Dispersion, Verfahren zu ihrer Herstellung und Verwendung als Klebstoff für Holzwerkstoffe
CN117801750A (zh) * 2023-05-22 2024-04-02 西南林业大学 一种无甲醛合成树脂胶粘剂的制备和使用方法

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RU2609164C2 (ru) * 2011-10-19 2017-01-30 Политекс С.А.С. Ди Фройденберг Политекс С.Р.Л. Связующая смола для нетканых материалов, в частности для изготовления основ для битуминозных мембран, способ ее приготовления и нетканый материал, полученный с использованием упомянутой смолы
WO2013057086A1 (fr) * 2011-10-19 2013-04-25 Politex S.A.S. Di Freudenberg Politex S.R.L. Résine liante pour non-tissés, en particulier pour la fabrication de supports pour membranes bitumineuses, son procédé de préparation et non-tissé ainsi obtenu
ITMI20111897A1 (it) * 2011-10-19 2013-04-20 Milano Politecnico Resina legante per nontessuti, in particolare per la produzione di supporti per membrane bituminose, procedura per la sua preparazione e nontessuto ottenuto con l'uso della resina suddetta.
EP2768865B1 (fr) 2011-10-19 2018-11-28 POLITEX s.a.s. di FREUDENBERG POLITEX s.r.l. Résine de liaison pour tissus non tissés en particulier pour la preparation des membranes bitumeuses, procédés de fabrication et tissus non tissés contenant ces résines.
WO2013163245A1 (fr) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Produits composites faits avec des compositions de liant comprenant des tanins et des composés aldéhydiques multifonctionnels
WO2013163242A1 (fr) * 2012-04-27 2013-10-31 Georgia-Pacific Chemicals Llc Produits composites constitués de compositions liantes catalysées à l'acide de lewis comprenant des acides tanniques et des aldéhydes multifonctions
US8674019B2 (en) 2012-04-27 2014-03-18 Georgia-Pacific Chemicals Llc Composite products made with lewis acid catalyzed binder compositions that include tannins and multifunctional aldehydes
CN104334326A (zh) * 2012-04-27 2015-02-04 佐治亚-太平洋化工品有限公司 采用含单宁和多官能醛的路易斯酸催化的粘合剂组合物制造的复合产品
US9790350B2 (en) 2012-08-01 2017-10-17 Cornell University Crosslinked native and waxy starch resin compositions and processes for their manufacture
US20150203667A1 (en) * 2012-08-01 2015-07-23 Cornell University Crosslinked native and waxy starch resin compositions and processes for their manufacture
WO2014022666A1 (fr) * 2012-08-01 2014-02-06 Cornell University Compositions de résine réticulée d'amidon natif et cireux et procédés pour leur fabrication
CN103272570A (zh) * 2013-06-14 2013-09-04 湖北省潜江市华山水产食品有限公司 一种半纤维素/壳聚糖/纳米TiO2杂化材料的制备方法及应用
CN113717656A (zh) * 2013-12-20 2021-11-30 新西兰森林研究机构有限公司 黏着剂
CN113831858A (zh) * 2013-12-20 2021-12-24 新西兰森林研究机构有限公司 黏着剂
US10428254B2 (en) 2014-01-08 2019-10-01 Cambond Limited Bio-adhesives
GB2524462A (en) * 2014-01-08 2015-09-30 Xiaobin Zhao Algal Bio-adhesives: Compositions, Process for Manufacturing, Formulations and Uses
EP3169741B1 (fr) 2014-07-17 2022-11-02 Knauf Insulation SPRL Compositions liant améliorées et leurs utilisations
CN107158453A (zh) * 2017-06-02 2017-09-15 武汉纺织大学 一种透明质酸组织粘合剂的制备方法
CN107629728A (zh) * 2017-10-17 2018-01-26 高昕文 一种标签胶专用复合淀粉胶黏剂的制备方法
EP4438683A3 (fr) * 2018-10-05 2024-10-16 Rockwool A/S Composition adhésive aqueuse pour matériaux lignocellulosiques tels que le bois et procédé de production
RU2802891C2 (ru) * 2018-10-05 2023-09-05 Роквул Интернэшнл А/С Водная клеевая композиция для лигноцеллюлозных материалов, таких как древесина, и способ ее получения
EP4183850A1 (fr) * 2018-10-05 2023-05-24 Rockwool A/S Composition adhésive aqueuse pour matériaux lignocellulosiques tels que le bois et procédé de production
WO2020069984A1 (fr) * 2018-10-05 2020-04-09 Aarhus Universitet Composition adhésive aqueuse pour matériaux lignocellulosiques tels que le bois et procédé de production
EP3633005A1 (fr) * 2018-10-05 2020-04-08 Aarhus Universitet Composition adhésive aqueuse pour matériaux lignocellulosiques tels que du bois et procédé de production
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CN110964478B (zh) * 2019-12-02 2021-05-07 北京林业大学 一种超支化聚酯和硼酸盐改性的高强度防腐大豆蛋白胶黏剂及其制备方法
CN110964478A (zh) * 2019-12-02 2020-04-07 北京林业大学 一种超支化聚酯和硼酸盐改性的高强度防腐大豆蛋白胶黏剂及其制备方法
US11690332B2 (en) 2020-04-03 2023-07-04 Rockwool A/S Method of growing plants
WO2021197624A1 (fr) * 2020-04-03 2021-10-07 Rockwool International A/S Liant à l'état solide
CN111726898A (zh) * 2020-05-14 2020-09-29 锦州大业炭素制品有限公司 一种生产真空感应炉所用大型石墨发热体多块材料粘接方法
CN112521871B (zh) * 2020-12-29 2023-02-17 太尔胶粘剂(广东)有限公司 一种保温棉用水性胶粘剂及其制备方法
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CN113652047B (zh) * 2021-09-23 2023-02-24 浙江科技学院 木质素纳米颗粒/聚乙烯醇/壳聚糖三元复合材料及其制备方法和应用
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WO2023070800A1 (fr) * 2021-10-28 2023-05-04 周霞 Procédé de production d'un adhésif de bois monoester d'anhydride cyclique d'origine biologique à l'aide d'une matière première en poudre d'origine biologique
CN114347193A (zh) * 2022-01-22 2022-04-15 漳州市桥头木业有限公司 一种胶合板及其生产工艺
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CN116289312A (zh) * 2023-04-26 2023-06-23 上海昶法新材料有限公司 一种生物基表面施胶剂及其制备方法
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