US20240043616A1 - Binder composition comprising amino acid polymer(s) as well as carbohydrates for composite articles - Google Patents

Binder composition comprising amino acid polymer(s) as well as carbohydrates for composite articles Download PDF

Info

Publication number
US20240043616A1
US20240043616A1 US18/269,022 US202118269022A US2024043616A1 US 20240043616 A1 US20240043616 A1 US 20240043616A1 US 202118269022 A US202118269022 A US 202118269022A US 2024043616 A1 US2024043616 A1 US 2024043616A1
Authority
US
United States
Prior art keywords
component
binder
amino acid
acid polymer
mol
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.)
Pending
Application number
US18/269,022
Other languages
English (en)
Inventor
Gereon Antonius SOMMER
Stephan Weinkoetz
David Tuerp
Ralph LUNKWITZ, IV
Claus Fueger
Guenter Scherr
Jessica Nadine Hamann
Joequim Henrique TELES
Jean-Pierre Berkan Lindner
Dagmar Pascale Kunsmann-Keitel
Thomas Servay
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of US20240043616A1 publication Critical patent/US20240043616A1/en
Assigned to BASF SE reassignment BASF SE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUNSMANN-KEITEL, DAGMAR PASCALE, SCHERR, GUENTER, SERVAY, THOMAS, LUNKWITZ, RALPH, TUERP, David, TELES, JOAQUIM HENRIQUE, WEINKOETZ, STEPHAN, FUEGER, CLAUS, HAMANN, Jessica Nadine, LINDNER, Jean-Pierre Berkan, SOMMER, Gereon Antonius
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • 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
    • C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/10—Alpha-amino-carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/04—Polyamides derived from alpha-amino carboxylic acids
    • 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
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/04—Polyamides derived from alpha-amino carboxylic acids
    • 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
    • C09J197/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the present invention relates to a binder composition
  • a binder composition comprising
  • the present invention relates to a composition kit for the preparation of lignocellulose-based composite articles comprising the binder composition, wherein component A and component B are stored separately, and to lignocellulose-based composite articles comprising a plurality of lignocellulosic pieces and the reacted binder composition. Moreover, the present invention relates to processes of forming lignocellulose-based composite articles comprising the reacted binder composition as well as to the reacted binder composition.
  • Lignocellulose-based composite articles such as oriented strand board (OSB), oriented strand lumber, chipboard, also called particleboard, scrimber, agrifiber board, flakeboard, and fiberboard, e.g. medium density fiberboard (MDF), are generally produced by blending or spraying lignocellulosic pieces with a binder composition, e.g. a resin, while the lignocellulosic pieces are tumbled or agitated in a blender or similar apparatus.
  • OSB oriented strand board
  • chipboard also called particleboard, scrimber, agrifiber board, flakeboard, and fiberboard, e.g. medium density fiberboard (MDF)
  • MDF medium density fiberboard
  • the lignocellulosic pieces After blending sufficiently to form a binder composition-lignocellulose mixture, the lignocellulosic pieces, which are now coated with the binder composition, are formed into a product, in particular a loose mat, which is subsequently compressed between heated platens or plates to set the binder composition and to bond these lignocellulosic pieces together in densified form, such as in a board, panel, or other shape.
  • Conventional processes for compressing the loose mat are generally carried out by hot pressing along with heat transfer from hot surfaces (usually between 180° C. and 240° C.) to the mat, in the presence of varying amounts of steam, either purposefully injected into the loose mat or generated by liberation of entrained moisture from the lignocellulosic pieces or the binder composition in the loose mat.
  • Binder compositions that have been used for making such lignocellulose-based composite articles include phenol formaldehyde (PF) resins, urea formaldehyde (UF) resins, melamine urea formaldehyde (MUF) resins and isocyanates (M. Dunky, P. Niemz, Holzwerkstoffe und Leime, Springer Verlag Heidelberg, 2002, pages 249 to 367). From an environmental perspective there is the need to provide binder compositions which are formaldehyde-free and isocyanate-free or have at least low formaldehyde-emissions and still have excellent properties.
  • Carbohydrate-based binder compositions are mainly derived from renewable resources. They require press conditions which are quite different from the traditional phenol-formaldehyde binder composition, urea formaldehyde or isocyanate resins. Carbohydrate polyamine binder compositions can substitute said traditional binder compositions. However, carbohydrate polyamine binder composition solutions are associated with a variety of disadvantages such as large binder composition amounts, long press times and poor structural properties of the resulting boards.
  • WO2015177114 describes a binder composition for wood boards comprising a reaction product of lysine and a carbohydrate component, but the obtained wood boards have low internal bond strengths even at long press times.
  • WO2016009062 describes a binder composition comprising a carbohydrate and a polyamine and a matrix polymer.
  • binder compositions for chipboards require long press times and result in chipboards with a low internal bond strength and an insufficient swelling value in water.
  • EP3359360 A1 describes a binder composition in the surface layer comprising a nitrogen source and reducing sugars, wherein the weight amount of reducing sugars is equal or higher than the weight amount of the nitrogen source to improve surface properties.
  • the internal bond strength and surface properties are insufficient.
  • a binder composition preferably a wood binder composition, comprising
  • Component B1 selected from the group consisting of pentoses, hexoses, disaccharides of pentoses and/or hexoses and mixtures thereof may comprise one, two or more different pentoses, one, two or more different hexoses and/or one, two or more different disaccharides thereof.
  • the binder composition according to the present invention may comprise at least 60 wt.-%, more preferably at least 65 wt.-%, most preferably at least 70 wt.-%, amino acid polymer(s) A1 based on the total weight of the amino acid polymer(s) A1 and component B1 selected from the group consisting of pentoses, hexoses, disaccharides of pentoses and/or hexoses and mixtures thereof.
  • the binder composition may comprise 60 to 90 wt.-%, preferably 70 to 85 wt.-% amino acid polymer(s) A1 based on the total weight of the amino acid polymer(s) A1 and the component B1 selected from the group consisting of pentoses, hexoses, disaccharides of pentoses and/or hexoses and mixtures thereof.
  • the pentoses and/or hexoses and/or disaccharides of pentoses and/or hexoses may be glucose, fructose, xylose, sucrose and/or mixtures thereof, preferably glucose and/or fructose.
  • component B1 is a mixture comprising
  • component B1 is a mixture consisting of
  • Binder composition means component A and component B and optionally any further component prior to reacting.
  • the binder composition may be cured by heating, which may be carried out by contact heating and/or heat transfer from hot air and/or steam and/or dielectric heating (e.g microwave heating, or high frequency heating) to obtain the reacted binder composition.
  • the binder composition may be cured by applying heat and optionally pressure at the same time or subsequently to obtain the reacted binder composition.
  • the reacted binder composition means the cured binder composition.
  • the reacted binder composition is obtainable or may be obtained by reacting the binder components A and B.
  • Reacting or reacted means that amino acid polymer(s) A1 react(s) with the component B1 selected from the group consisting of pentoses, hexoses, disaccharides of pentoses and/or hexoses and mixtures thereof.
  • further components may also react with amino acid polymer(s) A1 and/or the component B1 selected from the group consisting of pentoses, hexoses, disaccharides of pentoses and/or hexoses and mixtures thereof.
  • the reaction may lead to crosslinked polymers.
  • amino acid polymer(s) A1 react(s) with component B1 selected from the group consisting of pentoses, hexoses, disaccharides of pentoses and/or hexoses and mixtures thereof and
  • Component B2 is further explained below.
  • Component A may comprise 20 to 80 wt.-%, preferably 30 to 70 wt.-%, preferably 40 to 65 wt.-% of the amino acid polymer(s) A1 based on the total weight of component A.
  • the components A and B are not provided as a mixture, and this allows easy transportation and long storage for several months. Therefore, according to one aspect of the present invention, the binder composition is provided as a kit, wherein Component A and Component B are stored separately.
  • Components A and B may be brought into contact either directly on the lignocellulosic pieces, preferably made from wood, or by mixing them before the application to the lignocellulosic pieces, preferably made from wood.
  • Component A and/or B may be provided in the form of an aqueous solution or dispersion.
  • Wt.-% means weight-%.
  • Component A is a compound having Component A:
  • Amino acid polymer(s) A1 comprise(s) at least one or consists of at least one poly(amino acid) which is a polymerization product of amino acids and optionally other monomers selected from the group consisting of
  • amine and/or amino group as used according to the present invention does not include amide-groups such as e.g. R—CO—NH 2 and/or R—CO—NH—R.
  • Amino acid polymer(s) A1 may comprise a polymerization product of one or two or more different amino acids.
  • the term “polymer” is used for such polymerization product, even if the polymerization reaction is not run to completion.
  • These monomers may be present due to incomplete conversion of the monomers during the polymerization reaction and/or due to an addition of additional monomers after finishing the polymerization reaction, wherein the additional monomers are selected from the group of the monomers, which have been used for the polymerization reaction. Preferably, no monomers are added after finishing the polymerization reaction.
  • Amino acid polymer A1 may also include other monomers than amino acids, like e.g. di- and/or tricarboxylic acids and/or amines comprising at least two amino groups, wherein the amines and/or the di- and tricarboxylic acids are no amino acids.
  • other monomers than amino acids like e.g. di- and/or tricarboxylic acids and/or amines comprising at least two amino groups, wherein the amines and/or the di- and tricarboxylic acids are no amino acids.
  • the amino acid polymer may be a polymerization product of amino acids and optionally other monomers, wherein at least 70 wt.-%, preferably 80 wt.-%, more preferably 90 wt.-%, more preferably 95 wt.-%, more preferably 97 wt.-%, more preferably 98 wt.-%, more preferably 99 wt.-%, most preferably 100 wt.-% amino acids are used as monomers for the polymerization reaction based on total amount of monomers.
  • the amino acid polymer(s) A1 may be or comprise polymerization product(s) of
  • amino acid polymer also includes amino acid polymer derivatives, which may be obtained by modification of the amino acid polymer after polymer synthesis.
  • the modification of the amino acid polymer may be performed by reaction with
  • the polymerization of the amino acid polymer(s) A1 may not be proceeded until full conversion. Therefore, monomers, e.g. amines comprising at least 2 amino groups and/or amino acids and/or dicarboxylic acids and/or tricarboxylic acids, may be present in the amino acid polymer(s) A1 after synthesis of the amino acid polymer(s) A1 by polymerization.
  • monomers e.g. amines comprising at least 2 amino groups and/or amino acids and/or dicarboxylic acids and/or tricarboxylic acids
  • Each amino acid polymer A1 may contain less than 15 wt.-% monomers, more preferably less than 10 wt.-% monomers, more preferably less than 8 wt.-% monomers based on the total weight of amino acid polymer(s) A1.
  • the weight amount of monomers is calculated based on total weight of each polymer A1 including its monomers.
  • the monomers may be present as a result of incomplete conversion of the monomers in the polymerization or may be added after polymerization. Preferably, no monomers are added after finishing the polymerization reaction.
  • Amino acid polymer(s) A1 may comprise poly(amino acid)s, e.g. synthetic poly(amino acid)s, natural poly(amino acid)s, polypeptides, proteins or mixtures thereof.
  • Poly(amino acid)s are produced by polymerization of one or different amino acids.
  • Poly(amino acid)s can be obtained by chemical synthesis or by biosynthesis in living organisms.
  • proteins may be obtained by biosynthesis in living organisms.
  • Polypeptides may be obtained by hydrolysis of proteins.
  • poly(amino acid)s may also include poly(amino acid) derivatives, which may be obtained by modification of the poly(amino acid) after polymer synthesis.
  • the modification of poly(amino acid)s may be performed by reaction with
  • Amino acid(s) mean organic compounds comprising at least one primary amine (—NH 2 ) and at least one carboxyl (—COOH) functional groups.
  • the amino acid(s) may be lysine, histidine, isoleucine, leucine, methionine, phenylalanine, threonine, tryptophan, valine, arginine, aspartic acid, glutamic acid, serine, asparagine, glutamine, cysteine, selenocysteine, glycine, alpha-alanine, beta-alanine, tyrosine, gamma-amino-butyric acid, epsilon-aminocaproic acid, ornithine, diaminopimelic acid, 2,3-diaminopropionic acid, 2,4-diaminobutyric acid or mixtures thereof.
  • the amino acids can be used in their L- or D- or racemic form.
  • the amino acids may
  • Preferred amino acids which are used for the polymerization reaction are diamino acids comprising two amine groups (—NH 2 ) and at least one carboxyl (—COOH) functional group.
  • Such diamino acids may be ornithine, diaminopimelic acid, 2,3-diaminopropionic acid, 2,4-diaminobutyric acid, and/or lysine, preferably lysine, more preferably L-lysine.
  • Poly(amino acid)s may contain less than 15 wt.-% amino acid monomers, more preferably less than 10 wt.-% amino acid monomers, more preferably less than 8 wt.-% amino acid monomers based on the total weight of poly(amino acid)s.
  • the weight amount of monomers is calculated based on total weight of poly(amino acid)s including its monomers.
  • the amino acid polymer(s) A1 contain at least 70 wt.-%, preferably at least 75 wt.-%, preferably at least 80 wt.-%, preferably at least 85 wt.-%, preferably at least 90 wt.-%, preferably at least 95 wt.-%, preferably at least 98 wt.-%, preferably at least 99 wt.-%, preferably at least 99.5 wt.-%, most preferably 100 wt.-% poly(amino acid)s based on the total weight of the amino acid polymer(s) A1.
  • the poly(amino acid)(s) of amino acid polymer(s) A1 has (have) a weight-average molecular weight in the range from 800 g/mol to 10,000 g/mol, preferably 1,000 g/mol to 7,500 g/mol, preferably, 1,150 g/mol to 5,000 g/mol, more preferably 1,300 g/mol to 5,000 g/mol and optionally at least one poly(amino acid) of amino acid polymer(s) A1, preferably each poly(amino acid) of amino acid polymer(s) A1 has a degree of branching (DB) of from 0.2 to 0.7, preferably from 0.25 to 0.60, preferably from 0.30 to 0.50
  • DB degree of branching
  • Component A may comprise one amino acid polymer A1 having primary and/or secondary amino groups or different amino acid polymers A1 having primary and/or secondary amino groups, wherein amino acid polymer(s) A1 may have a primary and secondary amine nitrogen content (NC ps ) of at least 1 wt.-%.
  • NC ps primary and secondary amine nitrogen content
  • primary and/or secondary amino groups as used according to the present invention does not include amide-groups such as e.g. R—CO—NH 2 and/or R—CO—NH—R.
  • the primary amine nitrogen content (NC p ) is the content of nitrogen in wt.-% nitrogen which corresponds to the primary amine groups in amino acid polymer(s) A1.
  • the secondary amine nitrogen content (NC s ) is the content of nitrogen in wt.-% nitrogen which corresponds to the secondary amine groups in amino acid polymer(s) A1.
  • the primary and secondary amine group nitrogen content of the amino acid polymer(s) A1 (NC ps ) is calculated using the following equation:
  • NC ps NC p +NC s
  • the primary amino group nitrogen content (NC p ) and the secondary amino group nitrogen content (NC s ) can be measured based on EN ISO 9702:1998 (determination of primary, secondary and tertiary amino group nitrogen content).
  • amino acid polymer(s) A1 has(have) a primary and secondary amine group nitrogen content (NC ps ) of at least 1 wt.-%” means the following:
  • amino acid polymer(s) A1 consist(s) of one polymer having primary and/or secondary amino groups
  • the amino acid polymer A1 has a NC ps of at least 1 wt.-%, or if amino acid polymer(s) A1 consist of different polymers having primary and/or secondary amino groups, these amino acid polymers A1 in total have a NC ps of at least 1 wt.-%.
  • amino acid polymer(s) A1 has(have) a NC ps of at least 1 wt.-%, preferably 3 wt.-%, preferably at least 5 wt.-%, more preferably at least 7 wt.-% and optionally at least one amino acid polymer of amino acid polymers A1, preferably each amino acid polymer A1, has a NC ps of at least 1 wt.-%, preferably at least 3 wt.-%, preferably at least 5 wt.-%, more preferably at least 7 wt.-%.
  • amino acid polymer(s) A1 has(have) a NC ps from 1 to 33 wt.-%, preferably from 3 to 30 wt.-%, preferably from 5 to 25 wt.-%, preferably from 7 to 20 wt.-% and optionally at least one amino acid polymer of amino acid polymer(s) A1, preferably each amino acid polymer A1, has a NC ps from 1 to 33 wt.-%, preferably from 3 to 30 wt.-%, preferably from 5 to 25 wt.-%, preferably from 7 to 20 wt.-%.
  • component A comprises one amino acid polymer A1
  • this amino acid polymer A1 has a weight-average molecular weight M w of at least 800 g/mol, preferably at least 1,000 g/mol, preferably at least 1,150 g/mol more, preferably at least 1,300 g/mol, more preferably at least 1,400 g/mol and at most 10,000 g/mol, preferably at most 5,000 g/mol.
  • amino acid polymers A1 have a total weight-average molecular weight M w,total of at least 800 g/mol, preferably at least 1,000 g/mol, preferably at least 1,150 g/mol more, preferably at least 1,300 g/mol, more preferably at least 1,400 g/mol and amino acid polymers A1 have a total weight average molecular weight M w,total of at most 10,000 g/mol, preferably at most 5,000 g/mol.
  • Weight-average molecular weights are determined by size exclusion chromatography (SEC) as described in the example section (“Measured values and measuring methods”).
  • the weight-average molecular weight M w refers to the weight-average molecular weight of one single amino acid polymer A1 and is determined by size exclusion chromatography (SEC) for each amino acid polymer A1 separately.
  • M w , total ⁇ j ⁇ p j ⁇ M w , j 2 ⁇ j ⁇ p j ⁇ M w , j ( 1 )
  • the number portion p j is calculated from the mass portion m, and the weight-average molecular weight M w,j of each single amino acid polymer via equations (2) and (3).
  • n j n j ⁇ j ⁇ n j ( 2 )
  • n j m j M w , j ( 3 )
  • Amino acid polymer(s) A1 may contain less than 15 wt.-% monomers, more preferably less than 10 wt.-% monomers, more preferably less than 8 wt.-% monomers based on the total weight of amino acid polymer(s) A1 including its monomers.
  • Each amino acid polymer A1 may contain less than 15 wt.-% monomers, more preferably less than 10 wt.-% monomers, more preferably less than 8 wt.-% monomers based on the weight of said amino acid polymer A1 including its monomers.
  • amino acid polymer(s) A1 have a total weight-average molecular weight M w,total of at least 800 g/mol, preferably at least 1,000 g/mol, preferably at least 1,150 g/mol more, preferably at least 1,300 g/mol, more preferably at least 1,400 g/mol and amino acid polymers A1 have a total weight average molecular weight M w,total of at most 10,000 g/mol, preferably at most 5,000 g/mol, and optionally at least one amino acid polymer A1, preferably each amino acid polymer A1, has a weight-average molecular weight M w of at least 800 g/mol, preferably at least 1,000 g/mol, preferably at least 1,150 g/mol more, preferably at least 1,300 g/mol, more preferably at least 1,400 g/mol and at least one amino acid polymer A1, preferably each amino acid polymer A1, has a weight average molecular weight M w of at most 10,000 g/mol, preferably at most most
  • component A comprises one amino acid polymer A1
  • this amino acid polymer A1 is preferably a branched polymer.
  • component A comprises different amino acid polymers A1, preferably at least one of the amino acid polymers A1, more preferably each amino acid polymer A1, is a branched polymer.
  • At least one amino acid polymer A1, more preferably each amino acid polymer A1 has a degree of branching (DB) of at least 0.05, preferably from 0.05 to 0.99, preferably from 0.07 to 0.9, and more preferably from 0.1 to 0.5.
  • DB degree of branching
  • the DB is determined by 1 H-NMR-spectroscopy.
  • the DB is obtained by comparison of the intensity of the signals.
  • the degree of branching is calculated according to the following equation:
  • DB ( D+T )/( D+L+T ), wherein D, T and L are the fractions of dendritic, terminal or
  • amino acid polymer(s) A1 has (have) a total weight-average molecular weight M w,total of at least 800 g/mol, preferably at least 1,000 g/mol, preferably at least 1,150 g/mol more, preferably at least 1,300 g/mol, more preferably at least 1,400 g/mol and amino acid polymer(s) A1 has (have) a total weight-average molecular weight M w,total of at most 10,000 g/mol, preferably at most 5,000 g/mol, and optionally at least one amino acid polymer A1, preferably each amino acid polymer A1, has a weight-average molecular weight M w of at least 800 g/mol, preferably at least 1,000 g/mol, preferably at least 1,150 g/mol more, preferably at least 1,300 g/mol, more preferably at least 1,400 g/mol and at least one amino acid polymer, preferably each amino acid polymer A1, has a weight average molecular weight M w of at most
  • amino acid polymer(s) A1 comprise(s) at least one polylysine or consist(s) of one or more polylysine(s), which is (are) a polymerization product of monomer lysine, preferably L-lysine, and optionally other monomers selected from the group consisting of
  • These monomers can be present either due to incomplete conversion of the monomers during the polymerization reaction or due to an addition of additional monomers after finishing the polymerization reaction, wherein the additional monomers are selected from the group of the monomers, which have been used for the polymerization reaction. Preferably, no monomers are added after finishing the polymerization reaction.
  • amino acid polymer(s) A1 comprise(s) or consists of one or more polylysine(s), more preferably poly-L-lysine(s).
  • the amino acid polymer(s) A1 comprise at least 70 wt.-%, preferably at least 75 wt.-%, preferably at least 80 wt.-%, preferably at least 85 wt.-%, preferably at least 90 wt.-%, preferably at least 95 wt.-%, preferably at least 98 wt.-%, preferably at least 99 wt.-%, preferably at least 99.5 wt.-%, most preferably 100 wt.-% polylysine(s) based on the total weight of the amino acid polymer(s) A1.
  • polylysines means different polylysines, e.g. with different weight-average molecular weight and/or different degree of branching.
  • Optionally amino acid polymer(s) A1 comprise(s) polylysine(s) or consist(s) of polylysine(s), wherein polylysine(s) has (have) a total weight-average molecular weight M w,total in the range from 800 g/mol to 10,000 g/mol, preferably 1,000 g/mol to 7,500 g/mol, preferably, 1,150 g/mol to 5,000 g/mol, more preferably 1,400 g/mol to 5,000 g/mol, more preferably 1,300 g/mol to 5,000 g/mol.
  • amino acid polymer(s) A1 comprise(s) polylysine(s) or consist(s) of polylysine(s), wherein polylysines(s) has (have) a total weight-average molecular weight M w,total in the range from 800 g/mol to 10,000 g/mol, preferably 1,000 g/mol to 7,500 g/mol, preferably, 1,150 g/mol to 5,000 g/mol, more preferably 1,400 g/mol to 5,000 g/mol, more preferably 1,300 g/mol to 5,000 g/mol and optionally at least one polylysine of amino acid polymer(s) A1, preferably each polylysine of amino acid polymer(s) A1, has (have) a weight-average molecular weight in the range from 800 g/mol to 10,000 g/mol, preferably 1,000 g/mol to 7,500 g/mol, preferably 1,150 g/mol to 5,000 g/mol, more preferably 1,400 g/mol to
  • Lysine has two possibilities to react during polymerization. Either the ⁇ -NH 2 or the ⁇ -NH 2 can react with the carboxylic acid. Therefore, two linear polylysine types exist, i.e. ⁇ -polylysine or the ⁇ -polylysine. Polymerisation can also be performed in a manner, that both ⁇ -NH 2 and the ⁇ -NH 2 react with the carboxylic acid group to form both ⁇ -linkages and ⁇ -linkages.
  • the polylysine is a branched polylysine.
  • Preferred polylysine(s) as used according to the present invention have more ⁇ -linkages than ⁇ -linkages.
  • the ratio of ⁇ -linkages to ⁇ -linkages is between 1.0:1 and 6.0:1, preferably between 1.25:1 and 4.0:1, preferably between 1.5:1 and 3.0:1.
  • This ratio can be determined by integration of the corresponding signals in the 1 H-NMR spectra of the polylysines.
  • Polylysine(s) may contain less than 15 wt.-% lysine monomers, more preferably less than 10 wt.-% lysine monomers, more preferably less than 8 wt.-% lysine monomers based on the total weight of Polylysine(s).
  • Each polylysine may contain less than 15 wt.-% lysine monomers, more preferably less than 10 wt.-% lysine monomers, more preferably less than 8 wt.-% lysine monomers based on the total weight of said polylysine.
  • the branched polylysine may, for example, have a degree of branching (DB) from 0.2 to 0.7, preferably from 0.25 to 0.60, preferably from 0.30 to 0.50.
  • DB degree of branching
  • the NC ps of the polylysine may be from 5 to 12.5 wt.-%, more preferably from 7.5 to 12.5 wt. %, more preferably from 8.5 to 12 wt.-%, most preferably from 9 to 11.5 wt.-%.
  • the NC ps of polylysines in total may be from 5 to 12.5 wt.-%, more preferably from 7.5 to 12.5 wt. %, more preferably from 8.5 to 12 wt.-%, most preferably from 9 to 11.5 wt.-%, and preferably the NC ps of at least one polylysine, preferably of each polylysine, may be from 5 to 12.5 wt.-%, more preferably from 7.5 to 12.5 wt. %, more preferably from 8.5 to 12 wt.-%, most preferably from 9 to 11.5 wt.-%.
  • Optionally amino acid polymer(s) A1 comprise(s) or consist(s) of polylysine(s), wherein polylysine(s) has (have) a total weight-average molecular weight M w,total in the range from 800 g/mol to 10,000 g/mol, preferably 1,000 g/mol to 7,500 g/mol, preferably 1,150 g/mol to 5,000 g/mol, more preferably 1,400 g/mol to 5,000 g/mol, more preferably 1,300 g/mol to 5,000 g/mol and optionally at least one polylysine, preferably each poylysine, has a weight-average molecular weight in the range from 800 g/mol to 10,000 g/mol, preferably 1,000 g/mol to 7,500 g/mol, preferably 1,150 g/mol to 5,000 g/mol, more preferably 1,400 g/mol to 5,000 g/mol, more preferably 1,300 g/mol to 5,000 g/mol and optionally at least one poly
  • each polylysine has a NC ps from 5 to 12.5 wt.-%, more preferably 7.5 to 12.5 wt. %, more preferably from 8.5 to 12 wt.-%, most preferably from 9 to 11.5 wt.-%.
  • polylysine is generally known and may be performed as e.g. described in WO2016062578, preferably in claim 1 , most preferably in any Examples 4 to 10.
  • Another method for producing polylysine from lysine salts is described in WO2007060119.
  • polylysine(s) also include polylysine derivatives, which may be obtained by modification of the polylysine after polymer synthesis.
  • the modification of polylysine may be performed by reaction with
  • amines comprising two amino groups are selected from the group consisting of 1,2-ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, butylenediamine (for example 1,2- or 1,4-butylenediamine), diaminopentane (for example 1,2- and/or or 1,5 diaminopentane), diaminohexane (for example 1,2- and/or 1,6-diaminohexane), diaminoheptane (for example 1,2- and/or 1,7-diaminoheptane), diaminooctane (for example 1,2- and/or 1,8-diaminooctane), diaminononane (for example 1,2- and/or 1,9-diaminononane), diaminodecane (for example 1,2- and/or 1,10-diaminodecane),
  • diaminopentane for example 1,2- and/or or 1,5 diaminopen
  • Preferred amines comprising two amino groups are selected from the group consisting of: 1,2-ethylenediamine, 1,3-propylenediamine, bis-(3-aminopropyl)amine, N-(2-aminoethyl)-1,3-propylenediamine, bis-(2-aminoethyl)amine, bis-N-(2-aminoethyl)-1,3-propylenediamine, N,N′-bis-(3-aminopropyl)-1,2-ethylenediamine, N,N-bis-(3-aminopropyl)-1,2-ethylenediamine and mixtures thereof.
  • Suitable dicarboxylic acids for use as monomers in the polymerization to amino acid polymer A1 are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-1,11-dicarboxylic acid, dodecane-1,12-dicarboxylic acid, maleic acid, fumaric acid, malic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid as well as cis- and trans-cyclopentane-1,3-dicarboxylic acid or mixtures thereof, preferably malonic acid, succinic acid, glutaric acid
  • Suitable tricarboxylic acids or tetracarboxylic acids for use as monomers in the polymerization to amino acid polymer A1 are trimesic acid, trimellitic acid, pyromellitic acid, butanetricarboxylic acid, naphthalene tricarboxylic acid and cyclohexane-1,3,5-tricarboxylic acid, citric acid or mixtures thereof, preferably citric acid.
  • Component A comprises amino acid polymer(s) A1 and optionally comprises component A2 and comprises optionally component A3 which is water.
  • Component A comprises amino acid polymer(s) A1 and comprises component A3 which is water and optionally comprises further component A2.
  • Amino acid polymer(s) A1 and component A2 do not comprise water.
  • Component A3 which is water may be used to dissolve or disperse amino acid polymer(s) A1 and/or component A2.
  • Component A2 may comprise or consist of one or more substances selected from the group consisting of polyols, urea, urea derivatives like ethylene urea, 1,3-dimethylurea, co-solvents, rheology modifiers, and other auxiliaries like biocides, dyes, pigments, flame retardants, and mixtures thereof.
  • Polyols may be selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerine, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, and mixtures thereof.
  • Other suitable polyols are biopolyols, such as polyols derived from soya oil, rapeseed oil, castor oil, sunflower oil or mixtures thereof.
  • polyether polyols which can be obtained via polymerization of cyclic oxides, for example ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran in the presence of polyfunctional initiators or mixtures thereof.
  • Co-solvents may be selected from alcohols, like ethanol, and/or carbonates, like diethyl carbonate.
  • Rheology modifiers may be selected from the group of polymeric thickeners, e.g. carboxy-methylcellulose and/or polyvinylalcohol.
  • Component B comprises component B1 selected from the group consisting of pentoses, hexoses, disaccharides of pentoses and/or hexoses and mixtures thereof, which are preferably selected from the group consisting of glucose, fructose, xylose, sucrose and mixtures thereof, more preferably selected from fructose and/or glucose, and
  • Component B may comprise 20 to 80 wt.-%, preferably 30 to 75 wt.-%, preferably 40 to 70 wt.-% of component B1 based on the total weight of component B.
  • Component B2 may comprise less than 5 wt.-%, preferably less than 2.5 wt.-%, preferably less than 1 wt.-%, carbohydrates which are different from component B1, based on the total weight of component B1.
  • Component B2 does preferably not comprise any carbohydrate.
  • Carbohydrate means monosaccharides having the formula C n H 2n O n (polyhydroxyaldehydes (aldoses) and/or polyhydroxyketones (ketoses)) and/or higher molecular compounds, which can be transformed to these monosaccharides by hydrolysis, like disaccharides having the formula C n H 2n-2 O n-1 , oligosaccharides and polysaccharides (e.g. starches).
  • such carbohydrates are selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, polysaccharides and mixtures thereof, more preferably from the group consisting of monosaccharides, disaccharides and mixtures thereof.
  • Component B2 may comprise less than 5 wt.-%, preferably less than 2.5 wt.-%, preferably less than 1 wt.-% glycolaldehyde and/or hydroxyacetone based on the total weight of component B1 or may also comprise no glycolaldehyde and/or hydroxyacetone.
  • the carbohydrate component may be or comprise a monosaccharide in its aldose or ketose form or a mixture of different types, including a triose, tetrose, or a heptose; or a disaccharide, a polysaccharide; or combinations thereof, excluding pentoses, hexoses, disaccharides of pentoses and/or hexoses and/or mixtures thereof.
  • triose serves as carbohydrate component
  • glyceralaldehyd and/or dihydroxyacetone may be utilized.
  • a tetrose serves as the carbohydrate component aldotetrose sugars, such as erythrose and/or threose may be utilized; and/or ketotetrose sugars, such as erythrulose, may be utilized.
  • a heptose serves as the carbohydrate component
  • a ketoheptose sugar such as sedoheptulose may be utilized.
  • Other stereoisomers of such carbohydrate components not known to occur naturally are also contemplated to be useful as component B1 of component B.
  • the component B1 may be or comprise a disaccharide of hexoses and/or pentoses.
  • the carbohydrate component may be or comprise sucrose, maltose, lactose and/or cellobiose, preferably sucrose, maltose and/or lactose, more preferably sucrose.
  • the carbohydrate component in component B2 may be or comprise a polysaccharide.
  • the carbohydrate component may be or comprise a polysaccharide with a low degree of polymerization, including, for example, molasses, starch hydrolysates, cellulose hydrolysates, or mixtures thereof.
  • a starch hydrolysate e.g. maltodextrin, or a mixture thereof, forms (optionally with other components) components B1 and B2.
  • Component B comprises component B1 selected from the group consisting of pentoses, hexoses, disaccharides of pentoses and/or hexoses and mixtures thereof, which are preferably selected from the group consisting of glucose, fructose, xylose, sucrose and mixtures thereof, more preferably selected from glucose and/or fructose, and optionally comprises component B2 and optionally component B3 which is water.
  • Component B comprises component B1 and comprises component B3 which is water and optionally comprises component B2.
  • Component B1 and component B2 do not comprise water.
  • Component B3 which is water may be used to dissolve or disperse component B1 and/or component B2.
  • Component B2 may comprise or consist of one or more substances selected from the group consisting of polyols, urea, urea derivatives like ethylene urea, 1,3-dimethylurea, organic acids, co-solvents, rheology modifiers, and/or other auxiliaries like biocides, dyes, pigments, flame retardants, and mixtures thereof.
  • the organic acids may be e.g. lactic acid and/or formic acid.
  • Polyols may be selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, glycerine, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, and mixtures thereof.
  • Other suitable polyols may be biopolyols, such as polyols derived from soya oil, rapeseed oil, castor oil, sunflower oil or mixtures thereof.
  • polyether polyols which can be obtained via polymerization of cyclic oxides, for example ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran in the presence of polyfunctional initiators or mixtures thereof.
  • Co-solvents may be selected from alcohols, like ethanol, and/or carbonates, like diethyl carbonate.
  • Rheology modifiers may be selected from the group of polymeric thickeners, e.g. carboxymethyl-cellulose.
  • Component B May Comprise
  • Component B May Comprise
  • the binder composition according to the present invention may comprise urea as component A2 and/or B2, wherein preferably the binder composition comprises 0 to 70 wt.-%, preferably 10 to 60 wt.-%, more preferably 20 to 55 wt.-%, most preferably 25 to 50 wt.-% urea in total based on the total weight of the sum of amino acid polymer(s) A1 and component B1.
  • the binder composition according to the present invention may comprise 55 to 90 wt.-%, preferably 60 to 85 wt.-% preferably 70 to 85 wt.-% amino acid polymer(s) A1, based on the total weight of the sum of amino acid polymer(s) A1 and component B1.
  • the binder composition according to the present invention comprises
  • Component A may comprise
  • the binder composition according to the present invention comprises
  • Functional additives are additives for the improvement of certain properties of the lignocellulose-based composite article, e.g. the water resistance and/or the resistance against microorganisms.
  • Component C May Comprise or Consist of:
  • the functional additive C1 may be selected from the group of hydrophobizing agents, such as paraffin, rheology modifiers, fillers, fungicides, biocides, flame retardants, pigments, dyes, or mixtures thereof.
  • hydrophobizing agents such as paraffin, rheology modifiers, fillers, fungicides, biocides, flame retardants, pigments, dyes, or mixtures thereof.
  • component C is paraffin emulsion, in which paraffin (component C1) is emulsified in water (component C2).
  • the binder composition comprises 0 to 50 wt.-%, preferably 0 to 25 wt.-%, preferably 0 to 15 wt.-%, preferably 0 to 10 wt.-%, component C1 based on the total weight of the sum of amino acid polymer(s) A1 and component B1 and component C1.
  • the binder composition may comprise
  • the binder composition according to the present invention comprises
  • the present invention also relates to a composition kit comprising the above defined binder composition, wherein component A and component B and optionally component C are stored separately.
  • the binder kit comprises two separate components A and B, which are mixed either before or during or after application to a plurality of lignocellulosic particles.
  • the present invention also relates to a reacted binder composition obtainable or obtained by reacting the components A and B, in particular the binder composition, according to the present invention.
  • the present invention also relates to a reacted binder composition obtainable or obtained by reacting the binder composition according to the present invention.
  • the binder composition according to the present invention may be used as binder or adhesive for different materials in different shapes, such as mineral fibers (including slag wool fibers, stone wool fibers, glass fibers), aramid fibers, ceramic fibers, ceramic powder, metal fibers, metal powder, carbon fibers, polyimide fibers, polyester fibers, reyon fibers, cellulosic fibers, cellulosic sheets, cellulosic chips, cellulosic strands, cellulosic layers or lignocellulosic pieces.
  • mineral fibers including slag wool fibers, stone wool fibers, glass fibers
  • aramid fibers ceramic fibers, ceramic powder, metal fibers, metal powder, carbon fibers, polyimide fibers, polyester fibers, reyon fibers, cellulosic fibers, cellulosic sheets, cellulosic chips, cellulosic strands, cellulosic layers or lignocellulosic pieces.
  • the binder composition according to the present invention is used for lignocellulosic pieces, more preferably lignocellulosic particles, in particular wood particles.
  • a further aspect of the present invention relates to a lignocellulose-based composite article comprising:
  • the reacted binder composition preferably means a binder composition cured at 20 to 300° C., preferably 40 to 200° C., preferably 50 to 180° C., more preferably 70 to 150° C. and optionally at a pressure of 0.1 to 100 bar, preferably 1 to 100 bar, preferably 1 to 50 bar, preferably 1 to 25 bar.
  • a high-frequency electrical field may be applied during pressing until 80 to 200° C., preferably 80 to 180° C., more preferably 90 to 150° C. and most preferably 100 to 150° C. is reached in the center of the mat, optionally at a pressure of 0.1 to 100 bar, preferably 0.1 to 100 bar, preferably 0.1 to 50 bar, preferably 0.1 to 25 bar.
  • high-frequency electrical field designates and includes any kind of high-frequency electrical or electromagnetic field such as microwave irradiation or a high-frequency electrical field, which results after applying a high-frequency alternating voltage at a plate capacitor between two capacitor plates.
  • Suitable frequencies for the high-frequency electrical field are in the range of from 100 kHz to 30 GHz, preferably 6 MHz to 3 GHz, more preferably 13 MHz to 41 MHz.
  • Especially suitable and preferred are the respective nationally and internationally approved frequencies such as 13.56 MHz, 27.12 MHz, 40.68 MHz, 2.45 GHz, 5.80 GHz, 24.12 GHz, more preferably 13.56 und 27.12 MHz.
  • the electrical power used to create such a high-frequency electrical field in the processes of the present invention preferably is in the range of from 10 to 10.000 kWh, more preferably of from 100 to 5.000 kWh, most preferably of from 500 to 2.000 kWh.
  • the curing reaction is a crosslinking reaction, preferably crosslinking of the amino acid polymer(s) A1 by reaction with component B1, in particular pentoses, hexoses, and/or disaccharides thereof, wherein the temperature is the maximum temperature reached in the binder composition during the curing step.
  • Said reacted binder composition may still comprise unreacted amino acid polymer(s) A1, optionally unreacted component A2, optionally unreacted component B1, in particular pentoses, hexoses, and/or disaccharides thereof, optionally unreacted component B2 and/or optionally unreacted components C1.
  • said reacted binder composition comprises less than 15 wt.-%, preferably less than 10 wt.-%, more preferably less than 8 wt.-% unreacted amino acid polymer(s) A1, unreacted component B1, unreacted component A2 and unreacted component B2 in total based on the total weight of the sum of amino acid polymer(s) A1, component A2, component B1 and component B2 before reacting the binder composition.
  • Lignocellulosic pieces as used according to the present invention may be produced by cutting, sawing, crushing and/or grinding lignocellulose-containing materials. Cutting, sawing, crushing and/or grinding of the lignocellulosic materials into lignocellulosic pieces can be carried out by methods known in the art (cf. for example M. Dunky, P. Niemz, Holzwerkstoffe and Leime [Wood Materials and Glues], pp. 91 to 156, Springer Verlag Heidelberg, 2002). Suitable lignocellulosic materials may be ordinarily lignocellulose-containing plants and/or plant parts, in particular wood. Examples of suitable plants include trees, grasses, flax, hemp or mixtures thereof, preferably trees.
  • lignocellulosic pieces are made from wood.
  • Any desired type of coniferous wood and/or hardwood may be suitable for the production of the wood particles, such as industrial wood residues, forest timber and/or plantation timber, preferably eucalyptus , spruce, beech, pine, larch, linden, poplar, ash, oak, fir or mixtures thereof, more preferably eucalyptus , spruce, pine, beech or mixtures thereof.
  • lignocellulosic pieces can also be used for preparation of lignocellulosic pieces.
  • Palms and/or grasses with lignified stems, such as bamboo, are also suitable for preparation of lignocellulosic pieces.
  • a further source of lignocellulose-containing material for the preparation of lignocellulosic pieces may be waste wood, such as old furniture.
  • One or a plurality of lignocellulosic materials can be used for the production of lignocellulosic pieces.
  • density refers to the bulk density in a standard atmosphere (20° C./65% humidity) as defined in DIN 1306, i.e. taking into consideration the hollow space contained in the lignocellulose-containing starting material, e.g. the tree trunk.
  • Lignocellulosic pieces may comprise beams, lamellas, planks, veneers, strips, particles (like strands, chips or fibers), and/or dust.
  • the lignocellulose-containing pieces are used in the form of fibers, strands, chips, dust or mixtures thereof, preferably chips, fibers, dust or mixtures thereof, particularly preferably chips, fibers or mixtures thereof, most preferably chips.
  • the lignocellulosic pieces used can comprise foreign matter that does not originate from lignocellulose-containing plants.
  • the content of foreign matter can vary over a broad range, and is ordinarily 0 to 30 wt.-%, preferably 0 to 10 wt.-%, particularly preferably 0 to 5 wt.-%, in particular 0 to 1 wt.-%, based on the oven dry weight of the lignocellulosic pieces.
  • Foreign matter can be plastics, adhesives, coatings and/or dyes, etc. contained for example in waste wood.
  • the oven-dry weight of the lignocellulosic pieces is the weight of the lignocellulosic pieces minus the water present therein and can be determined according to EN 322:1993 by placing the pieces in a drying oven at a temperature of (103 ⁇ 2) ° C. until constant mass has been reached.
  • the lignocellulosic pieces may be totally or partially delignified before using them for the production of the composite articles.
  • at least 50 wt.-%, more preferably at least 75 wt.-%, more preferably at least 90 wt.-% of the lignin of the lignocellulosic pieces is removed by the delignification step.
  • Delignification may be performed by treatment with an aqueous solution of H 2 O 2 and acetic acid as described in M. Frey, et al., ACS Appl. Mater. Interfaces, 2018, 20, page 5030 to 5037, or by treatment with an aqueous solution of NaOH and Na 2 SO 3 as described in M. Zhu, et al., Adv. Mat. 2016, 28 page 5181 to 5187.
  • the lignocellulosic pieces are used without a previous delignification step.
  • the lignocellulose-based composite articles may belong to one of the categories solid wood composite (e.g. glulam), veneer composite (e.g. plywood), chip/strand composites (e.g. chipboard, oriented strand board) or fiber composites (e.g. medium density fiber board) as listed in M. Dunky, P. Niemz, Holzwerkstoffe and Leime [Wood Materials and Glues], page 7, Springer Verlag Heidelberg, 2002.
  • solid wood composite e.g. glulam
  • veneer composite e.g. plywood
  • chip/strand composites e.g. chipboard, oriented strand board
  • fiber composites e.g. medium density fiber board
  • Chip/strands composites and fiber composites are collectively referred to as composites made from particles.
  • lignocellulosic particles is used as a generic term for fibers, strands and chips.
  • the lignocellulosic particles can be dried according to common drying methods known to the person skilled in the art, resulting in the common low residual water content (within a common range of variability; so-called “residual moisture content”). Common drying methods are listed in M. Dunky, P. Niemz, Holzwerkstoffe and Leime [Wood Materials and Glues], page 111 to 118, Springer Verlag Heidelberg, 2002.
  • the moisture content of the particles can be measured according to EN 322:1993 by placing the particles in a drying oven at a temperature of (103 ⁇ 2) ° C. until constant mass has been reached. Chips may be dried to a moisture content of 1 to 8%, preferably 1 to 6%, before adding the binder composition.
  • the lignocellulose-based composite articles made from lignocellulosic particles, preferably from wood particles may be chipboard (also called particle board), oriented strand board (OSB), medium density fiber board (MDF), high density fiberboard (HDF) and/or wood fiber insulation board (WFI).
  • chipboard also called particle board
  • OSB oriented strand board
  • MDF medium density fiber board
  • HDF high density fiberboard
  • WFI wood fiber insulation board
  • the lignocellulose-based composite article is chipboard, MDF, HDF or WFI, more preferably chipboard.
  • Strands may be used for example for the production of oriented strand board (OSB) boards.
  • the average size of the strands is ordinarily 20 to 300 mm, preferably 25 to 200 mm, particularly preferably 30 to 150 mm.
  • Chips may be used for the production of chipboards. Chips needed for this purpose can be classified according to size by means of sieve analysis as described in M. Dunky, P. Niemz, Holzwerkstoffe and Leime [Wood Materials and Glues], page 665 and 666., Springer Verlag Heidelberg, 2002. Appropriate sieves are defined in DIN ISO 3310-1:2017-11.
  • the average size of the chips, as defined in M. Dunky, Holz Why und Holzverêt, 1988, 40, pages 126-133, may be 0.01 to 30 mm, preferably 0.05 to 25 mm, particularly preferably 0.1 to 20 mm.
  • Fibers may be wood fibers, hemp fibers, bamboo fibers, miscanthus fibers, bagasse fibers (sugar cane) or mixtures thereof, preferably wood fibers.
  • the length of the fibers may be 0.01 to 20 mm, preferably 0.05 to 15 mm, particularly preferably 0.1 to 10 mm.
  • Strands may be wood strands, hemp strands, bamboo strands, bagasse strands or mixtures thereof, preferably wood strands.
  • the length of the strands may be 20 to 500 mm, preferably 50 to 200 mm, particularly preferably 100 to 150 mm.
  • the width of the strands may be 1 to 50 mm, preferably 5 to 30 mm, particularly preferably 10 to 15 mm.
  • the thickness of the strands may be 0.2 to 2 mm, preferably 0.4 to 1.2 mm, particularly preferably 0.6 to 0.8 mm. Strands may also be called flakes. Wood wool belongs to the group of wood strands.
  • the total thickness of the lignocellulose-based composite articles made from lignocellulosic particles according to the present invention varies with the field of use.
  • Lignocellulose-based composite articles made from particles are preferably in the range from 0.5 to 100 mm, preferably in the range from 10 to 40 mm, especially 15 to 20 mm.
  • the lignocellulose-based composite articles made from lignocellulosic particles according to the present invention may comprise one or several layers.
  • Single-layered or multi-layered composite articles such as for example single-layered or three-layered chipboard are commonly known (M. Dunky, P. Niemz, Holzwerkstoffe and Leime [Wood Materials and Glues], page 18 to 22., Springer Verlag Heidelberg, 2002).
  • the lignocellulose-based composite article may be a multi-layer, preferably a three-layered chipboard.
  • the lignocellulose-based composite article consists of a core layer and two surface layers.
  • the lignocellulose-based composite article comprises the reacted binder composition according to the present invention in at least one layer.
  • the lignocellulose-based composite article may comprise the reacted binder composition according to the present invention in more than one layer, wherein binder compositions according to the present invention, which are used in the different layers may be the same or different for the different layers.
  • the surface layers comprise the reacted binder composition according to the present invention.
  • the core layer may comprise a reacted binder composition according to the present invention or a reacted binder composition selected from the group consisting of phenol-formaldehyde resins, amino resins, a binder based on organic isocyanate or mixtures thereof, preferably a reacted binder composition according to the present invention.
  • the multi-layer particle board preferably a three-layered chipboard, preferably has a formaldehyde emission measured according to EN717-2 lower than 2.0 mg/m 2 h, preferably lower than 1.5 mg/m 2 h.
  • Suitable phenol-formaldehyde resins are known to the person skilled in the art, see by way of example Kunststoff-Handbuch [Plastics Handbook], 2nd edn., Hanser 1988, vol. 10 “Duroplaste” [Thermosets], pp. 12 to 40. Skilled in the art, see by way of example Kunststoff-Handbuch [Plastics Handbook], 2nd edn., Hanser 1988, vol. 10 “Duroplaste” [Thermosets], pp. 12 to 40.
  • Suitable amino resin can be any of the amino resins known to the person skilled in the art, preferably those for the production of wood-based composites. These resins, and also production thereof, are described by way of example in Ullmanns Enzyklopädie der ischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 4th revised and extended edition, Verlag Chemie, 1973, pp. 403-424 “Amino-plaste” [Aminoplastics] and Ullmann's Encyclopedia of Industrial Chemistry, vol. A2, VCH Verlagsgesellschaft, 1985, pp. 115-141 “Amino Resins” and also in M. Dunky, P. Niemz, Holzwerkstoffe und Leime [Wood-based materials and glues], Springer 2002, pp.
  • Preferred polycondensates are urea-formaldehyde resins (UF resins), urea-formaldehyde resins (MF resins) and melamine-containing urea-formaldehyde resins (MUF resins), with particular preference urea-formaldehyde resins, for example Kaurit® glue products from BASF SE.
  • UF resins urea-formaldehyde resins
  • MF resins urea-formaldehyde resins
  • MAF resins melamine-containing urea-formaldehyde resins
  • Suitable organic isocyanates are organic isocyanates having at least two isocyanate groups and mixtures of these, in particular any of the organic isocyanates known to the person skilled in the art and mixtures of these, preferably those for the production of wood-based materials or of polyurethanes. These organic isocyanates, and also the production thereof, are described for example in Becker/Braun, Kunststoff Handbuch [Plastics handbook], 3rd revised edition, vol. 7 “Polyurethane” [Polyurethanes], Hanser 1993, pp. 17-21, pp. 76-88 and pp. 665-671.
  • Preferred organic isocyanates are oligomeric isocyanates having from 2 to 10, preferably from 2 to 8, monomer units and on average at least one isocyanate group per monomer unit, and mixtures of these.
  • the isocyanates can be either aliphatic, cycloaliphatic or aromatic.
  • Particular preference is given to the organic isocyanate MDI (methylenediphenyl diisocyanate) and/or the oligomeric organic isocyanate PMDI (polymeric methylenediphenyl diisocyanate), these being obtainable via condensation of formaldehyde with aniline and phosgenation of the isomers and oligomers produced during the condensation (see by way of example Becker/Braun, Kunststoff Handbuch [Plastics handbook], 3rd revised edition, vol. 7 “Polyurethane” [Polyurethanes], Hanser 1993, p. 18, final paragraph to p. 19, second paragraph and p. 76, fifth paragraph), and mixtures of MDI and/or PMDI.
  • Very particular preference is given to products in the LUPRANATE® range from BASF SE, in particular LUPRANATE® M 20 FB from BASF SE.
  • the organic isocyanate may be also an isocyanate-terminated prepolymer which is the reaction product of an isocyanate, e.g. PMDI, with one or more polyols and/or polyamines.
  • an isocyanate e.g. PMDI
  • the composite articles of the invention made from particles may have a mean overall density of 100 to 1000 kg/m 3 , preferably 400 to 850 kg/m 3 .
  • the chipboards of the invention may have a mean overall density of 400 to 750 kg/m 3 , more preferably 425 to 650 kg/m 3 , especially 450 to 600 kg/m 3 .
  • the density is determined 24 hours after production according to EN 323:1993.
  • the minimum amount of A1 based on the total oven-dry weight of the lignocellulosic pieces, preferably particles, is 1.5 wt.-%, preferably 2 wt.-%, preferably 2.5 wt. %, preferably 3 wt.-%.
  • the lignocellulosic pieces are fibers or chips, more preferably chips.
  • amino acid polymer(s) A1 and component B1 in total based on the total oven-dry weight of the lignocellulosic chips, preferably wood chips, are used for the preparation of composite articles, preferably chip boards.
  • amino acid polymer(s) A1 and component B1 in total based on the total oven-dry weight of the lignocellulosic fibers, preferably wood fibers are used for the preparation of composite articles, preferably fiber boards like medium density fiber board (MDF), high density fiberboard (HDF) or wood fiber insulation board (WFI), preferably MDF.
  • MDF medium density fiber board
  • HDF high density fiberboard
  • WFI wood fiber insulation board
  • a further aspect of the present invention relates to a process for the batchwise or continuous production of lignocellulose-based composite articles, in particular single-layered lignocellulose-based boards or multi-layered lignocellulose-based boards, with a core and with at least one upper and one lower surface layer, comprising the following steps.
  • the temperature given for step c) refers to the surface temperature of the heated surface used for pressing, in particular the surface temperature of the press-plates.
  • the temperature in the center of the pressed mat may be at least 80° C., preferably between 80 and 180° C., preferably between 90 and 150° C., more preferably 95 to 125° C.
  • the boards can be cooled down in a star cooler or more slowly by hot stacking.
  • the process according to the present invention for the batchwise or continuous production of multi-layered lignocellulose-based boards, with a core and with at least one upper and one lower surface layer, may comprise the following steps.
  • the temperature given for step c) refers to the surface temperature of the heated surface used for pressing, in particular the surface temperature of the press-plates.
  • the temperature in the center of the pressed mat may be at least 80° C., preferably between 80 and 180° C., preferably between 90 and 150° C., more preferably 95 to 125° C.
  • the boards can be cooled down in a star cooler or more slowly by hot stacking.
  • the process according to the present invention also relates to a method for the batchwise or continuous production of lignocellulose-based composite articles, in particular single-layered lignocellulose-based boards or multi-layered lignocellulose-based boards with a core and with at least one upper and one lower surface layer, comprising the following steps:
  • step c′ refers to the temperature in the center of the pressed mat at the end of step c′).
  • the boards can be cooled down in a star cooler or more slowly by hot stacking.
  • the process according to the present invention relates to a method for the batchwise or continuous production of multi-layered lignocellulose-based boards with a core and with at least one upper and one lower surface layer, comprising the following steps:
  • step c′ refers to the temperature in the center of the pressed mat at the end of step c′).
  • the boards can be cooled down in a star cooler or more slowly by hot stacking.
  • the measurement of the temperature in the center of the pressed mat may be carried out according to known methods, in particular according to Meyer/Thoemen, Holz als Roh-und Maschinenstoff [European Journal of Wood and Wood Products] (2007) 65, page 49 to 55 or Thoemen, 2010, “Vom Holz somehow Maschinenstoff-groundlegende füren Kunststoff Kunststoff und Struktur von Holztechnikstoffen [From wood to materials—basic investigations for the preparation and the structure of wood-based materials]”, ISBN 978-3-9523198-9-5, page 24 to 30 and page 78 to 85.
  • the wireless measurement of the temperature sensors such as the CONTI LOG- or EASYlog-sensors of the Fagus-Grecon Greten GmbH& Co. KG can be used, which can be inserted in the mat during the scattering of the mat.
  • the time from the start to the end of pressing in step c) or c′) is the press time.
  • the press time factor is the press time divided by the target thickness of the board as described in the example section (“Measured values and measuring methods”).
  • the press time factor is at most 20 s/mm, preferably at most 14 s/mm, preferably at most 12 s/mm, preferably at most 10 s/mm, preferably at most 8 s/mm and optionally in the process according to the present invention the press time factor is at least 2 s/mm, preferably at least 3 s/mm, preferably at least 4 s/mm, preferably at least 5 s/mm.
  • Components A and B of the binder composition may be added separately or as a mixture as defined below.
  • component C may be added as a mixture with components A and/or B or separately.
  • lignocellulose-based composites in particular single-layered lignocellulose-based boards or multi-layered lignocellulose-based boards with at least a core and two surface layers, comprising the steps a), b) and c) are generally known to the person skilled in the art, and are described for example in M. Dunky, P. Niemz, Holzwerkstoffe and Leime [Wood Materials and Glues], Part 1, Chapter 4, Springer Verlag Heidelberg, 2002 or in A. Wagenbow, F. Scholz, Taschenbuch der Holztechnik [Handbook of Wood Technology], Chapter 2, frabuchverlag Leipzig im Carl Hanser Verlag, 2012 or H. Thoemen, M. Irle, M. Sernek (ed.), Wood-Based Panels—An Introduction for Specialists, Chapter 1, COST Office, Brunel University Press, London, UB8 3PH, England.
  • the method according to the invention can be carried out discontinuously or continuously, and preferably continuously.
  • the mixture(s) obtained by step a) comprise(s) water.
  • the water can derive from the residual moisture comprised in the lignocellulosic particles and from the components A and B and optional C.
  • the water content of these mixture(s) may be adapted using lignocellulosic particles with an appropriate moisture and/or by increasing the water content in components A, B and/or C and/or by adding additional water to the mixture (which is not part of the components A, B and/or C) during step a), for instance by spraying.
  • the water content of the mixture(s) may be from 3 to 20 wt.-%, preferably from 3.5 to 16 wt.-%, particularly preferably from 4 to 14 wt.-%, very particularly preferably from 5 to 13 wt.-% by weight, based on the total dry weight of the mixture.
  • the water content in the mixture obtained in step a) for the surface layers is preferably greater than the water content in the mixtures for the core layer obtained in step a).
  • the water content [in wt.-%] in the mixture(s) obtained in step a) for the surface layers is greater than the water content [in wt.-%] in the mixture(s) obtained in step a) for the core layer.
  • the water content [in wt.-%] in the mixture(s) obtained in step a) for the surface layers is greater than the water content [in wt.-%] in the mixture(s) obtained in step a) for the core layer is 0.5 to 6 wt.-% by weight, very particularly preferably from 2 to 5 wt.-% higher.
  • the water content of the mixture obtained in step a) for the core layer is from 3 to 15 wt.-%, more preferably from 3.5 to 12 wt.-%, particularly preferably from 4 to 10 wt.-%, very particularly preferably from 5 to 9 wt.-%, based on the total dry weight of the mixture and the water content of the mixture(s) obtained in step a) for the surface layers is from 5 to 20 wt.-%, preferably from 6 to 16 wt.-%, particularly preferably from 7 to 14 wt.-%, very particularly preferably from 8 to 13 wt.-%, based on the total dry weight of the mixture(s).
  • the layer(s) may be pre-compressed at a pressure of 0.1 to 30 bar, preferably 0.1 to 25 bar, more preferably 1 to 20 bar, more preferably 1 to 15 bar.
  • the pre-compressing step may take from 1 sec to 120 sec, preferably from 2 to 60 sec, more preferably from 3 to 30 sec. Usually, the pre-compressing step is done without applying heat to the scattered mat.
  • energy can be introduced into the mat in a preheating step with one or more energy sources of any kind. Suitable energy sources are for example hot air, steam or steam/air mixtures. This increases the temperature of the mat and may change the moisture of the mat.
  • the temperature in the core of the mat may be between 40 to 80° C., preferably between 40 and 70° C.
  • the preheating with steam and steam/air mixtures can also be conducted in such a way that only the surface-near areas are heated, but the core is not.
  • the water content in the lignocellulosic composite obtained in step c) or c′) is from 3 to 20 wt. % by weight, preferably from 5 to 15 wt.-%, more preferably from 7 to 13 wt.-% measured according to EN 322:1993.
  • Precompression and preheating can be carried out by a method known to the person skilled in the art, such as those described in M. Dunky, P. Niemz, Holzwerkstoffe and Leime [Wood Materials and Glues], Springer Verlag Heidelberg, 2002, pg. 122 and 819 or in H.-J. Deppe, K. Ernst, MDF-Medium-Density Fiberboard, DRW-Verlag, 1996, pp. 44, 45 and 93 or in A. Wagenbow, F. Scholz, Taschenbuch der Holztechnik [Handbook of Wood Technology], subuchverlag für, 2012, pg. 219.
  • step c) or c′ the thickness of the mat is (further) reduced.
  • the temperature of the mat is increased by inputting energy.
  • a constant pressing force is applied, and the mat is simultaneously heated by means of a constant-power energy source.
  • both the inputting of energy and compression by means of a pressing force can take place at respectively different times and in a plurality of stages.
  • the inputting of energy in process step c) can be carried out by heat transfer from heated surfaces, for example press plates, to the mat or by other energy sources for example hot air, steam or steam/air mixtures.
  • the inputting of energy in method step c′) can be carried out by high-frequency heating (by applying a high-frequency electrical field) or by a combination of high-frequency heating and heat transfer from heated surfaces.
  • This pressing can be carried out by any methods known to the person skilled in the art (cf. examples in “Taschenbuch der Spanplattentechnik [Handbook of Particle Board Technology,” H.-J. Deppe, K. Ernst, 4th edition, 2000, DRW-Verlag Weinbrenner, Leinfelden vomerdingen, pp. 232 to 254, and “MDF—Mittel Why Faserplatten [Medium-Density Fiberboards]” H.-J. Deppe, K. Ernst, 1996, DRW-Verlag Weinbrenner, Leinfelden Echterdingen, pp. 93 to 104).
  • Optionally continuous pressing methods for example using double band presses, are used.
  • step c′) involves a combination of high-frequency heating and heat transfer from heated surfaces
  • the heated press plates preferably have temperatures from in the range of from 80 to 200° C., more preferably from 90 to 180° C., most preferably from 100 to 150° C.
  • step c′ of applying a high-frequency electrical field the temperature at the center of the pressed mat is increased to a maximum temperature in the range of from 80° C. to 200° C., preferably in the range of from 80° C.
  • step c′ the maximum temperature is reached in less than 40 s ⁇ (d/mm) after the start of applying a high-frequency electrical field, where d is the thickness of the compacted mixture in mm at the end of step c′), more preferably in less than 30 s ⁇ (d/mm), even more preferably in less than 20 s ⁇ (d/mm), most preferably in less than 15 s ⁇ (d/mm) after the start of applying a high-frequency electrical field, where d is the thickness of the pressed mat in mm at the end of step c′).
  • the maximum temperature is preferably reached in less than 400 s, more preferably in less than 300 s, even more preferably in less than 200 s, most preferably in less than 150 s after the start of applying a high-frequency electrical field.
  • center of the pressed mat designates the location which is approximately in the middle between the surfaces of the three-dimensional object defined by the pressed mat in step c) or c′).
  • Component A and component B can be added to the lignocellulosic pieces, in particular particles, in step a) either
  • An addition of components A and B separately from one another is understood here to mean that component A and component B are added to the lignocellulosic particles in step a) with the aid of separate application devices, for example nozzles or applicator disks.
  • the application devices may be arranged spatially in such a way or in such a time sequence that the addition of component A and component B is effected successively, in any sequence, or simultaneously.
  • the application devices are arranged such that component A and component B are added simultaneously but not as a mixture to the lignocellulosic particles. In general, this is achieved by virtue of the application devices being in immediate spatial proximity, e.g.
  • the distance between the application devices may be between 1 cm and 300 cm, preferably between 5 cm and 200 cm, more preferably between 10 cm and 100 cm.
  • the application devices may also be aligned here such that the components mix partly or completely even when they are on the way from the application devices to the lignocellulosic particles.
  • step a addition of component A and component B as a mixture means that
  • step a addition of component A and component B separate from one another means that
  • the resulting mixture is added to the lignocellulosic particles after a waiting time of less than 120 min, preferably 90 min or less than 90 min, preferably 60 or less than 60 min, preferably 40 or less than 40 min, preferably 20 or less than 20 min, more preferably 10 or less than 10 min, 5 or most preferably less than 5 min, 1 or less than 1 min.
  • Waiting time is the time period between the mixing and the addition to the lignocellulosic particle and may be at least 30 sec.
  • the mixture of might be exposed to a temperature of 10 to 50° C., preferably 15 to 40° C., preferably 20 to 30° C.
  • a further aspect of the present invention relates to the use of the lignocellulosic articles made from particles.
  • the lignocellulose-based composite articles are coated on one or more sides, for example, with melamine films, with veneers, with a plastic edge or with paint.
  • the lignocellulose-based composite articles for example the chipboard or the fiberboard are used as inner plies for sandwich materials.
  • the outer plies of the sandwich materials may consist of different materials, for example of metal such as aluminum or stainless steel, or of thin wood-based chipboards or fiberboards, preferably high-density fiberboards (HDF), or of laminates, for example high-pressure laminate (HPL).
  • HDF high-density fiberboards
  • HPL high-pressure laminate
  • Examples of uses of the lignocellulose-based composite article or of the coated lignocellulose-based composites produced therefrom or of the sandwich materials produced therefrom are as material for furniture, for example as material for cabinet side, as shelf in cabinets, as material for bookshelves, as furniture door material, as countertop, as kitchen unit front, as elements in tables, chairs and/or upholstered furniture.
  • Examples of uses of the lignocellulose-based composite article or of the coated lignocellulose-based composites produced therefrom or of the sandwich materials produced therefrom are as building and/or construction material, for example as material for interior fit-out, shopfitting and exhibition stand construction, as material for roof and/or wall paneling, as infill, cladding, floors and/or inner layers of doors, and/or as separating walls.
  • the weight of binder composition in wt.-% based on the total composite strongly depends on the size of the lignocellulosic beams, lamellas, blanks and/or veneers. Therefore, in such kind of composites the weight of binder composition is usually calculated in mass of binder composition per surface area of the piece to be glued.
  • Suitable amounts are 5 to 200 g/m 2 amino acid polymer(s) A1 and component B1 in total.
  • glue or adhesive are often used in the prior art instead of binder composition.
  • binder composition is used for all kind of lignocellulose-based composites articles.
  • Lignocellulose-based composite articles made from beams, lamellas, blanks and/or veneers may be glulam, plywood, cross laminated timber, solid wood board and/or blockboard.
  • the composite article made from veneers is a chipboard or fiberboard covered by one or more veneers at least on one side of the board.
  • a further aspect of the present invention relates to a process for the batchwise or continuous production lignocellulose-based composites, which may be glulam, plywood, cross laminated timber, blockboards or solid wood boards, preferably plywood, comprising the following steps,
  • Pressing in step c) may be at a temperature of 20 to 200° C., preferably 15 to 150° C., more preferably 10 to 110° C. and at a pressure of 1 to 100 bar, preferably 1 to 50 bar, more preferably 1 to 25 bar, wherein the temperature is the maximum temperature reached in the binder composition during step c)
  • a further aspect of the present invention relates to a process for the batchwise or continuous production of plywood, comprising the following steps
  • Plywood is composed at least of three plies of wood veneers glued on top of each other, wherein the directions of fiber of adjacent plies are arranged in angle of about 90° C.
  • the back veneer run through a glue spreader, which applies the glue to the upper surface of the back veneer.
  • the core veneer or several veneer stripes placed one beside the other are laid on top of the glued back veneer, and the whole sheet is run through the glue spreader a second time. Thereafter, the face veneer is laid on the top glued core.
  • This glued sheet or several of these glued sheets stacked on top of each other are loaded into a press, for example a multi-opening hot press.
  • the sheets may be pressed at 80 to 170° C. and at a pressure of 5 to 15 bar.
  • Multi-ply plywood e.g. five-ply of seven-ply plywood, are produced in a similar manner, just with more than one core veneer layers.
  • blockboards are similar to the process of a three-ply plywood. Instead of the core veneers a sheet is used which is made from several wood blanks glued together.
  • a further aspect of the present invention relates to the use of the lignocellulosic articles made from beams, lamellas, blanks and/or veneers:
  • Examples of uses are as material for furniture, for example as construction material for cabinets, as shelves, as furniture door material, as countertop, as kitchen unit front, and/or as elements in tables,
  • Examples of uses are as building and construction material, for example as material for interior fitout, shopfitting and/or exhibition stand construction, as material for roof and/or wall paneling, as infill, cladding, floors and/or inner layers of doors, and/or as separating walls, as material for car ports and/or for hall roofs.
  • the chips were produced in a disc chipper. Spruce trunk sections (length 250 mm) from Germany were pressed with the long side against a rotating steel disc, into which radially and evenly distributed knife boxes are inserted, each of which consists of a radially arranged cutting knife and several scoring knives positioned at right angles to it. The cutting knife separates the chip from the round wood and the scoring knives simultaneously limit the chip length. Afterwards the produced chips are collected in a bunker and from there they are transported to a cross beater mill (with sieve insert) for re-shredding with regard to chip width. Afterwards the reshredded chips were conveyed to a flash drier and dried at approx. 120° C.
  • the chips were then screened into two useful fractions (B: ⁇ 2.0 mm ⁇ 2.0 mm and >0.32 mm ⁇ 0.5 mm; C: ⁇ 4.0 mm ⁇ 4.0 mm and >2.0 mm ⁇ 2.0 mm), a coarse fraction (D: >4.0 mm ⁇ 4.0 mm), which is reshredded, and a fine fraction (A: ⁇ 0.32 mm ⁇ 0.5 mm).
  • Fraction B is used as surface layer chips for three-layered chipboards (“surface layer chips”)
  • a mixture of 60 wt.-% of fraction B and 40 wt.-% of fraction C is used either as core layer chips for three-layered chipboards and as chips for single-layered chipboards (“core layer chips”)
  • the moisture content of the particles (chips or fibers) before application of the binder was measured according to EN 322:1993 by placing the particles in a drying oven at a temperature of (103 ⁇ 2) ° C. until constant mass has been reached.
  • the press time factor is the press time, which is the time from closing to opening of the press, divided by the target thickness of the board.
  • the target thickness refers to the board at the end of pressing step c) or c′) and is adjusted by the press conditions, i.e. by the distance between the top and bottom press plate, which is adjusted by inserting two steel spacing strips in the press (if the hot press was used) or by the automatic distance control (if the HF press was used)
  • Press time factor [sec/mm] time from closing to opening of the press [sec]: target thickness of the pressed board [mm]. For example, when a 10 mm chipboard is made with a press time of 120 sec, a press time factor of 12 sec/mm results.
  • the density of the boards was measured according to EN 323:1993 and is reported as the arithmetic average of ten 50 ⁇ 50 mm samples of the same board.
  • Transverse tensile strength of the boards (“internal bond”) was determined according to EN 319:1993 and is reported as the arithmetic average of ten 50 ⁇ 50 mm samples of the same board.
  • binder amounts in the examples according to the present invention are reported as the total weight of the sum of the respective binder components amino acid polymer(s) A1 and component B1 in wt.-% based on the total dry weight of the wood particles (chips or fibers).
  • binder amounts in the comparative examples are reported as the total weight of the sum of all binder components in wt.-% (dry weight, which is the weight of the components without any water) based on the total dry weight of the wood particles (chips or fibers).
  • Formaldehyde emission was determined according to EN 717-2 and is given in [mg(HCHO)/m 2 h]
  • Ratio of Amino Acid Polymer(s) A1 and Component B1 Ratio A1:B1:
  • the ratio of amino acid polymer(s) A1 and component B1 refers to the weight ratio of amino acid polymer(s) A1 and component B1.
  • the NC ps are measured by potentiometric titration according to EN ISO 9702:1998.
  • the NC ps mean the weight of nitrogen of the primary and secondary amine groups per 100 g of amino acid polymer(s) A1 (given in wt.-%).
  • M w was determined by size exclusion chromatography under the following conditions:
  • the residual lysine monomer content of the polylysine solution was determined by HPLC/MS analysis under the following conditions:
  • the residual lysine monomer content in amino acid polymer A1 is given as wt.-% monomer based on the total weight of polylysine including the lysine monomer.
  • the 50 wt.-% solution of Polylysine-5 with a lysine monomer content of 2.0 wt.-% contains 1 wt. % lysine monomer and 49% wt.-% lysine polymer comprising at least 2 condensed lysine units.
  • a fiber-optic sensor was used in combination with a temperature measuring instrument suitable for measurements in an environment with strong electromagnetic radiation.
  • the instrument is integrated into the control system of the HF press (HLOP 170 press from Hoefer Presstechnik GmbH).
  • the sensor of the device is a Teflon-coated glass fiber with a gallium arsenide chip (GaAs chip).
  • 165 g of glucose monohydrate and 150 g of fructose are mixed with 285 g of water and stirred to a solution.
  • boards according to the present invention having an excess of polylysine in the surface layer provide an excellent internal bond strength as well a very low formaldehyde emission.
  • the pre-pressed chip mat was inserted in a HLOP 170 press from Hoefer Presstechnik GmbH, whereby a birch plywood (thickness 6 mm) was placed between the nonwoven separator and the press plate on each side of the mat.
  • the pre-pressed chip mat was then compacted to 10 mm thickness in the press within a period of 2 s, and then heated by applying a high-frequency electrical field (27.12 MHz, anode current 2.5 A) while the press was remaining closed.
  • a high-frequency electrical field 27.12 MHz, anode current 2.5 A
  • the pre-pressed chip mat was inserted in a HLOP 170 press from Hoefer Presstechnik GmbH, whereby a birch plywood (thickness 6 mm) was placed between the nonwoven separator and the press plate on each side of the mat.
  • the pre-pressed chip mat was then compacted to 16 mm thickness in the press within a period of 2 s, and then heated by applying a high-frequency electrical field (27.12 MHz, anode current 2.7 A) while the press was remaining closed.
  • a high-frequency electrical field 27.12 MHz, anode current 2.7 A

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Forests & Forestry (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
US18/269,022 2020-12-23 2021-12-22 Binder composition comprising amino acid polymer(s) as well as carbohydrates for composite articles Pending US20240043616A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP20216816 2020-12-23
EP20216812 2020-12-23
EP20216812.6 2020-12-23
EP20216816.7 2020-12-23
PCT/EP2021/087426 WO2022136611A1 (en) 2020-12-23 2021-12-22 Binder composition comprising amino acid polymer(s) as well as carbohydrates for composite articles

Publications (1)

Publication Number Publication Date
US20240043616A1 true US20240043616A1 (en) 2024-02-08

Family

ID=79730637

Family Applications (2)

Application Number Title Priority Date Filing Date
US18/269,022 Pending US20240043616A1 (en) 2020-12-23 2021-12-22 Binder composition comprising amino acid polymer(s) as well as carbohydrates for composite articles
US18/269,028 Active US11976168B2 (en) 2020-12-23 2021-12-22 Binder composition comprising poly(amino acid)s for fiber composite articles

Family Applications After (1)

Application Number Title Priority Date Filing Date
US18/269,028 Active US11976168B2 (en) 2020-12-23 2021-12-22 Binder composition comprising poly(amino acid)s for fiber composite articles

Country Status (7)

Country Link
US (2) US20240043616A1 (ko)
EP (2) EP4267638A1 (ko)
JP (2) JP2024503800A (ko)
KR (2) KR20230125010A (ko)
AU (2) AU2021405039A1 (ko)
CA (1) CA3203213A1 (ko)
WO (2) WO2022136611A1 (ko)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023148578A1 (en) * 2022-02-04 2023-08-10 Flooring Industries Limited, Sarl Glue for boards
WO2024008940A1 (en) 2022-07-08 2024-01-11 Covestro (Netherlands) B.V. Compositions for fibreboards with enhanced properties upon fast-curing at low temperature
WO2024008938A1 (en) 2022-07-08 2024-01-11 Covestro (Netherlands) B.V. Compositions for fibreboards with enhanced properties upon fast-curing at low temperature
WO2024008939A1 (en) 2022-07-08 2024-01-11 Covestro (Netherlands) B.V. Compositions for fibreboards with enhanced properties upon fast-curing at low temperature
WO2024038153A1 (en) 2022-08-19 2024-02-22 Covestro (Netherlands) B.V. Compositions for fibreboards with enhanced properties upon fast-curing at low temperature
WO2024038152A1 (en) 2022-08-19 2024-02-22 Covestro (Netherlands) B.V. Compositions for fibreboards with enhanced properties upon fast-curing at low temperature
WO2024074400A1 (en) 2022-10-05 2024-04-11 Basf Se Foam based on polylysine

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4214808A1 (de) 1992-05-04 1993-11-11 Basf Ag Verfahren zur Herstellung von Dihydroxyaceton
DE4230466A1 (de) 1992-09-11 1994-03-17 Basf Ag Verfahren zur katalytischen Herstellung von Kondensationsprodukten des Formaldehyds
DE102005056592A1 (de) 2005-11-25 2007-05-31 Basf Ag Herstellung und Verwendung von hochfunktionellen, hoch-oder hyperverzweigten Polylysinen
EP2093266A1 (en) * 2008-02-25 2009-08-26 Rockwool International A/S Aqueous binder composition
EP2386605B1 (en) 2010-04-22 2017-08-23 Rohm and Haas Company Durable thermosets from reducing sugars and primary polyamines
LT2566904T (lt) 2010-05-07 2021-10-25 Knauf Insulation Angliavandeniai poliamido rišikliai ir iš jų pagamintos medžiagos
US10208414B2 (en) * 2012-11-13 2019-02-19 Johns Manville Soy protein and carbohydrate containing binder compositions
US9145506B2 (en) * 2013-07-01 2015-09-29 Jr Co., Ltd. Natural adhesive
WO2015086074A1 (de) 2013-12-12 2015-06-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Formaldehyd-freie harze basierend auf hydroxyaldehyden
GB201408909D0 (en) 2014-05-20 2014-07-02 Knauf Insulation Ltd Binders
GB201412709D0 (en) 2014-07-17 2014-09-03 Knauf Insulation And Knauf Insulation Ltd Improved binder compositions and uses thereof
WO2016062578A1 (en) 2014-10-21 2016-04-28 Basf Se A process for preparing polylysines
MX2017011073A (es) * 2015-03-04 2017-11-10 Solenis Tech Lp Metodo para fabricar materiales compuestos lignocelulosicos.
GB201517882D0 (en) 2015-10-09 2015-11-25 Knauf Insulation Ltd Wood particle boards
WO2018190662A2 (ko) * 2017-04-13 2018-10-18 씨제이제일제당(주) 바인더 조성물, 물품 및 물품 제조방법
KR101922644B1 (ko) 2017-04-13 2018-11-27 씨제이제일제당 주식회사 바인더 조성물, 물품 및 물품 제조방법
CN108084959A (zh) * 2017-12-06 2018-05-29 常州杰轩纺织科技有限公司 一种复合改性大豆蛋白胶黏剂的制备方法

Also Published As

Publication number Publication date
JP2024503800A (ja) 2024-01-29
KR20230125256A (ko) 2023-08-29
EP4267635A1 (en) 2023-11-01
AU2021405761A1 (en) 2023-07-06
KR20230125010A (ko) 2023-08-28
CA3203213A1 (en) 2022-06-30
US20240043617A1 (en) 2024-02-08
US11976168B2 (en) 2024-05-07
JP2024503588A (ja) 2024-01-26
EP4267638A1 (en) 2023-11-01
WO2022136611A1 (en) 2022-06-30
WO2022136612A1 (en) 2022-06-30
AU2021405039A1 (en) 2023-07-06

Similar Documents

Publication Publication Date Title
US11976168B2 (en) Binder composition comprising poly(amino acid)s for fiber composite articles
CA3203220A1 (en) Binder composition comprising amino acid polymer(s) as well as carbohydrates for composite articles
KR20230125255A (ko) 복합체 물품을 위한, 폴리아민(들)과 하이드록시아세톤을포함하는 결합제 조성물
US6458238B1 (en) Adhesive binder and synergist composition and process of making lignocellulosic articles
US20200071530A1 (en) Unitary mat having increased green strength and method of forming the same
KR102652066B1 (ko) 카프로락탐 및 카프로락탐의 올리고머의 존재하 리그노셀룰로스 물질의 제조 방법
WO2023247437A1 (en) Binder for wood-based panels comprising amino acid polymer and polyaldehyde compound
EP4155338A1 (en) Tannin-based non-isocyanate polyurethane adhesives
WO2023247431A1 (en) Binder composition, comprising basic substances, for producing a lignocellulosic composite, respective process, use and products
WO2024088944A1 (en) Process of producing a lignocellulosic composite and corresponding binder composition, lignocellulosic composite, kit and use
US20180298195A1 (en) Production process of the resins containing polyflavonoid and derivatives and their application in the wood based composite board products

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

AS Assignment

Owner name: BASF SE, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SOMMER, GEREON ANTONIUS;WEINKOETZ, STEPHAN;TUERP, DAVID;AND OTHERS;SIGNING DATES FROM 20211221 TO 20230321;REEL/FRAME:067240/0152