Compositions Suitable for Enhancing the Flexural Properties of Objects Containing Vegetable Fibers

Abstract

The invention relates to compositions including a constituent-A, which constituent-A consists of a polylysine component and a fibrous component which fibrous component consists of at least one fibrous element which fibrous element includes vegetable fibers. The fibrous element is free of any fibers other than the vegetable fibers. The composition is free of any fibers other than the vegetable fibers of the fibrous component (compositions of the invention). The invention further relates to processes for obtaining an object from the compositions of the invention. The invention further relates to objects such as sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood (e.g. fibreboards) obtained by said processes. The invention further relates to articles including a) a part which is solid at 23 C. and 1 atm; and one or both of b) and c), wherein b) is a composition of the invention, and c) is an object of the invention (articles of the invention). The invention further relates to various uses of any one or any combination of the compositions of the invention, the objects of the invention and the articles of the invention.

Claims

1-22. (canceled)

23. A composition comprising a constituent-A, which constituent-A consists of: a polylysine component, and a fibrous component, wherein the polylysine component is selected from the group consisting of polylysines-X and mixtures thereof, and wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines, wherein each one of the polylysines-X has a degree of branching as determined by .sup.1H-NMR spectroscopy, of at least 0.30 and at most 0.60, an apparent viscosity as determined by the Rheometry Method, of at least 400 and at most 8000 mPa.Math.s, and a gel content as determined by the Gel-Content Method, of at most 4.0%, and the fibrous component consists of at least one fibrous element which fibrous element comprises vegetable fibers, and wherein the fibrous element is free of any fibers other than the vegetable fibers, and wherein the composition is free of any fibers other than the vegetable fibers of the fibrous component, and wherein the composition optionally comprises a constituent-B which is selected from the group consisting of proteins and mixtures thereof, and the constituent-B is different and distinct from any other component and constituent of the composition, in an amount of at most 0.30 wt. % of the composition, and wherein the composition optionally comprises a constituent-C which is selected from the group consisting of polyphenolic macromolecular compounds and mixtures thereof, wherein each of the polyphenolic macromolecular compounds is a macromolecular compound which bears a multitude of phenol or polyhydroxybenzene radicals, and the constituent-C is different and distinct from any other component and constituent of the composition, in an amount such that a ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.40.

24. The composition as claimed in claim 23, wherein the polylysines-X are selected from the group consisting of hyperbranched polylysines and primary ammonium salt of hyperbranched polylysines wherein the anion that counters the at least one primary ammonium cation (NH.sub.3.sup.+) present in the structure of the primary ammonium salt of hyperbranched polylysines is selected from the group consisting of fluoride, chloride, bromide and iodide.

25. The composition as claimed in claim 23, wherein the polylysines-X are hyperbranched polylysines.

26. The composition as claimed in claim 23, wherein the composition is free of constituent-B.

27. The composition as claimed in claim 23, wherein the ratio of the total weight of the constituent-C divided by the total weight of the polylysine component is at most 0.15.

28. The composition as claimed in claim 23, wherein each one of the polylysines-X has a degree of branching of at least 0.30 and at most 0.55.

29. The composition as claimed in claim 23, wherein each one of the polylysines-X has an apparent viscosity of at least 400 and at most 6000 mPa.Math.s.

30. The composition as claimed in claim 23, wherein each one of the polylysines-X has a gel content of at most 1.0%.

31. The composition as claimed in claim 23, wherein each one of the polylysines-X has: a number average molecular weight (M.sub.n) weight as determined by the Gel-Permeation Chromatography Method, of at least 1100 and at most 10000 Da, a weight average molecular weight (M.sub.wK.sub.N) as determined by the Gel-Permeation Chromatography Method, of at least 3000 and at most 50000 Da, a polydispersity calculated as the ratio of M.sub.w/M.sub.n, of at least 2 and at most 15, an apparent viscosity of at least 400 and at most 6000 mPa.Math.s, an amine number as determined by the Titration Method of at least 200 and at most 700 mg KOH/g, an acid value as determined by the Titration Method, of at least 10 and at most 150 mg KOH/g, and a gel content of at most 3.0%.

32. The composition as claimed in claim 23, wherein the polylysine component is present in an amount of at least 0.1 and at most 30.0 wt % of the composition.

33. The composition as claimed in claim 23, wherein the vegetable fibers are selected from the group consisting of natural cellulose fibers, natural lignocellulosic fibers, and mixtures thereof.

34. The composition as claimed in claim 23, wherein the vegetable fibers are selected from the group consisting of wood fibers, reed fibers, bamboo fibers, seaweed, jute fibers, flax fibers, hemp fibers, ramie fibers, manila fibers, sisal fibers, kapok fibers, cotton, banana fibers, coconut fibers, rye fibers, wheat fibers, rice fibers, kenaf fibers, straw fibers, grass fibers, leaf fibers, and mixtures thereof.

35. The composition as claimed in claim 23, wherein the vegetable fibers are selected from the group consisting of wood fibers, reed fibers, and mixtures thereof.

36. The composition as claimed in claim 23, wherein the fibrous element is selected from the group consisting of fibers, filaments, yarns, strips, strands, threads, staple fiber yarns, particles, chips, shavings, flakes, lamellae, pulp, and mixtures thereof.

37. The composition as claimed in claim 23, wherein the fibrous component consists of wood chips wherein the d50 which is the median value of the particle size distribution of the wood chips determined according to the ISO 17827-1:2016, is at least 1 and at most 50 mm.

38. A process for obtaining an object wherein the process comprises the steps of: providing a composition as claimed in claim 23; and subjecting the composition to heat and/or pressure and/or vacuum, preferably simultaneous heat and pressure, to form an object, and collecting the object.

39. An object obtained by a process as claimed in claim 38.

40. The object as claimed in claim 39, wherein the object is selected from the group consisting of sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood.

41. The object as claimed in claim 39, wherein the object is engineered wood.

42. The object as claimed in claim 39, wherein the object is fibreboard.

43. An article comprising: a) a part which is solid at 23 C. and 1 atm; and b) a composition as claimed in claim 23.

44. A method of producing at least one of: absorbents, 3D-printing articles, automotive applications articles, marine applications articles, aerospace applications articles, medical items, defense applications articles, sports/recreational applications articles, architectural applications articles, bottling applications articles, household applications articles, machinery applications articles, can applications articles, coil applications articles, energy related applications articles, and electricity related applications articles, the method comprising providing the composition as claimed in claim 23.

Description

[0151] For illustration, FIG. 1 depicts a hyperbranched polylysine which has a DB of 0.4 and a theoretical (calculated) molecular weight of 3350.6 Da. FIG. 2 depicts a primary ammonium salt of hyperbranched polylysine wherein the anion that counters some of the primary ammonium cations (NH.sub.3.sup.+) present in the structure of the primary ammonium salt of hyperbranched polylysines is chloride, and wherein the primary ammonium salt of hyperbranched polylysine of FIG. 2 has a DB of 0.4 and a theoretical (calculated) molecular weight of 3569.3 Da.

[0152] Lysine (in either of its two enantiomeric forms, namely D- and L-lysine; L and D refer to the chirality at lysine's central carbon atom) which is the precursor amino acid, contains two amino groups; one at the -carbon and one at the -carbon. Either of these two amino groups can be the location of polymerization. In principle polylysines are formed from lysine or lysine salt [L-lysine, D-lysine, or any mixture thereof of L-lysine, e.g. a racemic mixture; or L-lysine salt, D-lysine salt or any mixture thereof e.g. a racemic mixture) in a polycondensation reaction in which water is released when an amino group of one lysine molecule and a carboxyl group of another lysine molecule react with each other to form an amide bond under production of water. The removal of water from the reaction mixture favours the polylysine formation.

[0153] Hyperbranched polylysines may be prepared via various processes. In principle the processes for preparing hyperbranched polylysines may be categorized in four major categories: i) processes based on the ring opening addition polymerization of e-protected L-lysine-N-carboxyanhydrides (NCAs) with a nucleophilic starter, ii) processes where derivatives of L-lysine*xHCl that are activated on the carboxyl group, are used, iii) processes involving the direct thermal addition polymerization of L-lysines, and iv) processes where in the presence of at least one catalyst selected from the group consisting of tertiary amines, basic alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkoxides, alkanoates, chelates, organometallic compounds of metal groups IIIA to VIIIA or IB to VB in the Periodic Table of Elements, a salt of lysine with at least one acid is involved. The following paragraphs in this section provide for some examples of processes for preparing hyperbranched polylysines e.g. hyperbranched polylysines reading on the claimed invention.

[0154] Hyperbranched polylysines can be prepared by what is called the AB.sub.2 route. An AB.sub.2 molecule is a term used to refer to a trifunctional monomer containing one reactive group A and two reactive groups B; Where these groups A and B are reactive with one another, hyperbranched polymers can be produced by intermolecular reaction. Lysine is an example of such a trifunctional monomer where the reactive group A is the carboxyl group and each of the two reactive groups B is the amino group of the lysine and where these A and B groups in the lysine are reactive with one another; thus, an AB.sub.2 polymerization route of lysine leads to hyperbranched polylysines.

[0155] Hyperbranched polylysines can also be prepared as follows: a reactor, e.g. a glass-reactor equipped with a distillation set-up is charged with L-lysine in water (50 wt. %). Upon the completion of the charge of the reactor with L-lysine in water (50 wt. %), the reactor is slowly (over 2-8 hours) heated up to 120-190 C. (the slow increase in temperature is essential to avoid precipitation of unreacted L-lysine in the reactor, which can occur if too much water has distilled off before sufficient reaction conversion). When the desired reaction temperature has been reached, the reaction then proceeds for 2-30 hours at the desired temperature. Optionally, L-lysine in water (50 wt. %) can be added to the reactor as water is being distilled off, in order to maintain the reactor's filling at a certain level. The reaction is monitored by taking samples over regular time periods, diluting the samples to 60 wt. % in water, and measuring the apparent viscosity. When the apparent viscosity of these samples is at the desired viscosity, the reaction mixture is discharged. If necessary, water can be added to the reaction mixture prior to discharging in order to yield a product with the desired solids content and apparent viscosity. The reactor that may be used in this process can be a high-pressure reactor. If a high-pressure reactor is used in this process, then said high-pressure reactor, equipped with a distillation set-up which distillation set-up is connected to the reactor via a pressure release valve, is charged with L-lysine in water (50 wt. %). Upon charging the high-pressure reactor with L-lysine in water (50 wt. %), the pressure in the high-pressure reactor starts to build up while the pressure release valve is closed off and the reactor is heated up to 120-190 C. The pressure in the reactor is preferably maintained between 1-6 bar (1 bar=100000 Pa) during the reaction; this preferred pressure range is also maintained during the reaction when the pressure release valve is being carefully and periodically opened and closed to allow for the distillation of water and some pressure release. When the desired reaction temperature has been reached, the reaction then proceeds for 2-30 hours at the desired temperature. Optionally, L-lysine in water (50 wt. %) can be added to the reactor as water is being distilled off, in order to maintain the reactor's filling at a certain level. The reaction is monitored by taking samples over regular time periods, diluting the samples to 60 wt. % in water, and measuring the apparent viscosity. When the apparent viscosity of these samples is at the desired viscosity, the reaction mixture is discharged. If necessary, water can be added to the reaction mixture prior to discharging in order to yield a product with the desired solids content and apparent viscosity. The preparation of hyperbranched polylysines in agreement with the invention shown in the Examples offer examples of the processes described above in this paragraph.

[0156] Another way for preparing hyperbranched polylysines, uses L-lysine hydrochloride as starting material. The polymerisation of L-lysine hydrochloride was performed as follows: L-lysine hydrochloride (550 g, 3 mol) and NaOH (120 g, 3 mol) are added to a 1-L glass reactor with a distillation set-up. This reactor is heated to 120-190 C. and stirred for 2 to 30 hours. In order to follow the reaction, samples are taken every few hours, dissolved in water to a 60 wt. % solids content, and the apparent viscosity measured. To discharge, water (the amount added is calculated so the reaction mixture will have a resultant solid content of 70-80 wt. %) is added dropwise to the reactor and as water is added the temperature is lowered to 90 C. The resultant reaction mixture in water (solid content 70-80 wt. %) is then discharged at 90 C.

[0157] Another way for preparing hyperbranched polylysines, uses L-lysine hydrochloride and L-lysine as starting materials. According to this L-lysine in water (50 wt. %) (409.4 g, 1.4 mol), L-lysine hydrochloride (255.7 g, 1.4 mol), and NaOH (55.8 g,1.4 mol) were added to a 1-L glass reactor. This reactor is heated to 120-190 C. and stirred for 2 to 30 hours. In order to follow the reaction, samples are taken every few hours, dissolved in water to a 60 wt. % solids content, and the apparent viscosity measured. To discharge, water (the amount added is calculated so the reaction mixture will have a resultant solid content of 70-80 wt. %) is added dropwise to the reactor and as water is added the temperature is lowered to 90 C. The resultant reaction mixtures in water (solid content 70-80 wt. %) is then discharged at 90 C.

[0158] A yet another process for preparing hyperbranched polylysines is based on the ring-opening addition polymerization of -protected L-lysine-N-carboxyanhydrides (NCAs) with a nucleophilic starter. Examples of this process were disclosed by Klok et al., in WO 2003/064452 and in Macromolecules 2002, 35, 8718-8723 and by Rodriguez-Hernandez et al. in Biomacromolecules 2003, 4, 249-258. According to the latter, a mixture of N.sup.e-trifluoroacetyl-L-lysine-NCA (TFA-Lys-NCA) and Z-lysine-NCA were subjected to ring-opening polymerization with an aliphatic amine. In a separate coupling step N.sup.,N.sup.-di(9-fluorenyl-methoxycarbonyl)-L-lysine (N.sup.,N.sup.-diFmoc Lys) was introduced as a branching point. Deprotection with piperidine in dimethyl formamide (DMF) gave two new amine groups, which allowed ring-opening polymerization of TFA-Lys-NCA and Z-Lys-NCA. These reaction cycles were repeated a number of times. Structurally similar hyperbranched block copolymers have also been described by Birchall et al. in Chem. Commun. 1998, 1335-1336. a-Amino acid NCAs were subjected to ring-opening polymerization with an aliphatic amine. N,N-Di(benzyloxycarbonyl)-L-lysine p-nitrophenyl ester was introduced as a branching point, and after deprotection of H.sub.2/Pd/C had two free amine groups for the further ring opening of amino acid NCAs. These reaction cycles were repeated a number of times.

[0159] A yet another process for preparing hyperbranched polylysines is based on derivatives of L-lysine*2HCl which are activated on the carboxyl group. According to this process hyperbranched polylysines were prepared in a one-pot synthesis with activation of the carboxyl group by means of N-hydroxy succinimide (NHS). NHS-activated L-lysine*2HCl was stirred for 23 hours in dimethyl sulfoxide (DMSO) with the addition of catalytic amounts of dimethyl aminopyridine (DMAP) and 3 equivalents of diisopropyl-ethylamine (DIEA), and the polymer was precipitated from ethyl acetate.

[0160] A yet another process for preparing hyperbranched polylysines is based the thermal addition copolymerization of amino acid mixtures. The thermal addition polymerization of free lysine is known and has been carried out under various reaction conditions. Plaquet and co-workers (Biochimie 1975, 57 1395-1396) polymerized L-lysine in aqueous solution at 105 C. for a period of up to 10 weeks, or else by heating at 165 C. for 8 hours. The reaction was carried out without catalyst and the yields, at below 72.5% without exception, were very low. Harada (Bull. Chem. Soc. Japan 1959, 32, 1007-1008) polymerized L-lysine at 180 to 230 C. for between 30 minutes and 2 hours under a nitrogen atmosphere. Rohlfing and co-workers (Archives of Biochemistry and Biophysics 1969, 130, 441-448) polymerized L-lysine (free base) under a nitrogen atmosphere at between 186 and 192 C. WO 00/71600 described the condensation of L-lysine monohydrate in a pressure apparatus. Fox et al. (BioSystems 1976, 8, 40-44) used not only L-lysine but also L-lysine*HCl as starting monomers for the thermal polymerization at 195 C. L-Lysine*HCl was brought to reaction with the addition of orthophosphoric acid at 195 C.

[0161] U.S. Pat. No. 8,846,842 B2 disclosed yet another process for preparing polylysines that does not require protective-group operations or activation of carboxyl groups and in which it is also possible to attain higher molecular weights than those known from the prior art. The object has been achieved by means of a process for preparing non-crosslinked hyperbranched polylysines by reacting: [0162] (A) a salt of lysine with at least one acid, [0163] (B) if appropriate, at least one amino acid other than lysine, [0164] (C) if appropriate, at least one dicarboxylic or polycarboxylic acid or copolymerizable derivatives thereof and [0165] (D) if appropriate, at least one diamine or polyamine or copolymerizable derivatives thereof, [0166] (E) if appropriate, in at least one solvent at a temperature from 120 to 200 C. in the presence of at least one catalyst (F) selected from the group consisting of (F1) tertiary amines and amidines, (F2) basic alkali metal salts, alkaline earth metal salts or quaternary ammonium salts, and (F3) alkoxides, alkanoates, chelates or organometallic compounds of metals from groups IIIA to VIIIA or IB to VB in the Periodic Table of the Elements. With this process it is possible to prepare non-crosslinked hyperbranched polylysines having a weight average molecular weight M.sub.w of up to 750000 Da.

[0167] Hyperbranched polylysines can, for example, be synthesized by direct thermal addition polymerization of L-lysine or ammonium salts of L-lysine. The thermal addition polymerization of lysine is carried out in the absence of solvent. WO 2007/060119 described the polycondensation of L-lysine hydrochloride in the presence of sodium hydroxide, water (10 wt. % based on the L-lysine hydrochloride) and the catalyst dibutyltin dilaurate. The mixture was heated with stirring to an internal temperature of 150 C. After a reaction time of 5 hours, water was distilled off under reduced pressure (200 mbar), and after the major amount of water was removed the temperature was slowly raised to 180 C. and the pressure was reduced to 10 mbar. After 8 hours, 240 g of water distillate had been collected. Hennon et al. (Biochimie 1971, 53, 215-223) described the preparation of a brown resin starting from an aqueous solution of lysine (50 wt. %). The solution was concentrated by evaporation at 105 C. to 110 C. and then kept at 165 C. to 170 C. while it was agitated by directing a weak preheated nitrogen stream through it. The brown resin was obtained after 8 hours at 165 to 170 C. Ho et al. described the synthesis of polylysine by thermally heating an aqueous lysine solution for two days at 160 C. The obtained polylysine had a degree of branching between 0.50 and 0.54. When using microwave assisted heating at 200 C., the obtained polylysine had a degree of branching between 0.30 and 0.32. US 2013/0123148 disclosed the preparation of polylysine by heating an aqueous lysine solution in the presence of catalytical amounts of dibutyltin dilaurate. According to the examples of US 2013/0123148, the obtained polylysines had a degree of branching above 0.30.

[0168] WO 2016/062578 A1 disclosed a process for the preparation of hyperbranched polylysines suitable for large scale production of polylysine with improved yield. According to the WO 2016/062578 A1 polylysines can be prepared by a process comprising the steps of: (a) heating a boiling aqueous reaction mixture comprising lysine and water in a weight ratio of 1:10 to 3:1 within 2 to 8 hours, for example within 4 to 8 hours, to a temperature in the range from 135 to 165 C., and (b) keeping the reaction mixture of step (a) at a temperature in a range from 135 to 165 C. at a pressure below atmospheric pressure, wherein water is removed from the mixture, and any temperature increase is less than or equal to 30 C. in 60 minutes. Customary technical aqueous lysine solutions can be used in the process as disclosed in WO 2016/062578 A1 and no catalyst is required. At the end of the second step, the mixture is in a liquid state, e.g., a melt of polylysine, not a resin. Preferably, the aqueous starting mixture is an aqueous solution of lysine in water. The lysine comprised by the aqueous starting mixture can be L-lysine, D-lysine, or any mixture of L-lysine and D-lysine, e.g. a racemic mixture. The aqueous starting mixture can, for example, be an aqueous solution of L-lysine in water that contains 50 wt. % of L-lysine and 50 wt. % of water; e.g., ADM Liquid L-Lysine, Product Code: 035101 supplied by Archer Daniels Midland, Sewon L-Lysine 50 percent liquid feed supplied by Paik Kwang, or BestAmino L-Lysine liquid feed grade supplied by CJ CheilJedang. Polylysine is formed from lysine in a polycondensation reaction in which water is released when an amino group of one lysine molecule and a carboxyl group of another lysine molecule react with each other to form an amide bond under production of water. The removal of water from the reaction mixture favours the formation of the polylysine. In general, the temperature of the reaction mixture is increased continuously. The process as disclosed in WO 2016/062578 A1 requires that water is removed from the reaction mixture. Any means suitable for removing water may be applied in order to remove water from the reaction mixture. Water is preferably evaporated from the mixture. The water is most preferably removed from the mixture by distillation. This process requires a pressure below atmospheric pressure in the second step. The pressure reduction facilitates the evaporation of water and thus accelerates the polycondensation reaction. According to the WO 2016/062578 A1 the weight average molecular weight and number average molecular weight of the polylysine depends on the overall duration of the process and the temperature of the reaction mixture. If the reaction mixture is kept for longer times at higher temperatures, crosslinking is more likely to occur. Preferably, the process is carried out without a catalyst. The process may be carried out continuously or, preferably, batchwise. The process is preferably carried out in what is called a one-pot mode, in which the lysine is included in its entirety in the initial charge and the polycondensation reaction is carried out in a reactor with back-mixing. Also suitable, however, are reaction regimes in a multistage reactor system, a stirred-tank cascade, or in a tube reactor.

[0169] The primary ammonium salt of hyperbranched polylysines can for example be prepared via protonation of the amino groups of a hyperbranched polylysine with for example acidic agents e.g. protic acids, alkenylcarboxylic acids, alkylsulfonic acids. In the context of this specification the agents that may be used for the preparation of the primary ammonium salt of polylysines are called protonation agents. Such protonation, results in a primary ammonium salt of hyperbranched polylysine that contains in its structure at least one primary ammonium cation (NH.sub.3.sup.+) which cation is countered by an anion, and wherein the primary ammonium cation is the cationized form of an amino group of the hyperbranched polylysine. The structure of the anion depends on the reactant used for the protonation of the amino groups of the hyperbranched polylysine; exemplary anions include but are not limited to halide anions (e.g. fluoride, chloride, bromide, iodide) carboxylate anions, sulfonate anions. Preferably the anion is selected from the group consisting of halide anions, carboxylate anions, sulfonate anions, more preferably the anion is selected from the group consisting of halide anions, and carboxylate anions, even more preferably the anion is selected from the group consisting of halide anions, for example the anion is selected from the group consisting of fluoride, chloride, bromide, iodide, for example the anion is selected from the group consisting of chloride, bromide, iodide, for example the anion is selected from the group consisting of chloride and bromide, for example the anion is chloride.

[0170] 3b the Fibrous Component

[0171] The fibrous component is as disclosed in claim 1, or in any one of A1 to A38, or as in any combination derived from the disclosure in sections 1, 3 and the entire specification including the claims.

[0172] The fibrous component consists of at least one fibrous element which fibrous element comprises vegetable fibers, and wherein the fibrous element is free of any fibers other than the vegetable fibers, and wherein the composition is free of any fibers other than the vegetable fibers of the fibrous component. Thus, both the fibrous component and the inventive compositions do comprise only vegetable fibers. Preferably, the vegetable fibers are selected from the group consisting of natural cellulose fibers, natural lignocellulosic fibers, and mixtures thereof. More preferably, the vegetable fibers are selected from the group consisting of wood fibers, reed fibers, bamboo fibers, seaweed, jute fibers, flax fibers, hemp fibers, ramie fibers, manila fibers, sisal fibers, kapok fibers, cotton, banana fibers, coconut fibers, rye fibers, wheat fibers, rice fibers, kenaf fibers, straw fibers, grass fibers, leaf fibers, and mixtures thereof. Even more preferably, the vegetable fibers are selected from the group consisting of wood fibers, reed fibers, and mixtures thereof. Most preferably, the vegetable fibers are wood fibers.

[0173] Preferably the fibrous element comprises vegetable fibers in an amount of at least 20, preferably at least 30, more preferably at least 40, for example at least 50, for example at least 60, for example at least 70, for example at least 80, for example at least 90, for example at least 95, for example at least 96, for example at least 97, for example at least 98, for example at least 99, for example at least 99.5 wt. % of the fibrous element, for example the fibrous element consists of vegetable fibers.

[0174] Preferably the fibrous element is selected from the group consisting of fibers, filaments, yarns, strips, strands, threads, staple fiber yarns, particles, chips, shavings, flakes, lamellae, pulp, and mixtures thereof; preferably the fibrous element is selected from the group consisting of fibers, filaments, yarns, threads, staple fiber yarns, particles, chips, shavings, flakes, pulp, and mixtures thereof; more preferably the fibrous element is a wood chip.

[0175] Preferably, the fibrous component consists of wood chips wherein the d50 which is the median value of the particle size distribution of the wood chips determined according to the ISO 17827-1:2016, is at least 1 and at most 50, preferably at least 1 and at most 40, for example at least 1 and most 30, for example at least 1 and at most 20, for example at least 1 and at most 15, for example at least 1 and at most 10, for example at least 1 and at most 8 mm.

[0176] 4. Processes for Making the Compositions of the Invention

[0177] The compositions of the invention can be prepared via a variety of processes which are well-known to one of ordinary skill in the art. For example, compositions of the invention can be prepared by mixing the various components that constitute the compositions of the invention. This mixing can take place well-before the formation of an object of the invention or a short-time before the actual use of a composition of the invention to form an object of the invention. By short time is meant herein at most 60, preferably at most 30, most preferably at most 20, for example at most 15, for example at most 10, for example at most 6, for example at most 5 minutes. The polylysine component may be introduced in the composition as a liquid (e.g. an aqueous dispersion, or a solution), or as a solid (e.g. in a powder form), or as a mixture of a liquid and a solid when for example a mixture of polylysines-X is used. Preferably, the polylysine component is introduced in the compositions of the invention as an aqueous solution or as a solid. Preferably the polylysine component is introduced in the compositions of the invention as an aqueous solution. Preferably the polylysine component is introduced in the compositions of the invention as a solid. Preferably the polylysine component is introduced in the compositions of the invention as a powder.

[0178] A process for preparing a composition of the invention comprises the steps of: [0179] a) providing at least a constituent-A, which constituent-A consists of: [0180] a polylysine component, and [0181] a fibrous component, [0182] wherein [0183] the polylysine and the fibrous component are as disclosed in claim 1 or as in any one of A1 to A38, or as in any combination derived from the disclosure in sections 1, 3 and the entire specification including the claims, [0184] b) mixing the polylysine and fibrous components and any other component (if any at all; e.g. water) contained in the composition of the invention, to obtain the composition of the invention, and [0185] c) optionally collecting and isolating the obtained composition.

[0186] A process for preparing a composition of the invention is provided in the Examples.

[0187] 5. Processes for Making the Objects of the Invention

[0188] The process for making the objects (e.g. fibreboards) of the invention is as disclosed in any one of A39 to A44 or as in any combination derived from the disclosures in sections 1, 3, 4 and the entire specification including the claims.

[0189] A process for preparing objects of the invention is provided in the Examples.

[0190] 6. Objects of the Invention

[0191] The objects of the invention such as sheets, tapes, sticks, strips, films, cloths, containers, boards, panels, beams, frames, planks, engineered wood [for example plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), laminated timber (glulam; glued laminated timber), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel strand lumber (PSL), laminated strand lumber (LSL), finger joint, beams (including I-joints and I-beams), trusses (including roof and floor trusses), transparent wood composites], that contain vegetable fibers, especially vegetable fibers selected from the group consisting of natural cellulose fibers, natural lignocellulosic fibers, and mixtures thereof, more especially vegetable fibers selected from the group consisting of wood fibers, reed fibers, bamboo fibers, seaweed, jute fibers, flax fibers, hemp fibers, ramie fibers, manila fibers, sisal fibers, kapok fibers, cotton, banana fibers, coconut fibers, rye fibers, wheat fibers, rice fibers, kenaf (Hibiscus cannabinus) fibers, straw fibers, grass fibers, leaf fibers, and mixtures thereof, most especially vegetable fibers selected from the group consisting of wood fibers, reed fibers, and mixtures thereof, for example vegetable fibers selected from the group consisting of wood fibers, and mixtures thereof, for example vegetable fibers selected from the group consisting of reed fibers, and mixtures thereof, as disclosed in the claims and the specification (also mentioned herein as inventive objects), are as disclosed in any one of A45 to A49, or any combination derived from the disclosures in sections 1, 3, 4, 5, and the entire specification including the claims.

[0192] Preferably the objects of the invention are selected from the group consisting of plywood, densified wood (including chemically densified wood), fibreboard [the term includes low-density fibreboard (LDF; known also as particle board or chip board), medium-density fibreboard (MDF), and high-density fibreboard (HDF; known also as waferboard, flakeboard)], oriented strand board (OSB), as preferred objects of the invention. Even more preferred objects of the invention are engineered wood and fibreboards, and most preferred fibreboards.

[0193] The objects of the invention can be prepared via a variety of ways (processes) which are well-known to one of ordinary skill in the art. Certain of these processes are as disclosed in any one of A39 to A44, or as in any combination derived from the disclosures in sections 1, 3, 4, 5, and the entire specification including the claims.

[0194] Examples of objects of the invention (and process for obtaining them) are provided in the Examples.

[0195] 7. Articles of the Invention

[0196] The articles of the invention are as disclosed in A50 or as in any combination derived from the disclosures in sections 1, 3, 4, 5, 6 and the entire specification including the claims.

[0197] 8. Uses of the Invention

[0198] The invention provides for uses as disclosed in A51 or as in any combination derived from the disclosures in sections 1, 3, 4, 5, 6, 7 and the entire specification including the claims.

[0199] 9. Other Disclosed Embodiments of the Invention

[0200] The specification also discloses a process for making absorbents, 3D-printed items, automotive items (including but not limited to car parts, agricultural machines, composite structures, ceramic structures), marine items (including but not limited to ships, boats, parts for ships and boats), aerospace items (including but not limited to planes, helicopters, composite structures, ceramic structures, parts for planes, helicopters), medical items (including but not limited to artificial joints, meshes, woven or non-woven sheets, tapes, ribbons, bands, cables, tube-like products for e.g. ligament replacement, composite structures, ceramic structures), defense items (including but not limited to ballistic protection, body armour, ballistic vests, ballistic helmets, ballistic vehicle protection, composite structures, ceramic structures), sports/recreational items (including but not limited to toys, fencing, skates, skateboarding, snowboarding, suspension lines on sport parachutes, paragliders, kites, kite lines for kite sports, climbing equipment, composite structures, ceramic structures), architectural items, (including but not limited to windows, doors, (pseudo-)walls, cable), bottling items, household items (including but not limited to household appliances, whitegoods, furniture, computer housings), machinery (including but not limited to can and bottle handling machine parts, moving parts on weaving machines, bearings, gears, composite structures, ceramic structures, computer housings), can items, coil items, energy related items (including but not limited to generators for wind, tide or solar energy), and electricity related items (including but not limited to cabinets for electrical wire or switch boards), wherein the process comprises the step of providing any one or any combination of i) to iii): [0201] i) a composition as disclosed in claim 1 or in any one of A1 to A38 or as in any combination derived from the disclosure in sections 1, 3 and the entire specification including the claims; [0202] ii) an object as disclosed in any one of A45 to A49, or any combination derived from the disclosure in sections 1, 3, 4, 5, 6 and the entire specification including the claims; [0203] iii) an article according as disclosed in A50, or any combination derived from the disclosure in sections 1, 3, 4, 5, 6, 7 and the entire specification including the claims.

10. Examples

[0204] The invention is explained in more detail with reference to the following non-limiting examples which are by way of illustration only.

[0205] All the Examples shown in this section were carried out in a controlled laboratory environment at standard conditions (as these are defined in the specification), relative humidity of 501% and an airflow of 0.1 m/s, unless otherwise explicitly specified.

[0206] A. Chemicals, raw materials and other materials SEWON L-Lysine (50 wt. % of L-lysine in water, Lot No. 181224) was supplied by Daesang and it was used as supplied. SUPRO 500E (light yellow powder; soy protein isolate, with a protein content of >90 wt. % (reported by the supplier), and a dry content of 94 wt. % (reported by the supplier) was supplied by DuPont Danisco and it was used as supplied. The soy protein isolate (abbreviated as SPI) represents the protein content of the SUPRO 500E taking into account also the dry content of the SUPRO 500E. The amount of SPI shown in the compositions of Table 1 refers to the amount of protein having taken into account also the dry content of the SUPRO 500E used in the compositions of Table 1. Soy bean meal defatted (abbreviated as SBM) (light yellow powder with a protein content of 47 wt. %) was supplied by Extreme Carp Baits (www.ecbaits.nl). The amount of SBM shown in the compositions of Table 1 refers to the amount of protein of the SBM used in the compositions of Table 1. GOHSENX Z-220 [solid; acetoacetylated poly(vinylalcohol), saponification value 90.5-92.5 mol % (reported by the supplier), and volatile matter: max 5.0 (reported by the supplier); the GOHSENX Z-220 had a viscosity 11.5-15.0 mPa.Math.s (measured at 20 C. as a 4 wt. % aqueous solution; (reported by the supplier); pH: 3.5-5.5 (measured at 30 C. as a 4 wt. % aqueous solution; (reported by the supplier)] was supplied by Mitsubishi Chemicals. The GOHSENX Z-220 was diluted in water in order to prepare an 16.5 wt. % aqueous solution (abbreviated AAPVA-AQ); this aqueous solution (AAPVA-AQ) was used in the examples for the preparation of certain compositions and fibreboards; the abbreviation AAPVA refers to the solid content of the AAPVA-AQ. The Starlig MG50 supplied by LignoStart Internation B.V. was used as a source for magnesium lignosulfonate (CAS No.: 8061-54-9); Starlig MG50 is an aqueous solution that contains 50 wt. % of magnesium lignosulfonate in water (pH=5.5; Mg content is 6 wt. %); the amount of magnesium lignosulfonate shown in the compositions of Table 1 refers to the amount of magnesium lignosulfonate itself and not to that of Starlig MG50. -Polylysine (light yellow powder with a purity of 99.4%) was supplied by Bonding Chemical. The -Polylysine had a M.sub.n of 21301 Da, a M.sub.w of 22061 Da and a polydispersity (PD) (=M.sub.w/M.sub.n) of 1.04, determined by the GPC-Method described in this specification, and an apparent viscosity determined by the Rheometry Method described in this specification, of 32480 mPa.Math.s. This polylysine is mentioned in the examples as PLL-5 and it is not according to the claimed invention. Wood chips with a water content of 2.7 wt. %, density of 240 kg/m.sup.3 and a d50 (median value of the particle size distribution of the wood chips; according to the ISO 17827-1:2016) of 4.5 mm, were used to prepare the objects (fibreboards; FB) shown in the Examples.

[0207] B. Preparation of a Polylysine Component

[0208] B.1 Hyperbranched Polylysine 1 (PLL-1)

[0209] The preparation of the hyperbranched polylysine 1 (PLL-1) was carried out as follows: 3400 g of SEWON L-Lysine were added at room temperature, to a 5 litre high-pressure reactor equipped with a distillation set up which was connected to the reactor via a pressure release valve (herein PR valve); once all the amount of SEWON L-Lysine was introduced into the reactor, the PR valve was closed off. Subsequently, the temperature in the reactor was slowly (over 2 hours) raised to 130 C. and the pressure reached 3.5 bar. Once the temperature in the reactor reached 130 C., the PR valve was then carefully opened to allow for the distillation of water; the temperature of the reactor was maintained at 130 C. up until a solids content of 821 wt. % was obtained; during this stage and in order to maintain a mass of about 3400 g in the reactor, SEWON L-Lysine was being pumped into the reactor at the same rate that water was being distilled off. Once a solids content of 821 wt. % was obtained (at that time the pressure in the reactor dropped from 3.5 bar to 1.2 bar), then the PR valve was closed off. Subsequently, the temperature and the pressure in the reactor were raised to 160 C. and 50.5 bar, respectively. At this stage, the temperature and the pressure in the reactor were maintained at 160 C. and 50.5 bar, respectively for as long as the apparent viscosity of the content of the reactor (as the apparent viscosity is determined in the specification) reached 612 mPa.Math.s; during this stage, water was being distilled off by periodically and carefully opening the PR valve making sure that the pressure in the reactor was maintained at 50.5 bar. Once the apparent viscosity of 612 mPa.Math.s was achieved, the temperature in the reactor was then decreased to 90 C. whilst the PR valve was closed and whilst pumping into the reactor enough water to reach a solids content of 751 wt. %; subsequently, the content of the reactor was discharged into an aluminium tray. Immediately afterwards, the aluminium tray was placed into a vacuum oven at 100 C. under reduced pressure of 50 mbar for 16 hours to remove the water. The end productthe hyperbranched polylysine 1 (PLL-1)was obtained as a dark brown solid (at standard conditions). The hyperbranched polylysine 1 (PLL-1) was grinded with a KRUPS F203 grinder prior being used in the preparation of the fibreboards.

[0210] Characterization of the hyperbranched polylysine 1 (PLL-1): DB: 0.4 [D=18.8 (integral at 4.15-4.40 ppm); L=13.7 (integral at 3.90-4.10 ppm); L=43.9 (integral at 3.25-3.30 ppm)], gel content: 0.0%; M.sub.n: 3088 Da, M.sub.w: 16369 Da, polydispersity (PD) (=M.sub.w/M.sub.n): 5.30; amine number (AN): 361 mg KOH/g, acid value (AV): 46 mg KOH/g (three ERC peaks were recorded in the Titration Method), apparent viscosity: 701 mPa.Math.s.

[0211] B.2 Hyperbranched Polylysine 2 (PLL-2)

[0212] The preparation of the hyperbranched polylysine 2 (PLL-2) was carried out as follows: 6254 g of SEWON L-Lysine were added at room temperature, to a 10 litre glass reactor equipped with a distillation set up. Subsequently, the temperature in the reactor was slowly (over 4 hours) raised to 105 C. (the slow increase in temperature is essential to avoid precipitation of unreacted L-lysine in the reactor, which can occur if too much water has distilled off before sufficient reaction conversion). Once the temperature in the reactor reached 105 C., the distillation of water starts. The temperature of the reactor was slowly increased to 160 C. At the moment that the reaction reached 130 C., 2610 g SEWON L-Lysine was added slowly into the reactor at the same rate that water was being distilled off. Subsequently, when temperature reached 160 C., the temperature was maintained at 160 C. for 1 hour. After 1 hour at 160 C., vacuum was applied slowly to 100 mbar for as long as the apparent viscosity of the content of the reactor (as the apparent viscosity is determined in the specification) reached 450 mPa.Math.s. Once the apparent viscosity of 450 mPa.Math.s was achieved, the temperature in the reactor was then decreased to 90 C. and water was dosed into the reactor and reach a solids content of 751 wt. %; subsequently, the content of the reactor was discharged into an aluminium tray. Immediately afterwards, the aluminium tray was placed into a vacuum oven at 100 C. under reduced pressure of 50 mbar for 16 hours to remove the water. The end productthe hyperbranched polylysine 2 (PLL-2)was obtained as a dark brown solid (at standard conditions). The hyperbranched polylysine 2 (PLL-2) was grinded with a KRUPS F203 grinder prior being used in the preparation of the fibreboards.

[0213] Characterization of the hyperbranched polylysine 2 (PLL-2): DB: 0.31 [D=11.9 (integral at 4.15-4.40 ppm); L=11.4 (integral at 3.90-4.10 ppm); L=42.4 (integral at 3.25-3.30 ppm)], gel content: 0.0%; M.sub.n: 2678 Da, M.sub.w: 12599 Da, polydispersity (PD) (=M.sub.w/M.sub.n): 4.71 amine number (AN): 372 mg KOH/g, acid value (AV): 69 mg KOH/g (three ERC peaks were recorded in the Titration Method), apparent viscosity: 485 mPa.Math.s.

[0214] B.3 Hyperbranched Polylysine 3 (PLL-3)

[0215] The preparation of the hyperbranched polylysine 3 (PLL-3) was carried out as follows: 6254 g of SEWON L-Lysine were added at room temperature, to a 10 litre glass reactor equipped with a distillation set up. Subsequently, the temperature in the reactor was slowly (over 4 hours) raised to 105 C. (the slow increase in temperature is essential to avoid precipitation of unreacted L-lysine in the reactor, which can occur if too much water has distilled off before sufficient reaction conversion). Once the temperature in the reactor reached 105 C., the distillation of water starts. The temperature of the reactor was slowly increased to 160 C. At the moment that the reaction reached 130 C., 2610 g SEWON L-Lysine was added slowly into the reactor at the same rate that water was being distilled off. Subsequently, when temperature reached 160 C., the temperature was maintained at 160 C. for 1 hour. After 1 hour at 160 C., vacuum was applied slowly to 100 mbar for as long as the apparent viscosity of the content of the reactor (as the apparent viscosity is determined in the specification) reached 1500 mPa.Math.s. Once the apparent viscosity of 1500 mPa.Math.s was achieved, the temperature in the reactor was then decreased to 90 C. and water was dosed into the reactor and reach a solids content of 751 wt. %; subsequently, the content of the reactor was discharged into an aluminium tray. Immediately afterwards, the aluminium tray was placed into a vacuum oven at 100 C. under reduced pressure of 50 mbar for 16 hours to remove the water. The end productthe hyperbranched polylysine 3 (PLL3)was obtained as a dark brown solid (at standard conditions). The hyperbranched polylysine 3 (PLL-3) was grinded with a KRUPS F203 grinder prior being used in the preparation of the fibreboards.

[0216] Characterization of the hyperbranched polylysine 3 (PLL-3): DB: 0.33 [D=13.4 (integral at 4.15-4.40 ppm); L=11.7 (integral at 3.90-4.10 ppm); L=41.8 (integral at 3.25-3.30 ppm)], gel content: 0.0%; M.sub.n: 4535 Da, M.sub.w: 26478 Da, polydispersity (PD) (=M.sub.w/M.sub.n): 5.84, amine number (AN): 337 mg KOH/g, acid value (AV): 49 mg KOH/g (three ERC peaks were recorded in the Titration Method), apparent viscosity: 1520 mPa.Math.s.

[0217] B.4 Hyperbranched Polylysine 4 (PLL-4)

[0218] The preparation of the hyperbranched polylysine 4 (PLL-4) was carried out as follows: 3400 g of SEWON L-Lysine were added at room temperature, to a 5 litre high-pressure reactor equipped with a distillation set up which was connected to the reactor via a pressure release valve (herein PR valve); once all the amount of SEWON L-Lysine was introduced into the reactor, the PR valve was closed off. Subsequently, the temperature in the reactor was slowly (over 2 hours) raised to 130 C. about 2 hours and the pressure reached 3.5 bar. Once the temperature in the reactor reached 130 C., the PR valve was then carefully opened to allow for the distillation of water; the temperature of the reactor was maintained at 130 C. up until a solids content of 821 wt. % was obtained; during this stage and in order to maintain a mass of about 3400 g in the reactor, SEWON L-Lysine was being pumped into the reactor at the same rate that water was being distilled off. Once a solids content of 821 wt. % was obtained (at that time the pressure in the reactor dropped from 3.5 bar to 1.2 bar), then the PR valve was closed off. Subsequently, the temperature and the pressure in the reactor were raised to 190 C. and 50.5 bar, respectively. At this stage, the temperature and the pressure in the reactor were maintained at 190 C. and 50.5 bar, respectively for as long as the apparent viscosity of the content of the reactor (as the apparent viscosity is determined in the specification) reached 4800 mPa.Math.s; during this stage, water was being distilled off by periodically and carefully opening the PR valve making sure that the pressure in the reactor was maintained at 50.5 bar. Once the apparent viscosity of 4800 mPa.Math.s was achieved, the temperature in the reactor was then decreased to 90 C. whilst the reactor was closed and whilst pumping into the reactor enough water to reach a solids content of wt. %; subsequently, the content of the reactor was discharged into an aluminium tray. Immediately afterwards, the aluminium tray was placed into a vacuum oven at 100 C. under reduced pressure of 50 mbar for 16 hours to remove the water. The end productthe hyperbranched polylysine 4 (PLL-4)was obtained as a dark brown solid (at standard conditions). The hyperbranched polylysine 4 (PLL-4) was grinded with a KRUPS F203 grinder prior being used in the preparation of the fibreboards.

[0219] Characterization of the hyperbranched polylysine 4 (PLL-4): DB: 0.27 [D=12.45 (integral at 4.15-4.40 ppm); L=19.38 (integral at 3.90-4.10 ppm); L=42.76 (integral at 3.25-3.30 ppm)], gel content: 5.0%, M.sub.n: n.m. Da (insoluble), M.sub.w: n.m. Da (insoluble), polydispersity (PD) (=M.sub.w/M.sub.n): n.m., amine number (AN): 213 mg KOH/g, acid value (AV): 52 mg KOH/g (three ERC peaks were recorded in the Titration Method), apparent viscosity: 4900 mPa.Math.s.

[0220] C. Analytical Methods and Techniques

[0221] C.1 Determination of the M.sub.n, M.sub.w (Gel-Permeation Chromatography Method Abbreviated Also as GPC-Method)

[0222] The number average molecular weight (M.sub.n) and the weight average molecular weight (M.sub.w) were determined by Gel Permeation Chromatography (GPC) calibrated with a set of narrow polyethylene glycol standards (CAS 25322-68-3; product number PL2070-0201; molecular weights between 200 and 30000 Da) Standards are supplied by Agilent Technologies and using as eluent a solution of 100 mM Sodium Acetate and 50 mM acetic acid in MilliQ water (the solution having a pH of 4.5) at a flow rate of 1.0 mL/min at 40 C. 15 mg of sample dissolved in 1.5 ml of eluent were used for the measurement; the injection volume was 100 L. The GPC measurements were carried out on an Agilent 1260 MDS system equipped with: i) a refractive index (RI) detector [Aqilent 1260MDS (10 L cell); supplied by Agilent]; ii) a separation module equipped with two Suprema analytical SEC columns (7.8300 mm, pore size 100 , filled with particles having particle size of 3 m, product number: SUA0830031e2) supplied by Polymer Standards Service (PSS). The M.sub.n and M.sub.w were determined with the help of suitable software for data processing (ChemStation, supplied by Agilent).

[0223] C.2 Determination of the Polydispersity (PD)

[0224] Upon determining the M.sub.n and M.sub.w via the Gel-Permeation Chromatography Method, the polydispersity PD was calculated according to the following equation: PD=M.sub.w/M.sub.n.

[0225] C.3 Determination of the Amine Number (AN) and the Acid Value (AV) (Titration Method)

[0226] The amine number (AN) and the acid value (AV) were determined by back-titrimetric analysis using the titrator 808 Titrando (supplied by Metrohm AG) with the 814 USB sample processor (supplied by Metrohm AG), and two electrodes one for the measurement of the pH (pH glass electrode supplied by Metrohm AG with product No. 6.0150.100) and a reference electrode (conductivity measuring cell c=0.8 cm.sup.1 with Pt1000 (fixed cable) supplied by Metrohm AG with product No. 6.9303.110) equipped with a pH meter and titrating the titrate with a solution of 1.000 N KOH in water was used. The titrate consisted of 1.000 g of polylysine (sample) (the amount refers to solids content), 60.00 mL of Millipore Ultra RO water and 10.000 mL of a solution of 1.000 N HCl in water [Titripur supplied by Merck; product number 1.09057]. The data processing and control handling of all titrations described in this were accomplished via the use of the software Tiamo 2.4 supplied by Metrohm AG.

[0227] The titration curve [pH vs. Volume of titrant (x-axis)] (abbreviated as TC) and the first derivative curve of the TC [electrical potential vs. Volume of titrant (x-axis)] are recorded simultaneously and are plotted together in the same graph (pH on Y1-axis and electrical potential on Y2-axis, and volume of titrant on X-axis). The first derivative curve of the TC is known as ERC which stands for Equivalence point Recognition Criteria and is expressed in units for electrical potential (mV). The ERC affords either 2 or 3 peaks (ERC peaks) in succession to each other. Each of these ERC peaks corresponds to a certain volume of titrant. One of these ERC peakstypically the one of highest signal (delta voltage)corresponds to the lowest volume of the titrant (V.sub.min) (in mL) and another one ERC peak corresponds to the highest volume of the titrant (V.sub.max) (in mL).

[0228] The amine number (AN) is determined according to the following formula:

Amine number(mg KOH/g sample)=56.1*(V.sub.maxV.sub.min)

[0229] wherein V.sub.min and V.sub.max are as explained above.

[0230] The acid value (AV) is determined according to the following formula:

Acid value(mg KOH/g sample)=56.1*[V.sub.min[10.00(V.sub.maxV.sub.min)]]

[0231] wherein V.sub.min, V.sub.max are as explained above.

[0232] The measurements for the determination of the AN and AV were performed in duplicate and the reported values for each of the AN and AV were the average of these measurements.

[0233] C.4 Determination of the Apparent Viscosity (Rheometry Method)

[0234] The apparent viscosity (shear stress divided by the shear rate) was determined using the rotational rheometer RheolabQC supplied by Anton Paar, connected to a water bath, controlled at 23.0 C. This method is based on ISO 3219:1993. For this measurement, the appropriate spindle/cup combination and shear rate are chosen based on the estimated apparent viscosity. For all our experiments we used a Z3 spindle/cup combination which and a shear rate of 100 s.sup.1. The cup is then filled with sample (polylysine dissolved in water with a solids content of 601%). The spindle is inserted into the cup, the cup is mounted in the viscometer and the spindle is connected to the instrument. The correct program (for all our measurements we selected the program for the Z3 spindle in combination with a shear rate of 100 s.sup.1) is selected on the RheolabQC and the measurement is performed.

[0235] C.5 Determination of the solids content (Solids-content Method) The solids content (wt. %) was determined using a Halogen Moisture Analyzer HR73 supplied by Mettler Toledo. For this measurement, 1.00 g of sample (polylysine dissolved in water) is weighed onto a glass fiber pad which is placed on an aluminium pan and then heated at 140 C. for 30 minutes. The solids content is determined automatically based on the difference in mass before and after the heating at 140 C.

[0236] C.6 Determination of the Water Content (Water-Content Method)

[0237] The amount of water contained in a an entity for example in a composition, or in a polylysine component, or in a fibrous element or in wood chips, is determined by drying said entity at 120 C. for 24 hours under reduced pressure (50 mbar) in a Thermo Scientific VacuTherm vacuum oven supplied by Thermo Fischer Scientific. The amount of water contained in the entity was calculated according to the following equation:

Water(wt.% of the entity)=[1(M.sub.2/M.sub.1)]100

wherein [0238] M.sub.1: the mass of the entity prior to drying. [0239] M.sub.2: the mass of the entity upon drying (measured within 5 minutes after removing the sample from the oven).

[0240] C.7 Determination of the Degree of Branching

[0241] The degree of branching (DB) of a polylysine is determined by .sup.1H-NMR spectroscopy and calculated according to the equation 1:

[00002]$\begin{array}{cc}\mathrm{DB}=\frac{2D}{2D+L}& \left(\mathrm{equation}1\right)\end{array}$

wherein
D is equal to or higher than 0, L is equal to or higher than 0, and at least one of the D and L is higher than 0; and wherein
D is the integral of the .sup.1H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon; indicated in bold in Formulae D1a and D1b) of any number of the following group(s) shown in Formulae D1a and D1b that may be present in the polylysine (if no such methine protons are present in the polylysine, the D is equal to zero):

##STR00007##

L represents the sum of L.sub. and L.sub., wherein
L.sub. is the integral of the .sup.1H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon; indicated in bold in Formulae L1a and L1b) of any number of any one of the following group(s) shown in Formulae L1a and L1b that may be present in the polylysine (if no such methine protons are present in the polylysine, the L.sub. is equal to zero):

##STR00008##

[0242] and L.sub. is the integral of the .sup.1H-NMR peaks corresponding to the methine proton (shorthand for the proton to the tertiary carbon indicated in bold in Formulae L2a and L2b) of any number of any one of the following group(s) shown in Formulae L2a and L2b that may be present in the polylysine (if no such methine protons are present in the polylysine, the L.sub. is equal to zero):

##STR00009##

[0243] The DB ranges from and including 0 up to and including 1.

[0244] The .sup.1H-NMR spectra were recorded at room temperature on a Bruker Ascend 400 Spectrometer, using deuterated methanol (also known as tetradeuteromethanol or methanol-d.sub.4) as solvent. Methanol-d.sub.4 is the preferred solvent; however, other suitable deuterated solvents may be used. In the case of methanol-d.sub.4 the chemical shifts of the .sup.1H-NMR peaks corresponding to: [0245] the D-proton(s) are found at 4.15-4.40 ppm; [0246] the L.sub.-proton(s) are found at 3.90-4.10 ppm; and [0247] the L.sub.-proton(s) are found at 3.25-3.30 ppm.

[0248] C.8 Determination of the Gel Content (Gel-Content Method)

[0249] The gel content of a polylysine was determined as follows:

[0250] A mixture of 10 wt. % solids content of a polylysine in water was prepared and stored at room temperature for 24 hours. Subsequently, an amount of 3000 g of the mixture thus prepared (herein sample), was filtrated through a pre-weighed (Mf.sub.before) filter e.g. a folded qualitative filter paper, in order to remove any insoluble fraction of average size of at least 5 micron and higher. Once the filtration was completed, the filter was washed with water, the amount of which was double of the amount of the sample. Subsequently, the filter was placed in a vacuum oven at 40 C. under a pressure of 50 mbar, for 12 hours in order to remove any water. Subsequently, the filter was weighed again (Mf.sub.after).

[0251] The gel content was calculated from the equation 2:

[00003]$\begin{array}{cc}\mathrm{Gel}\mathrm{content}\left(\%\right)=\left(\frac{{\mathrm{Mf}}_{\mathrm{after}}-{\mathrm{Mf}}_{\mathrm{before}}}{M_{\mathrm{polylysine}}}\right)100& \left(\mathrm{equation}2\right)\end{array}$

wherein [0252] Mf.sub.after is the mass of the filter after the removal of the water, [0253] Mf.sub.before is the mass of the filter before the filtration of the sample, and [0254] M.sub.polylysine is the mass of the polylysine in the sample (taken into account the solids content of the sample). Thus, in 3000 g of sample having 10% solids content, the M.sub.polylysine is 30 g.

[0255] D. Preparation of the Comparative and Inventive Compositions and Objects (Fibreboards; FB) Thereof

[0256] D.1 Preparation of the Comparative and Inventive Compositions

[0257] The comparative and inventive compositions shown in Table 1 were prepared by mixing the various components of each of those compositions via hand-shaking for 5 minutes. It is reminded that: a) the abbreviation SPI represents the dry content of the SUPRO 500E which was used in preparing the compositions where SPI is mentioned; and b) the abbreviation AAPVA represents to the solid content of the AAPVA-AQ which is an aqueous solution of the GOHSENX Z-220 (16.5 wt. %); the AAPVA-AQ was used in preparing the compositions where the AAPVA is mentioned.

[0258] D.2 Preparation of the Comparative and Inventive Objects (Fibreboards; FB)

[0259] The comparative and inventive objects i.e. fibreboards, were prepared by subjecting their corresponding compositions to simultaneous heating (210 C.) and pressure [9 kg/cm.sup.2=882.6 kPa)] (hot-pressed) for 5 minutes using a suitable hot-press (e.g. Fontype TP800) to form boards of 17 (L)25 (W)1 (T) cm (surface of 425 cm.sup.2).

[0260] The thickness of the inventive fibreboard FB-I1 was 10.4 mm, and the density of the inventive fibreboard FB-I1 was 685 kg/m.sup.3. The thickness of each of the inventive fibreboards FB-I2 to FB-I5 was 10.0 mm. and the density of each of the inventive fibreboards FB-12 to FB-I5 was 700 kg/m.sup.3.

[0261] The thickness of each of the comparative fibreboards FB-C1 to FB-C10 was 10.0 mm. The density of the comparative fibreboard FB-C1 was 725 kg/cm.sup.3 while the density of each of the comparative fibreboards FB-C2 to FB-C10 was 700 kg/m.sup.3

[0262] E. Methods for Determining Properties of the Fibreboards

[0263] E.1 Determination of the Length, Width and Thickness

[0264] The length (L) of the specimens was measured with a ruler at 3 different points of a specimen and the average of these 3 measurements was recorded as the width of the specimen.

[0265] The width (W) of the specimens was measured with a digital ruler at 3 different points of a specimen and the average of these 3 measurements was recorded as the width of the specimen.

[0266] The thickness (T) of the specimens was measured with a digital ruler at 3 different points of a specimen and the average of these 3 measurements was recorded as the thickness of the specimen.

[0267] E.2 Determination of the Density (d)

[0268] Specimens were prepared by cutting the fibreboard prepared in one piece of 150 mm by 40 mm. The length (L; in m), width (W; in m) and thickness (T; in m) of the specimens were measured as mentioned above, as well as their weight (M; in kg).

[0269] The density (d; in kg/m.sup.3) of a specimen was calculated according to the following equation and the average of 2 calculationscorresponding to two different specimens of the fibreboardwas recorded as the density of the fibreboard:

d=M/(LWT)

[0270] E.3 Determination of the Flexural Properties (Static Bending Method)

[0271] The assessment of the flexural properties i.e. i) the modulus of rupture (R.sub.b) and ii) the apparent modulus of elasticity (E) were determined by static bending tests according to the ASTM D1037-12 and in particular section 9 (entitled Static Bending) of the ASTM D1037-12, subject to the following two differences from the provisions of the section 9 of the ASTM D1037-12: i) the specimens were prepared by cutting the produced panel in two pieces of 1501 mm by 401 mm, and ii) each specimen was placed in a 3-point (centre loading) fixture and the length of the span (L) was fixed to 100 mm.

[0272] The static bending tests were carried out on objects prepared upon subjecting their corresponding compositions to simultaneous heat (210 C.) and pressure (9 kg/cm.sup.2==882.6 kPa) for 5 min. In 9.7 of the ASTM D1037-12, the modulus of rupture (R.sub.b) and the apparent modulus of elasticity (E) are defined and calculated according to the following two equations:

[00004]$R_b=\frac{3P_{\max }L}{2{\mathrm{bd}}^2}E=\frac{L^3}{4{\mathrm{bd}}^3}\frac{P}{y}$

wherein [0273] b=width of specimen measured in dry conditions (in mm); [0274] d=thickness of specimen measured in dry conditions (in mm); [0275] P/y=slope of straight line portion of the load-deflection curve (in N/mm); [0276] P.sub.max=maximum load (in N); [0277] L=length of span (in mm); [0278] R.sub.b=modulus of rupture (kPa); [0279] E=apparent modulus of elasticity (kPa).

[0280] The static bending tests were carried out on ZMART.PRO 1445 supplied by ZwickRoell, at a constant rate of speed of 3 mm/min and with the load applied to the centre of each specimen. The test was continued until rupture of the specimen, while recording all force vs. deflection data. From the data obtained, one can calculate the modulus of rupture (R.sub.b) and apparent modulus of elasticity (E), according to the equations provided in 9.7 of the ASTM D1037-12 and which are offered above for convenience. In cases where the object e.g. fibreboard, has been shuttereddue to its fragilityonce it was attempted to be clamped on the ZMART.PRO 1445 and no measurement was carried out because of said sample's fragility, each of the values of R.sub.b and E were set as equal to zero. In other words objects e.g. fibreboards that were so fragile that no measurement of their flexural properties could be performed, received R.sub.b and E values equal to zero. An example of such situation is the comparative object FB-C2 shown in Table 1.

[0281] For any comparison of the flexural properties between an inventive and comparative specimenand in addition to well-established principles of proper comparison as those are known to the skilled person in the art, it is emphasized that: [0282] the total amount of polymeric and non-polymeric entities in the comparative and inventive compositions should be the same, [0283] the fibrous component of the comparative and inventive compositions should be the same (in species and amounts), and [0284] the rest of the components of the comparative and inventive compositions should be the same in species and amounts, [0285] the thickness of the comparative specimen should be within 8% from the thickness of the corresponding inventive specimen, and [0286] the density of the comparative specimen should be within 8% from the density of the corresponding inventive specimen.

[0287] F. Results and Discussion

[0288] Table 1 presents the compositions according to the invention 11 to 15 (inventive compositions), the objects (fibreboards) prepared from the inventive compositions 11 to 15, FB-I1 to FB-I5 (inventive objects) and the flexural properties (R.sub.b=modulus of rupture; E=apparent modulus of elasticity) of the inventive objects (fibreboards). In addition, Table 1 presents the compositions not according to the invention C1 to C10 (comparative compositions), the objects (fibreboards) prepared from the comparative compositions C1 to C10, namely FB-C1 to FB-C10 (comparative objects) and the flexural properties (R.sub.b=modulus of rupture; E=apparent modulus of elasticity) of the comparative objects (fibreboards).

[0289] PLL-1, PLL-2 and PLL-3 are hyperbranched polylysines according to the claimed invention. PLL-5 and PLL-4 are not according to the claimed invention.

[0290] C1 is a comparative composition and represents the best performing composition out of all the examples disclosed in US 2007/0277928 to AKZO Nobel Inc. This composition was shown in Example 3 (and Table 2) of the US 2007/0277928 wherein the weight ratio of SPI to AAPVA (=weight of SPI/weight of AAPVA) was equal to 2 (in Table 3 of the the US 2007/0277928, this corresponds to the experiment where the amount of SPI was 2 g and the amount of AAPVA was 1 g).

[0291] C2 is a comparative composition because the PLL-5 is not according to the invention. C3 is also comparative composition because the PLL-4 is not according to the invention.

[0292] Each one of C4 to C8 is a comparative composition because the protein content in each one of these compositions was higher than 0.3 wt % of the composition. The C6 to C8 offer a simulation of the compositions of CN 110903786 A with respect to various amounts of protein. C6 was formulated with the lowest possible amount of protein content potentially disclosed by CN 110903786 A as this is explained in the description.

[0293] The ratio of the weight of the magnesium lignosulfonate (representing constituent-C) divided by the weight of the PLL-3 (polylysine component) in C9 was equal to 1. The C9 offers a simulation of the compositions of WO 2016/009054 1 (magnesium lignosulfonate was one of the most preferred polyphenolic macromolecular compounds (cf. WO 2016/009054 1, p.3, II. 1-4).

[0294] The ratio of the weight of the magnesium lignosulfonate (representing constituent-C) divided by the weight of the PLL-3 (polylysine component) in C10 was equal to 2. The C10 offers a simulation of the compositions of WO 2016/009054 1 (magnesium lignosulfonate was one of the most preferred polyphenolic macromolecular compounds (cf. WO 2016/009054 1, p.3, II. 1-4).

[0295] The ratio of the weight of the magnesium lignosulfonate (representing constituent-C) divided by the weight of the PLL-3 (polylysine component) in 15 was equal to 0.13.

[0296] Each one of the objects (fibreboard) according to the invention FB-I1 to FB-I5 (herein inventive objects) had surprisingly enhanced flexural properties over any one of the objects (fibreboard) FB-C1 to FB-C10 not according to the invention (herein comparative objects) (see Table 1).

[0297] More specifically, the inventive objects FB-I1 to FB-I5 had: [0298] a modulus of rupture (R.sub.b) in the range of 12.2 to 19.1 MPa, and [0299] an apparent modulus of elasticity (E) in the range of 1250 to 1530 MPa.

[0300] And, the inventive objects FB-I1 to FB-I4 had: [0301] an even higher modulus of rupture (R.sub.b) in the range of 13.0 to 19.1 MPa, and [0302] an even higher apparent modulus of elasticity (E) in the range of 1430 to 1530 MPa.

[0303] The comparative objects FB-C1 to FB-C10 had: [0304] a modulus of rupture (R.sub.b) in the range of 0 to 9.2 MPa, and [0305] an apparent modulus of elasticity (E) in the range of 0 to 985 MPa.

[0306] Upon comparing the flexural properties of the inventive objects FB-I1 to FB-I5 over the comparative objects FB-C1 to FB-C10, the inventive objects FB-I1 to FB-I5 showed an improvement of at least 33% on the modulus of rapture (R.sub.b) and at least 27% on the modulus of elasticity (E) over the comparative objects FB-C1 to FB-C10.

[0307] Upon comparing the flexural properties of the inventive objects FB-I1 to FB-I4 over the comparative objects FB-C1 to FB-C10, the inventive objects FB-I1 to FB-I4 showed an even greater improvement of at least 41% on the modulus of rapture (R.sub.b) and at least 45% on the modulus of elasticity (E) over the comparative objects FB-C1 to FB-C10.

[0308] From the results, it becomes clear that the inventive objects had surprisingly significantly enhanced flexural propertiesi.e. modulus of rupture (R.sub.b) and apparent modulus of elasticity (E)over the comparative objects. Therefore, only the compositions of the claimed invention were able to provide for objects (e.g. fibreboards) having enhanced flexural properties.

TABLE-US-00001 TABLE 1 Composition Magnesium Flexural Properties of Index Wood PLL-5 PLL-4 PLL-2 PLL-3 PLL-1 SPI SBM AAPVA Lignosulfonate Object Object (Fibreboard) No. chips (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) (Fibreboard) R.sub.b (MPa) E (MPa) C2 290.4 17.4 FB-C2 0.0 0 C3 290.4 17.4 FB-C3 6.7 712 I2 290.4 17.4 FB-I2 19.1 1530 I3 290.4 32.3 FB-I3 15.8 1436 I4 290.4 17.4 FB-I4 15.6 1430 I1 290.4 17.4 FB-I1 13.0 1435 I5 290.4 15.4 2.0 FB-I5 12.2 1250 C4 290.4 14.2 3.2 FB-C4 9.2 985 C5 290.4 5.8 11.6 FB-C5 5.0 625 C1 290.4 11.6 5.8 FB-C1 5.5 889 C6 290.4 13.4 4.0 FB-C6 8.1 795 C7 290.4 10.4 7.0 FB-C7 4.5 590 C8 290.4 5.8 11.6 FB-C8 4.4 610 C9 290.4 8.7 8.7 FB-C9 7.1 963 C10 290.4 5.8 11.6 FB-C10 5.8 740