Composition for fiberboards with enhanced properties after rapid curing at low temperatures
By using a combination of polylysine and XL components with plant fibers, fiberboard can be rapidly cured at low temperatures, solving the problem of insufficient strength and elastic modulus of fiberboard in the prior art, and realizing the efficient preparation of durable fiberboard.
Patent Information
- Application Number
- CN202480048669.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2023-08-17
- Filing Date
- 2024-07-24
- Publication Date
- 2026-02-24
AI Technical Summary
Existing technologies make it difficult to rapidly cure fiberboard at low temperatures while simultaneously meeting the requirements for internal bond strength, modulus of rupture, and apparent modulus of elasticity. This results in insufficient resistance of fiberboard to mechanical and physical stress, limiting its application and lifespan.
A composition comprising polylysine, XL and plant fibers is rapidly cured at 120°C to form a fiberboard having an internal bond strength of at least 0.3 MPa, a modulus of rupture of at least 9 MPa and an apparent modulus of elasticity of at least 1600 MPa.
The fiberboard that can be rapidly cured at low temperatures has excellent mechanical and physical stress resistance, improving manufacturing efficiency and product durability, and meeting the needs of industrial applications.
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Abstract
Description
Invention Field
[0001] This invention belongs to the field of compositions comprising plant fibers, hyperbranched polylysine, and components having groups having the following formula. The composition is particularly suitable for preparing objects such as engineered wood, for example, fiberboard.
[0002] background In the context of this invention and in the literature, polylysine refers to various types of lysine homopolymers that may differ from each other in stereochemistry and linkage position. Lysine, as a precursor amino acid (in either of its two enantiomers, namely D- and L-lysine; “L” and “D” refer to the chirality at the central carbon atom of lysine), contains two amino groups; one at the α-carbon and one at the α-carbon. Either of these two amino groups can be the polymerization position, thereby producing α-polylysine or α-polylysine.
[0003] Fibers (or fibers; these terms are used interchangeably in the context of this invention) constitute a class of materials that are continuous filaments or discrete, elongated sheets, similar in length to thread. Human uses of fibers are diverse. They can be spun into filaments, strings, or ropes, used as reinforcing agents in composite materials made into sheets to manufacture products such as paper or felt. Fibers are commonly used in the manufacture of other materials. Fibers can be recycled. In the context of this invention, the term "fiber" also includes recycled fibers.
[0004] Based on their origin, fibers are divided into two main categories: natural fibers and synthetic fibers. Synthetic fibers are also called man-made, artificial, or manufactured fibers.
[0005] Natural fibers are further divided into: i) mineral fibers (e.g., asbestos, wollastonite, attapulgite, hydrous kaolinite), ii) animal fibers (e.g., silk, wool, sinew, cashmere, mohair, angora rabbit hair, animal hair), and iii) plant fibers based on the arrangement of cellulose (also known as "natural cellulose fibers") or the arrangement of cellulose with lignin (also known as "natural lignocellulose fibers"), and derived from sources of natural cellulose or natural cellulose with lignin, such as plants, which are living organisms that absorb water and inorganic substances through their roots and synthesize nutrients in their leaves through photosynthesis using the green pigment chlorophyll, exemplified by trees, bamboo, shrubs, herbs, grasses, ferns, and mosses. Examples of plant fibers include, but are not limited to, wood fiber, reed fiber, bamboo fiber, seaweed, jute fiber, flax fiber, hemp seed fiber, ramie fiber, Manila fiber, sisal fiber, kapok fiber, cotton, banana fiber, coconut fiber, rye fiber, wheat fiber, rice fiber, kenaf (hibiscus cannabinus) fiber, straw fiber, grass fiber, leaf fiber, and mixtures thereof.
[0006] Synthetic fibers (also known as man-made or artificial fibers) can be further classified into: i) cellulose fibers regenerated from natural resources, also known as regenerated cellulose fibers (e.g., rayon, modal, lyocell, cellulose acetate, cellulose triacetate), ii) inorganic fibers and iii) polymer fibers.
[0007] Cellulose fibers are a subset of fibers. Cellulose fibers are fibers derived from cellulose of any source, whether natural or manufactured (the latter also known as synthetic cellulose fibers). Therefore, cellulose fibers can be natural (e.g., from natural cellulose sources such as cellulose fibers from trees (including bamboo) and seaweed) or synthetic (e.g., cellulose fibers regenerated from natural cellulose, such as rayon, modal, lyocell, cellulose acetate, and cellulose triacetate). Synthetic cellulose fibers are also referred to in the art as man-made cellulose fibers, regenerated cellulose fibers, or manufactured cellulose fibers or artificial cellulose fibers.
[0008] In the context of this invention, the terms “synthetic cellulose fiber,” “man-made cellulose fiber,” “made cellulose fiber,” “artificial cellulose fiber,” or “regenerated cellulose fiber” are used interchangeably, and these terms are used to distinguish synthetic cellulose fiber from natural cellulose fiber and natural lignocellulose fiber, both of which are plant fibers.
[0009] One of the most important fiber types is wood fiber, including recycled wood fiber. There are two main types of wood: a) softwood and b) hardwood. Softwood comes from coniferous trees. Exemplary softwoods include, but are not limited to, pine, mahogany, and fir. Softwood can be used for furniture and doors, but is primarily used for the construction of roof trusses and vertical partition walls. Hardwood comes from leafy trees. These trees may have flowers and produce seeds, such as nuts and fruits. Exemplary hardwoods include, but are not limited to, oak, beech, and mahogany. Hardwood is denser and also stronger and more durable than softwood. They are used for furniture and are generally more expensive than softwood. Wood can be recycled. In the context of this invention, the term "wood" also includes recycled wood.
[0010] During timber preparation, timber (softwood, hardwood) is used to manufacture timber (also known as lumber); timber is actually the wood used to make beams and slats. In the context of this invention, the term "solid wood" is used to distinguish timber from engineered wood.
[0011] Engineered timber (also known as mass timber, composite timber, artificial timber, or engineered wood) includes a range of derivative timber products made by bonding or fixing together various wood elements (such as fibers, filaments, yarns, strips, bundles, threads, short fiber yarns, particles, fragments (such as wood chips, sawdust), shavings (such as sawmill shavings), veneers, sheets, boards, pulp (such as wood pulp), and mixtures thereof) through various fixing methods to effectively form composite materials. Exemplary types of engineered timber include, but are not limited to, plywood, densified timber (including chemically densified timber), fiberboard [this term includes low-density fiberboard (LDF; also known as particle board or chip board), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or 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 joints, beams (including I-joints and I-beams), trusses (including roof and floor trusses), and transparent wood composites. Engineered timber products are engineered to precise design specifications, tested to meet national or international standards, and provide consistency and predictability in their structural performance. Engineered timber products are used in a wide range of applications, from residential to commercial buildings and industrial products.
[0012] Fiberboard constitutes a subset of engineered wood. Types of fiberboard (in ascending order of density) include low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or chipboard). In the context of this invention, a density of up to 500 kg / m³ is used. 3 (Preferred to be at least 100 and at most 500 kg / m) 3 Fiberboard with a density higher than 500 kg / m³ is considered LDF. In the context of this invention, LDF refers to fiberboard with a density higher than 500 kg / m³. 3 And at most 1000 kg / m 3 (Preferred weight: at least 550 and at most 800 kg / m³) 3 Fiberboard with a density higher than 1000 kg / m³ is considered MDF. In the context of this invention, MDF refers to fiberboard with a density greater than 1000 kg / m³. 3(Preferred value is above 1000 and at most 1500 kg / m) 3 More preferably, higher than 1000 and at most 1100 kg / m 3 Fiberboard made from materials such as MDF is considered HDF. In principle, fiberboard can be formed using either wet or dry forming processes. In a wet forming process, water is used to distribute the fibers into a pad, which is then pressed into a board. In a dry process, fibers from a refiner pass through a dryer and spray line, where an adhesive is applied, and the fiber is then formed into a web, which is pressed into a board. Typical fiberboard manufacturing (on an industrial scale) begins with wood cutting: fresh or recycled wood material is cut and sorted into small pieces of similar size. The chips are washed to remove things like dust and sand. Metal scraps such as nails can be removed using magnets placed above a conveyor belt used to move the chips forward. In the case of MDF, for example, the chips are then steam-treated to soften them so that the fibers can separate. A small amount of paraffin wax is added to the steam-treated chips, and they are transformed into fluffy fibers in a fiber separator, and shortly thereafter sprayed with urea-formaldehyde (UF) or phenolic (PF) resin. The wax prevents the fibers from clumping together during storage. In the case of particleboard, the fibers or debris can also be sprayed with additional resin before the next step. The fibers or debris are arranged into a uniform "pad" on a conveyor belt. This pad is pre-compressed and then hot-pressed (applying heat and pressure simultaneously). The hot pressing bonds the fibers or debris together. The board is then cooled, trimmed, sanded, and can be faceted or laminated. UF resin is primarily used in the MDF industry.
[0013] In recent years, there has been an increasing need for compositions capable of rapid curing at low temperatures to prepare fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or chipboard)], said fiberboard having: - Internal bond strength of at least 0.3 MPa, - A fracture modulus of at least 9 MPa (R b ),and - Apparent elastic modulus (E) of at least 1600 MPa.
[0014] Fracture modulus (R) b Both apparent elastic modulus (R) and apparent elastic modulus (E) constitute the bending properties of an object, such as fiberboard. The internal bond strength and bending properties of fiberboard are crucial to their consumer acceptance and their commercial success. For internal bond strength, R... bFiberboards that do not meet at least one of the aforementioned thresholds, as defined in E, fail to exhibit a level acceptable to the end consumer. Therefore, fiberboards with enhanced internal bond strength and flexural properties are desirable. Enhanced flexural properties allow for greater resistance to mechanical and / or physical stresses experienced by the fiberboard during its service life, including but not limited to its preparation, packaging, unpacking, transport, storage, and use. Fiberboards suffering from poor flexural properties are typically brittle and exhibit little or no resistance to mechanical and / or physical stresses. Consequently, poor flexural properties severely limit their applications and uses (if any) and / or their lifespan (once used), and are therefore generally rejected by consumers. Furthermore, enhanced internal bond strength is also desirable because it ensures acceptable physical integrity and allows for greater resistance to mechanical and / or physical stresses experienced by the fiberboard during its service life. Rapid curing at low temperatures is also highly desirable for compositions suitable for preparing fiberboards, as it improves preparation efficiency, increases throughput, and reduces the amount of energy required to cure the composition.
[0015] EP 2614117 B1 relates to a multilayer lignocellulose-containing molding article. EP 2614117 B1 does not disclose compositions comprising, at least not one of, the polylysine component and the XL component as specified in this specification.
[0016] US 2017 / 198142 A1 relates to waterborne curable adhesive compositions comprising (i) a polyphenol macromolecule containing a large amount of phenolic or polyhydroxybenzene radicals (such as catechol radicals, preferably lignin sulfonates, condensed tannins, and mixtures thereof), and (ii) a polyamine functional compound containing primary and / or secondary amine functional groups and / or tertiary amine functional groups and / or quaternary amine functional groups, and / or the reaction product of (i) and (ii), wherein the ratio of the polyphenol macromolecule to the polyamine functional compound is 98:2 to 50:50% by weight, preferably 98:2 to 70:30% by weight, more preferably 95:5 to 80:20% by weight. US 2017 / 198142 A1 does not disclose compositions comprising, at least not one of, a polylysine component and an XL component as specified in this specification.
[0017] WO 2022 / 136612 A1 provides an adhesive composition comprising a component A containing one or more polymers A1 and optionally a component B containing a component B1 selected from monosaccharides, disaccharides, hydroxyacetone, glycolaldehyde, and mixtures thereof, wherein the one or more polymers A1 contains at least 70% by weight of a poly(amino acid) based on the total weight of the one or more polymers A1 and has a total weight-average molecular weight Mw of 800 g / mol to 10000 g / mol, wherein the adhesive composition contains 60 to 100% by weight of the one or more polymers A1 and component B1 and 0 to 40% by weight of component B1 based on the total weight of the one or more polymers A1 and component B1, wherein the weight amounts of the one or more polymers A1 and component B1 are selected such that the total weight of the sum of the one or more polymers A1 and component B1 is 100% by weight. WO 2022 / 136612 A1 does not disclose compositions containing polylysine components and XL components as specified in this specification.
[0018] WO 2022 / 096518 A1 discloses compositions comprising a polylysine component and a fiber component. WO 2022 / 096518 A1 aims to provide objects with enhanced bending properties, such as fiberboard; the fiberboard of WO 2022 / 096518 A1 is obtained after curing its composition at a high temperature of 210°C and a pressing time factor of 30 sec / mm. WO 2022 / 096518 A1 does not disclose compositions comprising, at least not an XL component as specified in this specification.
[0019] WO 2023 / 148578 A1 discloses a board comprising a cellulose-containing material, such as plant fibers and / or wood chips and / or wood components, and an adhesive for bonding these cellulose-containing materials together, wherein the adhesive is based on hyperbranched polyamide, as well as a method for manufacturing such a board and the adhesive for such a board. WO 2023 / 148578 A1 does not disclose compositions comprising, at least not those comprising, a polylysine component and an XL component as specified in this specification.
[0020] EP 2614117 B1, US 2017 / 198142 A1, WO 2022 / 136612 A1, WO 2022 / 096518 A1, WO 2023 / 148578 A1, CN 109056327, US 2012 / 202041 A1, WO 2022 / 096518 A1, WO 2020 / 230034 A1, WO 2008 / 057390 A2, WO 2008 / 068180 A1, WO 2016 / 009054 A1, WO 2016 / 009062 A1, WO 2022 / 096518, KR 102187998 B1, CN 110903786 A、WO None of the following patents disclose compositions as disclosed in this specification, and none relate to providing compositions capable of rapid curing at low temperatures to prepare fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or chipboard)], said fiberboard having: - Internal bond strength of at least 0.3 MPa, - A fracture modulus of at least 9 MPa (R b ),and - Apparent elastic modulus (E) of at least 1600 MPa.
[0021] Not to mention providing a solution to this problem.
[0022] Therefore, unless a technological solution can rapidly produce fiberboard at low temperatures while simultaneously ensuring enhanced internal bond strength, R... b And E, the use of fiberboard in its various (other potential) industrial applications is restricted.
[0023] Such a technological solution still represents an unmet need because solutions to this problem are particularly challenging and complex.
[0024] This specification includes discussions of documents, operations, materials, devices, articles, etc., solely for the purpose of providing background information on the invention. It does not imply or imply that any or all of these matters constitute part of the prior art or common knowledge in the relevant field of this invention, as they existed prior to the priority date of each claim. Invention Overview This invention relates to compositions comprising component A (the compositions of this invention), said component A being composed of a polylysine component, an XL component, and a fiber component, said fiber component being composed of at least one fiber element comprising plant fibers, and said fiber element containing no fibers other than plant fibers, and said composition containing no fibers other than plant fibers of said fiber component. The invention further relates to methods of obtaining objects from the compositions of this invention. The invention further relates to objects obtained by said method (objects of this invention), such as sheets, strips, rods, tapes, films, fabrics, containers, boards, panels, beams, frames, slats, engineered wood, such as fiberboard. The invention further relates to articles (articles of this invention) comprising a) a component that is solid at 23°C and 1 atm, and one or both of b) and c), wherein b) is the composition of this invention, and c) is the object of this invention. The invention further relates to various uses of any or any combination of the compositions of this invention, the objects of this invention, and the articles of this invention.
[0026] The objective of this invention is to provide compositions capable of rapid curing at low temperatures to prepare fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or chipboard)], said fiberboard having: - Internal bond strength of at least 0.3 MPa, - A fracture modulus of at least 9 MPa (R b ),and - Apparent elastic modulus (E) of at least 1600 MPa.
[0027] Surprisingly, this objective is achieved using the compositions described in the claims and disclosed in the specification.
[0028] More particularly, it has been surprisingly discovered that when the composition of the present invention is rapidly cured at 120°C to prepare fiberboard, the resulting fiberboard has: - Internal bond strength of at least 0.3 MPa, - A fracture modulus of at least 9 MPa (R b ),and - Apparent elastic modulus (E) of at least 1600 MPa.
[0029] The compositions of this invention constitute a significant technological advancement in many industries because the fiberboard prepared from the compositions of this invention, which are rapidly cured at low temperatures, has the following characteristics: - Internal bond strength of at least 0.3 MPa, - A fracture modulus of at least 9 MPa (R b ),and - Apparent elastic modulus (E) of at least 1600 MPa, However, existing compositions, after rapid curing at low temperatures, may cause delamination or fail to meet requirements for internal bonding strength and R... b And E's requirements.
[0030] The present invention is as set forth in the claims. Many other variations, combinations, and embodiments within the scope of the claims will be apparent to those skilled in the art. Brief description of the attached diagram The instruction manual contains two accompanying drawings.
[0032] The accompanying drawings are provided for illustration only and are not intended to define any limitation on this disclosure.
[0033] To assist those skilled in the art in practicing the disclosed invention, please refer to the accompanying drawings: Figure 1 This is a diagram of hyperbranched polylysine with a theoretical (calculated) molecular weight of 0.4 dB and 3350.6 Da.
[0034] Figure 2 This is a diagram of the primary ammonium salt of hyperbranched polylysine, showing some primary ammonium cations (-NH3) present in the structure of the primary ammonium salt that counteracts hyperbranched polylysine. + The anion of ) is chloride ion, and among them Figure 2 The primary ammonium salt of hyperbranched polylysine has a theoretical (calculated) molecular weight of 0.4 dB and 3569.3 Da.
[0035] Detailed disclosure of the present invention This specification provides definitions for certain technical terms used in the specification and / or claims. Any other technical terms used in the specification and / or claims that are not defined in the specification shall have the meanings assigned to them by one of ordinary skill in the art.
[0036] The term "lysine" refers to an α-amino acid with the following formula: Any reference to "lysine" in this specification refers to and covers the two enantiomers of lysine, namely D- and L-lysine; "L" and "D" refer to the chirality of the lysine carbon atom directly attached to the carbon atom of the carboxyl group.
[0037] The degree of branching (DB) of polylysine is determined by... 1 Determined by H-NMR spectroscopy and calculated according to Equation 1: (Equation 1) in D is equal to or greater than 0, L is equal to or greater than 0, and at least one of D and L is greater than 0; and in D is the methylene proton (abbreviation for the tertiary carbon proton, shown in bold in formulas D1a and D1b) corresponding to any number of the following groups that may be present in polylysine. 1 The integral of the H-NMR peak (D equals zero if such methylene protons are not present in polylysine): L represents L α and L ε The sum of, of which L α It corresponds to any number of the following groups shown in formulas L1a and L1b that may be present in polylysine, specifically the methylene proton (abbreviation for the tertiary carbon proton, indicated in bold in formulas L1a and L1b). 1 The integral of the H-NMR peak (if such methylene protons are not present in polylysine, then L α (equal to zero): and L ε This refers to the methine proton (abbreviated form of the tertiary carbon proton in bold in formulas L2a and L2b) corresponding to any number of the following groups shown in formulas L2a and L2b that may be present in polylysine. 1 The integral of the H-NMR peak (if such methylene protons are not present in polylysine, then L ε (equal to zero): DB is 0 (inclusive) to at most 1 (inclusive) (or equivalently, DB is at least 0 and at most 1).
[0038] "Polylysine" in this specification refers to a polymer composed of (reacted) lysine molecules linked by peptide bonds. Polylysine can be linear, branched, or dendritic. Obviously, the degree of branching (DB) of polylysine ranges from 0 (inclusive) to at most 1 (inclusive) (or equivalently, the DB of polylysine is at least 0 and at most 1). Examples of polylysine include α-polylysine, α-polylysine, hyperbranched polylysine, and dendritic polylysine.
[0039] The specification states that "primary ammonium salt of polylysine" refers to a structure containing at least one primary ammonium cation (-NH3). + The polylysine (as defined in the specification) contains cations counteracted by anions, wherein the primary ammonium cation is a cationized form of the amino group of the polylysine.
[0040] In the product manual, "α-polylysine" refers to a polymer having the following formula A: Where n is an integer equal to or greater than 2, and the branching degree (DB) is equal to 0.
[0041] The specification states that "primary ammonium salt of α-polylysine" refers to a salt containing at least one primary ammonium cation (-NH3) in its structure. + α-Polylysine (as defined in the specification), wherein the cation is counterbalanced by anion, and wherein the primary ammonium cation is a cationized form of the amino group of α-polylysine, and wherein the primary ammonium salt of α-polylysine has a branching degree (DB) equal to 0.
[0042] "α-Polylysine" in the product manual refers to a polymer having the following formula B: Where k is an integer equal to or greater than 2, and the branching degree (DB) is equal to 0.
[0043] The specification states that "α-polylysine primary ammonium salt" refers to a salt containing at least one primary ammonium cation (-NH3) in its structure. + α-polylysine (as defined in the specification), wherein the cation is counterbalanced by anion, and wherein the primary ammonium cation is a cationized form of the amino group of α-polylysine, and wherein the primary ammonium salt of α-polylysine has a degree of branching (DB) equal to 0.
[0044] "Hyperbranched polylysine" in the product information refers to polylysine with a branching degree (DB) greater than 0 and at most 0.99.
[0045] The specification states that "primary ammonium salt of hyperbranched polylysine" refers to a structure containing at least one primary ammonium cation (-NH3). +The hyperbranched polylysine (as defined in the specification) has a cation counteracted by an anion, wherein the primary ammonium cation is a cationized form of the amino group of the hyperbranched polylysine, and wherein the primary ammonium salt of the hyperbranched polylysine has a degree of branching (DB) greater than 0 and at most 0.99.
[0046] "Denial polylysine" in the product information refers to polylysine with a branching degree (DB) greater than 0.99 and at most 1.
[0047] The specification states that "dendritic polylysine primary ammonium salt" refers to a structure containing at least one primary ammonium cation (-NH3). + The dendritic polylysine (as defined in the specification) has a cation counteracted by an anion, wherein the primary ammonium cation is a cationized form of the amino group of the dendritic polylysine, and wherein the primary ammonium salt of the dendritic polylysine has a degree of branching (DB) greater than 0.99 and at most 1.
[0048] In the specification, "peptide" refers to a polymeric compound other than (and significantly different from) polylysine-X, wherein the polymeric compound consists of a chain having at least two and at most 50 amino acids linked by peptide bonds.
[0049] In the specification, “protein” refers to a polymeric compound other than (and distinctly different from) polylysine-X, wherein the polymeric compound consists of at least one chain having at least 51 amino acids linked by peptide bonds.
[0050] In the specification, "acetylacetoxy" refers to an organic group having the following formula C: In the specification, "ethylene oxide group" refers to an organic group having the following formula OD: In the specification, "ketone group" refers to an organic group according to any one of the following formulas: EK1 to EK2. In this specification, "olefinic unsaturated group" refers to an organic group according to any one of the following formulas EU1 to EU15:
[0051] In this specification, "vinyl unsaturated group" refers to an organic group according to any one of the following formulas VU1 to VU2: in In equation VU1, X is O or NH. In equation VU2, X is O or NH, and R is C1 to C2. 10 alkyl.
[0052] The term "metal-containing compound" in this specification refers to a compound containing metal atoms or metal cations. Examples of metal-containing compounds include, but are not limited to, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, and lithium) inorganic compounds, and alkaline earth metal (preferably calcium, magnesium, and barium) inorganic compounds. Examples of organometallic compounds include, but are not limited to, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metal (preferably potassium, sodium, and lithium), and alkaline earth metal (preferably calcium, magnesium, and barium). Examples of metal complexes include, but are not limited to, metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metal (preferably potassium, sodium, and lithium), and alkaline earth metal (preferably calcium, magnesium, and barium). Examples of alkali metal (preferably potassium, sodium, and lithium) inorganic compounds include, but are not limited to, alkali metal (preferably potassium, sodium, and lithium) hydroxides. Examples of alkaline earth metal (preferably calcium, magnesium, and barium) inorganic compounds include, but are not limited to, alkaline earth metal (preferably calcium, magnesium, and barium) hydroxides.
[0053] "Gel content" (in relation to polylysine) refers in the specification to the portion of polylysine that remains insoluble after being stored in water at room temperature (23°C) for 24 hours. The gel content is determined as described in the examples. Polylysine with a gel content greater than 20% (e.g., any of the polylysine-X components) is characterized as "crosslinked polylysine," while polylysine with a gel content of up to 20% (e.g., any of the polylysine-X components) is characterized as "non-crosslinked polylysine." The gel content is determined using the gel content method described in the examples.
[0054] The term "bending property" (referring to objects such as fiberboard) refers to the following material properties i) and ii): i) Modulus of rupture (R) b (i) and (ii) apparent elastic modulus (E). The bending properties were determined by the static bending method as described in the examples.
[0055] In the context of this invention, the term "delamination" refers to a failure mode in which, after hot pressing of the respective composition, the resulting material breaks into layers or fragments.
[0056] In the context of this invention, the pressing time factor (in sec / mm) (abbreviated as PTF) is the pressing time (i.e., the time from when the press is closed to when it is opened) divided by the target thickness of the fiberboard; the target thickness refers to the thickness of the fiberboard at the end of the pressing step. For example, when manufacturing 12 mm fiberboard with a pressing time factor of 9 sec / mm, the pressing time is 108 seconds.
[0057] In the context of this invention, the term "fast-curing" (or equivalently "fast-cured" or equivalently "fast-cure") refers to a pressing time factor equal to 19 sec / mm.
[0058] In the context of this invention, the term "low temperature" refers to 120°C.
[0059] In the context of this invention, the terms “synthetic cellulose fiber,” “man-made cellulose fiber,” “made cellulose fiber,” “artificial cellulose fiber,” or “regenerated cellulose fiber” are used interchangeably, and these terms are used to distinguish synthetic cellulose fiber from natural cellulose fiber and natural lignocellulose fiber, both of which are plant fibers.
[0060] Engineered timber (also known as mass timber, composite timber, artificial timber, or engineered wood) includes a range of derivative timber products made by bonding or fixing together various wood elements (such as fibers, filaments, yarns, strips, bundles, threads, short fiber yarns, particles, fragments (such as wood chips, sawdust), shavings (such as sawmill shavings), veneers, sheets, pulps (such as wood pulp), and mixtures thereof) through various fixing methods to effectively form composite materials. Exemplary types of engineered timber include, but are not limited to, plywood, densified wood (including chemically densified wood), fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or chipboard)], oriented strand board (OSB), laminated timber (glulam; plywood glulam), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel veneer glulam (PSL), laminated veneer lumber (LSL), finger joints, beams (including I-joints and I-beams), trusses (including roof and floor trusses), and transparent wood composites.
[0061] As used in this instruction manual, the term "fiberboard" includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or chipboard).
[0062] The term "wood chips" in this specification refers to shredded wood biomass in the form of fragments with a defined particle size produced by mechanical processing with a sharp tool such as a knife (ISO 16559-2014; §4.226). The particle size distribution of wood chips is determined by vibrating sieve method using a sieve with apertures of 3.15 mm or larger, according to ISO 17827-1:2016. According to this standard (ISO 17827-1:2016), the median (d50) of the particle size distribution is reported and defined as the calculated particle size of the sample in which 50% of the particles have a mass lower than or higher than d50%. The median is graphically established by the intersection of the cumulative distribution curve and the 50% line [(X-axis: particle / aperture size (mm), and Y-axis: cumulative weight % (%)].
[0063] In this article, "room temperature" refers to 23 ± 0.5℃.
[0064] The instruction manual defines "atmospheric pressure" as 1 atm (1 atm = 101325 Pa).
[0065] In the instruction manual, "standard conditions" refers to the combined terms of room temperature and atmospheric pressure.
[0066] In the specification, "below" means that the relevant maximum boundary value is not included in the range.
[0067] In the specification, "above" means that the relevant minimum boundary value is not included in this range.
[0068] "rpm" refers to revolutions per minute.
[0069] The decimal separator (also known as the radix character) in numbers is represented by a period ('.').
[0070] In the instruction manual, "pph" refers to parts by weight per 100 parts by weight.
[0071] The wavy line shown in any of the formulas in the specification and relating to the XL component means that the molecular structure beyond the point shown by the wavy line is not specified.
[0072] Each component and element of the composition of the present invention is different from and distinct from any other component and element of the composition of the present invention.
[0073] In the specification, including any quantities expressed as percentages in the claims, the sum of which (rounding errors are allowed) cannot exceed 100% by weight of the composition. For example, when expressed as a weight (or other) percentage of the composition (or its equivalents), the sum of all components contained in the composition (or a portion thereof) of the present invention may total 100% by weight, allowing for rounding errors. However, in cases where the list of components is not exhaustive, the sum of the percentages of each of such components may be less than 100% by weight, thus allowing for a certain percentage for any additional amounts of (one or more) additional components that may not be explicitly described herein.
[0074] All combinations of the minimum and maximum values of the parameters disclosed in the specification can be used to define the parameter ranges of various preferred options or embodiments of the present invention.
[0075] For any parameter given herein, all upper and lower limits, boundary values are included within the respective ranges of each parameter. All combinations of the minimum and maximum values of the parameters described herein can be used to define the parameter ranges of various embodiments and preferences of the invention.
[0076] Unless otherwise expressly stated, any feature, element, component, embodiment, scope, and especially any preferred feature, preferred element, preferred embodiment, preferred scope, preferred term, and preferred combination of embodiments of the present invention, as disclosed throughout the specification and in the claims, may be combined with each other.
[0077] Unless the context otherwise requires, the plural form of a term is to be interpreted in the specification as including the singular form, and vice versa.
[0078] The inclusion and / or use of certain parts, classes of matter, groups, repeating units, compounds, oligomers, polymers, materials, mixtures, compositions, and / or formulations of some or all of the inventions described in the specification may exist in one or more different forms, such as any of the following non-exhaustive list: stereoisomers (e.g., enantiomers (e.g., E and / or Z forms), diastereomers, and / or geometric isomers); tautomers (e.g., ketones and / or enols). The present invention includes and / or uses all such effective forms as defined in the specification.
[0079] This section (detailed disclosure of the invention) together with the claims provides a disclosure of the invention and specific preferred embodiments of the claimed invention; therefore, the disclosure presented in this section and these specific preferred embodiments disclosed in this section are within the scope of the claimed invention.
[0080] The present invention provides the composition as described in claim 1. The subject matter of this paragraph is referred to in the specification as “A0”.
[0081] More specifically, the present invention provides a composition comprising component A, said component A being composed of the following components: - Polylysine component, - XL components, and - Fiber components, in The polylysine component is selected from polylysine-X and mixtures thereof, wherein the polylysine-X is selected from hyperbranched polylysine and primary ammonium salts of hyperbranched polylysine, preferably the polylysine-X is selected from hyperbranched polylysine, wherein each of the polylysine-X has a content of at least 0.30 and at most 0.60 as disclosed in the specification. 1 The degree of branching as determined by H-NMR spectroscopy, the apparent viscosity of at least 400 and at most 8000 mPa·s as determined by rheological methods as disclosed in the specification, and a gel content of at most 4.0, preferably at most 3.0, more preferably at most 2.0, even more preferably at most 1.0, even more preferably at most 0.5, for example at most 0.4, for example at most 0.3, for example at most 0.2, for example at most 0.1, for example at most 0.05, for example at most 0.04, for example at most 0.03, for example at most 0.02, for example at most 0.015% as determined by gel content methods as disclosed in the specification, for example, a gel content of 0.0%. and The XL component is selected from monomeric or polymeric compounds, each having at least two XL groups per molecule, wherein the XL groups are selected from groups according to formula XL1 (also referred to herein as XL1 groups). and The fiber component comprises at least one fiber element, the fiber element containing plant fibers, and wherein the fiber element contains no fibers other than plant fibers. in The composition contains no fibers other than plant fibers of the fiber component, and in Component A is present in the composition in an amount of at least 10 and at most 100, preferably at least 20 and at most 100, more preferably at least 30 and at most 100, even more preferably at least 40 and at most 100, for example at least 50 and at most 100, for example at least 60 and at most 100, for example at least 70 and at most 100, for example at least 80 and at most 100% by weight. in The polylysine component is at least 0.5 and at most 30.0% of the composition, preferably at least 0.5 and at most 27.0%, more preferably at least 0.5 and at most 25.0%, for example at least 0.5 and at most 22.0%, for example at least 0.5 and at most 20.0%, for example at least 0.5 and at most 18.0%, for example at least 0.5 and at most 16.0%, for example at least 0.5 and at most 15.0%, for example at least 0.5 and at most 14.0%, for example at least 0.5 and at most 13.0%, for example at least 0.5 and at most 12.0%, for example at least 0.5 and at most 11.0%, for example at least 0.5 and at most 10.0%, for example at least 0.5 and at most 9.0%, for example at least 0.5 and at most 8.0%, for example at least 0.5 and at most 7%. 0, for example, at least 0.5 and at most 6.0, for example, at least 0.75 and at most 30.0, for example, at least 0.75 and at most 27.0, for example, at least 0.75 and at most 25.0, for example, at least 0.75 and at most 22.0, for example, at least 0.75 and at most 20.0, for example, at least 0.75 and at most 18.0, for example, at least 0.75 and at most 16.0, for example, at least 0.75 and at most 15.0, for example, at least 0.75 and at most 14.0, for example, at least 0.75 and at most 13.0, for example, at least 0.75 and at most 12.0, for example, at least 0.75 and at most 11.0, for example, at least 0.75 and at most 10.0, for example, at least 0.75 and at most 9.0, for example, at least 0.75 and at most 8.0, for example, at least 0.75 and at most 7.0, for example, at least 0.75 and at most 6.0, for example, at least 1.0 and at most 30.0, for example, at least 1.0 and at most 27.0, for example, at least 1.0 and at most 25.0, for example, at least 1.0 and at most 22.0, for example, at least 1.0 and at most 20.0, for example, at least 1.0 and at most 18.0, for example, at least 1.0 and at most 16.0, for example, at least 1.0 and at most 15.0, for example, at least 1.0 and at most 14.0, for example, at least 1.0 and at most 13.0, for example, at least 1.0 and at most 12.0, for example, at least 1.0 and at most 11.0, for example, at least 1.0 and at most 10.0, for example, at least 1.0 and at most 9.0, for example, at least 1. 0 and at most 8.0, for example, at least 1.0 and at most 7.0, for example, at least 1.0 and at most 6.0, for example, at least 1.25 and at most 30.0, for example, at least 1.25 and at most 27.0, for example, at least 1.25 and at most 25.0, for example, at least 1.25 and at most 22.0, for example, at least 1.25 and at most 20.0, for example, at least 1.25 and at most 18.0, for example, at least 1.25 and at most 16.0, for example, at least 1.25 and at most 15.0, for example, at least 1.25 and at most 14.0, for example, at least 1.25 and at most 13.0, for example, at least 1.25 and at most 12.0, for example, at least 1.25 and at most 11.0, for example, at least 1.25 and at most 10.0, for example, at least 1.25 and at most 9.0, for example, at least 1.25 and at most 8.0, for example, at least 1.25 and at most 7.0, for example, at least 1.25 and at most 6.0, for example, at least 1.50 and at most 30.0, for example, at least 1.50 and at most 27.0, for example, at least 1.50 and at most 25.0, for example, at least 1.50 and at most 22.0, for example, at least 1.50 and at most 20.0, for example, at least 1.50 and at most 18.0, for example, at least 1.50 and at most 16.0, for example, at least 1.50 and at most 15.0, for example, at least 1.50 and at most 14.0, for example, at least 1.50 and at most 13.0, for example, at least 1.50 and at most 12.0, for example, at least 1.50 and at most 11.0, for example, at most Less than 1.50 and more than 10.0, for example, less than 1.50 and more than 9.0, for example, less than 1.50 and more than 8.0, for example, less than 1.50 and more than 7.0, for example, less than 1.50 and more than 6.0, for example, less than 1.75 and more than 30.0, for example, less than 1.75 and more than 27.0, for example, less than 1.75 and more than 25.0, for example, less than 1.75 and more than 22.0, for example, less than 1.75 and more than 20.0, for example, less than 1.75 and more than 18.0, for example, less than 1.75 and more than 16.0, for example, less than 1.75 and more than 15.0, for example, less than 1.75 and more than 14.0, for example, less than 1.75 and more than 13.0, for example, less than 1.75 and more than 12.0, for example, For example, at least 1.75 and at most 11.0, for example, at least 1.75 and at most 10.0, for example, at least 1.75 and at most 9.0, for example, at least 1.75 and at most 8.0, for example, at least 1.75 and at most 7.0, for example, at least 1.75 and at most 6.0, for example, at least 2.0 and at most 30.0, for example, at least 2.0 and at most 27.0, for example, at least 2.0 and at most 25.0, for example, at least 2.0 and at most 22.0, for example, at least 2.0 and at most 20.0, for example, at least 2.0 and at most 18.0, for example, at least 2.0 and at most 16.0, for example, at least 2.0 and at most 15.0, for example, at least 2.0 and at most 14.0, for example, at least 2.0 and at most 13.0, for example, at least 2.0 and at most More than 12.0, for example, at least 2.0 and at most 11.0, for example, at least 2.0 and at most 10.0, for example, at least 2.0 and at most 9.0, for example, at least 2.0 and at most 8.0, for example, at least 2.0 and at most 7.0, for example, at least 2.0 and at most 6.0, for example, at least 2.25 and at most 30.0, for example, at least 2.25 and at most 27.0, for example, at least 2.25 and at most 25.0, for example, at least 2.25 and at most 22.0, for example, at least 2.25 and at most 20.0, for example, at least 2.25 and at most 18.0, for example, at least 2.25 and at most 16.0, for example, at least 2.25 and at most 15.0, for example, at least 2.25 and at most 14.0, for example, at least 2.25 and at most 13.0, for example, at least 2.25 and at most 12.0, for example, at least 2.25 and at most 11.0, for example, at least 2.25 and at most 10.0, for example, at least 2.25 and at most 9.0, for example, at least 2.25 and at most 8.0, for example, at least 2.25 and at most 7.0, for example, at least 2.25 and at most 6.0, for example, at least 2.5 and at most 30.0, for example, at least 2.5 and at most 27.0, for example, at least 2.5 and at most 25.0, for example, at least 2.5 and at most 22.0, for example, at least 2.5 and at most 20.0, for example, at least 2.5 and at most 18.0, for example, at least 2.5 and at most 16.0, for example, at least 2.5 and at most 15.0, for example, at least 2.5 and at most 14.0, for example, at least 2.5 and at most 13.0, for example, at least 2.5 and at most 12.0, for example, at least 2.5 and at most 11.0, for example, at least 2.5 and at most 10.0, for example, at least 2.5 and at most 9.0, for example, at least 2.5 and at most 8.0, for example, at least 2.5 and at most 7.0, for example, at least 2.5 and at most 6.0, for example, at least 2.75 and at most 30.0, for example, at least 2.75 and at most 27.0, for example, at least 2.75 and at most 25.0, for example, at least 2.75 and at most 22.0, for example, at least 2.75 and at most 20.0, for example, at least 2.75 and at most 18.0, for example, at least 2.75 and at most 16.0, for example, at least 2.75 and at most 15.0, for example, at least 2.75 and at most More than 14.0, for example, at least 2.75 and at most 13.0, for example, at least 2.75 and at most 12.0, for example, at least 2.75 and at most 11.0, for example, at least 2.75 and at most 10.0, for example, at least 2.75 and at most 9.0, for example, at least 2.75 and at most 8.0, for example, at least 2.75 and at most 7.0, for example, at least 2.75 and at most 6.0, for example, at least 3.0 and at most 30.0, for example, at least 3.0 and at most 27.0, for example, at least 3.0 and at most 25.0, for example, at least 3.0 and at most 22.0, for example, at least 3.0 and at most 20.0, for example, at least 3.0 and at most 18.0, for example, at least 3.0 and at most 16.0, for example, at least 3.0 and at most 15.0 For example, at least 3.0 and at most 14.0, for example, at least 3.0 and at most 13.0, for example, at least 3.0 and at most 12.0, for example, at least 3.0 and at most 11.0, for example, at least 3.0 and at most 10.0, for example, at least 3.0 and at most 9.0, for example, at least 3.0 and at most 8.0, for example, at least 3.0 and at most 7.0, for example, at least 3.0 and at most 6.0, for example, at least 3.5 and at most 30.0, for example, at least 3.5 and at most 27.0, for example, at least 3.5 and at most 25.0, for example, at least 3.5 and at most 22.0, for example, at least 3.5 and at most 20.0, for example, at least 3.5 and at most 18.0, for example, at least 3.5 and at most 16.0, for example, at least 3.5 and at most 15.0, for example, at least 3.5 and at most 14.0, for example, at least 3.5 and at most 13.5, for example, at least 3.5 and at most 12.0, for example, at least 3.5 and at most 11.0, for example, at least 3.5 and at most 10.0, for example, at least 3.5 and at most 9.0, for example, at least 3.5 and at most 8.0, for example, at least 3.5 and at most 7.0, for example, at least 3.5 and at most 6.0, for example, at least 4.0 and at most 30.0, for example, at least 4.0 and at most 27.0, for example, at least 4.0 and at most 25.0, for example, at least 4.0 and at most 22.0, for example, to Amounts of at least 4.0 and at most 20.0, such as at least 4.0 and at most 18.0, such as at least 4.0 and at most 16.0, such as at least 4.0 and at most 15.0, such as at least 4.0 and at most 14.0, such as at least 4.0 and at most 14.0, such as at least 4.0 and at most 12.0, such as at least 4.0 and at most 11.0, such as at least 4.0 and at most 10.0, such as at least 4.0 and at most 9.0, such as at least 4.0 and at most 8.0, such as at least 4.0 and at most 7.0, such as at least 4.0 and at most 6.0% by weight, are present, and. in The weight ratio K of the XL component divided by the weight of the polylysine component is defined as at least 0.30 and at most 5.0, preferably at least 0.30 and at most 4.0, for example at least 0.30 and at most 3.0, for example at least 0.30 and at most 2.0, for example at least 0.30 and at most 1.5, for example at least 0.30 and at most 1.0, for example at least 0.40 and at most 5.0, preferably at least 0.40 and at most 4.0, for example... At least 0.40 and at most 3.0, for example, at least 0.40 and at most 2.0, for example, at least 0.40 and at most 1.5, for example, at least 0.40 and at most 1.0, for example, at least 0.50 and at most 5.0, preferably at least 0.50 and at most 4.0, for example, at least 0.50 and at most 3.0, for example, at least 0.50 and at most 2.0, for example, at least 0.50 and at most 1.5, for example, at least 0.50 and at most 1.0, and in The wavy line shown in the formula associated with the XL component indicates that the molecular structure beyond the point shown by the wavy line is not specified.
[0082] The topic of this section is referred to as "A1" in the instruction manual.
[0083] To illustrate, Figure 1 Hyperbranched polylysine with a theoretical (calculated) molecular weight of 0.4 dB and 3350.6 Da was described, while Figure 2 The primary ammonium salts of hyperbranched polylysine were described, in which some primary ammonium cations (-NH3) exist in the structure of the primary ammonium salts that counteract hyperbranched polylysine. +The anion of ) is chloride ion, and among them Figure 2 The primary ammonium salt of hyperbranched polylysine has a theoretical (calculated) molecular weight of 0.4 dB and 3569.3 Da.
[0084] Lysine, as a precursor amino acid (either of its two enantiomers, namely D- and L-lysine; "L" and "D" refer to the chirality at the central carbon atom of lysine), contains two amino groups; one at the α-carbon and one at the α-carbon. Either of these two amino groups can be the polymerization position. In principle, polylysine is formed from lysine or a lysine salt (L-lysine, D-lysine, or any mixture of L-lysine, such as a racemic mixture; or L-lysine salt, D-lysine salt, or any mixture thereof, such as a racemic mixture) in a condensation polymerization reaction, wherein water is released when the amino group of one lysine molecule and the carboxyl group of another lysine molecule react with each other to form an amide bond in the presence of water. Removal of water from the reaction mixture favors the formation of polylysine.
[0085] Hyperbranched polylysine can be prepared by various methods. In principle, methods for preparing hyperbranched polylysine can be classified into four main categories: i) methods based on the ring-opening addition polymerization of e-protected L-lysine-N-carboxylic anhydride (NCA) with a nucleophilic primer; ii) methods using a derivative of L-lysine*xHCl activated at the carboxyl group; iii) methods involving the direct thermal addition polymerization of L-lysine; and iv) methods involving a salt of lysine with at least one acid in the presence of at least one catalyst selected from tertiary amines, basic alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkoxides, alkanoates, chelates, and organometallic compounds of metals from groups IIIA to VIIIA or IB to VB of the periodic table. The following paragraphs in this section provide some examples of methods for preparing hyperbranched polylysine, such as those for the claimed invention.
[0086] Hyperbranched polylysine can be prepared via the so-called AB2 pathway. AB2 is a term used to represent a trifunctional monomer containing one reactive group A and two reactive groups B; hyperbranched polymers can be prepared via intermolecular reactions when these groups A and B are reactive with each other. Lysine is an example of such a trifunctional monomer, wherein the reactive group A is a carboxyl group, and each of the two reactive groups B is an amino group of lysine, and wherein these A and B groups in lysine are reactive with each other; therefore, the AB2 polymerization pathway of lysine yields hyperbranched polylysine.
[0087] Hyperbranched polylysine can also be prepared as follows: 50% by weight of L-lysine in water is charged into a reactor, such as a glass reactor equipped with a distillation apparatus. After the L-lysine in water (50% by weight) has been charged into the reactor, the reactor is slowly heated (over 2-8 hours) to 120-190°C (this slow temperature increase is necessary to avoid precipitation of unreacted L-lysine in the reactor, which may occur if too much water is distilled off before full reaction). When the desired reaction temperature is reached, the reaction is then continued at the desired temperature for 2-30 hours. Optionally, 50% by weight of L-lysine in water can be added to the reactor during distillation to maintain a constant packing level. The reaction is monitored by taking samples at regular time intervals, diluting the samples in water to 60% by weight, 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 before discharge to produce a product with the desired solids content and apparent viscosity. A high-pressure reactor can be used for this method. If a high-pressure reactor is used in this method, L-lysine (50 wt%) in water is charged into the high-pressure reactor, which is equipped with a distillation apparatus connected to the reactor via a pressure relief valve. After the L-lysine (50 wt%) in water is charged into the high-pressure reactor, the pressure in the reactor begins to increase, while the pressure relief valve is closed and the reactor is heated to 120-190°C. During the reaction, the pressure in the reactor is preferably maintained between 1-6 bar (1 bar = 100,000 Pa); this preferred pressure range is also maintained during the reaction by carefully and periodically opening and closing the pressure relief valve to allow distillation of water and a certain amount of pressure release. When the desired reaction temperature is reached, the reaction is then continued at the desired temperature for 2-30 hours. Optionally, L-lysine (50 wt%) in water can be added to the reactor during distillation to maintain a certain packing level. The reaction is monitored by taking samples at regular time intervals, diluting the samples in water to 60 wt%, and measuring the apparent viscosity. When the apparent viscosity of these samples is at the desired viscosity, the reaction mixture is discharged. If desired, water can be added to the reaction mixture before discharge to produce a product with the desired solids content and apparent viscosity. The preparation of hyperbranched polylysine conforming to the invention shown in the examples provides an embodiment of the method described above in this section.
[0088] Another method for preparing hyperbranched polylysine is to use L-lysine hydrochloride as the starting material. The polymerization of L-lysine hydrochloride is carried out as follows: L-lysine hydrochloride (550 g, 3 mol) and NaOH (120 g, 3 mol) are added to a 1-L glass reactor equipped with a distillation apparatus. The reactor is heated to 120-190 °C and stirred for 2 to 30 hours. To monitor the reaction, samples are taken every few hours, dissolved in water to a solid content of 60 wt%, and the apparent viscosity is measured. For discharge, water (calculated to ensure the reaction mixture has a resulting solid content of 70-80 wt%) is added dropwise to the reactor, and the temperature is lowered to 90 °C during water addition. The resulting reaction mixture (70-80 wt% solid content) is then discharged in water at 90 °C.
[0089] Another method for preparing hyperbranched polylysine uses L-lysine hydrochloride and L-lysine as starting materials. Accordingly, L-lysine (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) in water are added to a 1-L glass reactor. The reactor is heated to 120–190 °C and stirred for 2–30 hours. To monitor the reaction, samples are taken every few hours, the solid content in water is reduced to 60 wt%, and the apparent viscosity is measured. For discharge, water (calculated to ensure the reaction mixture will have a resulting solid content of 70–80 wt%) is added dropwise to the reactor, and the temperature is lowered to 90 °C during water addition. The resulting reaction mixture (70–80 wt% solid content) is then discharged in water at 90 °C.
[0090] Another method for preparing hyperbranched polylysine is based on the ring-opening addition polymerization of α-protected L-lysine-N-carboxylic anhydride (NCA) with a nucleophilic primer. Examples of this method are disclosed by Klok et al. in WO 2003 / 064452 and Macromolecules 2002, 35, 8718-8723, and by Rodriguez-Hernandez et al. in Biomacromolecules 2003, 4, 249-258. According to the latter, N... e A mixture of trifluoroacetyl-L-lysine-NCA (TFA-Lys-NCA) and Z-lysine-NCA undergoes ring-opening polymerization with an aliphatic amine. In a separate coupling step, N is introduced as a branch point. α N ɛ -Di(9-fluorenyl-methoxycarbonyl)-L-lysine (N α N ɛ-Di(benzyloxycarbonyl)-L-lysine p-nitrophenyl ester was introduced as a branch point, and after deprotection with piperidine, two new amine groups were obtained, which allowed for the ring-opening polymerization of TFA-Lys-NCA and Z-Lys-NCA. These reaction cycles were repeated multiple times. Birchall et al. have also described structurally similar hyperbranched block copolymers in Chem. Commun. 1998, 1335-1336. α-amino acid NCA was subjected to ring-opening polymerization with an aliphatic amine. N,N'-di(benzyloxycarbonyl)-L-lysine p-nitrophenyl ester was introduced as a branch point, and after H2 / Pd / C deprotection, it had two free amine groups for further ring-opening of amino acid NCA. These reaction cycles were repeated multiple times.
[0091] Another method for preparing hyperbranched polylysine is based on a derivative of L-lysine*2HCl activated at the carboxyl group. According to this method, hyperbranched polylysine is prepared in a one-pot synthesis by activating the carboxyl group with N-hydroxysuccinimide (NHS). The NHS-activated L-lysine*2HCl is stirred in dimethyl sulfoxide (DMSO) for 23 hours with a catalytic amount of dimethylaminopyridine (DMAP) and 3 equivalents of diisopropylethylamine (DIEA), and the polymer is precipitated from ethyl acetate.
[0092] Another method for preparing hyperbranched polylysine is based on 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 et al. (Biochimie 1975, 57 1395-1396) polymerized L-lysine in aqueous solution at 105 °C for up to 10 weeks, or by heating at 165 °C for 8 hours. This reaction was carried out without a catalyst and the yields were very low, invariably below 72.5%. Harada (Bull. Chem. Soc. Japan 1959, 32, 1007-1008) polymerized L-lysine under a nitrogen atmosphere at 180 to 230 °C for 30 minutes to 2 hours. Rohlfing and colleagues (Archives of Biochemistry and Biophysics 1969, 130, 441-448) polymerized L-lysine (free base) under a nitrogen atmosphere between 186°C and 192°C. WO 00 / 71600 describes 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 a starting monomer for thermal polymerization at 195°C. L-lysine*HCl was reacted at 195°C with the addition of orthophosphoric acid.
[0093] US 8846842 B2 discloses yet another method for preparing polylysine that does not require protecting group manipulation or carboxyl group activation, and in which higher molecular weights can be achieved than those known in the prior art. This objective has been achieved by means of a method for preparing non-crosslinked hyperbranched polylysine, which involves the following reaction: (A) A salt of lysine and at least one acid. (B) If appropriate, at least one amino acid other than lysine. (C) If appropriate, at least one dicarboxylic acid or polycarboxylic acid or its copolymerizable derivative, and (D) If appropriate, at least one diamine or polyamine or its copolymerizable derivative. (E) If appropriate, in at least one solvent, at a temperature of 120 to 200 °C, in the presence of at least one catalyst (F), said catalyst (F) being selected from (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 of groups IIIA to VIIIA or IB to VB of the periodic table. This method can be used to prepare materials with a weight-average molecular weight M of up to 750,000 Da. w Non-crosslinked hyperbranched polylysine.
[0094] Hyperbranched polylysine can be synthesized, for example, by direct thermal addition polymerization of L-lysine or its ammonium salt. The thermal addition polymerization of lysine is carried out in the absence of a solvent. WO 2007 / 060119 describes the polycondensation of L-lysine hydrochloride in the presence of sodium hydroxide, water (10 wt%, based on L-lysine hydrochloride), and the catalyst dibutyltin dilaurate. The mixture was heated to an internal temperature of 150 °C with stirring. After a reaction time of 5 hours, water was distilled off under reduced pressure (200 mbar), and after removing the majority of the water, the temperature was slowly increased to 180 °C and the pressure reduced to 10 mbar. After 8 hours, 240 g of the aqueous distillate was 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, then maintained at 165°C to 170°C while being stirred by guiding a weak stream of preheated nitrogen through it. A brown resin was obtained after 8 hours at 165°C to 170°C. Ho et al. described the synthesis of polylysine by thermally heating an aqueous lysine solution at 160°C for 2 days. The obtained polylysine had a branching degree between 0.50 and 0.54. When microwave-assisted heating was used at 200°C, the obtained polylysine had a branching degree between 0.30 and 0.32. US 2013 / 0123148 discloses the preparation of polylysine by heating an aqueous lysine solution in the presence of a catalytic amount of dibutyltin dilaurate. According to the examples in US 2013 / 0123148, the obtained polylysine had a branching degree greater than 0.30.
[0095] WO 2016 / 062578 A1 discloses a method for preparing hyperbranched polylysine suitable for large-scale production of polylysine in improved yields. According to WO 2016 / 062578 A1, polylysine can be prepared by a method comprising the following steps: (a) heating a boiling aqueous reaction mixture containing lysine and water in a weight ratio of 1:10 to 3:1 to a temperature in the range of 135 to 165°C over 2 to 8 hours, for example, 4 to 8 hours; and (b) maintaining the reaction mixture from step (a) at a temperature in the range of 135 to 165°C and at a pressure below atmospheric pressure, wherein water is removed from the mixture, and any temperature rise is less than or equal to 30°C within 60 minutes. Conventional technical-grade aqueous solutions of lysine can be used in the method disclosed in WO 2016 / 062578 A1, and a catalyst is not required. At the end of the second step, the mixture is in a liquid state, such as a melt of polylysine, rather than a resin. Preferably, the aqueous starting mixture is an aqueous solution of lysine in water. The lysine contained in this aqueous starting mixture can be L-lysine, D-lysine, or any mixture of L-lysine and D-lysine, such as a racemic mixture. This aqueous starting mixture can be, for example, an aqueous solution of L-lysine in water containing 50% by weight of L-lysine and 50% by weight of water; for example, ADM liquid L-lysine supplied by Archer Daniels Midland, product code: 035101, or Sewon L-Lysine supplied by Paik Kwang. ®50% liquid feed, or BestAmino™ L-Lysine liquid feed grade supplied by CJ CheilJedang. Polylysine is formed from lysine in a polycondensation reaction, where water is released when the amino group of one lysine molecule and the carboxyl group of another lysine molecule react with each other to form an amide bond in the presence of water. Removal of water from the reaction mixture is beneficial for polylysine formation. Typically, the temperature of the reaction mixture is continuously increased. The method disclosed in WO 2016 / 062578 A1 requires the removal of water from the reaction mixture. Any means suitable for removing water can be used to remove water from the reaction mixture. It is preferred to evaporate water from the mixture. It is most preferred to remove water from the mixture by distillation. This method requires a pressure below atmospheric pressure in the second step. The pressure reduction promotes the evaporation of water and thus accelerates the polycondensation reaction. According to WO 2016 / 062578 A1, the weight-average molecular weight and number-average molecular weight of polylysine depend on the total duration of the method and the temperature of the reaction mixture. Crosslinking is more likely to occur if the reaction mixture is kept at a higher temperature for a longer period of time. Preferably, the method is carried out without a catalyst. This method can be carried out continuously or preferably in batches. It is preferably carried out in a so-called one-pot mode, where lysine is entirely contained in the initial charge and the polycondensation reaction takes place in a reactor with backmixing. However, reaction schemes in multi-stage reactor systems, stirred tank cascades, or tubular reactors are also suitable.
[0096] The primary ammonium salt of hyperbranched polylysine can be prepared, for example, by protonating the amino group of hyperbranched polylysine with an acidic agent, such as a protic acid, alkenyl carboxylic acid, or alkyl sulfonic acid. In the context of this specification, reagents used to prepare the primary ammonium salt of polylysine are referred to as "protonating reagents." Such protonation results in a structure containing at least one primary ammonium cation (-NH3). + The primary ammonium salt of hyperbranched polylysine, wherein the cation is counterbalanced by an anion, and wherein the primary ammonium cation is a cationized form of the amino group of the hyperbranched polylysine. The structure of the anion depends on the reactant used for protonation of the amino group of the hyperbranched polylysine; exemplary anions include, but are not limited to, halide anions (e.g., fluoride, chloride, bromide, iodide), carboxylate anions, and sulfonate anions. Preferably, the anion is selected from halide anions, carboxylate anions, and sulfonate anions; more preferably, the anion is selected from halide anions and carboxylate anions; even more preferably, the anion is selected from halide anions, such as fluoride ions, chloride ions, bromide ions, iodide ions, such as chloride ions, bromide ions, iodide ions, such as chloride ions and bromide ions, such as chloride ions.
[0097] The XL component can react with the polylysine component. Members of the XL component can be prepared by a variety of methods. For example, to prepare an XL component having at least two XL1 groups, a polyamine or diamine (e.g., isophorone diamine) and solid phosgene are dissolved separately in a suitable organic solvent; then, the polyamine or diamine solution is added dropwise to the phosgene solution at room temperature or up to 40°C, and the reaction time is typically 2 to 7 hours; after the reaction is complete, the product is distilled to obtain the XL component having at least two XL1 groups.
[0098] Examples of XL components include, but are not limited to, monomeric diisocyanates, monomeric polyisocyanates, isocyanate-functionalized polyurethanes, and isocyanurate trimers of diisocyanates (e.g., isocyanurate trimers of 1,6-hexamethylene diisocyanate, isocyanurate trimers of isophorone diisocyanate, isocyanurate trimers of toluene diisocyanate, and isocyanurate trimers of methylene diphenyl diisocyanate). Examples of isocyanurate trimers of diisocyanates (1,6-hexamethylene diisocyanate) are shown below. .
[0099] The aforementioned monomeric diisocyanates, monomeric polyisocyanates, isocyanate-functionalized polyurethanes, and isocyanurate trimers of diisocyanates can be one or a combination of aliphatic, alicyclic, and aromatic species. Specific examples of the XL component include, but are not limited to, isophorone diisocyanate (IPDI, commercially available examples being: Desmodur® Z 4470SN, Desmodur® Z 4470 BA, and Desmodur® XP 2565, all supplied by Covestro), and polymeric methylene diphenyl diisocyanate (also known as polymeric MDI; commercially available examples being: Desmodur® VK 5, Desmodur® VK 10, Desmodur® 44 V 20 L NP, Desmodur® 44 V 40 L, Desmodur® VL, Desmodur® VL R 20, and Desmodur® VL). 50 (all supplied by Covestro), toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, diphenylmethane 2,4'- and / or 4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethylxylene diisocyanate, 1,2-propylene diisocyanate, 2,2,4-trimethylene diisocyanate, tetramethylene diisocyanate, 2,3-butene diisocyanate The isocyanurate trimers of esters, 1,12-dodecane diisocyanate, 1,3-cyclohexane diisocyanate, 1,3-perhydrodiphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 3,2'-diisocyanate, 4-methyldiphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane 4,4'-triisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and mixtures thereof.
[0100] Preferably, the composition is as disclosed in A0 or A1, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X has a concentration of at least 0.30 and at most 0.55, more preferably at least 0.30 and at most 0.50, and even more preferably at least 0.30 and at most 0.45, as disclosed in the specification. 1 The degree of branching was determined by H-NMR spectroscopy. This topic is referred to as 'A2' in the instruction manual.
[0101] Preferably, the composition is as disclosed in A0 or any of A1 to A2, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the polylysine-X is selected from hyperbranched polylysine and primary ammonium salts of hyperbranched polylysine, wherein the at least one primary ammonium cation (-NH3) present in the structure counteracting the primary ammonium salt of hyperbranched polylysine is present. + The anion of the polylysine-X is selected from halogen anions, carboxyl anions, and sulfonate anions; more preferably, the composition is as disclosed in A0 or any of A1 to A2 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the polylysine-X is selected from hyperbranched polylysine and primary ammonium salts of hyperbranched polylysine, wherein the at least one primary ammonium cation (-NH3) present in the structure counteracting the primary ammonium salt of hyperbranched polylysine is present. + The anion of the composition is selected from halide anions and carboxylate anions; more preferably, the composition is as disclosed in A0 or any of A1 to A2 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the polylysine-X is selected from hyperbranched polylysine and a primary ammonium salt of hyperbranched polylysine, wherein the at least one primary ammonium cation (-NH3) present in the structure of the primary ammonium salt of hyperbranched polylysine is present. + The anion of the composition is selected from halide anions; even more preferably, the composition is as disclosed in A0 or any of A1 to A2 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the polylysine-X is selected from hyperbranched polylysine and a primary ammonium salt of hyperbranched polylysine, wherein the at least one primary ammonium cation (-NH3) present in the structure of the primary ammonium salt of hyperbranched polylysine is present. + The anion of the composition is selected from fluoride, chloride, bromide, and iodide ions; most preferably, the composition is as disclosed in A0 or any of A1 to A2 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the polylysine-X is selected from hyperbranched polylysine and a primary ammonium salt of hyperbranched polylysine, wherein the at least one primary ammonium cation (-NH3) present in the structure of the primary ammonium salt of hyperbranched polylysine is present. + The anion of the composition is selected from chloride, bromide, and iodide ions; particularly, the composition is disclosed as in A0 or any of A1 to A2 or as in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the polylysine-X is selected from hyperbranched polylysine and a primary ammonium salt of hyperbranched polylysine, wherein the at least one primary ammonium cation (-NH3) present in the structure counteracting the primary ammonium salt of hyperbranched polylysine is present. +The anion of the composition is selected from chloride and bromide ions; more particularly, the composition is disclosed as in A0 or any of A1 to A2 or as in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the polylysine-X is selected from hyperbranched polylysine and a primary ammonium salt of hyperbranched polylysine, wherein the at least one primary ammonium cation (-NH3) present in the structure counteracting the primary ammonium salt of hyperbranched polylysine is present. + The anion of ) is chloride ion. This topic is referred to as 'A3' in the instruction manual.
[0102] Preferably, the composition is as disclosed in A0 or any of A1 to A3 or in any combination of the disclosures in the entire specification, including the claims, wherein each of the polylysine-X has an apparent viscosity of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa·s as determined by rheological determination as disclosed in the specification. The topic of this section is referred to as 'A4' in the instruction manual.
[0103] Preferably, the composition is as disclosed in A0 or any of A1 through A4, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the amine value (abbreviated AN) of each of the polylysine-X, as determined by the titration method disclosed in the specification, is higher than its acid value (abbreviated AV) as determined by the titration method disclosed in the specification. The subject matter of this paragraph is referred to in the specification as 'A5'.
[0104] Preferably, the composition is as disclosed in A0 or any of A1 to A5, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X has a number-average molecular weight (abbreviated as M) of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 and at most 6000 Da, as determined by gel permeation chromatography-1 as disclosed in the specification. n This section is referred to as 'A6' in the instruction manual.
[0105] Preferably, the composition is as disclosed in A0 or any of A1 to A6, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X has a weight-average molecular weight (abbreviated as M) of at least 3,000 and at most 50,000 Da, preferably at least 5,000 and at most 40,000 Da, more preferably at least 10,000 and at most 30,000 Da, as determined by gel permeation chromatography-1 as disclosed in the specification. w This section is referred to as 'A7' in the instruction manual.
[0106] Preferably, the composition is as disclosed in A0 or any of A1 to A7, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X has an amine value (abbreviated as AN) determined by titration as disclosed in the specification, of at least 200 and at most 700 mg KOH / g, preferably at least 250 and at most 600 mg KOH / g, more preferably at least 250 and at most 500 mg KOH / g, and especially at least 300 and at most 400 mg KOH / g. The subject matter of this paragraph is referred to in the specification as 'A8'.
[0107] Preferably, the composition is as disclosed in A0 or any of A1 to A8, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X has an acid value (abbreviated as AV) of at least 10 and at most 150, preferably at least 10 and at most 100, for example at least 10 and at most 90, for example at least 30 and at most 150, for example at least 30 and at most 100, for example at least 30 and at most 90 mg KOH / g determined by titration as disclosed in the specification. The subject matter of this paragraph is referred to in the specification as 'A9'.
[0108] Preferably, the composition is as disclosed in A0 or any of A1 to A9, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X independently has an amine value (AN) of at least 50 and at most 2000, preferably at least 50 and at most 1500, more preferably at least 50 and at most 1200, for example at least 50 and at most 1000, for example at least 50 and at most 900, for example at least 50 and at most 800, for example at least 150 and at most 600, for example at least 200 and at most 500, for example at least 200 and at most 450, for example at least 200 and at most 400, for example at least 250 and at most 400 mgKOH / g determined by titration as disclosed in the specification. The subject matter of this paragraph is referred to in the specification as 'A10'.
[0109] Preferably, the composition is as disclosed in A0 or any of A1 to A10, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X independently has an amine value (AN) of at least 50 and at most 2000, preferably at least 50 and at most 1500, more preferably at least 50 and at most 1200, for example at least 50 and at most 1000, for example at least 50 and at most 900, for example at least 50 and at most 800, for example at least 150 and at most 600, for example at least 200 and at most 500, for example at least 200 and at most 450, for example at least 200 and at most 400, for example at least 250 and at most 400 mg KOH / g, determined by titration as disclosed in the specification, and wherein the AN is higher than the acid value (AV) determined by titration as disclosed in the specification. The subject matter of this paragraph is referred to in the specification as 'A11'.
[0110] Preferably, the composition is as disclosed in A0 or any of A1 to A11, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X independently has at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 The apparent viscosity (AN) is measured in mPa·s by rheological determination as disclosed in the specification, and wherein AN is higher than the acid value (AV) measured by titration as disclosed in the specification. This subject matter is referred to as 'A12' in the specification.
[0111] Preferably, the composition is as disclosed in A0 or any of A1 to A12, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X independently has: - A number-average molecular weight (abbreviated as M) of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 and at most 6000 Da, determined by gel permeation chromatography as disclosed in the specification. n ), - At least 3000 and at most 50000 Da, preferably at least 5000 and at most 40000 Da, more preferably at least 5000 and at most 30000 Da, for example at least 10000 and at most 30000 Da, as determined by gel permeation chromatography-1 as disclosed in the specification (abbreviated as M). w ), - Apparent viscosity measured by rheological determination of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa·s.
[0112] The topic of this section is mentioned as 'A13' in the instruction manual.
[0113] Preferably, the composition is as disclosed in A0 or any of A1 to A13, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X has: - A number-average molecular weight (abbreviated as M) of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 and at most 6000 Da, determined by gel permeation chromatography as disclosed in the specification. n ), - A weight-average molecular weight (abbreviated as M) of at least 3,000 and at most 50,000 Da, preferably at least 5,000 and at most 40,000 Da, more preferably at least 10,000 and at most 30,000 Da, determined by gel permeation chromatography-1 as disclosed in the specification. w ), - At least 2 and at most 15, preferably at least 2 and at most 10, more preferably at least 3 and at most 8 as M w / M n The ratio is used to calculate the polydispersity (PD). - An apparent viscosity of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa·s, as determined by rheological methods as disclosed in the specification. - An amine value (abbreviated as AN) of at least 200 and at most 700 mg KOH / g, preferably at least 250 and at most 600 mg KOH / g, more preferably at least 250 and at most 500 mg KOH / g, and especially at least 300 and at most 400 mg KOH / g, determined by titration as disclosed in the specification.
[0114] The topic of this section is mentioned as 'A14' in the instruction manual.
[0115] Preferably, the composition is as disclosed in A0 or any of A1 to A14, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each of the polylysine-X has: - A number-average molecular weight (abbreviated as M) of at least 1100 and at most 10000 Da, preferably at least 1500 and at most 8000 Da, more preferably at least 2000 and at most 6000 Da, determined by gel permeation chromatography as disclosed in the specification. n ), - A weight-average molecular weight (abbreviated as M) of at least 3,000 and at most 50,000 Da, preferably at least 5,000 and at most 40,000 Da, more preferably at least 10,000 and at most 30,000 Da, determined by gel permeation chromatography-1 as disclosed in the specification. w ), - At least 2 and at most 15, preferably at least 2 and at most 10, more preferably at least 3 and at most 8 as M w / M n The polydispersity of the ratio calculation - An apparent viscosity of at least 400 and at most 8000, preferably at least 400 and at most 6000, more preferably at least 400 and at most 4000, even more preferably at least 400 and at most 2500, most preferably at least 400 and at most 2000, for example at least 400 and at most 1800, for example at least 400 and at most 1550, for example at least 450 and at most 8000, for example at least 450 and at most 6000, for example at least 450 and at most 4000, for example at least 450 and at most 2000, for example at least 450 and at most 1800, for example at least 450 and at most 1550 mPa·s, as determined by rheological methods as disclosed in the specification. - An amine value of at least 200 and at most 700 mg KOH / g, preferably at least 250 and at most 600 mg KOH / g, more preferably at least 250 and at most 500 mg KOH / g, and especially at least 300 and at most 400 mg KOH / g, determined by titration as disclosed in the specification. - An acid value determined by titration as disclosed in the specification, of at least 10 and at most 150 mg KOH / g, preferably at least 30 and at most 100, more preferably at least 40 and at most 90 mg KOH / g. - Up to 3.0, preferably up to 2.0, more preferably up to 1.0, even more preferably up to 0.5, most preferably up to 0.1, especially up to 0.05% gel content, and even more especially 0.0% gel content.
[0116] The topic of this section is mentioned as 'A15' in the instruction manual.
[0117] Preferably, the composition is as disclosed in A0 or any of A1 to A15, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each member of the XL components has at least 100 and at most 10,000, for example at least 100 and at most 5,000, for example at least 100 and at most 4,000, for example at least 100 and at most 3,000, for example at least 100 and at most 2,500, for example at least 100 and at most 2,000, for example at least 150 and at most 5,000, for example at least 150 and at most 4,000, for example at least 150 and at most 3,000, for example at least 150 and at most 2,500, for example at least 150 and at most 2,000, for example at least 300 and at most 10,000, for example at least 400 and at most 10,000, for example at least 500 and at most 10,000. The number-average molecular weight of Da was determined by gel permeation chromatography-2 as disclosed in the product specification. This section is referred to as 'A16' in the product specification.
[0118] Preferably, the composition is as disclosed in A0 or any of A1 to A16, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each monomeric compound in the XL component has a number-average molecular weight of at least 100 and at most 5000, for example at least 100 and at most 4000, for example at least 100 and at most 3000, for example at least 100 and at most 2500, for example at least 100 and at most 2000, for example at least 150 and at most 5000, for example at least 150 and at most 4000, for example at least 150 and at most 3000, for example at least 150 and at most 2500, for example at least 150 and at most 2000 Da, determined by gel permeation chromatography-2 as disclosed in the specification. The subject matter of this paragraph is referred to in the specification as 'A17'.
[0119] Preferably, the composition is as disclosed in A0 or any of A1 to A15 and A17, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each polymeric compound in the XL component has at least 300 and at most 20,000, for example at least 300 and at most 15,000, for example at least 300 and at most 10,000, for example at least 300 and at most 8,000, for example at least 300 and at most 6,000, for example at least 300 and at most 5,000. For example, at least 300 and at most 4000; for example, at least 300 and at most 3000; for example, at least 300 and at most 2500; for example, at least 300 and at most 2000; for example, at least 500 and at most 20000; for example, at least 500 and at most 15000; for example, at least 500 and at most 10000; for example, at least 500 and at most 8000; for example, at least 500 and at most 6000; for example, at least 500 and at most 5000; for example, at least 500 and at most 4000; for example, at least 500 and... At most 3000, for example, at least 500 and at most 2500, for example, at least 500 and at most 2000, for example, at least 750 and at most 20000, for example, at least 750 and at most 15000, for example, at least 750 and at most 10000, for example, at least 750 and at most 8000, for example, at least 750 and at most 6000, for example, at least 750 and at most 5000, for example, at least 750 and at most 4000, for example, at least 750 and at most 3000, for example, at least 750 and at most 2500, for example... Number-average molecular weights of at least 750 and at most 2000, for example, at least 1000 and at most 20000, for example, at least 1000 and at most 15000, for example, at least 1000 and at most 10000, for example, at least 1000 and at most 8000, for example, at least 1000 and at most 6000, for example, at least 1000 and at most 5000, for example, at least 1000 and at most 4000, for example, at least 1000 and at most 3000, for example, at least 1000 and at most 2500, for example, at least 1000 and at most 2000 Da, determined by gel permeation chromatography-2 as disclosed in the specification. The subject of this section is referred to as 'A18' in the specification.
[0120] Preferably, the composition is as disclosed in A0 or any of A1 to A18, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein each polymeric compound in the XL components is a linear polymeric compound, and preferably each polymeric compound in the XL components is a linear unbranched polymeric compound. The subject matter of this paragraph is referred to in the specification as 'A19'.
[0121] Preferably, the composition is as disclosed in A0 or any of A1 to A18, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the XL component is a monomeric compound having at least two XL groups per molecule. The subject matter of this section is referred to in the specification as 'A20'.
[0122] Preferably, the composition is as disclosed in A0 or any of A1 to A18, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the XL component is a polymeric compound having at least two XL groups per molecule; more preferably, the XL component is a linear polymeric compound having at least two XL groups per molecule; even more preferably, the XL component is a linear unbranched polymeric compound having at least two XL groups per molecule. The subject matter of this paragraph is referred to in the specification as 'A21'.
[0123] Preferably, the composition is as disclosed in A0 or any of A1 to A21, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein both the monomeric compound of the XL component and the polymeric compound of the XL component do not contain Si atoms in their structure. The subject matter of this paragraph is referred to in the specification as 'A22'.
[0124] Preferably, the composition is as disclosed in A0 or any of A1 through A22, or in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein the composition may optionally contain water. The subject matter of this paragraph is referred to in the specification as 'A23'.
[0125] Preferably, the composition is as disclosed in A0 or any of A1 to A23, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition comprises at least 1 and at most 90, preferably at least 2 and at most 90, more preferably at least 3 and at most 90, even more preferably at least 5 and at most 90, for example at least 1 and at most 80, for example at least 2 and at most 80, for example at least 3 and at most 80, for example at least 5 and at most 80, for example at least 1 and at most 70, for example at least 2 and at most 70, for example at least 3 and at most 70, for example at least 5 and at most 70, for example at least 1 and at most 60, for example at least 2 and at most 60, for example at least 3 and at most 60, for example at least 5 and at most 60, for example at least 1 ... Up to 50, for example, at least 2 and up to 50, for example, at least 3 and up to 50, for example, at least 5 and up to 50, for example, at least 1 and up to 40, for example, at least 2 and up to 40, for example, at least 3 and up to 40, for example, at least 5 and up to 40, for example, at least 1 and up to 30, for example, at least 2 and up to 30, for example, at least 3 and up to 30, for example, at least 5 and up to 30, for example, at least 1 and up to 20, for example, at least 2 and up to 20, for example, at least 3 and up to 20, for example, at least 5 and up to 20, for example, at least 1 and up to 15, for example, at least 2 and up to 15, for example, at least 3 and up to 15, for example, at least 5 and up to 15, for example, at least 1 and up to 10, for example, at least 2 and up to 10, for example, at least 3 and up to 10, for example, at least 5 and up to 10, for example, at least 5 and up to 10 pph of water determined by the water content method disclosed in the specification. The subject of this paragraph is referred to in the specification as 'A24'.
[0126] Preferably, the composition is as disclosed in A0 or any of A1 to A22, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition contains water, and the total amount of component A and water in the composition is greater than 10, preferably at least 20, such as at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 92, at least 95, at least 97, at least 98, at least 99 pph, for example, the composition consists of component A and water, wherein the amount of water is determined by the water content method disclosed in the specification. The subject matter of this paragraph is referred to in the specification as 'A25'.
[0127] Preferably, the composition is disclosed as in A0 or any of A1 through A22, or as in any combination of the disclosures derived from this section and the entire specification including the claims, wherein component A is present in an amount of at least 85 and at most 100, for example at least 87 and at most 100, for example at least 90 and at most 100, for example at least 92 and at most 100, for example at least 95 and at most 100, for example at least 97 and at most 100, for example at least 98, for example at least 99 and at most 100% by weight of the composition. The subject matter of this paragraph is referred to in the specification as 'A26'.
[0128] Preferably, the composition is as disclosed in A0 or any of A1 to A26, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition comprises at most 50, preferably at most 40, more preferably at most 30, even more preferably at most 20, most preferably at most 10, especially at most 5, and even more especially at most 3 pph of an organic solvent. The subject matter of this paragraph is referred to in the specification as 'A27'.
[0129] Preferably, the composition is as disclosed in A0 or any of A1 through A26, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition is free of organic solvents. The subject matter of this paragraph is referred to in the specification as 'A28'.
[0130] Preferably, the composition is as disclosed in A0 or any of A1 through A28, or in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein the composition comprises component A and water. The subject matter of this paragraph is referred to in the specification as 'A29'.
[0131] Preferably, the composition is as disclosed in A0 or any of A1 to A29, or in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein the composition comprises component A. The subject matter of this paragraph is referred to in the specification as 'A30'.
[0132] Preferably, the composition is as disclosed in A0 or any of A1 to A30, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition may optionally contain component B, which is selected from proteins and mixtures thereof. More preferably, the composition may optionally contain up to 0.95, preferably up to 0.90, more preferably up to 0.80, for example up to 0.70, for example up to 0.60, for example up to 0.50, for example up to 0.40, for example up to 0.30, for example up to 0.20, for example up to 0.10, for example up to 0.05 pph of component B. The subject matter of this paragraph is referred to in the specification as 'A31'.
[0133] Preferably, the composition is as disclosed in A0 or any of A1 through A30, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain ingredient B, and ingredient B is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A32'.
[0134] Preferably, the composition is as disclosed in A0 or any of A1 to A32, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition may optionally contain component C, which is selected from polyphenol macromolecules and mixtures thereof, wherein each of the polyphenol macromolecules is a macromolecule with a plurality of phenolic or polyhydroxyphenyl groups, and the amount is such that the ratio of the total weight of component C to the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0. 25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, even more especially at most 0.13, and wherein component C is different from and distinct from any other component and ingredient of the composition; more preferably, the composition may optionally contain component C, which is selected from polyphenol macromolecules (each of which is a macromolecule with a number of phenolic or polyhydroxyphenyl groups) and mixtures thereof, in an amount such that the ratio of the total weight of component C to the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.40. 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, even more especially at most 0.13, and wherein component C is different from and distinct from any other component and ingredient of the composition, and wherein component C is tannin, lignin sulfonate or a mixture thereof, and wherein the composition does not contain any polyphenol macromolecular compound other than tannin, lignin sulfonate or any mixture of any combination of tannin and lignin sulfonate; even more preferably, the composition contains, as in A0 or any of A1 to A32 or as in the derivative As disclosed in this section and in any combination of the disclosures throughout the specification, including the claims, the composition may optionally comprise component C, selected from polyphenol macromolecules (each of which is a macromolecule with a number of phenolic or polyhydroxyphenyl groups) and mixtures thereof, in an amount such that the ratio of the total weight of component C to the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, and even more especially at most 0.13, wherein component C is different from and distinct from any other components and ingredients of the composition, and wherein component C is a condensed tannin, lignin sulfonate, or a mixture thereof, and wherein the composition does not contain any polyphenol macromolecular compound other than condensed tannin, lignin sulfonate, or any mixture of any combination of condensed tannin and lignin sulfonate; most preferably, the composition is as disclosed in A0 or any of A1 to A32 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition may optionally contain component C, which is selected from polyphenol macromolecular compounds (each of which is a macromolecular compound having a plurality of phenolic or polyhydroxyphenyl groups) and mixtures thereof, in an amount such that The ratio of the total weight of component C to the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, and even more especially at most 0.13, and wherein component C is different from and distinct from any other component and ingredient of the composition, and wherein component C is a lignin sulfonate or a mixture of lignin sulfonates, and wherein the composition does not contain any polyphenol macromolecular compounds other than lignin sulfonates and mixtures of lignin sulfonates; particularly, the composition is as in A0 or any of A1 to A32 or any combination of the disclosures derived from this section and the entire specification including the claims. The disclosed composition optionally includes component C, selected from polyphenol macromolecules (each of which is a macromolecule with a number of phenolic or polyhydroxyphenyl groups) and mixtures thereof, in an amount such that the ratio of the total weight of component C to the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, and even more especially at most 0.13, and wherein component C is different from and distinct from any other component and ingredient of the composition, and wherein component C is calcium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate or mixtures thereof, and wherein the composition does not contain any of the following: calcium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate or mixtures thereof. Any polyphenol macromolecular compound other than ammonium lignosulfonate, magnesium lignosulfonate, and mixtures thereof; more particularly, the composition as disclosed in A0 or any of A1 to A32 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition may optionally contain component C, selected from polyphenol macromolecular compounds (each of which is a macromolecular compound having a number of phenolic or polyhydroxyphenyl groups) and mixtures thereof, in an amount such that the ratio of the total weight of component C to the total weight of the polylysine component is at most 0.40, preferably at most 0.30, more preferably at most 0.25, even more preferably at most 0.20, most preferably at most 0.15, especially at most 0.14, and even more especially at most 0.13, and wherein component C is different from and distinct from any other components and ingredients of the composition, and wherein component C is magnesium lignosulfonate, and wherein the composition does not contain any polyphenol macromolecules other than magnesium lignosulfonate. This section is referred to as 'A33' in the specification.
[0135] Preferably, the composition is as disclosed in claim 1, A0, or any of A1 through A32, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain ingredient C, and wherein ingredient C is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A34'.
[0136] Preferably, the composition is as disclosed in claim 1, A0, or any of A1 through A34, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition may optionally contain component D, which is selected from: i) monosaccharides (in their aldose or ketose form), ii) oligosaccharides, iii) polysaccharides, iv) monomeric or polymeric compounds, for example, which produce one or more reducing sugars in situ upon heating, and mixtures of i) through iv), and component D is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A35'.
[0137] Preferably, the composition is as disclosed in A0 or any of A1 to A34, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain ingredient D, and wherein ingredient D is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A36'.
[0138] Preferably, the composition is as disclosed in A0 or any of A1 through A36, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition may optionally contain component E selected from peptides and mixtures thereof, and wherein component E is different from and distinct from any other components and ingredients of the composition, and is present in an amount of up to 0.30, for example up to 0.20, for example up to 0.10, for example up to 0.05% by weight of the composition. The subject matter of this paragraph is referred to in the specification as 'A37'.
[0139] Preferably, the composition is as disclosed in A0 or any of A1 to A36, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain ingredient E, and wherein ingredient E is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A38'.
[0140] Preferably, the composition is as disclosed in A0 or any of A1 through A38, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain ingredient F, which is selected from compounds comprising at least two acetylacetoxy groups and mixtures thereof, and wherein ingredient F is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A39'.
[0141] Preferably, the composition is as disclosed in A0 or any of A1 through A39, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain ingredient F1, which is selected from compounds containing only one acetylacetoxy group and mixtures thereof, and wherein ingredient F1 is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A40'.
[0142] Preferably, the composition is as disclosed in A0 or any of A1 to A40, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain component K, which is selected from compounds comprising at least two ethylene oxide groups and mixtures thereof, and wherein component K is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A41'.
[0143] Preferably, the composition is as disclosed in A0 or any of A1 through A41, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain component K1, which is selected from compounds containing only one ethylene oxide group and mixtures thereof, and wherein component K1 is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A42'.
[0144] Preferably, the composition is as disclosed in A0 or any of A1 to A42, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain component L, which is selected from compounds comprising at least two olefinic unsaturated groups and mixtures thereof, and wherein component L is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A43'.
[0145] Preferably, the composition is as disclosed in A0 or any of A1 through A43, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain component L1, which is selected from compounds containing only one olefinic unsaturated group and mixtures thereof, and wherein component L1 is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A44'.
[0146] Preferably, the composition is as disclosed in A0 or any of A1 through A44, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain component M, which is selected from compounds comprising at least two vinyl unsaturated groups and mixtures thereof, and wherein component M is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A45'.
[0147] Preferably, the composition is as disclosed in A0 or any of A1 through A45, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition does not contain component M1, which is selected from compounds containing only one vinyl unsaturated group and mixtures thereof, and wherein component M1 is different from and distinct from any other components and ingredients of the composition. The subject matter of this paragraph is referred to in the specification as 'A46'.
[0148] Preferably, the composition is as disclosed in A0 or any of A1 to A46, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition optionally comprises (preferably) component N in an amount of at least 0.01 and at most 10, preferably at least 0.02 and at most 8, more preferably at least 0.05 and at most 5, for example at least 0.01 and at most 4, for example at least 0.03 and at most 3, for example at least 0.05 and at most 2, for example at least 0.75 and at most 2% by weight, and said component N is selected from amines, amine salts, nitrogen compounds, metal-containing compounds, and mixtures thereof; preferably, said component N is selected from amines, amine salts, nitrogen compounds, and mixtures thereof. The components N are selected from amines, amine salts, diaza compounds, metal-containing compounds, and mixtures thereof. More preferably, the component N is selected from amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) hydroxides, alkaline earth metal (preferably calcium, magnesium, barium) hydroxides, and mixtures thereof. Even more preferably, the component N is selected from amines, amine salts, diaza compounds, metal-containing compounds, and mixtures thereof. For example, the component N is selected from amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkaline earth metal (preferably calcium, magnesium, barium) inorganic compounds, and mixtures thereof. Compounds and mixtures thereof; for example, the component N is selected from amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) hydroxides, alkaline earth metal (preferably calcium, magnesium, barium) hydroxides and mixtures thereof; for example, the component N is selected from tertiary amines, amine salts, diaza compounds, metal-containing compounds and mixtures thereof; for example, the component N is selected from tertiary amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) inorganic compounds, alkaline earth metal (preferably calcium, magnesium, barium) inorganic compounds and mixtures thereof; for example, the component N is selected from tertiary amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, lithium) hydroxides The composition comprises an amine, an alkaline earth metal (preferably calcium, magnesium, or barium) hydroxide, or a mixture thereof; for example, the component N is selected from tertiary amines, amine salts, diaza compounds, metal-containing compounds, or a mixture thereof; for example, the component N is selected from tertiary amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, or lithium) inorganic compounds, alkaline earth metal (preferably calcium, magnesium, or barium) inorganic compounds, or a mixture thereof; for example, the component N is selected from tertiary amines, amine salts, diaza compounds, organometallic compounds, metal complexes, alkali metal (preferably potassium, sodium, or lithium) hydroxides, alkaline earth metal (preferably calcium, magnesium, or barium) hydroxides, or a mixture thereof; for example, the composition contains component N, which is selected from amines, amine salts, diaza compounds, or aza compounds.The metal-containing compounds and mixtures thereof of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium); preferably, the component N is selected from amines, amine salts, aza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium), inorganic compounds of alkali metals (preferably potassium, sodium, lithium), and inorganic compounds of alkaline earth metals (preferably calcium, magnesium, barium); more Preferably, component N is selected from amines, amine salts, diaza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium), hydroxides of alkali metals (preferably potassium, sodium, lithium), hydroxides of alkaline earth metals (preferably calcium, magnesium, barium), and mixtures thereof; even more preferably, component N is selected from amines, amine salts, diaza compounds, tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals. Metal compounds and mixtures thereof (preferably calcium, magnesium, and barium); for example, the component N is selected from amines, amine salts, diaza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, and lithium), and alkaline earth metals (preferably calcium, magnesium, and barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, and lithium), and alkaline earth metals (preferably calcium, magnesium, and barium), inorganic compounds of alkali metals (preferably potassium, sodium, and lithium), and inorganic compounds of alkaline earth metals (preferably calcium, magnesium, and barium) and mixtures thereof; for example, the component N is selected from amines, amine salts, diaza compounds, tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, Organometallic compounds of aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium); metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium); hydroxides of alkali metals (preferably potassium, sodium, lithium), hydroxides of alkaline earth metals (preferably calcium, magnesium, barium), and mixtures thereof; for example, component N is selected from tertiary amines, amine salts, and nitrogen compounds; metal-containing compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium), and mixtures thereof; for example, component N is selected from tertiary amines, amine salts, and nitrogen compounds.Organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium); metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium); inorganic compounds of alkali metals (preferably potassium, sodium, lithium); inorganic compounds of alkaline earth metals (preferably calcium, magnesium, barium); and mixtures thereof; for example, the component -N is selected from tertiary amines. amine salts, nitrogen-containing compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium), metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium), hydroxides of alkali metals (preferably potassium, sodium, lithium), hydroxides of alkaline earth metals (preferably calcium, magnesium, barium), and mixtures thereof; for example, the aforementioned Component N is selected from tertiary amines, amine salts, diaza compounds, and metal-containing compounds and mixtures thereof of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium); for example, component N is selected from tertiary amines, amine salts, diaza compounds, and organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium), and metals containing tin, germanium, bismuth, titanium, zirconium, and ... Metal complexes of hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium), inorganic compounds of alkali metals (preferably potassium, sodium, lithium), inorganic compounds of alkaline earth metals (preferably calcium, magnesium, barium), and mixtures thereof; for example, the component N is selected from tertiary amines, amine salts, diaza compounds, organometallic compounds of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), and alkaline earth metals (preferably calcium, magnesium, barium).Metal complexes of tin, germanium, bismuth, titanium, zirconium, hafnium, cobalt, zinc, chromium, aluminum, chromium, alkali metals (preferably potassium, sodium, lithium), alkaline earth metals (preferably calcium, magnesium, barium), hydroxides of alkali metals (preferably potassium, sodium, lithium), hydroxides of alkaline earth metals (preferably calcium, magnesium, barium), and mixtures thereof; examples of amines include, but are not limited to, tributylamine (TBA), triethylamine (TEA), pyridine, dimethylaminopyridine, triphenylamine, and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine. Examples of amine salts include, but are not limited to, N,N-dimethylcyclohexylacetate ammonium. Examples of monoaza compounds include, but are not limited to, 1-azabicyclo[2.2.2]octane (also known as ABCO or quinine ring). Examples of diaza compounds include, but are not limited to, 1,4-diazabicyclo(2,2,2)octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-encarbamate, 1,8-diazabicyclo[5.4.0]undec-1-ene (DBU), diazabicyclononane (DBN), and 3,3,6,9,9-pentamethyl-2,10-diazabicyclo[4.4.0]dec-1-ene. Examples of metal-containing compounds, particularly organometallic compounds, include, but are not limited to, dibutyltin dilaurate (DBTDL), dibutyltin diacetate (DBTDA), dioctyltin maleate, monobutyltin monoacrylate, monobutyltin sulfide, monobutyltin oxide, trioctyltin laurate, bis(trioctyltin) oxide (TOTO), bis(tributyltin) oxide (TBTO), tetrabutyltin diacetate, and tri(-ethylhexanoate)butyltin. Metal-containing compounds,Examples of metal complexes include, but are not limited to, zinc acetylacetonate (II), zinc naphthenate, bismuth tris(2-ethylhexanoate), aluminum dionate complex, cobalt bis(2-ethylhexanoate), cobalt acetylacetonate (III), zirconium bis(2-ethylhexanoate), zinc bis(2-ethylhexanoate), tetra(acetylacetonate)titanium, tetra(ethyl acetoacetate)titanium, calcium bis(2-ethylhexanoate), chromium tris(2-ethylhexanoate), sodium methoxide, potassium methoxide, lithium methoxide, and 4,12-dibutyl-2,6,10,14-tetramethyl-1,7,9,15-tetraoxa-4,12 -diaza-8-stanzaspiro[7.7]pentadecane, 4,12-dibutyl-2,2,10,10-tetramethyl-1,7,9,15-tetraoxa-4,12-diaza-8-stanzaspiro[7.7]pentadecane, 4,12-dimethyl-1,7,9,15-tetraoxa-4,12-diaza-8-stanzaspiro[7.7]pentadecane, 4,12-diethyl-1,7,9,15-tetraoxa-4, 12-Daza-8-Stanzaspiro[7.7]pentadecane, 4,12-dibutyl-1,7,9,15-tetraoxa-4,12-daza-8-Stanzaspiro[7.7]pentadecane, 4,12-diethyl-2,6,10,14-tetramethyl-1,7,9,15-tetraoxa-4,12-daza-8-Stanzaspiro[7.7]pentadecane, 4,12-diethyl-2,2,10,10-tetramethyl -1,7,9,15-tetraoxa-4,12-diaza-8-stanzaspiro[7.7]pentadecane, 2,4,6,10,12,14-hexamethyl-1,7,9,15-tetraoxa-4,12-diaza-8-stanzaspiro[7.7]pentadecane, 2,2,4,10,10,12-hexamethyl-1,7,9,15-tetraoxa-4,12-diaza-8-stanzaspiro[7.7]pentadecane. Examples of metal-containing compounds, and especially alkali metal inorganic compounds, include, but are not limited to, LiOH, KOH, and NaOH. Examples of metal-containing compounds, and especially alkaline earth metal inorganic compounds, include, but are not limited to, Ca(OH)2, Mg(OH)2, and Ba(OH)2. Dimethylaminopyridine, tributylamine (TBA), triethylamine (TEA), 1,4-diazabicyclo(2,2,2)octane (DABCO), dibutyltin dilaurate (DBTDL), zinc acetylacetonate (II), zinc bis(2-ethylhexanoate), sodium methoxide, LiOH, Ca(OH)₂, and Mg(OH)₂ are particularly preferred. This section is referred to as 'A47' in the specification.
[0149] Preferably, the composition is as disclosed in A0 or any of A1 to A26 and any of A31 to A47, or in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein the composition comprises component A and component N. The subject matter of this paragraph is referred to in the specification as 'A48'.
[0150] Preferably, the composition is as disclosed in A0 or any of A1 to A28 or any of A31 to A47, or in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein the composition comprises component A, component N, and water. The subject matter of this paragraph is referred to in the specification as 'A49'.
[0151] Preferably, the composition is as disclosed in A0 or any of A1 to A49, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition is free of formaldehyde resin. The subject matter of this paragraph is referred to in the specification as 'A50'.
[0152] Preferably, the composition is as disclosed in A0 or any of A1 to A50, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition is free of urea-formaldehyde resin. The subject matter of this paragraph is referred to in the specification as 'A51'.
[0153] Preferably, the composition is as disclosed in A0 or any of A1 to A51, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition is free of melamine-formaldehyde resin. The subject matter of this paragraph is referred to in the specification as 'A52'.
[0154] Preferably, the composition is as disclosed in A0 or any of A1 to A49, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the composition is free of formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, and mixtures thereof. The subject matter of this paragraph is referred to in the specification as 'A53'.
[0155] The fiber component comprises at least one fiber element containing plant fibers, and wherein the fiber element contains no fibers other than plant fibers, and wherein the composition contains no fibers other than plant fibers of the fiber component. Therefore, both the fiber component and the composition of the present invention contain only plant fibers.
[0156] Preferably, the composition is as disclosed in A0 or any of A1 to A53, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the fiber component is present in an amount of at least 10 and at most 98, preferably at least 20 and at most 98, more preferably at least 30 and at most 98, most preferably at least 40 and at most 98, especially at least 50 and at most 98, even more especially at least 60 and at most 98, even more especially at least 70 and at most 98, and most especially at least 80 and at most 98, for example at least 85 and at most 98% by weight. The subject matter of this paragraph is referred to in the specification as 'A54'.
[0157] Preferably, the composition is as disclosed in A0 or any of A1 to A54, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the fibrous element comprises plant 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% by weight, for example, the fibrous element is composed of plant fibers. The subject matter of this paragraph is referred to in the specification as 'A55'.
[0158] Preferably, the composition is as disclosed in A0 or any of A1 to A55, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the plant fiber is selected from natural cellulose fibers, natural lignocellulose fibers, and mixtures thereof. The subject matter of this section is referred to in the specification as 'A56'.
[0159] Preferably, the composition is as disclosed in A0 or any of A1 to A56, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the plant fiber is selected from wood fiber, reed fiber, bamboo fiber, seaweed, jute fiber, flax fiber, hemp seed fiber, ramie fiber, Manila fiber, sisal fiber, kapok fiber, cotton, banana fiber, coconut fiber, rye fiber, wheat fiber, rice fiber, kenaf fiber, straw fiber, grass fiber, leaf fiber, and mixtures thereof. The subject matter of this section is referred to in the specification as 'A57'.
[0160] Preferably, the composition is as disclosed in A0 or any of A1 through A57, or in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein the plant fiber is selected from wood fiber, reed fiber, and mixtures thereof. The subject matter of this section is referred to in the specification as 'A58'.
[0161] Preferably, the composition is as disclosed in A0 or any of A1 to A58, or in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein the plant fiber is wood fiber. The subject matter of this section is referred to in the specification as 'A59'.
[0162] Preferably, the composition is as disclosed in A0 or any of A1 to A59, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the fibrous element is selected from fibers, filaments, yarns, strips, bundles, staple yarns, granules, wood chips, shavings, sheets, boards, pulp, and mixtures thereof; preferably, the fibrous element is selected from fibers, filaments, yarns, bundles, staple yarns, granules, wood chips, shavings, sheets, pulp, and mixtures thereof; more preferably, the fibrous element is wood chips. The subject matter of this paragraph is referred to in the specification as 'A60'.
[0163] Preferably, the composition is as disclosed in A0 or any of A1 to A60, or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the fibrous component consists of wood chips, wherein the median d50 of the particle size distribution of the wood chips, as determined according to 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 at 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. The subject matter of this paragraph is referred to in the specification as 'A61'.
[0164] In one embodiment of the present invention, a method for obtaining an object is provided, wherein the method includes steps a to c: a) Provide a composition disclosed in any of A0 or A1 through A61, or in any combination of the disclosures derived from this section and the entire specification including the claims; and b) Exposing the composition to heat and / or pressure and / or vacuum, preferably simultaneously, to form an object, and c) Collect the object.
[0165] The subject of this section is referred to as 'A62' in the instruction manual.
[0166] Preferably, the method for obtaining the object is disclosed as in A62 or as in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein step b is as follows: b) Exposing the composition to heat – preferably at any temperature in the range of 40°C (and including 40°C) to at most 300°C (and including 300°C), for example in the range of 100°C (and including 100°C) to at most 300°C (and including 300°C), for example in the range of 100°C (and including 100°C) to at most 280°C (and including 280°C), for example in the range of 100°C (and including 100°C) to at most 260°C (and including 260°C), for example in the range of 100°C (and including 100°C) to at most 250°C (and including 250°C), for example in the range of 100°C (and including 100°C) to at most 240°C (and including 240°C), for example in the range of 100°C (and including 100°C) to at most 230°C (and including 100°C). And including 230°C), for example, the range from 100°C (including 100°C) to at most 220°C (including 220°C), for example, the range from 100°C (including 100°C) to at most 210°C (including 210°C), for example, the range from 110°C (including 110°C) to at most 300°C (including 300°C), for example, the range from 110°C (including 110°C) to at most 280°C (including 280°C), for example, the range from 110°C (including 110°C) to at most 260°C (including 260°C), for example, the range from 110°C (including 110°C) to at most 250°C (including 250°C), for example, the range from 110°C (including 110°C). The range is up to 240°C (inclusive), for example, from 110°C (inclusive) to 230°C (inclusive), for example, from 110°C (inclusive) to 220°C (inclusive), for example, from 110°C (inclusive) to 210°C (inclusive), for example, from 120°C (inclusive) to 300°C (inclusive), for example, from 120°C (inclusive) to 280°C (inclusive), for example, from 120°C (inclusive) to 260°C (inclusive), for example, from 120°C (inclusive) to 230°C (inclusive), for example, from 110°C (inclusive) to 220°C (inclusive), for example, from 110°C (inclusive) to 210°C (inclusive), for example, from 120°C (inclusive) to 230°C (inclusive), for example, from 110°C (inclusive) to 220°C (inclusive), for example, from 120°C (inclusive) to 23 ... And including the range of 120°C to at most 250°C (including 250°C), for example, the range of 120°C (including 120°C) to at most 240°C (including 240°C), for example, the range of 120°C (including 120°C) to at most 230°C (including 230°C), for example, the range of 120°C (including 120°C) to at most 220°C (including 220°C), for example, the range of 120°C (including 120°C) to at most 210°C (including 210°C), for example, the range of 130°C (including 130°C) to at most 300°C (including 300°C), for example, the range of 130°C (including 130°C) to at most 280°C (including 280°C).For example, the range from 130°C (inclusive) to at most 260°C (inclusive); the range from 130°C (inclusive) to at most 250°C (inclusive); the range from 130°C (inclusive) to at most 240°C (inclusive); the range from 130°C (inclusive) to at most 230°C (inclusive); the range from 130°C (inclusive) to at most 220°C (inclusive); the range from 130°C (inclusive) to at most 210°C (inclusive); the range from 140°C (inclusive) to at most 300°C (inclusive). The range of 300°C, for example, from 140°C (inclusive) to at most 280°C (inclusive), for example, from 140°C (inclusive) to at most 260°C (inclusive), for example, from 140°C (inclusive) to at most 250°C (inclusive), for example, from 140°C (inclusive) to at most 240°C (inclusive), for example, from 140°C (inclusive) to at most 230°C (inclusive), for example, from 140°C (inclusive) to at most 220°C (inclusive), for example, from 140°C (inclusive) to at most 220°C (inclusive). A range of more than 210°C (including 210°C), for example, from 150°C (including 150°C) to at most 300°C (including 300°C), for example, from 150°C (including 150°C) to at most 280°C (including 280°C), for example, from 150°C (including 150°C) to at most 260°C (including 260°C), for example, from 150°C (including 150°C) to at most 250°C (including 250°C), for example, from 150°C (including 150°C) to at most 240°C (including 240°C), for example, from 150°C (including 150°C) to at most 230°C (including 230°C), for example, from 150°C (including 150°C) to at most 230°C (including 230°C), for example, from 150°C (including 210°C) to at most 240°C (including 240°C), for example, from 150°C (including 150°C) to at most 230°C (including 230°C), for example, from 150°C (including 21 ... The range includes 150°C to at most 220°C (including 220°C), for example, the range of 150°C (including 150°C) to at most 210°C (including 210°C), for example, the range of 160°C (including 160°C) to at most 300°C (including 300°C), for example, the range of 160°C (including 160°C) to at most 280°C (including 280°C), for example, the range of 160°C (including 160°C) to at most 260°C (including 260°C), for example, the range of 160°C (including 160°C) to at most 250°C (including 250°C), for example, the range of 160°C (including 160°C) to at most 240°C (including 240°C).For example, the range from 160°C (inclusive) to at most 230°C (inclusive); the range from 160°C (inclusive) to at most 220°C (inclusive); the range from 160°C (inclusive) to at most 210°C (inclusive); the range from 100°C (inclusive) to at most 160°C (inclusive); the range from 110°C (inclusive) to at most 160°C (inclusive); the range from 120°C (inclusive) to at most 160°C (inclusive); the range from 130°C (inclusive) to at most 160°C (inclusive); the range from 1... The temperature range from 40°C (including 140°C) to at most 160°C (including 160°C), for example, from 150°C (including 150°C) to at most 160°C (including 160°C), for example, at 100°C, for example, at 110°C, for example, at 120°C, for example, at 130°C, for example, at 140°C, for example, at 150°C, for example, at 160°C, for example, at 170°C, for example, at 180°C, for example, at 190°C, for example, at 200°C, for example, at 210°C, for example, at 220°C, for example, at 240°C, for example, at 250°C, for example, at 260°C, for example, at 270°C, for example, at 280°C, for example, at 290°C, for example, at 300°C, and / or subjected to pressure – For example, from 120 kPa (and including 120 kPa) to at most 10, 5 kPa (including 10 kPa) 5 Any pressure within the range of kPa, and / or subjected to a vacuum – for example, at 10 kPa. -10 kPa (including 10 kPa) -10 Under any vacuum ranging from 1 kPa to at most 90 kPa (and including 90 kPa), for a sufficient time – for example, at least 1 second and at most 60 minutes, more for example, at least 2 seconds and at most 30 minutes, for example, at least 3 seconds and at most 20 minutes, for example, at least 4 seconds and at most 10 minutes, for example, at least 5 seconds and at most 8 minutes, for example, at least 10 seconds and at most 6 minutes, for example, at least 10 seconds and at most 5 minutes, for example, at least 10 seconds and at most 3 minutes, for example, at least 10 seconds and at most 2 minutes, for example, at least 30 seconds and at most 5 minutes, for example, at least 30 seconds and at most 3 minutes, for example, at least 30 seconds and at most 2 minutes, for example, at least 60 seconds and at most 5 minutes, for example, at least 60 seconds and at most 3 minutes, for example, at least 60 seconds and at most 2 minutes – to form an object; for example, subjecting the composition to heat and pressure in any combination of the temperature and pressure ranges just disclosed above, for a duration of any time range just disclosed above, to form an object. The topic of this section is referred to as 'A63' in the instruction manual.
[0167] Preferably, the method of obtaining the object is disclosed in any of A62 to A63 or in any combination of the disclosures in the entire specification, including the claims, wherein the object is selected from sheets, strips, rods, slats, films, fabrics, containers, boards, panels, beams, frames, slats, engineered wood [e.g., plywood, densified wood (including chemically densified wood), fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF) and high-density fiberboard (HDF; also known as waffle board, chipboard)], oriented strand board (OSB), laminated timber (glulam; plywood glulam), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel veneer glulam (PSL), laminated veneer lumber (LSL), finger joints, beams (including I-joints and I-beams), trusses (including roof and floor trusses), and transparent wood composites. More preferably, the method of obtaining the object is disclosed in any of A62 to A63 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the object is selected from plywood, densified wood (including chemically densified wood), fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF) and high-density fiberboard (HDF; also known as waffle board, chipboard)], oriented strand board (OSB), laminated timber (glulam; plywood glulam), veneer laminated lumber (LVL), cross-laminated timber (CLT), parallel veneer laminated timber (PSL), shaving laminated lumber (LSL), finger joints, beams (including I-joints and I-beams), trusses (including roof and floor trusses), and transparent wood composites. Even more preferably, the method of obtaining the object is disclosed in any of claims A62 to A63 or in any combination of the disclosures in the entire specification including the claims, wherein the object is selected from plywood, densified wood (including chemically densified wood), fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or particleboard)], and oriented strand board (OSB); most preferably, the method of obtaining the object is disclosed in any of claims A62 to A63 or in any combination of the disclosures in the entire specification including the claims, wherein the object is selected from fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or particleboard)], and oriented strand board (OSB).In particular, the method of obtaining the object is disclosed in any of claims A62 to A63 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the object is selected from fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or chipboard)]. The method of obtaining the object is disclosed in any of claims A62 to A63 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the object is low-density fiberboard (LDF; also known as particleboard or chipboard). For example, the method of obtaining the object is disclosed in any of claims A62 to A63 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the object is medium-density fiberboard (MDF). For example, the method of obtaining the object is disclosed in any of A62 to A63 or in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein the object is high-density fiberboard (HDF; also known as waffle board, particleboard). The subject matter of this paragraph is referred to in the specification as 'A64'.
[0168] Preferably, the method of obtaining the object is disclosed in any of A62 to A64 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the object is selected from sheets, strips, rods, slats, films, fabrics, containers, boards, panels, beams, frames, slats, and engineered timber. The subject matter of this paragraph is referred to in the specification as 'A65'.
[0169] Preferably, the method for obtaining the object is disclosed in any of A62 to A65 or in any combination of the disclosures derived from this section and throughout the entire specification including the claims, wherein the object is engineered timber. The subject matter of this paragraph is referred to in the specification as 'A66'.
[0170] Preferably, the method for obtaining the object is disclosed in any of A62 to A66 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the object is fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or chipboard)]. The subject matter of this paragraph is referred to in the specification as 'A67'.
[0171] In one embodiment of the invention, an object is provided obtained by a method disclosed in any of A62 to A67 or in any combination of the disclosures derived from this section and the entire specification including the claims. The subject matter of this paragraph is referred to in the specification as 'A68'.
[0172] Preferably, the objects disclosed as in A68 or in any combination of the disclosures derived from this section and the entire specification including the claims are selected from sheets, strips, rods, slats, films, fabrics, containers, boards, panels, beams, frames, slats, engineered timber [e.g., plywood, densified timber (including chemically densified timber), fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF) and high-density fiberboard (HDF; also known as waffle board, chipboard)], oriented strand board (OSB), laminated timber (glulam; plywood glulam), laminated veneer lumber (LVL), cross-laminated timber (CLT), parallel veneer glulam (PSL), laminated veneer lumber (LSL), finger joints, beams (including I-joints and I-beams), trusses (including roof and floor trusses), and transparent wood composites. More preferably, the objects disclosed in A68 or in any combination of the disclosures derived from this section and the entire specification including the claims are selected from plywood, densified wood (including chemically densified wood), fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF) and high-density fiberboard (HDF; also known as waffle board or chipboard)], oriented strand board (OSB), laminated timber (glulam; plywood glulam), veneer laminated lumber (LVL), cross-laminated timber (CLT), parallel veneer laminated timber (PSL), shaving laminated lumber (LSL), finger joints, beams (including I-joints and I-beams), trusses (including roof and floor trusses), and transparent wood composites. Even more preferably, the objects disclosed in A68 or in any combination of the disclosures derived from this section and the entire specification including the claims are selected from plywood, densified wood (including chemically densified wood), fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or particleboard)], and oriented strand board (OSB). Most preferably, the objects disclosed in A68 or in any combination of the disclosures derived from this section and the entire specification including the claims are selected from fiberboard [this term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or particleboard)], and oriented strand board (OSB). In particular, the objects disclosed as in A68 or in any combination of the disclosures derived from this section and the entire specification including the claims are fiberboard [the term includes low-density fiberboard (LDF; also known as particleboard or chipboard), medium-density fiberboard (MDF), and high-density fiberboard (HDF; also known as waffle board or chipboard)].For example, the object disclosed as in A68 or in any combination of the disclosures derived from this section and the entire specification including the claims is low-density fiberboard (LDF; also known as particleboard or chipboard); for example, the object is medium-density fiberboard (MDF). For example, the object disclosed as in A68 or in any combination of the disclosures derived from this section and the entire specification including the claims is high-density fiberboard (HDF; also known as waffle board or particleboard). The subject matter of this paragraph is referred to in the specification as 'A69'.
[0173] Preferably, the object is as disclosed in A68 or in any combination of the disclosures derived from this section and the entire specification including the claims, wherein the object is selected from sheets, strips, rods, slats, films, fabrics, containers, plates, panels, beams, frames, slats, engineered timber. The subject matter of this paragraph is referred to in the specification as 'A70'.
[0174] Preferably, the object disclosed as in A68 or as in any combination of the disclosures derived from this section and throughout the entire specification including the claims is engineered timber. The subject matter of this paragraph is referred to in the specification as 'A71'.
[0175] Preferably, the object disclosed as in A68 or as in any combination of the disclosures derived from this section and throughout the entire specification including the claims is fiberboard. The subject matter of this paragraph is referred to in the specification as 'A72'.
[0176] In one embodiment of the invention, an article of article is provided comprising: a) a component that is solid at 23°C and 1 atm; and one or both of b) and c), wherein b) is a composition disclosed as in any of A0 or A1 to A61 or any combination of the disclosures derived from this section and the entire specification including the claims, and c) an object (especially engineered wood, more especially fiberboard) disclosed as in any of A68 to A72 or any combination of the disclosures derived from this section and the entire specification including the claims. The subject matter of this paragraph is referred to in the specification as 'A73'.
[0177] In one embodiment of the invention, use of any one or any combination of i) to iii) is provided: i) The composition disclosed in any of A0 or A1 to A61 or in any combination of the disclosures derived from this section and the entire specification including the claims; ii) The object disclosed in any of A68 to A72 or in any combination of the disclosures derived from this section and the entire specification including the claims; iii) Articles disclosed as in A73 or as in any combination of the disclosures derived from this section and the entire specification including the claims; The applications include absorbents, 3D printing, automotive applications (including but not limited to automotive parts, agricultural machinery, composite structures, and ceramic structures), marine applications (including but not limited to boats, boats, and components for boats and boats), aerospace applications (including but not limited to aircraft, helicopters, composite structures, ceramic structures, and components for aircraft and helicopters), medical supplies (including but not limited to artificial joints, meshes, woven or nonwoven sheets, strips, ribbons, bands, cables, tubular products for applications such as ligament replacement, composite structures, and ceramic structures), defensive applications (including but not limited to bulletproof protection, body armor, bulletproof vests, bulletproof helmets, bulletproof vehicle protection, composite structures, and ceramic structures), and sports / entertainment. Applications include: toys (including but not limited to toys, fencing, roller skates, skateboards, skis, suspension lines for sports parachutes, paragliders, kites, kite lines for kite flying, climbing equipment, composite structures, ceramic structures), architectural applications (including but not limited to windows, doors, (false) walls, cables), bottling applications, household applications (including but not limited to household appliances, white goods, furniture, computer casings), mechanical applications (including but not limited to can and bottle handling machinery parts, moving parts on looms, bearings, gears, composite structures, ceramic structures, computer casings), can applications, roll-to-roll applications, energy-related applications (including but not limited to wind, tidal, or solar generators), and electrical-related applications (including but not limited to cabinets for wires or switchboards). This section is referred to as 'A74' in the specification.
[0178] Further preferred embodiments and their preferred features are given in the claims and examples.
[0179] Unless otherwise expressly stated, any feature, element, component, embodiment, scope, and especially any preferred feature, preferred element, preferred embodiment, preferred scope, scope, or preferred combination thereof described throughout this specification may be combined with each other. Unless otherwise expressly stated, any feature, element, component, embodiment, scope, and especially any preferred feature, preferred element, preferred embodiment, preferred scope, scope, preferred combination thereof relating to any of the disclosures in any of A0 to A74 disclosed in this section may be combined with each other and with any other feature, element, component, embodiment, scope, and especially any preferred feature, preferred element, preferred embodiment, preferred scope, scope, preferred combination thereof disclosed throughout this specification, including the claims. All combinations of the minimum and maximum values of the parameters disclosed in this section may be used to define the parameter ranges of the various preferred options and embodiments of the invention disclosed in this section. Unless otherwise expressly stated, any feature, element, component, embodiment, scope, and especially any preferred feature, preferred element, preferred embodiment, preferred scope, scope, preference, and preferred combination of embodiments of the invention, as disclosed in this section, the claims, and throughout the specification, may be combined with each other. For all upper and lower limits of any parameter given in this section, boundary values are included within the respective ranges of each parameter. All combinations of the minimum and maximum values of the parameters disclosed in this section can be used to define the parameter ranges of the various preferences and embodiments disclosed in this section.
[0180] Examples & Methods The invention will be explained in more detail with reference to the following non-limiting embodiments, which are for illustrative purposes only.
[0181] Chemicals, raw materials and other materials used in the examples SEWON L-Lysine® (50 wt% L-lysine in water, lot number 181224) is supplied by Daesang and used as supplied. Desmodur® 44 V 20 L NP (pMDI) is a liquid dark brown polymeric isocyanate based on isomers and homologues of diphenylmethane-4,4'-diisocyanate with higher functionality (NCO content 30.5 wt%–32.5 wt%; viscosity at 25°C: 160 - 240 mPa·s; density at 20°C: 1.23 g / cm³). 3Desmodur® H (HDI) (Hexamethylene-1,6-diisocyanate; Molecular weight: 168 g / mol, Equivalent weight: 84; CAS No.: 822-06-0; NCO content: >49.6% wt%; Color value: <30 Hazen; Viscosity at 25°C: 3 mPa·s; Density at 20°C: 1.05 g / ml; Flash point: 135°C; Vapor pressure at 25°C: 1.4 × 10⁻⁶ -2 Desmodur® I (IPDI) (isophorone diisocyanate; molecular weight: 222 g / mol; equivalent weight: 111; CAS No.: 4098-71-9; NCO content: 37.4% wt%; color value: <30 Hazen; viscosity at 25°C: 10 mPa·s; density at 20°C: 1.06 g / ml; flash point: 150°C; vapor pressure at 25°C: 1.2 mPa·s) -3 D-(+)-glucose (anhydrous, 99% pure) was obtained from ThermoScientific (abbreviated as glucose). ε-polylysine (pale yellow powder, 99.4% pure) was supplied by Bonding Chemical. ε-polylysine has an M of 21301 Da as determined by the GPC method described in this specification. n 22061 Da of M w and polydispersity (PD) of 1.04 (=M) w / M n The apparent viscosity was 32480 mPa·s, as determined by the rheological method described in this specification. This polylysine is mentioned as PLL-2C in the examples and is not based on the claimed invention. The object (fiberboard; FB) shown in the examples was prepared using wood chips having a water content of 2.7 wt%, a density of 240 kg / m³, and a d50 (median particle size distribution of wood chips; according to ISO 17827-1:2016) of 4.5 mm.
[0182] Preparation of polylysine components 1.1.1 Hyperbranched polylysine 1 (abbreviated as PLL-1) The preparation of hyperbranched polylysine 1 (PLL-1) was carried out as follows: 6254 g of SEWON L-Lysine® was added to a 10-liter glass reactor equipped with a distillation apparatus at room temperature. The temperature in the reactor was then slowly (over 4 hours) raised to 105°C (this slow temperature increase is necessary to avoid precipitation of unreacted L-lysine in the reactor, which may occur if too much water is distilled off before full reaction and conversion). Once the temperature in the reactor reached 105°C, water distillation began. The reactor temperature was then slowly raised to 160°C. When the reaction reached 130°C, 2610 g of SEWON L-Lysine® was slowly added to the reactor at the same rate as the distilled water. The temperature was then maintained at 160°C for 1 hour. After 1 hour at 160°C, a vacuum of 100 mbar was slowly applied until the apparent viscosity of the reactor contents, as determined by rheological analysis as disclosed in the specification, reached 1300 mPa·s. Once an apparent viscosity of 1300 mPa·s was achieved, the temperature in the reactor was then reduced to 90°C, and water was metered into the reactor to achieve a solid content of 60 ± 1% by weight. The final product – hyperbranched polylysine 1 (PLL-1) – was obtained as a brown solution in water.
[0183] Characterization of hyperbranched polylysine 1 (PLL-1): DB: 0.43 [D = 18.2 (integrated at 4.15–4.40 ppm); Lα = 9.3 (integrated at 3.90–4.10 ppm); Lε = 47.4 (integrated at 3.25–3.30 ppm)], gel content: 0.0%; M n 2250 Da, M w : 10609 Da, polydispersity (PD) (=M w / M n ): 4.72, Amine value (AN): 386 mgKOH / g, Acid value (AV): 33 mg KOH / g (three ERC peaks were recorded in the titration method), Apparent viscosity: 1300 mPa.s.
[0184] 1.1.2. Hyperbranched polylysine 3 (PLL-3C) The preparation of hyperbranched polylysine 3 (PLL-3C) was carried out as follows: 3400 g of SEWON L-lysine® was added to a 5 L-pressure reactor equipped with a distillation apparatus connected to the reactor via a pressure relief valve (referred to herein as the "PR valve"). Once all the SEWON L-lysine® had been added to the reactor, the PR valve was closed. The temperature inside the reactor was then slowly (over 2 hours) increased to 130°C for approximately 2 hours, and the pressure was brought to 3.5 bar. Once the temperature in the reactor reached 130°C, the PR valve was carefully opened to allow distillation of water; the reactor temperature was maintained at 130°C until the solids content was 82 ± 1% by weight. During this stage, and to maintain the mass of approximately 3400 g in the reactor, SEWON L-lysine® was pumped into the reactor at the same rate as the distilled water. Once a solids content of 82 ± 1% by weight was achieved (at which point the pressure in the reactor decreased from 3.5 bar to 1.2 bar), the PR valve was closed. Subsequently, the temperature and pressure in the reactor were increased to 190°C and 5 ± 0.5 bar, respectively. During this stage, the temperature and pressure in the reactor were maintained at 190°C and 5 ± 0.5 bar, respectively, until the apparent viscosity of the reactor contents (as measured in the instructions) reached 4800 mPa·s; during this stage, the pressure in the reactor was maintained at 5 ± 0.5 bar by periodically and carefully distilling out water through the PR valve. Once the apparent viscosity of 4800 mPa·s was achieved, the temperature in the reactor was reduced to 90°C, and water was metered into the reactor to achieve a solid content of 60 ± 1% by weight. The final product – hyperbranched polylysine 3 (PLL-3C) – was obtained as a brown solution in water.
[0185] Characterization of hyperbranched polylysine 3 (PLL-3C): DB: 0.27 [D = 12.45 (integral at 4.15–4.40 ppm); Lα = 19.38 (integral at 3.90–4.10 ppm); Lε = 42.76 (integral at 3.25–3.30 ppm)], gel content: 5.0%, M n : nm Da (insoluble), M w :nm Da (insoluble), polydispersity (PD) (=M w / M n ): nm, Amine value (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.s.
[0186] This polylysine is not based on the claimed invention.
[0187] 1.1.3 Comparison of the preparation methods of fiberboard and the invented fiberboard The comparative and inventive compositions shown in Table 1 were prepared as follows: a) The fiber component was placed in a planetary mixer without any mixing; b) The polylysine component was added to the fiber component and mixed within 60 seconds; c) The XL component was then added to the mixture of the polylysine component and the fiber component prepared in b); d) After the XL component was added, the mixture in step c) was mixed for 4 minutes.
[0188] By using a suitable hot press (e.g., Fontijne TP800) to achieve a pressing time factor of 19 sec / mm, the corresponding compositions were subjected to simultaneous heating (120°C) and pressure [50 kg / cm²]. 2 = 4903.325 kPa)] (hot pressing) to prepare the comparative and inventive objects, namely fiberboard, to form a board of 28 (L) x 34 (W) x 1.5 (T) cm (425 cm) 2 (surface area).
[0189] All fiberboards prepared and tested had a thickness of 15 mm ± 10%.
[0190] All fiberboards prepared and tested had a density of 700 kg / m³. 3 ± 10%.
[0191] The weight of the polylysine component shown in Table 1 is calculated based on the solid content of the polylysine component determined by the solid content method disclosed in the specification; therefore, the reported weight of the polylysine component shown in Table 1 corresponds to a solid content of 100% for the polylysine component.
[0192] The weights of the XL components shown in Table 1 are calculated based on the solids content reported by the supplier (see § 1.1); therefore, the reported weights of the XL components shown in Table 1 correspond to a solids content of 100% for the XL components.
[0193] M n M w Measurement 1.1.4 M of polylysine-X n M w Determination of (“Gel Permeation Chromatography-1”) Number average molecular weight (M) of members of polylysine-X n ) and weight-average molecular weight (M wThe assay was performed by gel permeation chromatography (GPC) at 40 °C and a flow rate of 0.8 mL / min using a set of standards from egg white: lysozyme (CAS 12650-88-3; product number L6876; lyophilized powder, protein ≥90%, ≥40,000 units / mg protein; single-chain molecular weight 14.3 kDa) and bovine serum albumin (CAS 9048-46-8; product number A2153; lyophilized powder, ≥96%, molecular weight 66 kDa) (both supplied by Sigma-Aldrich). The assay was performed using a solution of 500 mM NaCl and 0.0425 wt% H3PO4 in MilliQ water (pH 2.2) as the eluent. 75 mg of sample dissolved in 1.425 mL of eluent was used for the measurement; the injection volume was 20 μL. GPC measurements were performed on the Waters® Acquity UPLC® H-Class Bio system, which is equipped with: i) a photodiode array (PDA) detector [Acquity TM UPLC TM (1.5 μL biocompatible cell; measurements taken at 225 nm); by WATERS ® [Supply]; ii) A separation module supplied by Agilent equipped with an Agilent Bio-SEC column (7.8 x 300 mm, 100 Å pore size, packed with 3 µm particles, product number: 5190-2501). Separation was performed using suitable data processing software (Empower). TM 3. By WATERS ® (Supply) Measurement M n and M w .
[0194] 1.1.5. M of the XL component n Determination of (“Gel Permeation Chromatography-2”) Number average molecular weight (M) of the XL component n (via a set of molecular weights ranging from 162 to at most 3.8 x 10) 6The polystyrene standard of Da was calibrated and determined by gel permeation chromatography (GPC) at 40 °C at a flow rate of 1 mL / min using stabilized tetrahydrofuran [THF containing 0.007–0.015% w / w butylhydroxytoluene (BHT)] (THF) modified with 0.8 (v / v %) acetic acid as the eluent. The XL1 group of the XL component member was reacted with n-hexylamine at a 1:1 molar ratio at room temperature (the resulting XL component member is referred to as r-XL component); the molar ratio was determined by measuring the equivalent (g / mol) of each XL1 group; the equivalent of each XL1 group was determined by measuring the XL1 group content (%) (isocyanate group content) according to DIN EN ISO 11909-2007. A solid sample of 50 mg of the XL component member was dissolved in 5 mL of eluent for 16 hours at room temperature without shaking and used for measurement. 40 µL of the solution thus prepared was injected into the system for measurement. GPC measurements were performed on a Waters Alliance system equipped with: i) a Waters Alliance 2414 refractive index detector at 40°C, and ii) a Waters Alliance 2695 separation module (supplied by Agilent) equipped with two consecutive mixed-C type PL gel columns (I / d = 300 / 7.5 mm and filled with particles of 20 micrometers in size).
[0195] 1.1.6. Determination of polydispersity (PD) The M members of polylysine-X were determined by gel permeation chromatography-1. n and M w Then, the polydispersity PD of the members of polylysine-X was calculated according to the following equation: PD = M w / M n .
[0196] 1.1.7. Determination of amine value (AN) and acid value (AV) (“titration method”) Amine value (AN) and acid value (AV) were determined by back titration analysis using a titrator 808 Titrando (supplied by Metrohm AG) equipped with an 814 USB sample processor (supplied by Metrohm AG), and using two electrodes equipped with a pH meter (one for measuring pH (pH glass electrode supplied by Metrohm AG, product number 6.0150.100), and one as a reference electrode (conductivity measurement cell c=0.8 cm). -1The titrant, consisting of PtI000 (fixed cable), supplied by Metrohm AG (product number 6.9303.110), was titrated with a solution of 1,000 N KOH in water. The titrant consisted of 1,000 g polylysine (sample) (amount refers to solid content), 60.00 mL 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]. All data processing and control operations for the titrations described herein were performed using Tiamo software supplied by Metrohm AG. TM 2.4 Completed.
[0197] Simultaneously record the titration curve [pH vs. titrant volume (x-axis)] (abbreviated as TC) and the first derivative curve of TC [potential vs. titrant volume (x-axis)] and plot them together on the same graph (pH on the Y1 axis, potential on the Y2 axis, and titrant volume on the X-axis). The first derivative curve of TC is called ERC, which represents the Equivalence point Recognition Criteria and is expressed in units of potential (mV). ERC provides two or three successive peaks (ERC peaks). Each of these ERC peaks corresponds to a certain volume of titrant. One of these ERC peaks (usually the one with the highest signal (delta voltage)) corresponds to the lowest volume of titrant (V). min (in mL), and another ERC peak corresponds to the highest volume of titrant (V). max (in mL).
[0198] The amine value (AN) is determined according to the following formula: Amine value (mg KOH / g sample) = 56.1 * (V max - V min ) Where V min and V max As explained above.
[0199] Acid value (AV) is determined according to the following formula: Acid value (mg KOH / g sample) = 56.1 * [V min - [10.00 - (V max - V min )]] Where V min V max As explained above.
[0200] Measurements for determining AN and AV are performed in duplicate, and the reported value for each of AN and AV is the average of these measurements.
[0201] 1.1.8. Determination of apparent viscosity (“rheological determination”) Apparent viscosity (shear stress divided by shear rate) was determined using a 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, an appropriate rotor / cup combination and shear rate were selected based on the estimated apparent viscosity. For all our experiments, we used a shear rate of 100 s⁻¹. -1 The Z3 rotor / cup assembly was used. The sample (polylysine dissolved in water, with a solids content of 60 ± 1%) was then filled into the cup. The rotor was inserted into the cup, the cup was mounted in the viscometer, and the rotor was connected to the instrument. The correct program was selected on the RheolabQC (for all our measurements, we selected the program for the Z3 rotor, with 100s). -1 (The shear rate is combined and measured).
[0202] 1.1.9. Determination of solid content (“Solid content method”) Solid 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) was weighed onto a glass fiber pad placed on an aluminum pan and then heated at 140 °C for 30 minutes. The solid content was automatically determined based on the mass difference before and after heating at 140 °C.
[0203] 1.1.10. Determination of water content (“water content method”) The amount of water contained in a solid, such as in the composition, the polylysine component, the fiber element, or the wood chips, is determined by drying the solid at 120°C under reduced pressure (50 mbar) for 24 hours in a Thermo Scientific® VacuTherm vacuum oven supplied by Thermo Fischer Scientific. The amount of water contained in the solid is calculated according to the following equation: Water (pph or weight %) = [1 - (M2 / M1)] x 100 in M1: Mass of the solid before drying.
[0204] M2: Mass of the dried entity (measured within 5 minutes after the sample is removed from the oven).
[0205] 1.1.11. Determination of branching degree The degree of branching (DB) of polylysine is determined by... 1 Determined by H-NMR spectroscopy and calculated according to Equation 1: (Equation 1) in D is equal to or greater than 0, L is equal to or greater than 0, and at least one of D and L is greater than 0; and in D is the methylene proton (abbreviation for the tertiary carbon proton, shown in bold in formulas D1a and D1b) corresponding to any number of the following groups that may be present in polylysine. 1 The integral of the H-NMR peak (D equals zero if such methylene protons are not present in polylysine): L represents L α and L ε The sum of, of which L α It is the methine proton (abbreviation for the tertiary carbon proton, shown in bold in formulas L1a and L1b) corresponding to any number of the following groups shown in formulas L1a and L1b that may be present in polylysine. 1 The integral of the H-NMR peak (if such methylene protons are not present in polylysine, then L α (equal to zero): and L ε It corresponds to any number of the following groups shown in formulas L2a and L2b that may be present in polylysine, specifically the methylene proton (abbreviated for the proton of the tertiary carbon, indicated in bold in formulas L2a and L2b). 1 The integral of the H-NMR peak (if such methylene protons are not present in polylysine, then L ε (equal to zero): DB is 0 (inclusive) to at most 1 (inclusive).
[0206] Using deuterated methanol (also known as tetradeuterated methanol or methanol-d4) as a solvent, in Bruker Ascend TM Recording at room temperature on a 400 spectrometer 1 H-NMR spectroscopy. Methanol-d4 is the preferred solvent; however, other suitable deuterated solvents can be used.
[0207] In the case of methanol-d4 1 The chemical shift of the H-NMR peak corresponds to: - One or more D-protons were found at 4.15–4.40 ppm; - One or more L were found at 3.90-4.10 ppm. α -proton; and - One or more L were found at 3.25-3.30 ppm. ε -Proton.
[0208] 1.1.12. Determination of gel content (“Gel content method”) The gel content of polylysine was determined as follows: A mixture of polylysine with a 10% solids content in water was prepared and stored at room temperature for 24 hours. Subsequently, 3000 g of this prepared mixture (the sample here) was pre-weighed (Mf...). 之前 A filter, such as folded qualitative filter paper, is used to remove any insoluble fractions with an average size of at least 5 micrometers and higher. Once filtration is complete, the filter is washed with twice the amount of water as the sample volume. The filter is then placed in a vacuum oven at 40°C and 50 mbar for 12 hours to remove any remaining water. The filter is then weighed again (Mf). 之后 ).
[0209] Calculate the gel content using Equation 2: (Equation 2) in Mf 之后 It refers to the quality of the filter after water removal. Mf 之前 It refers to the quality of the filter before filtering the sample, and M 聚赖氨酸 This is the mass of polylysine in the sample (considering the sample's solid content). Therefore, in 3000 g of a sample with a 10% solid content, M 聚赖氨酸 It is 30 g.
[0210] Methods for determining the properties of fiberboard 1.1.13. Measurement of Length (L), Width (W), and Thickness (T) Use a ruler to measure the length (L) of the specimen at three different points, and record the average of these three measurements as the width of the specimen.
[0211] The width (W) of the specimen is measured at three different points using a digital ruler, and the average of these three measurements is recorded as the width of the specimen.
[0212] The thickness (T) of the specimen is measured at three different points using a digital ruler, and the average of these three measurements is recorded as the thickness of the specimen.
[0213] 1.1.14. Determination of density (d) Specimens were prepared by cutting fiberboard sheets that were made in single pieces of 150 mm x 40 mm. The length (L; in m), width (W; in m), and thickness (T; in m) of the specimens, as well as their weight (m; in kg), were measured as described above.
[0214] Calculate the density (d; in kg / m³) of the sample according to the following equation. 3 (Calculation), and the average of two calculations corresponding to two different samples of the fiberboard is recorded as the density of the fiberboard: d = M / (L x W x T).
[0215] 1.1.15. Determination of bending properties (static bending method) According to ASTM D1037-12, and especially Section 9 of ASTM D1037-12 (titled "Static Bending"), the evaluation of bending properties is determined by static bending testing, namely i) modulus of rupture (R0). b ) and ii) the apparent modulus of elasticity (E), which is subject to the following two differences from the specification in Section 9 of ASTM D1037-12: i) the specimen is prepared by cutting the prepared panel into two pieces of 150 ± 1 mm x 40 ± 1 mm, and ii) each specimen is placed in a 3-point (center-loaded) fixture and the span length (L) is fixed to 100 mm.
[0216] The corresponding composition was subjected to heat (210°C) and pressure (9 kg / cm²) simultaneously. 2 A static bending test was performed on an object prepared at 882.6 kPa for 5 minutes. The modulus of fracture (R0) is defined and calculated according to §9.7 of ASTM D1037-12 based on the following two equations. b and apparent elastic modulus (E): in b = The width of the sample (in mm) measured under dry conditions; d = The thickness of the sample (in mm) measured under dry conditions; = The slope of the linear portion of the load-deflection curve (in N / mm). P max= Maximum load (in N); L = Span length (in mm); R b = Modulus of fracture (kPa); E = apparent elastic modulus (kPa).
[0217] Static bending tests were performed at a constant rate of 3 mm / min and under loads applied to the center of each specimen on a ZMART.PRO 1445 supplied by Zwick / Roell. The tests continued until the specimens fractured, while all force vs. deflection data were recorded. From the obtained data, the modulus of fracture (R0) was calculated according to the equations provided in §9.7 of ASTM D1037-12 and, for convenience, above. b ) and apparent elastic modulus (E).
[0218] 1.1.16. Determination of internal bond strength Evaluation of internal bond strength as determined by NEN-EN 319:1993.
[0219] 1.1.17. Results & Discussion Table 1 summarizes the internal bond strength and modulus of rupture (R0) of the comparative compositions and the compositions of the present invention, as well as the fiberboards produced by rapidly curing their respective compositions at low temperature (120°C) (pressing time factor equal to 19 sec / mm). b ) and apparent elastic modulus (E).
[0220] The abbreviation “DL” shown in Table 1 stands for delamination (for delamination, see the definition in the section titled “Detailed Description of the Invention”).
[0221] The results shown in Table 1 clearly demonstrate that only the compositions of the present invention provide a solution to the technical problem. More specifically, when the compositions of the present invention are rapidly cured at 120°C to prepare fiberboard, the resulting fiberboard has the following characteristics: - Internal bond strength of at least 0.3 MPa, - A fracture modulus of at least 9 MPa (R b ),and - Apparent elastic modulus (E) of at least 1600 MPa.
[0222] Compared with compositions C1, C2 (which provide a simulation of the composition of WO 2022 / 096518 A1), compositions C3, C4, C5, C6, C7, C8, C9, C10, C11 and C12 all caused delamination or a significant reduction in properties to achieve the desired internal bond strength, modulus of rupture and apparent elastic modulus.
[0223] The results shown in Table 1 also demonstrate the criticality and purposefulness of all the features of the compositions of the present invention, and in particular the ranges related to the amount of polylysine component in the composition and the ranges related to the weight ratio K, the type of polylysine component, and the gel content and combination of polylysine components.
[0224] More specifically, through comparison: a) The criticality and purpose of the weight ratio K becomes apparent when comparing the compositions I1 to I7 of the present invention with comparative compositions C4, C5 and C6 (C4 has a weight ratio K of 0.10, C5 has a weight ratio K of 0.20, and C6 has a weight ratio K of 6.00) which are outside the scope of the claims. b) The criticality and purpose of the amount of polylysine in the composition I12 of the present invention compared with that of compositions C3 and C7 (where the amount of polylysine in C3 is 0.30% by weight and the amount of polylysine in C6 is 35.0% by weight) outside the claimed scope, becomes apparent. c) The criticality and purpose of the type of polylysine component in the composition I2 of the present invention and the comparative composition C9, wherein C9 is formulated with ε-polylysine (which is linear polylysine and therefore not hyperbranched polylysine, let alone hyperbranched polylysine as claimed), become apparent. d) The composition I2 of the present invention and the comparative composition C8, wherein C8 is formulated with ε-polylysine (the gel content of which is outside the claimed range (the gel content of C8 is 5%)), the criticality and purpose of the gel content of the polylysine component becomes obvious; e) The criticality and purpose of the combination of all the compositions of the present invention and all the comparative compositions, and all the features of the claimed invention, become apparent, including but not limited to the type of polylysine, the amount of polylysine component, the weight ratio K, and the gel content of the polylysine component.
[0225] Therefore, only the compositions of the present invention provide a solution to the technical problem, and by achieving this, the compositions of the present invention constitute a major technological advancement in the field of fiberboard, while prior art compositions, when rapidly cured at low temperatures, cause delamination or significantly reduce performance in terms of desired internal bond strength, modulus of rupture, and apparent modulus of elasticity. .
Claims
1. A composition comprising component A, said component A being composed of the following components: - Polylysine component, - XL components, and - Fiber components, in The polylysine component is selected from polylysine-X and mixtures thereof, wherein the polylysine-X is selected from hyperbranched polylysine and primary ammonium salts of hyperbranched polylysine, wherein each of the polylysine-X has a content of at least 0.30 and at most 0.60 as disclosed in the specification. 1 The degree of branching as determined by H-NMR spectroscopy, the apparent viscosity of at least 400 and at most 8000 mPa·s as determined by rheological determination as disclosed in the specification, and the gel content of at most 4.0% as determined by gel content determination as disclosed in the specification. and The XL component is selected from monomeric or polymeric compounds, each having at least two XL groups per molecule, wherein the XL groups are selected from groups according to Formula XL1. and The fiber component comprises at least one fiber element, the fiber element containing plant fibers, and wherein the fiber element contains no fibers other than plant fibers. and in The composition contains no fibers other than plant fibers of the fiber component, and in Component A is present in the composition in an amount of at least 10% by weight and at most 100% by weight, and in The polylysine component is present in an amount of at least 0.5% by weight and at most 30.0% by weight of the composition, and in The weight ratio K of the XL component divided by the polylysine component is at least 0.30 and at most 5.
0. in, The wavy lines shown in the formulas involving XL components indicate that the molecular structure beyond the points indicated by the wavy lines is not specified.
2. The composition claimed in any of the preceding claims, wherein each of the polylysine-X has an apparent viscosity of at least 400 and at most 4000, for example at least 400 and at most 2500, for example at least 400 and at most 2000 mPa·s.
3. The composition claimed in any one of claims 1 to 4, wherein each of the polylysine-X comprises: - Number-average molecular weight (abbreviated as M) of at least 1100 and at most 10000 Da, determined by gel permeation chromatography as disclosed in the specification. n ), - Weight-average molecular weight (abbreviated as M) of at least 3000 and at most 50000 Da, determined by gel permeation chromatography as disclosed in the specification. w ), - At least 2 and at most 15 as M w / M n The polydispersity of the ratio calculation - Apparent viscosity of at least 400 and at most 8000, for example at least 400 and at most 4000, for example at least 400 and at most 2500, for example at least 400 and at most 2000 mPa·s. - An amine value of at least 200 and at most 700 mg KOH / g, determined by titration as disclosed in the product information. - An acid value of at least 10 and at most 150 mg KOH / g, determined by titration as disclosed in the instructions. - Up to 3.0%, preferably up to 2.0%, more preferably up to 1.0%, even more preferably up to 0.5% of the gel content as determined by the gel content method disclosed in the specification, and most preferably 0.0% of the gel content.
4. The composition claimed in any of the preceding claims, wherein the polylysine-X is selected from hyperbranched polylysine.
5. The composition claimed in any of the preceding claims, wherein the component A is present in an amount of at least 20% by weight and at most 100% by weight, more preferably at least 40% by weight and at most 100% by weight, for example at least 60% by weight and at most 100% by weight, for example at least 80% by weight and at most 100% by weight, of the composition.
6. The composition claimed in any of the preceding claims, wherein the polylysine component is present in an amount of at least 0.5% by weight and at most 25.0% by weight, preferably at least 0.5% by weight and at most 20.0% by weight, more preferably at least 0.5% by weight and at most 15% by weight, and most preferably at least 0.5% by weight and at most 10.0% by weight of the composition.
7. The composition claimed in any of the preceding claims, wherein the composition may optionally comprise component C, said component C being selected from polyphenol macromolecules, each of said polyphenol macromolecules being a macromolecule having a plurality of phenolic or polyhydroxyphenyl groups and mixtures thereof, in an amount such that the ratio of the total weight of said component C to the total weight of said polylysine component is at most 0.
40.
8. The composition claimed in any of the preceding claims, wherein the composition is free from any one or any combination of components B, D, E, F, F1, K, K1, L, L1, M, and M1, wherein each of these components is distinct from and separate from any other component and ingredient of the composition, and wherein component B is selected from proteins and mixtures thereof, and wherein component D is selected from: i) monosaccharides in the form of aldoses or ketoses, ii) oligosaccharides, iii) polysaccharides, iv) The in-situ production of monomeric or polymeric compounds of one or more reducing sugars, and mixtures of i) to iv), wherein component E is selected from peptides and mixtures thereof, wherein component F is selected from compounds containing at least two acetoacetoxy groups and mixtures thereof, wherein component F1 is selected from compounds containing only one acetoacetoxy group and mixtures thereof, wherein component K is selected from compounds containing at least two ethylene oxide groups and mixtures thereof, wherein component K1 is selected from compounds containing only one ethylene oxide group and mixtures thereof, wherein component L is selected from compounds containing at least two olefinic unsaturated groups and mixtures thereof, wherein component L1 is selected from compounds containing only one olefinic unsaturated group and mixtures thereof, wherein component M is selected from compounds containing at least two vinyl unsaturated groups and mixtures thereof, and wherein component M1 is selected from compounds containing only one vinyl unsaturated group and mixtures thereof.
9. The composition claimed in any of the preceding claims, wherein the composition optionally comprises component N in an amount of at least 0.01% by weight and at most 10% by weight, preferably at least 0.02% by weight and at most 8% by weight, more preferably at least 0.05% by weight and at most 5% by weight, for example at least 0.01% by weight and at most 4% by weight, for example at least 0.03% by weight and at most 3% by weight, for example at least 0.05% by weight and at most 2% by weight, for example at least 0.75% by weight and at most 2% by weight, and wherein component N is selected from amines, amine salts, nitrogen compounds, metal-containing compounds, and mixtures thereof.
10. The composition claimed in any of the preceding claims, wherein the plant fiber is selected from natural lignocellulose fibers.
11. A method for obtaining an object, wherein the method includes the following steps: - To provide a composition as claimed in any one of claims 1 to 10; and - Subjecting the composition to heat and / or pressure and / or vacuum, preferably simultaneously, to form an object, and - Collect the objects.
12. An object obtained by the method claimed in claim 11.
13. The object claimed in claim 12, wherein the object is fiberboard.
14. An article comprising: a) a component that is solid at 23°C and 1 atm; and one or both of b) and c), wherein b) is a composition claimed in any one of claims 1-9, and c) is an object claimed in any one of claims 12 to 13.
15. Any one or any combination of i) to iii): i) The composition claimed in any one of claims 1 to 10; ii) The object claimed as in any one of claims 12 to 13; iii) The article of protection as claimed in claim 14; Applications include absorbents, 3D printing, automotive, marine, aerospace, medical supplies, defense, sports / recreation, construction, bottling, household, machinery, cans, roll materials, energy, and electrical applications.
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