BIO-BASED BINDERS AND METHODS FOR PRODUCING SAME

Abstract

The present invention concerns the field of binders suitable for wood panel manufacturing. In particular, the invention regards a composition of bio-binder comprising unrefined biological material and a reactive prepolymer. In a further aspect a method for producing bio-based binders is presented. In an even further aspect the present invention describes bio-based formaldehyde-free binders obtainable from the described methods and their uses. The invention further describes methods for gluing articles and products obtainable from the methods of the present invention.

Claims

1. A bio-based binder composition comprising: a. an unrefined biological material; b. a liquid medium; c. a reactive prepolymer; wherein said unrefined biological material is selected from: oilseeds, beans, grains, yeast, larvae, or a combination thereof; and wherein said unrefined biological material comprises one or more of the following features: i. a fatty acid C═O stretching band of COOH between 1725 cm-1 and 1705 cm-1 that presents an absorbance of at least 0.02; ii. a prominent triacylglycerol C═O band between about 1750 cm-1 and 1740 cm-1 that presents an absorbance of at least 0.06; or iii. a prominent hydrocarbon chain C—H band between about 2950 cm-1 and 2850 cm-1 that presents an absorbance of at least 0.08 and is more prominent than the amide N—H band between 3350 cm-1 and 3250 cm-1; as determined by solid state Fourier Transform Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR).

2. The composition according to claim 1, wherein said unrefined biological material is oilseeds, selected from: jatropha seeds, soybeans, camelina seeds, castor seeds, cottonseeds, flaxseeds, jojoba seeds, mahua seeds, maize germs, neem seeds, pongamia seeds, rapeseeds, sunflower seeds, thistle seeds, and a combination thereof.

3. (canceled)

4. The composition according to claim 1, wherein the unrefined biological material is a comminuted unrefined biological material having a particle size in the range of from about 1 micron to about 300 microns as measured with a granulometer.

5. The composition according to claim 1, wherein the unrefined biological material used has been partially or fully dehulled.

6. The composition according to claim 1, wherein the unrefined biological material has been partially defatted removing no more than 50% of the lipid content of the unrefined biological material.

7. The composition according to claim 1, wherein the unrefined biological material has been partially or fully subjected to treatments that do not essentially modify its original composition in terms of lipid and protein content, said treatments comprising heat treatment, enzymatic treatment, ultrasound, microwaves, cavitation, or a combination thereof.

8-9. (canceled)

10. The composition according to claim 1, wherein the binder on dry weight comprises the unrefined biological matter in a range from about 1% to about 90% (w/w).

11. The composition according to claim 1, wherein the liquid medium is a lipid, water, or a mixture thereof.

12. The composition according to claim 1, wherein the liquid medium is camelina oil, corn oil, rapeseed oil, sunflower oil, jatropha oil, soybean oil, or a combination thereof.

13. The composition according to claim 1, wherein the liquid medium is a mixture comprising a vegetable oil and water in a ratio ranging from 6:1 to 1:6.

14. The composition according to claim 1, wherein the liquid medium is present from about 10% (w/w) to about 90% (w/w) of the liquid binder composition.

15. The composition according to claim 1, wherein, the reactive prepolymer is an isocyanate-based prepolymer, a poly(amidoamine)-based prepolymer, an aldehyde-based prepolymer or a mixture thereof.

16. The composition according to claim 1, wherein, the reactive prepolymer is selected from the group consisting of polymeric methylene diphenyl diisocyanate (pMDI), poly(amidoamine)-epichlorohydrin (PAE) and an aldehyde-based prepolymer selected from urea-formaldehyde (UF), urea-melamine-formaldehyde (UmF), melamine-urea-formaldehyde (MUF), and a mixture thereof.

17-18. (canceled)

19. The composition according to claim 1, further comprising a hydroxyfunctional compound selected from glycerine, polysaccharides, oligosaccharides, monosaccharides, and a combination thereof.

20. The composition according to claim 1, having one or more of the following features on dry weight: i. unrefined biological material present from about 1% to about 95% (w/w) of the binder composition; ii. lipid medium present from about 1% to about 95% (w/w) of the binder composition; iii. reactive prepolymer present from about 1% to about 95% (w/w) of the binder composition; iv. hydroxyfunctional compound present from about 1% to about 150% (w/w) of the comminuted biological material; v. viscosity agent present from about 0.1% to about 2% (w/w) of the comminuted biological material; vi. antifoam agent, defoam agent, or combination thereof present from about 0.001% to about 1% (w/w) of the comminuted biological material.

21-24. (canceled)

25. A method for producing a bio-based binder composition comprising the following steps: a. mixing an unrefined biological material with a liquid medium to obtain a slurry; b. mixing the slurry of step a. with a reactive prepolymer; c. obtaining the bio-based binder, wherein: the unrefined biological material is selected from: oilseeds, beans, grains, yeast, bacteria, larvae, and a combination thereof, and comprises one or more of the following features: i. a fatty acid C═O stretching band of COOH between 1725 cm-1 and 1705 cm-1 that presents an absorbance of at least 0.02; ii. a prominent triacylglycerol C═O band between about 1750 cm-1 and 1740 cm-1 that presents an absorbance of at least 0.06; or iii. a prominent hydrocarbon chain C—H band between about 2950 cm-1 and 2850 cm-1 that presents an absorbance of at least 0.08 and is more prominent than the amide N—H band between 3350 cm-1 and 3250 cm-1; as determined by solid state Fourier Transform Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR); the liquid medium is selected from a lipid, water, or a mixture thereof; and the reactive prepolymer is selected from an isocyanate-based prepolymer, a poly(amidoamine)-based prepolymer or an aldehyde-based prepolymer or a mixture thereof; and wherein a hydroxyfunctional compound selected from glycerine, polysaccharides, oligosaccharides, monosaccharides, and a combination thereof can be optionally added to step a. or step b.

26-27. (canceled)

28. The method according to claim 25, wherein the reactive prepolymer, the unrefined biological material and the liquid medium are fed separately to an in-line static, dynamic or combined static and dynamic mixer, prior to spraying the bio-based binder onto a substrate.

29. (canceled)

30. A method of gluing a first article to at least a second article to obtain a glued product comprising: a. applying the binder composition according to claim 20 to a surface of a first article to obtain a binding surface; and b. contacting the binding surface of the first article with a surface of at least a second article; and c. curing the binder.

31. The method according to claim 30, wherein the first and at least second articles are each independently a material selected from the group consisting of: a lignocellulosic material, a composite material containing a lignocellulosic material, a metal, a ceramic, a polymer, a plastic, a fabric, a glass, and a combination thereof, wherein said lignocellulosic material is wood.

32. (canceled)

Description

DESCRIPTION OF THE FIGURES

[0060] FIG. 1: FT-IR ATR spectrum for Unrefined Castor seeds

[0061] FIG. 2: FT-IR ATR spectrum for Unrefined Jatropha seeds

[0062] FIG. 3: FT-IT ATR spectrum for Unrefined Rapeseeds

[0063] FIG. 4: FT-IR ATR spectrum for Unrefined Soybeans

[0064] FIG. 5: FT-IR ATR spectra comparison of Unrefined Jatropha seeds and Unrefined Soybean

[0065] FIG. 6: FT-IR ATR spectrum for Unrefined Soybeans_1900_1200 cm-1

[0066] FIG. 7: FT-IR ATR spectrum for unrefined Soy oil

[0067] FIG. 8: FT-IR ATR spectrum for defatted soy flour

[0068] FIG. 9: FT-IR ATR spectra comparison of unrefined soybean and defatted (refined) soy flour.

DETAILED DESCRIPTION OF THE INVENTION

[0069] The present invention concerns a composition for an improved bio-binder. In an illustrative embodiment a bio-based binder composition comprising: [0070] a. an unrefined biological material; [0071] b. a liquid medium; [0072] c. a reactive prepolymer;

[0073] wherein said unrefined biological material is selected from: oilseeds, beans, grains, yeast, bacteria, larvae, algae, or a combination thereof; and wherein said unrefined biological material comprises one or more of the following features: [0074] i. a fatty acid C═O stretching band of COOH between 1725 cm-1 and 1705 cm-1 that presents an absorbance of at least 0.02; [0075] ii. a prominent triacylglycerol C═O band between about 1750 cm-1 and 1740 cm-1 that presents an absorbance of at least 0.06; or [0076] iii. a prominent hydrocarbon chain C—H band between about 2950 cm-1 and 2850 cm-1 that presents an absorbance of at least 0.08 and is more prominent than the amide N—H band between 3350 cm-1 and 3250 cm-1;

[0077] as determined by solid state Fourier Transform Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR).

[0078] The composition of the invention is a bio-based No-Added-Formaldehyde binder composition.

[0079] In a preferred aspect, the bio-based binder has a Global Warming Potential below 1.7 kg CO2-eq per kg of bio-binder dry matter weight; in an even more preferred aspect, the bio-based binder has a negative GWP.

[0080] In an aspect of the invention, the bio-based binder is fully biodegradable.

[0081] In a preferred aspect, in the composition of the invention said unrefined biological material is oilseeds, selected from: jatropha seeds, soybeans, camelina seeds, castor seeds, cottonseeds, flaxseeds, jojoba seeds, mahua seeds, maize germs, neem seeds, pongamia seeds, rapeseeds, sunflower seeds, thistle seeds, or a combination thereof.

[0082] More preferably said unrefined biological material is jatropha seeds, castor seeds, rapeseeds, soybeans or a combination thereof.

[0083] Surprisingly, it has been found that the unrefined biological material slurry can reduce pMDI or urea-formaldehyde dosages otherwise utilised to manufacture EN-312 P2 and/or P3 type fibreboards without compromising the productivity of the fibreboard mill. Even more surprisingly it was found that no further additivation was required when utilizing such a slurry to meet moisture resistance criteria nor is there a need for any pMDI designated release agents while running production.

[0084] Jatropha curcas (J. curcas) is an inedible drought resilient crop well known for its biofuels production, soil restoration in semi-arid areas and carbon sequestration potential. Baumert (2014) teaches that undomesticated varieties of J. curcas, cultivated in semi-arid areas while applying intercrop management intervention systems, that yield 1 ton of J. curcas oilseed per hectare per year, have a total carbon sink of about 4 kg CO.sub.2 equivalent per kg of J. curcas seeds. Recent developments towards domesticated varieties, hence genetically improved J. curcas plants that yield more biomass per cultivated area, accompanied by Sustainable Land Management (SLM) measures are means to further extent the carbon sink potential of J. curcas. Therefore, the cultivation of J. curcas in semi-arid areas is considered a means to mitigate climate change, a mitigation strategy that can be exploited even more when utilising J. curcas oilseeds in bio-based binders that are otherwise derived from edible crops utilising arable land.

[0085] J. curcas oilseeds are often processed by means of conventional mechanical expellers yielding oil and a press-cake that primarily consists of shells, protein and residual oil. In the past, projects related to the cultivation of J. curcas on industrial scale were often abandoned due to limited industrial applications for its oil co-product fractions, i.e. protein-rich press-cake due to the presence of antinutritional factors. Ever since, significant research has been put on upgrading the nutritional aspects of recoverable J. curcas oilseed fractions and exploring valorisation routes for each constituent fraction separately, i.e. the oil-, protein-, (hemi)cellulose, and lignocellulosic fraction, by applying different oilseed processing methods.

[0086] Besides the use of conventional mechanical expellers, organic solvents for processing deshelled J. curcas seeds, i.e. only the seeds kernel, are also used to recover oil and a co-product known as a defatted oilseed meal. However, utilising such a method presents several drawbacks related to safety concerns regarding flammability and inherently not being environmentally friendly.

[0087] The binder composition of the present invention avoids the above indicated drawbacks by providing cold tack, release of the panel from the metal plates while valorising a crop that can grow under marginal circumstances. The usage of J. curcas is a very valid alternative to the usage of edible material that have more noble destinations, such as human and animal nutrition.

[0088] Advantageously, in a preferred aspect, the binder composition not only allows to avoid adverse effects of the presence of indoor formaldehyde, but it also provides benefits in mitigating climate adversities.

[0089] In the described composition, the unrefined biological material is preferably a comminuted unrefined biological material having a particle size in the range of from about 1 micron to about 300 microns, or from about 10 microns to about 200 microns, as measured with a granulometer (for example Malvern or FKV, Sympatec).

[0090] By comminuting it is intended that the biological material is disrupted to have a paste-like or a flour-like appearance. This procedure does not refine the biological material or significantly modify its composition.

[0091] In a further aspect the unrefined biological material of the binder composition has been partially or fully dehulled.

[0092] By fully dehulled it is intended that the seed hull is removed.

[0093] In a further embodiment the unrefined biological material of the binder composition has been partially defatted removing no more than 50% of the lipid content of the unrefined biological material.

[0094] In a preferred aspect, the unrefined biological material has been partially or fully subjected to treatments that do not essentially modify its original composition in terms of lipid and protein content such as heat treatment, enzymatic treatment, ultrasound, microwaves, cavitation, or a combination thereof. By essentially or substantially modifying, it is intended that the FTIR spectrum absorbance of the biological material in terms of lipids and protein is at most 50%, preferably 30% and more preferably 10% modified.

[0095] Under a still preferred aspect, in the composition of the invention, the unrefined biological material comprises one or more of the following features:

[0096] i. a fatty acid C═O stretching band of COOH between 1725 cm.sup.−1 and 1710 cm.sup.−1 that presents an absorbance of at least 0.04;

[0097] ii. a prominent triacylglycerol C═O band between about 1750 cm.sup.−1 and 1740 cm.sup.−1 that presents an absorbance of at least 0.06; or

[0098] iii. a prominent hydrocarbon chain C—H band between about 2950 cm-1 and 2850 cm.sup.−1 that presents an absorbance of at least 0.09 and is more prominent than the amide N—H band between 3350 cm-1 and 3250 cm-1; [0099] as determined by solid state Fourier Transform Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR).

[0100] In a further preferred aspect, the unrefined biological material comprises one or more of the following features: [0101] i. a fatty acid C═O stretching band of COOH between 1725 cm.sup.−1 and 1705 cm.sup.−1 that presents an absorbance of at least 0.05; [0102] ii. a prominent triacylglycerol C═O band between about 1750 cm.sup.−1 and 1740 cm.sup.−1 that presents an absorbance of at least 0.08; [0103] iii. a prominent hydrocarbon chain C—H band between about 2950 cm.sup.−1 and 2850 cm.sup.−1 that presents an absorbance of at least 0.09 and is more prominent than the amide N—H band between 3350 cm.sup.−1 and 3250 cm.sup.−1; [0104] as determined by solid state Fourier Transform Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR).

[0105] In a specific aspect, in case the composition of the bio-binder presents no bands between about 1725 cm-1 and 1705 cm-1 or about 1750 cm-1 and 1740 more prominent than the band between about 1650-1620, as determined by solid state Fourier Transform Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR), the liquid medium comprises at least a lipid.

[0106] Preferably, in the composition of the invention, the binder on dry weight comprises the unrefined biological matter in a range from about 1% to about 90% (w/w). More preferably, in the composition of the invention the liquid medium is a lipid, water, or a mixture thereof, wherein the liquid medium is camelina oil, corn oil, rapeseed oil, sunflower oil, jatropha oil, soybean oil, or a combination thereof.

[0107] The liquid medium of the composition may be a mixture comprising a vegetable oil and water in a ratio ranging from 6:1 to 1:6, preferably from 5:1 to 1:5, and more preferably from 2:1 to 1:3.

[0108] The liquid medium may be present from about 10% (w/w) to about 90% (w/w) of the liquid binder composition.

[0109] In a preferred composition of the invention, the reactive prepolymer is an isocyanate-based prepolymer, a poly(amidoamine)-based prepolymer or an aldehyde-based prepolymer or a mixture thereof.

[0110] More preferably the reactive prepolymer of the composition is: [0111] polymeric methylene diphenyl diisocyanate (pMDI), [0112] poly(amidoamine)-epichlorohydrin (PAE), or [0113] an aldehyde-based prepolymer selected from urea-formaldehyde (UF), urea-melamine-formaldehyde (UmF), melamine-urea-formaldehyde (MUF), or a mixture thereof.

[0114] In a further embodiment the binder composition, further comprises a hydroxyfunctional compound selected from glycerine, polysaccharides, oligosaccharides, monosaccharides, or a combination thereof, preferably the hydroxyfunctional compounds are: sugars, preferably dextrose monohydrate or syrups preferably corn syrup having a dextrose content in the range from 0.1% to 100% on dry weight.

[0115] The binder composition may further comprise: [0116] a viscosity reducing agent; preferably ammonium sulfite, lithium sulfite, potassium sulfite, sodium metabisulfite, sodium sulfite, or a combination thereof; [0117] an anti-foam agent, a defoaming agent, or a combination thereof; preferably the anti-foam agent is an alcohol ethoxylate or an alcohol propoxylate and the defoaming agent is a fatty acid ethoxylates, or a combination thereof; [0118] a flame-retardant agent.

[0119] The binder composition of the invention preferably has one or more of the following features on dry weight: [0120] i. unrefined biological material present from about 1% to about 95% (w/w) of the binder composition; [0121] ii. lipid medium present from about 1% to about 95% (w/w) of the binder composition; [0122] iii. reactive prepolymer present from about 1% to about 95% (w/w) of the binder composition; [0123] iv. hydroxyfunctional compound present from about 1% to about 150% (w/w) of the comminuted biological material; [0124] v. viscosity agent present from about 0.1% to about 2% (w/w) of the comminuted biological material; [0125] vi. antifoam agent, defoam agent, or combination thereof present from about 0.001% to about 1% (w/w) of the comminuted biological material.

[0126] The present invention further concerns a method for producing a bio-based binder composition comprising the following steps:

[0127] a. mixing an unrefined biological material with a liquid medium to obtain a slurry;

[0128] b. mixing the slurry of step a. with a reactive prepolymer;

[0129] c. obtaining the bio-based binder,

[0130] wherein: [0131] the unrefined biological material is selected from: oilseeds, beans, grains, yeast, bacteria, larvae, algae, or a combination thereof, and comprises one or more of the following features: [0132] i. a fatty acid C═O stretching band of COOH between 1725 cm-1 and 1705 cm-1 that presents an absorbance of at least 0.02; [0133] ii. a prominent triacylglycerol C═O band between about 1750 cm-1 and 1740 cm-1 that presents an absorbance of at least 0.06; or [0134] iii. a prominent hydrocarbon chain C—H band between about 2950 cm-1 and 2850 cm-1 that presents an absorbance of at least 0.08 and is more prominent than the amide N—H band between 3350 cm-1 and 3250 cm-1;

[0135] as determined by solid state Fourier Transform Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR); [0136] the liquid medium is selected from a lipid, water, or a mixture thereof; and [0137] the reactive prepolymer is selected from an isocyanate-based prepolymer, an poly(aminoamine)-based prepolymer or an aldehyde-based prepolymer or a mixture thereof;

[0138] and wherein a hydroxyfunctional compound selected from glycerine, polysaccharides, oligosaccharides, monosaccharides, or a combination thereof can be optionally added to step a. or step b.

[0139] In the method for producing a bio-based binder composition: [0140] the unrefined biological material is comminuted prior, during, or after being mixed with the liquid medium or the reactive prepolymer, or [0141] the unrefined biological material is comminuted prior, during, or after being mixed with the reactive prepolymer.

[0142] Under a preferred aspect of the method, the reactive prepolymer, the unrefined biological material and the liquid medium are fed separately to an in-line static, dynamic or combined static and dynamic mixer, prior to spraying the bio-based binder onto a substrate.

[0143] Preferably, in the method for producing a bio-based binder composition, the reactive prepolymer in the bio-based binder of step c. has a droplets dimension from about 20 microns to about 200 microns, as measured with a granulometer.

[0144] Under a further aspect, the present invention relates to a method of gluing a first article to at least a second article to obtain a glued product comprising:

[0145] a. applying the binder composition of the invention to a surface of a first article to obtain a binding surface; and

[0146] b. contacting the binding surface of the first article with a surface of at least a second article; and

[0147] c. curing the binder.

[0148] In the present method for gluing, the binder is preferably cured by applying pressure, heat, or a combination thereof.

[0149] In a still preferred method, the first and at least second articles are each independently a material chosen from the group consisting of: a lignocellulosic material, a composite material containing a lignocellulosic material, a metal, a ceramic, a polymer, a plastic, a fabric, a glass, or a combination thereof, wherein said lignocellulosic material is preferably wood.

[0150] In a still further aspect, the invention describes a glued product obtainable by the method of gluing a first article to at least a second article, wherein:

[0151] a. the first and second articles are selected from the group consisting of a lignocellulosic material, a composite material containing a lignocellulosic material, a ceramic, a polymer, a fibreglass, a wood fibre, a ceramic powder, a plastic, a fabric and a glass, or a combination thereof; and

[0152] b. the cured binder has a weight between 1% and 30% of the dry weight of the product.

EXAMPLES

[0153] Reference is now made to the following examples, which together with the above descriptions illustrate some embodiments of the invention.

[0154] Particleboard Prepared from Binders on Lab Scale

[0155] Unless specified differently, the particleboard sample density was targeted at 680 kg/m3 having the dimensions 300×300×18 mm. A mixture of fibres from recycled origin was used, having a moisture content of about 2%, with a face to core ratio of 35/65. For each sample the following procedure was applied: weigh the fibres for the face layer to the nearest gram and load the fibres into a rotary blender. Weigh the binder such that the required amount of binder is dosed onto the fibres used for the face-layers of the particleboard. Continue mixing the fibres with the binder, after having sprayed or poured the desired amount of binder, for at least 4 minutes to ensure that the binder has been distributed evenly onto the fibres. Remove the resinated fibres and place it in a clean container. Repeat the same process for the core layer. For both resinated fibres, being for the core as well as for the face layer, take samples for humidity analysis to calculate the overall mat humidity. Spread half the amount of resinated surface layer fibres into a forming box that has been put onto a metal plate covered by an aluminium foil, having at least the surface area of the sample dimensions ought to be obtained. Take care in evenly distributing the fibres onto the metal plate to avoid any issues regarding density distribution in the particleboard sample. Evenly distribute all the core layer fibres onto the previously assembled face layer and complete the procedure by evenly distributing the remaining face layer fibres. Use a plywood panel having slightly smaller dimensions than the forming box to press down manually the formed mat and hold firmly for 10 seconds. Remove the forming box while keeping the pressure on the plywood panel to expose the mat. Remove the plywood panel, put another piece of release paper (aluminium foil) and apply another metal plate on top of the formed mat. Place the formed mat onto the loading area of the press and place support metal bars on the side of the mat having the desired thickness of the panel to be obtained. Verify the pressing temperature at the surface of the hotplates to be 200 degrees Celsius. Close the press immediately after loading and start the press cycle. The press cycle applies a pressure of 40 kg/cm2 to the mat and holds this pressure till a temperature of 105 degrees Celsius is achieved in the core of the mat measured by a thermosensor previously put in the core layer. Upon reaching the temperature a degassing step is initiated by relieving pressure to release excessive moisture. Afterwards, the press is closed again for a duration matching the desired press factor. Remove the panel from the press, remove the metal press platens and release papers, store the manufactured samples in an environmentally controlled room and cut and test specimen according to EN-312 P2 and EN-312 P3 requirements.

Example 1: Preparation of Binders from Castor, Jatropha curcas, Rapeseed and Soybean Oilseeds

[0156] Castor, Jatropha, Rapeseed and Soybeans seeds were comminuted separately. Prior to comminution the Castor and Jatropha seeds were partially dehulled into a shell fraction and a kernel fraction (with 10% hulls). The Rapeseeds and Soybeans were comminuted in their unrefined state. Each batch of oilseeds was crushed by a modified olive mill hammer crusher on which the grid had holes of 1.5 mm in diameter. The temperature of the obtained comminuted biological material, i.e. seed material after crushing, which can be a paste or a dry, flour-like material depending on the water and/or oil content of the starting biological material, was in the range of 30-70 degrees Celsius.

[0157] A paste-like texture was obtained for comminuting respectively Castor, Jatropha, and Rapeseeds whereas for comminuting soybeans a flour texture was obtained. Product compositions of the comminuted products are given in Table 1 below.

TABLE-US-00001 TABLE 1 Comminuted seeds Composition Seeds Fraction Humidity Lipids Protein Other Castor Kernel + 10% hull 5.1% 43.5% 20.8% 30.6% Jatropha Kernel + 10% hull 5.5% 40.4% 20.1% .sup. 34% Rapeseed Whole 10.1% 39.9% 20.0% 30.0% Soybean Whole 11.8% 20.7% 33.4% 34.1%

[0158] Table 1: Composition of Oilseed Fractions.

[0159] Samples of unrefined oilseeds were analysed by solid state Fourier Transform Infrared Spectroscopy-Attenuated Total Reflection (FTIR-ATR), with a Perkin Elmer Spectrum instrument (version 10.5.3). FIGS. 1-7 respectively show the FT-IR ATR spectrum for:

[0160] Unrefined Castor seeds (FIG. 1), Unrefined Jatropha seeds (FIG. 2), Unrefined Soybeans (FIG. 3), Unrefined Rapeseeds (FIG. 4), Unrefined Jatropha seeds and Unrefined Soybean (FIG. 5), Unrefined Soybeans_1900_1200 cm-1 (FIG. 6) and FT-IR ATR spectrum for Soy oil (FIG. 7).

[0161] As can be seen from the IR spectra, in which the Absorbance is measured in arbitrary units (a.u.) and the Frequency in cm.sup.−1, the unrefined nature of the oilseed is evident when comparing with a defatted soy flour (FIG. 8 and FIG. 9) since a prominent triacylglycerol C═O band between about 1750 cm-1 and 1740 cm-1 presents an absorbance of at least 0.06; a prominent hydrocarbon chain C—H band between about 2950 cm-1 and 2850 cm-1 presents an absorbance of at least 0.08 and is more prominent than the amide N—H band between 3350 cm-1 and 3250 cm-1; an unsaturated lipid ═C—H band between about 3015 cm-1 and 3005 cm-1 presents an absorbance of at least 0.02.

[0162] The obtained whole comminuted whole soybeans and rapeseed and partially dehulled Castor and Jatropha seeds were divided over batches to be used for mixing with water, oil, sugars, or a combination thereof, respectively section a), section b), and section c) as described below.

[0163] a) Aqueous Medium:

[0164] Each of the comminuted oilseed materials was mixed with water to obtain a slurry till a final solid content was reached of 32.5%.

[0165] The slurry codes are identified in Table 2a, 2b and 2c below.

TABLE-US-00002 TABLE 2a Slurry code Oilseed material S1 Partially dehulled Castor seeds S2 Partially dehulled Jatropha seeds S3 Whole Rapeseeds S4 Whole Soybeans

[0166] b) Oil Medium:

[0167] The comminuted materials obtained from soybeans was mixed with a precalculated amount of Jatropha oil, such that after dispersing the comminuted soybean material a pumpable product was obtained. The amount of oil used to render the comminuted soybean material fluid was according to a ratio of 4:3 respectively kgs of oil:kgs of soybeans. The solid content of the obtained slurry was about 95%. Prior to mixing the slurry to a reactive prepolymer, the slurry is dispersed in a precalculated amount of water such to obtain a solid content of 42.5%. It was observed that dispersing the comminuted soybean material present in oil in water was more convenient compared to the dispersion of only the comminuted soybean flour into water.

TABLE-US-00003 TABLE 2b Slurry code Oilseed material S4-O Whole Soybeans

[0168] c) Sugar Addition onto Slurries:

[0169] The obtained slurries, respectively Jatropha paste dispersed into water having a solid content of 32.5% and soybean flour dispersed into oil (soybean oil slurry) having a solid content of 95%, were mixed with a sugar solution. The sugar solution used was a precalculated amount of dextrose monohydrate dissolved into water such that when mixing the sugar solution with the slurry a final solid content of 45% was obtained. The Jatropha slurry, as described in section a), was mixed with a sugar solution having a solid content of 65% whereas the Soybean oil slurry, as described in section b), was mixed with a sugar solution having a solid content of 16.5%. The utilised ratio sugar solids to slurry solids was 0.9:1 and 0.3:1 respectively for Jatropha slurry and Soybean oil slurry.

TABLE-US-00004 TABLE 2c Slurry code Oilseed material S2-sug Partially dehulled Jatropha seeds S4-O-sug Whole Soybeans

[0170] The obtained slurries form above a), b), and c), i.e. S1, S2, S3, S4, S4-O, S2-sug, and S4-O-sug of tables, 2a, 2b, and 2c, binders are prepared by mixing each slurry separately with a commercially available pMDI. For mixing purposes, beakers were prepared where the pMDI was added onto the slurry according to different ratios ranging from about, on dry-weight solids that is, 3:1 to about 1:3.3 concerning resins utilized in the core and face layer respectively. After completion of the pMDI addition onto the slurry the mixture was vigorously mixed to obtain a homogenous mixture where no isocyanate droplets were longer observable, i.e. having any droplet size in the range of about 20 microns to about 200 microns. All binders prepared, obtained from mixing the various slurries with pMDI, resulted stable and applicable products from about 30 min to over 2 hours.

Example 2: Particleboard Preparation from Slurries with pMDI

[0171] Particleboards were manufactured according to the described particleboard manufacturing method. For each panel, the pMDI was pre-mixed with the slurry such that, upon pouring the binder onto the wood fibres, the desired dosage of pMDI solids, as well as slurry solids, was achieved. The dosage percentage represents the amount of binder in the particleboard layer on dry weight upon curing. The moisture content of the fibres at the end of the resination step for each manufactured matrass was about 3.5% and 11.5% for the core- and face layer respectively by means of adding water if required. After curing, the panels were tested to obtain the mechanical properties Internal bond and Surface soundness. The binder compositions utilised and their relative dosage onto the wood fibres are given in table 3 below.

TABLE-US-00005 TABLE 3 CORE FACE PAN- SLUR- Slur- Slur- ELS RY Dosage pMDI ry Dosage pMDI ry P1 S1 2.7% 2.1% 0.7% 6.6% 1.5% 5.1% P2 S2 2.7% 2.1% 0.7% 6.6% 1.5% 5.1% P3 S3 2.7% 2.1% 0.7% 6.6% 1.5% 5.1% P4 S4 2.7% 2.1% 0.7% 6.6% 1.5% 5.1% P5 S4-O 2.7% 2.1% 0.7% 6.6% 1.5% 5.1% P6 S2-sug 2.7% 2.1% 0.7% 6.6% 1.5% 5.1% P7 S4-O-sug 2.7% 2.1% 0.7% 6.6% 1.5% 5.1%

[0172] Table 3: Resin Solid Dosage onto Wood, in Terms of Dry Weight, of the Particleboards Manufactured.

[0173] Regarding the binders utilised to manufacture the core layer of the particleboard water was used to dilute the binder as such to render the binder fluid such that the binder can be poured or sprayed onto the wood fibres.

[0174] Samples were cut and tested accordingly after stabilization of the panels. Results of these tests are given in Table 4 below.

TABLE-US-00006 TABLE 4 RAW Thickness Internal Surface Density swelling bond soundness Panel EN-323 EN-317 EN-319 EN-319 # Slurry kg/m3 % (24 h) MPa MPa P1 S1 683 17.73% 0.39 1.10 P2 S2 681 20.34% 0.37 1.07 P3 S3 683 18.48% 0.38 1.03 P4 S4 680 17.43% 0.38 1.14 P5 S4-O 685 15.92% 0.35 1.19 P6 S2-sug 689 24.83% 0.35 1.23 P7 S4-O-sug 679 22.44% 0.36 1.25

[0175] Table 4: pMDI-Based Panel Results.

[0176] From the prepared panels it is evident that the combination of pMDI with unrefined oilseed material results in panels with mechanical characteristics conform EN-312 P2 criteria. It was observed that when utilising slurries with significant lipid content the panel, i.e. the composite, without applying any aluminium foil, was easy to detach from the metal platens. For Jatropha, i.e. S2, in particular a good release of the panel was obtained without further addition of oil whereas that for Soybean, i.e. S4, the composite remained stuck to the metal platens. However, the utilisation of Soybean dispersed in oil, i.e. S4-O, this problem was not encountered. It will appear evident to the skilled person the advantage of utilizing the unrefined bio-binders in combination with pMDI, as the latter is well known not to facilitate composite release from the metal platens of the hotpress without the usage of pMDI dedicated composite release agents.

Example 3: Particleboard Preparation from Slurries with PAE for Surface Layers

[0177] Particleboards were manufactured according to the described particleboard manufacturing method. For the panel, pMDI was utilised in the core while for the face layers a mixture was utilised containing a commercially available PAE, having a solid content of about 25%, with slurry S2-sug having a solid content of 45%. The dosage percentage represents the amount of binder in the particleboard layer on dry weight. Prior to resination of the fibres, the moisture content was adjusted, when necessary, to 3.5% and 11.5% for the core- and face layer respectively by means of adding water. The binder composition utilised and their relative dosage onto the wood fibres are given in table 5 below.

TABLE-US-00007 TABLE 5 FACE PAN- SLUR- CORE Slur- ELS RY Dosage pMDI Dosage PAE ry P8 S2 2.75% 2.75% 7.0% 1.5% 5.5%

[0178] Table 5: Resin Solid Dosage in Terms of Dry Weight of the Particleboard.

[0179] Upon stabilisation of the prepared panels samples were cut and tested accordingly. Results of these tests are given in Table 6 below.

TABLE-US-00008 TABLE 6 RAW Thickness Internal Surface Density swelling bond soundness Panel EN-323 EN-317 EN-319 EN-319 # kg/m3 % (24 h) MPa MPa P8 685 18.59% 0.35 0.99

[0180] Table 6: PAE Based Panel Performances According to EN-312 Testing Requirements

Example 4: Industrially Prepared Particleboard by Binder Derived from J. curcas

[0181] About 1200 kg of J. curcas seeds were partially decorticated to obtain a decorticated fraction. About 800 kg of partially decorticated J. curcas seeds were crushed through a 15 kW hammer crusher into a comminuted biological material which in this case has the consistency of a paste. The paste has been diluted and mixed with water to obtain a slurry having a solid content of about 38% w/w. The slurry was then pumped to an in-line dynamic mixer to be mixed with commercially available pMDI. The in-line dynamic mixer set-up was utilized for mixing the slurry with pMDI for the core as well as for the face layers of the particleboard and its dosages are given in table 7 below.

TABLE-US-00009 TABLE 7 CORE FACE Dosage pMDI Slurry Dosage pMDI Slurry 3.5% 2.0% 1.5% 6.0% 1.5% 4.5%

[0182] Table 7: Dosage of pMDI and Slurry onto the Wood Fibres for the Core and Face Layers of a Particleboard Panel.

[0183] The wood fibres were originated from recycled wood material and had a moisture content of 1.5% that was adjusted to 3.5% for the core layer and 11.5% for the face layer prior to dosing the binder. Flow-rates were set as such to manufacture particleboards having a density of 680 kg/m3 for which multiple press-factors were applied, respectively 7, 6, and 5 seconds per millimetre, of which its impact on panel performances are given in table 8 below.

TABLE-US-00010 TABLE 8 RAW Internal Surface Press Density Thickness bond soundness factor EN-323 EN-317 EN-319 EN-319 sec/mm kg/m3 % (24 h) MPa MPa 7 686 16.58% 0.43 1.21 6 681 17.44% 0.39 1.18 5 679 19.28% 0.35 1.19

[0184] Table 8: Particleboard Characteristics According to EN-312 Requirement Testing Procedures at Different Pressfactors.

[0185] No pMDI dedicated releasing agents were utilized.

[0186] No press built-up was observed utilising the binder composition, as given by table 13, while running continuous production for more than six hours.

[0187] The Global Warming Potential of the bio-based binder comprising Jatropha seeds has been estimated in the range of about −10 to −30 kg Co2-eq per m3 of particleboard panel. By comparison the GWP of Melamine-Urea-Formaldehyde binder is in the range of 150 kg CO2-eq per m3 panel (Wilson, 2009).

Example 5: Particleboard Preparation from Slurries with the Addition of Sugars in Combination with Formaldehyde-Free Prepolymers

[0188] A particleboard was manufactured according to the described particleboard manufacturing method. For each panel, pMDI was utilised in the core, while for the face layers a commercially available PAE based resin was utilised. The final bio-binder composition comprises PAE dextrose monohydrate and comminuted soybeans, according to the ratio, as described in table 9 below.

TABLE-US-00011 TABLE 9 SC PHS Added % % Component (%) # on wet on wet on dry Comminuted soybeans 88.0%.sup.  100.0 113.6 17.09% 15.04% PAE 25% 70.0 280.0 42.12% 10.53% Dextrose monohydrate 91% 115.0 126.4 19.01% 17.30% Water  0% 144.8 21.78% 0.0% Total: 285 664.8 100.0% 42.87%

[0189] Table 9: Binder Composition Applied to the External Face Layers of the Particleboard.

[0190] The binder obtained was sprayed onto the wood fibres. The dosage percentage represents the amount of binder in the particleboard layer on dry weight upon curing. Upon resination of the fibres, the moisture content was adjusted, when necessary, to 6% and 12.0% for the core- and face layer respectively by means of adding water. The binder compositions utilised and their relative dosages onto the wood fibres are given in table 10 below, where BIO represents the dosage of the combined solids coming from the comminuted whole soybeans and dextrose monohydrate.

TABLE-US-00012 TABLE 10 CORE FACE PANELS Dosage pMDI Dosage PAE BIO P9 2.5% 2.5% 7.0% 1.5% 5.5%

[0191] Table 10: Resin Solid Dosage in Terms of Dry Weight of the Particleboard to be Manufactured.

[0192] It was observed that the resinated fibres for the face layer exhibited a significant amount of cold tack; a cold tack that is comparable to resinated fibres utilizing UF resins.

[0193] Upon stabilisation of the prepared panel, samples were cut and tested accordingly. Results of these tests are given in Table 11 below.

TABLE-US-00013 TABLE 11 RAW Thickness Internal Surface Density swelling bond soundness Panel EN-323 EN-317 EN-319 EN-319 # kg/m3 % (24 h) MPa MPa P10 683 19.61% 0.35 1.10

[0194] Table 11: PAE Based Panel Performances According to EN-312 Testing Requirements

Example 6: Industrially Prepared Particleboard with Binder Derived from Soybean Oilseeds

[0195] About 400 kg of soybeans were crushed to obtain a flour that was afterwards dispersed with about 550 kg of J. curcas oil to obtain a slurry. The slurry had a solid content of about 96%. The slurry was then dispersed into an aqueous medium being a 15% sugar solution (dextrose monohydrate dissolved into water) such that the final solid content of the slurry was about 45%. Afterwards the slurry was passed through a 15 kW hammer crusher to obtain a homogeneous product. The slurry was then pumped to an in-line dynamic mixer where the slurry was mixed with commercially available pMDI. Dosages utilised for the core and face layers are given in the table 12 below.

TABLE-US-00014 TABLE 12 CORE FACE Dosage pMDI Slurry Dosage pMDI Slurry 3.0% 2.0% 1.0% 7.0% 1.5% 5.5%

[0196] Table 12: Dosage of pMDI and Slurry onto the Wood Fibres for the Core and Face Layers of a Particleboard Panel.

[0197] The wood fibres originated from recycled wood material and had a moisture content of 1.5%. No additional water was added to the core fibres keeping the moisture content of the core layer at about 3.3%, while for the face layers, water was added prior to adding the binder targeting a final moisture content, including the moisture given by the binder utilised, of about 11.5%. Flow-rates were set as such to manufacture particleboards having a density of 680 kg/m3 for which press-factors of 7 and 5 seconds per millimetre were applied. Panel performances of the industrial trial are given in table 13 below.

TABLE-US-00015 TABLE 13 RAW Thickness Internal Surface Press Density swelling bond soundness factor EN-323 EN-317 EN-319 EN-319 sec/mm kg/m3 % (24 h) MPa MPa 7 687 18.89% 0.37 1.28 5 680 21.84% 0.35 1.18

[0198] Table 13: Particleboard Characteristics According to EN-312 Requirement Testing Procedures at Different Press-Factors.

[0199] No pMDI dedicated releasing agents were utilized.

[0200] No press built-up was observed utilising the binder composition, as given by table 13, while running continuous production for more than six hours.

[0201] GWP of the bio-based binder utilised for the production of particleboard has been estimated in the range of about 15 to 30 kg CO2-eq per m3 particleboard panel. By comparison the GWP of Melamine-Urea-Formaldehyde binder is in the range of 150 kg CO2-eq per m3 panel.

Example 7: Particleboard Preparation from Slurries with UF

[0202] A particleboard was manufactured according to the described particleboard manufacturing method. For the panel, a standard E1 emissions class UF binder, having a solid content of 68%, was utilised in the core- and face layers in combination with Jatropha slurry S2 having a solid content of 42.5%. The utilised dosages onto the core layer and face layer fibres are given in table 14 below:

TABLE-US-00016 TABLE 14 CORE FACE PAN- SLUR- Slur- Slur- ELS RY Dosage UF ry Dosage UF ry P11 S2 8.0% 6.5% 1.5% 8.0% 4.0% 4.0%

[0203] Table 14: Dosages onto the Wood Fibres, in Terms of Dry Weight Solids Binder onto Dry Weight Solids Wood, Utilising UF-Based Reactive Prepolymers.

[0204] The Jatropha slurry was mixed with the UF binder such that the binder dosed the desired ratio of UF to slurry accordingly when poured onto the fibres. The Jatropha-UF binder for the core layer had a solid content of about 60% and for the face layer, including the addition of water, a solid content of about 45%. No additional water was added onto the wood fibres prior or after the resination step. The panel was pressed utilising a pressfactor of 8 sec/mm and was, after being stabilised, cut into specimen to test the internal bond, surface soundness, and swelling according to standard EN-312 P2 requirements.

[0205] Results of these tests are given in Table 15 below.

TABLE-US-00017 TABLE 15 RAW Thickness Internal Surface Density swelling bond soundness Panel EN-323 EN-317 EN-319 EN-319 # kg/m3 % (24 h) MPa MPa P11 695 25.69% 0.37 1.08

[0206] Table 15: UF Based Panel Performances According to EN-312 Testing Requirements.

[0207] As it can be noticed, over 30% of UF resin has been substituted by means of unrefined biological material. An advantage of such bio-binder is represented by its reduced emissions and full biodegradability.

[0208] From the above description and the above-noted examples, the advantage attained by the product described and obtained according to the present invention are apparent. While the invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention. The appended claims are intended to be construed to include all such embodiments and equivalent variations.

REFERENCES

[0209] 1. CARB (2007)—Airborne Toxic Control Measure to Reduce Formaldehyde Emissions from Composite Wood Products https://ww3.arb.ca.gov/regact/2007/compwood07/fro-final.pdf?_ga=2.90713882.1082449153.1562761880-1534676479.1562761880 [0210] 2. EuCIA (2015)—the 6th Adaptation to Technical Progress (ATP) to the classification, labelling and packaging of substances and mixtures (CLP) Regulation on 6 Jun. 2014 (Regulation 605/2014) https://eucia.eu/userfiles/files/20150107_New%20labelling%20for%20formaldehyde%20and%20styrene.pdf [0211] 3. Plastics Europe (2012)—Eco-profiles and Environmental Product Declarations of the European Plastics Manufactures—Toluene Diisocyanate (TDI) & Methylenediphenyl Diisocyanate (MDI) ISOPA https://www.isopa.org/media/2609/eco-profile-mdi-tdi.pdf [0212] 4. Baumert (2014)—Life cycle assessment of carbon and energy balances in Jatropha production systems of Burkina Faso https://d-nb.info/1052652662/34 [0213] 5. Espy, H. H., “Alkaline-curing polymeric amine-epichlorohydrin resins,” in L. L. Chan, Ed., Wet-Strength Resins and their Application, TAPPI Press, Atlanta, Ch. 2, 13-44 (1994) [0214] 6. United Soybean Board (2016)—“Update of Soybean Life Cycle Analysis” [0215] 7. Oregon State University, Wilson (2009)—“Life-cycle inventory of formaldehyde-based resins used in wood composites in terms of resources, emissions, energy and carbon”