JP2016509477A - Method for isolating cellulose from cellulose biomass, isolated type I cellulose, and composite material using the same - Google Patents

Abstract

Described herein are methods for producing cellulose pulp and for isolating cellulose from cellulose-containing biomass. The method of the present invention includes contacting the biomass with an anion source and a cation source, wherein the anion source and cation source are selected to undergo an exothermic reaction with and between the biomass. The method of the present invention has the specificity of producing an exothermic reaction through the enthalpy of reaction and mixing. Therefore, since the necessary energy energy is supplied by a chemical reagent present in the biomass or a chemical reagent added as necessary, the method of the present invention does not require an external energy supply. The present invention also relates to isolated cellulose obtained by these methods and its use in various materials. [Selection] Figure 1

Description

  This application claims priority based on Canadian Patent Application No. 2,803,863 (filed January 25, 2013). The contents of this application are hereby incorporated by reference in their entirety.

  The present invention relates to the fields of biomass delignification and cellulose extraction. More specifically, the present invention relates to a method for the production of cellulose pulp and a method for isolating cellulose from cellulose-containing biomass. The invention further relates to isolated cellulose obtained by such a method and its use in various materials.

  Plant biomass mainly consists of cellulose (~ 50%), lignin (~ 25%), and hemicellulose (~ 25%).

  Although cellulose was initially extracted using a mechanical method, in recent years, cellulose is mainly obtained by a chemical extraction method. Such a method was first developed on an industrial scale in Europe in the 1850s. Such chemical methods generally favor 80-96% cellulose pulp, but some lignin remains in such cellulose. Lignin is usually undesirable because it adversely affects the paper, especially due to its resistance and yellowing over time.

  Conventional chemical methods such as sulfurous acid or hydrogen sulfite (acid) and Kraft or sulfuric acid (alkaline) methods have been designed to remove extractant and hemicellulose along with most of the lignin from the cellulose. Chemical pulp is usually produced in large reactors at elevated temperatures (100 ° C. to 180 ° C.) and high pressures (5 to 7,5 bars). Biomass is usually pressure adjusted in the presence of the compound for 15-25 hours. Thereafter, the cellulose fibers are washed, rinsed, cleaned and bleached.

Chemical methods with sulfurous acid and hydrogen sulfite are mainly used for softwood. Both methods are based on the fact that wood lignin dissolves in sulfuric acid (sulfurous acid (SO ₃ ²⁻ ) or hydrogen sulfite (HSO ₃ ⁻ )) in a pH-dependent manner. Both methods occur in a wide pressure reactor. As the counter ion, sodium (Na ⁺ ), calcium (Ca ²⁺ ), potassium (K ⁺ ), magnesium (Mg ²⁺ ), or ammonium (NH ₄ ⁺ ) is used.

  The generally used sulfuric acid or Kraft method has the advantage that it can treat a wide variety of plants such as hardwood and softwood. Examples include sugar cane and strawberries. The Kraft method requires high temperature and pressure for several hours. The resulting pulp has a dark appearance and cannot be used for high quality paper that requires a high degree of whiteness. Therefore, it is necessary to subject the pulp to chemical bleaching. Despite efforts to find suitable chemicals since the 1930s, both methods are extremely polluting.

  Although chemical methods have been regularly improved since their discovery, they are still very similar to the original methods. Almost all methods tend to modify cellulose and lignin fibers due to exposure to high pressures and temperatures and because of the use of salts and counter ions that alter the chemical and physical structure of the molecule. Furthermore, chemical methods require large investments for the construction and operation of large industrial facilities. This is because these methods require large amounts of energy and water and must also deal with air and water pollutants.

  To overcome some of these drawbacks, combining simple and relatively mild chemical reagents and high physical constraints (temperature and pressure) remove lignin to obtain cellulosic materials of varying purity. Other methods have been developed. Examples of such known methods include steam explosion delignification or Iotech, organosolv, and CIMV methods (eg, US Pat. No. 1,655,618, US Pat. No. 4,645,541, Europe). Patent applications EP0503304 and EP0584675, and International PCT publications WO2010 / 071805, WO2009 / 092749, and WO2012 / 000093). However, since these methods all use high temperatures (95 ° C. to 270 ° C.) and high pressures (3 to 40 bars), expensive equipment is required. In addition, these methods are expensive for their equipment and cannot handle large amounts of material for industrial production.

  US Pat. No. 6,824,599 and International PCT Publication No. WO2005 / 017001 disclose a method for obtaining cellulose using an ionic liquid. In the methods described in these, biomass is immersed in an ionic liquid and subjected to pressure conditions under microwave radiation (energy source) and a plurality of different atmospheres. Such a method has several advantages over the Kraft method, but still has some disadvantages, such as the need for thermal energy, the use of high pressure, and a low pure cellulose yield.

  Therefore, there is a need for new chemical methods for delignification of biomass and extraction of cellulose. More specifically, there has been a demand for a method that can be performed under environmental pressure and that can generate the energy without requiring an external energy source such as heating. In addition, there is a pulp preparation and cellulose extraction method that can be carried out at various scales, such as large industrial facilities and smaller mobile facilities installed at or near wood processing work sites, but still relatively inexpensive and commercially feasible. It has been demanded. There is also a need for a more environmentally friendly method that requires less water and produces less polluted water and polluted gases. There is also a need for cellulose that is more reactive and has the desired purity, chemical and mechanical properties.

  The present invention addresses these needs and other needs that will be apparent upon reading the following disclosure, drawings and descriptions of the features of the present invention.

  The present invention relates to delignification of biomass and extraction of cellulose from cellulose biomass.

A specific aspect of the present invention is a method for producing cellulose pulp,
Providing biomass comprising cellulose, hemicellulose, and lignin;
Contacting the biomass with an anion source and a cation source, wherein the anion source and cation source are selected to undergo an exothermic reaction with and between the biomass;
Causing an exothermic reaction under conditions and for a time sufficient to break the intermolecular bonds existing between lignin, cellulose, and hemicellulose;
It relates to a process comprising obtaining a cellulose pulp comprising solubilized hemicellulose and solubilized lignin.

  According to one aspect, at least a portion of the anion source is provided by biomass.

A related aspect of the present invention is a method of producing cellulose pulp,
-Providing biomass comprising cellulose, hemicellulose, and lignin;
Providing an anion source A and a cation source B, wherein said anion source A and cation source B are anionic precursors of an ionic liquid of formula AB, wherein said anion source A and cation source B are selected for exothermic reaction with and between biomass,
-Contacting the biomass with an anion source A and a cation source B, wherein said contacting is carried out under conditions and over time allowing the formation of said ionic liquid AB, wherein said contacting comprises lignin, It is an exothermic reaction that breaks the intermolecular bonds existing between cellulose and hemicellulose,
-relates to a process comprising obtaining a cellulose pulp comprising i) a solid phase mainly composed of cellulose and ii) a heterogeneous viscous mixture comprising solubilized hemicellulose and solubilized lignin.

Another aspect of the present invention is a method for isolating cellulose from biomass comprising:
a) providing biomass comprising cellulose, hemicellulose, and lignin;
b) contacting the biomass with compound A to at least partially impregnate the biomass to obtain impregnated acidic biomass, wherein compound A is an anion source, wherein compound A reacts exothermically with the biomass. ,
c) contacting the impregnated acidic biomass with compound B, where compound B is a cation source, wherein compound B reacts exothermically with compound A impregnated within the acidic biomass;
d) an exothermic reaction under conditions and for a time sufficient to disrupt the intermolecular bonds existing between lignin, cellulose, and hemicellulose to produce a cellulose pulp comprising solubilized hemicellulose and solubilized lignin;
e) relates to a process comprising isolating cellulose from said pulp.

  Another aspect of the present invention relates to an isolated cellulose obtained by the method described in the specification of sound.

In particular, the present invention relates to an isolated cellulose characterized by an FTIR spectrum that can be distinguished from an FTIR spectrum of cellulose type II. According to one particular aspect, the FTIR spectrum of the isolated cellulose is characterized by a peak at 1730 cm ⁻¹ .

  The present invention also relates to an isolated cellulose characterized by an X-ray spectrum distinguishable from an X-ray spectrum of cellulose type II. According to one particular aspect, the X-ray spectrum of the cellulose has a peak at 2θ = 15.0 (1-10), a peak at 2θ = 16.6 (110), a peak at 2θ = 22,7 (200), and It includes a peak at 2θ = 34.5 (004). According to another embodiment, the X-ray spectrum of the cellulose contains two peaks at 2θ = 29.9 and 2θ = 38.3.

  A further aspect of the present invention relates to a composite material comprising a resin and / or curing agent in admixture with isolated cellulose as defined herein.

  A further aspect of the present invention relates to a composite material with unique properties, such as improved modulus and / or containing 15% w / w cellulose.

  The advantage of the present invention is that it provides a relatively simpler, cheaper and more efficient means than all other chemical methods of making cellulose pulp from biomass and extracting cellulose. is there. The method of the present invention can be implemented on a variety of scales, including large industrial facilities and smaller mobile facilities installed at or near a wood processing work site. The method of the present invention can be carried out at ambient pressure conditions and does not require an external energy source such as heating or pressurization. The chemical method of the present invention can be said to be more environmentally friendly because it requires less water and produces less polluted water and gases than other existing chemical methods. Furthermore, the cellulose obtained by these methods has advantages in terms of purity (ie, low lignin and low hemicellulose), cell integrity, reactivity, and abundance compared to typical commercial type I and type II celluloses. Have

  Further aspects, advantages and features of the present invention will become more apparent upon reading the following non-limiting description of preferred embodiments. In addition, the following description is an illustration and should not be understood as a thing which restrict | limits the scope of the present invention.

FIG. 1 is a flowchart showing a cellulose extraction method according to one embodiment of the present invention.

2A and 2B are schematic views for explaining the method of FIG. 2A shows steps 160, 170, and 180 of the method of FIG. 1, and FIG. 2B shows steps 200 and 220 of the method of FIG. The following symbols refer to the corresponding illustrated elements. (3) Biomass swelling; (4) Compound B; (5) Heating; (6) Outgassing; (7) Solid material; (8) Heterogeneous viscous mixture; (9) (10) Filtrate; (11) Wash; (12) Cellulose; (13) Filter; (14) Ventilation; (15) Mixing; (16) Sieve; and (17) Cellulose powder. Same as above.

FIG. 3 is a bar graph showing decomposition analysis of hemicellulose, lignin, and cellulose obtained according to Examples 1-4.

4A-4C are infrared spectral (IR) curves of [<20 μm] sieve fraction of cellulose obtained from birch wood chips according to one embodiment of the present invention (invention, type I; FIG. 4A), Sigma Aldrich FIG. 4 is an infrared spectrum (IR) curve of a commercially available cellulose Alpha (type II, FIG. 4B), and a graph (FIG. 4C) showing both curves superimposed. Same as above. Same as above.

5A-5D are RX diffractrograms curves for various celluloses. Fig. 5A: Avicel PH101 Type I cellulose (Park et al. 2010. Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulose performance. Biotechnol Biofuels. 2010; 3:10) Fig. 5B: Type II cellulose (Biganska O., 2002 Etude physico-chimique des solutions de cellulose dans la N-methylmorpholine-N-oxyde. Thesis, Ecole des Mines, Paris, 133p.). FIG. 5C: [20 μm, 45 μm] sieved fraction of cellulose obtained from birch wood chips according to one embodiment of the present invention; FIG. 5D: a graph showing the curves of FIGS. 5A and 5C overlaid. Same as above.

6A to 6D are photomicrographs obtained by scanning electron microscopy (SEM). [<45 μm] sieved fraction of cellulose obtained from maple wood chips according to one embodiment of the present invention, 200 μm scale (FIG. 6A) and 20 μm scale (FIG. 6B). Avicel PH101 type I cellulose, 300 μm scale (FIG. 6C) and 60 μm scale (FIG. 6D) (Ribet J., 2003. Fonctionnalisation des Excipients: Application a la comprimabilite des celluloses et des saccharoses, Thesis, Universite Limoges, France, 263p.) . Same as above. Same as above.

7A and 7B are bar graphs (μm units) showing the size distribution of length and width, respectively, of a [<45 μm] sieved fraction of cellulose obtained from maple wood chips according to one embodiment of the present invention. . FIG. 7C is a bar graph showing the size distribution of the length of the cellulose fiber (Avicel PH101 type I cellulose) illustrated in FIG. 6C.

FIG. 8 shows [<20 μm] and [20 μm, 45 μm] sieved fractions of cellulose obtained from birch wood chips according to one embodiment of the present invention, as well as commercially available type I cellulose (Avicel PH101, FMC Bio polymer). It is a curve which shows a polymerization degree by comparison with Epolam 2015 (trademark).

FIG. 9A is a thermogravimetric analysis (TGA) curve of a [<45 μm] sieved fraction of cellulose obtained from maple wood according to one embodiment of the present invention. FIG. 9B is a dynamic mechanical analysis (DMA) curve of the [<45 μm] sieved fraction of cellulose obtained from maple wood according to one embodiment of the present invention. The curve for sample 1 shows the resin epoxy Epon 862® and 10% cellulose, and the curve for sample 2 shows pure epoxy Epon 862®.

FIG. 10 is a photomicrograph of cellulose nanoparticles (less than 1 μm in size) obtained from birch wood chips according to one embodiment of the present invention.

FIG. 11A is a curve showing the FTIR spectrum of unoxidized isolated cellulose (DS approximately 0). FIG. 11B is a curve showing an FTIR spectrum of oxidized cellulose (DS = 3). FIG. 11C is a graph showing the curves of FIGS. 11A and 11B superimposed.

A) Summary of the Invention The present invention relates to the production of cellulose pulp and a process for isolating cellulose from cellulose-containing biomass. Contrary to known chemical processes that require large amounts of energy (for example high heat and high pressure), the process of the present invention has the peculiarity that an exothermic reaction occurs due to reaction enthalpy and mixed enthalpy. Thus, the process of the present invention can be used to adjust temperature and / or pressure since the required energy is supplied by chemical reagents already present in the biomass, or added as needed. No external energy supply is required.

  The essence of the invention depends on the use of two main compounds A and B that react with biomass. The compounds selected will supply anions and cations as a reagent to create an ionic liquid that will create a solution and finally solubilize lignin and hemicellulose and remove both components from the cellulose. It also acts as a source. When properly selected, administered, and / or mixed, compounds A and B react with the biomass to give enough energy to break the intermolecular bonds that exist between cellulose, lignin, and hemicellulose. And mixed enthalpy, which enables solubilization of lignin and hemicellulose.

  The process of the present invention does not require the addition of water, the process of the present invention requires fewer chemical products than known chemical processes, and these chemicals can be recycled in whole or in part. Also, the cellulose fibers obtained according to the present invention are reduced from most of the original lignin, these cellulose fibers can retain their original molecular properties, or these cellulose fibers are subject to selected operating conditions. It can be chemically modified accordingly.

B) Definitions For purposes of the present invention, the following terms are defined as follows:

  As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a (one) compound” includes one or more such compounds, and reference to “processing” is equivalent to steps and processes or methods known to those skilled in the art. Including references to what may be modified or substituted for the methods described herein.

  As used herein, the term “biomass” includes stems, bark, branches, roots and leaves, herbaceous plants, cannabis, firewood, vegetable waste, waste wood, wood chips, algae, paper, cardboard, etc. Refers to cellulose-containing products such as, but not limited to, hard wood and soft wood, wood biomass, plant biomass, and derivatives.

  As used herein, an “ionic liquid” has high thermal stability and is around room temperature (usually between −100 ° C. and 200 ° C., but may exceed 300 ° C.). Refers to a liquid salt that is liquid (Wassercheid, P., Welton. T., 2003, Ionic Liquids in Synthesis, Wiley-VCH, p. 1-6, 41-55 and 68-81). The ionic liquid mainly consists of ions and short-lived ion pairs, and most consists of organic anions or a combination of inorganic anions and organic cations. There are over a million possible combinations of cations and anions, and new combinations are constantly appearing. For example, the ionic liquid can be quaternary ammonium or quaternary phosphonium, in which case the cation is an amine group, ether or alcohol, acid or ester, thiol, vinyl, allyl, alkyne, nitrile, or even a chiral cation. Carry. These ionic liquids can be compounds selected from among chiral forms, hydroxyborate, Lewis bases, metal salts, or heteropolyyanions in which organic or inorganic anions are functionalized with nitriles. . Specific examples of ionic liquids according to the present invention include US Pat. No. 5,683,832 (A), US Pat. No. 5,827,602 (A), EP 2162435 and EP 2295440. However, it is not limited to these. These materials are variously referred to as room temperature ionic liquids (RTIL), liquid electrolytes, ionic melts, ionic fluids, molten salts, liquid salts, or ionic glasses.

As used herein, the term “cellulose” is an organic consisting of a linear chain of several β (1 → 4) linked D-glucose units having both reducing and non-reducing groups at the end of each chain. Oligomer or homopolymer (C ₆ H ₁₀ O ₅ ) _n is included. Cellulose is the most abundant organic polymer on the ground. The term “cellulose” encompasses any different form of cellulosic material, including but not limited to sheets, fibers, fibrils, strands, microcrystalline cellulose (MCC), nanocrystalline cellulose (NCC), and the like. As used herein, the term “isolated cellulose” refers to cellulose that has been obtained, extracted, purified, etc., from a cellulose-containing biomass, preferably by a process according to the present invention.

As used herein, the term “type I cellulose” or “cellulose type I” or “cellulose I” or “natural cellulose” means that all cellulose strands are parallel and inter-sheet hydrogen bonding. The cellulose which does not have is pointed out. Cellulose I contains two coexisting cellulose I _α (triclinic) and cellulose I _β (monoclinic) phases in various proportions depending on its origin, I _α being more algae and bacteria On the other hand, I _β is the main type of higher plant (Atalla RH. 1999. The individual structures of native celluloses. Proceedings of the 10th International Symposium on Wood and Pulping Chemistry, Main Symposium; Yokohama, Japan. 07-10 June 1999; pp.608-614). Cellulose I _alpha cellulose I _beta can be found in a proportion of a mixture in all sources (J. Am Chem Soc 9 vol 125 , no 47, 2003 14300-14306;...... J. Am Chem. Soc. 9 vol. 124, no. 31, 2002 9074-9082).

  As used herein, the terms “type II cellulose” or “cellulose ii type” or “cellulose II” refer to cellulose that is generally monoclinic and is more thermally stable than cellulose I. Point to. The structure of Cellulose II exhibits an antiparallel arrangement of strands, the structure having both intra-sheet and inter-sheet hydrogen bonds. Cellulose II can be obtained, for example, by mercerization of cellulose I. Cellulose II is generally produced after chemical treatment (ie mercerization) or chemical mechanical treatment of lingocellulosic biomass.

  As used herein, the term “cellulose pulp” is derived from chemical treatment of cellulose-containing biomass and is made from fibrous cellulosic material, solubilized hemicellulose, solubilized lignin and other residues or biomass thereof. It refers to a viscous or semi-liquid mixture containing components derived from its chemical treatment.

  As used herein, the term “reaction enthalpy” refers to the energy change ΔH of a reaction. Reaction enthalpy is the amount of energy or heat absorbed in a reaction. When energy is required, ΔH is a positive value, and when energy is released, ΔH is a negative value.

  As used herein, the term “mixed enthalpy” refers to the energy that is absorbed or released when two chemical substances are mixed. Mixing is endothermic when the mixing enthalpy is positive, while negative mixing enthalpy means exothermic mixing. Thus, as used herein, the term “exothermic reaction” means that heat and some pressure are present when two or more chemical substances (eg, biomass and compound A and / or B, compound A + B, etc.) are mixed. Refers to a chemical reaction that is released.

Process for Delignification of Biomass and Cellulose Extraction One particular aspect of the present invention relates to a process for producing cellulose pulp. Thus, the pulp can be washed, dried, crushed and / or milled according to operating conditions to produce natural or modified cellulose.

In one embodiment, the treatment for cellulose pulp production comprises
Providing a biomass comprising cellulose, hemicellulose, and lignin;
-Contacting the biomass with an anion source and a cation source selected to react exothermically with and between the biomass;
Allowing the exothermic reaction to occur under conditions and for a time sufficient to break the intermolecular bonds existing between lignin, cellulose and hemicellulose;
Obtaining a cellulose pulp comprising solubilized hemicellulose and solubilized lignin.

In another embodiment, the treatment for cellulose pulp production comprises
-Providing biomass comprising cellulose, hemicellulose and lignin;
Providing an anion source A and a cation source B that are anionic precursors of an ionic liquid of formula AB and are selected to undergo an exothermic reaction with and between the biomass;
-Contacting the biomass with the anion source A and the cation source B, under conditions and for a period of time capable of forming the ionic liquid AB, and being exothermic; Said contact that breaks intermolecular bonds existing between lignin, cellulose and hemicellulose;
Obtaining a cellulose pulp comprising (i) a solid phase composed primarily of cellulose, and (ii) a heterogeneous viscous mixture comprising solubilized hemicellulose and solubilized lignin and other residues from the reaction.

Another specific aspect of the invention relates to a process for isolating cellulose from biomass. According to one embodiment, the process is:
a) providing a biomass comprising cellulose, hemicellulose and lignin;
b) contacting the biomass with Compound A, which is an anion source and reacts exothermically with the biomass, to at least partially impregnate the biomass to obtain impregnated acidic biomass;
c) contacting the impregnated acidic biomass with compound B, which is a cation source and reacts exothermically with compound A impregnated in the acidic biomass;
d) exothermic reaction over conditions and time sufficient to break the intermolecular bonds existing between lignin, cellulose and hemicellulose and produce cellulose pulp containing solubilized hemicellulose and solubilized lignin;
e) isolating cellulose from the pulp.

  According to certain embodiments, the present invention allows extraction of natural and / or modified cellulose or functionalized and / or non-functionalized cellulose by either partial or total removal of lignin and hemicellulose Can be.

  In accordance with the principles of the present invention, the use, addition, and / or contact of anions (compound A) and cations (compound B) to biomass results in an exothermic reaction that occurs due to reaction enthalpy and mixed enthalpy, and the exothermic reaction. However, it leads to dissolution of lignin component and hemicellulose component and production of cellulose pulp. Thus, no other external energy supply is required for the reaction to occur. One skilled in the art can use a large number of Compound A and B pairs to make an ionic liquid, with each particular pair being characterized in terms of its characteristics and desired activity when used in the process. Understand that you can choose a pair.

  According to the invention, an anion source (compound A) is defined as any compound containing a proton in the meaning of the Laurie-Brensted theory and can be an anionic precursor in an ionic liquid. Thus, Compound A is defined as an anionic precursor of an ionic liquid in the sense that this compound becomes an anion source when mixed with a cation source which in this case is Compound B. Compound A can be a liquid, a solid or a gas.

Compound A may contain the same type of anionic precursor or different types. Thus, compound A may be defined as A ₁ A _2,... A _i , and the index i may vary, including all forms included in the dominant pH diagram (ie, compound A may be a salt or acid). Represents the number of anionic precursors. When Compound A is a gas (eg, hydrochloric acid) or a solid (eg, p-toluenesulfonic acid), prior to contacting with biomass to improve the reactivity of Compound A and optimize the process of the present invention The gas or solid can be solubilized in the solvent.

  According to the invention, the cation source (compound B) is a primary amine, secondary amine, tertiary amine or polyamine or phosphine or polyphosphine molecule, quaternary ammonium or quaternary phosphonium, ether or alcohol. , Acid or ester, thiol, vinyl, allyl, alkyne, nitrile or chiral cation, chiral compound functionalized with nitrile, hydroxyborate, Lewis base, metal salt, or heteropolyyanion. According to the present invention, compound B is a cation source when it reacts with compound A (an anion source) to produce solution AB or an ionic liquid.

Compound B may contain the same type of cationic precursor or different types. Thus, compound B may be defined as B ₁ B _2,... B _j , where the index j is various, including all forms included in the dominant pH diagram (ie, compound B can be a salt or a base). Represents the number of positive cation precursors. In one particular embodiment, the indices i and j can be the same or different. Compound B is preferably a liquid, but can also be a solid or a gas. Specific examples of Compound B include, but are not limited to, 2-aminoethanol, 2,2′-iminodiethanol and 2,2 ′, 2-nitrilotriethanol. In a preferred embodiment, compound B is 2-aminoethanol or 2,2′-iminodiethanol.

  Those skilled in the art will understand that A and B work together, and that the structure of the biomass is reached without reaching very high temperatures that will partially or totally denature or burn lignin, hemicellulose and / or cellulose. It will be understood that the selection is made to form a couple AB with sufficient mixing enthalpy to modify. If the enthalpy is too strong, chemically to prevent denaturation or combustion (ie by adding a neutral solvent such as ethanol or cold water) or physically to prevent denaturation or combustion (ie by cooling the reactor) It is possible to artificially cool the reaction.

  Usually, the anion (Compound A) and the cation (Compound B) are added separately in two different phases. In certain embodiments, compound A is added in the first phase before compound B, while in other embodiments, compound B is added in the first phase and then compound A is added in the second phase. The In certain embodiments, a certain time between the two phases (ie, the minimum contact time before the addition of the second compound to the mixture comprising the first compound) is sandwiched. The time is only a few seconds or minutes (eg, about 15 seconds, about 30 seconds, about 45 seconds, about 1 minute, about 2 minutes, about 5 minutes, about 10 minutes, about 15 minutes, about 30 minutes or more Or the time can be longer (at least 15 minutes, at least 30 minutes, at least 45 minutes, at least 1 hour, at least 2 hours or longer). Those skilled in the art can vary the time depending on various factors and conditions including, but not limited to, the type and state of biomass used as starting material, the identity and amount of compounds A and / or B, etc. I understand that.

  Alternatively, compounds A and B can be carried out by the same molecule when a change in pH corresponding to field dominance mainly produces compound A or compound B. Thus, the addition of A and B becomes dominant when choosing to add those two compounds in that order. Thus, the anion source and the cation source can be a single zwitterion or zwitterionic compound. Thus, the present invention contemplates using zwitterions in combination with or in place of one or both of components A and B. The zwitterions include, but are not limited to, amino acids such as histidine, leucine, lysine, methionine, phenylalamine, thronine, tryptophan, valine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine. Ornithine, proline, glycine, alanine, isoleucine, cystine, selenocysteine, serine, tyrosine), arsenobetaine, betaine, bicine, ceftazidime, cephaloridine, edelfosine, isoionic point, miltefosine, pierifosine, quinonoid zwitterion, tricine, And trimethylglycine.

  Alternatively, an anion / cation source may already be present in the biomass. In such cases, compound A or B may be omitted from the reaction. For example, some components (eg, betulinol, lupeol, oleanolic acid, betulinic acid, etc. contained in birch bark) may already be present in the biomass, for example, in the bark of some trees. is there.

  Without being bound by any theory, the impregnation of compound A or B into the biomass causes an expansion of the biomass volume that causes the breakage of hydrogen bonds and van der Waals bonds due to the space occupation of one or more external molecules Or an increase can be caused. In addition, the exothermic reaction that occurs during the treatment of the present invention weakens the intermolecular bonds that exist between lignin, cellulose and hemicellulose and eventually cleaves to produce cellulose pulp containing solubilized hemicellulose and solubilized lignin. Within that impregnated biomass, compound B (or A if A is added first) reacts with compound A (or B if A is added first) to convert O-methyl groups to —OH groups. It is postulated that the lignin is chemically modified (Wallis AFA. 1976. Wood pulping with mono-, di- and triethanolamine. Appita 31 (6): 443-448).

  Those skilled in the art understand how to select an acceptable amount of compounds A and B depending on the specific experimental conditions and the desired production. Typically, the reaction and mixed enthalpies are sufficient to break or break the intermolecular bonds existing between cellulose, lignin and hemicellulose while maintaining the original or natural chemical and physical molecular structure of each component. The amount of compounds A and B is adjusted to produce the correct amount of energy.

  The present invention includes hard wood and soft wood including stems, bark, branches, roots and leaves, herbaceous plants, cannabis, firewood, vegetable waste, waste wood, wood chips, algae, paper, cardboard, etc. It is generally applicable to non-limiting woody biomass and plant biomass and derivatives. Biomass can also be made from mixed biomass sources.

  According to certain embodiments, the treatment of the present invention may be performed before any contact with the anion source and / or cation with any undesirable impurities, contaminating contaminants, mud or extractable products (wax, tannins, minerals, essential oils, Cleaning or washing the biomass to remove pectin, vitamins, etc.). This cleaning can help to retain only the basic components of the biomass (ie cellulose, lignin, hemicellulose). For example, the treatment may include steps intended to prepare or mercerize biomass (eg, mercerize wood chips). Biomass cleaning can be done with or without surfactants, with cold, hot water, or steam, with ultrasonic or microwave, mercerised in solvent (eg ethanol) Can be performed according to several known processing methods including, but not limited to, washing by using.

  The process of the present invention can be carried out at room temperature (about 20 ° C.) and ambient pressure (1 atm or about 760 mmHg). Thus, since such energy is generated by the added reagent and / or the biomass itself, there is no need to add or subtract thermal energy. There is no mechanism required to raise or lower the pressure during the reaction.

  The process according to the invention can be carried out in an open or closed reactor. Suitable reactors include reactors made of stainless steel, glass, pyrex, high density polyethylene (HDPE) or other plastics, or preferably any suitable material that is resistant to corrosion, medium to high temperatures and pressure. obtain. In one particular embodiment, the reaction / extraction according to the present invention occurs in a simple non-pressurized HDPE open reactor.

Consequently, the process of the present invention includes the possibility of adjusting temperature and / or pressure in addition to that produced by the desired reaction enthalpy and mixing enthalpy. In certain embodiments, the process is performed inside the reactor, and the process includes control of temperature, atmosphere, and / or pressure within the reactor. For example, the temperature in the reactor can be between about −20 ° C. and about 270 ° C. In some embodiments, the temperature in the reactor is between about 15 ° C and about 150 ° C. In some embodiments, the temperature in the reactor is between about 30 ° C and about 140 ° C. If desired, the temperature in the reactor can be controlled and adjusted to be within the desired value range using any suitable technique (eg, cooling, heating, pressurization, etc.). The atmosphere in the reactor may be air, nitrogen inert atmosphere, CO ₂ -free atmosphere, O ₂ -free atmosphere, or the like. If desired, the atmosphere in the reactor can be controlled and controlled to be within the desired conditions using any suitable technique (specific gas injection, elimination of unwanted gases, addition of chemical reaction with O ₂ , etc.). Can be adjusted. The pressure in the reactor is about 0.003 atm (about 2 mmHg) to about 40 atm or more (eg, 0.003, 0.005, 0.01, 0.05, 1, 2, 3, 5, 10, 20, 30, 40 atmospheres, etc.). In preferred embodiments, the pressure is about 1 or 2 atmospheres. If desired, the pressure in the reactor is desired using any suitable technique (using a sealed reactor, creating or pressurizing a vacuum, modifying the proportion of reactants (eg, Compound A, Compound B, biomass), etc.) It can be controlled and adjusted to be within range.

  In some embodiments, the treatment further comprises reducing the viscosity of the exothermic reaction involving Compound A and Compound B. This can be done by the addition of Compound C which reduces the viscosity of the mixture and / or slows the reaction (inert or not inert). Compound C can be an aqueous solvent (eg, water), a non-aqueous solvent (eg, ethanol), or a combination thereof. Usually, compound C is added after the delignification and cellulose extraction steps (FIG. 1, 180), preferably after compound B (or after compound A, depending on the order in which both products were added to the reaction). Compound C may be added after a certain time and allowed to react. The time can be only a few minutes (eg, about 1 minute, about 2 minutes, about 5 minutes, about 10 minutes, about 15 minutes, about 30 minutes or longer), or the time is longer (at least 15 minutes, at least 30 minutes, at least 45 minutes, at least 1 hour, at least 2 hours, or longer).

Those skilled in the art will appreciate that the experimental conditions selected in the process of the present invention will vary depending on a number of factors, and that various choices can be made by the operator. For example, those skilled in the art understand that avoiding the improper selection of compounds A and B, and the unfavorable experimental conditions that can lead to partial or incomplete realization or failure of the process, or unsuccessful cellulose extraction. Understand avoidance. Examples 1-5 below provide examples of appropriate experimental selection depending on the particular purpose. One skilled in the art understands that experimental parameters need to be selected at various steps of the process to reach different results. Examples of tunable parameters that can affect the final result are: qualitative and quantitative selection of Compound A, qualitative and quantitative selection of Compound B, additional possibilities of Compound C, biomass properties and Condition (wood, vegetables, type, homogeneity, aging, decay, etc.), whether the biomass has been cleaned and the specific cleaning method used, biomass size (eg wood chip and sawdust size), use The temperature and pressure conditions, the duration of each step, the exact sequence of each step (e.g. A before B or its), whether raised or lowered artificially by the operator or operator Conversely), closed reactor versus open reactor, pressurized or non-pressurized reactor, controlled atmosphere conditions in the reactor (inert, CO ₂ free, oxygen free), temperature, etc. But these Not a constant.

  According to a particular embodiment, the treatment according to the invention further comprises isolation from cellulose pulp components contained in the biomass. For example, it may be possible to isolate cellulose, lignin, hemicellulose, waxes, tannins, minerals, essential oils, pectin and vitamins.

  Any suitable known technique and method can be used to isolate these components. For example, cellulose isolation can include one or more of the following optional steps: a washing step, a drying step, a bleaching step, a grinding step, and a sieving step. The resulting cellulose may be modified according to specific operating conditions, or may retain all natural molecular properties or may be functionalized. The ions can be removed, for example, using zinc metal to eliminate nitrate ions present in the solution. Another possible washing treatment using bicarbonate brings the pH value of the cellulose in the range of 5-7. A second wash with distilled water and potassium carbonate removes the ions and salts that would have been added by this last step.

Type I cellulose, including cellulose according to the present invention, can be obtained by simple chemical manipulations known to those skilled in the art (eg, Mazza, 2009, Modification chimique de la cellulose en milieu liquide ionique et CO ₂ supercritique, Universite de Toulouse, France, 172 p.) can be converted to other variants such as type II cellulose, type III cellulose, and type IV cellulose. Thus, the present invention encompasses such conversion and includes type II cellulose, type III cellulose, and type IV cellulose obtained from cellulose I according to the present invention.

  1, 2A and 2B illustrate one particular embodiment for isolating cellulose in accordance with the present invention. Process (100) includes a preparation step (120). As an example, the preparatory step (120) may require conditioning of the biomass (eg, cleaning of the biomass from coarse contaminated contaminants and disruption of the biomass) and solubilization and necessity of compounds A and B prior to carrying out the treatment. Including one or more preliminary steps such as selection of experimental parameters.

  The process described in FIG. 1 further includes an optional biomass washing step (140). This step is usually to exclude unwanted contaminating contaminants, mud and extractable products from the biomass to retain only the basic components of the biomass (cellulose, lignin, hemicellulose). The biomass washing step (140) may be performed before, after, or simultaneously with the preparation step (120).

  Once the preparation step (120) and the washing step (140) are complete, the process (100) involves a mixing step in which the biomass is contacted with compound A (160) as shown in FIG. 2A. In this stage, biomass (2) is contacted with compound A (1) in a reservoir or reactor by adding compound A to the biomass or by adding biomass into compound A. For example, different types of reactors, such as continuous reactors, countercurrent reactors, or batch reactors, can be used to contact the biomass with Compound A. Compound A can be added at any stage prior to delignification, such as, for example, a washing stage and a crushing stage.

  Considering the affinity of compound A (1) that permeates biomass, the contact step (160) between biomass (2) and compound A induces an exothermic reaction and the expansion (170) of the biomass and reaction enthalpy and mixed enthalpy ΔH Result in an example combination. At that time, depending on the experimental parameters, pressure and temperature increases, cellulosic gas emissions and viscosity increases can be observed. There may then be partial or complete modification of the biomass component.

  Those skilled in the art will know that the nature and concentration of Compound A, the amount and size of biomass, and the timing or duration of the contacting step (160) of biomass and Compound A are part of the experimental parameters and will vary depending on the expected results Understand what you can do.

  One of ordinary skill in the art can contact compound A (1) with biomass (2), resulting in partial or complete reaction, absorption, or adsorption, depending on the method of contacting, It is also understood that it remains unused or in excess in solution.

  It can then be decided to isolate or separate the soaked biomass from compound A in solution for use in the next step only soaked biomass. It is also possible to reuse the soaked biomass in the next step and sequester it for a certain period of time before contacting with compound B.

  Further, in the particular embodiment shown in FIGS. 1 and 2A, the process (100) includes a delignification and cellulose extraction step (180) after contacting the biomass (160 and 170) with Compound A. According to this particular embodiment, compound B (4) is a product or mixture resulting from the contacting step (160) (these products are biomass impregnated with compound A and a solution containing impregnated compound A). Added directly. For example, B can be added as in the contacting step (160) in a continuous reactor, countercurrent reactor, or batch reactor. The delignification and cellulose extraction step (180) may occur in step (160) where Compound A and biomass are contacted together.

Without being bound by any theory, the delignification and cellulose extraction step (180) is a reaction between Compound A and Compound B, for example when the compound A is an amine or polyamine It is postulated to cause a reaction that can be described by the chemical formula:
^{N-RR'R '' + H +} + anion ^{- → [NH-RR'R ''} ] + + anion - + ΔH
Where
N = nitrogen R, R ′ and R ″ = radical H ⁺ = hydrogen ion ΔH = enthalpy.

  This reaction between compounds A and B causes, above all, the production of possible ionic liquids AB while still releasing the mixing enthalpy and reaction enthalpy ΔH.

  The reaction (160) between compounds A and B allows at least partial solubilization of hemicellulose and lignin. Ultimately, the treatment comprises a heterogeneous viscous or semi-liquid mixture containing a colored solid material (7) containing natural or modified cellulose containing most or all lignin and dissolved lignin and hemicellulose ( 8) to produce a gelatinous material or cellulose pulp composed of The heterogeneous viscous mixture (8) is composed of several components such as Compound A, Compound B, Solution AB and / or ionic liquid residue, hemicellulose, degradation products of cellulose and lignin (eg glucose and furfural), wax, tannin, It may contain minerals, essential oils, pectin, vitamins, other extractable products or various residues or contaminants (such as mud, metal dust or pieces, plastic dust or pieces).

  In one particular embodiment shown in FIGS. 1 and 2B, the process (100) includes a separation / filtration step (200) for separating solid material (7) from the heterogeneous viscous mixture (8). In one particular embodiment, the solid material (7) and the heterogeneous viscous mixture (8) are placed on a filter (9) that allows separation of the heterogeneous viscous mixture (8) and solid material (7). . At the end of the filtration, the heterogeneous viscous mixture (8) has passed through the filter while solid material containing cellulose (12) is collected from the filter (9).

  It may be advantageous to accelerate or accelerate the separation / filtration step (200) by using a vacuum system under the filter. The filter (9) can be a sintered silica filter, a glass fiber filter, or a polyester or polymer filter. Selection of separation / filtration methods is known by those skilled in the art and is based on experimental selection. Separation (200) may be performed, for example, by filtration, pressure filtration, centrifugation, evaporative drying or sedimentation prior to vacuum, pumping or any combination of these methods and other methods not described.

  In one particular embodiment, the wash / bleach / dry step (220) is implemented after or simultaneously with the separation / filtration step (200) as shown in FIG. This step is optional and can be omitted. In order to wash the solid material (7) in the separation / filtration step (200), the solid material (7) can be washed in a solvent. The solvent selected is preferably neutral to cellulose, lignin and hemicellulose. As an example, water or ethanol can be considered neutral. Where water is selected, it may be preferable to use distilled water, deionized water, or demineralized water to prevent contaminants from untreated water.

  Cellulose (12) can be bleached (220) in several ways and with various reagents such as, for example, hydrogen peroxide or hydrochloric acid.

  Cellulose (12) may be dried (220). The drying can be performed, for example, using an oven or outdoors (14).

  The biomass and compound A contacting step (160), chemical separation step (180) and separation / filtration step (200) are performed once or several times to increase the proportion of cellulose in the solid phase (7). be able to. Thus, the term “biomass” as used herein from other steps such as the previous extraction step or contacting step (160), chemical separation step (180) or separation / filtration step (200). It also includes the resulting solid phase.

  Using mechanical work (eg, agitation, mixing, blending, or the like) at a particular stage of the process to increase efficiency, eg, mixing compound A and biomass during the contacting step (160) It may also be useful according to the present invention to mix the biomass during the chemical separation step (180) or any other step in which compounds, agents, reactants, or solvents are used.

  Those skilled in the art will appreciate that the present invention may provide numerous benefits or advantages over currently known techniques. Of course, the nature and degree of these advantages are used (eg, for the type and state of biomass used as starting material, identity and amount of compound A and / or B, etc.) and specific conditions and experimental parameters. Depending on the choice of A non-comprehensive, non-cumulative list of possible benefits is then provided: enabling extraction of natural or modified cellulose from various biomass components, natural types from various biomass components Or enables extraction of modified lignin, enables extraction of natural or modified hemicellulose from various biomass components, provides reaction in addition to the energy originally contained in compounds A and B Small scales in areas where energy is difficult to produce, expensive, scarce, or non-existing, and / or by not requiring external energy to regulate the supply of temperature and pressure parameters Allows the installation of unit equipment, the overall process generally (depending on experimental parameters) than traditional chemical extraction processes Respect environmental regulations, adapting to small scale industrial equipment and light industrial equipment, not requiring water, making it difficult to use water or developing small unit equipment in non-existing areas The possibility of reducing or avoiding the need for water treatment by recycling some or all of compound A or B or C and the final product to exceed, or as a precursor to ionic liquids To reduce or avoid the possibility of using environmentally friendly chemicals, the possibility of reusing or reusing some or all of the final product of ionic liquid AB that may be formed, denaturation or degradation of biomass Use low levels of enthalpy and preserve the original chemical and physical properties (eg type and structure) of cellulose, lignin and / or hemicellulose Sex.

  It is understood that the embodiment of FIGS. 2A and 2B is just one of many possible embodiments of suitable delignification and extraction processes. One skilled in the art understands that some steps may be optional and the order of the steps may vary depending on the situation.

Isolated cellulose The present invention also relates to an isolated cellulose obtained by the treatment described herein. In one embodiment, the isolated cellulose is at least 95% (w / w) (dry weight) microcrystalline cellulose (MCC) after crushing for 3 minutes after delignification, washing and drying. And / or less than 1% (w / w) (dry weight) nanocrystalline cellulose (NCC).

  As described below in Example 6, the cellulose of the present invention contains a number of distinct, advantageous and / or useful features when compared to known Type I or Type II cellulose. Table 1 provides a summary.

Thus, another aspect of the present invention provides the following features:
(I) the percentage of crystallin cellulose lower than 80% (w / w);
(Ii) including fibers characterized by a length / width ratio of 1 or more;
(Iii) FTIR spectrum including a peak at 1730 cm ⁻¹ ,
(Iv) RX spectrum including peaks at 2θ = 29.9 and 38.3,
(V) including a cellulose particle group composed of at least 55% of particles having a length / width ratio of greater than 3.
(Vi) an incomplete ratio of 110% or less,
(Vii) comprising a group of fibers having an average length of about 10 μm to about 70 μm;
(Viii) the ability to remain uniformly spread at a density of 1000 fibers / mm ² or higher without the need for a dispersant,
(Ix) containing less than 1.5 ions per fiber;
(X) a measured conductivity of less than 50 μS · cm ⁻¹ ,
(Xi) ability to coalesce and form a film;
(Xii) ability to improve epoxy resin refining by at least 30%;
(Xiii) ability to improve reticulation of epoxy resin by at least 18% compared to Avicel PH101;
(Xiv) a group of fibers comprising an incomplete ratio that is at least 50% lower than the commercially available Avicel type I cellulose fiber group;
(Xv) at least 90% pure,
(Xvi) containing less than 1.5% lignin,
(Xvii) containing less than 15% hemicellulose;
(Xviii) having a pH of about 6.5;
(Xix) containing about 5.8% (w / w) moisture,
(Xx) having an onset of decomposition above 250 ° C when mixed with epoxy resin;
(Xxi) miscible to at least 15% (weight / weight) in epoxy resin;
(Xxii) contain a sedimentation rate that is at least 20% slower than Avicel PH101;
(Xxiii) contain a coefficient of expansion that is at least 125% higher than Avicel PH101;
(Xxiv) Degree of substitution of alcohol functional group equal to 3 (DS)
For isolated cellulose of type I comprising one or more of

Applications A wide variety of products may benefit from the use or incorporation of cellulose according to the present invention. These uses and applications include
Cellulose: paper, fiber bedding and litter (for pets or livestock), sound insulation and insulation, textile materials, filters, dietary fiber for human or animal nutrition

Microcellulose:
(A) Microcrystalline cellulose: food additives (emulsifier, anti-caking agent, anti-tack agent, dispersant, stabilizer, thickener, filler, polish, coating agent, foaming agent, carrier, dietary fiber), Excipients for medical and beauty products (b) amorphous microcellulose: saccharification from cellulose to glucose by fermentation, ethanol production, protein production, emulsifiers or stabilizers, raw materials for functionalization

  Nanocellulose and / or microcellulose: microfilter paper for drinking water, automobiles, and analytical filter paper; oil recovery applications, biocomposites for bone replacement and dental restoration, medical barriers, light-shielding curtains, pharmaceutical and drug delivery, food Additives (non-calorie food thickeners) and cosmetic additives (emulsification / dispersion), improved paper and building products, security papers (such as protective substances against oxygen, water vapor, grease / oil in food packaging, etc. Advanced packaging or "high-end" packaging, high strength spun fibers and fabrics, environmental protective clothing; additives for coatings, paints, lacquers and adhesives, reinforced polymers and innovative bioplastics, advanced reinforced composites Materials, recyclable interior and structural parts for the transportation industry, air transport structures, iridescent films and protective films, iridescent dyes, light exchange films, dyes Ink, electronic paper printer, innovative dressing and new fillers for papermaking (reinforcing agent), the fuel cell, switchable optical filter and barrier

Functionalized cellulose: The cellulose hydroxyl group (—OH) reacts partially or totally with various reagents to produce derivatives with useful properties, mainly cellulose esters and cellulose ethers (—OR). Can be included, but is not limited to these.

Organic ester derivatives are: a) Cellulose acetate: film, plastic products (tool handle, eyeglass frame, toothbrush), high quality textile fibers and bands, optical films for LCD technology, fibers for filter media, tobacco filters,
b) Cellulose triacetate: shrink-resistant and form-stable fibers, special photographic films, packaging, semipermeable membranes used for water purification,
c) Cellulose propionate: Thermoplastic, (glasses frame),
d) Acetylpropionyl cellulose: nail care, printing ink,
e) Acetylbutylcellulose: Thermoplastic (including automotive exterior parts, tool handles, pens, blister packaging, outer wall lacquers, lenses, and plastic films.

Inorganic ester derivatives are a) cellulose nitrate: nail polish, ink, lacquer, explosives, celluloid, propellant,
b) Cellulose sulfate: Contains oil recovery, paint, paper, textiles, cosmetics, bactericides.

Ether derivatives are a) methylcellulose (E461): anti-sticking agent, emulsifier, thickener, stabilizer, laxative, artificial tears, wallpaper paste,
b) Ethylcellulose (E462): a commercially available thermoplastic used in coatings, inks, binders and controlled release chemical tablets,
c) Ethyl methyl cellulose (E465): emulsifier, thickener, stabilizer, foaming agent d) Hydroxyethyl cellulose: gelled thickener, drilling fluid e) Hydroxypropyl cellulose (E463): thickener, filler, food Fiber, anti-flocculating agent, emulsifier,
f) Hydroxyethyl methylcellulose: production of cellulose film,
g) Hydroxypropyl methylcellulose (HPMC, E464): viscosity modifier, gelling, foaming and binder,
h) Ethyl hydroxyethyl cellulose (E467): cosmetic additives (binder, emulsifier, stabilizer, film former, viscosity control additive),
i) Carboxymethylcellulose (CMC, E466): food additives (emulsifiers, thickeners, stabilizers), human lubricants, toothpastes, laxatives, thinning agents, aqueous paints, detergents, textile sizing, various paper products , Lubricants in non-volatile eye drops, and soil suspension polymers in laundry detergents.

Additional possible uses:
-Electrochemical preparation of (polyaniline) cellulose, (chlorophyll-fullerene) cellulose derivatives for bio-based photocurrent systems (Mari Granstrom, Finland, cellulose derivatives: Synthesis, properties and application),
-Modification of cellulose surface with organosilane for mechanical properties of paper and its softness (Olivier Paquet-dissertation),
-Use of pulp and paper to produce Li-ion batteries and cellulose fiber treatment (Lara Jabbour-Thesis)
-Production of photocatalytic paper (Souhelia Adjimi-dissertation).

Composite Material Another aspect of the present invention relates to a composite material comprising a resin and / or curing agent mixed with a cellulosic material, preferably an isolated cellulose as described herein. In certain embodiments, the composite material includes a number of characteristic, advantageous, and / or useful features when compared to the existing composite shown in Example 6.

  According to the invention, any suitable resin and / or curing agent may be used for the composite material. Examples of epoxy hardeners include aliphatic polyamines, aolyamino-amides, aromatic polyamines, acid anhydrides, monoethylamine (MEA) derived boron trifluoride complexes, and dicyandiamide. It is not limited to. Examples of epoxy resins include, but are not limited to, bisphenol formalin, phenol novolac, cycloaliphatic, and hydantoin. Examples of polyester curing agents include, but are not limited to, methyl ethyl ketone peroxide, acetyl ketone peroxide, cycloexanon and peroxide. In a particular embodiment, the resin is an epoxy resin or a polyester resin. In certain embodiments, the resin is Epolam 2015 or Epon 862 ™.

  In some embodiments, the composite material is greater than 10% (weight / weight), or greater than 15% (weight / weight), or greater than 20% (weight / weight), or 25% (with epoxy resin) Weight / weight), or more than 30% (weight / weight), or more than 35% (weight / weight). Preferably, the resin is an epoxy resin. Preferably, the cellulose is an isolated cellulose described herein and / or obtained according to the process of the present invention. In a particular embodiment, the resin is an epoxy resin comprising between about 15% and about 36% (weight / weight) of isolated cellulose according to the present invention.

  In some embodiments, the composite material includes an epoxy resin and cellulose, and the constituent material is 15% or more, 20% or more, 30%, as judged by Young's modulus, as compared to the epoxy resin not including the cellulose. Thus, it has an improved elasticity of 40% or more, 50% or more, or 53% or more.

  Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific methods, embodiments, claims, and examples described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims appended hereto. The invention is further illustrated by the following examples. These examples should not be construed as more restrictive.

These abbreviations are used in subsequent examples:
MXG Mannose, xylose, galactose HMF hydroxymethylfurfural HmO hemicellulose derivatives and other products ASL acid soluble lignin AIL acid insoluble lignin LI1 2-aminoethanol LI2 2,2′-iminodiethanol Cel cellulose lig lignin.

Examples 1 to 5: Cellulose extraction from woody biomass The experimental parameters in all subsequent examples are listed in Table 2 below.

  For each example, the biomass was first chipped and washed (water and ethanol) to promote delignification and to remove most of the unwanted contaminating contaminants, mud and extractable products.

  The biomass was then combined with a solution of Compound A to allow reaction enthalpy and mixing enthalpy to occur at least partially. After a few minutes, Compound B was added directly into the solution containing Compound A and biomass to finally form ionic liquid AB. After a certain period of time, these reactions resulted in a cellulose pulp containing i) a solid phase composed primarily of cellulose, and ii) a heterogeneous viscous mixture containing dissolved hemicellulose and dissolved lignin.

  The viscous and solid phases were then separated by filtration through a sintered silica filter. Purity determined by Amie Sluiter et al., Biomass Program, US Department of Energy, National Bioenergy Center, Biomass Analysis Technology Team, Laboratory Analysis Method, page 143, NREL protocol “LAP-Determination of Structural Carbohydrates and Lignin in Biomass” 2006 edition . Part of this method is ASTM E1758-01, “Standard Test Method for Determination of Carbohydrates in Biomass by High Performance Liquid Chromatography, ASTM, 2007” , 5p.) The free biomass samples that can be extracted were analyzed to determine the amount of structural carbohydrates and lignin in those samples, and the amount of cellobiose, glucose, and hydroxymethylfurfural in those samples. The cellulose content was estimated from the amount, while hemicellulose was estimated from the total content of arabinose, mannose-xylose-galactose, furfural and acetic acid.The amount of acid insoluble lignin (AIL) and acid soluble lignin (ASL) in those samples Also obtained according to this protocol, AIL was determined gravimetrically ASL was determined by UV-visible spectroscopy.

  The resulting filtered solid phase was analyzed by high performance liquid chromatography (HPLC) to determine the breakdown of cellulose, hemicellulose and lignin content according to National Renewable Energy Laboratory (NREL) standards. The results of the analysis are displayed in Table 3 and FIG.

  The results presented in Table 3 and FIG. 3 show that the percentage of cellulose obtained for the experimental conditions described in Examples 2-4 is higher than in Example 1 (control).

  To further confirm that the samples obtained according to Examples 1-4 contain cellulose, hemicellulose and lignin, additional tests (HPLC, AIL, ASL) based on the NREL protocol were performed using similar methods.

  The results of the HPLC test are presented in Table 4 below. The results presented in Table 3 complete and confirm the results presented in Table 3.

Example 5:
200 g of birch chips (Betula papyrifera var. Papyrifera) were washed with 750 ml of tap water, and heated in a microwave oven (maximum setting) for 5 minutes three times. After a fourth wash with 750 ml distilled water, the chips were dried at room temperature for 3 days. Thereafter, the chips were crushed so as to pass through a 10-mesh sieve and mercerized twice in 1000 ml of distilled ethanol for 5-6 days. The washed biomass was again dried for an additional day at room temperature. Thereafter, the chips were finely crushed and sieved through an 18 mesh sieve.

  150 g of washed birch sawdust was placed in a well-mixed open batch reactor made of HDPE that moved under the draft chamber. The reactor was installed half-tilted on the platform and equipped with a bi-directional motor shaft for lateral rotation. 200 ml of concentrated nitric acid (about 70%) was poured into the biomass. The solution was mixed for 12 minutes and allowed to impregnate without mixing for some time (about 3 minutes total). Mixing was done in two directions (each time about 1.5 minutes clockwise and 1.5 minutes counterclockwise). At the end of this time, 100 ml of diethanolamine (reagent grade, 98% or more) was added to the mixture. Stirring was continued for another 10 minutes in the same way but without stopping. As the viscosity of the mixture increased at some point, diluent (95% ethanol, 200 ml) was usually added 2 minutes before the end of the treatment. The temperature gradually increases (about 120 ° C.) after the first minute of contact with nitric acid, then decreases to about 75 ° C. after about 10 minutes, usually just below 100 ° C. immediately after the addition of diethanolamine, Alternatively, the temperature rises again to the ambient temperature and drops again to about 60 ° C. after about 5 minutes.

  The pulp was then washed with ethanol to isolate solid cellulose from the heterogeneous viscous mixture. Usually, at least 8 washes were performed. The cellulose solid fraction was separated by filtration and / or decantation. In order to reach a higher level of purity, the cellulose was washed with potassium carbonate and demineralized water to remove acidic ions, salts, and sugars.

  The washed cellulose was dried at room temperature for 1 day. The cellulose usually weighed between 68 and 72 g. The cellulose was finely pulverized to obtain a desired fraction size. The powder was then sieved for 60 minutes in Ro-Tap ™ with 4 successive sieves of 150 μm, 45 μm and 20 μm, respectively, and four different particle sizes of cellulose powder (less than 20 μm, 20-45 μm, 45 ˜150 μm, over 150 μm).

Example 6 Structural and Molecular Characterization of Isolated Cellulose Cellulose obtained from birch according to the process of Example 5 was further characterized by a series of inspection analyses. The cellulose was also compared with commercially available celluloses I and II.

Fourier transform infrared spectroscopy (FTIR)
Obtained to confirm the properties of cellulose of the present invention as cellulose by subjecting the cellulose fraction obtained from birch chips according to Example 5 to a sieved fraction of less than 20 μm by Fourier transform infrared spectroscopy (FTIR). The spectrum was compared with alpha cellulose (Sigma Aldrich). The FTIR spectral curve of isolated cellulose, the FTIR spectral curve of alpha cellulose, and the overlap of these two curves are shown in FIGS. 4A, 4B and 4C, respectively.

FIG. 4C shows a very good correlation between the alpha cellulose curve and the isolated cellulose curve, confirming that the solid material obtained from the process of the present invention is indeed cellulose. However, as shown in FIG. 4A, the FTIR spectrum of isolated cellulose shows at least one visible difference when compared to the FTIR spectrum of alpha cellulose. This difference appears as a peak at 1730 cm ⁻¹ . As shown in FIG. 4B, the commercial cellulose tested is a type II cellulose that does not have such a peak. The similarities and differences between these two types of cellulose are even more apparent when the two FTIR spectra are superimposed (FIG. 4C). Peak at 1730 cm ^-1 represents C = O at binding carboxyl functional groups (between 1700 and 1750 cm ^-1). This functional group originates from a C═O bond on hemicellulose or is caused by oxidation of isolated cellulose.

After the isolated cellulose was thoroughly washed as described in Example 5, a subsequent Failing alcohol test was performed on the isolated cellulose. The test was found to be negative, meaning that the isolated cellulose did not contain sugar and therefore did not contain hemicellulose. The test thus confirms that the 1730 cm ⁻¹ peak is rather caused by the oxidation of isolated cellulose.

Isolated cellulose has a strong tendency to oxidize as represented by the following equation:
R—CH ₂ —OH + 1 / 2O ₂ → R—COOH + H ₂ O, and R—COOH + OH ⁻ → R—COO ⁻ + H ₂ O

Bacterial cellulose is type I cellulose (Brown EE, 2007, Bacterial cellulose / thermoplastic polymer nanocomposites, MSC, Washington state university, p. 109), but Avicel PH101 does not exhibit such a peak. Not shown (Designing enzyme-compatible ionic liquids that can dissolve carbohydrates, Supplementary Material (ESI) for Green Chemistry, Royal Society of Chemistry 2008, 5p. Fig. 4). This strongly suggests that the peak at 1730 cm ⁻¹ is a unique feature of the isolated cellulose according to the present invention.

Furthermore, the absence of an aromatic peak at 1505 cm ^-1 represents that lignin has been completely removed during the cellulose extraction process (FIG. 4A), which is a measure indirectly indicating that the isolated cellulose does not contain lignin.

X-Ray Diffraction Analysis of a sample of cellulose fraction less than 20 μm obtained from white birch chips according to Example 5 to determine cellulose crystallin structure and atypical pseudomorphic type (I or II) Was analyzed.

  Figures 5A and 5B are obtained from Cellulose I (Avicel PH101, FMC Biopolymer) and Cellulose II (Olga Biganska 2002, Etude physico-chimique des solutions de cellulose dans la N-methylmorpholine-N-oxyde, PhD thesis, National Mining School, Paris A typical X-ray spectrum.

  The X-ray diffraction of the fraction less than 20 μm of isolated cellulose according to the invention is very different as shown in FIGS. 5C and 5D. In type II cellulose, major peaks are present at 2θ = 12.0 (1-10), 20.0 (110), 21.9 (020) and 35 (004), while the isolated cellulose has 2θ = The results indicate that it is Form I due to the presence of four peaks at 15.1 (1-10), 16.6 (110), 22.7 (2002), 34.5 (004). This is confirmed by the correlation of the spectra when the type I reference material and the isolated cellulose are superimposed (FIG. 5D). However, two additional peaks appear at 2θ = 29.9 and 2θ = 38.3. These peaks are probably (102) lattice plan for 2θ = 29.9 and (12-4) for 2θ = 38.3 (A. French 2013, Idealized powder diffraction patterns for cellulose polymorphs. Cellulose, August 2013) and is absent from the X-ray spectrum of other type I celluloses.

Crystallinity Several methods are used to determine crystallinity. One of those methods is X-ray spectral deconvolution. According to this method, the crystallinity is equal to the peak area of the lattice plane with respect to the entire curved surface.
Percentage of crystallinity = (peak surface / curved surface) × 100

  Noise and artifacts must be removed to measure the crystallinity of the isolated cellulose. Calculations were made using a Mercury modeling tool that approximated the experimental RX curve to a Gaussian distribution and displayed amorphous and crystallin peaks. The crystallinity was calculated for four samples and the results are shown in Table 5 below.

  Thus, the present invention is about 80% (weight / weight) or less, or about 75% (weight / weight) or less, or about 74% (weight / weight) or less, or about 73% (weight / weight) or less, or about Includes isolated cellulose characterized by a percentage of crystallin cellulose of 72% (w / w) or less, or about 71% (w / w) or less, or about 70% (w / w) or less. In one particular embodiment, the crystallinity of the cellulose is between 70% (w / w) and 74% (w / w).

Homogeneity of size and shape A 20-45 μm fraction of cellulose obtained from birch chips according to Example 5 was observed under both electron microscope and SEM microscope at both 200 μm and 20 μm scales, type I Avicel Comparison with PHP101 cellulose (FMC Biopolymer).

  Scanning electron microscopy (SEM) microscopic imaging of the isolated cellulose is shown in FIGS. 6A and 6B. FIG. 6A displays fibers that are well-defined and uniform in size and shape. In this particular picture, the average length of the fibers is 40.4 μm (standard deviation = 30.2 μm) and the average width is 8.1 μm (standard deviation = 4.7 μm). It was also possible to observe cellulose particles having a size smaller than 1 μm (FIG. 10).

  The length / width ratio is about 5. Such a ratio characterizes a shape that is five times longer than its width, so it is simply in contrast to other type I celluloses that are very non-uniform due to several rod-shaped fibers and many spherical structures. The cellulose release is clearly identified as rich in fibers (FIGS. 6C and 6D). On the smaller scale (FIG. 6B), the fibrils exhibit a regular shape without face holes, cracks or protrusions.

  The following results are obtained by counting cellulose particles having a length / width ratio of more than 3 in the 400 μm × 400 μm sampling zone on FIG. 6A (Table 5B).

  By defining cellulose fibers as cellulose particles having a length at least three times their width, 55% of the analyzed isolated cellulose particles can be considered as fibers.

  Thus, the present invention provides at least 25%, or at least 30%, or at least 40%, or at least 45%, or at least 50%, or at least 55%, or at least 60% of particles having a length / width ratio greater than 3. Including isolated cellulose comprising a group of cellulose particles composed of%. In certain embodiments, the isolated cellulose comprises a group of cellulose particles composed of at least 55% of particles having a length / width ratio of greater than 3.

  The size distribution of the cellulose length and width is shown in FIGS. 6A and 6B and is represented by the histograms shown in FIGS. 7A and 7B. The histograms of FIGS. 7A and 7B show that 90% of all cellulose fibers are in the 10-70 μm length range, which is clearly different from that of the comparative cellulose of FIG. 7C, where Most particles are between 1 μm and 40 μm and are spherical.

  Thus, the present invention has a length of 1 or more, or 1.5 or more, or 2 or more, or 2.5 or more, or 3 or more, or 3.5 or more, or 4 or more, or 4.5 or more, or 5 or more. Includes isolated cellulose comprising a group of cellulose fibers characterized by a / width ratio.

Physical Appearance A high magnification image (FIG. 6A) of an electron micrograph of a 20-45 μm fraction of cellulose obtained from a birch chip according to Example 5 shows the regularity of the cellulose fibers. The surface of the cellulose appears to be regular and smooth, in contrast to other type I celluloses available on the market (FIGS. 6C and 6D), with little or no holes, cracks or protrusions. These photographs show that the cellulose fibers preserved their integrity as calculated in Table 5C when compared to existing commercial cellulose. The treatment of the present invention does not use a strong acid to hydrolyze cellulose, nor does it use high heat and high pressure as in the case of a steam explosion characterizing Avicel PH101 cellulose, which is type I cellulose. There are two possible explanations.

  In contrast, the number of defects counted on the isolated cellulose of FIG. 6B is 23 defects per 50 particles, which corresponds to an incomplete ratio of 46%. This number is considerably less than the incomplete ratio of Avicel and Elcema (combined 134% on average) which are commercially available cellulose.

  Thus, the present invention provides 16 defects or less per fiber, 15 defects or less, 12 defects or less, 10 defects or less, or 8 or less defects per fiber. Includes isolated cellulose characterized by an imperfect ratio of 7 points or less, 6 points or less per fiber.

  Thus, the present invention provides no more than 3.5 holes per fiber, no more than 3 holes per fiber, or no more than 2.5 holes per fiber, or no more than 2 holes per fiber, or 1.5 holes per fiber. Includes isolated cellulose characterized by the following holes, or no more than 1 hole per fiber, or no more than 0.5 holes per fiber.

Distribution / Yield Table 6 below provides the results of the average size distribution of cellulose (isolated cellulose) obtained according to Example 5 measured and calculated in 20 cellulose purification experiments performed on birch chips. To do.

  Cellulose fibers of size greater than 150 μm were not calculated because they were sent back to delignification. The total treatment of the present invention produces about 32% (weight / weight) dry cellulose relative to the initial biomass, which is up to 71% of the initial weight of cellulose in the biomass. These results confirm the effectiveness of the treatment given that cellulose is about 45% to 50% of the total woody biomass. Thus, depending on the exact experimental conditions, the present invention may predict a cellulose extraction rate between 60% and 99% depending on the experimental conditions and the expected quality of cellulose.

  Thus, the present invention encompasses treatments that produce cellulose extraction rates of at least 60%, or at least 70%, or at least 80%, or at least 85%, or at least 90% or at least 95% or at least 99% or higher.

  Thus, the present invention includes an isolated cellulose comprising fibers having an average length of about 10 μm to about 70 μm. The nanoparticles should be less than 15 of the total mass.

Another characteristic of the cellulose obtained in Dispersion Example 5 is that this particular cellulose is not charged by sodium ions as it can be standard type II cellulose (for mercerization, the conductivity is See also). As a result, the isolated cellulose of the present invention may be less sensitive or slightly sensitive to electrostatic charges, thereby causing the isolated cellulose of the present invention to become dense or aggregate. This can be prevented. Thus, the type I isolated cellulose according to the present invention is naturally well dispersed (FIG. 6A) and provides the properties of a static-free powder. Image evaluation in FIG. 6A shows that the isolated cellulose particles spread uniformly without agglomeration, contrary to other commercially available type I celluloses such as those in FIG. 6C. In certain embodiments, the isolated cellulose according to the present invention exhibits the ability to remain uniformly spread at a density of, for example, 1000 fibers / mm ² or higher without the need for a dispersant, the present invention Includes isolated cellulose having characteristics.

Conductivity electrostatic charges may be naturally present in the biomass and the corresponding ions may still be present after cellulose extraction. Table 7 provides the results of the analysis performed on screened fractions of cellulose less than 20 μm obtained from birch chips according to Example 5.

  These results indicate that ions are actually present in the extracted cellulose. The results also indicate that the cellulose is not actually charged (ie, less than 1.5 ions per fiber), indicating that the process of the present invention does not have any charge in the cellulose. Indicates that it will not be introduced.

In addition, in one particular example, the cellulose has a measured conductivity of 13 μS · cm ⁻¹ . This value is very close to the value of pure demineralized water, confirming that all free charge may be able to be suppressed from the cellulose when needed.

  Thus, the present invention is less than 100 μS · cm −1, or less than 75 μS · cm −1, or less than 50 μS · cm −1, or less than 40 μS · cm −1, or less than 25 μS · cm −1, or Includes isolated cellulose having a conductivity of less than 20 μS · cm −1 or less than 15 μS · cm −1. Taken together, these results confirm that it is possible to obtain an isolated cellulose that has little or no charge or electrolyte.

According to one particular embodiment of the film, the screened fraction of cellulose obtained from birch chips according to Example 5 below 20 μm was thoroughly washed with water. The water was then evaporated without adding any solvent until the cellulose was dried on the porous glass. A thin layer made of 100% pure cellulose was obtained. The biofilm was about 100 μm thick and translucent and flexible, but it was brittle and easy to tear.

  A similar experiment was performed using commercially available Avicel PH101 cellulose with no success. Rather, the cellulose particles were scattered on the glass surface.

  Acquiring such a film confirms and enables the production of new biofilms that are non-toxic, biocompatible, biodegradable and easy to manufacture.

  Thus, one aspect of the invention provides an aqueous mixture comprising cellulose solubilized in an aqueous solvent, spreading the aqueous mixture on a surface, evaporating the solvent, and coalescing the cellulose. And a film forming method including forming a film.

  Another related aspect of the invention relates to a film of cellulose I. In various embodiments, the film comprises at least 100% (weight / weight) of cellulose type I, having a pH of about 6.3, and having a thickness of about 50 μm to about 300 μm. Features one or more.

Reactivity / Functionalization Both less than 20 μm sieved fraction and 20-45 μm sieved fraction of cellulose obtained from birch chips according to Example 5 were added to epoxy resin (Epolam 2015 ™) to 10 % (Weight / weight) was added and the polymerization of the resin was analyzed on a Brookfield ™ viscometer.

  FIG. 8 shows the corresponding curves for the polymerization of each of these two fractions and one commercial type I (Avicel PH101, FMC Biopolymer) when compared against the Epolam ™ reference material. As shown in FIG. 8 and Table 8, between each composite comprising cellulose according to the invention with a measurable reticulation time (t_cure) acceleration of 10% (weight / weight) compared to the reference sample. Exists.

  These results show that both fractions of cellulose according to the invention significantly improve the setting time over Avicel PH101 (FMC Biopolymer).

  Thus, the present invention provides at least 30%, or at least 35%, or at least 40%, or at least 45% of the refining of the same epoxy resin, as compared to the refining of an epoxy resin that does not contain isolated cellulose, Or including said isolated cellulose exhibiting at least 49% acceleration. The invention further includes an isolated cellulose that improves reticulation of the epoxy resin by at least 18% (eg, 225 minutes vs. 275 minutes) or at least 39% (eg, 167 minutes vs. 275 minutes) as compared to Avicel PH101.

Purity is considered as the percentage of cellulose molecules present in the final product after thorough washing. Purity generally depends on the efficiency of the washing step. Examples 2, 3 and Table 3 show a cellulose percentage close to 85%, while the presence of lignin decreases to less than 1% after 8 washes using ethanol.

Improve purity by adding an additional washing step to remove acidic ions with potassium carbonate (K ₂ CO ₃ ) and then a series of washings using demineralized water to remove sugars and ionic salts It can also be made. This treatment serves to obtain very pure (equal to or close to 100%) cellulose as shown in the section referring to film formation and FTIR analysis.

  Thus, the present invention provides a purity (%) of at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99%, or at least 99.9%. (Weight / weight), measured by MRN 300 MHz).

Color During the process of the present invention, at the end of the reaction (FIGS. 1, 220), the cellulose was usually a slightly off-white color after washing. By using a bleaching agent such as hydrogen peroxide according to customer requirements, the resulting cellulose can be strayed or leave a certain level of impurities.

pH
One gram of a sieving fraction less than 20 μm of cellulose obtained from birch chips according to Example 5 was soaked in 10 ml of pure demineralized water. The pH of the solution was measured with a pH meter, and the obtained value was pH 6.5. This value is exactly the same as the pH measured for demineralized water before contact with cellulose (pH 6.5). This indicates that the isolated cellulose according to the present invention is neutral (ie does not affect pH).

Swelling and Sedimentation 1 gram of cellulose less than 20 μm sieved fraction obtained from white birch chips according to Example 5 and 1 gram of commercial type I cellulose (Avicel PH101, FMC Biopolymer) in 10 ml in a test tube Soaked in demineralized water and allowed to settle. The height of the particles remaining in suspension after various times was measured. The results are presented in Table 9.

  As shown, the settling of the isolated cellulose of the present invention is slower than Avicel PH101 as more particles remain in suspension (higher). Although not shown, it was easier to return the cellulose of the present invention to a suspended state and re-disperse in solution compared to Avicel PH101, the latter having a tendency to remain attached to the bottom of the test tube.

  Thus, the isolated cellulose of the present invention is characterized by a sedimentation rate that is at least 20% slower, or at least 25% slower, or at least 30% slower, or at least 35% slower, or at least 38% slower than Avicel PH101.

  Thus, the isolated cellulose of the present invention is characterized by a coefficient of expansion that is at least 125% higher, or at least 150% higher, or at least 175% higher, or at least 200% higher, or at least 250% higher, or higher than Avicel PH101. To do.

Thermogravimetric analysis (TGA)
Thermogravimetric analysis (TGA) was performed on the screened fraction of cellulose obtained from maple chips according to Example 5 to less than 45 μm. A resin (Epon 862 ™) mixed with a curing agent (Epikure W ™) was mixed with 10% (weight / weight) of isolated cellulose. TGA indicates the loss of mass as a function of temperature. TGA was performed in high purity nitrogen and TGA revealed that the cellulose sample contained about 5.8% moisture and that the onset of decomposition was 314 ° C. (FIG. 9A). These results are measured as a function of the temperature at which the physical and chemical properties of the material increase (at a constant heating rate) or as a function of time (related to a constant temperature and / or a constant loss of mass). I will let you know.

Dynamic thermomechanical analysis (DMA)
A reference epoxy resin (Epon 862 (Epon 862) with or without sieving fraction less than 45 μm of cellulose obtained from maple chips according to Example 5 mixed with a curing agent (Epikure W ™) Trademark)) was subjected to dynamic thermomechanical analysis (DMA). By adding 10% (weight / weight) cellulose to the epoxy resin, the Tg of the epoxy resin decreases from 141 ° C. to 137 ° C., but the storage modulus of the epoxy resin increases by 15%. (FIG. 9B). These results are consistent with the results obtained from Young's modulus measurements (see below) and indicate the ability of the cellulose to improve the mechanical properties of the resin.

Young's modulus Young's modulus, also known as tensile modulus or modulus, is a measure of the stiffness of a resilient isotropic material and is an amount used to characterize the material. Young's modulus is defined as the ratio of the axial stress to the axial strain in the range of stresses for which Hooke's law is valid.

  Young's modulus analysis for epoxy resin (Epolam 2015 ™) with and without a screened fraction of cellulose obtained from maple chips according to example 5 (Epolam 2015 ™) and without (Epolam 2015 ™) Carried out. Briefly, the cellulose was dried between 70 ° C. and 80 ° C. overnight for dehydration. Cellulose was then added and mixed with Epolam 2015 ™ until 1% of the total weight of the final product reached 10% or 36%. Mechanical mixing followed for every 1% addition. When the final grade (10% or 36%) was achieved, the resin + curing agent + cellulose mixture was inserted into the mold for 2 days, after which post-curing was performed (1 hour at 70 ° C.). The composite is now ready for inspection with an Instron ™ tensile tester. The results of these measurements are presented in Table 10.

  Resin containing cellulose is more fragile than the reference material (ie reduction in maximum stress), but with the cellulose according to the invention of 36% of the total mass, the Young's modulus is significant (at least 15%), up to 50% The rise is shown from the results in Table 10.

  Accordingly, the present invention includes a composite material comprising a resin and / or curing agent mixed with isolated cellulose, wherein the composite material has improved elasticity compared to a composite material that does not include isolated cellulose. . In certain embodiments, the elasticity is at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least, as judged by Young's modulus, as compared to the composite material without isolated cellulose. Improved by 40%, or at least 45%, or at least 50%, or at least 53%.

Epoxy reticulated composites, such as epoxies, are made of a mixture of mixed resin and hardener. Resin manufacturers always show the best proportions to optimize curing. In the case of Epolam 2015 ™ and Epikure ™ curing agent, the ideal ratio is 100: 32 (100 parts resin and 32 parts curing agent). Curing agents are expensive and / or more toxic than the resin itself, and there is a need to reduce the proportion of curing agent.

Thus, a new recipe was tested at 100: 27 with the use of cellulose to check how much the cellulose could change the resin / curing agent ratio as illustrated in Table 11.
We handled and manipulated resins, hardeners and celluloses according to principles known to those skilled in the art (all experiments and calculations are CDCQ (Quebec Composite Development, an independent organism responsible for testing new materials) Carried out by the Center)).

  The proportion of additive calculated relative to the weight of the resin was completed by incorporating 5 g of cellulose in 50 g of resin when mixed with 10% additive, In the case of mixing, 17.82 g of cellulose is added.

The degree of reticulation was calculated from FTIR analysis of the peaks according to the following equation:

  The degree of reticulation refers to a measure of the polymerization kinetics within the composite. Post-curing is performed by heating the sample at 70 ° C. for 1 hour to promote the chemical reaction and to ensure that the polymerization is complete.

  Both a less than 20 μm screened fraction and a 20-45 μm screened fraction of cellulose obtained from a birch chip according to Example 5 mixed with a 100: 27 ratio of epoxy + curing agent were produced. It yielded a better degree of reticulation than the 100: 32 ratio reference material recommended by the vendor (91% and 88% vs. 83%, respectively). This represents a benefit in both reducing curative consumption and reticulation efficiency.

  A screened fraction of cellulose less than 20 μm obtained from birch chips according to Example 5 up to 36% (w / w) also improved the reticulation of the reference material in a ratio of 100: 27 (68 % Vs. 52%). Refining at the highest tested ratio (100: 32) was still acceptable and was not far from the manufacturer's recommendations (68% vs. 88%).

  In contrast, commercially available type I cellulose (Avicel PH101, FMC Biopolymer) mixed with a 100: 27 ratio of epoxy + curing agent reduced the reticulation of the 100: 32 ratio of the reference material (60 % Vs. 88%) improved slightly at 100: 27 (60% vs. 52%).

Degree of substitution (DS)
Cellulose is a polymer made of cellobiose units. Each cellobiose is made up of two glucoses, each glucose having three alcohols: one primary alcohol and two secondary alcohols. The oxidation of these three alcohols indicates the degree of substitution of these alcohols.

In various experiments, for changing the acidic functional group of the alcohol in the isolation of cellulose of the present invention in order to increase the degree of substitution, the isolated cellulose of the present invention (ClO ^- was obtained by oxidation of Ni ²⁺ by) Oxidized with NiO (OH). The oxidized cellulose was then subjected to Fourier transform infrared spectroscopy (FTIR) and the resulting spectrum was compared with the spectrum of non-oxidized cellulose. Their spectra are shown in FIGS. 11A, 11B and 11C. FIG. 11C displays overlapping portions of both FTIR spectra, where sample 1 refers to oxidized cellulose while sample 2 refers to unoxidized initial cellulose, showing the change in their peaks. Table 12 summarizes the major changes.

As observed in Table 12, the peaks associated with the alcohol functionality (# 3 and # 4 peaks) disappeared in oxidized cellulose. Furthermore, peak 1 related to the CH ₂ bond also disappeared. Conversely, the second peak (C = O of acidic functional group) is dominant, indicating that all alcohol functional groups (n = 3) have been changed to acidic functional groups, and therefore the substitution degree DS Is equal to 3.

  Thus, the present invention includes an isolated cellulose comprising a degree of substitution (DS) of alcohol functionality equal to 3.

  In the present specification, a heading is included for reference to help search for a specific item. These headings are not intended to limit the scope of the concepts presented herein. These concepts may apply to other items throughout the specification. That is, it is not intended that the present invention be limited to the embodiments shown in this specification. The present invention should be accorded the maximum extent consistent with the principles and novel features described herein.

  Unless otherwise indicated, all numbers used to represent component amounts, reaction conditions, concentrations, characteristics, etc. in this specification and the appended claims are all referred to as “about” in any case. It should be understood that it is modified by words. At a minimum, each numeric parameter should be solved at least by considering the number of significant digits reported and applying general numeric rounding. Accordingly, unless indicated to the contrary, all numerical parameters set forth in this specification and the appended claims are approximate and may vary depending on the intended characteristics. Although numerical ranges and parameters describing the broad range of each embodiment are approximate, the numerical values set forth in the individual examples are reported as accurate as possible. However, any numerical value may have a certain error due to fluctuations in experiments, test measurement methods, statistical analysis, and the like.

  It should be understood that the examples and aspects described herein are for illustrative purposes only, and that various modifications and alterations based thereon are suggested to those skilled in the art.

Claims (49)

A method for producing cellulose pulp, comprising:
Providing biomass comprising cellulose, hemicellulose, and lignin;
Contacting the biomass with an anion source and a cation source, wherein the anion source and cation source are selected to undergo an exothermic reaction with and between the biomass;
An exothermic reaction under conditions and for a time sufficient to break an intermolecular bond existing between lignin, cellulose, and hemicellulose;
Obtaining a cellulose pulp comprising solubilized hemicellulose and solubilized lignin.   The method of claim 1, wherein the biomass provides at least a portion of the anion source.   The method according to claim 1 or 2, wherein the cellulose pulp comprises i) a solid phase mainly composed of cellulose and ii) a heterogeneous viscous mixture containing the solubilized hemicellulose and the solubilized lignin. A method for producing cellulose pulp, comprising:
Providing biomass comprising cellulose, hemicellulose, and lignin;
An anion source A and a cation source B are provided, wherein said anion source A and cation source B are anionic precursors of an ionic liquid of formula AB, wherein said anion source A and cation source B are selected to react exothermically with and between biomass,
Biomass is contacted with an anion source A and a cation source B, where the contacting is carried out under conditions and over time that allow the formation of the ionic liquid AB, where the contact is exothermic. And also breaks intermolecular bonds existing between lignin, cellulose, and hemicellulose,
A method comprising obtaining a cellulose pulp comprising i) a solid phase mainly composed of cellulose and ii) a heterogeneous viscous mixture comprising solubilized hemicellulose and solubilized lignin.   5. The method according to claim 1, further comprising isolating a component selected from the group consisting of cellulose, lignin, hemicellulose, wax, tannin, mineral, essential oil, pectin, and vitamin from the cellulose pulp. The method described.   The method according to any one of claims 1 to 5, wherein the biomass is allowed to react with an anion source before contacting the biomass with the cation source.   The method according to any one of claims 1 to 5, wherein the biomass is brought into contact with the cation source and reacted before contacting the biomass with the anion source. A method for isolating cellulose from biomass comprising:
a) providing biomass comprising cellulose, hemicellulose, and lignin;
b) contacting the biomass with compound A to at least partially impregnate said biomass to obtain impregnated acidic biomass, wherein compound A is an anion source, wherein compound A exothermicly reacts with the biomass;
c) contacting the impregnated acidic biomass with compound B, where compound B is a cation source, wherein compound B reacts exothermically with compound A impregnated in acidic biomass;
d) The intermolecular bonds existing between lignin, cellulose, and hemicellulose are cleaved and subjected to an exothermic reaction under conditions and for a time sufficient to produce cellulose pulp containing solubilized hemicellulose and solubilized lignin;
e) A method comprising isolating cellulose from said pulp.   9. The method of claim 8, further comprising an intermediate step of reducing the viscosity of the exothermic reaction of step d) prior to step e).   10. The method of claim 9, wherein the viscosity reduction comprises the addition of an aqueous and / or non-aqueous solvent.   The method of claim 10, wherein the aqueous or non-aqueous solvent is selected from the group consisting of water and ethanol.   The method according to any one of claims 8 to 11, further comprising the step of separating the impregnated acidic biomass from the unimpregnated compound A before contacting the impregnated acidic biomass with compound B.   The method of claim 12, wherein the separation comprises filtration.   The process e) of isolating cellulose comprises one or more of a washing process, a drying process, a bleaching process, a crushing process, a sieving process, and a milling process, according to any one of claims 8 to 13. the method of.   The contact of step a) and / or the contact of step b) comprises injecting, atomizing, spraying, atomizing, pouring, vaporizing, mixing, and / or spraying of compound A and / or compound B. The method as described in any one of 8-14.   The process according to any one of claims 8 to 15, wherein the cellulose isolated in step e) is type I cellulose.   The method according to any one of the preceding claims, wherein the method is carried out in a reactor, wherein the method comprises adjusting the temperature, atmosphere and / or pressure in the reactor.   The method of claim 17, wherein the temperature in the reactor is adjusted to between about 15 ° C and about 150 ° C. Atmosphere adjusted within the reactor, air, nitrogen inert atmosphere, CO _2-free atmosphere, and O ₂ is selected from the group consisting of non-containing atmosphere, The method of claim 17 or 18.   20. A process according to any one of claims 17 to 19, wherein the regulated pressure in the reactor is about 1 atmosphere.   21. The method according to any one of claims 1 to 20, wherein the anion source is selected from the group consisting of hydrochloric acid, acetic acid, formic acid, phosphoric acid, p-toluenesulfonic acid, and nitric acid.   The method according to any one of claims 1 to 21, wherein the anion source is a liquid.   23. A method according to any one of claims 1 to 22, wherein the cation source is selected from the group consisting of amines, polyamines, phosphines, and polyphosphines.   The cation source is a compound selected from the group consisting of 2-aminoethanol, 2,2'-iminodiethanol, and 2,2 ', 2, -nitrilotriethanol. The method described in 1.   The method according to any one of claims 1 to 22, wherein the cation source is 2-aminoethanol or 2,2'-iminodiethanol.   26. A method according to any one of claims 1 to 25, wherein the cation source is a liquid.   27. A method according to any one of claims 1 to 26, wherein the anion source and the cation source are a single zwitterionic compound.   28. The zwitterion is selected from the group consisting of amino acids, arsenobetaine, betaine, bicine, ceftazidime, cephaloridine, edelfosine, isoionic point, miltefosine, perifosine, quinonoid zwitterion, tricine, and trimethylglycine. The method described in 1.   The method according to any one of claims 1 to 28, wherein the biomass is woody or plant biomass.   Biomass is from the group consisting of hardwood, softwood, waste wood, wood waste, trunk, bark, branch, root, leaf, whole plant, cannabis, corn stalk, peat, straw, vegetable waste, algae, paper, and corrugated paper 29. A method according to any one of claims 1 to 28, which is selected.   31. The method of any one of claims 1-30, further comprising purifying or washing the provided biomass to remove unwanted impurities prior to the contacting.   The isolated cellulose obtained by the method as described in any one of Claims 8-31.   An isolated cellulose characterized by an FTIR spectrum distinguishable from the cellulose type II FTIR spectrum.   34. The isolated cellulose according to claim 33, wherein the FTIR spectrum of the isolated cellulose can be distinguished when superimposed on the FTIR spectrum of cellulose α shown in FIG. 4C.   34. The isolated cellulose of claim 33, wherein the isolated cellulose is type I and is characterized by the FTIR spectrum of FIG. 4A. 36. The isolated cellulose according to any one of claims 33 to 35, wherein the FTIR spectrum of the isolated cellulose is characterized by a peak at 1730 cm- ¹ .   An isolated cellulose characterized by an X-ray spectrum distinguishable from an X-ray spectrum of cellulose type II.   38. The isolated cellulose according to claim 37, wherein the X-ray spectrum of the isolated cellulose can be distinguished when superimposed on the X-ray spectrum of the type I cellulose shown in FIG. 5D.   The X-ray spectrum of the isolated cellulose shows a peak at 2θ = 15.0 (1-10), a peak at 2θ = 16.6 (110), a peak at 2θ = 22.7 (200), and 2θ = 34. 39. The isolated cellulose of claim 37 or 38, comprising 5 (004) peaks.   40. The isolated cellulose according to any one of claims 37 to 39, wherein the X-ray has peaks at 2θ = 29.9 and 2θ = 38.3.   An isolated cellulose, wherein the cellulose comprises a group of particles, the length / width ratio of at least 30% of the particles being greater than 3.   42. The isolated cellulose of claim 41, wherein the length / width ratio of at least 55% of the cellulose particles group is greater than 3.   Divide the total number of holes, protuberances, outgrowths, and fissures identified in the cellulose particle group by the total number of particles in the particle group, and multiply by 100 Isolated cellulose characterized by an incomplete ratio, defined as the value obtained, of 110% or less. Type I cellulose,
i) the percentage of crystalline cellulose is less than 80% w / w;
ii) contain fibers characterized by a length / width ratio of 1 or more,
iii) FTIR spectrum including a peak at 1730 cm ⁻¹ ,
iv) RX spectrum including peaks at 2θ = 29.9 and 38.3 v) The length / width ratio of at least 55% of the cellulose particles is greater than 3.
vi) The incomplete ratio is 110% or less,
vii) including a group of fibers having an average length of about 10 μm to about 70 μm;
viii) have the ability to be uniformly deployed at a density of 1000 fibers / mm ² or more without the need for a dispersant;
ix) having less than 1.5 ions per fiber,
x) The measured conductivity is 50 μS. less than cm ⁻¹ ,
xi) have the ability to fuse to form a membrane;
xii) have the ability to improve the reticulation of the resin epoxy by at least 30%;
xiii) has the ability to improve resin epoxy reticulation by at least 18% compared to Avicel PH101;
xiv) a group of fibers containing at least 50% less imperfection than the Avicel commercial type I cellulose fibers group;
xv) having a purity of at least 90%;
xvi) the lignin content is less than 1.5%,
xvii) the hemicellulose content is less than 15%,
xviii) the pH is about 6.5;
xix) the water content is about 5.8% w / w,
xx) Decomposition start when mixed with epoxy resin is over 250 ° C,
xxi) miscibility with epoxy resin is at least 15% w / w,
xxii) the sedimentation rate is at least 20% slower than Avicel PH101,
xxiii) Expansion rate is at least 125% greater than Avicel PH101,
xxiv) the degree of substitution (DS) of the alcohol functional group is equal to 3,
An isolated cellulose having one or more properties.   45. The isolated cellulose according to any one of claims 32-44, wherein the isolated cellulose is extracted from woody or plant biomass.   A composite material comprising a resin and / or curing agent mixed with the isolated cellulose according to any one of claims 32-45.   47. The composite material of claim 46, wherein the composite material comprises a resin epoxy and the cellulose comprises greater than 15% w / w.   48. A composite material according to claim 46 or 47, wherein the elastic modulus measured by Young's modulus is improved by at least 15% when compared to the composite material without said isolated cellulose.   A composite material comprising a resin and / or curing agent and at least 15% w / w cellulose.