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    • 专利摘要:
    cellulosic nanofilaments, methods for producing cellulosic nanofilaments and for treating a paper product, cellulose nanofilaments, and mineral paper. cellulose nanofilaments of cellulose fibers, a method and a device for their production are described. nanofilaments are simple filaments with widths in the sub-micron range and lengths up to a millimeter bond. these nanofilaments are made from natural fibers of wood and other plants. the nanofilament surface can be modified to carry anionic, cationic, polar, hydrophobic or other functional groups. the addition of these nanofilaments to papermaking supplies substantially improves the concentration of wet continuous sheet and dry leaf strength much better than existing natural or synthetic polymers. the cellulose nanofilaments produced by the present invention are excellent additives for the reinforcement of paper and cardboard products and composite materials and can be used for the production of superabsorbent materials.
    公开号:BR112012028750B1
    申请号:R112012028750-8
    申请日:2011-05-11
    公开日:2020-09-29
    发明作者:Xujun Hua；Makhlouf Laleg；Tom OWSTON
    申请人:Fpinnovations；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [01] This invention relates to cellulose nanofilaments, a method for producing cellulose nanofilaments from natural fibers that originate from wood and other vegetable pulps, the nanofibrillation device used to manufacture nanofilaments and a method of increasing the strength of paper. PREVIOUS TECHNIQUE
    [02] The process and functional additives are commonly used in the manufacture of paper, cardboard and fabric products to improve material retention, sheet strength, hydrophobicity and other features. These additives are usually synthetic water-soluble polymers or emulsifiers or resins derived from petroleum or modified natural products, such as starches, guar gums and cellulose derivatives, such as carboxymethyl cellulose made from the dissolution of the cellulose pulp. Although most of these additives can improve the strength of dry paper, they do not really improve wet sheet resistance to never dry. Still, the high wet web resistance is essential for good paper machine functionality. Another disadvantage of these additives is their sensitivity to the pulp supply chemistry when they can be deactivated by high conductivity and high level of anionic and colloidal dissolved substances. To be effective, polymers must absorb on the surfaces of the fibers and fines and then retained in the web during manufacture. However, since the polymer absorption is never 100x, a large portion of the polymer will circulate in the white water system on the machine where the polymer can be deactivated or lost in the sewage that adds a load to the effluent treatment.
    [03] White bleached kraft fibers are commonly used for the development of strength in the manufacture of paper, fabric and cardboard types as a reinforcing component. However, to be effective, these must be well refined before combining with pulp supplies and added at levels that usually range from 10% to 40%, depending on the type. The refining introduces fibrillation to the pulp fibers and increases their binding potential.
    [04] Turbak et al. In 1983 (US 4,374,702) they described a finely divided cellulose, called microfibrillated cellulose (MFC), and a method for its production. Microfibrilated cellulose is made up of shortened fibers linked with many fine fibrils. During microfibrillation, lateral connections between fibrils in a fiber wall are disrupted to result in partial detachment of the fibrils or fiber branching as defined in US 6,183,596, US 6,214,163 and US 7,381,294. In the Turbak's process, microfibrillated cellulose is generated by the reinforcement of cellulosic fiber pulp, passing repeatedly through small holes in a homogenizer. This orifice generates a high cutting action and converts the pulp fibers to microfibrillated cellulose. High fibrillation increases chemical accessibility and results in a high water retention value, which allows a gel point to be reached at a low consistency. MFC has been shown to improve the strength of paper when used in a high dose. For example, the breaking strength of paper samples made from unbeaten pulp was improved by 77% when the sheet contained 20% microfibrillated cellulose. The length and aspect ratio of the microfibrillated fibers are not yet defined in the patent, but the fibers were pre-cut before passing through the homogenizer. Japanese patents (JP 58197400 and JP 62033360) also claimed that microfibrillated cellulose produced in a homogenizer improves the tensile strength of the paper.
    [05] The MFC, after drying, had difficulty in redispersing in water. Okumura et al. and Fukui et al of Daicel Chemical have developed two methods to allow the redispersion of dry MFC without loss of its viscosity (JP 60044538, JP 60186548).
    [06] Matsuda et al. They described a super-microfibrillated cellulose that was produced by adding a shredding stage before a high pressure homogenizer (US 6,183,596 & US 6,214,163). Even when in the previous description, microfibrillation in the Matsuda process proceeds by branching the fibers while the fiber shape is maintained to form the microfibrillated cellulose. However, supermicrofibrillated cellulose had a shorter fiber length (50 to 100 pm) and a higher water retention value compared to that previously described. The aspect ratio of the super MFC is between 50 and 300. The super MFC has been suggested for use in the production of coated papers and dyed papers.
    [07] MFC can also be produced by passing the pulp ten times through a shredder without further homogenization (Tangigichi and Okamura, Fourth European Workshop on Lignocellulosics and Pulp, Italy, 1996). A strong film formed from MFC has also been reported by Tangigichi and Okamura [Polymer International 47 (3): 291-294 (1998)]. Subramanian et al. [JPPS 34 (3) 146-152 (2008)] used MFC made from a crusher as a main supply component for the production of sheets containing more than 50% filler.
    [08] Suzuki et al. described a method for the production of microfibrillated cellulose fiber which is also defined as branched cellulose fiber (US 7,381,294 & WO 2004/009902). The method consists of treating the pulp in a refiner at least ten times but preferably 30 to 90 times. The inventors claim that this is the first process that allows for the continuous production of MFC. The resulting MFC has a shorter length than 200 pm, a very high water retention value, more than 10 mL / g, which causes it to form a gel at a consistency of about 4%. The preferred starting material of Suzuki's invention are short kraft hardwood pulp fibers.
    [09] The MFC suspension can be useful in a variety of products including food (US 4,334,807), cosmetics, pharmaceuticals, paints and drilling muds (US 4,500,546). MFC can also be used as a reinforcement filler in products molded by resin and other composites (WO 2008/010464, JP2008297364, JP2008266630, JP2008184492) or as a main component in molded products (US 7,378,149).
    [10] MFCs in the descriptions mentioned above are short cellulosic fibers with branches composed of fibrils and are not individual fibrils. The goals of fibrillation are to increase fiber accessibility and water retention. The significant improvement in the strength of the paper was achieved only by the addition of a large amount of MFC, for example, 201.
    [11] Cash et al. He described a method for making derived MFC (US 6,602,994), for example, microfibrillated carboxymethyl cellulose (CMC). Microfibrillated CMC improves paper strength in a similar way to ordinary CMC.
    [12] Charkraborty et al. He reported that a new method for generating cellulose microfibrils that involves refining with the crusher followed by cryo-compression in liquid nitrogen. The fibrils generated in this way had a diameter of about 0.1 to 1 pm and an aspect ratio between 15 and 85 [Holzforschung 59 (1): 102-107 (2005)].
    [13] Smaller cellulosic structures, microfibrils or nanofibrils with a diameter of about 2 to 4 nanometers are produced from plants other than wood containing only primary walls, such as sugar beet pulp (Dianand et al. US 5,964. 983).
    [14] To be compatible with hydrophobic resins, hydrophobicity can be introduced on the surface of microfibrils (Ladouce et al. US 6,703,497). Surface esterified microfibrils for composite materials are described by Cavaille et al (US 6,117,545). Redispersible microfibrils made from plants other than wood are described by Cantiani et al. (US 6,231,657).
    [15] To reduce energy and prevent clogging in the production of MFCs with fluidizers or humogenizers, Lindstrom et al. They proposed a pre-treatment of wood pulp with refining and enzyme before a homogenization process (W02007 / 091942, 6thInternational Paper and Coating Chemistry Symposium). The resulting MFC is smaller, with widths from 2 to 30 nm and lengths from 100 nm to 1 µm. To distinguish it from the precursor MFC, the authors called it nanocellulose [Ankerfors and Lindstrom, 2007 PTS Pulp Technology Symposium] or nanofibrils [Ahola et al., Celulose 15 (2): 303-314 (2008)]. Nanocellulose or nanofibrils had a very high water retention value and behaved like a gel in water. To improve the binding capacity, the pulp was methylated carboxy prior to homogenization. A film made with 100% of such MFC had tensile strength seven times as high as some ordinary papers and twice that of some wear-resistant papers [Henriksson et al., Biomacromolecules 9 (6): 1579-1585 (2008); US 2010 / 0065236A1]. However, because of the small size of this MFC, the film must be formed on a membrane. For the retention in a leaf, without the membrane, of these nanofibrils methylated by carboxy, a cationic wet strength agent was applied to the supply of pulp before the introduction of nanofibrils [Ahola et al., Celullose 15 (2): 303-314 ( 2008)]. The anionic nature of nanofibrils balances the cationic charge brought by the wet strength agent and improves the performance of the resistance agents. A similar observation has been reported with fibrillated nanocellulose by Schlosser [IPW (9): 41-44 (2008)]. Used alone, fibrillated nanocellulose acts as fiber fines in the paper load.
    [16] Nanofibers with a width of 3 to 4 nm have been reported by Isogai et al [Biomacromolecules 8 (8): 2485-2491 (2007)]. The nanofibers were generated by the oxidation of bleached kraft pulps with 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) before homogenization. The film formed from nanofibers is transparent and also has high tensile strength [Biomacromolecules 10 (1): 162-165 (2009)]. Nanofibers can be used for the reinforcement of composite materials (US Patent Application 2009/0264036 Al).
    [17] Even smaller cellulosic particles having unique optical properties, are described by Revol et al. (US 5,629,055). These microcrystalline celluloses (MCC) or nanocrystalline celluloses as recently renamed, are generated by the acid hydrolysis of cellulosic pulp and have a size of about 5 nm per 100 nm. There are other methods for producing MCC, for example, one described by Nguyen et al in US 7,497,924, which generates MCC containing higher levels of hemicellulose.
    [18] The products mentioned above, nanocellulose, microfibrils or nanofibrils, nanofibers and microcrystalline cellulose or nanocrystalline cellulose, are relatively short particles. These are usually much shorter than 1 micrometer, although some can be up to a few micrometers in length. There is no data to indicate that these materials can be used alone as a reinforcing agent to replace conventional strength agents for papermaking. In addition, with current methods for producing microfibrils or nanofibrils, pulp fibers must inevitably be cut. As indicated by Cantiani et al. (US 6,231,657), in the process of homogenization, micro or nanofibrils cannot be simply defibrated from the wood fibers without being cut. In this way, its length and aspect ratio is not limited.
    [19] More recently, Koslow and Suthar (US 7,566,014) described a method for producing fibrillated fibers using open channel refining in low consistency pulps (ie, 3.5% solids, by weight). These describe the open channel refining that preserves the length of the fiber, while the closed channel refining, such as a disc refiner, shortens the fibers. In their subsequent patent application (US 2008/0057307), the same inventors even described a method for producing nanofibrils with a diameter of 50 to 500 nm. The method consists of two steps: first using the open channel refining to generate fibrillated fibers without shortening, followed by an open channel refining to release the individual fibrils. The claimed length of the released fibers is said to be the same as that of the starting fibers (0.1 to 6 mm). We believe this is unlikely because closed channel refining inevitably shortens fibers and fibrils as indicated by the same inventors and other descriptions (US 6,231,657, US 7,381,294). The inventors' closed refining refers to commercial agitator, disc refiner and homogenizers. These devices were used for the generation of microfibrillated cellulose and nanocellulose in another previous technique already mentioned. None of these methods generates the detached nanofibril with such a high length (in 100 micrometers). Koslow et al. recognize in US 2008/0057307 that a closed channel refining leads to both fibrillation and reduced fiber length and generates a significant amount of fines (short fibers). In this way, the aspect ratio of these nanofibrils should be similar to those in the prior art and therefore relatively low. In addition, the method by Koslow et al. is that fibrillated fibers entering the second stage have a freedom of 50 to 0 ml of CSF, while the resulting nanofibers still have a freedom of zero after closed channel refining or homogenization. A zero freedom indicates that the nanofibrils are much larger than the screen size of the freedom tester and cannot pass through the holes in the screen, thus quickly forming a fibrous mat in the screen that prevents water from passing through the screen (the amount of water passed is proportional to the value of freedom). Because the screen size of a freedom tester has a diameter of 510 micrometers, it is obvious that nanofibers must be much wider than 500 nm.
    [20] Closed-channel refining has also been used to produce MFC-type cellulose material, termed as microdenominated cellulose or MDC (Weibel and Paul, UK Patent Application GB 2296726). Refining is carried out by multiple passages of cellulose fibers through a disc refiner that works at a low to medium consistency, typically 10 to 40 passes. The resulting MDC had a higher freedom value (730 to 810 ml CSF) although it is highly fibrillated because the size of the MDC is small although it passes through the screen of a freedom tester. Like another MFC, the MDC had a very high surface area and high water retention value. Another distinguishing feature of MDC is its high sedimented volume, above 50% at 1% consistency after 24 hours of sedimentation. SUMMARY OF THE INVENTION
    [21] In accordance with an aspect of the present invention, cellulosic nanofilaments are provided which comprise: a length of at least 100 µm and a width of about 30 to about 300 nm, wherein the nanofilaments are physically separated from each other and are substantially free of fibrillated cellulose, where the nanofilaments have an apparent freedom value of more than 700 ml according to the Paptac Cl Standard Test Method, where the suspension comprising 1% w / w nanofilaments in water at 25 ° C under a 100s-1 shear rate has a viscosity greater than 100 cps.
    [22] In accordance with another aspect of the present invention, a method is provided for producing cellulosic nanofilaments from a pulp of crude cellulosic material comprising the steps of: providing the pulp comprising cellulosic filaments having an original length of at least 100 pm and feed the pulp to at least one nanofilament step which comprises peeling the cellulosic filaments of the pulp by exposing the filaments to a peeling agitator with a blade having an average linear speed of at least 1000 m / min to 2100 m / min , in which the blade peels the cellulosic fibers apart while substantially maintaining the original length to produce the nanofilaments, where the nanofilaments are substantially free of fibrillated cellulose.
    [23] In addition, according to another aspect of the present invention, a method of treating a paper product is provided to improve the strength properties of the paper product compared to the untreated paper product comprising: adding up to 50 % by weight of cellulosic nanofilaments to the paper product, which comprises nanofilaments, a length of at least 100 pm, and a width of about 30 to about 300 nm, where the nanofilaments are substantially free of fibrillated cellulose, in that nanofilaments have an apparent freedom value of more than 700 ml according to the Paptac Cl Standard Test Method, in which a suspension comprising 1% w / w nanofilaments in water at 25 ° C under a shear rate of 100 s-1 has a viscosity greater than 100 cps, where the strength properties comprise at least one of wet sheet strength, dry paper strength and first pass retention.
    [24] Still, according to another aspect of the present invention, a cellulose nanofilament is provided to produce cellulose nanofilament from a crude cellulose material, the nanofilament comprising: a container adapted to process the crude cellulose material and which comprises an entrance and a wall, an inner surface wall, in which the container defines a chamber having a circular, square, triangular or polygonal cross section; a rotary axis operatively connected within the chamber and having a direction of rotation, an axis comprising a plurality of peeling agitators mounted on the axis; the stripping agitators, comprising: a central hub for connecting to an axis that rotates around a geometric axis; a first set of blades connected to the central hub opposite each other and extending radially out of the geometry axis, the first set of blades having a first radius defined from the geometry axis to a first end of the first blade; a second set of blades connected to the central hub opposite each other and extending radially out of the axis, the second set of blades having a second defined radius of the geometric axis at one end of the second blade, where each blade has an edge with a knife that moves in the direction of rotation of the axis and define a gap between the inner surface wall and the tip of the first blade, in which the gap is greater than the length of the nanofilament.
    [25] According to another aspect of the invention, a mineral paper is provided which comprises at least 50% by weight of mineral filler and at least this and up to 50% of cellulose nanofilaments as defined above. BRIEF DESCRIPTION OF THE DRAWINGS
    [26] Figure la is a micrograph of a crude cellulose material made of white wood kraft paper fiber according to an embodiment of the present invention, seen through an optical microscope; Figure 1b is a micrograph of the cellulose nanofilaments produced from the raw material of Figure 1a according to an embodiment of the present invention seen through an optical microscope; Figure 2 is a micrograph of cellulose nanofilaments produced in accordance with an embodiment of the present invention seen through a scanning electron microscope; Figure 3 is a schematic representation of a cellulose nanofilament device according to an embodiment of the present invention; Figure 4 is a block diagram for the production of cellulose nanofilaments according to an embodiment of the present invention; Figure 5 is a bar graph of tensile energy absorption of the wet continuous sheet never dried to the content of 50% solids (by dry weight) including the variation of the amount of cellulose nanofilaments according to an embodiment of the present invention compared to a prior art system; Figure 6 is a graph of the traction energy absorption (TEA in mJ / g) of the never dry wet web versus cellulose nanofilament dosage (% dry weight) according to an embodiment of the present invention; Figure 7 is a graph of tensile energy absorption (TEA in mJ / g) of a dry leaf including cellulose nanofilaments according to an embodiment of the invention compared to a prior art system; Figure 8 is a graphical plot of the traction energy absorption (TEA in mJ / g) of the wet continuous sheet containing 30% PCC as a function of wet solids versus cationic CNF (% dry weight) according to another form of carrying out the present invention compared to a prior art; Figure 9 illustrates a cross-sectional view of a nanofilament device according to an embodiment of the present invention; and Figure 10 illustrates a section taken along the cross-section lines 10-10 of Figure 9, illustrating an embodiment of a peeling agitator including blades according to an embodiment of the present invention. DESCRIPTION OF THE INVENTION
    [27] It is an objective of the present invention to provide a cellulosic material made of natural fibers, which is superior in all cellulosic materials described in the prior art mentioned above in terms of the aspect of the ratio and the ability to increase the strength of the paper, fabric, cardboard and plastic composite products. It is still an objective of this invention to provide a strengthening agent made of natural fibers whose performance is superior to commercial polymeric strengthening agents including starches and synthetic polymers or resins. And another objective to form a resistance agent made from the natural fibers of not only improves the resistance to dryness, but also the resistance of the wet continuous sheet before the drying of the sheet. A further object of the invention is to provide fibrous reinforcing materials for the manufacture of composites. Another objective of the invention is to supply the fibrous materials for the superabsorbent products. Yet another objective is to provide a method or a device or a process for producing the high-performance cellulosic material from natural fibers.
    [28] Consequently, we have recovered that cellulose nanofilaments produced from natural fibers using their method outperforms conventionally resistant polymers and are different from all cellulosic materials described in the prior art. Their nanofilaments are bundles of cellulosic fibril or branched fibers with separate fibrils or short fibrils. Cellulose nanofilaments are individual thin filaments shredded or peeled from natural fibers and are much longer than nanofibers, micro fibrils, or nanocelluloses as described in the prior art. These cellulose filaments are preferably 100 to 500 micrometers in length; typically 300 micrometers; or greater than 500 micrometers, and even a millimeter connection, it already has a very small width, about 30-300 nanometers, so it has an extremely high aspect ratio.
    [29] Because of their high aspect ratio, cellulose nanofilaments form a gel-like network in aqueous suspension at a very low consistency. The stability of the network can be determined by the determination test described by Weibel and Paul (UK Patent Application GB 2296726). In the test, a sample dispersed by reservoir with a known consistency is allowed to set by gravity in a graduated cylinder. A determined volume after a given time is determined by the level of the interface between the determined cellulose network and the supernatant liquid above. The determined volume is expressed as a percentage of the cellulose volume after determining the total volume. The MFC described by Weibel et al. has a determined volume greater than 50% (v / v) after 24 hours determined at an initial consistency of 1% (w / w). In contrast, CNF made in accordance with this invention never determines 1% consistency in the aqueous suspension. The CNF suspension practically never determines when its consistency is 0.1% (w / w). The resulting consistency at a determined volume of 50% (v / v) after 24 hours is below 0.025% (w / w), an order of magnitude lower than that of MDC or MFC described by Weibel et al. Therefore, the CNF of the present invention is significantly different from the MFC or MDC described prematurely.
    [30] CNF also exhibits a high shear viscosity. At a shear rate of 100 s'1, the viscosity of CNF in 100 centipoises when measured at a consistency of 1% (w / w) and 25 ° C. The CNF is established according to the Paptac Cl Standard Test Method.
    [31] Unlike nanocelluloses made by chemical methods, the CNF of the present invention has a degree of polymerization of the nanofilaments (DP) very close to that of the cellulose source. For example, the DPnanofiamentos of a CNF sample produced according to this invention was 1330, while the DPmidai of the white wood kraft paper fibers starting was around 1710. The DPnanofiiamentos / DPiniciai methods ratio is close to 1 and is at least 1 0.60; more preferably at least 0.75 and more preferably at least 0.80.
    [32] Because of this narrow CNF width and shorter length relative to the original fibers, the CNF in an aqueous suspension can pass through fractionation without forming a mat to obstruct the flow of water during the freedom test. This enables CNF to have a very high freedom value, close to the carrier liquid, that is, water by itself. For example, a CNF sample was determined to have a freedom of 790 ml of CSF. Because the freedom test is designed for normal sized papermaking fibers to determine their fibrillation, this high freedom value, or apparent freedom, does not reflect CNF drainage behavior, but an indication of its smaller size. The fact that CNF has a high freedom value considering the freedom of Koslow's nanofibers is close to zero is a clear indication that the two product families are different.
    [33] The surface of the nanofilaments must be rendered cationic or anionic and may contain various function groups, or grafted macromolecules to have varying degrees of hydrophilicity or hydrophobicity. These nanofilaments are extraordinarily efficient for improving both wet sheet strength and dry paper strength and performance as reinforcement in composite materials. In addition, nanofilaments significantly improve retention and fillers during papermaking. Figures la and lb show the micrograph of the raw material fibers and cellulose nanofilaments produced from these fibers according to the present invention, respectively. Figure 2 is a micrograph of the nanofilaments in a larger branch using a scanning electron microscope. It should be understood that "microfibrillated cellulose" is defined as cellulose having the numerous thin cellulose branching filaments outside one or a few points of a bundle in close proximity and the bundle is approximately the same width as the original fibers and the length of typical fiber in the range of 100 micrometers. "Substantially free" is defined as an absence or absence very close to microfibrillated cellulose.
    [34] The term "the nanofilaments are physically separated from each other" means that the nanofilaments are individual filaments that are not associated or attached to a bundle, that is, these are not fibrillated. Nanofilaments can, however, be in contact with each other as a result of their respective proximity. For a better understanding, nanofilaments can be represented as a random dispersion of individual nanofilaments as shown in Fig. 2.
    [35] We have also recovered that nanofilaments according to the present invention can be used in the manufacture of mineral papers. Mineral paper according to one aspect of the invention comprises at least 50% by weight of the mineral filler and at least 1% w / w and up to 50% w / w of cellulose nanofilaments as defined above. The term "mineral paper" means a paper that has as its main component, at least 50% by weight, a mineral filler, such as calcium carbonate, clay and talc, or a mixture thereof. Preferably, mineral paper has a mineral content of up to 90% w / w with adequate physical strength. The mineral paper according to this invention is more environmentally friendly compared to commercial mineral paper which contains about 20% by weight of synthetic binders based on petroleum. In the present application, a treated paper product comprises the cellulose nanofilaments produced therein while an untreated paper product requires these nanofilaments.
    [36] In addition, we have recovered that said cellulosic nanofilaments can be produced by exposing a suspension of aqueous cellulose fiber or pulp in a rotating agitator, including blade or blades has a sharp knife edge or a plurality of blade edges. sharp knives rotated at high speeds. The edge of the knife blade can be a straight shape, or a curved shape, or a helix. The average linear speed of the blade must be at least 1000 m / min and less than 1500 m / min. The size and number of blades influences the production capacity of nanofilaments.
    [37] The preferred stirring knife materials are metals or alloys, such as high carbon steel. The inventors have recovered to surprise that, counterintuitively, a sharp high speed knife used in accordance with the present invention does not cut the fibers but instead of generating the long filaments with narrower widths apparently by peeling the fibers from each other along the length of the fiber. Consequently, we have developed a device and a process for the manufacture of nanofilaments. Figure 3 is a schematic presentation of such a device that can be used to produce cellulosic nanofilaments. The nanofilament device includes 1: sharp blades on a rotating axis, 2: deflectors (optional), 3: pulp inlet, 4: pulp outlet, 5: motor and 6: container having a cylindrical, triangular, rectangular or prismatic shape in the cross section along the geometric axis of the axis.
    [38] Figure 4 is a block diagram process where in a preferred embodiment the process is conducted on a continuous basis on a commercial scale. The process can also be batch or semi-continuous. In one embodiment of the process, an aqueous suspension of cellulose fibers is first passed through a refiner (optional) and then enters a holding or storage tank. If desired, the refined fibers in a storage tank can be treated or impregnated with chemicals, such as the base, an acid, an enzyme, an ionic liquid, or a substituted one to intensify the production of the nanofilaments. The pulp is then pumped into a nanofilament device. In an embodiment of the present invention, several nanofilament devices can be connected in series. After nanofilamentation, the pulp is separated by a fractionation device. The fractionation device must be a set of sieves or hydrocyclones, or a combination of both. The fractionation device will separate the acceptable nanofilaments from the remaining pulp consisting of larger filaments and fibers. Larger filaments may comprise non-filament fibers or bundles of filaments. The term non-filament fibers means intact fibers identical to refined fibers. The term filament bundle means fibers that are not completely separated and still linked together by chemical bonds or hydrogen bond and their width is much larger than nanofilaments. The larger filaments and fibers are recycled back to the storage tank or directly at the entrance to the nanofilament device for further processing. Depending on the specific use, the nanofilaments produced can bypass the fractionation device and be used directly.
    [39] The generated nanofilaments can still be processed to have the surfaces modified to perform certain functions of the grafted group or molecules. The chemical modification of the surface is accomplished by absorbing the surface of the functional chemicals, or by the chemical bonding of the functional chemicals, or by making the surface hydrophobic. Chemical substitution must be introduced by existing methods known to the person skilled in the art, or by proprietary methods such as those described by Antal et al. in U.S. Patents 6,455,661 and 7,431,799.
    [40] While this is not the intention to be linked by any particular theory considered by the present invention, it is believed that the superior performance of nanofilaments is due to their relatively long length and very thin width. The thin width enables high flexibility and a larger bonding area due to the unit mass of the nanofilaments, while with their long lengths, they allow a nanofilament for bridging and interweaving with many fibers and other components together. In the nanofilament device, there are more spaces between the agitator and a solid surface, thus greater fiber movements than in the homogenizers, disc refiners, or crushers used in the prior art. When a sharp blade hits a fiber in the nanofilament device, it does not cut through the fiber because of the additional space and the need for solid support to retain the fiber such as bars in a crusher or the smaller hole in a homogenizer. The fiber is pushed out of the blade, but the high speed of the knife allows the nanofilaments to be stripped along with the length of the fiber and that without substantially reducing the original length. This partly explains the long length of the cellulose nanofilament obtained. EXAMPLES
    [41] The following examples are presented to describe the present invention and to carry out the method for producing said nanofilaments. These examples are to be taken as illustrative and are not meant to limit the scope of the invention. EXAMPLE 1
    [42] Cellulose nanofilaments (CNF) were made from a mixture of bleached white kraft paper pulp and bleached hardwood kraft paper pulp according to the present invention. The ratio of white wood to hardwood in the mix was 25:75.
    [43] The mixture was refined to a freedom of 230 ml of CSF before the nanofilament procedure, releasing some fibrils on the surface of the cellulose feed. The eighty g / m2 paper samples were made from the supply of typical thin paper with and without calcium carbonate filler (PCC) and with the varying amounts of the nanofilaments. Figure 5 shows the absorption of traction energy (TEA) of these wet leaves never dried at 50% of solid content. When 30% (w / w) PCC was incorporated into the leaves, the TEA index was reduced from 96 mJ / g (no filler) to 33 mJ / g. An addition of 8% CNF increases TEA to a level similar to that of unfilled leaves. With higher levels of CNF addition, wet sheet strength was further improved, by 100% in a non-PCC standard. At a dosage level of 28%, the tensile strength of wet continuous sheet was 9 times greater than the control sample with a 30% w / w PCC. This superior performance has been claimed before with any commercial additives or any other cellulosic materials. EXAMPLE 2
    [44] Cellulose nanofilaments were prepared following the same method as in Example 1, except that unrefined bleached hardwood kraft pulp or unrefined bleached white kraft paper pulp was used instead. A thin paper supply was used to manufacture paper samples with 30% w / w PCC. To demonstrate the effect of two nanofilaments, these were added to the supply at a dosage of 10% before preparing the leaf. As shown in Table 1, 10% hardwood CNF improves the continuous wet sheet TEA by 4 times. This is a very impressive performance. However, the white wood CNF still performs much better. The TEA of the solid sheet containing white wood CNF was close to seven times greater than that of the control sample. The poor performance of CNF from hardwood compared to white wood CNF is probably caused by having shorter fibers. Hardwood usually has a significant amount of parenchyma cells and other short or fine fibers. CNF generated from short fibers can be shorter as well, which reduce their performance. Thus, long fibers are a preferable starting material for CNF production, which is opposed to MFC which prefers short fibers as described by Suzuki et al (US 7,381,294). Table 1 - Resistance of continuous sheet to wet sheets containing 30% PCC and nanofilaments
    EXAMPLE 3
    [45] Cellulose nanofilaments were produced from 100% bleached white kraft paper pulp. The nanofilaments were further processed to enable the absorption of the surface of a cationic chitosan. Total chitosan absorption was chosen at 10% w / w based on the mass of CNF. The CNF surface treated in this way performs the cationic changes and primary amino groups and has a surface load less than 60 meq / kg. The surface-modified CNF was then mixed in a thin paper supply in varying quantities. Paper samples containing 50% PCC on a dry weight basis were prepared with the supply mixture. Figure 6 shows the wet sheet TEA index at 50% w / w solids as a CNF dosing function. Once again, the CNF exhibits extraordinary performance in enhancing wet sheet resistance. There is an increase in TEA of 60% at a dosage as low as 1%. The TEA increases linearly with the CNF dosage. At a 10% addition level, TEA was 13 times higher than the control. EXAMPLE 4
    [46] The cationic CNF was produced by the following method as in Example 3. The CNF was then mixed in a thin paper supply in varying quantities. Paper samples containing 50% w / w PCC were prepared with the supply mixture following the standard PAPTAC C4 method. For comparison, a commercial cationic starch was used instead of CNF. The dry tensile strength of these paper samples is shown in Figure 7 as a function of the additive dosage. Clearly, CNF is far superior to cationic starch. At a dosage level of 5% (w / w), CNF improves the dry tensile strength of the leaves by 6 times, more than doubling the performance produced by the starch. EXAMPLE 5
    [47] Cellulose nanofilaments were produced from white bleached kraft paper pulp following the same procedure as in Example 2. Paper samples containing 0.8% nanofilaments and 30% PCC were prepared. For comparison, some resistance agents including a dry strength and wet strength resin, a cationic starch were used instead of nanofilaments. Its wet sheet strength at 50% w / w solid content is shown in Table 2. Nanofilaments improve the TEA index by 70%. However, all other resistance agents failed to strengthen the wet web. His additional study showed that cationic starch still reduces wet sheet strength when the PCC content in the web is below 20%. Table 2 - Tensile strength of wet continuous sheets containing nanofilaments and conventional resistance agents
    EXAMPLE 6
    [48] Cellulose nanofilaments were produced from a bleached white kraft paper pulp following the same procedure as in Example 2, except that the white wood fibers were pre-cut to a length of less than 0.5 mm before nanofilamentation. The CNF was then added to a thin paper supply to produce paper samples containing 10% w / w CNF and 30% w / w PCC. For comparison, nanofilaments were also produced from uncut white kraft paper fibers. Figure 8 shows its wet tensile strength as a function of wet solids. Clearly, pre-cutting significantly reduces CNF performance afterwards. In contrast, pre-cutting is preferable for the production of MFC (U.S. Patent 4,374,702). This illustrates that the nanofilaments produced according to the present invention are more different from the MFC previously described.
    [49] Still to illustrate the difference between the cellulosic materials described in the prior art and the nanofilaments according to the present invention, paper samples were made with the same supply as described above, but with 10% of a commercial nanofibrilated cellulose (NFC ). Its wet sheet resistance is also shown in Figure 8. The performance of NFC is clearly much weaker than that of nanofilaments, even worse than the CNF of precut fibers according to the present invention. EXAMPLE 7
    [50] Cellulose nanofilaments were produced from white bleached kraft paper pulp following the same procedure as in Example 2. Nanofilaments have extraordinary binding potential for mineral pigments. This high binding capacity allows the formation of a sheet with extremely high filler content without the addition of any binding agents similar to polymer resins. Table 3 shows the tensile strength of paper samples containing 80 and 90% w / w of precipitated calcium carbonate or clay bound with CNF. The strength properties of a commercial copy paper are also listed by comparison. Clearly, the CNF strengthens the leaves containing high mineral well. CNF reinforced sheets containing 80% w / w PCC have a traction energy absorption index of 300 mJ / g, only 30% less than that of commercial paper. To the knowledge of the inventors, these sheets are the first in the world containing up to 90% w / w of mineral filler reinforced only with natural cellulosic materials. Table 3 - Tensile strength of mineral sheets reinforced with nanofilaments
    EXAMPLE 8
    [51] Cellulose nanocomposites with various matrices were produced by fusion in the presence and absence of nanofilaments. As shown in Table 4, nanofilaments significantly improved the tensile index and elastic modulus of composite films made with styrene-butadiene copolymer latex and carboxymethyl cellulose. Table 4 - Tensile strength of nanocomposite reinforced with nanofilaments
    EXAMPLE 9
    [52] Cellulose nanofilaments were produced from bleached white kraft paper pulp following the same procedure as in Example 2. These nanofilaments were added in a PCC paste, before mixed with a commercial thin paper supply (80% of bleached hardwood kraft paper / 20% bleached white kraft paper) p / p. A cationic starch was then added to the mixture. The first passage retention (FPR) and first combustion residue retention passage (FPAR) were determined with a dynamic drainage jar under the following conditions: 750 rpm, 0.5% consistency, 50 ° C. For comparison, the retention test was also conducted with an auxiliary system for commercial retention: a joint crop system consisting of 0.5 kg / t of cationic polyacrylamide, 0.3 kg / t of silica and 0.3 kg / t of anionic micropolymer.
    [53] As shown in Table 5, without retention aids and CNF, FPAR was only 18%. The microparticle improved to 53% FPAR. In comparison, using CNF increased retention to 73% even in the absence of retention aids. The combination of CNF and the microparticle further improved 89% retention. Clearly, CNF has the most positive effect on the filler and fine retention, which leads to the additional benefits for papermaking. Table 5 - CNF improves first pass retention and first pass combustion residue retention
    Note: 1. Dosages in kilograms are based on a metric ton of total supply; 2. CPAM: cationic polyacrylamide; S: silica; MP: micropolymer. EXAMPLE 10
    [54] Cellulose nanofilaments were produced from bleached white kraft paper pulp following the same procedure as in Example 2. The water retention value (WRV) of this CNF was determined to be 355 g of water per 100 g of CNF, while a conventional refined kraft paper pulp (75% hardwood / 25% white wood) w / w has a WRV of only 125 g per 100 g of fibers. In this way CNF has very high water absorbency. Example 11
    [55] Cellulose nanofilaments were produced from various pulp sources following the same procedure as in Example 2. A determination test was conducted according to the Weibel and Paul procedure described earlier. Table 6 shows the consistency of the aqueous suspension of CNF in which the volume of determination is 50% v / v after 24 hours. The value for a commercial MFC is also listed for comparison, it is noted that CNFs made in accordance with the present invention have much less consistency than the MFC sample to achieve the same determined volume. This inferior consistency reflects the high aspect ratio of CNF.
    [56] Table 6 also shows the shear viscosity of these samples determined at a consistency of 1% (units), 25 ° C and a shear rate of 100 s1. Viscosity was measured with a tension controlled rheometer (Haake RS 100) having an open cup coaxial cylinder geometry (Couette). Considering the fiber source, the CNFs of the present invention clearly have a much higher viscosity than the MFC sample. This high viscosity is caused by the high aspect ratio of CNF. Table 6 - Consistency resulting in 50% of determined volume and suspension viscosity of 1% w / w of several CNF samples and a commercial MFC sample.
    Note: 1. White wood kraft paper shot by North; 2. The fines in the hardwood pulp were removed prior to the manufacture of CNF.
    [57] Fig. 9 illustrates a nanofilament or nanofilament device 104 according to an embodiment of the present invention. Nanofilament 104 includes a container 106, with an inlet 102 and an outlet (not shown, but generally seen at the top of reservoir 106). Reservoir 106 defines a chamber 103 in which an axis 150 is operably connected to drive the motor (not shown) typically through a connection and a seal arrangement. Nanofilamentador 104 is indicated to resist the conditions for the processing of cellulosic pulp. In a preferred embodiment the reservoir 106 is mounted on a horizontal base and oriented with the axis 150 and the geometric axis of rotation of the axis 150 in a vertical position.
    [58] Inlet 102 for the raw material pulp is a preferred embodiment observed close to the base of the reservoir 106. The cellulosic pulp of raw material is pumped up towards the outlet (not shown). The residence time inside the reservoir 106 varies but is from 30 seconds to 15 minutes. The residence time depends on the flow rate of the pump in the nanofilament 104 and any required recirculation rate. In another preferred embodiment the reservoir 106 may include an external cooling shell (not shown) along with the full or partial length reservoir.
    [59] The reservoir 106 and the chamber 103 it defines can be cylindrical, however, in a preferred embodiment the shape can have a square cross section (see Fig. 10). Other cross-sectional shapes can also be used such as: a circular, a triangle, a hexagon and an octagon.
    [60] The axis 150 having a diameter 152 includes at least one stripping agitator 110 connected to an axis 150. A plurality or multiple stripping agitators 110 are usually observed together with the axis 150 where each agitator 110 is spaced apart from another. , for a typical spacer having a constant length 160, which is in the order of half a diameter 128 of the agitator 110 or so on. Clearly each blade 120, 130 has a radius 124 and 134 respectively. The shaft rotates at high speeds up to (about 20,000 rpm), with an average linear speed of at least 1000 m / min at tip 128 of the lower blade 120.
    [61] The peeling agitator 110 (as seen in Fig. 10) in a preferred embodiment includes at least four blades (120,130) extending from the central hub 115 which is mounted or connected to the axis of rotation 150. In a preferred embodiment, a set of two smaller blades 130 project upwards along the axis of rotation and another set of two blades 120 are oriented lower along the geometry axis. The diameter of two upper blades 130 is in a preferred embodiment of 5 to 10 cm and in a particularly preferred case is 7.62 cm (from the tip to the center of an axis). If seen in the cross section (as shown in Fig. 10) the radius 132 of the blades 130 varies from 2 to 4 cm in the horizontal plane. The lower leaf assembly 120 can have a diameter variation of 6 to 12 cm, with 8.38 cm being preferred in a laboratory installation. The blade width 120 is not generally uniform, it will be wider in the center and narrower at the tip 126 and irregularly 0.75 to 1.5 cm in the central portion of the blade, with a preferred width in the center of the blade 120 of about 1 centimeter. Each set of two blades has a leading edge (122, 132) that has a sharp knife edge moving in the direction of rotation of an axis 105.
    [62] Different orientations of the blades on the agitator are possible, where blades 120 are below the horizontal plate of the central tube and blades 130 are above the plate. In addition, blades 120 and 130 may have one blade above and one below the plate.
    [63] Nanofilament 104 includes slot 140 spacing between tip 126 of blade 120 and inner surface wall 107. This slot 140 is typically in the range of 0.9 and 1.3 cm to the closest container where the slot is much better than the final length of the obtained nanofilament. This dimension also holds for an upper and lower stirrer 110 respectively. The gap between the blades 130 and the inner surface wall 107 is similar to or slightly larger than that between the blade 120 and the surface of the wall 107.
    权利要求:
    Claims (18)
    [0001]
    1. Cellulosic nanofilaments, characterized by the fact that individual nanofilaments comprise: a length of at least 100 pm, and a width of 30 to 300 nm, in which the nanofilaments are made of natural fibers, in which the nanofilaments are physically separated from each other. other and are free from fibrillated cellulose, in which a suspension of the nanofilaments has an apparent freedom value of more than 700 ml according to the Paptac Cl Standard Test Method, in which a suspension comprising 1% w / w of nanofilaments in water at 25 ° C under a shear rate of 100 s-1 has a viscosity greater than 100 cps, where a DPnanofilament / DPinitial ratio is at least 0.60; preferably 0.75 and more preferably 0.80, where DPnanofilament is a degree of polymerization of cellulosic nanofilaments and DPinitial is a degree of polymerization from the natural fiber source.
    [0002]
    2. Nanofilaments according to claim 1, characterized by the fact that an aqueous suspension of more than 0.1% w / w fails to sediment according to a sedimentation test described in GB 2 296 726.
    [0003]
    3. Nanofilaments according to claim 1, characterized by the fact that an aqueous suspension less than 0.05% w / w settles at 50% volume according to the sedimentation test described in GB 2 296 726.
    [0004]
    4. Nanofilaments according to claim 1, characterized by the fact that the length is between 100 pm and 500 pm.
    [0005]
    5. Nanofilaments according to claim 1, characterized by the fact that it comprises a surface load of at least 60 meq / kg.
    [0006]
    6. Method for producing cellulosic nanofilaments as defined in claim 1 from a pulp of crude cellulosic material, characterized by the fact that it comprises the steps of: providing the pulp which comprises cellulosic filaments having an original length of at least 100 pm; and feeding the pulp to at least one nanofilamentation step which comprises, peeling the cellulosic filaments of the pulp by exposing the filaments to a peeling agitator with a blade having an average linear speed of 1000 m / min at 2100 m / min, in which the blade peels the cellulosic fibers apart while maintaining the original length to produce the nanofilaments, where the nanofilaments are free of fibrillated cellulose.
    [0007]
    7. Method according to claim 6, characterized by the fact that it comprises the separation of the nanofilaments from the larger filaments.
    [0008]
    8. Method according to claim 6, characterized in that it comprises recirculating the larger filaments for at least one nanofilament step.
    [0009]
    9. Method for treating a paper product to improve the strength properties of the paper product compared to the untreated paper product, characterized by the fact that it comprises: adding up to 50% by weight of cellulosic nanofilaments as defined in claim 1 to the paper product, where the strength properties comprise at least one of wet sheet strength, dry paper strength and first pass retention.
    [0010]
    Method according to claim 9, characterized in that the method comprises mixing a suspension less than 5% (w / w) of an aqueous suspension of the nanofilament to produce the treated paper product.
    [0011]
    Method according to claim 10, characterized by the fact that the wet strength of the paper product increases by at least 100% in terms of the absorption of tensile energy of a wet sheet never dry.
    [0012]
    12. Method according to claim 10, characterized in that the dry paper strength has improved more than twice the dry strength of paper samples made from starch.
    [0013]
    13. Cellulose nanofilament (104) to produce cellulose nanofilament as defined in claim 1 having a length of at least 100 pm from a raw cellulose material, the nanofilament characterized by the fact that it comprises: a container (106) adapted for processing the raw cellulose material and comprising an inlet (162), an outlet, and an inner surface wall, wherein the container defines a chamber (103) having a circular, square, triangular or polygonal cross section; a rotary axis (150) operatively mounted inside the chamber along with the geometric axis through the cross section and having a direction of rotation around the geometric axis, the axis comprising a plurality of peeling agitators (110) mounted on the axis (150) ; the stripping agitators (110) comprising: a first set of blades connected to the axis opposite one another and extending radially out of the geometry axis, the first set of blades comprising a first radius (124) defined from the geometric axis to a first end of the first blade and projecting in a direction along the geometric axis; a second set of blades connected to the central hub opposite each other and extending radially out of the geometry axis, the second set of blades comprising a second defined radius of the geometry axis at one end of the second blade and projecting in a direction along of the geometric axis, where each blade has a knife edge that moves in the direction of rotation of the axis, and defining a gap (140) between the inner surface wall and the tip of the first blade, where the gap is larger than than the length of the nanofilament.
    [0014]
    14. Nanofilamenter according to claim 13, characterized by the fact that the first ray is larger than the second ray.
    [0015]
    15. Nanofilamentador according to claim 13, characterized by the fact that the first set of blades is oriented in an axial direction and in a different plane from the central hub.
    [0016]
    16. Nanofilamenter according to claim 13, characterized by the fact that the blade has an average linear speed of at least 1000 m / min.
    [0017]
    17. Mineral paper, characterized by the fact that it comprises: at least 50% by weight of mineral filler and at least 1% and up to 50% of cellulose nanofilaments as defined in claim 1.
    [0018]
    18. Paper according to claim 17, characterized by the fact that it has a mineral content of up to 90%.
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    同族专利:
    公开号 | 公开日
    JP5848330B2|2016-01-27|
    JP2013526657A|2013-06-24|
    EP2569468B1|2017-01-25|
    CA2799123C|2013-09-17|
    CN103038402B|2015-07-15|
    BR112012028750A2|2016-07-19|
    CN103038402A|2013-04-10|
    MX337769B|2016-03-16|
    CN104894668A|2015-09-09|
    EP2569468B2|2019-12-18|
    CN104894668B|2017-04-12|
    RU2570470C2|2015-12-10|
    WO2011140643A1|2011-11-17|
    US20110277947A1|2011-11-17|
    EP2569468A4|2014-08-06|
    MX2012013154A|2013-03-21|
    US9856607B2|2018-01-02|
    AU2011252708B2|2015-02-12|
    EP2569468A1|2013-03-20|
    CL2012003159A1|2013-01-25|
    CA2799123A1|2011-11-17|
    RU2012153233A|2014-06-20|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-26| B06T| Formal requirements before examination|
    2020-03-10| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-08-25| B09A| Decision: intention to grant|
    2020-09-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/05/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US33350910P| true| 2010-05-11|2010-05-11|
    US61/333,509|2010-05-11|
    PCT/CA2011/000551|WO2011140643A1|2010-05-11|2011-05-11|Cellulose nanofilaments and method to produce same|
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