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    • 专利摘要:
    method for improving a paper substrate The invention provides methods and compositions for improving the characteristics of paper substrates. the method involves adding an ncc polymer to a paper substrate. ncc polymers have unique chemical properties that result in improvements in the wet strength, dry strength and drainage retention properties of paper substrates.
    公开号:BR112015032447B1
    申请号:R112015032447-9
    申请日:2014-08-04
    公开日:2022-01-18
    发明作者:Weiguo Cheng；David J. Castro；Rangarani Karnati；Shawnee M. Wilson；Mei Liu；Zhiyi Zhang
    申请人:Ecolab Usa Inc；
    IPC主号:
    专利说明:

    Fundamentals of the Invention
    [001] The invention relates to compositions, methods, and apparatus for improving drainage retention, wet strength, and dry strength of paper in a papermaking process. A typical papermaking process includes the steps of: 1) wood for papermaking or some other source of papermaking fibers; 2) producing a paper mat from the pulp, the paper mat being an aqueous slurry of cellulosic fiber which may also contain additives such as inorganic mineral fillers or pigments; 3) depositing this slurry onto a moving papermaking yarn or fabric; 4) forming a sheet from the solid components of the slurry by draining the water; 5) pressing and drying the sheet to further remove water, and 6) potentially rewetting the dried sheet by passing it through a size press and further drying it to form a paper product.
    [002] When conducting a papermaking process, several considerations need to be taken into account to ensure the quality of the resulting paper product. For example, when draining water from the slurry, as many fibers and chemical additives must be retained and not flow with the water. Similarly, the resulting sheet must have adequate wet strength and dry strength.
    [003] As described, for example, in US Patents 7,473,334, 6,605,674, 6,071,379, 5,254,221, 6,592,718, 5,167,776 and 5,274,055 various retention aids such as polymer flocculants, and Silica-based microparticles can be added to the slurry to facilitate retention in drainage. These retention aids function to retain solid matter within the slurry as water is drained from the slurry. In addition to retaining the fibers, the retention aid must also retain additives such as optical brighteners, fillers, and strength agents. The selection of such retention aids is complicated by the fact that they must both allow free drainage of water from the slurry and also must not interfere with or otherwise degrade the effectiveness of other additives present in the resulting paper product.
    [004] As described, for example, in US Patents 8,465,623, 7,125,469, 7,615,135 and 7,641,766, various materials function as effective wet strength agents. These agents can be added to the slurry to increase the strength properties of the resulting sheet. As with retention aids, however, they must both allow free drainage of water from the slurry and also must not interfere with or otherwise degrade the effectiveness of other additives present in the resulting paper product.
    [005] As described, for example, in US Patents 8,414,739 and 8,382,947, surface toughening agents are materials that increase the resistance of the resulting paper product to abrasive forces. Surface strength agents are often applied as a coating to the paper sheet formed in the size press. Of particular importance is that such agents are compatible with other items present in coatings such as sizing agents and optical brighteners. Furthermore, desirable surface strength agents should not unduly impart flexibility to the resulting paper product.
    [006] As it is difficult to increase dry strength, surface strength, and/or drainage retention while simultaneously not inhibiting other paper attributes or additives there, there is a continuing need for improved methods of improving dry strength, surface strength. , and/or retention in drainage. The technique described in this section is not intended to constitute an admission that any patent, publication or any other information referred to herein is "prior art" with respect to this invention, unless specifically designated as such. In addition, this section should not be interpreted to mean that a search has been made or that no other pertinent information as defined in 37 CFR § 1.56(a) exists. Brief Summary of the Invention
    [007] To satisfy the long-felt and unresolved needs identified above, at least one embodiment of the invention is directed to a method of improving a paper substrate used in a papermaking process. The method comprising the steps of: providing an NCC polymer, and adding the NCC polymer to a paper substrate at the dry end of a papermaking process, wherein the NCC polymer is distributed substantially over the surface of the substrate. The NCC polymer can be distributed using a size press.
    [008] The NCC polymer may comprise a polymer chain attached to an NCC core and the polymer chain made of one or more monomers selected from the list consisting of: vinyl acetate, acrylic acid, sodium acrylate, ammonium acrylate, methyl acrylate, acrylamide, acrylonitrile, N,N-dimethylacrylamide, 2-acrylamido-2-methylpropane-1-sulfonic acid, sodium 2-acrylamido-2-methylpropane-1-sulfonate, 3-acrylamidopropyl-trimethyl-ammonium chloride, diallyldimethyl ammonium chloride, 2-(dimethylamino)ethyl acrylate, 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride, benzyl chloride quaternary salt of N,N-dimethylaminoethyl acrylate, 2-( methyl acryloyloxy)-N,N,N-trimethylethanium, 2-(dimethylamino)ethyl methacrylate, 2-(methacryloyloxy)-N,N,N-trimethylethanaminium chloride, 3-(dimethylamino)propylmethacrylamide, 2-(sulfate) methacryloyloxy)-N,N,N-trimethylethanaminium methyl, methacrylic acid, methacrylic anhydride, methyl methacrylate, methyl chloride tacryloyloxyethyltrimethyl ammonium, 3-methacrylamidopropyl trimethyl ammonium chloride, hexadecyl methacrylate, octadecyl methacrylate, docosyl acrylate, n-vinyl pyrrolidone, 2-vinyl pyridine, 4-vinyl pyridine, epichlorohydrin, n-vinyl formamide, n-vinyl acetamide, 2-hydroxyethyl acrylate, glycidyl methacrylate, 3-(allyloxy)-2-hydroxypropane-1-sulfonate, 2-(allyloxy)ethanol, ethylene oxide, propylene oxide, 2,3-epoxypropyl trimethyl ammonium chloride, ( 3-glycidoxypropyl)trimethoxysilane, epichlorohydrin-dimethylamine, vinyl sulfonic acid sodium salt, sodium 4-styrene sulfonate, caprolactam and any combination thereof.
    [009] The NCC polymer can be a polymer grafted onto at least one NCC core. The NCC polymer may be a branched polymer having a first polymer chain that extends from an NCC core and at least one branch that deviates from the first polymer chain. The branch can be built out of a different selection of monomers from the first polymer chain, the different selection being different in monomer type, monomer ratio, or both. NCC polymer can increase the dry strength of the paper substrate.
    [0010] Additional features and advantages are described here, and will be apparent from the following detailed description. Brief Description of Drawings
    [0011] A detailed description of the invention is described in the following parts with specific reference being made to the drawings in which:
    [0012] FIG. 1 is an illustration of a reaction forming an NCC/AM/AA polyelectrolyte copolymer.
    [0013] For the purposes of this description, like reference numerals in the figures and refer to like aspects unless otherwise indicated. The drawings are only an exemplification of the principles of the invention and are not intended to limit the invention to the particular embodiments illustrated. Detailed Description of the Invention
    [0014] The following definitions are provided to determine how the terms used in this application, and in particular the claims, are to be interpreted. The organization of definitions is for convenience only and is not intended to limit any of the definitions to any particular category.
    [0015] "Wet end" means that portion of the papermaking process prior to a press section where a medium such as water typically comprises more than 45% of the substrate mass, additives added in a wet end typically penetrate and distribute within of the slurry.
    [0016] "Dry end" means that portion of the papermaking process including and subsequent to a press section where a liquid medium such as water typically comprises 45% of the substrate mass, dry end includes, but is not limited to, the portion of In the size press of a papermaking process, additives added to a dry end typically remain in a distinct coating layer outside the slurry.
    [0017] "Consisting Essentially of" means that the methods and compositions may include additional or similar steps, components, ingredients, but only if the additional steps, components and/or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.
    [0018] “Flocculant” ukipkfíec woc eqorquk>«q fg ocVfitkc swg when added to a liquid carrier phase within which certain particles are thermodynamically inclined to disperse, induce agglomeration of those particles to form as a result of weak physical forces such as tension and surface adsorption, flocculation often involves the formation of discrete globules of aggregated particles together with films of liquid carrier interposed between the aggregated globules, as used herein flocculation includes those descriptions cited in ASTME 20-85 as well as those cited in Kirk -Othmer Encyclopedia of Chemical Technology, 5th Edition, (2005), (Published by Wiley, John & Sons, Inc.).
    [0019] "Surface toughness" means the tendency of a paper substrate to resist damage due to abrasive force.
    [0020] "Dry strength" means the tendency of a paper substrate to resist damage due to shear force(s), it includes, but is not limited to, surface strength.
    [0021] "Wet strength" means the tendency of a paper substrate to resist damage due to shear force(s) when rewetted.
    [0022] "Wet strength of web" means the tendency of a paper substrate to resist shear force(s) while the substrate is still wet.
    [0023] "Substrate" means a mass containing paper fibers passing through or having undergone a papermaking process, substrates include wet web, paper mat, slurry, paper sheet, and paper products.
    [0024] "Paper product" means the end product of a papermaking process, it includes but is not limited to writing paper, printing paper, tissue paper, cardstock, cardboard, and packaging paper.
    [0025] “NCC qw "Púengq NC" means nanocrystalline cellulose. NCC core is a discrete mass of NCC crystal onto which polymers can be grafted, an NCC or NCC core may or may not have been formed by acid hydrolysis of fiber fibers. cellulose and NCC or NCC core may or may not have been modified by this hydrolysis to have functional groups attached thereto including, but not limited to, sulfate esters.
    [0026] "NCC polymer" means a composition of matter comprising at least one NCC core with at least one polymer chain extending therefrom.
    [0027] "NCC coupling" means a composition of matter comprising at least two NCC nuclei, the coupling may be a polymer bond in which at least in part a polymer chain connects the two NCC nuclei, or it may be an NCC twin or in which two (or more) NCC nuclei are directly connected to each other by a subpolymer bond (such as epoxide) and/or direct bond of one or more of the NCC nucleus atoms.
    [0028] "Consisting essentially of" means that the methods and compositions may include additional or similar steps, components, ingredients, but only if the additional steps, components and/or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.
    [0029] “Fluid pulp” ukgiikl'kec woc okuVwtc eqortggpfgpfq wo ogkqliquid such as water into which solids such as fibers (such as cellulose fibers) and optionally fillers are dispersed or suspended so that between >99% to 45 % by mass of the slurry is liquid medium.
    [0030] “Stensoactive” fi wo Vgtoq cornq swg kpenwk anionic, non-ionic, cationic and zwitterionic surfactants. Enabled descriptions of surfactants are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 8, pages 900-912, and in McCutcheon's Emulsifiers and Detergents, both of which are incorporated herein by reference.
    [0031] “Sizing Press” ukipkfíec c rcrtg of papermaking machine where dry paper is re-moistened by applying a water-based formulation containing surface additives such as starch, sizing agents and optical brightening agents, further descriptions Details of the size press are described in the Handbook for Pulpand Paper Technologists, 3rd Edition, by Gary A. Smook, Angus Wilde Publications Inc., (2002).
    [0032] In the event that the above definitions or a description specified elsewhere in this application is inconsistent with a meaning (explicit or implicit) that is commonly used in a dictionary, or specified in a source incorporated by reference within this application, the terms of the application and the claims in particular are understood to be interpreted in accordance with the definition or description in this application, and not in accordance with the common definition, dictionary definition, or the definition which has been incorporated by reference. In light of the above, in the event that a term can only be understood and it is interpreted by a dictionary, if the term is defined by the Kirk-Othmer Encyclopedia of Chemical Technology, 5th Edition, (2005), (Published by Wiley, John & Sons, Inc.) this definition shall govern how the term shall be defined in the claims.
    [0033] At least one embodiment of the invention is directed to adding at least one NCC polymer to a paper substrate in a papermaking process. The NCC polymer can be added at the wet end and/or at the dry end. The NCC polymer can be added as a coating outside the substrate or it can be dispersed within the substrate. A coating can partially or completely enclose the substrate. The NCC polymer may comprise linear, branched, cyclic polymers extending from the NCC core and/or may be an NCC graft polymer.
    [0034] As described in Published Patent Applications US 2011/0293932 , 2011/0182990 , 2011/0196094 , and US Patent 8,398,901 , NCC are naturally occurring crystals present in plant fibers. A typical fiber-containing cellulose comprises regions of amorphous cellulose and regions of crystalline cellulose. NCC can be obtained by separating the crystalline cellulose regions from the amorphous cellulose regions of a plant fiber. Because its compact nature makes regions of crystalline cellulose highly resistant to acid hydrolysis, NCC is often obtained by acid hydrolysis of plant fibers. NCC crystallites can be 5-10 nm in diameter and 100-500 nm in length. NCC can have a crystalline fraction of not less than 80% and often between 85% and 97%.
    [0035] NCC is an extremely strong material, but its use as an additive in paper products is restricted due to its small size. As specified in US Published Patent Application 2011/0277947 ^ [0019], because NCC is an extremely short subassembly of a fiber, it is not of sufficient length to impart strength aiding qualities to the long stretches of paper fibers.
    [0036] In at least one embodiment the composition added to a papermaking substrate comprises an NCC core with at least one polymer chain extending from the NCC core. NCC comprises a number of hydroxyl groups which are possible anchor sites from which polymer chains can extend. Without being limited by a particular theory or design of the invention or the scope provided when interpreting the appended claims, because of their unique aspect ratio, density, anchor sites, stiffness and support capabilities, NCC polymers are capable of arranging chains polymer in unique arrangements that provide a number of unique properties that enhance the paper's characteristics.
    [0037] In at least one embodiment the NCC polymer is added to the wet end of a papermaking process. In at least one embodiment the NCC polymer is added as a coating on the size press of a papermaking process. Detailed descriptions of the wet and dry parts of a papermaking process and addition points for chemical additives therein are described in the reference Handbook for Pulp and Paper Technologists, 3rd Edition, by Gary A. Smook, Angus Wilde Publications Inc., (2002). ). The NCC polymer may be added to the papermaking process at any addition point(s) described therein for any other chemical additive and in accordance with the methods and any of the apparatus described therein.
    [0038] In at least one embodiment the NCC polymer is formed by the derivatization of one or more hydroxyl groups on an NCC crystal through condensation polymerization or grafting of vinyl monomers by radical polymerization to satisfy the final requirements desired by the user.
    [0039] In at least one embodiment the polymer attached to the NCC core is a polysaccharide. In at least one embodiment the NCC polysaccharide polymer is used as a viscosity modifier in enhanced oil recovery, as flocculants for waste water treatment, and as a load-resistance agent in a papermaking process.
    [0040] In at least one embodiment the polymer attached to the NCC core is a vinyl polymer. In at least one embodiment it is a copolymer having structural units of at least two vinyl monomers including, but not limited to, acrylamide and acrylic acid. Polyacrylamide, polyacrylic acid, and 2-(methacryloyloxy)ethyltrimethyl ammonium chloride are effective flocculants for water treatment and various applications. However, vinyl polymers show limited biodegradability and poor shear stability, while nanocrystalline cellulose (NCC) is shear stable but less efficient as a flocculant. Connecting vinyl to nonionic, anionic, and/or cationic monomers over an NCC core produces better performing polyelectrolyte flocculants and filler materials.
    [0041] In at least one embodiment the NCC polymer is added to the papermaking process alongside 2-(methacryloyloxy)ethyltrimethyl ammonium chloride. In at least one embodiment the NCC polymer added to the papermaking process is exposed to excess shear to which a non-NCC polymer can withstand and still function, and continue to function.
    [0042] In at least one embodiment the NCC polymer is a branched polymer in which from the first chain of polymer structural units extending from the NCC core, one or more other distinct chains branch off from the first polymer chain and/or from other distinct branches. In at least one embodiment the first chain is comprised of a different variety of monomer units from the one or more of the branch chains. Differences in chain compositions allow for versatile polymer arrangements as a means of imparting a variety of functional groups to the polymer. It also allows the individual to combine the best properties of two or more polymers into a physical unit. For example, the first chain can be selected for its carrying capacity or position of the functionally active polymer branches according to a geometry that has superior effects.
    [0043] In at least one embodiment the polymer chain/branching is developed according to one or more of: a “feuepxqnxet rctc” *grow-to method), a “feuepxqnxet c rctVkt fe” method *grow-from ), and/or a “feuepxqnxet cVtcxfiu” *grow-through method) In the “feuepxqnxet rctc” (grow-to) approach a terminal group of a preformed polymer is coupled with a functional group on the NCC core. In the “feuepxqnxet c rctvkt fe” *grow-from approach), polymer chain development occurs from initiation sites attached to the NCC core. In the “feuepxqnxet cvtcxfiu” *grow-through) approach, a cellulose macromonomer is copolymerized from the NCC core with a low molecular weight comonomer.
    [0044] Representative examples of vinyl monomers that can be used for any of three developmental approaches include, but are not limited to vinyl acetate, acrylic acid, sodium acrylate, ammonium acrylate, methyl acrylate, acrylamide, acrylonitrile, N,N-dimethylacrylamide, 2-acrylamido-2-methylpropane-1-sulfonic acid, sodium 2-acrylamido-2-methylpropane-1-sulfonate, 3-acrylamidopropyl-trimethyl-ammonium chloride, diallyldimethyl ammonium chloride, 2-acrylate - (dimethylamino)ethyl, 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride, N,N-dimethylaminoethyl benzyl acrylate chloride quaternary salt, 2-(acryloyloxy)-N,N,N-sulfate methyl trimethylethaminium, 2-(dimethylamino)ethyl methacrylate, 2-(methacryloyloxy)-N,N,N-trimethylethanaminium chloride, 2-(methacryloyloxy)-N,N,N-trimethylethanaminium methyl sulfate, 3-(dimethylamino )propylmethacrylamide, methacrylic acid, methacrylic anhydride, methyl methacrylate, methacryloyloxyethyltrichloride methyl ammonium, 3-methacrylamidopropyl trimethyl ammonium chloride, hexadecyl methacrylate, octadecyl methacrylate, docosyl acrylate, n-vinyl pyrrolidone, 2-vinyl pyridine, 4-vinyl pyridine, epichlorohydrin, n-vinyl formamide, n-vinyl acetamide, 2-hydroxyethyl acrylate, glycidyl methacrylate, 3-(allyloxy)-2-hydroxypropane-1-sulfonate, 2-(allyloxy)ethanol, ethylene oxide, propylene oxide, 2,3-epoxypropyl trimethyl ammonium chloride, ( 3-glycidoxypropyl)trimethoxysilane, epichlorohydrin-dimethylamine, vinyl sulfonic acid sodium salt, sodium 4-styrenesulfonate, caprolactam and any combination thereof.
    [0045] In at least one embodiment the addition of an NCC polymer to a papermaking slurry or slurry improves drainage retention. As shown in the Examples, NCC polymers used alongside starch, a cationic flocculant and an acrylic acid polymer have superior retention performance for such drainage programs lacking NCC polymers. Improved retention of fines, fillers, and other mass components decreases the amount of such components lost to white water and consequently reduces the amount of scrap material, the cost of scrap disposal and adverse environmental effects. It is generally desirable to reduce the amount of material used in a papermaking process.
    [0046] In at least one embodiment the addition of NCC polymer to a papermaking slurry or slurry improves wet strength. As described in US8,172,983, a high degree of wet strength in the paper is desired to allow for the addition of more filler (such as PCC or GCC) to the paper. The increase in filler content results in superior optical properties and cost savings (cargo is cheaper than fiber).
    [0047] In at least one embodiment the NCC polymer is added as a coating or as part of a coating during the size press of a papermaking process. The NCC polymer may be added as a coating applied during a size press operation and may be added alongside starch, sizing agents or any other additive during the size press.
    [0048] In at least one embodiment the NCC polymer added to the papermaking process is an NCC graft polymer. The graft polymer comprises two or more NCC cores. The NCC graft polymer may include a single polymer chain bridged between the NCC cores. The NCC graft may also include two or more NCC cores with distinct polymer chains that are cross-linked with each other. As such an NCC polymer is cross-linked with at least one other NCC polymer where the cross-linking is located in one of the structural units of the polymer and not in the NCC core. Crosslinking can be achieved by one or more polymer crosslinking agents known in the art. The NCC graft polymer may be in the form of a hydrogel as described in Published Patent Application US 2011/0182990.
    [0049] In at least one embodiment a composition is added in a commercial process. The composition is a mixture comprising: a) NCC blended with a polymer additive which is not an NCC polymer, b) NCC blended with a polymer additive which is an NCC polymer, and/or c) a polymer additive which is a polymer NCC In at least one embodiment the polymer additive is a polymer made from one or more of NCC, nonionic monomers, water soluble monomers, anionic monomers, cationic monomers, and any combination thereof. Polymer additives can be manufactured according to any process described in references: Emulsion Polymerization and Emulsion Polymers, by Peter A. Lovellet al, John Wileyand Sons, (1997), Principles of polymerization, Fourth Edition, by George Odian, John Wileyand Sons, (2004), Handbookof RAFT Polymerization, by Christopher Barner-Kowollik, Wiley-VCH, (2008), Handbookof Radical Polymerization, by KrzysztofMatyjaszewski et al, John Wileyand Sons, (2002), Controlled/Living Radical Polymerization: Progress in ATRP, NMP, and RAFT: by K. Matyjaszewski, Oxford University Press (2000), and Progress in Controlled Radical Polymerization: Mechanismsand Techniques, by Krzyszt of Matyjaszewski et al, ACS Symposium Series 1023 (2009). The polymer additives can be manufactured according to any process including, but not limited to, solution, emulsion, inverse emulsion, dispersion, radical atom transfer polymerization (ATRP), addition-fragmentation reversible chain transfer polymerization (RAFT). ), and ring-opening polymerization.
    [0050] The polymer additive can be added at any known chemical feed point in any commercial process such as:• VtcVcogpVq fg áiwc fg tgfwiq kpfwuVtkcn kpenwkpfq< solid-liquid separations in clarification, dissolved air flotation, flotation by induced air, dewatering, and raw water treatment, • Crnkec>õgu fg ugrctc>«q fg „ngqo Cwzknkctgu fg finvtc>«q. metal removal.• Hcdtkec>«q fg rargl, rargl«q, Vgekfq. g pulp including: manufacturing process improvement, fine particle retention and water removal, coatings and surface treatments, functional additives• VtcVcogpVq fg water fg tguftkcogpVq kpenwkpfq< Kpkdkfqt fg calcium carbonate, calcium phosphate inhibitor, phosphate stabilizer of zinc, iron and/or sludge dispersant, biodispersant, silica scale inhibitor, scale inhibitor for other species (eg calcium fluoride, calcium sulfate, etc.), dual corrosion and scale inhibitor• Hnwkfqu de oil well treatment and its applications including: drilling fluids and operations, cement and cementing operations, completion fluids and operations, stimulation fluids and operations (acidification and fracturing), chemical and water forming applications, also products chemicals for intensified oil recovery and operation (EOR)• Crnkec>õgu fg ncxcigo fg nqw>c kpfwuVtkal kpenwkpfq< Reduction of hardness of washing water; Prevention of hard water film buildup; corrosion inhibition of metal dishes; Removal of dirt from dishes; Prevention of dirt redeposition• Crlkea>õgu fg laxaigo fg tqwra kpfwuVtkal kpelwkpfq< Reduction in wash water hardness; Prevention of hard water film buildup; Prevention of hard water fouling of fabrics; Removal of water from fabrics; Release of dirt from fabrics; Prevention of accumulation of dirt on fabrics; Prevention of redeposition of dirt in washing; Color retention of fabrics; Prevention of dye transfer in washing; Distribution of fabric softening agents; Delivery of antimicrobial agents to fabrics; Fabric fragrance distribution • Crnkec>õgu fg ewkfcfq fc ucúfg kpenwkpfq< Corrosion inhibition of metal instruments during cleaning/processing• Okpgtc>«qg rtqeguucogpVq fg okpgtcku kpenwkpfq< Process cfkvkxqu applied in mining or transport of a mineral substrate, in any mineral beneficiation process or related waste treatment process. Mining and mineral processing include, but are not limited to: alumina, coal, copper, precious metals, and sand and gravel. Applications covered include, but are not limited to: solid-liquid separations, flotation, scale control, dust control, removal of crystal growth modifier metals• OcVgtkcku fg uínkec and process applications including: Strength-enhancing binder, slip and wrap molding, catalyst industries (jig), refractories, abrasion and polishing, defoaming, printing (inkjet/offset), drainage aids.• Swcnswgt rtqeguuq eqogtekcn fguetkvq go wo qw ocku fg< Patent Applications US13/416,272 and 13/730,087 , Published Patent Application US 2005/0025659 , 2011/0250341 A1 , 2013/0146099 , 2013/0146102 2013/0146425 , 2013/0139856 , and/or US Patents 2,202,607, 8.6. and 062, 5,098,520, 7,829,738, 8,262,858, 8,012,758, 8,288,835, 8,021,518, 8,298,439, 8,067,629, 8,298,508, 8,066. 847, 8,298,439, 8,071,667, 8,302,778, 8,088,213, 8,366,877, 8,101,045, 8,382,950, 8,092,618, 8,440,052, 8,097,687, 8,446 4,812. 8,465,623, 8,082,649, 8,101,045, 8,123,042, 8,242,287, 8,246,780, 8,247,593, 8,247,597, 8,258,208, and/or 8,262,852.
    [0051] Representative water-soluble nonionic monomers suitable for use in the polymer additive include one or more of: acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide, N- vinylmethylacetamide, N-vinyl pyrrolidone, 2-vinyl pyridine, 4-vinyl pyridine, epichlorohydrin, acrylonitrile, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, glycidyl methacrylate , 3-(glycidoxypropyl)trimethoxysilane, 2-allyloxyethanol, docosyl acrylate, Nt-butylacrylamide, N-methyllacrylamide, epichlorohydrin-dimethylamine, caprolactam, and the like.
    [0052] Representative anionic monomers suitable for use in the polymer additive include one or more of: acrylic acid, and its salts, including, but not limited to, sodium acrylate, and ammonium acrylate, methacrylic acid, and its salts, including, but not limited to sodium methacrylate, and ammonium methacrylate, 2-acrylamido-2methylpropane sulfonic acid (AMPS), the sodium salt of AMPS, sodium vinyl sulfonate, styrene sulfonate, maleic anhydride, maleic acid, and their salts, including, but not limited to, the sodium salt, ammonium salt, itaconate sulfonate, sulfopropyl acrylate or methacrylate, or other water-soluble forms thereof or other polymerizable carboxylic or sulfonic acids and crotonic acid and salts thereof. Sulfomethyl Acrylamide, Allyl Sulfonate, Sodium Vinyl Sulfonate, Itaconic Acid, Acrylamidomethylbutanoic Acid, Fumaric Acid, Vinyl Phosphonic Acid, Vinyl Sulphonic Acid, Vinyl Sulphonic Acid Sodium Salt, Allyl Phosphonic Acid, 3-(Allyloxy)-2-hydroxypropane Sulfonate, sulfomethylated acrylamide, phosphono-methylated acrylamide, ethylene oxide, propylene oxide and the like.
    [0053] Representative cationic monomers suitable for use in the polymer additive include one or more of: dialkylaminoalkyl acrylates and methacrylates and their quaternary or acid salts, including, but not limited to, dimethylaminoethyl methyl acrylate chloride quaternary salt, salt dimethylaminoethyl methyl acrylate sulfate quaternary, dimethylaminoethyl benzyl acrylate chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, dimethylaminoethyl methyl methacrylate chloride quaternary salt, methyl methacrylate sulfate quaternary salt dimethylaminoethyl, dimethylaminoethyl methacrylate chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dialkylaminoalkylacrylamides or methacrylamidase and their quaternary or acid salts such as acrylamidopropyltrimethylammonium chloride, dimethylaminopropylacrylamide methyl sulfate quaternary salt, dimethylaminopropylacrylamide sulfuric acid salt, dimethylaminopropylacrylamide hydrochloric acid salt, methacrylamidepropyltrimethyl ammonium chloride, dimethylaminopropylmethacrylamide methyl sulfate quaternary salt, dimethylaminopropylmethacrylamide sulfuric acid salt, dimethylaminopropylmethacrylamide hydrochloric acid salt, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, diallyldiethylammonium chloride, diallyldimethylammonium chloride and 2,3-epoxypropyl trimethyl ammonium chloride. Alkyl groups are generally C1-4 alkyl. EXAMPLES
    [0054] The foregoing may be better understood by reference to the following examples, which are presented for purposes of illustration and are not intended to limit the scope of the invention. In particular the examples demonstrate representative examples of the principles innate for the invention and these principles are not strictly limited to the specific condition cited in these examples. As a result it should be understood that the invention encompasses various changes and modifications to the examples described herein and such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. For this reason it is intended that such changes and modifications will be covered by the appended claims. EXAMPLE #1:
    [0055] Several NCC polymers were made according to a fg “fgugpxqnxgt c rctVkt fg” (growing-from) approach. A 1.5 l, 4-bottle reactor was equipped with a) a mechanical top stirrer connected to a metal shaft and a conical stirrer, b) a nitrogen inlet and sprinkler tube, c) a claisen adapter equipped with a reflux condenser d) a temperature probe (RTD) inserted through the Teflon connector and the temperature was controlled by Athena. 562.5 mL of pH-adjusted NCC dispersion (1.14^10-6 mol, 2.81g, pH=2) was added to the reactor and purged with N2 for 30 minutes and then ceric ammonium nitrate (CAN, 1, 12^10-3 mol, 6.17 g) was allowed to react with the NCC backbone for 15 minutes under N2 at RT The reactor was set to 70oC then 52.41 g of acrylamide (7.38^10-1 mol ), 17.08 g of acrylic acid (3.16^10-1 mol) and water (84.67 g) were added to the reactor at 42°C. The reaction mixture was heated to 70°C and maintained at 70°C for 6 h. At 45 minutes 160 ppm sodium hypophosphite was added. The reaction was monitored by HNMR analysis of reaction aliquots (quenched with 500-1000 ppm hydroquinone) and reached 92% conversion in 6 h (Table 2). Post-modification was performed using potassium persulfate (KPS, 500μmol) and sodium metabisulfite (SBS, 3500μmol) to burn residual monomers. Nitrogen sparging was maintained throughout the reaction. The final pH of the polymer was adjusted to 3.5 with NaOH and subjected to the application test. All samples were analyzed for acrylamide and residual acrylic acid. The results are shown in Table 1. Table 1. Sample data of anionic NCC polymers.
    Note: Total active solids: 8% for all polyelectrolytes
    [0056] The NCC polymers were then added to a paper mass. The alkaline dough had a pH of 8.1 and was composed of 80% by weight of cellulosic fibers and 20% of precipitated calcium carbonate diluted to a consistency of 0.5% by weight. The fiber consisted of 2/3 bleached hardwood kraft and 1/3 bleached softwood kraft. The retention performance of NCC and polymer-grafted NCC was evaluated using the Britt jar test method. The test sequence is shown below.Table 2:

    [0057] 500 ml of dough was loaded into the Britte jar mixed at 1250 rpm. Starch Solvitose N was then charged at 4.4 kg/t (10 lb/ton) dry weight in 5 seconds. Cationic Flocculant 61067 was changed at 20 seconds. Then at 55 seconds, NCC or NCC polymer was loaded. Draining started at 60 seconds and ended at 90 seconds. Drainage (filtrate) was collected for turbidity measurement. Filtrate turbidity is inversely proportional to mass retention performance. The % turbidity reduction is proportional to the retention performance of the retention program. The greater the % turbidity reduction, the greater the retention of fines/or fillers. Two commercially available products, Nalco8677Plus (a polyacrylic acid polymer) and Nalco 8699 (a silica product), were tested for retention performance as a reference.Table 3. % turbidity reduction of Britt jar test filtrates


    [0058] As seen from the data, the tested dosage range of 0.22 kg/t to 0.88 kg/t (0.5 lb./ton to 2.0 lb./ton), NCC provided reduction of 28.8% to 39.1% additional turbidity compared to the blank example, which performed better than the two references 8677Plus and 8699. Nalco 8677Plus at 0.44 kg/t (1.0 lb./ ton) showed only 14.6% more turbidity reduction than blank and Nalco 8699 at 0.88 kg/t (2.0 lb./ton) showed only 16.2% more turbidity reduction than the blank. NCC polymer with acrylic acid (NCC/AA) and acrylamide/acrylic acid (NCC/AM/AA) showed 25% more haze reduction and 18% more haze reduction respectively than the blank. The results revealed that both NCC and NCC polymer significantly improved the cloudiness reduction of the tested mass, which can lead to better retention efficiency and cost reduction in paper production. EXAMPLE #2:
    [0059] The experiments contrasted the ability of NCC and NCC polymer to increase sheet dry strength compared to a conventional dry strength agent based on N-1044 polyacrylamide. The NCC polymer used in this example is 6653-145 listed in Table 1. The mass contained 60% hardwood and 20% softwood and 20% precipitated calcium carbonate (PCC) as filler. 7.92 kg/t (18 lb/ton) of Stalok 310 cationic starch was added as a conventional dry strength agent, and various doses of NCC, NCC polymer and N-1044 were added after the cationic starch. 0.44 kg/t (1 lb/ton) of N-61067 was added as a retention aid. The treated dough was used to make test sheet using the Noble & Wood test sheet mold. The paper was pressed using a static press and dried by passing it once through a tumble dryer at about 105°C. The resulting test sheets were allowed to equilibrate at 23°C and 50% relative humidity for at least 12 hours prior to testing. Five test sheet duplicates were made for each condition and mean values were reported.
    [0060] A summary of the test sheet results is listed in the table below.Table 4
    [0061] The addition of dry strength agents N-1044 and NCC polymer changed the charge retention and filler content within the sheet. But, sheet properties were compared at a fixed ash content of 20% based on the ratio of strength and filler content derived from exp. 1 and 2 assuming that the sheet strength (ZDT and tensile index) decreases linearly with ash content. As shown in the table, NCC did not significantly increase sheet strength. On the other hand, the NCC polymer increased ZDT and tensile strength above 20%. The NCC polymer was more effective than N-1044 especially at a low dose of 0.88 kg/t (2 lb/ton). EXAMPLE #3:
    [0062] Laboratory experiments were conducted to measure the ability of NCC and NCC polymer to increase paper surface strength. Base paper containing 16% ash and which had not passed through a size press was coated using the stretch method with solutions containing the desired chemicals. The mass of the paper before and after coating was used to determine the specific dose of chemicals. The paper was dried by passing it once through a tumble dryer at about 95°C and allowed to equilibrate at 23°C and 50% relative humidity for at least 12 hours prior to testing.
    [0063] Surface strength was measured using the TAPPI (Technical Association of Pulp and Paper Industries) method T476 om-01. In this measurement, the surface resistance is inversely proportional to the amount of mass lost from the surface of the paper after it has been systematically "rubbed" on a turntable by two abrasion wheels. Results are reported in mg of material lost per 1000 revolutions (mg/1000 rotation): the lower the number the stronger the surface.
    [0064] A first study compared the performance of NCC with an AA/AM copolymer known to increase paper surface strength. As part of the study, two blends of the NCC with the copolymer were tested. The table below shows the conditions and results:Table 5

    [0065] The first three conditions measured a starch dose range within which the conditions containing the NCC, the copolymer and the mixtures are dosed. After counting for the effect of starch strength, the abrasion loss results demonstrated that NCC and the AA/AM copolymer have a similar level of performance. The effect is further enhanced when the additives are mixed in a ratio of 50:50 and 33:67 of NCC:AA/AM.
    [0066] Next, a study was designed to determine whether developing an AA/AM copolymer on the surface of NCC improves the surface strength of the paper and compares its performance with that of NCC. As part of this study, three NCC polymers varying in AA/AM monomer ratio were tested. The table below shows the conditions and the results.Table 6

    [0067] The first three conditions measured a starch dose range within which the conditions containing the NCC and NCC polymers are dosed. After counting for the starch dose under each of the conditions, the abrasion loss results demonstrate that grafting the AA/AM copolymer onto the surface of the NCC is an improvement over the NCC. Surface strength performance is not affected, however, by the AA/AM monomer ratio in the range of 30/70 to 70/30.
    [0068] In the following, a study was designed to simultaneously compare the surface strength performance as a function of all conditions (i.e. unmodified, modified with an anionic polymer of different molar ratios, and blends of unmodified NCC with the AA/AM copolymer). The table below shows the conditions and the results.Table 7


    [0069] The first two conditions contained only starch, while the others contained about 0.46 or 1.38 g/t (1 or 3 lb/t) of the additive. Under conditions 15-18, unmodified NCC:AAAM blends were prepared at a mass ratio of 10:90. The contributions of the multiple variables in this study were better elucidated with a regression analysis of the results. The model for the analysis resulted in a correlation coefficient of 0.80 with all the variables (starch, the copolymer AA/AM, NCC, polymer NCC, and the mixtures of copolymer AA/AM and the NCC) contributing statistically to the model. . From highest to lowest, the magnitude of its contribution to strengthening the surface of the paper is as follows:1. AA/AM and NCC2 copolymer blends. AA/AM3 copolymer. NCC4 polymer. NCC
    [0070] While this invention may be carried out in many different ways, specific preferred embodiments of the invention are described in detail herein. The present description is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated. All patents, patent applications, scientific papers, and any other reference materials mentioned herein are incorporated by reference in their entirety. Furthermore, the invention encompasses any possible combination of any or all of the various embodiments mentioned herein, described herein and/or incorporated herein. Furthermore, the invention encompasses any possible combination that also specifically excludes any one or more of the various embodiments mentioned herein, described herein and/or incorporated herein.
    [0071] The above description is intended to be illustrative and not exhaustive. This description will suggest many variations and alternatives to those skilled in the art. All such alternatives and variations are intended to be included within the scope of the claims where the term "comprising" means "including, but not limited to". Those familiar with the art may recognize other equivalents for the specific embodiments described herein, equivalents which are also intended to be encompassed by the claims.
    [0072] All ranges and parameters described here are understood to encompass any and all sub-ranges included therein, and all numbers between qu rqpVqu fípciUo Rqt gzgornq. woc hcizc gurgeihiecfc fg “3 c 32” fgxg ugt eqpuifgtcfc eqoq ipenwipfq any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges starting with a minimum value of 1 or more, (e.g. 1 to 6.1), and ending with a maximum value of 10 or less, (e.g. 2.3 to 9.4, 3 to 8, 4 to 7), and finally for each number 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 contained within the range. All percentages, ratios and proportions herein are by weight unless otherwise specified.
    [0073] This completes the description of preferred and alternative embodiments of the invention. Those skilled in the art will recognize other equivalents for the specific embodiment described herein, equivalents which are intended to be encompassed by the appended claims.
    权利要求:
    Claims (5)
    [0001]
    1.Method for improving a paper substrate used in a papermaking process, the method characterized in that it comprises the steps of: providing an NCC polymer, and adding the NCC polymer to a paper substrate at the dry end of a process of papermaking, wherein the NCC polymer is distributed over the surface of the substrate at the dry end of a papermaking process, and wherein the NCC polymer comprises a polymer chain attached to a core of nanocrystalline cellulose (NCC) and the polymer chain is made up of one or more monomers selected from the list consisting of: vinyl acetate, acrylic acid, sodium acrylate, ammonium acrylate, methyl acrylate, acrylamide, acrylonitrile, N,N-dimethylacrylamide, 2- acrylamido-2-methylpropane-1-sulfonic acid, sodium 2-acrylamido-2-methylpropane-1-sulfonate, 3-acrylamidopropyl-trimethyl-ammonium chloride, diallyldimethyl ammonium chloride, 2-(dimethylamino)ethyl acrylate, 2-chloride -(acryloyloxy i)-N,N,N-trimethylethanaminium, N,N-dimethylaminoethyl benzyl acrylate chloride quaternary salt, methyl 2-(acryloyloxy)-N,N,N-trimethylethanium sulfate, 2-(dimethylamino)methacrylate ethyl, 2-(methacryloyloxy)-N,N,N-trimethylethanaminium chloride, 3-(dimethylamino)propylmethacrylamide, 2-(methacryloyloxy)-N,N,N-trimethylethanaminium methyl sulfate, methacrylic acid, methacrylic anhydride, methacrylate methyl, methacryloyloxyethyltrimethyl ammonium chloride, 3-methacrylamidopropyl trimethyl ammonium chloride, hexadecyl methacrylate, octadecyl methacrylate, docosyl acrylate, n-vinyl pyrrolidone, 2-vinyl pyridine, 4-vinyl pyridine, epichlorohydrin, n-vinyl formamide, n -vinyl acetamide, 2-hydroxyethyl acrylate, glycidyl methacrylate, 3-(allyloxy)-2-hydroxypropane-1-sulfonate, 2-(allyloxy)ethanol, ethylene oxide, propylene oxide, 2,3-epoxypropyl chloride trimethyl ammonium, (3-glycidoxypropyl)trimethoxysilane, epichlorohydrin-dimethylamine, vin acid sodium salt yl sulfonic acid, sodium 4-styrene sulfonate, and caprolactam.
    [0002]
    2. Method according to claim 1, characterized in that the NCC polymer is a polymer grafted onto at least one NCC core.
    [0003]
    A method according to claim 1, characterized in that the NCC polymer is a branched polymer having a first polymer chain extending from an NCC core and at least one branch that deviates from the first polymer chain.
    [0004]
    4. Method according to claim 3, characterized in that at least one branch is constructed out of a different selection of monomers of the first polymer chain, the different selection being different in monomer type, monomer ratio, or both .
    [0005]
    5. Method according to claim 1, characterized in that the NCC polymer is distributed over the surface of the substrate using a size press.
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    同族专利:
    公开号 | 公开日
    JP2016531213A|2016-10-06|
    KR20160042031A|2016-04-18|
    CA2913120C|2020-08-18|
    US20160312410A1|2016-10-27|
    EP3030715B1|2018-09-19|
    US9410288B2|2016-08-09|
    EP3030715A4|2017-04-19|
    BR112015032447A2|2017-07-25|
    EP3030715A1|2016-06-15|
    JP6509217B2|2019-05-08|
    CN105452565B|2017-10-13|
    WO2015020962A1|2015-02-12|
    US10132040B2|2018-11-20|
    CN105452565A|2016-03-30|
    KR102228519B1|2021-03-15|
    CA2913120A1|2015-02-12|
    US20150041088A1|2015-02-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2178139A|1938-07-30|1939-10-31|Emulsol Corp|Sulpho-carboxylic acid esters of alcohol amine derivatives|
    US2202601A|1939-05-13|1940-05-28|Separation Process Company|Flotation reagent|
    US3793299A|1972-10-02|1974-02-19|Procter & Gamble|Cellulose graft polymer ion exchange material|
    US4230610A|1979-08-01|1980-10-28|Calgon Corporation|Polyacrylate pigment dispersants for magnesium oxide|
    US4374702A|1979-12-26|1983-02-22|International Telephone And Telegraph Corporation|Microfibrillated cellulose|
    SE432951B|1980-05-28|1984-04-30|Eka Ab|PAPER PRODUCT CONTAINING CELLULOSA FIBERS AND A BINDING SYSTEM CONTAINING COLOIDAL MILIC ACID AND COTIONIC STARCH AND PROCEDURE FOR PREPARING THE PAPER PRODUCT|
    US4385961A|1981-02-26|1983-05-31|Eka Aktiebolag|Papermaking|
    GR79057B|1982-09-24|1984-10-02|Blue Circle Ind Plc|
    GB2157584B|1984-04-14|1988-04-20|Rosewater Engineering Limited|Removing sludge from settling tank|
    GB8602121D0|1986-01-29|1986-03-05|Allied Colloids Ltd|Paper & paper board|
    US4913775A|1986-01-29|1990-04-03|Allied Colloids Ltd.|Production of paper and paper board|
    US4966652A|1987-02-25|1990-10-30|American Cyanamid Company|Increasing the stiffness of paper|
    US4783314A|1987-02-26|1988-11-08|Nalco Chemical Company|Fluorescent tracers - chemical treatment monitors|
    US4743396A|1987-05-15|1988-05-10|Nalco Chemical Company|Pumpable magnesium hydroxide slurries|
    US4889653A|1987-10-28|1989-12-26|Colgate-Palmolive Company|Thixotropic aqueous liquid automatic dishwashing detergent composition containing anti-spotting and anti-filming agents|
    US5254221A|1988-04-22|1993-10-19|Allied Colloids Limited|Processes for the production of paper and paper board|
    US4992380A|1988-10-14|1991-02-12|Nalco Chemical Company|Continuous on-stream monitoring of cooling tower water|
    US5274055A|1990-06-11|1993-12-28|American Cyanamid Company|Charged organic polymer microbeads in paper-making process|
    US5182062A|1991-01-14|1993-01-26|Eastman Kodak Company|Responder target for theft detection apparatus|
    US5098520A|1991-01-25|1992-03-24|Nalco Chemcial Company|Papermaking process with improved retention and drainage|
    EP0531486B1|1991-02-21|2002-05-02|Genencor International, Inc.|A process for converting acellulosic materialinto crystalline cellulose|
    US5171450A|1991-03-20|1992-12-15|Nalco Chemical Company|Monitoring and dosage control of tagged polymers in cooling water systems|
    US5167776A|1991-04-16|1992-12-01|Hewlett-Packard Company|Thermal inkjet printhead orifice plate and method of manufacture|
    US5264009A|1992-09-01|1993-11-23|Texaco Inc.|Processing of sewage sludge for use as a fuel|
    US5877247A|1992-10-05|1999-03-02|Mahar; Robert Crouse|Stable magnesium hydroxide slurries|
    JPH06206741A|1992-10-20|1994-07-26|Rohm & Haas Co|Stable lime slurry|
    JP3729523B2|1994-11-29|2005-12-21|旭化成ケミカルズ株式会社|Water dispersion composition and composition using the same|
    US5840158A|1995-09-28|1998-11-24|Nalco Chemical Company|Colloidal silica/polyelectrolyte blends for pulp and paper applications|
    JP2617432B2|1995-11-27|1997-06-04|日本ピー・エム・シー株式会社|Method for producing water-soluble polymer for papermaking additive|
    US6071379A|1996-09-24|2000-06-06|Nalco Chemical Company|Papermaking process utilizing hydrophilic dispersion polymers of diallyldimethyl ammonium chloride and acrylamide as retention and drainage aids|
    JPH1193092A|1997-09-11|1999-04-06|Hymo Corp|Surface coating agent for paper|
    ES2289042T3|1997-09-30|2008-02-01|Nalco Chemical Company|PAPER PRODUCTION USING COLOID BOROSILICATE.|
    CO5070714A1|1998-03-06|2001-08-28|Nalco Chemical Co|PROCESS FOR THE PREPARATION OF STABLE COLOIDAL SILICE|
    EP1068387A2|1998-03-24|2001-01-17|Avantgarb LLC|Modified textile and other materials and methods for their preparation|
    DE19903546A1|1999-01-29|2000-08-03|Basf Ag|Defoamers and / or deaerators based on oil-in-water dispersions|
    US6605674B1|2000-06-29|2003-08-12|Ondeo Nalco Company|Structurally-modified polymer flocculants|
    GB0111706D0|2001-05-14|2001-07-04|Ciba Spec Chem Water Treat Ltd|Fine particle size lime slurries and their production|
    US6592718B1|2001-09-06|2003-07-15|Ondeo Nalco Company|Method of improving retention and drainage in a papermaking process using a diallyl-N,N-disubstituted ammonium halide-acrylamide copolymer and a structurally modified cationic polymer|
    US7497924B2|2003-05-14|2009-03-03|International Paper Company|Surface treatment with texturized microcrystalline cellulose microfibrils for improved paper and paper board|
    US7220382B2|2003-07-31|2007-05-22|Nalco Company|Use of disulfonated anthracenes as inert fluorescent tracers|
    US7125469B2|2003-10-16|2006-10-24|The Procter & Gamble Company|Temporary wet strength resins|
    US7955504B1|2004-10-06|2011-06-07|State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Oregon State University|Microfluidic devices, particularly filtration devices comprising polymeric membranes, and method for their manufacture and use|
    US7473334B2|2004-10-15|2009-01-06|Nalco Company|Method of preparing modified diallyl-N,N-disubstituted ammonium halide polymers|
    US20080265222A1|2004-11-03|2008-10-30|Alex Ozersky|Cellulose-Containing Filling Material for Paper, Tissue, or Cardboard Products, Method for the Production Thereof, Paper, Tissue, or Carboard Product Containing Such a Filling Material, or Dry Mixture Used Therefor|
    ES2538031T3|2004-12-14|2015-06-16|Solenis Technologies Cayman, L.P.|Retention and drainage aids|
    US7641776B2|2005-03-10|2010-01-05|Lsi Corporation|System and method for increasing yield from semiconductor wafer electroplating|
    JP4406882B2|2005-03-18|2010-02-03|ハリマ化成株式会社|Filler-attached paper and method for producing the same|
    US8071667B2|2005-06-02|2011-12-06|Nalco Company|Compositions comprising alpha olefins|
    US8246780B2|2005-09-19|2012-08-21|Nalco Company|Methods for enhancing brightness and resistance to thermal yellowing of bleached kraft pulp and paper|
    US8092649B2|2005-12-14|2012-01-10|Nalco Company|Method of decreasing the rate of photoyellowing with thiocyanic acid|
    US8066847B2|2005-12-29|2011-11-29|Nalco Corporation|Creping adhesives comprising blends of polyaminoamide epihalolhydrin resins and polyamides|
    US8440052B2|2006-01-25|2013-05-14|Nalco Company|Method and arrangement for feeding chemicals into a pulp process stream|
    US7622022B2|2006-06-01|2009-11-24|Benny J Skaggs|Surface treatment of substrate or paper/paperboard products using optical brightening agent|
    WO2008008576A2|2006-07-13|2008-01-17|Meadwestvaco Corporation|Selectively reinforced paperboard cartons|
    US7914646B2|2006-07-21|2011-03-29|Nalco Company|Compositions and processes for paper production|
    EP1945855B1|2006-09-12|2009-11-18|MeadWestvaco Corporation|Paperboard containing microplatelet cellulose particles|
    US20080105392A1|2006-11-03|2008-05-08|Duggirala Prasad Y|Method and composition for improving fiber quality and process efficiency in mechanical pulping|
    US8021518B2|2006-11-30|2011-09-20|Nalco Company|Method of applying a super-absorbent composition to tissue or towel substrates|
    US8012758B2|2007-02-16|2011-09-06|Nalco Company|Method of monitoring microbiological activity in process streams|
    US20080206126A1|2007-02-28|2008-08-28|Robert Benson|Higher than 30% concentration lime slurries, preparation and uses thereof|
    US7923790B1|2007-03-09|2011-04-12|Silicon Laboratories Inc.|Planar microshells for vacuum encapsulated devices and damascene method of manufacture|
    US8123042B2|2007-06-18|2012-02-28|Nalco Company|Methyl isobutyl carbinol mixture and methods of using the same|
    JP5188765B2|2007-09-10|2013-04-24|第一工業製薬株式会社|Fiber-reinforced composite material and method for producing the same|
    US8382950B2|2007-09-12|2013-02-26|Nalco Company|Recycling of waste coating color|
    US8088213B2|2007-09-12|2012-01-03|Nalco Company|Controllable filler prefloculation using a dual polymer system|
    US8172983B2|2007-09-12|2012-05-08|Nalco Company|Controllable filler prefloculation using a dual polymer system|
    US7718085B1|2007-11-12|2010-05-18|Applied Specialties, Inc.|High-solids lime slurry|
    US7520993B1|2007-12-06|2009-04-21|Water & Power Technologies, Inc.|Water treatment process for oilfield produced water|
    JP2009203401A|2008-02-29|2009-09-10|Agri Future Joetsu Co Ltd|Biomass nanofiber-reinforced ultraviolet curable aqueous paint and manufacturing method thereof|
    CN101952508B|2008-03-31|2013-01-23|日本制纸株式会社|Additive for papermaking and paper containing the same|
    US7995504B2|2008-05-12|2011-08-09|Microsoft Corporation|Locality-based routing table generation|
    US8247593B2|2008-05-13|2012-08-21|Nalco Company|Process for preparing substituted 7-cyano quinone methides|
    US8082649B2|2008-09-26|2011-12-27|Developmental Industries, Inc.|Roof-seaming apparatus including an adjustable panel guide|
    US8444812B2|2008-11-18|2013-05-21|Nalco Company|Creping adhesives with improved film properties|
    US8067629B2|2008-11-19|2011-11-29|Nalco Company|Dispersant antifoulant for acrylonitrile|
    US8088250B2|2008-11-26|2012-01-03|Nalco Company|Method of increasing filler content in papermaking|
    US8398901B2|2008-12-11|2013-03-19|Fpinnovations|Method for producing iridescent solid nanocrystalline cellulose films incorporating patterns|
    US8097687B2|2009-02-09|2012-01-17|Nalco Company|Multifunctional azo initiators for free radical polymerizations: uses thereof|
    US20100204361A1|2009-02-09|2010-08-12|Kurian Pious V|Novel multifunctional azo initiators for free radical polymerizations: methods of preparation|
    US8242287B2|2009-03-12|2012-08-14|Nalco Company|Process for reacting an α, β-unsaturated dicarboxylic acid compound with an ethylenically unsaturated hydrocarbon|
    BE1019037A3|2009-03-17|2012-02-07|Lhoist Rech & Dev Sa|LIME COMPOSITIONS, PROCESS FOR THE PRODUCTION THEREOF AND USE THEREOF IN TREATMENT OF WATER AND SLUDGE.|
    FI124464B|2009-04-29|2014-09-15|Upm Kymmene Corp|Process for the preparation of pulp slurry, pulp slurry and paper|
    JP2012525446A|2009-05-01|2012-10-22|エフピーイノベイションズ|Flexible iridescent nanocrystalline cellulose film and method for preparation|
    EP2432933A4|2009-05-18|2013-07-31|Swetree Technologies Ab|Method of producing and the use of microfibrillated paper|
    US7829738B1|2009-05-19|2010-11-09|Nalco Company|Production of N,N-dialklylaminoethyl acrylates|
    JP5528760B2|2009-09-30|2014-06-25|日本製紙株式会社|Paper made by adding cellulose nanofibers and method for producing the same|
    US8387777B2|2009-10-06|2013-03-05|Ecolab Usa Inc.|Conveyor chain tension monitor|
    CN102666984A|2009-10-20|2012-09-12|巴斯夫欧洲公司|Method for producing paper, paperboard and cardboard having high dry strength|
    US8092618B2|2009-10-21|2012-01-10|Nalco Company|Surface passivation technique for reduction of fouling|
    EP2319984B1|2009-11-04|2014-04-02|Kemira Oyj|Process for production of paper|
    FI123289B|2009-11-24|2013-01-31|Upm Kymmene Corp|Process for the preparation of nanofibrillated cellulosic pulp and its use in papermaking or nanofibrillated cellulose composites|
    WO2011075837A1|2009-12-21|2011-06-30|Fpinnovations|Coatings containing nanocrystalline cellulose, processes for preparation and use thereof|
    US8101045B2|2010-01-05|2012-01-24|Nalco Company|Modifying agent for yankee coatings|
    US8247597B2|2010-01-21|2012-08-21|Nalco Company|Continuous production of DMAEA quaternary salts|
    AU2011207070A1|2010-01-22|2012-08-09|Fpinnovations|Nanocomposite hydrogel and method for preparing it, for industrial and medical applications|
    RU2012138704A|2010-02-11|2014-03-20|ЭфПиИННОВЕЙШНЗ|NANOCOMPOSITE BIOMATERIALS FROM NANOCRYSTALLINE CELLULOSE AND LACTIC ACID |
    EP2536787B1|2010-02-18|2019-11-27|FPInnovations|Thermoplastic nanocomposite material based on nanocrystalline cellulose |
    US8366877B2|2010-03-10|2013-02-05|Nalco Company|Lipohydrophilic glycerol based polymers as digestion aids for improving wood pulping processes|
    FI20105275A|2010-03-19|2011-09-20|Upm Kymmene Oyj|PROCEDURE FOR PREPARING MICROCRISTALLIN AND NANOCRISTALLIN CELLULOSA|
    US8936772B2|2010-04-08|2015-01-20|Ecolab Usa Inc.|Silica containing particle|
    US9856607B2|2010-05-11|2018-01-02|Fpinnovations|Cellulose nanofilaments and method to produce same|
    CA2800141C|2010-05-27|2016-03-29|Fpinnovations|Adhesion with nanocrystalline cellulose|
    BR112013002163B8|2010-07-29|2020-11-24|Yissum Res Dev Co Of Hebrew Univ Jerusalem Ltd|method for producing cellulose nanocrystals from cellulose-containing waste materials|
    US8298508B2|2010-08-09|2012-10-30|Nalco Company|Recovery of alumina trihydrate during the bayer process using cross-linked polysaccharides|
    EP2428610A1|2010-09-13|2012-03-14|Södra Skogsägarna ekonomisk förening|Modified cellulose fibres|
    FI122548B|2010-09-17|2012-03-15|Upm Kymmene Corp|Procedure for improving dewatering|
    CN102180979B|2011-03-12|2012-07-25|牡丹江恒丰纸业股份有限公司|Cationization modification method for nano-crystalline cellulose and preparation method of high-strength cigarette paper|
    US8298439B2|2011-03-30|2012-10-30|Nalco Company|Chemical binder for coating payload in open top hopper cars, trucks, piles, and similar storage/shipping containers|
    US20130139856A1|2011-12-05|2013-06-06|Ecolab Usa Inc.|Low foaming solid sink detergent|
    WO2013090445A1|2011-12-13|2013-06-20|Ecolab Usa Inc.|A method of separating chemistries in a door-type dishmachine|
    CA2857277C|2011-12-13|2016-10-25|Ecolab Usa Inc.|Concentrated warewashing compositions and methods|
    US20130274149A1|2012-04-13|2013-10-17|Schlumberger Technology Corporation|Fluids and methods including nanocellulose|
    US20150072902A1|2012-04-13|2015-03-12|Schlumberger Technology Corporation|Fluids and Methods Including Nanocellulose|
    JP5969262B2|2012-05-10|2016-08-17|国立大学法人群馬大学|Method for producing graft polymer-modified cellulose fiber|
    US9034145B2|2013-08-08|2015-05-19|Ecolab Usa Inc.|Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention, wet strength, and dry strength in papermaking process|US8088250B2|2008-11-26|2012-01-03|Nalco Company|Method of increasing filler content in papermaking|
    US9567708B2|2014-01-16|2017-02-14|Ecolab Usa Inc.|Wet end chemicals for dry end strength in paper|
    US9920482B2|2014-10-06|2018-03-20|Ecolab Usa Inc.|Method of increasing paper strength|
    US9702086B2|2014-10-06|2017-07-11|Ecolab Usa Inc.|Method of increasing paper strength using an amine containing polymer composition|
    FI20146134A|2014-12-22|2016-06-23|Kemira Oyj|Process for the production of laminated polymer network material, manufactured product and use of the product|
    CN109072558A|2016-05-13|2018-12-21|艺康美国股份有限公司|Thin paper dust is reduced|
    WO2018013626A1|2016-07-12|2018-01-18|Isp Investments Llc|Hybrid polymers of polygrafted to cellulose ethers|
    SE540853C2|2016-10-28|2018-12-04|Stora Enso Oyj|A method to form a web comprising cellulose fibers|
    CN107353398B|2017-08-07|2019-02-15|南方医科大学南方医院|A kind of water solubility unsaturated aliphatic polyester and its preparation method and application|
    CN108017765B|2017-12-05|2019-10-18|华南理工大学|A kind of Chinese medicine dreg fiber base resin and its preparation and application|
    CN108276972A|2018-01-02|2018-07-13|中国石油天然气集团公司|A kind of filtrate reducer for drilling fluid and preparation method thereof and biodegrading process|
    CN112759126B|2020-12-29|2022-03-01|中国矿业大学|Mine water pretreatment method|
    CN112723512B|2020-12-29|2022-02-25|中国矿业大学|Preparation method and application of composite flocculant|
    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-07-20| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-09-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-11-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/08/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/962556|2013-08-08|
    US13/962,556|US9410288B2|2013-08-08|2013-08-08|Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process|
    PCT/US2014/049614|WO2015020962A1|2013-08-08|2014-08-04|Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process|
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