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    • 专利摘要:
    COMPOSITION, METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION, AND METHOD OF PRODUCTION OF A MEDIUM WITH CELLULOSIC FIBERS, comprises new glue mixtures to obtain glue intensification together with other benefits are presented and claimed; the present patent application is a composition comprising a sizing mixture having an amount of stabilizer of one or more polymers having an aldehyde function and a sizing amount of a sizing composition; the present patent application is also a method of improving the production of paper and cardboard and of bonding intensification by adding to the paper machine an effective amount of the presented bonding mixture and a method of producing a medium containing fibers cellulose, characterized in that the method includes the addition of the glue mixture presented to the medium at any time in a paper production process.
    公开号:BR112013010635B1
    申请号:R112013010635-2
    申请日:2011-11-01
    公开日:2020-12-08
    发明作者:Mark Grimm；Michael R. St. John
    申请人:Nalco Company；
    IPC主号:
    专利说明:

    APPLICATION FIELD
    [001] The present patent application refers in general to a new composition and method of improving the production of paper and cardboard. More specifically, the present application relates to a composition and method for using polymers with aldehyde function as a stabilizing emulsion for bonding emulsions. The present application for a patent has particular relevance to the application of such polymers in bonding emulsion compositions as a substitute for traditional polymers. HISTORIC
    [002] Polymers with aldehyde function based on polyacrylamide (and similar polymers as described above) provide several benefits for the manufacture of paper and cardboard, including temporary wet resistance, dry resistance, and wet-web resistance (or green resistance), Yankee drying adhesives and increased pressure water removal. Such polymers are most commonly used in the paper and cardboard industry as additives to provide temporary wet resistance and dry resistance (see, for example, U.S. Patent by Coscia et al. No.3,556,932, "Water-Soluble, ionic, glyoxalated, vinylamide , wet-stregnth resing and paper made therewith "; Farley, CE," Glyoxalated Polyacrylamide Resin, pp, 45-61, in Wet-Strength Resins and Their Application, TAPFI Press: Atlanta, GA, 1994). More recent innovations of these types of polymers are disclosed, for example, in U.S. Patent No. 7,641,766, "Method of Using Aldehyde-Functionalized Polymers to Enhance Machine Dewatering".
    [003] The addition of polymers with aldehyde function to the paper production process has been carried out in different ways to obtain the desired effects of resistance. Like all wet-tip additives, such polymers are commonly added to the thin or thick material of paper machine systems prior to the sheet forming process, but other approaches such as spraying the additive onto the wet sheet before the pressing section it has also been employed.
    [004] Bonding emulsions use polymers as emulsion stabilizers. Instead of being a variety of aldehyde functions as described in this document, these polymeric emulsion stabilizers are typically vinyl-added cationic polymers (See, for example, U.S. Patent No. 4,657,946) and diallylalkylammonium halide polymers and copolymers that are Substantially free of ammonia groups attached to the polymer or copolymer by only one chemical bond have also been used (for example, U.S. Patent No. 6,491,790). Such polymers, however, do not provide the benefit of polymers with aldehyde function as discussed above.
    [005] There is then a current need for the papermaking industry to develop bonding formulations that improve the bonding of paper and cardboard and that also provide other enhancements to the papermaking process to reduce the need for various chemical compounds. RESUME
    [006] The present invention patent application therefore offers new glue mixtures for obtaining glue improvement along with other benefits described here from the papermaking process. In a main aspect, the present application is a composition comprising a sizing mixture having a stabilizing amount of one or more polymers with aldehyde function and a sizing amount of a sizing composition. In various configurations, the polymers have an average weight of at least approximately 50,000 g / moles and are stable in an amount of approximately 2% by weight to approximately 33% by weight, based on the total weight of the composition.
    [007] In another aspect, the present application for a patent is a method of improving the production of paper and cardboard and intensifying the bonding by adding to the paper machine an effective amount of the bonding mixture presented. The composition can be added at any time or place to the papermaking process. In the method, the composition can be added to the wet end sites used for conventional wet end additives and / or to white water systems. In the method, the bonding mixture can also be added to the thin material, a thin material line approach a tank, or thick material in the papermaking process.
    [008] In another aspect, the present application for a patent is a method of producing a medium containing cellulose fibers, characterized in that the method includes the addition of the glue mixture presented to the medium at any time during the manufacturing process paper, the medium optionally having mineral fill.
    [009] It is an advantage of the present patent application to offer a composition and a gluing method that increases the gluing effect of a fixed dose take-off emulsion.
    [0010] It is another advantage of the present application for the invention to offer a takeoff method composition that reduces the amount of glue used to obtain a given bonding response.
    [0011] It is another advantage of the present patent application to offer a composition and method that improves the removal of water to increase the speed of the paper machine for greater production.
    [0012] It is also another advantage of the present patent application to offer a composition and method that reduces the amount of drying energy (i.e., steam demand) required at a fixed production speed.
    [0013] The foregoing has broadly described the characteristics and technical advantages of the present patent application so that a detailed description of the following patent application can be better understood. Additional features and advantages of the present application for a patent will be described hereinafter to be the subject of the claims of the present application for a patent. It should be noted by professionals in the field that the specific design and configurations presented can be readily used as a basis for modifying or designing other configurations to achieve the same objectives as the present application for an invention patent. It should also be noted by professionals in the field that the equivalent configurations do not deviate from the spirit and scope of the present application for an invention patent set out in the attached claims. BRIEF DESCRIPTION OF THE FIGURES Figure 1 is a graphical representation of the effect of a configuration of the present patent application on the humidity and vapor pressure coil as a function of time; Figure 2 shows distributions of Malvern Mastersizer (% by volume of emulsion particles with a given diameter) for ASA emulsions prepared with an existing emulsifier containing a surfactant and with the polymers of the present patent application; and Figure 3 shows that the effect of sizing on laboratory paper samples measured by the Hercules Bonding Test ("HST") method was unexpectedly better with the glyoxalated polymer emulsion. DETAILED DESCRIPTION
    [0014] It has been discovered, unexpectedly, that when one or more polymers with aldehyde function is used as a stabilizing agent for sizing mixtures, dramatic increases in water removal from paper machines, and thus, increases in paper production are achieved. "Sizing mixes" means, depending on the configurations, a sizing emulsion or sizing dispersion, and "emulsion" and "dispersion" are sometimes used interchangeably in this document to refer to a sizing mix. If a particular bonding mixture is an emulsion or dispersion, this will be seen by professionals in the field. Such increases in paper production have not been considered to occur when an equivalent amount of one or more polymers with an aldehyde function is added to the paper directly. . In addition, significant increases in internal sizing have been obtained using polymers with aldehyde function as a stabilizing agent for the sizing emulsion compared to equal amounts of stabilizing polymers consisting of starch or cationic acrylamide polymers of low or medium molecular weight (ie, emulsion) bonding stabilizer currently used in the papermaking industry). The latter polymers are generally copolymers of acrylamide with common cationic monomers (eg DADMAC, DMAEA * MCQ, and DMAEM * MCQ - see, for example, U.S. Patent No. 4,657,946, "Paper Sizing Method and Emulsion") but the use other cationic polymers have also been made and are generally well known.
    [0015] In the configurations of the present patent application, polymers with aldehyde function for inclusion in the composition and method are polymers with aldehyde function prepared by reacting a precursor or preformed polymer including one or more portions of reactive aldehyde with a or more aldehydes. Such polymers can have various architectures, including linear, branched, star, block, assembled, tree-shaped, and any other suitable architecture. Preferred polymers include those with amino or starch groups and portions of reactive aldehyde. precursor or preformed polymers can be derived from some suitable source and synthesized using some suitable method. For example, polymers with reactive aldehyde can be formed through emulsion, dispersion, or polymerization of the solution and may contain nonionic, cationic species , anionic, and zwitterionic monomeric species with the polymer. In addition, these monomeric species can be present in any amount and in any combination in the polymer.
    [0016] The following definitions are intended to clarify and not to limit.
    [0017] "Acrylamide monomer” means a monomer of formula
    characterized in that R1 is H or C1-C4 alkyl and R2 is H, C1-C4 alkyl, aryl or arylalkyl. The preferred acrylamide monomers are acrylamide and methacrylamide. Acrylamide is most preferred.
    [0018] "Aldehyde" means a compound containing one or more aldehyde groups (-CHO) or a group capable of forming a reactive aldehyde group, where aldehyde groups are able to react with reactive aldehyde groups (for example, amino groups or starch) of a polymer as described in this document. Representative aldehydes include formaldehyde, paraformaldehyde, glutaraldehyde, glyoxal, and the like, and any other suitable monofunctional or polyfunctional aldehyde. Glyoxal is preferred.
    [0019] "Aldehyde function" means the product of the reaction of a precursor polymer and an aldehyde, where the reactive aldehyde group of the precursor polymer reacted with the carbonyl terminal group of the aldehyde.
    [0020] "Alkyl" means a monovalent group derived from a straight or branched saturated hydrocarbon chair by removal of a single hydrogen atom. Representative alkyl groups include methyl, ethyl, n- and iso-propyl, cetyl, and the like.
    [0021] "Alkylene" means a divalent group derived from a branched or straight chain saturated hydrocarbon by the removal of two hydrogen atoms. Representative alkylene groups include methylene, ethylene, propylene, and the like.
    [0022] "Starch Group" means a group of the formula -C (O) NHY1 where Y1 is selected from H, alkyl, aryl, and arylalkyl.
    [0023] "Amino Group" means a group of the formula -NHY2 where Y2 is selected from H, alkyl, aryl, and arylalkyl.
    [0024] "Amphoteric" means a polymer derived from cationic and anionic monomers and possibly other nonionic monomers. Representative amphoteric polymers include copolymers composed of acrylic acid and DMAEA-MCQ, terpolymers composed of acrylic acid, DADMAC and acrylamide, and their peers.
    [0025] "Aryl" means a monocyclic or multicyclic aromatic ring system of approximately 6 to approximately 10 carbon atoms. Aryl is optionally substituted by one or more C1 to C20 of alkyl, alkoxy, or haloalkyl groups. Representative aryl groups include phenyl or naphthyl, or substituted phenyl or substituted naphthyl.
    [0026] "Arylalkyl" means an arylalkylene group where aryl and alkylene are defined herein. Representative arylalkyl groups include benzyl, phenylethyl, phenylpropyl, 1-naphthylmethyl, and the like. Benzyl is preferred.
    [0027] "Disubstituted N-N, N-substituted ammonium halide monomer" means a monomer of the following formula: (H2C-CH = CHCH2) 2N + R3R4X where R3 and R4 are independently C to C20 alkyl, aryl, or arylalkyl and X is Anionic ion. Representative counter ions include halogen, sulfate, nitrate, phosphate and halogen, sulfate, nitrate, phosphate, and the like. A preferred anionic counter ion is halide. Chloride is preferred. A disodium substituted N, N dially ammonium halide monomer. is diallyldimethylammonium chloride.
    [0028] "Polymer dispersion" means a water-soluble polymer dispersed in a continuous aqueous phase containing one or more organic or inorganic salts and / or one or more aqueous polymers. Representative examples of polymerization by dispersion of water-soluble polymers in a continuous aqueous phase can be found in U.S. Patent Nos. 5,605,970; 5,837,776; 5,985,992; 4,929,655; 5,006,590; 5,597,859; and 5,597,858 and in European Patent Nos. 183,466; 657,478; and 630,909.
    [0029] "Polymer emulsion" and "latex polymer" means a polymer emulsion comprising a polymer with an aldehyde function in the aqueous phase, according to this invention, a hydrocarbon oil for the oily phase and a water-in-oil emulsifying agent. The polymers of the reverse emulsion are continuous hydrocarbons with water-soluble polymers dispersed in the hydrocarbon matrix. The polymers of the reverse emulsion are then "inverted" or activated for use by releasing the polymer from the particles using shear, dilution and generally, another surfactant. See US Patent. No. 3,734,873, incorporated herein by reference. Representative preparations of high molecular weight reverse emulsion polymers are described in U.S. Pat. 2,982,749; 3,284,393; and 3,734,873. See also, Hunkeler, et li, "Mechanism, Kinetics and Modeling of the Inverse-Microsuspension Homopolymerization of Acrylamide," Polymer, vol. 30 (1), pp 127-42 (1989); and Hunkeler et al, "Mechanism, Kinetics and Modeling of Inverse-Microsuspension Polymerization: 2, Copolymerization of Acrylamide with Quaternary Ammonium Cationic Monomers," Polymer, vol. 32 (14), pp 2626-40 (1991).
    [0030] "Monomer" means a polymerizable ally, vinyl or acrylic compound. The monomer can be anionic, cationic, non-ionic or zwitterionic. Vinyl-type monomers are preferred, and acrylic monomers are more preferred.
    Representative non-ionic, water-soluble monomers include acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-vinyl formamide, N-vinylmethylacetamide, N-vinyl pyrrolidone, hydroxyethyl, hydroxyethyl, hydroxyethyl, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, Nt-butylacrylamide, N-methylolacrylamide, vinyl acetate, vinyl vinyl alcohol, and the like.
    [0032] Representative anionic monomers include 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-aerylamido acid -2- methylpropanesulfonic (AMPS), the sodium salt of AMPS, sodium vinyl sulfonate, styrene sulfonate, maleic acid and its salts, including but not limited to the sodium salt and ammonium salt, sulfonate, itaconate, sulfopropryl acrylate or methacrylate or other water-soluble forms of these or other polymerizable sulfonic or carboxylic acids. Sulfomethylated acrylamine, allyl sulphonate, sodium vinyl sulphonate, itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinylphosphonic acid, vinylsulfonic acid, allylphosphonic acid, sulfomethylated acrylamide, phosphonomethylated acrylamide, and its similar anhydride.
    [0033] Representative cationic monomers or combined forms include monoalyl amine, vinyl amine, dialkylaminoalkyl acrylates and methacrylates and their quaternaries or acid salts, including, but not limited to, dimethylaminoethyl methyl chloride (DMAEA * MCQ) quaternary salt, quaternary saline dimethylaminoethyl methyl acrylate sulphate, benzyl chloride dimethylaminoethyl acrylate quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl methacrylate methyl acetate acrylate, quaternary salt dimethylaminoethyl, dimethylaminoethyl methacrylated benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dialkylaminoalkylacrylamides or methacrylamide salts and their salts and their salts the metilacrilamidadimetilaminopropil sulfate, ácidosulfúricoacrilamidadimetilaminopropil salde, balance hydrochloric acid dimethylaminopropyl acrylamide, methacrylamidopropyltrimethylammonium chloride, quaternary salt of methyl methacrylamide sulphate, sulfuric acid salt methacrylamide, dimethylaminopropyl, clorídiro acid salt methacrylamide, dimethylaminopropyl, dietilaminoetilacrilato, dietilaminoetilmethacrilato chloride, dialildietilamônia chloride and diallyldimethyl ammonia (DADMAC). The alkyl groups are generally C1 to C4 alkyl.
    [0034] Representative zwitterionic monomers are those of a polymerizable molecule containing equal proportions of cationic and anionic (charged) function, so that the molecule is generally neutral. Specific representative zwitterionic monomers include N, N-dimethyl-N-acryloyloxyethyl-N- (3-sulfopropyl) -ammonium betaine; N, N-dimethyl-N-acrylamidopropyl-N- (2-carboxymethyl) - ammonium betaine; N, N-dimethyl-N-acrylamidopropyl-N- (3-sulfopropyl) -ammonium betaine; N, N-dimethyl-N-acrylamidopropyl- N- (2-carboxymethyl) -ammonium betaine, 2- (methylthio) ethyl methacryloyl-S- (sulfopropyl) -sulfonium betaine, 2 - [((2-acrylylethyl) dimethylammonium] ethyl 2 -methyl phosphate, 2- (acryloyloxyethyl) -2'- (trimethylammonium) ethyl phosphate, [(2-acrylylethyl) dimethylammonium] ethylphosphonic acid, 2- methacryloyloxyethyl phosphorylcholine (MPC), 2 - [(3- acrylamidopropyl) dimethylammonium] ethyl 2 '-isopropyl phosphate (AAPI), 1-vinyl-3- (3-sulfopropyl) imidazolium hydroxide, (2-acroxyethyl) carboxymethyl methylsulfonium chloride, 1 - (3-sulfopropyl) -2-vinylpyridinium betaine, N- (4 -sulfobutyl) - N-methyl-N, N-diallylamine ammonium betaine (MDABS), N, N-diayl- N-methyl-N- (2-sulfethyl) ammonium betaine, and the like.
    [0035] "Papermaking process" means a method of making paper and cardboard from a paste composed of an aqueous cellulosic mixture for the manufacture of paper (optionally, with mineral fillers, such as calcium carbonates, clay , etc.), draining the mixture to form a leaf, and drying that leaf. It should be noted that any suitable mixture can be used. Representative mixtures include, for example, virgin pulp, recycled pulp, kraft pulp (bleached or not), sulfite pulp, mechanical pulp, polymeric plastic fibers, the like, any combination of the aforementioned pulps. Mixing steps for papermaking, with drainage and drying can be carried out in a manner generally known to professionals in the field. In addition to the sizing emulsions described herein, other additives for papermaking can be used as adjuncts to the polymer treatment of the present patent application, although it should be emphasized that no additives are necessary for effective activity. Such papermaking additives include, for example, retention aids (for example, microparticles, flocculants, polymeric and inorganic coagulants, etc.), wet and dry strength additives (for example, cationic starches, polyamidoamine-based polymers epichlorohydrins), their peers, and combinations of the foregoing.
    [0036] In one embodiment, polyamines are prepared by modifying a preformed polyamide, for example, by hydrolysis of the acrylamide-vinylformamide copolymer using acid or base as described in U.S. Patent Nos. 6,610,209 and 6,426,383.
    [0037] In one embodiment, polyamines are prepared by direct amidation of polyalkyl carboxylic acids and transamidation of copolymers containing carboxylic acid and (meth) acrylamide units as described in U.S. Patent No. 4,919,821.
    [0038] In another configuration, the preformed polymers are prepared as an emulsion or latex polymer. For example, the aqueous phase is prepared by mixing in water one or more water-soluble monomers, and any polymerization additives, such as inorganic salts, chelators, pH buffers and the like. The oil phase is prepared by mixing an inert hydrocarbon liquid with one or more oil-soluble surfactants. The surfactant mixture has a low hydrophilic-lipophilic balance (HLB), to ensure the formation of a continuous oil emulsion. Surfactants suitable for water-in-oil emulsion polymerizations, which are commercially available are compiled in the North American Edition of “McCutcheon's Emulsifiers & Detergents”. The oily phase may need to be heated to ensure the formation of a homogeneous oily solution. The oil phase is then loaded into a reactor equipped with a mixer, a thermocouple, a nitrogen purge tube and a condenser. The aqueous phase is added to the reactor containing the oil phase under vigorous stirring to form an emulsion.
    [0039] The resulting emulsion is heated to the desired temperature, purged with nitrogen, and a free radical initiator is added. The reaction mixture is stirred for several hours under a nitrogen atmosphere at the desired temperature. Upon completion of the reaction, the water-in-oil emulsion polymer is cooled to room temperature, to which any desired additives after polymerization, such as antioxidants, or a high hydrophilic-lipophilic (HBL) surfactant (as described in US patent 3,734,873) may be added. The resulting emulsion polymer is a freely flowing liquid. An aqueous solution of the water-in-oil emulsion polymer can be generated by adding a desired amount of the emulsion polymer to the water under vigorous stirring in the presence of high HLB surfactant (as described in U.S. Patent 3,734,873).
    [0040] In another embodiment, the preformed polymer used in the present application can be a polymer dispersion. In a typical procedure for preparing a polymer dispersion, an aqueous solution containing one or more inorganic or organic salts, one or more water-soluble monomers, any polymerization additives such as processing aids, chelators, pH buffers and a polymer water-soluble stabilizer is loaded into a reactor equipped with a mixer, a thermocouple, a nitrogen purge tube and a water condenser. The monomer solution is vigorously homogenized, heated to the desired temperature, and then a free radical initiator is added. The solution is purged with nitrogen maintaining the temperature and homogenizing for several hours. After that, the mixture is cooled to room temperature, and any additives after polymerization are charged to the reactor. Continuous water dispersions of water-soluble polymers are free-flowing liquids with product viscosities generally in the range of approximately 0.1 Pa.s (100 cP) to approximately 10 Pa.s (10,000 cP), measured under low shear.
    [0041] In another configuration, the preformed polymers or precursors used in the present patent application are polymer solutions. In a typical procedure for preparing polymer solution, an aqueous solution containing one or more water-soluble monomers and any additional polymerization additives, such as chelators, pH buffers, and the like, are prepared. This mixture is charged to a reactor equipped with a mixer, a thermocouple, a nitrogen purge tube and a water condenser. The solution is vigorously homogenized, heated to a desired temperature, and then one or more free radical initiators are added. The solution is purged with nitrogen maintaining the temperature and homogenizing for several hours. Typically, the solution's viscosity increases during this period. After completion of the polymerization, the reactor contents are cooled to room temperature and then transferred to storage. The viscosities of polymer solutions vary widely, and depend on the concentration and molecular weight and structure of the active component of the polymer.
    [0042] Polymerization reactions are typically initiated by any means that result in the generation of a suitable free radical. Thermally derived radicals, in which the radical species result from thermal, homolytic dissociation of an azo compound, peroxide, hydroperoxide and perester are preferred. Preferred initiators are azo compounds including 2,2'-azobis (2-amidinopropane) dihydrochloride; 2,2 '-azo bis [2- (2-imidazoline-2-yl) propane] dihydrochloride; 2,2 '- azobis (isobutyronitrile) (AIBN); 2,2'-azobis (2,4-dimethyl valeronitrile) (AIVN), its similars, and combinations thereof. Most preferred initiators include peroxides, such as ammonium persulfate, sodium persulfate, the like and combinations thereof.
    [0043] In alternative configurations, the polymerization processes can be carried out as a batch process or in stages. In a representative batch process, all monomers react together, while in a step or semi-batch process, a portion of the monomer is retained from the main reaction and added over time to affect the resulting copolymer composition or the formation of the particle dispersion. In a continuous process configuration, all monomers are added over time and affect the resulting composition differently.
    [0044] The polymerization conditions and / or postpolymerization reaction are selected so that the resulting polymer comprising portions of reactive aldehyde (i.e., the preformed polymer or precursor) has a molecular weight of at least approximately 1,000 g / mol, preferably approximately 2,000 to approximately 10,000,000 g / mol. This polymer then receives the function of one or more aldehydes by reaction. Suitable aldehydes include any compound containing one or more aldehydes (-CHO) functional groups (i.e., mono- or poly-functional aldehydes) and having sufficient reactivity to react with the reactive aldehyde moieties (e.g., amino and starch groups) of the polymer. Representative aldehydes include formaldehyde, glutaraldehyde, glyoxal, the like and any other suitable reactive aldehyde.
    [0045] In one embodiment, the polymer with aldehyde function is prepared by reacting the polyamide or polyamine with one or more aldehydes at a pH between 4 to 12. The total concentration of the polymer structure (ie, preformed polymer or precursor having portions of aldehyde) plus aldehyde is between approximately 2 to approximately 35 weight percent. Generally, an aqueous solution of the polymer structure is prepared for better control of the reaction speed and increased stability of the product. The pH of the aqueous polymer structure solution is increased between approximately 4 to approximately 12. The reaction temperature is generally approximately 20 ° C to approximately 80 ° C, preferably approximately 20 ° C to approximately 40 ° C. A solution of aldehyde is added to the aqueous solution of the polymer structure under good homogenization to prevent gel formation. The increase in viscosity speed is monitored using a Brookfield viscometer to monitor the cross-linking reaction. An increase in viscosity of 0.5 cps indicates an increase in the molecular weight of the polymer and an increase in crosslinking of the polymer precursor.
    [0046] In general, the desired increase in viscosity corresponds to a desired level of activity that generally reaches a maximum or a point of decrease in activity at a specific viscosity. The speed of the reaction depends on the temperature, total concentration of polymer and aldehyde, the proportion of aldehyde in relation to the starch / amine functional groups, and pH. Higher rates of glyoxylation (in which case glyoxal is used as an aldehyde) are expected when temperature, total polymer and aldehyde concentration, the ratio of aldehyde to amide / amine functional groups or pH is increased. The reaction rate can be slowed by reducing the total polymer and aldehyde concentration, temperature, aldehyde ratio to the amide / amine functional groups or pH (between approximately 2 to approximately 3.5). The amount of aldehyde that did not react at the end of the reaction increases according to the increase in the proportion of aldehyde in relation to the amide / amine functional groups.
    [0047] In a preferred configuration, the precursor polymer is prepared from a DADMAC and acrylamide copolymer. The monomers of DADMAC and acrylamide can be present in weight-to-weight ratios in the precursor polymer, ranging from approximately 5-95 to approximately 95/5, respectively. This precursor copolymer preferably has an average molecular weight of approximately 17,000 g / moles and reacts, for example, with glyoxal. The amount of glyoxal may vary, but is generally added to obtain a ratio of moles of glyoxal to acrylamide of 0.1 to 1.0. A preferred weight-to-weight ratio of DADMAC / acrylamide is 10/90.
    [0048] The reaction conditions are preferably selected so that the molar ratio of the aldehyde to the reactive aldehyde portion is approximately 0.05 to approximately 1.5. This range of molar ratios can result in a wide range of reactive aldehyde portions of the precursor polymer with added function. For example, from approximately 0.5 mole percent to more than 40 mole percent portions of reactive aldehyde can be added as a function. In addition, depending on the particular combination of aldehydes chosen, approximately 2 to approximately 40 percent or more of the reacted portions may cross-link by means of multifunctional aldehyde.
    [0049] In one configuration, 15 mole percent, preferably at least approximately 20 mole percent of amino or starch groups in the polymer react with the aldehyde to form the polymer with aldehyde function. The resulting polymers with aldehyde function have an average molecular weight of at least 100,000 g / mol, preferably at least 300,000 g / mol.
    [0050] In one configuration, the polymer with aldehyde function is formed from one or more precursor polymers having portions of reactive aldehyde selected from a combination of amines, amides and hydroxyls.
    [0051] In another configuration, the polymer with aldehyde function is a copolymer comprising approximately 1 to approximately 99 mole percent of acrylamide monomers and approximately 95 mole percent to approximately 1 mole percent of one or more cationic, anionic monomers, not ionic or zwitterionic, or a mixture of them. Copolymers prepared from nonionic monomers with reactive aldehyde and cationic monomers preferably have a cationic charge of approximately 1 to approximately 50 mole percent, more preferably approximately to approximately 30 mole percent. Copolymers prepared from nonionic monomers with reactive aldehyde and anionic monomers preferably have an anionic charge of approximately 1 to approximately 50 mole percent, more preferably from approximately 1 to approximately 30 mole percent. The zwitterionic polymers preferably comprise 1 to approximately 95 mole percent, preferably 1 to approximately 50 mole percent zwitterionic monomers.
    [0052] In another configuration, the polymers with aldehyde function are amphoteric which preferably have a general positive charge. Preferred amphoteric polymers are composed of up to approximately 40 mole percent of cationic monomers and up to approximately 20 mole percent of anionic monomers with remaining monomers preferably being reactive aldehyde monomers. Most preferred amphoteric polymers comprise approximately 5 to approximately 10 mole percent of cationic monomers and approximately 0.5 to approximately 4 mole percent of anionic monomers with the remaining monomers preferably being monomers with reactive aldehyde.
    [0053] In one embodiment, the polymer composition shown comprises approximately 10 to approximately 90 mole percent aldehyde that remains unreacted. In configurations, the amount of aldehyde that remains unreacted can vary (all mole percentage ranges) from approximately 10 to approximately 80, or from approximately 10 to approximately 70, or from 10 to approximately 60. In other configurations, the quantity of aldehyde that remains unreacted is greater than approximately 60 mole percent.
    [0054] In configurations of the present patent application, any sizing agent can be used in the sizing emulsion. Representative sizing agents include resin size and water insoluble hydrophobic cellulose sizing agents, such as alkyl ketene dimer ("AKD") or alkenyl succinic anhydride (ASA) and mixtures thereof that are emulsified with the polymers of the present application. aqueous solution invention patent. Such bonding agents prepared from various alkyl or alkenyl hydrocarbon chains, for example, are well known to those skilled in the art.
    [0055] In AKD configurations and resin bonding agents are used as dispersions (ie, solid suspended in a liquid medium) instead of an emulsion. Such dispersions are sometimes used under circumstances where the melting point for certain AKDs and resin bonding agents is lower than the temperature of use. Dispersions, for example, can be made by melting and emulsifying the AKD or resin bonding agent, allowing it to cool and solidify, and dispersing in a liquid solvent. Thus, in such configurations, when the sizing agent is a solid at room temperature, converting the solid to a liquid, it is typically necessary to form the emulsion.
    [0056] Stabilized bonding emulsions can generally be prepared using the necessary procedures considered in colloid science (for example, S.E. Friberg & S. Jones, "Emulsions" in the Encyclopedia of Chemical Technology, Vol. 9 (4th edition)). The general concept consists of transmission energy to a mixture of hydrophobic material (size in this case) and water in the presence of the stabilizer (in this case, cationic polymers described in this document) which results in “small” droplets or particles of the hydrophobic material suspended in phase watery. The mixing can be done in several ways with the homogenization method being irrelevant to the application as long as the desired results are achieved.
    [0057] The desired results usually refer to the average particle size and particle size distribution. Mechanical emulsification media, for example, can include high speed agitators, mechanical homogenizers or turbine pumps. These are often used to prepare bonding emulsions. The equipment must be able to prepare an emulsion with particle sizes that generally vary between approximately 0.01 and approximately 10 microns. A preferred particle size is between approximately 0.5 to 3 microns. The bonding emulsion here refers to an average diameter of a percentage volume distribution obtained with the Malvern Mastersizer laser diffraction instrument (available from Malvem Instruments, Ltd., Malvem, UK). The mean is defined as the diameter at which 50% of the particles are greater than this value and 50% are less than this value. The emulsion glue can be controlled by the amount of energy and stabilizer added. Normally the emulsion would be prepared from a mixture of glue, the polymeric stabilizer, and sufficient water to obtain the desired dilution. As noted, for example, in U.S. Patent Nos. 4,657,946 and 7,455,751, a surfactant of the identified types can be added to enhance emulsification.
    [0058] The ratio of ASA glue to the cationic polymer stabilizer generally ranges from 1: 1 to 20: 1, preferably between 2: 1 to approximately 15: 1 and more preferably that ratio ranges from approximately 2.5: 1 to approximately 10: 1. The reasons are by weight of active ingredients. The glue can then be transferred to the paper or cardboard as an emulsion containing a solids content in an aqueous phase ranging from approximately 0.1 to approximately 10% by weight with that solids content containing the sizing ratios for cationic polymers above. The glue from the final emulsion is normally transferred to the wet end of the paper machine, which can include thin material systems, thick material or white water systems. More typically the glue is transferred to the thin material approach line to the tank, which it also includes the white water system (for example, fan pump). Although the addition of the glue emulsion to the wet end is the rule, any addition point that can introduce the glue to the final sheet of paper would be able to generate a sized sheet and would be used in the implementation of the method of the present patent application in various configurations. Examples are shown in U.S. Patent Nos. 4,657,946 and 7,455,751.
    [0059] In another configuration, a homogenization chamber is used to introduce the bonding emulsion to the papermaking process. Examples of such mixing chambers are shown in US Patent Series No. 11 / 339,169, "Method and Arrangement for Feeding Chemicals into a Process Stream," (available from Naleo Company in Naperville, IL) and Ultra Turax, model no. . ICU-25 (available from IKA® Works, Inc. in Wilmington, NC). It is envisaged that any suitable reactor or homogenization device / chamber can be used in the method of the present patent application.
    [0060] The foregoing can be better understood by reference to the following examples, for illustrative purposes and are not intended to limit the scope of the present invention patent application. Example 1
    [0061] In this example, a configuration of the present patent application using DADMAC glyoxalated polymer (diallyldimethylammonium chloride) / 5 mAmA mA with a ratio of 0.8 moles of glyoxal in mAmm was used as an emulsion stabilizer (Polymer I) and was compared against DMAEM * MCQ emulsion stabilizer (quaternary dimethylammoniomethylacrylate methylchloride) / 10 mA% (acrylamide) 10 mA (Polymer 2). The ASA used in the tests was a commercially available formulation derived from a mixture of C16 and C18 alkenyl chains (available in the form of N7540 from Nalco Company, Naperville, Illinois) at a concentration of 100% (typically ASA is available in pure form) was used for the following test method.
    [0062] Tests were carried out in a Fourdrinier cardboard machine with double tank producing approximately 600 tons / day of corrugated cardboard using 100% recycled fiber derived from old corrugated containers. The test method included the replacement of Polymer 1 in place of Polymer 2 as an emulsion stabilizer for an internal bonding application. The ratio of Polymer 1 to Polymer 2 was slowly increased, with a 1: 1 ratio occurring on Coil No. 5 ending with 1: 0 on Coil No. 8. On Coil No. 11, the ratio was changed to 0 : 1 (ie, a 100% reversal of Polymer 2), The various polymer ratios were added to the size turbine on the sliding board of the emulsification at the wet end of the paper machine, where the consistency ranged from 0.35- 0.90%. The emulsion was fed right after the pressure screen of the mixing approach to the tank. The results are shown in Table 1.Table 1

    [0063] From the results of Table 1, there was an unexpected and significant improvement in bonding with 100% Polymer 1 (Coil No. 10). In addition, the wet line seemed to go towards the board, even when the sheet on the bobbin became drier, and the fiber orientation by Tension Stiffness Orientation ("TSO") was performed enough to cause a need for adjustments to the paper machine (for example, speed to drag, indicating a significant increase in drainage speed). The partial replacement of Polymer 1 (Coil No, 5) did not result in observable effects. Example 2
    [0064] Tests were carried out in a double-tank Fourdrinier machine producing approximately 600 tons / day of corrugated cardboard using 100% recycled fiber derived from old corrugated containers. In this example, Polymer 1 and Polymer 2 were used and compared as the stabilizer emulsion in example 1. Figure 1 graphically illustrates the Moisture and Vapor Pressure Coil as a function of time.
    [0065] Several unexpected observations were made from data presented in Figure 1. The sheet moisture in the coil dropped dramatically from 7.6 to 6.1% by weight in a matter of a few minutes after switching from Polymer 1 to Polymer 2 The leaf moisture was then recovered automatically by means of steam reductions from 1103.16 to 1054.89 kPa (160 to 153 psi). Increases in the level of the crack in the vacuum seal of the upper layer were also observed, indicating more effective vacuum water removal, and the excess increase in the white overflow of the lower layer was observed in a few minutes, indicating increased water removal. . When the test returned to the Polymer 1 emulsion, an almost immediate reversal of these benefits was seen. In addition, CSF tests (ie, refined pulp) do not reveal any noticeable increase in drainage speed when the Polymer 2 bonding emulsion was added, indicating that this conventional drainage measurement has not changed. Example 3
    [0066] Tests were carried out in a Fourdrinier cardboard machine with double tank producing approximately 600 tons / day of corrugated cardboard using 100% recycled fiber derived from old corrugated containers. It was observed that the use of ADMAC / AcAm structure 5 mol% used to prepare Polymer 2 for emulsification resulted in a loss of glue, indicating that simple cationic copolymers without the aldehyde function impair the performance and demonstrate the need for such a function in this application. Example 4
    [0067] Tests were carried out in a Fourdrinier cardboard machine with double tank producing approximately 600 tons / day of corrugated cardboard using 100% recycled fiber derived from old corrugated containers. It has been observed that the use of Polymer 2 (itself without being emulsified with ASA glue additive) to the wet end of the paper machine (for example, thin material) actually generates less glue (as measured by the increase in the Cobb value) demonstrating that the The polymer of the present application must be added as part of the ASA sizing additive to obtain the demonstrated beneficial sizing results. Example 5
    [0068] It is known that emulsions prepared with smaller particle sizes and narrower distributions will produce improved bonding (eg, U.S. Patent No. 4,657,946; JC Roberts, "Neutral and Alkaline Sizing" in Paper Chemisüy, JC Roberts, Ed , Chapman and Hall: New York, 1991). FIG 2 shows distributions from Malvern Mastersizer (% particle emulsion volume with given diameter) for ASA emulsions prepared with an existing polymeric emulsifier containing approximately 1% by weight of the surfactant (for example, ethoxylated alkyl phosphate ester) and polymers with aldehyde function of the present application. As shown in FIG 2, the average diameter of the emulsion prepared with glyoxalated DADMAC / AcAm (10/90 weight ratio) with 0.8 glyoxal to AcAm (Polymer 1) ratio is 78% greater than with the best standard emulsifier (consisting of 19.8% by weight of DMAEM * MCQ (quaternary dimethylaminoethylmethacrylate methylchloride) / AcAm (acrylamide) (10/90 mole ratio) + 1% by weight of the tridecyl alcohol phosphate ester of the ethoxylated surfactant (Polymer 2) Additionally , the emulsion or the bonding emulsion larger than 2 microns in diameter is drastically larger for the emulsion prepared with the glyoxalated polymer. The size distribution of the emulsion prepared with the glyoxalated polymer is also observed to be broader. glyoxalated polymer produced a worse emulsion as assessed by the particle size properties.
    [0069] Although the particle size distribution of the ASA emulsion prepared with glyoxalated polymer was worse than the emulsion prepared with the standard emulsifier, FIG 3 shows that the sticking effect on samples prepared in the laboratory as measured by the HST method was unexpectedly better with the emulsion with glyoxalated polymer, as opposed to the belief accepted by professionals in the field that a better emulsion yields better bonding. The mixture used in the test of FIG 3 was a mixture of recycled cardboard. The HST test assesses the bonding (water penetration in the leaf) by optically measuring the time for a dye solution to penetrate the leaf. In the HST tests carried out, the dye solution also contained 1 wt% formic acid, FIG 3 shows the improved sizing obtained with the ASA emulsions prepared with particle size distribution of the ASA emulsion prepared with glyoxalated polymer although the size distribution emulsion with glyoxylated polymer although the emulsion size distribution is worse than the comparative emulsion.
    [0070] All the compositions and methods presented and claimed herein can be made and executed without undue experimentation in the light of the present presentation. While the present application for a patent can be configured in several ways, there are preferred and specific configurations of the present application for a patent described in detail in this document. The present disclosure is an example of the principles of the present patent application and is not intended to limit the present patent application to particular illustrated configurations. In addition, unless expressly provided to the contrary, the use of the term "one" is intended to include "at least one" or "one or more. For example, "a device" is intended to include "at least one device" or "one or more devices".
    [0071] Any variations given in absolute terms or in approximate terms are intended to include both, and any definitions used in that document are intended to clarify and not to limit. Although the numerical variations and parameters establishing the broad scope of the present patent application are approximations, the numerical values established in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective test measurements. In addition, all variations presented here should be understood to include any and all sub-variations (including all fractional and integer values) sub-added.
    [0072] Furthermore, the present application for a patent includes any and all combinations of some or all of the various configurations described herein. Any and all patents, patent applications, scientific documents, and other references cited in that application, as well as any references cited, are hereby incorporated by reference in their entirety. It should also be understood that several changes and modifications to the preferred configurations described here will be evident to professionals in the field. Such changes and modifications can be made without departing from the spirit and scope of the present invention patent application and without diminishing its intended advantages. It is intended, therefore, that such changes and modifications are covered by the attached claims.
    权利要求:
    Claims (34)
    [0001]
    1. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, the method consisting of adding an effective amount of a composition to the paper machine, the composition consisting of the glue mixture, having an amount of stabilizer of one or more polymer (s) functionalized by aldehyde and a sizing amount of a sizing composition, characterized in that the sizing mixture is a sizing emulsion and in which one or more polymer (s) functionalized by aldehyde has (in) an average molecular weight of at least 50,000g / moles.
    [0002]
    2. "METHOD OF IMPROVING PAPER AND PAPERBOARD PRODUCTION AND GLUE INTENSIFICATION", according to claim 1, characterized by one or more polymer (s) functionalized by aldehyde being (are) present stable in an amount of 2% by weight to 33% by weight based on the total weight of the composition.
    [0003]
    3. “METHOD OF IMPROVING PAPER AND PAPERBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by one or more polymer (s) functionalized by aldehyde being formed from of one or more precursor polymer (s), having reactive aldehyde portions selected from the group consisting of: amines, amides, hydroxyls and any combination of the foregoing.
    [0004]
    4. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by one or more polymer (s) functionalized by aldehyde containing (in) at least one species from reactive to aldehyde monomer present in any amount and in any combination in said aldehyde-functionalized polymer, said monomer species selected from the group consisting of: non-ionic monomers; cationic monomers; anionic monomers; zwitterionic monomers; and any combination of the precedent.
    [0005]
    5. "METHOD OF IMPROVING PAPER AND PAPERBOARD PRODUCTION AND GLUE INTENSIFICATION", according to claim 1, characterized by one or more polymer (s) functionalized by aldehyde having (in) a copolymer formed from diallyldimethylammonium chloride monomers and acrylamide monomers in a weight-to-weight ratio of about 10/90, respectively.
    [0006]
    6. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by one or more polymer (s) functionalized by aldehyde being (s) formed by the reaction of one or more precursor polymer (s), having reactive aldehyde portions, with one or more type (s) of monofunctional and / or polyfunctional aldehydes in a molar ratio of 0.05 to 1.5, respectively.
    [0007]
    7 .. "METHOD OF IMPROVING PAPER AND PAPERBOARD PRODUCTION AND GLUE INTENSIFICATION", according to claim 1, characterized by one or more polymer (s) functionalized by aldehyde being (from) formed from the reaction of a preformed polymer, having one or more reactive portion (s) of aldehyde, with one or more aldehyde (s) selected from the group consisting of: formaldehyde, paraformaldehyde, glyoxal, glutaraldehyde and respective combinations.
    [0008]
    8. "METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION", according to claim 1, characterized in that at least 2% in moles of the portions functionalized by aldehyde in said polymer functionalized by aldehyde participate in crosslinking through a multifunctional aldehyde.
    [0009]
    9. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized in that the polymers functionalized by aldehyde have an average molecular weight of at least 300,000 g / moles.
    [0010]
    10. "METHOD OF IMPROVING PAPER AND PAPERBOARD PRODUCTION AND GLUE INTENSIFICATION", according to claim 1, characterized in that the glue composition has rosin glues, ketene alkylene dimers, succinic alkenyl anhydrides and respective combinations.
    [0011]
    11. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by having, also, a solids content ranging from 0.1 to 10% by weight in an aqueous phase.
    [0012]
    12. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by the addition of the said composition to (i) wetted parts used for wetted additives conventional; and / or (ii) white water systems.
    [0013]
    13. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by the addition of the said composition to a thin material in the papermaking process.
    [0014]
    14. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by the addition of the said composition to a thin material access line in a feed unit in the papermaking process.
    [0015]
    15. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by the addition of the said composition to a thick material in the papermaking process.
    [0016]
    16. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by having, still, the addition of said composition at any point in the papermaking process that is capable of introducing a glue emulsion to the paper sheet.
    [0017]
    17. “METHOD OF IMPROVING PAPER AND PAPERBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized by the addition of the said composition to the paper machine using a mixing chamber.
    [0018]
    18. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized in that said collage composition has succinic alkenyl anhydrides.
    [0019]
    19. "METHOD OF IMPROVING PAPER AND PAPERBOARD PRODUCTION AND GLUE INTENSIFICATION", according to claim 18, characterized in that the ratio of alkenyl succinic anhydrides to one or more functionalized polymer (s) per aldehyde varies between 1 : 1 to 20: 1 and where the relationships take place in weight.
    [0020]
    20. "METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION", according to claim 1, characterized in that the glue emulsion has a particle size between about 0.01 and about 10 microns.
    [0021]
    21. “METHOD OF IMPROVING PAPER AND CARDBOARD PRODUCTION AND GLUE INTENSIFICATION”, according to claim 1, characterized in that the glue emulsion has a particle size between 0.5 and 3 microns.
    [0022]
    22. “EMULSION”, characterized by having: a) a bonding agent; b) an emulsifier; and c) an aqueous component.
    [0023]
    23. "EMULSION" according to claim 22, characterized in that a sizing agent is selected from the group consisting of: a rosin glue, an alkyl ketene dimer, a succinic alkenyl anhydride and respective combinations.
    [0024]
    24. "EMULSION" according to claim 22, characterized in that the emulsifier has an aldehyde-functionalized polymer.
    [0025]
    25. "EMULSION" according to claim 24, characterized in that the aldehyde-functionalized polymer has an average molecular weight of at least 50 kilodaltons (kD).
    [0026]
    26. "EMULSION" according to claim 24, characterized in that the aldehyde-functionalized polymer has a copolymer, having 1 to 99% moles of acrylamide monomers and 95% moles to 1 mol% of one or more monomers (s) selected from the group consisting of cationic monomers, anionic monomers, nonionic monomers, zwitterionic monomers and any respective mixture.
    [0027]
    27. "EMULSION" according to claim 24, characterized in that the aldehyde-functionalized polymer has amphoteric polymers that have a general positive charge.
    [0028]
    28. "EMULSION" according to claim 24, characterized in that the aldehyde-functionalized polymer is an aldehyde-functionalized acrylamide-poly (diallyldimethylammonium chloride) polymer.
    [0029]
    29. "EMULSION" according to claim 24, characterized in that the aldehyde-functionalized polymer is a glyoxylated acrylamide-poly (DADMAC) polymer.
    [0030]
    30. "EMULSION" according to claim 29, characterized in that the glyoxylated acrylamide-poly (DADMAC) polymer is derived from an AcAm-poly copolymer (DADMAC), having from 1 to 50% DADMAC monomer content.
    [0031]
    31. "EMULSION" according to claim 29, characterized in that the glyoxylated acrylamide-poly (DADMAC) polymer is formed by the reaction of the acrylamide-poly copolymer (DADMAC) with glyoxal, in which the amount of glyoxal is added to achieve a glyoxal to acrylamide molar ratio of 0.1 to 1.0.
    [0032]
    32. "EMULSION" according to claim 22, characterized in that the sizing agent is alkenyl succinic anhydride (ASA).
    [0033]
    33. "EMULSION" according to claim 22, characterized by having an average particle size less than or equal to 2.5 microns.
    [0034]
    34. “EMULSION”, characterized by having: a) an alkenyl succinic anhydride (ASA) bonding agent; b) an emulsifier; and c) an aqueous component.
    类似技术:
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    同族专利:
    公开号 | 公开日
    MY163925A|2017-11-15|
    TW201226659A|2012-07-01|
    WO2012061384A2|2012-05-10|
    RU2595681C2|2016-08-27|
    CA2816565A1|2012-05-10|
    MX2013004955A|2013-06-28|
    KR101789526B1|2017-10-25|
    EP2635634B1|2017-03-22|
    RU2013119833A|2014-12-10|
    WO2012061384A3|2012-07-19|
    CN102892832A|2013-01-23|
    AU2011323531A9|2017-02-09|
    MX351556B|2017-10-19|
    KR20140027054A|2014-03-06|
    CN102892832B|2016-01-20|
    JP2013543067A|2013-11-28|
    BR112013010635A2|2016-08-09|
    US8709207B2|2014-04-29|
    ES2627435T3|2017-07-28|
    JP5925794B2|2016-05-25|
    TWI582290B|2017-05-11|
    AU2011323531A1|2013-05-23|
    AU2011323531B2|2017-02-02|
    US20120103547A1|2012-05-03|
    CA2816565C|2020-08-04|
    EP2635634A4|2015-10-21|
    EP2635634A2|2013-09-11|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-03-10| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-09-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-08| 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 01/11/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/938,017|US8709207B2|2010-11-02|2010-11-02|Method of using aldehyde-functionalized polymers to increase papermachine performance and enhance sizing|
    US12/938,017|2010-11-02|
    PCT/US2011/058783|WO2012061384A2|2010-11-02|2011-11-01|Method of using aldehyde-functionalized polymers to increase papermachine performance and enhance sizing|
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