WO2013084062A2 - Preparation of polyvinylamide cellulose reactive adducts - Google Patents
Preparation of polyvinylamide cellulose reactive adducts Download PDFInfo
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- WO2013084062A2 WO2013084062A2 PCT/IB2012/002813 IB2012002813W WO2013084062A2 WO 2013084062 A2 WO2013084062 A2 WO 2013084062A2 IB 2012002813 W IB2012002813 W IB 2012002813W WO 2013084062 A2 WO2013084062 A2 WO 2013084062A2
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
Definitions
- the present disclosure is directed to a method for preparing a cellulose reactive adduct of polyvinylamide, the resulting adduct, methods of using the adduct and products comprising the adduct.
- Methods for preparing a cellulose reactive functional ized polyvinylamide adduct using a continuous process comprise reacting a substantially aqueous reaction mixture of a vinylamide polymer and a cellulose reactive agent at a temperature of about 1 °C to about 65 °C and a reaction pH set point of about 8.5 to about 12, for about 1 minutes to about 300 minutes,
- the concentration of the vinylamide polymer prior to and during formation of the adduct is about 0.25-15% of the total reaction mixture, thereby forming the adduct.
- the method comprises the step of reacting a substantially aqueous reaction mixture of a vinylamide polymer and a cellulose reactive agent at a temperature of about 1 °C to about 65 °C and a reaction pH set point of about 8.5 to about 12, for about 1 minutes to about 300 minutes,
- the pH of the reaction mixture may be adjusted to maintain a constant reaction rate based on the following equation:
- the concentration of the vinylamide polymer prior to and during formation of the adduct is about 0.25-15%) of the total reaction mixture, thereby forming the adduct.
- the adduct of the present method can be prepared at a temperature of about 2 °C to about 60 °C and a pH of about 8.5 to about 11.5, and a reaction time of about 2 to 200 minutes.
- the adduct of the present method can be prepared at a temperature of about 2 °C to about 50 °C and a pH of about 8.8 to about 11.5, for about 2 to 150 minutes.
- the adduct can be prepared at a temperature of about 2°C to about 40 °C and a pH of about 9.0 to about 11.5, for about 5 to 60 minutes.
- the adduct of the present method can be prepared at a temperature of about 4 °C to about 40 °C and a pH of about 9.0 to about 11.5, for about 2 to 120 minutes.
- the adduct of the present method can be prepared at a temperature of about 4 °C to about 30 °C and a pH of about 9.5 to about 11.5, for about 2 to 90 minutes.
- the concentration of the vinylamide polymer prior to and during formation of the adduct can be about 0.5 % to 6 %.
- the concentration of the vinylamide polymer prior to and during formation of the adduct can also be about 1.0% to 3.0 %.
- the concentration of the vinylamide polymer prior to and during formation of the adduct can be about 2%.
- cellulose reactive agent about 12 % to 85% of the cellulose reactive agent can be consumed during the course of the present method. Furthermore, about 20 % to 75% of the cellulose reactive agent can be consumed during the course of the present method.
- the adduct of the present method can be added to an aqueous cellulosic slurry.
- the adduct of the present method can be added to paper or board.
- the adduct of the present method can be added to paper or board as a film or coating.
- the cellulose reactive functionalized polyvinylamide adduct obtained by the present method can be a water-soluble thermosetting resin.
- the cellulose reactive functionalized polyvinylamide adduct obtained by the present method can contain more than one aldehyde functionality.
- the cellulose reactive agent can be glyoxal, glutaraldehyde, furan dialdehyde, 2-hydroxyadipaldehyde, succinaldehyde, dialdehyde starch, diepoxy compounds, or combinations thereof.
- the vinylamide polymer can be a homopolymer or copolymer formed from (meth)acrylamide, or a substituted (meth)acrylamide.
- the vinylamide polymer can also be nonionic, cationic, potentially cationic, anionic, potentially anionic or amphoteric, or combinations thereof.
- the vinylamide polymer can be formed from (meth)acrylamide monomer or a substituted (meth)acrylamide monomer and a cationic monomer selected from the group consisting of diallyldialkyl ammonium salts, (dialkylamino)alkyl (meth)acrylates acid addition or quaternary salts, 2-vinylpyridines acid addition or quaternary salts, dialkylamino
- alkyl(meth)acrylamides acid addition or quaternary salts, (p-vinylphenyl)- trimethylammonium chloride, and l-methacryloyl-4-methyl piperazine, and acid addition or quaternary ammonium salts thereof.
- the vinylamide polymer can be formed from about 20 to about 99 weight percent of the (meth)acrylamide or the substituted (meth)acrylamide monomer.
- the vinylamide polymer or the polyvinylamide adduct is linear, crosslinked, chain-transferred, or crosslinked and chain-transferred.
- the vinylamide polymer or the polyvinylamide adduct can be crosslinked using at least a difunctional monomer selected from the group consisting of methylene bis(meth)acrylamide,
- triallylammonium chloride tetraallyl ammonium chloride, polyethyleneglycol diacrylate, polyethyleneglycol dimethacrylate, N-vinyl acrylamide, divinylbenzene, tetra(ethyleneglycol) diacrylate, dimethylallylaminoethylacrylate ammonium chloride, sodium salt of diallyloxyacetic acid, diallyloctylamide, trimethyllpropane ethoxylate triacryalte, N-allylacrylamide, N-methylallylacrylamide, pentaerythritol triacrylate, and combinations thereof.
- the vinylamide polymer can be a copolymer of (meth)acrylamide and diallyldimethylammonium halide.
- the vinylamide polymer can have an average molecular weight of about 500 to about 5,000,000 Daltons, or 2500 to about 5,000,000 Daltons.
- the vinylamide polymer can also have an average molecular weight of at least about 10,000 to about 1,000,000 Daltons; at least about between 30,000 to about 750,000 Daltons; at least about between 50,000 to about 750,000 Daltons; or at least about between 75,000 to about 600,000 Daltons.
- Adduct formation can be monitored by measuring a change in turbidity or viscosity of the aqueous reaction, wherein the change in turbidity or viscosity is the difference in turbidity or viscosity of the aqueous reaction at the start of the reaction and at a predetermined endpoint.
- the vinylamide polymer concentration can be less than about 4 weight % of the total reaction mixture, and the vinylamide polymer can have an average molecular weight of about 30,000 to about 1,000,000 Dalton.
- the vinylamide polymer concentration can also be less than about 2.5 weight % of the total reaction mixture, and the vinylamide polymer can have an average molecular weight of about 100,000 to about 1,500,000 Daltons.
- the adduct can be characterized by a turbidity of 0.5 to 500 NTU
- the adduct can be characterized by a turbidity of 0.5 to 200 NTU
- the present disclosure is also directed to a cellulose reactive functionalized polyvinylamide adduct obtained by the process according to the present method.
- the present disclosure is further directed to a paper or a board comprising a cellulose reactive functionalized polyvinylamide adduct obtained by the present method.
- FIG. 1 is a bar graph illustrating a linear relationship between reaction pH Set Point and reaction temperature. The figure is based on data obtained from
- FIG. 2 is a bar graph illustrating dry Mullen Burst Index as a function of percent of glyoxal consumed during formation of the polyvinylamide cellulose reactive adduct. The figure is based on data obtained from experiments described in Examples 2 and 3.
- FIG. 3 is a bar graph illustrating wet Mullen Burst Index as a function of percent of glyoxal consumed during formation of the polyvinylamide cellulose reactive adduct. The figure is based on data obtained from experiments described in
- an element means one element or more than one element.
- adduct the product of the methods for preparing a cellulose reactive functionalized polyvinylamide adduct comprising reacting a substantially aqueous reaction mixture of vinylamide polymer and a cellulose reactive agent
- adduct the product of the methods for preparing a cellulose reactive functionalized polyvinylamide adduct comprising reacting a substantially aqueous reaction mixture of vinylamide polymer and a cellulose reactive agent
- adduct formed adduct
- cellulose reactive functionalized polyvinylamide adduct the product of the methods for preparing a cellulose reactive functionalized polyvinylamide adduct comprising reacting a substantially aqueous reaction mixture of vinylamide polymer and a cellulose reactive agent
- glyoxalation reaction a type of a cellulose reactive agent
- glyoxalation reaction a type of a cellulose reactive agent
- product of the glyoxalation reaction is referred to interchangeably as “glyoxalated-polyvinylamide” or
- vinylamide refers to any vinyl monomer containing an amide functionality including but not limited to acrylamide, methacrylamide, N-methyl acrylamide, or any other substituted acrylamide.
- copolymer refers to a polymer formed from two or more monomers.
- starting vinylamide polymer or "backbone vinylamide polymer” refers to a polymer of vinyl monomers (also known as “vinylamide polymer”) used in the preparation of a cellulose reactive functionalized polyvinylamide adduct.
- the starting vinylamide polymer may be a homopolymer, copolymer, or terpolymer.
- the starting vinylamide polymer may be cationic, potentially cationic, anionic, potentially anionic, nonionic, or amphoteric.
- the starting vinylamide polymer may also be a blend of vinylamide polymer and another water-miscible non- vinylamide polymer.
- adduct formation refers to the adduct resulting from reacting a substantially aqueous reaction mixture of vinylamide polymer and a cellulose reactive agent.
- catalyzed adduct formation refers to adduct formation carried out in an environment such that physical or chemical conditions cause the reaction to progress at a moderate to accelerated rate, wherein the desired reaction is obtained in less than about 12 hours, in less than 6 hours, less than 3 hours , less than about 1 hour, or less than 10 minutes.
- Adduct formation may occur under alkaline conditions or by addition of a base or basic buffer.
- substantially aqueous reaction mixture refers to adduct formation carried out under conditions where the presence of organic oils does not exceed the weight of vinylamide polymer.
- adduct formation may be carried out under conditions where the total weight of the organic oils is less than 50 wt. % of the vinylamide polymer, is less than about 20 wt. % of the vinylamide polymer, less than 10 wt. % of the vinylamide polymer, less than about 5 wt.% of the vinylamide polymer, or less than about 1 wt. % of the vinylamide polymer.
- adduct formation may be carried out under conditions where there is no amount of oil is added during the adduct formation.
- the "wt. % of the vinylamide polymer” is defined as follows:
- Wt. % glyoxal consumed is based on total weight of glyoxal charged.
- Molecular weight refers to the mean weight average molecular weight (Mw). Molecular weight can be determined by standard methods such as GPC. For example, the average molecular weight may be determined by conventional calibration techniques using acetate buffer and the following columns: TSK PWXL (Guard+G6000+G3000). Polyethylene oxide and polyethylene glycol standards may be used to calibrate the column set.
- the concentration of vinylamide polymer refers to the concentration of vinylamide polymer
- incoming water refers to water that is used as solvent and/or reaction medium during adduct formation.
- reaction pH set point refers to the pH of the aqueous reaction solution during the reaction between vinylamide polymer and cellulose reactive agent.
- cellulose reactive agent refers to a compound that contains two or more functional groups capable of forming covalent bonds with cellulose, for example, dialdehydes and, more specifically, glyoxal or gluteraldehyde.
- (meth)acrylamides includes both acrylamide and methacrylamide.
- self-substantive refers to the property of having affinity for cellulose fibers.
- a vinylamide copolymer that is self-substantive has natural affinity for cellulose fibers. When these copolymers are put into aqueous solution with fibers, there will be an electrostatic attraction between the cationic polymer and the anionic cellulose fibers, resulting in "retention" of the polymer chains on the fibers.
- constant reaction rate refers to the reaction rate of a glyoxalation reaction between a polyvinylamide and a cellulose reactive agent when carried out in a continuous manner.
- the reaction rate is a function of reaction time and reaction extent, where the reaction extent is defined as the proportion of the cellulose reactive agent consumed during the reaction, i.e., 50% for example.
- a "constant reaction rate" has been established when both the reaction time and the reaction extent remains unchanged over a given period of time.
- the disclosed method offers unexpected advantages over batch processes and conventional continuous processes.
- the reaction solution temperature and the required reaction time can be automatically measured and used to calculate the solution pH required to maintain a constant quality of final adduct, using the mathematical equation disclosed, and thereby produce a constant quality of final adduct.
- a batch process or a conventional continuous process needs to be shut down and recalibrated to accommodate the changing temperature of the incoming water supply (e.g., where municipal water is used). Process shut-downs result in the loss of productivity and therefore increased costs for modifying the process to accommodate an increase or decrease in the temperature of the incoming water.
- the embodiments comprise the components and/or steps disclosed therein.
- the embodiments consist essentially of the components and/or steps disclosed therein.
- the embodiments consist of the components and/or steps disclosed therein.
- the vinylamide polymers that are used in adduct formation can be of any molecular weight obtainable by methods of polymer synthesis known to those skilled in the art.
- the vinylamide polymer may be nonionic, cationic, anionic, or amphoteric.
- the vinylamide polymer may be crosslinked or structured.
- the starting vinylamide polymer has an average molecular weight of at least 500.
- the average molecular weight of the vinylamide polymer may range from at least 500 to about 5,000,000 or even 10,000,000 Daltons.
- the starting vinylamide polymer may be at least about 10,000 to about 5,000,000.
- a starting vinylamide polymer with an average molecular weight of about 30,000 to 2,000,000, or about 70,000 to 1,000,000 is envisioned.
- the process of the disclosure includes adduct formation using vinylamide polymers of about 50,000 or greater, about 70,000 or greater and even about 85,000 or 100,000 or greater.
- Average molecular weight ranges of the starting vinylamide polymer include between 5,000 to about 150,000; 10,000 to about 150,000; or 25,000 to about 150,000.
- the vinylamide polymer can also have an average molecular weight of at least about 10,000 to about 1,000,000 Daltons; at least about between 30,000 to about 750,000 Daltons; or at least about between 50,000 to about 750,000 Daltons; or at least about between 75,000 to about 600,000 Daltons; or at least about 50,000 to about 1,000,000 Daltons.
- Suitable vinylamide monomers include (meth)acrylamide, Ci -4 mono substituted (meth)acrylamide, such as N-methyl(meth)acrylamide and N- ethyl(meth)acrylamide.
- the vinylamide monomers are acrylamide and methacrylamide.
- the vinylamide content of the polymers of the present disclosure provides the sites to which substituents of the cellulose reactive agent (for example, glyoxal substituents) are attached.
- the minimum proportion of vinylamide units that should be present in the vinylamide polymer should be sufficient so that the resulting adduct is thermosetting, such that the adduct forms a water-insoluble film when it is laid down from water solution on a glass plate and heated for 5 minutes at about 105°C.
- the starting vinylamide polymer (prior to adduct formation) may be prepared using at least about 10 wt. % vinylamide monomers.
- the starting vinylamide polymer may be formed from at least about 20 to about 100 wt. % vinylamide monomers.
- the starting vinylamide polymer may be formed from at least about 20 to about 99 wt % vinylamide monomer, at least about 25 to about 90 wt. % vinylamide monomer, or at least about 50 wt. % vinylamide monomer, or at least about 70 wt % vinylamide monomer.
- the wt. % vinylamide monomer is based on the weight of the total weight of monomers charged to form the vinylamide polymer. Once the monomers polymerize, they become incorporated units in the polymer.
- units in the polymers of the present disclosure which may confer ionic properties upon the polymer, or those which act as diluents or spacers, or which confer particular properties, for example, improved or diminished water- solubility.
- Ionic co-monomers which can be used in conjunction with vinylamide monomers, can be cationic, potentially cationic, anionic, potentially anionic, or amphoteric.
- cationic co-monomers one or more cationic monomers can be used, and the total amount of cationic monomer should be such that an adduct of the vinylamide copolymer is self-substantive cellulose fibers in aqueous suspension.
- Cationic co-monomers may be used to impart substantivity to cellulose fiber.
- substantially means that there is an inherent attraction between the copolymers and the fibers, and that no additional additive is needed to facilitate the attraction.
- Suitable cationic monomers or potentially cationic monomers include diallyldialkyl amines, 2-vinylpyridine, 2-(dialkylamino)alkyl(meth)acrylates, and dialkylamino alkyl(meth) acrylamides, and acid addition and quaternary ammonium salts thereof.
- Exemplary cationic monomers or potentially cationic monomers include diallyldimethyl ammonium chloride, (meth)acryloyloxy ethyl trimethylammonium chloride (dimethyl amino ethyl(meth)acrylate, methyl chloride quaternary salt), 2- vinyl-N-methylpyridinium chloride, (p-vinylphenyl)-trimethylammonium chloride, (meth)acrylate 2-ethyltrimethylammonium chloride, l-methacryloyl-4-methyl piperazine, Mannich poly acrylamides (i.e., polyacrylamide reacted with dimethyl amine formaldehyde adduct to give N-(dimethyl amino methyl), and
- Potentially cationic monomers may be, for example, monomers that give a cationic charge under acidic conditions such as when amine functionality on the potentially cationic monomer is protonated.
- the amount of cationic co-monomer may range from about 0% to about 90 wt. %, about 0.1 to about 80 wt %, about 0.1 to about 40, about 0.1 to about 30, about 0.1 to about 25 wt % or about 0.1 to about 15 or about 10 wt. %.
- the wt. % of cationic co-monomer is based on the total weight of monomer(s) charged to form the vinylamide polymer.
- the vinylamide monomers may be copolymerized with vinyl tertiary amines such as dimethylaminoethyl acrylate or vinylpyridine.
- the tertiary amine groups can then be converted into quaternary ammonium groups by reaction with methyl chloride, dimethyl sulfate, or benzyl chloride to produce a cationic polymer.
- polyacrylamide can be rendered partially cationic by reaction with glycidyl dimethyl ammonium chloride.
- Suitable anionic monomers include vinyl acidic materials such as acrylic acid, methacrylic acid, maleic acid, allyl sulfonic acid, vinyl sulfonic acid, itaconic acid, fumaric acid, potentially anionic monomers (such as maleic anhydride and itaconic anhydride and their alkali metal and ammonium salts), 2-acrylamido-2-methyl- propanesulfonic acid and its salts, and sodium styrene sulfonate.
- the starting vinylamide polymer is polyacrylamide, it may be partially hydrolyzed to achieve some anionic character then functionalized with the cellulose reactive agent.
- Potentially anionic monomers may be, for example, acrylamide, which, when partially hydrolyzed, forms an acid which may give anionic character to the polymer under basic conditions.
- the potentially anionic monomers may be, for instance, an anhydride monomer, such as maleic anhydride or itaconic anhydride, which can be hydrolyzed to form the corresponding acid.
- the starting vinylamide polymer may be amphoteric.
- the starting vinylamide polymer may include anionic and cationic functionality.
- the amphoteric starting vinylamide polymer may be formed from both anionic and cationic monomers, or may alternatively be formed from zwitterionic monomers.
- Various anionic, cationic, and/or zwitterionic monomers may be reacted in any weight ratio to form the amphoteric starting vinylamide polymer.
- the predominate charge on the formed amphoteric vinylamide polymer may be cationic.
- the mole % of cationic monomer dominates over the mole % anionic monomer incorporated into the amphoteric vinylamide polymer.
- Suitable non-ionic monomers other than the vinylamide may be selected from the group consisting of (meth) acrylic esters such as (octadecyl(meth)acrylate, ethyl acrylate, butyl acrylate, methylmethacrylate, hydroxyethyl(meth)acrylate and 2- ethylhexylacrylate), N-alkyl acrylamides, N-octyl(meth)acrylamide, N-tert-butyl acrylamide, N-vinylpyrrolidone, N,N-dialkyl(meth)acrylamides (such as ⁇ , ⁇ '- dimethyl acrylamide), styrene, vinyl acetate, hydroxy alkyl acrylates, and
- methacrylate such as 2-hydroxy ethyl acrylate and acrylonitrile
- the starting vinylamide polymer may be crosslinked, branched or otherwise structured or linear.
- the starting vinylamide polymer may be linear, chain-transferred, or crosslinked and chain-transferred (i.e., structured).
- Cross linking agents that may be used include polyethylenically unsaturated crosslinking agents.
- Non-limiting examples of cross linking agents are methylene bis(meth)acrylamide, trial lylammonium chloride, tetraallyl ammonium chloride, polyethyleneglycol diacrylate, polyethyleneglycol dimethacrylate, N-vinyl acrylamide, divinylbenzene, tetra(ethyleneglycol) diacrylate,
- dimethylallylaminoethylacrylate ammonium chloride diallyloxyacetic acid, Na salts, diallyloctylamide, trimethyllpropane ethoxylate triacryalte, N-allylacrylamide N- methylallylacrylamide, pentaerythritol triacrylate, and combinations thereof.
- Other systems for crosslinking can be used instead of, or in addition to these cross linking agents.
- covalent crosslinking through pendant groups can be achieved by the use of ethylenically unsaturated epoxy or silane monomers, or by the use of polyfunctional crosslinking agents such as silanes, epoxies, polyvalent metal compounds, or other known crosslinking systems.
- the backbone vinylamide polymers which are used to prepare the adduct, may be synthesized by free radical or redox catalysis polymerization of a vinylamide monomer, and optionally one or more ionic co-monomer(s) or nonionic co- monomers.
- Cross-linking agents with multiple polymerizable vinyl functionalities can also be included in the formulations to impart structure to the backbone polymer.
- a chain transfer agent such as sodium hypophosphite, may be used to control the molecular weight of the polymer molecules, as well as to introduce branching.
- a water soluble starting vinylamide polymer may be formed by any suitable polymerization process.
- the starting vinylamide polymer may be prepared as gel polymers by solution polymerization, water-in-oil suspension polymerization or by water-in-oil emulsion polymerization.
- the starting vinylamide polymer may also be produced as beads by suspension polymerization or as a water- in-oil emulsion or dispersion by water-in-oil emulsion polymerization, for example according to the process set forth in EP-A-150933, EP-A-102760, or EP-A-126528.
- the water soluble polymer may be provided as a dispersion in an aqueous medium.
- This may, for instance, be a dispersion of polymer particles of at least 20 microns in an aqueous medium containing an equilibrating agent as given in EP-A-170394.
- This may, for example, also include aqueous dispersions of polymer particles prepared by the polymerization of aqueous monomers in the presence of an aqueous medium containing dissolved low intrinsic viscosity polymers such as poly diallyl dimethyl ammonium chloride and optionally other dissolved materials, for instance, electrolyte and/or multi-hydroxy compounds, e.g., polyalkylene glycols, as given in WO-A-9831749 or WO-A-9831748.
- Chain transfer agents may be used to synthesize the starting vinylamide polymer.
- Suitable chain transfer agents include, but are not limited to 2- mercaptoethanol; low molecular weight organic acids such as lactic acid, formic acid, malic acid, or butyric acid; isopropyl alcohol; thioacids and hypophosphites.
- the cellulose reactive agent will comprise more than one aldehyde functionality.
- exemplary cellulose reactive reagents include glyoxal, glutaraldehyde, furan dialdehyde, 2-hyroxyadipaldehyde, succinaldehyde, dialdehyde starch, diepoxy compounds, and combinations thereof.
- the molar ratio of amide (on the vinylamide polymer) to cellulose reactive agent may vary from about 12: 1 to about 2: 1, for example, about 10: 1 to about 2.5: 1, about 10: 1 to about 1 : 1, about 6: 1 to about 2.5: 1 and about 6: 1 to about 3: 1, and integer values there between.
- the molar content of amide on the vinylamide polymer may be determined experimentally by methods well known in the art or calculated from the known monomer composition.
- Conventional additives which may be added to the adduct formation reaction are chelating agents to remove polymerization inhibitors, pH adjusters, initiators, buffers, surfactants, and other conventional additives.
- ком ⁇ онент such as sodium chloride, surfactant, and polar solvents such as methanol may be present in the reaction mixture.
- Low molecular weight cationic polymers such as polysaccharides, polydiallyldimethylammonium chloride (polyDADMAC), and polyamines.
- Inorganic cationic flocculants may also be present, such as ferric chloride, aluminum sulfate, polyaluminum chloride, and aluminum chlorohydrate, etc., may be present in the reaction mixture.
- the vinylamide polymer or formed adduct may be further combined with a second polymer (different than the vinylamide polymer), which may be cationic, anionic, non-ionic or amphoteric.
- a second polymer different than the vinylamide polymer
- the glyoxalated polyvinylamide polymer may be combined with a polyamine or polyaminopolyamide epichlorohydrin (PAE), polyvinylamine.
- the second polymer may be cationic, or may be formed from cationic or potentially cationic monomers, such as those described herein.
- the second polymer may be a Mannich base, polyamine, polyethyleneimine,
- dicyandiamide polymers including polyamine-dicyandiamide and polydicyandiamide formaldehyde polymers
- cationic starch additional examples of the second polymer may include polyamine-epihalohydrin resins, such as polyaminopolyamide- epihalohydrin resins, which may be cationic thermosetting materials used to increase the wet strength of papers.
- Preparation of the cellulose reactive functionalized polyvinylamide adduct may be catalyzed by a basic pH.
- a pH range of about 8.5 to about 12 is generally considered to be a catalytic environment for the reaction.
- a concentrated pH buffer solution may be added to the reaction to maintain pH in the desired catalytic range.
- the concentration of vinylamide polymer refers to the concentration of the starting polymer before reaction with the cellulose reactive agent or adduct formation.
- cellulose reactive adducts can be formed from starting vinylamide polymers of significantly higher Mw than those adducts enabled by the processes of the prior art. This process enables the use of vinylamide polymers of any Mw, so long as the concentration of the vinylamide polymer is at or below its own critical concentration during the reaction between that polymer and the cellulose reactive agent.
- Critical Concentration of a vinylamide polymer coincides with an inflection point in the rheological behavior of a solution of that vinylamide polymer during the adduct formation reaction.
- This rheological inflection point can be defined as the point on a plot of vinylamide polymer concentration versus change in reaction mixture viscosity resulting from adduct formation.
- the inflection point, and therefore the Critical Concentration is the theoretical point at which the slope of the plot line reverses direction.
- the Critical Concentration for adduct formation using a vinylamide polymer may be determined through empirical studies involving a vinylamide polymer with one or more cellulose reactive agents. Multiple reactions of the vinylamide polymer with one or more cellulose reactive agents should be carried out in a number of independent reaction solutions, wherein each solution has a known and different vinylamide polymer concentration which is expressed as a wt. % of the total reaction mixture.
- the rheological behavior or change in viscosity of a reaction mixture is measured as adduct formation proceeds, and this change in viscosity can be either a continued increase in viscosity or a continued decrease in viscosity as the reaction proceeds, or even no statistically significant change in viscosity as the reaction proceeds.
- the concentration of vinylamide polymer in the reaction mixture is said to be above the Critical Concentration for that vinylamide polymer. If the viscosity trend decreases as the reaction proceeds, then the concentration of the vinylamide polymer in the reaction mixture is below the Critical Concentration for that vinylamide polymer. If no statistically significant change in viscosity is measured as the reaction proceeds, then the concentration of vinylamide polymer in the reaction solution is at or very near the Critical Concentration of that vinylamide polymer.
- the Critical Concentration of a particular vinylamide polymer is strongly influenced by the vinylamide polymer molecular weight, and is therefore specific for vinylamide polymers with specific molecular weights, and with other equivalent characteristics. Other factors including but not limited to cross-linking, branching or other structuring, monomer composition, polymer ionicity and reaction solution ionic strength also affect the Critical Concentration. However, molecular weight has by far the most profound impact on the value of the Critical Concentration. When considering a specific vinylamide polymer composition with all variables held constant except for molecular weight, the plot of the reaction mixture vinylamide polymer concentration versus molecular weight depicts an inversely proportional relationship between molecular weight and Critical Concentration. As the molecular weight of vinylamide polymers is increased, the value of the Critical Concentration decreases.
- the Critical Concentration can therefore vary considerably between vinylamide polymers of differing average molecular weights.
- the Critical Concentration may vary from 0.2% to about 4.5 wt. % of the vinylamide polymer, about 0.3 wt. % to less than 4.0 wt. %, about 0.5 to about 3.5 or 1.0 to about 3.0 or about 1.5 to about 2.5 wt. % of the vinylamide polymer.
- Vinylamide polymers with the highest efficiency for developing strength in paper have been found to have Critical Concentrations in the range of about 1.0% to about 3.0%.
- the Critical Concentration varies with the weight average molecular weight of vinylamide polymers, and considering specific vinylamide polymers composed of 90 weight percent acrylamide and 10 weight percent diallyldimethylammonium chloride (DADMAC), and with no compounds present in the reaction mixture other than the vinylamide polymer, glyoxal, deionized water and a catalytic quantity of sodium hydroxide; a polymer with a Mw of approximately 4,000,000 has a Critical Concentration of about 0.35 wt. % of the reaction mixture, and a polymer with a Mw of approximately 13,000 has a Critical Concentration of about 3.5 wt. % of the reaction mixture.
- DADMAC diallyldimethylammonium chloride
- compositional and process related advantages have been found when adduct formation occurs at or below the Critical Concentration. It is also possible to realize the advantages of the process when the vinylamide polymer concentration is slightly above the Critical Concentration. For example, the concentration can be about 1 percentage points above the Critical Concentration and the adduct produced will benefit from more efficient consumption of the cellulose reactive agent reactant and better performance on paper, when compared to those adducts produced at higher concentrations known previously (typically 8 to 12 wt. %).
- Another advantage of the process is the ability to form adducts using relatively high average molecular weight vinylamide polymer without premature gelling of the glyoxalated adduct.
- subjecting various samples of the adduct to conditions that break aldehyde-amide bonds allows one to determine the Mw of the starting or "backbone" polymer. This can be done by subjecting the adduct to basic conditions for a period of time.
- the concentration of the vinylamide polymer may vary considerably, for example, in the following manner: less than 4 wt. %, about 0.1 to less than 4, less than 3.5, 0.5 to about 3.5 wt. % vinylamide polymer, about 1.0 to about 3.5 or 1.0 to about 3.0 or about 1.5 to about 3.0 wt. % vinylamide polymer.
- the Critical Concentration of the vinylamide polymer is generally at or less than 5.0 weight percent vinylamide polymer based on the total weight of glyoxalation reaction solution when the molecular weight is above 2,000.
- a vinylamide polymer of molecular weight ranging from about
- the glyoxal consumed in the described methods may be determined by measuring the residual glyoxal (unbound glyoxal) remaining in the glyoxalation reaction mixture. The reaction is continued until at least about 15 wt. % of the total glyoxal has been consumed, and the reaction may also be usefully continued until as much as 90 or more weight % of the total glyoxal is consumed in the reaction.
- the method of analysis is described in the Examples section.
- Consumption of the cellulose reactive agent may be at least about 10 wt. %, or even at least 20, 40, 60, 65, 75, 85 or 90 wt. % of cellulose reactive agent during adduct formation.
- Reactant cellulose reactive agent (such as glyoxal) is the amount of total cellulose reactive agent charged before, during or after the adduct formation reaction.
- Cellulose reactive agent (such as glyoxal) is charged in any number of increments before and/or during the reaction.
- adduct formation between vinylamide polymer and a cellulose reactive agent, such as glyoxal is monitored by measuring the viscosity of the reaction over time. Once a certain increase in viscosity is achieved for a particular vinylamide polymer, the reaction is quenched by dilution and/or addition of acid.
- the disclosed adduct formation shows only a very moderate increase in viscosity, a slight decrease in viscosity, or no increase at all. It was observed for the method disclosed herein that as the glyoxalation of the vinylamide polymer proceeds, the turbidity of the reaction solution increases. Thus, the adduct formation method may be monitored using a turbidimeter or a viscometer. Therefore, adduct formation may be determined by measuring the change in turbidity or viscosity of the aqueous reaction at the start of the reaction or To and at a predetermined endpoint T e (T e -To).
- the predetermined endpoint is, for example, a desired increase in turbidity (measure of glyoxalation) for a particular vinylamide polymer.
- a vinylamide polymer of 100,000 average molecular weight may give a turbidity of 0 to 5 NTU (nephelometric units) at the beginning of the reaction (T 0 ) and a turbidity change of between 0.5 to 500 NTU at the predetermined endpoint.
- Turbidity measurements can be useful to monitor adduct formation when the reaction takes place at or below the Critical Concentration.
- Turbidity can be measured using turbidimeters are known in the art.
- turbidimeters are known in the art.
- SURFACE SCATTER 7SC turbidimeter is a continuous-monitoring instrument designed for measuring turbidity in fluids.
- the instrument design is based on the nephelometric principle, where light scattered by particles suspended in the fluid is measured to determine the relative amount of particulate matter in the fluid.
- Viscosity can be measured using viscometers are known in the art. Viscosity typically can be measured during the reaction using the UL adapter for a
- BROOKFIELD LV series viscometer The UL adapter has no spindle number. Only one setting is possible. The base of the adapter cup is removed and the assembly is placed directly into the reaction mixture. Viscosity measurements can be automatically recorded every second during the length of the catalyzed reaction. The viscometer is set to a speed of 60 rpm and the temperature of the reaction mixture is maintained at about 25 °C.
- the adduct is prepared in a continuous mode, wherein one or more of the reaction parameters is automatically recalibrated as needed to maintain a constant reaction rate.
- the process of the present disclosure may include a method comprising reacting a substantially aqueous reaction mixture of a vinylamide polymer and a cellulose reactive agent at a temperature of about 1 °C to about 60 °C and a reaction pH set point of about 8.5 to about 12, for about 1 minutes to about 300 minutes,
- the pH of the reaction mixture is adjusted to maintain an approximately constant reaction rate (see e.g., Example 2 and Figure 1);
- the concentration of the vinylamide polymer prior to and during formation of the adduct is about 0.25-15% of the total reaction mixture, thereby forming the adduct.
- the process of the present disclosure is particularly favorable for
- the continuous process may also be programmed such that the temperature of incoming water is monitored and the reaction time of adduct formation is varied while keeping the pH constant.
- the pH may be kept constant using a buffer that maintains the reaction at a high pH, i.e., a pH of about 10 to about 11. This is an improvement over known methods where storing the adduct at high pH shortened the shelf life of the adduct because the aldehyde functional groups of the adduct would be hydrolyzed. It was surprisingly found that the adduct formed at high pH from the disclosed process can be stored for a longer time than adduct formed from traditional methods.
- reaction may be run at ambient temperatures.
- the reaction may also be carried out over a wide temperature range. For instance, the reaction may be carried out at a temperature of about 1 °C to about 65 °C.
- Adduct formation may be carried out for about 2 minutes to about 200 minutes. Furthermore, adduct formation may be run at the concentration of the vinylamide polymer is 0.5-20%.
- the adduct may be used in the manufacture of paper as dilute aqueous solutions.
- the aqueous solutions can be applied to preformed paper by the tub or impregnation method, or by adding the solutions directly to paper-making fibrous suspensions, such as an aqueous cellulosic slurry, at any point in the paper-making process where wet- and dry-strength resins are ordinarily applied.
- the cellulose reactive polyvinylamide adducts may be applied or incorporated in the wet-end of the papermaking process or applied to the wet paper.
- the adduct may be added in the thick or thin stock. When added to the thin stock, it may be added before the fan pump.
- a substantial amount of wet- or dry-strength is imparted when as little as about 0.05 wt. % of the adduct, based on dry fiber weight of the furnish is added to the furnish.
- dosages of about 0.1 to about 20 (0.05-10 kg/metric ton) pounds dry polymer per ton of dry furnish, about 1 to about 12, (0.5-6 kg/metric ton) about 1 to about 9 (0.5-4.5 kg/metric ton), about 1 to about 8 (0.5-4 kg/metric ton) pounds dry polymer per ton of dry furnish is envisioned. More typically ranges of 1.5 to about 6 (1.0-3 kg/metric ton) pounds dry polymer per ton of dry furnish are envisioned.
- adduct to wet paper or board may be accomplished by any conventional means. Examples include but are not limited to size press, padding, spraying, immersing, printing, or curtain coating.
- the adduct may be absorbed by the paper-making fibers at pH values ranging from about 3.5 to about 8.
- Example 1 Comparative example of glyoxalated polyvinylamides synthesized by the process of the invention and alternatively by a batch process.
- a vinylamide copolymer composed of 9 weight percent DADMAC and 91 weight percent acrylamide was synthesized by redox polymerization as an aqueous solution containing 30 percent polymer solids by weight, with a weight average molecular weight of 110,000. This polymer was used as the base polymer for the two comparative glyoxalation reactions, Reaction A and Reaction B, which follow.
- Reaction A was run as a "batch" reaction at an ambient temperature of 21 °C.
- the reaction solution for Reaction A was prepared by combining 28.33 grams of the 30% solids vinylamide base polymer, 5.0 grams of 40% aqueous glyoxal and 467.92 grams of deionized water to make a solution of 1.7 weight percent vinlyamide polymer and 0.4 weight percent glyoxal.
- the reaction solution was mixed to homogeneity by way of overhead mixing, and mixing was continued for the duration of the reaction.
- An aqueous solution of 5 weight percent sodium hydroxide was added dropwise to the reaction mixture until the pH reached 9.5, and was added intermittently to maintain the solution pH at 9.5 for the duration of the reaction.
- the initial turbidity of the reaction solution was measured once the reaction solution reached a pH of 9.5 and was recorded as T(i).
- the turbidity of the reaction solution was measured intermittently until the turbidity increased by 5 NTU above T(i). Once a 5 NTU increase in turbidity was achieved, a solution of 5 weight percent sulfuric acid was added dropwise to lower the pH of the solution to 3.5 to stop the forward progress of the reaction. A sample of the final product was collected and labeled as Product A.
- Reaction B was run by the process of the present application at an ambient temperature of 22 °C.
- a portion of the vinylamide base polymer was diluted to 2.21 percent solids with deionized water to make four liters of base polymer feed stock.
- a portion of 40% aqueous glyoxal was diluted to 1.88 percent glyoxal with deionized water to make one liter of glyoxal feed stock.
- a solution of 2.0 percent sodium hydroxide feed stock was made by diluting 50 percent aqueous sodium hydroxide solution with deionized water.
- a 16.5 meter section of 0.2 centimeter (inside diameter) polyurethane tubing was wound around a cylinder to function as a continuous tubular reactor.
- the base polymer feed stock and the glyoxal feed stock were pumped continuously by peristaltic pumps at feed rates of 2.0 and 0.55 milliliters per minute respectively, and the two flows were combined with a "Y" connector into a 50 centimeter section of 0.2 centimeter (ID) polyurethane tubing.
- the 2.0 percent sodium hydroxide feed stock was pumped continuously using a syringe pump at a flow rate of 0.03 to 0.06 milliliters per minute, and was combined with the base polymer and glyoxal feed stock flow using a separate "Y" connector, which combined the flows directly into the 16.5 meter section of reaction tubing.
- the reaction solution was sampled immediately following the combination of the three raw materials into one flow, and the turbidity of the solution was measured and recorded as the initial turbidity, T(i).
- T(i) initial turbidity
- the continuous reaction system was allowed to run for one hour to reach a steady state, after which time a sample of the material dripping from reaction tubing was collected and turbidity of the sample was measured and recorded as the final turbidity T(f).
- a sample of material exiting the tubular reactor was collected and the pH of the reaction sample was lowered to 3.5 by the dropwise addition of 5% sulfuric acid solution. This sample was labeled as Product B.
- Sample A and Sample B were evaluated in a hand sheet evaluation.
- the Canadian Standard Freeness (CSF) of the fiber slurry was adjusted to 350 by beating.
- Aliquots of Samples A and B were diluted to 0.25% solids for dosing to the fiber slurry.
- Aliquots of the fiber slurry, each containing approximately 3.0 grams of oven dry solids, were individually heated to 50 degrees Celsius and placed under overhead mixing.
- the diluted strength additive solutions were added to the heated aliquots of fiber slurry and mixed for twenty seconds.
- the treated slurry was then added to a 200 square centimeter hand sheet mold where it was mixed with additional dilution water.
- the fiber slurry in the sheet mold was then dewatered by gravity over a screen to form a wet fibrous mat, the mat was couched from the screen, pressed at 40 psi on a rolling nip press, and the pressed hand sheets were dried on a rotating drum dryer.
- the dried hand sheets weighed approximately 3.0 grams each, representing a basis weight of approximately 150 grams per square meter.
- the finished hand sheets were tested for Ring Crush strength using a 17-76 Compression Tester from TESTING MACHINES INC.
- the Ring Crush results were indexed to basis weight. Specifically, the strength results for each sheet in kilonewtons (kN) were divided by the basis weight of each sheet in grams per square meter. The data are depicted in Table 2.
- a series of glyoxalation reactions was performed to determine the feasibility to overcome temperature-induced changes in glyoxalation reaction rate by manipulation of reaction solution pH. Specifically, the goal of this experiment was to determine if reaction rate could be held constant across a range of temperatures by predictive control of reaction solution pH.
- Example 3 Adduct efficiency as a function of % Glyoxal Consumed and Net Turbidity Change
- a series of glyoxalation reactions were performed with the same starting vinylamide polymer described in Example 1.
- the duration and the reaction solution pH were varied to produce adducts with varying extents of reaction between the vinylamide polymer and glyoxal.
- the extent of reaction was quantified by measuring the quantity of unreacted glyoxal remaining in the adduct solutions after formation was completed. The goal of these experiments was to determine the effect of varying the extent of reaction on the efficiency of the formed adducts as dry and wet strength aids.
- reaction solution pH was controlled by the drop-wise addition of 5 percent by weight solutions of sodium hydroxide or sulfuric acid. In each reaction, the pH was held constant at the prescribed value for the full extent of the reaction duration. The data are depicted in Table 3.
- the twelve adducts were incorporated into hand sheets by the following method: A slurry of cellulose fibers containing 50% bleached hardwood fibers and 50% bleached softwood fibers, a freeness of 500 (CSF), a consistency of 0.86% and a pH of 6.8 was produced for this experiment. Four hundred (400) gram aliquots of the fiber slurry were heated to 130 degrees F, placed under mixing, and the various adducts were added at a rate of 5 pounds per ton of oven dried fibers. After adduct addition, the fiber slurries were mixed for 20 seconds and then transferred to a sheet mold, where hand sheets with an approximately area of 200 square centimeters and bone dry mass of 3.0 grams were formed.
- the wet fiber webs were then couched from the sheet mold onto blotter paper and run through a pneumatic press at a nip pressure of 40 psi.
- the pressed sheets were then fed into a steam heated rotary drum drier for a period of 2 minutes at 240 degrees Fahrenheit (°F).
- the dried sheets were then placed in a controlled atmosphere of 73 °F and 50% relative humidity for a period of 24 hours prior to performing strength tests on the sheets.
- the mass of each hand sheet was measured and recorded, and then the hand sheets were tested for dry and initial wet Mullen burst strength. The measurements for the Mullen burst strength were then divided by the mass of the individual hand sheets to eliminate the effect of variations in sheet weight on the strength results.
- a set of seven compositionally-equivalent vinylamide polymers was synthesized with varying weight average molecular weights.
- the seven polymers were all copolymers of 90 weight percent acrylamide and 10 weight percent polydiallyldimethylammonium chloride (DADMAC).
- DADMAC polydiallyldimethylammonium chloride
- Samples A, B, C, and D were synthesized by heterogeneous suspension polymerization, and samples E, F, and G were synthesized by aqueous solution polymerization.
- DAWN multi-angle light scattering detector in combination with a differential refractive index detector.
- the amount of light scattered at a given angle was directly proportional to the weight average molar mass and the concentration.
- a second order Zimm plot was used to generate molar mass data with a dn/dc (specific refractive index increment) value of 0.1800 (angles 4-15).
- the average molecular weight was determined by conventional calibration techniques using acetate buffer and the following columns: TSK PWXL (Guard+G6000+G3000). Polyethylene oxide and polyethylene glycol standards were used to calibrate the column set.
- Sample E lies between 1.50 and 1.75%
- Sample G lies between 3.20 and 3.6% vinylamide polymer concentration, based on the total weight of the reaction mixture.
- Example 6 Adduct efficiency as a function of base polymer molecular weight
- the cellulose substrate used for the testing was obtained from a linerboard machine with a 100% post-consumer stock stream. Hand sheets of 140 grams per square meter weight were prepared for this testing.
- Table 6 The results in Table 6 show the dry strengthening efficiency of each adduct when added at a rate of 6 dry pounds of adduct per dry ton of paper (3 kg/metric ton).
- the Commercial Product has a Mw of approximately 10,000 and a glyoxal to amide molar ratio of about 1 to about 2.5.
Abstract
Description
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CN201280060190.5A CN103987746B (en) | 2011-12-06 | 2012-12-06 | The preparation of polyvinylamide cellulose reactive addition product |
BR112014013259-3A BR112014013259B1 (en) | 2011-12-06 | 2012-12-06 | METHOD FOR PREPARING A CELLULOSE REACTIVE FUNCTIONALIZED POLYDINILAMIDE ADDUCT, AND REACTIVE CELLULOSE FUNCTIONALIZED POLYDINILAMIDE ADDUCT |
EP12820893.1A EP2788392B1 (en) | 2011-12-06 | 2012-12-06 | Preparation of polyvinylamide cellulose reactive adducts |
CA2858310A CA2858310C (en) | 2011-12-06 | 2012-12-06 | Preparation of polyvinylamide cellulose reactive adducts |
PL12820893T PL2788392T3 (en) | 2011-12-06 | 2012-12-06 | Preparation of polyvinylamide cellulose reactive adducts |
KR1020147018345A KR102102238B1 (en) | 2011-12-06 | 2012-12-06 | Preparation of polyvinylamide cellulose reactive adducts |
ES12820893.1T ES2670003T3 (en) | 2011-12-06 | 2012-12-06 | Preparation of polyvinyl amide adducts reactive with cellulose |
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Also Published As
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EP2788392A2 (en) | 2014-10-15 |
EP2788392B1 (en) | 2018-02-21 |
US8920606B2 (en) | 2014-12-30 |
US20130139985A1 (en) | 2013-06-06 |
NO2878018T3 (en) | 2018-04-14 |
CN103987746B (en) | 2018-04-20 |
HUE037230T2 (en) | 2018-08-28 |
BR112014013259B1 (en) | 2020-09-29 |
CA2858310A1 (en) | 2013-06-13 |
KR102102238B1 (en) | 2020-04-20 |
CA2858310C (en) | 2021-02-16 |
ES2670003T3 (en) | 2018-05-29 |
US20170159242A9 (en) | 2017-06-08 |
US20150204019A1 (en) | 2015-07-23 |
EP2963067A1 (en) | 2016-01-06 |
CN103987746A (en) | 2014-08-13 |
KR20140100979A (en) | 2014-08-18 |
US9879381B2 (en) | 2018-01-30 |
WO2013084062A3 (en) | 2014-07-10 |
HRP20180663T1 (en) | 2018-06-01 |
PL2788392T3 (en) | 2018-08-31 |
PT2788392T (en) | 2018-04-27 |
BR112014013259A2 (en) | 2017-06-13 |
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