WO2022110102A1 - Polyacrylamide glyoxalé anionique - Google Patents

Polyacrylamide glyoxalé anionique Download PDF

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Publication number
WO2022110102A1
WO2022110102A1 PCT/CN2020/132621 CN2020132621W WO2022110102A1 WO 2022110102 A1 WO2022110102 A1 WO 2022110102A1 CN 2020132621 W CN2020132621 W CN 2020132621W WO 2022110102 A1 WO2022110102 A1 WO 2022110102A1
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Prior art keywords
dialdehyde
modified polymer
mol
kda
polymer mixture
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Inventor
Jinming Zhang
Meng Zhang
Qun DONG
Zhi Chen
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Ecolab USA Inc
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Ecolab USA Inc
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Priority to CN202080107561.5A priority Critical patent/CN116568889A/zh
Priority to PCT/CN2020/132621 priority patent/WO2022110102A1/fr
Publication of WO2022110102A1 publication Critical patent/WO2022110102A1/fr
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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
    • 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
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/50—Acyclic compounds

Definitions

  • Glyoxalated polyacrylamides are used in the papermaking process as strength aids, playing a role in enhancing paper strength properties such as, for example, dry tensile strength, wet tensile strength, temporary wet tensile strength, ring crush, burst, and Scott bond.
  • Treatment of a paper sheet precursor with a GPAM strength aid can improve certain properties of the finished product and/or the papermaking process.
  • Treatment with a GPAM strength aid can, for example, allow for increased ash content in the finished paper, boost strength properties of the finished paper, increase retention during the papermaking process, and improve dewatering efficiency during the papermaking process.
  • GPAM polymer products are prepared by reacting a polyacrylamide polymer backbone with an excess amount of glyoxal under basic conditions, e.g., a pH of about 9 (see, for example, U.S. Patent Application Publication 2017/0002519, “the ’519 publication” ) .
  • a pH of about 9 see, for example, U.S. Patent Application Publication 2017/0002519, “the ’519 publication”
  • the glyoxalation process is retarded by reacting with an acid until the reaction reaches a pH of 3 or less (quenching) .
  • quenching does not completely terminate the glyoxalation reaction as demonstrated by the continued increase in the molecular weight of GPAM polymers after quenching.
  • gelation of conventional GPAM polymers typically occur within about three weeks when stored at temperatures above 25 °C.
  • the ’519 publication provides a two-step method, where the polymer ingredients are stabilized at a low pH, and then shipped to the consumer for on-site preparation of the GPAM.
  • said two-step method requires marketing an unfinished product, and facilities on-site to prepare the GPAM strength aid.
  • a dialdehyde-modified polymer mixture comprises a solvent and a dialdehyde modified polymer comprising: (a) a polymer backbone comprising: (i) one or more monomer unit (s) derived from a monomer of Formula I:
  • R 1 is H or C 1 -C 4 alkyl and each R 2 is independently selected from H or a linear or branched C 1 -C 10 aliphatic group, and (ii) about 10 mol%to about 50 mol%of one or more anionic monomer unit (s) , and (b) a dialdehyde modification to the polymer backbone, wherein the dialdehyde-modified polymer mixture has a pH of from about 4.0 to about 7.0.
  • a method of making a dialdehyde-modified polymer comprises: (i) initiating a chemical reaction by treating a polymer backbone with a dialdehyde, wherein the polymer backbone comprises: (a) one or more monomer unit (s) derived from a monomer of Formula I:
  • R 1 is H or C 1 -C 4 alkyl and each R 2 is independently selected from H or a linear or branched C 1 -C 10 aliphatic group, and (b) about 10 mol%to about 50 mol%of one or more anionic monomer unit (s) and (ii) quenching the chemical reaction by adjusting the pH until a pH of from about 4.0 to about 7.0 is reached.
  • the resulting dialdehyde-modified product is shelf stable and can be used for any application demanding an anionic dialdehyde-modified polymer (e.g., the papermaking industry) .
  • FIG. 1 illustrates the viscosity results for Example 1.
  • FIG. 2 illustrates the viscosity results for Example 2.
  • FIG. 3 illustrates the viscosity results for Example 3.
  • FIG. 4 illustrates the viscosity results for Example 4.
  • a dialdehyde-modified polymer mixture comprises a solvent and a dialdehyde modified polymer comprising: (a) a polymer backbone comprising: (i) one or more monomer unit (s) derived from a monomer of Formula I:
  • R 1 is H or C 1 -C 4 alkyl and each R 2 is independently selected from H or a linear or branched C 1 -C 10 aliphatic group, and (ii) about 10 mol%to about 50 mol%of one or more anionic monomer unit (s) , and (b) a dialdehyde modification to the polymer backbone, wherein the dialdehyde-modified polymer mixture has a pH of from about 4.0 to about 7.0.
  • the dialdehyde-modified polymer mixture comprises a solvent and a dialdehyde modified polymer.
  • the solvent can be any suitable solvent, including, e.g., water, ethanol, methanol, acetonitrile, etc., or a combination thereof.
  • the solvent is water.
  • the water can be from any suitable source.
  • the water can be tap water, deionized water, distilled water, ground water, waste water, white water, etc.
  • the mixture further comprises a solvent other than water.
  • the solvent can be any suitable solvent (e.g., ethanol, methanol, acetonitrile, etc., or a combination thereof) .
  • the dialdehyde-modified polymer comprises a polymer backbone.
  • polymer backbone refers to any polymer comprising (i) one or more monomer unit (s) derived from a monomer of Formula I and (ii) one or more anionic monomer unit (s) .
  • the polymer backbone can be considered a copolymer comprising one or more monomer unit (s) derived from a monomer of Formula I and one or more anionic monomer unit (s) .
  • the polymers described herein are considered anionic.
  • the polymer backbone can exist as any suitable copolymer.
  • the polymer backbone copolymer can exist as an alternating copolymer, random copolymer, block copolymer, graft copolymer, linear copolymer, branched copolymer, cyclic copolymer, or a combination thereof.
  • the polymer backbone copolymer can contain any suitable number of differing monomer units.
  • the polymer backbone copolymer can contain 2 different monomer units, 3 different monomer units, 4 different monomer units, 5 different monomer units, or 6 different monomer units.
  • the polymer backbone can comprise the one or more monomer unit (s) derived from a monomer of Formula I and the one or more anionic monomer unit (s) in any suitable concentration and any suitable proportion such that the polymer backbone comprises at least 10 mol%of the one or more anionic monomer unit (s) .
  • the polymer backbone comprises one or more monomer unit (s) derived from a monomer of Formula I:
  • R 1 is H or C 1 -C 4 alkyl (e.g., methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl) and each R 2 is independently selected from H or a linear or branched C 1 -C 10 aliphatic group.
  • “derived” when referring to a monomer unit means that the monomer unit has substantially the same structure of a monomer from which it was made. For example, when a carbon-carbon double bond of a terminal olefin is transformed to a carbon-carbon single bond during the process of polymerization.
  • Each R 2 is independently selected from H or a linear or branched C 1 -C 10 .
  • the terms “independent” and “independently, ” when referring to one or more constituent (e.g., R 2 ) means that each substituent is individually selected from the list and can be the same or different. For example, if constituent R 2 appears more than once in a formula and R 2 is independently selected from a recited list, then each R 2 may be the same or different and selected from the recited list.
  • linear or branched C 1 -C 10 aliphatic group refers to a saturated, unsaturated, branched, straight-chained, cyclic, or a combination thereof aliphatic group having from 1 to 10 carbon atoms (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms) .
  • An exemplary list of linear or branched C 1 -C 10 aliphatic groups is methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, neo-pentyl, hexyl, etc.
  • the linear or branched C 1 -C 10 aliphatic group is further substituted with one or more heteroatoms (e.g., O, S, N, and/or P) .
  • substituted means that one or more hydrogens on the designated atom or group are replaced with another group provided that the designated atom's normal valence is not exceeded.
  • substituent is oxo (i.e., ⁇ O)
  • two hydrogens on the carbon atom are replaced.
  • substituents are permissible provided that the substitutions do not significantly adversely affect synthesis or use of the dialdehyde-modified polymer.
  • the monomer of Formula I is acrylamide, methacrylamide, ethylacrylamide, N-methyl acrylamide, N-butyl acrylamide, or any combination thereof. In certain embodiments, the monomer of Formula I is acrylamide and/or methacrylamide. In preferred embodiments, the monomer of Formula I is acrylamide.
  • the polymer backbone can comprise the one or more monomer unit (s) derived from a monomer of Formula I in any suitable concentration such that the polymer backbone comprises at least 10 mol%of the one or more anionic monomer unit (s) (i.e., the polymer backbone comprises 90 mol%or less of the one or more monomer unit (s) derived from a monomer of Formula I) .
  • the polymer backbone can comprise about 40 mol%or more of the one or more monomer unit (s) derived from a monomer of Formula I, for example, about 50 mol%or more, about 60 mol%or more, about 65 mol%or more, about 70 mol%or more, or about 75 mol%or more.
  • the polymer backbone can comprise about 90 mol%or less, for example, about 88 mol%or less, about 85 mol%or less, about 80 mol%or less, about 75 mol%or less, about 70 mol%or less, about 65 mol%or less, about 60 mol%or less, about 55 mol%or less, or about 50 mol%or less.
  • the polymer backbone can comprise the one or more monomer unit (s) derived from a monomer of Formula I in a concentration bounded by any two of the aforementioned endpoints.
  • the polymer backbone can comprise from about 40 mol%to about 90 mol%of the one or more monomer unit (s) derived from a monomer of Formula I, for example, from about 50 mol%to about 90 mol%, from about 60 mol%to about 90 mol%, from about 65 mol%to about 90 mol%, from about 70 mol%to about 90 mol%, from about 75 mol%to about 90 mol%, from about 50 mol%to about 88 mol%, from about 60 mol%to about 88 mol%, from about 65 mol%to about 88 mol%, from about 70 mol%to about 88 mol%, from about 75 mol%to about 88 mol%, from about 50 mol%to about 85 mol%, from about 60 mol%to about 85 mol%, from about 65 mol%to about 85 mol%, from about 70 mol%to about 85 mol%, from about 75 mol%to about 85 mol%, from about 50 mol%to about 80
  • the polymer backbone comprises one or more anionic monomer unit (s) .
  • the one or more anionic monomer unit (s) can be any suitable anionic monomer unit derived from any suitable anionic monomer.
  • the anionic monomer unit is derived from a monomer selected from 2-acrylamido-2-methylpropane sulfonic acid ( “AMPS” ) , 2-acrylamido-2-methylbutane sulfonic acid ( “AMBS” ) , [2-methyl-2- [ (1-oxo-2-propenyl) amino] propyl] -phosphonic acid, methacrylic acid, acrylic acid, salts thereof, and combinations thereof.
  • the anionic monomer unit is derived from methacrylic acid and/or acrylic acid.
  • the anionic monomer unit is derived from acrylic acid.
  • the polymer backbone can comprise the one or more anionic monomer unit (s) in any suitable concentration such that the polymer backbone comprises at least 10 mol%of the one or more anionic monomer unit (s) .
  • the polymer backbone can comprise about 10 mol%or more of the one or more anionic monomer unit (s) , for example, about 12 mol%or more, about 15 mol%or more, or about 20 mol%or more.
  • the polymer backbone can comprise about 60 mol%or less the one or more anionic monomer unit (s) , for example, about 50 mol%or less, about 40 mol%or less, about 30 mol%or less, or about 25 mol%or less.
  • the polymer backbone can comprise the one or more anionic monomer unit (s) in a concentration bounded by any two of the aforementioned endpoints.
  • the polymer backbone can comprise from about 10 mol%to about 60 mol%of the one or more anionic monomer unit (s) , for example, from about 10 mol%to about 50 mol%, from about 10 mol%to about 40 mol%, from about 10 mol%to about 30 mol%, from about 10 mol%to about 25 mol%, from about 12 mol%to about 60 mol%, from about 12 mol%to about 50 mol%, from about 12 mol%to about 40 mol%, from about 12 mol%to about 30 mol%, from about 12 mol%to about 25 mol%, from about 15 mol%to about 60 mol%, from about 15 mol%to about 50 mol%, from about 15 mol%to about 40 mol%, from about 15 mol%to about 30 mol%, from about 15 mol%to about
  • the polymer backbone can be synthesized by any suitable polymerization method.
  • the polymer backbone can be made through free radical polymerization, addition polymerization, cationic polymerization, anionic polymerization, emulsion polymerization, solution polymerization, suspension polymerization, precipitation polymerization, or a combination thereof.
  • polymerization occurs through free radical polymerization.
  • the polymer backbone has a weight average molecular weight of from about 1 kDa to about 100 kDa.
  • the polymer backbone can have a weight average molecular weight of about 100 kDa or less, for example, about 80 kDa or less, about 50 kDa or less, about 40 kDa or less, about 30 kDa or less, or about 20 kDa or less.
  • the polymer backbone can have a weight average molecular weight of about 1 kDa or more, for example, about 2 kDa or more, about 5 kDa or more, about 10 kDa or more, about 15 kDa or more, or about 20 kDa or more.
  • the polymer backbone can have a weight average molecular weight bounded by any two of the aforementioned endpoints.
  • the polymer backbone can have a weight average molecular weight of from about 1 kDa to about 100 kDa, from about 1 kDa to about 60 kDa, from about 1 kDa to about 50 kDa, from about 1 kDa to about 40 kDa, from about 1 kDa to about 30 kDa, from about 1 kDa to about 20 kDa, 2 kDa to about 100 kDa, from about 2 kDa to about 50 kDa, from about 2 kDa to about 40 kDa, from about 2 kDa to about 30 kDa, from about 2 kDa to about 20 kDa, from about 5 kDa to about 100 kDa, from about 5 kDa to about 50 kDa, from about 5 kDa to about 40 kD
  • Weight average molecular weight can be determined by any suitable technique. While alternate techniques are envisioned, in some embodiments, the weight average molecular weight is determined using size exclusion chromatography (SEC) equipped with a set of TSKgel PW columns (TSKgel Guard+ GMPW+GMPW+G1000PW) , Tosoh Bioscience LLC, Cincinnati, Ohio) and a Waters 2414 (Waters Corporation, Milford, Massachusetts) refractive index detector or a DAWN HELEOS II multi-angle light scattering (MALS) detector (Wyatt Technology, Santa Barbara, California) . Moreover, the weight average molecular weight is determined from either calibration with polyethylene oxide/polyethylene glycol standards ranging from 150-875,000 Daltons or directly using light scattering data with known refractive index increment ( “dn/dc” ) .
  • SEC size exclusion chromatography
  • MALS multi-angle light scattering
  • dialdehyde-modified refers to a polymer (e.g., a polyacrylamide copolymer) comprising monomer units that have been modified with a chemical compound containing at least two aldehydes (e.g., two aldehydes) .
  • Any suitable monomer unit can be dialdehyde-modified.
  • acrylamide can be dialdehyde-modified.
  • the dialdehyde can be any suitable chemical compound with at least two aldehydes (e.g., two aldehydes) .
  • the dialdehyde can be glyoxal, malondialdehyde, succinic dialdehyde, or glutaraldehyde.
  • the dialdehyde is glyoxal.
  • the dialdehyde-modified polymer can comprises any suitable amount of the dialdehyde modification. Without wishing to be bound by any particular theory, it is believed that the amount of dialdehyde modification has an impact on the viscosity of the dialdehyde-modified polymer, such that as the amount of dialdehyde modification increases, the viscosity increases. Accordingly, it is believed that quenching the dialdehyde modification reaction with an acid until reaching a pH of greater than about 4.0 significantly decreases the rate of the glyoxalation reaction during storage, thereby increasing the shelf life of the resulting dialdehyde-modified polymer.
  • the dialdehyde-modified polymer comprises from about 0.1 mol%to about 20 mol% (e.g., from about 0.1 mol%to about 15 mol%, from about 0.1 mol%to about 10 mol%, from about 0.1 mol%to about 7 mol%, from about 0.1 mol%to about 5 mol%, from about 1 mol%to about 20 mol%, from about 1 mol%to about 15 mol%, from about 1 mol%to about 10 mol%, from about 1 mol%to about 7 mol%, or from about 1 mol%to about 5 mol%) of the dialdehyde modification.
  • the dialdehyde-modified polymer comprises from about 0.1 mol%to about 10 mol%of the dialdehyde modification.
  • the dialdehyde-modified polymer can have any suitable weight average molecular weight. Generally, the dialdehyde-modified polymer has a weight average molecular weight of from about 10 kDa to about 10,000 kDa.
  • the dialdehyde-modified polymer can have a weight average molecular weight of about 10,000 kDa or less, for example, about 8,000 kDa or less, about 6,000 kDa or less, about 5,000 kDa or less, about 4,000 kDa or less, about 2,000 kDa or less, or about 1,000 kDa or less.
  • the dialdehyde-modified polymer can have a weight average molecular weight of about 10 kDa or more, for example, about 100 kDa or more, about 200 kDa or more, about 300 kDa or more, about 400 kDa or more, about 500 kDa or more, or about 750 kDa or more.
  • the dialdehyde-modified polymer can have a weight average molecular weight bounded by any two of the aforementioned endpoints.
  • the dialdehyde-modified polymer can have a weight average molecular weight of from about 10 kDa to about 10,000 kDa, from about 10 kDa to about 5,000 kDa, from about 100 kDa to about 10,000 kDa, from about 100 kDa to about 5,000 kDa, from about 100 kDa to about 1,000 kDa, from about 100 kDa to about 2,000 kDa, from about 200 kDa to about 1,000 kDa, from about 300 kDa to about 1,000 kDa, from about 400 kDa to about 1,000 kDa, from about 500 kDa to about 1,000 kDa, from about 750 kDa to about 1,000 kDa, from about 750 kDa to about 2,000 kDa, from about 750 kDa to about 4,000 kDa, from about 750 kDa to about 6,000 kDa, from about 750 kDa to about 4,000
  • the dialdehyde-modified polymer mixture can comprise any suitable amount of the dialdehyde-modified polymer, referred to as “solids content. ”
  • the mixture comprises from about 1 wt. %to about 40 wt. % (e.g., from about 1 wt. %to about 30 wt. %, from about 1 wt. %to about 25 wt. %, from about 1 wt. %to about 20 wt. %, from about 1 wt. %to about 15 wt. %, from about 1 wt. %to about 10 wt. %, from about 2 wt. %to about 30 wt.
  • the mixture comprises from about 5 wt. %to about 25 wt. %solids content.
  • the dialdehyde-modified polymer mixture can have any suitable pH so long as the method for making the dialdehyde-modified polymer includes the step of quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH until a pH of from about 4.0 to about 7.0 is reached.
  • the improved stability of the dialdehyde-modified polymer described herein is a result of quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH until reaching a pH of greater than about 4.0 (e.g., greater than about 4.5 or greater than about 5.0) .
  • the pH is further adjusted after quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH until reaching a pH of greater than about 4.0 (e.g., greater than about 4.5 or greater than about 5.0) .
  • the pH of the dialdehyde modified polymer is not adjusted after quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH until reaching a pH of greater than about 4.0 (e.g., greater than about 4.5 or greater than about 5.0) .
  • the dialdehyde-modified polymer mixture can have a pH of about 4.0 or greater (e.g., about 4.5 or greater or about 5.0 or greater) .
  • the dialdehyde-modified polymer mixture has a pH of from about 4.0 to about 7.0 (e.g., from about 4.1 to about 7.0, from about 4.2 to about 7.0, from about 4.3 to about 7.0, from about 4.4 to about 7.0, from about 4.5 to about 7.0, from about 4.6 to about 7.0, from about 4.7 to about 7.0, from about 4.8 to about 7.0, from about 4.9 to about 7.0, from about 5.0 to about 7.0, from about 5.1 to about 7.0, from about 5.2 to about 7.0, from about 5.3 to about 7.0, from about 5.4 to about 7.0, from about 5.5 to about 7.0, from about 6.0 to about 7.0, from about 4.5 to about 6.5, from about 4.5 to about 6.0, from about 4.5 to about 5.5, from about 5.0 to about 6.5, from about 5.0 to about 5.5, from about 5.5 to about 6.5, or from about 5.5 to about 6) .
  • the dialdehyde-modified polymer mixture
  • the dialdehyde-modified polymer mixture can have any suitable Brookfield viscosity as measured using an aqueous solution containing the dialdehyde-modified polymer.
  • the dialdehyde-modified polymer as an 8 wt. %solution in deionized water, can have a Brookfield viscosity of about 50 cps or less, about 45 cps or less, about 40 cps or less, about 35 cps or less, about 30 cps or less, about 25 cps or less, or about 20 cps or less.
  • the dialdehyde-modified polymer as an 8 wt.
  • the dialdehyde-modified polymer as an 8 wt. %solution in deionized water, can have a Brookfield viscosity bounded by any two of the aforementioned endpoints.
  • the dialdehyde-modified polymer as an 8 wt.
  • %solution in deionized water can have a Brookfield viscosity of from about 0.5 cps to about 50 cps, from about 1 cp to about 50 cps, from about 2 cps to about 50 cps, from about 3 cps to about 50 cps, from about 4 cps to about 50 cps, from about 5 cps to about 50 cps, from about 10 cps to about 50 cps, from about 0.5 cps to about 30 cps, from about 1 cp to about 30 cps, from about 2 cps to about 30 cps, from about 3 cps to about 30 cps, from about 4 cps to about 30 cps, from about 5 cps to about 30 cps, from about 10 cps to about 30 cps, from about 0.5 cps to about 45 cps, from about 0.5 cps
  • the viscosity can be measured by any suitable method.
  • the viscosity can be measured by a Brookfield viscometer at about 25 °C and a rotation speed of 60 rpm.
  • the dialdehyde-modified polymer described herein has improved stability, as measured by Brookfield viscosity, as compared to an identical dialdehyde-modified polymer (i.e., identical monomer units, identical concentration of monomer units, and identical degree of dialdehyde modification) that has been synthesized by quenching a chemical (e.g., glyoxalation) reaction by adjusting the pH until reaching a pH of less than 4.0.
  • a chemical e.g., glyoxalation
  • the viscosity of an aqueous mixture containing a dialdehyde-modified polymer quenched by adjusting the pH until reaching a pH of greater than about 4.0 and a viscosity of 5 cps will increase less rapidly than the viscosity of the same dialdehyde-modified polymer quenched by adjusting the pH until reaching a pH of less than 4.0 and a viscosity of 5 cps.
  • the stability of the dialdehyde-modified polymer can be assessed by the dialdehyde-modified polymer’s ability to maintain a Brookfield viscosity of less than about 50 cps.
  • the dialdehyde-modified polymer has a Brookfield viscosity of from about 0.5 cps to about 50 cps over the span of at least 100 days from synthesis when stored as an 8 wt. %solution in deionized water in a polyethylene bottle in an oven at 25 °C, as measured by a Brookfield viscometer at about 25 °C and a rotation speed of 60 rpm.
  • the dialdehyde-modified polymer has a Brookfield viscosity of from about 0.5 cps to about 50 cps over the span of at least 50 days from synthesis when stored as an 8 wt. %solution in deionized water in a polyethylene bottle in an oven at 30 °C, as measured by a Brookfield viscometer at about 25 °C and a rotation speed of 60 rpm. In some embodiments, the dialdehyde-modified polymer has a Brookfield viscosity of from about 0.5 cps to about 50 cps over the span of at least 75 days from synthesis when stored as an 8 wt.
  • the dialdehyde-modified polymer has a Brookfield viscosity of from about 0.5 cps to about 50 cps the span of at least 100 days from synthesis when stored as an 8 wt. %solution in deionized water in a polyethylene bottle in an oven at 30 °C, as measured by a Brookfield viscometer at about 25 °C and a rotation speed of 60 rpm.
  • the dialdehyde-modified polymer has a Brookfield viscosity of from about 0.5 cps to about 50 cps over the span of at least 40 days from synthesis when stored as an 8 wt. %solution in deionized water in a polyethylene bottle in an oven at 37 °C, as measured by a Brookfield viscometer at about 25 °C and a rotation speed of 60 rpm. In some embodiments, the dialdehyde-modified polymer has a Brookfield viscosity of from about 0.5 cps to about 50 cps over the span of at least 50 days from synthesis when stored as an 8 wt.
  • the dialdehyde-modified polymer has a Brookfield viscosity of from about 0.5 cps to about 50 cps the span of at least 60 days from synthesis when stored as an 8 wt. %solution in deionized water in a polyethylene bottle in an oven at 37 °C, as measured by a Brookfield viscometer at about 25 °C and a rotation speed of 60 rpm.
  • the mixture further comprises or is used with any suitable conventional papermaking product.
  • the mixture further comprises or is used with one or more inorganic filler (s) , dye (s) , retention aid (s) , drainage aid (s) , or combinations thereof.
  • the mixture further comprises or is used with one or more inorganic filler (s) .
  • the inorganic filler can be any suitable inorganic filler, capable of increasing opacity or smoothness, decreasing the cost per mass of the paper, or combinations thereof.
  • the mixture further comprises or is used with kaolin, chalk, limestone, talc, titanium dioxide, calcined clay, urea formaldehyde, aluminates, aluminosilicates, silicates, calcium carbonate (e.g., ground and/or precipitated calcium carbonate) , or combinations thereof.
  • the mixture further comprises or is used with one or more dye (s) .
  • the dye can be any suitable dye, capable of controlling the coloration of paper.
  • the dye can be a direct dye, a cationic direct dye, acidic dye, basic dye, insoluble colored pigment, or combinations thereof.
  • the mixture further comprises or is used with one or more drainage and/or retention aid (s) .
  • the drainage and/or retention aids can be any suitable drainage and/or retention aids, capable of helping to maintain efficiency and drainage of the paper machine, while improving uniformity, and retaining additives.
  • the drainage and/or retention aid can be a cationic polyacrylamide ( “PAM” ) polymer, an anionic polyacrylamide ( “PAM” ) polymer, a cationic polyethylenimine ( “PEI” ) polymer, polyamines, ammonium-based polymers (e.g., polydiallyldimethylammonium chloride ( “DADMAC” ) , colloidal silica, bentonite, polyethylene oxide ( “PEO” ) , starch, polyaluminum sulfate, polyaluminum chloride, or combinations thereof.
  • PAM cationic polyacrylamide
  • PAM anionic polyacrylamide
  • PEI cationic polyethylenimine
  • PEI cationic polyethylenimine
  • PEI cationic polyethylenimine
  • PEI cationic polyethylenimine
  • polyamines e.g., polyamines, ammonium-based polymers (e.g., polydially
  • the mixture further comprises or is used with one or more coagulant (s) .
  • the coagulant can be any suitable coagulant.
  • coagulant refers to a water treatment chemical used in a solid-liquid separation stage to neutralize charges of suspended particles so that the particles can agglomerate.
  • coagulants may be categorized as cationic, anionic, amphoteric, or zwitterionic.
  • coagulants may be categorized as inorganic coagulants, organic coagulants, and blends thereof.
  • Exemplary inorganic coagulants include, e.g., aluminum or iron salts, such as aluminum sulfate, aluminum chloride, ferric chloride, ferric sulfate, polyaluminum chloride, and/or aluminum chloride hydrate.
  • Exemplary organic coagulants include, e.g., diallyldimethylammonium chloride ( “DADMAC” ) , dialkylaminoalkyl acrylate and/or a dialkylaminoalkyl methacrylate, or their quaternary or acid salts.
  • DADMAC diallyldimethylammonium chloride
  • the mixture is used with one or more strength aid (s) .
  • the strength aid can be any suitable strength aid.
  • the strength aid can improve dry strength of the paper sheet, wet strength or rewetted strength of the paper sheet, wet web strength of the paper sheet, or a combination thereof.
  • Exemplary strength aids include, e.g., polyamidoamine-epichlorohydrin ( “PAAE” ) , starch, cationic polyacrylamide ( “PAM” ) polymer, an anionic polyacrylamide ( “PAM” ) polymer, a cationic polyethylenimine ( “PEI” ) polymer, polyamines, ammonium-based polymers (e.g., polydiallyldimethylammonium chloride ( “DADMAC” ) , and blends thereof.
  • PAAE polyamidoamine-epichlorohydrin
  • PAM cationic polyacrylamide
  • PAM anionic polyacrylamide
  • PEI cationic polyethylenimine
  • PEI cationic polyethylenimine
  • the mixture does not contain additional components known to stabilize conventional GPAM.
  • the mixture does not contain a second portion of dialdehyde (e.g., glyoxal) added after the step of quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH until reaching a pH of greater than about 4.0.
  • the mixture does not contain a buffer to stabilize the pH (e.g., to stabilize at a pH of less than about 4) .
  • the mixture is free or substantially free of a weak acid or a weak base, such as citric acid with sodium citrate, disodium phosphate with citric acid, succinic acid with borax, acetic acid with sodium acetate, monopotassium phthalate with hydrochloric acid, bicarbonates, carbonate esters, complex carbonate salts of organic acids, hydrogen phosphates, phosphate esters, phosphinate esters, borates, borate esters, hydrogen sulfates, sulfinates, and sulfate esters.
  • a weak acid or a weak base such as citric acid with sodium citrate, disodium phosphate with citric acid, succinic acid with borax, acetic acid with sodium acetate, monopotassium phthalate with hydrochloric acid, bicarbonates, carbonate esters, complex carbonate salts of organic acids, hydrogen phosphates, phosphate esters, phosphinate esters, borates, borate esters, hydrogen
  • buffers include potassium bicarbonate, potassium biphthalate, potassium bisulfate, potassium dihydrogen citrate, dipotassium hydrogen citrate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydrogen tartrate, potassium hydrogen oxolate, potassium hydrogen maleate, potassium hydrogen succinate, potassium hydrogen glutarate, potassium hydrogen adipate, potassium tetraborate, potassium pentaborate, potassium octaborate and all the corresponding sodium salts, and complex calcium carbonate salts of organic acids (such as octanoic acid, iso-octanoic acid, 2-ethyl hexanoic acid, hexanoic acid, and the like) .
  • the mixture is free or substantially free of aldehyde scavengers, such as, for example, lactic acid, malic acid, citric acid, and choline chloride.
  • a method of making a dialdehyde-modified polymer comprises: (i) initiating a chemical reaction by treating a polymer backbone with a dialdehyde, wherein the polymer backbone comprises: (a) one or more monomer unit (s) derived from a monomer of Formula I:
  • R 1 is H or C 1 -C 4 alkyl and each R 2 is independently selected from H or a linear or branched C 1 -C 10 aliphatic group, and (b) about 10 mol%to about 50 mol%of one or more anionic monomer unit (s) and (ii) quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH until a pH of from about 4.0 to about 7.0 is reached.
  • the phrase “chemical reaction” refers to the interaction between two molecules (e.g., a polymer backbone and a dialdehyde or two polymer backbones comprising dialdehyde modifications) .
  • the chemical reaction is a glyoxalation reaction.
  • the method of making a dialdehyde-modified polymer comprises initiating a chemical reaction by treating a polymer backbone with a dialdehyde.
  • the term “treating” refers to a process of contacting a polymer backbone with a dialdehyde.
  • the polymer backbone and the dialdehyde can be contacted by any suitable method (e.g., pouring, mixing, dropping, etc., or a combination thereof) in any suitable solvent (e.g., water, ethanol, methanol, acetonitrile, etc., or a combination thereof) .
  • the step of initiating a chemical reaction by treating a polymer backbone with a dialdehyde can occur at any suitable pH.
  • the step of initiating a chemical reaction by treating a polymer backbone with a dialdehyde occurs at a pH of at least about 7.0.
  • the step of initiating a chemical reaction by treating a polymer backbone with a dialdehyde can occur at a pH of from about 7.0 to about 14 (e.g., from about 7.0 to about 13, from about 7.0 to about 12, from about 7.0 to about 11, from about 7.0 to about 10, from about 7.0 to about 9.0, from about 8.0 to about 12, from about 8.0 to about 11, from about 8.0 to about 10, from about 9.0 to about 14, or from about 9.0 to about 11) .
  • the step of initiating a chemical reaction by treating a polymer backbone with a dialdehyde can occur at a pH of from about 8.0 to about 10.
  • the step of initiating a chemical reaction by treating a polymer backbone with a dialdehyde can occur at a pH of about 9.0.
  • the method of making a dialdehyde-modified polymer comprises a quenching step with an acid, after initiating a chemical reaction by treating a polymer backbone with a dialdehyde.
  • quenching refers to a process of retarding the rate of a chemical (e.g., glyoxalation) reaction such that the degree of dialdehyde modification is substantially slowed or stopped (i.e., the rate of increase of the molecular weight and/or the viscosity is substantially reduced) .
  • the chemical (e.g., glyoxalation) reaction is quenched by adjusting the pH of the reaction mixture until it reaches a pH of from about 4.0 to about 7.0.
  • the terms “reach” , “reaches” , or “reaching” when referring to the quenching pH, means the pH of the reaction mixture when the quenching process is discontinued.
  • the glyoxalation reaction is quenched with an acid.
  • the acid can be any suitable acid (e.g., hydrochloric acid, sulfuric acid, nitric acid, acetic acid, etc., or a combination thereof) used in any suitable amount such that the pH of the solution resulting from the step of quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH to about 4.0 to about 7.0.
  • a suitable base e.g., triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium carbonate, etc. or a combination thereof
  • an acid e.g., triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium carbonate, etc. or a combination thereof
  • the step of quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH of the reaction mixture (e.g., the dialdehyde-modified polymer mixture) until reaching a pH of from about 4.0 to about 7.0.
  • the chemical reaction mixture e.g., the dialdehyde-modified polymer mixture
  • the step of quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH of the reaction mixture can occur until reaching a pH of from about 4.0 to about 7.0, e.g., about 4.1 to about 7.0, about 4.2 to about 7.0, about 4.3 to about 7.0, about 4.4 to about 7.0, about 4.5 to about 7.0, about 4.6 to about 7.0, about 4.7 to about 7.0, about 4.8 to about 7.0, about 4.9 to about 7.0, about 5.0 to about 7.0, about 5.1 to about 7.0, about 5.2 to about 7.0, about 5.3 to about 7.0, about 5.4 to about 7.0, about 5.5 to about 7.0, about 6.0 to about 7.0, about 4.5 to about 6.5, about 4.5 to about 6.0, about 4.5 to about 5.5, about 5.0 to about 6.5, about 5.0 to about 5.5, about 5.5 to about 6.5, or about 5.5 to about 6.0.
  • a pH of from about 4.0 to about 7.0
  • the step of quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH of the reaction mixture (e.g., the dialdehyde-modified polymer mixture) until reaching a pH of from about 4.5 to about 7.0. In other embodiments, the step of quenching the chemical (e.g., glyoxalation) reaction by adjusting the pH of the reaction mixture (e.g., the dialdehyde-modified polymer mixture) until reaching a pH of from about 5.0 to about 7.0.
  • a method of enhancing paper strength properties comprises treating a paper sheet precursor with a dialdehyde-modified polymer (s) or mixture (s) described herein.
  • the method of enhancing paper strength properties comprises treating a paper sheet at any suitable pH.
  • the overall treatment can have a pH of from about 4.0 or more, e.g., about 4.5 or more, about 5.0 or more, about 5.5 or more, about 6.0 or more, about 6.5 or more, about 7.0 or more, about 7.5 or more, about 8.0 or more, or about 8.5 or more.
  • the treatment can have a pH of about 11 or less, e.g., about 10.5 or less, about 10 or less, about 9.5 or less, or about 9.0 or less.
  • the treatment can have a pH bounded by any two of the above endpoints recited.
  • the treatment can have a pH of from about 4.5 to about 9.0, e.g., from about 5.0 to about 9.0, from about 5.5 to about 9.0, from about 6.0 to about 9.0, from about 6.5 to about 9.0, from about 7.0 to about 9.0, from about 7.5 to about 9.0, from about 8.0 to about 9.0, from about 8.5 to about 9.0, from about 8.5 to about 11, from about 8.5 to about 10.5, from about 8.5 to about 10, from about 8.5 to about 9.5, from about 8.5 to about 9.0, from about 4.0 to about 11, from about 7.0 to about 10, or about 8.0.
  • a pH of from about 4.5 to about 9.0 e.g., from about 5.0 to about 9.0, from about 5.5 to about 9.0, from about 6.0 to about 9.0, from about 6.5 to about 9.0, from about 7.0 to about 9.0, from about 7.5 to about 9.0, from about 8.0 to about 9.0, from about 8.5 to about 9.0, from about 8.5 to about 11, from
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture can be added to any suitable paper sheet precursor.
  • paper sheet precursor refers to any component of the papermaking process upstream of the point at which the fiber slurry begins being rolled into a paper sheet.
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture can be added to pulp (e.g., virgin pulp, recycled pulp, or a combination thereof) , pulp slurry, cellulosic fibers, a solution used for any of the aforementioned components, and any combination thereof.
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture can be added to the paper sheet precursor at any one or more of various locations during the papermaking process, up to and including a headbox.
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture can be added to the pulp slurry in a pulper, latency chest, reject refiner chest, disk filter or Decker feed or accept, whitewater system, pulp stock storage chests (either low density ( “LD” ) , medium consistency ( “MC” ) , or high consistency ( “HC” ) ) , blend chest, machine chest, headbox, save-all chest, paper machine whitewater system, or combinations thereof.
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture is added to the headbox.
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture is stored in the absence of fiber and added to the paper sheet precursor upstream of a wet end of a paper machine (e.g., before the wet end) .
  • wet end refers to any component of the papermaking process including the headbox and downstream thereof.
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture can be added to any component of the papermaking process up to but not including the headbox.
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture is added to a stock prep section of the paper machine.
  • stock prep section refers to any component of the papermaking process wherein the pulp is refined and/or blended.
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture can be added to the pulp stock storage chests (either low density ( “LD” ) , medium consistency ( “MC” ) , or high consistency ( “HC” ) ) , blend chest, machine chest, save-all chest, or a combination thereof.
  • the dialdehyde-modified polymer or dialdehyde-modified polymer mixture is added to pulp slurry upstream of a head box of a papermaking process.
  • the pulp slurry comprises recycled fibers.
  • the recycled fibers can be obtained from a variety of paper products or fiber containing products, such as paperboard, newsprint, printing grades, sanitary or other paper products. In some embodiments, these products can comprise, for example, old corrugated cardboard ( “OCC” ) , old newsprint ( “ONP” ) , mixed office waste ( “MOW” ) , magazines, books, or a combination thereof.
  • the pulp slurry comprises virgin fibers. In embodiments comprising virgin fibers, the pulp can be derived from softwood, hardwood, or blends thereof.
  • the virgin pulp can include bleached or unbleached Kraft, sulfite pulp or other chemical pulps, and groundwood ( “GW” ) or other mechanical pulps such as, for example, thermomechanical pulp ( “TMP” ) .
  • GW groundwood
  • TMP thermomechanical pulp
  • the method of enhancing paper strength properties may enhance any suitable paper strength property.
  • treatment according to the methods described herein can, for example, allow for increased ash content in the finished paper, boost strength properties of the finished paper, increase retention during the papermaking process, and improve dewatering efficiency during the papermaking process.
  • a dialdehyde-modified polymer mixture comprising a solvent and a dialdehyde modified polymer comprising: (a) a polymer backbone comprising: (i) one or more monomer unit (s) derived from a monomer of Formula I:
  • R 1 is H or C 1 -C 4 alkyl and each R 2 is independently selected from H or a linear or branched C 1 -C 10 aliphatic group, and (ii) about 10 mol%to about 50 mol%of one or more anionic monomer unit (s) , and (b) a dialdehyde modification to the polymer backbone, wherein the dialdehyde-modified polymer mixture has a pH of from about 4.0 to about 7.0.
  • dialdehyde-modified polymer mixture of any one of embodiments (1) - (5) wherein the dialdehyde-modified polymer is modified with a dialdehyde selected from glyoxal, malondialdehyde, succinic dialdehyde, and glutaraldehyde.
  • a dialdehyde selected from glyoxal, malondialdehyde, succinic dialdehyde, and glutaraldehyde.
  • dialdehyde-modified polymer mixture of any one of embodiments (1) - (7) wherein the dialdehyde-modified polymer mixture has a pH of from about 4.5 to about 7.0.
  • dialdehyde-modified polymer mixture of embodiment (13) wherein the dialdehyde-modified polymer has a weight average molecular weight of from about 100 kDa to about 2,000 kDa.
  • dialdehyde-modified polymer mixture of any one of embodiments (1) - (14) wherein the polymer backbone has a weight average molecular weight of from about 2 kDa to about 50 kDa in the absence of the dialdehyde modification.
  • dialdehyde-modified polymer mixture of any one of embodiments (1) - (16) wherein the dialdehyde-modified polymer mixture has a solids content of from about 1 wt. %to about 40 wt. %.
  • dialdehyde-modified polymer mixture of any one of embodiments (1) - (18) , wherein the dialdehyde-modified polymer mixture has a Brookfield viscosity of from about 5 cps to about 50 cps at a solids content of 8 wt. %.
  • dialdehyde-modified polymer mixture of embodiment (19) wherein the dialdehyde-modified polymer mixture has a Brookfield viscosity of from about 5 cps to about 30 cps at a solids content of 8 wt. %.
  • a method of making a dialdehyde-modified polymer comprising: (i) initiating a chemical reaction by treating a polymer backbone with a dialdehyde, wherein the polymer backbone comprises: (a) one or more monomer unit (s) derived from a monomer of Formula I:
  • R 1 is H or C 1 -C 4 alkyl and each R 2 is independently selected from H or a linear or branched C 1 -C 10 aliphatic group, and (b) about 10 mol%to about 50 mol%of one or more anionic monomer unit (s) and (ii) quenching the chemical reaction by adjusting the pH until a pH of from about 4.0 to about 7.0 is reached.
  • the one or more anionic monomer unit (s) is derived from a monomer selected from 2-acrylamido-2-methylpropane sulfonic acid ( “AMPS” ) , 2-acrylamido-2-methylbutane sulfonic acid ( “AMBS” ) , [2-methyl-2- [ (1-oxo-2-propenyl) amino] propyl] -phosphonic acid, methacrylic acid, acrylic acid, salts thereof, and combinations thereof.
  • AMPS 2-acrylamido-2-methylpropane sulfonic acid
  • AMBS 2-acrylamido-2-methylbutane sulfonic acid
  • dialdehyde-modified polymer is modified with a dialdehyde selected from glyoxal, malondialdehyde, succinic dialdehyde, and glutaraldehyde.
  • polymer backbone comprises from about 20 mol%to about 50 mol%of the one or more anionic monomer unit (s) .
  • dialdehyde-modified polymer has a weight average molecular weight of from about 10 kDa to about 5,000 kDa.
  • dialdehyde-modified polymer has a weight average molecular weight of from about 100 kDa to about 2,000 kDa.
  • dialdehyde-modified polymer has a Brookfield viscosity of from about 5 cps to about 50 cps at a solids content of 8 wt. %in water.
  • dialdehyde-modified polymer has a Brookfield viscosity of from about 5 cps to about 30 cps at a solids content of 8 wt. %in water.
  • a polymer backbone comprising acrylamide and an anionic monomer unit or acrylamide and a cationic monomer unit is modified with a dialdehyde in an aqueous solution at a pH of about 9. Once the desired viscosity is reached, the dialdehyde-modification reaction is quenched with acid until the desired pH value is reached.
  • Samples (100 g) of the anionic GPAM polymers formed from quenching the glyoxalated polymer mixture by adjusting the pH to 2.51, 3.57, 4.5, 5.59, and 6.47 were individually stored, as an 8 wt. %solution in deionized water, in polyethylene bottles and placed at 25 °C. Their viscosity was monitored as a function of time using a Brookfield viscometer equipped with a #61 spindle at room temperature (i.e., about 25 °C) and 60 rpm rotation speed, respectively. The results are set forth in FIG. 1.
  • Samples (100 g) of the anionic GPAM polymers formed from quenching the glyoxalated polymer mixture by adjusting the pH to 2.51, 3.57, 4.5, 5.59, and 6.47 were individually stored, as an 8 wt. %solution in deionized water, in polyethylene bottles and placed at 30 °C. Their viscosity was monitored as a function of time using a Brookfield viscometer equipped with a #61 spindle at room temperature (i.e., about 25 °C) and 60 rpm rotation speed, respectively. The results are set forth in FIG. 2.
  • Samples (100 g) of the anionic GPAM polymers formed from quenching the glyoxalated polymer mixture by adjusting the pH to 2.51, 3.57, 4.5, 5.59, and 6.47 were individually stored, as an 8 wt. %solution in deionized water, in polyethylene bottles and placed at 37 °C. Their viscosity was monitored as a function of time using a Brookfield viscometer equipped with a #61 spindle at room temperature (i.e., about 25 °C) and 60 rpm rotation speed, respectively. The results are set forth in FIG. 3.
  • solutions of DMP 1, DMP 2, and DMP 3 maintain a Brookfield viscosity of less than about 40 cps for 100 days, demonstrating that DMP 1, DMP 2, and DMP 3 are stable at 37 °C for at least 100 days.
  • aqueous solution containing an 88/12 mol%acrylamide/diallyldimethylammonium chloride ( “DADMAC” ) polymer was treated with glyoxal (48 wt. %in water) at a pH of about 9. Once the resulting glyoxalated polymer mixture had reached a viscosity of about 22 cps to about 24 cps, the reaction was quenched by adjusting the pH to 2.8 ( “Comparative Polymer 3” ) and 5.3 ( “Comparative Polymer 4” ) with sulfuric acid.
  • Samples (100 g) of the cationic GPAM polymers formed from quenching the glyoxalated polymer mixture by adjusting the pH to 2.8 and 5.3 were individually stored, as an 8 wt. %solution in deionized water, in polyethylene bottles and placed at 37 °C. Their viscosity was monitored as a function of time using a Brookfield viscometer equipped with a #61 spindle at room temperature (i.e., about 25 °C) and 60 rpm rotation speed, respectively. The results are set forth in FIG. 4.

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Abstract

Un mélange polymère modifié par un dialdéhyde est prévu. Le mélange polymère modifié par un dialdéhyde comprend un solvant et un polymère modifié par un dialdéhyde comprenant : (a) un squelette polymère comprenant : (i) une ou plusieurs unités monomères dérivées d'un monomère de formule I, dans laquelle R1 est du H ou un alkyle en C1-C4 et chaque R2 est choisi indépendamment parmi H ou un groupe aliphatique linéaire ou ramifié en C1-C10, et (ii) d'environ 10 % en mole à environ 50 % en mole d'une ou plusieurs unités monomères anioniques, et (b) une modification par un dialdéhyde du squelette polymère, le mélange polymère modifié par un dialdéhyde ayant un pH d'environ 4,0 à environ 7,0. Un procédé de fabrication du polymère modifié par un dialdéhyde est également prévu.
PCT/CN2020/132621 2020-11-30 2020-11-30 Polyacrylamide glyoxalé anionique Ceased WO2022110102A1 (fr)

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