WO2000043429A1 - Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties - Google Patents

Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties Download PDF

Info

Publication number
WO2000043429A1
WO2000043429A1 PCT/US2000/001615 US0001615W WO0043429A1 WO 2000043429 A1 WO2000043429 A1 WO 2000043429A1 US 0001615 W US0001615 W US 0001615W WO 0043429 A1 WO0043429 A1 WO 0043429A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
group
branched
substituted
paper sheet
Prior art date
Application number
PCT/US2000/001615
Other languages
French (fr)
Inventor
Thomas Gerard Shannon
Daniel Arthur Clarahan
Mike Thomas Goulet
Wen Zyo Schroeder
Original Assignee
Kimberly-Clark Worldwide, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kimberly-Clark Worldwide, Inc. filed Critical Kimberly-Clark Worldwide, Inc.
Priority to AU27350/00A priority Critical patent/AU770362B2/en
Priority to EP20000905706 priority patent/EP1165640B1/en
Priority to BRPI0007706-2A priority patent/BR0007706B1/en
Priority to DE2000627417 priority patent/DE60027417T2/en
Publication of WO2000043429A1 publication Critical patent/WO2000043429A1/en

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers 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
    • C08F222/04Anhydrides, e.g. cyclic anhydrides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00Copolymers 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02Copolymers 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C08F226/04Diallylamine
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/28Condensation with aldehydes or ketones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/30Introducing nitrogen atoms or nitrogen-containing groups
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249962Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
    • Y10T428/249964Fibers of defined composition
    • Y10T428/249965Cellulosic
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31942Of aldehyde or ketone condensation product
    • Y10T428/31949Next to cellulosic
    • Y10T428/31964Paper
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate
    • Y10T428/31975Of cellulosic next to another carbohydrate
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate
    • Y10T428/31975Of cellulosic next to another carbohydrate
    • Y10T428/31978Cellulosic next to another cellulosic
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate
    • Y10T428/31975Of cellulosic next to another carbohydrate
    • Y10T428/31978Cellulosic next to another cellulosic
    • Y10T428/31982Wood or paper

Definitions

  • wet end chemical addition Another limitation, which is associated with wet end chemical addition, is the limited availability of adequate bonding sites on the papermaking fibers to which the chemicals can attach themselves. Under such circumstances, more than one chemical functionality competes for the limited available bonding sites, oftentimes resulting in the insufficient retention of one or both chemicals on the fibers. For more complex chemical systems it may desirable to have two or more functional additives retained in a specified ratio and/or spatial arrangement relative to one another. Although the addition of chemicals in a predetermined ratio is easily achieved, retention of these chemicals in a predictable ratio is difficult using wet end chemical addition because of site competition and other influencing factors. Another limitation of either wet end or topical chemical addition is the inability to predictably locate functional chemical moieties in proximity to each other on the fiber surface.
  • two or more chemical functionalities can be combined into a single molecule, such that the combined molecule imparts at least two distinct product properties to the final paper product that heretofore have been imparted through the use of two or more different molecules.
  • synthetic polymers which are commonly used in the paper industry as dry strength resins, wet strength resins and retention aids, can be combined into a single molecule with modified aliphatic hydrocarbons, which are commonly utilized, in conjunction with cationic moieties, as softeners, debonders, lubricants and sizing agents.
  • the resulting molecule is a synthetic polymer having hydrogen bonding capability and an aliphatic hydrocarbon moiety which can provide several potential benefits, depending on the specific combination employed, including: (a) strength aids that soften; (b) softeners that do not reduce strength; (c) wet strength with improved wet/dry strength ratio; (d) debonders with reduced linting and sloughing; (e) strength aids with controlled absorbency; and (g) retention aids that soften.
  • aliphatic hydrocarbon moieties are functional groups derived from a broad group of organic compounds, including alkanes, alkenes, alkynes and cyclic aliphatic classifications.
  • the aliphatic hydrocarbon moieties can be linear or branched, saturated or unsaturated, substituted or non-substituted.
  • the synthetic polymers as described herein have a portion of their structure derived from the polymerization of ethylenically unsaturated compounds which contain pendant groups that can form hydrogen bonds, ionic bonds or covalent bonds with cellulose molecules in fibers, thereby increasing interfiber bonding. They include polyacrylamide, polyvinyl alcohol, polyacrylic acid, polymaleic anhydride, polymaleic acid, polyitaconic acid, cationic polyacrylamides, anionic polyacrylamides, and the like.
  • the synthetic polymers as described herein may be water soluble, organic soluble or soluble in mixtures of water and water miscible organic compounds. Preferably they are water- soluble or water dispersible but this is not a necessity of the invention.
  • the salts of the above mentioned acidic polymers include the alkali metals such as K and Na usually added in form of their hydroxides, the aliphatic amines and alkanol amines, such salts and methods of preparing such salts being well known to those skilled in the art.
  • the synthetic polymers of this invention may be applied to the paper web by any of the means known to those skilled in the art. Such means include wet end addition, spray addition on the wet web, as a creping chemical sprayed on the Yankee dryer, or as a post treatment addition, including spraying, printing or coating.
  • the invention resides in a synthetic polymer having hydrogen bonding capability and containing one or more aliphatic hydrocarbon moieties, said synthetic polymer having the following structure:
  • Q . a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose.
  • Preferred pendant groups for hydrogen bonding are — CONH 2 , —COOH, —COO " M + , —OH and mixtures of said groups.
  • Preferred pendant groups for covalent bonding are aldehydes and anhydrides.
  • M + can be any suitable counter ion including Na ⁇ K + , Ca +2 and the like.
  • Q 2 a monomer unit or a block or graft copolymer containing a C 8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety.
  • Q 2 may take the form of -Z 1 -Q 2 -Z 1 '- where Z Z are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 2 is as defined previously;
  • Q 3 a monomer unit or a block or graft copolymer containing a charge functionality. Such charge functionality is preferably cationic but may be anionic or amphoteric; and
  • Q 4 a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking.
  • Q 4 may take the form of -Z 2 -Q 4 -Z 2 '- where Z 2 , Z 2 ' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 4 is as defined previously. Q 4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • Q 4 moieties are (but not limited to) the aliphatic polyether derivatives of the formula — [(CR 1 R 2 ) x O] y — R 3 , wherein R ⁇ R 2 is H or CH 3 , x > 2, y > 1 and R 3 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , - NH 2 .
  • the invention resides in a synthetic polymer having the following structure:
  • R 1 ,R 1 ',R 2 ,R 3 H, C M alkyl; a, b > 0; c,d > 0 such that c+d > 0;
  • Q 4 a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking.
  • Q 4 may take the form of -Z 2 -Q 4 -Z 2 '- where Z 2 Z 2 ' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 4 is as defined previously.
  • Q 4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • Q 4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR 1 R 2 ) x O] y — R 3 , wherein R.,, R 2 is H or CH 3 , x > 2, y > 1 and R 3 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , -
  • Z aryl, -CH 2 -, -COO-, -CONR'-, -O-, -S-, -OSO 2 O-, -CONHCO-,-CONHCHOHCHOO- or any other radical capable of bridging the R 6 group to the vinyl backbone portion of the molecule.
  • R 1 H, alkyl
  • R 6 any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon;
  • Z 2 aryl, -CH 2 -, -COO-, -CONH-, -O-, -S-, -OSO 2 O-, any radical capable of bridging the
  • R 10 group to the vinyl backbone portion of the molecule;
  • the invention resides in a paper sheet, such as a tissue sheet, comprising a synthetic polymer having hydrogen bonding capability and containing an aliphatic hydrocarbon moiety, said polymer having the following structure:
  • Q a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose.
  • Preferred pendant groups for hydrogen bonding are — CONH 2 , —COOH, — COO- M + , —OH and mixtures of said groups.
  • Preferred pendant groups for covalent bonding are aldehydes and anhydrides.
  • M + can be any suitable counter ion including Na + , K ⁇ Ca +2 and the like;
  • Q 2 a monomer unit or a block or graft copolymer containing a C 8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety.
  • Q 4 may take the form of -Z 2 -Q 4 -Z 2 '- where Z 2 , Z_' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 4 is as defined previously. Q 4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • Q 4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR 1 R 2 ) x O] y — R 3 , wherein R,, R 2 is H or CH 3 , x > 2, y > 1 and R 3 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , -
  • the invention resides in a paper sheet, such as a tissue sheet, comprising a synthetic polymer having hydrogen bonding capability and containing an aliphatic hydrocarbon moiety, said polymer having the following structure:
  • Q 4 a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking.
  • Q 4 may take the form of -Z 2 -Q 4 -Z 2 '- where Z 2 , Z 2 ' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 4 is as defined previously.
  • Q 4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • Q 4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR 1 R 2 ) x O] y — R 3 , wherein R-,, R 2 is H or CH 3 , x > 2, y > 1 and R 3 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , -
  • R 4 Z - R 6 - Y radical
  • Z aryl, -CH 2 -, -COO-, -CONR'-, -O-, - S -, -OSO 2 O-, -CONHCO-, -
  • R 1 -H, alkyl
  • R 6 any aliphatic, linear or branched, saturated or unsaturated, substituted or non- substituted hydrocarbon
  • Y -H, -N + R 7 R 8 R 9 , -NR 7 R 8 , where R 7 , R 8 , R 9 are same or different and are H or C 1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons
  • At least one of R 6 , R 7 , R 8 , R 9 must be an aliphatic, linear or branched, substituted or non- substituted, hydrocarbon of chain length 8 or higher;
  • R 5 Z 2 -R 10 -W
  • Z 2 aryl, -CH 2 , -COO-, -CONH-, -O-, -S-, -OSO 2 O- or any radical capable of bridging the R 10 group to the vinyl backbone portion of the molecule;
  • R 10 any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH 2 CH 2 )-, -C(CH 3 ) 2 CH 2 CH 2 -; and
  • W -N'R ⁇ .R ⁇ .R ⁇ where R , R 12 , R 13 is a C M alkyl group.
  • the invention resides in a method of making a paper sheet, such as a tissue sheet, comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of papermaking fibers onto a forming fabric to form a web; and (c) dewatering and drying the web to form a paper sheet, wherein a synthetic polymeric additive is added to the aqueous suspension of fibers or to the web, said polymeric additive having the following structure:
  • Q a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose.
  • Preferred pendant groups for hydrogen bonding are — CONH 2 , —COOH, —COO- + M, —OH and mixtures of said groups.
  • Preferred pendant groups for covalent bonding are aldehydes and anhydrides.
  • M+ can be any suitable counter ion including Na + , K + , Ca +2 and the like;
  • Q 2 a monomer unit or a block or graft copolymer containing a C 8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety.
  • Q 2 may take the form of -ZrQz-Z - where Z , Z are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 2 is as defined previously;
  • Q 3 a monomer unit or a block or graft copolymer containing a charge functionality.
  • Such charge functionality is preferably cationic but may be anionic or amphoteric;
  • Q 4 a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking.
  • Q 4 may take the form of -Z 2 -Q 4 -Z 2 '- where Z 2 , Z 2 ' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 4 is as defined previously.
  • Q 4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • Q 4 moieties are (but is not limited to) the aliphatic poiyether derivatives of the formula — [(CR 1 R 2 ) x O] y — R 3 , wherein R ⁇ R 2 is -H or - CH 3 , x > 2, y > 1 and R 3 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , - NH 2 .
  • the invention resides in a method of making a paper sheet, such as a tissue sheet, comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of papermaking fibers onto a forming fabric to form a web; and (c) dewatehng and drying the web to form a paper sheet, wherein a synthetic polymeric additive is added to the aqueous suspension of fibers or to the web, said polymeric additive having the following structure:
  • R 1 ,R 1 ',R 2 , R 3 H, C M alkyl; a, b > 0; c,d > 0;
  • Q 4 a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking.
  • Q 4 may take the form of -Z 2 -Q 4 -Z 2 '- where Z 2 , Z 2 ' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 4 is as defined previously.
  • Q 4 may be incorporated to offset the increased . polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • Q 4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — I(CR 1 R 2 ) x O] y — R 3 , wherein R ⁇ R 2 is H or CH 3 , x > 2, y > 1 and R 3 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , -
  • R 4 Z - R 6 - Y radical
  • Z aryl, -CH 2 -, -COO-, -CONR'-, -O-, -S-, -OSO 2 O-, -CONHCO-, -CONHCHOHCHOO- or any radical capable of bridging the R 6 group to the vinyl backbone portion of the molecule.
  • R 6 any aliphatic, linear or branched, saturated or unsaturated, substituted or non- substituted hydrocarbon
  • Y H, -N + R 11 ,R 12 ,R 13 , -NR 7 R 8 , where R 7 , R 8 , R 9 are same or different and are H or C 1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons; At least one of R 6 , R 7 , R 8 , R 9 must be an aliphatic, linear or branched, substituted or non- substituted, hydrocarbon of chain length 8 or higher;
  • R 5 Z 2 -R 10 -W;
  • Z 2 aryl, -CH 2 -, -COO-, -CONH-, -O-, -S-, -OSO 2 O- or any radical capable of bridging the R 10 group to the vinyl backbone portion of the molecule;
  • R 10 any linear or branched, aliphatic or aromatic
  • W -N + Rn.R ⁇ .R ⁇ where R 11 t R 12 , R 13 is a C 1-4 alkyl group.
  • the amount of the synthetic polymeric additive added to the fibers or the tissue web can be from about 0.02 to about 4 weight percent, on a dry fiber basis, more specifically from about 0.05 to about 2 weight percent, and still more specifically from about 0.1 to about 1 weight percent.
  • the synthetic polymer can be added to the fibers or web at any point in the process, but it can be particularly advantageous to add the synthetic polymer to the fibers while the fibers are suspended in water.
  • R 1 f R 2 , R 3 , R 4 may be H, halogen, alkyl, functional alkyl, aryl, functional aryl.
  • R 4 — CONH 2
  • PAMs polyacrylamides
  • PAMs per se are nonionic materials and have very little attraction to papermaking fibers. Therefore it is necessary to incorporate charged groups into the polymer structure to make it useful for papermaking. Both anionic and cationic polyacrylamides are known in the art.
  • Anionic polyacrylamides can be produced by (1 ) the copolymerization of acrylamide with acrylic acid or the (2) hydrolysis of some of the amide groups on the polyacrylamide chain.
  • the resultant polymer will contain a mixture of acrylamide and acrylic acid groups.
  • Anionic polyacrylamides were first produced in the 1950's via copolymerization of acrylamide with acrylic acid.
  • the acrylic acid groups introduce an ionizable carboxyl group on the polymer backbone, lonization of these carboxyl groups is highly pH dependent, where above pH 7 essentially 100% of the carboxyl groups are ionized. Since anionic polyacrylamides are negatively charged they are not directly attracted to the like-charged cellulose papermaking fibers.
  • a cationic substance such as alum must be used in conjunction with them to promote their retention.
  • Cationic polyacrylamides are produced by copolymerization of acrylamide with cationic monomers or by modification of some of the amide groups.
  • Typical cationic monomers include: (1) methacryloyloxyethyi trimethyl ammonium methosulfate (METAMS); (2) dimethyldiallyl ammonium chloride (DMDAAC); (3) 3- acryloamido-3-methyl butyl trimethyl ammonium chloride (AMBTAC); (4) trimethylamino methacrylate; and (5) vinyl benzyl trimethyl ammonium chloride (VBTAC).
  • METAMS methacryloyloxyethyi trimethyl ammonium methosulfate
  • DMDAAC dimethyldiallyl ammonium chloride
  • AMBTAC 3- acryloamido-3-methyl butyl trimethyl ammonium chloride
  • VBTAC vinyl benzyl trimethyl ammonium chloride
  • cationic polyacrylamides by the modification of the amide groups of PAMs is most often accomplished via the Mannich reaction as illustrated in Figure 3.
  • Generally cationic polyacrylamides synthesized in this manner will contain from about 5 to about 70 mole percent cationic groups.
  • dry strength PAMs are supplied as ready to use aqueous solutions or as water-soluble powders which must be dissolved prior to use. They may be added to thin or thick stock at a point of good mixing for best results. Addition rates of 0.1% to 0.5% of dry fiber typically give best results. High addition rates may cause over-cationization of the furnish and reduce the effectiveness of other additives.
  • dry strength additives usually around 10 mole % of the monomers will contain charged groups.
  • cationic PAMs can be effectively charged across the entire pH range.
  • Typical molecular weights (Mw) for cationic PAM dry strength aids are in the range of 100,000 to 500,000. The molecular weight is important so as to be low enough to not bridge between particles and cause flocculation, and yet high enough to retard migration of the polymer into the pores of the fibers. Such migration would cause a reduction in dry strength activity.
  • polyacrylamide retention aids When used as retention aids a broader range of molecular weights and charge densities may be employed. Key characteristics of polyacrylamide retention aids include the molecular weight, the type of charge, the charge density and the delivery form. For the average molecular weight, the range can be: low (1 ,000 - 100,000); medium (100,000 - 1 ,000,000); high (1 ,000,000 - 5,000,000); very high (>5,000,000).
  • the charge type can be nonionic, cationic, anionic or amphote c.
  • the charge density can be: low (1 - 10%); medium (10 - 40%); high (40 - 80%); or very high (80 - 100%).
  • the delivery form can be an emulsion, an aqueous solution or a dry solid.
  • High molecular weight/ low charge density flocculants are used most often for retention of fine particles in high shear and turbulence environments.
  • Low Mw, high charge density products are used for their charge modifying capabilities and for retention in low shear environments.
  • the portion of the synthetic polymer [Q,] capable of forming hydrogen, covalent and ionic bonds can constitute from about 10 to about 90 weight percent of the total polymer, more specifically from about 20 to about 80 weight percent of the total polymer and still more specifically from about 30 to about 70 weight percent of the total polymer.
  • the aliphatic hydrocarbon portion [QJ of the synthetic polymer can constitute from about 10 to about 90 weight percent of the synthetic polymer, more specifically from about 20 to about 80 weight percent of the synthetic polymer and still more specifically from about 30 to about 70 weight percent of the synthetic polymer.
  • the charge containing portion [Q 3 ] of the synthetic polymer can be comprised of monomer units constituting from 0 to about 80 mole percent of the total monomer units in the synthetic polymer, more specifically from 0 to about 30 mole percent and still more specifically from about 5 to about 15 mole percent.
  • the [Q 4 ] functionality will be comprised of monomer units constituting from 0 to about 80 mole percent of the total monomer units in the synthetic polymer, more specifically from 0 to about 40 mole percent and still more specifically from 0 to about 20 mole percent.
  • the molecular weight of the synthetic polymers of the present invention will largely depend on the specific application of the material and is not overly critical to the invention.
  • the weight average molecular weight range can be from about 1 ,000 to about 5,000,000, more specifically from about 10,000 to about 2,000,000 and still more specifically from about 20,000 to about 1 ,000,000.
  • these polymers are added for dry strength it is important that the molecular weight of the polymer be low enough so as to not bridge between particles and cause flocculation, and yet high enough so as to retard migration of the polymer into the pores of the fibers.
  • These materials can have weight average molecular weights in the range of from about 5,000 to about 1 ,000,000, more specifically from about 10,000 to about 1 ,000,000 and still more specifically from about 20,000 to about 600,000.
  • Block copolymerization and/or grafting Block copolymerization and/or grafting.
  • one or more of the [Q], elements of the polymer exists as a block or graft copolymer on the vinyl backbone.
  • the aliphatic hydrocarbon portion of the modified vinyl polymer was incorporated in such a manner, the aliphatic hydrocarbon portion would exist as a block copolymer of polyethylene, polypropylene, isobutylene, polytetraflouroethylene, or any other linear or branched, saturated or unsaturated, substituted or non-substituted hydrocarbon, such co-polymer incorporated either as block or graft onto the vinyl backbone.
  • the aliphatic hydrocarbon blocks would be built as a result of the free radical polymerization of the corresponding ethylenically unsaturated monomers including, ethylene, propylene, perflouroethylene, isobutylene and the like including mixtures of said monomers.
  • These synthetic polymers are distinguished from those of the direct monomer incorporation in that the aliphatic hydrocarbon portion of the molecule would be incorporated linearly within the polymer chain rather than in a pendant fashion.
  • any of the synthetic polymer elements or combination of the synthetic polymer elements Q 1 f Q 2 , Q 3) Q 4 could be incorporated via this approach. Note that where a polyacrylamide is employed that these polymers maintain pendant amide functionality and are therefore capable of being glyoxylated to form materials possessing temporary wet strength. A general example of preparing such a material is shown in Figure 4.
  • R 0 any group capable of forming hydrogen or covalent bonds with cellulose. Preferred are -CONH 2 , COOH, COO " , -OH, CONHCHOHCHO, and anhydride including mixtures of said groups;
  • M_ an unsaturated vinyl monomer unit capable of being polymerized into a polymer containing a C 8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety.
  • M. could be an oligomer or polymer of such an unsaturated vinyl monomer.
  • Q 2 a block copolymer which is or contains a C 8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety.
  • Q 4 a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking.
  • Q 4 may take the form of -Z 2 -Q 4 -Z 2 '- where Z 2 , Z 2 ' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 4 is as defined previously.
  • Q 4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • suitable Q 4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR 1 R 2 ) x O] y — R 3 , wherein R.,, R 2 is H or CH 3 , x > 2, y > 1 and R 3 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , - NH 2
  • R 5 Z 2 -R 10 -W
  • Z 2 Aryl, CH 2 , COO-, CONH-, - O-, - S -, - OSO 2 O-, any radical capable of bridging the R 10 group to the vinyl backbone portion of the molecule.
  • R 10 any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH 2 CH 2 )-, -C(CH 3 ) 2 CH 2 CH 2 -
  • W -N ⁇ n.Ru.R ⁇ , NRnR ⁇ , whereR ⁇ , R 12 , R 13 is a C 1-4 alkyl group.
  • R 5 may also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride.
  • the residue will be the form of monomers with repeat units of structure:
  • incorporación of the aliphatic moieties can be accomplished via copolymerization with vinyl type monomers containing aliphatic groups. Almost any vinyl type monomer containing a pendant aliphatic hydrocarbon can be co-polymerized with acrylamide or a similar vinyl monomer containing a pendant hydrogen-bonding moiety to be incorporated into the polymer backbone. Generically the synthesis can be described in Figure 5.
  • R 0 any group capable of forming hydrogen or covalent bonds with cellulose. Preferred are -CONH 2 , COOH, COO " , -OH, CONHCHOHCHO, and anhydride including mixtures of said groups;
  • R 4 Z - R 6 - Y radical
  • Z Aryl, CH 2 , COO-, CONH-, - O-, - S -, - OSO 2 O-, -CONHCO-, CONHCHOHCHOO-, any radical capable of bridging the R 6 group to the vinyl backbone portion of the molecule;
  • Y H, - N+R 7 R 8 R 9 , -NR 7 R 8 , where R 7 , R 8 , R 9 are same or different and are H or C 1-30 aliphatic hydrocarbons;
  • R 14 may take the form of -Z R 14 where Z 1 is any bridging radical whose purpose is to provide incorporation into the polymer backbone and R 14 is as defined previously. R 14 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • R 14 moieties are (but is not limited to) the aliphatic polyether.
  • derivatives of the formula R 2 is H or CH 3 , x > 2, y > 1 and R 15 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , -NH 2 and the like; and At least one of R 6 , R 7 , R 8 , R 9 must be a C 8 or higher linear or branched, saturated or unsaturated, substituted or non-substituted, aliphatic hydrocarbon.
  • R 5 Z 2 -R 10 -W, where:
  • Z 2 Aryl, CH 2 , COO-, CONH-, - O-, - S -, - OSO 2 O-, any radical capable of bridging the R10 group to the vinyl backbone portion of the molecule;
  • R 10 any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH 2 CH 2 )-, -C(CH 3 ) 2 CH 2 CH 2 -; and
  • W -N + R 11 ,R 12 ,R 13 whereRjj, R 12) R 13 is a C 1-4 alkyl group.
  • R 5 can also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride.
  • the residue will be the form of monomers with repeat units of structure:
  • Long chain acrylates including octadecyl acrylate, octadecyl methacrylate, 2- ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, lauryl acrylate, lauryl methacrylate and the like including mixtures of said monomers are known commercially available materials and are all suitable for incorporation of the aliphatic hydrocarbon moiety.
  • vinyl ethers dodecyl vinyl ether, tridecyl vinyl ether, tetradecyl vinyl ether, pentadecyl vinyl ether, hexadecyl vinyl ether, and esters such as those derived from aliphatic alcohols and ⁇ , ⁇ -ethylenic unsaturated carboxylic acids including vinyl neodecanoate, vinyl neononaoate, vinyl stearate, vinyl 2-ethylhexanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl hexadecanoate and the like including mixtures of said monomers, all of which are suitable for incorporation of the aliphatic hydrocarbon moiety.
  • ⁇ -unsaturated and ⁇ -unsaturated olefinic hydrocarbon derivatives such as 1-octadecene, 1-dodecene, 1-hexadecene, 1 -heptadecene, 1-tridecene, 1-undecene, 1-decene, 1-pentadecene, 1-tetradecene, 2-octadecene, 2-dodecene, 2-hexadecene, 2- heptadecene, 2-tridecene, 2-undecene, 2-decene, 2-pentadecene, 2-tetradecene, and the like including mixtures of said monomers.
  • any vinyl type polymer such as polyacrylamide, polyvinyl alcohol, polyacrylic acid, polyvinyl acetate, polymethacrylic acid, polyitaconic, poly(maleic acid), poly(maleic anhydride), polyacrylonitrile and the like.
  • the polyacrylamides, polyvinyl alcohols and polyacrylic acids are most preferred. They would be incorporated directly into the polymer via copolymerization with the associated ethylenically unsaturated monomers including acrylamide, vinyl alcohol, acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylonitrile and the like including mixtures of said monomers during the polymerization process as described below.
  • the description shown is specific for a polyacrylamide but is applicable to any vinyl type polymer. When incorporated in such a manner the long chain aliphatic groups are arranged on the polymer in a pendant fashion.
  • Suitable monomers for incorporating a charge functionality into the polymer include, but are not limited to methacryloyloxyethyl trimethyl ammonium methosulfate
  • METAMS dimethyldiallyl ammonium chloride
  • AMBTAC 3-acryloamido-3-methyl butyl trimethyl ammonium chloride
  • VTAC vinyl benzyl trimethyl ammonium chloride
  • Suitable monomers for incorporating a functionality for making the polymer into a form suitable for papermaking includes but is not limited to: ethylene glycol acrylate, ethylene glycol methacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, 2-allyloxyethanol, 3-allyloxy-1 ,2-propanediol, poly(ethylene glycol) acrylate, poly(ethylene glycol) methacrylate, poly(ethylene glycol) diacrylate, poly(ethylene glycol) dimethacrylate, poly(ethylene glycol) methyl ether acrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, poly(ethylene glycol) divinyl ether, poly(ethylene glycol) phenyl ether acrylate, poly(propylene glycol) acrylate, poly(propylene glycol) methacrylate, poly(propylene glycol)
  • R 1 ,R 1 ',R 2 , R 3 H, C 1 _ 4 alkyl; a, b > 0; c,d > 0;
  • R 4 Z - R 6 - Y radical
  • Z Aryl, CH 2 , COO-, CONR'-, - O-, - S -, - OSO 2 O-, -CONHCO-, -CONHCHOHCHOO-, any radical capable of bridging the R 6 group to the vinyl backbone portion of the molecule.
  • R' H, alkyl
  • R 6 any aliphatic, linear or branched, saturated or unsaturated, substituted or non- substituted hydrocarbon;
  • Y H, - N+R 7 R 8 R 9 , -NR 7 R 8 , where R 7 , R 8 , R 9 are same or different and are H or C 1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons;
  • At least one of R 6 , R 7 , R 8 , R 9 must be an aliphatic, linear or branched, substituted or non- substituted, hydrocarbon of chain length 8 or higher;
  • R 5 Z 2 -R 10 -X
  • Z 2 Aryl, CH 2 , COO-, CONH-, - O-, - S -, - OSO 2 O-, any radical capable of bridging the R 10 group to the vinyl backbone portion of the molecule;
  • R 10 any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH 2 CH 2 )-, -C(CH 3 ) 2 CH 2 CH 2 -; and
  • X -N+R ⁇ .R ⁇ .R ⁇ whereR 1l 7 R 12 , R 13 is a C 1-4 alkyl group.
  • R 5 may also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride.
  • the residue will be the form of monomers with repeat units of structure:
  • the third approach to synthesis of materials of this invention is to modify the functional groups on the polymer backbone.
  • the vinyl type polymers such as polyacrylamides, modified polyacrylamides, polyacrylic acids, polyvinyl alcohols, polymaleic acid, polymaleic anhydride and polyacrylonitriles contain functional groups which may be further derivatized to produce materials of the structure of Figure 4.
  • the polymer functional groups which may be reacted upon include but are not limited to: amide, carboxyl, hydroxyl, anhydride, cyano, thiol and aldehyde (from glyoxylation or similar reaction). In general the starting polymer will be one of that shown in Figure 9.
  • R H. C ⁇ alkyl; a, b >1 ; c,d >0;
  • Q_ a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose.
  • Preferred pendant groups for hydrogen bonding are — CONH 2 , — COO ' + M, — OH and mixtures of said groups.
  • Preferred pendant groups for covalent bonding are aldehydes and anhydrides.
  • M+ can be any suitable counter ion including Na ⁇ K + , Ca +2 and the like;
  • Q 3 a monomer unit or a block or graft copolymer containing a charge functionality.
  • Such charge functionality is preferably cationic but may be anionic or amphoteric;
  • Z 4 -CONHCHOHCHO, -CHO, -CONH 2 , -COOH, -CN, -OH, -SH, -NH 2 , -R'OH,
  • Q 4 may take the form of -Z 2 -Q 4 -Z 2 '- where Z 2 , Z 2 ' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 4 is as defined previously. Q 4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • Q 4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR 1 R 2 ) x O] y — R 3 , wherein R 1 f R 2 is H or CH 3 , x > 2, y > 2 and R 3 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , - NH 2 .
  • R H, C 1-4 alkyl; a, b >1 ; c,d >0;
  • Qi a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose.
  • Preferred pendant groups for hydrogen bonding are — CONH 2 , — COO " + M, — OH and mixtures of said groups.
  • Preferred pendant groups for covalent bonding are aldehydes and anhydrides. M+ can be any suitable counter ion including Na + , K ⁇ Ca +2 and the like;
  • Q 3 a monomer unit or a block or graft copolymer containing a charge functionality. Such charge functionality is preferably cationic but may be anionic or amphoteric;
  • Z 4 -CONHCHOHCHO, -CHO, -CONH 2 , -COOH, -CN, -OH, -SH, -NH 2 , -R'OH,
  • Q 4 may take the form of -Z 2 -Q 4 -Z 2 '- where Z 2 , Z 2 ' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q 4 is as defined previously. Q 4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
  • Q 4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR 1 R 2 ) x O] y — R 3 , wherein R R 2 is H or CH 3 , x > 2, y > 2 and R 3 is any suitable terminal group including -CH 3 , -H, -C 2 H 5 , - NH 2 .
  • R 6 any aliphatic, linear or branched, saturated or unsaturated, substituted or non- substituted hydrocarbon
  • R 7 , R 8 , R 9 are same or different and are H or C 1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons; and where at least one of R 6 , R 7 , R 8 , R 9 must be a C 8 or higher linear or branched, substituted or non-substituted, aliphatic hydrocarbon.

Abstract

Synthetic polymers having hydrogen bonding capability and one or more aliphatic hydrocarbon moieties are capable of providing two distinct properties to paper products, such as tissues, which properties heretofore have been imparted through the use of at least two different molecules. The backbone of these synthetic polymers is based on modified vinyl polymers, such as polyvinyl alcohol, polyacrylamides and polyacrylic acids.

Description

SYNTHETIC POLYMERS HAVING HYDROGEN BONDING CAPABILITY AND CONTAINING ALIPHATIC HYDROCARBON MOIETIES
Background of the Invention
In the manufacture of paper products, such as facial tissue, bath tissue, paper towels, dinner napkins and the like, a wide variety of product properties are imparted to the final product through the use of chemical additives. Examples of such additives include softeners, debonders, wet strength agents, dry strength agents, sizing agents, opacifiers and the like. In many instances, more than one chemical additive is added to the product at some point in the manufacturing process. Unfortunately, there are instances where certain chemical additives may not be compatible with each bther or may be detrimental to the efficiency of the papermaking process, such as can be the case with the effect of wet end chemicals on the downstream efficiency of creping adhesives. Another limitation, which is associated with wet end chemical addition, is the limited availability of adequate bonding sites on the papermaking fibers to which the chemicals can attach themselves. Under such circumstances, more than one chemical functionality competes for the limited available bonding sites, oftentimes resulting in the insufficient retention of one or both chemicals on the fibers. For more complex chemical systems it may desirable to have two or more functional additives retained in a specified ratio and/or spatial arrangement relative to one another. Although the addition of chemicals in a predetermined ratio is easily achieved, retention of these chemicals in a predictable ratio is difficult using wet end chemical addition because of site competition and other influencing factors. Another limitation of either wet end or topical chemical addition is the inability to predictably locate functional chemical moieties in proximity to each other on the fiber surface.
Therefore, there is a need for a means of applying more than one chemical functionality to a paper web that mitigates the limitations created by limited number of bonding sites and the unpredictable nature of chemical additive retention which limits the ability to retain functional groups in a specified ratio and/or spatial arrangement with respect to one another.
Summary of the Invention
In certain instances, two or more chemical functionalities can be combined into a single molecule, such that the combined molecule imparts at least two distinct product properties to the final paper product that heretofore have been imparted through the use of two or more different molecules. More specifically, synthetic polymers, which are commonly used in the paper industry as dry strength resins, wet strength resins and retention aids, can be combined into a single molecule with modified aliphatic hydrocarbons, which are commonly utilized, in conjunction with cationic moieties, as softeners, debonders, lubricants and sizing agents. The resulting molecule is a synthetic polymer having hydrogen bonding capability and an aliphatic hydrocarbon moiety which can provide several potential benefits, depending on the specific combination employed, including: (a) strength aids that soften; (b) softeners that do not reduce strength; (c) wet strength with improved wet/dry strength ratio; (d) debonders with reduced linting and sloughing; (e) strength aids with controlled absorbency; and (g) retention aids that soften.
As used herein, "aliphatic hydrocarbon moieties" are functional groups derived from a broad group of organic compounds, including alkanes, alkenes, alkynes and cyclic aliphatic classifications. The aliphatic hydrocarbon moieties can be linear or branched, saturated or unsaturated, substituted or non-substituted.
The synthetic polymers as described herein, have a portion of their structure derived from the polymerization of ethylenically unsaturated compounds which contain pendant groups that can form hydrogen bonds, ionic bonds or covalent bonds with cellulose molecules in fibers, thereby increasing interfiber bonding. They include polyacrylamide, polyvinyl alcohol, polyacrylic acid, polymaleic anhydride, polymaleic acid, polyitaconic acid, cationic polyacrylamides, anionic polyacrylamides, and the like. The synthetic polymers as described herein may be water soluble, organic soluble or soluble in mixtures of water and water miscible organic compounds. Preferably they are water- soluble or water dispersible but this is not a necessity of the invention. Also included within the definition are the salts of the above mentioned acidic polymers. Substances which can be combined with the acidic portion of the polymers to make the salts include the alkali metals such as K and Na usually added in form of their hydroxides, the aliphatic amines and alkanol amines, such salts and methods of preparing such salts being well known to those skilled in the art. Depending upon the chemical and the desired impact on the paper sheet, the synthetic polymers of this invention may be applied to the paper web by any of the means known to those skilled in the art. Such means include wet end addition, spray addition on the wet web, as a creping chemical sprayed on the Yankee dryer, or as a post treatment addition, including spraying, printing or coating. Hence in one aspect, the invention resides in a synthetic polymer having hydrogen bonding capability and containing one or more aliphatic hydrocarbon moieties, said synthetic polymer having the following structure:
E-Qi-ir Q lr 1 Qa-fc-t where:
Figure imgf000005_0001
a, b > 0; c,d > 0 such that c+d > 0; w ≥ 1 ;
Q. = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose. Preferred pendant groups for hydrogen bonding are — CONH2, —COOH, —COO" M+, —OH and mixtures of said groups. Preferred pendant groups for covalent bonding are aldehydes and anhydrides. M+ can be any suitable counter ion including Na\ K+, Ca+2 and the like. Q2 = a monomer unit or a block or graft copolymer containing a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety. Q2 may take the form of -Z1-Q2-Z1'- where Z Z are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q2 is as defined previously; Q3 = a monomer unit or a block or graft copolymer containing a charge functionality. Such charge functionality is preferably cationic but may be anionic or amphoteric; and Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking. Q4 may take the form of -Z2-Q4-Z2'- where Z2, Z2' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q4 is as defined previously. Q4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties. Examples of suitable Q4 moieties are (but not limited to) the aliphatic polyether derivatives of the formula — [(CR1R2)xO]y — R3, wherein R^ R2 is H or CH3, x > 2, y > 1 and R3 is any suitable terminal group including -CH3, -H, -C2H5, - NH2.
It should be appreciated that when the Q3 or other charged moiety is present in the synthetic polymer, that a suitable countehon will be necessary. Such counterions may or may not be represented in the formulas. Where such counterions are not represented in the formula it should be understood that such an ion will exist. The specific countehon is not critical for the invention, such countehon is only necessary for providing charge balance. For cationically charged groups the most common anions are those of the halides and alkyl sulfates. For anionically charged groups on the polymer the most common counter ions will be those of the alkali and alkaline earth metals as well as ammonia and amine derivatives.
More specifically, the invention resides in a synthetic polymer having the following structure:
f CRffe-f CH2CR2i — f- CH2CR3 frf Q4^
W
Rn where: w ≥ 1 ;
R1,R1',R2,R3 = H, CM alkyl; a, b > 0; c,d > 0 such that c+d > 0;
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking. Q4 may take the form of -Z2-Q4-Z2'- where Z2 Z2' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q4 is as defined previously. Q4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties. Examples of suitable Q4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR1R2)xO]y — R3, wherein R.,, R2 is H or CH3, x > 2, y > 1 and R3 is any suitable terminal group including -CH3, -H, -C2H5, -
NH2; R0 = any group capable of forming hydrogen or covalent bonds with cellulose. Preferred are -CONH2, -COOH, COO'M*. -OH, -CONHCHOHCHO and mixtures of said groups; r\, = -H, -COOH; R4= Z - R6 - Y radical where:
Z = aryl, -CH2-, -COO-, -CONR'-, -O-, -S-, -OSO2O-, -CONHCO-,-CONHCHOHCHOO- or any other radical capable of bridging the R6 group to the vinyl backbone portion of the molecule. (R1 = H, alkyl); R6= any linear or branched, saturated or unsaturated, substituted or non-substituted aliphatic hydrocarbon;
Y = H, - N+R7R8R9, -NR7R8, where R7, R8, R9 are same or different and are H or C1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons; At least one of R6, R7, R8, R9 must be an aliphatic, linear or branched, substituted or non- substituted, hydrocarbon of chain length 8 or higher; R5 = Z2-R10-W;
Z2 = aryl, -CH2-, -COO-, -CONH-, -O-, -S-, -OSO2O-, any radical capable of bridging the
R10 group to the vinyl backbone portion of the molecule; R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH2CH2)-, -C(CH3)2CH2CH2-; and W =
Figure imgf000007_0001
where R11 f R12, R13 is a C1-4 alkyl group.
-[CH2CR3R5]C- may also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride. In this case the charge-containing residue -[CH2CR3R5]C- will be the form of monomers with repeat units of structure:
Figure imgf000007_0002
In another aspect, the invention resides in a paper sheet, such as a tissue sheet, comprising a synthetic polymer having hydrogen bonding capability and containing an aliphatic hydrocarbon moiety, said polymer having the following structure:
Figure imgf000008_0001
where:
a, b > 0; c,d > 0; w ≥ 1 ;
Q, = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose. Preferred pendant groups for hydrogen bonding are — CONH2, —COOH, — COO- M+, —OH and mixtures of said groups. Preferred pendant groups for covalent bonding are aldehydes and anhydrides. M+ can be any suitable counter ion including Na+, K\ Ca+2 and the like; Q2 = a monomer unit or a block or graft copolymer containing a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety. Q2 may take the form of -Z^Q^Z - where Z1; Z are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q2 is as defined previously; Q3 = a monomer unit or a block or graft copolymer containing a charge functionality. Such charge functionality is preferably cationic but may be anionic or amphoteric; and Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking. Q4 may take the form of -Z2-Q4-Z2'- where Z2, Z_' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q4 is as defined previously. Q4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties. Examples of suitable Q4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR1R2)xO]y — R3, wherein R,, R2 is H or CH3, x > 2, y > 1 and R3 is any suitable terminal group including -CH3, -H, -C2H5, -
NH2. More specifically, the invention resides in a paper sheet, such as a tissue sheet, comprising a synthetic polymer having hydrogen bonding capability and containing an aliphatic hydrocarbon moiety, said polymer having the following structure:
fc Q "
Figure imgf000009_0001
where: w ≥ 1 ;
R1.RΛ 21R3 = H, C1- alkyl; a, b > 0; c,d >,= 0;
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking. Q4 may take the form of -Z2-Q4-Z2'- where Z2, Z2' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q4 is as defined previously. Q4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties. Examples of suitable Q4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR1R2)xO]y— R3, wherein R-,, R2 is H or CH3, x > 2, y > 1 and R3 is any suitable terminal group including -CH3, -H, -C2H5, -
NH2;
R0 = any group capable of forming hydrogen or covalent bonds with cellulose. Preferred are -CONH2, -COOH, COO"M+, -OH, -CONHCHOHCHO, and anhydride including mixtures of said groups; A, = H, COOH;
R4= Z - R6 - Y radical where:
Z = aryl, -CH2-, -COO-, -CONR'-, -O-, - S -, -OSO2O-, -CONHCO-, -
CONHCHOHCHOO-or any radical capable of bridging the R6 group to the vinyl backbone portion of the molecule. (R1 =-H, alkyl); R6= any aliphatic, linear or branched, saturated or unsaturated, substituted or non- substituted hydrocarbon; Y = -H, -N+R7R8R9, -NR7R8, where R7, R8, R9 are same or different and are H or C1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons; At least one of R6, R7, R8, R9 must be an aliphatic, linear or branched, substituted or non- substituted, hydrocarbon of chain length 8 or higher;
R5 = Z2-R10-W;
Z2 = aryl, -CH2, -COO-, -CONH-, -O-, -S-, -OSO2O- or any radical capable of bridging the R10 group to the vinyl backbone portion of the molecule;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH2CH2)-, -C(CH3)2CH2CH2-; and
W = -N'R^.R^.R^ where R , R12, R13 is a CM alkyl group.
-[CH2CR3R5]C- may also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride. In this case the charge-containing residue -[CH2CR3R5]C- will be the form of monomers with repeat units of structure:
Figure imgf000010_0001
In another aspect, the invention resides in a method of making a paper sheet, such as a tissue sheet, comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of papermaking fibers onto a forming fabric to form a web; and (c) dewatering and drying the web to form a paper sheet, wherein a synthetic polymeric additive is added to the aqueous suspension of fibers or to the web, said polymeric additive having the following structure:
Figure imgf000010_0002
where: a, b > 0; c,d > 0; w ≥ 1 ;
Q, = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose. Preferred pendant groups for hydrogen bonding are — CONH2, —COOH, —COO- +M, —OH and mixtures of said groups. Preferred pendant groups for covalent bonding are aldehydes and anhydrides. M+ can be any suitable counter ion including Na+, K+, Ca+2 and the like;
Q2 = a monomer unit or a block or graft copolymer containing a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety. Q2 may take the form of -ZrQz-Z - where Z , Z are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q2 is as defined previously;
Q3 = a monomer unit or a block or graft copolymer containing a charge functionality.
Such charge functionality is preferably cationic but may be anionic or amphoteric; and
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking. Q4 may take the form of -Z2-Q4-Z2'- where Z2, Z2' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q4 is as defined previously. Q4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties. Examples of suitable Q4 moieties are (but is not limited to) the aliphatic poiyether derivatives of the formula — [(CR1R2)xO]y — R3, wherein R^ R2 is -H or - CH3, x > 2, y > 1 and R3 is any suitable terminal group including -CH3, -H, -C2H5, - NH2.
More specifically, the invention resides in a method of making a paper sheet, such as a tissue sheet, comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of papermaking fibers onto a forming fabric to form a web; and (c) dewatehng and drying the web to form a paper sheet, wherein a synthetic polymeric additive is added to the aqueous suspension of fibers or to the web, said polymeric additive having the following structure:
Figure imgf000011_0001
where: w ≥ 1 ;
R1,R1',R2, R3 = H, CM alkyl; a, b > 0; c,d > 0;
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking. Q4 may take the form of -Z2-Q4-Z2'- where Z2, Z2' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q4 is as defined previously. Q4 may be incorporated to offset the increased . polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties. Examples of suitable Q4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — I(CR1R2)xO]y — R3, wherein R^ R2 is H or CH3, x > 2, y > 1 and R3 is any suitable terminal group including -CH3, -H, -C2H5, -
NH2;
R0 = any group capable of forming hydrogen or covalent bonds with cellulose. Preferred are -CONH2, COOH, COO", -OH, CONHCHOHCHO, and anhydride including mixtures of said groups; A, = -H, -COOH;
R4= Z - R6 - Y radical where:
Z = aryl, -CH2-, -COO-, -CONR'-, -O-, -S-, -OSO2O-, -CONHCO-, -CONHCHOHCHOO- or any radical capable of bridging the R6 group to the vinyl backbone portion of the molecule. (R' = H, alkyl); R6= any aliphatic, linear or branched, saturated or unsaturated, substituted or non- substituted hydrocarbon; Y = H, -N+R11,R12,R13, -NR7R8, where R7, R8, R9 are same or different and are H or C1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons; At least one of R6, R7, R8, R9 must be an aliphatic, linear or branched, substituted or non- substituted, hydrocarbon of chain length 8 or higher; R5 = Z2-R10-W; Z2 = aryl, -CH2-, -COO-, -CONH-, -O-, -S-, -OSO2O- or any radical capable of bridging the R10 group to the vinyl backbone portion of the molecule; R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH2CH2)-, -C(CH3)2CH2CH2-; and
W = -N+ Rn.R^.R^ where R11 t R12, R13 is a C1-4 alkyl group.
-[CH2CR3R5]C- may also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride. In this case the charge-containing residue -[CH2CR3R5]C- will be the form of monomers with repeat units of structure:
Figure imgf000013_0001
The amount of the synthetic polymeric additive added to the fibers or the tissue web can be from about 0.02 to about 4 weight percent, on a dry fiber basis, more specifically from about 0.05 to about 2 weight percent, and still more specifically from about 0.1 to about 1 weight percent. The synthetic polymer can be added to the fibers or web at any point in the process, but it can be particularly advantageous to add the synthetic polymer to the fibers while the fibers are suspended in water.
Detailed Description of the Invention
To further describe the invention, examples of the synthesis of some of the various chemical species are given below.
First with regard to the synthetic polymers, they can be made via free radical polymerization of vinyl monomers of the form:
R^K2C = _>K3K4
where R1 f R2, R3, R4 may be H, halogen, alkyl, functional alkyl, aryl, functional aryl. For papermaking the polyacrylamides (R4 = — CONH2), polyvinyl alcohols (R4 = — OH), and polyacrylates (R4 = — COOR', R -H, Me) are the most widely used.
Of the modified vinyl synthetic polymers, polyacrylamides (PAMs) are used as dry strength additives in addition to their widespread use as drainage and retention aids.
They are water-soluble polymers containing primary amide groups that can form hydrogen bonds with cellulose molecules in fibers thereby increasing interfiber bonding. They are synthesized by the free radical polymerization of acrylamide as shown in Figure 1.
Figure imgf000014_0001
Figure 1
(PAMs) per se are nonionic materials and have very little attraction to papermaking fibers. Therefore it is necessary to incorporate charged groups into the polymer structure to make it useful for papermaking. Both anionic and cationic polyacrylamides are known in the art.
Anionic polyacrylamides can be produced by (1 ) the copolymerization of acrylamide with acrylic acid or the (2) hydrolysis of some of the amide groups on the polyacrylamide chain. The resultant polymer will contain a mixture of acrylamide and acrylic acid groups. Anionic polyacrylamides were first produced in the 1950's via copolymerization of acrylamide with acrylic acid. The acrylic acid groups introduce an ionizable carboxyl group on the polymer backbone, lonization of these carboxyl groups is highly pH dependent, where above pH 7 essentially 100% of the carboxyl groups are ionized. Since anionic polyacrylamides are negatively charged they are not directly attracted to the like-charged cellulose papermaking fibers. A cationic substance such as alum must be used in conjunction with them to promote their retention.
To avoid the need for a cationic promoter, another approach is to incorporate cationic groups directly into the polymer backbone. Having been commercially produced since the late 1960's, these cationically charged polyacrylamides are the most common form of dry strength PAM's. Cationic polyacrylamides are produced by copolymerization of acrylamide with cationic monomers or by modification of some of the amide groups. Typical cationic monomers include: (1) methacryloyloxyethyi trimethyl ammonium methosulfate (METAMS); (2) dimethyldiallyl ammonium chloride (DMDAAC); (3) 3- acryloamido-3-methyl butyl trimethyl ammonium chloride (AMBTAC); (4) trimethylamino methacrylate; and (5) vinyl benzyl trimethyl ammonium chloride (VBTAC). A typical reaction for co-polymerization with METAMS is illustrated in Figure 2. CH3 O H2C=C — C-0-CH2-CH2-N(CH3)3 + "S04CH3 + H2C=CHCNH2
METAMS
Figure imgf000015_0001
CH3
Figure imgf000015_0002
Figure 2
Production of cationic polyacrylamides by the modification of the amide groups of PAMs is most often accomplished via the Mannich reaction as illustrated in Figure 3. Generally cationic polyacrylamides synthesized in this manner will contain from about 5 to about 70 mole percent cationic groups.
+CH2CH fc
f CH2CH j + HCO + (CH3)2NH o -- . NH, 0 "NH H2C- N(CH3)2
Figure 3
Generally dry strength PAMs are supplied as ready to use aqueous solutions or as water-soluble powders which must be dissolved prior to use. They may be added to thin or thick stock at a point of good mixing for best results. Addition rates of 0.1% to 0.5% of dry fiber typically give best results. High addition rates may cause over-cationization of the furnish and reduce the effectiveness of other additives. When used as dry strength additives usually around 10 mole % of the monomers will contain charged groups. Unlike the anionic PAMs, cationic PAMs can be effectively charged across the entire pH range. Typical molecular weights (Mw) for cationic PAM dry strength aids are in the range of 100,000 to 500,000. The molecular weight is important so as to be low enough to not bridge between particles and cause flocculation, and yet high enough to retard migration of the polymer into the pores of the fibers. Such migration would cause a reduction in dry strength activity.
When used as retention aids a broader range of molecular weights and charge densities may be employed. Key characteristics of polyacrylamide retention aids include the molecular weight, the type of charge, the charge density and the delivery form. For the average molecular weight, the range can be: low (1 ,000 - 100,000); medium (100,000 - 1 ,000,000); high (1 ,000,000 - 5,000,000); very high (>5,000,000). The charge type can be nonionic, cationic, anionic or amphote c. The charge density can be: low (1 - 10%); medium (10 - 40%); high (40 - 80%); or very high (80 - 100%). The delivery form can be an emulsion, an aqueous solution or a dry solid.
High molecular weight/ low charge density flocculants are used most often for retention of fine particles in high shear and turbulence environments. Low Mw, high charge density products are used for their charge modifying capabilities and for retention in low shear environments.
There are several envisioned pathways in which synthetic polymers containing hydrogen bonding groups and aliphatic hydrocarbons can be combined onto a single molecule for purposes of this invention. These include, but are not limited to: (1) block copolymerization and/or grafting ; (2) direct monomer incorporation ; and (3) derivatization of functional groups on the polymer backbone. Each of these methods is described below.-Since these materials maintain their bonding and/or charge characteristics they would be expected to maintain their dry strength and or retention capabilities as well as provide for materials with enhanced tactile properties due to introduction of the aliphatic hydrocarbon moieties. The molar and weight ratios of the various functional groups on the polymer will largely depend on the specific application of the material and is not a critical aspect of the invention. However, the portion of the synthetic polymer [Q,] capable of forming hydrogen, covalent and ionic bonds can constitute from about 10 to about 90 weight percent of the total polymer, more specifically from about 20 to about 80 weight percent of the total polymer and still more specifically from about 30 to about 70 weight percent of the total polymer. The aliphatic hydrocarbon portion [QJ of the synthetic polymer can constitute from about 10 to about 90 weight percent of the synthetic polymer, more specifically from about 20 to about 80 weight percent of the synthetic polymer and still more specifically from about 30 to about 70 weight percent of the synthetic polymer. The charge containing portion [Q3] of the synthetic polymer can be comprised of monomer units constituting from 0 to about 80 mole percent of the total monomer units in the synthetic polymer, more specifically from 0 to about 30 mole percent and still more specifically from about 5 to about 15 mole percent. The [Q4] functionality will be comprised of monomer units constituting from 0 to about 80 mole percent of the total monomer units in the synthetic polymer, more specifically from 0 to about 40 mole percent and still more specifically from 0 to about 20 mole percent.
Likewise the molecular weight of the synthetic polymers of the present invention . will largely depend on the specific application of the material and is not overly critical to the invention. The weight average molecular weight range can be from about 1 ,000 to about 5,000,000, more specifically from about 10,000 to about 2,000,000 and still more specifically from about 20,000 to about 1 ,000,000. Where these polymers are added for dry strength it is important that the molecular weight of the polymer be low enough so as to not bridge between particles and cause flocculation, and yet high enough so as to retard migration of the polymer into the pores of the fibers. These materials can have weight average molecular weights in the range of from about 5,000 to about 1 ,000,000, more specifically from about 10,000 to about 1 ,000,000 and still more specifically from about 20,000 to about 600,000.
Block copolymerization and/or grafting.
In this aspect of the invention one or more of the [Q], elements of the polymer exists as a block or graft copolymer on the vinyl backbone. For example, if the aliphatic hydrocarbon portion of the modified vinyl polymer was incorporated in such a manner, the aliphatic hydrocarbon portion would exist as a block copolymer of polyethylene, polypropylene, isobutylene, polytetraflouroethylene, or any other linear or branched, saturated or unsaturated, substituted or non-substituted hydrocarbon, such co-polymer incorporated either as block or graft onto the vinyl backbone. Generally the aliphatic hydrocarbon blocks would be built as a result of the free radical polymerization of the corresponding ethylenically unsaturated monomers including, ethylene, propylene, perflouroethylene, isobutylene and the like including mixtures of said monomers. These synthetic polymers are distinguished from those of the direct monomer incorporation in that the aliphatic hydrocarbon portion of the molecule would be incorporated linearly within the polymer chain rather than in a pendant fashion. Although the above example and the example in figure 4 are specific to the aliphatic hydrocarbon moiety incorporated via this approach it should be appreciated that any of the synthetic polymer elements or combination of the synthetic polymer elements Q1 f Q2, Q3) Q4 could be incorporated via this approach. Note that where a polyacrylamide is employed that these polymers maintain pendant amide functionality and are therefore capable of being glyoxylated to form materials possessing temporary wet strength. A general example of preparing such a material is shown in Figure 4.
h [M_]
Figure imgf000018_0001
Figure 4
where:
R-ii R3.R1' = H, c,. , alkyl g, h, x > 1 χ * y = g b * y = h a, b > 0 c,d > 0
R0 = any group capable of forming hydrogen or covalent bonds with cellulose. Preferred are -CONH2, COOH, COO", -OH, CONHCHOHCHO, and anhydride including mixtures of said groups;
A, = H, COOH
M_ = an unsaturated vinyl monomer unit capable of being polymerized into a polymer containing a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety. Alternatively M., could be an oligomer or polymer of such an unsaturated vinyl monomer.
Q2 = a block copolymer which is or contains a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety. Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking. Q4 may take the form of -Z2-Q4-Z2'- where Z2, Z2' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q4 is as defined previously. Q4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties. Examples of suitable Q4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR1R2)xO]y — R3, wherein R.,, R2 is H or CH3, x > 2, y > 1 and R3 is any suitable terminal group including -CH3, -H, -C2H5, - NH2
R5 = Z2-R10-W
Z2 = Aryl, CH2, COO-, CONH-, - O-, - S -, - OSO2O-, any radical capable of bridging the R10 group to the vinyl backbone portion of the molecule.
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH2CH2)-, -C(CH3)2CH2CH2-
W = -N^n.Ru.R^ , NRnR^, whereR^, R12, R13 is a C1-4 alkyl group.
R5 may also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride. In this case the residue will be the form of monomers with repeat units of structure:
CH?-CH CH- CH?
I I
H2C CH2
H3C CH3
Direct monomer incorporation.
Incorporation of the aliphatic moieties can be accomplished via copolymerization with vinyl type monomers containing aliphatic groups. Almost any vinyl type monomer containing a pendant aliphatic hydrocarbon can be co-polymerized with acrylamide or a similar vinyl monomer containing a pendant hydrogen-bonding moiety to be incorporated into the polymer backbone. Generically the synthesis can be described in Figure 5.
Figure imgf000020_0001
-f CR,'CRι ft CH2CR!" % E-CH2C ,m -fc E-CH2CR1 »I, d
AT RO R4 5 4 w
Figure 5 where:
Ri, R-i', R-i", Ri"', Ri = H, C1-4 alkyl; a, b > 1 ; c ,d > 0; w ≥ 1 ; r,s > 1 ; t,u > 0; a*w = r; b*w = s; c*w = t; d*w = u;
R0 = any group capable of forming hydrogen or covalent bonds with cellulose. Preferred are -CONH2, COOH, COO", -OH, CONHCHOHCHO, and anhydride including mixtures of said groups;
A, = H, COOH;
R4 = Z - R6 - Y radical where:
Z = Aryl, CH2, COO-, CONH-, - O-, - S -, - OSO2O-, -CONHCO-, CONHCHOHCHOO-, any radical capable of bridging the R6 group to the vinyl backbone portion of the molecule;
Y = H, - N+R7R8R9, -NR7R8, where R7, R8, R9 are same or different and are H or C1-30 aliphatic hydrocarbons;
R5 = any aliphatic, linear or branched, saturated or unsaturated, substituted or non- substituted hydrocarbon; R14 = a moiety necessary for making the material into a form suitable for papermaking.
R14 may take the form of -Z R14 where Z1 is any bridging radical whose purpose is to provide incorporation into the polymer backbone and R14 is as defined previously. R14 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties.
Examples of suitable R14 moieties are (but is not limited to) the aliphatic polyether. derivatives of the formula
Figure imgf000021_0001
R2 is H or CH3, x > 2, y > 1 and R15 is any suitable terminal group including -CH3, -H, -C2H5, -NH2 and the like; and At least one of R6, R7, R8, R9 must be a C8 or higher linear or branched, saturated or unsaturated, substituted or non-substituted, aliphatic hydrocarbon.
More specifically, R5 = Z2-R10-W, where:
Z2 = Aryl, CH2, COO-, CONH-, - O-, - S -, - OSO2O-, any radical capable of bridging the R10 group to the vinyl backbone portion of the molecule;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH2CH2)-, -C(CH3)2CH2CH2-; and
W = -N+R11,R12,R13 whereRjj, R12) R13 is a C1-4 alkyl group.
R5 can also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride. In this case the residue will be the form of monomers with repeat units of structure:
H?C_CH CH-CH I I H2C^+/CH2
H3C A CH3
A specific example of the synthesis is shown in Figure 6.
-v" CH, CH3 O a H2C=C' + b H2C=C + , , ' " + - 0 )=o H2C=c C-0-CH2-CH2-N(CH3)3 S04CH3
H2N CH3(CH2)17θ
Figure imgf000022_0001
e*w = a ; f*w = b ; g*w = c
Figure 6
Long chain acrylates, including octadecyl acrylate, octadecyl methacrylate, 2- ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, lauryl acrylate, lauryl methacrylate and the like including mixtures of said monomers are known commercially available materials and are all suitable for incorporation of the aliphatic hydrocarbon moiety.
Also known are various vinyl ethers dodecyl vinyl ether, tridecyl vinyl ether, tetradecyl vinyl ether, pentadecyl vinyl ether, hexadecyl vinyl ether, and esters such as those derived from aliphatic alcohols and α,β-ethylenic unsaturated carboxylic acids including vinyl neodecanoate, vinyl neononaoate, vinyl stearate, vinyl 2-ethylhexanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl hexadecanoate and the like including mixtures of said monomers, all of which are suitable for incorporation of the aliphatic hydrocarbon moiety.
Also suitable for incorporation of the aliphatic hydrocarbon moiety, but less preferred, are the α-unsaturated and β-unsaturated olefinic hydrocarbon derivatives such as 1-octadecene, 1-dodecene, 1-hexadecene, 1 -heptadecene, 1-tridecene, 1-undecene, 1-decene, 1-pentadecene, 1-tetradecene, 2-octadecene, 2-dodecene, 2-hexadecene, 2- heptadecene, 2-tridecene, 2-undecene, 2-decene, 2-pentadecene, 2-tetradecene, and the like including mixtures of said monomers. They can be incorporated into any vinyl type polymer such as polyacrylamide, polyvinyl alcohol, polyacrylic acid, polyvinyl acetate, polymethacrylic acid, polyitaconic, poly(maleic acid), poly(maleic anhydride), polyacrylonitrile and the like. For the purposes of papermaking, the polyacrylamides, polyvinyl alcohols and polyacrylic acids are most preferred. They would be incorporated directly into the polymer via copolymerization with the associated ethylenically unsaturated monomers including acrylamide, vinyl alcohol, acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylonitrile and the like including mixtures of said monomers during the polymerization process as described below. The description shown is specific for a polyacrylamide but is applicable to any vinyl type polymer. When incorporated in such a manner the long chain aliphatic groups are arranged on the polymer in a pendant fashion.
Suitable monomers for incorporating a charge functionality into the polymer include, but are not limited to methacryloyloxyethyl trimethyl ammonium methosulfate
(METAMS); dimethyldiallyl ammonium chloride (DMDAAC); 3-acryloamido-3-methyl butyl trimethyl ammonium chloride (AMBTAC); trimethylamino methacrylate; vinyl benzyl trimethyl ammonium chloride (VBTAC), 3-allyloxy-2-hydroxy-1 propane sulfonic acid sodium salt and the like including mixtures of said monomers. Suitable monomers for incorporating a functionality for making the polymer into a form suitable for papermaking includes but is not limited to: ethylene glycol acrylate, ethylene glycol methacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, 2-allyloxyethanol, 3-allyloxy-1 ,2-propanediol, poly(ethylene glycol) acrylate, poly(ethylene glycol) methacrylate, poly(ethylene glycol) diacrylate, poly(ethylene glycol) dimethacrylate, poly(ethylene glycol) methyl ether acrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, poly(ethylene glycol) divinyl ether, poly(ethylene glycol) phenyl ether acrylate, poly(propylene glycol) acrylate, poly(propylene glycol) methacrylate, poly(propylene glycol) diacrylate, poly(propylene glycol) dimethacrylate, poly(propylene glycol) methyl ether acrylate, polypropylene glycol) methyl ether methacrylate, polypropylene glycol) ethyl ether acrylate, poly(propylene glycol) ethyl ether methacrylate, polypropylene glycol) phenyl ether acrylate and the like including mixtures of said monomers.
Note that where acrylamide is employed that the resultant polymers contain pendant amide functionality that is capable of being glyoxylated to form materials possessing temporary wet strength as shown in Figures 7 and 8. Glyoxal
Figure imgf000024_0001
Figure 7
Figure imgf000024_0002
O HΛ^H Glyoxal
Figure imgf000024_0003
e + f=
Figure 8 Where: w ≥ 1 ;
R1,R1',R2, R3 = H, C1_4 alkyl; a, b > 0; c,d > 0;
R4= Z - R6 - Y radical where:
Z = Aryl, CH2, COO-, CONR'-, - O-, - S -, - OSO2O-, -CONHCO-, -CONHCHOHCHOO-, any radical capable of bridging the R6 group to the vinyl backbone portion of the molecule. (R' = H, alkyl); R6= any aliphatic, linear or branched, saturated or unsaturated, substituted or non- substituted hydrocarbon;
Y = H, - N+R7R8R9, -NR7R8, where R7, R8, R9 are same or different and are H or C1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons;
At least one of R6, R7, R8, R9 must be an aliphatic, linear or branched, substituted or non- substituted, hydrocarbon of chain length 8 or higher;
R5 = Z2-R10-X;
Z2 = Aryl, CH2, COO-, CONH-, - O-, - S -, - OSO2O-, any radical capable of bridging the R10 group to the vinyl backbone portion of the molecule;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons, preferably -(CH2CH2)-, -C(CH3)2CH2CH2-; and
X = -N+R^.R^.R^ whereR1l 7 R12, R13 is a C1-4 alkyl group.
R5 may also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride. In this case the residue will be the form of monomers with repeat units of structure:
Figure imgf000025_0001
Derivatization of functional groups on the polymer backbone:
The third approach to synthesis of materials of this invention is to modify the functional groups on the polymer backbone. The vinyl type polymers such as polyacrylamides, modified polyacrylamides, polyacrylic acids, polyvinyl alcohols, polymaleic acid, polymaleic anhydride and polyacrylonitriles contain functional groups which may be further derivatized to produce materials of the structure of Figure 4. The polymer functional groups which may be reacted upon include but are not limited to: amide, carboxyl, hydroxyl, anhydride, cyano, thiol and aldehyde (from glyoxylation or similar reaction). In general the starting polymer will be one of that shown in Figure 9.
— t-Qi-fef CH2CR! -J -e- QaH -e Q "id z4
Figure 9
where: R^ H. C^ alkyl; a, b >1 ; c,d >0;
Q_ = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose. Preferred pendant groups for hydrogen bonding are — CONH2, — COO' +M, — OH and mixtures of said groups.
Preferred pendant groups for covalent bonding are aldehydes and anhydrides. M+ can be any suitable counter ion including Na\ K+, Ca+2 and the like; Q3 = a monomer unit or a block or graft copolymer containing a charge functionality.
Such charge functionality is preferably cationic but may be anionic or amphoteric; Z4 = -CONHCHOHCHO, -CHO, -CONH2, -COOH, -CN, -OH, -SH, -NH2, -R'OH,
-R'CHO, -RCONH2, -RCOOH, -R'CN, -R'OH, -R'SH, -R'NH2 or any other functional group capable of being reacted upon in a manner so as to incorporate a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon into the polymer and R' can be any bridging radical, organic or inorganic whose purpose is to attach the functional group to the polymer; and Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking. Q4 may take the form of -Z2-Q4-Z2'- where Z2, Z2' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q4 is as defined previously. Q4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties. Examples of suitable Q4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR1R2)xO]y — R3, wherein R1 f R2 is H or CH3, x > 2, y > 2 and R3 is any suitable terminal group including -CH3, -H, -C2H5, - NH2.
Such structures as those shown in Figure 9 are amenable to reaction with a large variety of reagents as a means of incorporating aliphatic residues into the polymer. The general scheme for such syntheses is shown in Figure 10.
f Q, -+Γ fCH2CRT Q 3 1τf- Q4 -fc
+
Z, - Rή - Y
Figure 10
where:
R = H, C1-4 alkyl; a, b >1 ; c,d >0;
Qi = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose. Preferred pendant groups for hydrogen bonding are — CONH2, — COO" +M, — OH and mixtures of said groups. Preferred pendant groups for covalent bonding are aldehydes and anhydrides. M+ can be any suitable counter ion including Na+, K\ Ca+2 and the like; Q3 = a monomer unit or a block or graft copolymer containing a charge functionality. Such charge functionality is preferably cationic but may be anionic or amphoteric;
Z4 = -CONHCHOHCHO, -CHO, -CONH2, -COOH, -CN, -OH, -SH, -NH2, -R'OH,
-R'CHO, -R'CONH2, -R OOH, -R'CN, -R'OH, -R'SH, -R'NH2 or any other functional group capable of being reacted upon in a manner so as to incorporate a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon into the polymer and R' can be any bridging radical, organic or inorganic whose purpose is to attach the functional group to the polymer; and Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking. Q4 may take the form of -Z2-Q4-Z2'- where Z2, Z2' are any bridging radicals, the same or different, whose purpose is to provide incorporation into the polymer backbone and Q4 is as defined previously. Q4 may be incorporated to offset the increased polymer hydrophobicity caused by introduction of the aliphatic hydrocarbon moieties. Examples of suitable Q4 moieties are (but is not limited to) the aliphatic polyether derivatives of the formula — [(CR1R2)xO]y — R3, wherein R R2 is H or CH3, x > 2, y > 2 and R3 is any suitable terminal group including -CH3, -H, -C2H5, - NH2.
Z5= HOOC-, CIOC-, HO-, HS-, -COOOC-, H2N-, HCO-, CISO2O-, XOC- (X = halo),
CICOO-, or any other functional group capable of reaction with a Z4 type functional group so as to attach the -R6-Y residue onto the polymer;
R6= any aliphatic, linear or branched, saturated or unsaturated, substituted or non- substituted hydrocarbon;
Y = H, - N+R7R8R9, -NR7R8, where R7, R8, R9 are same or different and are H or C1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons; and where at least one of R6, R7, R8, R9 must be a C8 or higher linear or branched, substituted or non-substituted, aliphatic hydrocarbon. Some specific examples of such reactions are given in Figures 11 and 12.
CH3(CH2)7CH=CH(CH2)8OH
Figure imgf000029_0001
Figure imgf000029_0002
R = H, Oleyl
Figure 11
Figure imgf000029_0003
Figure 12
It will be appreciated that the foregoing examples, given for purposes of illustration, are not to be construed as limiting the scope of this invention, which is defined by the following claims and all equivalents thereto.

Claims

We claim:
1. A synthetic polymer containing one or more aliphatic hydrocarbon moieties, said synthetic polymer having the following structure:
-f-Qrfc 1- QTJV 1 Qrt-f- Q4- w where: a, b > 0; c,d > 0 such that c+d > 0; w ≥ 1 ;
Qi = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose;
Q2 = a monomer unit or a block or graft copolymer containing a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety;
Q3 = a monomer unit or a block or graft copolymer containing a charge functionality; and
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking.
2. The polymer of claim 1 wherein the pendant group on Q, capable of forming hydrogen or covalent bonds is selected from the group consisting of -CONH2, -COOH, -COO"M+, - OH, -CONHCHOHCHO and mixtures thereof, wherein M+ is a counter ion.
3. The polymer of claim 1 wherein Q2 is of the form -Z^Q^Z - where Z Z are bridging radicals, which can be the same or different.
4. The polymer of claim 1 wherein Q4 is of the form -Z2-Q4-Z2'- where Z2, Z2' are bridging radicals, which can be the same or different.
5. The polymer of claim 1 wherein Q4 is a radical of the form
Figure imgf000031_0001
R0 is an aliphatic polyether derivative of the formula — [(CR2R2)xO]y — R3 where:
R„ R,' is -H, C alkyl; R2, R2' is -H or -CH3; x > 2; y > 2; and
R3 is a terminal group selected from the group consisting of -CH3, -H, -C2H5, and NH2.
CH? _CH CH- CH?
I I
H2C^+ /CH2 N
6. The polymer of claim 1 wherein Q3 is H3C CH3
7. The polymer of claim 1 wherein Q3 is a radical of the form — CHR^RQR — wherein R0 = a pendant group of the form ZrR10-W, where Z, is a radical bonding the R10 group to the polymer;
R, and R are -H or a C1-4 alkyl group;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; and
W =
Figure imgf000031_0002
where R„, R12, R13 is a C1-4 alkyl group.
8. The polymer of claim 7 wherein Z, is selected from the group consisting of aryl, -CH2-, -COO-, -CONH-, - O-, - S -, and - OSO2O-.
9. The polymer of claim 7 wherein R10 is -(CH2CH2)- or -C(CH3)2CH2CH2-.
10. The polymer of claim 1 wherein "c" is 0.
11. The polymer of claim 1 wherein "d" is 0.
12. The polymer of claim 1 wherein the pendant group on Q1 capable of forming hydrogen bonds is -CONH2.
13. The polymer of claim 1 wherein the pendant group on Qj capable of forming covalent bonds is -CONHCHOHCHO.
14. The polymer of claim 1 wherein Q. has -CONH2 and -CONHCHOHCHO pendant groups.
15. A synthetic polymer having hydrogen bonding capability and containing one or more aliphatic hydrocarbon moieties, said polymer having the following structure:
Figure imgf000032_0001
where: w ≥ 1 ;
Rj.RΛR,, R3 = H or C1-4 alkyl; a, b > 0; c,d >0 such that c+d > 0;
R0 = a group capable of forming hydrogen or covalent bonds with cellulose;
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety;
A, = -H, -COOH;
R4= a Z - R6 - Y radical, where:
Z, = any radical capable of bonding the R6 group to the polymer;
R6= any linear or branched, saturated or unsaturated, substituted or non- substituted aliphatic hydrocarbon; Y = -H, -N+R7R8R9, or -NR7R8, where R7, R8, R9 are same or different and are
H or C1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons and where: at least one of R6, R7, R8, R9 must be a linear or branched, substituted or non- substituted, aliphatic hydrocarbon having a carbon chain length of 8 or higher; R5 = ZrRu-W, where:
Zj = any radical capable of bonding the R10 group to the polymer;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; and W = - Η^.R^.R^ , where Rn, R12, R13 are C1-4 alkyl groups.
16. The polymer of claim 15 wherein R0 is selected from the group consisting of - CONH2, -COOH, -COO'M+, -OH, -CONHCHOHCHO, and mixtures thereof, wherein M+ is a counter ion.
17. The polymer of claim 15 wherein Q4 is of the form -Z2-Q4-Z2'- where Z2, Z2' are bridging radicals, which can be the same or different.
18. The polymer of claim 15 wherein Z. is selected from the group consisting of aryl, -CH2- , -COO-, -CONR'-, -O-, -S-, -OSO2O-, -CONHCO-, and -CONHCHOHCHOO- , and where R' is H or C^ alkyl.
19. The polymer of claim 15 wherein R5 is Z R10-W .
20. The polymer of claim 19 wherein Z, is selected from the group consisting of aryl, - CH2-, -COO-, -CONH-, -O-, -S-, and -OSO2O-.
21. The polymer of claim 19 wherein R10 is -(CH2CH2)- or -C(CH3)2CH2CH2-.
22. The polymer of claim 15 wherein A^ is -H and R0 is -CONH2.
23. The polymer of claim 15 wherein A_ is -H and R0 is -CONHCHOHCHO.
24. The polymer of claim 15 wherein R0 consists of both -CONH2 and - CONHCHOHCHO groups.
25. A synthetic polymer having hydrogen bonding capability and containing one or more aliphatic hydrocarbon moieties, said polymer having the following structure:
Figure imgf000033_0001
where: w ≥ 1 ;
R1,R1',R2, R3 = H or C1-4 alkyl; a, b > 0; c,d >0 such that c+d > 0;
R0 = a group capable of forming hydrogen or covalent bonds with cellulose;
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety;
A, = -H, -COOH;
R4= a Z - R6 - Y radical, where:
Zj = any radical capable of bonding the R6 group to the polymer;
R6= any linear or branched, saturated or unsaturated, substituted or non- substituted aliphatic hydrocarbon; Y = -H, -N+R7R8R9, or -NR7R8, where R7, R8, R9 are same or different and are
H or C-,.30 linear or branched, saturated or unsaturated aliphatic hydrocarbons and where: at least one of R6, R7, R8, R9 must be a linear or branched, substituted or non- substituted, aliphatic hydrocarbon having a carbon chain length of 8 or higher.
26. A paper sheet comprising a synthetic polymer having hydrogen bonding capability and containing one or more aliphatic hydrocarbon moieties, said polymer having the following structure:
Figure imgf000034_0001
where: a, b > 0; c,d > 0; w≥ 1 ;
Q, = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose; Q2 = a monomer unit or a block or graft copolymer containing a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety;
Q3 = a monomer unit or a block or graft copolymer containing a charge functionality; and
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking.
27. The paper sheet of claim 26 wherein the pendant group on Q capable of forming hydrogen or covalent bonds is selected from the group consisting of -CONH2, -COOH,
-COO"M+, -OH, -CONHCHOHCHO and mixtures thereof, wherein M+ is a counter ion.
28. The paper sheet of claim 26 wherein Q2 is of the form
Figure imgf000035_0001
where Z Z_' are bridging radicals, which can be the same or different.
29. The paper sheet of claim 26 wherein Q4 is of the form -Z2-Q4-Z2'- where Z2, Z2' are bridging radicals, which can be the same or different.
30. The paper sheet of claim 26 wherein Q4 is a radical of the form -CHRJCRQR - wherein R0 is an aliphatic polyether derivative of the formula — [(CR2R2)xO]y — R3 where:
Rj, R/ is -H, C1-4 alkyl; R2, R2' is -H or -CH3; x > 2; y > 2; and
R3 is a terminal group selected from the group consisting of -CH3, -H, -C2H5, and -NH2.
CH?-CH CH- CH?
I I
H2C^ CH2 N
31. The paper sheet of claim 26 wherein Q3 is H3C CH3
32. The paper sheet of claim 26 wherein Q3 is a radical of the form — CHRΪCRQR — wherein
R0 = a pendant group of the form ZrR10-W where Z. is a radical capable of bonding the
R10 group to the polymer; Rj and R are -H or a C alkyl group;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; and
W = -N+Rn.Ri. ia where R^, R12, R13 is a C1-4 alkyl group.
33. The paper sheet of claim 32 wherein Z is selected from the group consisting of aryl, -CH2-, -COO-, -CONH-, - O-, - S -, and - OSO2O-.
34. The paper sheet of claim 32 wherein R10 is -(CH2CH2)- or -C(CH3)2CH2CH2-.
35. The paper sheet of claim 26 wherein "c" is 0.
36. The paper sheet of claim 26 wherein "d" is 0.
37. The paper sheet of claim 26 wherein the pendant group on Q1 capable of forming hydrogen bonds is -CONH2.
38. The paper sheet of claim 26 wherein the pendant group on Q capable of forming covalent bonds is -CONHCHOHCHO.
39. The paper sheet of claim 26 wherein Qj has -CONH2 and -CONHCHOHCHO pendant groups.
40. A paper sheet comprising a synthetic polymer having hydrogen bonding capability and containing one or more aliphatic hydrocarbon moieties, said polymer having the following structure:
Figure imgf000036_0001
where: w ≥ 1 ;
R^R/.Ra, R3 = H or C^ alkyl; a, b > 0; c,d >0;
R0 = a group capable of forming hydrogen or covalent bonds with cellulose; Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety;
A, = -H. -COOH;
R4= a Z_ - R6 - Y radical, where:
Z_ ~ any radical capable of bonding the R6 group to the polymer;
R6= any linear or branched, saturated or unsaturated, substituted or non- substituted aliphatic hydrocarbon; Y = -H, -N+R7R8R9, or -NR7R8, where R7, R8, R9 are same or different and are
H or Cj.30 linear or branched, saturated or unsaturated aliphatic hydrocarbons and where: at least one of R6, R7, R8) R9 must be a linear or branched, substituted or non- substituted, aliphatic hydrocarbon having a carbon chain length of 8 or higher; R5 = ZrR10-W,
where:
Zj = any radical capable of bonding the R10 group to the polymer;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; and W = -N+R11,R12,R13 , where R^, R12, R13 are C1-4 alkyl groups.
41. The paper sheet of claim 40 wherein R0 is selected from the group consisting of
- CONH2, -COOH, -COO M\ -OH, -CONHCHOHCHO, and mixtures thereof, wherein M+ is a counter ion.
42. The paper sheet of claim 40 wherein Q4 is of the form -Z2-Q4-Z2'- where Z2, Z2' are bridging radicals, which can be the same or different.
43. The paper sheet of claim 40 wherein Z is selected from the group consisting of aryl, -CH2-, -COO-, -CONR'-, -O-, -S-, -OSO2O-, -CONHCO-, and -CONHCHOHCHOO- , and where R' is H or CM alkyl.
44. The paper sheet of claim 40 wherein R5 is Zj-R10-W .
45. The paper sheet of claim 44 wherein Z., is selected from the group consisting of aryl, -CH2-, -COO-, -CONH-, -O-, -S-, and -OSO2O-.
46. The paper sheet of claim 44 wherein R10 is -(CH2CH2)- or -C(CH3)2CH2CH2-.
47. The paper sheet of claim 40 wherein Aj is -H and R0 is -CONH2.
48. The paper sheet of claim 40 wherein A^ is -H and R0 is -CONHCHOHCHO.
49. The paper sheet of claim 40 wherein R0 consists of both -CONH2 and -CONHCHOHCHO groups .
50. A paper sheet comprising a synthetic polymer having hydrogen bonding capability and containing one or more aliphatic hydrocarbon moieties, said polymer having the following structure:
Figure imgf000038_0001
where: w ≥ 1 ;
RLR/.RZ, R3 = H or C1-4 alkyl; a, b > 0; c,d >0 such that c+d > 0;
R0 = a group capable of forming hydrogen or covalent bonds with cellulose; Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety; A, = -H, -COOH; R4= a ZΛ - R6 - Y radical, where:
Z, = any radical capable of bonding the R6 group to the polymer;
R6= any linear or branched, saturated or unsaturated, substituted or non- substituted aliphatic hydrocarbon; Y = -H, -N+R7R8R9, or -NR7R8, where R7, R8, R9 are same or different and are
H or C1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons and where: at least one of R6, R7, R8, R9 must be a linear or branched, substituted or non-substituted, aliphatic hydrocarbon having a carbon chain length of 8 or higher.
51. A method of making a paper sheet comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of papermaking fibers onto a forming fabric to form a web; and (c) dewatering and drying the web to form a paper sheet, wherein a synthetic polymer is added to the aqueous suspension of fibers and/or the web, said polymer having the following structure:
Figure imgf000039_0001
where: a, b > 0; c,d > 0; w ≥ 1 ;
Q, = a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose;
Q2 = a monomer unit or a block or graft copolymer containing a C8 or higher linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon moiety;
Q3 = a monomer unit or a block or graft copolymer containing a charge functionality; and
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking.
52. The method of claim 51 wherein the pendant group on Q1 capable of forming hydrogen or covalent bonds is selected from the group consisting of -CONH2, -COOH, - COO'M*. -OH, -CONHCHOHCHO and mixtures thereof, wherein M+ is a counter ion.
53. The method of claim 51 wherein Q2 is of the form -Z^Q^Z - where Z Z are bridging radicals, which can be the same or different.
54. The method of claim 51 wherein Q4 is of the form -Z2-Q4-Z2'- where Z2, Z2' are bridging radicals, which can be the same or different.
55. The method of claim 51 wherein Q4 is a radical of the form
Figure imgf000040_0001
wherein R0 is an aliphatic polyether derivative of the formula — [(CR2R2)xO]y — R3 where:
Rj, R/ is -H, CM alkyl; R2, R2' is -H or -CH3; x > 2; y > 2; and
R3 is a terminal group selected from the group consisting of -CH3, -H, -C2H5, and -NH2.
CH?-CH CH CH?-
I I
H2C + /CH N
56. The method of claim 51 wherein Q3 is H3C CH3
57. The method of claim 51 wherein Q3 is a radical of the form — CHR^RoR — wherein R0 = a pendant group of the form Z R10-W, where Z is a radical capable of bonding the R10 group to the polymer;
Ri and R are -H or a C1-4 alkyl group;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; and
W = -N+R^.R^.R^ where R11 f R12, R13 is a C1-4 alkyl group.
58. The method of claim 57 wherein Z_ is selected from the group consisting of aryl, - CH2-,
-COO-, -CONH-, - O-, - S -, and - OSO2O-.
59. The method of claim 57 wherein R10 is -(CH2CH2)- or -C(CH3)2CH2CH2-.
60. The method of claim 51 wherein "c" is 0.
61. The method of claim 51 wherein "d" is 0.
62. The method of claim 51 wherein the pendant group on Q_ capable of forming hydrogen bonds is -CONH2.
63. The method of claim 51 wherein the pendant group on Q_ capable of forming covalent bonds is -CONHCHOHCHO.
64. The method of claim 51 wherein Q, has -CONH2 and -CONHCHOHCHO pendant groups.
65. A method of making a paper sheet comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of papermaking fibers onto a forming fabric to form a web; and (c) dewatering and drying the web to form a paper sheet, wherein a synthetic polymer is added to the aqueous suspension of fibers and/or the web, said polymer having the following structure:
Figure imgf000041_0001
where: w ≥ 1 ;
R1,R1',R2, R3 = H or C1-4alkyl; a, b > 0; c,d >0;
R0 = a group capable of forming hydrogen or covalent bonds with cellulose;
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety;
A, = -H, -COOH;
R4= a Z - R6 - Y radical, where:
Z1 = any radical capable of bonding the R6 group to the polymer;
R6= any linear or branched, saturated or unsaturated, substituted or non- substituted aliphatic hydrocarbon; Y = -H, -N+R7R8R9, or -NR7R8, where R7, R8, R9 are same or different and are
H or C,.30 linear or branched, saturated or unsaturated aliphatic hydrocarbons and where: at least one of R6, R7, R8, R9 must be a linear or branched, substituted or non- substituted, aliphatic hydrocarbon having a carbon chain length of 8 or higher;
R5 = ZrR10-W, where:
Z, = any radical capable of bonding the R10 group to the polymer;
R10 = any linear or branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; and W = -^R^.R^.R^ . where R^, R12, R13 are C1-4 alkyl groups.
66. The method of claim 65 wherein R0 is selected from the group consisting of - CONH2, -COOH, -COO"M+, -OH, -CONHCHOHCHO, and mixtures thereof, wherein M+ is a counter ion.
67. The method of claim 65 wherein Q4 is of the form -Z2-Q4-Z2'- where Z2, Z2' are bridging radicals, which can be the same or different.
68. The method of claim 65 wherein Z., is selected from the group consisting of aryl, -CH2-
, -COO-, -CONR'-, -O-, -S-, -OSO2O-, -CONHCO-, and -CONHCHOHCHOO- , and where R' is H or C1-4 alkyl.
69. The method of claim 65 wherein R5 is Zj-R10-W .
70. The method of claim 69 wherein Z is selected from the group consisting of aryl, - CH2-, -COO-, -CONH-, -O-, -S-, and -OSO2O-.
71. The method of claim 69 wherein R10 is -(CH2CH2)- or -C(CH3)2CH2CH2-.
72. The method of claim 65 wherein A is -H and R0 is -CONH2.
73. The method of claim 65 wherein A, is -H and R0 is -CONHCHOHCHO.
74. The method of claim 65 wherein R0 consists of both -CONH2 and -CONHCHOHCHO groups .
75. . A method of making a paper sheet comprising the steps of: (a) forming an aqueous suspension of papermaking fibers; (b) depositing the aqueous suspension of papermaking fibers onto a forming fabric to form a web; and (c) dewatering and drying the web to form a paper sheet, wherein a synthetic polymer is added to the aqueous suspension of fibers and/or the web, said polymer having the following structure: -rCR,'CR,]a CH2CR2" b-t CH2CH- CHCIζl f Q4
A, R, R4 H2Cχ 7CH2 w
H3C /?\ CH3 where: w ≥ 1 ;
Rj.R/.R;,, R3 = H or CM alkyl; a, b > 0; c,d >0 such that c+d > 0;
R0 = a group capable of forming hydrogen or covalent bonds with cellulose;
Q4 = a monomer unit or a block or graft copolymer containing a hydrophilic moiety;
A, = -H, -COOH;
R4= a Z - R6 - Y radical, where:
Z = any radical capable of bonding the R6 group to the polymer;
R6= any linear or branched, saturated or unsaturated, substituted or non- substituted aliphatic hydrocarbon; Y = -H, -N+R7R8R9, or -NR7R8, where R7, R8, R9 are same or different and are
H or C1-30 linear or branched, saturated or unsaturated aliphatic hydrocarbons and where: at least one of R6, R7, R8, R9 must be a linear or branched, substituted or non- substituted, aliphatic hydrocarbon having a carbon chain length of 8 or higher.
PCT/US2000/001615 1999-01-25 2000-01-25 Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties WO2000043429A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU27350/00A AU770362B2 (en) 1999-01-25 2000-01-25 Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties
EP20000905706 EP1165640B1 (en) 1999-01-25 2000-01-25 Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties
BRPI0007706-2A BR0007706B1 (en) 1999-01-25 2000-01-25 synthetic polymers having a hydrogen bonding capability and containing aliphatic hydrocarbon moieties.
DE2000627417 DE60027417T2 (en) 1999-01-25 2000-01-25 HYDROGEN-CONTAINABLE SYNTHETIC POLYMERS CONTAINING ALIPHATIC HYDROCARBON GROUPS

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11716799P 1999-01-25 1999-01-25
US60/117,167 1999-01-25
US09/299,977 US6274667B1 (en) 1999-01-25 1999-04-27 Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties
US09/299,977 1999-04-27

Publications (1)

Publication Number Publication Date
WO2000043429A1 true WO2000043429A1 (en) 2000-07-27

Family

ID=26815002

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/001615 WO2000043429A1 (en) 1999-01-25 2000-01-25 Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties

Country Status (11)

Country Link
US (2) US6274667B1 (en)
EP (1) EP1165640B1 (en)
KR (1) KR100606304B1 (en)
CN (1) CN1337973A (en)
AR (1) AR028142A1 (en)
AU (1) AU770362B2 (en)
BR (1) BR0007706B1 (en)
CO (1) CO5210978A1 (en)
DE (1) DE60027417T2 (en)
TW (1) TW498082B (en)
WO (1) WO2000043429A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002048457A2 (en) * 2000-12-14 2002-06-20 Kimberly-Clark Worldwide, Inc. Soft tissue with improved lint and slough properties
WO2003057984A1 (en) * 2001-12-27 2003-07-17 Kimberly-Clark Worldwide, Inc. Toilet tissue and method of production
US6673205B2 (en) 2001-05-10 2004-01-06 Fort James Corporation Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products
WO2004044319A2 (en) * 2002-11-06 2004-05-27 Kimberly-Clark Worldwide, Inc. Low slough tissue products and method for making same
US7041197B2 (en) 2003-04-15 2006-05-09 Fort James Corporation Wet strength and softness enhancement of paper products

Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6749721B2 (en) 2000-12-22 2004-06-15 Kimberly-Clark Worldwide, Inc. Process for incorporating poorly substantive paper modifying agents into a paper sheet via wet end addition
US6824650B2 (en) * 2001-12-18 2004-11-30 Kimberly-Clark Worldwide, Inc. Fibrous materials treated with a polyvinylamine polymer
EP1532433A2 (en) * 2002-08-28 2005-05-25 Wayne State University System for infrared imaging by inducing acoustic chaos
US7994079B2 (en) 2002-12-17 2011-08-09 Kimberly-Clark Worldwide, Inc. Meltblown scrubbing product
US6949167B2 (en) * 2002-12-19 2005-09-27 Kimberly-Clark Worldwide, Inc. Tissue products having uniformly deposited hydrophobic additives and controlled wettability
US6994770B2 (en) * 2002-12-20 2006-02-07 Kimberly-Clark Worldwide, Inc. Strength additives for tissue products
US20040118540A1 (en) * 2002-12-20 2004-06-24 Kimberly-Clark Worlwide, Inc. Bicomponent strengtheninig system for paper
US7147751B2 (en) * 2002-12-20 2006-12-12 Kimberly-Clark Worldwide, Inc. Wiping products having a low coefficient of friction in the wet state and process for producing same
US6896766B2 (en) * 2002-12-20 2005-05-24 Kimberly-Clark Worldwide, Inc. Paper wiping products treated with a hydrophobic additive
US6916402B2 (en) * 2002-12-23 2005-07-12 Kimberly-Clark Worldwide, Inc. Process for bonding chemical additives on to substrates containing cellulosic materials and products thereof
US7306699B2 (en) * 2002-12-31 2007-12-11 Kimberly-Clark Worldwide, Inc. Tissue product containing a topical composition in the form of discrete droplets
US20040163785A1 (en) * 2003-02-20 2004-08-26 Shannon Thomas Gerard Paper wiping products treated with a polysiloxane composition
US7396593B2 (en) 2003-05-19 2008-07-08 Kimberly-Clark Worldwide, Inc. Single ply tissue products surface treated with a softening agent
US7517433B2 (en) * 2003-08-28 2009-04-14 Kimberly-Clark Worldwide, Inc. Soft paper sheet with improved mucus removal
US7186318B2 (en) 2003-12-19 2007-03-06 Kimberly-Clark Worldwide, Inc. Soft tissue hydrophilic tissue products containing polysiloxane and having unique absorbent properties
US7147752B2 (en) 2003-12-19 2006-12-12 Kimberly-Clark Worldwide, Inc. Hydrophilic fibers containing substantive polysiloxanes and tissue products made therefrom
US7479578B2 (en) * 2003-12-19 2009-01-20 Kimberly-Clark Worldwide, Inc. Highly wettable—highly flexible fluff fibers and disposable absorbent products made of those
US7811948B2 (en) * 2003-12-19 2010-10-12 Kimberly-Clark Worldwide, Inc. Tissue sheets containing multiple polysiloxanes and having regions of varying hydrophobicity
US20050136765A1 (en) * 2003-12-23 2005-06-23 Kimberly-Clark Worldwide, Inc. Fibrous materials exhibiting thermal change during use
US7676088B2 (en) * 2004-12-23 2010-03-09 Asml Netherlands B.V. Imprint lithography
US7670459B2 (en) 2004-12-29 2010-03-02 Kimberly-Clark Worldwide, Inc. Soft and durable tissue products containing a softening agent
US20060144536A1 (en) * 2004-12-30 2006-07-06 Nickel Deborah J Soft and durable tissues made with thermoplastic polymer complexes
US20060144541A1 (en) * 2004-12-30 2006-07-06 Deborah Joy Nickel Softening agent pre-treated fibers
US20070020315A1 (en) * 2005-07-25 2007-01-25 Kimberly-Clark Worldwide, Inc. Tissue products having low stiffness and antimicrobial activity
US20070048357A1 (en) * 2005-08-31 2007-03-01 Kimberly-Clark Worldwide, Inc. Fibrous wiping products
US20070135542A1 (en) * 2005-12-08 2007-06-14 Boonstra Lykele J Emulsifiers for use in water-based tackifier dispersions
US7842163B2 (en) 2005-12-15 2010-11-30 Kimberly-Clark Worldwide, Inc. Embossed tissue products
US7879191B2 (en) 2005-12-15 2011-02-01 Kimberly-Clark Worldwide, Inc. Wiping products having enhanced cleaning abilities
US8444811B2 (en) * 2005-12-15 2013-05-21 Kimberly-Clark Worldwide, Inc. Process for increasing the basis weight of sheet materials
US7820010B2 (en) * 2005-12-15 2010-10-26 Kimberly-Clark Worldwide, Inc. Treated tissue products having increased strength
US7837831B2 (en) 2005-12-15 2010-11-23 Kimberly-Clark Worldwide, Inc. Tissue products containing a polymer dispersion
US7807023B2 (en) * 2005-12-15 2010-10-05 Kimberly-Clark Worldwide, Inc. Process for increasing the basis weight of sheet materials
US7879188B2 (en) 2005-12-15 2011-02-01 Kimberly-Clark Worldwide, Inc. Additive compositions for treating various base sheets
US20070137811A1 (en) * 2005-12-15 2007-06-21 Kimberly-Clark Worldwide, Inc. Premoistened tissue products
US7883604B2 (en) 2005-12-15 2011-02-08 Kimberly-Clark Worldwide, Inc. Creping process and products made therefrom
WO2008156454A1 (en) 2007-06-21 2008-12-24 Kimberly-Clark Worldwide, Inc. Wiping products having enhanced oil absorbency
US7879189B2 (en) 2005-12-15 2011-02-01 Kimberly-Clark Worldwide, Inc. Additive compositions for treating various base sheets
US7785443B2 (en) 2006-12-07 2010-08-31 Kimberly-Clark Worldwide, Inc. Process for producing tissue products
US8697934B2 (en) 2007-07-31 2014-04-15 Kimberly-Clark Worldwide, Inc. Sensor products using conductive webs
US8058194B2 (en) * 2007-07-31 2011-11-15 Kimberly-Clark Worldwide, Inc. Conductive webs
US8372766B2 (en) * 2007-07-31 2013-02-12 Kimberly-Clark Worldwide, Inc. Conductive webs
AU2009252769B2 (en) * 2008-05-29 2014-03-20 Kimberly-Clark Worldwide, Inc. Conductive webs containing electrical pathways and method for making same
US7944401B2 (en) 2008-05-29 2011-05-17 Kimberly-Clark Worldwide, Inc. Radiating element for a signal emitting apparatus
US8172982B2 (en) * 2008-12-22 2012-05-08 Kimberly-Clark Worldwide, Inc. Conductive webs and process for making same
US8105463B2 (en) 2009-03-20 2012-01-31 Kimberly-Clark Worldwide, Inc. Creped tissue sheets treated with an additive composition according to a pattern
KR101676928B1 (en) 2011-08-25 2016-11-16 솔레니스 테크놀러지스 케이맨, 엘.피. Method for increasing the advantages of strength aids in the production of paper and paperboard
CN107034724B (en) 2011-09-30 2019-12-17 凯米罗总公司 Paper and method of making paper
US9777434B2 (en) 2011-12-22 2017-10-03 Kemira Dyj Compositions and methods of making paper products
WO2013179139A1 (en) 2012-05-30 2013-12-05 Kemira Oyj Compositions and methods of making paper products
CA2876651C (en) 2012-06-22 2018-10-09 Kemira Oyj Compositions and methods of making paper products
CA2886043A1 (en) 2012-09-26 2014-04-03 Kemira Oyj Absorbent materials, products including absorbent materials, compositions, and methods of making absorbent materials
US9562326B2 (en) 2013-03-14 2017-02-07 Kemira Oyj Compositions and methods of making paper products
CN104419008A (en) * 2013-08-30 2015-03-18 北京化工大学 Method for grafting polymer chain employing biomass polysaccharide
US9289520B2 (en) 2014-02-27 2016-03-22 Kimberly-Clark Worldwide, Inc. Method and system to clean microorganisms without chemicals
BR112018007748B1 (en) 2015-11-03 2022-07-26 Kimberly-Clark Worldwide, Inc. PAPER FABRIC PRODUCT, CLEANING PRODUCT, AND, PERSONAL CARE ABSORBING ARTICLE
MX2018004722A (en) 2015-11-03 2018-07-06 Kimberly Clark Co Foamed composite web with low wet collapse.
EP3417104A1 (en) 2016-02-16 2018-12-26 Kemira OYJ Method for producng paper
MX2018010386A (en) 2016-02-29 2018-11-29 Kemira Oyj A softener composition.
WO2017214616A1 (en) 2016-06-10 2017-12-14 Ecolab Usa Inc. Low molecular weight dry powder polymer for use as paper-making dry strength agent
KR20200037264A (en) 2017-07-31 2020-04-08 에코랍 유에스에이 인코퍼레이티드 Dry polymer application method
EP3661998A1 (en) 2017-07-31 2020-06-10 Ecolab USA Inc. Process for fast dissolution of powder comprising low molecular weight acrylamide-based polymer
WO2019118675A1 (en) 2017-12-13 2019-06-20 Ecolab Usa Inc. Solution comprising an associative polymer and a cyclodextrin polymer
CA3118086C (en) 2018-11-02 2023-08-01 Buckman Laboratories International, Inc. Synthesis of re-pulpable temporary wet strength polymer for tissue application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372787A (en) * 1971-08-10 1974-11-06 Calgon Corp Non-woven fibre products
US4835234A (en) * 1986-09-08 1989-05-30 Exxon Research And Engineering Company Hydrophobically functionalized cationic polymers
EP0374478A2 (en) * 1988-12-19 1990-06-27 Cytec Technology Corp. Emulsified functionalized polymers
US5368744A (en) * 1993-08-03 1994-11-29 Betz Laboratories, Inc. Methods for treating wastewater
US5541252A (en) * 1993-10-19 1996-07-30 Rohm Gmbh Method of manufacturing water-soluble polymer dispersions having high polymer content

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872039A (en) 1974-02-01 1975-03-18 Dow Chemical Co Cellulosic materials internally sized with low molecular weight copolymers of alpha, beta-ethylenically unsaturated hydrophobic monomers and ammoniated carboxylic acid comonomers
FR2377447A2 (en) * 1977-01-17 1978-08-11 Tennant Co Detergent compsn. useful for treating dirty surfaces - contg. alkaline agent improving the detergency, wetting and flocculating agents (SW 23.5.78)
US4392917A (en) 1979-10-15 1983-07-12 Diamond Shamrock Corporation Amphoteric water-in-oil self-inverting polymer emulsion
US4426485A (en) 1982-06-14 1984-01-17 Union Carbide Corporation Polymers with hydrophobe bunches
US4599390A (en) 1983-03-11 1986-07-08 Union Carbide Corporation High molecular weight water-soluble polymers and flocculation method using same
US4801387A (en) 1983-10-26 1989-01-31 Betz Laboratories, Inc. Water treatment polymers and methods of use thereof
US4535098A (en) 1984-03-12 1985-08-13 The Dow Chemical Company Material for absorbing aqueous fluids
US4684708A (en) * 1985-03-11 1987-08-04 Akzo N.V. Cationic grafted starch copolymers
US4835206A (en) * 1986-10-01 1989-05-30 Allied Colloids, Ltd. Water soluble polymeric compositions
US5252692A (en) 1990-11-23 1993-10-12 Kingston Technologies, Inc. Hydrophilic acrylic copolymers and method of preparation
US5234604A (en) 1991-02-26 1993-08-10 Betz Laboratories, Inc. Water soluble block copolymers and methods of use therof
CA2165768C (en) 1993-07-01 1999-11-30 Peter Marte Torgerson Thermoplastic elastomeric copolymers and hair and skin care compositionscontaining the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372787A (en) * 1971-08-10 1974-11-06 Calgon Corp Non-woven fibre products
US4835234A (en) * 1986-09-08 1989-05-30 Exxon Research And Engineering Company Hydrophobically functionalized cationic polymers
EP0374478A2 (en) * 1988-12-19 1990-06-27 Cytec Technology Corp. Emulsified functionalized polymers
US5368744A (en) * 1993-08-03 1994-11-29 Betz Laboratories, Inc. Methods for treating wastewater
US5541252A (en) * 1993-10-19 1996-07-30 Rohm Gmbh Method of manufacturing water-soluble polymer dispersions having high polymer content

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002048457A2 (en) * 2000-12-14 2002-06-20 Kimberly-Clark Worldwide, Inc. Soft tissue with improved lint and slough properties
WO2002048457A3 (en) * 2000-12-14 2002-11-07 Kimberly Clark Co Soft tissue with improved lint and slough properties
AU2002227420B2 (en) * 2000-12-14 2005-12-22 Kimberly-Clark Worldwide, Inc. Soft tissue with improved lint and slough properties
KR100826418B1 (en) 2000-12-14 2008-04-29 킴벌리-클라크 월드와이드, 인크. Soft tissue with improved lint and slough properties
US6673205B2 (en) 2001-05-10 2004-01-06 Fort James Corporation Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products
US8067524B2 (en) 2001-05-10 2011-11-29 Georgia-Pacific Consumer Products Lp Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products
WO2003057984A1 (en) * 2001-12-27 2003-07-17 Kimberly-Clark Worldwide, Inc. Toilet tissue and method of production
US6758943B2 (en) 2001-12-27 2004-07-06 Kimberly-Clark Worldwide, Inc. Method of making a high utility tissue
WO2004044319A2 (en) * 2002-11-06 2004-05-27 Kimberly-Clark Worldwide, Inc. Low slough tissue products and method for making same
WO2004044319A3 (en) * 2002-11-06 2004-09-10 Kimberly Clark Co Low slough tissue products and method for making same
AU2003286629B2 (en) * 2002-11-06 2008-05-29 Kimberly-Clark Worldwide, Inc. Low slough tissue products and methods for making same
US7041197B2 (en) 2003-04-15 2006-05-09 Fort James Corporation Wet strength and softness enhancement of paper products

Also Published As

Publication number Publication date
EP1165640B1 (en) 2006-04-19
US6274667B1 (en) 2001-08-14
BR0007706B1 (en) 2010-11-30
BR0007706A (en) 2001-11-20
KR100606304B1 (en) 2006-07-28
AU2735000A (en) 2000-08-07
CN1337973A (en) 2002-02-27
CO5210978A1 (en) 2002-10-30
AU770362B2 (en) 2004-02-19
DE60027417T2 (en) 2006-09-28
KR20010103741A (en) 2001-11-23
US6365667B1 (en) 2002-04-02
TW498082B (en) 2002-08-11
DE60027417D1 (en) 2006-05-24
AR028142A1 (en) 2003-04-30
EP1165640A1 (en) 2002-01-02

Similar Documents

Publication Publication Date Title
EP1165640B1 (en) Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties
US6287418B1 (en) Modified vinyl polymers containing amphiphilic hydrocarbon moieties
EP1161467B1 (en) Modified vinyl polymers containing amphiphilic hydrocarbon moieties
EP1147145B1 (en) Synthetic polymers having hydrogen bonding capability and containing polysiloxane moieties
CA2542772C (en) Temporary wet strength additives
ES2425634T3 (en) Polymers functionalized with aldehyde and its use to increase the elimination of water from a paper machine
EP2021388A2 (en) Michael addition adducts as additives for paper and papermaking
EP1242466B1 (en) Wet strength agent and method for production thereof
CA2427343C (en) Soft tissue with improved lint and slough properties
CA2599469A1 (en) Processes for making temporary wet strength additives
JP5382705B2 (en) Paper manufacturing method
MXPA01007209A (en) Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties
MXPA01007124A (en) Modified vinyl polymers containing amphiphilic hydrocarbon moieties
FI122734B (en) Process chemical for use in the manufacture of paper or board
EP1316565A2 (en) Wet strength agent and method for production thereof

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 00803042.1

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 27350/00

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/007209

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 1020017009055

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2000905706

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020017009055

Country of ref document: KR

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 2000905706

Country of ref document: EP

CFP Corrected version of a pamphlet front page

Free format text: REVISED TITLE RECEIVED BY THE INTERNATIONAL BUREAU AFTER COMPLETION OF THE TECHNICAL PREPARATIONS FOR INTERNATIONAL PUBLICATION

WWG Wipo information: grant in national office

Ref document number: 27350/00

Country of ref document: AU

WWG Wipo information: grant in national office

Ref document number: 2000905706

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1020017009055

Country of ref document: KR