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 PDFInfo
- 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
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
- C08F226/04—Diallylamine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular 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
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249962—Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
- Y10T428/249964—Fibers of defined composition
- Y10T428/249965—Cellulosic
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31942—Of aldehyde or ketone condensation product
- Y10T428/31949—Next to cellulosic
- Y10T428/31964—Paper
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31975—Of cellulosic next to another carbohydrate
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31975—Of cellulosic next to another carbohydrate
- Y10T428/31978—Cellulosic next to another cellulosic
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31971—Of carbohydrate
- Y10T428/31975—Of cellulosic next to another carbohydrate
- Y10T428/31978—Cellulosic next to another cellulosic
- Y10T428/31982—Wood 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
Description
Claims
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 |
DE2000627417 DE60027417T2 (en) | 1999-01-25 | 2000-01-25 | HYDROGEN-CONTAINABLE SYNTHETIC POLYMERS CONTAINING ALIPHATIC HYDROCARBON GROUPS |
BRPI0007706-2A BR0007706B1 (en) | 1999-01-25 | 2000-01-25 | synthetic polymers having a hydrogen bonding capability and containing aliphatic hydrocarbon moieties. |
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)
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)
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 |
US6998616B2 (en) * | 2002-08-28 | 2006-02-14 | Wayne State University | System and method for acoustic chaos and sonic infrared imaging |
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 |
US6896766B2 (en) * | 2002-12-20 | 2005-05-24 | Kimberly-Clark Worldwide, Inc. | Paper wiping products treated with a hydrophobic additive |
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 |
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 |
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 |
MXPA06001734A (en) * | 2003-08-28 | 2006-05-12 | Kimberly Clark Co | 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 |
US7811948B2 (en) * | 2003-12-19 | 2010-10-12 | Kimberly-Clark Worldwide, Inc. | Tissue sheets containing multiple polysiloxanes and having regions of varying hydrophobicity |
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 |
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 |
US20060144541A1 (en) * | 2004-12-30 | 2006-07-06 | Deborah Joy Nickel | Softening agent pre-treated fibers |
US20060144536A1 (en) * | 2004-12-30 | 2006-07-06 | Nickel Deborah J | Soft and durable tissues made with thermoplastic polymer complexes |
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 |
US8444811B2 (en) * | 2005-12-15 | 2013-05-21 | Kimberly-Clark Worldwide, Inc. | Process for increasing the basis weight of sheet materials |
US7837831B2 (en) | 2005-12-15 | 2010-11-23 | Kimberly-Clark Worldwide, Inc. | Tissue products containing a polymer dispersion |
US20070137811A1 (en) * | 2005-12-15 | 2007-06-21 | Kimberly-Clark Worldwide, Inc. | Premoistened tissue products |
US8282776B2 (en) | 2005-12-15 | 2012-10-09 | Kimberly-Clark Worldwide, Inc. | Wiping product having enhanced oil absorbency |
US7807023B2 (en) * | 2005-12-15 | 2010-10-05 | Kimberly-Clark Worldwide, Inc. | Process for increasing the basis weight of sheet materials |
US7883604B2 (en) | 2005-12-15 | 2011-02-08 | Kimberly-Clark Worldwide, Inc. | Creping process and products made therefrom |
US7879191B2 (en) | 2005-12-15 | 2011-02-01 | Kimberly-Clark Worldwide, Inc. | Wiping products having enhanced cleaning abilities |
US7820010B2 (en) * | 2005-12-15 | 2010-10-26 | Kimberly-Clark Worldwide, Inc. | Treated tissue products having increased strength |
US7879188B2 (en) | 2005-12-15 | 2011-02-01 | Kimberly-Clark Worldwide, Inc. | Additive compositions for treating various base sheets |
US7842163B2 (en) | 2005-12-15 | 2010-11-30 | Kimberly-Clark Worldwide, Inc. | Embossed tissue products |
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 |
US8372766B2 (en) * | 2007-07-31 | 2013-02-12 | Kimberly-Clark Worldwide, Inc. | Conductive webs |
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 |
EP2283177B1 (en) * | 2008-05-29 | 2016-04-13 | 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 |
WO2013026578A1 (en) | 2011-08-25 | 2013-02-28 | Ashland Licensing And Intellectual Property Llc | Method for increasing the advantages of strength aids in the production of paper and paperboard |
ES2633188T3 (en) | 2011-09-30 | 2017-09-19 | Kemira Oyj | Paper and papermaking process |
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 |
WO2013192082A1 (en) | 2012-06-22 | 2013-12-27 | Oyj, Kemira | Compositions and methods of making paper products |
EP2900870A1 (en) | 2012-09-26 | 2015-08-05 | 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 |
CN108348113B (en) | 2015-11-03 | 2023-09-22 | 金伯利-克拉克环球有限公司 | Foamed composite web with low wet collapse |
MX2018004729A (en) | 2015-11-03 | 2018-07-06 | Kimberly Clark Co | Paper tissue with high bulk and low lint. |
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. |
US10920065B2 (en) | 2016-06-10 | 2021-02-16 | Ecolab Usa Inc. | Low molecular weight dry powder polymer for use as paper-making dry strength agent |
WO2019027994A1 (en) | 2017-07-31 | 2019-02-07 | Ecolab Usa Inc. | Dry polymer application method |
MX2020001348A (en) | 2017-07-31 | 2020-08-31 | Ecolab Usa Inc | Process for fast dissolution of powder comprising low molecular weight acrylamide-based polymer. |
US11708481B2 (en) | 2017-12-13 | 2023-07-25 | Ecolab Usa Inc. | Solution comprising an associative polymer and a cyclodextrin polymer |
MX2021005066A (en) | 2018-11-02 | 2021-06-15 | Buckman Laboratories Int Inc | Synthesis of re-pulpable temporary wet strength polymer for tissue application. |
Citations (5)
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)
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 |
CA1329283C (en) * | 1986-10-01 | 1994-05-03 | David Farrar | 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 |
CN1061055C (en) | 1993-07-01 | 2001-01-24 | 普罗克特和甘保尔公司 | Thermoplastic elastomeric copolymers and hair and skin care, compositions containing the same |
-
1999
- 1999-04-27 US US09/299,977 patent/US6274667B1/en not_active Expired - Lifetime
-
2000
- 2000-01-21 CO CO00003484A patent/CO5210978A1/en not_active Application Discontinuation
- 2000-01-25 DE DE2000627417 patent/DE60027417T2/en not_active Expired - Lifetime
- 2000-01-25 EP EP20000905706 patent/EP1165640B1/en not_active Expired - Lifetime
- 2000-01-25 AR ARP000100311 patent/AR028142A1/en unknown
- 2000-01-25 KR KR1020017009055A patent/KR100606304B1/en not_active IP Right Cessation
- 2000-01-25 BR BRPI0007706-2A patent/BR0007706B1/en not_active IP Right Cessation
- 2000-01-25 WO PCT/US2000/001615 patent/WO2000043429A1/en active IP Right Grant
- 2000-01-25 AU AU27350/00A patent/AU770362B2/en not_active Ceased
- 2000-01-25 CN CN00803042A patent/CN1337973A/en active Pending
- 2000-02-02 TW TW89101096A patent/TW498082B/en active
- 2000-08-21 US US09/642,346 patent/US6365667B1/en not_active Expired - Lifetime
Patent Citations (5)
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)
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 |
KR20010103741A (en) | 2001-11-23 |
AU770362B2 (en) | 2004-02-19 |
CN1337973A (en) | 2002-02-27 |
US6365667B1 (en) | 2002-04-02 |
BR0007706B1 (en) | 2010-11-30 |
AR028142A1 (en) | 2003-04-30 |
BR0007706A (en) | 2001-11-20 |
DE60027417D1 (en) | 2006-05-24 |
DE60027417T2 (en) | 2006-09-28 |
AU2735000A (en) | 2000-08-07 |
US6274667B1 (en) | 2001-08-14 |
TW498082B (en) | 2002-08-11 |
EP1165640A1 (en) | 2002-01-02 |
CO5210978A1 (en) | 2002-10-30 |
KR100606304B1 (en) | 2006-07-28 |
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 |