WO2000043428A1 - Modified vinyl polymers containing amphiphilic hydrocarbon moieties - Google Patents
Modified vinyl polymers containing amphiphilic hydrocarbon moieties Download PDFInfo
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- WO2000043428A1 WO2000043428A1 PCT/US2000/001617 US0001617W WO0043428A1 WO 2000043428 A1 WO2000043428 A1 WO 2000043428A1 US 0001617 W US0001617 W US 0001617W WO 0043428 A1 WO0043428 A1 WO 0043428A1
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- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
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- 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
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- 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
- C08F293/005—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 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C08F8/00—Chemical modification by after-treatment
- C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
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- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
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- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
Definitions
- 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 amphiphiiic hydrocarbons which are utilized in the paper industry as surface modifiers, release agents, antifoams, softeners, debonders and lubricants.
- the resulting molecule is a synthetic polymer having moieties capable of bonding to cellulose and amphiphiiic hydrocarbon moieties which can provide several potential benefits, depending on the specific combination employed, including: strength aids that impart softness; softeners that do not reduce strength; wet strength with improved wet/dry strength ratio; surface feel modifiers with reduced linting and sloughing; strength aids with controlled absorbency; retention aids that soften; and improved retention of the amphiphiiic hydrocarbon when added as a wet end additive.
- 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.
- salts of the above mentioned acidic polymers are also included within the definition.
- Substances which can be combined with the acidic portion of the polymers to make the salts include the alkali metals such as Potassium and Sodium 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.
- amphiphiiic hydrocarbon moieties are organic compounds including alkanes, alkenes, alkynes, cyclic aliphatic and aromatic hydrocarbons that contain surface-active agents or are capable of acting as a surface active agent.
- the hydrocarbon portion of such materials may be linear or branched, saturated or unsaturated, substituted or unsubstituted.
- 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 moieties capable of bonding to cellulose and containing one or more amphiphiiic hydrocarbon moieties, said synthetic polymer having the following structure:
- Q T a monomer unit or a block or graft copolymer containing a pendant group capable of forming hydrogen or covalent bonds with cellulose.
- Suitable 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 block or graft copolymer unit where the amphiphiiic functionality is built in.
- hydrocarbons with hydrophilic (such as -OH, ethoxy, and propoxy groups) functionality, or aliphatic hydrocarbons with hydrophilic functionality.
- the hydrocarbons could be linear or branched, saturated or unsaturated, substituted or unsubstituted, with 2 or more hydrocarbons.
- Q 1 may take the form of -Z 1 -Q 1 -Z 1 - where
- Zi is any bridging radical whose purpose is to provide incorporation into the polymer backbone and Q, is as defined previously.
- 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 amphiphiiic hydrocarbon moieties.
- Q 4 moieties are (but not limited to) the aliphatic polyether derivatives of the formula — [(CR ⁇ O]., — 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 .
- counterion when the Q 3 or other charged moiety is present in the synthetic polymer, that a suitable counterion 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 counterion is not critical for the invention, such counterion 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 cationic ammonia and amine derivatives.
- the invention resides in a synthetic polymer having the following structure:
- R 1 ,R 1 ',R 2 ,R 3 H, C ⁇ 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 amphiphiiic moieties.
- R 0 any group capable of forming hydrogen or covalent bonds with cellulose. Preferred are -CONH 2 , -COOH, COO " M + , -OH, -CONHCHOHCHO and mixtures of said groups;
- R 4 Z - R 6 radical
- Z aryl, -CH 2 -, -COO-, -CONR'-, -0-, -S-, -OS0 2 0-, -CONHCO-,-CONHCHOHCHOO- or any other radical capable of bridging the R 6 group to the vinyl backbone portion of the molecule.
- R' H, alkyl
- R 6 an amphiphiiic hydrocarbon; It may be an alkyl hydrocarbon radical with hydrophilic functionality such as -OH, or ethoxy or propoxy groups, or an aliphatic hydrocarbon radical with hydrophilic functionality.
- the hydrocarbons can be linear or branched, saturated or unsaturated, substituted or unsubstituted, with 2 or more hydrocarbons.
- R 5 Z 2 -R 10 -W;
- Z 2 aryl, -CH 2 -, -COO-, -CONH-, -0-, -S-, -OS0 2 0-, 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 moieties capable of bonding to cellulose and containing an amphiphiiic hydrocarbon moiety, said polymer having the following structure: + Q Hi — f- Q 2 1 Q 3 -i --- Q 4 -ia- w
- 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 block or graft copolymer unit where the amphiphiiic functionality is built in.
- It may be alkyl hydrocarbons with hydrophilic (such as -OH, ethoxy and propoxy groups) functionality, or aliphatic hydrocarbons with hydrophilic functionality.
- the hydrocarbons could be linear or branched, saturated or unsaturated, substituted or unsubstituted, with 2 or more hydrocarbons.
- Q may take the form of -Z ⁇ C ⁇ ,- where ⁇ ! is any bridging radical whose purpose is to provide incorporation into the polymer backbone and Q., is as defined previously.
- Q 3 a monomer unit or a block or graft copolymer containing a charge functionality.
- 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 amphiphiiic 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 .
- a paper sheet such as a tissue sheet
- a synthetic polymer having hydrogen bonding capability and containing an amphiphiiic hydrocarbon moiety, said polymer having the following structure: ff R i CRri a -fOH 2 CR 2 iB— CH 2 CR 3 ⁇ Q 4 ⁇ -
- 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 amphiphiiic 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 , -NH 2 ;
- R 0 any group capable of forming hydrogen or covalent bonds with cellulose. Suitable groups are -CONH 2 , -COOH, COO " M + , -OH, -CONHCHOHCHO, and anhydride including mixtures of said groups;
- R 4 Z - R 6 radical
- Z aryl, -CH 2 -, -COO-, -CONR'-, -0-, - S -, -0S0 2 0-, -CONHCO-, -CONHCHOHCHOO-or any radical capable of bridging the R 6 group to the vinyl backbone portion of the molecule.
- R' -H, alkyl
- R 6 an amphiphiiic hydrocarbon radical; It may be an alkyl hydrocarbon radical with hydrophilic functionality such as -OH, or ethoxy or propoxy groups, or an aliphatic hydrocarbon radical with hydrophilic functionality.
- the hydrocarbons can be linear or branched, saturated or unsaturated, substituted or unsubstituted, with 2 or more hydrocarbons.
- R 5 Z 2 -R 10 -W
- Z 2 aryl, -CH 2 , -COO-, -CONH-, -0-, -S-, -OS0 2 0- or any radical capable of bridging the
- 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:
- C- ! 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 block or graft copolymer unit where the amphiphiiic functionality is built in. It may be alkyl hydrocarbons with hydrophilic (such as -OH, or ethoxy groups) functionality, or aliphatic hydrocarbons with hydrophilic functionality. The hydrocarbons could be linear or branched, saturated or unsaturated, substituted or unsubstituted, with 2 or more hydrocarbons.
- Q 1 may take the form of -Z- t -C Z-,- where Z 1 is any bridging radical whose purpose is to provide incorporation into the polymer backbone and Q ⁇ 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 amphiphiiic hydrocarbon moieties.
- Q 4 moieties are (but not limited to) the aliphatic polyether derivatives of the formula 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) 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:
- R 1 l R 1 ',R 2 , R 3 H, C 1 ⁇ 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 amphiphiiic hydrocarbon moieties.
- R 1 H, alkyl
- R 6 an amphiphiiic hydrocarbon radical; It may be an alkyl hydrocarbon radical with hydrophilic functionality such as -OH, or ethoxy or propoxy groups, or an aliphatic hydrocarbon radical with hydrophilic functionality.
- the hydrocarbons can be linear or branched, saturated or unsaturated, substituted or unsubstituted, with 2 or more hydrocarbons.
- R 5 Z 2 -R 10 -W;
- Z 2 aryl, -CH 2 -, -COO-, -CONH-, -0-, -S-, -OS0 2 0- or any radical capable of bridging the
- -[CH 2 CR 3 R 5 ] C - may also be the residue formed by co-polymerization with dimethyldiallyl ammonium chloride. In this case the charge-containing residue [CH 2 CR 3 R 5 ] C - will be the form of monomers with repeat units of structure:
- the amount of the modified vinyl polymer containing amphiphiiic hydrocarbon moieties added to the papermaking fibers can be from about 0.02 to about 4 weight percent, on a dry fiber basis, more specifically from about 0.05 to about 3 weight percent, and still more specifically from about 0.1 to about 2 weight percent.
- the modified vinyl polymer can be added to the fibers at any point in the process where the fibers are suspended in water.
- modified vinyl polymers they can be made via free radical polymerization of vinyl monomers of the form:
- R R 2 , R 3 , R 4 may be H, halogen, alkyl, functional alkyl, aryl, functional aryl.
- R 4 — CONH 2
- polyacrylamides 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 or photoinitiated polymerization of acrylamide as shown in Figure 1. Any free radical initiator or photoinitiator may be used. The polymerization may be done via a variety of procedures including solution, bulk, suspension and emulsion polymerizations.
- PAMs 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 ) copolymerization of acrylamide with acrylic acid; and (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, ionization 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 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. A typical reaction is illustrated in Figure 2 for co-polymerization with Methacryuloyloxyethyl trimethyl ammonium methosulfate (METAMS).
- METAMS Methacryuloyloxyethyl trimethyl ammonium methosulfate
- Typical cationic monomers include: (1 ) methacryuloyloxyethyl trimethyl ammonium methosulfate; (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).
- DMDAAC dimethyldiallyl ammonium chloride
- AMBTAC 3- acryloamido-3-methyl butyl trimethyl ammonium chloride
- VTAC vinyl benzyl trimethyl ammonium chloride
- Such materials have structures similar to that shown in Figure 2 for METAMS copolymerized cationic PAM.
- 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 overcationization of the furnish and reduce the effectiveness of other additives.
- cationic PAM's When used as dry strength additives usually around 5 - 10 mole % of the monomers will contain charged groups. Unlike the anionic PAM's, cationic PAM's are effectively charged across the entire pH range. Typical molecular weights for cationic PAM dry strength aids are in the range of 10,000 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 amphoteric.
- the charge density can be: low (1 - 10%); medium (10 - 40%); high (40 - 80%); or very high (80 - 100%).
- the delivery form can be either 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 molecular weight/high charge density products are used for their charge modifying capabilities and for retention in low shear environments.
- a second class of charged polyacrylamides that has found widespread use in tissue and papermaking is the so-called "glyoxylated" polyacrylamides.
- Coscia, et ai., U.S. Patent 3,556,932 assigned to the American Cyanamid Company describes the preparation and properties of glyoxylated polyacrylamides in detail.
- These polymers are ionic or nonionic water-soluble potyvinyl amides, having sufficient glyoxai substituents to be thermosetting.
- the amount of cationic component in the polymers should be sufficient to render the polymer substantive to cellulose fibers in aqueous suspensions.
- the amount of cationic charge in these polymers may vary.
- incorporación of the charge onto the polymer backbone can be accomplished through any of the methods known in the art.
- a preferred approach is to incorporate a cationic vinyl monomer with the acrylamide or other vinyl monomers during the polymerization of the base polymer.
- the specific monomer used to introduce the cationic charge onto the polyacrylamide is not overly critical and may be chosen from any such monomers known to be capable of incorporating a cationic charge into a polyacrylamide backbone.
- Dimethyldiallyl ammonium chloride is an especially preferred monomer for introducing the cationic charge. Where substantivity to cellulose fibers in aqueous solution is not required the cationic charge moiety may be absent from the polymer backbone.
- Anionic versions of the polymers may be easily prepared from the appropriate raw materials, these anionic polymers capable of being deposited on fibers with use of alum or various cationic retention aids.
- the minimum amount of pendant amide groups that need to be reacted with the glyoxai for the polymer to be thermosetting is around two mole percent of the total number of available amide groups. It is usually preferred to have an even higher degree of reaction so as to promote greater wet strength development, although above a certain level additional giyoxal provides only minimal wet strength improvement.
- the optimal ratio of glyoxylated to non-glyoxylated acrylamide groups is around 10 to 20 mole percent of the total number of amide reactive groups available on the parent polymer.
- the reaction can be easily carried out in dilute solution by stirring the glyoxai with the polyacrylamide base polymer at temperatures of about 25°C to 100°C at a neutral or slightly alkaline pH.
- the reaction is run until a slight increase in viscosity is noted.
- the majority of the glyoxai reacts at only one of its functionalities yielding the desired aldehyde functional acrylamide.
- the molecular weight of the acrylamide base polymer is not overly critical to the ability to react with glyoxai and generally polymers of molecular weight less than two million are adequately water soluble and dilutable so as not to not severely hinder reaction capability.
- lower molecular weight polymers having a molecular weight less than 25,000 are generally preferred due to their lower solution viscosity and ease at which they can be diluted in water.
- a structure for a typical cationic glyoxylated polyacrylamide is shown in figure 4.
- the polymer is retained on the fiber by means of the cationic quaternary amine group that is attracted to anionic sites on the cellulose.
- the amide and aldehyde functionalities are reactive.
- Approximately 2 - 30 moi% of the entire glyoxylated PAM copolymer exists as the active aldehyde group.
- the pendant amide groups on this polymer form hydrogen bonds with cellulose increasing the dry strength of the sheet.
- the aldehyde group can either cross-iink with an amide group in another part of the polymer or react with a hydroxyl group on cellulose fibers.
- thermoset or "cure” at pH's in the approximate range of 4 - 8 and moderately elevated temperatures that are common to most papermaking systems. Since they can be cured over a broad pH range including neutral pH, precise control of pH is not required in the paper making system.
- the polymers develop the large majority of their wet and dry strength wile passing through the drying section of the paper process with sheet temperatures as low as 70°F to 90°F being adequate.
- An additional advantage to the glyoxylated polyacrylamides is that they possess what is referred to as "temporary wet strength". A portion of the wet strength developed within the paper web is lost when soaked in water for a moderate period of time.
- Amphiphiiic hydrocarbon moieties are a group of surface active agents (surfactants) capable of modifying the interface between phases.
- Surfactants are widely used by the industry for cleaning (detergency), solubilizing, dispersing, suspending, emulsifying, wetting and foam control. In the papermaking industry, they are often used for deinking, dispersing and foam control. They have an amphiphiiic molecular structure containing at least one hydrophilic (polar) region and at least one lipophilic (non-polar, hydrophobic) region within the same molecule. When placed in a given interface, the hydrophilic end leans toward the polar phase while the lipophilic end orients itself toward the non-poiar phase.
- hydrophilic end lipophilic end can be added to a hydrophobe synthetically to create the amphiphiiic molecular structure.
- Figure 5 shows a possible schematic pathway for making a variety of surfactants:
- surfactants can be grouped as amphoteric, anionic, cationic and nonionic.
- amphoteric surfactants the charges on the hydrophilic end change with the environmental pH: positive in acidic pH, negative at high pH and become zwitterions at the imtermediate pH.
- Surfactants included in this category include alkylamido alkyl amines and aikyl substituted amino acids.
- R 0 a C 4 or higher alkyl or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted; n > 2;
- Ri hydroxy or carboxy ended alkyl or hydroxyalkyl groups, C chain > 2C, with or without ethoxylation, propoxylation or other substitution;
- Z H or other cationic counterion.
- Ri alkyl or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, C chain > 4C; n > 2;
- Anionics consist of five major chemical structures: acyiated amino acids/acyl peptides, carboxylic acids and salts, suifonic acid derivatives, sulfuric acid derivatives and phosphoric acid derivatives.
- R 0 alkyl or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, C chain > 4C;
- R alkyi or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, with or without esterification, with or without etherification,
- the structure commonly shared by sulfuric acid derivatives is shown as follows:
- R aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, with or without esterification, with or without etherification, with or without sulfonation, with or without hydroxylation, with or without ethoxylation or propoxylation, C chain > 4C
- cationics these are surfactants with positively charged atom, most commonly nitrogen, on the hydrophobic end.
- the charge may be permanent and non-pH dependent (such as quaternary ammonium compounds) or pH dependent (such as cationic amines). They include alkyl substituted ammonium salts, heterocyclic ammonium salts, alkyl substituted imidazolinium salts and alkyl amines. The structure commonly shared by this group is shown as follows:
- R H, alkyl, hydroxyalkyl, ethoxylated and/or propoxylation alkyl, benzyl, or aliphatic hydrocarbon, normal or branched, saturated or unsaturated, substituted or unsubstituted, with or without esterification, with or without etherification, with or without sulfonation, with or without hydroxylation, with or without carboxylation, with or without ethoxylation or propoxylation, C chain > 4C.
- the hydrophilic end often contains a polyether (polyoxyethylene) or one or more hydroxyl groups. They generally include alcohols, alkylphenols, esters, ethers, amine oxides, alkylamines, alkyiamides, polyalkylene oxide block copolymers.
- modified vinyl polymers and amphiphiiic hydrocarbons can be combined onto a single molecule for purposes of this invention. These include, but are not limited to: (1 ) direct monomer incorporation or copolymerization; (2) derivatization of functional groups on the polymer backbone; and (3) block co-polymerization.
- the portion of the synthetic polymer [Q capable of forming hydrogen, covalent and ionic bonds can constitute from about 10 to about 95 mole percent of the total polymer, more specifically from about 20 to about 90 mole percent of the total polymer and still more specifically from about 30 to about 85 mole percent of the total polymer.
- the amphiphiiic hydrocarbon portion [Q 2 ] of the synthetic polymer can constitute from about 1 to about 90 mole percent of the synthetic polymer, more specifically from about 2 to about 80 mole percent of the synthetic polymer and still more specifically from about 3 to about 70 mole 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 2 to about 20 moie 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 specificaliy 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 fiocculation, 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 2,000,000, more specifically from about 10,000 to about 1 ,500,000 and still more specifically from about 20,000 to about 1 ,000,000.
- Incorporation of the amphiphiiic moieties can be accomplished via copolymerization with vinyl type monomers containing amphiphiiic groups. Almost any vinyl type monomer containing a pendant amphiphiiic moiety 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 7.
- R 4 an amphiphiiic hydrocarbon radical; It may be an alkyl hydrocarbon radical with hydrophilic functionality such as -OH, or ethoxy or propoxy groups, or an aliphatic hydrocarbon radical with hydrophilic functionality.
- the hydrocarbons can be linear or branched, saturated or unsaturated, substituted or unsubstituted, with 2 or more hydrocarbons.
- R 5 Z 2 -R 10 -W, where:
- Z 2 Ar, CH 2 , COO-, CONH-, - O-, - S -, - OS0 2 0-, 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 )-, -
- W -N+R ⁇ .R- ⁇ .R ⁇ , where R ⁇ , R 12 , R 13 is a C M 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
- R 14 a hydrophilic moiety, which is desirable for making the material into a form suitable for papermaking to compensate for any increased hydrophobicity that may be introduced via incorporation of the amphiphiiic hydrocarbon moiety.
- mono-aryi ether derivatives which include poly(ethylene glycol) 4-nonylphenyl ether acrylate, poly(ethylene glycol) phenyl ether acrylate, poly(ethylene glycol) 2,4,6-tris(1-phenylethyl)phenyl ether methacrylate and the like.
- Such monomers can easily be derived from the esterification of acrylic acid, me.hacrylic acid and the like with the poly(ethylene glycol) and poly(propylene) glycol and corresponding mono ethers including but not limited to such materials as poly(ethylene glycol) mono butyl ether, poly(ethylene glycol) mono octyl ether, poly(ethylene giycol) mono decyl ether, poly(ethylene giycol) mono dodecyl ether, poly(ethylene giycol) mono lauryl ether, poly(ethylene glycol) mono octadecyl ether, the corresponding poly(propylene glycol) and mixed poly(propylene glycol) and poly(ethylene glycol) mono ether derivatives.
- allyl ether derivatives of polyethylene glycol and polypropylene glycol are generally synthesized from the reaction of an allyl halide and hydroxy compound in the presence of sodium hydroxide.
- monomers include allyl polyethylene glycol, methallyl polyethylene glycol, methoxy allyl polyethylene glycol, butoxy allyl polyethylene glycol and the like.
- allyl ether materials generally conforming to the formula:
- R H, C ⁇ alkyl
- R' polyethylene glycol, polypropylene glycol, or mixed polyethylene / polypropylene glycol radical
- R" C-, - C 30 alkyl or aryl radical
- the copolymers of these materials with hydroxyalkyl acrylates were found to be useful for binders in various applications. Additional examples include but are not limited to such materials as those described by Valint, et al., in U.S. 5,177,165 and Robinson in U.S 5,874,495.
- the second approach to synthesis of materials of this invention is to modify the functional groups on the polymer backbone.
- the vinyl type polymers including the modified polyacrylamides, polyacrylic acid and polyvinyl alcohol contain functional groups that may be further derivatized to produce materials of Figure 4.
- the polymer functional groups which may be reacted upon include but are not limited to: amide, carboxyl, hydroxyl, cyano, and aldehyde (from glyoxylation or similar reaction).
- the general scheme for such syntheses is shown in Figure 9.
- 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,
- R' can be any bridging radical whose purpose is to attach the functional group to the polymer;
- 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.
- R R an amphiphiiic hydrocarbon radical.
- R alkyl, aliphatic hydrocarbon, branched or linear or cyclic, substituted or non- substituted, with or without ethoxylation
- R' ethoxylated alkyl or aliphatic hydrocarbon, branched or linear or cyclic, substituted or nonsubstituted.
- Block copolymerization PAM's containing block copolymers of polyethylene, polytetraflouroethylene, or any other linear or branched, saturated or unsaturated, substituted or non-substituted, hydrocarbon where such co-polymers are incorporated either as block copolymers as grafts onto the vinyl backbone. Note that since these polymers maintain pendant amide functionality they are capable of being glyoxylated to form materials possessing temporary wet strength. A general example of such materials is shown in Figure 13.
- R 0 any group capable of forming hydrogen or covalent bonds with cellulose.
- Preferred are -CONH 2 , COOH, COO-, -OH, -CONHCHOHCHO including mixtures of said groups;
- A, H, COOH;
- Q radical of form -Z-R 2 -Z-;
- R 2 a block or graft copolymer where the amphiphiiic functionality is built in. It may be alkyl hydrocarbons with hydrophilic (such as -OH, or ethoxy groups) functionality, or aliphatic hydrocarbons with hydrophilic functionality. The hydrocarbons could be linear or branched, saturated or unsaturated, substituted or unsubstituted, with 4 or more hydrocarbons.
- Z any bridging radical whose purpose is to provide incorporation into the polymer backbone;
- R 5 Z 2 -R 0 -W, where:
- Z 2 Ar, CH 2 , COO-, CONH-, - 0-, - S -, - OS0 2 0-, any radical capable of bridging the
- 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
Abstract
Description
Claims
Priority Applications (4)
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EP00906996A EP1161467B1 (en) | 1999-01-25 | 2000-01-25 | Modified vinyl polymers containing amphiphilic hydrocarbon moieties |
DE60025468T DE60025468T2 (en) | 1999-01-25 | 2000-01-25 | AMPHIPHILIC HYDROCARBON GROUPS CONTAINING MODIFIED VINYL POLYMERS |
AU28567/00A AU758134B2 (en) | 1999-01-25 | 2000-01-25 | Modified vinyl polymers containing amphiphilic hydrocarbon moieties |
BRPI0007707-0A BR0007707B1 (en) | 1999-01-25 | 2000-01-25 | sheet of paper, process for making a sheet of paper and synthetic polymer. |
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US11716599P | 1999-01-25 | 1999-01-25 | |
US60/117,165 | 1999-01-25 | ||
US09/449,260 US6287418B1 (en) | 1999-01-25 | 1999-11-24 | Modified vinyl polymers containing amphiphilic hydrocarbon moieties |
US09/449,260 | 1999-11-24 |
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WO2000043428A1 true WO2000043428A1 (en) | 2000-07-27 |
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US (1) | US6472487B2 (en) |
EP (1) | EP1161467B1 (en) |
KR (1) | KR100565406B1 (en) |
CN (1) | CN1337972A (en) |
AU (1) | AU758134B2 (en) |
BR (1) | BR0007707B1 (en) |
CO (1) | CO5180563A1 (en) |
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WO (1) | WO2000043428A1 (en) |
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Also Published As
Publication number | Publication date |
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DE60025468T2 (en) | 2006-08-03 |
US20020004571A1 (en) | 2002-01-10 |
KR100565406B1 (en) | 2006-03-30 |
CN1337972A (en) | 2002-02-27 |
AU2856700A (en) | 2000-08-07 |
BR0007707A (en) | 2002-01-15 |
EP1161467B1 (en) | 2006-01-11 |
KR20010104700A (en) | 2001-11-26 |
BR0007707B1 (en) | 2010-01-26 |
CO5180563A1 (en) | 2002-07-30 |
EP1161467A1 (en) | 2001-12-12 |
US6472487B2 (en) | 2002-10-29 |
AU758134B2 (en) | 2003-03-13 |
DE60025468D1 (en) | 2006-04-06 |
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