MXPA02005108A

MXPA02005108A - Method for using hydrophobically associative polymers in preparing cellulosic fiber compositions, and cellulosic fiber compositions incorporating the hydrophobically associative polymers.

Info

Publication number: MXPA02005108A
Application number: MXPA02005108A
Authority: MX
Inventors: T Zhang Huashi
Original assignee: Hercules Inc
Priority date: 1999-12-06
Filing date: 2000-11-30
Publication date: 2002-12-09
Also published as: EP1257709A1; CA2390353A1; US20020053413A1; CN1408039A; BR0016160A; PL366291A1; WO2001040578A1; ZA200205443B; AR026734A1; RU2002114071A; KR20020058086A; AU1813801A; JP2003517104A

Abstract

A papermaking method and a composition which utilize, as a drainage aid, a water soluble hydrophobically associative polymer which is a copolymer prepared from monomers which include a hydrophobic ethylenically unsaturated monomer, and one or more of a nonionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer, and an anionic ethylenically unsaturated monomer.

Description

, METHOD FOR USING ASSOCIATIVE POLYMERS HYDROPHOBICALLY IN THE PREPARATION OF COMPOSITIONS OF CELLULOSE FIBERS AND COMPOSITIONS OF CELLULOSE FIBERS THAT INCORPORATE ASYMMARY POLYMERS HYDROPHOBICALLY BACKGROUND OF THE INVENTION CROSS REFERENCE TO RELATED APPLICATIONS 1. Field of the Invention The present invention relates to the use of hydrophobically modified water-soluble polymers, also referred to thereafter as hydrophobically associative polymers or HAPs, in the preparation of compositions of cellulose fibers. The present invention also relates to compositions of cellulosic fibers such as paper and cardboard that incorporate the PAHs. 2. Description of the Background and Other Information The production of cellulosic fiber sheets, particularly paper and cardboard, includes the following: -produce an aqueous slurry of cellulosic fibers that may also contain organic mineral extenders or pigments; - depositing this slurry on a wire or cloth for the manufacture of paper; Y -forming a sheet from the solid components of the grout by draining the water. The above is followed by the pressing and drying of the sheet to eliminate the additional water. Organic and inorganic chemicals are frequently added to the slurry prior to the phase in which the sheet is formed to make the papermaking method less expensive and faster, or to achieve specific paper properties in the final product.

The paper industry continually strives to improve the quality of paper, increasing its productivity and reducing manufacturing costs. Chemists are often added to the fibrous slurry before it reaches the papermaking yarn or cloth, to improve the method of draining / removing water and retaining solids; these chemicals are called drain aids and / or retention aids. With regard to improving drainage / water removal, draining or removing water from the fibrous slurry in the wire or papermaking fabric is often the limiting step or step to achieve faster method speeds. Improved water removal can also result in a dryer sheet in the press and drying sections resulting in reduced steam consumption. In addition, this is the epata in which the method of Papermaking determines many of the final properties of the sheet. With regard to the retention of solids, the retention aids in papermaking are used to increase the retention of the fine solids of the paper or cardboard web during the turbulent drainage method and form the web or web of the paper. Without adequate retention of the fine solids, they are lost to the effluent of the method or accumulate at high levels in the recirculating white water circuit, potentially causing deposit formation and causing the drainage of the paper machine to decompose. Additionally, insufficient retention of the fine solids increases the cost of papermaking due to the loss of additives that are intended to be absorbed into the fiber to provide the respective opacity, strength or bonding properties and respective paper dimensions. High molecular weight water soluble polymers with both cationic and anionic charge have traditionally been used as drainage and retention aids. The recent development of inorganic microparticles known as drainage and retention aids in combination with high molecular weight water soluble polymers show drainage and retention efficiency superior compared to water-soluble polymers of high molecular weight. U.S. Patent Nos. 4,294,885 and 4,388,150 show the use of starch polymers with colloidal silica. U.S. Patent No. 4, 753,710 shows flocculating the pulp or pulp of the paper or cardboard mixture provided with a cationic flocculant of high molecular weight that induces the cutting of the flocculated paper or cardboard mixture by introducing then bentonite clay to the paper or cardboard mixture. U.S. Patent Nos. 5,274,055 and 5,167,766 describe the use of micro-polymers or chemically cross-linked organic microparticles as drainage and retention aids in papermaking processes. Hydrophobically modified water soluble polymers are also referred to hereafter as hydrophobically associative polymers or HAPs, which are known to those skilled in the art, see for example the Encyclopedia of Polymer Science and Engineering, 2nd edition, 17, 112- 119 U.S. Patent Nos. 4,432,881 and 4,861,499 describe the use of these polymers as thickening agents for paint formulations and for applications in oil recovery methods such as slurry formulations in perforations, fracture fluids, agents for mobility control. liquid, agents that reduce friction, hydraulic fluids and lubricants These patents do not show or suggest the use of polymers in cellulosic compositions such as paper, or in methods for preparing these cellulosic compositions. U.S. Patent 4,305,860 discloses the preparation of stable, solvent-free, solvent-free, polyamfolly crosslinkers (colloidal dispersions of a copolymer in water) characterized by their colloidal nature and high solids content and low viscosity volume. The lattices are prepared by polarization, approximately 10 to 30 mol% of at least one cationic monomer, 5 to 30 mol% of at least one anionic monomer, 15 to 35 mol% of at least one hydrophobic monomer and from 5 to 70% by mol of at least one hydrophilic monomer, with the percentages of the monomer totalizing 100% by mol, in the presence of water and a free radical initiator and optionally a chelating agent. The lattices are shown to be particularly useful as auxiliaries in the retention and drainage of pigments, in the manufacture of paper and can be added to the pulp or paste while subsequently stored in a headbox, blender, hydrotriturator or pulp box. The high content of the hydrophobic group (> 15% mol) makes this polymer it is insoluble in aqueous solution, which distinguishes it from the HAP polymers described in the present invention. EP 0 896 966 A1 discloses the preparation of associative polymers by inverse emulsion processes in which a pendant or pendant acrylate hydrophobic chain extending with a polyoxyethylene group is used. The associative acrylic polymers comprise from 95 to 99.95 mol% of at least one monomer selected from neutral ethylene, cationic or anionic monomers, from 0.05 to 5 mol% of at least one acrylic monomer containing the radical 2,4,6-triphenol benzene and from 0 to 0.2 mol% of at least one polyunsaturated monomer. It is preferred that the associative polymers contain from 0.5 to 5 mol% of polyoxyethylene 2,4,6-triphenol benzene methacrylate. The polymers can be used in various areas such as paints, adhesives and adhesives, in construction, textiles and paper. The composition is claimed to be used as a thickener or binder, flocculating agent, and / or charge retention agent; No additional data or specifications are provided for the use. BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a composition of cellulose fibers, particularly to a cellulose sheet. such as paper or cardboard. The invention also relates to a method for making the composition. The present invention relates to a method for making a cellulosic fiber composition that includes adding a slurry of cellulose pulp or pulp to HAP and refers to a composition of cellulosic fibers that include an aqueous slurry of pulp or cellulose pulp and a HAP . The PAH is preferably a copolymer which includes hydrophobic groups which are capable of forming a structure of physical networks through the hydrophobic association having at least one monomer selected from the group consisting of ethylenically unsaturated nonionic monomers, cationic ethylenically unsaturated monomers or monomers ethylenically unsaturated anionic. The PAH is highly associative and forms a net-like structure in an aqueous solution as demonstrated by the value of tan of d less than an analogous polymer without the hydrophobic modification determined by the viscoelastic characterizations of a 0.5% solution. A significant improvement in the drainage and retention activity is obtained when the PAH is applied to a pulp or paste of paper or cardboard mixture and at the same time the satisfactory leaf formation is maintained, which is the only property that a Traditional flocculant can not achieve. PAH is usually soluble in water. The PAH may include at least one ethylenically unsaturated monomer, hydrophobic, present in an amount from about 0.001 mole percent to about 10 mole percent and at least one monomer selected from a nonionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer, or an ethylenically unsaturated anionic monomer with the condition that at least one hydrophobic ethylenically unsaturated monomer does not contain 2,4,6-trifenthyl benzene. At least one hydrophobic ethylenically unsaturated monomer can be an ethylenically unsaturated monomer having at least one pendant hydrophobic group of the general structure: CH, i. R, Rj - R4 - R5 Z- Figure 1 wherein Ri is hydrogen or methyl; R2 when present is -CH2-, -C (0) -0, -O-C (O) -, -C (0) -NR6-, -NR6-C (0) -, or -0-; R3, when present is - (-CH2-CHR? -0-) n-, C? -C20 alkyl or hydroxy C? -C2o alkyl wherein n is equal to 1 to 40 and Ri is as described above; R, when present is -NR6- or -N + (Re) 2-; R5 is the pendant hydrophobic group selected from one or more C-C20 alkyls, C4-C20 cycloalkyls, polynuclear aromatic hydrocarbon groups, aralkyls wherein the alkyl has one or more carbons, or haloalkyls or four or more carbons; Re when present is hydrogen, methyl, CH2 = CR? -CH2-, equivalent to the pendant hydrophobic R5 group as described above, or a mixture thereof; and Z present when R4 is -N + (R6) 2- is the conjugate base of an acid; with the proviso that R5 is not 2, 6-triphenol benzene. The polynuclear aromatic hydrocarbon group may be naphthyl. Haloalkyls of four or more carbons may be perfluoroalkyls that are preferably selected from one or more of CFg-C20F ?. The pendant hydrophobic group may be polyalkyleneoxy groups wherein the alkylene is propylene or higher alkylene and there is at least one alkyleneoxy unit per hydrophobic radical or it may be selected from one or more C4-C20 alkyl groups or preferably from one or more alkyl groups C8-C2o. Preferably, the hydrophobic ethylenically unsaturated monomers described in Figure 1 can be selected from one or more hydrocarbon esters of ethylenically unsaturated carboxylic acids and their salts, N-alkyl ethylenically unsaturated amides, α-olefins, vinyl esters, ethers of vinyl, N-vinyl amides, alkylstyrenes, polyethylene glycol (meth) alkyl acrylates or N-monomers ethylenically unsaturated, cationic alkyl. The ethylenically unsaturated carboxylic acids can preferably be selected from C 1 or C 2 alkyl esters of acrylic or methacrylic acid and more preferably of dodecyl acrylate or dodecyl methacrylate. The ethylenically unsaturated amides can be preferably selected from N-octadecyl acrylamide, N-octadecyl methacrylamide, or N, N-dioctyl acrylamide. The α-olefins can be preferably selected from 1-octene, 1-decene, 1-dodecene, or 1-hexadecene. The vinyl esters may preferably be vinyl laurate or vinyl stearate. The alkyl vinyl ethers may preferably be dodecyl vinyl ether or hexadecyl vinyl ether. The N-vinyl amides may preferably be N-vinyl aluramide or N-vinylolamine stearamide. The alkylstyrene may preferably be t-butyl styrene. The polyethylene glycol (meth) alkyl acrylates can preferably be selected from lauryl polyethoxy (23) methacrylate. The N-alkyl ethylenically unsaturated, cationic monomers may preferably be selected from quaternary salts of C? 0-C20 alquilo alkyl halide of methyldialiamine, N, N-dimethylaminoalkyl (meth) acrylates, and N, N-dialkylaminoalkyl (meth) acrylamides. At least one ethylenically unsaturated, nonionic monomer may be one or more of acrylamide, methacrylamide, N- alkyl acrylamides, N-N-dialkylacrylamides, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methyl acetamide, N-vinyl methyl formamide, vinyl acetate, or N-vinyl pyrrolidone. The N-alkyl acrylamide is preferably N-methylacrylamide and the N, N-dialkylacrylamine is preferably N, N-dimethylacrylamide. At least one nonionic ethylenically unsaturated monomer is preferably one or more of acrylamide, methacrylamide, or N-methylacrylamide and more preferably acrylamide. At least one anionic ethylenically unsaturated monomer may be one or more of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulfoethyl (meth) acrylate, vinylsulfonic acid, styrene sulfonic acid, maleic acid or salts of the same. same, preferably one or more of acrylic acid, methacrylic acid salts thereof and more preferably one or more sodium or ammonium salts of acrylic acid. At least one cationic ethylenically unsaturated monomer can be selected from one or more of diallylamine, the methacrylates of the dialkylaminoalkyl compounds, the (meth) acrylamides of the dialkylaminoalkyl compounds, the N-vinylamide N-vinylamide hydrolyzate and the quaternary salts thereof. The quaternary diallylamine salt may preferably be diallyldimethylammonium chloride. The Dialkylaminoalkyl (meth) acrylamide may preferably be N, N-dimethylaminopropylacrylamide, the acid or quaternary salt thereof may preferably be N, N, N-trimethylaminopropylacrylamide chloride. The dialkylaminoalkyl (meth) acrylate may preferably be N, N-dimethylaminoethylacrylate, the acid or quaternary salt thereof may preferably be N, N, N-trimethylaminoethylacrylate chloride. At least one cationic ethylenically unsaturated monomer can also be selected from one or more of the compounds of the following general formula: Figure 2 -Rs Z " wherein Ri is hydrogen or methyl, R2, R3 and R are hydrogen, Ci to C3 alkyl, or hydroxyethyl, R2 and R3 or R2 and R4 may be combined to form a cyclic ring containing one or more heteroatoms, Z is the conjugate base of an acid, X is oxygen or NRi wherein Ri is as defined above, and A is an alkylene group of Ci to C 2; or Figure 3 wherein R5 and R6 are hydrogen or methyl, R7 and R8 are hydrogen, Ci to C3 alkyl, or hydroxyethyl; Y Z is as defined above; or N-vinylformamides and the associated hydrolysates represented by the recurring units of Figure 4 Figure 5 Figure 6 wherein Ri, R2 and R3 are each H or alkyl Ci to C3 and Z is defined as above. It is noted that the description of ethylenically unsaturated, hydrophobic monomers encompasses the ethylenically unsaturated, cationic monomers described in Figures 2 to 6 where for example, the definition of R2 of Figures 2, 4 to 5 and R7 of Figure 3 are substituted with a pendant hydrophobic R5 radical of Figure 1. It is preferable that the HAP according to this invention (a 0.5% aqueous solution of HAP) have a dynamic oscillation frequency deflection with a tan delta value at 0.0068 Hz lower that an analogous polymer absent from the ethylenically unsaturated, hydrophobic monomer, preferably less than 1. It is also preferable that at least one group of ethylenically unsaturated, hydrophobic monomers be present in an amount of about 0.01 mole percent to about 10 percent mole mol and more preferably in an amount of about 0.1 mole percent to about 5.0 mole percent. The PAH used in this invention can be an anionic, nonionic, cationic or amphoteric copolymer and preferably an anionic copolymer. The anionic copolymer can include at least one hydrophobic ethylenically unsaturated monomer and at least one hydrophobic ethylenically unsaturated monomer and may further include at least one hydrophobic ethylenically unsaturated monomer. The anionic copolymer may include from about 0.001 mole percent to about 10 mole percent of at least one hydrophobic ethylenically unsaturated monomer, about 1 mole percent to about 99.999 mole percent of at least one anionic ethylenically unsaturated monomer, and about 1 mole percent of about 99.999 mole percent of at least one nonionic ethylenically unsaturated monomer, preferably about 0.01 mole percent to about 5 mole percent of at least one hydrophobic ethylenically unsaturated monomer, about 10 percent mole percent to about 90 mole percent of at least one anionic ethylenically unsaturated monomer and about 10 mole percent to about 90 mole percent of at least one nonionic ethylenically unsaturated monomer; and more preferably about 0.1 mole percent to about 2.0 mole percent of at least one hydrophobic ethylenically unsaturated monomer, about 30 mole percent of about 70 mole percent of at least one anionic ethylenically unsaturated monomer and about 50 mole percent. percent in mole to approximately 70 per one mole percent of at least one nonionic ethylenically unsaturated monomer. The slurry of the inventive cellulose pulp or pulp containing the HAP can also include, according to the option of workers skilled in the art, other components such as at least one flocculant, at least one starch, at least one organic and inorganic coagulant or at least one filling. The present invention also includes a cellulosic sheet produced by the inventive method. The cellulose sheet may include paper and cardboard that incorporates the HAP. The present invention also relates to a method for making a cellulosic fiber composition that includes adding to a slurry of cellulose pulp or pulp, a PAH and refers to a cellulosic fiber composition that includes an aqueous slurry of cellulose pulp or pulp and a PAH, wherein the PAH includes at least one hydrophobic ethylenically unsaturated monomer present in an amount of about 0.001 mole percent to about 10 mole percent and selected from one or more esters of C 0 0 C 2 o alkyl Acrylic and methacrylic acid; and at least one monomer selected from: a) about 1 mole percent to about 99.999 mole percent of at least one nonionic ethylenically unsaturated monomer selected from one or more of acrylamide, methacrylamide, N- alkyl acrylamide, N, N-dialkylacrylamides, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methyl formamide, vinyl acetate or N-vinyl pyrrolidone; b) about 1 mole percent to about 99.999 mole percent of at least one anionic ethylenically unsaturated monomer selected from one or more of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulfoethyl - (meth) acrylate, vinylsulfonic acid, styrene sulfonic acid, maleic acid or salts thereof; or c) about 1 mole percent to about 99.999 mole percent of at least one cationic ethylenically unsaturated monomer selected from one or more of diallylamine, the (methacrylates) of the dialkylaminoalkyl compounds, the (meth) acrylamides of the compounds of dialkylaminoalkyl, the hydrolyzate of N-vinylamine of N-vinylformamide and the quaternary salts thereof. The PAH may preferably include at least one hydrophobic ethylenically unsaturated monomer present in an amount of about 0.001 mole percent to about 10 mole percent and selected from one or more C o-C2o alkyl esters of acrylic and methacrylic acid; and at least one monomer selected from: a) about 1 mole percent to about 99,999 mole percent of at least one ethylenically unsaturated monomer, non-ionic, selected from one or more of acrylamide, methacrylamide, or N-alkylacrylamides; b) about 1 mole percent to about 99.999 mole percent of at least one anionic ethylenically unsaturated monomer selected from one or more of acrylic acid, methacrylic acid or the salts thereof; or c) about 1 mole percent to about 99.999 mole percent of at least one cationic ethylenically unsaturated monomer selected from one or more of N, N-dialkylaminoalkyl acrylates, N, N-dialkylaminoalkyl methacrylates, quaternary acid or salts from the same. Preferably, at least one hydrophobic ethylenically unsaturated monomer can be selected from one or more of dodecyl dodecyl acrylate or dodecyl methacrylate, the nonionic ethylenically unsaturated monomer can be acrylamides, at least one anionic ethylenically unsaturated monomer can be selected from one or More sodium or ammonium salts of acrylic acid, and the cationic ethylenically unsaturated monomer may be the quaternary methyl chloride of N, N-dimethylaminoethylacrylate. The slurry of the pulp or paste mentioned above containing the HAP can be added, according to the worker's option skilled in the art, additional components such as at least one flocculant, at least one starch, at least one coagulant, or at least one filler. The present invention also relates to a method for making a cellulosic fiber composition that includes adding an anionic HAP to a slurry of cellulose pulp or pulp and refers to a composition of cellulosic fibers that include an aqueous slurry of pulp or cellulose pulp and an anionic HAP, wherein the anionic HAP preferably includes at least one hydrophobic ethylenically unsaturated monomer selected from one or more of lauryl acrylate or lauryl methacrylate, at least one nonionic ethylenically unsaturated monomer which is acrylamide, and at least an ethylenically unsaturated anionic monomer which is acrylic acid. To the aforementioned paste slurry containing the HAP may be added the option of the worker skilled in the art, additional components such as at least one flocculant, at least one starch, at least one organic or inorganic coagulant, or at least one filler. The invention also relates to a cellulosic sheet produced by the above-mentioned method and from the aforementioned composition. The cellulose sheet may include paper and cardboard that incorporates the HAP.

The cellulosic fiber composition of the invention preferably comprises the PAH and its viscoelastic properties raised. Preferred cellulosic fiber compositions of the invention include paper.

DESCRIPTION OF THE INVENTION 1. Definitions As used herein, the term "HAP" refers to hydrophobically associative polymers of this invention. As used herein, the term "hydrocarbon" includes "aliphatics", "cycloaliphatics", and "aromatics". The terms "aliphatic" and "cycloaliphatic" - unless otherwise indicated - are meant to include "alkyl", "alkenyl", "alkynyl", and "cycloalkyl". The term "aromatic" - unless otherwise indicated - is understood to include "aryl", "aralkyl", and "alkaryl". It is understood that the hydrocarbon groups include both the unsubstituted hydrocarbon groups and substituted hydrocarbon groups with the latter referring to the hydrocarbon portion bearing the substituents in addition to the carbon and the hydrogen. Correspondingly, the aliphatic, cycloaliphatic and aromatic groups are understood to include both unsubstituted aliphatic, cycloaliphatic and aromatic groups and substituted aliphatic groups, cycloaliphatics and aromatics with the latter which refers to the aliphatic, cycloaliphatic and aromatic portion that produce additional substituents except carbon and hydrogen.

Also as discussed herein, it is to be understood that copolymers that include polymers consist of, or consist substantially of or consist essentially of two different monomer units. It is further understood that the copolymers include polymers that incorporate three or more different monomer units for example, terpolymers, etc. 2. Method of the Invention The invention comprises a method for making cellulosic fiber compositions-particularly cellulosic fiber networks, more particularly sheets of cellulosic fibers, and even more particularly paper and paperboard. This method comprises the addition of at least one HAP to a suitable paper or cardboard mixture - for example, a pulp or pulp of cellulose fibers or pulp, particularly a pulp or pulp of cellulosic wood fiber or pulp. Preferably this polymer is added to a slurry comprising an aqueous suspension of the paper or cardboard mixture. Also as a matter of preference, a network cellulosic particularly a sheet and even more particularly paper or cardboard - it is formed from the slurry. The method of the invention may involve the steps of providing a paper mixture comprising cellulosic fibers with or without additional mineral fillers suspended in water, which deposit the paper or cardboard mixture in the manufacture of paper, yarn or cloth forming a sheet of the solid components by removing water from the slurry, with at least one HAP that is added to one or more points during this method . Preferably, this polymer is introduced into the slurry prior to the water removal sequence. The PAHs serve to provide an increase in the retention of fine particles and / or in the increase in the removal of water from the fibers. This polymer is particularly effective in providing retention of both the filler - when employed - and the fines of the cellulosic fibers, these fines or short fibers are generated from the fiber during the method of the invention. It is postulated that PAHs form physical network structures through the hydrophobic group in aqueous solution as demonstrated by their viscoelasticbehavior. Since the three-dimensional structure of PAH is less absorbed at the surface of the particle, better bonding is provided between the particles, which leads to better retention and drainage activity. The "viscoelastic behavior" as discussed here (Rheology: Principles, Measurements, and Applications, CW Macosko, New York, NY.) Denotes a response time dependent on a deformation, that is, in a short time the material hardens and becomes glassy, while in a longer time the material stretches like rubber or becomes viscous.A common way to measure this phenomenon is through the relaxation of the effort, where an instantaneous deformation is imposed on the material, and the resulting stress is recorded that decreases over time.A purely viscous material will exhibit a stress of zero once the deformation becomes constant, while an elastic solid will not show a decrease in stress.A viscoelastic material will exhibit a stress decomposition between these two extremes, thus exhibiting a combined elastic and viscous response or viscoelasticity.The dynamic oscillation characterizations are cond ucidas in the HAP materials to characterize the viscoelastic properties, where a sample is deformed senosoidally. The test is conducted via a deflection due to the effort, where a constant frequency is applied with an increase in effort (amplitude), or inversely a deflection due to effort, where a constant effort is applied with varied frequency. The measured deformation of the elastic component of the material will be in the phase with the imposed stress, while the viscous component of the material will be 90n out of the phase. The tan of d is the proportion of the viscosity for the elastic components of the material, and characterizes the material that exhibits more viscous or elastic properties. Thus, a material having a tan d greater than 1 at a specific frequency will exhibit a predominantly viscous behavior, and a tan d less than 1 will exhibit a predominantly elastic behavior. The PAHs can be used as retention / drainage aids. Alternatively, this polymer can be used in combination with at least one flocculant, such as a flocculant in conventional papermaking for example, a cationic anionic or nonionic high molecular weight flocculant. The method of the invention can be practiced using an apparatus or system for making paper as discussed herein. It is emphasized that the inventive method is not limited to this particular apparatus or system, which is provided only as a representative example that can be employed.

As reviewed in Hannbook for Pulp and Paper Technologists (G?. Smook, TAPPI Pres, Atlanta, GA), the components of the pulp or pulp are usually measured within the tub of the pulp at a level of consistency between 2.8 and 3.2% by weight. The pulp feeding tub will usually contain the final mixture, however in some cases, small concentrations of additives can be adjusted prior to the headbox. The pulp of the feed tub is usually circulated to a constant feed tank (tow press) that feeds the diluted pulp through a control valve (the basic weight of the valve) into the inlet system of the feed. paper machine The center of the entrance system is the ventilation pump that serves to mix the diluted pulp with the white or pouring water and sends the mixture to the constant feeding tank. Here / the pulp is combined with the recirculation of the white water from a wire well and in which the consistency is reduced to the required level of the head or feed box (usually between about 0.5% by weight and about 1.0% in weight of consistency). White water that typically has a solids concentration of about 0.1% by weight or less is a liquid obtained from the removal of water from the pulp slurry or pulp in the paper making wire that drains into the well in the form of wire for paper making. After the ventilation pump, the slurry of the pulp or paste typically passes through a spin cleaner and then through a pressure filter into a head or feed box. The centrifugal cleaner removes debris such as fiber bundles and chips, the pressure filter eliminates excessive contamination and deflocculates the fibers. The box of head or feeding serves to distribute the pulp of diluted paper on the wire or wire mesh for the manufacture of paper that moves endlessly indicated at the beginning; This can be a Fourdrinier metallic endless belt or dual metal belt former. In the moving metal cloth or paper tape, the grout is dehydrated; The resulting liquid is white water as stated above, which is drained from the slurry into the wire well or metal tape. This drainage forms the slurry within a sheet as it is carried out in the cloth or metal tape to the press section.

When traveling through the pressing section, the sheet is pressed between rollers thus submitting to an additional water removal. The sheet continues through the pressing section to a drying section in which it is further dried. From the drying section, the sheet continues through satin rollers. In the rolls to satin the sheet is pressed between the metal rollers to reduce the thickness and smooth the surface. From these rollers for satin, the sheet is rolled on a reel. The resulting paper may be a surface coated with a sizing agent or coating material. The materials used in the method of the invention include cellulose pulp and at least one HAP. One or more additional materials including at least one starch, at least one filler, at least one organic and inorganic coagulant and at least one conventional flocculant may also be employed. When a flocculant is used, the flocculant and PAH can be added simultaneously, or at different points in the method without an intermittent cutoff point or at different points with an intermittent cut-off point between their respective additions. Preferably, the flocculant and the HAP are introduced into the method of the invention sequentially that is, at different points or times. The flocculant can be added before or after the PAH. A cut can affect the pulp diluted between the addition of the flocculant and the HAP "when added sequentially." In an apparatus or system as discussed here, the high cut is made in the ventilation pump, centrifuge and pressure cleaner. Consistent with the foregoing, the apparatus or system is preferably provided with suitable feeding points to add the previously discussed materials such as the flocculant and the HAP.In this regard, the flocculant and / or the HAP can be added at a feeding point. before the ventilation pump (for example, between the base weight valve and the ventilation pump) and / or at the feeding point before the centrifugal cleaner (for example, between the ventilation pump and the centrifuge cleaner) , and / or at a feeding point before the pressure filter (for example, between the centrifugal cleaner and the pressure filter). Ion for other materials, starch, fillers or coagulants can be added at numerous points within the process as is known to those skilled in the art.

The order in which the different materials are introduced within the method of the invention is not limited to that established in the preceding discussion, but will generally be based on practice and development for each specific application. 3. Materials Used a. Pulp or Cellulosic Pulp Cellulosic pulps or pulps suitable for the method of the invention include conventional pulp for papermaking, such as a pulp or traditional chemical pulp. For example, sulfate pulp and bleached or unbleached sulfite pulp, mechanical pulp such as pulp, thermomechanical pulp, chemical-thermomechanical pulp, recycled pulp such as old corrugated containers, newspaper, office waste, waste paper, etc. can be used. magazines and other waste of non-de-inked paper, de-inked waste and mixtures thereof. b. Starch The starch adds strength properties, particularly resistance to drying, to the cellulosic product obtained from the method of the invention. In particular, starch increases the interfiber bond in the pulp Diluted paper basket. The starch will also affect the drainage properties. Starches that can be used in the method of the invention include amphoteric and cationic starches. Suitable included starches are those derived from corn, potato, wheat, rice, tapioca and the like. Cationicity is imparted by the introduction of cationic groups, and amphotericity by the additional introduction of anionic groups. For example, cationic starches can be obtained by starch which reacts with tertiary amines or with quaternary ammonium compounds for example, dimethylaminoethanol and 3-chloro-2-hydroxypropyltrimethylammonium chloride. The cationic starches preferably have a cationic degree of substitution (DS) - that is, the average number of cationic groups substituted by hydroxyl groups per anhydroglucose unit - from about 0.01 to about 1.0, more preferably about 0.01 to about 0.10, more preferably approximately 0.02 to 0.04. Amphoteric starches can be provided by the introduction of several different anionic groups. Preferred amphoteric starches are those with a net cationicity.

As an example, the anionic phosphate groups can be introduced into cationic starches through the reaction with phosphate salts or phosphate etherifying reagents. Where the starting material of the cationic starch is diethylaminoethyl ether starch, the amount of phosphate reagent employed in the modification is preferably that which will provide about 0.07-0.18 mol of anionic groups per mole of cationic groups. Other amphoteric starches that may be used are those made by the introduction of sulfosuccinate groups within the cationic starches. This modification is carried out by the addition of semi-ester groups of maleic acid to a cationic starch and the reaction of the double bond of the maleate with sodium bisulfite. As further examples, the cationic starch can be etherified with 3-chloro-2-sulfopropionic acid, carboxyl groups can be introduced into the starches by the reaction with sodium chloroacetate or by the oxidation of hypochlorite, propane sultone can be used to treat cationic starches to provide amphotericity. Amphoteric starches useful additionally can be obtained by the xantation of the ethers of diethylaminoethyl starch and 2- (hydroxypropyl) trimethylammonium.

Additionally still, the modification can be extended by the introduction of nonionic hydroxyalkyl groups from the treatment with ethylene oxide or propylene oxide. The starch is preferably used in the method of the invention, in a proportion of about 0.4536 kg (1 lb.) per ton to about 45.36 kg (100 lbs) per ton of cellulose pulp, based on the dry weight of the pulp. The concentration of starch is more preferably from about 1134 kg (2.5 lbs) per ton to about 22.68 kg (50 lbs) per ton and even more preferably about 2.268 kg (5 lbs) per ton to about 11.34 kg (25 lbs) per ton of pasta. c. Fillers Fillers provide optical properties to the cellulosic product. This provides opacity and gloss to the finished sheet and improves its printing properties. Fillers that are suitable include calcium carbonate (both the ground carbonate and the synthetically produced precipitated carbonate occur naturally), titanium oxide, talc, clay and gypsum. The amount of filler used can result in a cellulose product of up to about 50 percent by weight of filler based on the dry weight of the dough. d. Coagulant Coagulant is used in addition to flocnt and HAP to increase retention and drainage properties. The coagulant used can be either organic and inorganic. The most common inorganic coagulant is a kind of alumina. Suitable examples include aluminum sulfate in technical grade (alum), polyaluminum chloride, polyhydroxy aluminum chloride, polyhydroxy aluminum sulfate, sodium aluminate and the like. The organic coagulant is typically a synthetic polymeric material. Suitable examples include polyamines, poly (amido amines), polyDADMAC, polyethyleneimine, hydrolysates and quaternized hydrolysates of N-vinyl formamide polymers, copolymers and the like. The coagulant is preferably employed in the method of the invention, in a ratio of about 0.004536 kg (0.01 lb) per ton to about 22.68 kg (50 lbs.) Per ton of cellulose pulp, based on the dry weight of the pulp. The concentration of the coagulant is more preferable from approximately 0.02268 kg (0.05 lbs.) Per ton to approximately 9.072 kg (20 lbs.) Per ton, and even more preferably about 0.04536 kg (0.1 lbs.) per ton to about 4.536 kg (10 lbs.) per ton of pulp. and. Flocnt Conventional ionic flocnts in papermaking are suitable as flocnts for the method of the present invention. Cationic polymers can be used, non-ionic, and amphoteric flocculants, particularly cationic, anionic, nonionic, and amphoteric. Polymers suitable as flocculants in the method of the invention include homopolymers of a non-ionic ethylenically unsaturated monomer. The copolymers of the monomers comprising two or more ethylenically unsaturated monomers can be used as copolymers of monomers comprising at least one nonionic ethylenically unsaturated monomer and at least one cationic ethylenically unsaturated monomer and / or at least one ethylenically unsaturated anionic monomer. The nonionic, cationic and anionic ethylenically unsaturated monomers that may be employed are those discussed herein as being suitable for the at least one HAP of the invention.

Ethylenically unsaturated, nonionic monomers include acrylamide; methacrylamide; N-alkyl acrylamides such as N-methylacrylamide; N, N-dialkylacrylamides such as N, N-dimethylacrylamide; methyl acrylate; methyl methacrylate; acrylonitrile; N-vinyl methylacetamide; N-vinyl methyl formamide; vinyl acetate; N-vinyl pyrrolidone; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate; mixtures of any of the aforementioned and similar. Of the aforementioned, acrylamide, methacrylamide, and N-alkyl acrylamides are preferred, acrylamide is particularly preferred. Among the cationic ethylenically unsaturated monomers that can be used are diallylamine, the (meth) acrylates of dialkylamino compounds, the (meth) acrylamides of the dialkylaminoalkyl compounds, the N-vinylamide N-vinylamide hydrolyzate, and the salts and quaternary thereof. N, N-dialkylaminoalkyl acrylates and methacrylates and their acid and quaternary salts are preferred with the quaternary methyl chloride of N, N-dimethylaminoethylacrylate which is particularly preferred. In addition to the cationic monomers, suitable examples include those of the following general formula: wherein Ri is hydrogen or methyl, R2 is hydrogen or reduced alkyl of Ci to C4, R3 and / or R are hydrogen, Ci to C12 alkyl, aryl or hydroxyethyl, and R2 and R3 or R2 and R can be combined to form a cyclic ring containing one or more hetero atoms, Z is the conjugate base of an acid, X is oxygen or NRi, where Ri is as defined above, and A is an alkylene group of Ci to C? 2; or R7R, wherein R5 and R6 are hydrogen or methyl, R7 is hydrogen or Ci to C12 alkyl, and Rs is hydrogen, Ci to C2 alkyl, or hydroxyethyl, and Z is as defined above; or N-vinylformamide and the associated hydrolysates as represented by the recurring units of CH.-CIÍ N / \ R1 CO-R2 CH.-CH N / \ R > R2 wherein R1, R2 and R3 are each H or Ci to C3 alkyl, and Z is defined above. The ethylenically unsaturated, anionic monomers include acrylic acid, methacrylic acid and its salts; 2-acrylamido-2-methylpropane sulfonate; sulfoethyl (meth) acrylate; vinylsulfonic acid; styrene sulfonic acid; maleic acid and other dibasic acids and their salts. Preferred are acrylic acid, methacrylic acid and its salts with sodium and ammonium salts of acrylic acid which is particularly preferred.

The monomers can be polymerized into polymers by a number of initiator systems including a free radical, (thermal and redox methods), cationic and anionic synthesis methods. The flocculating polymer can be prepared by a number of commercial means including bulk or bulk polymerization, solution polymerization, dispersion polymerization and inverse emulsion / emulsion polymerization. The resulting polymer can ultimately provide the use of a number of physical forms including an aqueous solution, dry solid powders, dispersion, and emulsion forms. The flocculant can be nonionic, cationic, anionic or amphoteric. The nonionic polymeric flocculants will contain one or more of the non-ionic monomers previously described. The flocculants of the cationic polymer will contain one or more of the cationic monomers described above. The level of the total cationic monomer is based on the molar concentrations, the range will be from about 1 to about 99%, preferably from about 2 to about 50%, and even more preferably from about 5 to about 40 mole% of cationic monomers with the remaining monomer which is one of the nonionic monomers previously described.

The flocculants of the anionic polymer will contain one or more of the anionic monomers described above. The level of the total anionic monomer based on the molar concentrations will be in a range of about 1 to about 99%, preferably about 2 to about 50%, and even more preferably about 5 to about 40% mole of cationic monomers, with the remaining monomer which is one of the non-ionic monomers previously described.

Amphoteric polymer flocculants will contain a combination of one or more of the cationic and anionic monomers described. Any combination of cationic or anionic monomers is preferred, they provide at least one cationic monomer and an anionic monomer. The polymer may contain an excess of cationic monomers, an excess of anionic monomers or equivalent amounts of both cationic or anionic monomers. The level of the total ionic monomer is the combined amount of both cationic and anionic monomers based on the molar concentrations, are within the range of about 1 to about 99%, preferably about 2 to about 80%, and even more preferably about 5 to about 40 mol% of cationic monomers, with the remaining monomer being one of the nonionic monomers previously described.

The flocculant is preferably used in the method of the invention, in a proportion of about 0.004536 kg (0.01 lbs) per ton to approximately 4.536 kg (10 lbs) per ton of cellulose pulp based on the weight of the active polymer and the weight of the dry pulp. The concentration of the flocculant is more preferably from about 0.02268 kg (0.05 Ibs) per ton to about 2,268 kg (5 lbs) per ton, and even more preferably from about 0.04536 kg (0.1 lbs) per ton to about 0.4536 kg (1 Ib) per ton of pulp or pulp.

F. Hydrophobically Associative Polymer (HAP) The invention comprises at least one HAP. Suitable HAPs of the invention include copolymers comprising at least one ethylenically unsaturated, hydrophobic monomer with the proviso that at least one ethylenically unsaturated, hydrophobic monomer does not contain 2,4,6-tripenethylbenzene.

These copolymers further include at least one nonionic ethylenically unsaturated monomer, and / or at least one cationic ethylenically unsaturated monomer, and / or at least one ethylenically unsaturated anionic monomer. The hydrophobic ethylenically unsaturated monomers include hydrophobic ethylenically unsaturated monomers insoluble in water. Also because the monomers ethylenically unsaturated, hydrophobic ones include ethylenically unsaturated monomers, particularly water-insoluble monomers and monomeric surfactants having hydrophobic groups. The hydrophobic groups include hydrophobic organic groups such as those having a hydrophobicity comparable to one of the following: aliphatic hydrocarbon groups having at least four carbons such as C4 to C2o alkyls and cycloalkyls; polynuclear aromatic hydrocarbon groups such as benzyl, substituted benzyl and naphthyl with the proviso that the substituted benzyl group is not 2,4,6-tripenethyl benzene; aralkyls wherein the alkyl has one or more carbons; haloalkyls of four or more carbons, preferably perfluoroalkyls; polyalkyleneoxy groups wherein the alkylene is propylene or higher alkylene and there is at least one alkyleneoxy unit per hydrophobic radical. Preferred hydrophobic groups include those having at least 4 carbons or more hydrocarbon groups such as the C4 to C20 alkyl groups or those having at least four carbons or more per perfluorocarbon group such as C4F9-C20F4 ?. Particularly preferred groups are the Cs_Co alkyl.

Suitable ethylenically unsaturated monomers containing a hydrocarbon group include esters or amides of C and higher alkyl groups. Particularly suitable esters include dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate, tetradecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, nonyl-a-phenyl acrylate, nonyl-a-phenyl methacrylate. , dodecyl-a-phenyl acrylate, and dodecyl-a-phenyl methacrylate. C 1 -C 2 C alkyl esters of acrylic and methacrylic acid are preferred. Of these, methacrylate and dodecyl acrylate are particularly preferred. The following ethylenically unsaturated monomers containing hydrocarbon groups can also be used: N-alkyl ethylenically unsaturated amides such as N-octadecyl acrylamide, N-octadecyl methacrylamide, N, N-dioctyl acrylamide and similar derivatives thereof; α-olefins such as 1-octene, 1-decene, 1-dodecene and 1-hexadecene; vinyl esters wherein the ester has at least eight carbons such as vinyl laurate and vinyl stearate; vinyl ethers such as dodecyl vinyl ester and hexadecyl vinyl ether; N-vinyl amides, such as N-vinyl lauramide and N-vinyl stearamide; alkylstyrenes, such as t-butyl styrene; alkyl polyethylene glycol (meth) acrylates such as lauryl polyethoxy (23) methacrylate; and N-alkyl ethylenically unsaturated cationic monomers such as the quaternary salts of the C10-C20 alkyl halide of methyldiallylamine, N, N-dimethylaminoalkyl (meth) acrylates, and N, N-dialkylaminoalkyl (meth) acrylamides. Suitable nonionic ethylenically unsaturated monomers include acrylamide; methacrylamide; N-alkyl acrylamides such as N-methylacrylamide; N, N-dialkylacrylamides such as N, N-dimethylacrylamide; methyl acrylate; methyl methacrylate; acrylonitrile; N-vinyl methylacetamide; N-vinyl methyl formamide; vinyl acetate; N-vinyl pyrrolidone, mixtures of any of the aforementioned and the like. Of the aforementioned, acrylamide, methacrylamide, and N-alkyl acrylamide are preferred, acrylamide is particularly preferred. Among the ethylenically unsaturated, cationic monomers that can be used are diallylamine, (meth) acrylates of dialkylaminoalkyl compounds, (meth) acrylamides of dialkylaminoalkyl compounds, N-vinylformamide N-vinylamide hydrolyzate and the quaternary salts thereof. Preferred are N, N-dialkylaminoalkyl acrylates and methacrylates and their acids and quaternary salts, N, N-dimethylaminoethylacrylate quaternary methyl chloride is particularly preferred. In addition, as the cationic monomers, suitable examples include those of the following general formula: wherein Ri is hydrogen or methyl; R2, R3 and R are hydrogen, Ci to C3 alkyl or hydroxyethyl; and R2 and R3 or R2 and R can be combined to form a cyclic ring containing one or more hetero atoms; Z is the conjugate base of an acid; X is oxygen or NRi where Ri is as defined above; and A is an alkylene group of Ci to C? 2; or wherein R5 and Re are hydrogen or methyl, R7 and R8 are hydrogen, Ci to C3 alkyl, or hydroxyethyl; and Z is as defined above; or N-vinylformamides and the associated hydrolysates represented by the recurring units of CH2 = CH N / \ R1 CO-R2 CH, = CH N / \ R'R2 or CH.-CH I N * -R3 Z "/ \ R'R2 wherein R1, R2 and R3 are each H or C1 to C3 alkyl and Z is defined above. The ethylenically unsaturated, anionic monomers include acrylic acid, methylacrylic acid and its salts; 2-acrylamido-2-methylpropane sulfonate; sulfoethyl (meth) acrylate; vinylsulfonic acid, styrene sulfonic acid; and maleic acid and other dibasic acids and their salts. Acrylic acid, methacrylic acid and its salts are preferred with the sodium and ammonium salts of acrylic acid which is particularly preferred. As a matter of preference, the proportion of hydrophobic ethylenically unsaturated monomers in the HAP is within the range that supplies the hydrophobically associative polymer ie the concentration of hydrophobic monomers is quite low so that the polymer is still water soluble or dispersible. , but sufficiently to provide the associative property as discussed here. In this regard, at least one HAP preferably comprises from about 0.001 mole percent to about 10 mole percent more preferably about 0.01 mole percent to about 5 mole percent and even more preferably about 0.1 mole percent to about 2.0 mole percent of at least one ethylenically unsaturated, hydrophobic monomer.

The PAHs used in the invention include anionic, nonionic, cationic and amphoteric copolymers. Of these, anionic copolymers are preferred. The anionic copolymers comprise at least one hydrophobic ethylenically unsaturated monomer and at least one ethylenically unsaturated anionic monomer. Preferably, the anionic copolymers comprise at least one nonionic ethylenically unsaturated monomer. Particularly preferred are terpolymers which consist of, or consist essentially of, or substantially of, at least one hydrophobic ethylenically unsaturated monomer, at least one ethylenically unsaturated anionic monomer, and at least one nonionic ethylenically unsaturated monomer. For the anionic copolymers the preferred hydrophobic ethylenically unsaturated monomers are the hydrocarbon esters of α, β-ethylenically unsaturated carboxylic acids and their salts, they are particularly preferred with dodecyl acrylate and dodecyl methacrylate.The ethylenically unsaturated, non-ionic monomers Preferred are acrylamide and methacrylamide The anionic ethylenically unsaturated monomers are acrylic acid and methacrylic acid The anionic copolymers preferably comprise about 0.001 mole percent to about 10 mole percent hydrophobic ethylenically unsaturated monomers, about 1 percent in mole to about 99.999 mole percent of the ethylenically unsaturated, nonionic monomer, and about 1 mole percent to about 99.999 mole percent of at least one ethylenically unsaturated anionic monomer. comprise about 0.01 mole percent to about 5 mole percent of a ethylenically unsaturated hydrophobic monomer, about 10 mole percent to about 90 mole percent of at least one nonionic ethylenically unsaturated monomer, and about 10 mole percent of about 90 mole percent of at least one ethylenically unsaturated anionic monomer . Even more preferably, these comprise about 0.1 mole percent to about 2.0 mole percent of at least one hydrophobic ethylenically unsaturated monomer, about 50 mole percent to about 70 mole percent of at least one nonionic ethylenically unsaturated monomer. , and about 30 mole percent to about 70 mole percent of at least one ethylenically unsaturated anionic monomer. The monomers can be polymerized in a HAP polymer by a number of initiator systems including free radical methods (redox and thermal methods), anionic and cationic synthesis methods. HAP can be prepared by a number of commercial media including volume or bulk polymerization and emulsion / inverse emulsion polymerization. The resulting polymer can be provided to the end user in a number of physical forms including aqueous solutions, dry solid powder, dispersion and emulsion forms.

The HAP is preferably employed in the method of the invention, in a proportion of about 0.004536 kg (0.01 lb) per ton to about 4.536 kg (10 lbs) per ton of cellulose pulp based on the dry weight of the pulp. The concentration of PAH is more preferably from about 0.02268 kg (0.05 lb) per ton to about 2,268 kg (5 lbs) per ton and even more preferably from about 0.04536 kg (0.1 lb) per ton to about 0.4536 kg (1 lb) per ton. ton of pulp. g. Additional Additives The method of the invention may still additionally include conventional additives employed in their usual amounts for their usual purposes. Suitable examples include preparers, promoters, resistance agents, color fixatives, polymeric coagulants and the like. The paper produced can also be a treated surface with a surface size or coating material. 4. Composition of the Invention One factor that affects the concentration of PAH in the cellulosic composition of the invention is the ratio of the polymer added during the preparation of the method. The cellulosic composition of the invention - which preferably is a cellulosic sheet, and more preferably is cardboard or paper - preferably comprises about 0.004536 kg (0.01 lb) to about 4.536 kg (10 lbs) per ton - more preferably to about 0.02268 kg (0.05) lb) at about 2,268 kg (5 lbs) per ton and even more preferably about 0.1 weight percent to about 4,536 kg (1 lb) per ton of HAP based on the dry weight of the composition.

EXPERIMENTAL SECTION The invention is illustrated by the following procedures and tests; These are provided for the purpose of representation and are not construed to limit the scope of the invention. Unless otherwise indicated, all percentages, parts, etc., are by weight. 1. Preparation of the PAHs of the Flocculant of the Invention and Controls a) Polymerization in Solution The PAHs used in the invention, the anionic copolymers II, III and V to VII are prepared from acrylamide (AM), acrylic acid (AA) and acrylate. of lauryl (THE) . The control copolymers, the anionic copolymers I and IV are prepared without the hydrophobically modified lauryl acrylate monomer, that is, from acrylamide and acrylic acid alone. The polymers I-VII are all prepared by solution polymerization. The relative proportions of the monomers used in each case are indicated below.

TABLE I Description of the Polymer Sample in Solution Polymer Monomers Proportion of Feeding (% mol) I (control) AA / AM 45/55 II AA / AM / LA 45/54/1 III AA / AM / LA 45/54/1 IIVV ((ccoonnttrrooll)) AAAA // YMCA 30/70 V AA / AM / LA 30 / 69.5 / 0.5 VI AA / AM / LA 30/69/1 VII AA / AM / LA 30/68/2 In the case of Polymers II and III, a solution of 2.75 parts of acrylamide, 0.17 parts (1 % in mol of monomers) of lauryl acrylate, 2.25 parts of acrylic acid, 1 part of the non-ionic surfactant (Tergitol 15-S-9) and 100 parts of deionized water are deoxygenated under stirring at room temperature by means of nitrogen mist for 45 minutes. 0.5 parts of a 2 mg KBr03 solution and 10 parts of 0.03% NaS205 were injected via a syringe pump for 60 minutes. He Copolymer is obtained by precipitation of the polymerization solution in acetone and dried under vacuum at 50 ° C overnight. Polymers V, VI and VII are prepared in the same manner except for the ratio of the monomers. For the polymer V, the proportion of the monomer is 3.4 parts of acrylamide, 0.1 parts (0.5 mole% of the monomers) of lauryl acrylate, and 1.5 parts of acrylic acid. For polymer VI, the proportion of the monomer is 3.4 parts of acrylamide, 0.19 parts (1 mole% of the monomers) of lauryl acrylate, and 1.5 parts of acrylic acid. For polymer VII, the proportion of the monomer is 3.4 parts of acrylamide, 0.38 parts (2% mole of the monomers) of lauryl acrylate and 1.5 parts of acrylic acid. The polymer is prepared using the same method and proportions as with Polymers II and III except without lauryl acrylate. Polymer IV is prepared in the same manner as Polymer I except that for polymer IV the monomer ratio is 3.5 parts acrylamide and 1.5 parts acrylic acid. For each of the Polymers I, II and III, the resulting dry product is redissolved in deionized water to produce a solution of the polymer which is subjected to a viscosity characterization. b. Dispersion Polymerization Hydrophobic associative polymers are prepared via dispersion polymerization. TABLE 2 Description of the Brine Dispersion Sample Polymer Monomer Feeding Ratio (% mol) VIII (control) AA / AM 50/50 IX AA / AM LMA 49.9 / 50 / 0.1 X AA / AM / LMA 49.8 / 50 / 0.2 XI AA / AM / LA 50 / 49.75 / 0.25 XII AA / AM / LA 50 / 49.5 / 0.5 LMA - Lauryl methacrylate LA - Lauryl acrylate 2. Characterization of Viscosity a). Polymerization of the Solution The viscosity of each solution at 5% is measured by a Brookfield viscometer at 12 rpm and at room temperature. The results are published in Table 3 below. The molecular weights of the HAPs II and III and the non-associative Polymer I are assumed to be similar due to their preparation under substantially identical synthesis conditions. He -fold increase in the viscosity in the solution at 0.5% of the HAPs II and III, the control sample of the polymer I is a qualitative indication of the incorporation of the hydrophobic monomer in Polymers II and III. The extremely high viscosity of the 5% solution for Polymers II and III also indicates that the PAHs of the invention are strongly associative in the aqueous solution.

TABLE 3 Characterization of the Viscosity Samples Monomers Viscosity of the Solution at 0.5% (cP) I (control) AA / AM 600 II AA / AM / LA 14,000 III AA / AM / LA 12,000 The viscosity and the rheological characterizations were further conducted in Samples IV through VII to demonstrate the associative properties of the modified samples compared to the unmodified control. The described studies are conducted in a 0.5% aqueous solution. As is previously shown in Table 3, the Brookfiled viscosity at 12 rpm is conducted in samples exhibiting a significant increase in apparent viscosity with increased levels of hydrophobes. The highest level of hydrophobic presents a 10-fold increase in Brookfield viscosity due to associative interactions. Additional studies are also conducted with a controlled stress rheometer equipped with cone and plate geometry, with a cone 60 mm in diameter and fixed at an angle of 2 degrees. The apparent viscosity of the polymer samples with a solids content of 0.5% is determined at a constant cut rate of 10 sec-1 with similar results observed with the Brookfield viscometer in which a 10-fold increase in viscosity is observed. observe with the highest level of hydrophobes indicating strong associative behavior. A continuous effort is conducted with the instrument in a dynamic stress oscillation mode at a frequency of 1 Hz constant and an effort range of 0.1 to 10.0 Pa in 20 logarithmic steps. The storage module G is assigned as the equilibrium value in the linear viscoelastic region and is defined as: G '= (tQ /? Q) eos d where t0 is the amplitude stress,? 0 is the deformation amplitude, and d is the displacement of phase angle between the stress and the resulting deformation. The storage module G is also referred to as the gel module and is taken as an indication of the degree of resistance of the structure of the network determined by the hydrophobic inter- / intra-molecular associations. At equivalent applied stress the materials with a high value of G 'will deform or have a lesser deformation thereby exhibiting a strong gel complex or network structure. The data demonstrate a linear relationship between the hydrophobic concentration and the storage modulus G for the highest level of hydrophobic substitution. The unmodified IV polymer exhibits a 2 Pa storage modulus while the modified Polymer VII containing 2 mol% of lauryl acrylate exhibits a storage modulus of 25.6 Pa. A frequency range in dynamic oscillation mode is subsequently conducted with the instrument in dynamic oscillation mode at a constant effort of 0.1 Pa in the linear viscoelasticity regime and a frequency in the range of 0.0068 Hz to 10 Hz with 3 readings for each decade of frequency. The tan of d is the ratio of the modulus of (viscous) loss to the storage modulus (elastic) determined according to: tan d = loss modulus / storage modulus = G '' / G 'Materials that have a high value of tan d show more viscous properties, while a tan d minor will indicate more elastic properties. At a low frequency like 0.0068 Hz, the proportion of the effort of the sample will allow a linear polymer to relax and exhibit a response of the viscous type or a higher tan d. The polymers comprised of both a chemical and a physical network exhibit a significant structure of the polymer chains. These network-structured materials are mechanically stable and do not relax within the set time or frequency of the experiment.These materials exhibit low values of tan d and are more elastic.As shown in Table 4, one observes 0.0068 Hz of 20 for the unmodified control polymer while the high hydrophobic level provides a tan d of 0.224. The low levels of tan d are observed with high levels of hydrophobic substitution over a wide range of frequencies up to 6.8 Hz. This clearly demonstrates that the strong associative behavior of PAH is consistent with the viscosity data discussed above.

TABLE 4 Dynamic Oscillation Studies with Controlled Effort Rheometer Proportion of Brookfield Deflection Speed Feed Deflection (% RPM Cut = 10 sec due to Frequency so mol) 0.5% of -1 Effort d, .0068 Polymer Monomer soliution vise, 0.5% Modulus of Hz mPas solution vis, Storage in G 'Pa V (control) AA / AM 30/70 650 1070 2 19.9 V AA / AM / LA 30 / 69.5 / 0.5 1700 2350 2.3 1.1 VI AA / AM / LA 30/69/1 8500 16400 12 0.363 VII AA / AM / LA 30/68/2 7000 10500 25.6 0.224 b) Dispersion polymerization The dispersion polymers are characterized according to the equivalent methods as described in the polymerization polymers of the solution. The data presented in Table 5 demonstrate similar results with the polymerization products of the solution. It is observed that the apparent viscosity of the 0.5% solution increases with the introduction of the hydrophobic monomer. A stress range study in dynamic oscillation mode demonstrates an increase in storage modulus G 'with samples IX and XI compared to sample VIII of unmodified control. A study of the frequency range in the dynamic oscillation mode shows a d as low for the hydrophobic associative polymer compared to the unmodified control.

TABLE 5 Dynamic Oscillation Studies with Controlled Effort Rheometer Proportion of Deflection Speed Density of Feed Deflection (% Cut Load = 10 sec Effort Frequency so mol) Meq / g -1 Module of d, .0068 Polymer Monomer 0.5% of Storage, solution G 'Pa mPas V? II (control) AM / AA 50/50 6.4 530 3.39 7.23 IX AM / AA / L 50 / 49.9 / 0.1 7.5 1230 10.9 0.92 MA X AA / AA / LMA 50 / 49.8 / 0.2 7.0 510 Non-linear n / a XI AA / AM / LA 50 / 49.75 / 0.25 7.6 1270 10.9 0.72 XII AA / AM / LA 50 / 49.5 / 0.5 7.3 410 Non-linear n / a LA - Lauryl acrylate LMA - Lauryl methacrylate The viscosity properties of the diluted solution of the HAP samples in Table 5 are determined in aqueous solutions at various concentrations of NACÍ compared to Poliflex CP.3, an auxiliary commercial polyacrylamide water removal (Cytec Industries, Inc., West Patterson, NJ) and Polymer E, a commercial high molecular weight anionic polyacrylamide flocculant. The data are presented in Table 5.1. As discussed in Introduction to Physical Polymer Science by L.H. Sperling (Wiley Interscience, 1992), the properties of the diluted solution provide a relative indication of the molecular weight of the polymer. In this experiment, the viscosity? 0 of the solvent is compared to the viscosity? of the solution of polymer. The relative viscosity is the dimensionless ratio of the two: and the specific viscosity is the relative viscosity minus one: f = r | rel ~~ 1 the reduced specific viscosity is henceforth denoted as the RSV, which is the specific viscosity divided by the concentration of the polymer (C) in units of gram per deciliter. RSV =? Sp / C The units for the RSV are deciliters per gram (dL / g) and as such describes the hydrodynamic volume (HDV) of a polymer in solution. Thus, a high RSV indicates a large HDV in solution and a higher molecular weight compared to conventional polymers. The experiment is conducted in the diluted regime so that the overlapping of the polymer spiral is not present. The RSV values can be determined capillary or by rotational viscometer methods by measuring the efflux time or apparent viscosity of both the solvent and the polymer solutions. The data described in Table 5.1 are determined with a Brookfield rotational viscometer equipped with an ultra-low (UL) adapter capable of determining the viscosity of the solutions with low viscosity. The data demonstrates the effect on RSV of the polyelectrolyte with the variation of salt concentrations as known to those skilled in the art. Inventive HAP products demonstrate a higher RSV in 1 M NaCl containing an additional 0.1% nonylphenol surfactant (NPE) ethoxylate than in 1 M NaCl alone. This phenomenon, which will be referred to as "RSV Proportion" is a specific property of the diluted solution for associative polymers that contain hydrophobes and does not occur in branched, linear or crosslinked polymers. It is observed that the RSV ratio increases dramatically with the high levels of hydrophobic monomers, and does not occur in the control polymer, Polyflex CP.3 or Polymer E. This phenomenon is well established in the literature and is defined as a bond of hydrophobic domains with the surfactant thus providing an increase in the viscosity of the diluted solution or RSV: TABLE 5.1 Determinations of RSV in the Diluted Solution Polymer Monomer Proportion of RSV-DI RSV-0.01 M RSV-1 M RSV-1 M Proportion - Feeding (% Water dL / g NaCl - dL / g NaCl - dL / g NaCl + lM NaCl - 1 mol) 0.1% of M NaCl + NPE 0.1% NPE . { control) AM / AA 50/50 730 113 21 23 1.1 IX AM / AA / LM 50 / 49.9 / 0.1 990 106 12 20 1.7 A X AM / AA / LM 50 / 49.8 / 0.2 700 23 2 15 1.5 A XI AA / AM / LA 50 / 49.75 / 0.25 930 128 16 24 7.5 xp AA / AM / LA 50 / 49.5 / 0.5 650 34 4 17 4.3 Poliflex CP.3 AM / AA ** 40/60 ** 580 47 13 13 1.0 Polymer E AM / AA 50/50 1216 184 44 44 1.0 [ConcentradL / g .001 .005 .025 .025 Polymer] LA - lauryl methacrylate LMA - lauryl methacrylate NPE - ethoxylated nonylphenol surfactant ** Poliflex CP.3 is cross-linked with an unknown monomer at an unknown level 3. Retention and Drainage Tests A first series of Britt jar retention tests and Canadian Standard Frenes (CSF) drainage tests are conducted to compare the development of the HAPs of the invention with those of the following: a non-hydrophobic associative polymer; a conventional anionic polyacrylamide flocculant; and organic and inorganic drainage aids commonly referred to within the industry as "microparticles" or "micropolymers." The Britt jar retention test (Paper Research Materials, Inc., Gig Harbor, WA) is known in the art. In the Britt jar retention test a specific volume of the paper or cardboard mix is mixed under dynamic conditions and an aliquot of the paper or cardboard mixture is dried through the bottom of a jar sieve so that the level of the fine materials that are retained can quantify The Britt jar used for the present tests is equipped with 3 vanes inside the cylinder walls to induce turbulent mixing and a 76 μ sieve is used at the bottom of the plate. The CSF device (Lorentzen &Wettre, Code 30, Stockholm, Sweden) used to determine the proportion of drainage or water removal properties is also known in the art (TAPPI test procedure T-227). The CSF device comprises a water removal chamber and a funnel measuring the proportion mounted both on a suitable support. The chamber of drainage properties is cylindrical, adapted with a plate in the form of a perforated screen and a plate hinged on the bottom and with a hermetically hinged cover, vacuum, on the upper part. The funnel that measures the proportion is equipped with a hole in the bottom and a leak hole. The CSF test is conducted by placing 1 liter of paper or cardboard mix typically at 0.30% consistency, in the drainage chamber, closing the top cover and immediately after opening the bottom plate. It is allowed to drain the water freely into the funnel that measures the proportion, the excess water flow determined by the bottom hole will be spilled through the side hole and collected in a graduated cylinder. The values generated are described in millimeters (mis) of filtering; the highest quantitative values represent the highest levels of water removal. The mixture of paper or cardboard used in this first series of tests is a mixture of synthetic paper or alkaline cardboard. The paper or cardboard mix is prepared from dried pasta from supermarket wrappers, hardwood and softwood, and from water and additional materials. First, dry pasta from hardwood and softwood supermarket wrappers are separately refined in a laboratory with a Valley blender (Voith, Appleton, Wl). These pastes are then added to an aqueous medium. The aqueous medium used in the preparation of the dough comprises a mixture of local hard water and deionized water for a representative hardness. The inorganic salts are added in amounts so as to provide the medium with representative alkalinity and total conductivity. To prepare the paste, the hardwood and softwood are dispersed within the aqueous medium in a typical weight ratio of hardwood and softwood. The precipitated calcium carbonate (PCC) is introduced into the pulp at 25 weight percent based on the combined dry weight of the pulps, so as to provide a final pulp comprising 80% fiber and 20% filled PCC.

This first series of tests is conducted with the following: polymer II, a hydrophobically associative anionic polyacrylamide of the invention as discussed herein; polymer I, an unmodified anionic polyacrylamide control polymer as discussed herein; polymer E, a high molecular weight commercial anionic flocculant; Poliflex CP.3, a commercial polyacrylamide drainage aid (Cytec Industries, Inc., West Patterson, NJ); and bentonite clay also commonly used in the industry as a drainage and retention aid. The Britt jar retention test in this first series is conducted with 500 ml of the paper or synthetic paperboard blend having a typical solids concentration of 0.5%. The test is conducted at a constant rpm speed according to the following parameters, consistent with the sequence published in Table 2; a mixture of starch is added, a mixture of alum is added; a flocculant mixture of the polymer is added; a mixture of drainage aids is added; to obtain a filtering. The starch of the cationic potato used is Stalok 600 (A.E. Stanley, Decatur, IL), and the alum is aluminum sulfate octadecahydrate available as a 50% solution (Delta Chemical Corporation, Baltimore, MD). The cationic flocculant used referred to as CPAM-P is 90/10% mol of acrylamide / N, N-dimethylaminoethylacrylate methyl quaternary chloride; This material is commercially available as a water immersion oil emulsion. The retention values reported in Table 2 are short retention fibers where the total fines or short fibers in the paper or cardboard mix are determined by washing "500 ml of paper or cardboard mix with 10 liters of water under conditions of mixing to remove all fine particles defined as particles smaller than those of a 76 μ sieve of Britt jar. The retention of fines or short fibers for each treatment is then determined by draining 100 ml of the filtrate after the sequence After filtering, the filtrate is filtered through a pre-estimated filter paper of 1.5 [mu] The fines retention is calculated according to the following equation:% fine retention = (filtered weight &less) fine weight ) / weight of the filtrate in which the weight of the filtrate and the fines are both normalized to 100 mL The retention values represent the average of 2 runs in duplicate The drainage tests CSF are conducted with 1 liter of the paper or cardboard mixture at a solids concentration of 0.30%. the mixture of paper or cardboard is prepared by the treatment described externally from the CSF device, using equivalent speeds and mixing several times as described in the Britt jar tests in a conventional blender to provide turbulent mixing. At the completion of the addition of the additives and the mixing sequence, the treated paper and cardboard mixture is placed inside the top of the CSF device and the test conducted. In both the Britt jar retention and the CSF drainage tests, the higher quantitative values indicate a high activity and a more desired response. The data published in Table 6 illustrate the superior activity provided by the polymer II of the invention compared to the results obtained with the unmodified control Polymer I and the flocculant of the conventional anionic polymer E. In addition, the polymer of the invention provides an activity equivalent to that of a bentonite clay and is close to that of Poliflex CP.3. The doses of the material described are all based on the activities of the product unless otherwise indicated.

Table 6 ADD # 1 Kg / ton ADD # 2 Kg / ton Polymer Kg / ton Auxiliary Kg / ton% of CSF (Lbs / ton) (Lbs / ton) (Lbs / ton) Drained (Lbs / ton) Active active active retentives average activation Starch of 4.536 Alum 2.268 none 27.79 395 potato (10) (5) cationic Starch of 4.536 Alum 2.268 Flocculant 0.2268 none 48.43 380 potato (10) (5) CPAM-P (0.5) cationic Starch of 4.536 Alum 2.268 Flocculant 0.2268 Polymer II 0.3402 69.54 620 potato (10) (5) CPAM-P (0.5) (0.75) cationic Starch of 4.536 Alum 2.268 Flocculant 0.2268 Polymer I 0.3402 50.46 535 potato (10) (5) CPAM-P (0.5) (0.75) cationic Starch 4.536 Alum 2.268 Flocculant 0.2268 Polymer E 0.3402 53.16 540 Potato (10) (5) CPAM-P (0.5) (0.75) cationic Starch of 4.536 Alum 2.268 Flocculant 0.2268 PolyfIex CP.3 0.3402 77.85 650 potato (10) (5) CPAM- P (0.5) (0.75) cationic Starch of 4.536 Alum 2.268 Flocculant 0.2268 Ventolite HS 1.8144 64.72 600 potato (10) (5) CPAM-P (0.5) (4) cationic A series of retention and drainage tests are conducted using a pulsed drainage device (PDD). The substrate of the test, test conditions and associated chemical additives are identical to those used in the Table 6. The PDD is equipped with a rotating hydropulse and a vacuum capacity below a wire mesh. This is an internally developed instrument (described in the Patent No. 5,314,581) as a reasonable simulation of current, drained retention and leaf formation operations. During the operation of the experiment, a vacuum is applied to the fibrous slurry to assist in the formation of a fibrous mat and the vacuum is continued until a constant equilibrium state of the vacuum is achieved. A variety of measurements can be taken with the use of the PDD. For example, the PDD can be used in determining first the retention step, maximum vacuum, vacuum equilibrium, maximum vacuum equilibrium ratio (PEVR) and vacuum draining time. The first step for the retention of fines is determined by calculating the mass balance that involves the weight of the final sheet, the total mass introduced into the PDD and the total fines fraction of the pulp that is defined as the fraction of pulp having a particle size less than 76 μ. As with Britt jar fineness retention, the highest values indicate the desired response. The maximum vacuum is the total vacuum required during the formation of the mat until the air is extracted through the formed mat and the vacuum is interrupted. The equilibrium vacuum is the constant vacuum state extracted through the formed sheet. Both the maximum vacuum and the vacuum of equilibrium are measured in inches of Hg. A low quantitative value for maximum vacuum indicates a fibrous matrix in which it is easy to remove water. The maximum vacuum balance ratio (PEVR) is the smallest unit ratio of these two outputs. Studies have shown that this parameter is useful as an indicator of leaf formation in which a lower PEVR value indicates the formation of a more desirable or more uniform leaf. The vacuum draining time is the time for the maximum vacuum and is measured by an instrument in units of time of seconds. It is believed that this response is similar to that of a wet line on a paper machine at the point at which the water has enough drainage so that the sheet loses brightness or is visible to water. The position of the wet line is commonly monitored as an indication of drainage of the paper machine. The desired responses for the vacuum draining parameters are reduced (low) values that indicate an improvement in drainage. The second series of drainage tests used in the PDD are taken with the same drainage aids as in the first series except in the absence of bentonite. The associated starch, alum and cationic flocculant are as previously described. The results in Table 7 publish the values obtained for the measurements above from taking the PDD measurements. These results demonstrate that polymer II of the invention provides a definite drained dose response. Specifically, as the dose is increased, gravity drainage, maximum vacuum and vacuum draining times improve correspondingly. It is noted that the unmodified control polymer I and the flocculant of the conventional polymer E do not show a dosage response. In this regard, as the dose of polymer hedges increases, the retention and associated drainage responses do not increase or decrease. The improved draining activity of Polymer II as compared to control polymer I and Polymer E is also clearly shown in the data of Table 7. Polymer II provides finer retention than the Poliflex CP.3 and approaches the drainage activity of the Poliflex CP.3 as of 0.4536 kg / ton (1.0 lb / ton), the polymer II provides approximately equal drainage at 0.2268 kg / ton (0.5 lbs / ton) of Poliflex CP.3. It is observed that in equal draining times, Polymer II provides lower PEVR values than Poliflex CP.3 which is an indication of the improvement of the formation and uniformity of the sheet.

TABLE 7 10 lbs / ton Dose First% Drained by Vacuum Equilibrium Proportion of Potato Starch Drain Kg / ton Gravity retention MAXIMUM EMPTY Cationic Vacuum Equilibrium +5 (Ibs / T) Time step- mm Hg mm Hg empty Maximum Time-lbs / Ton fine seconds (in Hg) (in Hg) seconds in Sulphate (measurement of (Aluminum Time mass) Empty) +0.5 lbs / ton Flocculant CPAM-P + Auxiliary Drain Without Auxiliary 89.09% 3.25 91.694 130.81 1.43 1.028 Drained (3.61) (5.15) Poliflex CP.3 0.2268 93.47% 3.04 75.438 112.776 1.49 0.679 (0.5) (2.97) (4.44) Poliflex CP.3 0.3402 95.10% 2.99 68.834 103.378 1.50 0.622 (0.75) (2.71) (4.07) Poliflex CP.3 0.4536 95.37% 3.01 67.31 101.854 1.51 0.068 (1) (2.65) (4.01) Polymer I 0.2268 92.34% 3.16 89.662 123.952 1.38 0.798 (0.5) (3.53) (4.88) Polymer I 0.3402 91.34 % 3.18 89.662 122.174 1.36 0.801 (0.75) (3.53) (4.81) Polymer 1 0.4536 94.74% 3.13 89.408 122.174 1.37 0.778 (1) (3.52) (4.81) Polymer II 0.2268 96.05% 3.09 83.058 118.364 1.42 0.731 (0.5) (3.27) (4.66) Polymer II 0.3402 95.64% 3.05 78.74 115.062 1.46 0.685 (0.75) (3.10) (4.53) Polymer II 0.4536 93.31% 2.91 76.454 112.522 1.47 0.673 (1) ( 3.01) (4.43) Polymer E 0.2268 92.20% 3.14 88.90 122.174 1.37 0.793 (0.5) (3.50) (4.81) Polymer E 0.3402 94.21% 3.18 87.122 121.412 1.39 0.786 (0.75) (3.43) (4.78) 87. 122 122.68 Polymer E 0.4536 94.21% 4.67 (3.43) (4.83) 1.41 0.792 (1) A series of CSF retention and Britt jar retention tests are conducted with the following: Polymer III, the hydrophobically associative, anionic polyacrylamide of the invention as discussed herein; Polymers V-VII, the hydrophobically associative polymers of the invention sequentially showing increased levels of hydrophobic modification; Polymer IV, an unmodified anionic polyacrylamide control polymer as discussed herein; Polymer E; and Poliflex CP.3. The tests are conducted according to the methods previously described. The data demonstrates the superior activity of the invention provided by Polymer III and Polymer VII compared to Unmodified Control Polymer IV. The retention and drainage activities are observed with increases in the level of hydrophobic substitution with Polymer VII approximated to the activity of Poliflex CP.3. The data are published in Table 8.

TABLE 8 ADD # 1 Kg / ton ADD # 2 Kg / ton ADD # 3 Kg / ton Auxiliary Kg / ton% CSF Lbs / ton Lbs / ton Lbs / ton Drained Lbs / ton Retention (active) (active) (active ) (active) on prom Starch of 4.536 Alum 2.268 Flocculant 0.2268 None 0 51.4 100 potato 10 5 CPAM-P 0.5 cationic Starch of 4.536 Alum 2.268 Flocculant 0.2268 Polymer 0.3402 77.5 640 Potato 10 5 CPAM-P 0.5 CP.3 0.75 Cationic Starch of 4.536 Alum 2.268 Flocculant 0.2268 Polymer E 0.3402 19.5 530 Potato 10 5 CPAM-P 0.5 0.75 Cationic Starch of 4.536 Alum 2 2..226688 F Fllooccuullaannttee 0 0..22226688 P Poollíímmeerroo IIVV 0 0..33440022 12.0 510 papa 10 5 CPAM-P 0.5 0.75 cathonic Starch of 4.536 Alum Flocculant 0.2268 Polymer V 0.3402 12.4 505 Papa 10 2.268 CPAM-P 0.5 0.75 cationic 5 Starch of 4.536 Alum 5 Flocculant 0.2268 Polymer VI 0.3402 55.4 545 Papa 10 CPAM-P 0.5 0.75 Cationic Alum Starch 2.268 Flocculant 0.2268 Polymer VII 0.3402 66.3 585 Papa 4.536 5 CPAM-P 0.5 0.75 cationic 10 Starch of 4.536 Alum 2.268 Flocculant 0.2268 Polymer III 0.3402 69.0 610 potato 10 5 CPAM-P 0.5 0.75 cationic Another series of drainage and retention tests were conducted similarly to the second series with the PDD. The conditions and the material are the same used for the previous series, except that the draining aids are as follows: Polymer III of the invention and Poliflex CP.3 as discussed herein; Polymer M a commercially available high molecular weight polyacrylamide emulsion flocculant and bentonite clay. The polymeric materials are evaluated at 0.5, 0.75 and the active polymer at 1.0 lbs / ton while the bentonite clay is evaluated at 2, 4 and 6 lbs / ton. In agreement with the levels of milled doses typically used. The results are published in Table 9. Table 9 illustrates the activity of the polymer of the invention. Poliflex CP.3, bentonite clay and Polymer III provide equal or greater drainage or retention activity compared to bentonite clay. In addition to the comparative activity shown in Table 9, Polymer M provides retention and drainage just like Polymer III, but at distinctly higher PEVRs; this reduction in the uniformity of the sheet / formation with the same drainage is undesirable. The drainage activity of Polymer III is close to Poliflex CP.3 as 1.0 lb./ton of Polymer III close to the drainage of 0.5 lb./ton of Poliflex CP.3- It is observed again that in times of equal drainage, the PEVR of the polymer of the invention is lower than Poliflex CP.3 which is an indication of the improvement of the uniformity or formation of the leaf.

TABLE 9 10 lbs / ton Dose First% Drained by Equilibrium of the Void Drain Rate of the Drain Potato starch Kg / ton Gravity retention MAXIMUM VACUUM Vacuum Cationic vacuum +5 (lbs / T) Time step- mm Hg Mm Hg Maximum Time-lbs / Sulfate ton fine seconds (in Hg) (in Hg) Equilibrium seconds of Aluminum (vacuum measurement (Time of + 0.5 lds / ton. of dough) Empty) Flocculant CPAM-P + Drain Aid None 0 87.60% 3.37 86.868 126.238 1.455 0.880 (3.42) (4.97) Poliflex CP.3 0.2268 96.42% 3.17 70.358 102.87 1.465 0.627 (0.5) (2.77) (4.05) Poliflex CP.3 0.3402 98.81 % 3.30 66.294 97.536 1.472 0.577 (0.75) (2.61) (3.84) Poliflex CP.3 0.4536 97.65% 3.18 63.246 93.98 1.486 0.515 (1) (2.49) (3.70) Polymer III 0.2268 95.39% 3.28 76.2 109.728 1.440 0.672 (0.5) ( 3.00) (4.32) Polymer III 0.3402 86.26% 3.09 75.692 108.966 1.442 0.662 (0.75) (2.98) (4.29) Polymer III 0.4536 95.54% 3.09 73.914 107.188 1.451 0.649 (1) (2.91) (4.22) Polymer M 0.2268 95.27% 3.32 73.914 109,982 1.487 0.662 (0.5) (2.91) (4.33) Polymer M 0.3402 95.80% 3.22 69.596 106.172 1.523 0.649 (0.75) (2.74) (4.18) Polymer M 0.4536 96.23% 3.38 68.834 108.966 1.583 0.651 (i) (2.71) (4.29) Clay of 0.9072 89.95% 3.32 82.55 114.554 1.391 0.724 Bentonite (2) (3.25) (4.51) Clay of 1.8144 93.96% 3.11 78.232 1 11.252 1.420 0.678 Bentonite (4) (3.08) (4.38) Clay 2.7216 96.47% 4.61 75.184 106.934 1.423 0.649 Bentonite (6) (2.96) (4.21) Another series of CSF drainage and Britt jar retention tests are conducted with Polymer III and Poliflex CP.3 using high levels of CPAM-P flocculant and an additional flocculant, polyvinylamine (PVAm). The PVAm is produced via a polymerization of the aqueous solution of the monomer N-vinylformamide, then with a subsequent hydrolysis of the polymer to produce N-vinylamine. The polymer in question is hydrolyzed at 90% in such a way that the resulting copolymer is 90 mol% N-vinylamine / 10 mol% N-vinylformamide; the polymer has 5% solids and exhibits an intrinsic viscosity in 1M NaCl of 3 dL / g. The data in Table 10 demonstrate the utility of PAH at high levels of the CPAM-P flocculant and activity with a PVAm flocculant.

TABLE 10 ADD # 1 Kg / ton ADD # 2 Kg / ton ADD # 3 Kg / ton Auxiliary Kg / ton% CSF Lbs / ton Lbs / ton Lbs / ton Drained Lbs / ton Retention (active) (active) (active ) (active) prom Starch of 4.536 Alum 2.268 Flocculant 0.2268 None 0 53.6 370 potato (10) (5) CPAM-P (0.5) cationic Starch of 4.536 Alum 2.268 Flocculant 0.2268 Poliflex CP.3 0.3402 78.6 650 potato (10) (5) CPAM-P (0.5) (0.75) cation? Co Starch 4.536 Alum 2.268 Flocculant 0.2268 Polymer III 0.3402 70.8 595 Potato (10) (5) CPAM-P (0.5) (0.75) cationic Starch of 4.536 Alum 2.268 Flocculant 0.4536 None 0 66.6 395 Potato (10) (5) CPAM-P (cationic Starch of 4.536 Alum 2.268 Flocculant 0.4536 Poliflex CP.3 0.3402 91.6 680 potato (10) (5) CPAM-P (1) (0.75) cationic 4. 536 2.268 0. 4536 0.3402 Starch (10) Alum (5) Flocculant (1) Polymer (0.75) 80. 9 610 potato CPAM-P III cationic Starch 4.536 2.268 Flocculant 0.2268"None of potato (10) Alum (5) PV Am (0.5) 35.9 435 cationic Starch 4.536 Alum 2.268 Flocculant 0.2268 Poliflex 0.3402 91.1 730 potato (10) (5) PV Am (0.5) "" CP.3 (0.75) cationic Starch 4.536 Alum 2.268 Flocculant 0.2268 Polymer 0.3402 74.0 665 potato (10) (5) PV Am (0.5) III (0.75) cationic Another series of PDD experiments are conducted as presented in Table 11 under the procedures previously described with Polymer III, Poliflex CP.3 and two products. of Poliflex additional, Poliflex CS and Poliflex CP.2 also available from Cytec Industries Inc. The data in Table 11 demonstrate that Polymer III provides improved retention and drainage activity compared to Poliflex CP.2, activity equivalent to that of Poliflex CS and the activity close to Poliflex CP.3.

TABLE 11 10 lbs / ton Dose First% Drained by Equilibrium of the Void Rate of Drain of the Potato starch Kg / ton Gravity step EMPTY MAXIMUM vacuum Maximum Cationic void +5 (lbs / T) Time retention- mmHg mm Hg vacuum Time-lbs / Ton fine seconds (in Hg) (in Hg) balance seconds 0. 5 lbs / Ton. of Flocculant CPAM-P + Drain Aid None 0 85.2% 3.44 91., 694 137.414 1.50 0.15 (3. .61) (5.41) Poliflex 0.2268 92.6% 3.12 70. .358 108.712 1.55 0.64 CP.3 (0.5) (2., 77) (4.28) 0.2268 64. .008 100.838 Poliflex (0.75) 94.1% 3.09 (2. .52) (3.97) 1.5E 0.55 CP.3 Polymer 0.4536 93.5% 3.00 61. .976 96.266 1.55 0.54 CP.3 (1) (2. .44) (3.79) Poliflex CS 0.2268 91.6% 3.12 81 .20 120.65 1.46 0.75 (0.5) (3. .20) (4.75) Poliflex CS 0.3402 92.8% 3.13 77. .978 117.094 1.50 0.72 (0.75) (3. .07) (4.61) Poliflex CS 0.4536 95.9% 3.20 74., 168 113.538 1.53 0.67 (1) (2., 92) (4.47) Poliflex 0.2268 91.6% 3.16 84., 582 121.412 1.43 0.75 CP.2 (0.5) (3., 33) (4.78) Poliflex 0.3402 92.7% 3.16 83, .058 120.142 1.45 0.77 CP.2 (0.75) (3, .27) (4.73) Poliflex 0.4536 91.2% 3.27 86.. 106 120.65 1.40 0.75 CP.2 (1) (3. .39) (4.75) Polymer III 0.2268 89.5% 3.35 83 .82 121.158 1.44 0.80 (0.5) (3, .30) (4.77) Polymer III 0.3402 94.0% 3.11 77., 978 117.856 1.51 0.73 (0.75) (3. .07) (4.64) Polymer III 0.4536 94.3% 3.13 76., 454 116.078 1.52 0.68 (1.00) (3., 01) (4.57) Polymer E 0.2268 91.9% 3.14 75. 438 116.84 1.55 0.70 (0.5) (2. 97) (4.60) Polymer E 0.3402 95.4% 3.08 69.85 115.316 1.65 0.70 (0.75) (2.75) (4.54) Polymer E 0.4536 92.9% 3.20 67. 564 116.84 1.73 0.75 (1) (2. 66) (4.60) A series of CSF drainage and Britt jar retention studies are conducted with the previously described brine dispersion polymers. These studies published in Table 2 are conducted with Polymers IX to X, polymers of the inventive method modified with lauryl methacrylate; Polymer VIII is the control polymer produced under equivalent conditions as the hydrophobically associated polymers but does not contain the hydrophobic substitution; Poliflex CP.3 and Polymer A, a high molecular weight anionic polyacrylamide powder flocculant. The test conditions and associated additives are those described above with the exception of the cationic flocculant used CPAM-N; This material is equivalent in composition and physical forms as the previously used CPAM-P. An anionic polyacrylamide flocculant (APAM) is also used. This material is a 30% sodium acrylate / 70% by weight acrylamide copolymer commercially available as a self-immersing emulsion. The data in Table 12 demonstrate the improved activity of the inventive material. Polymers IX and XI demonstrate high drainage and retention activity compared to the commercial drainage aid and bentonite clay, the control Polymer VIII and the conventional flocculant of Polymer A. This improved activity is observed when used with a CPAM flocculant, with a APAM flocculant and without a flocculant.

TABLE 12 ADD # 1 Kg / ton ADD # 2 Kg / ton ADD # 3 Kg / ton Auxiliary Kg / ton% CSF Lbs / ton Lbs / ton Lbs / to Drained Lbs / ton Drain retention (active) (active) (active) (active) prom Starch 4.536 Alum 2.268 Flocculant 0.226 None 0 53.6 370 of potato (10) (5) CPAM-N (0.5) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.3402 71.1620 of potato (10) (5) CPAM-N (0.5) VIII (0.75) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.3402 78.9 650 of potato (10) (5) CPAM-N (0.5) IX (0.75) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.3402 76.4640 potato (10) (5) CPAM-N (0.5) XI (0.75) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.3402 73.1 630 potato (10) (5) CPAM-N (0.5) X (0.75) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.3402 555 of potato (10) (5) CPAM-N (0.5) XII (0.75) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.3402 86.0 680 potato (10 ) (5) CPAM-N (0.5) CP 3 (0.75) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.3402 68.1620 potato (10) (5) CPAM-N (0.5) A (0.75) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Bentolit 1.8144 70.7 630 potato (10) (5) CPAM-N (0.5) to HS (4) cationic Starch 4.536 Alum 2.268 None 0 Polymer 0.2268 59.6 560 potato (10) (5) VIII (0.5) cationic Starch 4.536 Alum 2.268 None Polymer 0.2268 66.0 545 of potato (10) (5) IX (0.5) cationic Starch 4.536 Alum 2.268 None Polymer 0.2268 67 .8 555 of potato (10) (5) XI (0.5) cationic Starch 4.536 Alum 2.268 None 0 Polymer 0.226B 52.0 495 of potato (10) (5) X (0.5) cationic Starch 4.536 Alum 2.268 None 0 Polymer 0.2268 435 potato (10) (5) XII (0.5) cationic Starch 4.536 Alum 2.268 None 0 Poliflex 0.2268 71.5 585 potato (10) (5) CP.3 (0.5) cationic Starch 4.536 Alum 2.268 None 0 Polymer 0.2268 57.1 560 potato ( 10) (5) A (0.5) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.2268 530 potato (10) (5) APAM (0.5) VIII (0.5) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.2268 565 potato (10) (5) APAM (0.5) IX (0.5 ) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.22ET8 540 potato (10) (5) APAM (0.5) XI (0.5) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.2268 540 potato (10) (5) APAM (0.5) X (0.5) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.2268 520 of potato (10) (5) APAM (0.5) XII (0.5) cationic To my gift 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.2268 630 potato (10) (5) APAM (0.5) CP.3 (0.5) cationic Starch 4.536 Alum 2.268 Flocculant 0.226 Polymer 0.2268 505 of potato (10) (5) APAM (0.5) A (0.5) cationic A series of evaluations is conducted in the PDD using equivalent methods as described in Table 12. The studies published in Table 13 are conducted with Polymers IX and X, the polymers of the inventive method modified with lauryl methacrylate; Polymers XI and XII, polymers of the modified inventive method with lauryl acrylate; Polymer VII is the control polymer produced under equivalent conditions such as hydrophobically associated polymers but which do not contain the hydrophobic substitution and Poliflex CP.3. The data in Table 13 demonstrate the draining activity for Polymers IX, X and XI compared to Polymer VIII of unmodified control. Polymers IX, X and XI also indicate a positive response dose to a low PEVR, while the unmodified control does not demonstrate a remarkable response dose.

TABLE 13 Potato Starch Dose First% Drained by Vacuum Equilibrium Cationic Drainage Ratio 10 Kg / ton Gravity Retention EMPTY MAXIMUM vacuum Maximum Vacuum Ibs / ton (Ibs / T) fine pitch Time- mm Hg mm Hg vacuum of Time- + 5 Ibs / ton seconds (in Hg) (in Hg) balance seconds + 0.5 lbs / ton. CPAM-N + Drain Aid None 86.1% 3.98 84.58 129.794 1.53 0.94 (3.33) (5.11) Polymer HIV 0.2268 93.1% 3.76 73.406 111.252 1.52 0.67 (0.5) (2.89) (4.38) Polymer VIII 0.4536 95.6% 3.79 69.088 106.172 1.54 0.63 (1) (2.72) (4.18) Polymer 0.2268 93.7% 3.71 70.358 104.648 1.49 0.64 IX (0.5) (2.77) (4.12) Polymer 0.4536 94.5% 3.64 63.754 95.25 1.50 0.54 IX (1) (2.51) (3.75) Polymer X 0.2268 92.5% 3.69 70.866 104.648 1.48 0.65 (0.5) (2.79) (4.12) Polymer X 0.4536 97.2% 3.66 62.992 94.488 1.50 0.55 0) (2.48) ) (3.72) Polymer XI 0.2268 94.0% 3.65 69.596 103.378 1.49 0.62 (0.5) (2.74) (4.07) Polymer XI 0.4536 93.7% 3.68 63.246 98.298 1.55 0.54 (1) (2.49) (3.87) Polymer XII 0.2268 86.0% 3.86 82.042 119.126 1.45 0.77 (0.5) (3.23) (4.69) Polymer XII 0.4536 89.1% 3.73 76.2, 112.522 1.47 0.71 (1) (3.00) (4.43) Poliflex CP.3 0.2268 95.8% 3.70 66.04 99.822 1.51 0.57 (0.5) (2.60) (3.93) Poliflex CP.3 0.4536 94.9% 3.55 58.166 89.408 1.54 0.49 (1) (2.29) (3.52) It is noted that the aforementioned examples have been provided solely for the purpose of explanation and should not in any way be construed as limiting the present invention. While the present invention has been described with respect to an exemplary embodiment, it is understood that the words that have been used herein are description and illustration words rather than words of limitation. The changes may be made within the scope of the appended claims as stated and as amended without departing from the scope and spirit of the present invention in its aspects. Although the present invention has been described herein with reference to particular means, materials and embodiments, the present invention is not intended to be limited to the features described herein; rather, the present invention extends to all functionally equivalent structures, methods and uses such as those within the scope of the appended claims.

Claims

CLAIMS 1. A method for making a cellulosic fiber composition characterized in that it comprises adding to a slurry of cellulose pulp or pulp, a hydrophobically associative polymer comprised of recurring units of at least one ethylenically unsaturated, hydrophobic monomer, present in an amount of about 0.001 mole percent to about 10 mole percent and recurring units of at least one monomer selected from a non-ionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer, or an ethylenically unsaturated anionic monomer, with the proviso that at least a hydrophobic ethylenically unsaturated monomer does not contain 2,4, β-triphenol benzene. The method of claim 1, characterized in that the ethylenically unsaturated, hydrophobic monomer comprises an ethylenically unsaturated monomer having at least one pendant or pendant hydrophobic group. 3. The method of claim 2, characterized in that the pendant hydrophobic group is selected from one or more C4 to C20 alkyls, C4 to C20 cycloalkyls, polynuclear aromatic hydrocarbon groups, aralkyls wherein the alkyl has one or more carbons; Haloalkyls of four or more carbons or polyalkyleneoxy groups. 4. The method of claim 3, characterized in that the hydrophobic group is selected from one or more of the C-C2 alkyl groups. The method of claim 3, characterized in that the hydrophobic group is selected from one or more of the Cg-C2o alkyl groups. The method of claim 1, characterized in that the hydrophobic ethylenically unsaturated monomer is selected from one or more hydrocarbon esters of ethylenically unsaturated carboxylic acids and their salts. The method of claim 1, characterized in that the ethylenically unsaturated, hydrophobic monomer is selected from one or more of the C este or C C alq alkyl esters of acrylic and methacrylic acid. The method of claim 1, characterized in that the nonionic ethylenically unsaturated monomer is selected from one or more of acrylamide, methacrylamide, N-alkyl acrylamides, N, N-dialkylamides, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methyl formamide, vinyl acetate or N-vinyl pyrrolidone. 9. The method of claim 8, characterized in that the N-alkyl acrylamide is N-methylacrylamide. The method for making the cellulosic fiber composition of claim 8, characterized in that the at least one non-ionic ethylenically unsaturated monomer is selected from one or more of acrylamide, methacrylamide or N-alkyl acrylamides. The method for making the cellulose fiber composition of claim 8, characterized in that the at least one ethylenically unsaturated monomer is acrylamide. The method for making the cellulosic fiber composition of claim 1, characterized in that the at least one ethylenically unsaturated anionic monomer is selected from one or more of acrylic acid, methacrylic acid, 2-acrylamido-2-sulfonate. methyl propane, sulfoethyl (meth) acrylate, vinylsulfonic acid, styrene sulfonic acid, maleic acid or salts thereof. The method for making the cellulosic fiber composition of claim 12, characterized in that the at least one ethylenically unsaturated anionic monomer is selected from one or more of acrylic acid, methacrylic acid or salts thereof. 14. The method for preparing the composition of the cellulosic fiber of claim 13, characterized in that the less an ethylenically unsaturated, anionic monomer is selected from one or more of the sodium or ammonium salts of the acrylic acid. 15. The method for making the cellulosic fiber composition of claim 1, characterized in that the at least one ethylenically unsaturated, hydrophobic monomer is present in an amount of about 0.01 mole percent to about 1 mole percent. 16. A method for preparing the composition of the cellulosic fiber comprising adding to a slurry of pulp or cellulose pulp, a hydrophobically associative, water-soluble polymer, characterized in that it comprises: recurring units of at least one ethylenically unsaturated, hydrophobic monomer, in an amount of from about 0.001 mole percent to about 10 mole percent and is selected from one or more C 1 -C 20 alkyl esters of acrylic or methacrylic acid. recurring units of at least one non-ionic ethylenically unsaturated monomer, selected from one or more of acrylamide, methacrylamide, N-acrylamides, N, N-dialkylacrylamides, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, formamide of N-vinyl methyl, vinyl acetate or N-vinyl pyrrolidone; recurring units of at least one anionic ethylenically unsaturated monomer, selected from one or more of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulphoethyl- (meth) acrylate, vinylsulfonic acid, styrene sulfonic acid , maleic acid or salts thereof. The method for making a cellulosic fiber composition of claim 16, characterized in that the hydrophobically associative, water-soluble polymer comprises: recurring units of at least one hydrophobic, ethylenically unsaturated monomer present in an amount of about 0.001 percent in mol to about 10 mole percent and selected from one or more C 1 -C 2 alkyl esters of acrylic and methacrylic acid. recurring units of at least one ethylenically unsaturated, nonionic monomer selected from one or more of acrylamide, methacrylamide or N-alkyl acrylamides; recurring units of at least one ethylenically unsaturated, nonionic monomer selected from acrylic acid, methacrylic acid or salts thereof. 18. A method for making the composition of the cellulosic fiber, characterized in that it comprises adding to a slurry of pulp or cellulose pulp, a hydrophobic anionic associative polymer comprising at least one hydrophobic ethylenically unsaturated monomer, selected from one or more of lauryl acrylate or lauryl methacrylate, acrylamide and acrylic acid. The method of claim 18, characterized in that the ethylenically unsaturated, hydrophobic monomer is lauryl acrylate. The method of claim 18, characterized in that the ethylenically unsaturated, hydrophobic monomer is lauryl methacrylate. 21. A cellulosic fiber composition comprising an aqueous slurry of cellulose pulp or pulp and a hydrophobically associative, water soluble polymer, characterized in that it comprises: recurring units of at least one ethylenically unsaturated, hydrophobic monomer present in an amount of about 0.001 mole percent to about 10 mole percent and recurring units of at least one monomer selected from an ethylenically unsaturated, cationic monomer, or an ethylenically unsaturated, anionic monomer, with the proviso that the at least one ethylenically unsaturated, hydrophobic monomer does not contain 2,4,6-triphenol benzene. The composition of the cellulosic fiber of claim 21, characterized in that at least one hydrophobic ethylenically unsaturated monomer comprises an ethylenically unsaturated monomer having at least one pendant or pendant hydrophobic group. 23. The composition of the cellulosic fiber of claim 22, characterized in that the pendant hydrophobic group is selected from one or more C to C2o alkyls, C to C2o cycloalkyls, nuclear aromatic hydrocarbon groups, aralkyls wherein the alkyl has one or more carbons; haloalkyls of four or more carbons, or polyalkyleneoxy groups. 24. The composition of the cellulosic fiber of claim 23, characterized in that the at least one hydrophobic group is selected from one or more C4 to C2o alkyl groups. 25. The composition of the cellulosic fiber of claim 24, characterized in that at least one hydrophobic group is selected from one or more C8 to C20 alkyl groups. 26. The composition of the cellulosic fiber of claim 21, characterized in that at least one ethylenically unsaturated, hydrophobic monomer is selected from one or more hydrocarbon esters of ethylenically unsaturated carboxylic acids and their salts. 27. The composition of the cellulosic fiber of claim 26, characterized in that at least one hydrophobic ethylenically unsaturated monomer is selected from one or more of the C? 0 -C 20 alkyl esters of acrylic or methacrylic acid. 28. The composition of the cellulosic fiber of claim 21, characterized in that at least one nonionic ethylenically unsaturated monomer is selected from one or more of acrylamide, methacrylamide, N-alkyl acrylamides, N, N-dialkylacrylamides, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, formamide of N-vinyl methyl, vinyl acetate or N-vinyl pyrrolidone. 29. The composition of the cellulosic fiber of claim 28, characterized in that the at least one nonionic ethylenically unsaturated monomer is acrylamide. The composition of the cellulosic fiber of claim 21, characterized in that the at least one ethylenically unsaturated, anionic monomer is selected from one or more of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulfoethyl (meth) acrylate, vinylsulfonic acid, styrene sulfonic acid, maleic acid or salts thereof. The composition of the cellulosic fiber of claim 30, characterized in that the at least one ethylenically unsaturated, anionic monomer is selected from one or more of sodium or ammonium salts of acrylic acid 32. The composition of the cellulosic fiber of claim 21, characterized in that the at least one ethylenically unsaturated, hydrophobic monomer is present in an amount of about 0.01 mole percent to about 1 mole percent. 33. A cellulosic fiber composition comprising an aqueous slurry of cellulose pulp or pulp and a hydrophobically associative, water soluble polymer characterized in that the polymer comprises: recurring units of at least one hydrophobic ethylenically unsaturated monomer present in an amount of about 0.001 percent in mol to approximately 10 mole percent and selected from one or more C 0 to C 20 alkyl esters of acrylic and methacrylic acid. recurring units of at least one non-ionic ethylenically unsaturated monomer selected from one or more of acrylamide, methacrylamide, N-alkyl acrylamides, N-alkyl acrylamides, N, N-dialkylacrylamides, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methyl formamide, vinyl acetate or pyrrolidone of N-vinyl; recurring units of at least one anionic ethylenically unsaturated monomer selected from one or more of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulphoethyl- (meth) acrylate, vinylsulfonic acid, styrene sulfonic acid, maleic acid or salts thereof. 34. The composition of the cellulosic fiber of claim 33, characterized in that the water-soluble hydrophobically associative polymer comprises at least one ethylenically unsaturated, hydrophobic monomer selected from one or more of dodecyl acrylate or dodecyl methacrylate, the at least one ethylenically unsaturated nonionic monomer is acrylamide, the at least one ethylenically unsaturated anionic monomer is selected from one or more of the sodium or ammonium salts of acrylic acid. 35. The cellulosic sheet of claim 33, characterized in that it comprises paper. 36. A cellulosic fiber composition comprising an aqueous slurry of cellulose pulp or pulp and a hydrophobically associative, water soluble polymer, characterized in that the polymer comprises: recurring units of a hydrophobic ethylenically unsaturated monomer selected from one or more of lauryl acrylate or lauryl methacrylate, recurring units of a non-ionic ethylenically unsaturated monomer, which is acrylamide and recurring units of an ethylenically unsaturated, anionic monomer, which is acrylic acid. 37. The composition of the cellulosic fiber of claim 36, characterized in that it is in paper form.