CA2592262A1 - Improved retention and drainage in the manufacture of paper - Google Patents

Abstract

A method of improving retention and drainage in a papermaking process is disclosed. The method provides for the addition of an associative polymer, an inorganic particle and optionally a siliceous material to the papermaking slurry. Additionally, a composition comprising an associative polymer, and an inorganic particle and optionally further comprising cellulose fiber is disclosed.

Description

IMPROVED RETENTION AND DRAINAGE IN THE MANUFACTURE OF
PAPER

CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 60/640,163, filed December 29, 2004; U.S. Provisional Application No.
60/639,897, filed December 29, 2004; U.S. Provisional Application No.
60/640,166, filed December 29, 2004; U.S. Provisional Application No.
60/694,057, filed June 24, 2005; U.S. Provisional Application No. 60/694,059, filed June 24, 2005, the entire contents of each are herein incorporated by reference.
FIELD OF THE INVENTION

[0002] This invention relates to the process of making paper and paperboard from a cellulosic stock, employing a flocculating system.
BACKGROUND

[0003] Retention and drainage is an important aspect of papermaking. It is known that certain materials can provide improved retention and/or drainage properties in the production of paper and paperboard.

[0004] The making of cellulosic fiber sheets, particularly paper and paperboard, includes the following: 1) producing an aqueous slurry of cellulosic fiber which may also contain inorganic mineral extenders or pigments; 2) depositing this slurry on a moving papermaking wire or fabric; and 3) forming a sheet from the solid components of the slurry by draining the water.

[0005] The foregoing is followed by pressing and drying the sheet to further remove water. Organic and inorganic chemicals are often added to the slurry prior to the sheet-forming step to make the papermaking method less costly, more rapid, and/or to attain specific properties in the final paper product.

[0006] The paper industry continuously strives to improve paper quality, increase productivity, and reduce manufacturing costs. Chemicals are often added to the fibrous slurry before it reaches the papermaking wire or fabric to improve drainage/dewatering and solids retention; these chemicals are called retention and/or drainage aids.

[0007] Drainage or dewatering of the fibrous slurry on the papermaking wire or fabric is often the limiting step in achieving faster paper machine speeds.
Improved dewatering can also result in a drier sheet in the press and dryer sections, resulting in reduced energy consumption. In addition, as this is the stage in the papermaking method that determines many of the sheet final properties, the retention and/or drainage aid can impact performance attributes of the final paper sheet.

[0008] With respect to solids, papermaking retention aids are used to increase the retention of fine furnish solids in the web during the turbulent method of draining and forming the paper web. Without adequate retention of the fine solids, they are either lost to the mill effluent or accumulate to high levels in the recirculating white water loop, potentially causing deposit buildup.
Additionally, insufficient retention increases the papermakers' cost due to loss of additives intended to be adsorbed on the fiber. Additives can provide opacity, strength, sizing or other desirable properties to the paper.

[0009] High molecular weight (MW) water-soluble polymers with either cationic or anionic charge have traditionally been used as retention and drainage aids. Recent development of inorganic microparticles, when used as retention and drainage aids, in combination with high MW water-soluble polymers, have shown superior retention and drainage efficacy compared to conventional high MW water-soluble polymers. U.S. Patent Nos. 4,294,885 and 4,388,150 teach the use of starch polymers with colloidal silica. U.S. Patent Nos. 4,643,801 and 4,750,974 teach the use of a coacervate binder of cationic starch, colloidal silica, and anionic polymer. U.S. Patent No. 4,753,710 teaches flocculating the pulp furnish with a high MW cationic flocculant, inducing shear to the flocculated furnish, and then introducing bentonite clay to the furnish. U.S. Patent Nos.
5,274,055 and 5,167,766 disclose using chemically cross-linked organic micropolymers as retention and drainage aids in the papermaking process.

[0010] The efficacy of the polymers or copolymers used will vary depending upon the type of monomers from which they are composed, the arrangement of the monomers in the polymer matrix, the molecular weight of the synthesized molecule, and the method of preparation.

[0011] It had been found recently that water-soluble copolymers when prepared under certain conditions exhibit unique physical characteristics.
These polymers are prepared without chemical cross linking agents. Additionally, the copolymers provide unanticipated activity in certain applications including papermaking applications such as retention and drainage aids. The anionic copolymers which exhibit the unique characteristics were disclosed in WO
03/050152 Al, the entire content of which is herein incorporated by reference.
The cationic and amphoteric copolymers which exhibit the unique characteristics were disclosed in U.S. serial number 10/728,145, the entire content of which is herein incorporated by reference.

[0012] The use of inorganic particles with linear copolymers of acrylamide, is known in the art. Recent patents teach the use of these inorganic particles with water-soluble anionic polymers (US 6,454,902) or specific crosslinked materials (US 6,454,902, US 6,524,439 and US 6,616,806).

[0013] However, there still exists a need to improve drainage and retention performance.

SUMMARY OF THE INVENTION

[0014] A method of improving retention and drainage in a papermaking process is disclosed. The method provides for the addition of an associative polymer and an inorganic particle to a papermaking slurry.

[0015] Additionally, a composition comprising an associative polymer, and an inorganic particle and optionally further comprising cellulose fiber is disclosed.

[0016] Additionally, a composition comprising an associative polymer, inorganic particle(s), a siliceous material and optionally further comprising cellulose fiber is disclosed.

[0017] A method of improving retention and drainage in a papermaking process is disclosed. The method provides for the addition of an associative polymer and an aluminum compound to a papermaking slurry.

[0018] A method of improving retention and drainage in a papermaking process is disclosed. The method provides for the addition of an associative polymer and a chelating agent to a papermaking slurry.

[0019] A method of improving retention and drainage in a papermaking process is disclosed. The method provides for the addition of an associative polymer and a metal salt to a papermaking slurry.

[0020] A method of improving retention and drainage in a papermaking process is disclosed. The method provides for the addition of an associative polymer and a silicone polymer to a papermaking slurry.

DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention provides for a synergistic combination comprising a water soluble copolymer prepared under certain conditions (hereinafter referred to as "associative polymer") and inorganic particles. It has surprising been found that this synergistic combination results in retention and drainage performance superior to that of the individual components.
Synergistic effects occur when the combination of components are used together.

[0022] It has been found, unexpectedly, that the use of inorganic particles in combination with associative polymers prepared under certain conditions, as disclosed in WO 03/050152 Al or US 2004/0143039 Al, results in enhanced retention and drainage.

[0023] The present invention also provides for a composition comprising an associative polymer and inorganic particles.

[0024] The present invention also provides for a composition comprising an associative polymer, inorganic particles and a siliceous material.

[0025] The present invention also provides for a composition comprising an associative polymer and inorganic particles and cellulose fiber.

[0026] The present invention also provides for a composition comprising an associative polymer, inorganic particles, a siliceous material and cellulose fiber.

[0027] The use of multi-component systems in the manufacture of paper and paperboard provides the opportunity to enhance performance by utilizing materials that have different effects on the process and/or product. Moreover, the combinations may provide properties unobtainable with the components individually. Synergistic effects occur in the multi component systems of the present invention.

[0028] It is also observed that the use of the associative polymer as a retention and drainage aid has an impact on the performance of other additives in the papermaking system. Improved retention and/or drainage can have both a direct and indirect impact. A direct impact refers to the retention and drainage aid acting to retain the additive. An indirect impact refers to the efficacy of the retention and drainage aid to retain filler and fines onto which the additive is attached by either physical or chemical means. Thus, by increasing the amount of filler or fines retained in the sheet, the amount of additive retained is increased in a concomitant manner. The term filler refers to particulate materials, typically inorganic in nature, that are added to the cellulosic pulp slurry to provide certain attributes or be a lower cost substitute of a portion of the cellulose fiber.
Their relatively small size, on the order of 0.2 to 10 microns, low aspect ratio and chemical nature results in their not being adsorbed onto the large fibers yet too small to be entrapped in the fiber network that is the paper sheet. The term "fines" refers to small cellulose fibers or fibrils, typically less than 0.2 mm in length and /or ability to pass through a 200 mesh screen.

[0029] As the use level of the retention and drainage aid increases the amount of additive retained in the sheet increases. This can provide either an enhancement of the property, providing a sheet with increased performance attribute, or allows the papermaker to reduce the amount of additive added to the system, reducing the cost of the product. Moreover, the amount of these materials in the recirculating water, or whitewater, used in the papermaking system is reduced. This reduced level of material, that under some conditions can be considered to be an undesirable contaminant, can provide a more efficient papermaking process or reduce the need for scavengers or other materials added to control the level of undesirable material.

[0030] The term additive, as used herein, refers to materials added to the paper slurry to provide specific attributes to the paper and/or improve the efficiency of the papermaking process. These materials include, but are not limited to, sizing agents, wet strength resins, dry strength resins, starch and starch derivatives, dyes, contaminant control agents, antifoams, and biocides.

[0031] The associative polymer useful in the present invention can be described as follows:

[0032] A water-soluble copolymer composition comprising the formula:
{-B-co-F-}- (I) wherein B is a nonionic polymer segment formed from the polymerization of one or more ethylenically unsaturated nonionic monomers; F is an anionic, cationic or a combination of anionic and cationic polymer segment(s) formed from polymerization of one or more ethylenically unsaturated anionic and/or cationic monomers; the molar % ratio of B:F is from 95:5 to 5:95; and the water-soluble copolymer is prepared via a water-in-oil emulsion polymerization technique that employs at least one emulsification surfactant consisting of at least one diblock or triblock polymeric surfactant wherein the ratio of the at least one diblock or triblock surfactant to monomer is at least about 3:100 and wherein; the water-in-oil emulsion polymerization technique comprises the steps of: (a) preparing an aqueous solution of monomers, (b) contacting the aqueous solution with a hydrocarbon liquid containing surfactant or surfactant mixture to form an inverse emulsion, (c) causing the monomer in the emulsion to polymerize by free radical polymerization at a pH range of from about 2 to less than 7.

[0033] The associative polymer can be an anionic copolymer. The anionic copolymer is characterized in that the Huggins' constant (k') determined between 0.0025 wt. % to 0.025 wt. % of the copolymer in 0.01 M NaCI is greater than 0.75 and the storage modulus (G') for a 1.5 wt. % actives copolymer solution at 4.6 Hz greater than 175 Pa.

[0034] The associative polymer can be a cationic copolymer. The cationic copolymer is characterized in that its Huggins' constant (k') determined between 0.0025 wt. % to 0.025 wt. % of the copolymer in 0.01 M NaCI is greater than 0.5;
and it has a storage modulus (G') for a 1.5 wt. % actives copolymer solution at 6.3 Hz greater than 50 Pa.

[0035] The associative polymer can be an amphoteric copolymer. The amphoteric copolymer is characterized in that its Huggins' constant (k') determined between 0.0025 wt. % to 0.025 wt. % of the copolymer in 0.01 M NaCI

is greater than 0.5; and the copolymer has a storage modulus (G') for a 1.5 wt. %
actives copolymer solution at 6.3 Hz greater than 50 Pa.

[0036] Inverse emulsion polymerization is a standard chemical process for preparing high molecular weight water-soluble polymers or copolymers. In general, an inverse emulsion polymerization process is conducted by 1) preparing an aqueous solution of the monomers, 2) contacting the aqueous solution with a hydrocarbon liquid containing appropriate emulsification surfactant(s) or surfactant mixture to form an inverse monomer emulsion, 3) subjecting the monomer emulsion to free radical polymerization, and, optionally, 4) adding a breaker surfactant to enhance the inversion of the emulsion when added to water.

[0037] Inverse emulsions polymers are typically water-soluble polymers based upon ionic or non-ionic monomers. Polymers containing two or more monomers, also referred to as copolymers, can be prepared by the same process.
These co-monomers can be anionic, cationic, zwitterionic, nonionic, or a combination thereof.

[0038] Typical nonionic monomers, include, but are not limited to, acrylamide; methacrylamide; N-alkylacrylamides, such as N-methylacrylamide;
N,N-dialkylacrylamides, such as N,N-dimethylacrylamide; methyl acrylate;
methyl methacrylate; acrylonitrile; N-vinyl methylacetamide; N-vinyl formamide; N-vinyl methyl formamide; vinyl acetate; N-vinyl pyrrolidone;
hydroxyalky(meth)acrylates such as hydroxyethyl(meth)acrylate or hydroxypropyl(meth)acrylate; mixtures of any of the foregoing and the like.

[0039] Nonionic monomers of a more hydrophobic nature can also be used in the preparation of the associative polymer. The term 'more hydrophobic' is used here to indicate that these monomers have reduced solubility in aqueous solutions; this reduction can be to essentially zero, meaning that the monomer is not soluble in water. It is noted that the monomers of interest are also referred to as polymerizable surfactants or surfmers. These monomers include, but are not limited to, alkylacryamides; ethylenically unsaturated monomers that have pendant aromatic and alkyl groups, and ethers of the formula CH2=CR'CH2OAmR
where R' is hydrogen or methyl; A is a polymer of one or more cyclic ethers such as ethyleneoxide, propylene oxide and/or butylene oxide; and R is a hydrophobic group; vinylaikoxylates; allyl alkoxylates; and aliyi phenyl polyolether sulfates.

Exemplary materials include, but are not limited to, methylmethacrylate, styrene, t-octyl acrylamide, and an allyl phenyl polyol ether sulfate marketed by Clariant as Emulsogen@ APG 2019.

[0040] Exemplary anionic monomers include, but are not limited to, the free acids and salts of: acrylic acid; methacrylic acid; maleic acid; itaconic acid;
acrylamidoglycolic acid; 2-acrylamido-2-methyl-l-propanesulfonic acid; 3-allyloxy-2-hydroxy-l-propanesulfonic acid; styrenesulfonic acid; vinyisulfonic acid;
vinylphosphonic acid; 2-acrylamido-2-methylpropane phosphonic acid; mixtures of any of the foregoing and the like.

[0041] Exemplary cationic monomers include, but are not limited to, cationic ethylenically unsaturated monomers such as the free base or salt of:
diallyidialkylammonium halides, such as diallyidimethylammonium chloride; the (meth)acrylates of dialkylaminoalkyl compounds, such, as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethyl aminopropyl (meth)acrylate, 2-hydroxydimethyl aminopropyl (meth)acrylate, aminoethyl (meth)acrylate, and the salts and quaternaries thereof; the N,N-dialkylaminoalkyl(meth)acrylamides, such as N,N-dimethylaminoethylacrylamide, and the salts and quaternaries thereof and mixture of the foregoing and the like.

[0042] The co-monomers may be present in any ratio. The resultant associative polymer can be non-ionic, cationic, anionic, or amphoteric (contains both cationic and anionic charge).

[0043] The molar ratio of nonionic monomer to anionic monomer (B:F or Formula I) may fall within the range of 95:5 to 5:95, preferably the range is from about 75:25 to about 25:75 and even more preferably the range is from about 65:35 to about 35:65 and most preferably from about 60:40 to about 40:60. In this regard, the molar percentages of B and F must add up to 100%. It is to be understood that more than one kind of nonionic monomer may be present in the Formula I. It is also to be understood that more than one kind of anionic monomer may be present in the Formula I.

[0044] In one preferred embodiment of the invention the associative polymer, when it is an anionic copolymer, is defined by Formula I where B, the nonionic polymer segment, is the repeat unit formed after polymerization of acrylamide; and F, the anionic polymer segment, is the repeat unit formed after polymerization of a salt or free acid of acrylic acid and the molar percent ratio of B:F is from about 75:25 to about 25:75 [0045] The physical characteristics of the associative polymer, when it is an anionic copolymer, are unique in that their Huggins' constant (k') as determined in 0.01 M NaCI is greater than 0.75 and the storage modulus (G') for a 1.5 wt. %
actives polymer solution at 4.6 Hz is greater than 175 Pa, preferably greater than 190 and even more preferably greater than 205. The Huggins' constant is greater than 0.75, preferably greater than 0.9 and even more preferably greater than 1.0 [0046] The molar ratio of nonionic monomer to cationic monomer (B:F of Formula I) may fall within the range of 99:1 to 50:50, or 95:5 to 50:50, or 95:5 to 75:25, or 90:10 to 60:45, preferably the range is from about 85:15 to about 60:40 and even more preferably the range is from about 80:20 to about 50:50. In this regard, the molar percentages of B and F must add up to 100%. It is to be understood that more than one kind of nonionic monomer may be present in the Formula I. It is also to be understood that more than one kind of cationic monomer may be present in the Formula I.

[0047] With respect to the molar percentages of the amphoteric copolymers of Formula I, the minimum amount of each of the anionic, cationic and non-ionic monomer is 1% of the total amount of monomer used to form the copolymer. The maximum amount of the non-ionic, anionic or cationic is 98% of the total amount of monomer used to form the copolymer. Preferably the minimum amount of any of anionic, cationic and non-ionic monomer is 5%, more preferably the minimum amount of any of anionic, cationic and non-ionic monomer is 7% and even more preferably the minimum amount of any of anionic, cationic and non-ionic monomer is 10% of the total amount of monomer used to form the copolymer. In this regard, the molar percentages of anionic, cationic and non-ionic monomer must add up to 100%. It is to be understood that more than one kind of nonionic monomer may be present in the Formula I, more than one kind of cationic monomer may be present in the Formula I, and that more than one kind of anionic monomer may be present in the Formula I.

[0048] The physical characteristics of the associative polymer, when it is a cationic or amphoteric copolymer, are unique in that their Huggins' constant (k') as determined in 0.01 M NaCI is greater than 0.5 and the storage modulus (G') for a 1.5 wt. % actives polymer solution at 6.3 Hz is greater than 50 Pa, preferably greater than 10 and even more preferably greater than 25, or greater than 50, or greater than 100, or greater than 175, or greater than 200. The Huggins' constant is greater than 0.5, preferably greater than 0.6, or greater than 0.75, or greater than 0.9 or greater than 1Ø

[0049] The emulsification surfactant or surfactant mixture used in an inverse emulsion polymerization system have an important effect on both the manufacturing process and the resultant product. Surfactants used in emulsion polymerization systems are known to those skilled in the art. These surfactants typically have a range of HLB (Hydrophilic Lipophilic Balance) values that is dependent on the overall composition. One or more emulsification surfactants can be used. The emulsification surfactant(s) of the polymerization products that are used to produce the associative polymer include at least one diblock or triblock polymeric surfactant. It is known that these surfactants are highly effective emulsion stabilizers. The choice and amount of the emulsification surfactant(s) are selected in order to yield an inverse monomer emulsion for polymerization.
Preferably, one or more surfactants are selected in order to obtain a specific HLB
value.

[0050] Diblock and triblock polymeric emulsification surfactants are used to provide unique materials. When the diblock and triblock polymeric emulsification surfactants are used in the necessary quantity, unique polymers exhibiting unique characteristic result, as described in WO 03/050152 Al and US 2004/0143039 Al, the entire contents of each is herein incorporated by reference. Exemplary diblock and triblock polymeric surfactants include, but are not limited to, diblock and triblock copolymers based on polyester derivatives of fatty acids and poly[ethyleneoxide] (e.g., Hypermer0 B246SF, Uniqema, New Castle, DE), diblock and triblock copolymers based on polyisobutylene succinic anhydride and poly[ethyleneoxide], reaction products of ethylene oxide and propylene oxide with ethylenediamine, mixtures of any of the foregoing and the like. Preferably the diblock and triblock copolymers are based on polyester derivatives of fatty acids and poly[ethyleneoxide]. When a triblock surfactant is used, it is preferable that the triblock contains two hydrophobic regions and one hydrophilic region, i.e., hydrophobe-hydrophile-hydrophobe.

[0051] The amount (based on weight percent) of diblock or triblock surfactant is dependent on the amount of monomer used to form the associative polymer. The ratio of diblock or triblock surfactant to monomer is at least about 3 to 100. The amount of diblock or triblock surfactant to monomer can be greater than 3 to 100 and preferably is at least about 4 to 100 and more .preferably 5 to 100 and even more preferably about 6 to 100. The diblock or triblock surfactant is the primary surfactant of the emulsification system.

[0052] A secondary emulsification surfactant can be added to ease handling and processing, to improve emulsion stability, and/or to alter the emulsion viscosity. Examples of secondary emulsification surfactants include, but are not limited to, sorbitan fatty acid esters, such as sorbitan monooleate (e.g., Atlas G-946, Uniqema, New Castle, DE), ethoxylated sorbitan fatty acid esters, polyethoxylated sorbitan fatty acid esters, the ethylene oxide and/or propylene oxide adducts of alkylphenols, the ethylene oxide and/or propyiene oxide adducts of long chain alcohols or fatty acids, mixed ethylene oxide/propylene oxide block copolymers, alkanolamides, sulfosuccinates and mixtures thereof and the like.

[0053] Polymerization of the inverse emulsion may be carried out in any manner known to those skilled in the art. Examples can be found in many references, including, for example, Allcock and Lampe, Contemporary Polymer Chemistry, (Englewood Cliffs, New Jersey, PRENTICE-HALL, 1981), chapters 3-5.

[0054] A representative inverse emulsion polymerization is prepared as follows. To a suitable reaction flask equipped with an overhead mechanical stirrer, thermometer, nitrogen sparge tube, and condenser is charged an oil phase of paraffin oil (135.0g, Exxsol D80 oil, Exxon - Houston, TX) and surfactants (4.5g Atlas G-946 and 9.Og Hypermer B246SF). The temperature of the oil phase is then adjusted to 37 C.

[0055] An aqueous phase is prepared separately which comprised 53-wt. %
acrylamide solution in water (126.5g), acrylic acid (68.7g), deionized water (70.0g), and Versenex 80 (Dow Chemical) chelant solution (0.7g). The aqueous phase is then adjusted to pH 5.4 with the addition of ammonium hydroxide solution in water (33.1g, 29.4 wt. % as NH3). The temperature of the aqueous phase after neutralization is 39 C.

[0056] The aqueous phase is then charged to the oil phase while simultaneously mixing with a homogenizer to obtain a stable water-in-oil emulsion.
This emulsion is then mixed with a 4-blade glass stirrer while being sparged with nitrogen for 60 minutes. During the nitrogen sparge the temperature of the emulsion is adjusted to 50 1 C. Afterwards, the sparge is discontinued and a nitrogen blanket implemented.

[0057] The polymerization is initiated by feeding a 3-wt. % solution of 2,2'-azobisisobutyronitrile (AIBN) in toluene (0.213g). This corresponds to an initial AIBN charge, as AIBN, of 250 ppm on a total monomer basis. During the course of the feed the batch temperature was allowed to exotherm to 62 C (-50 minutes), after which the batch was maintained at 62+1 C. After the feed the batch was held at 62+1 C for 1 hour. Afterwards 3-wt. % AIBN solution in toluene (0.085g) is then charged in under one minute. This corresponds to a second AIBN charge of 100 ppm on a total monomer basis. Then the batch is held at 62+1 C for 2 hours.
Then batch is then cooled to room temperature, and breaker surfactant(s) is added.

[0058] The associative polymer emulsion is typically inverted at the application site resulting in an aqueous solution of 0.1 to 1% active copolymer.
This dilute solution of the associative polymer is then added to the paper process to affect retention and drainage. The associative polymer may be added to the thick stock or thin stock, preferably the thin stock. The associative polymer may be added at one feed point, or may be split fed such that the associative polymer is fed simultaneously to two or more separate feed points. Typical stock addition points include feed point(s) before the fan pump, after the fan pump and before the pressure screen, or after the pressure screen.

[0059] The associative polymer may be added in any effective amount to achieve flocculation. The amount of copolymer could be more than 0.5 Kg per metric ton of cellulosic pulp (dry basis). Preferably, the associative polymer is employed in an amount of at least about 0.03 lb. to about 0.5 Kg. of active copolymer per metric ton of cellulosic pulp, based on the dry weight of the pulp.
The concentration of copolymer is preferably from about 0.05 to about 0.5 Kg of active copolymer per metric ton of dried cellulosic pulp. More preferably the copolymer is added in an amount of from about 0.05 to 0.4 Kg per metric ton cellulose pulp and, most preferably, about 0.1 to about 0.3 Kg per metric ton based on dry weight of the cellulosic pulp.

[0060] The second component of the retention and drainage system is an inorganic material, often, not necessarily, referred to as a mineral. These materials include, but are not limited to, clay, swellable clays, calcium carbonate, talc, titanium dioxide, aluminosilicates, diatomaceous silica, calcium sulfate, zinc oxide and zeolites. These materials may be found in nature or synthesized via a chemical process. Further, the materials may be modified via chemical or physical treatment; both chemical and physical treatments, either sequentially or simultaneously, may be done on these materials. Calcium carbonate may be ground or precipitated.

[0061] The term clay is applied to a number of mineral groups considered to be phyllosilicates, a subclass of silicates. Clays, therefore, include chlorites, illites, kaolinites and smectites. Smectites are swellable clays, examples include, but are not limited to hectorite; montmorillonites, nontronites, saponite, sauconite, hormites, attapulgites and sepiolites, and the like. The chemical and physical nature of these materials is described in Aloi, F.G., and Trsksak, R.M., in Retention and Fines Fillers During Papermaking, J.M. Gess, ed., TAPPI Press, 1998, Chapter 5, p 61-108.

[0062] Montmorillonite is a common swellable clay used in the art.
Montmorillonite has a di-octahedral structure and a strong negative charge in water. It is the high anionic charge, electrical double layer in solution, and small particle size that make montmorillonite a colloidal particle. Montmorillonites are three-dimensional particles up to 2000 nm long with a thin uniform thickness of <1 nm and consist of oxygen, silicon, and a metal ion, typically aluminum and/or magnesium.

[0063] Bentonite, the most common clay now in commercial use in retention drainage, is predominately montmorillonite. Bentonite is a term in the art applied to a class of clay materials, typically aggregates of two or more minerals.
These mineral aggregates occur naturally, although these materials may undergo chemical and/or physical processing to modify their properties. Zeolites are microporous crystal solids with well defined structures. They contain, in general, silicon, aluminum and oxygen atoms. Zeolites can be natural, synthetic or modified.

[0064] Other inorganic materials can be used, including, but not limited to, perlite and vermiculite.

[0065] An alternative second component of the retention and drainage system can be one of several aluminum compounds, particularly alum (aluminum sulfate). The chemistry of alum and other aluminum compounds is unique.

[0066] Other aluminum compounds have found utility for the present invention. These include aluminum chloride, aluminum chlorohydrate (ACH), polyaluminum silicate sulfate (PASS) and polyaluminum chloride (PAC). PAC is the name given to a complex of polyhydroxyl chloride of aluminum having the general formula:

Aln (OH)m C13n-m [0067] Where n is an integer greater than 0, and m is an integer greater than 0.

[0068] The simplest PAC is a dimer, having the chemical formula:
Ain (OH)2 (H2O)8' [0069] While the accepted formula for the PAC is:
[A104 AI12 (OH)24 (H20)12)+7 [0070] Complex aluminum compounds are characterized by the basicity, or the total level of hydroxyl ions in the aluminum materials, as determined simply by the percentage of m/3n. Three advantages of PAC over alum are that it is more cationic, has a higher molecular weight and retains its cationic charge for a longer period of time.

[0071] The amount of aluminum compound in relationship to the amount of associative polymer used in the present invention can be from about 100:1 to about 1:100 by weight, or from about 50:1 to about 1:50, or from about 10:1 to about 1:10.

[0072] An alternative second component of the retention and drainage system is a chelating agent based on a metal such as aluminum, titanium or zirconium. These materials act by reacting with other materials and can interact with multiple sites to form bridges; bridging can occur through hydroxyl, amino, amido, carboxyl or thio groups. These reactions are useful in viscosity control and surface modification. The organic titanates and zirconates are used in augmenting coating, printing inks and adhesives.

[0073] Titanate and zirconate esters are one example of these materials, with tetraalkyl esters being most common. Suitable alkyl groups for organic titanates and organic zirconates include, but are not limited to, isopropyl, butyl and ethylhexyl groups.

[0074] Organic chelants can also be used. The chelants can comprise of acetylacetonate, ethyl acetoacetate, lactate, glycolate, and triethanolamine derivatives. Exemplary materials are sold under the Tyzor trademark. (DuPont, Wilmington, DE).

[0075] Zirconium carbonates can also be used, of which ammonium zirconium carbonate is the most common. Ammonium zirconium carbonate is used as a insolubilizer in the paper industry.

[0076] An alternative second component of the retention and drainage system can be a metal salt, including, but not limited to, salts of magnesium, calcium, barium, iron, cobalt, nickel, copper, zinc, aluminum and silicon.
Simple salts consist of positive and negative ions in a structural arrangement that results in the minimum distance between the two ions with maximum shielding of like charges from one another. A given metal salt may be, depending on its composition, soluble or insoluble. Solubility in aqueous media can be affected by temperature, pH, and presence of other materials. The use of soluble salts is preferred.

[0077] The soluble materials can interact with other ionic material in solution, modifying their properties and activity in specific applications.
These species can mediate the activity of another material, acting in many ways, including but not limited to, bridging and neutralizing. The impact of these species may be particularly significant for polyelectrolytes, for the presence of salt ions can dramatically affect the structure of the polymer in solution and its charge density. One example of modifying soluble salts is to produce a soluble metal silicate, as described in US Patents 6,379,501 and 6,358,365. These patents teach the combination of a monovalent cationic silicate and divalent metal ions in an aqueous environment to form a water-soluble metal silicate complex. The complex contains at least one aluminum compound, and at least one water-soluble silicate. The water-soluble silicate can be a monovalent cationic silicate or a water-soluble metal silicate complex. The water-soluble metal silicate complex can be a reaction product of a monovalent cationic silicate and divalent metal ions. The molar ratio of the aluminum compound to the water-soluble silicate, based on A1203 and Si02, is from about 0.1 to 10, preferably from about 0.2 to 5, and more preferably from about 0.5 to 2.

[0078] Examples of inetal salts useful in the present invention include, but are not limited to, metal silicates, ferric (II) chloride, anhydrous FeC13, ZnSO4 4H20, MgCI2 and combinations thereof.

[0079] An alternative second component of the retention and drainage system can be one of several materials based on silicone. For the purpose of this invention, materials can be described by one of the following:
1. "Silicone oil", which refers only to silicone oil comprising primarily polydimethylsiloxane, such as Dow Corning 200 Fluids (Dow Corning Corporation, Midland, Michigan), or General Electric's SF 97 fluids (Wilton, CT).

2. Modified silicone product, such as a grafted or crosslinked silicone polymeric system. An example is the silicone polyether with the following structure:

I I I
(-Si - O - SI - O - Si - O-)n I I I

where X = polyether, such as poly(ethylene glycol), poly(propylene glycol) or copolymers. Many of these modified silicone products have surface active properties and are silicone surfactants.
3. Formulated silicone product. This contains a formulated mixture that comprises one of more silicone oils (as above) and modified silicone products (as above).
4. "Silicone material". This term refers to modified silicone products (as above) and/or formulated silicone product (as above).
5. "Silicone". This term refers to silicone oil and/or modified silicone product (as above) and/or formulated silicone products (as above).

[0080] Exemplary materials include, but are not limited to, silicone polymer, a term originally applied to poly(dimethylsiloxane), poly(phenyl methyl silicone) and poly(tetermethyl tetraphenyisiloxane.

[0081] The second component of the retention and drainage system can be added at amounts up to 10 Kg of active material per metric ton of cellulose pulp based on dry weight of the pulp, with the ratio of the associative polymer to second component being 1:100 to 100:1. It is contemplated that more than one second component can be used in the papermaking system.

[0082] Optionally siliceous materials can be used as an additional component of a retention and drainage aid used in making paper and paperboard.
The siliceous material may be any of the materials selected from the group consisting of silica based particles, silica microgels, amorphous silica, colloidal silica, anionic colloidal silica, silica sols, silica gels, polysilicates, polysilicic acid, and the like. These materials are characterized by the high surface area, high charge density and submicron particle size.

[0083] This group includes stable colloidal dispersion of spherical amorphous silica particles, referred to in the art as silica sols. The term sol refers to a stable colloidal dispersion of spherical amorphous particles. Silica gels are three dimensional silica aggregate chains, each comprising several amorphous silica sol particles, that can also be used in retention and drainage aid systems;
the chains may be linear or branched. Silica sols and gels are prepared by polymerizing monomeric silicic acid into a cyclic structure that result in discrete amorphous silica sols of polysilicic acid. These silica sols can be reacted further to produce three-dimensional gel network. The various silica particles (sols, gels, etc.) can have an overall size of 5-50 nm. Anionic colloidal silica can also be used.

[0084] The siliceous material can be added to the cellulosic suspension in an amount of at least 0.005 Kg per metric ton based on dry weight of the cellulosic suspension. The amount of siliceous material may be as high as 50 Kg per metric ton. Preferably, the amount of siliceous material is from about 0.05 to about 25 Kg per metric ton. Even more preferably the amount of siliceous material is from about 0.25 to about 5.0 Kg per metric ton based on the dry weight of the cellullosic suspension.

[0085] The components of a retention and drainage system may be added substantially simultaneously to the cellulosic suspension. The term retention and drainage system is used here to encompass two or more distinct materials added to the papermaking slurry to provide improved retention and drainage. For instance, the components may be added to the cellulosic suspension separately either at the same stage or dosing point or at different stages or dosing points.
When the components of the inventive system are added simultaneously any two or more of the materials may be added as a blend. The mixture may be formed in-situ by combining any two or more of the materials at the dosing point or in the feed line to the dosing point. Alternatively the inventive system comprises a preformed blend of the any two or more of the materials. In an alternative form of the invention the components of the inventive system are added sequentially. A
shear point may or may not be present between the addition points of the components. The components can be added in any order.

[0086] The inventive system is typically added to the paper process to affect retention and drainage. The inventive system may be added to the thick stock or thin stock, preferably the thin stock. The system may be added at one feed point, or may be split fed such that the inventive system is fed simultaneously to two or more separate feed points. Typical stock addition points include feed points(s) before the fan pump, after the fan pump and before the pressure screen, or after the pressure screen.

[0087] The amount of siliceous material in relationship to the amount of associative polymer copolymer used in the present invention can be about 100:1 to about 1:100 by weight, or from about 50:1 to 1:50 or about 10:1 to 1:10.

[0088] Optionally, an additional component of the retention and drainage aid system can be a conventional flocculant. A conventional flocculant is generally a linear cationic or anionic copolymer of acrylamide. The additional component of the retention and drainage system is added in conjunction with the inorganic material and the associative polymer to provide a multi-component system which improves retention and drainage.

[0089] The conventional flocculant can be an anionic, cationic or non-ionic polymer. The ionic monomers are most often used to make copolymers with a non-ionic monomer such as acrylamide. These polymers can be provided by a variety of synthetic processes including, but not limited to, suspension, dispersion and inverse emulsion polymerization. For the last process, a microemulsion may also be used.

[0090] The co-monomers of the conventional flocculant may be present in any ratio. The resultant copolymer can be non-ionic, cationic, anionic, or amphoteric (contains both cationic and anionic charge.

[0091] Yet other additional components that can be part of the inventive system are aluminum sources such as alum (aluminum sulfate), polyaluminum sulfate, polyaluminum chloride and aluminum chlorohydrate.

EXAMPLES

[0092] To evaluate the performance of the present invention, a series of drainage tests were conducted utilizing a synthetic alkaline furnish. This furnish is prepared from hardwood and softwood dried market lap pulps, and from water and further materials. First, the hardwood and softwood dried market lap pulp are refined separately. These pulps are then combined at a ratio of about 70 percent by weight of hardwood to about 30 percent by weight of softwood in an aqueous medium. The aqueous medium utilized in preparing the furnish comprises a mixture of local hard water and deionized water to a representative hardness.
Inorganic salts are added in amounts so as to provide this medium with a total alkalinity of 75 ppm as CaCO3 and hardness -of 100 ppm as CaCO3. Precipitated calcium carbonate (PCC) is introduced into the pulp furnish at a representative weight percent to provide a final furnish containing 80% fiber and 20% PCC
filler.
The drainage tests were conducted by mixing the furnish with a mechanical mixer at a specified mixer speed, and introducing the various chemical components into the furnish and allowing the individual components to mix for a specified time prior to the addition of the next component. The specific chemical components and dosage levels are described in the data tables. The drainage activity of the invention was determined utilizing the Canadian Standard Freeness (CSF) . The CSF test, a commercially available device (Lorentzen & Wettre, Stockholm, Sweden), can be utilized to determine relative drainage rate or dewatering rate is also known in the art; standard test method (TAPPI Test Procedure T-227) is typical. The CSF device consists of a drainage chamber and a rate measuring funnel, both mounted on a suitable support. The drainage chamber is cylindrical, fitted with a perforated screen plat and a hinged plate on the bottom, and with a vacuum tight hinged lid on the top. The rate-measuring funnel is equipped with a bottom orifice and a side, overflow orifice.

[0093] The CSF drainage tests are conducted with I liter of the furnish.
The furnish is prepared for the described treatment externally from the CSF
device in a square beaker to provide turbulent mixing. Upon completion of the addition of the additives and the mixing sequence, the treated furnish is poured into the drainage chamber, closing the top lid, and them immediately opening the boitom plate. The water is allowed to drain freely into the rate-measuring funnel;
water flow that exceeds that determined by the bottom orifice will overflow through the side orifice and is collected in a graduated cylinder. The values generated are described in milliliters (ml) of filtrate; higher quantitative values represent higher levels of drainage or dewatering.

[0094] The table 1 illustrates the utility of the invention. The test samples were prepared as follows: the furnish prepared as described above, is added, first, 5 Kg of cationic starch (Stalok 400, AE., Staley, Decatur, IL) per metric ton of furnish (dry basis), then 2.5 Kg of alum (aluminum sulfate octadecahydrate obtained from Delta Chemical Corporation, Baltimore, MD as a 50% solution) per metric ton of furnish (dry basis), and then 0.25 Kg of PerForm PC8138 (Hercules Incorporated, Wilmington, DE) per metric ton of furnish (dry basis).

[0095] The additive(s) of interest, as noted in table I were then added in the examples provided in table 1. SP9232 is PerForm SP9232, a retention and drainage aid produced under certain conditions (see PCT WO 03/050152 A), is a product of Hercules Incorporated, Wilmington, DE; zeolite is Valfor CBV, a hydrated alkali aluminum silica (PQ Corporation, Berwyn, PA); clay is Spectrafil@
LA calcined clay (Englehard Corporation, Iselin, NJ); Ti02 is Zopaque RG, an anatase form of titanium dioxide (SCM Glidden, Baltimore, MD); PCC is AlbacarO
5970 precipitated calcium carbonate (Specialty Minerals, Inc., Bethlehem, PA);
PS is Huberfil@ 96 amorphous precipitated silica (JM Huber Corporation, Edison, NJ); and and silica is NP780, a colloidal silica product ( Eka Chemicals, Marietta, GA).

Table 1 Additive(s) Addition CSF Freeness Example of Interest(a) Scheme(b) (ml) 1 None - 464 3 Silica - 641 4 Silica/SP9232 SIM 696 Zeolite - 478 6 Clay - 501 7 Ti02 - 476 Zeolite/SP9232 SIM 657 11 Zeolite/Silica/SP9232 SIM 703 12 Zeolite/SP9232 SEQ 663 13 Zeolite/Silica/SP9232 SEQ 712 14 Clay/SP9232 SIM 657 Clay/Silica/SP9232 SIM 702 16 Clay/SP9232 SEQ 661 17 Clay/Silica/SP9232 SEQ 712 18 Ti02/SP9232 SIM 658 19 Ti02/Silica/SP9232 SIM 702 Ti02/SP9232 SEQ 660 21 Ti 2/Silica/SP9232 SEQ 714 23 PCC/Silica/SP9232 SIM 700 PCC/Silica/SP9232 SEQ 717 27 PS/Silica/SP9232 SIM 711 29 PS/Silica/SP9232 SEQ 713 (a) SP9232 and silica added at a level of 0.25 Kg per metric ton of furnish (dry basis). All other additives used at 5.0 Kg per metric ton of furnish (dry basisl (b) SIM indicates simultaneous addition and SEQ indicates sequential addition [0096] These data indicate that the addition of the inorganic material, when used with PerFormTM SP9232, provide increased drainage. PS provided the largest increase in performance, with clay, PCC and zeolites also showing a large increase in drainage.

[0097] Ti02 showed a significant increase, albeit lower than the others.

[0098] The use of the third component, silica, provides additional benefit.

[0099] Sequential addition is preferred, although large improvements were also observed with simultaneous addition.

[0100] The following materials are used in the examples provided in Table 2. Alum is aluminum sulfate octadecahydrate obtained from Delta Chemical Corporation, Baltimore, MD as 50% solution). PB9007 is PerForm 9007, (Hercules Incorporated, Wilmington, DE) an aluminum chlorohydrate, PB9008 is PerForm@ PB9008, a polyaluminum chloride, SP9232 is PerForm SP9232, a retention and drainage aid produced under certain conditions (see PCT WO
03/050152 Al), PC8138 is PerForm PC8138, a cationic copolymer of polyacrylamide, PA8137 is PerForm PA8137, an anionic copolymer of acrylamide.

[0101] Table 2 provides the CSF drainage of an embodiment of the invention.

RUN # ADD # 2 Kg/MT, as ADD # 3 Kg/MT ADD # 4 Kg/MT CSF
Al (active) (active) I None PC 8138 0.2 SP 9231 0.2 503 2 alum 0.5 PC 8138 0.2 SP 9232 0.2 570 3 PB 9007 0.5 PC 8138 0.2 SP 9232 0.2 648 4 PB 9008 0.5 PC 8138 0.2 SP 9232 0.2 647 alum 1.5 PC 8138 0.2 SP 9232 0.2 638 6 PB 9007 1.5 PC 8138 0.2 SP 9232 0.2 671 7 PB 9008 1.5 PC 8138 0.2 SP 9232 U.2 617 8 alum 2.5 PC 8138 0.2 SP 9232 0.2 659 9 PB 9007 2.5 PC 8138 0.2 SP 9232 0.2 680 PB 9008 2.5 PC 8138 0.2 SP 9232 0.2 682 11 None PA 8137 0.2 SP 9232 0.2 421 12 alum' 0.5 PA 8137 0.2 SP 9232 0.2 504 13 PB 9007 0.5 PA 8137 0.2 SP 9232 0.2 582 14 PB 9008 0.5 PA 8137 0.2 SP 9232 0.2 587 alum 1.5 PA 8137 0.2 SP 9232 0.2 614 16 PB 9007 1.5 PA 8137 0.2 SP 9232 0.2 648 17 PB 9008 1.5 PA 8137 0.2 SP 9232 0.2 649 18 alum 2.5 PA 8137 0.2 SP 9232 0.2 643 19 PB 9007 2.5 PA 8137 02 SP 9232 0.2 673 PB 9008 2.5 PA 8137 0.2 SP 9232 0.2 665 [0102] The data in Table 2 illustrate the improvements in drainage affected by the introduction of an alumina species as a component of the retention and drainage program.

[0103] The test samples in table 3 were prepared as follows: the furnish prepared as described above, is added, first, 5 Kg. of cationic starch (Stalok 400, AE., Staley, Decatur, IL) per ton of furnish (dry basis), then 2.5 Kg of alum (aluminum sulfate octadecahydrate obtained from Delta Chemical Corporation, Baltimore, MD as a 50% solution) per metric ton of furnish (dry basis), and then 0.25 Kg of PerForm PC8138 (Hercules Incorporated, Wilmington, DE) per metric ton of furnish (dry basis). The additive(s) of interest, as noted in the table were then added in the examples provided in the table. SP9232 is PerForm SP9232, a retention and drainage aid produced under certain conditions (see PCT WO
03/050152 A), is a product of Hercules Incorporated, Wilmington, DE; silica is BMA 780 colloidal silica, a product of Eka Chemicals, Marietta, GA, and AZC is ammonium zirconium carbonate (Aldrich Chemicals, Milwaukee, WI).

[0104] The data in Table 3 demonstrate the impact of AZC on drainage.

Table 3 Addtive(s) Additiion CSF Fmene5s Exanoe af In6mee) SdhMM(b) (ml) 1 None - 430 2 Spg232 - 654 3 51'lica - 606 6 AZC1SiIica/SP9232 SIM 680 8 AZCJS1Iica1SP9232 SEQ 683 (a) SP9232 and silica added at a level of 0.25 Kg per metric ton of furnish (dry basis) and AZC is added at a level of 0.5 Kg per metric ton of furnish (dry basis) (b) SIM indicates simultaneous addition and SEQ indicates sequential addition [0105] The test samples in table 4 were prepared as follows: the furnish prepared as described above, is added, first, 5 Kg of cationic starch (Stalok 400, A.E. Staley, Decatur, IL) per metric ton of furnish (dry basis), then 0.25 Kg of alum (aluminum sulfate octadecahydrate obtained from Delta Chemical Corporation, Baltimore, MD as a 50% solution) per metric ton of furnish (dry basis), and then 0.25 Kg of PerForm PC8138 (Hercules Incorporated, Wilmington, DE) per metric ton of furnish (dry basis). The additive(s) of interest, as noted in the table were then added in the examples provided in the table.
SP9232 is PerForm SP9232, a retention and drainage aid produced under certain conditions (see PCT WO 03/050152 A), is a product of Hercules Incorporated, Wilmington, DE; silica is NP780 colloidal silica, a product of Eka Chemicals, Marietta, GA; metal silicates are a mixture of PerForm@ ( PM 9026 and PM 9028 metal silicates, a product of Hercules Incorporated, Wilmington, DE, Ferric (II) is ferric (II) chloride, obtained from Aldrich Chemical, Milwaukee, WI.
Ferric (III) is anhydrous FeCI3, a product of Fisher Scientific, Hampton, NH.
Zn salt is ZnSO4. 4H20 (zinc sulfate, a product of Aldrich, Milwaukee, WI; Mg salt is MgCI2.6H20 (magnesium chloride, a product of Spectrum Chemical, Gardena, CA).

Additive(s) Addition CSF Freeness Example of lnterest(a) Scheme(b) (ml) 1 None - 435 3 Silica - 606 4 Silicate - 568 Ferric II - 437 6 Ferric III - 494 7 Zn Salt - 436 8 M Salt - 426 9 Silicate/SP9232 SIM 666 Silica/SP9232 SIM 675 11 Silicate/Silica/SP9232 SIM 697 12 Silica/SP9232 SEQ 662 13 Silicate/Silica/SP9232 SEQ 694 14 Ferric II /SP9232 SIM 618 Ferric II /Silica/SP9232 SIM 678 16 Ferric II /SP9232 SEQ 625 17 Ferric II /Silica/SP9232 SEQ 674 18 Ferric III /SP9232 SIM 614 19 Ferric III /Silica/SP9232 SIM 680 Ferric III /SP9232 SEQ 621 21 Ferric III /Silica/SP9232 SEQ 688 22 Zn Salt/SP9232 SIM 620 23 Zn Sait/Silica/SP9232 SIM 676 24 Zn Salt/SP9232 SEQ 626 Zn Salt/Silica/SP9232 SEQ 695 26 Mg Salt/SP9232 SIM 632 27 Mg Salt/Silica/SP9232 SIM 672 28 Mg Salt/SP9232 SEQ 631 29 Mg Salt/Silica/SP9232 SEQ 689 (a) SP9232 and silica are added at a level of 0.25 Kg per metric ton of furnish (dry basis).
All other materials are added at a level of 0.5 Kg per metric ton of furnish (dry basis).

SIM indicates simultaneous addition and SEQ indicates sequential addition.

[0106] These data in table 4 indicate that the metal salts have a synergistic effect on the ability of PerForm SP9232 to enhance drainage. The addition of the optional third component has an additional impact.

[0107] The test samples in table 5 were prepared as follows: the furnish prepared as described above, is added, first, 5 Kg of cationic starch (Stalok@
400, AE., Staley, Decatur, IL) per metric ton of furnish (dry basis), then 2.5 Kg of alum (aluminum sulfate octadecahydrate obtained from Delta Chemical Corporation, Baltimore, MD as a 50% solution) per metric ton of furnish (dry basis), and then 0.25 Kg of PerForm PC8138 (Hercules Incorporated, Wilmington, DE) per metric ton of furnish (dry basis). The silicone materials, as noted in the table, were then added in the examples provided in the table. SP9232 is PerForm SP9232, a retention and drainage aid produced under certain conditions (see PCT WO
03/050152 A), is a product of Hercules Incorporated, Wilmington, DE; silica is BMA 780 colloidal silica (Eka Chemical, Marietta, GA): and silicone is Dow Corning 200 Silicone oil (Dow Corning, Midland, Ml):
Table 5 Addition CSF Freeness Example Additive(s)(a) Scheme(b) (mi) 2 Silicone - 465 3 Silicone/SP9232 SIM 643 4 Silicone/Silica/SP9232 SIM 707 Silicone/SP9232 SEQ 658 6 Silicone/Silica/SP9232 SEQ 712 (a) SP9232 and silica are added at a level of 0.25 Kg per metric ton of furnish (dry basis) and silicone is added at a level of 0.5 Kg per metric ton of furnish (dry basis) (b) SIM indicates simultaneous addition and SEQ indicates sequential addition

Claims (15)

1. A method of improving retention and drainage in a papermaking process wherein the improvement comprising adding to a papermaking slurry, an associative polymer and at least one inorganic particle, wherein the associative polymer comprising the formula:

~B-co-F~ (I) wherein B is a nonionic polymer segment comprising one or more ethylenically unsaturated nonionic monomers; F is an polymer segment comprising at least one ethylenically unsaturated anionic or cationic monomer; and the molar percent ratio of B:F is 99:1 to 1:99 and wherein the associative polymer has associative properties provided by an effective amount of at least emulsification surfactant chosen from diblock or triblock polymeric surfactants, and wherein the amount of the at least one diblock or triblock surfactant to monomer is at least about 3:10.

2. The method in claim 1 where the at least one inorganic particle is selected from the group consisting of clay, swellable clays, calcium carbonate, talc, titanium dioxide, aluminosilicates, diatomaceous silica, calcium sulfate, zinc oxide, zeolites and combinations thereof.

3. The method of claim 2 wherein the at least one inorganic particle is selected from the group consisting of aluminosilicates, diatomaceous silica, calcium sulfate, zinc oxide and combinations thereof.

4. The method of claim 1 further comprising a siliceous material.

5. The method of claim 4 wherein the siliceous material is selected from the group consisting of silica based particles, silica microgels, amorphous silica, colloidal silica, anionic colloidal silica, silica sols, silica gels, polysilicates, polysilicic acid, and combinations thereof.

6. The method of claim 1 wherein the inorganic particle and associative polymer are added to the papermaking slurry as a blend, simultaneously or sequentially.

7. The method of claim 1 wherein the associative polymer is anionic.

8. The method of claim 1 wherein non-ionic monomer comprises acrylamide and the anionic monomer comprises a free acid or salt of acrylic acid.

9. The method of claim 1 wherein the associative polymer is cationic.

10. The method of claim 1 wherein the associative polymer comprises both anionic and cationic monomers.

11. A composition comprising an associative polymer and at least one inorganic particle wherein the associative polymer comprising the formula:

~B-co-F-] (I) wherein B is a nonionic polymer segment comprising one or more ethylenically unsaturated nonionic monomers; F is an polymer segment comprising at least one ethylenically unsaturated anionic or cationic monomer; and the molar percent ratio of B:F is 99:1 to 1:99 and wherein the associative polymer has associative properties provided by an effective amount of at least emulsification surfactant chosen from diblock or triblock polymeric surfactants, and wherein the amount of the at least one diblock or triblock surfactant to monomer is at least about 3:10.

12. The composition of claim 11 further comprising cellulosic fiber.

13. The composition of claim 11 further comprising a siliceous material.

14. The method in claim 11 where the at least one inorganic particle is selected from the group consisting of clay, swellable clays, calcium carbonate, talc, titanium dioxide, aluminosilicates, diatomaceous silica, calcium sulfate, zinc oxide, zeolites and combinations thereof.

15. The method of claim 14 wherein the at least one inorganic particle is selected from the group consisting of aluminosilicates, diatomaceous silica, calcium sulfate, zinc oxide and combinations thereof.