MX2007006434A - Retention and drainage aids - Google Patents

Abstract

The present invention describes polymeric retention and drainage aids for cellulosic fiber compositions and methods of use of the same.

Description

RETENTION AND DRAINAGE AID REFERENCE TO RELATED REQUESTS This application claims the benefit of US Provisional Application No. 60 / 636,448, filed on December 14, 2004, the complete contents of which are incorporated herein by reference FIELD OF THE INVENTION The present invention relates generally to cellulosic fiber compositions, and particularly to polymeric retention and drainage aids. BACKGROUND OF THE INVENTION Making sheets of cellulosic fiber, particularly paper and board, includes producing an aqueous suspension of cellulosic fiber, depositing this fiber in a wire or mobile papermaking fabric, and forming a sheet of the solid components of the suspension by draining Water. The suspension may also contain inorganic mineral extenders or pigments. Also, organic and inorganic chemicals are often added to the slurry prior to the papering step to make the papermaking method less costly, faster and / or to achieve specific properties in the final paper product. After draining, the sheet is pressed and dried to further remove water. The paper industry is currently struggling to improve paper quality, increase productivity, and reduce manufacturing costs. Chemicals are added frequently before they reach the wire or papermaking fabric, to improve the method of drainage / dewatering and solids retention. These chemicals are called retention and / or drainage aids. Drainage or dehydration of the fibrous suspension in the wire or papermaking fabric is often the limiting step in achieving faster method speeds. Improved dehydration can also result in a dry sheet in the press and dryer sections, thus requiring less energy. Asymmetries, this step in the papermaking method determines many final sheet properties. Regarding the retention of solids, the retention aids of papermaking are used to increase the retention of fine retention solids in a web during the turbulent method of draining and forming the paper web. Without adequate retention of fine solids, they are lost to the method effluent or accumulate at high levels in the recirculating white water circuit, potentially causing deposit buildup. Additionally, insufficient retention increases the cost of papermakers due to the loss of additives intended to be adsorbed on the fiber to provide the opacity, strength or paper sizing property. It is desirable to develop new retention and drainage aids. The present invention is directed to these, as well as to other important purposes. BRIEF COMPENDI OF THE INVENTION In one embodiment, the present invention includes water-compatible (water-soluble or water-dispersible) polymers comprising a polymer segment formed from at least one ethylenically unsaturated (A) monomer, substituted with at least one group aryl and at least one fraction S (= 0)) 20Ri u -OS (= 0) 2 (0) pRi is independently of each occurrence, H, alkyl, aryl, or a cation, and the polymer has an average molecular weight by weight of around 5 million or more. Preferably, these polymers are anionic. These water-compatible polymers provide remarkable retention and drainage activity in cellulosic fiber compositions. In another embodiment, the present invention includes said polymers compatible with water and cellulose fiber. DETAILED DESCRIPTION OF THE INVENTION In one embodiment, the present invention includes a water compatible polymer, comprising a polymer segment formed from at least one ethylenically unsaturated monomer (A) substituted by at least one aryl group and at least one moiety - S (= 0) 20Ri u -OS (= 0) 2 (0) pRi, where p is 0 or 1, Rx is, independently of each occurrence, H, alkyl, aryl, or a cation, and the polymer has a weight average molecular weight of about 5 million or greater. In some preferred embodiments, the water compatible polymer is anionic. Examples of acceptable cations include Na +, K +, Li +, NH 4 +, or alkyl-NH 3 +, but preferably the cation is sodium or ammonium. It is understood that the requirement that A be substituted with at least one aryl group is at least a fraction of -S (= 0) 20Ri or -OS (= 0) 2 (0) pRi means that the ethylene fraction must to be directly substituted with both the aryl and the fraction -S (= 0) 20Ri or -OS (= 0) 2 (0) pRi (e.g., Formula IA below). This arrangement is a part of the present invention, however A is also intended to include embodiments wherein the aryl is attached to the ethylene fraction, and the fraction -S (= 0) 20Ri or -OS (= 0) 2 ( 0) pRi is fixed to the aryl (see, e.g., Formula I below). Also, the requirement for the presence of an aryl group can be met by embodiments wherein Ri is aryl (see, e.g., Formula IB below). Examples of monomer A include, but are not limited to, the free acids or salts of: styrenesulfonic acid, vinyltoluenesulfonic acid, α-methylstyrene sulfonic acid, anetolsulfonic acid, vinylphenylsulfuric acid, 4-sulfonate N-benzylacrylamide, 4-N-phenylacrylamide. -sulfonate, vinylpirenesulfonic acid, vinylantransulphonic acid, or vinylpyridiniumpropane sulfonate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), or vinylsufonic acid and mixtures thereof. In a preferred embodiment, monomer A is a free acid or salt of the above compounds. In an additional mode, A has Formula I: wherein Ri is a cation such as Na +, K +, Li +, NH, O 6 NH 3 +, and R 3, R 4 and R 5 are, independently H or alkyl. In formula I, the -SO3R1 groups may be in the ortho, meta or para position. In some embodiments, monomer A comprises a styrenesulfonic acid salt. Preferably the salt is sodium or ammonium salt.

Alternatively, an additional modality has the formula IA or IB: IA IB wherein: Ri is a cation such as Na +, K +, Li +, NH +, or R5NH3 +; and R3 and R4 are, independently, H or alkyl, and Ar is aryl. It can be readily appreciated that the polymers of the present invention can be homopolymers, ie, fully comprised of polymer segments formed of ethylenically unsaturated monomer A. A preferred homopolymer includes polymer segments having the Formula II: where: Ri is a cation such as Na +, K +, Li +. NH4 +, or R5NH3 +; and R3, 4 and R5 are, independently, H or alkyl. In formula II, the -SO3R1 groups may be in the ortho, meta or para position. In some preferred embodiments, Ri is Na +. In another embodiment, the present invention encompasses copolymers that include polymer segments of different monomers A, as described herein. In another embodiment, the present invention also encompasses copolymers that include monomer A polymer segments and a polymer segment formed from at least one anionic or nonionic ethylenically unsaturated monomer (B). It is understood that the term copolymer is intended to be limitative, and includes all possible monomer sequences involving a and B, include random, block and alternating sequences. Examples of monomer B include, but are not limited to, acrylamide, methacrylamide, N-alkyl acrylamide, N-methylarylamide, N, N-dialkylacrylamide, NB, N-dimethylacrylamide, acrylonitrile, N-vinylmethacetamide, N-vinylformamide, N-vinylmethylformamide. , N-vinylpyrrolidone, styrene, butadienevinyl acetate, methyl acrylate, methyl methacrylate, alkyl acrylate, alkyl ratacrilate, alkylacrylamide, alkoxylated acrylate, methacrylate, alkylpolyethylene glycol acrylate, alkylpolyethylene glycol methacrylate, acid free salt of: acid (meth) acridium, maleic acid, furmalic acid, itaconic acid, acrylamido glycolic acid, or mixtures thereof. While any anionic or nonionic monomer that allows the polymer to remain compatible with water is preferably contemplated, monomer B is acrylamide, acrylic acid or an acrylic acid salt. Examples of suitable salts include those having Na +, K +, Li +, NH +, or R5NH3 +, but preferably the salt is a sodium or ammonium salt. In one embodiment, the molar ratio of A: B is from about 5:95 to about 100: 0. In another embodiment, the molar ratio of A_B is from about 20:80 to about 100: 0. in another embodiment, the molar ratio of A: B is from about 30:70 to about 100: 0. A preferred embodiment includes copolymers wherein monomer A comprises a sodium or ammonium salt of styrenesulfonic acid and the monomer B is acrylamide. A preferred polymer of such embodiments includes polymer segments having the Formula II and Formula II, respectively.

In some preferred embodiments, Ri is Na. Another preferred embodiment includes copolymers wherein monomer A comprises a sodium or ammonium salt of styrenesulfonic acid and monomer B is an acrylic acid salt. A preferred polymer of such embodiments includes polymer segments having the Formula II and Formula IV, respectively: Formula IV Where Ri is a cation such as Na +, K +, Li +, NH4 +, or R5NH3 +. In a preferred embodiment, R1 is Na +. In another embodiment of the present invention, the cellulosic fiber composition is provided comprising cellulose fiber and one or more of any of the polymers described above. In some embodiments the cellulose fiber comprises a pulp suspension, in other embodiments, the cellulose fiber comprises paper or cardboard. The cellulosic fiber compositions are typically aqueous suspensions, and thus, in those embodiments, the cellulosic fiber compositions further comprise water. Optionally, the cellulosic fiber composition may further comprise at least one of inorganic mineral extenders, pigments, sizing agents, starches, deposit control agents, fillers, opacifying agents, optical brighteners, strength agents, organic or inorganic coagulants, and conventional flocculants. In another embodiment of the present invention, there is provided a method for preparing a cellulosic fiber composition, the method comprising adding one or more of any of the polymers described above to an aqueous cellulosic fiber suspension. In another embodiment of the present invention, there is provided a method for oving drainage and retention of solids in a cellulosic fiber composition, the method comprising adding one or more of any of the above-described polymers to the cellulosic fiber composition. As used herein, the term "alkyl" includes both branched and straight chain, saturated aliphatic hydrocarbon groups having a specified number of carbon atoms, e.g., methyl (Me), ethyl (Et), propyl (Pr), isopropyl (i-Pr), isobutyl (i-Bu), secbutyl (s-Bu), tertbutyl (t-Bu), isopentyl, isohexyl and the like. When any of the above substituents has or contains an alkyl substituent group, it may be linear or branched and may contain up to 12 carbon atoms, preferably up to 6 carbon atoms, more preferably 1 or 2 carbon atoms. The term "aryl" means an aromatic carbocyclic moiety of up to 20 carbon atoms, which may be a single ring (monocyclic) or multiple rings (polycyclic, up to three rings) fused together or covalently linked. Any appropriate ring position of the aryl moiety can be covalently linked to the defined chemical structure. Examples of aryl moieties include, but are not limited to, chemical groups such as phenyl, 1-naphthyl, 2-naphthyl, dihydronaphthyl, tetrahydronaphthyl, biphenyl, pyrenyl, anthryl, phenanthryl, fluoroenyl, indanyl, biphenylenyl, acenaphtenyl, acenaphthylenyl, and the similar. It is understood that the claims encompass all possible stereoisomers, tautomers, salts and proformas. In addition, unless otherwise stated, each alkyl and aryl is contemplated as being optionally substituted. An optionally substituted moiety can be substituted with one or more substituents. Substituent groups that are optionally present by one or more of those employed in a customary manner. Specific examples of such substituents include halogen, nitro, cyano, thiocyanate, cyanate, hydroxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, amino, alkylamino, dialkylamino, formyl, alkoxycarbonyl, carboxyl, alkanoyl, alkylthio, alkylsulfinyl, slkylsulfonyl, carbamoyl, alkylamido. , phenyl, phenoxy, benzyl, benzyloxy, heterocyclyl or cycloalkyl groups, preferably halogen atoms or lower alkyl or lower alkoxy groups, Typically 0-4 substituents may be present. The polymers (both homopolymers and copolymers) of the present invention are preferably unbranched or crosslinked polymers. For example, preferably no branching or crosslinking agents are used in the preparation. The making of sheets of cellulosic fiber, particularly paper and cardboard, includes producing an aqueous suspension of cellulosic fiber, which may also contain inorganic mineral extenders or pigments.; depositing this suspension on a wire or mobile papermaking fabric; and forming a sheet of the solid components of the suspension by draining the water. The present invention provides a cellulosic fiber composition comprising cellulose fiber and the polymers of the present invention. The present invention also provides a method for making the cellulosic fiber composition comprising the step of adding the polymers of the present invention to a cellulosic suspension or cellulose pulp suspension. The polymers of the invention can be used in papermaking systems and proces and are particularly useful as drainage and retention aids. As noted above, in commercial papermaking, a suspension of cellulosic fibers or pulp is deposited on a mobile papermaking wire or fabric. The suspension may contain other chemicals, such as sizing agents, starches, deposit control agents, mineral spreaders, pigments, fillers, opacifying agents, optical brighteners, organic or inorganic coagulants, conventional flocculants, or other additives common to pulp. paper. As the water in the deposited suspension is removed, the sheet is formed. Ordinarily, the sheets are then pressed and dried to form paper or cardboard. The polymers of the invention are preferably added as it reaches the wire to improve drainage or dehydration and retention of fiber fines and fillers in the suspension. Suitable cellulosic fiber pulps that can be employed for the methods of the invention include conventional papermaking material such as traditional chemical pulp. For example, bleached and unbleached sulphate pulp and sulphite pulp, mechanical pulp such as ground wood, thermomechanical pulp, quimi-thermomechanical pulp, recycled pulp such as co-rounded containers, newspaper, office waste, magazine paper and other waste not de-inking, de-inking and mixtures thereof can be used. The currently described polymer is typically diluted at the application site to produce an aqueous solution of about 0.01 to about 1% active polymer and then added to the paper process to affect retention and drainage. The currently described polymer can be added to the coarse material or thin material, preferably the thin material. The polymer can be added at a feed point, or it can be fed divided so that the polymer is fed simultaneously at two or more separate feed points. Typical material addition points include supply point (s) before the fan pump, after the fan pump and before the pressure screen, or after the pressure display.

The presently described polymer is preferably used in a proportion of about 0.0045 g (0.01 Ib) to about 4.536 kg (10 pounds) of active polymer per ton of cellulose pulp, based on the dry weight of the pulp. The polymer concentration is more preferably from about 0.023 g (0.05 Ib) to about 2268 kg (5 Ib) of active polymer per ton of dry cellulose pulp. The polymerization of aromatic, high molecular weight, anionic, water soluble or water dispersible sulfonated polymers can be carried out in any manner known to those skilled in the art, for example see Allcock and Lampe, Contemporary Polymer chemistry (Englewood Cliffs, New Jersey, PRENTICE-HALL, 1981), chapters 3-5. The polymers can be produced through inverse emulsion polymerization, solution polymerization, suspension polymerization, precipitation polymerization, etc. The polymers can also be produced through sulfonation of an original polystyrene, wherein a non-ionic polystyrene polymer, insoluble in water, is sulfonated to a polystyrene sulfonate. Examples of these reactions include the use of a number of sulfonation reagents, including but not limited to sulfur trioxide (S03), sulfur trioxide with triethyl phosphate, acetyl sulfate (produced in situ by mixing concentrated sulfuric acid with acetic anhydride. chlorosulfonic acid, and the like. Any of the chain transfer agents known to those skilled in the art can also be used to control molecular weight. These include, but are not limited to, lower alkyl alcohols such as isopropanol, amines, mercaptans such as mercaptoethanol, phosphites, thioacids, allyl alcohol, and the like. It should be understood that the aforementioned polymerization methods do not limit in any way the synthesis of the polymers according to the invention. In another embodiment, a method for making the polymers described above is described in the copending US patent application Serial No. 11 / 012,010, filed on December 14, 2004, the entire disclosure of which is incorporated herein by reference . The present compounds are further described in the following examples. EXAMPLES Example 1 To an appropriate reaction flask equipped with an overhead mechanical stirrer, thermometer, nitrogen spray tube, and condenser was charged a paraffin oil oil phase (139.0 g ESQUIAD® 110 oil; ExxonMobil - Houston, TX) and surfactants (3.75 g of CIRRASOL® G-1086 and 11.25 g of SPAN® 80, both from Uniqema-New Castle, DE). The aqueous phase was prepared separately, comprising 50% by weight of acrylamide solution in water (51.1 g, 50 mole% based on the total monomer), styrenesulfonic acid, sodium salt powder (74.44 g (50 mole% based on total monomer), deionized water (218.47 g), and VERSENEX® 80 chelation solution (Dow Chemical, Midland, MI) 0.47 g). The aqueous phase was heated to about 35-45 ° C to dissolve the monomers. The pH of the aqueous solution varies from 9-11. The aqueous phase was then charged to the oil phase while mixing simultaneously with a homogenizer to obtain a stable water-in-oil emulsion. This emulsion is then mixed with a curtain-glass stirrer 4 while being sprayed with nitrogen for 60 minutes. During the nitrogen sparge, the temperature of the emulsion was adjusted to 57 + 1 ° C. Subsequently, the spray was discontinued and a blanket of nitrogen was applied. Polymerization was initiated by feeding a solution of 3% by weight of AIBN in toluene corresponding to an initial AIBN load of 75 ppm on a molar basis of total monomer. Four hours after loading Initial AIBN, a solution of 3% by weight AIBN in toluene corresponding to a second load of 75 ppm AIBN on a total molar monomer base, it was charged to the reactor for - 30 seconds and heated to 65 + 1 ° C and retained for about 0.5 hours. The batch was then cooled to room temperature and the product was collected. Optionally, a breaker surfactant is added to the polymeric reverse emulsion to improve the inversion of the emulsion when it is added to water. Examples 2-7 The polymer preparation was conducted according to the method of Example 1, except for the changes provided in Table 1. TABLE 1 Example Composition Molar Mw, g / mol (106) 1 50% NaSS / 50% AM 10 2 30% NaSS / 70% AM 8.7 3 50% NaSS / 50% AM 25.9 4 70% NaSS / 30% AM 10 5 70% NaSS / 30% AM 11.8 6 100% NaSS 7.0 7 100% NaSS 5.4 Molecular weight Weight average Mw was determined by multi-angle laser light scattering per batch (MALLS) using an Interferometric Damp DSP Laser PSP Refractometer (yatt Technology, Santa Barbara, CA). In the MALLS batch mode, several concentrations of polymer solution in 1 M NaNC were analyzed in order to extrapolate the light scattering and the refractive index data at very low scattering angles and concentrations. Zimm traces were then constructed, using the light scattering data of various polymer concentrations and detection angles, to obtain the weight average molecular weight M2. The method for determining the absolute weight average molecular weight Ms is light scattering. While size exclusion chromatography (SEC) or gel permeation chromatography (GPC) can also provide a weight average molecular weight Mw, this is a relative determination of M "based on the comparison of the tested polymer with the standards of molecular weight of polymer. Light scattering is the only method described herein to determine the weight average molecular weight M2 The weight average molecular weight Mw was determined as above for a number of comparative polymers also, listed in Table 2. TABLE 2 Polymer Composition Molar M ", g / mol (105) VERSA® TL-501 100% NaSS 1.7 SP2 - # 625 100% NaSS 0.26 * SP2 - # 626 100% NaSS 0.51 * EM 1030 Na 100% NaAc 6.4 AN 132 32% AMPS / 68% AM 3.7 EM 1010 100% AMPS 9.4 * MX reported by determined provider of light scattering. VERSA® TL-501 is a (sodium salt of poly (styrenesulfonate), commercially available from Aleo Chemicals (Chattanooga, TN) as an aqueous solution. SP2 product numbers 625 and 626 are molecular weight standards of poly (solid salt of styrenesulfonate), available from Scientific Polymer Products (Notary, NY) as dry powders, EM 1030 Na is a poly (sodium acrylate) commercially available from SNF Floerger (Riceboro GA) as a reversed, self-reversing emulsion. is a poly (acrylamide-co-2-acrylamido-2-methyl propansulphonic acid) at 32:68 mole% of SNF Floerger as a dry powder EM 1010 is pol (2-acrylamido-2-methyl-propanesulfonic acid, sodium salt) Available from SNF Floerger as a reversal, self-inverting emulsion NaSS - sodium styrenesulfonate AM - acrylamide NaAc - sodium acrylate AMPS - 2-acrylamido-2-methyl-propanesulfonic acid, sodium salt Mw - weight average molecular weight determined by laser light scattering of m multiple angles (MALLS) techniques paper sheet formation and retention chemistry is well known in the art. For example, see Handbook for Pulp and Paper Technologist, ed. G.A. Smook (Atlanta, GA, TAPPI Press, 1989), and PULP AND PAPER, Chemistry and Chemical Technology, 3rd edition, ed. J.P. Casey, (New York, Wiley-Interscience, 1981). To evaluate the performance of the examples of the present invention, a series of drainage experiments were conducted using the Dynamic Drain Analyzer (DDA). The currently described and comparative polymers were compared to NP 780 (Eka Chemicals, Marietta, GA), an inorganic silica drainage aid commonly dominated in the industry as a "microparticle". Unless it manifests otherwise, all percentages, parts, etc. , are in weight. The DDA (AB Akribi Kemikonsulter, Sundsvall, Sucia) is known in the industry. The unit consists of a mixer jar with partitions, a vacuum vessel, and a control box equipped with electronic and pneumatic controls. The DDA will measure the time of drainage, retention, and wet leaf permeability of a pulp supply. In the operation of the DDA, a slurry of pulp is added to the mixing chamber. At the start of the test, a mechanical stirrer will start mixing at a specified speed. The various additives are added to the mixing chamber at specified interval times. At the end of the mixing, a vacuum of 300 mbar is applied to the tank under the mixing chamber, draining the suspension and collecting the filtrate in the vacuum vessel. The supply will continue to drain until the vario is interrupted through the provision, and a wet mat is formed, analogous to the wet line in a paper machine. The vacuum will then continue to operate until a specified time after the mat is formed. The DDA drainage time is assigned as the vacuum run time, where the vacuum decreases from the 300 mbar applied level. The leaf permeability is the equilibrium vacuum of the wet mat at the end of the test. A shorter drainage time in seconds is a more desired response, since the pulp will dehydrate more easily. An upper sheet permeability is desired, since this is an indication of the degree of flocculation of the wet mat formed. Low permeability indicates an undesirable high degree of flocculation, resulting in large lumps that would not easily release interstitial water. This type of crumb would not easily dehydrate in a paper machine in the press and drying sections. A low permeability could also result in low printing capacity and cost capacity of the resulting formed sheet. When comparing different systems, a lower drainage time in combination with a superior leaf permeability is the desired response. The provision used in this series of tests was a mechanical, acid pH, synthetic supply. This provision is prepared from coated and uncoated damaged paper obtained from a paper mill in the south of the USA. The coated and uncoated damaged paper is dispersed in water using a TAPPI disintegrator (Testing Machines Inc., Amityville, NY). The water used in preparing the supply comprises a mixture of 3 parts of deionized water to 1 part of local hard water, further modified with 0.075% sodium sulfate and 0.0025% Slendid® 100 pectin gum (CP Kelco, Atlanta, GA ). The pH of the supply is adjusted to 4.5. The DDA drainage tests were conducted with 500 ml of the synthetic supply, which has a total solids concentration of 0.5%. The test is conducted at 1, 600 rpm with the sequential addition of a cationic starch, followed by a cationic coagulant, followed by polymer flocculant, followed by drainage aid; the materials are all mixed at the specified interval times. After the drainage aid has been introduced and mixed, the drainage test is conducted. The cationic starch is added to a level of 4.536 kg (10 pounds) per ton of dry provision. The cationic coagulant is added to a level of 453.6 grams (1 pound) of active coagulant per ton of dry supply. The polymer flocculant is added at a level of 226 g (0.5 lbs) per ton of dry supply. The doses of the drainage aids are in pounds of active drainage aid per ton of dry supply, with the specific doses noted in the data tables. In DDA drainage tests, the cationic starch used is STALOK® 400 potato starch (A.e. Staley, Decatur, IL). The cationic coagulant is a branched epichlorohydrin-dimethylamine condensation polymer sold under the trademark PERFORM® PC 1279 (Hercules, ILMINGTON, DE). The cationic flocculant is an acrylamide / acryloyloxyethyltrimethylammonium chloride, 90/10 mol%, sold under the trademark PERFORM® PC8715 (Hercules, Wilmington, DE), commercially available as a dry povo. The results of the DDA drainage masses are shown in Table 3 below. TABLE 3 Test Description Help of # / T (ac- Permeate time- DRAINAGE / DRAIN) Drain lity Polymer (s) sheet (mbar 3-1 none 0 22.5 228 3-2 Conventional NP 780 0.5 21.1 230 3-3 Conventional NP 780 1 19.1 232 3-4 Conventional NP 780 1.5 18.1 237 3-5 Example 2 33618-52 0.3 24.6 232 3-6 Example 2 33618-52 0.6 22.9 230 3-7 Example 2 33618-52 0.9 21.4 229 3-8 Example 1 33651-7 0.3 22.9 232 3-9 Example 1 33651-7 0.6 19.9 229 3-10 Example 1 33651-7 0.9 17.7 229 3-11 Example 4 33651-37 0.3 22.1 230 3-12 Example 4 33651-37 0.6 18.7 227 3-13 Example 4 33651-37 0.9 15.5 222 3-14 Example 6 33632-10 0.3 20.5 233 3-15 Example 6 33632-10 0.6 17.6 236 3-16 Example 6 33632-10 0.9 15.9 243 3-17 Comparative EM 1030 Na 0.3 24.7 237 3-18 Comparative EM 1030 Na 0.6 23.6 242 3-19 Comparative EM 1030 Na 0.9 23.0 248 3-20 Comparative AN 132 0.3 24.4 230 3-21 Comparative AN 132 0.6 24.8 237 3-22 Comparative AN132 0.9 24 245 3-23 Comparative EM 1010 0.3 23.6 237 3-24 Comparative EM 1010 0.6 21.6 243 3-25 Comparative EM 1010 0.9 20.7 251 The data set forth in Table 3 illustrate the drainage activity of the aromatic, anionic sulfonated polymers of the present invention compared to the results obtained with carboxylated and aliphatic sulfonated polymers. The polymers in tests 8 to 16 with 50%, 70% and 100% NaSS polymers improve the drainage time compared to the cationic flocculant alone, without affecting the leaf permeability. The EM 1030 Na, EM 1010 and AN 132 did not improve drainage on the control program of the cationic flocculant alone. Contrary to expectations, the data herein demonstrate that the sulfonated, aromatic, high molecular weight anionic polymers of the present invention are far superior to affect retention and drainage, that the aliphatic sulfonated polymers and carboxylated polymers provide no comparative improvement. with the control not treated. A second series of drainage tests were carried out with mechanical, acidic pH, synthetic provision, using the DDA.

TABLE 4 Test Description Help of # / T (ac-) Permeate time- Drainage tivo) Drain of the sheet (mbar) 4-1 none 0 24.1 237 4-2 Conventional NP 780 0.5 23.2 237 4-3 Conventional NP 780 1 20.2 237 4-4 Conventional NP 780 1.5 18.5 236 4-5 Comparative SP2 - # 625 0.3 23.8 240 4-6 Comparative SP2 - # 625 0.6 21.3 248 4-7 Comparative SP2 - # 625 0.9 20.8 257 4-8 Comparative SP2 - # 626 0.3 23.3 241 4-9 Comparative SP2 - # 626 0.6 20.6 249 4-10 Comparative SP2 - 626 0.9 20.1 256 4-11 7 33562-88 0.3 23.0 240 4-12 7 33562- 0.6 19.6 241 4-13 7 33562-í 0.9 17.1 242 4-14 33651-37 0.3 23.4 240 4-15 33651-37 0.6 19.3 233 4-16 33651-37 0.9 16.4 231 The data in Table 4 show that polymers of Mw greater than 5 million provided good drainage activity, exceeding that provided by NP 780 at lower profutive doses. PSS homopolymers possessing M "of 220,000 and 510,000 provided minimal drainage activity compared to the polymers currently described with Mw greater than 5 million, and demonstrate the requirement of M2 greater than 5 million to affect drainage performance. This result is unexpected. A series of drainage tests were also conducted using a vacuum drain test (VDT) with a free supply of wood, acid, synthetic pH; the data is shown in table 4. The device installation is similar to the Buchner funnel test as described in various retention reference books for example see Chemical Engineers' Handbook by Perry, 7th edition (McGraw-Hill, New York , 1999) p. 18-78. The VDT consists of a 300 ml magnetic Gelman filter funnel, a 250 ml graduated cylinder, a quick disconnect, a water trap, and a vacuum pump with a vacuum gauge and regulator. The VDT test is conducted by first adjusting the vacuum to the desired level, typically 25.4 cm Hg (10 inches), and placing the funnel appropriately in the cylinder. Then 250 g of 0.5% by weight paper material is loaded into a weighted beaker and then the additives required in accordance with the treatment program (e.g., starch, alum and test flocculants) are added to the material under agitation provided by an overhead mixer. The material is then poured into the filter funnel and the vacuum pump is switched on while a stop clock is simultaneously started. Drainage efficiency is reported as the time required to obtain 230 ml of filtrate. The principle of the VDT is based on the cake filtration theory, for reference see Solid-Liquid Separation, 3rd edition, ed. L. Svarovsky, (London, Butterworths, 1990), chapter 9. Initially, the solids in the suspension are deposited on a thin filter medium that serves to support the filter cake. The successive deposition of solids layer to form the filter cake, or mat, depends on the density of the lump, distribution of lump size in the mat, and levels of residual polymeric materials in the aqueous phase. A flocculant that forms dense granules of uniform size and has a low residual level in water (ie, good formulation characteristics) will demonstrate good drainage in the VDT test, and vice versa. The free acid supply of synthetic wood is prepared from overlapping pulps from dry market of hardwood and softwood, and from water and other materials. First the dry market overlap pulp of hardwood and softwood are separately refined in a laboratory Valley Blender (Voith, Appleton, WI). These pulps are then added to an aqueous medium. The water used to prepare the supply comprises a mixture of 3 parts of deionized water to 1 part of local hard water, additionally modified with 0.075% sodium sulfate and 0.0025% pectin gum.

Slendid® 100 (CP Kelco, Atlanta, GA). The pH of the supply is adjusted to 4.5. To prepare the provision, hardwood and softwood are dispersed in the aqueous medium at a weight ratio of 70:30 of hardwood: softwood. Clay fill is added to the 25 percent by weight feed, based on the combined dry weight of the pulps so as to provide a final supply of 80% fiber and 20% clay fill. The pH of the supply is adjusted to 4.5. The starch, coagulant and flocculant additives, the doses, and addition sequence are as used in the previous examples. TABLE 5 Test Description Help of # / T (active) Time of Dre- # Drainage / naje (s) Polymer 5.1 - none 0 31.4 5.2 Conventional NP 780 0.3 19.0 5-3 Conventional NP 780 0.6 17.4 5-4 Conventional NP 780 0.9 17.5 5-5 Comparative EM 1030 Na 0.3 21.5 5-6 Comparative EM 1030 Na 0.6 21.8 5-7 Comparative EM 1030 Na 0.9 23.1 5-8 Example 4 33651-37 0.3 22.1 5-9 Example 4 33651-37 0.6 19.9 5- 10 Example 4 33651-37 0.9 18.0 5-11 Example 6 33632-10 0.3 20.9 5-12 Example 6 33632-10 0.6 19.7 5-13 Example 6 33632-10 0.9 19.5 5-14 Comparative EM 1010 0.3 29.8 5-15 Comparative EM 1010 0.6 28.7 5-16 Comparative EM 1010 0.9 29.9 5-17 Comparative SP2- # 625 0.3 22.0 5-18 Comparative SP2- # 625 0.6 23.2 5-19 Comparative SP2- # 625 0.9 25.0 5-20 Comparative SP2- # 626 0.3 20.9 5-21 Comparative SP2- # 626 0.6 22.8 5-22 Comparative SP2- # 626 0.9 22.9 The data in Table 5 demonstrate the good activity of the currently described polymers compared to, EM 1010 that does not affect the drains je, and PSS polymers of lower Mw, which do not increase in drainage as the dose increases. PSS polymers of lower M2 provide slower drainage as the dose is increased, an unwanted response. The currently described polymers possessing Mw greater than 5 million demonstrate dramatically better drainage than the EM1010 aliphatic sulfonate polymer and the low Mw PSS homopolymers. This result is unexpected. Another series of drainage experiments was conducted DDA with the polymers currently described utilizing a southern paper mill supply that produces lightweight coated grades. The mill was carrying out a program of silica NP 780 in combination with cationic coagulant and cationic flocculant. The provision was prepared by mixing box material and white water in a mill machine to a representative consistency. For the DDA test, the provision was treated with a cationic coagulant at a level of 453.6 grams (1 pound) of active coagulant per ton of dry supply, a polymer flocculant at a level of 226.8 grams (0.5 pounds) of active flocculant per ton of dry provision, and the drainage aids are in pounds of active drainage aid per ton of dry supply, with the specific doses noted in the data box. The cationic coagulant is PERFORM® PC 1279, and the cationic flocculant used is PERFORM® PC 8715 flocculant.

TABLE 6 TEST Description Help # / T (ac- Permeate Time- # Drain / tive) Drain of Polymer (s), Sheet (mbar) 6-1 - none 0 32.6 249 6-2 Conventional NP 780 0.25 24.6 236 6-3 Conventional NP 780 0.5 25.0 240 6-4 Conventional NP 780 1 24.0 237 6-5 Comparative EM 1030 Na 0.25 30.2 242 6-6 Comparative EM 1030 Na 0.5 31.5 246 6-7 Example 3 33562-30 0.25 24.7 235 6-8 Example 3 33562-3 0.5 20.7 232 6-9 Comparative VERSA® 0.25 25.3 242 TL-501 6-10 Comparative VERSA® 0.5 25.0 247 TL-501 Another series of DDA drainage experiments were conducted with the polymers described herein using provision of a paper mill from the south of USA that produces newspaper. The mill is doing a NP 780 silica program in combination with alum and cationic flocculant. The provision was prepared by mixing box material and white water in a mill machine to a representative consistency. For the DDA test, the provision was treated with aluminum sulphate octahecahydrate at a level of 1,814 kg (4 pounds) per ton of dry supply, a polymer flocculant at a level of 0.113 g (0.25 lbs) per ton of dry supply, and the drainage aids are like pounds of active drainage aid per ton of dry supply, with the specific doses noted in the data box . The cationic flocculant used is flocculant PERFORM® PC 8715. TABLE 7 Test Description Help of # / T (ac- Permeab time- Drainage tivo) Drainage of the sheet (mbar) 7-1 none 36.8 262 7-2 Conventional NP 780 25 28.5 260 7-3 Conventional NP 780 5 27.6 260 7-4 Conventional NP 780 75 27.1 264 7-5 Conventional NP 780 28 264 7-6 Comparative EM 1030 Na 0.25 36.3 261 7-7 Comparative EM 1030 Na 0.5 36.3 262 7-8 Example 5 33618-18 0.25 27.8 261 7-9 Example 5 33618-18 0.5 25.3 255 7-10 Example 5 33618-18 24.6 247 7-11 Comparative VERSA ^ TL-501 0.25 31.8 278 7-12 Comparative VERSA * TL-501 0.5 33.2 282 The data in Tables 6 and 7 illustrate the good drainage of the polymers described herein in provision of actual mill, which exceeds the drain provided by NP 780, EM 1030 Na, and a PSW homopolymer of Mw under Versa® TL-t01. The polymers described herein that possess Mw greater than 5 million demonstrate dramatically better than the low Mw PSS homopolymer. This result is unexpected. Another series of VDT drainage experiments was conducted using a synthetic alkaline supply; the data are shown in Table 8. The synthetic alkaline supply is prepared from overlapping market pulps dried from hardwood and softwood, and from water and other materials. First the market lapped pulp dried from hardwood and softwood are retined separately in a laboratory mixer Valley (Voith, Appleton, WI). These pulps are then added to an aqueous medium. The water used to prepare the supply comprises a mixture of 3 parts of deionized water to 1 part of local hard water, additionally modified with 0.01% sodium bicarbonate and 0.03% sodium chloride. To prepare the supply, hardwood and soft wood are dispersed in the aqueous medium at a weight ratio of 70:30 of hardwood to softwood. Filling of precipitated calcium carbonate (PCC) is introduced into the 25 percent by weight feed, combined into the combined weight of the pulps, so as to provide a final supply comprising 80% fiber and 20% PCC filler . The resulting pH is 8.3. The VDT test was conducted at 1.2009 rpm with the sequential addition of a cationic starch, followed by alum, followed by polymer flocculant, followed by drainage aid; the materials are all mixed at the specified interval times. After the drainage aid has been introduced and mixed, the drainage test is conducted. The cationic starch is added to a level of 4.536 kg (10 pounds) of starch per ton of dry supply. The alum (aluminum sulfate octadecahydrate) is added to a level of 2,268 kg (5 pounds) of alum per ton of dry supply. The polymer flocculant is added at a level of 0.181 gr (0.4 pounds) of active flocculant per ton of dry supply. The doses of the drainage aids are like pounds of active drainage aid per ton of dry provision. With the specific doses noted in the data tables. The cationic starch and alum are as described in other data tables. The cationic flocculant used is a 90/10 molar% acrylamide / acryloyloxyethyltrimethylammonium chloride sold under the trademark PERFORM® PC 8138 (Hercules, Wilmington, DE), commercially available as a self-inverting emulsion. The PERFORM® SP9232 drainage aid (Hercules, Wilmington, DE) is a drainage aid, commercially available as a self-investment emulsion. TABLE 8 Test Description Help of # / T (active) Drain Time- # Drain je (s) 8-1 - none 0 33.8 8-2 Comparative PERFORM® SP 9232 0.2 28.4 8-3 Comparative PERFORM® SP 9232 0.4 23.8 8 -4 Comparative PERFORM® SP 9232 0.8 18.1 8-5 Example 4 33651-37 0.2 24.2 8-6 Example 4 33651-37 0.4 20.6 8-7 Example 4 33651-37 0.8 17.1 8-8 Example 1 33651-7 0.2 25.0 8 -9 Example 1 33651-7 0.4 22.5 8-10 Example 1 33651-7 0.8 19.3 8-11 Example 6 33652-10 0.2 22.5 8-12 Example 6 33652-10 0.4 19.8 8-13 Example 6 33632-10 0.8 18.1 Drainage data in Table 8 demonstrate the comparable activity of the polymers described herein compared to a commercial drainage aid in an alkaline supply. The exposures of each patent, patent application, and publication cited or described in this document are hereby incorporated by reference, in their entirety. Various modifications of the invention, in addition to those described herein, will be apparent to those skilled in the art of the foregoing description. These modifications are also intended to be within the scope of the appended claims.

Claims (9)

1. CLAIMS 1. - A cellulosic fiber composition comprising: cellulose fiber and a water compatible polymer comprising a polymer segment formed from at least one ethylenically unsaturated monomer (A) substituted by at least one aryl group and at least one fraction -S (= 0) 2ORi u -OS (= 0) 2 (0) pRi is, independently at each occurrence, H, alkyl, aryl, or a cation, and the polymer has a weight average molecular weight of about 5. millions or more.
2. 2. The cellulosic fiber composition according to claim 1, wherein the monomer A is selected from the group consisting of the free acid or salt of: styrenesulfonic acid, vinyltoluenesulfonic acid, a-methylstyrene sulfonic acid, anetolesulfonic acid, vinylphenylsulfuric acid , 4-sulfonate N-benzylacrylamide, 4-sulfonate N-phenylacrylamide, vinylpirenesulfonic acid, vinylantransulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), vinylsulfonic acid, vinylpyridiniumpropane sulfonate, and mixtures thereof.
3. 3. The cellulosic fiber composition according to claim 1, wherein the monomer A comprises an acid or salt free of styrenesulfonic acid.
4. 4. - The cellulosic fiber composition according to claim 1, wherein the monomer A has the Formula I: wherein Ri is Na +, K +, Li +, NH4 +, or R5NH3 +; and R3, R < i and R5 are, independently, H or alkyl, and the -SO3R1 group is in the ortho, meta or para position.
5. 5. The cellulosic fiber composition according to claim 1, wherein the monomer A has the Formula IA or IB: IA IB wherein Ri is a cation R3, RA and R5 are, independently, H or alkyl; and Ar is aryl.
6. 6. The cellulosic fiber composition according to claim 1, further comprising a polymer segment formed from at least one anionic or non-ionic ethylenically unsaturated monomer (B).
7. 7. The cellulosic fiber composition according to claim 3, further comprising a polymer segment formed from at least one anionic or non-ionic ethylenically unsaturated monomer (B).
8. 8. The cellulosic fiber composition according to claim 6, wherein the monomer B is selected from the group consisting of acrylamide, methacrylamide, N-alkyl acrylamide, N-methylacrylamide, N, N-dialkylacrylamide, N, N -dimethylacrylamide, acrylonitrile, N-vinylmethylacetamide, N-vinylformamide, N-vinylmethylformamide, N-vinylpyrrolidone, styrene, butadiene, vinyl acetate, methylacrylate, methylmethacrylate, alkyl acrylate, alkylmethacrylate, alkylacrylamide, alkylmethacrylamide, alkoxylated acrylate, methacrylate, alkylpolyethylene glycol acrylate, alkylpolyethylene glycol methacrylate, the acidic acid or salt of: (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, acrylamido glycolic acid and mixtures thereof. 9 - The cellulosic fiber composition according to claim 6, wherein the monomer B is acrylamide. 10. The cellulosic fiber composition according to claim 6, wherein the monomer B is an acrylic acid salt. 11. The cellulosic fiber composition according to claim 9, wherein the monomer A comprises a sodium or ammonium salt of styrenesulonic acid. 12. The cellulosic fiber composition according to claim 10, wherein the monomer A comprises a sodium or ammonium salt of styrenesulfonic acid. 13. The cellulosic fiber composition according to claim 6, wherein the molar ratio of A: B is from about 5:95 to about 100: 0. 14. The cellulosic fiber composition according to claim 6, wherein the molar ratio of A: B is from about 20:80 to about 100: 0. 15. The cellulosic fiber composition according to claim 6, wherein the molar ratio of A: B is from about 30:70 to about 100: 0. 16. - The cellulosic fiber composition according to claim 1, wherein the cellulose fiber comprises a slurry of pulp. 17. The cellulosic fiber composition according to claim 1, wherein the cellulose fiber comprises paper or cardboard. 18. - The cellulosic fiber composition according to claim 1, further comprising at least one of inorganic mineral extenders, pigments, sizing agents, starches, deposit control agents, fillers, opacifying agents, optical brighteners, fillers, resistance, organic or inorganic coagulants and conventional flocculants. 1
9. 9. - A method for preparing a cellulosic fiber composition, comprising: adding to an aqueous cellulosic fiber suspension an anionic polymer compatible with water comprising a polymer segment formed from at least one ethylenically unsaturated (A) monomer substituted with when minus an aryl group and at least one fraction -S (= 0) 2ORi or -OS (= 0) 3 (O) pRi, where p is 0 or 1, Ri is, independently of each occurrence, H, alkyl, aryl , or a cation, and the polymer has a weight average molecular weight of about 5 million or greater. 20. - A method for improving drainage and retention of solids in a cellulosic fiber composition, comprising: adding to the cellulosic fiber composition an anionic polymer compatible with water comprising a polymer segment formed of at least one monomer (A ethylenically unsaturated substituted with at least one aryl group and at least one fraction -S (= 0) 20Ri or -OS (= 0) 2 (0) pRi, where p is 0 or 1, Rx is, independently at each occurrence, H, alkyl, aryl, or a cation, and the polymer has a weight average molecular weight of about 5 million or greater.