MXPA99004497A

MXPA99004497A - Aqueous dispersion polymers

Info

Publication number: MXPA99004497A
Application number: MXPA/A/1999/004497A
Authority: MX
Inventors: J Connors Edward; Chen Fu; L Cotter Michelle
Original assignee: Betzdearborn Inc
Priority date: 1996-11-15
Filing date: 1999-05-14
Publication date: 2000-01-01

Abstract

Water soluble, aqueous salt solution dispersible polymers and aqueous salt solutions containing dispersed polymers are produced by polymerization of ethylenically unsaturated soluble monomers in an aqueous salt solution in the presence of at least one carbohydrate. The polymers and aqueous salt solutions containing the dispersed polymers are useful for paper making, water clarification and emulsion breaking.

Description

AQUEOUS DISPERSION POLYMERS FIELD OF THE INVENTION The present invention relates to dispersible polymers. More particularly, the present invention relates to dispersible polymers in salty aqueous solution, soluble in water; to water soluble polymers dispersed in a salty aqueous solution; and methods for making and methods for using said polymers.

BACKGROUND OF THE INVENTION Cationic polyacrylamides are extensively used in numerous aqueous applications and treatment processes. Their high molecular weight and variable loading density make them extremely useful as flocculation agents for liquid / solid separation, such as flotation aids and emulsifiers for oil / water clarification and as drainage and retention aids -in the paper making The high viscosity of the solution associated with these polymers when dissolved in water generally makes it impossible to handle them as aqueous solutions due to a low active content (usually less than 6%) that can be obtained.

As a result, cationic polyacrylamides have generally been handled as drying powders or water-in-oil emulsions. Due to the increasing interest for the environment that involves oil and surfactants in the emulsions as well as the inconvenience "and to the expense associated with the dry feed powders, the efforts to develop alternative delivery systems for these polymers have intensified in the recent The goal of these efforts has been to develop the delivery systems, in liquid form, having a high content, which does not contain hydrocarbon oil or volatile organic compounds (VOCs) and which act comparably in polymer powder and emulsion products. analogous THE RELATED ART Patent 4,929,655 to Takeda et al, discloses a process for the production of a water soluble dispersion and includes the polymerization of 5 to 100 percent gram molecule of a water soluble cationic monomer represented by the following formula (1) which has a benzyl functionality, 0 to 60% gram molecule of another cationic monomer represented by the following formula (II) and 0 to 95 percent gram-molecule (meth) acrylamide, in the presence of 1 to 10% by weight of a high molecular weight multivalent organic dispersant cation including a water soluble polymer produced by at least one monomer of the formula (II), based on the total weight of monomers in an aqueous solution of multivalent anionic salt having a concentration of 15% by weight or more. Formula I has the formula: CH2 = C-Rx R2 0 = C i-Ai-Bi-N '+ CH2' • < , 0 > X "(I) R 3 where Ri is both hydrogen or CH3, R2 and R3 are each an alkyl group, having from 1 to 3 carbon atoms; Ai is both an oxygen atom or NH; Bi is both alkylene group, having 2 to 4 carbon atoms or a hydroxypropylene group, and X is an anionic counterion. Formula II has the formula: CH2 = C-R R5 I I 0 = C-A2-B2-N + R7 X "(II) R 6 where R4 is both hydrogen or CH3, R5 and R6 are each alkyl group having 1 or 2 carbon atoms; R7 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; A2 is both an oxygen atom or NH; B2 is both an alkylene group having 2 to 4 atoms of a hydroxypropylene group and X is an anionic counterion. A polyol, such as a glycerin or ethylene glycol can be used to increase the precipitation of the polymer. U.S. Patent No. 5,006,590, Takeda et al, and EP 364175 are similar to Takeda '655, except that the polymerization is carried out in the presence of both: (1) a water soluble cationic polymer bubble that is insoluble in an aqueous solution of a polyvalent anionic salt; and (2) a water-soluble cationic dispersant polymer that is soluble in an aqueous solution of a polyvalent anionic salt. The polymer bubble Water soluble cationic which is insoluble in aqueous solution of a polyvalent anionic salt contains at least 5 gram-molecule per cent of cationic monomer units having a benzyl functionality and which are represented by the aforementioned formula (1) above and the water-soluble cationic dispersant polymer that is soluble in an aqueous solution of a polyvalent anionic salt containing at least 20 gram-percent molecules of cationic monomer units represented by the general formula (II) above.

EP 0183466B1 for Takeda et al, is also similar to Takeda '655 except that a soluble polyol in a salt solution in water, can be used as a substitute for or in addition to a polymer electrolyte dispersant. The disclosed method allows the production of polymer dispersions free of benzyl functional groups in the active polymer. EP 0630909 A1 discloses a process for preparing a water-soluble polymer dispersion in which a portion of monomer is fed from the reaction of the mixture after the polymerization reaction has been initiated to reduce the bulk viscosity of the reactive mixture during the polymerization without a high charge of polyvalent salt. EP 6574782A2 discloses that the optimization of the multivalent anion salt concentration controls the measurement of the particle and reduces the viscosity of the dispersions of the water soluble polymer. Efforts in the prior art have focused on polymer dispersions prepared from mixtures of water-soluble monomer containing at least 5 percent molecule-gram of a cationic monomer with an aromatic functional group, which is preferably a quaternary ammonium salt obtained from the reaction of benzyl chloride and dimethylaminoethyl acrylate (AEDBAC), in aqueous solution of an anionic polyvalent salt. The polymerization is carried out in the presence of a water-soluble cationic acrylamide copolymer containing at least 5 gram-percent molecule of a cationic monomer of the formula (1) and a water-soluble cationic acrylamide copolymer containing at least 20 gram-percent molecule '' of a cationic monomer of the formula (II). The insoluble polymer in salt solution acts as a polymer bubble for the polymerization process where the polymer in brine acts as a dispersing polymer for the resulting dispersion. Thus polymerization techniques of the prior art may require significant raw material costs and time to produce dispersing bubbles and polymers having particular repeating units and molecular weight. Therefore, there is a need that dispersions of water-soluble polymers can be produced in a convenient and economical process that does not require prior synthesis of polymer bubbles, having repeating units of benzyl quaternary or dispersing polymer, having units repeats of quaternary ammonium alkylate. Accordingly, it is an object of this invention to provide water-dispersible, salt-dispersible polymers, processes for producing salt-dispersible, water-soluble polymers and processes that use water-dispersible, salt-soluble polymers that are free of the limitations found in polymerization techniques cited in prior arts.

COMPENDIUM OF THE INVENTION To achieve the above objects and others, the present invention provides water soluble polymers dispersed in an aqueous saline solution. The polymers are produced by polymerizing ethylenically unsaturated monomers in an aqueous salt solution in the presence of at least one carbohydrate. In other embodied inventions, the invention provides water soluble polymers dispersed in a salty aqueous solution which are useful as drainage and retention aid in the manufacture of paper, as a sediment that aids in the removal of water and as a flocculating agent in the treatment of water and as an aid in the separation of water and oil in refineries and in applications in oil fields.

DETAILED DESCRIPTION OF THE INVENTION We have discovered that by the use of carbohydrates or carbohydrates and tannins, or carbohydrates and tannins cationically modified in a salty aqueous solution, we can produce dispersible polymers in salty, water-soluble aqueous solution, with or without benzyl quaternary functionality, functionally in a substantially bubble-free polymer reactive medium having repeating benzyl quaternary units and dispersing polymers that have repeating units of quaternary ammonium alkylates. Thus, we have eliminated the necessary time and costly presynthesis of specific polymer bubbles having repetitive benzyl quaternary units and dispersing polymers that have repeating units of quaternary ammonium alkylate.

In this invention, the monomers are polymerized in an aqueous solution containing salt, water in dilution, at least one naturally occurring or chemically modified carbohydrate and / or cationically modified tannin and tannin and optionally branching agents and / or degrading agents. The beginning of the polymerization is evidenced by the change in the appearance of the mixture of a clear solution or a milky white dispersion. The final product is in the form of a stable polymer dispersion that readily dissolves in water to produce a viscous polymer solution.

The details of the invention are described below. Carbohydrates and Tannins. Carbohydrates are compounds of carbon, hydrogen and oxygen that contain the saccharide unit or its reactive product. Carbohydrates useful for this invention include monosaccharides such as fructose and glucose, disaccharides such as sucrose, maltose, cellobiose and lactose; and polysaccharides. Polysaccharides are preferred carbohydrates for use in this invention. Polysaccharides such as starch, cellulose and gums are particularly preferred. Starch is a mixture of linear (amylose) and branched (amylopeptin) naturally producing polymers that have D-Glucopyranosyl (glucose) unit. It is the main component of almost all seeds, canes and roots and is produced commercially from corn, wheat, rice, tapioca, potatoes and others. The most commercial starch is produced from corn that is relatively cheap and abundant. Starch as a polyhydroxy compound can withstand many reactions characteristic of alcohols, including esterification and etherification. For example, by reacting with metal hydroxides and alkyl oxides, various hydroxy alkyl derivative starches such as hydroxyethyl and hydroxypropyl can be obtained. They can be prepared cationic starches of a thick starch reacted with tertiary and with amino alkyl quaternary compounds. The products are generally characterized as amino-modified functional starches. Examples of modified corn starch useful for the dispersions of this invention are Cato 31 and 237 which are available from National Starch and Chemical Company. Cationic starches can also be obtained by reacting the starches with cationic monomers, such as 2-acryloxyethyl trimethyl ammonium chloride (AETAC), 2-acryloxyethyldimethyl benzyl ammonium chloride (AEDBAC) and 3-methacryl amidopropyl trimethyl ammonium chloride (MAPTAC). , or with certain cationic reagents such as N- (3-chloro-2-hydroxypropyl) trimethyl ammonium chloride (Quat 188 from Dow Chemical). Similar modifications can be applied to gums and other polysaccharides containing hydroxyl groups. The gums are also polysaccharides, in general, that hydrate in hot or cold water to form viscous solutions or dispersions. They can refer to the gums as cellulose, mannans, galactomannan and glucomannans, dependent on hexose (s) building spine and side chains. Natural gums can be obtained from seaweed extract, exudates from plants, seeds or roots and by microbial fermentation. Seaweed extract includes agar and gums, carrageenans of certain marine algae, belonging to the class of Rhodoficesa, red seaweed and algin or alginic acid of the Faeoficeae class, brown seaweed. Plant exudates include gum arabic, Karaya, Tragacanth and Ghatti depending on the provenance of the tree. The gums seeds include guar gum, derived from the guar plant seed, gum from the carob bean obtained from the "ever green" legume plant or the carob tree and others. Microbial gums, such as dextren, and xanthan gum, are polysaccharides produced by micro-organisms via a fermentation process. Chemically modified gums include those such as methoxyl pectin, propylene glycol alginate, detriethanolamine alginate, carboxymethyl of the algarrobo bean gum and guar gum carboxymethyl. Examples of gums that can be used in this innovation are xanthan gum, such as Kelco's Kaltrol BT, and cationic guar gum, such as Galactasol B0H4FDS from Aqualon, a Division of Hercules Inc. Cellulose is a primary framework of almost all the plants. For industrial purposes, cellulose is a derivative mainly of cotton fibers or wood pulp obtained from both mechanical and chemical means. Cellulose esters, such as cellulose, acetate, propyanate, bulirate, valerate, caproate, Heptilate, caprate, laurate, myristate and palmitate are obtained by reaction with organic acids and anhydrides, or chlorinated acids. The cellulose esters are derived from the cellulose reaction with alkylated agents such as chloroacetic acid and alkylene oxides under basic conditions. The cellulose esters include, but are not limited to, ammonium sodium, carboxymethyl cellulose (CMC) and nonionic hydroxymethylcellulose HEC and HEC modified with a long chain alkyl group, for example HMHEC (Hydrophobically Modified HEC). The cellulose esters are available in Aqualon, under the trademark Natrosol and Natrosol Plus. Chitin is a glucosamine polysaccharide that is structurally related to cellulose and is a major structural element in the hard shell of insects and crustaceans. Chitin is also found in some yeasts, algae and fungi. Chitosan is a deacylate derived from Chitin. Both chitin and chitosan are expected to be useful in the practice of this invention. The amount of polysaccharides used in the invention may be from about 0.01 to 10.0 weight percent, preferably from about 0.01 to 5.0 weight percent, preferably from about 0.01 to 1.0 weight percent based on the total weight of the dispersion. The carbohydrates discussed above may also optionally be used in combination with one or more tannins to prepare a stable dispersion. Tannins are a large group of complex, water-soluble organic compounds that are naturally produced in the leaves, small branches, bark, "wood and fruits of many plants and are generally obtained from the extraction of a plant material. The structure of the tannins will vary from the source and extraction methods, but the empirical formula is represented by C76H52046 The examples of the crusts from which the tannin can be derived are: wattle, mangrove, oak, eucalyptus, hemlock, pine, larch , and willow The examples of wood are quebracho, chestnut, oak and urunday.The examples of fruits are myrobalanes, valoría, divi-di i, tara and carob tree.The examples of leaves are the zumac and the gambier. roots are the canaigre and the palmito.The cationically modified tannins can also be used in this invention.The cationically modified tannins are obtained by the reaction of tannins with cationic monomers ta such as, but not limited to, methyl chloride, benzyl chloride and quaternary salts, dimethylaminoethyl acrylate sulfate, diethylaminoethyl acrylate, aminoethyl dimethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylamide, and dimethylaminopropyl methacrylamide, or dimethyl diallyl ammonium chloride .

The reaction produced by the tannin products with formaldehyde and amines is also useful as reaction mixture components for the polymerization in this invention.

Preferred tannins for use in this invention are those extracted from quebracho, mimosa and sumac and the cationically modified derivatives thereof. The amount of tannins used in the invention may be more than 5 weight percent, preferably about 0.005 to 2.5 weight percent, and more preferably about 0.01 to 1.0 weight percent based on the total weight of the product. dispersion.

II. The Sales.

The salts useful in this invention are monovalent metal salts, polyvalent metal salts or mixtures thereof. The salt is present to precipitate the polymer from the reactive mixture of aqueous salt solution. The salts include but are not limited to salts having anions selected from the group of chloride, bromate, fluoride, sulfate and phosphate and cations selected from the group of ammonium, sodium, potassium, magnesium and aluminum. The salt concentration in brine is at the level of at least 15% of the weight based on the initial weight of the dispersion.

III. Initiators The polymerization can be initiated by a thermal process or by oxidation reduction via a free radical mechanism. The initiators suitable for polymerization, can be selected from peroxides, persulphates, bromates and initiators of the azo type, such as 2,2-azobis (2-amidinopropane), dihydrochloride (V-50 from Wako) and 2,2-azobis (N, N-dimethylone) isobutyramidine) dihydrochloride (VA-044 Wako), etc. Sulfites, bisulfites, sulfur dioxide and citrates and other reducing agents used with oxidation initiators to form a redox initiator pair that can also be used. The amount of initiator used can range from about 5ppm to 1000ppm based on the total weight of the monomers. The polymerization can also be initiated by photochemical or ionic irradiation, such as with the Co60 radiation coefficient.

IV. Branching agents.

Branching agents may also, optionally, be used to branch and degrade the polymers of this invention. Branching or degrading agents include compounds having at least two double bonds, one double bond and one reactive group or two reactive groups. Representative compounds include, but are not limited to polyethylene glycol di (meth) acrylate, methylene bis (meth) acrylamide, N-vinyl acrylamide, allyl glycidyl ether, glycidyl acrylate, glyoxal, glycidyl (meth) acrylate, divinyl benzene, N-methyl -alicylaramide, triallylammonium salts, methylolacrylamide and the like can be added, provided that the resulting polymer is soluble in water. It is understood that the aforementioned materials do not limit in any way the synthesis of the polymers according to the present invention. Any of the well-known chain transfer agents familiar to those skilled in the art can be used to control the molecular weight of the polymer. These include, but are not limited to, low alkyl alcohols, such as isopropanol, amines, mercaptans, phosphites, thioacids, alkyl alcohols, and the like.

V. - The means of Reaction.

The polymerization of the monomers of the present invention is carried out in a reactive medium comprising water, at least one salt as described in II above, and at least one carbohydrate and tannin as described in I above. The reaction medium can also containing a polymerization initiator as described in III above and may optionally contain a branching agent as described in IV above. The reaction medium may also optionally contain polymer bubbles, including polymer bubbles having repeating benzyl quaternary units and dispersing polymers, including dispersing polymers having repeating units of quaternary ammonium alkylate. However, the preferred reaction medium is substantially free of polymer bubbles having repeating units of benzyl quaternary and free of dispersing polymers having repeating units of quaternary ammonium alkylate. In the preferred embodiment of this invention the reaction medium contains at least one salt, at least one carbohydrate, a tannin and a polymerization initiator.

SAW. Monomers Monomers suitable for use in this invention may be non-ionic, hydrophobic or cationic monomers with or without benzyl quaternary functionality. The monomers are selected from the groups (1) hydrophobic monomers such as N-alkyl acrylamides, N-alkyl methacrylamide, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl, acrylates, alkyl methacrylates and alkylstyrene having 1 to 16 carbon atoms in the alkyl group, suitable hydrophobic monomers may also include dodecyl methacrylate, tridecyl acrylate, tridecylmethacrylate, octadecyl acrylate, octadecyl methacrylate, maleic anhydride ethyl ester medium, diethyl maleate, and other alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms with ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and aconilic acid, alkyl acid ester ethylenically unsaturated carboxylic acid such as nonyl-a-phenyl acrylate, nonyl-a-phenyl methacrylate, dodecyl-a-phenyl acrylate and dodecyl-a-phenyl methacrylate; Ethylenically unsaturated N-alkyl amides, such as an N-isopropyl acrylamide, N-tertiary butyl acrylamide, N, N-dimethyl acrylamide, N-octadecyl methacrylamide, N-octadecyl methacrylamide, N, N-dioctyl acrylamide and the like derivatives of the same; vinyl alkylates such as vinyl laurate and vinyl stearate, vinyl alkyl ester such as dodecyl vinyl ether and hexadecyl vinyl ether, N-vinyl amide such as N-vinyl lauramide and N-vinyl stearamide; (II) monomers represented by the formula: Ri (CH2 C) - ^ O NH, where Ri is H or a Ci to C3 alkyl; and monomers (III) represented by the formula: R2 - (CH2 - C) - C = 0 where R2 is H or a Cx to C3 alkyl, F is an NHR3N + (R4,5, 6,) M-o 0R3N + (R4, 5, 6) R3 is a Ci to C branched or linear alkylene group, R, R5 and R6 are hydrogen, Ci and C linear or branched alkyl groups, C5 to C8 cycloalkyl groups, groups aromatics or alkyl aromatics and M- is chloride, bromide, fluoride, iodide, methyl or hydrogen sulphates. Preferably the group (I) hydrophobic monomer is an N-alkyl acrylamide such as N-isopropyl acrylamide and N-tertiary butyl acrylamide or a N, N-dialkyl acrylamide having 1 to 8 carbon atoms in the alkyl group, such as NN-dimethyl acrylamide. The preferred group (II) of monomers includes nonionic monomers such as acrylamide and Cx to C3 alkyl acrylamides. Preferred monomer groups (III) are cationic monomers such as: 2-acryloxyethyltrimethyl ammonium chloride (AETAC), 2-methacryloxyethyltrimethyl ammonium chloride (METAC) 2-acryloxyethyldimethylbenzyl ammonium chloride (AEDBAC), 2-methacryloxyethyltrimethyl ammonium chloride (MEDBAC) 3-methacrylamidopropyltrimethyl ammonium chloride (MAPTAC), 3-acrylamidopropyltrimethyl ammonium chloride (APTAC), and diallyl dimethyl ammonium chloride (DADMAC), etc.

In this invention, the most preferred monomers of group (I) are N-isopropyl acrylamide (IPAM) and N-tert-butyl acrylamide (t-BAM) as well as N, N-dimethyl acrylamide (DMAM). The most preferred monomers of group (II) are acrylamide or methacrylamide; and the most preferred monomers of group (III) are 2-acryloxyethyltrimethyl ammonium chloride (AETAC), 2- acryloxyethyldimethylbenzyl ammonium chloride (AEDBAC) or mixtures of AETAC and AEDBAC. The copolymers produced by the polymerization process of this invention have the general structure represented by Z: Ri R2 [E] W- (CH2-C) X- (CH2-C) (Z) C = 0 C = 0 NH2 where E represents the hydrophobic or non-water soluble monomers, such as N-alkyl acrylamide, N-alkyl methacrylamide, N, N-dialkyl acrylamide, N, N-dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate and alkylstyrene having 1 to 16 carbon atoms of the alkyl group, such as dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, ethyl half ester of elemental anhydride, diethyl maleate and other alkyl esters derived from the reaction of alkanols having 1 to 16 carbon atoms with ethylenically unsaturated carboxylic acids, such as: acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and aconitic acid; alkylaryl esters of ethylenically unsaturated carboxylic acids, such as: nonyl-a-phenyl acrylate, nonyl-a-phenyl methacrylate, dodecyl-a-phenyl acrylate, and dodecyl-a-phenyl methacrylate; N-alkyl unsaturated amides, such as an N-isopropyl acrylamide, N-tertiary-butyl acrylamide, N, N-dimethylacrylamide, N-octadecyl acrylamide, N-octadecylmethacrylamide, N, N-dioctyl acrylamide and similar derivatives of the same, vinyl alkylates, such as vinyl laurate and vinyl stearate, vinyl alkyl ethers such as dodecyl vinyl ether and hexadecyl vinyl ether, N-vinyl amides such as N-vinyl lauramide, and N-vinyl esteramide. The monomer x is a non-ionic monomer such as acrylamide or alkylacrylamide, Ri is H or a Ci to C3, alkyl. The monomer y is a cationic monomer. R2 is H or a Ci to C3 alkyl; F is an NHR3N + (R4.5, e) (M- or 0R3N + (R4, 5, 6), R3 is Ci to C4 linear or branched alkyl group, R4, Rs and Re are hydrogen, Ci to C4 linear or alkyl groups branched, C5 to C8 cycloalkyl, aromatic or alkylaromatic groups and M- is chloride, bromide, fluoride, iodide or methyl or hydrogen sulfate.The molar percentages of monomers w, x and y can vary within a broad spectwith the exception of that the sum of the molar percentages of w, x and y must be added above 100 percent of the molar percentage. Preferably, the percentage of molecule-gram of w is around 0 to 60 molecule-gram percent, x is about 20 to 95 percent of molecule and gram is about 6 to 80 percent molecule gram. More preferably w is from about 0 to 40 gram-percent molecule, x is from about 20 to 80 gram-percent molecule, and y is from about 20 to 40 gram-percent molecule. It is understood that more than one class of hydrophobic or cationic monomer may be present in Formula Z. Although the preferred water-soluble salt dispersible polymers produced by this invention are terpolymers, salt dispersible homopolymers and copolymers may also be produced. Water. Stable dispersions can be produced using quaternary ammonium salt of methyl chloride as the only cationic monomer. The copolymers of acrylamide with an N-alkyl-acrylamide or N, N-dialkyl acrylamide monomer, together with a cationic monomer of methyl quaternary chloride and with or without a cationic monomer of benzyl quaternary chloride which can also be prepared in the form of dispersions watery stable. It is expected that dispersions with up to about 30% active polymer content can be prepared.

The number average molecular weight (Mn) of the polymer described above is not critical and may vary in a range of 5,000 to 20,000,000 for desired applications. The dispersions prepared by the teaching of this invention remain in liquid form for several months without any sign of separation or solidification. As such, the dispersions provide a convenient vehicle for the delivery of high molecular polymers in liquid form and are useful in many applications, some of which are discussed in more detail herein, below. The polymer can be further isolated via precipitation, in a non-solvent, such as acetone and dried in powder form for final use. Alternatively, the dispersion can be simply sprayed dry directly to obtain polymers in powder form. In any case, the powder can be easily dissolved in an aqueous medium for its use. The polymers and polymer dispersions of this invention are useful in a variety of operations such as, but not limited to, paper manufacture, water clarification and water drainage sediments.

VII. Paper manufacturing The dispersion polymers of the present invention are particularly useful as a drainage and retention aid for papermaking.

To increase drainage and retention, an effective amount of the polymer dispersion of the invention is added to an aqueous supply of paper containing pulp to drain water from the paper or board paper while the retention of ends in the paper or paper product is added. board A microparticular material can also be added in conjunction with the dispersed polymer of this invention in an aqueous paper supply. The microparticles useful for the drainage and retention process with the polymers of the invention have positive or negative amphoteric changes and include silica materials, alumina compounds, phosphorus compounds, zinc compounds, titanium compounds, zirconium compounds, aluminum, borium compounds and organic and inorganic polymer microparticles. Preferred silica materials include colloidal silica, clays that include water-absorbing clays, such as bentonite and nonabsorbent clays such as kaolin, water-dispersible silica, silica gels, silica silica, precipitated silicas, silica acid, silicates, silica based on microcrops, such as polysilic acid, polysilicate and polymetal silica icrogels. In addition, in the papermaking system, the dispersion of the invention can be used in conjunction with polymers cationics such as acrylamide dimethylaminoethyl. { meth) methyl quaternary chloride acrylate (AETAC-METAC), diallyldimethyl ammonium chloride, epichlorohydrin dimethylamine ethylene diamine, polyethylene amines, polyvinylamine and its copolymers and mixtures thereof and anionic polymers such as acrylamide / acrylic acid, acrylamide / 2-acrylamide 2-methyl-propanesulfonic acid copolymer or mixtures thereof and both non-ionic polymers comprising polyacrylamide, polyvinyl alcohol, polyvinylacetate, and their copolymers and polystyrene bubbles. The polymer dispersions of the invention are also expected to be useful in papermaking operations and processes for controlling viscosity and debris to aid in deinking, to clarify the recycled fiber and to deplete sediments from the deinking process. The dispersions are expected to be useful for operations to make alkaline paper.

VIII. Water clarification Water clarification is the removal of suspended matter from water by various methods to provide adequate water for domestic and industrial purposes. The material may include materials such as solids • in suspension, hydrophobic hydrocarbons emulsified, material protein, suspension paint, and the like. The removal is usually carried out by coagulation, flocculation and sedimentation. Coagulation is the process of destabilization by charge neutralization. Once neutralized, the material in suspension does not repel more each one and can be extracted together. Flocculation is the process of bringing the material destabilized or coagulated to form a larger agglomeration or "floc". Sedimentation refers to the physical removal of the suspension, or establishment that occurs once the material has been coagulated or flocculated. The dispersion polymers of this invention, when added to a water system in sufficient quantities, can act as flocculation agents for water clarification and removal of sludge when water is dewatered, and as an air flotation solvent. and induced air flotation aids for oily water and water loss treatment, increasing the size of the floc "via bonding in place and the molecular connection.The dispersing polymers can be used alone or in a combination with other flocculants and conventional coagulants such as conventional polymers, clays, silicates and the like and are expected to be compatible with surfactants to break down oil-in-water or water-in-oil emulsions in the oil field, refineries, metal processing and chemical treatments. The invention is more particularly described by the following examples, which are considered only as illustrative and not as a restrictive scope of this invention.

Examples In a typical dispersion preparation, monomers, salt, water dilution and carbohydrates are added to a 1000-cal resin kettle and mixed completely dissolved. A chelating agent is then added to deactivate any polymerization inhibitor present in the monomers. The boiler is equipped with an overhead stirrer, reflux condenser, thermocouple, membrane loading inlet and a nitrogen spray pipe. The mixture is generally mixed at 500-600 rpm and heated slowly to 50 ° C. A 1% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride (V-50) or another suitable initiator is prepared and a portion of which is thrown into the reactor to initiate the polymerization. At the beginning of the reaction, all system components they are dispersible in continuous phase in the brine so the mixture is initially transparent or a little misty. The onset of polymerization is evidenced by a change in the appearance of the reaction mixture from light to hazy. This change is consistent with the initiation of the polymer chains in the continuous phase brine which is initially soluble at low molecular weight, but which precipitates from the brine while its molecular weight is increased. The carbohydrate materials provide an integral matrix in the dispersion polymerization system preventing the agglomeration of precipitated polymer particles and by stabilizing the final dispersion. As the polymerization continues, the mixture becomes increasingly foggy until a milky white dispersion is obtained. The bulk viscosity of the mixture is generally seen to increase during the polymerization process, but typically remains below 5000 cps (cycles per second). The additional salt can be added during or after the polymerization process to reduce bulk viscosity to less than 2600 cps and improve stability. After heating the dispersion for several hours, a second charge of the initiator can be added to reduce the residual monomer content. The mixture is then cooled to room temperature to produce a fine white dispersion. The final dispersion dissolves rapidly in an aqueous solution when water is added with minimal agitation. Within minutes, a maximum solution viscosity is obtained.

Example 1 /15/80 AEDBAC / AETAC / AM AQUEOUS DISPERSION It was added to a 1000 ce reaction kettle, 67. 67 grams of acrylamide (AMD, 53% aqueous solution), 7.64 grams of dimethylaminoethyl acrylate methylchloroquaternary (AETAC, 80% aqueous solution), 30.97 grams of dimethylaminoethyl acrylate benzyl quaternary chloride (AEDBAC, 82.4% aqueous solution), 90.00 grams of ammonium sulfate, 0.50 grams of diethylenetriamine pentaacetic acid, pentasodium salt (Versenex 80, 40% aqueous from Dow Chemicals), and 52.21 grams of deionized water. To 197.21 grams of deionized boiling water was added 0.77 grams of Galactasol 80H2C guar gum and 2.03 grams of Cato 31 Cationic Starch with mixing. The starch / gum solution was heated to solution and then added to the reaction kettle. The mixture was stirred until a homogeneous solution was obtained. The boiler was equipped with an overhead stirrer, thermocouple, reflux condenser, nitrogen spray pipe, load inlet with separating membrane and a heated layer. The mixture was then heated to 50 ° C under constant nitrogen dispersion, while stirring at 500 rpm. After reaching 50 ° C, 0.50 grams of a 1% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride (Wako V-50) was added to the reactor. After approximately 90 minutes, another 0.50 grams of V-50 solution was added. The temperature was maintained for six hours.

Grams AETAC (80%) 7.64 AEDBAC (82.4%) 30.97 Acrylamide (53%) 67.67 Galactasol 80H2C Guar gum 0.77 Cato 31 Cationic starch 2.03 Deionized water 249.42 Ammonium sulphate 90.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.50 Additional V- 50 (after 90 min.) 0.50 450.00 Contents of Final Assets - 15.0% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 560 cps. A 0.5% solution of active polymer in deionized water (DI) had a Brookfield viscosity of 237 cps. Using the procedure and the similar described equipment for Example 1, the following dispersions were prepared: Example 2 /15/80 AEDBAC / AETAC / AM AQUEOUS DISPERSION Grams AETAC (80%) 8.47 AEDBAC (82.4%) 34.41 Acrylamide (53%) 75.20 Galactasol 80H2C Guar gum 0.86 Natrosol 250MHR (hydroxyethylcellulose) 2.00 Deionized water 283.00 Ammonium sulfate 115.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.56 520.00 of Final Assets - 14.4% The final product was in the form of a soft, milky white dispersion with a viscosity of 1120 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 195 cps.

Example 3 /40/38 AETAC / AM / DMAM / t-BAM AQUEOUS DISPERSION Grams AETAC (80%) 30.43 Acrylamide (53%) 33.72 N, N-dimethyl acrylamide (99%) 23.89 N-tert-butyl acrylamide (99%) 1.62 Galactasol 80H4FDS Guar gum 0.77 Natrosol 250MHR (hydroxyethylcellulose) 1.13 Deionised water 267.44 Sulfate Ammonium 110.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.50 470.00 Contents of Final Assets - 14.4! The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 2516 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 130 cps.

Example 4 /40/38/2 AETAC / AM / DMAM / t-BAM AQUEOUS DISPERSION Grams AETAC (80%) 30.43 Acrylamide (53%) 33.72 N, N-dimethyl acrylamide (99%) 23.89 N-tert-butyl acrylamide (99%) 1.62 Galactasol 80H4FDS Guar gum 0.77 Cato 237 Cationic starch 2.03 Deionized water 251.54 Ammonium sulfate 115.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.50 460.00 Final Asset Content - 14.7% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 1068 cps. A 0.5% solution of active polymer in deionized water (DI) had a Brookfield viscosity of 49 cps.

Example 5 /40/38/2 AETAC / AM / DMAM / t-BAM AQUEOUS DISPERSION Grams AETAC (80%) 30.43 Acrylamide (53%) 33.72 N, N-dimethyl acrylamide (99%) 23.89 N-tert-butyl acrylamide (99%) 1.62 Galactasol 80H4FDS Guar gum 0.77 Natrosol 250MHR (hydroxyethylcellulose) 1.80 Deionized water 266.77 Sulfate Ammonium 100.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.50 460.00 Contents of Final Assets - 14.7% The final product was in the form of a soft, milky white dispersion with a viscosity of 1496 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 80 cps.

Example 6 /30/60 AEDBAC / AETAC / AM AQUEOUS DISPERSION Grams AETAC (80%) 12.71 AEDBAC (80%) 52.81 Acrylamide (53%) 42.22 Galactasol 80H4FDS Guar Gum 0.85 Cato 31 Cationic Starch 2.25 Deionized Water 298.16 Ammonium Sulfate 100.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.50 510.00 Final Asset Content - 14.7% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 360 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 115 cps.

Example 7 /15/80 AEDBAC / AETAC / AM AQUEOUS DISPERSION Grams AETAC (80%) 5.68 AEDBAC (80%) 23.79 Acrylamide (53%) 50.47 Galactasol 80H2C Guar Gum 1.00 Deionised Water 313.06 Ammonium Sulfate 105.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.50 500.00 Final Asset Content - 10.0% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 164 cps. A 0.5% solution of active polymer in deionized water (DI) had a Brookfield viscosity of 95.5 cps.

Example 8 /30/60 AEDBAC / AETAC / AM AQUEOUS DISPERSION Grams AETAC (80%) 8.47 AEDBAC (80%) 35.21 Acrylamide (53%) 28.15 Galactasol 80H4FDS Guar Gum 1.00 Deionized Water 326.17 Ammonium Sulfate 100.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.56 500.00 Final Asset Content - 10.0% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 136 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 44.5 cps.

Example 9 /40/38/2 AETAC / AM / DMAM / t-BAM AQUEOUS DISPERSION Grams AETAC (80%) 20.29 Acrylamide (53%) 22.48 N, N-dimethyl acrylamide (99%) 15.93 N-tert-butyl acrylamide (99%) 1.08 Galactasol 80H4FDS Guar gum 0.77 Deionised water 283.45 Ammonium sulfate 105.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.50 450.00 Contents of Final Assets - 10.0% The final product was in the form of a soft, milky white dispersion, with a bulk viscosity of 1644 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 52.0 cps.

Example 10 /15/80 AEDBAC / AETAC / AM AQUEOUS DISPERSION Grams AETAC (80%) 12.42 AEDBAC (80%) 50.52 Acrylamide (53%) 110.38 Galactasol 80H2C Guar Gum 0.55 Modified Cationic Tannin (40.0%) 1.62 Deionized Water 262.78 Ammonium Sulfate 129.98 Versenex 80 0.50 Wako V-50 (5.0%) 1.25 570.00 Final Asset Content - 19.3% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 708 cps. A 0.5% solution of active polymer in deionized water (DI) had a Brookfield viscosity of 80.5 cps.

Example 11 /40/40 AETAC / AM / DMAM AQUEOUS DISPERSION Grams AETAC (80%) 50.04 Acrylamide (53%) 55.25 N, N-dimethyl acrylamide (99%) 41.20 Galactasol 80H2C Guar gum 0.44 Cationically modified tannin (40%) 4.13 Deionised water 269.19 Ammonium sulphate 148.00 Versenex 80 0.50 Wako V-50 (5.0%) 1.25 570.00 Final Asset Content - 19.3% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 1024 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 35 cps.

Example 12 /30/60 AEDBAC / AETAC / AM AQUEOUS DISPERSION Grams AETAC (80%) 21.04 AEDBAC (80%) 88.05 Acrylamide (53%) 70.05 Galactasol 80H2C Guar gum 0.55 Cationically modified tannin (40%) 1.62 Deionized water 256.96 Ammonium sulphate 109.98 Versenex 80 0.50 Wako V-50 (5.0%) 1.25 550.00 Final Asset Content - 22.6% The final product was in the form of a soft, milky white dispersion, with a bulk viscosity of 820 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 42.0 cps.

Example 13 /15/80 AEDBAC / AETAC / AM AQUEOUS DISPERSION Grams AETAC (80%) 12.59 AEDBAC (82.4%) 52.16 Acrylamide (53%) 110.38 Galactasol 80H2C Guar Gum 0.55 Tannin 0.28 Deionized Water 262.29 Ammonium Sulphate 140.00 Versenex 80 0.50 Wako V-50 (5.0%) 1.25 580.00 Final Asset Content - 19.0% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 884 cps. A 0.5% solution of active polymer in deionized water (DI) had a Brookfield viscosity of 69.5 cps.

Example 14 /40/40 AETAC / AM / DMAM AQUEOUS DISPERSION Grams AETAC (80%) 50. 04 Acrylamide (53%) 55. 25 N, N-Dimethyl acrylamide (99%, 41. 20 Galactasol 80H2C Guar Gum 0. 44 Tannin 0. 55 Deionized Water 272.77 Ammonium Sulfate 128.00 Versenex 80 0. 50 Wako V-50 (5.0%) 1 .25 550.00 Final Asset Content - 20.0% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 750 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 21.0 cps.

Example 15 /30/60 AEDBAC / AETAC / AM AQUEOUS DISPERSION Grams AETAC (80%) 18.64 AEDBAC (80%) 77.85 Acrylamide (53%) 61.92 Galactasol 80H2C Guar Gum 0.55 Tannin 0.17 Deionized Water 299.12 Ammonium Sulphate 110.00 Versenex 80 0.50 Wako V-50 (5.0%) 1.25 570.00 Final Asset Content - 19.3% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 84 cps. A 0.5% solution of active polymer in water Di had a Brookfield viscosity of 44.0 cps.

Example 16 /30/60 AEDBAC / AETAC / AM AQUEOUS DISPERSION Dimethyl amino methacrylate methyl quaternary chloride (80%) 21.44 grs.

Dimethylaminoethylacrylate benzyl quaternary chloride (80%) 89.53 Aacrylamide (53%) 71.21 Galactasol 80H2C Guar Gum 1.27 Tannin (1% solution) 4.13 Water DI 296.75 Ammonium Sulfate 98.00 Versenex 80 0.50 Wako V-50 (5.0%) 0.50 583.33 grs.

Final Asset Content - 21.7% The final product was in the form of a soft, milky white dispersion with a bulk viscosity of 808 cps. A 0.5% solution of active polymer in DI water had a viscosity of 85 cps.

Examples 17-20 /30/60 AEDBAC / AETAC / AM AQUEOUS DISPERSION The results for the process and the similar formulation of Example 16 are shown in the following table: Example Active Solids 0.5% Vise. Vise. Grnl.

No.%% (cps) (cps) 17 37.5 22.0 102 1128 18 39.4 22.2 100 1160 19 39.4 22.2 89 1028 20 39.4 22.2 97 1176 Example 1 Comparative /15/80 AEDBAC / AETAC / AM AQUEOUS DISPERSION Grams AETAC (80%) 7.64 AEDBAC (80%) 31.90 Acrylamide (53%) 67.67 Deionized Water 251.79 Ammonium Sulfate 110.00 Versenex 80 0.50 Wako V-50 (1.0%) 1.25 470.00 Contents of Final Assets - 14.4% In the absence of carbohydrate in the dispersion medium, the precipitated polymer particles agglomerate during the polymerization. The system remains liquid under constant agitation, but quickly separates when agitation is stopped. Within one hour after the mixture is discontinued, the entire system was separated into two phases yielding a clear brine layer and a polymer gel.

Example 2 Comparative /30/60 AEDBAC / AETAC / AM AQUEOUS DISPERSION (2194-43) Grams AETAC (80%) 12.71 AEDBAC (80%) 52.81 Acrylamide (53%) 42.22 Deionized Water 301.26 Ammonium Sulfate 110.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.50 510.00 Final Asset Content - 14.7% In the absence of a carbohydrate, the precipitated polymer particles agglomerate during polymerization. The system remains liquid under constant agitation, but quickly separated when the agitation stopped. Within one hour after the mixture was discontinued, the entire system was separated into two phases yielding a clear brine layer and a polymer gel.

Example 3 Comparative /40/38/2 AETAC / AM / DMAM / t-BAM AQUEOUS DISPERSION Grams AETAC (80%) 30.43 Acrylamide (53%) 33.72 N, N-dimethyl acrylamide (99%) 23.89 N-tert-butyl acrylamide (99%) 1.62 Deionized Water 254.34 Ammonium Sulfate 115.00 Versenex 80 0.50 Wako V-50 (1.0%) 0.50 460.00 Final Asset Content - 14.7% In the absence of a carbohydrate, the precipitated polymer particles agglomerate during polymerization. The system remains liquid under constant agitation, but quickly separates when agitation is stopped. Within one hour after the mixture is discontinued, the entire system is separated into two phases yielding a clear brine layer and a polymer gel. As can be seen in the preceding examples, using at least one carbohydrate in a dispersion reaction medium allows the production of the high molecular weight polymers in the form of an aqueous stable dispersion with a low bulk viscosity. It is expected to achieve the contents of active polymer up to 30% while maintaining a fluid dispersion system. All dispersion polymers easily descend in water to produce homogeneous polymer solutions.

X. Efficacy of the Tests.

The polymer samples of the Examples above were evaluated using a clay sedimentation test Hydrite R. The test was used to measure the increase in the sedimentation rate of a fine clay suspension induced by the polymer aggregate. The type of test has long been used as a screening tool to evaluate the potential loss of the treatment polymers before testing the actual water expense. The clay used in the suspension (Hydrite R available from George Kaolin Co.), has an anionic net surface charge that causes the clay particles to repel each other and resist sedimentation. In addition to the addition of the cationic polymer to the sludge, it neutralizes the surface charge so that the rejection of interparticles is reduced. The polymer also serves to connect the neutralized particles to form larger agglomerates or "floc" that accelerates sedimentation out of the clay. To investigate the active polymer embodiment, the sedimentation index is measured as a function of polymer dosage and compared to the sedimentation rate observed in the absence of any polymer (blank index).

Sedimentation rate (m / sec) in Active Polymer Dosaing Blank 0.048 mm / sec Polymer Datum (ppm) Example: No 6 9 15 21 1 3.3 4.5 7.3 10.3 2 3.4 5.3 11.5 17.9 3 3.3 5.1 7.2 11.7 4 - 3.3 319 4.9 5 3.8 4.7 6.5 10.0 6 2.1 5.4 12.6 18.0 Emulsion Polymer A 3.2 4.4 4.7 Polymer Dose (ppm) Example No. 24 27 30 33 42 1 1 111..88 17.3 2 3 13.7 15.4 4 5.4 8.7 14.5 12.2 17.0 6 Emulsion Polymer A 6.5 9.6 14.6 The Polymer A emulsion is an EM-145 Polymer, in AETAC / AM copolymer commercially available from SNF Floeger, Inc. The results of the clay sedimentation test indicate a significant increase in the sedimentation rate of the clay in the presence of the very low dosages of the dispersion polymers of the invention. In the absence of the polymer, the clay settles to an extremely low rate. The increase in the sedimentation rate when using dispersion polymers of the invention is equivalent to or exceeds that of the polymer of the conventional emulsion in an active base. The polymer examples of the above mentioned Examples were also evaluated by a Modified Buchner Funnel Test, using a biological sludge taken from the chemical plant Sougheatern U.S. A portion of substrate (200cc) was dosed with the required amount of each polymer and mixed for 15 seconds to allow the formation of floc. The conditioned sludge was then discharged into a Buchner funnel that contained a mesh network allowing drainage of the free water through the funnel into a graduated cylinder. While the water falls, a mud cake forms on the mesh. The volume of filtrate collected after 20 seconds of free drainage was recorded as a function of polymer dosing. The results were as follows: Filtering Collected (ce) after 20 seconds in Active Polymer Dose (ppm) Polymer Dose (ppm) Example No. 125 150 175 200 1 - - - 74 / (3) 2 - - - 86 / (3) 3 72 (3) 100 / (2) 114 / (1) 112 / (1 ) 4 - 86 / (3) 96 / (2) 5 68 / (3) 95 / (2) 108 / (1) 106 / (1) Polymer Dose (ppm) Example No. 225 250 275 300 350 1 1 1 13300 // ((11)) 1 14400 // ((11)) 1 15522 // ((11)) 158 (1) 168 / (1) 2 114 / (1) 148 / (1) 158 / (1) 150 / (1) 162 / (1) 3 124 / (1) 120 / (1) 120 / (1) 4 110 / (1) 108 / (1) 112 / (1) 134 / (1) 124 / (1) 1 13388 // ((11)) 1 12222 // ((11)) - where the first number corresponds to filtered cubic centimeters, using an index system of (1) to (5) to measure the clarity of the filtering, (1) denotes excellent clarity of filtering and (5) denotes very poor clarity and where blank It is 135cc / (5).

To better demonstrate the effectiveness of the dispersion polymers of the present invention for water clarification and sludge drainage test, the tests were conducted in the laboratory on various water waste samples from different industries and locations. Test of free drainage in waste water from a biological sludge from a chemical plant. Filtering coupled after 20 sec., Ml. Dose Pol.ppm act Polymer B _ Example 17 Example 18 4 444 '30 30 54 50 63 86 66 64 66 72 104 7 777 96 81 122 82 112 106 128 130 90 128 99 142 146 108 144 110 150 134 126 146 Polymer B is a 1154L polymer, a cationic emulsion polymer commercially available from BetzDearborn Inc.

Clarification test using substrate of a secondary clarifier Turbidity (ntu) Dose, active ppm Polymer B Example 18 Example 19 22 60.2 50.6 27 57.6 53.4 47.6 33 42.1 41 36 38.2 38.5 37.4 38 29.7 43.9 40 24.8 41 25 43 22.2 35.9 Polymer B is a polymer 1154L, a 40% AETAC / AM cationic emulsion polymer commercially available from BetzDearbon Inc.

Clarification test using a primary clarifier substrate: All treatments contain 300 ppm alum. Turbidity (ntu) Dose, active ppm Polymer B Polymer C Example 19 0. 5 19.8 0. 9 15.2 15.'5 1.1 13.8 1. 6 15.3 1. 8 12.4 9.69 2.2 17.4 2 2..77 12.8 9.29 Polymer B is a 1154L polymer, 40% AETAC / AM cationic emulsion polymer commercially available from BetzDearborn Inc. and polymer C is a Polymer 2680, 40% AETAC / AM cationic emulsion polymer commercially available from BetzDearborn.

Drainage of the mud in a de-inking plant: The dispersion of the polymer of the invention was evaluated in a deinking plant in the application of sludge drainage.

Polymer Dose (as a product) Free Drain ppm # / T mL a > 5 sec mL (a> 10 sec mL to 15 sec E Ejjeemmpplloo 1177 4 455 5 5..00 40 65 -90 5 555 6 6..55 50 75 105 8 800 9 9..00 70 105 130 8 855 9 9..55 90 130 150 1 10055 1 122..00 95. 150 160 1 13300 1 144..88 130 155 160 Polymer D 53 6 20 32 38 70 8 30 42 55 88 10 30 50 70 105 12 60 100 125 1 12233 1 144 70 115 135 123 14 90 135 150 Polymer D is a commercial emulsion polymer.

The results of the Buchner test indicate the drainage efficiency for the dispersion polymers. The clarity of the filtrate was much better in the presence of the dispersion polymers compared to the unconditioned sludge, indicating high solids capture.

Thus, the dispersion polymers of this invention have utility in a process for draining sludge by adding an aqueous slurry suspension to an effective amount of a dispersion comprising an aqueous dispersible, water soluble polymer dispersed in an aqueous saline solution, wherein said dispersion is obtained by polymerization of ethylenically unsaturated monomers in an aqueous salt solution comprising at least one carbohydrate, salt, a polymerization initiator, water and optionally a degrading agent to produce a sediment-aqueous polymer complex. The water can be separated from the polymer-sediment complex by free drainage, filtration, centrifugation and / or comparable treatments. The polymer samples of the various Examples were also evaluated using a Standard Britt Jar Test, to determine their effectiveness as retention aid for papermaking. A synthetic alkaline supply was prepared consisting of a 70/30 stock mixture of hardwood and softwood together with 20% and 0.5% by weight of precipitated calcium carbonate and cationically modified potato starch, respectively, as fillers. The evaluations were conducted by 500cc portions of synthetic supply (consistency = 0.52%) with known concentrations of each polymer in the presence and absence of bentonite clay as a retention aid high school. Following the addition of polymer, the treated feed was subjected to cutting at 1200 rpm for 10 seconds. In the test where the bentonite clay was added, the cut at 1200 rpm was continued for another 10 seconds following the addition of clay. The volumetric analysis of the effluent acid collected from Pitcher Britt then produced the% calcium carbonate retained in paper reel. The realization of the retention was evaluated in relation to the unconditioned supply (blank). The results were as follows: % Precipitated Calcium Carbonate Retention Example No. 1.0 # / T active polymer 1.0 # / T active polymer +2.0 # / T Bentonite 1 62 1% 84.0% 2 33. 1% 53.9% 3 35. 7% 60.6% 5 34.2% 59.9% Blank 20. 8 The results indicate an increase in retention of the filler in the presence of the dispersion polymers of the present invention. Increased retention is obtained when the polymers are used in combination with clay Bentonite as part of a microparticle treatment system. Retention and drainage studies were also conducted using, respectively, dynamic Britt Jar and Canadian Standard Freeness devices in synthetic acid and alkaline supplies.

Alkaline Supply # / T starch + 5 # / Talum. + 0.5 # / T polymer (based on assets). Polymer No.% Retention purposes CSF Drain (seconds) Blank 20.27 370 Polymer C 33.39 430 Example 17 38.79 430 Example 18 32.38 420 Example 19 32 410 Polymer C is a polymer 2680, 40% AETAC / AM cationic emulsion polymer commercially available from BezDearborn.

Acid Supply # / T starch + 0.5 # / T polymer (based on assets) Polymer No.% Retention ends CSF Drainage (seconds) Blank 29.16 460 Polymer C 50.52 560 Example 17 45.46 540 Example 18 46.22 560 Example 19 43.7 550 Polymer C is a polymer 2680, 40% cationic emulsion polymer commercially available from BetzDearborn. Thus, the present invention provides water-dispersible, salt-dispersible polymers, methods for preparing water-dispersible salt dispersible polymers, and methods for using such polymers. The polymers of the invention and the polymer dispersions do not require presynthesis of polymer bubbles having repeating benzyl quaternary units or dispersing polymers having repeating units of quaternary ammonium alkylate. While this invention has been described with respect to particular embodiments thereof, it is apparent that numerous other forms and modifications of the invention will be obvious to those skilled in the art. The appended claims and this invention should be constructed to cover such obvious and modifications that are within the spirit of the present invention.

Claims

1. An aqueous dispersion comprising a water soluble polymer dispersed in an aqueous salt solution, the polymer obtained by polymerization of ethylenically unsaturated monomers selected from the group consisting of (i) N-alkyl acrylamides, N-alkyl ethacrylamides, N, N- dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates and alkyl styrenes having 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: i - (CH2 - C) - I c = or I NH2 wherein Ri is H or Ci to C3 alkyl; and (iii) monomers having the formula: R2 I - (CH2 - C) - i C = O I F wherein R2 is H or an alkyl of Ci to C3, F is NHR3N + (R, 5, e) Mo OR3N + (R, 5, ß) M-, R3 is a linear or branched alkylene group of Ci to C4, R R5 and Re are hydrogen, linear or branched alkyl groups of C ± a C4, cycloalkyl groups of C5 to C8, aromatic alkyl aromatic groups and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen and an aqueous solution of salt comprising at least one carbohydrate, salt, water, a polymerization initiator and a compound selected from the group consisting of tannins, cationically modified tannins, tannin reaction products with formaldehyde and amines, and a mixture thereof, and optionally a crosslinking agent and with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii) and the condition that the carbohydrate is present in an amount of from about 0.01 to 1% by weight, with based on the total weight of the dispersion.

2. The dispersion of claim 1, wherein the polymer has a number average molecular weight from about 5,000 to about 20,000,000.

3. The dispersion of claim 1, wherein the carbohydrate is a monosaccharide, a disaccharide or a polysaccharide.

4. The dispersion of claim 3, wherein the polysaccharide is a starch, a cellulose, a gum, a chitin or a mixture thereof.

5. The dispersion of claim 3, wherein the polysaccharide is a starch or a mixture of starches.

6. The dispersion of claim 5, wherein the starch is hydroxyalkyl starch, functional amine modified starch or a cationically modified starch.

7. The dispersion of claim 4, wherein the polysaccharide is a gum or mixture of gums.

8. The dispersion of claim 7, wherein the gum is a morning, galacto anana, glucomannan, agar, a carrageen gum, an alginate, an alginic acid, gum arabic, Karaya gum, tragacanth gum, Ghaltica gum , guar gum, algaroba gum, dextrin, xanthan gum, pectin with low methoxyl content, propylene glycol alginate, triethanolamine alginate, carboxymethyl locust bean gum or carboxymethyl guar gum or a cationically modified guar gum.

9. The dispersion of claim 4, wherein the polysaccharide is a cellulose or a mixture of celluloses.

10. The dispersion of claim 9, wherein the cellulose is a cellulose ester or a cellulose ether.

11. The dispersion of claim 9 wherein the cellulose is a cellulose format, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose valerate, cellulose caproate, cellulose heptilate, cellulose caprate, cellulose laurate, myristate cellulose, cellulose palmitate, sodium carboxymethyl cellulose, hydroxymethyl cellulose, hydrophobically modified hydroxymethyl cellulose, hydroxyethyl cellulose or hydrophobically modified hydroxyethyl cellulose.

The dispersion of claim 3, wherein the polysaccharide is a chitosan.

The dispersion of claim 1, wherein the aqueous salt solution is composed of a monovalent metal salt, a polyvalent metal salt or a mixture thereof in water.

The dispersion of claim 1, wherein the aqueous salt solution contains anions selected from the group consisting of chloride, bromide, fluoride, sulfate and phosphate, and cations selected from the group consisting of ammonium, sodium, potassium, magnesium and aluminum.

15. The dispersion of claim 1, wherein the aqueous salt solution contains ammonium sulfate.

16. The dispersion of claim 1 further contains a polymerization initiator.

17. The dispersion of claim 16, wherein the Polymerization initiator is selected from the group consisting of peroxides, persulfates, bromates, azoalkylaminohydrohalides, sulfites, bisulfites, sulfur dioxides, citrates and mixtures thereof.

18. The dispersion of claim 16, wherein the polymerization initiator is 2,2-azobis (2-amidinopropane) dihydrochloride.

19. The dispersion of claim 1 further comprises a branching agent.

The dispersion of claim 19, wherein the branching agent is selected from the group consisting of polyethylene glycol di (meth) acrylate, methylene bis (meth) acrylamide, N-vinyl acrylamide, glycidyl ether and allyl glycidyl acrylate.

21. The dispersion of claim 1, wherein the tannin is derived from quebracho, mimosa, sumac or a mixture thereof.

22. The dispersion of claim 1, wherein the cationically modified tannin is obtained by reaction of tannin with methyl chloride, benzyl chloride, and quaternary salts of dimethyl sulfate of dimethyl aminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate. , diethylaminoethyl methacrylate, dimethyl aminopropyl acrylamide and dimethyl aminopropyl methacrylamide or diallyl dimethyl ammonium chloride.

23. An aqueous dispersion comprising a polymer dispersible in aqueous solution of salt, soluble in water dispersed in an aqueous solution of salt, the polymer obtained by polymerization of unsaturated monomers selected from the group consisting of: (i) N-alkyl acrylamides, N- alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylate, alkyl methacrylates and alkyl styrenes of 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: I - (CH2 - C) - I C = O I NH2 wherein Ri is H or an alkyl of Ci to C3; and (iii) monomers having the formula: R2 I - (CH2-C) - I c = or I F where R2 is H or an alkyl of C | a C3, F is an NHR3N + (R4,5,6) M- or OR3N + (R, 5,6) M-, R3 is an alkylene group linear or branched Ci to C, R, R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C4, cycloalkyl groups of C5 to C8, alkyl aromatic aromatic groups, and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen in the aqueous salt solution, in the presence of at least one carbohydrate, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixture thereof , wherein the aqueous salt solution is free of seed polymers having quaternary benzyl repeating units or dispersing polymers having quaternary ammonium alkylate repeat units and with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii), and the condition that the carbohydrate is present in an amount from about 0.01 to 1% by weight, based on the total weight of the product. to dispersion.

24. A process for producing a polymer dispersible in aqueous salt solution, soluble in water, dispersed in an aqueous salt solution, the process comprises: the polymerization of unsaturated monomers selected from the group consisting of: (i) N-alkyl acrylamides , N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylates, methacrylates alkyl and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: I - < CH2-C) - I C = O I NH2 wherein Ri is H or Ci to C3 alkyl; and (iii) monomers having the formula: R2 I - (CH2-C) - I C = 0 I F wherein R2 is H or a Cx to C3 alkyl, F is NHR3N + (R4.5.6) -o OR3N + (R4.5, ß) M-, R3 is a linear or branched alkylene group of Ci to C, R4 , R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C4, cycloalkyl groups of C5 to C, alkyl aromatic aromatic groups and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen in an aqueous solution of salt in the presence of at least one carbohydrate, a compound selected from the group consisting of tannins, cationically modified tannins, tannin reaction products with formaldehyde and amines, and a mixture thereof wherein the aqueous salt solution is free of seed polymers having quaternary benzyl repeating units or dispersing polymers having quaternary ammonium alkylate repeat units and with the provided that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii) and the condition that the carbohydrate is present in an amount of from about 0.01 to 1% by weight based on the total weight of the the dispersion.

25. A process for producing a polymer dispersible in aqueous salt solution, soluble in water, dispersed in an aqueous salt solution, the process comprises: the polymerization of ethylenically unsaturated monomers selected from the group consisting of: (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: I -. { CH2 - C) - I C = O I NH2 wherein Ri is H or an alkyl of Ci to C3; and (iii) monomers having the formula: R2 I - (CH2-C) - IC = O IF where R2 is H or an alkyl of Ci to C3, F is NHR3N + (R, 5, ß) Mo OR3N + (R4 , 5f6) M-, R3 is a linear or branched alkylene group of Ci to C, R, R5 and Re are hydrogen, linear or branched alkyl groups of O. to C4, cycloalkyl groups of C5 to Cs, aromatic alkyl aromatic groups and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen, in a salt solution, aqueous containing at least one carbohydrate, or a compound selected from the group consisting of tannins, cationically modified tannins, reaction products of tannin with formaldehyde and amines, and a mixture thereof and at least one tannin, salt, a polymerization initiator and water, and with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or ( iii) and the condition that the carbohydrate is present in an amount from about 0.01 to 1% by weight, based on the total weight of the dispersion.

26. A process for production of dispersible polymer in aqueous salt solution, soluble in water, dispersed in an aqueous salt solution, the process comprises the polymerization of: a) from about 0 to 60 mole percent of a monomer selected from the group which consists of (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; b) from about 20 to 95 mole percent of monomer selected from the group consisting of acrylamide and Ci alkyl to C3 acrylamides; and c) from about 5 to 80 mole percent of monomers selected from the group consisting of the monomers having the formula: R2 I - (CH2-C) - i C = O p I wherein R2 is H or an alkyl of Ci to C3, F is NHR3N + (R4 / 5f6) M- or OR3N + (R, 5, e) M-, R3 is a linear or branched alkylene group of Ci to C4, R4, R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C4, cycloalkyl group of C5 to Cs, aromatic alkyl aromatic groups and M- is chloride, bromide, fluoride, iodide or methyl sulfate or hydrogen, with the proviso that the sum of the molar percentages of a), b) and c) is equal to 100 mole percent, in a solution containing from about 0.01 to 1% by weight of at least one carbohydrate, up to 5% by weight of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, or mixtures thereof, and from about 15% by weight of at least one salt in water.

The process of claim 26, wherein the carbohydrate is a monosaccharide, a disaccharide or a polysaccharide.

28. The process of claim 27, wherein the polysaccharide is a starch, a cellulose, a gum, a chitin or a mixture thereof.

29. The process of claim 27, wherein the polysaccharide is a starch or a mixture of starches.

The process of claim 29, wherein the starch is hydroxyalkyl starch, an amino functional modified starch or a cationically modified starch.

31. The process of claim 27, wherein the polysaccharide is a gum or mixture of gums.

32. The process of claim 31, wherein the gum is morning, galactomannan, glucomannan, agar, a carrageenan gum, an algin, an alginic acid, gum arabic, Karaya gum, Tragacanato gum, gum, guar gum, locust bean gum, dextrin, xanthan gum, pectin with low methoxyl content, propylene glycol alginate, triethanolamine alginate, carboxymethyl locust bean gum, carboxymethyl guar gum or a cationically modified guar gum.

33. The process of claim 27, wherein the polysaccharide is a cellulose or cellulose mixture.

34. The process of claim 33, wherein the cellulose is a cellulose ester or a cellulose ether.

35. The process of claim 33, wherein the cellulose is a cellulose format, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose valerate, cellulose caproate, cellulose hetpilate, cellulose caprate, cellulose laurate, cellulose myristate, cellulose palmitate, sodium carboxymethylcellulose, hydroxymethylcellulose or hydrophobically modified hydroxymethylcellulose, hydroxyethylcellulose and hydrophobically modified hydroxyethylcellulose.

36. The process of claim 27, wherein the Polysaccharide is a chitosan.

37. The process of claim 26, wherein the salt is composed of a monovalent metal salt, a polyvalent metal salt or a mixture thereof, in water.

38. The process of claim 26 wherein the salt is a salt having anions selected from the group consisting of chloride, bromide, fluoride, sulfate and phosphate and cations selected from the group consisting of ammonium, sodium, potassium, magnesium and aluminum .

39. The process of claim 26, wherein the salt is composed of ammonium sulfate.

40. The process of claim 26, wherein the solution further contains from about 5 ppm to 1000 ppm polymerization initiator, based on the total weight of the monomer.

41. The process of claim 40, wherein the polymerization initiator is selected from the group consisting of peroxides, persulfates, bromates, azoalkylaminohydrohalides, sulfites, bisulfites, sulfur dioxides, citrates, and mixtures thereof.

42. The process of claim 41, wherein the polymerization initiator is 2,2-azobis (2-amidinopropane) dihydrochloride.

43. The process of claim 26, wherein the solution further comprises a branching agent.

44. The process of claim 43, wherein the branching agent is selected from the group consisting of polyethylene glycol di (meth) acrylate, methylene bis (meth) acrylamide, N-vinyl acrylamide, glycidyl ether and allyl glycidyl acrylate.

45. The process of claim 26 wherein the tannin is derived from quebracho, mimosa, sumac or a mixture thereof

46. The process of claim 26, wherein the cationically modified tannin is obtained by reaction of tannin with quaternary salts. of methyl chloride, benzyl chloride and dimethyl sulfate of dimethylaminoethyl acrylate, dimethyl aminoethyl methacrylate, methacrylate diethyl aminoethyl, dimethyl aminopropyl acrylamide and dimethyl aminopropyl methacrylamide or diallyl di ethylammonium chloride.

47. A process for producing a polymer dispersible in aqueous salt solution, soluble in water, dispersed in an aqueous solution, the process comprises the polymerization of: a) from about 0 to 40 mole percent of the monomer selected from the group consisting of (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, -dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; b) from about 20 to 80 mole percent of monomer selected from the group consisting of acrylamide and N-alkyl of Ci to C3 acrylamides; and c) from about 20 to 80 mole percent of monomers selected from the group consisting of monomers having the formula: R 2 -. { CH2 - C) - i C = O wherein R2 is H or an alkyl of Ci to C3, F is NHR3N + (R, 5rβ) - or OR 3 N + (R, 5,6) M-, R 3 is a linear or branched alkylene group of Ci to C, R, R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C4, cycloalkyl groups of C5 to C8, aromatic alkyl aromatic groups, and M- is chloride, bromide, fluoride, iodide or methyl sulfate or hydrogen, with the proviso that the sum of the molar percentages of a), b) and c) are - equal to 100 mole percent, in a solution comprising from about 0.01 to 1% by weight of at least one carbohydrate, up to 5% by weight of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, or mixtures of the same, and from approximately 15% by weight of at least one salt, in water.

48. A process for preparing paper, comprising the steps of: a) adding to an aqueous pulp containing the raw materials for paper, an aqueous dispersion comprising a polymer dispersible in aqueous salt solution, soluble in water, dispersed in a aqueous salt solution, wherein the dispersion is obtained by polymerization of ethylenically unsaturated monomers selected from the group consisting of: (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides , alkyl acrylates, alkyl methacrylates and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically carboxylic acids unsaturated; (ii) monomers having the formula: I - (CH2-C) - I C = O I NH2 wherein Ri is H or an alkyl of Ci to C3; and (iii) monomers having the formula: R2 I - (CH2-C) - I C = O I F where R2 is H or an alkyl of C | a C3, F is an NHR3N + (R, 5, e) M- or OR3N + (R, 5, ß) M-, R3 is a linear or branched alkylene group of Ci to C4, R, R5 and e are hydrogen, alkyl groups linear or branched Ci to C, cycloalkyl groups of C5 to Cg, aromatic groups, alkyl aromatics, and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen, in an aqueous solution of salt containing at least one carbohydrate, salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixture thereof, water and optionally a crosslinking agent, with the provided that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii) and the condition that the carbohydrate is present in an amount of from about 0.01 to 1% by weight based on the total weight of the dispersion; b) forming and drying the product of step (a).

49. The process of claim 48 further comprises adding microparticles to the raw materials.

50. The process of claim 49, wherein the Microparticles are selected from the group consisting of siliceous materials, alumina compounds, phosphorus compounds, zinc compounds, titanium compounds, zirconium compounds, tin compounds, boron compounds and polymeric, organic and inorganic microparticulates.

51. The process of claim 50, wherein the siliceous materials are selected from the group consisting of bentonite and kaolin clays, water dispersible silica, silica gels, silica sols, precipitated silicas, silicic acid, silicates and microgels. silicate base.

52. A process for the preparation of paper comprising the steps of: adding to an aqueous pulp containing the raw materials, an aqueous dispersion containing a dispersible polymer in aqueous solution of salt, soluble in water, dispersed in an aqueous solution of salt, wherein the dispersion is obtained by polymerization of ethylenically unsaturated monomers selected from the group consisting of (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, -dialkyl acrylamides, N, -dialkyl methacrylamides, alkyl acrylate, methacrylates of alkyl and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms. carbon in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: i - (CH2 - C) - I C = O I NH2 wherein Rx is H or an alkyl of Ci to C3; and (iii) monomers having the formula: R2 I - (CH2-C) -C = OIF wherein R2 is H or an alkyl of Ci to C3, F is an NHR3N + (R4.5, e) M- or OR3N + (R4,5,6) M-, R3 is a linear or branched alkylene group of O. to C, R, R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C, cycloalkyl groups of C5 to Cs, groups aromatic alkyl aromatics, and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen, in an aqueous salt solution containing at least one carbohydrate, salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixture thereof, water and optionally an agent crosslinker, with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii), and the condition that the carbohydrate is present in an amount of from about 0.01 to 1% by weight, based on in the total weight of the dispersion.

53. A process for preparing paper from pulp raw materials, having improved retention and drainage properties, comprising: adding to the raw materials an effective amount of an aqueous dispersion comprising a dispersible polymer in aqueous salt solution , soluble in water, dispersed in an aqueous salt solution, wherein the dispersion is obtained by polymerization of ethylenically unsaturated monomers selected from the group consisting of: (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylate, alkyl methacrylates and alkyl styrenes having 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: I - (CH2 - C) - i C = O | NH2 wherein Ri is H or an alkyl of Ci to C3; and (iii) monomers having the formula: R2 i - (CH2-C) - I OO IF wherein R2 is H or an alkyl of Ci to C3, F is an NHR3N + (R4 / 5,6) M- or OR3N + (R4,5,6) M-, R3 is a linear or branched alkylene group of Ci a C4, R, R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C4, cycloalkyl groups of C5 to Cs, aromatic alkyl aromatic groups, and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen, in an aqueous salt solution containing at least one carbohydrate, salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixture of the same, water and optionally a crosslinking agent, with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii) and the condition that the carbohydrate is present in an amount from about 0.01 to 1 % by weight, based on the total weight of the dispersion.

54. A process for deinking waste paper containing printed electrostatic ink, ink printed by impact or combinations thereof, consisting of adding to an aqueous slurry of waste paper an amount effective to deink, of an aqueous dispersion comprising a dispersible polymer in aqueous solution of salt, soluble in water, dispersed in an aqueous solution of salt, wherein the dispersion is obtained by polymerization of ethylenically unsaturated monomers selected from the group consisting of: (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, -dialkyl methacrylamides, alkyl acrylate , alkyl methacrylates and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: I - (CH2-C) - I C = O I NH2 wherein Ri is H or an alkyl of Ci to C3; and (iii) monomers having the formula: p? 1 - (CH2 - C) - C = O I F wherein R2 is H or an alkyl of Ci to C3, F is an NHR3N + (R4.5, e) M- or OR3N + (R4.5, e) M-, R3 is a linear or branched alkylene group of Ci to C , R, R5 and e are hydrogen, linear or branched alkyl groups of Ci to C cycloalkyl groups of C5 to Cs, aromatic alkyl aromatic groups, and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen, in the solution aqueous salt containing at least one carbohydrate, salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixture thereof, water and optionally a crosslinking agent, with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii), and the condition that the carbohydrate is present in an amount of from about 0.01 to 1% by weight , based on the total weight of the dispersion.

55. A method for controlling the passage in papermaking machinery during manufacture, which consists in applying an effective amount on the papermaking machinery to control the passage of an aqueous dispersion comprising a polymer dispersible in aqueous salt solution, soluble in water, dispersed in an aqueous salt solution, wherein the dispersion is obtained by polymerization of ethylenically unsaturated monomers, selected from the group consisting of: (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates and alkyl styrenes having from 1 to 16 carbon atoms; carbon in the alkyl group and alkyl esters derived from or the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: I - (CH2-C) - C = O I NH2 wherein Ri is H or an alkyl of Ci to C3; and (iii) monomers having the formula: R2 I - (CH2-C) - 1 C = O I F wherein R2 is H or an alkyl of Ci to C3, F is an NHR3N + (R, 5, ß) - or OR3N + (R, 5, d) -, R3 is a linear or branched alkylene group of Ci to C, R4 , R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C, cycloalkyl groups of C5 to C8, aromatic alkyl aromatic groups, and M- is chloride, bromide, fluoride, iodide, sulfate methyl or hydrogen, in an aqueous salt solution containing at least one carbohydrate, salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixtures thereof, water and optionally a crosslinking agent, with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii) and the condition that the carbohydrate is present in an amount from about 0.01 to 1% by weight, based on the total weight of the dispersion.

56. A process for removing suspended materials from an aqueous stream, to produce clarified water comprising: adding to the aqueous stream an effective amount of a dispersion comprising a polymer dispersible in aqueous solution of salt, soluble in water dispersed in a solution aqueous salt, wherein the dispersion is obtained by polymerization of ethylenically unsaturated monomers selected from the group consisting of (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, acrylates of alkyl, alkyl methacrylates and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 atoms of carbon in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: I - (CH2 - C) - I C = O I NH2 wherein Ri is H or an alkyl of Ci to C3; and (iii) monomers having the formula: R2 I - < CH2 - C) - i c = o wherein R2 is H or an alkyl of Ci to C3, F is an NHR3N + (R4.5fe) M- or OR3N + (R4.5.6) M-, R3 is a linear or branched alkylene group of Ci to C, R , R5 and e are hydrogen, linear or branched alkyl groups of Ci to C4, cycloalkyl groups of C5 to C8, aromatic alkyl aromatic groups, and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen, in an aqueous solution of salt containing at least one carbohydrate, salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixture thereof, water and optionally an agent crosslinker, with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii) and the condition that the carbohydrate is present in an amount of from about 0.01 to 1% by weight, based on the total weight of the dispersion.

57. The process of claim 56, wherein the effective amount is from about 10 ppm to 1000 ppm of active polymer.

58. A process for water clarification comprising: a) adding to an aqueous stream containing suspended materials an effective amount of a dispersion comprising a polymer dispersible in aqueous solution of salt, soluble in water, dispersed in an aqueous solution of salt , wherein the dispersion is obtained by polymerization of ethylenically unsaturated monomers selected from the group consisting of: (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylate , alkyl methacrylates and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; (ii) monomers having the formula: i - (CH2 - C) - I C = O I NH2 wherein Ri is H or an alkyl of Ci to C3; and (iii) monomers having the formula: R2 I -. { CH2 - C) - I C = O I F wherein R2 is H or an alkyl of Ci to C3, F is an NHR3N + (R4.5, e) M- or OR3N + (R4.5.6) M-, R3 is a linear or branched alkylene group of Ci to C , R, R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C4, cycloalkyl groups of C5 to C8, aromatic alkyl aromatic groups, and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen, in an aqueous salt solution containing at least one carbohydrate, salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixture thereof, water and optionally a crosslinking agent, to produce a flocculated material and with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii) and the condition that the carbohydrate is present in an amount from about 0.01 to 1% by weight, based on the total weight of the dispersion; and b) removing the flocculated material from the stream.

59. The process of claim 58, wherein the effective amount is from about 10 ppm to 1000 ppm of active polymer.

60. An aqueous dispersion comprising a polymer dispersible in an aqueous solution of salt, soluble in water, dispersed in an aqueous solution of salt, the polymer has the structure: Rl R2 [E] w (CHJ-C) X - (CH2 -b)? c = or c = or N k: wherein E represents N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates and alkyl styrenes having from 1 to 16 carbon atoms in the group alkyl and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsaturated carboxylic acids; Ri is H or an alkyl of Ci to C3; R2 is H or an alkyl of Ci to C3, F is an NHR3N + (R, 5, d) M- or OR3N + (R4f, d) M-, R3 is a linear or branched alkylene group of Ci to C4, R, R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C, cycloalkyl groups of C5 to C8, aromatic or alkyl aromatics and M- is chloride, bromide, fluoride, iodide or methyl sulfor hydrogen, with the proviso that the sum of the molar percentages of, x and y must add up to 100 mole percent, and where the polymer is obtained by polymerization of unsatur monomers in an aqueous salt solution containing at least one carbohydr salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixing thereof and, optionally, a crosslinking agent, with the proviso that the carbohydris present in an amount from about 0.01 to 1% by weight, based on the total weight of the dispersion.

61. A process for improving the removal of w from an aqueous slurry slurry consisting of: a) adding an effective amount of a dispersion to an aqueous slurry slurry, the dispersion comprising a polymer dispersible in aqueous salt solution, soluble in w, dispersed in an aqueous salt solution, wherein the dispersion is obtained by polymerization of ethylenically unsatur monomers selected from the group consists of: (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acryl alkyl methacryl and alkyl styrenes having from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsatur carboxylic acids; (ii) monomers having the formula: I -. { CH2-C) - I c = or I NH2 wherein Rx is H or an alkyl of Ci to C; and (iii) monomers having the formula: R2 I - (CH2-C) - IC = OIF wherein R2 is H or an alkyl of Ci to C3, F is an NHR3N + (R4.5, d) M- or OR3N + (R4.5, d) M-, R3 is a linear or branched alkylene group of Ci to C4, R4, 5 and Rd are hydrogen, linear or branched alkyl groups of Ci to C4, cycloalkyl groups of C5 to C8, aromatic groups alkyl aromatics, and M- is chloride, bromide, fluoride, iodide, sulfate methyl or hydrogen, in an aqueous salt solution containing at least one carbohydr salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixtures thereof, w and optionally a crosslinking agent to produce a polymer complex, sludge and with the proviso that at least one of the ethylenically unsatur monomers is a monomer of (ii) or (iii) and the condition that the carbohydrit is present in an amount from about 0.01 to 1% by weight based on the total weight of the dispersion; and b) removing the w from the mud polymer complex by free draining, filtration and / or centrifugation.

62. A method of separating an oil-in-w or w-in-oil emulsion consisting of: adding an oil-in-w or w-in-oil emulsion to an emulsion effective for the separation of an aqueous dispersion containing a dispersible polymer in aqueous solution of salt, soluble in w, dispersed in an aqueous salt solution, wherein the dispersion is obtained by polymerization of ethylenically unsatur monomers from the group consisting of: (i) N-alkyl acrylamides, N-alkyl methacrylamides, N, N-dialkyl acrylamides, N, N-dialkyl methacrylamides, alkyl acryl alkyl methacryl and alkyl styrenes which they have from 1 to 16 carbon atoms in the alkyl group and alkyl esters derived from the reactions of alkanols having from 1 to 16 carbon atoms in the alkyl group with ethylenically unsatur carboxylic acids; (ii) monomers having the formula: i - (CH2 - C) - I C = O I NH2 wherein Ri is H or an alkyl of Ci to C3; and (iii) monomers having the formula: R2 I - (CH2-C) - IC = 0 IF where R2 is H or an alkyl of Ci to C3, F is an NHR3N + (Rf5, ß) M- or OR3N + ( R, 5, d) M-, R3 is a linear or branched alkylene group of Ci to C, R, R5 and Re are hydrogen, linear or branched alkyl groups of Ci to C4, C5 to C8 cycloalkyl groups, alkyl aromatic groups aromatics, and M- is chloride, bromide, fluoride, iodide, methyl sulfate or hydrogen, in an aqueous salt solution containing at least one carbohydrate, salt, a polymerization initiator, a compound selected from the group consisting of tannin, cationically modified tannin, tannin reaction products with formaldehyde and amines, and a mixture thereof, water and, optionally, a crosslinking agent, with the proviso that at least one of the ethylenically unsaturated monomers is a monomer of (ii) or (iii) , and the condition that the carbohydrate is present in an amount from about 0.01 to 1% by weight, based on the total weight of the dispersion.