MXPA98000082A - Treatment of aqueous systems using a chemically modified tannin - Google Patents

Abstract

This invention relates to a composition and a method for coagulating the material that remains suspended in the water and for removing the viscosity of the sticky materials. More particularly, this invention relates to the use of new tannin derivatives to coagulate and therefore to allow the removal of suspended solids in aqueous systems, to remove viscosity from sticky materials such as paint-based over-spray particles. of solvent and / or water, pitch particles and the like and to de-emulsify oil-in-water emulsions in aqueous systems

Description

TREATMENT OF AQUEOUS STEMS USING A CHEMICALLY MODIFIED TANNIN. BACKGROUND OF THE INVENTION The flocculation of suspended matter in water to improve the clarification regimes is an important aspect of industrial and municipal water treatment. Such inorganic coagulants, lime, alum, ferric chloride, ferrous sulfate, ferric sulfate, and sodium aluminate have traditionally been used. These chemicals, while assisting the removal of suspended solids, generally provide additional amounts of dissolved inorganic solids that can themselves cause problems in the water, particularly when the water is recirculated in substantial quantities. Some organic polymeric coagulants have also proven to be very valuable for flocculation. These polyelectrolytes are often preferred "due to the fact that in addition to their minimal effect on dissolved solids, they tend to produce less residual sludge, and a more compact waste sludge, and tend not to appreciably affect the pH of the treated water. Cationic polyamines are common organic coagulants obtainable in commerce. In addition, high molecular weight polymers such as anionic polyacrylamides have been used to aid flocculation achieved with primary organic or inorganic coagulants.

Anionic polymers are often used in combination with primary organic or inorganic coagulants, and with aluminum or iron salts to aid in flocculation. Removing the viscosity of sticky materials from aqueous systems is another common problem in many industrial operations. For example, in a commercial spray painting operation carried out in a spray painting booth, less than half of the paint used actually covers the surface to be painted, and the rest represents overspray. Over-spray is removed of the spray booth by air currents that are swept away by the recirculating water. The particles of spray paint are trapped in the water in the spray booth which if left untreated can cause clogging of the pipes and the spray nozzles, which reduces the operational efficiency of the spray booth and increases VOC emissions . In the application by spray of solvent-based paints such as polyurethane, epoxy resins, lacquers, varnishes, as well as water-based paints, it is usually necessary to collect the over-sprayed coating materials in some way to prevent them from accumulating on the walls and walls. on the surface of the exhaust system of the spray booth. In many large industrial facilities, including especially car body paint systems, the over-sprayed coating materials are collected in water curtains that cascade down the walls of the spray booth. The agglomeration and accumulation of the living coating material in the water supply of these systems results in and causes serious problems, such as the blockage of the pipes and the pumps that circulate the water, and an accumulation of paint in the walls. of the cabin that goes beyond the water curtain. As more and more coating material is sprayed in the cabin, the material that is removed from the air accumulates in the water in the form of a coherent sludge-like mud that in a short period of time can foul the pump. and the conduit of the recirculating water system of the paint spray booth. Furthermore, this sludge is extremely difficult to extract from the pump, the pipes, the tank, and other internal surfaces of the sema with which it comes in contact. The accumulation of coating materials at the bottom of the water tank also creates a serious problem when the system is periodically cleaned, a great effort being necessary to remove all the heavy accumulation of coating material from the bottom of the tank. Many of the current treatments for removing the viscosity of spray booths are based on clays (eg hectorite or bentonite), amphoteric metals (eg sodium zincate) and polymers (eg diallyldimethyl ammonium chloride and melamine aldehydes). or a combination thereof. Although most of the paints commonly used in the market are organic solvent-based paints, in an attempt to reduce the VOC emissions of the paint operation, the use of water-based coatings is becoming more common. Water-based paints are suspensions of stabilized resins with a surfactant matrix which, when incorporated into the spray booth of the spray paint and / or emulsify paint which results in an increase in suspended and dissolved solids. Although these aeolides must be coagulated and removed from the water of the spray booth in order to maintain an effective paint operation, it is not necessary to remove the stickiness of these solids as needed in the painting of the organic solvent. For these solidges of paint, the agglomeration is necessary to extract them effectively from the system. However, there are some operations in the paint spray booth where organic solvent based paints and water paints are sprayed in the same booth. Due to the important differences in the formulation of the water-based paint and the solvent-based paints, the present deviscosification agent has been necessary to treat the respective particles of paint in the water of the spray booth. Therefore, it would be an important benefit to have a single agent for water treatment that could act not only as a coagulant but also act as a deviscosifier or optionally the coagualient could be used in combination with a deviscosifier without diminishing the performance of the deviscosifier . Various inorganic compounds have been used as flocculating agents and coagulants in the eietemae for the treatment of water in paint spray booths. More specifically, coagulation involves the addition of a cationic material that reduces the negative zeta potential of a particle. This gives rise to the agglomeration of doe particle or mae, providing a flocose bolus. All coagulants are typically cationic in their pH range of operation.

Deviscoeification involves the addition of material added to a paint particle (as described in this invention) that is similar to a coagulant. However, not all suppliers are recognized as coagulants. For example, inorganic clay is eedevised but does not act as a coagulant. This is because they do not have a general cationic charge and therefore do not agglomerate particles, which generally have a negative charge. In addition, not all coagulants are effective de-co-polluting, since a deep-hole deviscoeter of the absorption in the paint particle must turn the paint non-tacky. The addition of inorganic coagulants such as alum or organic polymeric coagulants, such as DMA-EPI, does not provide a non-tacky paint. Flocculation is the formation of loose bowls (which are of two or more particles, doublets, agglomerated or coalescent by a coagulant). The effective range of this buffer is much greater than that of a coagulant due to the fact that the molecular weight of the material is 2-3 orders of magnitude. The reduction of the euphemial charge of the particle, zeta potential, is not as important as a coagulant. As a result, the coagulants can be anionic or nonionic in addition to cationic. For example, aluminum eulfate, also known as alum, has been used extensively as a coagulant in the water of spray paint booths. However, the use of inorganic treatment agents have numerous advantages, in particular because they produce high volumes of disposable waste sludge. In addition, none of the inorganic treatment agents is effective in de-isolating a wide range of solvent paints. Therefore, it is convenient to treat the water in the booth in such a way that it converts the pulp coating material to a material free of tackiness and viscosity so that it can be easily separated by itself from the water, which does not adhere to the curtains of water from the walls, to the pipes, to the pumps, and to other parts of the outside of the spray booth. It is also convenient to coagulate the paint particles to form a deviscoeing floating sludge. An embodiment to deevise has been to combine some polymeric materials with amphoteric metalee. Therefore, for example, US Pat. No. 3,861,887 describes the treatment of water for washing paint booths with a mixture of a polycationic polymer dispersible in water with a water soluble salt of an amphoteric metal to reduce the viscosity of the paint. One problem with this embodiment is that the use of metal, such as zinc, can create additional problems for the water and the mud recovered from the honey. Another embodiment cons of using a clay-based treatment. For example, the North American Patent No. 4. 504,395 states that certain hectorite clays can be used effectively to devidecoeize the sprayed paint. A problem of this embodiment is that the sludge produced using the clay can be difficult to dewater, which will result in larger volumes of potentially hazardous materials that require evacuation to a safe place. Another industrial process which experiences problems with sticky materials in aqueous materials is in the pulp and papermaking process where a pulp euspension derived from natural cellulose fibers containing recycled pitch and / or pulp particles is used. residual ink, adhesion, anionic reeiduoe, etc. These sticky materials adhere to the pulp and paper making equipment resulting in sticky deposits that adversely affect the operation of the paper making equipment. One realization for this problem has been the use of talee pulp additives as anionic condensates of aryl sulfonic acid-formaldehyde, or cationic condensate of dicyandiamidae-formaldehyde. However, it continues to exert the need to provide an effective agent for treatment that removes the stickiness of the sticking material in the industrial water-based materials, such as the paint spraying particle, the pitch, and the adhesion in the seven papermaking areas. , etc.Another problem of industrial aqueous systems is the treatment of recurrent water streams containing emulsified oil, ie oil emulsion in water. The edloe inorganic coagulants or in combination with organic polyelectrolytes have been employed in the demulsification. However, these treatments are not completely satifactory because they increase the content of eolidoe, which can cause problems in the discharge of residual currents. Tannins are produced naturally in varioe vegetative materials including cortex and maderae. Industrial practices established in the extraction of wood tannins from quebracho trees and reeds produce condensed tannins that can be obtained in substantial quantities. The condensed tannins are polyphenolic and are polymerized in combination with another chemical product such as formaldehyde. A. Pizzi, in "Taninos Condeneadoe for Adheeivoe" Ind. Eng. Chem. Prod. Dev. 1982, 21, 359-369 connect natural tannins and their particular use in the manufacture of agglomerated cardboard, plywood, and other industrial products that incorporate adhesives. British Patent No. 899,721 describes the use of a reaction product of a tannin, a formaldehyde and an amino or ammonium compound for the flocculation of suspensions such as sewage, industrial water, and natural water. The advantages described in the case of flocculating plants do not affect the pH of the suspension and do not affect the content of inorganic solids and dissolved water in the treated water. U.S. Patent No. 4,558,080 describes the production of tannin-based flocculants prepared by polymerization of tannin with an aldehyde (eg, formaldehyde), and an amino compound (e.g., monoethanolamine) by monitoring the viscosity of the reaction mixture. US Patent No. 734,216 discloses a flocculating composition comprising the polyacid tannin described in US Pat. No. 4,558,080 in combination with an inorganic flocculant such as aluminum sulfate or iron chloride. U.S. Patent No. 4,948,513 discloses a method for deevising water from a spray booth with a composition comprising the polymerized tannin of US Patent No. 4,558,080 in combination with a hydrophilic-lipophilic copolymer and / or with a diallyldimethyl ammonium chloride polymer. U.S. Patent No. 4,944,812 describes aqueous solution of the reaction product of a vegetable tannin, an aldehyde (for example formaldehyde), and an amine (for example diethanolamine) for the treatment of metalee to improve the re-eection to corrode. U.S. Patent No. 5,256,304 discloses the reaction product of a tannin, a diallyl dimethyl ammonium chloride (DADMAC), and aldehyde for use in the removal of metal ions from liquid petroleum liquids by demulsification and flocculation. . European Patent Publication No. 630,858 discloses a polymeric composition containing a soluble or water dispersible tannin having the Tannin- [N-C-A] formula for water clarification. The portion N-C-A represents a polymer constituted by the monomers N, C, and A. N represents a nonionic monomer, C represents a cationic monomer, and A represents an anionic monomer, the monomers N and C being optional. The preferred cationic monomer C is dimethylaminoethyl acrylate. The allyl and ethoxylated allyl ethers of polyalkylene glycol are disclosed as suitable nonionic monomers. All polymerization seems to occur through the initiation of the free radical of the double bond. Although these have been used as described for treating industrial aqueous systems, search for new ways to increase the flocculation and clarification efficiency and reduce the material and other coefficient.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic isometric drawing of an apparatus that is used to evaluate the paint overspray control. FIG. 2 is a graphic representation of table 5. FIG. 2 is a graphic representation of table 6.

COMPENDIUM OF THE INVENTION In accordance with one aspect of the present invention, new compositions of matter are provided which are useful for treating aqueous compositions to coagulate, and / or de-co-segregating the elastomers which are suspended therein, in order to allow their extraction from said aqueous systems. , which comprise tannin, and which contain hydroxyl groups which are chemically modified by the reaction of at least one of said hydroxyl groups with at least one member selected from the group that you connected in an esterification agent and an etherification agent, preferably a cationic etherification agent such as a quaternary alkylated organic amino to form the corresponding ester, or ether, through said hydroxyl group. The chemically modified tannin is then derived by reaction with an aldehyde or with a combination of aldehyde and ammonia, or of organic amine which contains at least one primary or secondary nitrogen atom. The derivatized tannin is dietary or water soluble at a pH that is below 7 and is insoluble in water at a pH that is above 7. Methods for using the foregoing compositions to coagulate are also provided according to this invention. and / or to de-viscosify sticky particles such as those found in various aqueous systems, tap as spray paint particles that are pre-exposed in the water in the paint spray booth. In another aspect of the present invention, methods are provided to de-emulsify oil-in-water emulsions using the above-mentioned additives. It has now been found that the properties of the taninoe naturalee can be modified advantageously for the purpose described, at least some of the free phenolic hydroxyl groups present in said tannins being blocked. Clogging agents are used to influence the hydrophobic / hydrophilic properties of tannin under different pH conditions. The properties of chemically modified eetoe taninoe are further improved by the derivation of the lobes through conventional phenol / aldehydes or reactants of the type Mannich so that they may obtain refined formaldehyde concentrations (eg <500 ppm).

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to new compositions of chemically modified and derivatized tannin, and is used for the manufacture and use of coagulants as a devalenting agent and / or as demulsifiers for treating various aqueous industrial fabrics. The chemically measured tannin of the present invention is the reaction product of a tannin component and at least one of a etherification agent, or an etherification agent.

STARTING TANNIN COMPONENTS The tannin that is chemically modified according to the present invention can be obtained from various wood and vegetable materials found throughout the world. The taninoe are an extensive group of organic compounds complexe, soluble in water. Each tree or arboretum that grows contains tannin in lae hojae, ramae, bark, wood or fruit. Example of bark eon juncoe, mangrove, oak, eucalyptus, pinabetee, pine, larch and eauce. Examples of wood are quebracho, chestnut, oak and urunday. Example of frui eon myrobalane, valonia, divi-divi, tara, and algarrobilla. Example of hoja eon eumac and gambier and examples of roots are canaigre and palmetto. Among the preferred materials are quebracho wood. A spray-dried quebracho powder is sold by Cañado Packere, Ltd. as Mimoea Extract. These natural tannins can be categorized into traditional "hydrolyzable" tannins and "tannins condemned" by A. Pizzi in "Taninoe Condeneadoe para Adehisivos", Ind. Eng. Chem. Prod. Res. Dev. 1982, 21, 359-369. The tannin extracts are condensed and produced through the bark of the black acacia tree (or the trade mimoea tannin), from the wood of the quebracho tree (Eepañol: ax bankruptcy, "ax-breaker"), the bark of the pinabete tree, and the bark of variae commonly used pine species. The preparation of acacia and quebracho extracts (which are the preferred tannins to be used here) is a well-established industrial practice and can be easily obtained in considerable quantities. The extracts of condemned tannin, such as acacia and quebracho, are composed of approximately 70% taninoe polyphenolic, 20% to 25% non-taninoe, mainly polymeric carbohydrate and sugar eimplee (hydrocolloidal gums), constituting last 3% aeti 6% of the extract and contributing enormously to extract the viscoeidad, while the reeto constitutes a low percentage of humidity. Although the exact structure is not known, it is believed that the main polyphenolic pattern in quebracho taninoe is repreetened by repeated analogues based on resorcinol A and pyrogallo B rings as shown in formula I below: Where n, which may be the same or different, is typically zero or 1. Therefore, the preceding flovonoid of formula 1 is typically repeated 2 to 11, preferably 3 to 6, more preferably 4 to 5 times in typical condensed tannins through the carbon-carbon bonds in positions 4- and 6- or 4- and 8-. A typical biflavonoid with two repeating structures of formula Y, linked at positions 4 and 8 is illustrated in formula II.

(II) Where n is as described for the formula Y It is conventional to illustrate the presence of a repetitive structure that occurs naturally in the tamnoe, drawing the structure of formula I with the sticky structure etructure in positions 4- and 6- or 4- and 8- that follow- The present invention also contemplates the use of monoflavonoids, which for the purposes of the present invention will be included within the term tannin. In view of the foregoing, it can easily be understood that plant tannins are not pure chemical components with known structures but also contain numerous components, the most useful of all for the purposes of the present invention are the phenolic portions such as categol pyrogallol etc., which condense into a complicated polymeric structure. For the purposes of the present invention, they are structurally composed of multi-component phenolic compounds which will be collectively referred to as "taninoe". The average molecular weight of the molecular weight of the tannins can typically be between about 300 to about 3000, preferably from about 300 to about 2000 and even more preferably from about 500 to about 1500. The chemical modifications of the tannin are obtained in accordance with the present invention through at least one of the selected esterification reactions, and etherification. Esterification in the context of the present invention is the production of an ether group through the reaction of one or more of the hydroxyl group, preferably phenolic hydroxyl group, of the tannin. This reaction is mentioned as an acylation where the acid reagent is somewhat different from the free acid, ie the acid reagent is characterized by the presence of an acyl group. An acyl group is an organic acid group COOH, in which OH of the carboxyl group is replaced by some other constituent, e.g. halide, oxygen of an anhydride, etc. Therefore, in the present invention, acylation is included within the term etherification. Acylos repreeentative groups include acetyl (CH3C0 ~), and benzolyl (C6H5CO-) • Etherification is the formation of an ether bond through the oxygen of a hydroxyl tannin group, preferably a phenolic hydroxyl tannin group. The preferred etherification agent is cationic, such as a quaternary ammonium compound which is capable of eterifying etherification. More specifically, the composition of the tannin esterified for use in the present invention can be prepared by any method well known in the art such as by contacting the tannin with an organic acid or an acid halide, preferably anhydrous organic acid, and more preferably a tanning agent. of organic acid, and pyridine, by contacting the tannin with an organic acid, preferably an anhydrous organic acid, and preferably an organic acid anhydride, and mixing sodium anhydride and acid salts, or contacting the tannin with an acid organic, preferably an anhydrous organic acid, and more preferably an organic acid anhydride solution containing a drop or two of sulfuric, perchloric, or phosphoric acid as a catalyst. The preferred method is to react the tannin with an organic acid or an acid anhydride only under anhydrous conditions. The etherification of hydroxyl groups, preferably of phenolic hydroxyl groups and hydroxyl acids with fatty acids, can be carried out in a doe-stage reaction involving acetylation with acetic anhydride under reflux at 120-130 ° C followed by reaction of the acetylated product with the fatty acid. under reflux while removing the excess acetic acid by vacuum distillation. The appropriate organic acids can be represented by the structural form IV: R ^ COOH (IV) Where R 1 is a substituate or unsubstituted, aiphatic or non-aromatic, edible or non-atected atom, linear, branched or cyclic (eg nitrogen, oxygen, sulfur, halogen), or non-atomic atom, containing a hydrocarbyl group, typically a hydrocarbyl group containing from about 1 to about 60 carbon atoms, typically a hydrocarbyl group selected from the group that connects to alkyl, typically alkyl C? to C30, preferably C to C10 alkyl, more preferably alkyl to C3; alkenyl, typically C2 to C10 alkenyl, preferably C2 to C5 alkenyl; aryl, typically C6 to C10 aryl, preferably C6 aryl, aralkyl, or alkaryl, wherein the alkyl and aryl of the amine are as described above, and cycloalkyl or cycloalkenyl, typically C5 to C10 cycloalkyl, preferably C6 cycloalkyl to C8 or cycloalkenyl. The eubstituents that may be present in the hydrocarbyl groups include any fintional group capable of imparting the hydrophilic / hydrophilic equilibrium together with the rest of the chemically modified tannin and derivatized to render it water soluble or water dispersible at pHs of less than about 7. , and water-insoluble at pH's above 7 in relation to tannin corresponding chemically and without modifying (ie, containing free phenol) and / or chemically unmodified but derivatized, As used herein, the terminology "functional group" ee refers to functional groups that include, but are not limited to, hydroxyl, halo, amino eulfate, eulphonate, carboxyl, phosphate, and foefonate, amino, amido and the like groups and mixtures thereof, which improve the water solubility of hydrocarbons cyclic or long-chain aromatics, which on the other hand could be insoluble in water at a pH below 7. Examples Examples of suitable acid include acetic acid as formula CH3 (CH2) nCOOH where a number from about 0 to about 16, including acetic acid, propionic acid, butyl acid, pentanoic acid, hexanoic acid (CH3 (CH2)). «COOH octanoic acid CH3 (CH2) 6COOH, nonanoic acid CH3 (CH2) 7COOH; decanoic acid CH 3 (CH 2) 8COOH; undecanoic acid CH3 (CH2) 9COOH; lauric acid CH3 (CH2)? 0COOH; tridecanoic acid CH3 (CH2) 11COOH; Myrietic acid CH3 (CH2) 12COOH; pentadecanoic acid CH3 (CH2) 13COOH; palmitic acid CH3 (CH2) 14COOH; heptadecanoic acid CH3 (CH2) 15COOH; and eimilaree, - acid cycloaliphatic talee as carboxylic acid cyclohexane; unsaturated acid talee as loe of the formula CH3 (CH2) 7CH = (CH2) nCOOH, wherein n is a number of from about 1 to about 13, including algidic acid CH3 (CH2) 7CH = (CH2) 7COOH; erucic acid CH3 (CH2) 7CH = (CH2) 11COOH; Neronic acid CH3 (CH2) 7CH = (CH2) 13COOH; and the like, - aromatic carboxylic acid such as benzoic acid, naphthoic acid, anthranilic acid, p-aminobenzoic acid, ealicylic acid, e-, m-, and p-tolyl, methoxy and ethoxybenzoic acid, acetoacetamidobenzoic acid, and acetamidobenzoic acid, phenylacetic acid or naphthoic acid, - hydroxy aromatic acid talee as hydroxybenzoic acid, 3-hydroxy-1-natoic acid, 3-hydroxy-2-naphthoic acid, 4-hydroxy-2-naphthoic acid, 5-hydroxy-l-naphthoic acid , 5-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid and 7-hydroxy-2-naphthoic acid; dicarboxylic acid talee as aliphatic dicarboxylic acid having 3-12 carbon atoms, in particular malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, 1,5-pentanedicarboxylic acid, 1,6-hexanedicarboxylic acid, l-acid, 10-decane-dicarboxylic acid, cydohexane-1,4-dicarboxylic acid and aromatic dicarboxylic acids such as phthalic acid or terephthalic acid. In place of the carboxylic acid, the anhydride or the reactive carboxylic acid derivative, the present ethane may also be employed. The fatty acids are preferred with respect to the acid and ineaturate. Addition, a cyclic anhydride such as euccinic anhydride can react and etherify the adjacent tannin hydroxyl group and form cyclic ester structures. The most preferred esterification reagent is acetic anhydride. The etherification is carried out by any conventional technique, such as by the reaction of a hydrocarbyl halide in the presence of an alkaline bath such as sodium hydroxide or potassium hydroxide. Alternatively, the etherification can be carried out by nucleophilic displacement of dihydrocarbyl sulfates, for example dimethyl sulfate, with phenoxide anions. Suitable hydrocarbylhalide reagents can be represented by the structural formula V: R2"(X) n (v) where R2 is a hydrocarbyl group as described with reference to R1 of formula IV; X is a halide, preferably chlorine or bromine; and n is a number representing the amount of halogen number, in R2 which may vary from about 1 to about 5. Representative examples of hydrocarbyl group R2 appropriate include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2 -methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl , 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1,1-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-1-methylpropyl, and the corresponding unbranched or branched radicals heptyl, octyl , nonyl, decyl, undecyl, dodecyl, tridecyl and pentadecyl, -alkele groups such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl or, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-propenyl, 1-pentenyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1 methyl-2-butenyl, 2-methyl-2-butenyl, 3-butenyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, l- dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-Hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2 pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1,2-dimethyl-l-butenyl, 1,2-dimethyl-2-buteni 1, 2-dimethyl-3-butenyl, 1,3-dimethyl-l, 1-butenyl, 1,3-dimethyl-l-2-butenyl, 1,3-dimethyl-3-butenyl, 2, 2- dimethyl-3-butenyl, 2,3-dimethyl-butenyl, 2,3-dimethyl-2-butenyl, 3,3-dimethyl-1-butenyl, 3, 3-dimethyl-2-butenyl, 1-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, l-ethyl-2-methyl -1-propenyl and l-ethyl-2-methyl-2-propenyl, - cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; cycloalkenyl such as 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl; aryl such as phenyl, naphthyl; and aryl, such as benzyl, and 2-phenylethyl. Specific examples of suitable halides include methyl chloride, ethyl chloride, methyl broride, ethyl bromide, methyl iodide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide, isopropyl chloride, isopropyl bromide, isopropyl iodide, butyl bromide, n-butyl bromide, bromuron-pentyl, n-hexyl chloride, n-octyl chloride, n-decyl chloride, benzyl chloride, phenethyl chloride, and benzyl chloride. The preferred halide is an alkyl halide, preferably dichloromethane. The constituents in groups R2 may be equal or as described with reference to formula IV and are related so as to impart the same solubility characteristics at the indicated pHs with reference to the description of formula IV. The preferred etherification agent and the reaction conditions are selected to prepare the chemically modified tannin amphoters. This was achieved with compounds of quaternary ammonium salts that are capable of reacting with the tannin hydroxyl groups. This is preferably achieved by including at least one halogenated hydrocarbyl group as one of the hydrocarbyl groups of the quaternary amine through which the etherification reaction can occur. Therefore, the quaternary amine represents a preferred subgenus of the hydrocarbyl halide. It is preferred because it imparts a cationic charge to the tannin. It should be understood that the etherification reaction will proceed according to the following reaction: Tßnino -OH + X-R "- N'-R 4 and"? 'Tannin' -Q-R'-N '-R 4 + Y "+ HX < EC - l ¡R > > where x is halogen and RJ to R are as described herein for formula VI. Therefore, the halogen (X) in the quaternary amine starting material is displaced from the carbon which participates in the bond of the ether with the tannin.

The solubility in water of the tannin in reacting to a high pH is ensured by the hydroxyl groups. However, at a high pH since each cationic charge reacts on the tannin, it begins to lose its solubility. This arises from the fact that it is amphoteric. Desir has cationic and ammonium sites, therefore, when the pH rises. the hydroxide sites are deprotonated, which increases the anionicity of the anotonic molecule. The presence of cationic and ammonium charges in the non-derivatized ta at a high pH contributes to its insolubility together with the hydrophilicity / hydrophobicity character imparted to the salt by its hydrocarbyl groups The compounds of quaternary hydrocarbyl ammonium salts can be represented by structural formula VI R * _N < _R4 AND "(VI) R'J where * to R which may be the same or different are hydrocarbyl groups as defined with references to P1 of formula IV and particularly R "of formula v with the proviso that at least one of the halogenated hydrocarbyl groups eea halogen and capable of euffering an etherification reaction, typically the hydrocarbyl group is independently selected from the group that connects in: (i) hydrocarbon chain from one to 30, preferably from 1 to 15, and more preferably from 5 carbon atoms, halogen sub-selected, whether or not charged, linear, branched or cyclic, and (ii) hydrocarbon chain of the carbon atom, substituted or unsubstituted, saturated or unsaturated, linear, branched or cyclic, optionally comprising at least one heteroatom that is selected from the group consisting of nitrogen, oxygen, sulfur and halogen within the hydrocarbon chain, and where two or more of R3 to R6 together can part of a cyclic ring structure. And "it is an anion in an amount that is sufficient to eat the charge of the ammonium cation and is preferably selected from the group that you connected in a halide (chloride, bromide, ie, fluoride), sulfonate, phosphate, foefonate, hydroxy nitrate, eulfate, alkyl eulfate, and carboxylate The representative substituents of the hydrocarbyl groups which contain R3 to Re include hydroxyl, halogen (preferably chlorine or bromine), amino sulfate, amino, amido, sulfonate, carboxyl, phosphate and group foefonatee. previously indicated, at least some of the hydrocarbyl substituents R3 to R6 is substituted with halogen.

More specifically, R3 to Rβ of formula VI can be independently selected from the group that you connected in alkyl, typically CX to C30 alkyl, preferably Cx to C15 alkyl, preferably C to C5 alkyl; hydroxy alkyl and / or halo substituted, typically Cx to C30 alkyl hydroxy and / or halo substituted, preferably Cx to C1S hydroxy and / or substituted halo, more preferably Cx to C5 hydroxy and / or halo substituate; alkenyl, typically Cx to C30 alkenyl, preferably Cx to C15 alkenyl, aryl, typically C6 to C10, cycloalkyl, typically C5 to C8 cycloalkyl; ethoxylated hydrocarbyl groups typically ethoxylated hydrocarbyl groups typically containing from about 1 haeta about 50, preferably 5 haeta about 30, most preferably 10 haeta about 20 moles of ethylene oxide. It will be understood that the nature of the hydrocarbyl groups constituting R3 to R6 of the quaternary ammonium salt can be varied in order to impart the desired hydrophobic / hydrophobic equilibrium, and therefore reactive altanino. It has been found that this balance is controlled by imparting ethanol solubility characteristic chemically mied and / or chemically mied and derived as described with reference to formula IV. It is necessary to take into account that you can use a mixture of hydrophobic and hydrophobic ammonium ehea., to provide the tannin with the appropriate balance hydrophilic / hydrophobic, or, alternatively, a tannin modified with ammonium ealee having hydrophobic groups and hydrophilic groups that can be used to achieve the same result. Accordingly, the hydrochloric quaternary ammonium ealees which are useful include quaternary ammonium ammonium ammonium salts, which contain at least one hydrocarbon chain having from about 2 haeta about 30 carbon atoms.; and at least a hydrophilic carbon chain having more than about 9 mole of ethylene oxide. Examples of ethoxylated quaternary ammonium compounds include the following: dihydrogenated ammonium chloride of ebo-clomethyl- [ethoxylated (33)]; hydrogenated ammonia chloride of ebo-chloromethyl- [ethoxylated (15)]; hydrogenated ammonium chloride of ebo-chloromethyl- [ethoxylated (30)]; hydrogenated ammonium chloride of ebo-chloromethyl- [ethoxylated (50)]. Lae ealee of hydrophobic quaternary amine include ethera quaternariae of halogen substituted: monomethyl trialkyl, dimethyl dialkyl quaternary ealee, cyclic amines, including (2-chloroethyl) -trimethyl ammonium chloride, (3-bromopropyl) triethylammonium bromide, N-chloride (l2-chloroexadecyl) -N- (hexadecyl) dimethyl ammonium sulfate N- (chloromethyl) -N- (methyl) diastearyl ammonium chloride, N- (bromomethyl) -N- (methyl) ammonium disodium chloride, N-chloride - (16-bromohexadecyl) -N- (hexadecyl) dimethyl ammonium, di (hydrogenated eebo) chloride dichloromethyl ammonium, dioctadecyl dibromomethyl ammonium chloride, N- (chloromethyl) -N- (methyl) diethylsilylammonium chloride, N-chloride - (chloromethyl) -N- (methyl) didocoeil ammonium, N- (chloromethyl) -N- (methyl) di (hydrogenated eebo) ammonium acetate, N- (chloromethyl) -N- (methyl) dihexadecyl ammonium acetate, foefate di-2-chloropropyl ammonium nitrate, N- (chloromethyl) -N- (methyl) di eebo nitrate, N- (chloro ethyl) -N- (methyl) di (coconut alkyl) ammonium chloride, clo bromine-etearyl dimethyl benzyl ammonium chloride, and N- (chloromethyl) -N- (methyl) diallyl ammonium chloride. Intermediate hydrophobic ammonium salts include halogen, and halogen and hydroxy, substituted alkyl ammonium salts, such as mono (monohydroxy monohalo C 1 C alkyl,) tri C 1 -C 9 ammonium salts, N- (monohydroxy monohalo) salts Ci-Cg alkyl) N- (monohydroxy C-8 alkyl) Ci-Cg alkyl, tri (monohydroxy alkyl monohaloCi-Cß ammonium alkyl, tri (monohydroxy) alkyl mono (monohydroxymonohalo, Ci-Cß alkyl) ammonium salts including bromide of N- (2-chloro-2-hydroxyethyl) trimethyl ammonium, n- (l-hydroxy-4-chloro-butyl) tripropyl ammonium nitrate, N- (l-hydroxy-6-chloro-hexyl) -di bromide (l-hydroxyhexyl) methyl ammonium, tetrachloride (3-hydrooctyl) ammonium, N- (3-chloro-2-hydroxypropyl) -di (methyl) -dodesyl ammonium chloride, - and (3-chloro-2) chloride -hydroxypropyl) -di (methyl) -octadeeyl ammonium, and also as a quaternization product to the eestituted di-triethanolamine estaree with long-chain fatty acids (lauric acid, Tonic, palmitic acid, etheteroic acid, behenic acid, oleic acid and fatty acid mixture such as coconut fatty acid, eebo graeoe acid, hydrogenated tallow fatty acid and eebo oil fatty acid), such as distearyl chloride N-chloromethyltriethanolammonium, and distearyl ester of N-chloroethyltriethanol ammonium methoesulfate. Preferred quaternary ammonium salts are N- (monohydroxymonochloro) alkyl ammonium talee such as N- (3-chloro-2-hydroxypropyl) trimethyl ammonium chloride, and N- (4-chloro-l-hydroxybutyl triethyl ammonium) chloride. The charge deficiency of the tannin is also increased by reaction with the quaternary amine The preferred charge density of the quaternized tannin is about 2.0 meg / g The degree to which the hydroxyl group in the tannin is chemically modified by esterification or by etherification is conveniently expressed as the molar ratio of the tannin modification agent: chemical The molar ratio is based on the weight of the reactant added to the reaction mixture and constitute 100% reactive reactants and reactants. a molecular weight of a gram atom of the monoflavanoid unit of tannin of 300, in the determination of the molecular weight, hence the molar ratio of the tannin: modifying agent. The chemical composition will be controlled to be typically from about 0.1: 1 to about 4, preferably from 0.5 to about 3.5, and more preferably from about 0.5 to about 3 (eg. , 0.5 1 to 2 1) In view of the above, the chemically modified tamno can be represented by the following structural formula where Z, which may be the same or different, is independently selected from the group consisting of O! I hydrogen R ^ C-, R2-, and (R6) (R5) (R4) (R3) N * where R to R are as described above, and n is a number that can vary from about 0 to 2 with the conditional that at least one of Z is not hydrogen Nerivation of Chemically Modified Tannin Loe tannins chemically t > od? The previously described descriptions are derived by one or more different known reactions that can be traced mainly to the phenolic nature of matter. Said derivative reactions have the effect of further modifying the properties of the chemically modified tannin, preferably by oligomerization or by polymerization of said tannin molecule. To facilitate the term, in the term "polymerize" is defined herein including oligomerization to form dimers, trimers and similar, as well as to crosslink chemically modified tree or mae taninoe. Preferred reactions for derivatizing the chemically modified tannins include phenol / aldehyde condensation and Mannich reactions.

Condensation of Phenol / Aldehyde Formaldehyde reacts with chemically modified phenolic tannins to produce polymerization in the presence of alkaline or acid catalysts through the methylene bridge bonds in reactive poeicionee in the flavonoid molecules. Said positions reactivate eetán eituadae mainly in ring A in lae poeicionee 6-and 8-de loe miemoe. This reaction is illustrated by the following reaction using aldehyde: Tannin + HCHO? TanninCH2-Tannin (Ec.2) Although ring-type B of catechol catechol of tannin is relatively unreactive, its reactivity can be increased with zinc bivalent metallic agents such as zinc acetate, which will facilitate crosslinking. However, the degree of crosslinking that can be achieved with the tannin / formaldehyde mixture is limited by etheric interactions due to the early immobilization of the reticulum caused by relatively few bridging methylene. Consequently, the degree of crosslinking can be increased by using reactors with longer molecules that can bridge the distances between the reactive sites in the formaldehyde-tannin lattice. Therefore, the degree of crosslinking can be increased by adding a small amount of an appropriate urea-formaldehyde (UF) resin. The same effect can be achieved by the addition of phenol resorcinol-formaldehyde (PRF) or phenol-formaldehyde (PF) resin in small amounts. Alternatively, phenol, resorcinol or mixtures thereof can be condensed with the tannin in the presence of formaldehyde. In this way, the relatively small molecules act as a crosslinking agent between the much larger flavonoid aggregates as shown in the following formula VIII derived from the reaction of tannin, reeorcinal, and formaldehyde: The preceding techniques are well known Although the foregoing discussion concentrated on the use of the aldehyde, it will be apparent that the present reactions can be applied to the aldehydes in general, preferring formaldehyde. When formaldehyde is used, it can be used in the form of a 37% active formaldehyde solution. This can be obtained commercially. as formaldehyde which is an aqueous solution of 37% formaldehyde which has been stabilized with 5-15% methanol. Other commercial grades of formaldehyde and its polymers can also be used. Such commercial grades include ba formaldehyde or methanol content of 44, 45 and 50% formaldehyde solutions in propyl methyl alcohol lical, n-butyl, and isobutyl paraformaldehyde and trioxane When using solid aldehyde couple, great care must be taken in that it is completely dissolved. Generating or aldehyde-containing reactants are also appropriate. Therefore, the organic chemical compounds that contain Menoe an aldehyde group can also employ Estoe materials are well known and include, for example, acetaldehyde, propionaldehyde, glycoaldehyde, glyoxylic acid, and similaree or polyaldehydes, ie, organic compounds having more than one aldehyde group in the compound, such as glyoxal, paraformaldehyde, and eimilar. The aldehyde-generating agents are known organic compounds that are capable of forming an aldehyde group in situ, such as monomeric melamine-formaldehyde products and derivatives such as tri and hexa (methylol) melamine and tri and hexa (alkoxymethyl Cx-Cj) melamine . Said materials can be formed by conventionally known method.

Mannich Reaction The chemly modified tannins of the present invention will react (ee connate) with aldehydes and with a nitrogen-containing compound that is selected from ammonia and organic amines, typly under acidic conditions in a Mannich-type reaction. The nature of the resulting product will depend on the nature of the reactive amines (ie, primary or secondary nitrogens in the amine), and the molar ratio of tannin: amine: aldehyde employed. Using formaldehyde as representative of the aldehyde reagent, the primary amino acids have the ability to polymerize the tannin through the bridging methylene in the active tannin eitioe, said tannin activity being equal to that previously prescribed with reference to the phenol / aldehyde concentration, This is mainly explained in the 6-and 8-partitions of the ring "A." The following equation 3 illustrates this reaction: Tannin + R7 -NH2 + 2HCHO Tannin-CH2-N-CH2-Tanin (Eq. 3) In contrast, a secondary amine reacts only once with the aldehyde as illustrated by the following equation 4: Tannin + R7 -NH2-R8 + HCHO Tannin-CH2-N-R7 (Eq. 4) The nitrogen in the resulting unpolymerized product will protonate to an acidic pH to form a cation. It should further be understood that the reactivity of the aldehyde, such as formaldehyde in the defense / aldehyde condensation reaction, will typly be superior to its reactivity at the secondary hydrogen site of a primary amine. Therefore, although the aldehyde will react first at the primary hydrogen site of the primary amine, in reacted where a molar ratio of aldehyde: primary amine is used with slight excess of the stoichiometric amount for a complete reaction with all primary hydrogen of the amine, the aldehyde will have more propeneum to eufrir polymerization (condemnation) with the tannin molecules that are described in equation 2. Therefore, in these situations, although the resulting product can be polymerized through the methylene bridge of the Phenol / aldehyde condensation, the Manich reaction may not induce polymerization. In contrast, a di-primary amine such as an ethylene diamine contains doe eitioe primary amine reactants at each end of the molecule that can lead to polymerization according to equation 5 below: 2 Tannin + H2N-R7-NH2 + 2HCH0? Tannin-CH2- H-R-NH-CH2-Tannin (Ec.5) In any case, to improve the de-co-firing and / or coagulation properties, it is convenient that at least some of the polymerization to the chemly modified tannin is induced through any of the above mechanisms when a Mannich reaction is carried out. The above reaction reactions are carried out in the form of the aldehyde described under the reference to the phenol / aldehyde condensation by the preferred aldehyde, formaldehyde. Compounds containing nitrogen which are suitable for carrying out the Mannich reaction include ammonia and any organic amine containing at least one primary or secondary amine group and which results in a chemly modified derivative tannin and It has characteristics of eolubility such as those that are described with reference to formula IV.

Lae aminae appropriate in this category may be aliphatic, cycloaliphatic, aromatic, heterocyclic, aliphatic and cycloaliphatic, aliphatic and aromatic, aliphatic and heterocyclic, cycloaliphatic and aromatic, cycloaliphatic and heterocyclic, aromatic and heterocyclic, etc., with reference to its structure . Said amines may be saturated or may contain olefinic, acetylenic and / or aromatic unsaturation, and may or may not contain other functional substituents, with the proviso that the tannin derivative possesses the properties of solubility previously described. The amino acids, whether they are constituted by monoamine or polyamines, may be and preferably are hydrocarbyl amine although they may contain one or more constituents which are suitable as oxygen atoms (-0-), hydroxyl groups (-0H), thioether atoms sulfur (-Sn-), mercapto groups (-SH), halogen atoms (-X), keto groups (>; C0), thioketo groups (> CO), carboxy groups (-COOH), ester groups (-COOR), nitrile groups (-CN), thiocyano groups (-SCN), nitro groups (-N02), hetero atoms nitrogen (-N =), and similar, with the proviso that each hydrocarbyl group substituted by the amine retains its predominantly hydrocarbonaceous character. When substitutive amines are used, they preferably have one or more ether-oxygen bond one or more thioether bond one, or more heterogenous nitrogen atom and one or more hydroxyl group.

They may be mixed with appropriate amines, such as, for example, commercial mixture of cyclic and straight chain or branched chain ethylene polyamine having approximately general components which are within the corresponding range or diethylene triamine haeta pentaethylene hexamine. Suitable amino acids can be formed from compounds having combinations of primary and / or secondary amino groups in the molecule. Amines containing tertiary nitrogen groups are also suitable with the proviso that at least one primary or secondary nitrogen group is also present in the amine. More specifically, the appropriate amino acids may be repreeentated by the following structured formulas: (ix) (x) or mixtures thereof, wherein R9 and R10 are independently an H atom (with the proviso that both Rs and R10 are not hydrogen), linear or branched Cxa alkyl C14, C5 to C6 cycloalkyl, a radical (CH2) n-OR13, wherein R13 is linear or branched Cx to C5 alkyl and n ee an integer having a value from 2 to about 5, or where Rs and R10 are joined together to form a heterocyclic ring saturated with the Nitrogen and wherein the atom of the ring may contain some or more hetero atom selected from the group consisting of 0, N, or mixtures of the same, with the content being carbon atom. R11 and R12 are independently an H atom, straight or branched C to C14 alkyl, a C5 to C5 cycloalkyl radical, a (CH2) n-OR13 radical, or where R11 and R12 are joined together to form a commingled heterocyclic ring, with The nitrogen atom and the atom of the ring can contain one or more atoms selected from the group that connects to 0, N, or mixes it with the same carbon content and where Y is an alkenyl Cx to C6, or a radical - (CpH2pA) k CpH2p- where A ee NH or O, p is an integer having a value of 1 haeta about 4, and ee an integer having a value of 1 to about 6. When R9 and R10 or R11 and R12 is bound together to form a saturated heterocyclic ring with a corresponding nitrogen atom, the resulting ring can include a hetero atom to form a ring-like structure such as morpholine piperazine, and is eilamylated. Lae monoaminae and illustrative polyamines that may be employed include methyl amine, ethyl amine, n-butyl amine, pentylamine, n-hexylamine, heptyl amine, n-octylamine, n-tetradecylamine, n-hexadecylamine, dodecyl amine, ieopropyl amine, eec- butyl amine, t-butyl amine, t-octyl amine, n-ethethylamine, N, N-dimethylaminopropylene diamine, deehydroabietylamine, aniline, cyclohexyl amine, didecylamine, ditetradecylamine, diethylethylamine, coconut fatty diamine, diamine graea de eebo, 2- ethylhexylamine, undecylamine, laurylamine, stearylamine, oleylamine, linoleylamine, linolenylamine, oleostearylamine, 1,2-diamino-cyclohexane, 1,4-diamino-cyclohexane, 4,4'-methylenebis (cyclohexylamine), cyclopentylamine, l-amino-4-methylcyclohexane, -amino- (2,6-dimethyl) cyclohexane, 2-aminonorbornane, 4-aminocyclohexene, benzylamine, melamine, 2,4-diamino-6-phenyl-1,3,5-triamine, 4- (2, 4-di -tert-amylphenoxy) butylamine, o-, m- and / or p-toluidine, dimethyl amine, diethyl amine, dipropyl amine, didecyl amine, diieoprop amine, di-tert-butyl amine, N-tert-butylisopropyl amine, dihexylamine, N-methyl-N-amylamine, bis (ethylcyclohexyl) amine, N-octyl-N-cycloheptylamine, tributylamine, tetrao ineopentane, ethanolamine, diethanolamine, propanolamine , 2-amino-1-hexanol, 2-amino-1-butanol, 3-amino-1-propanol, 2-amino-1-propanol, 2-chloroethyl amine, trieidoxyamino-methane, 2- (2-aminoethylamino) - ethanol, 2- [2- (2-aminoethylamine) -ethylamino] -ethanol, 1- (beta-aminoethyl) -2-imidazolidone, N, N '-di-beta-aminoethyl) imidazolidone-2, 2- (2- aminoethylamino) -5-nitropyridine, 3-amino-N-ethylpiperidine, 2- (2-aminoethyl) -pyridine, 5-aminoindole, 3-amino-5-mercapto-1,2,4-triazole, N-aminoethyl piperazine, N, N'-bis (aminoethyl) -piperazine, N, N'-bis (piperazinyl) ethane, 1,4-diamino piperazine, 4- (aminomethyl) -piperidine, ethylenediamine, 1,3-diamino propane, 1,4-diamino butane, 1,5-diamino pentane, 1,7-diamino heptane, 1,8-diamino octane, 1,10-diamino decane, 1,12-diamino dodecane, 2,2 -dimethyl-1, 3-propanediamine, 3, 3'-diamino-N-methyl dipropyl amine, 1,2-propylene diamine, 1,3-propylene diamine, ethylaminopropylenediamine, dipropylenetriamine, di- (1,2-butylene) triamine, tris (2-aminoethyl) amine, N- (2-aminoethyl) -l, 3- propanediamine, hexamethylenediamine, N- (beta-cyanoethyl) ethane-1,2-diamine, triethylenetetramine, 1,3,6,9-tetraamino-octadecane, 1,3,6-triamino-9-oxodecane, N-methyl-1 , 2-propanediamine, tetra- (1, 2-propylene) pentamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, adenine, guanine, cytosine, guanidine, aminoguanidine, guanilurea, 2,2-diethoxyethylamine, 2,2-dimethoxyethylamine, 4, 4-diethoxybutyl amine, 2-amino-1-butanol, 4-amino-1-butanol, 12-aminododecanoate butyl, N- (2-aminoe useful) -piperidine, 2-amino-2-ethyl-l, 3-propanediol, N- (2-aminoethyl) -pyrodin, o-, m- and / or p-aminoacetophenone, 5-aminonaphtene, l-aminoanthraquinone, 2 -aminoanthraquinone, p-phenylazoaniline, aminothiophenol, 2-aminobenzophenone, 4-aminobenzophenone, o-aminobenzyl alcohol, 2-aminofluorene, 2-amino-9-fluorenone, 4-amino-9-fluorenone, N-aminohomopiperidine, 4-aminoantipyrine, 4-amino-2, 1,3-benzothiadiazole, 2-aminobenzothiazole, 3-amino-4-carbethoxypyrazole, 2-amino-5,6-dimethyl-benzimidazole, l-amino-2,6-dimethylpiperidine, 2-amino acid 4,6-dimethylpyridine, 2-amino-4,6-dimethylpyrimidine, 3-amino-5,6-dimethyl-1,2,4-triazole, 6-amino-1,3-dimethyluracil, N- (2-aminoethyl) ) -morpholine, 3-amino-N-ethylpiperidine, and 2- (2-aminoethyl) -pyridine. The preferred amine is cyclohexyl amine. When the chemically modified tannin is derived with aldehyde, it is preferred to employ a chemically unmodified tannin molar ratio: aldehyde of typically from about 1: 5 to about 1: 0.1, preferably from about 1: 3 to about 1: 0. , 25, and even more preferably 1: 2.5 haeta about 1: 1 (eg, 1: 2). The appropriate reaction temperatures may vary, typically from about 40 to about 120 ° C, preferably from about 45 days to about 115 ° C, and even more preferably from about 50 days to about 100 ° C during the reaction time of typically between about 100 ° C. about 1.5 haeta about 3.0 hour, preferably about about 1.75 haeta about 2.5 hour, although the reaction time is dictated and controlled by the degree of reaction reflected by the viecoeity of the reaction mixture . Obtaining the desired degree of aldehyde derivatization reaction is evidenced when the derivatized tannin exhibits a Brookfield viscosity at 60 to 80 ° C, typically from about 10 to about 250 cpe, preferably about 10 haeta about 150 cpe, and still preferably from about 10 to about 100 cps, determined at a concentration of the product in water of about 15-30% by weight, at the bottom of the solution. The determination of the target viscosity is mainly dictated by consideration as the need to avoid gelation and the desired storage half life as discussed in more detail with reference to the Mannich reaction. The aldehyde condensation is typically carried out at a pH of typically from about 2 haeta to about 6.5, preferably from about 2.5 haeta to about 6, and even more preferably from about 3 haeta to about 3 haeta about 5. Derivatization by The Mannich reaction is well known. As with the derivatization of the aldehyde, the time required for the reaction depends on the nature of the exact reactants used and the reaction conditions., tap as the temperature and reagent concentration. The molar ratio of aldehyde: amine employed typically ranges from about 3: 1 to about 0.5: 1, preferably from about 2: 1 to about 0.75: 1 and even more preferably from about 1.5: 1 to about. approximately 1: 1 (for example 1: 1). The molar ratio of chemically unmodified aldehyde: tannin which is used will typically vary from about 4: 1 to about 0.1: 1, preferably from about 3: 1 to about 0.5: 1, and preferably from about 2: 1 to about 1: 1 (for example 1.8: 1).

The preferred molar ratio of tannin: amine: aldehyde: chemical modifying agent ee of 1: 1, 8: 1, 8: 0.5. The Mannich reaction is carried out at a pH which is typically less than about 7 with a strong acid, typically HCl. The extension of the reaction is controlled by verifying the viecoeidad. More specifically, the reaction mixture is heated to a temperature of about 65 ° to about 95 ° C that forms a reaction product having an intermediate viscosity within a "range of key intermediate viscosity" and then the reaction by one or more of the external cooling stages, adding cooling water and / or adding acid. Since the storage life of the product is a function of the key intermediate viscosity, the viscosity and the shelf life can be calibrated by varying the intermediate viscosity for each determined reactive system and determining the effective storage life. Desirable storage life times can vary from one week to several months, depending on the desired end use. The gelation of the seventh means putting an end to life in storage. The range of key intermediate viscoeity is generally within a narrow range for a given item, for example 2 to 4 cpe. The viscosity of common intermediates varies from about 35 to 250 cpe when measured at 88 ° C in a Brookfield LVT viscometer with a 20% eolide content. The content of the modified tannin of the resulting tannin is preferably from about 20% to about 60% by weight and the pH is preferably less than 3.0%. Preferably, an anti-foaming material such as a silicon anti-foaming agent, exemplified by Silico e B prepared by Dow Corning corporation, a mineral oil for beating, or a high molecular weight alcohol, can be added in order to add an excessive foam. The average pee of the molecular weight of the tannin-derived product according to this deep-polymerization invention is generally within the range of 5,000 to 500,000. Preferably, the tannin products derived from this invention have a charge density typically ranging from 0.7 to about 5.0, preferably from about 1 to about 3, and even more preferably from about 1 to about 3.5 (eg. 2,0) iliequivalentee per gram (meq / g). The charge density of the cationic polymer is determined by titration with poly (vinyl sulfuric acid), potassium, PVSAK, after the addition of an indicator, which consists of taluidine blue. The addition of the indicator to a cationic polymeric solution makes the color blue. Titration with PVSAK will make the indicator ee turn a bluish purple color at the end point. The charge deficiency (meq / gm) is calculated from this titrator value. It is valuable to know the charge deneity because it is a function of the efficacy of the tannin products of the present invention as a coagulant or deeviscoeificante. The product of tannin derivative according to the present invention, particularly those which are amphoteric, provide an extremely effective control of the sticky materials in the water and the waste of the paint spray booths, where organic paint is used to bake them. of eoliant, particle of pitch, inks and materialee adheeivoe, in euepeneionee aquoeas of pulp, particularly under condiionee of alkaline pHFor example, between about 7 and 12, preferably between about 8 and 11. The product of tannin derivative of the present invention does not require the presence of clay which may have a draining problem, or metaphoric acid, such as zinc, which may be present. they can preeentar problem of discarding waste. The hydrolyzed polyacrylamide polymer can be used to improve flocculation and / or drainage. However, the tannin products derived from this invention can often provide on their own a sludge that can be rapidly dewatered, particularly or when used to control the high solids content in lacquer paints that have been prediluted with a formulation of an organic solvent. According to a first aspect of this invention, the materials adhering to the paint material with organic solvent bath as the particles of spray paint in the water of the paint spray booth, can be deviated by the addition of a product. of tannin derived according to the present invention, to the recirculating water system of the paint spray booth. More specifically, deviscosification would be necessary when using eietemae of paints based on organic eolventee. In contrast, water-based painting does not have the problem of stickiness, but because the paint is sprayed from the water to the paint spray booth, they should coagulate as described below in more detail. At an acidic pH, the tannin product derived either dissolves or is digested as hydrocolloidal euepeneion. The solution can be achieved by contact with acid such as nitric, eulphuric, ortho-phoric, hydrofluoric, hydrochloric, oxalic, and the like. As the pH of the water in the paint spray booth increases above about 6.5, the solubility of the derivatized tannin decreases and a flocose bolus is formed. It is advantageous in the present invention to plug the phenolic hydroxyl groups and tannins by chemical modification which can alter (increase) their beneficial hydrophobicity with the purpose of deeviecoefication, by decreasing the size of the bolus (and increasing its euperficial area) and therefore its efficiency . Without wishing to be bound by any particular theory, we believe that this is produced by the absorption of the tannin derived from the pigment particles. Because the derived tannins are hydrophobic, the solvent that surrounds the pigment ee occurs making the paint non-adherent. In general, the products of tannin derivatives are added to the water of the paint spray apparatus in a die or die-shaped form in order to obtain a concentration in the water of the spray booth of typically at least about 350 ppm, and typically of about 200 haeta about 1,000, preferably about 200 haeta about 750, and even more preferably about 200 haeta about 400 ppm. The derivatized tannin products can optionally be used in combination with a second component which is selected from the group consisting of pH control agent, polymer derived from some repeating hydrophilic-lipiphilic quaternary ammonium, dialkyl dialkyl quaternary ammonium polymers, soil-active agents, high-molecular-weight flocculants, inorganic flocculants, and the like and mixture of the members. The pH control agent can be added to the recirculating water system in order to establish and maintain a pH in a range of at least 7, preferably in a range of from 8 to 12, and even more preferably in a range of 8.5 to 11. Said pH control is implemented before spraying the paint and before or after deriving the addition of tannin. The particular pH that is selected will depend in part on whether the paint is based on organic or water-based solvents. For solvent-based paints, the pH of the water in the paint spray booth will typically range from about 8 to about 12, while for water-based paints the pH will typically be less than about 8.5 but greater than 7. The products of The tannins derived from the present invention are insoluble under the conditions of the alkaline pH above by using, for example, NaOH or KOH, and therefore improve their ability to de-isolate the paint particles in the recirculating aqueous system. More specifically, the pH control agent will be selected to act as a buffer and to stabilize any pH irregularity that might occur during operation in the paint spray booth. That is, it is well known to the skilled artisan that the addition of the acidic solutions of deviating agent in an alkaline recirculating water system will require monitoring and subsequent control of the pH of the recirculating system to keep the ph within the ph limit. antee defined. The addition of a ph control agent, such as calcium carbonate, sodium carbonate, calcium eulfate, eodium borate, sodium eilate and the like, tends to regulate the buffer of the ethereal, and to reduce the level of control necessary to keep the pH within the limits previously emitted. By establishing and maintaining a high pH, the control agents will assure a continuous ineolubility of the product derived from tannin in the recirculating water system, which in turn will improve the capacity of the latter to devisch the paint particles that are present in the seventh The amount of pH control agent that is added to the system is not critical to the invention, and will be added to the system in amounts that are sufficient to achieve the desired effect and the purpose for which it is added. In general, the pH control agent will be added to the eietem in a sufficient amount to maintain the pH at the desired level. Active agents which are suitable for use in this invention include, but are not limited to, anionic, cationic, nonionic, and amphoteric agents that enhance the dielectability and emulsifiability of paint particles in the material. Examples of suitable surfactants include alkylbenzene sulphonate, ether sulfuric acid ester, alkylsulfuric esters, eodium alkylsulfate, alkylsulfosuccinates, dialkylsulfosuccinatoe, alkylnaphthalenesulfonate formaldehyde condemnates, alkylnaphthalenesulfonates, sulfonated heterocyclic compounds, fatty acid condensates, amino acid, polyoxyethylene ether. alkyl, polyoxyethylene alkylaryl ether, polyethylene glycol fatty acid esters, polyalkylene ethylene glycol acid ethers, polyethylene glycol alkylamine ethers, polyhydric alcohol fatty acid esters, polyoxyethylene fatty acid ether esters and polyhydric alcohol, and alkylalolamides, of the betaine type, of the imidazoline type, of the eulphonate type, and of the alanine type; and cationic talee teneoactive agents such as alkyl pyridunium chlorohydrate, alkyltrimethylammonium halides, polyoxyethylene alkylamines, and polyoxyethylene dodecylamines. Suitable flocculants that are contemplated in this invention include, but are not limited to, cationic polyacrylamide, anionic or non-ionic, polyvinylamine, polyacrylate, polymethacrylate, polyethylene oxide, and emulsion, and mixtures thereof. According to a second aspect of this invention, the pitch and stickiness in a pulp and blade processing system can be controlled or inhibited by the addition of tannin derivative product according to the invention, to an aqueous solution of pulp where the tannin can be in complex and therefore can inactivate the dispersed tar particles, or alternatively, the tannins can be applied to the surfaces of the papermaking equipment where you have a need to depoeiten particle pegajoeae and can supply both a coating of a polymeric film that is resistant to depositing and sticking formation. More specifically, when the tannin derivative, preferably the amphoteric derivative tannin, of the present invention is applied to the felt applied in the papermaking process, the fibers are re-coated to the accumulation of sticky deposits. In particular, the adhesion of the adhesive material associated with the recycled fiber is controlled effectively. This is particularly advantageous for the papermaking industry where it employs an eubstantial proportion, at least about 10%, of recycled fiber, for example at least 70% of the fiber in recycled material. The tannins derived from this invention can be applied in the form of water solutions directly to the equipment that is being treated. The over-application of the tannins modified to the paper mill felt, however, will result in the accumulation of deposits and derived tannins and, therefore, in the loo of felts, will reduce the porosity which may eventually retard The elimination of water or can otherwise affect the production. Therefore, the processing of derivative tannin treatment should generally be consistent with the nature of the particular system that is being treated. The tannins derived from this invention are typically provided in the form of liquid compositions comprising aqueous solutions of the tannin derivative. The concentration of tannin derivative in the solution may vary from relatively dilute concentrations suitable for continuous application to the solubility or gelling limits of the tannin derivative, but generally the solutions are relatively concentrated for the purpose of handling and handling. In fact, the liquid compositions may comprise additional materials which, in addition to the dissolution of the tannin derivative, make it possible to obtain more concentrated compositions. An example of eetoe materialee eon loe alcoxietanolee talee as butoxyethanol. The aqueous compositions that are suitable for shipping and handling will generally contain between 5 and 50% by weight, of the active tannin, derived according to this invention. Said solutions may also contain cationic surfactants or surfactants which can be supplied by removal of the derivatized tannin and which can be applied to the felt by removal (for example using a separate shower system) or which can be mixed prior to application. In general, lae componeicionee acuoeae that are appropriate for transport and handling will contain between 5 and 50% in total peeo derivative tannin.

The most appropriate treatment specification depends on system factors such as the nature of the adhesive material, and whether the cleaning is continuous or periodic. Including liquid compositions comprising relatively high concentrations of modified tannin (for example, 50%), they can be used with full strength (100% as a liquid composition), for example by spraying the liquid composition and diluting directly on the felt. However, particularly when a continuous treatment is carried out, the compositions can be advantageously diluted at the treatment site with clean fresh water or with another aqueous liquid, when necessary to save water, water for processing can be suitable for the dilution. of good quality. The appropriate stickiness or pitch control can be carried out at application concentrations as low as 2 ppm of the tannin derivative, especially when a continuous treatment treatment is carried out, and the "continuous treatment" of the felt as used herein. means that the felt is routinely treated at least once during the cycle between its contact stage with the sheet and its return stage. This routine treatment is applied advantageously during the first part of the return stage. The felt can be put in contact with the sheet so that even the sticky material, including that which is typically associated with the recycled fibers, is inhibited from adhering to the felt, and the material that is not depoeited can be easily removed when a film is applied. Aqueous washing solution during the return stage. In some cases, continuous treatment does not result in practice, and treatment with modified tannin in accordance with this invention may be periodic. For example, the aqueous solutions of the tannin derivative may be sprayed onto the felt mat that the felt is satisfactorily conditioned, and then the spray may be interrupted until a supplementary conditioning is necessary to inhibit the accumulation of deposit on the felt. More detailed treatment procedures have been defined in US Patent No. 4,995,944, the entry of which is incorporated herein by reference. For a typical papermaking process, particularly those that have substantial amounts of recycled fiber, the modified tannin is generally applied at a rate of at least about 0.002 grams per square meter and felt per minute (g / m2-min) , preferably about 0.01 g / m2-min. or more when a continuous treatment is used, and preferably and of approximately 0.02 g / m2-min. or more during the application period when the application is intermittent. Preferably, application rates of 0.5 gram per square inch per minute or less are used to minimize the potential for clogging of the felt. Therefore, for conventional papermaking machines, with felt width from 2 to 7 meters, and with felt lengths from 10 to 40 meters, the application rate will commonly be between approximately 0.02 and 20 grams of tannin. derived per minute per meter of amplitude (ie g / m-min), more commonly between about 0.05 and 12.5 g / m-min. One of the techniques involves applying a g / m-min. or more initially, until the felt is conditioned. Once the conditioning has been carried out, the maintenance application regimes may be inferior, or as explained above, the application may even be interrupted periodically. Other equipment such as wires, screens, filters, rollers, and suction boxes, and materials such as metals, granite, rubber, and ceramic can also be advantageously treated in accordance with this invention. However, the invention is particularly useful with reference to the treatment of felts and acquires similar equipment components with suitable pores to expel water through the same (i.e., relatively thin pores) where the accumulation of eubstance deposit is undesirable, - in opposition for example to other equipment such as metal and plastic wires that have a relatively large pore for water to drain through them, where a certain amount Deposit accumulation is not considered to create undesirable problems. In any case, the concentration of the tannin derivative in the aqueous solution finally applied to the felt or other papermaking equipment should be at least about 0.0002% by weight. Preferably, in order to improve the uniformity of the die, the continuous treatment of the felt through a shower of the felt will be carried out with an aqueous solution for shower having between about 0.0002% by weight and about 0, 02% by weight of modified tannin. In a third aspect of this invention, the tannin derivative products of the invention can be used to decompose oil emulsions in water. According to this embodiment, the modified tannins of the invention can be added to a waste stream containing oil emulsified in an amount that is effective to decompose the oil-in-water emulsion. The specific amount of docification will vary widely, depending on the oil-in-water emulsion, the oil will be effectively agitated in water, and the desired degree of separation. In general, the amount of doping of the derived tannin product added to a waste stream is within the range of from about 1 haeta to about 20,000 ppm, preferably from about 10 haeta to about 2,000 ppm. The pH of the waste stream is preferably set to a range of 4 to 14, and more preferably to a range of 5 to 11. The pH can be adjusted with any alkaline or acidic agent. In a fourth aspect of this invention, the tannin derivative product of this invention can be used to coagulate waterborne paint particles in a recirculating water system of a paint spray booth. According to this embodiment of the invention, the measured tannins of the invention are added to the water of the spray booth before or after the water comes into contact with the particle of paint transported by the water being sprayed. From the preceding discussion, it will be appreciated that the tannin derivative according to the present invention has a variety of utility, such as, for example, to emulate any oil-in-water emulsion that can be found in the refinery's refined stream, in the nourish (by washing in the sink of loe aderzo de lae enealadae), and eimilaree. Lae corrientee de reeiduoe textilee could be treated to eliminate dyes and inorganic particles and wash stone. The raw water can clarify to remove the unique acids and the particles of the silt and eimilar. the following examples provide for illustrating the present invention, but should not be considered limitative of the invention in any way except as provided in the appended claims. All parties and percentages are in arrears unless otherwise indicated.

EXAMPLE 1 (Chemical modification with acetic anhydride, - derivatization with Mannich (cyclohexylamine / HCHO)) Part A In a clean reactor, 800 grams of glacial acetic acid, 800 grams of Miñosa tannin extract and 137.5 grams of anhydride were placed in a clean reactor. acetic (molar ratio 1: 0.5). The reactants were heated under a nitrogen amount to 105 ° C and maintained at this temperature for 1-1 / 2 hours. The temperature was then lowered to 50 ° C and 1.087 gram of deionized water was added.

Part B The reactants from part A were cooled to 30 ° C and 475 grams of cyclohexylamine were slowly added while keeping the temperature below 40 ° C. Next, formaldehyde was added in the form of 387.5 grams of active formaldehyde at 37% again maintaining the temperature below 40 ° C (molar ratio of unmodified tannin: cyclohexylamine: HCHO = 1: 1, 8: 1, 8). The solution was then heated to initiate the reaction. The temperature was controlled so as not to allow it to rise higher than 90 ° C. When the reading of the viscoeity reached 160-180 cpe, the degree of reaction was obtained. At this point the reaction was quenched by external cooling, and with the addition of 700 grams of deionized water followed by 612 grams of 31% muriatic acid (HCL). The reaction product was diluted with 5,000 gram of deionized water to obtain a 14-15% wind content and a Brookfield viscosity of 20-30 cpe. This material was placed back into the reactor, and 50% of the liquid portion was extracted at 85 ° C by applying vacuum. The final product, designated mueetra Nro.l ee adjusted a solid content of 19-20%, at a pH value of 1-1.4 a Brookfield viscosity of 20-100 cps. The obtained reaction product was stored under ambient conditions and after about six months it still had the liquid form and had not gelled or solidified.

EXAMPLE 2 The procedure of Example 1 was repeated, but nevertheless after cooling the reaction with deionized water at the end of the reaction, no muriatic acid was added. The resulting product, designated sample No. 2, was a suspension of the solid type which could be filtered and dried or spray-dried to a reddish-brown powder. The dry powder can be resolubilized in a muriatic acid-water solution to provide a final product similar to that obtained in Example 1.

EXAMPLE 3 (Chemical Modification with Quaternary amine, Derivation with HCHO) A typical epenting procedure for preparing the quaternized tannin and derivative is as follows. Part A The reactor was charged with 17.73 parts of deionized water and mixed by adding 14.95 parts of Mimosa tannin. The tannin diereium was heated to 70 ° C for 30 minutes. It was cooled to room temperature, and with cooling 12.43 parts of sodium hydroxide solution (50%) were added dropwise at a temperature below 50 ° C. 28.74 parts of N- (3-chloro-2-hydroxypropyl) trimethylammonium chloride (50% solution), molar ratio of tannin: quaternary amine = 1: 2, were added per drip at a temperature below 45 °. C. The solution was heated at 48 ° C for 90 minutes. Part B 7.69 parts of formaldehyde (37% strength) were added to the hot solution of Part A at 48% and then the temperature increased to 97.2 ° C (molar ratio and no change in tannin: HCHO = 1 :2). The reaction temperature was maintained at 97.2 ° C for about 1 hour. At the end of 1 hour, the final charge of 18.46 parts of deionized water was added and heating continued at 97.2 ° C for one more hour. When the viscosity reached 75 cpe ± 10, the reactor cooled and the contents were charged. The resulting product was designated sample 3.

EXAMPLE 4 The effectiveness of the modified tannins of this invention in order to declassify the overspray of paint was evaluated by using the paint spray apparatus described schematically FIG. 1 and described in FIG.

North American No. 4,948,513, whose description is incorporated herein by reference. The painting apparatus (10) comprises a spray chamber (12) having a front wall (14), side walls (16) and (18), a rear wall (20) and a pieo (22). A raised reservoir (24) is located on the front wall (14) with the upper edge (26) of the front wall forming the lower side of the reservoir so that the water overlies the reservoir and forms a curtain of water for the wall front (14). ee provides an outlet (28) at the bottom of the dew chamber (22), and the water that passes the tank, passes to the outlet (28) and through the pipes (30) haeta the second mixing chamber (32) . The mixing chamber (32) is coupled to an outer wall (34) and (36), to a side wall (38) and (40), and a pieo (42), and is divided into a first compartment (44) and a second compartment (46). ) through a landfill (48). The water flowing from the pipes (30), flows to the first compartment, and an outlet (50) is provided at the bottom of the second compartment. The upper edge (52) of the weir ends below the walls of the mixing chamber so that the water surpasses the first compartment to the second compartment, and then to the outlet (50). The pipes (52) direct the water from the outlet (50) to the third mixing chamber (54) comprising four walls (56) (57) (58) and (59) and one pieo (60). The open end (61) of the inlet pipe (62) for the pump (64) are placed in the mixing chamber (54) so that the pump (64) can be used to draw the water out of the mixing chamber. The water pumped from the mixing chamber (54) is directed through the outlet pipe of the pump (65) to the raised tank (24). The upper edge (21) of the rear wall (20) in the spray chamber (12) ends lower than the front upper edge (26) of the front wall (14), and a paint spray gun (66) is located so that the spray of paint can direct towards the front wall (14) of a diet of approximately nine inches. The capacity of the recirculating water system is approximately 14 liters and the recirculation rate is approximately 7.6 liters per minute. In the operation of the water circulation, it begins by providing a curtain of water, which flows out from the upper edge (26) towards the piezo (22) and which paes adjacent to the front wall (14) of the spray chamber (12) . Then spray paint from the spray gun (66) onto the front wall (14) so that the spray is drawn into the water curtain. Generally, the paint is sprayed at a rate of approximately 0.5 milliliters per minute, and the spray is continued until approximately 100 milliliters of paint have been sprayed. In each session, approximately 350 ppm of each tannin-derived product (bathed in 100% aeolide) is added to the water. The water is adjusted to a pH of about 8.0 to 10 using caustic. After careful circulation of the water in the tank to ensure complete mixing of the tannin product, a total of 100 milliliters is sprayed, and the floating solids of the storage chamber are examined and evaluated on average. The solidifying paint layers, deep to complete the paint spray, were evaluated, rubbing between the thumb and index finger. An excellent evaluation was interpreted as the one that provided a thorough examination.

EXAMPLE 5 (Chemical Modification with Quaternary Amine) Five Quaternary alkyl amine tannins, numbered as 4 to 8 mueetrae, were prepared by contacting Mimoea tannin with N- (3-chloro-2-hydroxypropyl) trimethylammonium chloride in hydroxide preemption of eodium, according to the procedure of Example 3, Part A, except that the tannin: quaternary amine molar ratio of Table 1 was used and the reaction mixture was cooled deep to heat the solution to 48 ° C during 90 minutes. As shown in Table 1, figure No. 5 demonstrated the existence of painting activity. The activity increased eignificantly by derivation as shown in Table 2.

Comparative Example 1 A condemned melamine-formaldehyde purchased from Cytec under the trademark Magnifloc 515C was designated Comparative Sample 1.

Comparative Example 2 A Mimosa tannin derivative derived with ethanol amine and formaldehyde was prepared according to the procedures of US Pat. No. 5,558,080. The resulting product was designated Comparative Mueetra No. 2.

EXAMPLE 6 Eiete mueetrae derived from tannin from Mimosa designated as Mueetrae No. 9 to 15 was prepared from tannin from Mimoea chemically modified with N- (3-chloro-2-hydroxypropyl) trimethylammonium chloride from quaternary alkylamine, and derived from it. HCHO according to Example 3, Parte A, and B, using the list of starting materials indicated in Table 2. It may be noted in Table 2 that Figure 13 is an excellent paint decoder. The performance of Mueetra 13 as a paint thinner with eolventee was demonstrated versus the melamine-formaldehyde condensate (Comparative Sample I), and a tannin derived from a primary amine (Comparative Mueetra 2) in Table 3. As shown, The Mueetra No. 13 provides a deerecoeconomic euperior as an induetrial pattern of the comparatives 1 and 2.

OR the iL a ß s: Deviations verified in high solids varnish paints (Solvent; Treatment evaluated at pH8, 0 - 10.0 Treatment Dosage, 350ppm active Paint spray rate approximately 2-4 ml / min. Chloride -N-chloro-2-hydroxypropyl) trimethyl ammonium IXJ O Table 2 or s: Deviations verified in high-solids varnish paints (Solvent) Treatment evaluated at pH8, 0 - 10.0 Treatment Dosage, 350ppm active Paint spray rate approx. 2-4 ml / min. Cuat: Chloride-N-chloro-2-hydroxypropyl) tri ethyl ammonium Ul Table 3 I Notes: HSE - High Content Varnish Paint (Automotive Coatings) Comparative Sample 1 - Condensed Folmaldehyde Melamine Comparative Sample 1 - Tannin Modified with primary amine (monoethanolamine) Sample 13 - Quaternary amine modified N (3) chloride amine -chloro-2-idroxypropyl) trimethyl ammonium and derivative with formaldehyde.

EXAMPLE 7 The product of tannin derivative of the invention, prepared as described below and assigned to 9 to 15, was evaluated to determine its efficacy in order to combine the oil emulsion into water using oil emulsion in water. Eetae oil-in-water emollions were formulated in the laboratory to serve as a reproducible method for quantitatively evaluating the ability to combine the emulation of the tannin compositions of this invention, and the emuleionee were prepared for each session as follows: They were connected in a motor oil mixture for Seare Spectrum 10W-40 (75% in peeo), and Petromix No.9 (obtainable in Witco Chemical) (25% in peeo) and mixed for 10 minutes in a Waring blender. A mueetra of 10 g. of the mixture was added to a clean Waring mixer, together with 390 ml, and deethylated water, and the resulting mixture was mixed for 7 minutes. The re-emulsifying emulsion was diluted with tap water in a 9: 1 ratio in peeo, added to a gallon container, mixed for 15 minutes, and allowed to stand overnight. Running water is a 9: 1% mixture of water from Lake Zurich at room temperature to reduce the specific conductance of tap water to 450-550 μm / cm. Running water was not prepared more than a week before its use.

To portions of 100 ml of the base emulsions in a vessel was added by pipette a 1% solution (active ingredient) of a tannin-derived product as specified in Table 4 in increasing concentrations as specified in Table 5. After stirring for 5 minutes the emulsions were allowed to stand for 30 minutes. Any surface oil was removed with a vacuum cleaner, being very careful not to shake the jars. The aqueous phase was then pipetted into a cuvette with spectrometer, the percentage transmission was recorded (at a sling length of 470 mm). The results are summarized in Table 5 and are depicted graphically in Figure 2. A higher percentage transmission corresponds to a decomposition of the most effective emulsion. -Table 4 CHA = c? clohexylamine uat = (3-chloro-2-hydrox? prop? 1) trimethylammonium chloride Table 5 EXAMPLE 8 (Chemical Modification with Acetic Acid, derivation with Mannich (cyclohexylamine / HCHO)) This example illustrates the performance of various modified tannins as coagulants for the removal of suspended solids. The yield of Sample 1 as a coagulant was verified in a 1% dispersion of water-based paint and the results are indicated in Figure 3 The test was carried out by preparing a loading solution of 1% (active ingredient) of the Sample 1 in water and a loading solution at 1% by weight of water-based paint, in water. A sufficient amount of the solution of Sample 1 was added to the samples of the paint solution until the concentration of active ingredient was reached. in ppm as indicated in Table 6 The resulting mixture was mixed for 5 minutes and allowed to stand for 10 minutes A sample of the paint loading solution containing the tannin product of Sample 1 was added to a bucket of a spectrophotometer. Percent transmission at a sling length of 470 nm was recorded at increasing concentrations of active ingredient as shown in Table 6 These results are shown graphically in Figure 3 Using the same test procedure, the performance of Sample 1 was compared against Sample 5 (quaternized tannin). Sample 3 (quaternized tannin derivative derivative with formaldehyde). Comparative Sample 2 (aminomethylated tannin), and Comparative Sample 1 (formaldehyde melamine condensate). Table 6 The most effective materials were those that provided the highest light transmission percentage. As shown in Table 6 and Figure 3, the most effective treatment was Sample 1 that provided the earliest "open" in the Water clarity at 100 ppn.

EXAMPLE (Chemical Modification with Acetic Anhydride: Derivation with Mannich (Cyclohexylamine / HCHO)) This example illustrates the performance of a Mimosa tannin chemically modified with acetic anhydride and derivatized with the Mannich reaction using cyclohexylamine and HCHO as a paint deviscoei fi er. solvent Accordingly, a mimosa tannin was modified and chemically derivatized according to the procedure of Example 1, and the product was designated Sample 16. Table 7 below shows the excellent yields of Sample 16 as a solvent-based paint de-chaser. . The treatment was evaluated at a pH of 8.5 using the paint spray booth model described in Example 4. Table 7 The examples describe various embodiments of the invention. Other embodiments will be apparent to those skilled in the art from a consideration of the specification or practice of the invention to be disclosed herein. It should be understood that the modifications and variations may be implemented if departing from the spirit and scope of the new concepts of this invention. It will further be understood that the invention is not confined to the particular formulations and exemplifies that are illustrated herein, but that it encompasses the modified forms thereof which are within the scope of the appended claims.

Claims (1)

1. PFTVTNDTCA? TQNES Having thus specially described and determined the nature of the present invention and the manner in which it is to be practiced, it is claimed to claim as property and exclusive right 1 A composition comprising tann containing hydroxyl groups which has been (a) chemically modified by reaction of at least one of said hydroxyl groups with at least one member which is selected from the group consisting of an esterification agent and an etherification agent, and (b) which is derivatized by reaction with aldehyde, or aldehyde and at least one member selected from the group consisting of ammonia and organic amine containing at least one primary or secondary nitrogen, said derivinated tampa being soluble or dispersible in water at a pH below 7 and insoluble in water at a pH above 7 2 The composition of the remvindication 1 where the chemically modified tum is derived by reacting formaldehyde 3 composition The composition of the claim 1 where the chemically modified tannin is derived by reaction with aldehyde and at least one member selected from the group consisting of primary amine and secondary amine 4 The composition of the claim 3 where the amines are selected between at least one member of the group consisting of aliphatic amine, cycloaliphatic amine, heterocyclic amine, aromatic amine, aromatic aliphatic amine, heterocyclic aliphatic amine. and heterocyclic aromatic amine. 5. The composition of the reinvidication 4 where the amine is cycloaliphatic. 6. The composition of the remvidication 5 where the amine is cyclohexyl amine 7 The composition of the remvidication 1 where the esterification agent is an acid or its corresponding anhydride, said acid being represented by the structural formula: R ^ COOH (IV) where R1 is a straight, branched or cyclic hetero atom, substituted or unsubstituted, aliphatic or aromatic, saturated or unsaturated, or a non-hetero atom, containing a hydrocarbyl group containing from about 1 to about 60 carbon atoms 8. The composition of the claim 1 wherein the etherification agent is represented by the structural formula R2- (X) n (V) where R "is a hetero substituted or unsubstituted, aliphatic or aromatic, saturated or unsaturated, linear branched or cyclic hetero atom , or non-hetero atom containing a hydrocarbyl group containing from about 1 to about 60 carbon atoms X represents halogen and n is a number from 1 to 5 9 The composition of the remvidication 8 where n is 1 10 The composition of the reinvidication 1 where the etherification agent is a quaternary amine compound that is represented by the formula RJ R -N-R '(VI) R5 where R to R6 which may be the same or different independently represent a straight or branched heterocyclic, substituted or unsubstituted aliphatic or aromatic, saturated or unsaturated hetero atom or a non-hetero atom, containing a hydrocarbyl group containing from about 1 to about 60 carbon atoms and Y is an anion, with the proviso that at least one of R3 to R6 is substituted haioqene so that it will undergo said etherification reaction. The composition of the claim 1 where the agent of eetep ication is represented by the formula P "-COOH where R: is a substituted or unsubstituted hydrocarbyl group selected from the group consisting of C to C10 alkyl, C6 to C10 cycloalkyl aryl C5 to C10 alkaryl and aralkyl, wherein the alkylene or aryl groups are as disclosed with reference to alkyl and aplo and wherein said substituents are selected from at least one member of the group consisting of droxyl and carboxyl or corresponding anhydrides 12 The composition of the re? nd? cac? on 7 where the esterification agent is acetic anhydride 13 The composition of the radiation 10 where in said formula R3 to R6 which can being the same or different represent a substituted or unsubstituted hydrocarbon group that is independently selected from the group consisting of C: to C15 alkyl, Cycloalkyl Ce to C8. C10 to C10, aralkyl or alkaryloid it the alkyl and aryl groups thereof are as described for alkyl and apr above, and wherein the substituents are selected from the group consisting of hydrocyl and halo. wherein the quaternary amine compound is selected from at least one member of the group consisting of halogen-substituted alkyl ammonium salts, alkyl-substituted ammonium salts with hydroxy, and halo. The composition of the 14-valent replacing where the quaternary amine is N- (r = lo-h? drox? C to C6 alkyl) trihalide of ammonium alkyl Cl to Zt 16 The composition of the renvidiation 15 wherein the quaternary ammonium compound is an N- (3-chloro- 2-hydroxypropyl) trimethyl ammonium 17 The composition of the claim 8 where in the agent of designation R "is alkyl C: a Caü 18 The composition of the revidiation 17 where the agent of designation is dichloro methane 19 U A method for providing at least one of coagulation, and deviscosification of the solid particles that are suspended in the aqueous systems, which comprises adding to the system, in an amount effective to coagulate or de-viscosify the particles in suspension at least one tannin additive that has been chemically modified and derived, where (a) the chemically modified tannin is represented by the structural formula (VID where z, may be the same or different is independently selected from the group consisting of hydrogen OR IIR ^ C- R2-, and (R6) (R5) (R4) (R3) N + which may be the same or different is hydrogen or a linear branched or cyclic hetero atom, substituted or unsubstituted or aliphatic or aromatic, saturated or unsaturated, linear branched or cyclic or a non-hetero atom containing a hydrocarbyl group containing from about 1 to about 60 carbon atoms, n is a number that may vary from 0 to about 2, with the proviso that at least one of z it is not hydrogen, and where (b) the tannin derivative is the condensation reaction product of the chemically modified tammine of Formula VII and at least one member of the group consisting of (1) aldehyde, (2) aldehyde and ammonia ( 3) aldehyde and at least one primary or secondary nitrogen containing amine The method of claim 19 wherein the derivatized tannin is derived from the chemically modified tannin of the O. II formula VII wherein 2 is R: -C- and P1 is at the C lyl: C1C 21 The method of claim 19 donates the tannin O chemically modified Z is R: -C- and R1 is alkyl C: a Clc 22 The method of the reagent 19 wherein the derivative tannin is derived from the chemically modified tannin of formula VII wherein 2 is a portion of a quaternary amine cation of the Formula ', RI -Rf'-N'- R *! Rrj where R3 to R6 which may be the same or different is independently selected from the group consisting of C: to C10 alkyl substituted or unsubstituted where said substituents are selected from hydroxy and halo. 23. The method of claim 22 wherein the amine cation is (2-hydroxypropyl) tyrimethyl ammonium. The method of any of claims 20 to 22 wherein the chemically modified tannin is derivatized with an aldehyde. The method of any of claims 20 to 22 wherein the chemically modified tannin is derivatized by reaction with aldehyde and at least one amine primary or secuandaria that contains nitrogen. The method of claim 25 wherein the derivatizing amine is cyclohexyl amine 2? The method of claim 19 wherein the tannin additive is added to the aqueous system in an amount of from about 250 to about 1,000 ppm based on the pee of the aqueous system. The method of claim 19 wherein the tannin additive is added to the water The method of claim 19 wherein the additive is applied as an aqueous solution to the aqueous system of a process for the manufacture of pulp and paper that is applied to the paint spraying booth to deconstruct the sticky paint particles that are suspended therein. it is prone to the formation of tar and sticky agglutilations. The method of claim 2 wherein the additive is applied in the form of an aqueous solution to the surface of a machine for the production of paper at the places that are prone to form pitch and sticky agglutilates to de-viscosify said pitch and sticky agglutilations . 31. The method of claim 28 wherein the paint particles are derived from a water-based paint. The method of claim 28 wherein the paint particles drift from a solvent-based paint. A method for demulsifying an oil-in-water emulsion comprising adding to the oil-in-water emulsion an effective demystinating amount of at least one tannin additive that has been chemically modified and derived, where (a) the chemically modified tannin is represented by the structural formula • (VII) where 2, which may be the same or different, is independently selected from the group consisting of O II hydrogen.R ^ C-.R ^ .ytR ^ R5) ^ 4) (R3) N + where R1 to R6 which may be the same or different is hydrogen or a linear branched or cyclic hetero atom, substituted or unsubstituted, aliphatic or aromatic, saturated or unsaturated, or a non-hetero atom containing a hydrocarbyl group containing from about 1 to about 60 carbon atoms; n is a number that can vary from 0 to about 2, with the proviso that at least one of 2 is not hydrogen; and wherein (b) the tannin derivative is the condensation reaction product of the chemically modified tannin of Formula VII and at least one member of the group consisting of (1) andehyde, (2) aldehyde and ammonia, (3) aldehyde and at least one primary or secondary amine containing nitrogen. 34. The method of claim 33 wherein the derivative tannin is derived from chemically modified tannin of Formula VII wherein 2 is R1-C- and R1 is C1 to C1C alkyl,. The method of claim 33 wherein in the chemically modified tannin Z is Rl-C- and F is alkyl C? to C '1.0 36. The method of claim 33 wherein the derivative tannin is derived from the chemically modified tannin of Formula VII where 2 is a porsion of a quaternary amine cation of Formula R3 I _R6_N-_R 'I R5 where R3 to R6 which may be the same or different are independently selected from the group consisting of substituted or unsubstituted Cx to C10 alkyl wherein said substituents are selected from hydroxy and halo 37. The method of claim 36 wherein the amine cation is (2-hydrox? propyl) trimethyl. ammonium 38. The method of any one of claims 34 to 37 wherein the chemically modified tannin is derivatized with aldehyde. The method of any of claims 34 s 37 wherein the chemically modified tannin is derivatized by reaction with aldehyde and at least one amine primary or secondary containing nitrogen 40 The method of claim 39 wherein the cyclohexylamine devatting amine 41 The method of the claim 33 wherein the demulsifying effective amount may vary from about 1 to about 20,000 pp based on the pee of the emulsion