MXPA97009262A - Soluble polymers in water and compositions of losmis - Google Patents

Abstract

Water-soluble polymers are exposed including functionality from the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, aza crown groupther, oxy-crown ether groups, guanidine, amide groups, deester groups, aminoadicarboxylic groups, permethylated polyvinylpyridine groups, permethylated amine groups, mercaptosuccinic acid groups, alkyl thiol groups and N-alkylotiour groups

Description

SOLUBLE POLYMERS IN WATER AND COMPOSITIONS OF THE SAME FIELD OF THE INVENTION The present invention relates to water soluble polymers and compositions thereof; such as water-soluble polymers and compositions thereof useful, for example, in processes for the selective separation of metal ions from aqueous streams, and processes for the selective separation of metals from solid matrices. This invention is the result of a contract with the Department of Energy of the United States (Contract No. -7405-ENG-36). BACKGROUND OF THE INVENTION Water soluble polymers are well known for the retention or recovery of certain metal ions from solutions under certain conditions, for example, certain pH conditions (see, for example, Pure and Applied Chemistry, Vol.52, pp.1833-1905 (1980), Talanta, vol.36, No.8, pp.861-863 (1989), and US Pat. No. 4, 741, 831). In addition, higher molecular weight varieties of water soluble polymers such as polyethyleneimine have been used as coatings on, for example, silica gel, for the separation and recovery of metal ions. However, the selectivity of the polymer for target metals due to the competition of competing or interfering ions - - within the solutions can present unique challenges. It is an object of the present invention to provide novel water soluble polymers. It is a further object of the present invention to provide water soluble polymer compositions having defined molecular weight ranges. It is still another object of the present invention to provide water soluble polymer compositions that include at least two different water soluble polymers, differing the different water soluble polymers in functionality, molecular weight range or both. SUMMARY OF THE INVENTION In order to achieve the foregoing and other objectives, and according to the purposes of the present invention, as it is incorporated and is widely described herein, the present invention provides a water soluble polymer of the formula. (CH3-CH2-N-CH2-CH2NX?) N- (i) CH2-CH2NX2X3 where Xi, X2, X3 in each polymer unit is a group independently selected from a substituent selected from H, C (O) CH2CH (SH) COOH, - (CH2) mYZP where when m is a selected integer 0.2.3, and 4, Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown oxi ethers, azela crown ethers, thio crown ethers, and H, and when m is 1, Y is selected from C = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown oxi ethers, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between approximately 12 and 12,000; or (CH2), (R -.) PYCHY (R2) P where m is an integer from 0 to 6, Y is selected from C = 0, P = 0, and C = S, Ri and R2 are selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol, alkyl, aryl, and H, p is an integer from 1 to 2, and n is an integer between about 12 and 12,000 with the proviso that at least one of Xi, X2, X3 is not hydrogen; - (CH2-CH) N- (ii) (CH2) q-NX4X5 where X4 and X5 in each polymer unit is a group independently selected from a substituent selected from H, C (0) CH2CH (SH) COOH, - (CH2) mYZp where q is an integer from 0 to 4, and where when m is a selected integer of 0.2.3, and 4, Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, and when m is 1, Y is selected from C = 0 , C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown oxysethers, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between about 24 and 24,000 with the condition that at least one of X4 and X5 is not hydrogen; - (CH2-CH) n- (iii) I ox6 where X6 in each unit of the polymer is a group independently selected from a substituent selected from C (O) CH2CH (SH) COOH, where m is an integer selected from 0 , 2,3, and 4, and is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, aza crown ethers, thio crown ethers, and H, and when m is 1, Y is selected from C = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazole -thione, methylphenylpyrazolethione, crown oxy ethers, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between approximately 24 and 24,000; - (CHX7-CH2) n- (CH2-CX5X9) m- (iv) where X7, and XT and X9 in each polymer unit is a group independently selected from a substituent of C (O) CH2CH (SH) COOH , - (CH2) mY p where m is a selected integer of 0.2.3, and 4, Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, and when m is 1, Y is selected from C = 0 , C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown oxy ethers, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between about 12 and 12,000, or - (CH2-CH) n- (v) NXioXn where X? 0 and Xn in each polymer unit are a thiolacto or a group independently selected from a substituent selected from C (O) CH2CH (SH) COOH, and - (CH2) mYZp where m is an integer from 0 up to 4, Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S; Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between approximately 24 and 24,000. The present invention also provides a water soluble polymer of the formula (CH2-CH2-N-CH2-CH2NX) "- (i) wherein Xi, X2, X3 in each unit of the polymer is a group independently selected from a substituent selected from H, C (0) CH2CH (SH) COOH, - (CH2) mYZP where m is an integer from 0 to 4, and Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, p is an integer from 1 to 2, and n is an integer between approximately 12 and 12,000; where m is an integer from 0 to 6, Y is selected from C = 0, P = 0, and C = S, Ri and R2 is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, and H, p is an integer from 1 to 2, and n is an integer between about 12 and 12,000; - (CH2-CH) n- (ii) where X4 and X5 in each polymer unit is a group independently selected from a substituent selected from H, C (0) CH2CH (SH) COOH, where q is an integer from 0 to 4, m is an integer from 0 to 4, and Y is selected from C = 0, P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazole -thione, methylphenylpyrazolethione, crown oxy ethers, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between approximately 24 and 24,000; - (CH2-CH) n- (iii) ' OX6 where X6 in each polymer unit is a group independently selected from a substituent selected from C (O) CH2CH (SH) COOH, - (CH2) mYZp where m is an integer selected from 0 to 4, and is selected from from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, p is an integer from 1 to 2, and n is an integer between approximately 24 and 24,000; - (CHX7-CH2) n- (CH2-CX8X9) m- (iv) where X7, Xs, and X9 in each polymer unit is a group independently selected from a substituent selected from C (O) CH2CH (SH) COOH, where m is an integer from 0 to 4, and is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, p is an integer from 1 to 2, and n is an integer between approximately 12 and 12,000, or - (CH2-CH) n- (v) I NXioXu where Xi0 and Xu in each polymer unit are a thiolacto or a group independently selected from a substituent selected from C (0) CH2CH (SH) COOH, and where m is an integer from 0 to 4, and Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S; Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between about 24 and 24,000, said water soluble polymer having a molecular weight greater than about 10,000 and further characterized as essentially free of molecular weights less than about 10,000. In one embodiment of the present invention, there is provided a water soluble polymer having nitrogen, oxygen, or sulfur containing groups capable of binding selected metal ions, said water soluble polymer having a molecular weight greater than about 30,000 and characterized as essentially free of molecular weights less than about 30,000. In another embodiment of the present invention, the water-soluble polymer includes the operation of the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, ether groups of aza-crown, oxy-crown ether groups, guanidino groups, amide groups, ester groups, aminodicarboxylic groups, permethyl polvinylpyridine groups, permethyl amine groups, mercaptosuccinic acid groups, alkylthiol groups, and N-alkyl thiourea groups. DETAILED DESCRIPTION The present invention relates to water-soluble polymers, such water-soluble polymers useful, for example, in the separation of various metals, for example, toxic and / or precious metals and / or dirty metals from aqueous streams. The water-soluble polymers useful in the practice of the present invention are synthetic water-soluble polymers, that is, they are not naturally occurring water-soluble polymers such as starch, cellulose, and the like and do not comprise water-soluble polymers. that occur naturally modified. The water-soluble polymers used in the present invention generally include a nitrogen-containing group, oxygen, or sulfur. Exemplary water soluble polymers used in the present invention are polyalkyleneimines such as polyethylenimine and modified polyalkyleneimines, ie, polyalkyleneimines such as polyethylenimine wherein the water soluble polymer includes the functionality selected from the group consisting of carboxylic acid groups, ester groups, amide groups, hydroxamic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, aza crown ether groups, oxy ether crown groups, guanidine groups, thiolacto groups, catechol groups, mercaptosuccinic acid groups , alkyl thiol groups, and N-alkylthioiurea groups. In addition to polyethyleneimine as the basic structure of many of the water-soluble polymers, other structures of the water-soluble polymer can be used with nitrogen-containing groups such as poly (vinylamine), polyvinylpyridine, poly (acrylamide), and poly (allylamine) . Also, water-soluble polymer structures can be used with oxygen-containing groups such as poly (vinylalcohol), or oxygen and nitrogen containing groups such as polyvinylpyrrolidone. The amine bases can also be permeated to give permethyl polyethyleneimine, permethylated polyvinylpyridine, permethylated polyallylamine, or permethylated polyvinylamine. The water soluble polymers can also be constructed from the polymerization reactions of the vinyl monomer to give a number of pendant groups, acrylamide copolymer and bisphosphonic ethers and acids. Water soluble polymers with metal ligation properties can be obtained from the open ring reactions, for example, the treatment of polypyrrolidone with base or hydroxylamine. Exemplary exemplary water-soluble polymers are the product of the reaction of polyethylenimine and an arylalkylhaloacetylpyrazolone such as phenylmethylchloroacetylpyrazolone or dimethylchloroacetylpyrazolone to produce a substituted phenylethylacetyl pyrazolone or dimethylacetylpyrazolone substituted polyethylenimine, the reaction product of polyethylenimine (polyallylamine, polyvinylamine) and an acid halocarboxylic acid such as bromoacetic acid or chloroacetic acid to produce a substituted polyethylenimine of amino carboxylate (polyallylamine, polyvinylamine), the reaction product of polyethylenimine (polyvinylamine) and phosphoric acid and formaldehyde to give a substituted polyethylene imine of phosphonic acid (polyvinylamine), the reaction of the polyethylenimine and a monohydroxamic acid of succinic acid to give a substituted polyethylenimine of hydroxamic acid, the reaction of the polyethylenimine with acrylamide or ethylacrylate to give a or a substituted polyethyleneimine of amide, the reaction of vinylalcohol with a crown alcohol to give a substituted vinylalcohol of oxy-crown, the permethylation of polyvinylpyridine or polyethylenimine or polyvinylamine or polyallylamine to give the respective permethylated polymers, the open ring of polypyrrolidone with hydroxylamine to give the hydroxamic acid polymer, the copolymerization of a beta-bisphosphonic acid or ester with acrylamide to give a copolymer, the reaction of the polyethylenimine with a bisphosphonic acid or ester to give bisphosphonic acid or ester polyethyleneimine, and the product of the polyethylenimine reaction and a haloacetylase ring material such as a coloracetylase crown ether to produce a substituted polyethyleneimine of aza crown ether. When polyethylenimine is functionalized, care must be taken to control the level of functionality according to the solubility problems of certain pH values may exist depending on the type of functional groups and the base used. The water-soluble polymers used in the present process preferably maintain their solubility in water over the entire pH range, for example, pH 1 to 14. Preferably, any polyethylenimine used in the present invention includes primary, secondary, and tertiary amines. Bisfunctionality can be performed for primary nitrogens considering the multidentate character of some of the chelating groups. Polyethyleneimine is a branched polymer, which gives it a globular nature and a high charge density, which partly accounts for its uniqueness in the polyamine family of polymers. The highly branched character also considers better chelate site interactions with metal ions within the polymer. Other polyamines, that is; polyvinylamine and polyallylamine, can be used as foundations, and are composed of all primary nitrogens, but are linear polymers and if over-functionalized can lead to insolubility in different pH ranges. The use of a pre-purified polymer (sizing) functionality may be preferred in the process. The use of the pre-purified polymer, for example, polyethyleneimine, has the advantage that the reagents used in the subsequent functional steps do not lose the low molecular weight polyethylenimine that will be lost in the subsequent purification of the functional polymers, in addition, this It gives an extra margin of assurance that there will be no escape of the polymer during the use of the polymers in any ultrafiltration process. The conditions in the preparation of the water-soluble polymers can be important to ensure that there is no detectable leakage through an ultrafiltration membrane during some subsequent processes. Several factors are important in assisting the pre-sizing of water-soluble polymers; the concentration of the polymer, the pH value, and the ionic strength in which the polymers are pre-dimensioned, are all important. Since water-soluble polymers can be added in solution and since polymers can be expanded or reduced in size, the conditions that effect these trends must be controlled. For example, it is known that polyethyleneimine can change its average size to 60% between a basic and acidic solution (higher in the acidic solution and lower in the basic solution). In this way, the polyethyleneimine must be prepurified at the pH where its size is smaller to also ensure that the smaller fragments are removed from the larger fragments (at a pH of about 10-11).

Other polymers due to either cationic, anionic, or neutral nature will have different optimum pH values for prepurification depending on the pH that gives the smallest polymer volume in the solution. The ionic strength of a solution can also effect the polymer volume in the solution in a manner similar to the effects of pH. If the polymer concentrations are too high in the solution, they will be added, again making the potential ability to obtain polymers that will not escape through the membranes during any ultrafiltration process. The prior art in the preparation of polyethyleneimine or other water-soluble polymers for use in the separation of metals has been completely uncertain in how it is prepared and processed for use in ultrafiltration techniques. The present process for purifying polyethyleneimine is unique in that the purification scheme does not obstruct the ultrafiltration membranes. In contrast, some polyethyleneimine manufacturers have been unable to develop a purification technique to size the polymer using ultrafiltration without severely and irreversibly obstructing the membranes. Note that another main use of polyethyleneimine is as an adhesive and polyethyleneimine is known to be attached to many surfaces, especially cellulose and anionic surfaces. It has been reported that polyethyleneimine is fractionated by size using GPC (size exclusion chromatography), precipitation, and by exhaustive dialysis. The determinations of the average molecular weight were carried out by means of osmometry, ultracentrifugation, viscometry, and light scattering techniques. Generally, the literature refers to determining the average molecular weight instead of producing fractions that do not pass a cut of absolute molecular weight. The water-soluble polymers of the present invention can be used in various potential compositions for the selective separation of metal ions from aqueous streams or metals from solid matrices. There may be only one polymer that will selectively bond with only one metal ion on all other ions and materials under the conditions of the process. The separation is carried out by joining that metal ion to the water soluble polymer and then using a separation technique such as ultrafiltration to remove water and other polymer materials. The metal ion bonded to the polymer is thus concentrated. The polymer bonded metal can be released from the polymer by a variety of processes as shown in the following equations: M (P) + H + >; HP + M + (ec.l) M (P) + L > ML + (P) (ec.2) M (P) + e "> MX + (P) (ec.3) where M is the metal ion, (P) is the water soluble polymer, L is a complex competitor , H + is a proton, x is the valid state of the metal, and e is an electron for an oxidation change reaction. Where the metal is released by a proton (ec.l) or by a competing molecular binder (ec.2), the polymer-free metal ion is recovered by a diafiltration process. In some examples, the metal ion can be bound very tightly to the polymer that is most desirable to concentrate the heating process to destroy the polymer (incineration, hot acid digestion, casting, etc.) and recover the metal. Optionally, for the purposes of waste management it may be desirable to solidify the polymer bonded metal, for example, in a cement grout or cement material, in such a manner that it passes the toxic leaching tests (TCLP). Another potential composition may include a single polymer that will bind to a combination of metal ions under the conditions of the process. Separation and selectivity are carried out by linking this combination of metal ions and then using a separation technique such as ultrafiltration to remove water and other materials from the metal-polymer complexes. The metals bonded to the polymer can be selectively released from the polymer by a variety of processes as shown above in equations 1, 2, and 3. Where the selected metal is released by protons (ec.l) or by a competent molecular binder ( ec.2) the polymer free metal ion can be recovered by a diafiltration process. The purification is repeated until all the desired metals have been selectively recovered. Again in some cases, the metal ions can be bonded very tightly to the polymer that is most desirable to concentrate the heating process to destroy the polymer to recover the metals. Optionally, for the purposes of waste management it may be desirable to solidify the polymer bonded metal, for example, in a slurry or cement material, in such a manner as to pass the toxic leaching tests (TCLP). Yet another composition uses a polymer formulation (two or more polymers of the same molecular weight range) bound in such proportion and with such functionality to have the desired selectivity that a, a combination of metal ions under certain pH conditions, counter-ion , and / or ionic strength. The separation is achieved by linking the metal ions to the water soluble polymers and then using a separation technique such as ultrafiltration to remove water and other polymer materials. The metals bound to mixed polymer are therefore concentrated and furthermore can be purified by washing with a clean solution in a diafiltration process to remove any final impurity. The metals bound to polymer can be selectively released from the polymers by a variety of processes as shown in equations 1, 2, and / or 3. When the process uses equation 1 and / or 2, the water-soluble polymers are they can selectively separate from the respective metal or groups of metals by, for example, proper pH control in a range where a polymer is separated from its particular metal while the second water-soluble polymer retains its particular metal as a metal bonded to it. water soluble polymer. The second and subsequent polymers can be separated from the remaining metal ions as desired for the separation process and the regeneration of the polymers for further reuse in the separation process. Still another composition uses a formulation of the polymer (two or more polymers of different molecular weight range) mixed in such proportion and with such functionality to have the desired selectivity that a, a combination of metal ions under certain conditions of pH, counter-ion, and / or ionic strength. The separation is achieved by linking the metal ions to the water soluble polymer and then using a separation technique such as ultrafiltration to remove water and other polymer materials. The mixed polymer-bound metals are therefore concentrated and can further be purified by washing them with a clean solution in a diafiltration process to remove any final impurity. The metals bound to polymer can be selectively released from the polymers by a variety of processes as shown in equations 1, 2, and / or 3. When the process uses equation 1 and / or 2, the water soluble polymers can selectively separating from the respective metal ions or metal ion group by, for example, an appropriate pH control in a range where a polymer is separated from its particular metal while the second water-soluble polymer retains its particular metal as a metal bound to the water soluble polymer. The second and subsequent polymers can be separated from the remaining metal ions as desired for the separation process and the regeneration of the polymers for further reuse in the separation process. Alternatively, since the water-soluble polymers are of different size ranges, it is possible to remove the metal from a polymer by equations 1 through 3, and to separate the smaller polymer that contains one type of functionality from the larger polymer. with a different kind of functionality. One of the functionalities is chosen to bind the metal ion of interest so closely that the polymer containing that functionality and the bound metal ions can be dimensioned separately from the other size of the polymer (s). Another composition may include a single polymer or formulation of polymers that will bond with a single metal ion or a combination of metal ions under the conditions of the method. The separation and selectivity is carried out by linking that combination of metal ions to the water-soluble polymer or polymers, and then using a one-step separation technique such as ultrafiltration to remove the water and other materials from the metals bound to the polymer. . The polymer bonded metals are further concentrated until dried or nearly dried on a flat ultrafiltration membrane. The membrane either dissolves or is digested in an appropriate medium or leached with an appropriate acid or binder until the metals that were on the membrane are fully recovered. The recovered solution, which constitutes a concentrate of the metal ions selected from the original solution, can then be analyzed using an appropriate analytical instrument or wet chemistry techniques. Another composition may include a single polymer or polymer formulation that will bond with a single metal ion or a combination of metal ions under the process conditions. The separation is achieved by linking the selected metal ions to the water soluble polymer or polymers and then using a separation technique such as biphasic liquid-liquid extraction to remove other unbound metal materials and ions from the aqueous polymer solution. Metals that do not bind to the polymer and go to the second or organic phase are separated from the aqueous phase containing the polymer by standard phase separation techniques, for example, mixer-settlers, liquid extraction membranes, or centrifugal contactors , etc. The metals can be extracted again from the second phase into another aqueous phase for the purposes of recovery. The polymers can be regenerated from the aqueous stream by first the concentration ultrafiltration followed by the diafiltration. This process can be reversed by extracting again the metal ion of interest from a two-phase system using aqueous solutions of the water-soluble polymer. Usually, the concentration of the water-soluble polymer in the metal separation is from about 0.001 percent of the volume by weight to about 25 percent by volume of the final mixed solution, more preferably from about 0.001 volume percent by weight to about 5 percent volume by weight of the final solution. It is sufficient and in some cases desirable to have at least one sufficient polymer right in the solution such that the molar ratio of the polymer to the metal ions in the solution is one. Using high concentrations of water-soluble polymer may often result in a lower flux or flux during a stage of ultrafiltration. The use of high polymer concentration can also cause an aggregation effect where little or no metal ion bond occurs to the polymer when the metal ion sees a high initial polymer concentration. During the diafiltration phase the polymer and the polymer bound to the metal can often become too high and in the case where the solution goes almost towards drying it can approach 90% by weight of the concentrate. After the solution containing the water-soluble polymer contacts the aqueous solution for a sufficient period of time to form the water-soluble polymer metal complex, the separation of the metal complex from the water-soluble polymer is preferably carried out by the ultrafiltration. Ultrafiltration is a pressure-driven separation that occurs on a molecular scale. As a pressure gradient is applied to the process stream that contacts the ultrafiltration membrane, the liquid that includes small dissolved materials is forced through the pores in the membrane while the larger dissolved materials and the like they hold onto the stream of the process. Pressure gradients can be created, as desired, from the use of vacuum systems, centrifugal force, mechanical pumping, and pressurized gas and / or air systems (eg, nitrogen). In the use of the present water-soluble polymers, an ultrafiltration unit may generally consist of hollow fiber cartridges or membrane material having 1,000 M CO up to 1,000,000 M CO, preferably 10,000 MWCO up to 100,000 MWCO. Other membrane configurations such as spiral wound modules, stirred cells (separated by a membrane), thin channel devices, centrifugal units (separated by a membrane) and the like may also be used, although hollow fiber cartridges are preferred. generally for filtration units of the continuous / semi-continuous process. Preferred for analytical applications for preconcentration purposes are agitated cells and centrifugal ultrafiltration units. Small hollow fiber cartridges can also be used for continuous preconcentration for analytical applications. Useful ultrafiltration membranes include cellulose acetate, polysulfone, and polyamide membranes such as polybenzamide, polybenzamidazole, and polyurethane. The use of ultrafiltration for separation is further described in Kirk: Othmer: Encyclopedia of Engineering and Polymer Science, 2nd Ed. Vol.17, pp.75-104,1989, such a description is incorporated herein by reference. Generally, water soluble polymers have molecular weights greater than about 1,000 to about 1,000,000 and preferably greater than about 10,000 to 100,000. Some polymers with molecular weights above 1,000,000 tend to lose solubility, but not polymers below the molecular weight of about 1000, retention by suitable filtration membranes can present problems such as low flux velocities.

The water-soluble polymers of the present invention can be provided with various pre-selected molecular weight ranges through purification or sizing. For example, by filtering polyethyleneamine through a particular size ultrafiltration membrane (for example, UFP-10-C-5 available from AG Technologies, Corp, with available MWCO's of 10,000, 30,000 and 100,000), polyethylenimine it can be provided with: (1) a molecular weight range greater than about 10,000 and essentially free of molecular weights less than about 10,000; (2) a molecular weight range greater than about 30,000 and essentially free of molecular weights less than about 30,000; (3) a molecular weight range greater than about 100,000 and essentially free of molecular weights less than about 100,000; (4) a molecular weight range from about 10,000 to about 30,000 and essentially free of molecular weights less than about 10,000 and greater than about 30,000; (5) a molecular weight range from about 10,000 to about 100,000 and essentially free of molecular weights less than about 10,000 and greater than about 100,000; and, (6) a molecular weight range from about 30,000 to about 100,000 and essentially free of molecular weights less than about 30,000 and greater than about 100,000. Other water-soluble polymers can be sized in a similar manner. Other preselected ranges should become available as other membranes with other MWCO's become available. The water-soluble polymers can be used in the recovery of metal ions from aqueous streams as described by Smith and Cois, in the US Patent Application Series Number XXX, XXX, presently presented with the present one, entitled "Water-soluble Polymers for the Recovery of Metal Ions from Aqueous Currents" ("Water-Soluble Poymers for Recovery of Metals Ions from Aqueous Streams") can be used in the recovery of metals from solids as described by Smith and Cois, in the US Patent Application Series Number xxx, xxx, currently filed with in the present, entitled "Soluble Water Polymers for the Recovery of Metals from Solids" ("Water-Soluble Polymers for Recovery of Metals from Solids"), and can be used for the displacement of cyanide ions from metal cyanide complexes as described by Smith and Cois, in the U.S. Patent Application Serial Number xxx, xxx filed herein, entitled "Process for Displacement of Cyanide Ions from Metal Cyanide Complexes" ("Process for the Displacement of Cyanide Ions from Metal - Cyanide Complexes"), such descriptions are incorporated herein by reference. The present invention is described in more detail in the following examples, which are intended to be illustrative only, since numerous modifications and variations will be apparent to those skilled in the art. Examples 1-31 show the preparation of PEI, PEI derivatives, and other water soluble polymers. Example 32 shows the use of such polymers in the separation of metal ions from aqueous streams.

Example 1 (polymer A) Polyethylene imine (PEI) was prepared as follows. Crude polyethyleneimine (obtained from BASF as PEI polyimine anhydrous and PE PE homopolymer) was obtained in two molecular weight ranges. The polyimide anhydrous polymer was reported to have a molecular weight in the range of 10,000 to 25,000, while the PE PE homopolymer was reported to have a molecular weight range of 70,000 to 750,000, depending on the method of molecular weight measurement. In fact, both of these polymers had a wide molecular weight range and had material that passed through the ultrafiltration membranes that had a high molecular weight., 000 MWCO and 30,000 MWCO and 100,000 MWCO. These polymers from BASF were highly branched having a primary to secondary to tertiary nitrogen ratio of about 1: 2: 1. To demonstrate the effect of pH on the polymer size, 1% w / v was adjusted. of an anhydrous solution of polyimine with acid or base to spread over the pH region between 2 and 10. The solution was diafiltered through a membrane of 30,000 MWCO with infiltrated samples taken periodically to determine the concentration of the polymer using the copper method described down. The concentration of the polymer infiltrating the membrane at a high pH was considerably higher (0.014% in 15 min) than that which passes through lower pH values (0.003% in 15 min). The large difference occurred between pH 10 and 8, with the sequential decrease in pH leading to smaller effects on the size of the polymer, with a very small difference in size at a pH of 4 and 2. Due to this drastic change in the polymer size, polyethyleneimine was purified by diafiltration at a relatively high pH value (10.8 pH per PEI). The polymer was purified using the hollow fiber membranes prepared by a special extrusion process, the ultrafiltration membrane cartridges prepared from polysulfone material in a special homogeneous fiber construction, where the microporous structure has no macro-spaces. Membranes such as UFP-10-C-5 (currently manufactured by AG Technologies, Corp.) were the only type of material found to purify polyethyleneimine and considering membrane washing to recover full flux velocities after substantial use . The polyethyleneimine was diluted in water to about 10-15% by weight. The pH was about 10.5 until the dissolution of the polyethyleneimine. The solution was diafiltered using membranes of 10,000 MWCO, 30,000 MWCO, and 100,000 MWCO (keeping the volume constant) until volume equivalents 6-7 of water were passed through the system at less than, or equal to 25PSI. Following the diafiltration step, the volume of the solution was reduced by approximately 85% to concentrate the polymer. The remaining water was removed under vacuum and moderate heat to produce clear, viscous, colorless polyethylenimine. In this way, 25% by weight of the PEI polyimine anhydride passed through the 10,000 MWCO membrane, 10% by weight of PEI passed through the 30,000 MWCO membrane and not the 10,000 MWCO membrane, and 65% by weight was retained by the membrane of 30,000 MWCO (this fraction referred to hereinafter as polymer Aa). With the Polyimine P polymer, 16% by weight passed through the 10,000 MWCO membrane, 3% by weight was less than 30,000 MWCO and greater than 10,000 MWCO, 5% by weight was less than 100,000 MWCO and higher to 30,000 MWCO, and 76% by weight was greater than 100,000 MWCO (this fraction referred to hereinafter as polymer Ab). The resulting material from the retentate of 30,000 MWCO (polymer Aa, when filtered on a 10,000 MWCO membrane, gave a non-detectable step of the polymer through a 10,000 MWCO membrane using a copper test developed to detect less than 1 ppm of the polyethyleneimine polymer Similar to the collected material greater than 100,000 MWCO (Ab polymer) when tested on a 30,000 MWCO membrane, no detectable polymer was observed in the infiltration For some applications the polymer concentrate did not require drying but It was able to concentrate to a feasible volume as the subsequent functional reactions were carried out in water.The copper test includes placing 0.5 ml of the test sample in a 10 ml volumetric flask, adding 0.5 ml of an acetate solution of copper (1.99 g of copper acetate diluted in 100 ml with 0.01 of MHC1), 1.0 ml of a regulator of 5.8 pH (0.6 ml of dilute acetic acid in 100 ml with deionized water with the addition of 11.2 g of anhydrous sodium acetate and enough sodium acetate or acetic acid to adjust the pH to 5.8), and deionized water to dilute up to the mark. This solution was mixed well. A standard curve for a UV-VIS spectrophotometer was prepared using 0.01%, 0.02%, 0.05% and 0.08% weight / vol. of PEÍ solutions. A blank reagent was used as a reference sample and read at 284 nanometers. The specifications of the membrane included hollow fiber of a material to which polyethyleneimine does not adhere to any significant extent, ie, detrimental effect on the flux. The routine operational pH range of the cartridges was detected between 2 and 12 with the ability to process solutions below a pH of 0 to 1 for limited periods of time (30 min) without damaging the cartridges. The minimum flux rates were 0.01 gallons / mins / square feet at 25 ° C and at a transmembrane pressure of 15 PSI with a 5% by weight solution of branched polyethyleneimine (Polyamine Anhydrous 10,000-25,000 MW). The original speeds of the cartridge flow were regenerated immediately after use by a simple cleaning process of a period of 10 minutes with water, followed by 30 minutes with 500 ppm of hypochlorite and washing with water. The cartridge had at least a minimum operating pressure of 50 PSI at 25 ° C. The cartridges had the ability to be operated at temperatures above 80 ° C.

Example 2 (polymer B) A carboxylic acid-amino containing the water-soluble polymer of the structure (C CHz N ChtfH) CH Mz CHjCQzH N HCQjCH N? ÍjCOaH was prepared on polyethyleneimine (PEI, polyimine anhydride used as received from BASF, ie, doped), using a molar ratio of carboxylic acid moiety to CH2CH2N subunits within the PEI of about 4 to 1 as follows A solution of potassium hydroxide (260.4) in water (400 ml) was added dropwise over a period of 30 minutes to a solution of polyethyleneimine (25.02 g) and bromoacetic acid (322.4 g) in water (500 ml) maintaining the temperature below 50 ° C. After the addition was complete, the solution was stirred at reflux for 3 hours. The solution was cooled to room temperature and then diluted to 2 liters with deionized water. The pH of the solution was adjusted to 5.8 using hydroxide or potassium hydrochloric acid. The polymer was purified by diafiltration by collecting five equivalents of the infiltration volume using hollow fiber cartridges with 30,000 MWCO. The retained solution was then concentrated and the remaining water was removed under reduced pressure. The waste material (hereinafter referred to as polymer B) was dried in a vacuum oven at 60 ° C overnight to give 50.78 g of a brittle, light tan solid. IR (ATR): 1630 cm "1 (C = 0) The elemental analysis found: C, 32.58%, H, 4.97%, N, 8.54%, 0.28.99%.

Example 3 (polymer C) A partially functional carboxylic acid containing the water soluble polymer of the following structure: • (C- ^ CHz N CHCHjMH) - CHJCHJ N HCQjCH '? ÍOOjH was prepared on polyethyleneimine (BASF, polyimine anhydrous, purified as in Example A,> 30,000 MWCO) using a molar ratio of carboxylic acid half to subunits of CH 2 CH 2 N within the PEI of about 0.5 to 1. The source of carboxylic acid was chloroacetic acid in one case and bromoacetic acid in another case. The procedure, as in example B, was followed except for the difference noted here. The elemental analysis found: C, 44.72%; H, 8.35%; 0.29.3%. The polymer is hereinafter referred to as polymer C. A partially functionalized carboxylic acid containing the water soluble polymer was prepared on polyethylenimine (BASF, of polyimine P, doped, in a range of 70,000 to 700,000 MW) using a molar ratio of carboxylic acid half to CH2CH2N subunits within the PEI of about 0.5 to 1. The carboxylic acid source was chloroacetic acid. The procedure, as in Example B, was followed except for the differences noted here. The material was diafiltered through several molecular weight cutting membranes such that a molecular weight fraction greater than 10,000 MWCO but less than 30,000 MWCO and a molecular weight fraction greater than 30,000 MWCO but less than 100,000 MWCO ( hereinafter referred to as polymer Ca) and a fraction greater than about 100,000 MWCO (hereinafter referred to as polymer Cb).

Example 4 (polymer D) A fully functional phosphonic acid containing the water soluble polymer of the structure: (CHjCH2 N CH? CHJ) CHJCHJ N (OHfeíOPCHí CHjPÍOXOHfe it was prepared on a polyethyleneimine (Polyimine Anhydrous from BASF, used as received, ie, doped). The polyethyleneimine (2.50 g, approximately equivalent to 0.058 mol of monomer) was dissolved in 6 M hydrochloric acid (80 ml) followed by the addition of solid phosphorous acid (19.0 g, 0.29 mol) at room temperature. The homogeneous solution was induced to reflux followed by the dropwise addition of formaldehyde (38 ml of 37% of the solution, 0.47 mol) for one hour. After the addition was complete, the solution was stirred at reflux for an additional hour. The heat was removed and the flask allowed to settle overnight at room temperature. The sticky solid precipitate was collected by dripping the liquid from the flask. The solid was dissolved in water and adjusted to 6.8 pH with sodium hydroxide. The solution was purified by diafiltration through a 30,000 MWCO membrane. A total infiltration volume of 3.5 liters was collected.

The solution was then concentrated to approximately 150 ml. After removing the water under reduced pressure, the residue (referred to hereinafter as polymer D) was dried under a high vacuum at 60 ° C overnight to give 6.3 g of a light yellow solid. The elemental analysis found: C, 22.46%; H, 5.48%; N, 8.70%; P, 16.88%.

Example 5 (polymer E) A fully functional phosphonic acid containing the water soluble polymer of the structure: (CHzO -CHCHzNH) ^ - CHjOfe N (OHWO CHJ CHzPfOXOHh it was prepared on a polyethyleneimine. Polyethyleneimine (BASF Polyimine Anhydrous, 10,000 - 25,000 MW and pre-purified by diafiltration through a 30,000 MWCO cartridge before use as in Example A, 25.0 g, equivalent to 0.58 mol of monomer) was dissolved in 6 M of hydrochloric acid (300 ml) followed by the addition of solid phosphorous acid (47.56 g, 0.58 mol) at room temperature. The homogeneous solution was induced at reflux followed by the dropwise addition of formaldehyde (23.53 ml of a 37% solution, 0.29 mol) for one hour.

After the addition was complete, the solution was stirred at reflux for an additional hour. The heat was removed and the flask was allowed to settle overnight at room temperature. The reaction mixture was diluted in water and adjusted to 6.8 pH with potassium hydroxide. The solution was purified by diafiltration through a MWCO of 30,000. A total infiltration volume of 6 liters was collected. The solution was then concentrated to approximately 200 ml. After removing the water under reduced pressure, the residue (hereinafter referred to as polymer E) was dried under a high vacuum at 60 ° C overnight to give 32 g of a light yellow solid. The elementary analysis: C, 30.18%; H, 8.42%; N, 13.95%; P, 14.05%; K 0.15%. A partially functional phosphonic acid containing the water soluble polymer was prepared on polyethylenimine (BASF, Polyimine P, doped, in a range of 70,000 to 700,000 MW) using a molar ratio of half of the phosphonic acid to subunits of CH 2 CH 2 N within the PEI of approximately 0.5 to 1. The procedure, as in Example E, above was followed except for the differences noted here. The material was diafiltered through several molecular weight cutting membranes such that a molecular weight fraction greater than 10,000 MWCO but less than 30,000 MWCO and a molecular weight fraction greater than 30,000 MWCO but less than 100,000 MWCO ( hereinafter referred to as polymer Ea) and a fraction greater than 100,000 MWCO (hereinafter referred to as polymer Eb).

Example 6 (polymer F) An acylmethylpyrazolone containing the water-soluble polymer of the structure: was prepared on a polyethyleneimine as follows: A precursor (4-chloroacetyl-1,3-diemethyl-pyrazole-5-one) was first prepared as the main one. In a 500 ml three-necked round bottom flask fitted with a reflux condenser, a mechanical stirrer, and an additional equalizing funnel, 1,3-dimethylpyrazole-5-one (6.03 g, 53.84 mol) was added. and dioxane (55 ml, distilled from the sodium metal). The mixture was heated to 40-50 ° C to dissolve the suspended solids and give a clear yellow solution. The reaction mixture was cooled to 30-35 ° C followed by the addition of Ca (OH) (7.98 g, 107.68 mmol). After 10 minutes of stirring, chloroacetyl chloride (6.82 g, 59.22 mmol) in dioxane (20 ml) was added over a period of 30 minutes. The reaction mixture was heated to reflux for 24 hours. The reaction mixture was filtered while heating and the mass of the filter was washed with hot dioxane (2 x 20 ml) followed by methanol (2 x 20 ml). The solvent was removed under reduced pressure yielding 14 g of the product as the calcium salt. The solid was passed through a column of strongly cationic exchange resin of 50W-Dowex acid. The water was removed under reduced pressure leaving a white solid, which was further dried under vacuum at 60 ° C overnight to give the product (61%, m.p.-161-165 ° C) as a white solid in 61% yield. aH NMR (CDCl 3, ppm) 54.38 (s), 3.60 (s), 2.41 (s). 13 CNMR (CDC13, ppm) 15.6, 32.7, 45.7, 101.0, 146.0, 159.3, 188.2. The polymer was prepared as follows: PEI polymer (4.00 g of Polimin Anhydrous, prefiltered through a 30,000 MWCO cartridge as in Example A, dissolved in water (100 ml) and refluxed. 4-Chloroacetyl-1,3-dimethyl-pyrazole-5-one above (4.40 g, 23.33 mmol) and triethylamine (4.68 g, 46.25 mmol) dissolved in water (20 ml) were added dropwise for a period of 10 minutes The solution was stirred at reflux for 2.5 hours while turning yellow to orange and then red.After cooling to room temperature, the material was diluted with deionized water to a volume of 1 liter and the polymer was purified by diafiltration through a 30,000 MWCO cartridge collecting 5 liters of the infiltration The water was removed under reduced pressure and the residue (hereinafter referred to as polymer F) was dried under vacuum at 60 ° C to give a brittle solid , orange-reddish (5.49 g, 73%), IR (ATR); 3435 (N-H), 1626 (C = 0) cm_1. Elemental analysis: C, 53.85%; H, 8.65%; N, 24.59%; O, 12.98%.

Example 7 (polymer G) An acylphenylpiirazolone containing the water soluble polymer of the structure: rt - fCHjCH2- N- -CHJCHJ H ^ - CHjOfe NHCH2 - C was prepared on a polyethyleneimine as follows: PEI (1.00 g, Polyimine Anhydrous, doped) and triethylamine (2.34 g, 23.1 mmol) were dissolved in chloroform (30 mL) and refluxed. L-phenyl-3-methyl-4-chloroacetyl-pyrazole-5-one) prepared following the procedures of - - Jensen In ACTA Chem. Scand, 1959,13,1668 and Okafor and Cois, in Synth. React. Inorg. Met. Org. Chem, 1991.21 (5), 826, (3.18g, 5.8mmol), in chloroform (lOml) was added dropwise to the solution resulting in the precipitation of a tan solid. After stirring for 1.5 hours the mixture was cooled and the suspended solid was collected by filtration. The solid was dissolved in water (400 ml), adjusted to a pH of 3.0, and the solution was diafiltered using a 30,000 MWCO cartridge. The water was removed under reduced pressure and the residue (referred to hereinafter as polymer G) was dried in a vacuum oven at 60 ° C to give 1.56 g as a brittle red solid. IR (ATR): 3430 (N-H), 1630 (C = 0) cm_1.

Example 8 (polymer H) A hiroxamic acid containing a water-soluble polymer of the structure: it was prepared on polyethyleneimine (PEI). Hydroxylamine hydrochloride (2.78 g. 39.97 mmol) was dissolved in methanol (15 ml). Potassium hydroxide (2.24 g, 39.97 mmol), was dissolved in methanol (10 ml), added dropwise to the hydroxylamine solution. The mixture was stirred for 1 hour, after which the precipitated potassium chloride was collected by filtration. Solid succinic anhydride (4.00 g, 39.90 mmol) was added to the filtrate. The mixture was stirred at room temperature for 3 hours. The solvent was removed under reduced pressure leaving a white sticky solid. The solid was allowed to settle under diethyl anhydrous ether for one hour. The solid was collected by filtration giving 4.80 g of monohydroxamic acid of succinic acid as a white solid with a melting point of 72-82 °. This solid (1.OOg, 7.51 mmol), dicyclohexylcarbodiimide (DCC) (1.54g, 7.51 mmol) and a catalytic amount of 4- (dimethylamino) pyridine were dissolved in tetrahydrofuran (THF) (10 mL). After stirring for 24 hours at room temperature, the solution was filtered to remove the byproduct of (dicyclohexylurea) DCU. This THF solution was added to a methanolic solution containing polyethylenimine (1.29 g, 29.95 mmol of monomer C. Prepurified as in Example A,> 30,000 MWCO), a small amount of phenolphthalein, and enough sodium methoxide to make the pink solution. The solution was stirred for 5 hours. The solvent was evaporated and the product was purified by dissolving in water and diafiltration through a hollow fiber membrane of 30,000 MWCO. Evaporation of the water followed by drying under vacuum at 60 ° C gave 1.21 g of a white polymer (hereinafter referred to as polymer H). Testing with the iron chloride test gave a dark red color indicating a positive test for the presence of hydroxamic acid.

Example 9 (polymer I) A hiroxamic acid containing water-soluble polymer of the structure: - (CHjCH * ^ - NH (CHjfc c H (OH) was prepared from the open ring of polyvinylpyrrolidone with hydroxamic acid to give polyvinylamine-N (hydroxamic pentanoic acid) (PVA-PHA). The polyvinyl pyrrolidone (1.Og, MW 40,000, Aldrich), the sodium hydroxide (40 ml of 1.0 M) and the hydroxylamine hydrochloride (2.71 g) were mixed together and heated to 90 ° C. A pH 12 was maintained by small additions of sodium hydroxide if necessary. The solution was heated for two days, cooled and dialyzed through a 20,000 MWCO membrane. The water was removed from the polymer solution, under vacuum to give a clear solid material until dried in an oven at 60 ° C (hereinafter referred to as polymer I), which gave a positive acid chloride test for acid hiroxámico (Hydroxylamine does not give a positive ferric chloride test).

Example 10 (polymer J) An ester-functional water-soluble polymer of the structure: was prepared as follows: Polyethylenimine (1.00 g, purified as in Example A, <30,000 MWCO) was dissolved in ethyl acrylate (9.21 g, 92 mmol) and the solution was stirred at reflux for 3 hours. The excess ethyl acrylate was removed under vacuum maintaining the temperature below 70 ° C to avoid polymerization. This viscous polymeric material was used in the next step without further purification (hereinafter referred to as polymer J).

Example 11 (polymer K) A functional water soluble polymer of hydroxamic acid of the structure: It was prepared as follows. The polymer of Example 1 was treated with potassium hydroxide (15.46 g, 0.28 mol) followed by a solution of hydroxylamine hydrochloride (12.79 g, 0.18 mol) in methanol (100 ml) maintaining a temperature below 20 ° C. The mixture was stirred for one hour and then filtered. The filtrate was added to the crude ethyl acrylate / PEI adduct and stirred at room temperature for 14 hours. The methanol was removed under reduced pressure and the residue was dissolved in water (50 ml). The polymer was purified by ultrafiltration using a stirred cell with a polysulfone membrane of 30,000 MWCO. After collection of the infiltration equivalent to 6 volumes (300 ml), the water was removed from the retentate under reduced pressure and the material was dried in a vacuum oven at 60 ° C overnight to give 92.22 g. of the polymer (hereinafter referred to as polymer K) as a brittle, light tan solid which was very hygroscopic. IR (ATR): 1732 (C = 0) cm "1 Example 12 (polymer L) An aza crown ether containing a water soluble polymer of the structure: was prepared on polyethyleneimine as follows: N-chloroacetyl-aza-18-crown -6 (0.56 g, 1.65 mmol), polyethylene imine (0.29 g, prepurified as in Example A,> 30,000 MWCO) and potassium carbonate were combined in acetonitrile and stirred at reflux for 16 hours. After cooling to room temperature, the solvent was removed under reduced pressure leaving a brown oil. The residue was dissolved in water and the polymer was purified by diafiltration. Evaporation of the water followed by drying under vacuum to 60 ° C gave 0.81 g of a tan solid (hereinafter referred to as polymer L) characterized by IR, tE and 13CNMR.

Example 13 (Polymer M) A complete water soluble polymer containing crown ether of the structure was prepared: composed of ether 15-crown-5 on polyvinyl alcohol, 247 mg (4.94 mmol) of the polyvinyl alcohol (88% hydrolysed) in 10 ml of dry DMF, was heated at 50-60 ° C until dissolved. The clear solution was then cooled to room temperature and 341 mg (2.47 mmol) of K2C03 was added. The mixture was stirred for 30 min. Then, 0.67 g (0.33 mmol) of the 15-crown-5 in 2 ml of dry dimethylformamide was added to the reaction mixture. The colorless mixture turned to a green blue in 45 minutes and became slightly yellow in 2 hours. The yellow mixture was allowed to settle at 50-60 ° C overnight. The reaction was warmed in water, the suspension was filtered and the polyvinyl alcohol crown ether was purified by ultrafiltration with a 30,000 MWCO cartridge and produced 150 mg of polymer (hereinafter referred to as polymer M) and characterized by IR, aH and 13CNMR.

Example 14 (polymer N) A water soluble polymer of permeated poly (vinylamine) of the structure: NÍCHJJJ4 X " it was prepared as follows: the poly (vinylamine) (10.0 g) was dissolved in 50 ml of methanol and transferred to a four-necked round bottom flask containing an additional 50 ml of methanol. Phenolphthalein (10.0 mg) was added resulting in a light pink solution. Sodium methoxide (38.85 g, 0.72 mol) suspended in 450 ml of methanol and dimethyl sulfate (90.69 g), 0.72) dissolved in 100 ml of methanol were added simultaneously by separate addition funnels that equalized the pressure at such a rate as to maintain a slight pink color. The addition process was conducted under a nitrogen atmosphere at room temperature. It was necessary to add additional sodium methoxide (3.0 g in 50 ml of methanol) to maintain the pink color through the addition of dimethyl sulfate. The total addition time was approximately 1.5 hours. After the addition was complete, the solution was refluxed and stirred for about 1.5 hours. After cooling to room temperature, the solution was transferred to a single neck flask and the solvent removed under reduced pressure leaving a dark yellow material. The material was redissolved in 450 ml of deionized water and the solution was diafiltered using a 30,000 MWCO hollow fiber cartridge. Five volume equivalent or approximately 2.5 L of the infiltration was collected. For the anion exchange of sulphate to chloride, 50 g of sodium chloride in 150 ml of water were added and the solution was allowed to settle overnight. The solution was diafiltered with 3 L of deionized water. The water from the retentate was removed under reduced pressure and the residue (hereinafter referred to as polymer N) was dried under vacuum at 60 ° C overnight to yield 19.58 g (69%) of a brown-orange crystalline solid. . IR (KBr): 3437 (N-H), 2928, 1629 (C = 0), 1481 cm "1. Elemental Analysis: C, 48.25%; H, 10.68%; N, 10.92%; Cl, 15.87%; S, < 0.97%.

Example 15 (polymer O) A permethyl polyallylamine of the structure: Preparation: The polyallylamine (10.0 g, Aldrich) was dissolved in 100 ml of methanol and transferred to a four-necked round bottom flask containing an additional 50 ml of methanol. Phenolphthalein (14.0 mg) was added to the solution. Sodium methoxide (23.70 g, 0.44 mol) suspended in 400 ml of methanol and dimethyl sulfate (42.0 g, 0.33 mol) dissolved in 70 ml of methanol were added simultaneously by separate addition funnels that equalized the pressure at such a rate as to Keep a light pink color. The addition process was conducted under a nitrogen atmosphere at room temperature. It was necessary to add additional sodium methoxide (3.0 g in 50 ml of methanol) to maintain the pink color through the addition of dimethyl sulfate. The total addition time was approximately 30 minutes. After the addition was complete, the solution was refluxed and stirred for about 1.5 hours. After cooling to room temperature, the solution was transferred to a single neck flask and the solvent was removed under reduced pressure leaving an opaque pink material. The material was re-dissolved in 500 ml of deionized water and the solution was diafiltered using a 30,000 MWCO hollow fiber cartridge. Five volume equivalent or about 2.5 L of the infiltration was collected. For the anionic exchange of sulphate to chloride, 50 g of sodium chloride in 150 ml of water were added and the solution allowed to settle overnight. The solution was then diafiltered with 2.6 L of deionized water. The water from the retentate was removed under reduced pressure and the residue was dried under vacuum at 60 ° C overnight to yield 10.18 g (70%) of a pale yellow crystalline solid (hereinafter referred to as polymer O). IR (KBr): 3437, 2929, 1686, 1485, 1251 cm "1. Elemental Analysis: C, 47.85%; H, 10.62%; N, 10.62%; Cl, 11.78%; S, 1.13%.

Example 16 (polymer P) A PEI polymer containing guanidine of the following structure: was prepared as follows: polyethyleneimine (as prepurified in Example A,> 30,000 MWCO, 5.0 g, 116 mmol of amine) and O-methyloisourea-hemisulfate (Jansen, 14.35 g, 116 mmol) were placed in a 125-ml flask. ml and dissolved in 12 ml of water with stirring. The solution was allowed to settle for 2 days, and was then placed in a dialysis tube (Spectra Por, 15,000 MWCO). The tube with the reaction mixture was placed in a 1 L bottle containing deionized water, and the water was changed 5 times. The content of the dialysis tube was concentrated to a white foam by rotary evaporation, and then dried to a colorless vitreous foam (hereinafter referred to as polymer P) under vacuum at 60 ° C overnight. Produced: 5. 04 g. Elemental Analysis: C, 33.88%, H, 7.70%, N, 26.69%, S, 9.63%.

Example 17 (polymer Q) A permethylated PEI polymer of the structure: was prepared: purified PEI (20.0 g as prepared in Example A,> 30,000 MWCO) was dissolved in 200 ml of methanol and placed in a round-bottomed flask fitted with a condenser under argon. Dimethyl sulfate (120 g, 0.95 mol, Eastman) dissolved in 110 ml of methanol was added slowly from an addition funnel. After the addition (approximately 3 hours) the reaction was induced to reflux while the potassium carbonate (64.2 g, 0.046 mol, Janssen) was added slowly from a solid addition funnel (care must be taken to make an addition slow to avoid excess foam). The solution was cooled, filtered, and the methanol removed under vacuum. The mass of the solid filter was dissolved in 600 ml of water and combined with the residue from the filtrate. The combined solution was purified by diafiltration (30,000 MWCO) using water. The sulfate anion is exchanged for chloride by adding 120 gm of sodium chloride in 400 ml of water and then stirring for 48 hours. The solution was concentrated and further diafiltered (30, 000 MWCO) with water at 5L volume changes. The final solution was concentrated by ultrafiltration to 500 ml and then concentrated and dried under vacuum to give 21.6 g of a white vitreous polymer (hereinafter referred to as polymer Q). Elemental Analysis before chloride exchange: C, 34.15%, H, 8.07%, N, 8.96%, S, 15.56%. Potentiometric titration of the polymer gave a sharp strong base-rate titration curve indicating that all the amine sites were methylated. (If the curve was not pronounced, this would indicate that the methylation was incomplete).

Example 18 (polymer R) An amide containing the water-soluble polymer of the structure: was prepared as follows: polyethyleneimine (2.OOg, prepared as in Example A,> 30,000 MWCO) was dissolved in methanol (20 ml) and refluxed. Acrylamide (4.95 g, 70 mmol), and butylated hydroxytoluene (BHT, 200 ppm in solution) were dissolved in methanol (20 ml) and added dropwise to the reaction flask for a period of 15 minutes. The solution was stirred at reflux for 24 hours. After cooling to room temperature, the deionized water (400 ml) was added and the polymer was purified by diafiltration using a 30,000 MWCO cartridge. The water was removed under reduced pressure and the polymer was dried in a vacuum oven at 60 ° C to produce 4.5 g of a clear vitreous solid (hereinafter referred to as polymer R) and characterized by IR, aH and 13CNMR.

Example 19 (polymer S) A permeated polyvinyl pyridine of the structure: was prepared as follows: To a solution of polyvinyl pyridine (3 g as a 25% solution in methanol, Reilly Industries) was added dropwise iodomethane (4.85 g, 0.03 mol) in 2 ml of methanol at room temperature. After the addition was complete, the solution was stirred for approximately 2 hours giving it a slight green color. An additional amount of iodomethane (2g) was added and stirred for about 2 hours. The deionized water (200 ml) was added to the reaction mixture and the diafiltrate solution with 1 liter of permeate collected through a 30,000 MWCO membrane. The water from the retentate was removed under reduced pressure and the residue was dried under vacuum at 60 ° C overnight to yield 4.82 g (68%) of a yellowish green crystalline solid (hereinafter referred to as polymer S). IR (KBr): 3437 (N-H), 3028, 2930, 1640 (C = 0), 1156 cm "1. Elemental Analysis: C, 40.74%; H, 4.43%; N, 6.22%; I, 36.93%.

The iodide salt of polymer S was converted to the chloride salt by stirring the polymer overnight with sodium chloride (hereinafter referred to as polymer Sa). Elemental Analysis: C, 52.65%; H, 7.07%; N, 8.27%; Cl, 12.74%.

Example 20 (polymer T) A partially functional carboxylic acid containing the water soluble polymer of the following structure: HNCHzCOOH Nhfe was prepared in polyaliloamine. A solution of sodium hydroxide (2.139 g) in water (50 ml) was added dropwise over a period of 43 minutes to a solution of polyallyloamine (5.0 g, Aldrich) and chloroacetic acid (2.53 g) in water (60 ml. ) keeping the temperature below 50 ° C. After the addition was complete, the solution was stirred at reflux for 3 hours. The solution was cooled to room temperature. The polymer was purified by diafiltration by collecting five equivalents of the infiltration volume using a hollow fiber cartridge with 30,000 MWCO. The volume of water was removed from the retentate under reduced pressure. The residual material was dried in a vacuum oven at 60 ° C overnight to give 4.2 g of a light tan solid (hereinafter referred to as polymer T). UV / VIS; lambda max = 296nm. IR (ATR): 1638 cm "1 (C = 0).

Example 21 (polymer U) A partially functional carboxylic acid containing the water soluble polymer of the following structure: was prepared in polyvinylamino. A solution of sodium hydroxide (9.29 g) in water (160 ml) was added dropwise over a period of 35 minutes to a solution of polyvinyl amine (10.0 g) and chloroacetic acid (10.97 g) in water (240 ml) maintaining the temperature below 50 ° C. After the addition was complete, the solution was stirred at reflux for 3 hours. The solution was cooled to room temperature. The pH of the solution was 11.8 and adjusted using sodium hydroxide or hydrochloric acid. The solution started to precipitate between a pH of 7 and 8.5. the polymer was purified by diafiltration and rinsed with deionized water and adjusted to a pH of 11.3. Five equivalents of the infiltration volume were collected using a hollow fiber cartridge with 30,000 MWCO. The volume of the water was removed under reduced pressure. The residual material was dried in a vacuum oven at 60 ° C overnight to give 12.42 g of a light tan brittle solid (hereinafter referred to as polymer U). UV / VIS; lambda max = 294nm. IR (ATR): 1603 c "1 (C = 0).

Example 22 (polymer V) A water-soluble copolymer containing amide and betadiphosphonic ester groups of the following structure: "CJCHjQHfc CHCH2 CH2C);; - 8N ^ i PíOXOCHzCHafc was prepared by copolymerization. Acrylamide (664 mg, 9.35 mmol), tetraethyl-ethenylodienebis (phosphonate) (500 mg, 1.67 mmol), and ammonium persulphide (21 mg, 1%) as a polymerization initiator was dissolved in 20 ml of deionized water. The mixture was stirred vigorously at 65-70 ° C for 48 hours and the solution remained clear through this. The reaction was cooled to room temperature and diluted with 250 ml deionized water. The polymer was purified by diafiltration using a 30,000 MWCO cartridge and five equivalents of the infiltration volume were collected. The retentate was concentrated and dried in a vacuum oven at 60 ° C. A colorless polymer (250 mg) (hereinafter referred to as polymer V) was obtained. Characterized by IR, NMR, 31PNMR (PPM) 26.02, 27.42.

Example 23 (polymer W) A water soluble copolymer containing the amide and betadiphosphonic acid ester groups of the following structure: HOPfOjOttfeCH, CHOFE CHfi) CWhi H0PÍO) 0CH2CH, was prepared by copolymerization. The polymer V prepared as above (87 mg) was dissolved in 10 ml of deionized water. Excess NaOH (24 mg) was added. The clear solution was stirred at room temperature overnight. The reaction was tempered by diluting with 200 ml water, and purified by diafiltration using a 30,000 MWCO membrane. The concentrate was dried under a vacuum at 60 ° C to give 80 mg of a light brown solid (hereinafter referred to as polymer W). The polymer was characterized by IR, NMR, 31P NMR (PPM) 27.2.

Example 24 (polymer X) A water-soluble copolymer containing the amide and diabidobisphosphonic groups of the following structure: HOP (0) 0H was prepared by copolymerization. The vinyl bisphosphonate (5.07 g, 16.9 mmol) was dissolved in trimethylbromosilane (20.7 g, 135.2 mmol) under argon. The reaction mixture was stirred at room temperature overnight. Excess trimethylbromosilane and other volatiles were removed under reduced pressure and the residual oil was treated with 95% EtOH (15 ml). The mixture was stirred overnight at room temperature. The volatile materials were removed again under reduced pressure to give 3.0 g (90% produced) of pure vinyl biphosphonic acid. Acrylamide (1.08 g, mg, 15.22 mmol), vinyl bisphosphonic acid (500 mg, 2.72 mmol) and ammonium persulfate (34 mg, 1%) as a polymerization initiator were dissolved in 20 ml of deionized water. The mixture was stirred vigorously at 50-55 ° C for 40 hours and the solution remained clear through this. The reaction was cooled to room temperature and diluted with 50 ml deionized water. The polymer was purified by diafiltration using a cartridge ,000 MWCO and 5 equivalents were collected to the volume of the infiltration. The retentate was concentrated and dried in a vacuum oven at 60 ° C. A colorless polymer (700 mg) was obtained (hereinafter referred to as polymer X). Characterized by IR, NMR, 31P NMR (PPM). Example 25 (polymer Y) A partially functional mercaptosuccinic acid containing the water soluble polymer of the following structure: (CHjO-fc N ttijoy *!) - CtOjCHaCHtSHJCOOH it was prepared in polyethyleneimine. In a typical synthesis, 10.OOg (233 milliequivalents of PEI, prepurified as in Example A,> 30,000 MWCO) were dissolved in 200 ml of water and the solution was clarified with argon for 20 minutes. The solid S-acetylmercaptosuccinic anhydride, 10.00 g (57.5 mmol), was added with stirring. After the solid disappeared, 10 g (94 mmol) of sodium carbonate were slowly added taking care to ensure that the vigorous evolution of gas and the resulting foam would not cause an overflow. The solution was stirred overnight and then acidified to a pH of 4 with concentrated nitric acid. After clarifying it with argon for 20 minutes, the solution was induced at pH 7 with sodium hydroxide. The slightly cloudy mixture was filtered through a fine glass frit. The product was purified by diafiltration with at least five times the volume of the final solution with millipore water. The lyophilization of the retentate yielded the product (hereinafter referred to as polymer Y). Characterization: XH and 13C NMR and IR. Elemental Analysis of 3 lots different lot (1) C 42.57, H 7.19, N 12.85, S 9.17, S * 10.5 lot (2) C 42.78, H 7.09, N 12.38, S 10.16, S * 8.4 lot (3) C 41.72 , H 7.68, N 12.03, S 9.35, S * 8.2 S * Thiol sulfide content when analyzed by iodometric titration. Example 26 (polymer Z) A partially functional ethyl thiol containing the water soluble polymer of the following structure: (CHjCHz N CHjCH ^ H) n CHjCH u / \ H CHjCHzSH it was prepared in polyethyleneimine. In a typical synthesis, 10. OOg (233 milliequivalents of PEI, prepared as in Example A, 30,000 MWCO) were dissolved in 200 ml of water and the pH adjusted to 7 with concentrated HN03. The solution was clarified with argon for 20 minutes and 3.45 ml (57.5 mmol) of ethylene sulfide was added with stirring. The biphasic mixture was stirred overnight and the slightly cloudy mixture was filtered through a fine glass frit. The product was purified by diafiltration with at least five times the volume of the final solution with millipore water. Freeze-drying of the retentate produced 13.5 g of the product as a white powder (hereinafter referred to as polymer Z). Characterization: lU and 13C NMR and IR. Example 27 (AA polymer) A partially functional N-methylthiourea containing the water soluble polymer of the following structure: (CHJCHJ N CHaCHjNH) CHaCH? N H qsjNHCHj it was prepared on polyethyleneimine. In a typical synthesis, 11.20 g (260 milliequivalents of PEI, prepared as in example A,> 30,000 MWCO) were dissolved in 200 ml of ethanol and the solution was clarified with argon for 20 minutes. Methylisothiocyanate was heated at 35 ° C and 4.75 g (65.1 mmol) was mixed with 10 ml of ethanol. The isothiocyanate solution was added to the PEI at 0 ° C and the solution was stirred for one hour, in which a viscous precipitate formed. The solvent was removed by rotary evaporation and the product was redissolved in 100 ml of water, to which 5.86 ml of concentrated HN03 was added. After stirring overnight, the slightly cloudy mixture was filtered through a glass frit and the product was purified by diafiltration with at least five times the volume of the final solution with millipore water. The lyophilization of the retentate produced 13.8 g of the product as a white powder (hereinafter referred to as AA polymer). Characterization- aH and 13C NMR and IR. Example 28 (polymer BB) A phosphonic acid in a polyvinylamine base with the following structure: - (CHaCH - CHaCH) ^ - H NHz \ CHaPíOXOHfe He prepared. A solution of formaldehyde (9.42 ml) was added dropwise during reflux for a period of 22 minutes to a solution of polyvinylamine (10 g) and phosphorous acid (19.04 g) in 3N HCl. After the addition was complete the solution was stirred at reflux for an additional hour. The heat was removed and cooled to room temperature. The solution was evaluated at a pH of 6.8 with NaOH. The polymer was purified by diafiltration by collecting five equivalents of the infiltration volume using a hollow fiber cartridge with 30,000 MWCO. The volume of the water was removed under reduced pressure. The residual material was dried in a vacuum oven at 60 ° C overnight to give 18.21 g of a brittle yellow-orange solid (hereinafter referred to as polymer BB). UV / VIS: lambda max = 296nm. IR (ATR): 1628 c "1 (C = 0) Example 29 (polymer CC) A thiolactam from polyvinylpyrrolidone with the structure: It was prepared as follows. In an oven-dried flask, the flask clarified with nitrogen, was placed 1.03 g (9.26 mmol) of polyvinylpyrrolidone (MW 40, 000, Aldrich, used as received), 15 ml of dry chloroform and 2.00 g (9.0 mmol) of P2 S5, and phosphorous pentasulfide. The container was sealed and placed in an ultrasonic bath for 3 hours. After the reaction the solution was centrifuged and the supernatant was removed and evaporated with nitrogen. The viscous solid was then dried at 60 ° C in a vacuum oven to give a crystalline product (0.78 g). The same reaction was carried out with different proportions of P2 S5 from an excess of 2 parts at ratios of 1: 1 to 0.5: 1 to give different levels of conversion of lactam to thiolactam. IR analysis of dry polymers (hereinafter referred to as polymer 0-2 / 1; polymer 0-1 / 1; and polymer O-0.5 / 1 effectively giving three different levels of conversion with the excess of P2 and S5, completely eliminating the carbonyl tension between 1700 to 1800 cm "1. The carbonyl peak was reduced proportionally with the 1: 1 and 0.5: 1 treatment.

Example 30 A water soluble polymer containing pyrocatechin of the formula: • (CHjCHj was prepared by the following procedure. 2,3-Dihydroxybenzoic acid (7.6 g, 50 mmol) was dissolved in thionyl chloride (25 ml). The solution was stirred at reflux for 3 hours. The excess thionyl chloride was removed under reduced pressure using a Dean Stark separator. The residue was sublimated under vacuum at 120 ° C to yield 7.5 g (70%) of a white solid (melting point 84 ° C). Polyethylenimine (polyimine anhydride, 2.50 g) in tetrahydrofuran (35 ml) was dissolved in a reaction flask. The acid chloride (3.17) was slowly added to the reaction flask resulting in the formation of a precipitate. The solution was stirred for one hour and the solvent was removed under reduced pressure leaving a light brown solid. The solid was dissolved in water and adjusted to a pH of 10.5 with potassium hydroxide followed by purification by ultrafiltration through a 30,000 MWCO cartridge to produce a reddish-brown solid until water removal under vacuum. Example 31 The copolymerization of vinyl bisphosphoric acid and acrylic acid was as follows. Vinyl bisphosphoric acid cyclohexylamine (0.64 g, 1.09 mmol) acrylic acid was dissolved in deionized water (15 ml) (0.44 g, 6.12 mmol) and ammonium persulfate (20 mg). The mixture was stirred vigorously at 50-55 ° C for 48 hours. The reaction was cooled to room temperature and diluted with 50 ml deionized water. The polymer was purified by diafiltration using a 30,000 MWCO cartridge by collecting 5 equivalents of the infiltration volume (pH = 6). The retentate (pH = 5) was concentrated and dried under vacuum at 60 ° C to yield 480 mg (30%) of the polymer as a white solid. Example 32 0.1% t / vol of the polymeric hydroxamic acid solution of Example 1 was prepared at each of the pH values of 2, 6 and 8. Each solution was rendered useless with americium and filtered on a 10,000 MWCO ultrafiltration membrane. . Almost no retention of americium was observed at lower pH values. But 99% of the retention was observed at the pH of 8. Thus, the polymeric hydroxamic acid can bind an actinide such as an americium under conditions of pH 8. The other polymers described above also have utility in the selective separation of the metal ion from the solution, in the recovery of metals from solids, and for the displacement of cyanide ions from metal-cyanide complexes and such descriptions have been incorporated for reference from the patent applications currently filed , above mentioned. Although the present invention has been described with reference to specific details, it is not intended that such details be considered as limitations to the scope of the invention, except and for the scope of which they are included in the accompanying claims.

Claims (31)

1. NOVELTY OF THE INVENTION Having described the present invention it is considered as a novelty and therefore the claim described in the following claims is claimed as property. A water-soluble polymer of the formula (CH2-CH2-N-CH2-CH2NX!) N - (i) I CH2-CH2NX2X3 where Xi, X2, X3 in each polymer unit is a group independently selected from a substituent selected from H, C (0) CH2CH (SH) COOH, where when m is an integer selected from 0.2, 3, and 4, Y is selected from C = 0, P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown oxy ethers, aza crown ethers, thio crown ethers, and H, and when m is 1, Y is selected from C = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl , hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, chole ethers na oxy, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between about 12 and 12,000; Y (CH2), (Ra) pYCHY (R2) P where m is an integer from 0 to 6, Y is selected from C = 0, P = 0, and C = S, Rx and R2 is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol, alkyl, aryl, and H, p is an integer from 1 to 2, and n is an integer between about 12 and 12,000 with the proviso that at least one of Xi, X2, X3 is not hydrogen; - (CH2-CH) n- (Ü) I (CH2) q-NX4X5 where X4 and X5 in each polymer unit is a group independently selected from a substituent selected from H, C (0) CH2CH (SH) COOH , - (CH2) mYZp where q is an integer from 0 to 4, and where when m is an integer selected from 0, 2, 3, and 4, Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, and when m is 1, Y is selected from C = 0 , C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown oxysethers, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between approximately 24 and 24,000 with the condition that at least one of X4 and X5 is not hydrogen; - (CH2-CH) n- (iii) I 0X6 wherein X6 in each polymer unit is a group independently selected from a substituent selected from C (0) CH2CH (SH) COOH, - (CH2)? Zp in where m is an integer selected from 0, 2, 3, and 4, and is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, and when m is 1, Y is selected from C = 0 , C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown oxy ethers, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between approximately 24 and 24,000; - (CHX7-CH2) n- (CH2-CX5X9) m- (iv) wherein X7, X8, and X9 in each polymer unit is a group independently selected from a substituent selected from C (0) CH2CH (SH ) COOH, - (CH2) mYZp where m is an integer selected from 0, 2, 3, and 4, and is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, and when m is 1, Y is selected from C = 0 , C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown oxysethers, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between about 12 and 12,000; or - (CH2-CH) "- (v) | NXioXn where X? 0 and Xu in each polymer unit are a thiolactam or are a group independently selected from a substituent selected from C (0) CH2CH (SH) COOH, and - (CH2) mYZp where m is an integer from 0 to 4, Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S; Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between approximately 24 and 24,000.
2. 2. A water-soluble polymer of the formula (CH2-CH2-N-CH2-CH2NXa) n- (i) I CH2-CH2NX2X3 wherein Xi, X2, X3 in each unit of the polymer is a group selected independently from a substituent selected from H, C (O) CH2CH (SH) COOH, - (CH2) mYZP wherein m is an integer from 0 to 4, and is selected from C = 0. P = 0, C = S, S02 / C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, p is an integer from 1 to 2, and n is an integer between approximately 12 and 12,000; I (CH2) m I (Ra) pYCHY (R2) P where m is an integer from 0 to 6, Y is selected from C = 0, P = 0, and C = S, Ri, and R2 is selected from starting from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, and H, p is an integer from 1 to 2, and n is an integer between about 12 and 12,000; - (CH2-CH) n- (ii) I (CH2) q-NX4X5 wherein X4 and X5 in each polymer unit is a group independently selected from a substituent selected from H, C (0) CH2CH (SH) COOH, where q is an integer from 0 to 4, m is an integer from 0 to 4, and is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, p is an integer from 1 to 2, and n is an integer between approximately 24 and 24,000; - (CH2-CH) n- (iii) OX6 wherein X6 in each polymer unit is a group independently selected from a substituent selected from C (O) CH2CH (SH) COOH, - (CH2) mYZp where m is an integer from 0 to 4, and Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, p is an integer from 1 to 2, and n is an integer between approximately 24 and 24,000; - (CHX7-CH2) n- (CH2-CXsX9) m- (iv) wherein X7, Xs, and X9 in each polymer unit is a group independently selected from a substituent selected from C (0) CH2CH (SH ) COOH, - (CH2) mYZp where m is an integer selected from 0 to 4, and is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkyllol , alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, crown ethers aza, crown ether thio, and H, p is an integer from 1 to 2, and n is an integer between approximately 12 and 12,000, or - (CH2-CH) n- (v) I wherein X? 0 and Xn in each polymer unit are a thiolactam or a group independently selected from a substituent selected from C (0) CH2CH ( SH) C00H, and - (CH2) mYZp where m is an integer from 0 to 4, and Y is selected from C = 0. P = 0, C = S, S02, C (0) CH2C (0), and S; Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazole, dimethylpyrazolethione, methylphenylpyrazolethione, crown ethers oxy, aza crown ethers, thio crown ethers, and H, p is an integer from 1 to 2, and n is an integer between about 24 and 24,000, said water soluble polymer having a molecular weight greater than about 10,000 and further characterized as essentially free of molecular weights less than about 10,000.
3. 3. The water soluble polymer according to claim 1 characterized in that at least one of Xi, X2, and X3, at least one of X4, and Xs, Xe, and at least one of X7, X8, and X9 are - ( CH2) mYZp wherein Y is C = 0, and Zp is selected from a group of dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, and the other X are H.
4. 4. The water soluble polymer according to the claim 1 characterized in that the polymer is of the formula (i), at least one of X-, X2, and X3, is - (CH2) mYZp where m is 0, Y is C (0) CH2C (0), Zp is hydroxylamine, and the other X are H.
5. 5. The water soluble polymer according to claim 1 characterized in that, the polymer is of the formula (i), at least one of Xx, X2, and X3, is - (CH2 ) mYZp where m is 2, Y is C = 0, Zp is oxyalkyl, and other X are H.
6. 6. The water soluble polymer according to claim 1 characterized in that, the polymer is of the formula (i), at least one of Xi, X2, and X3, is - (CH2) mYZp where I s 2, Y is C = 0, Zp is hydroxylamine, and the other X are H.
7. 7. The water soluble polymer according to claim 1 characterized in that, the polymer is of the formula (i), at least one of Xi, X2, and X3, is - (CH2) mYZp where m is 2, Y is C = 0, Zp is amine, and the other X are H.
8. 8. The water-soluble polymer according to claim 1 characterized in that, the polymer is of the formula (i), at least one of Xi, X2, and X3, is - (CH2) mYZp where m is 1, Y is C = 0, Zp is aza crown ether, and the other X are H
9. 9. The water-soluble polymer according to claim 1, characterized in that the polymer is of the formula (iii) and X6 is an oxy-crown ether
10. 10. The water-soluble polymer according to claim 2 characterized in that, at least one of Xi, X2, and X3, at least one of X4, and X5, Xß, and at least one of X, Xe, and X9 are - (CH2) mYZp where Y is C = 0, and Zp is selected from a group of dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazolethione, methylphenylpyrazolethione, and the other X are H.
11. 11. The water soluble polymer according to claim 2 characterized in that, the polymer is of the formula (i) , at least one of Xx, X, and X3, is - (CH2) mYZp where m is 0, Y is C (0) CH2C (0), Zp is hydroxylamine, and the other X's are H.
12. 12. The polymer water soluble according to claim 2 characterized in that, the polymer is of the formula (i), at least one of Xx, X2, and X3, is - (CH2) mYZp where m is 2, Y is C = 0, Zp is oxyalkyl, and the other X are H.
13. 13. The water-soluble polymer according to claim 2 characterized in that, the polymer is of the formula (i), at least one of Xx, X2, and X3, is - (CH2) mYZp where m is 2, Y is C = 0, Zp is hydroxylamine, and the other X are H.
14. 14. The polymer s oluble in water according to claim 2 characterized in that, the polymer is of the formula (i), at least one of Xx, X2, and X3, is - (CH2) mYZp where m is 2, Y is C = 0, Zp is amine, and the other X are H.
15. 15. The water soluble polymer according to claim 2 characterized in that, the polymer is of the formula (i), at least one of Xx, X2, and X3, is - (CH2) mYZp where m is 1, Y is C = 0, Zp is aza crown ether, and the other X are H.
16. 16. The water-soluble polymer according to claim 2 characterized in that the polymer is of the formula (iii) and X6 is an oxy-17-crown ethers.
17. The water-soluble polymer according to claim 1 characterized in that the polymer is of the formula ( ii), q is 1 and at least one of X4 and Xs is CH2C00H.
18. 18. The water-soluble polymer according to claim 1, characterized in that the polymer is of the formula (v), and at least one of Xxo and Xxx is CH2C00H.
19. 19. The water soluble polymer according to claim 1 characterized in that, the polymer is of the formula (iv), for X7 m is 0, Y is C = 0 and Z is amine and p is 1 and for X8 and Xg m is 0 , Y is P = 0, p is 2 and Z is oxyalkyl.
20. 20. A permethylated water soluble polymer selected from the group consisting of poly (vinylamine), poly (allylamine), polyethylene imine and polyvinyl pyridine or substituted polymers thereof, said water soluble polymer having a molecular weight greater than about 10,000 and characterized in addition as essentially free of molecular weights less than about 10,000.
21. 21. A water soluble polymer having nitrogen, oxygen, or sulfur containing groups capable of binding selected metal ions, said water soluble polymer having a molecular weight greater than about 10,000 and characterized as essentially free of molecular weights less than about 10,000 .
22. 22. A water soluble polymer having nitrogen, oxygen, or sulfur containing groups capable of binding selected metal ions, said water soluble polymer having a molecular weight of greater than about 30,000 and characterized as essentially free of molecular weights less than about 30,000 .
23. 23. A water soluble polymer having nitrogen, oxygen, or sulfur containing groups capable of binding selected metal ions, said water soluble polymer having a molecular weight greater than about 100,000 and characterized as essentially free of molecular weights less than about 100. ,.
24. 24. A water soluble polymer having nitrogen, oxygen, or sulfur containing groups capable of binding selected metal ions, said water soluble polymer having a molecular weight of from about 10,000 to about 30,000 characterized as essentially free of molecular weights less than about 10,000 and more than approximately 30,000.
25. 25. A water soluble polymer having nitrogen, oxygen, or sulfur containing groups capable of binding selected metal ions, said water soluble polymer having a molecular weight of from about 10,000 to about 100,000 and characterized as essentially free of molecular weights less than about 10,000 and more than approximately 100,000.
26. 26. A water soluble polymer having nitrogen, oxygen, or sulfur containing groups capable of binding selected metal ions, said water soluble polymer having a molecular weight of from about 30,000 to about 100,000 and characterized as being essentially free of molecular weights less than 30,000 and more than approximately 100,000.
27. 27. The water-soluble polymer according to claim 21, characterized in that said water-soluble polymer includes groups selected from a group consisting of carboxylic acid groups, phosphonic acid groups, acylpyrazolone groups, hydroxamic acid groups, groups aza crown ether, guanidine groups, thiolactam groups, amide groups, permethylated p.vinvinylpyridine groups, mercaptosuccinic acid groups, alkytol groups, N-alkyl thiourea groups, and pyrocatechin groups.
28. 28. The water-soluble polymer according to claim 21 characterized in that said water-soluble polymer is polyethyleneimine.
29. 29. The water-soluble polymer according to claim 22, characterized in that said water-soluble polymer includes groups selected from the group consisting of carboxylic acid groups., phosphonic acid groups, acylpyrazolone groups, hydroxamic acid groups, aza crown ether groups, guanidine groups, thiolactam groups, amide groups, permethylated polyvinylpyridine groups, mercaptosuccinic acid groups, alkyl thiol groups, N-alkyl thiourea, and pyrocatechin groups.
30. 30. The water soluble polymer according to claim 23 characterized in that said water soluble polymer is polyethyleneimine. The water soluble polymer according to claim 24 characterized in that said water soluble polymer includes groups selected from a group consisting of carboxylic acid groups, phosphonic acid groups, acylpyrazolone groups, hydroxamic acid groups, groups aza crown ether, guanidine groups, thiolactium groups, amide groups, permethylated polvinylpyridine groups, mercaptosuccinic acid groups, alkyl thiol groups, N-alkyl thiourea groups, and pyrocatechin groups,