# US 4,391,945 A · Chelate resin prepared by reacting butane-1,2,3,4-tetra-carboxylic acid or anhydride with polyethylene polyamine > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,391,945 A - Document ID: US4391945A - Status: Granted - Kind: A - Application number: 06/251,789 - Filed: 1981-04-07 - Granted: 1983-07-05 - Earliest claimed: 1980-04-10 - Assignees: Mitsi Toatsu Inorganic Chemicals, Inc. - Inventors: Fujio Mashio; Shuji Kitamura - Web page: https://patentgrep.com/patent/US4391945A ## CPC - C08G 73/028: {Polyamidoamines} - C22B 3/42: by ion-exchange extraction - Y02P 10/20: Recycling - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract The present invention relates to an amphoteric resin obtained by condensation of polyethylenepolyamine and butane-1,2,3,4-tetra-carboxylic acid. The present invention can provide several forms of amphoteric resins such as linear structure, somewhat cross-linked water insoluble and water swellable structure and water insoluble and cross-linked structure, since the resin contains in its repeating units an imino group, a carboxylic radical and an amido group. The resin can form a chelate with several kinds of metal ions. Furthermore, the resin can also be modified by introducing several kinds of functional groups to bestow upon the resin particular chelating ability. Therefore the invention can provide novel resins, which have a strong chelating faculty and are suitably used for removing and recovering agents of heavy metals and noble metals. ## Claims ### Claim 1 A resin having the formula (I): ##STR15## wherein, m stands for an integer of 2 to 6 or for a mixture having an average value of 4 to 5, n stands for a mixture having an average value of 4 to 10, X stands for --OH or --NH--CH.sub.2 CH.sub.2).sub.m NH.sub.2, and Y signifies H or ##STR16## ### Claim 2 A resin obtained by heat-treating the resin having the formula (I) according to claim (1) at a temperature of 130.degree. C. to 160.degree. C. for 0.5 to 3 hours. ### Claim 3 A process for preparing a resin having the formula (I): ##STR17## wherein, m stands for an integer of 2 to 6 or for a mixture having an average value of 4 to 5, n stands for a mixture having an average value of 4 to 10, X stands for --OH or --NH--CH.sub.2 CH.sub.2).sub.m NH.sub.2, and Y signifies H or ##STR18## which comprises reacting butane-1,2,3,4-tetra-carboxylic acid or anhydride thereof with polyethylenepolyamine in the absence of presence of solvent. ### Claim 4 (depends on 3) A process according to claim 3, wherein the reaction is carried out at a temperature of 100.degree. to 140.degree. C. ### Claim 5 (depends on 3) A process according to claim 3, wherein substantially equi-molar amounts of butane-1,2,3,4-tetra-carboxylic acid and polyethylenepolyamine are reacted. ### Claim 6 (depends on 5) A process according to claim 5, wherein the mol ratio of butane-1,2,3,4-tetra-carboxylic acid to polyethylenepolyamine is about 0.9 to about 1.1. ### Claim 7 (depends on 3) A process according to claim 3, wherein the reaction is carried out for about 0.5 to about 8 hours. ### Claim 8 (depends on 3) A process according to claim 3, wherein the polyethylenepolyamine is an amine selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneoctamine and a mixture thereof. ### Claim 9 (depends on 3) A process according to claim 3, wherein the polyethylenepolyamine is a distillation product of the bottom obtained in the course of the production of ethylenediamine. ### Claim 10 (depends on 3) A process according to claim 3, wherein the reaction is carried out in anhydrous state. ### Claim 11 (depends on 3) A process according to claim 3, wherein the reaction is carried out in the presence of a small amount of water in a paste state. ### Claim 12 (depends on 3) A process according to claim 3, wherein the reaction is carried out in an organic solvent. ### Claim 13 (depends on 12) A process according to claim 12, wherein the solvent is selected from the group consisting of dimethylformamide, cresol and dimethylsulfoxide. ### Claim 14 (depends on 3) A process according to claim 3, wherein butane-1,2,3,4-tetra-carboxylic acid anhydride is mono-anhydride. ### Claim 15 (depends on 3) A process according to claim 3, wherein butane-1,2,3,4-carboxylic acid anhydride is dianhydride. ### Claim 16 (depends on 3) A process for preparing a resin which comprises heat-treating the resin prepared according to claim 3 at a temperature of about 130.degree. to 160.degree. C. for about 0.5 to 3 hours. ### Claim 17 (depends on 4, 16) A process according to claim 16, wherein the heat-treatment is carried out succeeding to the process according to claim 4 without isolating the resin prepared according to claim 4. ### Claim 18 (depends on 16) A process according to claim 16, wherein the reaction is carried out in anhydrous state. ### Claim 19 (depends on 16) A process according to claim 16, wherein the reaction is carried out in the presence of a small amount of water in a paste state. ### Claim 20 (depends on 16) A process according to claim 16, wherein the reaction is carried out in the presence of solvent. ### Claim 21 (depends on 12) A process according to claim 12, wherein the solvent is selected from the group consisting of dimethylformamide, cresol and dimethylsulfoxide. ### Claim 22 (depends on 1, 2) A heavy metal capturing and noble metal recovering agent which comprises the resin according to claim 1 or 2 as a main component. ### Claim 23 (depends on 22) A heavy metal capturing and noble metal recovering agent according to claim 22, wherein the agent is in the form of an aqueous solution. ### Claim 24 (depends on 22) A heavy metal capturing and noble metal recovering agent according to claim 22, wherein the agent is in the form of a powder. ### Claim 25 (depends on 22) A heavy metal removing and noble metal recovering agent according to claim 22, wherein the recovered and removed ion is selected from the group consisting of Ag.sup.+, Hg.sup.+, Hg.sup.2+, Zn.sup.2+, Cd.sup.2+, Al.sup.3+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+, Ag.sup.2+, Au.sup.3+, Pd.sup.2+, Pt.sup.2+, Ti.sup.4+, V.sup.3+, V.sup.4+, Cr.sup.3+, Fe.sup.2+, Fe.sup.3+, Co.sup.3+, Pd.sup.4+, Pt.sup.4+, Sn.sup.2+, SN.sup.4+, Pb.sup.2+, Pb.sup.4+, Mo.sup.4+, W.sup.4+ and U.sup.4+. ### Claim 26 A resin having the formula (III): ##STR19## wherein, m signifies an integer of 2 to 6 or a mixture having an average value of 4 to 5, n signifies a mixture having an average value of 4 to 10, X' signifies ##STR20## Y signifies H or ##STR21## Z signifies H atom, carboxy lower alkyl group, dithiocarbamate radical or lower alkyl group, provided that Z is not hydrogen atom in all of its occurrences. ### Claim 27 A process for preparing a resin having the formula (III): ##STR22## wherein, m signifies an integer of 2 to 6 or a mixture having an average value of 4 to 5, n signifies a mixture having an average value of 4 to 10, X' signifies ##STR23## Y signifies H or ##STR24## Z signifies H atom, carboxy lower alkyl group, provided that Z is not hydrogen atom in all of its occurences, which comprises reacting a resin having the formula (I): ##STR25## wherein, m stands for an integer of 2 to 6 or for a mixture having an average value of 4 to 5, n stands for a mixture having an average value of 4 to 10, X stands for --OH or --NH--CH.sub.2 CH.sub.2).sub.m NH.sub.2, and Y signifies H or ##STR26## with monochloro-lower alkyl-carboxylic acid in water or organic solvent in the presence of hydrogen chloride removing agent. ### Claim 28 (depends on 27) A process according to claim 27, wherein the monochloro-lower alkyl-carboxylic acid is monochloroacetic acid. ### Claim 29 A process for preparing the resin having the formula (III): ##STR27## wherein, m signifies an integer of 2 to 6 or a mixture having an average value of 4 to 5, n signifies a mixture having an average value of 4 to 10, X' signifies ##STR28## Y signifies H or ##STR29## Z signifies H atom or dithiocarbamate group, provided that Z is not hydrogen atom in all of its occurrences, which comprises reacting a resin having the formula (I): ##STR30## wherein, m stands for an integer of 2 to 6 or for a mixture having an average value of 4 to 5, n stands for a mixture having an average value of 4 to 10, with carbondisulfide in an aqueous solution of sodium hydroxide. ### Claim 30 A process for preparing a resin having the formula (III): ##STR31## wherein, m signifies an integer of 2 to 6 or a mixture having an average value of 4 to 5, n signifies a mixture having an average value of 4 to 10, X' signifies ##STR32## Y signifies H or ##STR33## Z signifies H atom, lower alkyl group, provided that Z is not hydrogen atom in all of its occurrences, which comprises reacting a resin having the formula (I): ##STR34## wherein, m stands for an integer of 2 to 6 or for a mixture having an average value of 4 to 5, n stands for a mixture having an average value of 4 to 10, X stands for --OH or --NH--CH.sub.2 CH.sub.2).sub.m NH.sub.2, and Y signifies H or ##STR35## with di-lower alkyl-sulfate in water in the presence of acid-removing agent. ### Claim 31 (depends on 30) A process according to claim 30, wherein the acid-removing agent is sodium hydroxide.