A PROCESS FOR SYNTHESIZING PHOSPHONIC ACID-CONTAINING POLYMERS AND THE POLYMERS THEREOF

Abstract: A high temperature, pressurized process is described to synthesize phosphonated acrylamide polymers represented by the structure: wherein X is from the group H, OR, Cl, Br, I, -COOM, -SO₃M, , and mixtures thereof.

Description: This invention relates generally to a process to synthesize water-soluble phosphonated polymers containing a phosphonate group, and, in addition, which polymers may also contain other functional groups which may be useful when applied to aqueous solutions or environments. The synthesis of water-soluble phosphonated polymers has generally been limited. This synthesis of vinylic phosphonated polymers containing the phosphonate group has been limited from the point of view that only certain of these kinds of phosphonated monomers are commercially produced. As a result, the use of these phosphonated water-soluble polymers is extremely limited commercially. It would therefore be an advance in the art if water-soluble polymeric chemical structures could be synthesized on a polymeric backbone which structures would contain the phosphonate group, either in the acid or salt form, and which structures might also contain other functional groups which could enhance the use of these water-soluble phosphonated polymers in certain applications such as dispersants in water treatment, scale inhibitors in natural and industrial waters, flocculants and coagulants, and the like. It is desired to develop a synthetic procedure which can generally be applicable to the synthesis of various types of water-soluble polymers containing the phosponate group with or without the additional presence of other functional groups which may be useful when these polymers are added to aqueous systems. Another aim of this invention is to synthesize and recover certain types of phosphonate containing water-soluble polymers which polymers may contain other functional groups such as hydroxyl, chloro, bromo, iodo, and/or mixtures thereof, which polymers have not heretofore been known or used. We have discovered a process for modifying water-soluble polymers containing pendant amide functional groups, such polymers primarily derived from acrylamide containing vinylic polymers/copolymers or from alkyl substituted acrylamide containing vinylic polymers or copolymers, and which polymers/copolymers are water soluble and contain pendant amide functional groups derived from acrylamide, methyl acrylamide, ethylacrylamide, and the like. This process in accordance with the invention uses the equivalent of a transamidation reaction with the pendant amide group on the polymer and a chemical reactant. The process is to synthesize water-soluble phosphonated polymers having randomly repeated units represented by the general formula wherein R' is a multi-covalent hydrocarbonaceous bridging group having 1 to 16 carbon atoms and being chosen from linear, branched or cyclic alkyl, alkaryl, arylalkyl, aromatic, heterocyclic, olefinic functional groups and mixtures thereof, X is chosen from Cl, Br, I, -COOM, -SO₃M, -OH, -OR, and mixtures thereof, R is individually chosen at each occurrence from H and lower alkyl (C₁-C₄) groups, M is chosen from hydrogen, lower alkyl (C₁-C₄) groups, alkali metal, an equivalent of alkaline earth metals, alkylated and tertiary amines, quaternary amines, and ammonium ion, and mixtures thereof, and a, b and d are integers with the following relationships: a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of (a+b+d) is sufficient to provide a molecular weight of at least 500, and the ratio of d/(a+b) is from 100:1 to 1:100, p ranges between 1 and 16, m ranges between 0 and 16, and n ranges between 1 and 16, provided that when m is zero, the sum of (m+n) is from 1 to 20, which process comprises reacting, in a common solvent, at a temperature of at least 100°C (A) a polymer having a molecular weight of at least 500 and having pendant amide functional groups and being represented by the structure wherein R, M, a and b have the meaning as above, with (B) a chemical reactant having the structure wherein R, R', M, X, p, m and n have the meaning as above, wherein the mole ratio of chemical reactant to pendant amide groups in the polymer ranges between about 5:1 and about 1:100, and reacting to accomplish at least a 25 percent conversion of chemical reactant to phosphonated pendant groups on the polymer, and then recovering the water-soluble phosphonated polymer. Preferably R' has at least two carbon atoms and is linear, cyclic, aromatic and mixtures thereof, X is chosen from -OH, -COOH, and mixtures thereof, R is individually chosen at each occurrence from hydrogen, methyl and ethyl groups, M is individually chosen at each occurrence from hydrogen, lower alkyl (C₁-C₄) groups, sodium, potassium, tertiary amines, quaternary amines, ammonium and mixtures thereof, p is from 1 to 12, m is from 0 to 4, n is from 1 to 4, and the molecular weight of the water-soluble phosphonated polymer ranges between about 2,000 and about 20,000,000. The used solvent is preferably chosen from the group consisting of water and water emulsified in a continuous oil phase such that the water-soluble phosphonated polymer is recovered either as a water-in-oil emulsion or as an aqueous solution. A preferred embodiment of the invention provides to synthesize water-soluble phosphonated polymers of the formula wherein R is H, and R' is chosen from multi-covalent branched alkyl, linear alkyl or cyclic hydrocarbonaceous bridging groups having 1 to 8 carbon atoms, which process comprises reacting, in an aqueous solvent (A) a polymer having pendant amide functional groups and represented by the structure wherein R, M, a and b have the meaning above and the sum of (a+b) achieves a molecular weight of at least 500, with (B) a reactant having the structure wherein R', M, X, m and n have the meaning above, under the following reaction conditions: (I) reaction temperature of at least 100°C, (II) reaction time of at least 1/4 hour, (III) mole ratio of chemical reactant to polymer ranging between about 2:1 and about 1:50, (IV) pressure ranging from atmospheric pressure to 35 times atmospheric pressure, thereby achieving and thereafter recovering said phosphonated polymers. In said process it is preferred that R' is a linear alkylene bridging group having 2 to 6 carbon atoms; X is chosen from -OH, -COOH, -(-OCH₂CH₂-) p -OH and mixtures thereof; R is individually chosen at each occurrence from hydrogen and methyl; M is individually chosen at each occurrence from hydrogen, lower alkyl(C₁-C₄) groups, sodium, potassium, ammonium and mixtures thereof; a, b and d are integers having the following relationship: a/b ranges from 0 to 50, a/d ranges from 0 to 50, b/d ranges from 0.01 to 10, and d/(a+b) ranges between 4:1 and 1:20, and the sum of (a+b+d) is such that the phosphonated polymer has a molecular weight ranging from 1,000 to 20,000,000, and which process comprises reacting at a temperature of at least 110°C for at least 1/4 hour, in a common aqueous solvent, (A) a polymer having the structure wherein R, M, a and b have the meaning above and the sum of (a+b) is such that the molecular weight of the polymer is at least 2,000, with (B) a chemical reactant having the structure wherein R₁, M and X are defined as above and m is from 0 to 3, n is from 1 to 3 and the sum of (m+n) is from 1 to 4, and the ratio of reactant to polymer ranges between about 1:1 to about 1:10 and the reaction pressure is at least 123 kPa, and then recovering said phosphonated polymer. The present invention also provides a phosphonated polymer having the general formula and being synthesized, in a pressure controlled reactor, by reacting a precursor polymer having the formula with a chemical reactant H₂N(R₁)PO₃M₂ in an aqueous solvent at a temperature of at least 100°C for at least 1/4 hour at a mole ratio of precursor polymer to chemical reactant ranging between about 20:1 to about 1:2, and wherein R₁ is a lower linear or branched alkylene bridging group containing from 1 to 6 carbon atoms, R is chosen individually at each occurrence from hydrogen and methyl groups, M is chosen individually at each occurrence from hydrogen, lower alkyl (C₁-C₄) groups, alkali metal, tertiary amines, quaternary amines and ammonium ions and mixtures thereof, a, b and d are integers having the relationships: a/d is from 0 to 100, a/b is from 0 to 100, b/d is from 0.01 to 100, and d/(a+b) ranges between 10:1 and 1:100, and wherein the sum of (a+b+d) is such that the phosphonated polymer has a molecular weight of at least 1,000. The phosphonated polymer is preferably synthesized in an aqueous reaction solvent at a temperature of at least 120°C for at least 1 hour at a mole ratio of precursor polymer to chemical reactant of from 10:1 to 1:1 and wherein R is hydrogen, M is chosen from hydrogen, sodium, potassium and ammonium ions and mixtures thereof, and the polymer has a molecular weight between 2,000 and 20,000,000. A preferred phosphonated polymer is represented by the general formula wherein M is individually chosen at each occurrence from hydrogen, sodium and ammonium ions, X is chosen from the group -OH, -COOH, -(OCH₂CH₂) p -OH, -SO₃H and mixtures thereof, p is from 1 to 6, a, b and d are integers such that the sum of (a+b+d) is sufficient to achieve a molecular weight of at least 1,000, a/d is from 0 to 100, b/d is from 0.01 to 100, a/b is from 0 to 100, and the ratio d/(a+b) ranges between 5:1 and 1:50. Another preferred phosphonated polymer is represented by the general formula wherein M, a, b, d have the above meaning. A further phosphonated polymer is represented by the general formula wherein R' is a multivalent hydrocarbonaceous bridging group having 1 to 6 carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic and olefinic groups and mixtures thereof; X is chosen from -OH and -COOM and mixtures thereof; R is individually chosen at each occurrence from hydrogen and methyl groups; M is individually chosen at each occurence from hydrogen, lower (C1-C4) alkyl groups, sodium, potassium and ammonium ions and mixtures thereof; a, b and d are integers, the sum of which is such that the molecular weight of the phosphonated polymer is at least 2,000, wherein the following relationship exists: a/b is from 0 to 100, a/d is from 0 to 100, b/d is from 0.01 to 100, and the ratio d/(a+b) is between about 10:1 to about 1:100; m is equal to 0 to 6, n is equal to 1 to 6, and the sum of (m+n) is between 1 and 6. Another phosphonated polymer is represented by the general formula wherein R is individually chosen at each occurence from hydrogen and methyl groups; M is individually chosen at each occurence from hydrogen, a methyl group, sodium, potassium and ammonium ions, and mixtures thereof, and a, b and d are the same as above. THE CHEMICAL REACTANT The chemical reactant described above is primarily an amino substituted compound which also contains the phosphonate functional group, and wherein the amine functional group contains at least one active hydrogen substituted on the amino nitrogen. Although phosphonate compounds having both primary and secondary amines can react under our transamidation reaction conditions to achieve modified phosphonate containining polymers, it is preferable that when a secondary amine is chosen to accomplish this modification of pendant amide containing polymers, that the alkyl group substituted on the amino nitrogen contain no more than 4 carbon atoms, i.e. the alkyl substitution should be limited to methyl, ethyl, propyl and butyl functionality, and isomers thereof. However, it is most preferred that the amine substitution on the phosphonate containing chemical reactant be a primary amino functional group. When a primary amino functional group is used to accomplish the transamidation reaction, the reaction easily proceeds so as to incorporate at least 2, and preferably 60 mole percent of the chemical reactant used into the water-soluble polymer chain containing pendent amide groups. In addition to the amine substitution in the chemical reactant described above, this chemical reactant does contain at least one phosphonate functional group in either its acid form, partial or complete ester form, or its salt form, wherein the salt form is chosen from a salt of an alkali metal, an alkaline earth metal, tertiary amines, quaternary amines, and ammonium ions, and mixtures thereof. The ester or salt forms may be in existence prior to the transamidation reaction or they may be synthesized by known techniques during the transamidation reaction or after the transamidation reaction has been completed. In addition to the phosphonate functional group and the amine functional group, the chemical reactant may also contain other functional groups chosen from the groups consisting of chlorine, bromine, iodine, hydroxyl, ethoxyl, propoxyl, carboxyl, ester, ether, sulfonate groups and the like, and mixtures thereof. Preferably, the chemical reactant is limited to contain a primary amino group responsible for the transamidation reaction, at least one phosphonate group which allows the formation of an anionic phosphonate containing water-soluble polymer, and an hydroxyl, an ethoxylated or propoxylated group or a carboxylate functional group, the presence of which may enhance the activity of water-soluble phosphonate containing polymers synthesized by the process. Most preferably, the chemical reactant contains a primary amine, zero or more carboxyl, hydroxyl, or ethoxylated groups, and one or more phosphonate groups either in the free acid form, ester forms, salt form, or mixtures thereof. Several preferred species of the chemical reactant described above are demonstrated in the following formulations: wherein, M is chosen from H, lower alkyl (C₁-C₄) groups, alkali metals, an equivalent amount of alkaline earth metals, and alkylated amine, ammonium, or quaternary nitrogen containing moieties. THE PENDANT ACRYLAMIDE CONTAINING POLYMERS The pendant acrylamide containing polymers are water-solube polymers which have a general structure allowing the presence of a pendant amide group as demonstrated in Formula III: In Formula III, as one can observe, the pendant amide group may be a primary amide, a secondary amide, or a tertiary amide group and mixtures thereof. Preferably, to obtain reasonable conversions of these pendant amide groups to the phosphonate containing functional groups described above, the pendant amide group is a primary amide group. The most likely water-soluble polymers containing pendant amide functionality which polymers are easily modified under the conditions of our transamidation reaction, are those water-soluble polymers described by Formula IV: In Formula IV, R is independently chosen, at each occurrence, from the group consisting of hydrogen, and lower alkyl groups containing from 1-4 carbon atoms; M is independently chosen, at each occurrence, from hydrogen, lower alkyl (C₁-C₄) groups, alkali metals, an equivalent amount of alkaline earth metals and ammonium ions and mixtures thereof; and a and b are integers having the following relationships: a/b ranges between 0 to 100, and a + b is sufficient so as to provide a polymer having a molecular weight of at least 500. Preferably the sum a + b is sufficient to provide a molecular weight ranging between about 1,000-20,000,000. As can be seen, the polymers described above may be homopolymers of acrylamide or its alkyl homologs, i.e. methacrylamide and the like, they may be copolymers of acrylamide with acrylic acid or its lower alkyl (C₁-C₄) esters, and their homologs such as methacrylic acid or methylacrylate and the like, or they may be terpolymers and above with other monomers of a vinylic nature which terpolymers contain acrylamide and acrylic acid or its esters, and their homologs such as methacrylic acid, methyl acrylate, metharcylamide, and the like. THE CHEMICAL REACTION The chemical reaction which is preferred to obtain the phosphonate polymers of this invention is a reaction which can generally be referred to as a transamidation reaction. This reaction substitutes an amine compound which may also contain other functional groups such as the phosphonate function group for the nitrogen portion of a pendant amide group contained on a polymeric backbone as described above. This transamidation reaction has been discovered to be a general reaction which can achieve the substitution of the amine and phosphonate containing moiety for the amide nitrogen group of the pendant amide functionality of a water-soluble polymer, thereby obtaining unique phosphonated polymers. The reaction conditions require that polymers containing pendant amide groups be dissolved or readily dispersed in a solvent which is a common solvent for the chemical reactant of the class described above. In other words, both the polymer which is to be modified and the chemical reactant should be soluble or dispersible in the same solvent system. Common solvents which have been found useful in this reaction include, but are not limited to, water, diethylenglycol dimethylether, dimethylformamide, dimethylsulfoxide, admixtures thereof, and admixtures of these solvents, either singly or taken together with other miscible solvents such as ethanol, tertiary butanol diglyme, and the like. A preferred solvent which is a common solvent for both the polymer containing pendant amide groups and the chemical reactants above is water, particularly if the polymer containing pendant amide group is initially water-soluble, as in the case of most acrylamide containing vinylic polymers. Another preferred common solvent for our reaction is a water-in-oil emulsion wherein the dispersed water phase contains dissolved therein both the polymers containing pendant amide groups and the chemical reactants described above. After having dissolved the polymers containing pendant amide groups in the common solvent, preferably water, the chemical reactant can be added to obtain a solution or dispersion of amide containing polymer and the chemical reactants of this invention. Whether the polymer or the reactant is first added to the common solvent is of no consequence. This admixture is then added to or contained in a reaction vessel capable of withstanding a pressurized chemical reaction, for example, a Parr Bomb type of vessel. The vessel is closed and then heated to a temperature of at least 100°C, preferably at least 110°C, and most preferably to a temperature of at least 120°C. If the temperature is increased above 100°C, the vessel contents can expand and the pressure within the vessel can exceed one atmosphere and depending upon the solvent, the phosphonates used or the reactants used, can reach up to about 5 to 15 atmospheres, and possibly more. The pressure within the reaction vessel is a non-controlled variable and is controlled only to the extent that the vessel is closed, that a reaction temperature of at least 100°C or higher is reached, and the vessel may contain solvents or reactants of more or less volatile nature, which solvents and reactants have vapor pressures of such a nature that pressure vessels are required at temperatures above 100°C. Once the reaction vessel contents have reached at least 100°C, and preferably 110°C, the reaction is allowed to occur for at least 3 minutes at this temperature, and preferably for whatever length of time is necessary to accomplish a minimum of at least a 2 percent, and preferably at least a 25 percent, conversion of the added amount of chemical reactant. The chemical reactant is, of course, converted to a pendant phosphonate containing substituted amide being the product of the transamidation chemical reaction summarized above. If the polymer is a homopolymer of acrylamide, methacrylamide, or a copolymer of vinyl amide containing monomers such that no other pendant functional group is present besides amide functional groups, the condition of the reaction is such that at least some degree of amide hydrolysis may also occur in those reactions in which water or a water containing solvent is utilized. In such cases, a carboxylate functional group is also obtained in addition to the phosphonate modified amide and any unreacted starting amide groups from the starting polymer. Polymer recovery may be accomplished in several ways known to the person familiar with the art. For example, the polymers may be precipitated by addition of precipitating solvents, or non-solvents, to the reaction mixture. For example, methanol or acetone may be added to the reaction mixture either as is or after concentration by distillation or vacuum distillation to precipitate the polymers. The polymers may also be recovered by vacuum distillation of solvent and unreacted chemical reactant from the reaction product mixture. The polymers may also be recovered by gel permeation chromatographic techniques, however, for the most part the polymers are recovered simply as a solution in the solvent used to perform the transamidation reaction, and used as such. Preferably, the process is a method to synthesize water-soluble phosphonated polymers having randomly repeated mer units represented by the formula: wherein R' is a multi-covalent hydrocarbonaceous bridging group having from one to sixteen carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic, aromatic, heterocyclic, and mixtures thereof, functional groups; X is chosen from -COOM, OR, and mixtures thereof; R is individually chosen at each occurrence from H and lower alkyl (C₁-C₄) groups; M is chosen from hydrogren, lower alkyl (C₁-C₄) groups, alkali metal, 1/2 alkaline earth metal, tertiary amines, quaternary amines, and ammonium ions and mixtures thereof; and wherein a, b, and d are integers with the following relationships; a/b is from zero to 100, b/d is from 0.01 to 100, a/d is from zero to 100, and the sum of a+b+d is sufficient to provide a molecular weight of at least 3,000, and the ratio of d:(a + b) is from 20:1 to 1:100; and wherein p ranges from 1 and 16, m ranges between 0 and 16, n ranges between 1 and 16, provided that when m is zero, the sum of m + n is from 1 to 20; which process comprises reacting, in a common solvent, at a temperature of at least 100°C: A. a polymer having a molecular weight of at least 500, and having pendant amide functional groups, and represented by the structure: wherein R, M, a, b have the same meanings as above; with B.a chemical reactant having the structure: wherein R, R', M, X, p, m, and n have the meanings above; and wherein the mole ratio of chemical reactant to pendant amide groups ranges between about 5:1 to about 1:100; and wherein the reaction occurs for an effective amount of time to accomplish at least a 25-60 percent conversion of chemical reactant to water-soluble phosphonated polymer; and then recovering the water-soluble phosphonated polymer. Most preferably, our process is a method for the synthesis of water-soluble phosphonted polymers represented by the formula: wherein R' is chosen from multi-covalent, branched alkyl, linear alkyl or cyclic hydrocarbonaceous bridging groups having from one to eight carbon atoms; X is chosen from -COOM, (OCH₂CH₂)OR, OH, and mixtures thereof; R is individually chosen at each occurrence from hydrogen and C₁ to C₄ lower alkyl groups; M is individually chosen at each occurrence from hydrogen, lower alkyl (C₁-C₄) groups, alkali metals, and ammonium ions, m ranges between 0 to 6; n ranges between 1 to 4; a, b, and d are integers with the following relationships: a/b ranges from 0 to 100, a/d ranges from 0 to 100, b/d ranges from 0.01 to 100, and the ratio d:(a+b) is between about 5:1 to about 1:25, and wherein the occurrence of mer units of a, b, and d is random and the sum of a+b+d will achieve a molecular weight of at least 1000; which process comprises reacting, in an aqueous solvent: A. a polymer having pendant amide functional groups and represented by the structure: wherein R, M, a, and b have the meanings above and wherein the sum of a+b achieves a molecular weight of at least 500; and B. a chemical reactant having the structure: wherein R', M, X, m, and n have the meanings above; under the following reaction conditions: I. a reaction temperature of at least 100°C and preferably at least 110°C; II. a reaction time of at least 1/4 hour and preferably at least 1/2 hour; III. a mole ratio of chemical reactant to polymer ranging between about 2:1 to about 1:50; IV. a pressure ranging from atmospheric pressure to 35 times atmospheric pressure, or more; thereby achieving the synthesis of the phosphonated polymers described above. It is particularly of interest that our synthetic procedures permit the synthesis of a phosphonated polymer represented by: wherein: R' is a linear or branched alkylene bridging group having from 1 to 6 carbon atoms; X is chosen from -OH, -COOM, and and mixtures thereof; R is individually chosen, at each occurrence, from the group hydrogen, methyl and ethyl groups; M is individually chosen, at each occurrence, from the group hydrogen, lower alkyl (C₁-C₄) groups, sodium, potassium, ammonium ions and mixtures thereof; p is from 1 to 12; m is from 0 to 3; n is from 1 to 3; and a, b, and d are integers having the relationships: a/d is from 0 to 50, a/b is from 0 to 50, b/d is from 0.1 to 20, d:(a + b) is from 5:1 to 1:10, the sum of a + b + d is sufficient to provide a molecular weight of at least 1,000; which process comprises the reaction, in an aqueous solvent, for at least 1/4 hour at a temperature of at least 110°C, in a pressure controlling reactor, of the ingredients: A. a reactant: wherein X is from the group -OH, -COOM, and mixtures thereof, and wherein R', M, p, m and n have the above meanings; and B. a water-soluble vinyl polymer having pendant amide groups represented by: wherein R, M, a, and b have the above meanings; and wherein the mole ratio of reactant to pendant amide groups ranges between about 1:1 to about 1:5; and then recovering the phosphonated polymer. To further illustrate our invention, we provide the following examples. Example I A solution of poly(acrylic acid [25 mole %]: acrylamide [75 mole%]) (27.5% actives, 37.2g), 3-aminopropyl phosphonic acid (4g), sodium hydroxide (50% solution, 2.3g.) was heated to 150°C for five hours. The product was characterized by L.C. and C13, P31 NMR methods. The molecular weight of the polymer was found to be 11,100. NMR analysis of the sample showed that the polymer contained 8 mole % N-3-phosphonopropyl acrylamide. In addition, the following polymers are synthesized if acrylamide containing polymers were reacted according to the procedures described above with the following chemical reactants. The obtained polymer products are described in Table I.

Claims: A process to synthesize water-soluble phosphonated polymers having randomly repeated units represented by the general formula wherein R' is a multi-covalent hydrocarbonaceous bridging group having 1 to 16 carbon atoms and being chosen from linear, branched or cyclic alkyl, alkaryl, arylalkyl, aromatic, heterocyclic, olefinic functional groups and mixtures thereof, X is chosen from Cl, Br, I, -COOM, -SO₃M, -OH, -OR, and mixtures thereof, R is individually chosen at each occurrence from H and lower alkyl (C₁-C₄) groups, M is chosen from hydrogen, lower alkyl (C₁-C₄) groups, alkali metal, an equivalent of alkaline earth metals, alkylated and tertiary amines, quaternary amines, and ammonium ion, and mixtures thereof, and a, b and d are integers with the following relationships: a/b is from zero to 100 b/d is from 0.01 to 100 a/d is from zero to 100, and the sum of (a+b+d) is sufficient to provide a molecular weight of at least 500, and the ratio of d/(a+b) is from 100:1 to 1:100, p ranges between 1 and 16, m ranges between 0 and 16, and n ranges between 1 and 16, provided that when m is zero, the sum of (m+n) is from 1 to 20, which process comprises reacting, in a common solvent, at a temperature of at least 100°C (A) a polymer having a molecular weight of at least 500 and having pendant amide functional groups and being represented by the structure wherein R, M, a and b have the meaning as above, with (B) a chemical reactant having the structure wherein R, R', M, X, p, m and n have the meaning as above, wherein the mole ratio of chemical reactant to pendant amide groups in the polymer ranges between about 5:1 and about 1:100, and reacting to accomplish at least a 25 percent conversion of chemical reactant to phosphonated pendant groups on the polymer, and then recovering the water-soluble phosphonated polymer. The process of claim 1 wherein R' has at least two carbon atoms and is linear, cyclic, aromatic and mixtures thereof, X is chosen from -OH, -COOH, and mixtures thereof, R is individually chosen at each occurrence from hydrogen, methyl and ethyl groups, M is individually chosen at each occurrence from hydrogen, lower alkyl (C₁-C₄) groups, sodium, potassium, tertiary amines, quaternary amines, ammonium and mixtures thereof, p is from 1 to 12, m is from 0 to 4, n is from 1 to 4, and the molecular weight of the water-soluble phosphonated polymer ranges between about 2,000 and about 20,000,000. The process of claim 1 or 2 wherein the common solvent is chosen from the group consisting of water, dimethylformamide, dimethylsulfoxide, diethyleneglycol dimethylether and mixtures thereof. The process of claim 1 or 2 wherein the solvent is chosen from the group consisting of water and water emulsified in a continuous oil phase such that the water-soluble phosphonated polymer is recovered either as a water-in-oil emulsion or as an aqueous solution. The process of any of claims 1 to 4 to synthesize water-soluble phosphonated polymers of formula V wherein R is H, and R' is chosen from multi-covalent branched alkyl, linear alkyl or cyclic hydrocarbonaceous bridging groups having 1 to 8 carbon atoms, which process comprises reacting, in an aqueous solvent (A) a polymer having pendant amide functional groups and represented by the structure wherein R, M, a and b have the meaning above and the sum of (a+b) achieves a molecular weight of at least 500, with (B) a reactant having the structure wherein R', M, X, m and n have the meaning above, under the following reaction conditions: (I) reaction temperature of at least 100°C, (II) reaction time of at least 1/4 hour, (III) mole ratio of chemical reactant to polymer ranging between about 2:1 and about 1:50, (IV) pressure ranging from atmospheric pressure to 35 times atmospheric pressure, thereby achieving and thereafter recovering said phosphonated polymers. The process of claim 5 wherein R' is a linear alkylene bridging group having 2 to 6 carbon atoms; X is chosen from -OH, -COOH, -(-OCH₂CH₂-) p -OH and mixtures thereof; R is individually chosen at each occurrence from hydrogen and methyl; M is individually chosen at each occurrence from hydrogen, lower alkyl(C₁-C₄) groups, sodium, potassium, ammonium and mixtures thereof; a, b and d are integers having the following relationship: a/b ranges from 0 to 50, a/d ranges from 0 to 50, b/d ranges from 0.01 to 10, and d/(a+b) ranges between 4:1 and 1:20, and the sum of (a+b+d) is such that the phosphonated polymer has a molecular weight ranging from 1,000 to 20,000,000, and which process comprises reacting at a temperature of at least 110°C for at least 1/4 hour, in a common aqueous solvent, (A) a polymer having the structure wherein R, M, a and b have the meaning above and the sum of (a+b) is such that the molecular weight of the polymer is at least 2,000, with (B) a chemical reactant having the structure wherein R₁, M and X are defined as above and m is from 0 to 3, n is from 1 to 3 and the sum of (m+n) is from 1 to 4, and the ratio of reactant to polymer ranges between about 1:1 to about 1:10 and the reaction pressure is at least 123 kPa, and then recovering said phosphonated polymer. The process of claim 5 or 6 wherein the solvent is water or a water-in-oil emulsion. The process of claim 1 or 2 to synthesize a phosphonated polymer of formula V wherein R' is a linear or branched alkylene bridging group having 1 to 6 carbon atoms, X is chosen from -OH and -COOH and mixtures thereof, R is individually chosen at each occurrence from hydrogen, methyl and ethyl groups, M is individually chosen at each occurrence from hydrogen, lower alkyl (C₁-C₄) groups, sodium, potassium, tertiary amines, quaternary amines and ammonium ions and mixtures thereof; m is from 0 to 3, n is from 1 to 3, and the sum of (n+m) is from 1 to 4, a, b and d are integers having the relationships: a/d is from 0 to 50, a/b is from 0 to 50, b/d is from 0.1 to 20, d/(a+b) is from 5:1 to 1:10, the sum of (a+b+d) is sufficient to provide a molecular weight of at least 2,000, which process comprises reacting in an aqueous solvent, for at least 1/2 hour at a temperature of at least 110°C, in a pressure controlled reactor the ingredients (A) a chemical reactant of the formula wherein R', X, M, m and n have the above meaning, and (B) a water-soluble vinyl polymer having pendant amide groups represented by the formula wherein R, M, a and b have the above meaning, and wherein the mole ratio of reactant to pendant amide groups on the polymer ranges between about 1:1 to about 1:5, and then recovering the phosphonated polymer. A phosphonated polymer having the general formula and being synthesized, in a pressure controlled reactor, by reacting a precursor polymer having the formula with a chemical reactant H₂N(R₁)PO₃M₂ in an aqueous solvent at a temperature of at least 100°C for at least 1/4 hour at a mole ratio of precursor polymer to chemical reactant ranging between about 20:1 to about 1:2, and wherein R₁ is a lower linear or branched alkylene bridging group containing from 1 to 6 carbon atoms, R is chosen individually at each occurrence from hydrogen and methyl groups, M is chosen individually at each occurrence from hydrogen, lower alkyl (C₁-C₄) groups, alkali metal, tertiary amines, quaternary amines and ammonium ions and mixtures thereof, a, b and d are integers having the relationships: a/d is from 0 to 100, a/b is from 0 to 100, b/d is from 0.01 to 100, and d/(a+b) ranges between 10:1 and 1:100, and wherein the sum of (a+b+d) is such that the phosphonated polymer has a molecular weight of at least 1,000. The phosphonated polymer of claim 9 which is synthesized in an aqueous reaction solvent at a temperature of at least 120°C for at least 1 hour at a mole ratio of precursor polymer to chemical reactant of from 10:1 to 1:1 and wherein R is hydrogen, M is chosen from hydrogen, sodium, potassium and ammonium ions and mixtures thereof, and the polymer has a molecular weight between 2,000 and 20,000,000. The phosphonated polymer represented by the general formula wherein M is individually chosen at each occurrence from hydrogen, sodium and ammonium ions, X is chosen from the group -OH, -COOH, -(OCH₂CH₂) p -OH, -SO₃H and mixtures thereof, p is from 1 to 6, a, b and d are integers such that the sum of (a+b+d) is sufficient to achieve a molecular weight of at least 1,000, a/d is from 0 to 100, b/d is from 0.01 to 100, a/b is from 0 to 100, and the ratio d/(a+b) ranges between 5:1 and 1:50. The phosphonated polymer represented by the general formula wherein M, a, b, d have the meaning as defined in claim 11. The phosphonated polymer represented by the general formula wherein R' is a multivalent hydrocarbonaceous bridging group having 1 to 6 carbon atoms and being chosen from linear alkyl, branched alkyl, cyclic and olefinic groups and mixtures thereof; X is chosen from -OH and -COOM and mixtures thereof; R is individually chosen at each occurrence from hydrogen and methyl groups; M is individually chosen at each occurence from hydrogen, lower (C1-C4) alkyl groups, sodium, potassium and ammonium ions and mixtures thereof; a, b and d are integers, the sum of which is such that the molecular weight of the phosphonated polymer is at least 2,000, wherein the following relationship exists: a/b is from 0 to 100, a/d is from 0 to 100, b/d is from 0.01 to 100, and the ratio d/(a+b) is between about 10:1 to about 1:100; m is equal to 0 to 6, n is equal to 1 to 6, and the sum of (m+n) is between 1 and 6. The phosphonated polymer represented by the general formula wherein R is individually chosen at each occurence from hydrogen and methyl groups; M is individually chosen at each occurence from hydrogen, a methyl group, sodium, potassium and ammonium ions, and mixtures thereof, and a, b and d are the same as in claim 13.

Inventors: FONG, DODD WING, KOWALSKI, DAVID JOSEPH
Applicants: NALCO CHEMICAL COMPANY
Application year: 1987
Main classification: C08F8
IPC codes: C08F8