Ionene polymers containing biologically-active anions

Claim 2

A water-soluble ionene polymer of formula I: ##STR3## wherein n is an integer from 4 to 400 corresponding to the degree of polymerization of the polymer; R 1 , R 2 , R 3 and R 4 represent the same or different substituent selected from the group consisting of hydrogen, a C 1 to C 16 alkyl group, a C 1 to C 16 alkyl group substituted with one or more hydroxyl groups, a benzyl group, and a benzyl group substituted with one or more C 1 to C 16 alkyl groups; B represents a divalent C 2 to C 16 aliphatic hydrocarbon radical which can be substituted by hydroxyl, a divalent C 5 to C 9 cyclic hydrocarbon radical, a di-(C 2 to C 6 )-alkylene ether, a phenylene or alkyl-substituted phenylene radical, or the divalent group R 1 R 2 NBNR 3 R 4 of formula I represents a divalent radical of the structure: R.sub.1 R.sub.2 N--(CH.sub.2).sub.p --NR.sub.5 --C(O)--NR.sub.6 --(CH.sub.2).sub.p --NR.sub.3 R.sub.4 where p is an integer from 2 to 6, R 1 , R 2 , R 3 and R 4 are the same as defined above, and R 5 and R 6 are the same or different and are selected from the group consisting of hydrogen and a C 1 to C 16 alkyl group, or the divalent radical R 1 R 2 NBNR 3 R 4 forms a heterocyclic group selected from 1,2-pyrazolidinyl, 1,3-imidazolindiyl, 1,4-piperazindiyl, aminopyrrolidinyl, or aminopiperidiyl wherein the heterocyclic group may be substituted with one or more groups selected from a C 1 to C 6 alkyl group, a hydroxyl group, a halide, or a phenyl group; A - is an anion derived from a biologically-active compound having at least one acid functionality with the proviso that said anion is not a halide anion; X - is an anion derived from a mineral or organic acid; and the degree of substitution of the polymer is from about 0.005 to 0.5.

Claim 3

An ionene polymer according to claim 1, wherein the anion A - is derived from a herbicide.

Claim 4

An ionene polymer according to claim 2, wherein the herbicide is 2,4-dichlorophenoxyacetic acid.

Claim 5

An ionene polymer according to claim 1, wherein the anion A - is derived from a disinfectant and the anion X - is selected from the group consisting of halide ions.

Claim 6

An ionene polymer according to claim 4, wherein the disinfectant is selected from the group consisting of phenol and phenol derivatives.

Claim 7

An ionene polymer according to claim 1, wherein the anion A - is derived from a pharmaceutical compound and the anion X - is selected from the group consisting of halide ions.

Claim 8

An ionene polymer of claim 1, wherein n is from 5-50; R 1 , R 2 , R 3 and R 4 are each methyl, ethyl, or benzyl; B is methylene, ethylene, propylene, 2-hydroxypropylene, butylene, isobutylene, diethylene ether, or phenylene; and X - is a halide.

Claim 9

An ionene polymer of claim 7, wherein R 1 , R 2 , R 3 and R 4 are each methyl, B is ethylene, and X - is chloride.

Claim 10

An ionene polymer of claim 1, wherein the group R 1 R 2 NBNR 3 R 4 is a radical of the structure: R.sub.1 R.sub.2 N--(CH.sub.2).sub.p --NR.sub.5 --C(O)--NR.sub.6 --(CH.sub.2).sub.p --NR.sub.3 R.sub.4.

Claim 11

An ionene polymer of claim 9, wherein n is from 5-50; R 1 , R 2 , R 3 and R 4 are each methyl, ethyl or benzyl; R 5 and R 6 are each methyl or ethyl; p is 2 or 3; and X - is a halide.

Claim 12

An ionene polymer of claim 10, wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are methyl, p is 3, and X - is a halide.

Claim 13

The ionene polymer of claim 1 wherein the anion A - is I 3 - .

Claim 14

A method for the preparation of an ionene polymer of formula I according to claim 1, the method comprising the steps of: reacting a protonated diamine of formula IV ##STR4## with an epihalohydrin under conditions sufficient to form an intermediate of formula VI ##STR5## and polymerizing said intermediate with a diamine of formula III ##STR6## under conditions sufficient to form said polymer.

Claim 15

A method of claim 13, further comprising, before said reaction step, the steps of neutralizing a diamine of formula III with up to one equivalent of a biologically-active acid, HA, per amine group; and adding sufficient acid, HX, so that the total amount of acid used is approximately equivalent to the amine groups present, thereby forming the protonated diamine of formula IV.

Claim 16

A method according to claim 13, wherein the epihalohydrin is epichlorohydrin.

Claim 17

A method of claim 13, wherein the anion A - is I 3 - .

Claim 18

A method of claim 13, wherein the anion A - is a phenolate anion.

Claim 19

A water-soluble ionene polymer of formula II: ##STR7## wherein n is an integer from 4 to 400 corresponding to the degree of polymerization of the polymer; R 1 , R 2 , R 3 and R 4 represent the same or different substituent selected from the group consisting of hydrogen, a C 1 to C 16 alkyl group, a C 1 to C 16 alkyl group substituted with one or more hydroxyl groups, a benzyl group and a benzyl group substituted with one or more C 1 to C 16 alkyl groups; B represents a divalent C 2 to C 16 aliphatic hydrocarbon radical which can be substituted by hydroxyl, a divalent C 5 to C 9 cyclic hydrocarbon radical, a di-(C 2 to C 6 )-alkylene ether, a phenylene or alkyl-substituted phenylene radical or the divalent group R 1 R 2 NBNR 3 R 4 of formula II represents a divalent radical of the structure: R.sub.1 R.sub.2 N--(CH.sub.2).sub.p --NR.sub.5 --C(O)--NR.sub.6 --(CH.sub.2).sub.p --NR.sub.3 R.sub.4 where p is an integer from 2 to 6, R 1 , R 2 , R 3 , and R 4 are the same as defined above, and R 5 and R 6 are the same or different and are selected from the group consisting of hydrogen and a C 1 to C 16 alkyl group, or the divalent radical R 1 R 2 NBNR 3 R 4 forms a heterocyclic group selected from 1,2-pyrazolidinyl, 1,3-imidazolindiyl, 1,4-piperazindiyl, aminopyrrolidinyl, or aminopiperidiyl wherein the heterocyclic group may be substituted with one or more groups selected from a C 1 to C 6 alkyl group, a hydroxyl group, a halide, or a phenyl group; A - is an anion derived from a biologically-active compound having at least one acid functionality with the proviso that said anion is not a halide anion; X - is an anion derived from a mineral or organic acid; and the degree of substitution of the polymer is from about 0.005 to 0.333.

Claim 20

A water-soluble ionene polymer of formula II: ##STR7## wherein n is an integer from 4 to 400 corresponding to the degree of polymerization of the polymer; R 1 , R 2 , R 3 and R 4 represent the same or different substituent selected from the group consisting of hydrogen, a C 1 to C 16 alkyl group, a C 1 to C 16 alkyl group substituted with one or more hydroxyl groups, a benzyl group and a benzyl group substituted with one or more C 1 to C 16 alkyl groups; B represents a divalent C 2 to C 16 aliphatic hydrocarbon radical which can be substituted by hydroxyl, a divalent C 5 to C 9 cyclic hydrocarbon radical, a di-(C 2 to C 6 )-alkylene ether, a phenylene or alkyl-substituted phenylene radical or the divalent group R 1 R 2 NBNR 3 R 4 of formula II represents a divalent radical of the structure: R.sub.1 R.sub.2 N--(CH.sub.2).sub.p --NR.sub.5 --C(O)--NR.sub.6 --(CH.sub.2).sub.p --NR.sub.3 R.sub.4 where p is an integer from 2 to 6, R 1 , R 2 , R 3 , and R 4 are the same as defined above, and R 5 and R 6 are the same or different and are selected from the group consisting of hydrogen and a C 1 to C 16 alkyl group, or the divalent radical R 1 R 2 NBNR 3 R 4 forms a heterocyclic group selected from 1,2-pyrazolidinyl, 1,3-imidazolindiyl, 1,4-piperazindiyl, aminopyrrolidinyl, or aminopiperidiyl wherein the heterocyclic group may be substituted with one or more groups selected from a C 1 to C 6 alkyl group, a hydroxyl group, a halide, or a phenyl group; A - is an anion derived from a biologically-active compound having at least one acid functionality with the proviso that said anion is not a halide anion; X - is an anion derived from a mineral or organic acid; and the degree of substitution of the polymer is from about 0.005 to 0.333.

Claim 21

An ionene polymer according to claim 18, wherein the anion A - is derived from a herbicide.

Claim 22

An ionene polymer according to claim 19, wherein the herbicide is 2,4-dichlorophenoxyacetic acid.

Claim 23

An ionene polymer according to claim 18, wherein the anion A - is derived from a disinfectant and the anion X - is selected from the group consisting of halide ions.

Claim 24

An ionene polymer according to claim 21, wherein the disinfectant is selected from the group consisting of phenol and phenol derivatives.

Claim 25

An ionene polymer according to claim 18, wherein the anion A - is I 3 - .

Claim 26

An ionene polymer of claim 18, wherein, n is from 5-50; R 1 , R 2 , R 3 and R 4 are each methyl, ethyl, or benzyl; B is methylene, ethylene, propylene, 2-hydroxypropylene, butylene, isobutylene, diethylene ether, or phenylene; X - is a halide.

Claim 27

An ionene polymer of claim 24, wherein, R 1 , R 2 , R 3 and R 4 are each methyl, B is ethylene, and X - is chloride.

Claim 28

An ionene polymer of claim 18, wherein the group R 1 R 2 NBNR 3 R 4 is a radical of the structure: R.sub.1 R.sub.2 --(CH.sub.2).sub.p --NR.sub.5 --C(O)--NR.sub.6 --(CH.sub.2).sub.p --NR.sub.3 R.sub.4.

Claim 29

An ionene polymer of claim 26, wherein n is from 5-50; R 1 , R 2 , R 3 and R 4 are each methyl, ethyl or benzyl; R 5 and R 6 are each hydrogen, methyl or ethyl; p is 2 or 3; and X - is a halide.

Claim 30

An ionene polymer of claim 26, wherein R 1 , R 2 , R 3 and R 4 are methyl, R 5 and R 6 are hydrogen, p is 3, and X - is a halide.

Claim 31

A method for the preparation of an ionene polymer of formula II according to claim 18, the method comprising the steps of: reacting a protonated diamine of formula IV ##STR8## with an epihalohydrin under conditions sufficient to form an intermediate of formula VI ##STR9## and polymerizing said intermediate with a secondary amine of formula VII ##STR10## under conditions sufficient to form said polymer.

Claim 32

A method of claim 29, further comprising, before said reaction step, the steps of neutralizing a diamine with up to one equivalent of a biologically-active acid, HA, per amine group; and adding sufficient acid, HX, so that the total amount of acid used is approximately equivalent to the amine groups present, thereby forming the protonated diamine of formula IV.

Claim 33

A method according to claim 29, wherein the epihalohydrin is epichlorohydrin.

Claim 34

A method according to claim 30, wherein the biologically-active acid is the herbicide 2,4-dichlorophenoxyacetic acid.

Claim 35

A method according to claim 30, wherein the anion A - is a phenolate anion.

Claim 36

A method according to claim 29, wherein the anion A - is I 3 - .

Claim 39

A compound of formula VI: ##STR11## wherein R 1 , R 2 , R 3 and R 4 represent the same or different substituent selected from the group consisting of hydrogen, a C 1 to C 16 alkyl group, a C 1 to C 16 alkyl group substituted with one or more hydroxyl groups, a benzyl group and a benzyl group substituted with one or more C 1 to C 16 alkyl groups; B represents a divalent C 2 to C 16 aliphatic hydrocarbon radical which can be substituted by hydroxyl, a divalent C 5 to C 9 cyclic hydrocarbon radical, a di-(C 2 to C 6 )-alkylene ether, a phenylene or alkyl-substituted phenylene radical, or the divalent group R 1 R 2 NBNR 3 R 4 in formula VI represents a divalent radical of the structure: R.sub.1 R.sub.2 N--(CH.sub.2).sub.p --NR.sub.5 --C(O)--NR.sub.6 --(CH.sub.2).sub.p --NR.sub.3 R.sub.4 where p is an integer from 2 to 6 and R 5 and R 6 are the same or different and selected from the group consisting of hydrogen and a C 1 to C 16 alkyl group, or the divalent radical R 1 R 2 NBNR 3 R 4 forms a heterocyclic group selected from 1,2-pyrazolidinyl, 1,3-imidazolindiyl, 1,4-piperazindiyl, aminopyrrolidinyl, or aminopiperidiyl wherein the heterocyclic group may be substituted with one or more groups selected from a C 1 to C 6 alkyl group, a hydroxyl group, a halide, or a phenyl group; A - is an anion derived from a biologically-active compound having at least one acid functionality with the proviso that said anion is not a halide anion; and X - is an anion derived from a mineral acid.

Claim 40

A compound of formula VI: ##STR11## wherein R 1 , R 2 , R 3 and R 4 represent the same or different substituent selected from the group consisting of hydrogen, a C 1 to C 16 alkyl group, a C 1 to C 16 alkyl group substituted with one or more hydroxyl groups, a benzyl group and a benzyl group substituted with one or more C 1 to C 16 alkyl groups; B represents a divalent C 2 to C 16 aliphatic hydrocarbon radical which can be substituted by hydroxyl, a divalent C 5 to C 9 cyclic hydrocarbon radical, a di-(C 2 to C 6 )-alkylene ether, a phenylene or alkyl-substituted phenylene radical, or the divalent group R 1 R 2 NBNR 3 R 4 in formula VI represents a divalent radical of the structure: R.sub.1 R.sub.2 N--(CH.sub.2).sub.p --NR.sub.5 --C(O)--NR.sub.6 --(CH.sub.2).sub.p --NR.sub.3 R.sub.4 where p is an integer from 2 to 6 and R 5 and R 6 are the same or different and selected from the group consisting of hydrogen and a C 1 to C 16 alkyl group, or the divalent radical R 1 R 2 NBNR 3 R 4 forms a heterocyclic group selected from 1,2-pyrazolidinyl, 1,3-imidazolindiyl, 1,4-piperazindiyl, aminopyrrolidinyl, or aminopiperidiyl wherein the heterocyclic group may be substituted with one or more groups selected from a C 1 to C 6 alkyl group, a hydroxyl group, a halide, or a phenyl group; A - is an anion derived from a biologically-active compound having at least one acid functionality with the proviso that said anion is not a halide anion; and X - is an anion derived from a mineral acid.

Claim 41

A compound of claim 36, wherein n is from 5-50; R 1 , R 2 , R 3 , R 4 are each methyl, ethyl, or benzyl; B is methylene, ethylene, propylene, 2-hydroxypropylene, butylene, isobutylene, diethylene ether, or phenylene; and X - is a halide.

Claim 42

A compound of claim 37, wherein; R 1 , R 2 , R 3 , R 4 are each methyl, B is ethylene, and X - is chloride.

Claim 43

A compound of claim 36, wherein the group R 1 R 2 NBNR 3 R 4 is a radical of the structure: R.sub.1 R.sub.2 N--(CH.sub.2).sub.p --NR.sub.5 --C(O)--NR.sub.6 --(CH.sub.2).sub.p --NR.sub.3 R.sub.4.

Claim 44

A compound of claim 39, wherein R 1 , R 2 , R 3 and R 4 are each methyl, ethyl or benzyl; R 5 and R 6 are each hydrogen, methyl or ethyl; p is 2 or 3; and X - is a halide.

Claim 45

A compound of claim 40, wherein R 1 , R 2 , R 3 and R 4 are methyl, R 5 and R 6 are hydrogen, p is 3, and X - is a halide.

Claim 46

A method according to claim 14, wherein the biologically-active acid is the herbicide 2,4-dichlorophenoxyacetic acid.

Claim 47

A fertilizer comprising a polymer of claim 1 or 18.

Claim 48

A pesticide comprising a polymer of claim 1 or 18.

Claim 49

A therapeutic agent comprising a polymer of claim 1.

Claim 50

A dispersant comprising a polymer of claim 1 or 18.

Claim 51

A microbicide comprising a polymer of claim 1 or 18.

Claim 52

A preservative comprising a polymer of claim 1 or 18.

Claim 53

A disinfectant comprising a polymer of claim 1 or 18.

Claim 54

A plant growth regulator comprising a polymer of claim 1 or 18.

Claim 55

A sizing agent comprising a polymer of claim 1 or 18.

Claim 56

A surfactant comprising a polymer of claim 1 or 18.

Claim 57

A herbicide comprising a polymer of claim 1 or 18.

Claim 58

A sanitizer comprising a polymer of claim 1 or 18.

Claim 59

A scale control agent comprising a polymer of claim 1 or 18.

Claim 60

A fluorescent agent comprising a polymer of claim 1 or 18.

Claim 61

A termicide comprising a polymer of claim 1 or 18.

Claim 62

A method for fertilizing comprising applying to foliage the fertilizer of claim 43.

Claim 63

A method to destroy pests comprising applying to the pests or to the locus of the pests the fertilizer of claim 44.

Claim 64

A method for promoting the formation and stabilization of a dispersion of at least one substance in another substance comprising adding the dispersant of claim 46 to the dispersion.

Claim 65

A method to destroy microorganisms comprising applying to the microorganisms or to the locus of the microorganisms the microbicide of claim 47.

Claim 66

A method to preserve a substance comprising applying or adding to the substance the preservative of claim 48.

Claim 67

A method for disinfecting a substance comprising applying to the substance the disinfectant of claim 49.

Claim 68

A method to regulate plant growth comprising applying to the plant or to the locus of the plant the plant growth regulator of claim 50.

Claim 69

A method to destroy or inhibit plant growth comprising applying to a plant or to the locus of the plant the herbicide of claim 53.

Claim 70

A method of sanitizing a substance comprising cleaning or sterilizing the substance with the sanitizer of claim 54.

Claim 71

A method to destroy termites comprising applying to the termites or to the locus of the termites the termiticide of claim 57.

Claim 72

A method to treat udder infections in dairy cattle comprising administering a pharmaceutically effective amount of a formulation comprising the polymer of claim 1 or 18.

Claim 73

An algicide comprising a polymer of claim 1 or 18.

Claim 74

A method for disinfecting water comprising applying or adding to said water the algicide of claim 69.

Claim 75

A topical antiseptic comprising the polymer of claim 1 or 18.