Water-soluble polymers and compositions thereof

FIELD OF THE INVENTION 
The present invention relates to water-soluble polymers and compositions 
thereof, such water-soluble polymers and compositions thereof useful, 
e.g., in processes for selective separation of metal ions from aqueous 
streams, and processes for the selective separation of metals from solid 
matrixes. 
BACKGROUND OF THE INVENTION 
Water-soluble polymers are well known for the retention or recovery of 
certain metal ions from solutions under certain conditions, e.g., certain 
pH conditions (see, e.g., Pure and Applied Chemistry. Vol. 52, pp. 
1883-1905 (1980), Talanta, vol. 36, No. 8, pp. 861-863 (1989), and U.S. 
Pat. No. 4,741,831). Additionally, higher molecular weight varieties of 
the water-soluble polymers such as polyethyleneimine have been used as 
coatings on, e.g. silica gel, for separation and recovery of metal ions. 
However, the selectivity of the polymer for target metals due to 
competition from competing or interfering ions within 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 invention to provide compositions of 
water-soluble polymers having defined molecular weight ranges. 
Still another object of the present invention is to provide compositions of 
water-soluble polymers including at least two different water-soluble 
polymers, the different water-soluble polymers differing in functionality, 
molecular weight range or both. 
SUMMARY OF THE INVENTION 
To achieve the foregoing and other objects, and in accordance with the 
purposes of the present invention, as embodied and broadly described 
herein, the present invention provides a water soluble polymer of the 
formula 
##STR1## 
wherein X.sub.1, X.sub.2, and X.sub.3 in each unit of the polymer is a 
group independently selected from a substituent selected from H, 
C(O)CH.sub.2 CH(SH)COOH, 
EQU --(CH.sub.2 ).sub.m YZ.sub.p 
where when m is an integer selected from 0, 2, 3, and 4, Y is selected from 
C.dbd.O, P.dbd.O, C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is 
selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, 
oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, 
alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, 
dimethylpyrazol-thione, methylphenylpyrazol-thione, oxycrown ethers, 
azacrown ethers, thiocrown ethers, and H, and when m is 1, Y is selected 
from C.dbd.O, C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is selected 
from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
ethers, and H, p is an integer from 1 to 2, and n is an integer between 
about 12 and 12,000; or 
##STR2## 
where m is an integer from 0 to 6, Y is selected from C.dbd.O, P.dbd.O, 
and C.dbd.S, R.sub.1 and R.sub.2 are 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 with the 
proviso that at least one of X.sub.1, X.sub.2, and X.sub.3 is not 
hydrogen; 
##STR3## 
wherein X.sub.4 and X.sub.5 in each unit of the polymer is a group 
independently selected from a substituent selected from H, C(O)CH.sub.2 
CH(SH)COOH, 
EQU --(CH.sub.2).sub.m YZ.sub.p 
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.dbd.O, P.dbd.O, C.dbd.S, 
SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is selected from an amine, 
alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
ethers, and H, and when m is 1, Y is selected from C.dbd.O, C.dbd.S, 
SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is selected from an amine, 
alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
ethers, and H, p is an integer from 1 to 2, and n is an integer between 
about 24 and 24,000 with the proviso that at least one of X.sub.4 and 
X.sub.5 is not hydrogen; 
##STR4## 
wherein X.sub.6 in each unit of the polymer is a group independently 
selected from a substituent selected from C(O)CH.sub.2 CH(SH)COOH, 
EQU --(CH.sub.2).sub.m YZ.sub.p 
where m is an integer selected from 0, 2, 3, and 4, Y is selected from 
C.dbd.O, P.dbd.O, C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is 
selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, 
oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, 
alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, 
dimethylpyrazol-thione, methylphenylpyrazol-thione, oxycrown ethers, 
azacrown ethers, thiocrown ethers, and H, and when m is 1, Y is selected 
from C.dbd.O, C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is selected 
from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
ethers, and H, p is an integer from 1 to 2, and n is an integer between 
about 24 and 24,000; 
EQU --(CHX.sub.7 --CH.sub.2).sub.n --(CH.sub.2 --CX.sub.8 X.sub.9).sub.m --(iv) 
wherein X.sub.7 and X.sub.8, and X.sub.9 in each unit of the polymer is a 
group independently selected from a substituent selected from C(O)CH.sub.2 
CH(SH)COOH, 
EQU --(CH.sub.2).sub.m YZ.sub.p 
where m is an integer selected from 0, 2, and 4, Y is selected from 
C.dbd.O, P.dbd.O, C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is 
selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, 
oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, 
alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, 
dimethylpyrazol-thione, methylphenylpyrazol-thione, oxycrown ethers, 
azacrown ethers, thiocrown ethers, and H, and when m is 1, Y is selected 
from C.dbd.O, C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is selected 
from an amine, alkylamine, arylamine, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
ethers, and H, p is an integer from 1 to 2, and n is an integer between 
about 12 and 12,000, or 
##STR5## 
wherein X.sub.10 and X.sub.11 in each unit of the polymer are a thiolactum 
or are a group independently selected from a substituent selected from 
C(O)CH.sub.2 CH(SH)COOH, and 
EQU --(CH.sub.2).sub.m YZ.sub.p 
where m is an integer from 0 to 4, Y is selected from C.dbd.O, P.dbd.O, 
C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S; Z is selected from an amine, 
alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
ethers, and H, p is an integer from 1 to 2, and n is an integer between 
about 24 and 24,000. 
The present invention also provides a water soluble polymer of the formula 
##STR6## 
wherein X.sub.1, X.sub.2, and X.sub.3 in each unit of the polymer is a 
group independently selected from a substituent selected from H, 
C(O)CH.sub.2 CH(SH)COOH, 
EQU --(CH.sub.2).sub.m YZ.sub.p 
where m is an integer from 0 to 4, Y is selected from C.dbd.O, P.dbd.O, 
C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is selected from an amine, 
alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
ethers, and H, p is an integer from 1 to 2, and n is an integer between 
about 12 and 12,000; 
##STR7## 
where m is an integer from 0 to 6, Y is selected from C.dbd.O, P.dbd.O, 
and C.dbd.S, R.sub.1 and R.sub.2 are 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; 
##STR8## 
wherein X.sub.4 and X.sub.5 in each unit of the polymer is a group 
independently selected from a substituent selected from H, C(O)CH.sub.2 
CH(SH)COOH, 
EQU --(CH.sub.2).sub.m YZ.sub.p 
where q is an integer from 0 to 4, m is an integer from 0 to 4, Y is 
selected from C.dbd.O, P.dbd.O, C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and 
S, Z is selected from an amine, alkylamine, arylamine, hydroxyl, oxyalkyl, 
oxyaryl, hydroxylamine, alkylhydroxylamine, arylhydroxylamine, thiol, 
alkylthiol, alkyl, aryl, dimethylpyrazolone, methylphenylpyrazolone, 
dimethylpyrazol-thione, methylphenylpyrazol-thione, oxycrown ethers, 
azacrown ethers, thiocrown ethers, and H, p is an integer from 1 to 2, and 
n is an integer between about 24 and 24,000; 
##STR9## 
wherein X.sub.6 in each unit of the polymer is a group independently 
selected from a substituent selected from C(O)CH.sub.2 CH(SH)COOH, 
EQU --(CH.sub.2).sub.m YZ.sub.p 
where m is an integer from 0 to 4, Y is selected from C.dbd.O, P.dbd.O, 
C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S; Z is selected from an amine, 
alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
ethers, and H, p is an integer from 1 to 2, and n is an integer between 
about 24 and 24,000; 
EQU --(CHX.sub.7 --CH.sub.2).sub.n --(CH.sub.2 --CX.sub.8 X.sub.9).sub.m --(iv) 
wherein X.sub.7, X.sub.8, and X.sub.9 in each unit of the polymer is a 
group independently selected from a substituent selected from C(O)CH.sub.2 
CH(SH)COOH, 
EQU --(CH.sub.2).sub.m YZ.sub.p 
where m is an integer from 0 to 4, Y is selected from C.dbd.O, P.dbd.O, 
C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S, Z is selected from an amine, 
alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
ethers, and H, p is an integer from 1 to 2, and n is an integer between 
about 12 and 12,000; or 
##STR10## 
wherein X.sub.10 and X.sub.11 in each unit of the polymer are a thiolactum 
or are a group independently selected from a substituent selected from 
C(O)CH.sub.2 CH(SH)COOH, and 
EQU --(CH.sub.2).sub.m YZ.sub.p 
where m is an integer from 0 to 4, Y is selected from C.dbd.O, P.dbd.O, 
C.dbd.S, SO.sub.2, C(O)CH.sub.2 C(O), and S; Z is selected from an amine, 
alkylamine, arylamine, hydroxyl, oxyalkyl, oxyaryl, hydroxylamine, 
alkylhydroxylamine, arylhydroxylamine, thiol, alkylthiol, alkyl, aryl, 
dimethylpyrazolone, methylphenylpyrazolone, dimethylpyrazol-thione, 
methylphenylpyrazol-thione, oxycrown ethers, azacrown ethers, thiocrown 
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 
of 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, a water-soluble polymer is 
provided 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. 
In another embodiment of the invention, the water-soluble polymer includes 
functionalization from the group of amino groups, carboxylic acid groups, 
phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, 
hydroxamic acid groups, aza crown ether groups, oxy crown ethers groups, 
guanidinium groups, amide groups, ester groups, aminodicarboxylic groups, 
permethylated polvinylpyridine groups, permethylated amine groups, 
mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea 
groups. 
DETAILED DESCRIPTION 
The present invention is concerned with water-soluble polymers, such 
water-soluble polymers useful, e.g., in the separation of various metals, 
e.g., toxic metals and/or precious and/or nuisance metals from aqueous 
streams. 
The water-soluble polymers useful in practicing the present invention are 
synthetic water-soluble polymers, i.e., they are not naturally occurring 
water-soluble polymers such as starch, cellulose, and the like and do not 
involve modified naturally occurring water-soluble polymers. The 
water-soluble polymers used in the present invention generally include a 
nitrogen-, oxygen-, or sulfur-containing group. Exemplary of the 
water-soluble polymers used in the present invention are 
polyalkyleneimines such as polyethyleneimine and modified 
polyalkyleneimines, i.e., polyalkyleneimines such as polyethyleneimine 
where the water-soluble polymer includes functionalization 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-crown ether 
groups, guanidinium groups, thiolactam groups, catechol groups, 
mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea 
groups. In addition to polyethyleneimine as the basic structure of many of 
the water-soluble polymers, other water-soluble polymer structures with 
nitrogen-containing groups such as poly(vinylamine), polyvinylpyridine, 
poly(acrylamide), and poly(allylamine), can be used. Also, water-soluble 
polymers structures with oxygen-containing groups such as 
poly(vinylalcohol) or oxygen- and nitrogen-containing groups such as 
polyvinylpyrrolidone can be used. The amine backbones can also be 
permethylated to give permethylpolyethyleneimine, permethylated 
polyvinylpyridine, permethylated polyallylamine, or permethylated 
polyvinylamine. Water-soluble polymers can be constructed from vinyl 
monomer polymerization reactions to give a number of pendent groups, 
copolymer of acrylamide and bis-phosphonic esters and acids. Water-soluble 
polymers with metal binding properties can be obtained from ring-opening 
reactions, e.g., the treatment of polypyrrolidone with base or 
hydroxylamine. 
Exemplary of suitable functionalized water-soluble polymers are the 
reaction product of polyethyleneimine and an 
arylalkylhaloacetylpyrazolones such as phenylmethylchloroacetylpyrazolone 
or dimethylchloroacetylpyrazolone to yield a 
phenylmethylacetylpyrazolone-substituted or 
dimethylacetylpyrazolone-substituted polyethyleneimine, the reaction 
product of polyethyleneimine (polyallylamine, polyvinylamine) and a 
halocarboxylic acid such as bromoacetic acid or chloroacetic acid to yield 
an amino-carboxylate-substituted polyethyleneimine (polyallylamine, 
polyvinylamine), the reaction product of polyethyleneimine 
(polyvinylamine) and phosphorous acid and formaldehyde to give a 
phosphonic acid substituted polyethyleneimine (polyvinylamine), the 
reaction of polyethyleneimine and a monohydroxamic acid of succinic acid 
to give a hydroxamic acid substituted polyethyleneimine, the reaction of 
polyethyleneimine with acrylamide or ethylacrylate to give an ester or 
amide substituted polyethyleneimine, the reaction of vinylalcohol with a 
crown alcohol to give an oxycrown substituted vinylalcohol, the 
permethylation of polyvinylpyridine or polyethyleneimine or polyvinylamine 
or polyallylamine to give the respective permethylated polymers, the ring 
opening of polypyrrolidone with hydroxylamine to give the hydroxamic acid 
polymer, the copolymerization of a betabisphosphonic acid or ester with 
acrylamide to give a copolymer, the reaction of polyethyleneimine with a 
bisphosphonic acid or ester to give bisphosphonic acid or ester 
polyethyleneimine, and the reaction product of polyethyleneimine and a 
haloacetylaza crown material such as a chloroacetylaza crown ether to 
yield an aza crown ether-substituted polyethyleneimine. 
When the polyethyleneimine is functionalized, care must be taken to control 
the level of functionalization as solubility problems at certain pH values 
can exist depending upon the type of functional groups and backbone used. 
The water-soluble polymers used in the present process preferably 
maintains their water solubility over the entire pH range of, e.g., pH 1 
to 14. Preferably, any polyethyleneimine used in the present invention 
includes primary, secondary and tertiary amines. Bisfunctionalization can 
be realized for primary nitrogens allowing for multidentate character of 
some of the chelating groups. The polyethyleneimine is a branched polymer, 
giving it a globular nature and high charge density which partly accounts 
for its uniqueness in the polyamine family of polymers. This highly 
branched character also allows for better chelating site interactions with 
metal ions within the polymer. Other polyamines, i.e., polyvinylamine and 
polyallylamine, can be used as backbones, and are composed of all primary 
nitrogens, but they are linear polymers and if over functionalized can 
lead to insolubility in different pH ranges. 
The use of prepurified (sized) polymer in the functionalization can be 
preferred in the process. Use of pre-purified polymer, e.g., 
polyethyleneimine, has the advantage that reagents used in subsequent 
functionalization steps are not lost on low molecular weight 
polyethyleneimine that will be lost in subsequent purification of the 
functionalized polymers. Further, it gives an extra margin of assurity 
that there will be no polymer leakage during the use of the polymers in 
any ultrafiltration process. 
Conditions in the preparation of the water-soluble polymers can be 
important to assure that there is no detectable leakage through an 
ultrafiltration membrane during some subsequent processes. Several factors 
are important in aiding the presizing of the water-soluble polymers; the 
polymer concentration the pH value, and the ionic strength at which the 
polymers are presized are all important. Because water-soluble polymers 
can aggregate in solution and because the polymers can expand or contract 
in size, conditions that effects these tendencies should be controlled. 
For example, it is known that polyethyleneimine can change it average size 
by 60% between a basic and acidic solution (larger in the acidic solution 
and smaller in basic). Thus, polyethyleneimine should be prepurified at 
the pH where its size is smallest to further assure the smaller fragments 
are remover from the larger fragments (at a pH of about 10-11). Other 
polymers because of either their neutral, anionic, or cationic nature will 
have different optimum pH values for prepurifying depending upon the pH 
that gives the smallest polymeric volume in solution. The ionic strength 
of a solution can also effect the polymeric volume in solution similarly 
to pH effects. If polymer concentration are too high in solution they will 
aggregate, again effecting the potential ability of obtaining polymers 
that are not going to leak through the membranes during any 
ultrafiltration process. 
The prior art in the preparation of polyethyleneimine or other 
water-soluble polymers for use in metal separations has been quite vague 
in how it is prepared and treated for use in ultrafiltration techniques. 
The present process to purify polyethyleneimine is unique in that the 
purification scheme does not clog the ultrafiltration membranes. In 
contrast, some polyethyleneimine manufacturers have been unable to develop 
a purification technique for sizing the polymer using ultrafiltration 
without severely and irreversibly clogging the membranes. Note that one 
other main use of polyethyleneimine is as an adhesive and 
polyethyleneimine is known to bind to many surfaces, especially cellulose 
and anionic surfaces. Polyethyleneimine has been reported to be 
fractionated by size using GPC (size exclusion chromatography), 
precipitation, and by exhaustive dialysis. Average molecular weight 
determinations were performed by 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 an absolute molecular weight cutoff. 
The water-soluble polymers of the present invention can be used in several 
potential compositions for selective separation of metal ions from aqueous 
streams or metals from solid matrixes. There can be a single polymer that 
will bind selectively with only one metal ion over all other ions and 
materials under the conditions of the process. Separation is achieved by 
binding that metal ion to the water-soluble polymer and then using a 
separation technique such as ultrafiltration to remove the water and other 
materials from the polymer. The polymer-bound metal ion is thus 
concentrated. The polymer-bound metal can be released from the polymer by 
a variety of processes as shown in the following equations: 
EQU M(P)+H.sup.+ .fwdarw.HP+M.sup.+ (eq. 1) 
EQU M(P)+L.fwdarw.ML+(P) (eq. 2) 
EQU or 
EQU M(P)+e.sup.- .fwdarw.M.sup.x +(P) (eq. 3) 
where M is the metal ion, (P) is the water-soluble polymer, L is a 
competing complexant, H.sup.+ is a proton, x is the valent state of the 
metal, and e.sup.- is an electron for an oxidation change reaction. Where 
the metal is released by a proton (eq. 1) or by a competing molecular 
ligand (eq. 2), the polymer-free metal ion is recovered by a diafiltration 
process. In some instances, the metal ion may be so tightly bound to the 
polymer that it is more desirable to heat process the concentrate to 
destroy the polymer (incineration, hot acid digestion, smelting, etc.) and 
recover the metal. Optionally, for waste management purposes it may be 
desirable to solidify the polymer-bound metal, e.g., in a grout or cement 
material, such that it passes toxic leach tests (TCLP). 
Another potential composition can include a single polymer that will bind 
with a combination of metal ions under the process conditions. Separation 
and selectivity is realized by binding that combination of metal ions then 
using a separation technique such as ultrafiltration to remove the water 
and other materials from the polymer-metal complexes. The polymer-bound 
metals 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 (eq. 1) or by a competing molecular ligand 
(eq. 2), the polymer-free metal ion can be recovered by a diafiltration 
process. Stripping is repeated until all the desired metals have been 
selectively recovered. Again in some instances, the metal ions may be so 
tightly bound to the polymer that it is more desirable to heat process the 
concentrate to destroy the polymer to recover the metals. Optionally, for 
waste management purposes it may be desirable to solidify the 
polymer-bound metal, e.g., in a grout or cement material, such that it 
passes toxic leach tests (TCLP). 
Still another composition uses a polymer formulation (two or more polymers 
of same molecular weight range) blended in such a ratio and with such 
functionality to have the desired selectivity that binds a combination of 
metal ions under certain conditions of pH, counter ion, and/or ionic 
strength. Separation is achieved by binding the metal ions to the 
water-soluble polymers and then using a separation technique such as 
ultrafiltration to remove the water and other materials from the polymer. 
The mixed polymer-bound metals are thus concentrated and can be further 
purified by washing with a clean solution in a diafiltration process to 
remove any final impurities. The polymer-bound metals 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 may be selectively stripped of the respective metal 
or group of metals by, e.g., appropriate pH control into a range whereat 
one polymer is stripped of its particular metal while the second 
water-soluble polymer retains its particular metal as a water-soluble 
polymer-bound metal. The second and subsequent polymers can be stripped of 
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 polymer formulation (two or more polymers 
of different molecular weight range) blended in such a ratio and with such 
functionality to have the desired selectivity that binds a combination of 
metal ions under certain conditions of pH, counter ion, and/or ionic 
strength. Separation is achieved by binding the metal ions to the 
water-soluble polymer and then using a separation technique such as 
ultrafiltration to remove the water and other materials from the polymer. 
The mixed polymer-bound metals are thus concentrated and can be further 
purified by washing with a clean solution in a diafiltration process to 
remove any final impurities. The polymer-bound metals 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 may be selectively stripped of the respective metal 
ions or group of metal ions by, e.g., appropriate pH control into a range 
whereat one polymer is stripped of its particular metal while the second 
water-soluble polymer retains its particular metal as a water-soluble 
polymer-bound metal. The second and subsequent polymers can be stripped of 
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 one polymer by the 
equations 1 to 3, and to separate the smaller polymer containing one type 
of functionality from the larger polymer with a different type of 
functionality. One of the functionalities is chosen to bind the metal ion 
of interest so tightly that the polymer that contains that functionality 
and the bound metal ions can be size separated from the other size 
polymer(s). 
Another composition can include a single polymer or formulation of polymers 
that will bind with a single metal ion or a combination of metal ions 
under the conditions of the method. Separation and selectivity is realized 
by binding that combination of metal ions to the water-soluble polymer or 
polymers, then using a single pass separation technique such as 
ultrafiltration to remove the water and other materials from the 
polymer-bound metals. The polymer-bound metals are further concentrated to 
dryness or near dryness onto a flat ultrafiltration membrane. The membrane 
is either dissolved or digested in appropriate medium or leached with an 
appropriate acid or ligand to totally recover the metals that were on the 
membrane. The recovered solution which constitutes a concentrate of 
selected metal ions from the original solution can then be analyzed using 
appropriate analytical instrument or wet chemistry techniques. 
Another composition can include a single polymer or formulation of polymers 
that will bind with a single metal ion or a combination of metal ions 
under the conditions of the process. Separation is achieved by binding 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 materials and unbound metal ions from the aqueous polymer 
solution. The metals that are unbound to the polymer and go into the 
organic or second phase are separated from the polymer-containing aqueous 
phase by standard phase separation techniques, e.g., mixer settlers, 
liquid extraction membranes, or centrifugal contactors, etc. The metals 
can be back-extracted from the second phase to another aqueous phase for 
recovery purposes. The polymer can be regenerated from the aqueous stream 
by first concentration ultrafiltration followed by diafiltration. This 
process can be reversed by back extracting the metal ion of interest from 
a biphasic system using aqueous solutions of the water-soluble polymer. 
Generally, the concentration of the water-soluble polymer in metals 
separation is from about 0.001 weight to volume percent to about 25 weight 
to volume percent of final mixed solution, more preferably from about 
0.001 weight to volume percent to about 5 weight to volume percent of 
final solution. It is sufficient and in some cases desirable to have at 
least just enough polymer in solution such that the molar ratio of polymer 
to metal ions in solution is one. Using high concentrations of the 
water-soluble polymer can most often result in a lower flux or flow during 
an ultrafiltration stage. The use of high polymer concentration can also 
cause an aggregation effect where no or little metal ion binding occurs to 
the polymer when the metal ion sees a high initial concentration of 
polymer. During the diafiltration stage the polymer and metal bound 
polymer concentration can often become quite high and in the case where 
the solution goes to near dryness it can approach 90% of the weight of the 
concentrate. 
After the solution containing the water-soluble polymer is contacted with 
the aqueous solution for a sufficient period of time to form water-soluble 
polymer-metal complex, separation of the water-soluble polymer-metal 
complex is preferably accomplished by ultrafiltration. Ultrafiltration is 
a pressure driven separation occurring on a molecular scale. As a pressure 
gradient is applied to a process stream contacting the ultrafiltration 
membrane, liquid including small dissolved materials are forced through 
pores in the membrane while larger dissolved materials and the like are 
retained in the process stream. Pressure gradients can be created, as 
desired, from the use of vacuum systems, centrifugal force, mechanical 
pumping, and pressurized air and/or gas systems (e.g., nitrogen). 
In the use of the present water-soluble polymers, an ultrafiltration unit 
can generally consist of hollow-fiber cartridges or membrane material 
having a 1,000 MWCO to 1,000,000 MWCO preferably 10,000 MWCO to 100,000 
MWCO. Other membrane configurations such as spiral-wound modules, stirred 
cells (separated by a membrane), thin-channel devices, centrifuge units 
(separated by a membrane) and the like may also be used although 
hollow-fiber cartridges are generally preferred for the 
continuous/semicontinuous process filtration units. For analytical 
applications for preconcentration purposes stirred cells and centrifuge 
ultrafiltration units are preferred. Small hollow-fiber cartridges also 
can be used for continuous preconcentration for analytical applications. 
Among the useful ultrafiltration membranes are included 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 Polymer Science and Engineering, 2nd Ed., vol. 17, 
pp. 75-104, 1989, such description incorporated herein by reference. 
Generally, the water-soluble polymers have molecular weights of from 
greater than 1,000 to about 1,000,000, and preferably from greater than 
10,000 to 100,000. Above molecular weights of 1,000,000 some polymers tend 
to lose solubility, while polymers below molecular weight of about 1000, 
retention by suitable ultrafiltration membranes can present problems such 
as low flux rates. 
The water-soluble polymers of the present invention can be provided with 
distinct preselected molecular weight ranges through purification or 
sizing. For example, by filtering polyethyleneimine through the particular 
size ultrafiltration membrane (e.g., UFP-10-C-5 available from AG 
Technologies, Corp. with available MWCO's of 10,000, 30,000 and 100,000), 
polyethyleneimine can be provided with: (1) a molecular weight range of 
greater than about 10,000 and essentially free of molecular weights of 
less than about 10,000; (2) a molecular weight range of greater than about 
30,000 and essentially free of molecular weights of less than about 
30,000; (3) a molecular weight range of greater than about 100,000 and 
essentially free of molecular weights of less than about 100,000; (4) a 
molecular weight range of from about 10,000 to about 30,000 and 
essentially free of molecular weights of less than about 10,000 and 
greater than about 30,000; (5) a molecular weight range of from about 
10,000 to about 100,000 and essentially free of molecular weights of less 
than about 10,000 and greater than about 100,000; and, (6) a molecular 
weight range of from about 30,000 to about 100,000 and essentially free of 
molecular weights of less than about 30,000 and greater than about 
100,000. Other water-soluble polymers can be sized in a similar fashion. 
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 et al., in U.S. patent application 
Ser. No. 08/453,406, filed concurrently herewith, entitled "Water-Soluble 
Polymers for Recovery of Metal Ions from Aqueous Streams", can be used in 
the recovery of metals from solids as described by Smith et al., in U.S. 
patent application Ser. No. 08,453,596, filed concurrently herewith, 
entitled "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 et al., in U.S. patent application Ser. 
No. 08/453,597, filed concurrently herewith, and now U.S. Pat. No. 
5,643,456, entitled "Process for the Displacement of Cyanide Ions from 
Metal-Cyanide Complexes", such descriptions incorporated herein by 
reference.

The present invention is described in more detail in the following examples 
which are intended as illustrative only, since numerous modification 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 separation of metal 
ions from aqueous streams. 
EXAMPLE 1 
(polymer A) 
The polyethyleneimine (PEI) was prepared as follows. Crude 
polyethyleneimine (obtained from BASF as Polymin Waterfree PEI and as PEI 
homopolymer P) was obtained in two molecular weight ranges. The Polymin 
Waterfree polymer was reported to have a molecular weight in the range of 
10,000 to 25,000, while the PEI homopolymer P was reported to have a 
molecular weight range of 70,000 to 750,000, depending upon the method of 
molecular weight measurement. In reality both of these polymers had a 
broad molecular weight range and had material that passed through 
ultrafiltration membranes that have 10,000 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 approximately 1:2:1. 
To demonstrate the effect of pH on polymer size a 1 wt/vol % solution of 
Polymin Waterfree was adjusted with acid or base to span the pH region 
between 2 and 10. The solutions were diafiltered through a 30,000 MWCO 
membrane with permeate samples taken periodically to determine polymer 
concentration using the copper method described below. The concentration 
of polymer permeating the membrane at a high pH was considerably greater 
(0.014% at 15 min) than that passing through at lower pH values (0.003% at 
15 min). The largest difference occurred between pH 10 and 8, with the 
sequential lowering of the pH leading to smaller effects on the polymer 
size, with very little difference in size at a pH of 4 and 2. Due to this 
dramatic change in polymer size, polyethyleneimine was purified by 
diafiltration at a relatively high pH value (pH 10.8 for PEI). 
The polymer was purified using hollow-fiber membranes prepared by a special 
extrusion process, ultrafiltration membrane cartridges prepared from 
polysulfone material in a special homogeneous fiber construction, where 
the microporous structure does not have macrovoids. Membranes such as 
UFP-10-C-5 (currently manufactured by AG Technologies, Corp.) were the 
only type of material found to purify polyethyleneimine and allow for 
membrane washing to recover full flux rates after substantial use. 
The polyethyleneimine was diluted in water to approximately 10-15% by 
weight. The pH was about 10.5 upon dissolution of the polyethyleneimine. 
The solution was diafiltered using 10,000 MWCO, 30,000 MWCO, and 100,000 
MWCO membranes (keeping the volume constant) until 6-7 volume equivalents 
of water were passed through the system at less than or equal to 25 PSI. 
Following the diafiltration step, the solution volume was reduced 
approximately 85% to concentrate the polymer. The remaining water was 
removed under vacuum and mild heat to yield colorless, viscous purified 
polyethyleneimine. Thus, with Polymin Waterfree 25% by weight PEI came 
through the 10,000 MWCO membrane, 10% by weight PEI came through the 
30,000 MWCO and not the 10,000 MWCO membrane, and 65% by weight was 
retained by the 30,000 MWCO membrane (this fraction referred to 
hereinafter as polymer Aa). With the Polymin 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 greater than 30,000 MWCO, and 76% by weight was greater than 100,000 
MWCO (this fraction referred to hereinafter as polymer Ab). The material 
resulting from the retentate from the 30,000 MWCO (polymer Aa), when 
filtered on a 10,000 MWCO membrane, gave no detectable passage of the 
polymer through a 10,000 MWCO membrane using a copper test developed to 
detect less than 1 ppm of polyethyleneimine polymer. Similarly for 
material collected at greater than 100,000 MWCO (polymer Ab) when tested 
on a 30,000 MWCO membrane no detectable polymer was observed in the 
permeate. For some applications the polymer concentrate did not require 
drying but could be concentrated to a workable volume as subsequent 
functionalization reactions were performed in water. 
The copper test involved placing 0.5 mL of the test sample into a 10 mL 
volumetric flask, adding 0.5 mL of a copper acetate solution (1.99 g of 
copper acetate diluted to 100 mL with 0.01M HCl), 1.0 mL of pH 5.8 buffer 
(0.6 mL of acetic acid diluted to 100 mL with deionized water with 
addition of 11.2 g of anhydrous sodium acetate and sufficient sodium 
acetate or acetic acid to adjust pH to 5.8), and deionized water to dilute 
to mark. This solution was mixed well. A standard curve for an UV-VIS 
spectrophotometer was prepared using 0.01%, 0.02%, 0.05%, and 0.08 wt/vol 
% solutions of PEI. A reagent blank was used as a reference sample and 
read at 284 nanometers. 
The specifications for the membrane included hollow-fibers of a material to 
which polyethyleneimine does not adhere to any significant extent, i.e., 
detrimental effect on flux. The routine operational pH range of the 
cartridges fell between 2 and 12 with the ability to process solutions 
down to a pH of 0 to 1 for limited periods of time (30 min) without damage 
to the cartridges. Minimum flux rates were 0.01 gallons/min/sq.ft. at 
25.degree. C. and at a transmembrane pressure of 15 PSI with a solution of 
5% by weight branched polyethyleneimine (Polymin Waterfree 10,000-25,000 
MW). Original flux rates of the cartridge were readily regenerated after 
use by a simple cleaning process of a 10 minute flush with water followed 
by 30 min with 500 ppm hypochlorite and rinsing with water. The cartridge 
had at least a minimum operational pressure of 50 PSI at 25.degree. C. The 
cartridges had the ability to be operated at temperatures up to 80.degree. 
C. 
EXAMPLE 2 
(polymer B) 
An amino-carboxylic acid containing water-soluble polymer of the structure: 
##STR11## 
was prepared on polyethyleneimine (PEI, Polymin Waterfree used as received 
from BASF, i.e., unpurified)) using a molar ratio of carboxylic acid 
moiety to sub-units of CH.sub.2 CH.sub.2 N within the PEI of about 4 to 1 
as follows: A solution of potassium hydroxide (260.4 g) 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) keeping the temperature below 50.degree. C. After the addition was 
complete, the solution was stirred at reflux for 3 hours. The solution was 
cooled to room temperature then diluted to 2 liters with deionized water. 
The pH of the solution was adjusted to 5.8 using potassium hydroxide or 
hydrochloric acid. The polymer was purified by diafiltration collecting 
five volume equivalents of permeate using hollow fiber cartridges with a 
30,000 MWCO. The retentate solution was then concentrated and the 
remaining water was removed under reduced pressure. The residual material 
(referred to hereinafter as polymer B) was dried in a vacuum oven at 
60.degree. C. overnight to give 50.78 g of a light tan brittle solid. IR 
(ATR): 1630 cm.sup.-1 (C.dbd.O). Elemental Analysis Found: C, 32.58%; H, 
4.97%; N, 8.54%; O, 28.99%. 
EXAMPLE 3 
(polymer C) 
A partially functionalized carboxylic acid containing water-soluble polymer 
of the following structure: 
##STR12## 
was prepared on polyethyleneimine (BASF, Polymin Waterfree, purified as in 
Example A, &gt;30,000 MWCO) using a molar ratio of carboxylic acid moiety to 
sub-units of CH.sub.2 CH.sub.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 differences noted here. Elemental Analysis Found: 
C, 44.72%; H, 8.35%; O, 29.3%. The polymer is referred to hereinafter as 
polymer C. 
A partially functionalized carboxylic acid containing water-soluble polymer 
was prepared on polyethyleneimine (BASF, Polymin P, unpurified, 70,000 to 
700,000 MW range) using a molar ratio of carboxylic acid moiety to 
subunits of CH.sub.2 CH.sub.2 N within the PEI of about 0.5 to 1. The 
source of carboxylic acid was chloroacetic acid. The procedure as in 
example B was followed except for differences noted here. The material was 
diafiltered through several molecular weight cutoff membranes such that a 
molecular weight fraction of 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 (referred to hereinafter as polymer Ca) and a fraction 
greater than 100,000 MWCO (referred to hereinafter as polymer Cb) were 
obtained. 
EXAMPLE 4 
(polymer D) 
A fully functionalized phosphonic acid containing water-soluble polymer of 
the structure: 
##STR13## 
was prepared on a polyethyleneimine (Polymin Waterfree from BASF used as 
received, i.e., unpurified). Polyethyleneimine (2.50 g, about 0.058 mole 
monomer equivalent) was dissolved in 6M hydrochloric acid (80 mL) followed 
by the addition of solid phosphorous acid (19.0 g, 0.29 mole) at room 
temperature. The homogeneous solution was brought to reflux followed by 
the dropwise addition of formaldehyde (38 mL of a 37% solution, 0.47 mole) 
over a 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 sit overnight at room temperature. The sticky solid precipitate was 
collected by decantation of the liquid from the flask. The solid was 
dissolved in water and adjusted to pH 6.8 with sodium hydroxide. The 
solution was purified by diafiltration through a 30,000 MWCO membrane. A 
total permeate 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 high vacuum at 60.degree. C. overnight to give 6.3 g of a 
light yellow solid. Elemental analysis found: C, 22.46%; H, 5.48%; N, 
8.70%; P, 16.88%. 
EXAMPLE 5 
(polymer E) 
A partially functionalized phosphonic acid containing water-soluble polymer 
of the structure: 
##STR14## 
was prepared on a polyethyleneimine. Polyethyleneimine (BASF Polymin 
-Waterfree, 10,000-25,000 MW and pre-purified by diafiltration through a 
30,000 MWCO cartridge prior to use as in example A, 25.0 g, 0.58 mole 
monomer equivalent) was dissolved in 6M hydrochloric acid (300 mL) 
followed by the addition of solid phosphorous acid (47.56 g, 0.58 mole) at 
room temperature. The homogeneous solution was brought to reflux followed 
by the dropwise addition of formaldehyde (23.53 mL of a 37% solution, 0.29 
mole) over a 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 sit overnight at room temperature. The reaction mixture 
was diluted with water to 2 liters and the pH adjusted to 6.8 using 
potassium hydroxide. The solution was purified by diafiltration through a 
30,000 MWCO. A total permeate volume of 6 liter was collected. The 
solution was then concentrated to approximately 200 mL. After removing the 
water under reduced pressure, the residue (referred to hereinafter as 
polymer E) was dried under high vacuum at 60.degree. C. overnight to give 
32 g of a light yellow solid. Elemental analysis: %C, 30.18; %H, 8.42; %N, 
13.95; %P, 14.05; %K, 0.15. 
A partially functionalized phosphonic acid containing water-soluble polymer 
was prepared on polyethyleneimine (BASF, Polymin P, unpurified, 70,000 to 
700,000 MW range) using a molar ratio of phosphonic acid moiety to 
subunits of CH.sub.2 CH.sub.2 N within the PEI of about 0.5 to 1. The 
procedure as in example E above was followed except for differences noted 
here. The material was diafiltered through several molecular weight cutoff 
membranes such that a molecular weight fraction of 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 (referred to hereinafter as 
polymer Ea) and a fraction greater than 100,000 MWCO (referred to 
hereinafter as polymer Eb) were obtained. 
EXAMPLE 6 
(polymer F) 
An acylmethylpyrazone containing water-soluble polymer of the structure: 
##STR15## 
was prepared on a polyethyleneimine as follows: A precursor 
(4-chloroacetyl-1,3-dimethyl-pyrazol-5-one) was first prepared as first. 
To a 500 mL three-neck round bottom flask fitted with a reflux condenser, 
mechanic stirrer, and a pressure equalizing additional funnel, 
1,3-dimethylpyrazol-5-one (6.03 g, 53.84 mmole) and dioxane (55 mL, 
distilled from sodium metal) were added. The mixture was heated to 
40.degree.-50.degree. C. to dissolve the suspended solids and give a light 
yellow solution. The reaction mixture was cooled to 30.degree.-35.degree. 
C. followed by the addition of Ca(OH).sub.2 (7.98 g, 107.68 mmole). After 
10 minutes of stirring, chloroacetyl chloride (6.82 g, 59.22 mmole) in 
dioxane (20 mL) was added over a period of 30 minutes. The reaction 
mixture was heated at reflux for 24 hours. The reaction mixture was 
filtered while hot and the filter cake washed with hot dioxane (2.times.20 
mL) followed by methanol (2.times.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 Dowex-50W strongly acid cation 
exchange resin. Water was removed under reduced pressure leaving a white 
solid which was further dried under vacuum at 60.degree. C. over night to 
give the product (61%, m.p.--161.degree.-165.degree. C.) as a white solid 
in 61% yield. .sup.1 H NMR (CDCl.sub.3, ppm) .delta.4.38(s), 3.60(s), 2.41 
(s). .sup.13 C NMR (CDCl.sub.3, ppm) 15.6, 32.7, 45.7, 101.0, 146.0, 
159.3, 188.2. 
The polymer was then prepared as follows: PEI polymer (4.00 g, prefiltered 
through a 30,000 MWCO cartridge as in example A, was dissolved in water 
(100 mL) and brought to reflux. The 
4-chloroacetyl-1,3-dimethyl-pyrazole-5-one precursor from above (4.40 g, 
23.33 mmol) and triethylamine (4.68 g, 46.25 mmol) dissolved in water (20 
mL) were added dropwise over a 10 minute period. The solution was stirred 
at reflux for 2.5 hours at which time it turned from yellow to orange and 
then to red. After cooling to room temperature, the material was diluted 
with deionized water to a volume of 1 liter and the polymer purified by 
diafiltration through a 30,000 MWCO cartridge collecting 5 liters of 
permeate. The water was removed under reduced pressure and the residue 
(referred to hereinafter as polymer F) was dried under vacuum at 
60.degree. C. to give a reddish-orange, brittle solid (5.49 g, 73%). IR 
(ATR): 3435 (N--H), 1626 (C.dbd.O) cm.sup.-1. Elemental Analysis: C, 
53.85%; H, 8.65%; N, 24.59%; O, 12.98%. 
EXAMPLE 7 
(polymer G) 
An acylphenylpyrazolone containing water-soluble polymer of the structure: 
##STR16## 
was prepared on a polyethyleneimine as follows. PEI (1.00 g, Polymin 
Waterfree, unpurified) and triethylamine (2.34 g, 23.1 mmol) were 
dissolved in chloroform (30 mL) and brought to reflux. The 
1-phenyl-3-methyl-4-chloroacetyl-pyrazole-5-one, prepared following the 
procedures of Jensen in ACTA Chem. Scand., 1959, 13, 1668 and Okafor et 
al. in Synth. React. Inorg. Met. Org. Chem., 1991, 21(5), 826, (3.18 g, 
5.8 mmol), in chloroform (10 mL) 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 collected by 
filtration. The solid was dissolved in water (400 mL) adjusted to a pH of 
3.0, and the solution diafiltered using a 30,000 MWCO cartridge. The water 
was removed under reduced pressure and the residue (referred to 
hereinafter as polymer G) dried in a vacuum oven at 60.degree. C. to give 
1.56 g as a red brittle solid. IR (ATR): 3430 (N--H), 1630 (C.dbd.O) 
cm.sup.-1. 
EXAMPLE 8 
(polymer H) 
A hydroxamic acid containing water-soluble polymer of the structure: 
##STR17## 
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), dissolved in methanol (10 mL), was added dropwise to 
the hydroxylamine solution. The mixture was stirred for 1 hour after which 
the precipitated potassium chloride was collected by filtration. To the 
filtrate was added solid succinic anhydride (4.00 g, 39.90 mmol). 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 sit under anhydrous diethyl ether for one hour. The solid was 
collected by filtration giving 4.80 g of the monohydroxamic acid of 
succinic acid as a white solid with a melting point of from 
72.degree.-82.degree.. 
This solid (1.00 g, 7.51 mmol), dicyclohexylcarbodiimide (DCC) (1.54 g, 
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 DCU 
(dicyclohexylurea) byproduct. This THF solution was added to a methanolic 
solution containing polyethyleneimine (1.29 g, 29.95 mmol monomer eq., 
prepurified as in Example A, &gt;30,000 MWCO), a small amount of 
phenolphthalein, and enough sodium methoxide to make the solution pink. 
The solution was stirred for 5 hours. The solvent was evaporated and the 
product purified by dissolving in water and diafiltration through a 30,000 
MWCO hollow-fiber membrane. Evaporation of the water followed by drying 
under vacuum at 60.degree. C. gave 1.21 g of a white polymer (referred to 
hereinafter 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 hydroxamic acid containing water-soluble polymer of the structure: 
##STR18## 
was prepared from the ring opening of polyvinylpyrrolidone with hydroxamic 
acid to give polyvinylamine-N(pentanoic hydroxamic acid) (PVA-PHA). 
Polyvinylpyrrolidone (1.0 g, MW 40,000, Aldrich), sodium hydroxide (40 mL 
of 1.0M), and hydroxylamine hydrochloride (2.71 g) were mixed together and 
heated to 90.degree. 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. Water was removed from 
the polymer solution under vacuum to give a clear solid material upon 
drying in an oven at 60.degree. C. (referred to hereinafter as polymer I) 
which gave a positive ferric chloride test for hydroxamic acid 
(hydroxylamine does not give a positive ferric chloride test). 
EXAMPLE 10 
(polymer J) 
A ester functionalized water-soluble polymer of the structure: 
##STR19## 
was prepared as follows: Polyethyleneimine (1.00 g, purified as in Example 
A, &gt;30,000 MWCO) was dissolved in ethyl acrylate (9.21 g, 92 mmol)) and 
the solution stirred at reflux for 3 hours. The excess ethyl acrylate was 
removed under vacuum keeping the temperature below 70.degree. C. to avoid 
its' polymerization. The viscous polymeric material was used in the next 
step without further purification (referred to hereinafter as polymer J). 
EXAMPLE 11 
(polymer K) 
A hydroxamic acid functionalized water-soluble polymer of the structure: 
##STR20## 
was prepared as follows. The polymer from Example I was treated with 
potassium hydroxide (15.46 g, 0.28 moles) followed by a solution of 
hydroxylamine hydrochloride (12.79 g, 0.18 moles) in methanol (100 mL) 
maintaining a temperature below 20.degree. C. The mixture was stirred for 
1 hour then filtered. The filtrate was added to the crude PEI/ethyl 
acrylate adduct and stirred at room temperature for 14 hours. The methanol 
was removed under reduced pressure and the residue dissolved in water (50 
mL). The polymer was purified by diafiltration using a stirred cell with a 
30,000 MWCO polysulfone membrane. After the collection of 6 volume 
equivalents (300 mL) of permeate, the water was removed from the retentate 
under reduced pressure and the material dried in a vacuum oven at 
60.degree. C. overnight to give 92.22 g of the polymer (referred to 
hereinafter as polymer K) as a light tan brittle solid which was very 
hygroscopic. IR (ATR): 1732 (C.dbd.O) cm.sup.-1. 
EXAMPLE 12 
(polymer L) 
An aza crown ether containing water-soluble polymer of the structure: 
##STR21## 
was prepared on a polyethyleneimine as follows: 
N-Chloroacetyl-aza-18-crown-6 (0.56 g, 1.65 mmol), polyethyleneimine (0.29 
g, prepurified as in example A, &gt;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 
purified by diafiltration. Evaporation of the water followed by drying 
under vacuum at 60.degree. C. gave 0.81 g of a tan solid (referred to 
hereinafter as polymer L) characterized by IR, .sup.1 H and .sup.13 C NMR. 
EXAMPLE 13 
(polymer M) 
An all oxygen contain crown ether water-soluble polymer of the structure: 
##STR22## 
composed of 15-crown-5 ether on polyvinylalcohol was prepared. 247 mg 
(4.94 mmole) of the polyvinylalcohol (88% hydrolyzed) in 10 mL of dried 
DMF was warmed to 50.degree.-60.degree.C. to dissolve. The clear solution 
was than cooled down to room temperature and 341 mg (2.47 mmole) of 
K.sub.2 CO.sub.3 was added. The mixture was stirred for 30 min. Then, 0.67 
g (0.33 mmole) of the 15-crown-5 in 2 mL of dried dimethylformamide was 
added to the reaction mixture. The colorless mixture turned to green-blue 
in 45 minutes and became light yellow in 2 hours. The yellow mixture was 
allowed to stir at 50.degree.-60.degree. C. for overnight. The reaction 
was quenched in water, the suspension was filtered and the 
polyvinylalcohol-crown ether was purified by ultrafiltration with a 30,000 
MWCO cartridge and yielded 150 mg of polymer (referred to hereinafter as 
polymer M) and characterized by IR, .sup.1 H and .sup.13 C NMR. 
EXAMPLE 14 
(polymer N) 
A permethylated poly(vinylamine) water-soluble polymer of the structure: 
##STR23## 
was prepared as follows: Poly(vinylamine) (10.0 g) was dissolved in 50 mL 
of methanol and transferred to a four-neck round bottomed 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 mole) 
suspended in 450 mL of methanol and dimethylsulfate (90.69 g, 0.72 mole) 
dissolved in 100 mL of methanol were added simultaneously by separate 
pressure equalizing addition funnels at such a rate as to maintain 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 throughout the 
dimethylsulfate addition. The total addition time was about 1.5 hours. 
After the completed addition, the solution was brought to reflux 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 
re-dissolved in 450 mL of deionized water and the solution diafiltered 
using a 30,000 MWCO hollow-fiber cartridge. Five volume equivalents or 
about 2.5 L of permeate was collected. For anion exchange, 50 g of sodium 
chloride in 150 mL of water was added and the solution allowed to stand 
overnight The solution was then diafiltered with 3 L of deionized water. 
The water from the retentate was removed under reduced pressure and the 
residue (referred to hereinafter as polymer N) dried under vacuum at 
60.degree. C. overnight to yield 19.58 g (69%) of an orange-brown 
crystalline solid. IR (KBr): 3437 (N--H), 2928, 1629 (C.dbd.O), 1481 
cm.sup.-1. Elemental Analysis: C, 48.25%; H, 10.68%; N, 10.92%; Cl, 
15.87%; S, &lt;0.97%. 
EXAMPLE 15 
(polymer O) 
A permethylated polyallylamine of the structure: 
##STR24## 
was prepared. Polyallylamine (10.0 g, Aldrich) was dissolved in 100 mL of 
methanol and transferred to a four-neck round bottomed flask containing an 
additional 50 mL of methanol. Phenolphthalein (14.0 mg) was added to the 
solution. Sodium methoxide (23.70 g, 0.44 mole) suspended in 400 mL of 
methanol and dimethylsulfate (42.0 g, 0.33 mole) dissolved in 70 mL of 
methanol were added simultaneously by separate pressure equalizing 
addition funnels at such a rate as to maintain 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 throughout the 
dimethylsulfate addition. The total addition time was about 30 minutes. 
After the completed addition, the solution was brought to reflux 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 an opaque pink material. The material was 
re-dissolved in 500 mL of deionized water and the solution diafiltered 
using a 30,000 MWCO hollow-fiber cartridge. Five volume equivalents or 
about 2.5 L of permeate was collected. For anion exchange, 50 g of sodium 
chloride in 150 mL of water was added and the solution allowed to stand 
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 dried under vacuum at 60.degree. C. overnight to yield 10.18 g 
(70%) of a light yellow crystalline solid (referred to hereinafter as 
polymer O). IR (KBr): 3437, 2929, 1686, 1485, 1251 cm.sup.-1. Elemental 
Analysis: C, 47.85%; H, 10.62%; N, 10.62%; Cl, 11.78%; S, 1.13%. 
EXAMPLE 16 
(polymer P) 
A guanidinium-containing PEI polymer of the following structure: 
##STR25## 
was prepared as follows: Polyethyleneimine (as prepurified in example A, 
&gt;30,000 MWCO, 5.0 g, 116 mmole amine) and O-methylisourea-hemisulfate 
(Jansen, 14.35 g, 116 mmol) were placed in a 125 mL flask and dissolved in 
12 mL water with shaking. The solution was allowed to stand for 2 days, 
and was then placed in dialysis tubing (Spectra Por, 15,000 MWCO). The 
tubing with the reaction mixture was placed in a 1 L jar containing 
deionized water, and the water was changed 5 times. The contents of the 
dialysis tubing was concentrated to a white foam by rotary evaporation, 
and then dried to a colorless glassy foam (referred to hereinafter as 
polymer P) under vacuum at 60.degree. C. overnight. Yield: 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: 
##STR26## 
was prepared. Purified PEI (20.0 g as prepared as in example A, &gt;30,000 
MWCO) was dissolved in 200 mL of methanol and placed in a round bottom 
flask outfitted with a condenser under argon. Dimethyl sulfate (120 g, 
0.95 moles, Eastman) dissolved in 110 mL methanol was added slowly from an 
addition funnel. After addition (about 3 hours) the reaction was brought 
to reflux while potassium carbonate (64.2 g, 0.046 moles, Janssen) was 
added slowly from a solids addition funnel (care should be taken to do a 
slow addition to prevent excess foaming). The solution was cooled, 
filtered, and the methanol removed under vacuum. The solid filter cake was 
dissolved in 600 mL of water and combined with the residue from the 
filtrate. The combined solution was purified by dialfiltration (30,000 
MWCO) using water. The anion was exchanged for chloride by adding 120 gm 
sodium chloride in 400 mL water and then stirring for 48 hours. The 
solution was concentrated and further diafiltered (30,000 MWCO) with water 
to 5 L volume changes. The final solution was concentrated by 
ultrafiltration to 500 mL and then further concentrated and dried under 
vacuum to give a 21.6 g of an off-white glassy polymer (referred to 
hereinafter as polymer Q). Elemental Analysis: C 34.15%, H 8.07%, N 8.96%, 
S 15.56%. Potentiometric titration of the polymer gave a sharp 
strong-acid-base type titration curve indicating that all the amine sites 
were methylated. (If the curve was not sharp, it would indicate that 
methylation was incomplete). 
EXAMPLE 18 
(polymer R) 
An amide containing water-soluble polymer of the structure: 
##STR27## 
was prepared as follows: Polyethyleneimine (2.00 g, prepared as in Example 
A, &gt;30,000 MWCO) was dissolved in methanol (20 ml) and brought to reflux. 
Acrylamide (4.95 g, 70 mmol) and butylated hydroxytoluene (BHT, 200 ppm in 
solution) was dissolved in methanol (20 ml) and added dropwise to the 
reaction flask over a 15 minute period. The solution was stirred at reflux 
for 24 hours. After cooling to room temperature, deionized water (400 ml) 
was added and the polymer purified by diafiltration using a 30,000 MWCO 
cartridge. The water was removed under reduced pressure and the polymer 
dried in a vacuum oven at 60.degree. C. to yield 4.5 g of a clear glassy 
solid (referred to hereinafter as polymer R) and characterized by IR, 
.sup.1 H and .sup.13 C NMR. 
EXAMPLE 19 
(polymer S) 
A permethylated polyvinylpyridine of the structure: 
##STR28## 
was prepared as follows: To a solution of polyvinylpyridine (3 g as a 25% 
solution in methanol, Reilly Industries) was added dropwise iodomethane 
(4.85 g, 0.03 mole) in 2 mL of methanol at room temperature. After 
addition was complete, the solution was stirred for about 2 hours giving a 
light green color. An additional amount of iodomethane (2 g) was added and 
allowed to stir for about 2 hours. Deionized water (200 mL) was added to 
the reaction mixture and the solution diafiltered with 1 L of permeate 
collected through a 30,000 MWCO membrane. The water from the retentate was 
removed under reduced pressure and the residue dried under vacuum at 
60.degree. C. overnight to yield 4.82 g (68%) of a yellowish green 
crystalline solid (referred to hereinafter as polymer S). IR (KBr): 3437 
(N--H), 3028,2930,1640 (C.dbd.O), 1156 cm.sup.-1. Elemental Analysis: C 
40.74%, H 4.43%, N 6.22%, 1 36.93%. 
The iodide salt of polymer S was converted to the chloride salt by stirring 
the polymer overnight with sodium chloride (referred to hereinafter as 
polymer Sa). Elemental Analysis: C 52.65%, H 7.07%, N 8.27%, Cl 12.74%. 
EXAMPLE 20 
(polymer T) 
A partially functionalized carboxylic acid containing water-soluble polymer 
of the following structure: 
##STR29## 
was prepared on polyallylamine. 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 polyallylamine (5.0 g, Aldrich) and chloroacetic acid (2.53 g) 
in water (60 mL) keeping the temperature below 50.degree. 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 collecting five volume equivalents of permeate using 
hollow-fiber cartridges with a 30,000 MWCO. The bulk of the water was 
removed from the retentate under reduced pressure. The residual material 
was dried in a vacuum oven at 60.degree. C. overnight to give 4.2 g of a 
light tan solid (referred to hereinafter as polymer T). UV/VIS: lambda 
max=296 nm. IR(ATR): 1638cm.sup.-1 (C.dbd.O). 
EXAMPLE 21 
(polymer U) 
A partially functionalized carboxylic acid containing water-soluble polymer 
of the following structure: 
##STR30## 
was prepared on polyvinylamine. 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 polyvinylamine (10.0 g) and chloroacetic acid (10.97 g) in 
water (240 mL) keeping the temperature below 50.degree. 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 pH 7 and 8.5. The polymer was purified by 
diafiltration and rinsed with deionized water and adjusted to pH 11.3. 
Five volume equivalents of permeate was collected using hollow-fiber 
cartridges with a 30,000 MWCO. The bulk of the water was removed under 
reduced pressure. The residual material was dried in a vacuum oven at 
60.degree. C. overnight to give 12.42 g of a light tan brittle solid 
(referred to hereinafter as polymer U). UV/VIS: lambda max=294 nm. IR 
(ATR): 1603 cm.sup.-1 (C.dbd.O). 
EXAMPLE 22 
(polymer V) 
A water-soluble copolymer containing betadiphosphonic ester and amide 
groups of the following structure: 
##STR31## 
was prepared by copolymerization. Acrylamide (664 mg, 9.35 mmole), 
tetraethylethenyldienebis(phosphonate) (500 mg, 1.67 mmole), and ammonium 
persulfate (21 mg, 1%) as a polymerization initiator were dissolved in 20 
mL of deionized water. The mixture was stirred vigorously at 
65.degree.-70.degree. C. for 48 hours and the solution remained clear 
throughout. The reaction was cooled to room temperature and diluted with 
deionized water to 250 mL. The polymer was purified by diafiltration using 
a 30,000 MWCO cartridge and collected 5 volume equivalents of permeate. 
The retentate was concentrated and dried in a vacuum oven at 60.degree. C. 
A colorless polymer was obtained (250 mg) (referred to hereinafter as 
polymer V). Characterized by IR, NMR, .sup.31 P NMR (PPM) 26.02, 27.42. 
EXAMPLE 23 
(polymer W) 
A water-soluble copolymer containing betadiphosphonic acid ester and amide 
groups of the following structure: 
##STR32## 
was prepared by copolymerization. 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 
quenched by diluting with water to 200 mL, 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 light brown solid (referred to hereinafter as 
polymer W). The polymer was characterized by IR, NMR, .sup.31 P NMR (PPM) 
27.2. 
EXAMPLE 24 
(polymer X) 
A water-soluble copolymer containing betadiphosphonic diacid and amide 
groups of the following structure: 
##STR33## 
was prepared by copolymerization. The vinyl bisphosphonate (5.07 g, 16.9 
mmole) was dissolved in trimethylbromosilane (20.7 g, 135.2 mmole) 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 treated with 95% EtOH (15 mL). The mixture 
was stirred overnight at room temperature. Volatile materials were remover 
again under reduced pressure to give 3.0 g (90% yield) of pure vinyl 
bisphosphonic acid. Acrylamide (1.08g mg, 15.22 mmole), vinylbisphosphonic 
acid (500 mg, 2.72 mmole), 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.degree.-55.degree. C. for 40 hours 
and the solution remained clear throughout. The reaction was cooled to 
room temperature and diluted with deionized water to 50 mL. The polymer 
was purified by diafiltration using a 30,000 MWCO cartridge and collected 
5 volume equivalents of permeate. The retentate was concentrated and dried 
in a vacuum oven at 60.degree. C. A colorless polymer was obtained (700 
mg) (referred to hereinafter as polymer X). Characterized by IR, NMR, 
.sup.31 P NMR (PPM). 
EXAMPLE 25 
(polymer Y) 
A partially functionalized mercaptosuccinic acid containing water-soluble 
polymer of the following structure: 
##STR34## 
was prepared on polyethyleneimine. In a typical synthesis, 10.00 g (233 
milliequivalents of PEI, prepurified as in example A, &gt;30,000 MWCO) was 
dissolved in 200 mL water and the solution purged with argon for twenty 
minutes. Solid S-acetylmercaptosuccinic anhydride, 10.00 g (57.5 mmole), 
was added with stirring. After the solid disappeared, 10 g (94 mmole) of 
sodium carbonate was slowly added with care taken to ensure that the 
vigorous evolution of gas and resultant foaming did not cause an overflow. 
The solution was stirred overnight and then acidified to pH 4 with 
concentrated nitric acid. After purging with argon for twenty minutes, the 
solution was brought to 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 as much millipore water as the 
final solution volume. Lyophilization of the retentate yielded the product 
(referred to hereinafter as polymer Y). Characterization: .sup.1 H and 
.sup.13 C NMR and IR. 
Elemental analysis of 3 different batches: batch (1) C 42.57, H 7.19, N 
12.85, S 9.17, S* 10.5; batch (2) C 42.78, H 7.09, N12.38, S 10.16, S* 
8.4; batch (3) C 41.72, H 7.68, N 12.03, S 9.35, S* 8.2. S* Thiol sulfur 
content when analyzed by iodometric titration. 
EXAMPLE 26 
(polymer Z) 
A partially functionalized ethyl thiol containing water-soluble polymer of 
the following structure: 
##STR35## 
was prepared on polyethyleneimine. In a typical synthesis, 10.00 g (233 
milliequivalents of PEI prepared as in Example A, 30,000 MWCO) was 
dissolved in 200 ml water and the pH was adjusted to 7 with concentrated 
HNO.sub.3. The solution was purged with argon for twenty minutes and 3.45 
mL (57.5 mmole) 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 as much millipore water as the final solution volume. 
Lyophilization of the retentate yielded 13.5 g of the product as a white 
powder (referred to hereinafter as polymer Z). Characterization: .sup.1 H 
and .sup.13 C NMR and IR. 
EXAMPLE 27 
(polymer AA) 
A partially functionalized N-methylthiourea containing water-soluble 
polymer of the following structure: 
##STR36## 
was prepared on polyethyleneimine. In a typical synthesis, 11.20 g (260 
milliequivalents of PEI, prepared as in Example A, &gt;30,000 MWCO) was 
dissolved in 200 ml of ethanol and the solution was purged with argon for 
twenty minutes. Methylisothiocyanate was warmed to 35.degree. C. and 4.75 
g (65.1 mmole) was mixed with 10 mL of ethanol. The isothiocyanate 
solution was added to the PEI at 0.degree. C. and the solution was stirred 
one hour at which time a gooey precipitate formed. The solvent was removed 
via rotary evaporation and the product redissolved in 100 mL of water to 
which 5.86 mL of concentrated HNO.sub.3 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 as 
much millipore water as the final solution volume. Lyophilization of the 
retentate yielded 13.8 g of the product as a white powder (referred to 
hereinafter as polymer AA). Characterization--.sup.1 H and .sup.13 C NMR 
and IR. 
EXAMPLE 28 
(Polymer BB) 
A phosphonic acid on a polyvinylamine backbone with the following 
structure: 
##STR37## 
was prepared. A solution of formaldehyde (9.42 mL) was added dropwise 
during reflux over a period of 22 minutes to a solution of polyvinylamine 
(10 g) and phosphorus 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 titrated 
to pH 6.8 with NaOH. The polymer was purified by diafiltration collecting 
five volume equivalents of permeate using hollow-fiber cartridges with a 
30,000 MWCO. The bulk of the water was removed under reduced pressure. The 
residual material was dried in a vacuum oven at 60.degree. C. overnight to 
give 18.21 g of a brittle yellow-orange solid (referred to hereinafter as 
polymer BB). UV/VIS: lambda max=296 nm. IR(ATR): 1628 cm.sup.-1 (C.dbd.O). 
EXAMPLE 29 
(Polymer CC) 
A thiolactam from polyvinylpyrrolidone with the structure: 
##STR38## 
was prepared as follows. In an oven dried flask, nitrogen purged flask 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 
P.sub.2 S.sub.5, phosphorous pentasulfide. The vessel was sealed and 
placed in an ultrasonic bath for 3 hours. After reaction the solution was 
centrifuged and the supernatant removed and evaporated under nitrogen. The 
gooey solid was then dried at 60.degree. C. in a vacuum oven to give a 
crystalline product (0.78 g). The same reaction was performed with 
different proportions of P.sub.2 S.sub.5 from a 2 fold excess to 1:1 to 
0.5:1 ratios to give different levels of conversion of the lactam to the 
thiolactam. IR analysis of the dried polymers (referred to hereinafter as 
polymer O-2/1; polymer O-1/1; and polymer O-0.5/1) indeed gave three 
different levels of conversion with the excess P.sub.2 S.sub.5 completely 
eliminating the carbonyl stretch between 1700 to 1800 cm.sup.-1. The 
carbonyl peak was reduced proportionally with the 1:1 and 0.5:1 treatment. 
EXAMPLE 30 
A catechol-containing water-soluble polymer of the formula: 
##STR39## 
was prepared by the following procedure. 2,3-Dihydroxybenzoic acid (7.6 g, 
50 mmole) was dissolved in thionyl chloride (25 mL). The solution was 
stirred at reflux for three hours. The excess thionyl chloride was removed 
under reduced pressure using a Dean Stark trap. The residue was sublimed 
under vacuum at 120.degree. C. to yield 7.5 g (70%) of a white solid 
(melting point 84.degree. C.). 
In a reaction flask, polyethyleneimine (Polymin Waterfree, 2.50 g) was 
dissolved in tetrahydrofuran (35 mL). 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 removed under 
reduced pressure leaving a light brown solid. The solid was dissolved in 
water and adjusted to pH of 10.5 with potassium hydroxide followed by 
purification by ultrafiltration through a 30,000 MWCO cartridge to yield a 
reddish-brown solid upon removal of water under vacuum. 
EXAMPLE 31 
Copolymerization of vinyl bisphosphoric acid and acrylic acid was as 
follows. Vinyl bisphosphoric cyclohexylamine salt (0.64 g, 1.09 mmol), 
acrylic acid (0.44 g, 6.12 mmol) and ammonium persulfate (20 mg) were 
dissolved in deionized water (15 mL). The mixture was stirred vigorously 
at 50.degree.-55.degree. C. for 48 hours. The reaction was cooled to room 
temperature and diluted with deionized water to 50 ml. The polymer was 
purified by diafiltration using a 30,000 MWCO cartridge by collecting 5 
volume equivalents of permeate (pH=6). The retentate (pH=5) was 
concentrated and dried under vacuum at 60.degree. C. to yield 480 mg (30%) 
of the polymer as a white solid. 
EXAMPLE 32 
A 0.1 wt/vol % solution of the polymeric hydroxamic acid from example I, 
was prepared at each of the pH values 2, 6 and 8. Each solution was spiked 
with americium and filtered in a 10,000 MWCO ultrafiltration membrane. 
Almost no retention of the americium was observed at the lower pH values, 
but 99% retention was observed at the pH of 8. Thus, polymeric hydroxamic 
acid can bind an actinide such as americium under conditions of pH 8. 
The other above described polymers also have utility in the selective 
separation of metal ion from 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 by reference from 
the above mentioned concurrently filed patent applications. 
Although the present invention has been described with reference to 
specific details, it is not intended that such details should be regarded 
as limitations upon the scope of the invention, except as and to the 
extent that they are included in the accompanying claims.