| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | November 6, 2001 |
| PATENT TITLE |
Fluorescent monomers and polymers containing same for use in industrial water systems |
| PATENT ABSTRACT |
Fluorescent monomers of the formula ##STR1## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9; are provided which are useful in the production of pyranine-tagged polymers which can be detected using a fluorometer and can be used in industrial water systems as treatment polymers. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | December 16, 1999 |
| PATENT REFERENCES CITED |
Kriechbaum, Manfred et al. Evaluation of critical micelle concentrations of non-ionic detergents using new superpolar lipid probes. 1987, vol. 44, No. 1, pp. 19-29 (Abstract Only). Registry No. 110995-88-5. Structure of 1,3,6-Pyrenetrisulfonic acid, 9-(decyloxy)-, trisodium salt, prior to filing date. Registry No. 115787-92-3. Structure of 1,3,6-Pyrenetrisulfonic acid, 8-(dodecyloxy)-, trisodium salt, prior to filing date. Registry No. 115787-91-2. Structure of 1,3,6-Pyrenetrisulfonic acid, 8-ethoxy-, trisodium salt, prior to filing date. |
| PATENT CLAIMS |
That which is claimed is: 1. A process for the preparation of 8-(3- or 4-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid which comprises reacting pyranine with either 3- or 4-vinylbenzyl chloride in an organic solvent selected from the group consisting of methanol, dimethyl formamide, methyl pyrrolidinone and dimethylsulfoxide. 2. A process for the preparation of 8-(allyloxy)-1,3,6-pyrene trisulfonic acid which comprises reacting pyranine with allyl chloride in an organic solvent selected from the group consisting of methanol, dimethyl formamide, methyl pyrrolidinone and dimethylsulfoxide. 3. A fluorescent pyranine-tagged polymer, selected from the group consisting of: A.sub.x B.sub.y I) where x+y=100; where A is a fluorescent monomer selected from the group consisting of compounds of the formula: ##STR6## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9; x is from about 0.001 to about 1 mol %; and B is selected from the group consisting of acrylic acid and salts, methacrylic acid and salts, maleic acid and salts, maleic anhydride, acrylamide, crotonic acid and salts, and y is from about 99.000 to about 99.999 mol %; A.sub.x B.sub.j C.sub.k II) where x+j+k=100; A is as defined above; x is as defined above; B is as defined above; j is from about 1 to about 98 mol %; and C is selected from the group consisting of methacrylic acid and salts, maleic acid and salts, maleic anhydride, crotonic acid and salts, itaconic acid and salts, acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid and salts, polyethylene glycol monomethacrylate, vinyl phosphonic acid and salts, styrene sulfonic acid and salts, vinyl sulfonic acid and salts, 3-allyloxy-2-hydroxypropane sulfonic acid and salts, N-alkyl (meth)acrylamide, t-butyl (meth)acrylate, N-alkyl (meth)acrylate, N-alkanol-N-alkyl(meth)acrylate, vinyl acetate, 2-Hydroxy N-alkyl(meth)acrylate, alkyl vinyl ether, alkoxyethyl acrylate, N-alkanol (meth)acrylamide, N,N-dialkyl(meth)acrylamide and 1-vinyl-2-pyrrolidinone; k is from about 1.999 to about 98 mol %; A.sub.x B.sub.m D.sub.q III) where x+m+q=100; A is as defined above; x is as defined above; B is as defined above; m is from about 1 to about 95 mol %; D is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide; q is from about 4.999 to about 40 mol %; and A.sub.x B.sub.r C.sub.s D.sub.t IV) where x+r+s+t=100; A is as defined above, x is from about 0.001 to about 1 mol % B is as defined above, r is from about 1 to about 89.999 mol % C is as defined above, s is from about 1 to about 89.999 mol % and D is as defined above, t is from about 5 to about 40 mol %. 4. A fluorescent pyranine-tagged polymer of claim 3 wherein said fluorescent monomer is 8-(3-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid. 5. A fluorescent pyranine-tagged polymer of claim 3 wherein said fluorescent monomer is 8-(4-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid. 6. A fluorescent pyranine-tagged polymer of claim 3 wherein said fluorescent monomer is a mixture of 8-(3-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid and 8-(4-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid. 7. A fluorescent pyranine-tagged polymer of claim 3 wherein said fluorescent monomer is 8-(allyloxy)-1,3,6-pyrene trisulfonic acid. 8. A fluorescent pyranine-tagged polymer of claim 3 wherein said fluorescent monomer is present in an amount in the range of from about 0.001 to about 1.0 mol %. 9. The polymer of claim 3 wherein the molecular weight is between about 500 a.m.u. and about 200,000 a.m.u. 10. A method for maintaining the desired amount of pyranine-tagged polymer in an industrial water system comprising the steps of: a) adding a pyranine-tagged polymer selected from the group consisting of: A.sub.x B.sub.y I) where x+y=100; where A is a fluorescent monomer selected from the group consisting of compounds of the formula: ##STR7## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9; x is from about 0.001 to about 1 mol %; and B is selected from the group consisting of acrylic acid and salts, methacrylic acid and salts, maleic acid and salts, maleic anhydride, acrylamide, crotonic acid and salts, and y is from about 99.000 to about 99.999 mol %; A.sub.x B.sub.j C.sub.k II) where x+j+k=100; A is as defined above; x is as defined above; B is as defined above; j is from about 1 to about 98 mol %; and C is selected from the group consisting of methacrylic acid and salts, maleic acid and salts, maleic anhydride, crotonic acid and salts, itaconic acid and salts, acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid and salts, polyethylene glycol monomethacrylate, vinyl phosphonic acid and salts, styrene sulfonic acid and salts, vinyl sulfonic acid and salts, 3-allyloxy-2-hydroxypropane sulfonic acid and salts, N-alkyl (meth)acrylamide, t-butyl (meth)acrylate, N-alkyl (meth)acrylate, N-alkanol-N-alkyl(meth)acrylate, vinyl acetate, 2-Hydroxy N-alkyl(meth)acrylate, alkyl vinyl ether, alkoxyethyl acrylate, N-alkanol (meth)acrylamide, N,N-dialkyl(meth)acrylamide and 1-vinyl-2-pyrrolidinone; k is from about 1.999 to about 98 mol %; A.sub.x B.sub.m D.sub.q III) where x+m+q=100; A is as defined above; x is as defined above; B is as defined above; m is from about 1 to about 95 mol %; D is selected from the group consisting of sulfomethylacrylamide and Sulfoethylacrylamide; q is from about 4.999 to about 40 mol %; and A.sub.x B.sub.r C.sub.s D.sub.t IV) where x+r+s+t=100; A is as defined above; x is from about 0.001 to about 1 mol %; B is as defined above; r is from about 1 to about 89.999 mol %; C is as defined above; s is from about 1 to about 89.999 mol %; D is as defined above; t is from about 5 to about 40 mol %; to water such that a desired concentration of said pyranine-tagged polymer is present in said water, b) using a fluorometer to detect the fluorescent signal of said pyranine-tagged polymer; c) converting the fluorescent signal of the polymer to the concentration of said pyranine-tagged polymer; d) adjusting the concentration of said pyranine-tagged polymer according to what the desired concentration is for said pyranine-tagged polymer in the industrial water system. 11. A method for maintaining the desired amount of pyranine-tagged polymer in an industrial water system comprising the steps of: a) adding an inert tracer and a pyranine-tagged polymer selected from the group consisting of: A.sub.x B.sub.y I) where x+y=100; where A is a fluorescent monomer selected from the group consisting of compounds of the formula: ##STR8## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9; x is from about 0.001 to about 1 mol %; and B is selected from the group consisting of acrylic acid and salts, methacrylic acid and salts, maleic acid and salts, maleic anhydride, acrylamide, crotonic acid and salts, and y is from about 99.000 to about 99.999 mol %; A.sub.x B.sub.j C.sub.k II) where x+j+k=100; A is as defined above; x is as defined above; B is as defined above; j is from about 1 to about 98 mol %; and C is selected from the group consisting of methacrylic acid and salts, maleic acid and salts, maleic anhydride, crotonic acid and salts, itaconic acid and salts, acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid and salts, polyethylene glycol monomethacrylate, vinyl phosphonic acid and salts, styrene sulfonic acid and salts, vinyl sulfonic acid and salts, 3-allyloxy-2-hydroxypropane sulfonic acid and salts, N-alkyl (meth)acrylamide, t-butyl (meth)acrylate, N-alkyl (meth)acrylate, N-alkanol-N-alkyl(meth)acrylate, vinyl acetate, 2-Hydroxy N-alkyl(meth)acrylate, alkyl vinyl ether, alkoxyethyl acrylate, N-alkanol (meth)acrylamide, N,N-dialkyl(meth)acrylamide and 1-vinyl-2-pyrrolidinone; k is from about 1.999 to about 98 mol %; A.sub.x B.sub.m D.sub.q III) where x+m+q=100; A is as defined above; x is as defined above; B is as defined above; m is from about 1 to about 95 mol %; D is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide; q is from about 4.999 to about 40 mol %; and A.sub.x B.sub.r C.sub.s D.sub.t IV) where x+r+s+t=100; A is as defined above; x is from about 0.001 to about 1 mol %; B is as defined above; r is from about 1 to about 89.999 mol %; C is as defined above; s is from about 1 to about 89.999 mol %; D is as defined above; t is from about 5 to about 40 mol %; to water such that a desired concentration of said pyranine-tagged polymer is present in said water, b) using a fluorometer to detect the fluorescent signals of the inert tracer and the pyranine-tagged polymer; c) converting the fluorescent signals of the inert tracer and the pyranine-tagged polymer to the concentration of the inert tracer and the pyranine-tagged polymer; d) adjusting the concentration of said pyranine-tagged polymer according to what the desired concentration is for said pyranine-tagged polymer in the industrial water system. 12. A fluorescent monomer selected from the group consisting of 8-(3-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid and its sodium, potassium, cesium, rubidium, lithium and ammonium salts. 13. A fluorescent monomer selected from the group consisting of 8-(4-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid and its sodium, potassium, cesium, rubidium, lithium and ammonium salts. 14. A fluorescent monomer selected from the group consisting of 8-(allyloxy)-1,3,6-pyrene trisulfonic acid and its sodium, potassium, cesium, rubidium, lithium and ammonium salts. 15. A fluorescent pyranine-tagged polymer, selected from the group consisting of: A.sub.x B.sub.y I) where x+y=100; where A is a fluorescent monomer selected from the group consisting of compounds of the formula: ##STR9## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9; x is from about 0.001 to about 1 mol %; and B is selected from the group consisting of acrylic acid and its salts, and y is from about 99.000 to about 99.999 mol %; A.sub.x B.sub.j C.sub.k II) where x++k=100; A is as defined above; x is as defined above; B is as defined above; j is from about 1 to about 98 mol %; and C is acrylamide; k is from about 1.999 to about 98 mol %; A.sub.x B.sub.m D.sub.q III) where x+m+q=100; A is as defined above; x is as defined above; B is as defined above; m is from about 1 to about 95 mol %; D is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide; q is from about 4.999 to about 40 mol %; and A.sub.x B.sub.r C.sub.s D.sub.t IV) where x+r+s+t=100; A is as defined above, x is from about 0.001 to about 1 mol % B is as defined above, r is from about 1 to about 89.999 mol %. C is as defined above, s is from about 1 to about 89.999 mol % and D is as defined above, t is from about 5 to about 40 mol %. 16. A fluorescent pyranine-tagged polymer, selected from the group consisting of: A.sub.x B.sub.y I) where x+y=100; where A is a fluorescent monomer selected from the group consisting of compounds of the formula: ##STR10## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9; x is from about 0.001 to about 1 mol %; and B is selected from the group consisting of acrylic acid and its salts, and y is from about 99.000 to about 99.999 mol %; A.sub.x B.sub.j C.sub.k III) where x+j+k=100; A is as defined above; x is as defined above; B is as defined above; j is from about 1 to about 98 mol %; and C is acrylamide; k is from about 1.999 to about 98 mol %; A.sub.x B.sub.m D.sub.q III) where x+m+q=100; A is as defined above; x is as defined above; B is as defined above; m is from about 1 to about 95 mol %; D is sulfomethylacrylamide; q is from about 4.999 to about 40 mol %; and A.sub.x B.sub.r C.sub.s D.sub.t IV) where x+r+s+t=100; A is as defined above, x is from about 0.001 to about 1 mol %; B is as defined above, r is from about 1 to about 89.999 mol %; C is as defined above, s is from about 1 to about 89.999 mol % and D is as defined above, t is from about 5 to about 40 mol %. 17. The use of a pyranine-tagged polymer as a scale-inhibitor in an industrial water system comprising the steps of: i) providing an industrial water system susceptible to unwanted scaling; and ii) adding to the water of said industrial water system from about 1 ppm to about 30 ppm of a scale inhibitor; wherein said scale inhibitor is a pyranine-tagged polymer selected from the group consisting of compounds of the formula: A.sub.x B.sub.y I) where x+y=100; where A is a fluorescent monomer selected from the group consisting of compounds of the formula: ##STR11## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9; x is from about 0.001 to about 1 mol %; and B is selected from the group consisting of acrylic acid and salts, methacrylic acid and salts, maleic acid and salts, maleic anhydride, acrylamide, crotonic acid and salts, and y is from about 99.000 to about 99.999 mol %; A.sub.x B.sub.j C.sub.k II) where x+j+k=100; A is as defined above; x is as defined above; B is as defined above; j is from about 1 to about 98 mol %; and C is selected from the group consisting of methacrylic acid and salts, maleic acid and salts, maleic anhydride, crotonic acid and salts, itaconic acid and salts, acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid and salts, polyethylene glycol monomethacrylate, vinyl phosphonic acid and salts, styrene sulfonic acid and salts, vinyl sulfonic acid and salts, 3-allyloxy-2-hydroxypropane sulfonic acid and salts, N-alkyl (meth)acrylamide, t-butyl (meth)acrylate, N-alkyl (meth)acrylate, N-alkanol-N-alkyl(meth)acrylate, vinyl acetate, 2-Hydroxy N-alkyl(meth)acrylate, alkyl vinyl ether, alkoxyethyl acrylate, N-alkanol (meth)acrylamide, N,N-dialkyl(meth)acrylamide and 1-vinyl-2-pyrrolidinone; k is from about 1.999 to about 98 mol %; A.sub.x B.sub.m D.sub.q III) where x+m+q=100; A is as defined above; x is as defined above; B is as defined above; m is from about 1 to about 95 mol %; D is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide; q is from about 4.999 to about 40 mol %; and A.sub.x B.sub.r C.sub.s D.sub.t IV) where x+r+s+t=100; A is as defined above; x is from about 0.001 to about 1 mol %; B is as defined above; r is from about 1 to about 89.999 mol %; C is as defined above; s is from about 1 to about 89.999 mol %; and D is as defined above; t is from about 5 to about 40 mol %. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION This invention relates generally to the field of fluorescent monomers and polymers made with them. These polymers incorporating fluorescent monomers are useful in industrial water systems. BACKGROUND OF THE INVENTION There are many industrial water systems, including, but not limited to, cooling water systems and boiler water systems. Because water resources are becoming limited and efficient utilization of water is required, various methods have been adopted to reduce the amount of water used. As the methods for reducing the amount of water are put into practice, unfavorable events occur, such as the occurrence of corrosion and the formation of scale, because the quality of the water in the system is progressively deteriorated. To prevent or minimize these troubles, various kinds of treatment agents for treatment of water systems have been used. It has been found that organic substances, including certain types of treatment polymers, are effective for preventing formation of scale and suppressing the occurrence of corrosion. These certain types of treatment polymers are known to persons of ordinary skill in the art of industrial water treatment and are widely used by themselves or as one of many possible components in scale and corrosion inhibition products. Such treatment polymers generally exhibit activity against scale and corrosion when added to water in an amount in the range of from about 1 to about 100 milligrams of solid component active per liter of water. When a treatment polymer is used for preventing formation of scale and suppressing the occurrence of corrosion, the concentration of the treatment polymer in the water system is the important factor to perform the desired function with good efficiency. For example, a treatment polymer added to a cooling water system can be consumed by many causes. With consumption, the amount of the treatment polymer dissolved in the cooling water does not remain the same as the amount added to the cooling water. Therefore, it is important for the optimum operation of an industrial water system that practical methods are known to determine the concentration of treatment polymers in the water of the industrial water system. In general practice, the amount of the treatment polymer added to the water in an industrial water system can be measured using various analytical methods. The use of an inert fluorescent tracer or mass balance measurement method as described in U.S. Pat. Nos. 4,783,314; 4,992,380; and 5,171,450, hereby incorporated by reference, to perform this analysis, is known in the art. In the inert fluorescent tracer method, an inert fluorescent tracer is added to an industrial water system, with the amount of inert fluorescent tracer added being proportional to the amount of the treatment polymer added. By using a fluorometer to measure the fluorescent signal of the inert fluorescent tracer, the amount of the inert fluorescent tracer can be determined by using a calibration curve to relate the amount of fluorescent signal detected to the amount of the inert fluorescent tracer present. Because the inert fluorescent tracer and the treatment polymer are added to the industrial water system in known proportions, by knowing the amount of inert fluorescent tracer present it also means that the amount of treatment polymer present is known. The inert fluorescent tracer method can be conducted on-line in real time so that any changes in the amount of treatment polymer being added to the system can be made immediately. As a complement to the use of an inert tracer system, it has been found that treatment polymers to be used as components of scale and corrosion inhibitors in industrial water systems could be monitored if tagged with a fluorescent monomer. The amount of fluorescent monomer incorporated into the polymer must be enough so that the fluorescence of the polymer can now be adequately measured, however, it must not be so much that the performance of the polymer as a treatment agent for the water is decreased. Because the concentration of the tagged treatment polymer itself can be determined using a fluorometer, it is now possible to measure consumption of the treatment polymer directly. It is important to be able to measure consumption directly because consumption of a treatment polymer usually indicates that a non-desired event, such as scaling, is occurring. Thus by being able to measure consumption of the polymeric additive, there can be achieved an on-line, real time in situ measurement of scaling activity in the cooling system. Certain tagged polymers are known, see U.S. Pat. No. 5,986,030, hereby incorporated by reference. However, there is not an abundance of viable tagged polymers for use in industrial water systems. Therefore, it is desirable to provide additional tagged polymers that have a fluorescent signal so that you can use a fluorometer to measure the fluorescent signal of the tagged treatment polymer and determine the concentration of tagged treatment polymer currently present in the industrial water system from that information. It is known that tagging of polymers is difficult to accomplish because of the difficulty in chemically combining fluorescent moieties with non-fluorescent polymers. In order to synthesize tagged treatment polymers it is also desirable to provide fluorescent monomers that are readily polymerized to form tagged treatment polymers. The aspects, objects and the several advantages of this invention will be apparent from the following specification and appended claims. SUMMARY OF THE INVENTION The first aspect of the instant claimed invention are fluorescent monomers selected from the group consisting of compounds having the formula of: ##STR2## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9. The second aspect of the instant claimed invention is a process for the preparation of 8-(3- or 4-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid comprising reacting pyranine with either 3- or 4-vinylbenzyl chloride in an organic solvent selected from the group consisting of methanol, dimethyl formamide, methyl pyrrolidinone and dimethylsulfoxide. The third aspect of the instant claimed invention is a process for the preparation of 8-(allyloxy)-1,3,6-pyrene trisulfonic acid which comprises reacting pyranine with allyl chloride in an organic solvent selected from the group consisting of methanol, dimethyl formamide, methyl pyrrolidinone and dimethylsulfoxide. The fourth aspect of the instant claimed invention is a fluorescent pyranine-tagged polymer selected from the group consisting of: A.sub.x B.sub.y I) where x+y=100; where A is a fluorescent monomer selected from the group consisting of compounds of the formula: ##STR3## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9; x is from about 0.001 to about 1 mol %; and B is selected from the group consisting of acrylic acid and salts, methacrylic acid and salts, maleic acid and salts, maleic anhydride, acrylamide, crotonic acid and salts, and y is from about 99.000 to about 99.999 mol %; A.sub.x B.sub.j C.sub.k II) where x+j+k=100; A is as defined above; x is from about 0.001 to about 1 mol %; B is as defined above; j is from about 1 to about 98 mol %; and C is selected from the group consisting of methacrylic acid and salts, maleic acid and salts, maleic anhydride, crotonic acid and salts, itaconic acid and salts, acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid and salts, polyethylene glycol monomethacrylate, vinyl phosphonic acid and salts, styrene sulfonic acid and salts, vinyl sulfonic acid and salts, 3-allyloxy-2-hydroxypropane sulfonic acid and salts, N-alkyl (meth)acrylamide, t-butyl (meth)acrylate, N-alkyl (meth)acrylate, N-alkanol-N-alkyl(meth)acrylate, vinyl acetate, 2-Hydroxy N-alkyl(meth)acrylate, alkyl vinyl ether, alkoxyethyl acrylate, N-alkanol (meth)acrylamide, N,N-dialkyl(meth)acrylamide and 1-vinyl-2-pyrrolidinone; k is from about 1.999 to about 98 mol %; A.sub.x B.sub.m D.sub.q III) where x+m+q=100; A is as defined above; x is from about 0.001 to about 1 mol %; B is as defined above; m is from about 1 to about 95 mol %; D is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide; q is from about 4.999 to about 40 mol %; and A.sub.x B.sub.r C.sub.s D.sub.t IV) where x+r+s+t=100; A is as defined above; x is from about 0.001 to about 1 mol %; B is as defined above; r is from about 1 to about 89.999 mol %; C is as defined above; s is from about 1 to about 89.999 mol %; D is as defined above; t is from about 5 to about 40 mol %; The fifth aspect of the instant claimed invention is the use of the fluorescent pyranine-tagged polymer previously described as a water-soluble polymeric treatment agent. The sixth aspect of the instant claimed invention is a method for maintaining the desired amount of fluorescent pyranine-tagged polymer in an industrial water system comprising the steps of: a) adding the previously described pyranine-tagged polymer to the water of an industrial water system such that a desired concentration of said pyranine-tagged polymer is present in said water, b) using a fluorometer to detect the fluorescent signal of said pyranine-tagged polymer; c) converting the fluorescent signal of said pyranine-tagged polymer to the concentration of said pyranine-tagged polymer; d) adjusting the concentration of said pyranine-tagged polymer according to what the desired concentration is for said pyranine-tagged polymer in the industrial water system. The seventh aspect of the instant claimed invention is a method for maintaining the desired amount of pyranine-tagged polymer in an industrial water system comprising the steps of: a) adding an inert tracer and a pyranine-tagged polymer previously described to the water of an industrial water system such that a desired concentration of said pyranine-tagged polymer is present in said water, b) using a fluorometer to detect the fluorescent signals of the inert tracer and the pyranine-tagged polymer; c) converting the fluorescent signals of the inert tracer and the pyranine-tagged polymer to the concentration of the inert tracer and the pyranine-tagged polymer; d) adjusting the concentration of said pyranine-tagged polymer according to what the desired concentration is for said pyranine-tagged polymer in the industrial water system. DETAILED DESCRIPTION OF THE INVENTION The present invention is based upon the discovery of certain fluorescent monomers prepared from pyranine. These fluorescent monomers are useful in the preparation of tagged polymers. These tagged polymers can be used as treatment polymers in industrial water systems. The fluorescent monomers of the instant claimed invention are selected from the group consisting of compounds of the formula: ##STR4## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9. Preferably M is selected from the group consisting of hydrogen, sodium and potassium. More preferably, M is selected from the group consisting of sodium and potassium. Preferably the fluorescent monomers are selected from the group consisting of 8-(3-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid, 8-(4-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid and 8-(allyloxy)-1,3,6-pyrene trisulfonic acid and the sodium, potassium, cesium, rubidium, lithium and ammonium salts thereof. Thus, the terms vinyl benzyl pyranine and allyl pyranine and the abbreviations VBP and AP, as used herein, mean: 8-(3-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid (3-VBP), 8-(4-vinylbenzyloxy)-1,3,6-pyrene trisulfonic acid (4-VBP) and 8-(allyloxy)-1,3,6-pyrene trisulfonic acid (AP) including the sodium, potassium, cesium, rubidium, lithium and ammonium salts thereof. Other abbreviations used in this patent application are: AA for acrylic acid, AcAm for acrylamide, and SMA for sulfomethacrylamide. The fluorescent monomers of the instant claimed invention can be synthesized through the reaction of pyranine, also known as 8-hydroxy-1,3,6-pyrene trisulfonic acid (available from Lancaster Synthesis Inc., P.O. Box 1000, Windham, N.H. 03087-9977, telephone number (800) 230-0372), and an alkylating agent such as 3-vinylbenzyl chloride, 4-vinylbenzyl chloride, a mixture of 3- and 4-vinyl benzyl chloride, allyl chloride (or allyl bromide) for n=1; 4-bromo-1-butene, for n=2; 5-bromo-1-pentene, for n=3; 6-bromo-1-hexene, for n=4; 8-bromo-1-octene, for n=6; and 11-bromo-1-undecene, for n=9. All of these alkylating agents are available from Aldrich Chemical Company, P.O. Box 2060, Milwaukee, Wis. 53201 USA; Telephone Numbers (414) 273-3850 and (800) 558-9160. In addition to Aldrich as a source, the mixture of 3-vinyl benzyl chloride and 4-benzyl chloride is available from The Dow Chemical Company, 2020 Dow Center, Midland Mich. 48686-0440, telephone numbers (517) 496-4000. The reaction can be accomplished in a polar organic solvent. A stoichiometrical amount of base is used to deprotonate the pyranine. A slight excess of alkylating agent is preferably used to ensure complete conversion of pyranine to the desired monomer. Although many organic solvents such as dimethyl sulfoxide (hereinafter "DMSO"), methanol, dimethylformamide and methyl pyrrolidinone can be used in the reaction, reaction in DMSO is preferred since it gives near quantitative yield even at typical room temperatures of from about 20.degree. C. to about 25.degree. C. Higher reaction temperatures can be used to shorten the reaction time. Generally the reaction is carried out at a temperature in the range of about 20.degree. C. to about 60.degree. C. for a period of time in the range of about 3 to about 10 hours. The product can be collected by stripping off the solvent under reduced pressure. Alternatively, the product can be isolated by precipitation into acetone and recovery of the yellow solid. Further purification, to remove residual solvent, can be accomplished by washing or stirring the crude product with acetone or isopropanol followed by filtration. After preparation and isolation of the fluorescent monomer, fluorescent pyranine-tagged polymers containing these fluorescent monomers can be prepared by inclusion of the fluorescent monomer into a base polymer. The amount of fluorescent monomer that is used should be an amount sufficient to allow the polymer to be detected in the aqueous environment that it is used. The minimum amount of fluorescent moiety that can be used is that amount which gives a signal-to-noise ratio (S/N) of 3 at the desired polymer dosage. The signal-to-noise ratio is that value where the magnitude of the transduced signal (including but not limited to electronic and optical signals) due to the presence of a target analyte in a measurement device is greater than or equal to a level three (3) times the magnitude of a transduced signal where the analyte (species) of interest is not present in the measurement device. The amount of fluorescent monomer in the tagged polymers is in the range of from about 0.01 wt. percent to about 10.0 wt. percent, preferably from about 0.1 wt. percent to about 2 wt. percent, and most preferably from about 0.25 wt. percent to about 1.0 weight percent. (When mol percents are given in this patent application it is understood that these are calculated mol percents, not measured. The weight percents were measured and converted to mol percents. The conversion used was 1.0 wt. % VBP=0.11 mol % VPP, and 1.0 wt. % AP=0.13 mol % AP.) The remainder of the polymer can have one, two or three additional monomers in it. For purposes of this patent application the subscripts x, y, j, k, m, q, r, s and t refer to the mole percent of each component of the polymers. The polymers are selected from the group consisting of: A.sub.x B.sub.y I) where x+y=100; where A is a fluorescent monomer selected from the group consisting of compounds of the formula: ##STR5## wherein M is selected from the group consisting of hydrogen, sodium, potassium, cesium, rubidium, lithium and ammonium, and n is selected from the group consisting of 1, 2, 3, 4, 6 and 9; x is from about 0.001 to about 1 mol %; and B is selected from the group consisting of acrylic acid and salts, methacrylic acid and salts, maleic acid and salts, maleic anhydride, acrylamide, crotonic acid and salts, and y is from about 99.000 to about 99.999 mol %; A.sub.x B.sub.j C.sub.k II) where x+j+k=100; A is as defined above; x is from about 0.001 to about 1 mol %; B is as defined above; j is from about 1 to about 98 mol %; and C is selected from the group consisting of methacrylic acid and salts, maleic acid and salts, maleic anhydride, crotonic acid and salts, itaconic acid and salts, acrylamide, methacrylamide, 2-acrylamido-2-methylpropanesulfonic acid and salts, polyethylene glycol monomethacrylate, vinyl phosphonic acid and salts, styrene sulfonic acid and salts, vinyl sulfonic acid and salts, 3-allyloxy-2-hydroxypropane sulfonic acid and salts, N-alkyl (meth)acrylamide, t-butyl (meth)acrylate, N-alkyl (meth)acrylate, N-alkanol-N-alkyl(meth)acrylate, vinyl acetate, 2-Hydroxy N-alkyl(meth)acrylate, alkyl vinyl ether, alkoxyethyl acrylate, N-alkanol (meth)acrylamide, N,N-dialkyl(meth)acrylamide and 1-vinyl-2-pyrrolidinone; k is from about 1.999 to about 98 mol %; A.sub.x B.sub.m D.sub.q III) where x+m+q=100; A is as defined above; x is from about 0.001 to about 1 mol %; B is as defined above; m is from about 1 to about 95 mol %; D is selected from the group consisting of sulfomethylacrylamide and sulfoethylacrylamide; q is from about 4.999 to about 40 mol %; and A.sub.x B.sub.r C.sub.s D.sub.t IV) where x+r+s+t=100; A is as defined above; x is from about 0.001 to about 1 mol %; B is as defined above; r is from about 1 to about 89.999 mol %; C is as defined above; s is from about 1 to about 89.999 mol %; D is as defined above; t is from about 5 to about 40 mol %; All molecular weights in this patent application are weight average molecular weights. The weight average molecular weight of these polymers is from about 500 atomic mass units (hereinafter "a.m.u.") to about 200,000 a.m.u. . Preferably the molecular weight is from about 2000 a.m.u. to about 100,000 a.m.u. Most preferably, the molecular weight is from about 5000 a.m.u. to about 40,000 a.m.u. The weight average molecular weight was measured using gel permeation chromatography using polystyrene sulfonate molecular weight standards. The columns used were Micra.TM. GPC 500+GPC 100. The mobile phase was 70/30 water/acetonitrile containing 0.15M ammonium formate (to reduce sticking of the small amount of highly aromatic unreacted fluorescent monomer). Labeling of the polymer through the use of the fluorescent monomers of this invention is achieved by synthesizing the polymer in the presence of the fluorescent monomer. The polymerization is generally carried out in an aqueous or mixed aqueous solution through the copolymerization of one of the fluorescent monomers with one or more water soluble ethylenically unsaturated monomers. Various polymer initiators can be used in the polymerization including thermal and redox initiators. One method of polymerization is as follows: 0.25 to 1.0 weight percent of the fluorescent monomer, based on total monomer, is dissolved in monomer solution consisting of the other monomers. The monomer solution is adjusted to a pH of about 5 by addition of a 50 percent sodium hydroxide solution. Ammonium persulfate and sodium bisulfite are used as initiating and chain transfer agents. Monomer solution and initiator solutions are added separately into a reactor over a period of 2 hours. The temperature is kept at 60.degree. C. To make sulfomethylated polymer products, the polymer is further reacted with sodium bisulfite and formaldehyde at elevated temperature to give a sulfomethylated polymer product. Once created, the fluorescent pyranine-tagged polymers of the instant claimed invention can be used as scale inhibitors in any industrial water system where a scale inhibitor is needed. Industrial water systems, include, but are not limited to, cooling tower water systems (including open recirculating, closed and once-through systems); petroleum wells, downhole formations, geothermal wells and other oil field applications; boilers and boiler water systems; mineral process waters including mineral washing, flotation and benefaction; paper mill digesters, washers, bleach plants and white water systems; black liquor evaporators in the pulp industry; gas scrubbers and air washers; continuous casting processes in the metallurgical industry; air conditioning and refrigeration systems; industrial and petroleum process water; indirect contact cooling and heating water, such as pasteurization water; water reclamation and purification systems; membrane filtration water systems; food processing streams (meat, vegetable, sugar beets, sugar cane, grain, poultry, fruit and soybean); and waste treatment systems as well as in clarifiers, liquid-solid applications, municipal sewage treatment and industrial or municipal water systems. As stated previously, these fluorescent pyranine-tagged polymers function as scale inhibitors. As these polymers are consumed performing that function, their fluorescent signal will decrease and thus the decrease in the fluorescent signal can be used to indicate that undesired scaling is taking place. The polymer tagged with the fluorescent monomer may be used in the industrial water systems singly or in combination with other polymers, which are not tagged. The amount of the polymer tagged with the fluorescent monomer added to an industrial water system is in the range of about 1.0 milligrams (mg) to about 30 milligrams of the total solid polymer actives per liter of water in the system. This is equivalent to about 1 part per million (hereinafter "ppm") to about 30 ppm. When used in an industrial water system, the fluorescent signal of the pyranine-tagged polymers can be used to determine how much polymer is present in the industrial water system. The method to do this is described as follows: A method for maintaining the desired amount of pyranine-tagged polymer in an industrial water system comprising the steps of: a) adding a pyranine-tagged polymer to water such that a desired concentration of said pyranine-tagged polymer is present in said water, b) using a fluorometer to detect the fluorescent signal of said pyranine-tagged polymer; c) converting the fluorescent signal of the polymer to the concentration of said pyranine-tagged polymer; d) adjusting the concentration of said pyranine-tagged polymer according to what the desired concentration is for said pyranine-tagged polymer in the industrial water system. An additional method for maintaining the desired amount of pyranine-tagged polymer in an industrial water system is as follows: A method for maintaining the desired amount of pyranine-tagged polymer in an industrial water system comprising the steps of: a) adding an inert tracer and a pyranine-tagged polymer to water such that a desired concentration of said pyranine-tagged polymer is present in said water, b) using a fluorometer to detect the fluorescent signals of the inert tracer and the pyranine-tagged polymer; c) converting the fluorescent signals of the inert tracer and the pyranine-tagged polymer to the concentration of the inert tracer and the pyranine-tagged polymer; d) adjusting the concentration of said pyranine-tagged polymer according to what the desired concentration is for said pyranine-tagged polymer in the industrial water system. An advantage of the fluorescent monomers of this invention is that in their use in the formation of a tagged polymer, the fluorescent monomer is not significantly affected by other structures in the polymer or by other ingredients in the system. Thus the polymers are stable in the presence of STA.cndot.BR.cndot.EX.TM., an oxidizing biocide available from Nalco Chemical Company, One Nalco Center, Naperville, Ill. 60563. A further advantage of the tagged polymers of this invention is that the spectral properties, i.e. both excitation and emission of the polymers are in the visible wavelength region, thus allowing the use of solid state instrumentation and potentially minimize interferences that generally occur in the UV wavelength region. |
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