| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | June 20, 2000 |
| PATENT TITLE |
Cationic chemiluminescent monomers and polymers |
| PATENT ABSTRACT | Luminol derived monomers, and luminol derived water-treatment polymers formed from the luminol derived monomers, as well as methods for monitoring of the chemiluminescence of such water-treatment polymers are disclosed. The novel chemiluminescent polymers require only a very low level of incorporation of the chemiluminescent moiety, and are useful for monitoring, even in systems containing impurities which either quench fluorescence or fluoresce themselves |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | September 30, 1998 |
| PATENT REFERENCES CITED |
Omote et al., Bulletin of The Chemical Society of Japan, vol. 40, pp. 1693-1695, (1967). Abruna et al., Journal of The American Chemical Society, vol. 104, pp. 2641-2642, (1982). |
| PATENT CLAIMS |
What is claimed is: 1. A chemiluminescent monomer compound comprising: a vinylic monomer having a pendant amide-linked phthalhydrazide chemiluminescent group, wherein the chemiluminescent monomer is formed by reacting a vinylic monomer having a terminal amine group with an alpha-haloacetyl containing phthalhydrazide chemiluminescent group. 2. The chemiluminescent monomer compound of claim 1 wherein said phthalhydrazide chemiluminescent group is selected from the group consisting of: 5-amino-2,3-dihydro-1,4-phthalazinedione, 6-amino-2,3-dihydro-1,4-phthalazinedione and N-(4-aminobutyl)-N-ethyl-6-amino-2,3-dihydro-1,4-phthalazinedione. 3. The chemiluminescent monomer compound of claim 1 of formula ##STR5## wherein a is an integer of from 1 to 10, R.sub.1, R.sub.6 and R.sub.7 are selected from the group consisting of hydrogen and methyl groups, R.sub.2 and R.sub.3 are methyl groups and X is selected from the group consisting of chloride, iodide and bromide ions. 4. The chemiluminescent monomer compound of claim 3 that is N,N-dimethylaminopropylmethacrylamide-N-(chloroacetyl)-3-aminophthalhydraz ide quaternary salt. 5. The chemiluminescent monomer compound of claim 1 of formula ##STR6## wherein a is an integer of from 1 to 10, R.sub.1, R.sub.6, and R.sub.7 are selected from the group consisting of hydrogen and methyl groups, R.sub.2 and R.sub.3 are methyl groups and X is selected from the group consisting of chloride, iodide and bromide ions. 6. The chemiluminescent monomer compound of claim 1 wherein said vinylic monomer having a terminal amine group is selected from the group consisting of: dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate. 7. A chemiluminescent water-soluble or water-dispersible polymer compound comprising: a chemiluminescent water-soluble polymer formed from free radical polymerization of at least a first chemiluminescent vinylic monomer and a second vinylic monomer, wherein said first monomer has a pendant amide-linked phthalhydrazide chemiluminescent group and wherein said first monomer is formed by reacting a vinylic monomer having a terminal amine group with an alpha-haloacetyl containing phthalhydrazide chemiluminescent group. 8. The polymer of claim 7 wherein said phthalhydrazide chemiluminescent group is selected from the group consisting of: 5-amino-2,3-dihydro-1,4-phthalazinedione, 6-amino-2,3-dihydro-1,4-phthalazinedione and N-(4-aminobutyl)-N-ethyl-6-amino-2,3-dihydro-1,4-phthalazinedione. 9. The polymer of claim 7 wherein said second monomer is selected from the group consisting of: acrylamide, acrylic acid, methacrylamide, vinyl acetate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate cetyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, diallyldimethyl ammonium chloride, 2-acrylamido-2-methylpropane sulfonic acid, N-vinyl formamide, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate cetyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride and combinations thereof. 10. The polymer of claim 7 wherein said polymer has a luminescent repeating mer unit represented by the formula ##STR7## wherein a is an integer of from 1 to 10, R.sub.1 is selected from the group consisting of hydrogen and methyl groups, R.sub.2 and R.sub.3 are methyl groups and X is selected from the group consisting of chloride, iodide and bromide ions and wherein said polymer also contains a remaining portion of randomly distributed vinylic mer units. 11. The polymer of claim 10 wherein said vinylic mer units are derived from monomers selected from the group consisting of acrylamide, acrylic acid, methacrylamide, vinyl acetate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate cetyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, diallyldimethyl ammonium chloride, N-vinyl formamide, 2-acrylamido-2-methylpropane sulfonic acid, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate cetyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride and combinations thereof. 12. The polymer of claim 10 wherein said luminescent mer unit is from about 0.001 to about 10 mole percent of said polymer, and said vinylic mer unit is from about 90 to 99.999 mole percent of said polymer. 13. The compound of claim 7 wherein said polymer is poly(acrylamide/dimethylaminoethylacrylate benzyl chloride quaternary salt/N,N-dimethylaminopropylmethacrylamide N-(chloroacetyl)-3-aminophthalhydrazide quaternary salt. 14. The compound of claim 7 wherein said polymer has a luminescent repeating mer unit represented by the formula ##STR8## wherein a is an integer of from 1 to 10, R.sub.1 is selected from the group consisting of hydrogen and methyl groups, R.sub.2 and R.sub.3 are methyl groups and X is selected from the group consisting of chloride, iodide and bromide ions and wherein said polymer also contains a remaining portion of randomly distributed vinylic mer units. 15. The polymer of claim 14 wherein said vinylic mer units are derived from monomers selected from the group consisting of: acrylamide, acrylic acid, methacrylamide, vinyl acetate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate cetyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, diallyldimethyl ammonium chloride, N-vinyl formamide, 2-acrylamido-2-methylpropane sulfonic acid, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate cetyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride and combinations thereof. 16. The polymer of claim 14 wherein said luminescent mer unit is from about 0.001 to about 10 mole percent of said polymer, and said vinylic mer unit is from about 90 to about 99.999 mole percent of said polymer. 17. The polymer of claim 7 wherein said first monomer having a terminal amine group is selected from the group consisting of: dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate. 18. A method for increasing the efficiency of a water-soluble or water-dispersible polymeric flocculating agent in a fluid stream containing solids comprising the steps of: a) incorporating a detectable chemiluminescent moiety into said polymeric agent by polymerizing one or more vinylic monomers to form said agent under free radical polymerization conditions, wherein at least one of said vinylic monomers has an amide-linked chemiluminescent pendant group, to form chemiluminescent polymer; b) adding an effective flocculating amount of said chemiluminescent agent to said fluid stream; c) flocculating said solids from said solids containing stream to form a clarified stream; d) separating flocculated solids from said clarified fluid stream; and then, e) determining amount of chemiluminescent agent present in said clarified stream with chemiluminescent analytical techniques, whereby concentration of said agent in said clarified stream indicates that a modification in dosage selected from the group consisting of: increasing, decreasing, and not changing said dosage should be made. 19. The method of claim 18 wherein said fluid stream is an aqueous stream and said chemiluminescent polymer contains repeating chemiluminescent mer units of the formula selected from the group consisting of: ##STR9## wherein a is an integer of from 1 to 10, R.sub.1 is selected from the group consisting of hydrogen and methyl groups, R.sub.2 and R.sub.3 are methyl groups and X is selected from the group consisting of chloride, iodide and bromide ions and wherein the polymer also contains a remaining portion of randomly distributed vinylic mer units. 20. The method of claim 18 wherein said vinylic mer units are derived from monomer selected from the group consisting of: acrylamide, acrylic acid, methacrylamide, vinyl acetate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate cetyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, diallyldimethyl ammonium chloride, N-vinyl formamide, 2-acrylamido-2-methylpropane sulfonic acid, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate cetyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride and combinations thereof. 21. The method of claim 18 wherein said chemiluminescent mer unit is from about 0.001 to about 10 mole percent of said polymer, and said vinylic mer unit is from about 90 to about 99.999 mole percent of said polymer. 22. The method of claim 18 wherein said chemiluminescent polymer is poly(acrylamide/dimethylaminoethylacrylate benzyl chloride quaternary salt/N,N-dimethylaminopropylmethacrylamide N-(chloroacetyl)-3-aminophthalhydrazide quaternary salt. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION Luminol derived monomers, and water-soluble polymers formed using the luminol derived monomers, as well as methods for monitoring of the chemiluminescence of such polymers are disclosed. The novel chemiluminescent polymers require only a very low level of incorporation of the chemiluminescent moiety, and are useful for monitoring the location and concentration of such polymers, even in systems containing impurities which either quench fluorescence or fluoresce themselves. BACKGROUND OF THE INVENTION The present invention relates generally to the treatment and monitoring of industrial systems and, more specifically, to the treatment and monitoring of industrial systems using luminol-tagged polymers in combination with fluorescent or chemiluminescent detection techniques. The ability to track the polymer location and concentration in industrial systems is highly desirable. Typically, these processes are complex and dynamic, and therefore the means to monitor the polymeric coagulant or flocculent can result in increases in efficiency of the chemical treatment program, allow for diagnostic troubleshooting, insure that regulatory discharge limits are met, and may allow for automated control of the polymer treatment program by relating the monitoring parameter to some other system parameter of interest, for example, drainage rate or turbidity reduction. The industries in which such water soluble polymers are used include papermaking, mining and mineral process, sludge dewatering, and oil recovery, for example. Water soluble polymers of the type described herein are also used extensively to treat water used for steam generation (boilers) and cooling, among other things. The typical approach to monitoring the level of water soluble polymer coagulants or flocculants in a system has been to blend fluorescent dyes with the polymer program in small amounts and to use the fluorescence of the mixture to determine the concentration of the polymer in the system, as exemplified by U.S. Pat. Nos. 4,783,314; 5,645,799 and 5,435,969, the disclosures of which are hereby incorporated by reference. Another approach involves the preparation of "tagged" polymers, wherein a fluorescent moiety is covalently attached to the polymer, either during or after the polymerization, and then utilized for fluorescence monitoring and dosage control. This approach is described in U.S. Pat. Nos. 4,813,973, 5,171,450 and 5,705,394, the disclosures of which are also hereby incorporated by reference. Fluorescent compounds incorporated into monomers have also been disclosed in GB 1,141,147. This approach is advantageous in that the detection of flourescence positively indicates the presence of the polymeric additive. While both approaches for monitoring fluorescence have been relatively successful, they have limitations. Many aqueous systems wherein water soluble polymers are utilized often contain other sources of fluorescence. Therefore, the use of a fluorescent marker may be impractical, as it becomes difficult to reliably distinguish low levels of fluorescence from the polymeric species against high levels of fluorescence arising from the process stream or waste water. Moreover, such process waters oftentimes contain substances which may not be fluorescent themselves, but which will quench the fluorescence of other species in the system, including the fluorescence of the traced or tagged polymer additive. This also makes reliable detection of the polymer additive difficult or impossible. Finally, if the levels of the background fluorescence or the quenching materials fluctuate, this renders useless automated control schemes based on the calibration of a fluorescent response. Accordingly, there is a need for a polymer that can be modified with a marker chemically incorporated into or otherwise attached to the polymer. Because the marker and polymer would be physically attached, detection of the marker would necessarily result in a detection of the polymer. Of course, it would be economically important that the marker be readily detectable at low concentrations. A chemiluminescent marker would therefore be desirable, since chemiluminescence is based upon a non-irradiative excitation process, and therefore is not subject to the same limitations of fluorescence-based monitoring techniques already discussed. Further, for widespread applicability, a water soluble polymer is required. Accordingly, there is a need for a modified water soluble polymer in which the marker is highly chemiluminescent and which could be readily detected in the part per million (ppm) or part per billion (ppb) range using existing chemiluminescent techniques. Luminescent labels are attractive candidates for use as markers for a variety of reasons. Chemiluminescence is broadly defined as the production of visible light by atoms that have been excited by the energy produced in a chemical reaction, usually without an associated production of heat. Chemical energy excites electrons in the light-emitting molecules to higher energy states, from which electrons eventually fall to lower energy states with the emission of quanta of energy in the form of visible light. Luminescence is observed in several synthetic chemical compounds and also in naturally occurring biological compounds such as found in some bacteria, fireflies and certain varieties of marine life. One of the most important families of chemiluminescent molecules are the phthalhydrazides. The most familiar member of this family is luminol, or 5-amino-2,3-dihydro-1,4-phthalazinedione, which has a chemical composition of C.sub.8 H.sub.7 N.sub.3 O.sub.2 and a double ring structure with a melting point of about 320.degree. C. Luminol is commercially available from several suppliers and is well characterized. Certain luminol analogs are also chemiluminescent, such as those wherein the position of the amino group is shifted (e.g., isoluminol, the amino group being at the 6 position), or is replaced by other substituents, as well as annelated derivatives and those with substitution in the non-heterocyclic ring. Some luminol analogs produce light more efficiently than does luminol itself, while others have lower efficiency. (As used herein, the term "luminol" encompasses such related species.) Generally, luminol produces light in an oxidizing reaction, wherein the luminol combines with oxygen or an oxidizer to produce a reaction product and photons at a wavelength of about 425-450 nanometers (nm). The precise reaction formula and the quantum efficiency of light production, i.e., the ratio of luminescing molecules to total molecules of the luminescent species, depend upon the medium in which the luminol resides, temperature and other reaction conditions. Typical oxidizers used in conjunction with luminol include oxygen, hydrogen peroxide, hypochlorite, iodine and permanganate. The oxidation of luminol with the associated production of light occurs rather slowly at ambient temperatures, unless the reaction is catalyzed. A variety of different substances can catalyze the reaction, including organic enzymes, such as horseradish peroxidase, other organic molecules such as microperoxidase and heme, positively charged metallic ions such as the cupric ion, and negatively charged ions such as the ferricyanate ion among others. Luminol has been diazo-linked to hydroxyindole to form water-soluble luminescent compounds having repeating units, for use in immunoassays as described in U.S. Pat. No. 5,003,050. Moreover, post-polymerization modification of water-soluble polymers with luminol to produce filling agents or immunologically active complexes for quantitative assays was disclosed in JP 58137759A and JP 05034330. However, therein structurally different polymers were first formed, and luminol was afterwards attached, in contrast to the instant invention wherein luminol is incorporated into a monomer prior to polymerization. Luminescent molecules would appear to be highly desirable as markers because of their stability, sensitivity, the potential ease of detecting their emitted visible light and their lack of toxicity. There is a need for a luminescent water treatment agent which is water soluble, is highly quantum efficient, and provides long-lived chemiluminescence. Accordingly, it is an object of the present invention to provide a water-soluble luminescent water treatment agent. The inventors have discovered that use of a luminol derived marker, incorporated into a polymeric water treatment agent by free radical polymerization of luminol derived monomers achieves such goals. The novel chemiluminescent polymers will have utility for polymer detection, product fate determination and dosage control. Moreover, since emission is chemically induced, no photo excitation source is used, and fluorescence resulting from other components or contaminants of the system to be treated will not interfere with quantitation. Moreover, since chemiluminescence may be detected at very low levels, the tagged polymers disclosed herein provide the additional advantage of more exact quantitation. Other objects, aspects and advantages of the present invention will be apparent to those skilled in the art from a reading of the following detailed disclosure of the invention. SUMMARY OF THE INVENTION Luminol derived monomers, and water soluble, water-treatment polymers formed using the luminol derived monomers, as well as methods for monitoring of the chemiluminescence of such water-treatment polymers are disclosed. The novel chemiluminescent polymers require only a very low level of incorporation of the chemiluminescent moiety, and are useful for monitoring, even in systems containing impurities which either quench fluorescence or fluoresce themselves. DESCRIPTION OF THE INVENTION The polymers which could be manufactured using the present invention include all water-soluble polymers which are prepared by free radical polymerization. Such chemiluminescent polymers could be non-ionic, cationic, or anionic, depending upon the monomers which are selected to be copolymerized with the described luminol-derived monomer. The polymers may be low, medium or high molecular weight, depending upon the conditions of the polymerization. The polymers may be prepared as solution, dispersion, inverse emulsion, or as gel polymers. When a water-soluble polymer has been made chemiluminescent (tagged or "marked") by virtue of incorporation of the chemiluminescent monomer, then a means for detecting the polymer is provided for. Specifically, the polymer can be detected in water samples by treating the water sample with the proper reagents, in the presence of a light-sensitive detector, and observing the emission of light. This detection process may be manual, wherein a water sample is removed from a process stream and analyzed as described, or it may be continuous, wherein a sidestream from a process is diverted and mixed with the activating reagents just before encountering an in-line detector. The concentration of the polymer in the stream can then be determined, since the observed luminescent intensity is proportional to polymer concentration. Once known, the polymer concentration can be used to control and optimize various aspects of the process which are related to polymer dosage. Alternately, determining the location and concentration of the polymer in post-process streams, water recycle loops, and effluent discharge pathways can be useful for regulatory compliance, product fate determination or environmental monitoring, and can be accomplished in the same manner. The monomers and polymers described herein are also fluorescent, and so could be detected using an excitation light source in conjunction with an emission detector. Under these circumstances, no additional reagents need be added to the water sample containing the tagged polymer prior to detection. However, as has been discussed, chemiluminescent detection provides a number of advantages over fluorescent detection, and so is the preferred method. When used to treat industrial waters, the dosage of the modified polymers should usually vary from a few parts per million (ppm) up to several hundred ppm depending upon the system to be treated and the intrinsic viscosity of the polymeric agent utilized. When used as a coagulant, the dosage should typically be between a few ppm up to approximately 100 ppm. While as great a mole ratio of amide-linked chemiluminescent monomer can be incorporated into a polymer treatment agent as desired, one advantage of this invention is that due to the sensitivity of chemiluminescent techniques, only a very small amount of incorporation of the chemiluminescent moiety is actually necessary. Furthermore, the incorporation of only a very low percentage of chemiluminescence insures that the efficiency of the treatment polymer will not be modified. It is envisaged that with proper selection of vinylic monomers, chemiluminescent polymers for use in non-aqueous systems can be formed. One aspect of this invention is a chemiluminescent monomer compound comprising: a vinylic monomer having a pendant amide-linked chemiluminescent group. For the practice of any aspect of this invention, the following applies. The chemiluminescent monomer may be formed from reaction of a vinylic monomer having a terminal amine group with an alpha-haloacetyl containing chemiluminescent group. The chemiluminescent group may be selected from the group consisting of: 5-amino-2,3-dihydro-1,4-phthalazinedione, 6-amino-2,3-dihydro-1,4-phthalazinedione and N-(4-aminobutyl)-N-ethyl-6-amino-2,3-dihydro-1,4-phthalazinedione. The monomer may be of the formula ##STR1## wherein a is an integer of from 1 to 10, R.sub.1, R.sub.6 and R.sub.7 are selected from the group consisting of hydrogen and methyl groups, R.sub.2 and R.sub.3 are methyl groups and X is selected from the group consisting of chloride, iodide and bromide ions. More specifically, the monomer may be N,N-dimethylaminopropylmethacrylamide N-(chloroacetyl)-3-aminophthalhydrazide quaternary salt. Alternatively, the monomer may be of the formula ##STR2## wherein a is an integer of from 1 to 10, R.sub.1, R.sub.6, and R.sub.7 are selected from the group consisting of hydrogen and methyl groups, R.sub.2 and R.sub.3 are methyl groups and X is selected from the group consisting of chloride, iodide and bromide ions. The vinylic monomer having a terminal amine group may be selected from the group consisting of: dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate. Another aspect of the invention is a chemiluminescent water-soluble or water-dispersible polymer compound comprising: a chemiluminescent water-soluble polymer formed from free radical polymerization of at least a first chemiluminescent vinylic monomer and a second vinylic monomer, wherein said first monomer has a pendant amide-linked chemiluminescent group. The following information may apply to any aspect of this invention. The first monomer may be formed from reaction of a vinylic monomer having a terminal amine group with an alpha-halo acetyl containing chemiluminescent group. The second monomer may be selected from the group consisting of: acrylamide, acrylic acid, methacrylamide, vinyl acetate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate cetyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, diallyldimethyl ammonium chloride, N-vinyl formamide, 2-acrylamido-2-methylpropane sulfonic acid, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate cetyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride and combinations thereof. The polymer may have a luminescent repeating mer unit represented by the formula ##STR3## wherein a is an integer of from 1 to 10, R.sub.1 is selected from the group consisting of hydrogen and methyl groups, R.sub.2 and R.sub.3 are methyl groups and X is selected from the group consisting of chloride, iodide and bromide ions and wherein said polymer also contains a remaining portion of randomly distributed vinylic mer units. Alternatively, the polymer may have a luminescent repeating mer unit represented by the formula ##STR4## wherein a is an integer of from 1 to 10, R.sub.1 is selected from the group consisting of hydrogen and methyl groups, R.sub.2 and R.sub.3 are methyl groups and X is selected from the group consisting of chloride, iodide and bromide ions and wherein said polymer also contains a remaining portion of randomly distributed vinylic mer units. The vinylic mer units may be derived from monomers selected from the group consisting of acrylamide, acrylic acid, methacrylamide, vinyl acetate, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate cetyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, diallyldimethyl ammonium chloride, N-vinyl formamide, 2-acrylamido-2-methylpropane sulfonic acid, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate cetyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethyl ammonium chloride, acrylamidopropyl trimethyl ammonium chloride and combinations thereof. The luminescent mer unit may be from about 0.001 to about 10 mole percent of said polymer, and said vinylic mer unit is from about 90 to 99.999 mole percent of said polymer. Specifically, the polymer may be poly(acrylamide/dimethylaminoethylacrylate benzyl chloride quaternary salt/N,N-dimethylaminopropylmethacrylamide N-(chloroacetyl)-3-aminophthalhydrazide quaternary salt. Another aspect of this invention is a method for increasing the efficiency of a water-soluble or water-dispersible polymeric flocculating agent in a fluid stream containing solids comprising the steps of: a) incorporating a detectable chemiluminescent moiety into said polymeric agent by polymerizing one or more vinylic monomers to form said agent under free radical polymerization conditions, wherein at least one of said vinylic monomers has an amide-linked chemiluminescent pendant group, to form a chemiluminescent polymer; b) adding an effective flocculating amount of said chemiluminescent agent to said fluid stream; c) flocculating said solids from said solids containing stream to form a clarified stream; d) separating flocculated solids from said clarified fluid stream; and then, e) determining amount of chemiluminescent agent present in said clarified stream with chemiluminescent analytical techniques, whereby concentration of said agent in said clarified stream indicates that a modification in dosage selected from the group consisting of increasing, decreasing and not changing said dosage should be made. As used herein the term acrylamide is meant to also encompass substituted acrylamides. The terms tagged and marked have been used interchangeably, and are meant to describe a luminescent moiety chemically bonded to a monomer, which monomer is subsequently incorporated into the backbone of a polymer under free radical polymerization conditions. The term "n" as utilized herein signifies that a unit described within parentheses repeats, and is not intended to indicate any specific or definite numerical range for the number of repeat units. In the Examples which follow, aspects of the present invention, an amide-linked chemiluminescent polymer, useful for the treatment of industrial waters are illustrated. Specifically, the luminol-tagged polymers made in accordance with the present invention can be used to monitor treated water residuals, control polymeric agent addition, and be used in the analysis of mechanisms of polymeric treatment agent action. By improving the detectability of polymeric agents and by improving the ability to control the dosage levels of these agents, the present invention allows polymeric agents to be utilized more efficiently, as chemiluminescent monitoring can indicate whether or not more water-treatment agent is necessary, or in fact if a lower dosage may have been adequate. |
| PATENT EXAMPLES | available on request |
| PATENT PHOTOCOPY | available on request |
|
Want more information ? Interested in the hidden information ? Click here and do your request. |