MXPA99010943A - Luminol tagged polymers for treatment of industrial systems - Google Patents
Luminol tagged polymers for treatment of industrial systemsInfo
- Publication number
- MXPA99010943A MXPA99010943A MXPA/A/1999/010943A MX9910943A MXPA99010943A MX PA99010943 A MXPA99010943 A MX PA99010943A MX 9910943 A MX9910943 A MX 9910943A MX PA99010943 A MXPA99010943 A MX PA99010943A
- Authority
- MX
- Mexico
- Prior art keywords
- polymer
- luminol
- epichlorohydrin
- dimethylamine
- copolymer
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- HWYHZTIRURJOHG-UHFFFAOYSA-N Luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000001514 detection method Methods 0.000 claims abstract description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 15
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- 239000008235 industrial water Substances 0.000 abstract description 6
- 230000001112 coagulant Effects 0.000 description 20
- 239000000701 coagulant Substances 0.000 description 20
- ROSDSFDQCJNGOL-UHFFFAOYSA-N dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 230000001809 detectable Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- 230000003466 anti-cipated Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000003745 diagnosis Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005429 turbidity Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M CHEMBL593252 Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003467 diminishing Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 101700050638 thi1 Proteins 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
A polymer tagged with luminol is provided which enables the fluorescent or chemiluminescent detection of the tagged polymer at low concentrations. The chromophore may be covalently bonded to the polymer backbone without sacrificing the chromophore's fluorescent or chemiluminescent properties. The present invention has been found useful in the treatment and monitoring of industrial waters.
Description
POLYMERS MARKED WITH LUMINQL FOR THE TREATMENT OF INDUSTRIAL SYSTEMS
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 polymers labeled with luol in combination with fluorescent or chemiluminescent detection techniques. Polymer coagulants are added to industrial water systems and waste water systems as monitoring agents because technological advances have enabled those skilled in the art to reliably monitor the residual level of such polymeric coagulant additives. Knowledge of the fate of polymeric coagulants in industrial water and wastewater systems allows operators to monitor the residual content of polymeric coagulants and therefore the residual content of other compositions in the water. In addition, by monitoring the residual level of polymeric coagulants in wastewater, operators are able to better control the addition of such coagulants. Specifically, the knowledge that the concentration of a REF: 32169 polymeric coagulant in a downstream position is rather high allowed the operator to reduce the addition of the polymeric coagulant in an upstream position. As a result, the coagulant dosage can be automated. In addition, a knowledge of the fate of the coagulant in a system helps in the diagnosis of treatment difficulties, and potentially, a diagnosis of treatment difficulties before reducing the difficulties in treated water that does not comply. The typical solution for monitoring the level of water-soluble polymeric coagulants in a system has been to combine fluorescent dyes in small amounts and use the fluorescence of the mixture to determine the concentration of the polymer in the system. Although this solution has been relatively successful, it has limitations. Specifically, dyes are associated with other components of the system, such as sample particulates. Consequently, a subsequent fluorescent detection of the dye may not necessarily provide evidence of the position or detection of the polymeric coagulant. Accordingly, there is a need for a polymer that can be modified so that the dye is chemically incorporated or otherwise bound to the polymer. Because the dye and the polymer must be physically bound, the detection of the dye necessarily results in a detection of the polymer. Of course, it would be economically important that the dye be easily detectable at low concentrations. Therefore, a highly fluorescent or chemiluminescent dye would be desirable. In addition, for dispersed applicability, a water soluble polymer is required. Accordingly, there is a need for a water soluble polymer modified with dye in which the dye is highly fluorescent or chemiluminescent and which can easily be detected in the range of parts per million (ppm) or parts per billion or billion ( ppb) using existing fluorescent detection techniques and / or chemiluminescent techniques.
BRIEF DESCRIPTION OF THE INVENTION
The present invention meets the aforementioned needs by providing a composition that is capable of being detected in a solution by chemiluminescent techniques as well as by fluorescent techniques. More specifically, the present invention provides a polymer labeled with luminol that can be detected even at very low concentrations in a solution using either chemiluminescent or fluorescent techniques. The present invention also provides an improved method for detecting the presence of a substance or composition in a solution.
In one embodiment, the present invention provides a composition capable of being detected in a solution by chemiluminescent or fluorescent detection techniques., which comprises a polymer marked with luminol. In one embodiment, the polymer comprises monomeric units of epichlorohydrin. In one embodiment, the polymer is further characterized in that it is a copolymer comprising monomer units of epichlorohydrin and monomer units of dimethylamine. In one embodiment, the polymer is a copolymer comprising monomer units of epichlorohydrin and monomer units of dimethylamine with luminol covalently linked between some of the monomer units of epichlorohydrin and monomer units of dimethylamine, luminol is present in the copolymer in a varying amount from about 0.05% to about 2% in peeo. In one embodiment, a labeled portion of the polymer of the present invention has the following formula:
In one embodiment, the present invention provides a composition comprising luminol-labeled epichlorohydrin monomer. In one embodiment, the present invention provides the composition comprising a monomer labeled with luminol. Therefore, an advantage of the present invention is to provide a monomer labeled with a chemiluminescent and / or fluorescent chromophore that can be detected in a solution at low concentrations using conventional chemiluminescent or fluorescent detection techniques. Another advantage of the present invention is to provide a polymer labeled with a chemiluminescent / fluorescent chromophore such as luminol, which can be detected in a solution at low concentrations using conventional chemiluminescent or fluorescent techniques. Another additional advantage of the present invention is the ability to label a polymer with luminol during the polymeric condensation reaction which results in luminol bound covalently to the polymer. Another additional advantage of the present invention is to provide an improved method of labeling a monomer or polymer with luminol.
Another advantage of the present invention is to provide an improved method of labeling a monomer or polymer with luminol. Another advantage of the present invention is to provide an improved composition for use in dosing control, monitoring of waste substances, automated control of particle sizing, and in general in industrial water treatment.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 illustrates, graphically, the ability of the composition prepared according to the present invention to act as a coagulant while being detectable at low dosages; Figure 2 illustrates, graphically, the ability of a composition prepared according to the present invention to provide fluorescent information over a low dosage range; and Figure 3 illustrates, graphically, the correlation of a composition prepared in accordance with the present invention with respect to the apparent color removal performance and the lack of correlation of a prior art composition with respect to the apparent color removal performance. .
DETAILED DESCRIPTION OF CURRENTLY PREFERRED MODALITIES
The present invention provides an improved composition that can be detected at low concentrations using conventional fluorescent or chemiluminescent detection methods. One embodiment of the present invention is a luminol-labeled epichlorohydrin-dimethylamine polymer. Luminol is a chemiluminescent species in which its structure is shown below:
luminol
The structure of epichlorohydrin and dimethylamine are shown below:
DMA epichlorohydrin The structure of a labeled portion of an epichlorohydrin-dimethylamino marked with luminol is shown below:
It is also anticipated that, in addition to luminol, they can also be used as blue nylon and thionin chromophores. In addition, it is also anticipated that a monomer, such as epichlorohydrin, may be labeled with a chromophore to provide a composition capable of being detected by fluorescent or chemiluminescent methods at low concentrations, according to the present invention. The invention comprises epichlorohydrin-dimethylamine copolymers which contain 0.05% -2% by weight of luminol. It should be noted that any condensation polymerization process can incorporate luminol insofar as the fluorescent properties of the chromophore are retained. The invention further contemplates the use of these polymers in water treatment applications such as, but not limited to, coagulation. This allows the dosage and residual amounts of the polymers to be monitored and monitored, using conventional fluorescence / chemiluminescent detection equipment even though the polymers are present in the ppb range. The reaction of luminol, epichlorohydrin and dimethylamine to provide the epichlorohydrin-dimethylamine polymer labeled with luminol. The assumed structure is shown below:
luminol epichlorohydrin DMA
Using the primary aromatic amir girupo in luminol, luminol is incorporated into the main structure of the polymer. The hydrocarbon bond is essentially a tertiary amine leaving the ring nitrogens available for fluorescent or chemiluminescent applications. Theoretically it is also possible to react epichlorohydrin with luminol and then to polymerize it in the usual epichlorohydrin / dimethylamine reaction, to form essentially the same labeled polymer. Luminol and dimethylamine are desirably reacted with epichlorohydrin at 80 ° C using general synthesis methods that are known to those skilled in the art. Specifically, luminol-modified epichlorohydrin polymers can be synthesized using known techniques of condensation polymerization. The resulting copolymers can contain from about 0.05% to about 2% by weight of the luminol monomer. Of course, luminol is a monomer and can potentially be incorporated at higher concentrations. Preferably, the amount of fluorescent monomer is within the range of 0.1% to 1% by weight of the resulting labeled polymer. A luminol-labeled epichlorohydrin-dimethylamine monomer prepared according to the present invention has an average molecular weight of 10,000 amu (atomic mass units) versus 20,000 amu for an unmodified epichlorohydrin-dimethylamine polymer. For most water treatment applications, such as coagulation, the molecular weight must be less than c.a. 100,000 amu. When used to treat industrial waters, the dosage of the modified polymers will usually vary from a few parts per million (ppm) to several hundred ppm, depending on the seventh in question and the intrinsic viscosity of the polymer in use. When used as a coagulant, the dosage should typically be between a few ppm, up to about 100 ppm.
EXAMPLE 1
The following laboratory procedure is used to prepare the embodiment of the present invention comprising epichlorohydrin-dimethylamine polymers labeled with luminol. To a Parr reactor of 300 ml, 1.67 g of luminol, 79.67 g of water and 70.70 g of dimethylamine 61.3% in water are added. After sealing the Parr reactor, the temperature increases to 65 ° C. Epichlorohydrin is then added at approximately 1.5 ml / min., Until the temperature reaches 80 ° C. Since the reaction is exothermic, the speed of adding epichlorohydrin is varied to maintain the temperature at about 80 ° C. Once a total of 86,655 g of epichlorohydrin have been added, the reaction temperature is maintained at 80 ° C for 2 hours, after which the mixture is cooled to room temperature. The following procedures are used to characterize the polymer. The Brookfield viscosity is obtained using a rod # 2, at 30 rpm. For two batches of the invention, the Brookfield viscosity ranges from 100 cps to 400 cps. Dialysis experiments are performed using a cut-off membrane of 12,000 to 14,000 amu MW (molecular weight). Since luminol is not soluble in water, dialysis is carried out in methanol. This separates the luminol that has not reacted from the invention. The test shows that the luminol monomers are fully incorporated, essentially to 0.7% by weight of product obtaining at least 99% incorporation of the dye in the polymer. The total polymer solids of the labeled poly DADMAC are measured at 54.4%. The composition of the present invention has the following characteristics:
TABLE 1
Epi-DMA labeled Epi-DMA Appearance Clear yellow Transparent yellow Viscosity Brookfield: 100-400 cps 270 cps Average MW weight: 10,000 20,000 Polymer Solids: 54.5% 55.
The composition of the present invention has characteristics similar to that of the unlabeled epichlorohydrin / dimethylamine polymer. The incorporation of luminol is determined analytically. An activity test is performed to determine the effluent from a paper mill with a fresh and aged luminol copolymer-epichlorohydrin / dimethylamine. The coagulation power does not change. It is noted that the invention is sensitive to light and room temperature and will darken in a period of six months. A portion stored in the dark during the same time period at 4 ° C shows only a moderate color change.
TEST SCORES
Wastewater from an effluent from a paper mill is used for activity tests. Figure 1 shows the activity of the labeled polymer versus the unlabeled polymer. This result proves that the chemically-labeled epichlorohydrin / dimethylamine exhibits similar coagulation activity as compared to the unlabeled epichlorohydrin / dimethylamine polymer. The turbidity activity of the effluent measured in NTU (nephrolitic turbidity units) is determined. Additional tests of the invention are performed to compare the operation in TRASAJR applications. The paper mill effluent is treated with traced epichlorohydrin / dimethylamine (as opposed to the marked one). Normally, an inverse correlation is observed with the apparent color removal. Figure 2 demonstrates that the invention has the same expected fluorescence residuals with apparent color removal. Occasionally, the traced product shows no correlation; the water in figure 2 and 3 is made with such water. From Figure 3, it is illustrated that the invention demonstrates a correlation with the apparent color removal while the epichlorohydrin / dimethylamine plotted does not show correlation. Therefore, the invention has an improvement in the performance with respect to the drawn products and advances the state of the art for automated dosing applications. Accordingly, the present invention provides a labeled polymer that is useful in the treatment of industrial waters. Specifically, the labeled polymers made according to the present invention can be used to monitor treated wastewater, control the addition of coagulant and can be used in the analysis of coagulation mechanisms. By improving the detection ability of polymeric coagulants and by improving the ability to control the dosage levels of these coagulants, the present invention helps minimize the contribution to contamination attributable to polymeric coagulants. In addition, by covalently attaching a chromophore to a polymer, the present invention avoids the drawbacks associated with the prior art method of combining fluorescent dyes with polymeric coagulants which, as discussed above, results in a physical separation or dissociation between the dye and the coagulant. As illustrated in FIGS. 1 and 2, the polymers labeled with a chromophore according to the present invention are detectable at low dosage levels. Finally, as illustrated in Figure 1, the modified or labeled polymer prepared according to the present invention has an activity similar to an unmodified polymer. It should be understood that the various changes and modifications to the presently preferred embodiments described herein will be apparent to those familiar with the art. Such changes and modifications can be made without departing from the spirit and scope of the present invention, and without diminishing their concomitant disadvantages. Therefore, it is intended that all changes and modifications be encompassed by the appended claims. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers.
Claims (12)
1. A composition capable of being detected in a solution by chemiluminescent or fluorescent detection, the composition comprises a polymer labeled with luminol.
2. The composition according to claim 1, characterized in that the polymer comprises monomer units of epichlorohydrin.
3. The composition according to claim 1, characterized in that the polymer is a copolymer comprising monomer units of epichlorohydrin and monomeric units of dimethylamine.
4. The composition according to claim 1, characterized in that the polymer is a copolymer comprising monomeric units of epichlorohydrin and monomeric units of dimethylamine, and luminol is present in the copolymer in an amount ranging from about 0.05% to about 2% in weight.
5. The composition according to claim 1, characterized in that a marked portion of the polymer has the formula:
6. A method to detect the presence of a substance of a system, the method is characterized in that it comprises the following steps: adding the substance to the system, the substance comprises a composition capable of being detected in a solution by chemiluminescent or fluorescent detection, the composition comprises a polymer marked with lumiriol, detecting the presence of the composition with chemiluminescent or fluorescent detection.
7. The method according to claim 6, characterized in that the polymer comprises monomeric units of epichlorohydrin.
8. "The method according to claim 6, characterized in that the polymer is a copolymer comprising monomer units of epichlorohydrin and monomeric units of dimethylamine.
9. The method according to claim 6, characterized in that the polymer is a copolymer comprising monomer units of epichlorohydrin and monomer units of dimethylamine, and the chromophore comprises luminol present in the copolymer in an amount ranging from about 0.05% to about 2% in weigh.
10. The method according to claim 6, characterized in that a marked portion of the polymer has the formula:
11. A copolymer, characterized in that it comprises monomer units of epichlorohydrin and monomer units of dimethylamine, the copolymer further comprises luminol covalently linked between one of the monomeric units of epichlorohydrin and one of the monomer units of dimethylamine.
12. The copolymer according to claim 11, characterized in that the labeled portion of the copolymer has the formula:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08864656 | 1997-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA99010943A true MXPA99010943A (en) | 2000-09-04 |
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