CN102731457A - Water-soluble fluorescent tracing polymer and its preparation method - Google Patents
Water-soluble fluorescent tracing polymer and its preparation method Download PDFInfo
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- CN102731457A CN102731457A CN2012102087138A CN201210208713A CN102731457A CN 102731457 A CN102731457 A CN 102731457A CN 2012102087138 A CN2012102087138 A CN 2012102087138A CN 201210208713 A CN201210208713 A CN 201210208713A CN 102731457 A CN102731457 A CN 102731457A
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Abstract
The invention relates to a fluorescent monomer, a fluorescent tracing polymer and its preparation method. Its synthetic method comprises the following steps of: dissolving 7-diethylamino-4-methylcoumarin in a solvent, adding dropwisely bromopropylene, heating, cooling to obtain the fluorescent monomer allyl-7-diethylamino-4-methylcoumarin-ammonium bromide, and copolymerizing the fluorescent monomer with acrylamide and acrylic acid. The fluorescent polymer can be used as an oil field tracer to be applied in oilfield water-flooding and polymer flooding processes, and has good fluorescent tracer ability and chemical stability.
Description
Technical field
The present invention relates to a kind of fluorescent monomer and preparation method of fluorescent polymer who is applicable in oil-field flooding and the polymer flooding process.
Background technology
The oil field tracer technique is one of situ production measuring technology; Its technology is to inject tracer agent from injecting well; By certain sampling be defined on every side withdrawal well sampling, monitor its tracer agent over time, can instruct the design of oil mining and the adjustment of latter period of oilfield development thereafter.For a long time, tracer agent commonly used mainly contains chemical tracer and two kinds of isotopic tracers in the oil field, but all has shortcoming in various degree: the chemical tracer consumption is big, cost is high, the detection error is bigger; It must be the professional construction personnel that isotopic tracer then requires, and the application specific Equipment Inspection is unfavorable for large-scale promotion application.
Detection technique of fluorescence has detection sensitivity height, simple to operate, advantage such as cost is low, sensing range is adjustable, can be used for spike field, oil field.But must find the fluorescent tracer that is fit to the oil field subsurface environment in this technology implementation process, promptly have good water solubility, fluorescence intensity reaches characteristics such as good stability greatly.A lot of optical dyes are lacked in validity period, are subject to disturb and can't realize using because of it.To this kind situation, can consider to use the optical dye or derivatives thereof as fluorescent monomer, with some water-soluble monomer copolymerization, or optical dye and water-soluble polymers and derivatives reaction thereof make fluorescent polymer.Can carry out quick, easy, highly sensitive detection to this type fluorescent polymer through spectrophotofluorometer, thereby can reach the purpose of effective spike.
The method of common fluorescent mark polymkeric substance has two kinds, the one, the reaction through functional group with fluorescent substance to this base polymer chemical modification; As the pyrenyl after will modifying is directly linked (T. Costa on the SEPIGEL 305 side group; J. S. S. Melo, C. S.Castro, S. Gago; M. Pillinger; I. S. Gon alves, Picosecond Dynamics of Dimer Formation in a Pyrene Labeled Polymer
J. Phys. Chem. B, 2010,
114, 12439-12447; T. Costa; M. G. Miguel, B. Lindman, K. Schill é n; J. S. S. Melo; Dynamics and Energetics of the Self-Assembly of a Hydrophobically Modified Polyelectrolyte:Naphthalene-Labeled Poly (AcrylicAcid), J.Phys.Chem.B
2005, 109,11478-11492.).Another method is that the acrylic amide water-soluble monomer obtains with the monomer copolymerization that can participate in polymeric optical dye group and mark thereof; (L. F. Campo; F. S. Rodembusch; V. Stefani; New fluorescent monomers and polymers displaying an intramolecular proton-transfer mechanism in the electronically excited state (ESIPT). IV. Synthesis of acryloylamide and diallylamino benzazole dyes and its copolymerization with MMA, J. Appl. Polym. Sci.
2006, 99:2109-2116; L. F. Campo; F. S. Rodembusch; V. Stefani, New fluorescent monomers and polymers displaying an intramolecular proton-transfer mechanism in the electronically excited state. III. Thermogravimetric stability study of the benzazolylvinylene derivatives, J. Appl. Polym. Sci.; 2006,99:495 – 500.).
The acrylic amide fluorescent polymer that obtains has the double properties of polymkeric substance and optical dye concurrently, can be used for a plurality of fields such as water conditioner.But up to the present, fluorescent polymer reports seldom in Application in Oilfield Development then still less, therefore, to have important theoretical research and be worth and prospects for commercial application at home as the oil field tracer agent.
Summary of the invention
The objective of the invention is: be to solve the prior art problem, developed and a kind ofly have good water-solubility, fluorescence, and detection sensitivity is high, does not influence each other and interferential novel fluorescence spike polymkeric substance and preparation method thereof with polymkeric substance.
In order to achieve the above object, technical scheme of the present invention is:
(1) a kind of fluorescent monomer allyl group-7-diethylin-4-methylcoumarin brometo de amonio, its molecular structural formula (1) be as follows:
（1）
(2) preparation method of the described fluorescent monomer of scheme (1), its step is following:
7-diethylin-4-methylcoumarin is dissolved in the acetonitrile, and under agitation the dripping bromine propylene heats, and product is separated out in cooling, through underpressure distillation, drying, obtains having the fluorescent monomer allyl group-7-diethylin-4-methylcoumarin brometo de amonio of two keys.
In the step of preparation fluorescent monomer, the ratio of 7-diethylin-4-methylcoumarin and the amount of substance of bromopropylene is in the 1:3-1:1 scope, and in addition, the heating described in the reactions step is meant that temperature is controlled in the 75-85 ℃ of scope.
The prepared fluorescent monomer maximum emission wavelength of the present invention is 468nm, is positioned at visible spectrum blue wavelength region 435-480nm, demonstrates blue-fluorescence.In the complicated test environment of oil well produced water, its working concentration and fluorescent emission intensity are good linear relationship, and linearly dependent coefficient reaches 0.99991.
Blue-fluorescence monomer of the present invention can synthesize the polymkeric substance with blue-fluorescence characteristic with acrylic amide and Acrylic Acid Monomer copolymerization, as the oil field tracer agent.
In addition, the present invention also provides following technical scheme:
(3) a kind of fluorescent tracing polymkeric substance, its structural formula (2) is as follows:
（2）
X in the following formula, y, z represents the polymerization degree, for greater than 0 integer.
The present invention also provides following technical scheme:
(4) a kind of fluorescent tracing polymkeric substance, it prepares through following method:
7-diethylin-4-methylcoumarin is dissolved in the acetonitrile, and under agitation the dripping bromine propylene heats, and product is separated out in cooling, through underpressure distillation, drying, obtains having the fluorescent monomer allyl group-7-diethylin-4-methylcoumarin brometo de amonio of two keys.
In the step of preparation fluorescent monomer, the ratio of 7-diethylin-4-methylcoumarin and the amount of substance of bromopropylene is in the 1:3-1:1 scope, and in addition, the heating described in the reactions step is meant that temperature is controlled in the 75-85 ℃ of scope.
With initiator ammonium persulfate and sodium sulfite anhy 96 is initiator system; Utilize step (2) institute's synthetic fluorescent monomer and acrylic amide and Acrylic Acid Monomer to carry out polyreaction; The raw materials quality ratio of wherein said fluorescent monomer and acrylic amide and Acrylic Acid Monomer is fluorescent monomer 0.05%-1%; Acrylic amide 55-79.95%; Vinylformic acid 20-44%; With NaOH regulation system pH value, be controlled at 7-10; Temperature is controlled at 40 ℃-70 ℃, and initiator amount is the 0.3%-0.7% of monomer total mass, and wherein the ratio of sodium sulfite anhy 96 and ammonium persulphate amount of substance is 1:1.
The resulting fluorescent tracing polymer architecture of above-mentioned preparation method formula (2) is:
（2）
X in the following formula, y, z represents the polymerization degree, for greater than 0 integer.
The fluorescent tracing polymkeric substance that the present invention is prepared, maximum emission wavelength is 461nm in fluorescence spectrometry, is positioned at visible spectrum blue wavelength region 435-480nm, demonstrates blue-fluorescence.Fluorescent tracing polymkeric substance of the present invention and oilfield polymer do not influence each other and disturb; This polymkeric substance can guarantee the linear relationship of its concentration and fluorescence intensity in the complicated test environment of oil well produced water simultaneously; Linearly dependent coefficient reaches 0.99981, and therefore can be used as tracer agent is applied to fields such as oil-field flooding and polymer flooding.
The present invention has following remarkable advantage: the multipolymer that (1) adopts copolymerization posthydrolysis method to make, introduced carboxylic acid sodium, and it is water-soluble that the spike polymkeric substance is had; (2) reaction conditions of synthetic fluorescent tracing polymkeric substance is gentle, and the maximum emission wavelength of this polymkeric substance is in visible region and strong blue-fluorescence is arranged, and fluorescence intensity and polymer concentration are linear.Therefore in oil-field flooding and polymer flooding process, can change through fluorescence intensity and in time, fast, accurately measure its content; (3) this tracer agent and oilfield polymer do not influence each other and disturb, and fluorescence property is stable, and detection sensitivity is high.
Description of drawings
Fig. 1 is the fluorescence excitation spectrum and the emmission spectrum figure of fluorescent monomer allyl group of the present invention-7-diethylin-4-methylcoumarin brometo de amonio.
Fig. 2 is the fluorescent monomer allyl group of the present invention-7-diethylin-concentration of 4-methylcoumarin brometo de amonio and the graph of relation of fluorescence intensity.
Fig. 3 is the linear fit graphic representation of fluorescent monomer allyl group of the present invention-7-diethylin-4-methylcoumarin brometo de amonio different concns and fluorescent emission intensity.
Fig. 4 is the fluorescence excitation spectrum and the emmission spectrum figure of fluorescent tracing polymkeric substance of the present invention.
Fig. 5 is the graph of relation of the concentration and the fluorescence intensity of fluorescent tracing polymkeric substance of the present invention.
Fig. 6 is the linear fit graphic representation of fluorescent tracing polymkeric substance different concns of the present invention and fluorescent emission intensity.
Fig. 7 is the graph of relation of fluorescence intensity in inorganic salt solution of fluorescent tracing polymkeric substance of the present invention.
Embodiment
The preparation of embodiment 1 fluorescent monomer allyl group-7-diethylin-4-methylcoumarin brometo de amonio
Preparation feedback formula (3) is as follows:
（3）
Round-bottomed flask is put into oil bath pan add 7-diethylin-4-methylcoumarin 0.5775g (0.0025mol); Make dissolution with solvents with the 10mL acetonitrile; Dripping bromine propylene 0.4537g (0.00375mol) under evenly stirring; Condensing reflux, oil bath temperature rise to 80 ℃, and reaction is 20 hours under this temperature.After the cooling, underpressure distillation is poured product in ether recrystallization, and underpressure distillation again, drying get white solid product allyl group-7-diethylin-4-methylcoumarin brometo de amonio, productive rate 67.3%.
Resulting fluorescent monomer is adopted Agilent 6224 spectrometer analysis, can find out molecular ion peak (ESI, the m/z of compound
+) be 272, because product is a salt compounds, in solution, dissociate into X
+Br
-, allyl group-7-diethylin-4-methylcoumarin brometo de amonio relative molecular mass is 352, Br
-Relative molecular mass is 79.9, i.e. X
+Relative molecular mass be 272.Therefore show that title product allyl group-7-diethylin-4-methylcoumarin brometo de amonio generates.
In addition, the WQF-520 type IR (KBr compressing tablet) that adopts Beijing Rayleigh company to produce makes to carry out infrared spectrum characterization to product, and by seeing on the infrared spectrogram, (C=C) skeletal vibration absorbs characteristic peak 1610cm to aromatic ring
-1, (C-H) stretching vibration absorbs characteristic peak 2978 cm to methyl
-1, 2930 cm
-1, 2865 cm
-1, 861-798cm on collection of illustrative plates
-1Between tangible C-H out-of-plane bending absorption peak is arranged, heterocycle (absorption of vibrations characteristic peak 1710cm C=O)
-1, prove that product is title product.
The fluorescence spectrum test of embodiment 2 fluorescent monomers
Take by weighing allyl group-7-diethylin-4-methylcoumarin brometo de amonio and be dissolved in the oil well produced water, be made into 100 μ g/L.Fixedly XRF slit width 10nm scans excitation spectrum and emmission spectrum respectively.The excitation spectrum of fluorescent monomer solution and emmission spectrum are seen accompanying drawing 1; The maximum excitation wavelength and the maximum emission wavelength that obtain are respectively 381nm and 468nm; Maximum emission wavelength is positioned at visible spectrum blue light range (435nm-480nm), has very strong fluorescence intensity.
Fixedly excitation wavelength 381nm and slit width 10 nm; Measure the fluorescence intensity of the oil field produced aqueous solution of fluorescent monomer under 468nm of 10,30,50,100,200,300 μ g/L; The test result of concrete fluorescence intensity is seen accompanying drawing 2; In addition, obtain the different concns of this monomer solution and the linear regression graphic representation (Fig. 3) of fluorescent emission intensity; Can be found out that by Fig. 3 the concentration of this monomer solution and fluorescent emission intensity are good linear relationship, linearly dependent coefficient reaches 0.99991.
The preparation of embodiment 3 fluorescent polymers
Preparation feedback formula (4) is as follows:
（4）
In the 100 mL single port bottles that induction stirring is housed, add 0.01 g allyl group-7-diethylin-4-methylcoumarin brometo de amonio, 0.005g OP-10 emulsifying agent and 40 g deionized waters; Fully stir and treat that emulsification adds 5.99g acrylic amide, 4.0 g vinylformic acid and 2.2222g sodium hydroxide in the back fully; Be made into monomer total mass percentage concentration 20% aqueous solution; Regulation system pH is 8, logical N
220 min; Add initiator ammonium persulfate solution and sodium sulfite solution again, the ammonium persulphate of adding is 1:1 with the ratio of sodium sulfite anhy 96 amount of substance, and add-on is 0.5% of a monomer total mass, continues to feed N
220 min react 8h down for 50 ℃ in temperature, and reaction finishes the post polymerization thing purifies with absolute ethyl alcohol, and deposition is cut into granule, and 40 ℃ got the fluorescent tracing polymkeric substance down in dry 2 days.
The WQF-520 type IR (KBr compressing tablet) that adopts Beijing Rayleigh company to produce is done to carry out infrared spectrum characterization to product, by seeing N-H (NH on the infrared spectrogram
2) stretching vibration peak is at 3406cm
-1The place, (C=C) skeletal vibration absorbs characteristic peak 1612cm to aromatic ring
-1, 1561cm
-1,-C=O stretching vibration peak is at 1665cm
-1, C-O (C-O-C) stretching vibration peak is at 1121 cm
-1The place.The functional group that has fluorescent monomer and acrylic amide and sodium acrylate to have on the polymkeric substance is described.
The fluorescence spectrum test of embodiment 4 fluorescent tracing polymkeric substance
It is the aqueous solution of 1000mg/L that the polymer formulation of embodiment 3 is become concentration; Fixedly XRF slit width 10nm scans excitation spectrum and emmission spectrum figure respectively; The result sees accompanying drawing 4; Its maximum excitation wavelength and maximum emission wavelength are respectively 357nm and 461nm, and maximum emission wavelength is positioned at visible spectrum blue light range (435nm-480nm), has very strong fluorescence intensity.
Fixedly excitation wavelength 357nm and slit width 10nm; The fluorescence intensity of fluorescent tracing polymkeric substance oil field recovered water solution under 461nm of mensuration 100,200,400,500,600,800,1000mg/L; The test result of concrete fluorescence intensity is seen accompanying drawing 5; In addition, obtain the different concns of this monomer solution and the linear regression graphic representation (Fig. 6) of fluorescent emission intensity; Can be found out that by Fig. 6 the concentration of this monomer solution and fluorescent emission intensity are good linear relationship, linearly dependent coefficient reaches 0.99981.
The test of embodiment 5 fluorescent polymer water solution system fluorescent stability
It is 0.1% solution that the polymer formulation of embodiment 3 is become concentration, at NaCl, CaCl
2, MgCl
2Concentration respectively is to measure the fluorescence intensity of polymkeric substance under 1-12 ‰ condition, and data are as shown in Figure 7, can be known by figure, adding different concns Na respectively
+, Ca
2+And Mg
2+After, the variation of polymer fluorescent intensity all is lower than 10, and the result shows inorganic salt NaCl, CaCl
2, MgCl
2Very little or do not have influence to the influence of the fluorescence property of this polymkeric substance, show that the fluorescence property of this polymkeric substance is stable, can be applied to the oil reservoir of different salinities.
Claims (8)
1. fluorescent monomer, allyl group-7-diethylin-4-methylcoumarin brometo de amonio, its molecular structural formula (1) is as follows:
（1）。
2. the preparation method of the described fluorescent monomer of claim 1; It is characterized in that: 7-diethylin-4-methylcoumarin is dissolved in the acetonitrile; Under agitation the dripping bromine propylene heats, and product is separated out in cooling; Through underpressure distillation, drying, obtain having the fluorescent monomer allyl group-7-diethylin-4-methylcoumarin brometo de amonio of two keys.
3. fluorescent polymer, its structural formula (2) is as follows:
（2）
X in the following formula, y, z represents the polymerization degree, is the integer greater than 0.
4. fluorescent polymer, it prepares through following method:
(1) 7-diethylin-4-methylcoumarin is dissolved in the acetonitrile; Under agitation the dripping bromine propylene heats, and product is separated out in cooling; After underpressure distillation, drying, obtain having the fluorescent monomer allyl group-7-diethylin-4-methylcoumarin brometo de amonio of two keys;
(2) be initiator system with initiator ammonium persulfate and sodium sulfite anhy 96; Utilize step (1) institute's synthetic fluorescent monomer and acrylic amide and Acrylic Acid Monomer to carry out polyreaction; The mass ratio of wherein said fluorescent monomer, acrylic amide and Acrylic Acid Monomer is fluorescent monomer 0.05%-1%; Acrylic amide 55-79.95%; Vinylformic acid 20-44%; With NaOH regulation system pH value, be controlled at 7-10; Temperature is controlled at 40 ℃-70 ℃.
5. the preparation method of a fluorescent polymer, it comprises the steps:
(1) 7-diethylin-4-methylcoumarin is dissolved in the acetonitrile; Under agitation the dripping bromine propylene heats, and product is separated out in cooling; After underpressure distillation, drying, obtain having the fluorescent monomer allyl group-7-diethylin-4-methylcoumarin brometo de amonio of two keys;
(2) be initiator system with initiator ammonium persulfate and sodium sulfite anhy 96; Utilize step (1) institute's synthetic fluorescent monomer and acrylic amide and Acrylic Acid Monomer to carry out polyreaction; The mass ratio of wherein said fluorescent monomer and acrylic amide and Acrylic Acid Monomer is fluorescent monomer 0.05%-1%; Acrylic amide 55-79.95%; Vinylformic acid 20-44%; With NaOH regulation system pH value, be controlled at 7-10; Temperature is controlled at 40 ℃-70 ℃.
6. the preparation method of the preparation method of fluorescent monomer according to claim 2, the described polymkeric substance of claim 4 or the described polymkeric substance of claim 5; Wherein, 7-diethylin-4-methylcoumarin and the ratio of the amount of substance of bromopropylene are in the 1:3-1:1 scope.
7. the preparation method of the preparation method of fluorescent monomer according to claim 2, the described polymkeric substance of claim 4 or the described polymkeric substance of claim 5; It is characterized in that: in the step of preparation fluorescent monomer, the indication heating is that temperature is controlled at 75 ℃-85 ℃.
8. the preparation method of polymkeric substance according to claim 4 or the described polymkeric substance of claim 5 is characterized in that: initiator amount is the 0.3%-0.7% of monomer total mass, and wherein the ratio of sodium sulfite anhy 96 and ammonium persulphate amount of substance is 1:1.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554126A (en) * | 2013-11-15 | 2014-02-05 | 西安石油大学 | Preparation method and application of fluorescein derivative serving as tracer agent for oil field |
| CN106749142A (en) * | 2016-11-15 | 2017-05-31 | 山西大学 | A kind of SO32‑/HSO3‑Detection reagent and its synthetic method and application |
| CN110054728A (en) * | 2019-04-25 | 2019-07-26 | 河北华北石油天成实业集团有限公司 | A kind of preparation method of embedded tracer polymer microballoon |
| CN110093177A (en) * | 2019-04-11 | 2019-08-06 | 南京中微纳米功能材料研究院有限公司 | A kind of preparation method of fluorescent visual oil field low-temperature demulsifying agent |
| CN110317294A (en) * | 2018-03-30 | 2019-10-11 | 长春理工大学 | A kind of novel temperature sensitive fluorescent polymer of triphen amine and preparation method thereof |
| CN112708010A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Polymer microsphere emulsion and preparation method and application thereof |
| US10995610B2 (en) | 2018-04-27 | 2021-05-04 | Ypf Technologia S.A. | Nanotracer for oil recovery and method of preparation thereof |
| US11193368B2 (en) | 2018-04-27 | 2021-12-07 | Ypf Tecnologia S.A. | Nanotracer for oil recovery comprising an occluded polynucleotide and method of preparation thereof |
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|---|---|---|---|---|
| CN103554126A (en) * | 2013-11-15 | 2014-02-05 | 西安石油大学 | Preparation method and application of fluorescein derivative serving as tracer agent for oil field |
| CN103554126B (en) * | 2013-11-15 | 2016-04-13 | 西安石油大学 | The fluorescein derivative preparation method of oil field tracer agent and application |
| CN106749142A (en) * | 2016-11-15 | 2017-05-31 | 山西大学 | A kind of SO32‑/HSO3‑Detection reagent and its synthetic method and application |
| CN106749142B (en) * | 2016-11-15 | 2019-01-25 | 山西大学 | A kind of SO32-/HSO3-Detection reagent and its synthetic method and application |
| CN110317294A (en) * | 2018-03-30 | 2019-10-11 | 长春理工大学 | A kind of novel temperature sensitive fluorescent polymer of triphen amine and preparation method thereof |
| CN110317294B (en) * | 2018-03-30 | 2021-06-18 | 长春理工大学 | Triphenylamine temperature-sensitive fluorescent polymer and preparation method thereof |
| US10995610B2 (en) | 2018-04-27 | 2021-05-04 | Ypf Technologia S.A. | Nanotracer for oil recovery and method of preparation thereof |
| US11193368B2 (en) | 2018-04-27 | 2021-12-07 | Ypf Tecnologia S.A. | Nanotracer for oil recovery comprising an occluded polynucleotide and method of preparation thereof |
| CN110093177A (en) * | 2019-04-11 | 2019-08-06 | 南京中微纳米功能材料研究院有限公司 | A kind of preparation method of fluorescent visual oil field low-temperature demulsifying agent |
| CN110054728A (en) * | 2019-04-25 | 2019-07-26 | 河北华北石油天成实业集团有限公司 | A kind of preparation method of embedded tracer polymer microballoon |
| CN112708010A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Polymer microsphere emulsion and preparation method and application thereof |
| CN112708010B (en) * | 2019-10-24 | 2023-03-28 | 中国石油化工股份有限公司 | Polymer microsphere emulsion and preparation method and application thereof |
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