CN105175613A - Methyl polystyrene 2-crotonate, and preparation method and application thereof - Google Patents
Methyl polystyrene 2-crotonate, and preparation method and application thereof Download PDFInfo
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- CN105175613A CN105175613A CN201510423072.1A CN201510423072A CN105175613A CN 105175613 A CN105175613 A CN 105175613A CN 201510423072 A CN201510423072 A CN 201510423072A CN 105175613 A CN105175613 A CN 105175613A
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- acid methyl
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Abstract
The invention provides a methyl polystyrene 2-crotonate, and a preparation method and an application thereof. The preparation method is characterized in that the methyl polystyrene 2-crotonate is obtained through a polymerization reaction of styrene and 2-methyl crotonate as reaction monomers with water as a solvent in the presence of polyvinyl alcohol and benzoyl peroxide. The invention also provides the methyl polystyrene 2-crotonate prepared through the preparation method, an application of the methyl polystyrene 2-crotonate in preparation of horizontal well oil production profile monitoring tracers, and a horizontal well oil production profile monitoring tracer containing methyl polystyrene 2-crotonate. The methyl polystyrene 2-crotonate can be completely dissolved in crude oil, can be used to monitor the oil production condition in every stage after horizontal well multistage fracturing, and can realize the purposes of analysis of the oil production condition in every stage and drawing of the oil liquid production profile in every stage.
Description
Technical field
The present invention relates to a kind of polystyrene 2-butylene acid methyl esters and preparation method thereof and application, belong to petroleum exploration and development technical field.
Background technology
At present in In Oil Field Exploration And Development process, prospect pit many employings horizontal well, and multi-layer multi-stage pressure break is the first-selected technique of stratum transformation, but in the process that layer position is selected, there is no specific aim, be all by experience to select layering, therefore post-fracturing Data acquisition and issuance fracturing effect just seemed particularly important.In prior art, by the monitoring of the method such as micro seismic method, potentiometry and fracture intensity after pressure break can be analyzed, more whether have commercial oil by the row's of returning situation awareness reservoir, but effective monitoring method is not still had for the produce oil situation of each section after staged fracturing.
Therefore, after developing a kind of level monitoring well multistage fracturing, the processing method of each section of produce oil situation has great importance to the evaluation of fracturing effect and the deployment of next step well location.
Multistage fracturing technique building technology and relevant support equipment ripe, realized 30 grades of pressure breaks in the world, largest domestic pressure break progression is more than 15 grades.Because pressure break progression is more, in addition at long horizontal sections, physical property there are differences, and after every grade of pressure break, discharge opeing situation has great importance for the evaluation of fracturing effect and next step well site deployment, but does not have effective monitoring method for the produce oil situation of each section after staged fracturing.Because current largest domestic pressure break progression is more than 15 grades, correspondingly need the horizontal well produce oil profile monitoring tracer agent of more than 15 kinds.Existing oil field tracer agent is water-soluble tracer, and the kind of tracer agent is few, consumption is large, is not suitable for the monitoring of each section of produce oil situation after horizontal well multi-layer multi-stage pressure break.
Therefore, develop a kind of suitable horizontal well produce oil profile monitoring tracer agent and become the technical problem that this area needs solution badly.
Summary of the invention
In order to solve the problems of the technologies described above, the object of the present invention is to provide the preparation method of a kind of polystyrene 2-butylene acid methyl esters.
The present invention also aims to provide a kind of polystyrene 2-butylene acid methyl esters prepared by the preparation method of above-mentioned polystyrene 2-butylene acid methyl esters.
The present invention also aims to provide a kind of above-mentioned polystyrene 2-butylene acid methyl esters in the application preparing horizontal well produce oil profile monitoring tracer agent.
The present invention also aims to provide a kind of horizontal well produce oil profile monitoring tracer agent comprising above-mentioned polystyrene 2-butylene acid methyl esters.
In order to achieve the above object, the invention provides the preparation method of a kind of polystyrene 2-butylene acid methyl esters, the method comprise with vinylbenzene and 2-butylene acid methyl esters for reaction monomers, under the existence of polyvinyl alcohol and benzoyl peroxide, be that dispersion medium carries out polyreaction with water, obtain described polystyrene 2-butylene acid methyl esters;
Wherein, polyvinyl alcohol is dispersion agent, and benzoyl peroxide is initiator.
Wherein said 2-butylene acid methyl esters (C
3h
5cOOCH
3), polyvinyl alcohol ([C
2h
4o] n), vinylbenzene (C
8h
8) and benzoyl peroxide (C
6h
5c (O) O
2) being the conventional reagent of this area, conventional 2-butylene acid methyl esters, polyvinyl alcohol, vinylbenzene and the benzoyl peroxide in any commercially available this area may be used to the present invention.
Above-mentioned polyvinyl alcohol ([C
2h
4o] mean polymerisation degree n) is 2400-2500.
According to preparation method of the present invention, preferably, the whole material gross weights added in reaction are for 100%, institute adds each weight of material per-cent and is respectively: 2-butylene acid methyl esters is 20wt%-45wt%, vinylbenzene is 2.5wt%-5wt%, polyvinyl alcohol is 0.1wt%-0.2wt%, benzoyl peroxide is 0.2wt%-0.9wt%, and surplus is water.
According to preparation method of the present invention, preferably, the temperature of reaction of described polyreaction is 70 DEG C-80 DEG C, and more preferably the temperature of reaction of described polyreaction is 80 DEG C.
According to preparation method of the present invention, preferably, the reaction times of described polyreaction is 8-10h, and more preferably the reaction times of described polyreaction is 10h.
In the preparation process of polystyrene 2-butylene acid methyl esters of the present invention, the change of temperature of reaction and time is little on its impact, as long as control temperature of reaction at 70 DEG C-80 DEG C, the reaction times controls at 8-10h.
According to preparation method of the present invention, preferably, described method comprises: first polyvinyl alcohol dissolution in water, add 2-butylene acid methyl esters, vinylbenzene and benzoyl peroxide mixing solutions, be obtained by reacting after having added described polystyrene 2-butylene acid methyl esters.
According to preparation method of the present invention, preferably, described method comprises: first polyvinyl alcohol dissolution in 70 DEG C of-80 DEG C of hot water, then add 2-butylene acid methyl esters, vinylbenzene and benzoyl peroxide mixing solutions.
According to preparation method of the present invention, preferably, described method comprises: first polyvinyl alcohol dissolution in water, be warmed up to 70 DEG C-80 DEG C constant temperature 20-30min, then add 2-butylene acid methyl esters, vinylbenzene and benzoyl peroxide mixing solutions.
According to preparation method of the present invention, preferably, dropping is incorporated as described in; More preferably, the speed of dropping is that 5-10 drips/min, and rate of addition is too fast easily causes sticky still.
According to preparation method of the present invention, preferably, described method also comprises: after being obtained by reacting described polystyrene 2-butylene acid methyl esters, be cooled to room temperature discharging again.
Present invention also offers the polystyrene 2-butylene acid methyl esters prepared by the preparation method of above-mentioned polystyrene 2-butylene acid methyl esters.
Present invention also offers above-mentioned polystyrene 2-butylene acid methyl esters in the application preparing horizontal well produce oil profile monitoring tracer agent.
According to application of the present invention; in multistage fracturing process; different types of solid oil dissolubility tracer particles is mixed in every section of fracturing propping agents; along with the output of crude oil; solid oil dissolubility tracer particles can constantly be dissolved in crude oil; by analyzing the concentration of tracer agent in production fluid, just can reach and analyzing every section of produce oil situation and the object of drawing every section of produce oil liquid section.
Present invention also offers a kind of horizontal well produce oil profile monitoring tracer agent, this tracer agent comprises above-mentioned polystyrene 2-butylene acid methyl esters.
The horizontal well produce oil profile monitoring tracer agent prepared by polystyrene 2-butylene acid methyl esters of the present invention is oil soluble tracer agent, and it can be dissolved in crude oil completely, and when concentration is low, accuracy of detection is high, and consumption is low.In multistage fracturing process, every section is mixed into different types of solid oil dissolubility tracer particles in fracturing propping agents, along with the output of crude oil, solid oil dissolubility tracer particles is constantly dissolved in crude oil, by analyzing the concentration of polystyrene 2-butylene acid methyl esters tracer agent in production fluid, can reach and analyze every section of produce oil situation and the object of drawing every section of produce oil liquid section.
Embodiment
The beneficial effect of implementation process of the present invention and generation will be explained by specific embodiment below, be intended to help reader to understand essence of the present invention and feature better, but not as can the restriction of practical range to this case.
Embodiment 1
Present embodiments provide the preparation method of a kind of polystyrene 2-butylene acid methyl esters, it comprises the following steps:
A, be dissolved in 80 DEG C of hot water of 55g by 0.1g polyvinyl alcohol (mean polymerisation degree is 2400-2500), constant temperature 30min, obtains the aqueous solution of polyvinyl alcohol;
B, again with 5-10 drip/speed of min drips the mixing solutions of 2-butylene acid methyl esters, the vinylbenzene of 4.5g and the benzoyl peroxide of 0.6g of 40g in the aqueous solution of above-mentioned polyvinyl alcohol, be added dropwise to complete rear reaction 10h, be down to room temperature discharging, obtain described polystyrene 2-butylene acid methyl esters, the particle diameter of this polystyrene 2-butylene acid methacrylate particles is 0.300mm-0.600mm (30 order-50 order).
Embodiment 2
Present embodiments provide the preparation method of a kind of polystyrene 2-butylene acid methyl esters, it comprises the following steps:
A, be dissolved in 80 DEG C of hot water of 65g by 0.15g polyvinyl alcohol (mean polymerisation degree is 2400-2500), constant temperature 30min, obtains the aqueous solution of polyvinyl alcohol;
B, again with 5-10 drip/speed of min drips the mixing solutions of 2-butylene acid methyl esters, the vinylbenzene of 4g and the benzoyl peroxide of 0.5g of 30g in the aqueous solution of above-mentioned polyvinyl alcohol, be added dropwise to complete rear reaction 10h, be down to room temperature discharging, obtain described polystyrene 2-butylene acid methyl esters, the particle diameter of this polystyrene 2-butylene acid methacrylate particles is 0.250mm-0.425mm (40 order-60 order).
Embodiment 3
Present embodiments provide the preparation method of a kind of polystyrene 2-butylene acid methyl esters, it comprises the following steps:
A, be dissolved in 80 DEG C of hot water of 75g by 0.2g polyvinyl alcohol (mean polymerisation degree is 2400-2500), constant temperature 30min, obtains the aqueous solution of polyvinyl alcohol;
B, again with 5-10 drip/speed of min drips the mixing solutions of 2-butylene acid methyl esters, the vinylbenzene of 3g and the benzoyl peroxide of 0.4g of 20g in the aqueous solution of above-mentioned polyvinyl alcohol, be added dropwise to complete rear reaction 10h, be down to room temperature discharging, obtain described polystyrene 2-butylene acid methyl esters, the particle diameter of this polystyrene 2-butylene acid methacrylate particles is 0.212mm-0.300mm (50 order-70 order).
Embodiment 4
Present embodiments provide polystyrene 2-butylene acid methyl esters that above-described embodiment 1, embodiment 2 and embodiment 3 prepare in the application preparing horizontal well produce oil profile monitoring tracer agent, this application process can each section of produce oil situation after level monitoring well multistage fracturing, and it comprises the following steps:
Polystyrene 2-butylene acid methyl esters oil soluble tracer agent 0.1g embodiment 1, embodiment 2 and embodiment 3 prepared respectively is dissolved in 100g emerging buried hill block crude oil, be warmed up to 70 DEG C to make tracer agent dissolution rate raising in a solvent, shorten evaluation time, after polystyrene 2-butylene acid methyl esters oil soluble tracer agent dissolves mix completely, get the above-mentioned mixed solution of 1g, sherwood oil is used to dilute 20 times, use the content of polystyrene 2-butylene acid methyl esters oil soluble tracer agent in gas chromatograph-mass spectrometer working sample again, test result is as shown in table 1.
The measurement result of polystyrene 2-butylene acid methyl esters in table 1 sample
Claims (10)
1. the preparation method of a polystyrene 2-butylene acid methyl esters, wherein, described method comprises with vinylbenzene and 2-butylene acid methyl esters for reaction monomers, under the existence of polyvinyl alcohol and benzoyl peroxide, be that dispersion medium carries out polyreaction with water, obtain described polystyrene 2-butylene acid methyl esters.
2. preparation method according to claim 1, wherein, the whole material gross weights added in reaction are for 100%, institute adds each weight of material per-cent and is respectively: 2-butylene acid methyl esters is 20wt%-45wt%, vinylbenzene is 2.5wt%-5wt%, polyvinyl alcohol is 0.1wt%-0.2wt%, benzoyl peroxide is 0.2wt%-0.9wt%, and surplus is water.
3. preparation method according to claim 1 and 2, wherein, the temperature of reaction of described polyreaction is 70 DEG C-80 DEG C.
4. preparation method according to claim 1 and 2, wherein, the reaction times of described polyreaction is 8-10h.
5. preparation method according to claim 1 and 2, wherein, described method comprises: first polyvinyl alcohol dissolution in water, add 2-butylene acid methyl esters, vinylbenzene and benzoyl peroxide mixing solutions, be obtained by reacting after having added described polystyrene 2-butylene acid methyl esters;
Dropping is incorporated as preferably; More preferably the speed dripped is that 5-10 drips/min.
6. preparation method according to claim 5, wherein, described method comprises: first polyvinyl alcohol dissolution in 70 DEG C of-80 DEG C of hot water, then add 2-butylene acid methyl esters, vinylbenzene and benzoyl peroxide mixing solutions.
7. preparation method according to claim 5, wherein, described method comprises: first polyvinyl alcohol dissolution in water, be warmed up to 70 DEG C-80 DEG C constant temperature 20-30min, then add 2-butylene acid methyl esters, vinylbenzene and benzoyl peroxide mixing solutions.
8. described in any one of claim 1-7 polystyrene 2-butylene acid methyl esters preparation method prepare polystyrene 2-butylene acid methyl esters.
9. polystyrene 2-butylene acid methyl esters according to claim 8 is in the application preparing horizontal well produce oil profile monitoring tracer agent.
10. a horizontal well produce oil profile monitoring tracer agent, wherein, this tracer agent comprises polystyrene 2-butylene according to claim 8 acid methyl esters.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110114437A (en) * | 2016-11-07 | 2019-08-09 | 沙特阿拉伯石油公司 | Polymer tracer and the detection method for using pyrolysis |
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| US2276596A (en) * | 1937-03-23 | 1942-03-17 | Stanley Herbert Muggleton | Polymerization of styrene and its homologs |
| CN101314624A (en) * | 2008-05-21 | 2008-12-03 | 安徽省电力公司合肥供电公司 | High oil suction resin and uses thereof |
| CN103752289A (en) * | 2014-01-26 | 2014-04-30 | 福州大学 | Organic solvent absorbing agent and preparation method thereof |
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Cited By (3)
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| CN110114437A (en) * | 2016-11-07 | 2019-08-09 | 沙特阿拉伯石油公司 | Polymer tracer and the detection method for using pyrolysis |
| US11092003B2 (en) | 2016-11-07 | 2021-08-17 | Saudi Arabian Oil Company | Polymeric tracers |
| CN110114437B (en) * | 2016-11-07 | 2021-12-10 | 沙特阿拉伯石油公司 | Polymeric tracers and detection methods using pyrolysis |
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| CN105175613B (en) | 2017-11-10 |
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