CN105085806A - Polystyrene butene diacid dibutyl ester, and preparation method and application thereof - Google Patents
Polystyrene butene diacid dibutyl ester, and preparation method and application thereof Download PDFInfo
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- CN105085806A CN105085806A CN201510423122.6A CN201510423122A CN105085806A CN 105085806 A CN105085806 A CN 105085806A CN 201510423122 A CN201510423122 A CN 201510423122A CN 105085806 A CN105085806 A CN 105085806A
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Abstract
The invention provides polystyrene butene diacid dibutyl ester, and a preparation method and application thereof. The preparation method comprises the step of carrying out polymerization reaction with styrene and butene diacid dibutyl ester as reaction monomers and water as a dispersion medium in the presences of polyving akohol and azodiisobutyronitrile so as to obtain the polystyrene butene diacid dibutyl ester. The invention also provides the polystyrene butenediacid dibutyl ester prepared by using the above-mentioned preparation method, application of the polystyrene butene diacid dibutyl ester in preparation of a tracer used for monitoring an oil-production profile of a horizontal well, and the tracer containing the polystyrene butene diacid dibutyl ester and used for monitoring the oil-production profile of the horizontal well. The polystyrene butene diacid dibutyl ester provided by the invention can be completely dissolved in crude oil, is used for monitoring oil-production situations in each section after multistage fracturing of the horizontal well, and can achieve purposes of analyzing the oil-production situations in each section and drawing oil-production profile in each section.
Description
Technical field
The present invention relates to a kind of polystyrene butene dioic acid dibutylester 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
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of preparation method of polystyrene butene dioic acid dibutylester.
The present invention also aims to provide a kind of polystyrene butene dioic acid dibutylester prepared by the preparation method of above-mentioned polystyrene butene dioic acid dibutylester.
The present invention also aims to provide a kind of above-mentioned polystyrene butene dioic acid dibutylester 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 butene dioic acid dibutylester.
For reaching above-mentioned purpose, the invention provides a kind of preparation method of polystyrene butene dioic acid dibutylester, the method comprises with vinylbenzene and butene dioic acid dibutylester for reaction monomers, under the existence of polyvinyl alcohol and Diisopropyl azodicarboxylate, be that dispersion medium carries out polyreaction with water, obtain described polystyrene butene dioic acid dibutylester;
Wherein, polyvinyl alcohol is dispersion agent, and Diisopropyl azodicarboxylate is initiator.
According to preparation method of the present invention, preferably, described butene dioic acid dibutylester comprises dibutyl maleate or dibutyl fumarate;
Also preferred described dibutyl maleate comprises maleic acid two (1-fourth) ester, maleic acid two (2-fourth) ester, maleic acid two (2-methyl isophthalic acid-the third) ester or maleic acid two (2-methyl-2-third) ester;
Described dibutyl fumarate comprises FUMARIC ACID TECH GRADE two (1-fourth) ester, FUMARIC ACID TECH GRADE two (2-fourth) ester, FUMARIC ACID TECH GRADE two (2-methyl isophthalic acid-the third) ester or FUMARIC ACID TECH GRADE two (2-methyl-2-third) ester.
Wherein said butene dioic acid dibutylester ((CHCOOC
4h
9)
2), polyvinyl alcohol ([C
2h
4o] n), vinylbenzene (C
8h
8) and Diisopropyl azodicarboxylate (C
8h
12n
4) being the conventional reagent of this area, conventional butene dioic acid dibutylester, polyvinyl alcohol, vinylbenzene and the Diisopropyl azodicarboxylate in any commercially available this area may be used to the present invention.
The mean polymerisation degree of above-mentioned polyvinyl alcohol 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: butene dioic acid dibutylester 20wt%-45wt%, vinylbenzene 2.5wt%-5wt%, polyvinyl alcohol 0.1wt%-0.2wt%, Diisopropyl azodicarboxylate 0.2wt%-0.9wt%, surplus is water.
According to preparation method of the present invention, preferably, the temperature of reaction of described polyreaction is 80 DEG C-90 DEG C, and more preferably described temperature of reaction is 85 DEG C.
According to preparation method of the present invention, preferably, the reaction times of described polyreaction is 8-10h, and more preferably the described reaction times is 10h.
In the preparation process of polystyrene butene dioic acid dibutylester 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 80 DEG C-90 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 the mixing solutions of butene dioic acid dibutylester, vinylbenzene and Diisopropyl azodicarboxylate, after having added, be obtained by reacting described polystyrene butene dioic acid dibutylester.
According to preparation method of the present invention, preferably, described method comprises: first polyvinyl alcohol dissolution in 80 DEG C of-90 DEG C of hot water, then add the mixing solutions of butene dioic acid dibutylester, vinylbenzene and Diisopropyl azodicarboxylate.
According to preparation method of the present invention, preferably, described method comprises: first polyvinyl alcohol dissolution in water, be warmed up to 80 DEG C-90 DEG C constant temperature 20-30min, then add the mixing solutions of butene dioic acid dibutylester, vinylbenzene and Diisopropyl azodicarboxylate.
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 butene dioic acid dibutylester, be cooled to room temperature discharging again.
Present invention also offers the polystyrene butene dioic acid dibutylester prepared by the preparation method of above-mentioned polystyrene butene dioic acid dibutylester.
Present invention also offers above-mentioned polystyrene butene dioic acid dibutylester 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 butene dioic acid dibutylester.
The horizontal well produce oil profile monitoring tracer agent prepared by polystyrene butene dioic acid dibutylester 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 butene dioic acid dibutylester 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 a kind of preparation method of polystyrene maleic acid two (1-fourth) ester, it comprises the following steps:
A, 0.1g polyvinyl alcohol (mean polymerisation degree is 2400-2500) is dissolved in the hot water of 55g, is warmed up to 85 DEG C of constant temperature 30min, obtains the aqueous solution of polyvinyl alcohol;
B, again with 5-10 drip/speed of min slowly drips the mixing solutions of 40g maleic acid two (1-fourth) ester, 4g vinylbenzene and 0.9g Diisopropyl azodicarboxylate in the aqueous solution of above-mentioned polyvinyl alcohol, be added dropwise to complete rear reaction 10h, be cooled to room temperature discharging, obtain polystyrene maleic acid two (1-fourth) ester, its particle diameter is 0.600mm-0.850mm (20 order-30 order).
Embodiment 2
The present embodiment provides a kind of preparation method of polystyrene maleic acid two (1-fourth) ester, and it comprises the following steps:
A, 0.15g polyvinyl alcohol (mean polymerisation degree is 2400-2500) is dissolved in the hot water of 65g, is warmed up to 85 DEG C of constant temperature 30min, obtains the aqueous solution of polyvinyl alcohol;
B, again with 5-10 drip/speed of min slowly drips the mixing solutions of 30g maleic acid two (1-fourth) ester, 3g vinylbenzene and 0.6g Diisopropyl azodicarboxylate in the aqueous solution of above-mentioned polyvinyl alcohol, be added dropwise to complete rear reaction 10h, be cooled to room temperature discharging, obtain polystyrene maleic acid two (1-fourth) ester, its particle diameter is 0.300mm-0.600mm (30 order-50 order).
Embodiment 3
Present embodiments provide a kind of preparation method of polystyrene maleic acid two (1-fourth) ester, it comprises the following steps:
A, 0.2g polyvinyl alcohol (mean polymerisation degree is 2400-2500) is dissolved in the hot water of 75g, is warmed up to 85 DEG C of constant temperature 30min, obtains the aqueous solution of polyvinyl alcohol;
B, again with 5-10 drip/speed of min slowly drips the mixing solutions of 20g maleic acid two (1-fourth) ester, 2g vinylbenzene and 0.3g Diisopropyl azodicarboxylate in the aqueous solution of above-mentioned polyvinyl alcohol, be added dropwise to complete rear reaction 10h, be cooled to room temperature discharging, obtain polystyrene maleic acid two (1-fourth) ester, its particle diameter is 0.212mm-0.300mm (50 order-70 order).
Embodiment 4
Present embodiments provide polystyrene maleic acid two (1-fourth) ester 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:
Respectively by 0.1g embodiment 1, polystyrene maleic acid two (1-fourth) the ester oil dissolubility tracer agent that embodiment 2 and embodiment 3 prepare 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 maleic acid two (1-fourth) ester oil dissolubility 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 maleic acid two (1-fourth) ester oil dissolubility tracer agent in gas chromatograph-mass spectrometer working sample again, test result is as shown in table 1.
Polystyrene maleic acid two (1-fourth) ester measurement result in table 1 sample
Claims (10)
1. the preparation method of a polystyrene butene dioic acid dibutylester, wherein, described method comprises with vinylbenzene and butene dioic acid dibutylester for reaction monomers, under the existence of polyvinyl alcohol and Diisopropyl azodicarboxylate, be that dispersion medium carries out polyreaction with water, obtain described polystyrene butene dioic acid dibutylester;
Preferred described butene dioic acid dibutylester comprises dibutyl maleate or dibutyl fumarate;
Also preferred described dibutyl maleate comprises maleic acid two (1-fourth) ester, maleic acid two (2-fourth) ester, maleic acid two (2-methyl isophthalic acid-the third) ester or maleic acid two (2-methyl-2-third) ester;
Described dibutyl fumarate comprises FUMARIC ACID TECH GRADE two (1-fourth) ester, FUMARIC ACID TECH GRADE two (2-fourth) ester, FUMARIC ACID TECH GRADE two (2-methyl isophthalic acid-the third) ester or FUMARIC ACID TECH GRADE two (2-methyl-2-third) ester.
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: butene dioic acid dibutylester is 20wt%-45wt%, vinylbenzene is 2.5wt%-5wt%, polyvinyl alcohol is 0.1wt%-0.2wt%, Diisopropyl azodicarboxylate 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 80 DEG C-90 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 the mixing solutions of butene dioic acid dibutylester, vinylbenzene and Diisopropyl azodicarboxylate, after having added, be obtained by reacting described polystyrene butene dioic acid dibutylester;
Dropping is incorporated as preferably; The speed of preferred dropping is that 5-10 drips/min.
6. preparation method according to claim 5, wherein, described method comprises: first polyvinyl alcohol dissolution in 80 DEG C of-90 DEG C of hot water, then add the mixing solutions of butene dioic acid dibutylester, vinylbenzene and Diisopropyl azodicarboxylate.
7. preparation method according to claim 5, wherein, described method comprises: first polyvinyl alcohol dissolution in water, be warmed up to 80 DEG C-90 DEG C constant temperature 20-30min, then add the mixing solutions of butene dioic acid dibutylester, vinylbenzene and Diisopropyl azodicarboxylate.
8. the polystyrene butene dioic acid dibutylester that the preparation method of the polystyrene butene dioic acid dibutylester described in any one of claim 1-7 prepares.
9. polystyrene butene dioic acid dibutylester 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 butene dioic acid dibutylester according to claim 8.
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| DE1795845A1 (en) * | 1964-06-27 | 1976-11-25 | Texaco Ag | METHOD FOR MANUFACTURING THERMOPLASTIC COPOLYMERIZES FROM STYRENE AND FUMAR ACID ESTERS OF SECONDARY ALCOHOLS |
| JPS5197661A (en) * | 1975-02-25 | 1976-08-27 | BINIRUKEIKYOJUGOTAINO ZORYUHOHO | |
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