CN105085760B - A kind of polystyrene vinyl benzoic acid ester and its synthetic method and application - Google Patents
A kind of polystyrene vinyl benzoic acid ester and its synthetic method and application Download PDFInfo
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- CN105085760B CN105085760B CN201510423463.3A CN201510423463A CN105085760B CN 105085760 B CN105085760 B CN 105085760B CN 201510423463 A CN201510423463 A CN 201510423463A CN 105085760 B CN105085760 B CN 105085760B
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- benzoic acid
- acid ester
- vinyl benzoic
- styrene
- polyethylene glycol
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Abstract
The present invention provides a kind of polystyrene vinyl benzoic acid ester and its synthetic method and applications.The polystyrene vinyl benzoic acid ester of the present invention is prepared by the method included the following steps：Using vinyl benzoic acid ester and styrene as reaction monomers, in the presence of dispersant polyethylene glycol and initiator azodiisobutyronitrile, suspension polymerization is carried out by decentralized medium of water.The polystyrene vinyl benzoic acid ester of the present invention has the following advantages that：Test result shows that the polystyrene vinyl benzoic acid ester that synthetic method using the present invention is produced can be completely dissolved in crude oil, by gas chromatograph-mass spectrometer can Accurate Determining its concentration, dosage is few, meets the needs of horizontal well oil-producing profile monitoring.
Description
Technical field
The present invention relates to oil exploration and development fields, specifically, be related to a kind of polystyrene vinyl benzoic acid ester and
Its synthetic method and application.
Background technology
At present during In Oil Field Exploration And Development, prospect pit uses horizontal well more, and multi-layer multi-stage pressure break is stratum transformation
Preferred technique, but layer position select during, be all to select to be layered by experience without specific aim, thus for pressure break after
Data acquisition and issuance fracturing effect be just particularly important.In the prior art, the prisons such as micro seismic method, potentiometry can be passed through
Fracture intensity after pressure break is surveyed and analyzed, whether has commercial oil, but for staged fracturing by the row's of returning situation awareness reservoir
Each section of oil-producing situation does not have effective monitoring method afterwards.
Multistage fracturing technique building technology and corollary equipment are ripe, have realized 30 grades of pressure breaks, largest domestic in the world
Pressure break series is more than 15 grades.Since pressure break series is more, long horizontal sections physical property has differences in addition, drain feelings after every grade of pressure break
Condition has great importance for the evaluation of fracturing effect and next step well site deployment, but for each section after staged fracturing of oil-producing
Situation does not have effective monitoring method.To solve the technical problem, during multistage fracturing, every section is mixed in fracturing propping agents
Enter different types of solid oil-soluble tracer particles, be constantly dissolved in original with the output solid oil-soluble tracer particles of crude oil
In oil, by analyzing the concentration of tracer in production fluid, reach the mesh that every section of oil-producing situation of analysis draws every section of oil-producing liquid section
's.Since current largest domestic pressure break series is more than 15 grades, mutually in requisition for 15 kinds of level above well oil-producing profile monitorings
Use tracer.
Previous oil field is water solubility with tracer, and to lack dosage big for type, is not suitable for horizontal well multi-layer multi-stage pressure
The monitoring of rear each section of oil-producing situation is split, tracer of the present invention is oil-soluble, and accuracy of detection is high when concentration is low, and dosage is low.
During multistage fracturing, every section is mixed into different types of solid oil-soluble tracer particles in fracturing propping agents, with original
The output solid oil-soluble tracer particles of oil are constantly dissolved in crude oil, by analyzing the concentration of tracer in production fluid, are reached
Analyze the purpose that every section of oil-producing situation draws every section of oil-producing liquid section.
Invention content
It is an object of the present invention to provide a kind of synthetic methods of polystyrene vinyl benzoic acid ester；
The polystyrene vinyl benzoic acid ester being prepared another object of the present invention is to provide the synthetic method；
It is still another object of the present invention to provide the polystyrene vinyl benzoic acid esters to prepare horizontal well oil-producing
The application of profile monitoring tracer；
Another object of the present invention is to provide the horizontal well oil-producing containing the polystyrene vinyl benzoic acid ester
Profile monitoring tracer.
In order to achieve the above object, on the one hand, the present invention provides a kind of synthetic method of polystyrene vinyl benzoic acid ester,
The method includes using vinyl benzoic acid ester and styrene as reaction monomers, existing in polyethylene glycol and azodiisobutyronitrile
Under, carry out polymerisation by decentralized medium of water.
Polyethylene glycol therein is dispersant, and azodiisobutyronitrile is initiator.
Wherein described vinyl benzoic acid ester (CH2CHOCOC6H5), azodiisobutyronitrile (C8H12N4), styrene (C8H8)
With polyethylene glycol (HO (CH2CH2O) nH) for this field conventional reagent, any commercially available vinyl benzoic acid ester commonly used in the art,
Azodiisobutyronitrile, styrene and polyethylene glycol may be used to the present invention.
According to some preferred embodiments of the invention, the polyethylene glycol is the poly- of viscosity average molecular weigh 3600-4400
Ethylene glycol.
According to some preferred embodiments of the invention, in the synthetic method, to react the whole objects added in
Total weight is expected for 100% meter, and adding in each weight of material percentage is respectively：Vinyl benzoic acid ester is 25-45%, styrene
It is 50-70% for 2.5-5%, polyethylene glycol 0.1-0.2%, azodiisobutyronitrile 0.2-0.9% and water.
According to some of the invention preferred embodiments, the reaction temperature of polymerisation of the present invention can be 60 DEG C~
70℃；Wherein it is preferably 65 DEG C.
According to some preferred embodiments of the invention, the reaction time of the polymerisation can be 8-10h；It is wherein excellent
It is selected as 8h.
According to some of the invention preferred embodiments, the method includes：Polyethylene glycol is dissolved into water first, is added
Enter the mixed solution of vinyl benzoic acid ester, styrene and azodiisobutyronitrile, the polyphenyl second is obtained by the reaction after the completion of adding in
Alkene vinyl benzoic acid ester.
According to some of the invention preferred embodiments, the method includes：First polyethylene glycol be dissolved into 60 DEG C~
In 70 DEG C of water, the mixed solution of vinyl benzoic acid ester, styrene and azodiisobutyronitrile is added.
According to some of the invention preferred embodiments, the method includes：Polyethylene glycol is dissolved into water first, is risen
Temperature adds the mixed solution of vinyl benzoic acid ester, styrene and azodiisobutyronitrile to 60 DEG C~70 DEG C constant temperature 30min.
According to some of the invention preferred embodiments, the method includes：Polyethylene glycol is dissolved into water first, is risen
Temperature adds the mixed solution of vinyl benzoic acid ester, styrene and azodiisobutyronitrile to 65 DEG C of constant temperature 30min.
It is described to be incorporated as being added dropwise according to some preferred embodiments of the invention；
According to some preferred embodiments of the invention, the speed of the dropwise addition is 5-10 drops/min.
According to some preferred embodiments of the invention, the method further includes：The polystyrene second is being obtained by the reaction
After enyl benzoate, it is cooled to room temperature and discharges again.
The present invention provides a kind of synthetic method of oil-soluble tracer polystyrene vinyl benzoic acid ester, with weight percent
Than meter, 0.1%~0.2% polyethylene glycol is dissolved into 50%~70% hot water first, is warming up to 60 DEG C~70 DEG C perseverances
Warm 30min, with per minute 5~10 drop speed be added dropwise 25%~45% vinyl benzoic acid ester, 2.5%~5% styrene and
The mixed solution of 0.5%~1% azodiisobutyronitrile reacts 8h~10h after being added dropwise to complete, be cooled to room temperature discharging.
On the other hand, the present invention also provides the polystyrene second that synthetic method described in any one of the present invention is prepared
Enyl benzoate.
In another aspect, it is cutd open the present invention also provides the polystyrene vinyl benzoic acid ester preparing horizontal well oil-producing
The application of face monitoring tracer.
Another aspect, the present invention also provides the horizontal well oil-producings containing the polystyrene vinyl benzoic acid ester to cut open
Face monitoring tracer.
In conclusion the present invention provides a kind of polystyrene vinyl benzoic acid ester and its synthetic method and applications.This
The polystyrene vinyl benzoic acid ester of invention has the following advantages that：
Test result shows that the polystyrene vinyl benzoic acid ester that synthetic method using the present invention is produced can be complete
Be dissolved into crude oil, by gas chromatograph-mass spectrometer can Accurate Determining its concentration, dosage is few, meets horizontal well oil-producing profile monitoring
It needs.
Specific embodiment
Below by way of the specific embodiment implementation process that the present invention will be described in detail and the advantageous effect generated, it is intended to which help is read
Reader more fully understand the present invention essence and feature, not as to this case can practical range restriction.
Embodiment 1
0.1g polyethylene glycol (PEG4000 average molecular weight 3600~4400) is dissolved into the hot water of 50g, is warming up to 65
The mixed solution of 45g vinyl benzoic acids ester, 4.5g styrene and 0.9g azodiisobutyronitriles is slowly added dropwise in DEG C constant temperature 30min,
8h is reacted after being added dropwise to complete, is cooled to room temperature discharging.
Embodiment 2：
0.15g polyethylene glycol (PEG4000 average molecular weight 3600~4400) is dissolved into the hot water of 60g, is warming up to
65 DEG C of constant temperature 30min, the mixing that 35g vinyl benzoic acids ester, 3.5g styrene and 0.65g azodiisobutyronitriles is slowly added dropwise are molten
Liquid reacts 8h after being added dropwise to complete, and is cooled to room temperature discharging.
Embodiment 3：
0.2g polyethylene glycol (PEG4000 average molecular weight 3600~4400) is dissolved into the hot water of 70g, is warming up to 65
DEG C constant temperature 30min, the mixing that 25g vinyl benzoic acids ester, 2.5g styrene and 0.35g azodiisobutyronitriles is slowly added dropwise are molten
Liquid reacts 8h after being added dropwise to complete, and is cooled to room temperature discharging.
Application examples 1
0.1g polystyrene vinyl benzoic acid esters prepared by embodiment 1 are dissolved in 100g crude oil, 70 DEG C is warming up to and treats
It is completely dissolved and 1g is taken to dilute 20 times with petroleum ether after mixing, with polystyrene vinyl benzene in gas chromatograph-mass spectrometer determination sample
Formic acid ester content, test result are shown in Table 1.
Polystyrene vinyl benzoic acid ester measurement result in 1 sample of table
Claims (8)
1. polystyrene vinyl benzoic acid ester is in the application for preparing horizontal well oil-producing profile monitoring tracer, the polyphenyl second
The synthetic method of alkene vinyl benzoic acid ester is included using vinyl benzoic acid ester and styrene as reaction monomers, in polyethylene glycol and
In the presence of azodiisobutyronitrile, polymerisation is carried out by decentralized medium of water, using react whole material total weights for being added in as
100% meter, adding in each weight of material percentage is respectively：Vinyl benzoic acid ester is 25-45%, styrene 2.5-5%,
Polyethylene glycol is 0.1-0.2%, azodiisobutyronitrile 0.2-0.9% and water are 50-70%.
2. application according to claim 1, which is characterized in that the reaction temperature of the polymerisation is 60 DEG C~70 DEG C.
3. application according to claim 1, which is characterized in that the reaction time of the polymerisation is 8-10h.
4. application according to claim 1, which is characterized in that the method includes：Polyethylene glycol is dissolved into water first
In, the mixed solution of vinyl benzoic acid ester, styrene and azodiisobutyronitrile is added in, is obtained by the reaction after the completion of adding in described poly-
Styrene ethylene yl benzoic acid ester.
5. application according to claim 4, which is characterized in that described to be incorporated as being added dropwise.
6. application according to claim 5, which is characterized in that the speed of dropwise addition is 5-10 drops/min.
7. application according to claim 4, which is characterized in that the method includes：Polyethylene glycol is dissolved into 60 first
DEG C~70 DEG C of water in, add the mixed solution of vinyl benzoic acid ester, styrene and azodiisobutyronitrile.
8. application according to claim 4, which is characterized in that the method includes：Polyethylene glycol is dissolved into water first
In, 60 DEG C~70 DEG C constant temperature 20-30min are warming up to, add the mixed of vinyl benzoic acid ester, styrene and azodiisobutyronitrile
Close solution.
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Citations (5)
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| CN1396247A (en) * | 1997-01-31 | 2003-02-12 | 三井化学株式会社 | Lubricating oil compatibility improver containing alpha-olefin/aromatic vinyl compound atatic copolymer |
| WO2006096331A1 (en) * | 2005-03-07 | 2006-09-14 | S. C. Johnson & Son, Inc. | Thickened bleach compositions |
| CN103709274A (en) * | 2013-12-11 | 2014-04-09 | 中国科学院过程工程研究所 | Hydrophilic modification method of polystyrene material, and product thereof |
| CN103752289A (en) * | 2014-01-26 | 2014-04-30 | 福州大学 | Organic solvent absorbing agent and preparation method thereof |
| CN104018822A (en) * | 2014-05-23 | 2014-09-03 | 中国石油化工股份有限公司江汉油田分公司采油工艺研究院 | Oil well staged fracturing effect monitoring method |
-
2015
- 2015-07-17 CN CN201510423463.3A patent/CN105085760B/en active Active
Patent Citations (5)
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|---|---|---|---|---|
| CN1396247A (en) * | 1997-01-31 | 2003-02-12 | 三井化学株式会社 | Lubricating oil compatibility improver containing alpha-olefin/aromatic vinyl compound atatic copolymer |
| WO2006096331A1 (en) * | 2005-03-07 | 2006-09-14 | S. C. Johnson & Son, Inc. | Thickened bleach compositions |
| CN103709274A (en) * | 2013-12-11 | 2014-04-09 | 中国科学院过程工程研究所 | Hydrophilic modification method of polystyrene material, and product thereof |
| CN103752289A (en) * | 2014-01-26 | 2014-04-30 | 福州大学 | Organic solvent absorbing agent and preparation method thereof |
| CN104018822A (en) * | 2014-05-23 | 2014-09-03 | 中国石油化工股份有限公司江汉油田分公司采油工艺研究院 | Oil well staged fracturing effect monitoring method |
Non-Patent Citations (2)
| Title |
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| Chirality Induction in Cyclocopolymerization of Bis(p-viny1benzoate)s of Carbohydrates With Styrene: Chiroptical Study of Resulting Polymer by Exciton Chirality Method;OSAMU HABA 等;《Chirality》;19950203;第7卷(第4期);第194-195页 * |
| 分子量规整聚p-乙烯基苯甲酸及苯乙烯p-乙烯基苯甲酸两嵌段共聚物的合成;魏柳荷等;《高分子学报》;20020228;第1卷(第1期);第123-126页 * |
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