CN103614124B - A kind of delayed cross-linking deep electrical structure and preparation method thereof - Google Patents

A kind of delayed cross-linking deep electrical structure and preparation method thereof Download PDF

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CN103614124B
CN103614124B CN201310581760.1A CN201310581760A CN103614124B CN 103614124 B CN103614124 B CN 103614124B CN 201310581760 A CN201310581760 A CN 201310581760A CN 103614124 B CN103614124 B CN 103614124B
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phenol
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cyclodextrin
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CN103614124A (en
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徐斌
杨欢
张永刚
魏开鹏
斯容
刘学全
卢榆林
刘岳龙
蒋成龙
徐亚丽
董芳
杨秀艳
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Engineering Technology Research Institute Of North China Branch china Petroleum & Chemical Corp
China Petroleum and Chemical Corp
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Abstract

The invention discloses a kind of delayed cross-linking deep electrical structure and preparation method thereof, belong to technical field of oilfield chemistry.This deep electrical structure is made up of the component of following mass concentration: hydrophobic association polyacrylamide 0.1 ~ 1.0%, cyclodextrin/phenol clathrate 0.1 ~ 1.0%, urotropine 0.1 ~ 0.5%, citric acid 0.1 ~ 0.4%, and solvent is water.Wherein, hydrophobic association polyacrylamide is a kind of novel water-soluble polyacrylamide, there is critical association concentration, after polymer concentration is greater than critical association concentration, hydrophobic grouping generation Interpolymer Association causes soltion viscosity to increase considerably and presents good heatproof, salt tolerant, the performance such as anti-shearing.The present invention is by the competitive inclusion effect slow releasing phenol of hydrophobic grouping Pyrogentisinic Acid in hydrophobic association polyacrylamide, can effective dela yed crosslink time, gelation time can regulate and control simultaneously, thus selectively carries out deep profile controlling to high permeable cement, macropore and crack etc.

Description

A kind of delayed cross-linking deep electrical structure and preparation method thereof
Technical field
The present invention is specifically related to a kind of delayed cross-linking deep electrical structure, and the preparation method of this amendment, belongs to technical field of oilfield chemistry.
Background technology
At home and abroad in oil and water well profile control technique, common concern crosslinked polymer gel technique, mix on ground with linking agent by polymers soln, be mixed with single liquid profile control working fluid and inject earth formation deep with heavy dose, polymkeric substance and linking agent are slowly cross-linked to form and have cancellated polymer gel under formation conditions, so as to shutoff Thief zone high permeability formation and macropore.
The main component of gel profile-controlling system is polymkeric substance and linking agent.Polymkeric substance conventional at present has xanthan gum and polyacrylamide.Linking agent one class is phenols, water soluble phenol resin, terpolycyantoamino-formaldehyde resin, phenol-amine resin etc., and another kind of is transition metal organic crosslinking agent, mainly Al + 3, Cr 3+, Zr 4+formed on metal and suitable intercalating agent.
Chinese patent (application number: the water plugging profile control agent 201210000833.9) disclosing a kind of high temperature resistant high salinity, (molecular weight is 1500 ~ 3,000 ten thousand to comprise polyacrylamide, degree of hydrolysis is 15 ~ 30%), multiple crosslinking agent, cyclodextrin, mphenylenediamine and oxygen scavenger (as thiocarbamide), wherein multiple crosslinking agent is made up of aldehydes (as the one in phenyl aldehyde, paraformaldehyde or arbitrary combination), phenols (as the one in phenol, Resorcinol, Resorcinol or arbitrary combination) and Tiorco 677.The crosslinking ability of this water plugging profile control agent is strong, and high temperature resistant high salinity, has permanent stability, and resistance to local water washes away required intensity for a long time.But the ability of its delayed cross-linking is very limited, be unsuitable for carrying out deep profile controlling to high permeable cement, macropore and crack etc.
Summary of the invention
The object of this invention is to provide a kind of delayed cross-linking deep electrical structure.
Meanwhile, the present invention also provides a kind of preparation method of delayed cross-linking deep electrical structure.
In order to realize above object, the technical solution adopted in the present invention is:
A kind of delayed cross-linking deep electrical structure, be made up of the component of following mass concentration: hydrophobic association polyacrylamide 0.1 ~ 1.0%, cyclodextrin/phenol clathrate 0.1 ~ 1.0%, urotropine 0.1 ~ 0.5%, citric acid 0.1 ~ 0.4%, solvent is water.
The molecular weight of described hydrophobic association polyacrylamide is 2.0 × 10 6~ 1.0 × 10 7, degree of hydrolysis is 25 ~ 30%.In hydrophobic association polyacrylamide molecule, the mol ratio of hydrophobic grouping and phenol is (1 ~ 2): 1; Hydrophobic grouping (as alkylphenol polyoxyethylene, OP-10, OP-20 etc.) is greater than the Inclusion constant of phenol and cyclodextrin with the Inclusion constant of cyclodextrin.
Described cyclodextrin/phenol clathrate cyclodextrin and the mol ratio of phenol are 1:(1 ~ 2).
Described hydrophobic association polyacrylamide can be commercial goods, also can adopt and prepare with the following method:
(1) get acrylamide, hydrophobic monomer and vinylformic acid three kinds of monomers to be added to the water, be 8 ~ 9 by the pH value of NaOH regulator solution, to ensure that vinylformic acid alkalizes as sodium acrylate completely, stirring in atmosphere of inert gases makes hydrophobic monomer dissolve, then stirring 30 ~ 60min clarifies to solution at 25 ~ 65 DEG C of temperature;
(2) add initiator, in atmosphere of inert gases, stirring reaction 1 ~ 24 hour, to obtain final product.
In described step (1), hydrophobic monomer is alkylphenol polyoxyethylene acrylate.Preferred polyoxyethylene octylphenol ether acrylate.
Described alkylphenol polyoxyethylene acrylate is commercial goods, and structural formula is shown in following formula 1:
In formula: as m=8, it is polyoxyethylene octylphenol ether acrylate; Now, when n value is 10, commercial disignation is OP-10, n value when being 20, and commercial disignation is OP-20; By that analogy.
Described polyoxyethylene octylphenol ether acrylate can be adopted and prepare with the following method, comprises the following steps: get polyoxyethylene octylphenol ether and toluene, and reflux divides water 1 ~ 12 hour, to without globule wall built-up, is cooled to 50 ~ 70 DEG C; Add vinylformic acid, catalyzer and stopper, reflux divides water 6 ~ 12h, removes toluene and excessive vinylformic acid and get final product after cooling.
Described catalyzer is benzene methanesulfonic acid; Stopper is Resorcinol.Wherein, polyoxyethylene octylphenol ether and acrylic acid mol ratio are (0.95 ~ 1): 1; Toluene accounts for 60 ~ 120% of two kinds of monomer total masses; Benzene methanesulfonic acid accounts for 0.1 ~ 1.0% of two kinds of monomer total masses; Resorcinol accounts for 0.01 ~ 0.1% of two kinds of monomer total masses.Removing toluene and excessive vinylformic acid mainly adopt Rotary Evaporators, namely steam toluene and vinylformic acid under vacuum.
In described step (1), acrylamide, hydrophobic monomer and acrylic acid mol ratio are (45 ~ 74): (1 ~ 25): (25 ~ 30).
The mass concentration that in described step (1), three kinds of monomers are total is 5 ~ 30%.
Be stirred in atmosphere of inert gases in described step (1) and carry out, as nitrogen etc.
In described step (2), initiator is Potassium Persulphate and sodium bisulfite; The quality of initiator accounts for 0.05 ~ 0.5% of three kinds of monomer total masses; Potassium Persulphate and sodium bisulfite mol ratio be (1 ~ 2): 1.Potassium Persulphate first adds, and adds sodium bisulfite again after crossing 5 ~ 15min.
In described step (2), atmosphere of inert gases is nitrogen etc.
After reaction, sealing and standing 6 ~ 10h obtains transparent jelly material in described step (2), and fragmentation is placed in acetone soaks 20 ~ 28h and obtain white solid, dry, pulverize to obtain Powdered thick product.Preferably, by soluble in water for thick product, purify 2 ~ 5 times with acetone precipitation, dry, granulation and get final product.
The preparation method of described cyclodextrin/phenol clathrate comprises the following steps:
(1) by mixing soluble in water for cyclodextrin, solution A is obtained for subsequent use;
(2) phenol is dissolved in 70 ~ 80% ethanolic solns, then joining stirring and evenly mixing in solution A, to obtain solution B for subsequent use;
(3) get solution B and leave standstill 30 ~ 60 minutes at 25 ~ 40 DEG C, to guarantee the complete inclusion phenol of cyclodextrin, then be drying to obtain.
Drying in described step (3) comprises depressurized solvent volatilization and freeze-day with constant temperature two steps, and concrete grammar is: at 0.1 ~ 0.5atm pressure, 60 ~ 80 DEG C of temperature, be dried to solvent-free volatilization, then be placed in 40 ~ 50 DEG C of environment freeze-day with constant temperature 20 ~ 28 hours.
Preferably, the mass concentration of the solution B cyclodextrin of described step (2) is 1.6 ~ 2.0g/mL, and the mass concentration of phenol is 0.12 ~ 0.18g/mL.Above-mentioned inclusion method is saturated solution solvent evaporation method.
Described cyclodextrin can be alpha-cylodextrin, beta-cyclodextrin etc., preferred beta-cyclodextrin.
A preparation method for delayed cross-linking deep electrical structure, comprises the following steps: accurately get each component, first that hydrophobic association polyacrylamide is soluble in water, then adds urotropine, citric acid, cyclodextrin/phenol clathrate successively, stirs evenly and get final product.
Hydrophobicity power can represent with lipid, and lipid shows that more greatly the hydrophobicity of this material is stronger.The lipid of phenol is 1.61, for polyoxyethylene octylphenol ether, during n=1, its LogP=4.8, the hydrophobicity often increasing hydrophobic monomer during its LogP of oxyethyl group reduction about 0.16, n≤20 is all better than phenol, and phenol can be guaranteed to replace out from the hydrophobic cavity of cyclodextrin.
Beneficial effect of the present invention:
Hydrophobic association polyacrylamide is a kind of novel water-soluble polyacrylamide, has good heatproof, salt tolerant, the performance such as anti-shearing, can be widely used in the every field of tertiary oil recovery, as the displacement of reservoir oil, profile control and water plugging etc.Hydrophobic association polyacrylamide has critical association concentration in the solution, after polymer concentration is greater than critical association concentration, hydrophobic grouping generation Interpolymer Association causes soltion viscosity to increase considerably and presents good heatproof, salt tolerant, the performance such as anti-shearing.Hydrophobic monomer needed for synthetizing hydrophobic associated polyacrylamide is generally water insoluble, need with tensio-active agent as sodium lauryl sulphate etc. carries out solubilising to it, and vinylformic acid and polyoxyethylene octylphenol ether (OP-10, OP-13, OP-15, OP-20, OP-30 etc.) the polyoxyethylene octylphenol ether acrylate that is obtained by reacting, can with acrylamide, sodium acrylate generation solution polymerization, and in OP-n series, the higher corresponding hydrophobic monomer of ethoxyl content is water-soluble better.
Delayed cross-linking deep electrical structure of the present invention is phenolic resin type gel.Hydrophobic association polyacrylamide and formaldehyde, phenol reactant form phenolic resin gel.In this delayed cross-linking gelling system, formaldehyde is that linking agent urotropine is heated and slowly releases under weak acid environment; Phenol, is slowly released under the competitive inclusion effect of the hydrophobic grouping in hydrophobic association polyacrylamide molecule by inclusion among the hydrophobic cavity of cyclodextrin.In the present invention, the hydrophobic monomer of hydrophobic association polyacrylamide is alkylphenol polyoxyethylene acrylate, and its hydrophobicity is better than phenol, phenol can be replaced out from the hydrophobic cavity of cyclodextrin.In hydrophobic association polyacrylamide solution, after polymer concentration is greater than critical association concentration, hydrophobic grouping is based on Interpolymer Association, after adding cyclodextrin/phenol clathrate, hydrophobic grouping is competed gradually and is entered cyclodextrin hydrophobic cavity and replace out by phenol, thus can reach the object of delayed cross-linking.
In the present invention, delayed cross-linking deep electrical structure is by the competitive inclusion effect slow releasing phenol of hydrophobic grouping Pyrogentisinic Acid in hydrophobic association polyacrylamide, can effective dela yed crosslink time, gelation time can regulate and control simultaneously, thus selectively carries out deep profile controlling to high permeable cement, macropore and crack etc.
The preparation method of delayed cross-linking deep electrical structure of the present invention is simple, easy to operate, is suitable for large-scale industrial production and application.
Accompanying drawing explanation
Fig. 1 is the synthetic route schematic diagram of hydrophobic monomer alkyl polyoxyethylene ether acrylate in the embodiment of the present invention 1;
Fig. 2 is the synthetic route schematic diagram of hydrophobic association polyacrylamide in embodiment 1.
Embodiment
Following embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Embodiment 1
Delayed cross-linking deep electrical structure in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.4g, beta-cyclodextrin/phenol clathrate 0.5g, urotropine 0.4g, citric acid 0.15g, and solvent is 100mL deionized water.
In the present embodiment, the preparation method of delayed cross-linking deep electrical structure comprises the following steps: accurately get each component, first hydrophobic association polyacrylamide is dissolved in deionized water, add urotropine, citric acid, cyclodextrin/phenol clathrate successively again, stirring and dissolving evenly and get final product.
The preparation method of described hydrophobic association polyacrylamide is:
(1) prepare hydrophobic monomer (octyl group Soxylat A 25-7 acrylate): the toluene adding polyoxyethylene octylphenol ether (OP-20) 100g and 100mL in the 250mL there-necked flask that mechanical stirrer, water-and-oil separator, reflux condensing tube are housed, reflux divides water to flask without globule wall built-up; Then reaction solution is cooled to 60 DEG C, again vinylformic acid 10g, catalyzer tosic acid 0.3g and hydroquinone of polymerization retarder 0.03g are added in flask, reflux divides water 8 hours, be cooled to normal temperature, toluene and excessive vinylformic acid is steamed with Rotary Evaporators, obtain orange oily liquids, obtain hydrophobic monomer, synthetic route chart refers to Fig. 1;
(2) get acrylamide, hydrophobic monomer, vinylformic acid three kinds of monomers add in deionized water, wherein acrylamide, hydrophobic monomer and acrylic acid mol ratio are 5:2:3, be 8 by the pH value of the NaOH solution regulator solution of 6mol/L, to ensure that vinylformic acid alkalizes as sodium acrylate completely, be transferred in 250mL there-necked flask, pass into N 2and constantly stirring makes hydrophobic monomer dissolve, then add deionized water to 100mL, the mass concentration making three kinds of monomers is 25%, then there-necked flask is placed in constant temperature water bath, keeps temperature to be 45 DEG C, passes into N 2and stir 60min make solution become clarification;
(3) initiator potassium persulfate and sodium bisulfite are dissolved in 5mL deionized water respectively, wherein the mol ratio of Potassium Persulphate and sodium bisulfite is 1:1, the quality of initiator accounts for 0.5% of three kinds of monomer total masses, with syringe, potassium persulfate solution is injected there-necked flask, reinject after 10min sodium sulfite solution, passes into N 2continuous stirring, stop when mixture becomes sticky stirring, 8h is placed in flask sealing and obtains transparent colloid shape material, taking-up is cut into small pieces, be placed on and soak 24h in excessive acetone and obtain white solid, then be placed in that 45 DEG C of baking ovens are dry, the thick product of powder all to pieces, thick product is dissolved in deionized water, purify 3 times with acetone precipitation, (molecular weight is 3.7 × 10 namely to obtain hydrophobic association polyacrylamide through vacuum-drying, granulation 6).
The preparation method of described beta-cyclodextrin/phenol clathrate is: be dissolved in deionized water by beta-cyclodextrin under normal temperature, and beta-cyclodextrin mass concentration is in the solution 1.8g/100mL; Be dissolved in by phenol in 75% ethanolic soln, then add in beta-cyclodextrin solution, phenol concentration is in the solution 0.15g/100mL, leaves standstill 60min, make the complete inclusion phenol of beta-cyclodextrin after stirring; The solution got after leaving standstill carries out depressurized solvent volatilization, and under temperature 70 C, pressure 0.2atm, be dried to solvent-free volatilization, then be placed in 45 DEG C of thermostat container freeze-day with constant temperature and namely obtain hydrophobic association polyacrylamide in 24 hours, synthetic route chart refers to Fig. 2.In Fig. 2, a, b, c only represent to there is mol ratio between three kinds of monomers, do not affect its molecular order, i.e. lack of alignment between each group in hydrophobic association polyacrylamide.
Embodiment 2
Delayed cross-linking deep electrical structure in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.5g, beta-cyclodextrin/phenol clathrate 0.5g, urotropine 0.2g, citric acid 0.2g, and solvent is 100mL deionized water.
The preparation method of described hydrophobic association polyacrylamide is:
(1) prepare hydrophobic monomer (octyl group Soxylat A 25-7 acrylate): the toluene adding polyoxyethylene octylphenol ether (OP-15) 100g and 100mL in the 250mL there-necked flask that mechanical stirrer, water-and-oil separator, reflux condensing tube are housed, reflux divides water to flask without globule wall built-up; Then reaction solution is cooled to 50 DEG C, again vinylformic acid 10g, catalyzer tosic acid 0.5g and hydroquinone of polymerization retarder 0.05g are added in flask, reflux divides water 12 hours, be cooled to normal temperature, toluene and excessive vinylformic acid is steamed with Rotary Evaporators, obtain orange oily liquids, obtain hydrophobic monomer, synthetic route chart refers to Fig. 1;
(2) get acrylamide, hydrophobic monomer, vinylformic acid three kinds of monomers add in deionized water, wherein acrylamide, hydrophobic monomer and acrylic acid mol ratio are 11:4:5, be 8.5 by the pH value of the NaOH solution regulator solution of 6mol/L, to ensure that vinylformic acid alkalizes as sodium acrylate completely, be transferred in 250mL there-necked flask, pass into N 2and constantly stirring makes hydrophobic monomer dissolve, then add deionized water to 100mL, the mass concentration making three kinds of monomers is 30%, then there-necked flask is placed in constant temperature water bath, keeps temperature to be 65 DEG C, passes into N 2and stir 30min make solution become clarification;
(3) initiator potassium persulfate and sodium bisulfite are dissolved in 5mL deionized water respectively, wherein the mol ratio of Potassium Persulphate and sodium bisulfite is 2:1, the quality of initiator accounts for 0.1% of three kinds of monomer total masses, with syringe, potassium persulfate solution is injected there-necked flask, reinject after 5min sodium sulfite solution, passes into N 2continuous stirring, stop when mixture becomes sticky stirring, 10h is placed in flask sealing and obtains transparent colloid shape material, taking-up is cut into small pieces, be placed on and soak 24h in excessive acetone and obtain white solid, then be placed in that 50 DEG C of baking ovens are dry, the thick product of powder all to pieces, thick product is dissolved in deionized water, purify 3 times with acetone precipitation, namely obtain hydrophobic association polyacrylamide through vacuum-drying, granulation.
The preparation method of described beta-cyclodextrin/phenol clathrate is: be dissolved in deionized water by beta-cyclodextrin under normal temperature, and beta-cyclodextrin mass concentration is in the solution 1.8g/100mL; Be dissolved in by phenol in 80% ethanolic soln, then add in beta-cyclodextrin solution, phenol concentration is in the solution 0.15g/100mL, leaves standstill 50min, make the complete inclusion phenol of beta-cyclodextrin after stirring; The solution got after leaving standstill carries out depressurized solvent volatilization, is dried to solvent-free volatilization, then is placed in 40 DEG C of thermostat container freeze-day with constant temperature and namely obtains hydrophobic association polyacrylamide in 28 hours under temperature 60 C, pressure 0.3atm.
Embodiment 3
Delayed cross-linking deep electrical structure in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.8g, beta-cyclodextrin/phenol clathrate 0.8g, urotropine 0.5g, citric acid 0.4g, and solvent is 100mL deionized water.
The preparation method of described hydrophobic association polyacrylamide is:
(1) prepare hydrophobic monomer (octyl group Soxylat A 25-7 acrylate): the toluene adding polyoxyethylene octylphenol ether (OP-13) 100g and 100mL in the 250mL there-necked flask that mechanical stirrer, water-and-oil separator, reflux condensing tube are housed, reflux divides water to flask without globule wall built-up; Then reaction solution is cooled to 70 DEG C, again vinylformic acid 10g, catalyzer tosic acid 0.1g and hydroquinone of polymerization retarder 0.01g are added in flask, reflux divides water 6 hours, be cooled to normal temperature, toluene and excessive vinylformic acid is steamed with Rotary Evaporators, obtain orange oily liquids, obtain hydrophobic monomer, synthetic route chart refers to Fig. 1;
(2) get acrylamide, hydrophobic monomer, vinylformic acid three kinds of monomers add in deionized water, wherein acrylamide, hydrophobic monomer and acrylic acid mol ratio are 9:5:6, be 9 by the pH value of the NaOH solution regulator solution of 6mol/L, to ensure that vinylformic acid alkalizes as sodium acrylate completely, be transferred in 250mL there-necked flask, pass into N 2and constantly stirring makes hydrophobic monomer dissolve, then add deionized water to 100mL, the mass concentration making three kinds of monomers is 15%, then there-necked flask is placed in constant temperature water bath, keeps temperature to be 30 DEG C, passes into N 2and stir 60min make solution become clarification;
(3) initiator potassium persulfate and sodium bisulfite are dissolved in 5mL deionized water respectively, wherein the mol ratio of Potassium Persulphate and sodium bisulfite is 1:1, the quality of initiator accounts for 0.3% of three kinds of monomer total masses, with syringe, potassium persulfate solution is injected there-necked flask, reinject after 15min sodium sulfite solution, passes into N 2continuous stirring, stop when mixture becomes sticky stirring, 10h is placed in flask sealing and obtains transparent colloid shape material, taking-up is cut into small pieces, be placed on and soak 20h in excessive acetone and obtain white solid, then be placed in that 40 DEG C of baking ovens are dry, the thick product of powder all to pieces, thick product is dissolved in deionized water, purify 4 times with acetone precipitation, (molecular weight is 3.7 × 10 namely to obtain hydrophobic association polyacrylamide through vacuum-drying, granulation 6).
The preparation method of described beta-cyclodextrin/phenol clathrate is: be dissolved in deionized water by beta-cyclodextrin under normal temperature, and beta-cyclodextrin mass concentration is in the solution 1.8g/100mL; Be dissolved in by phenol in 75% ethanolic soln, then add in beta-cyclodextrin solution, phenol concentration is in the solution 0.15g/100mL, leaves standstill 50min, make the complete inclusion phenol of beta-cyclodextrin after stirring; The solution got after leaving standstill carries out depressurized solvent volatilization, is dried to solvent-free volatilization, then is placed in 50 DEG C of thermostat container freeze-day with constant temperature and namely obtains hydrophobic association polyacrylamide in 20 hours under temperature 80 DEG C, pressure 0.5atm.
Embodiment 4
Delayed cross-linking deep electrical structure in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.6g, beta-cyclodextrin/phenol clathrate 0.5g, urotropine 0.1g, citric acid 0.15g, and solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol clathrate and amendment is with embodiment 1.
Embodiment 5
Delayed cross-linking deep electrical structure in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.9g, beta-cyclodextrin/phenol clathrate 0.9g, urotropine 0.5g, citric acid 0.1g, and solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol clathrate and amendment is with embodiment 1.
Embodiment 6
Delayed cross-linking deep electrical structure in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.7g, beta-cyclodextrin/phenol clathrate 0.7g, urotropine 0.4g, citric acid 0.2g, and solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol clathrate and amendment is with embodiment 1.
Embodiment 7
Delayed cross-linking deep electrical structure in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.1g, beta-cyclodextrin/phenol clathrate 0.1g, urotropine 0.1g, citric acid 0.15g, and solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol clathrate and amendment is with embodiment 1.
Embodiment 8
Delayed cross-linking deep electrical structure in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 1.0g, beta-cyclodextrin/phenol clathrate 1.0g, urotropine 0.5g, citric acid 0.1g, and solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol clathrate and amendment is with embodiment 1.
Embodiment 9
Delayed cross-linking deep electrical structure in the present embodiment is composed of the following components: hydrophobic association polyacrylamide 0.2g, beta-cyclodextrin/phenol clathrate 0.5g, urotropine 0.4g, citric acid 0.2g, and solvent is 100mL deionized water.The preparation method of hydrophobic association polyacrylamide, beta-cyclodextrin/phenol clathrate and amendment is with embodiment 1.
Test example
Delayed cross-linking deep electrical structure prepared by Example 1 ~ 6 carries out gellifying property mensuration, and method is as follows: homogeneous solution prepared by rapid measuring Example 1 ~ 6 proceeds in ampoule, is sealed by ampoule; Investigate its gel time and gel-strength at the ampoule of sealing is placed in 45 DEG C respectively, treatment condition and measurement result as shown in table 1 below, gel-strength code method represents.
The gellifying property of delayed cross-linking gel profile control agent prepared by table 1 embodiment 1 ~ 3
(2) sealing characteristics
At 45 DEG C, the middle gelling system of embodiment 1 is 8.54 μm to rate of permeation 2the sealing ratiod of fill out sand tube is 99.1%, and plugging strength is 4.75MPa/m; Gelling system in embodiment 2 is 6.74 μm to rate of permeation 2the sealing ratiod of fill out sand tube is 99.2%, and plugging strength is 5.14MPa/m.Gelling system in embodiment 3 is 8.65 μm to rate of permeation 2the sealing ratiod of fill out sand tube is 99.5%, and plugging strength is 7.14MPa/m.Gelling system in embodiment 4 is 11.5 μm to rate of permeation 2the sealing ratiod of fill out sand tube is 99.2%, and plugging strength is 5.45MPa/m.Gelling system in embodiment 5 is 9.34 μm to rate of permeation 2the sealing ratiod of fill out sand tube is 99.8%, and plugging strength is 8.56MPa/m.Gelling system in embodiment 6 is 7.13 μm to rate of permeation 2the sealing ratiod of fill out sand tube is 99.4%, and plugging strength is 6.58MPa/m.Carry out displacement test further to above-mentioned six fill out sand tube, experiment confirms that above-mentioned blocking agent system all has very strong erosion resistibility.

Claims (8)

1. a delayed cross-linking deep electrical structure, it is characterized in that: be made up of the component of following mass concentration: hydrophobic association polyacrylamide 0.1 ~ 1.0%, cyclodextrin/phenol clathrate 0.1 ~ 1.0%, urotropine 0.1 ~ 0.5%, citric acid 0.1 ~ 0.4%, solvent is water; The preparation method of described cyclodextrin/phenol clathrate comprises the following steps:
(1) by mixing soluble in water for cyclodextrin, solution A is obtained for subsequent use;
(2) phenol is dissolved in 70 ~ 80% ethanolic solns, then joining stirring and evenly mixing in solution A, to obtain solution B for subsequent use;
(3) get solution B and leave standstill 30 ~ 60 minutes at 25 ~ 40 DEG C, to guarantee the complete inclusion phenol of cyclodextrin, then be drying to obtain.
2. delayed cross-linking deep electrical structure according to claim 1, is characterized in that: the molecular weight of described hydrophobic association polyacrylamide is 2.0 × 10 6~ 1.0 × 10 7, degree of hydrolysis is 25 ~ 30%, and in hydrophobic association polyacrylamide molecule, the mol ratio of hydrophobic grouping and phenol is (1 ~ 2): 1.
3. delayed cross-linking deep electrical structure according to claim 2, is characterized in that: the preparation method of described hydrophobic association polyacrylamide is:
(1) getting acrylamide, hydrophobic monomer and vinylformic acid three kinds of monomers to be added to the water, is 8 ~ 9 by the pH value of NaOH regulator solution, stirs hydrophobic monomer is dissolved in atmosphere of inert gases, then stirring 30 ~ 60min clarifies to solution at 25 ~ 65 DEG C of temperature;
(2) add initiator, in atmosphere of inert gases, stirring reaction 1 ~ 24 hour, to obtain final product.
4. delayed cross-linking deep electrical structure according to claim 3, is characterized in that: in described step (1), acrylamide, hydrophobic monomer and acrylic acid mol ratio are (45 ~ 74): (1 ~ 25): (25 ~ 30).
5. delayed cross-linking deep electrical structure according to claim 3, is characterized in that: in described step (1), hydrophobic monomer is polyoxyethylene octylphenol ether acrylate.
6. delayed cross-linking deep electrical structure according to claim 5, it is characterized in that: the preparation method of described polyoxyethylene octylphenol ether acrylate is: get polyoxyethylene octylphenol ether and toluene, reflux divides water 1 ~ 12 hour, to without globule wall built-up, is cooled to 50 ~ 70 DEG C; Add vinylformic acid, catalyzer and stopper, reflux divides water 6 ~ 12h, removes toluene and excessive vinylformic acid and get final product after cooling.
7. delayed cross-linking deep electrical structure according to claim 3, it is characterized in that: sealing and standing 6 ~ 10h after reaction in described step (2), broken, be placed in acetone and soak 20 ~ 28h, soluble in water again after drying, pulverizing, purify 2 ~ 5 times with acetone precipitation, dry, granulation and get final product.
8. the preparation method of a delayed cross-linking deep electrical structure as claimed in claim 1, it is characterized in that: comprise the following steps: accurately get each component, first that hydrophobic association polyacrylamide is soluble in water, then add urotropine, citric acid, cyclodextrin/phenol clathrate successively, stir evenly and get final product.
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