CN110669488B - Preparation method and application of double-braid polymer surfactant containing aromatic group - Google Patents
Preparation method and application of double-braid polymer surfactant containing aromatic group Download PDFInfo
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Abstract
The invention provides a preparation method and application of a double-braid polymer surfactant containing an aromatic group. The surfactant has a structure shown in the following formula (I); in the formula (I), x/(x + y + z) x 100% is 0.1-0.5%, y/(x + y + z) x 100% is 90.8-93.3%, and z/(x + y + z) x 100% is 6.6-8.7%; r1And R2Each independently selected from hydrogen atom or C1～C20Linear or branched alkyl of (a); n is 1-30; the polymer provided by the invention has good interfacial activity, and can form a stable oil-in-water emulsion from thick oil under the condition of low shearing of stratum, thereby realizing the purpose of viscosity reduction:
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a double-braid polymer surfactant as well as a preparation method and application thereof, and more particularly relates to a double-braid polymer surfactant containing diaryl groups as well as a preparation method and application thereof.
Background
The heavy oil development method comprises thermal recovery (steam stimulation, steam flooding, in-situ combustion, SAGD) and cold recovery (water flooding), the water flooding heavy oil reserves in China account for 30.1% of the total reserve of the heavy oil, the water flooding heavy oil yield accounts for 18% of the total yield of the heavy oil, and the heavy oil water flooding recovery ratio is only 5-30% (the thin oil water flooding recovery ratio is 40%) due to high viscosity of the heavy oil and severe reservoir heterogeneity.
In order to improve the recovery efficiency of thick oil water flooding, people use conventional crude oil (thin oil) recovery efficiency improving technologies, which mainly comprise polymer flooding, surfactant flooding (viscosity reducing agent flooding), compound flooding, gas flooding and the like. The indoor research has made a great progress, and the Yan Wenhua research shows that (contemporary chemical industry, 2017, 46 (8): 1553-1555) the polymer flooding improves the recovery rate by 7.04 percent on the basis of water flooding (recovery rate is 17.04 percent). The Chinese invention patent 201410553381.6 discloses a thickened oil emulsifying viscosity reducer, which is a compound system of anionic and nonionic surfactants, and has viscosity reduction rate of more than 99% for thickened oil. The US patent US 4237018A provides surfactants alkyl polyethoxy sulfates or alkyl aryl polyalkoxy sulfates for use in oil recovery. The Yang Kan study showed that (fine petrochemical development, 2017, 18 (3): 22-25) the compound flooding (surfactant and reducer) increases the recovery ratio by 26.1% on the basis of water flooding (recovery ratio of 43.2%). But the chemical agents in the composite flooding system have a certain chromatographic separation phenomenon, and the synergistic effect cannot be fully exerted.
The mine field test of the technology for improving the thickened oil water-drive recovery efficiency does not obtain the expected oil increasing and water reducing effects. The main reason is that for polymer flooding, the polymer only increases the viscosity of the displacement fluid and cannot reduce the viscosity of the thickened oil, so that the amplitude of reducing the viscosity-water flow ratio of the thickened oil is small, and the amplitude of expanding the swept volume is small; for low molecular weight emulsified viscosity-reducing agent flooding, under the indoor strong stirring (shearing) condition, oil-in-water emulsion can be formed to achieve the purpose of viscosity reduction, but under the formation low shearing condition, oil-in-water emulsion is difficult to form and the purpose of viscosity reduction is difficult to achieve.
Disclosure of Invention
The invention aims to provide a double-braid polymer surfactant, which has good interfacial activity and can form a stable oil-in-water emulsion from thick oil under the condition of low shearing of a stratum so as to realize the purpose of reducing viscosity; meanwhile, the oil-water-drive thickening agent has certain viscosity-increasing performance on a water phase, and has important application value in improving the water-drive recovery ratio of thickened oil.
The invention also aims to provide a preparation method of the double-braid polymer surfactant.
The invention further aims to provide a thickened oil viscosity reducer.
To achieve the above object, in one aspect, the present invention provides a double-braid polymer surfactant, wherein the surfactant has a structure represented by the following formula (I):
in the formula (I), x/(x + y + z) x 100% is 0.1-0.5%, y/(x + y + z) x 100% is 90.8-93.3%, and z/(x + y + z) x 100% is 6.6-8.7%; r1And R2Each independently selected from hydrogen atom or C1～C20Linear or branched alkyl of (a); n is 1 to 30.
According to some embodiments of the invention, wherein the surfactant has a viscosity average molecular weight of 2.1 × 106～4.5×106g/mol。
According to some embodiments of the invention, wherein R1And R2Each independently selected from the group consisting of propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1-dimethylpropyl, 2-methylbutyl, neopentyl, hexyl, 1-methylpentyl, 2-ethylbutyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1-dimethylpropyl, 2-methylbutyl, neopentyl, hexyl, 1-methylpentyl, 2-ethylbutyl, 2-ethylpentyl, 2-ethylpropyl, and,One of 4-methylpentyl, 1, 3-dimethylbutyl, 2-methyl-1-ethylpropyl, 1-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, 1, 2-dimethylbutyl, 1-methyl-1-ethylpropyl, 2-ethylbutyl, 3-dimethylbutyl, 1,2, 2-trimethylpropyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 1, 2-trimethylpropyl, heptyl, octyl, nonyl, and decyl.
On the other hand, the invention also provides a preparation method of the double-braid polymer surfactant, wherein the method comprises the following steps of taking diaryl polyoxyethylene ether maleic diester shown in the formula (II), acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid as raw materials, and carrying out polymerization reaction in the presence of a surfactant, an oxidant and a reducing agent to obtain the double-braid polymer surfactant:
R1、R2each independently selected from hydrogen atom or carbon atom number C1～C20One of linear or branched alkyl; n is 1 to 30.
According to some embodiments of the invention, the method comprises the steps of:
(1) dissolving diaryl polyoxyethylene ether maleic diester shown in formula (II), acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and a surfactant in deionized water to obtain a mixed solution, and adding an alkaline agent to adjust the pH value of the solution to 6-9 to obtain a reaction solution;
(2) adjusting the temperature of the reaction solution obtained in the step (1) to 20-40 ℃, adding an oxidant and a reducing agent, and reacting to obtain a colloidal substance;
(3) and (3) carrying out post-treatment on the colloidal substance obtained in the step (2) to obtain the double-braid polymer surfactant containing diaryl polyoxyethylene ether maleic diester as shown in the formula (I).
According to some embodiments of the present invention, the mass percentage of the diaryl polyoxyethylene ether maleate diester is 0.1% to 0.5% based on 100% of the total mass of the diaryl polyoxyethylene ether maleate diester, the acrylic acid and the 2-acrylamido-2-methylpropanesulfonic acid; the mass percentage of the acrylic acid is 90.8 percent to 93.3 percent; the mass percentage of the 2-acrylamide-2-methyl propane sulfonic acid is 6.6-8.7%.
According to some embodiments of the invention, wherein the surfactant is an anionic surfactant.
According to some embodiments of the invention, the surfactant is selected from the group consisting of sodium dodecyl sulfate, and sodium dodecyl benzene sulfonate.
According to some embodiments of the invention, the surfactant is used in an amount of 1.2 to 2.6% by mass based on the total mass of the three reactive monomers.
According to some specific embodiments of the present invention, the total mass concentration of the three reaction monomers in the mixed monomer aqueous solution in the step (1) is 15-30%.
According to some specific embodiments of the present invention, in the step (1), the alkaline agent is one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate.
According to some embodiments of the present invention, in the step (1), after the pH of the solution is adjusted to 6 to 9 by adding an alkaline agent, nitrogen is introduced for 20 to 40 minutes, and then the solution is sealed to obtain the reaction solution.
According to some embodiments of the present invention, the oxidant in step (2) is one or more selected from sodium persulfate, hydrogen peroxide, potassium persulfate, and ammonium persulfate.
According to some embodiments of the present invention, the amount of the oxidant used in step (2) is 0.05 to 0.35% by mass of the total mass of the three reaction monomers.
According to some specific embodiments of the present invention, the reducing agent in step (2) is selected from one or more of sodium bisulfite, sodium sulfite, tetramethylethylenediamine and sodium thiosulfate.
According to some embodiments of the present invention, the amount of the reducing agent used in step (2) is 0.11-0.5% by mass of the total mass of the three reaction monomers.
According to some embodiments of the present invention, in the step (2), the temperature of the reaction solution obtained in the step (1) is adjusted to 25 to 35 ℃.
According to some specific embodiments of the present invention, the reaction time in the step (2) is 4 to 20 hours.
According to some embodiments of the present invention, the reaction time in the step (2) is 5 to 10 hours.
According to some embodiments of the present invention, the post-treatment in step (3) comprises the steps of granulating, washing, drying, pulverizing and sieving.
According to some embodiments of the invention, wherein the preparation of the compound of formula (II) comprises the steps of:
the compound is prepared by reacting aromatic polyoxyethylene ether serving as a raw material with maleic anhydride in a solvent in the presence of a catalyst.
According to some embodiments of the invention, the method comprises the steps of:
(a) mixing aryl polyoxyethylene ether, maleic anhydride, a catalyst and a solvent, stirring for dissolving, and heating for reaction to obtain a reaction solution;
(b) and (b) after the reaction is finished, washing and concentrating the reaction solution obtained in the step (a) to obtain the diaryl polyoxyethylene ether maleic diester.
According to some embodiments of the present invention, in step (a), the aromatic polyoxyethylene ether, the maleic anhydride, the catalyst and the solvent are added into a reaction device equipped with a water separator, a reflux condenser, a thermometer and a stirrer, stirred and dissolved, and heated for reaction.
According to some embodiments of the invention, wherein the solvent of step (a) is selected from the group consisting of toluene, benzene, and a mixture of one or more of p-xylene; toluene is preferred.
According to some embodiments of the invention, the catalyst of step (a) is selected from the group consisting of p-toluenesulfonic acid, phosphoric acid, sulfuric acid and hydrochloric acid.
According to some embodiments of the invention, wherein the catalyst of step (a) is p-toluenesulfonic acid.
According to some embodiments of the present invention, the amount of the catalyst used in step (a) is 0.5-2.5% by mass of the total mass of the reactants (aryl polyoxyethylene ether and maleic anhydride).
According to some embodiments of the present invention, the ratio of the aromatic polyoxyethylene ether to the maleic anhydride is (2-5): 1.
According to some embodiments of the present invention, the reaction temperature of the reaction in the step (a) is 115 to 150 ℃.
According to some embodiments of the invention, the reaction time of the reaction of step (a) is 4-7h
According to some embodiments of the present invention, the washing in the step (b) comprises washing with 1 to 10 wt% aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution.
It is understood that any combination of the above embodiments is possible without contradiction.
In still another aspect, the invention further provides a thickened oil viscosity reducer, wherein the thickened oil viscosity reducer is prepared by the polymeric surfactant according to any one of the aspects of the invention or the method according to any one of the aspects of the invention.
In conclusion, the invention provides a double-braid polymer surfactant as well as a preparation method and application thereof. The double-braid polymer surfactant has the following advantages:
1. the raw materials used in the invention are easy to obtain, the preparation is simple, the use is safe, and the storage is convenient.
2. The preparation method provided by the invention has the advantages of mild polymerization conditions, high yield and simple product post-treatment process.
3. The polymeric surfactant of the present invention has the following advantages: (1) under the condition of low shearing of stratum, the thickened oil forms a stable oil-in-water emulsion to realize the purpose of viscosity reduction; (2) has certain viscosity increasing performance on a water phase, and the two have synergistic effect to improve the oil-water fluidity ratio, thereby enlarging swept volume and improving the water drive recovery ratio of thickened oil.
Drawings
FIG. 1 is a dinonylphenol polyoxyethylene ether maleic acid diester (NP) containing 10 ethyleneoxy EO units prepared in example 1 of the present invention10Nuclear magnetic resonance of MA: (1H-NMR) spectrum.
FIG. 2 is an infrared (FT-IR) spectrum of the product of example 4 of the present invention. The three monomers are all involved in the polymerization by the analysis of the map.
FIG. 3 shows NMR of a product obtained in example 4 of the present invention: (1H-NMR) spectrum. From the chemical shifts of the peaks, it is known that all three monomers are involved in the polymerization.
FIG. 4 is a thermogravimetric analysis (TGA) profile of the product of example 4 of the present invention. The thermal degradation temperature of the polymer backbone can reach 390 ℃.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
Example 1
(1) Nonylphenol polyoxyethylene ether (n ═ 10) (10.0000g,15.131mmol) containing 10 ethyleneoxy EO units, maleic anhydride (0.3810g,3.886mmol), p-toluenesulfonic acid (0.1556g,0.902mmol) and toluene (50mL) were charged into a reaction flask equipped with a water separator, a condenser, a thermometer and a stirrer, and after stirring and dissolution, the reaction was heated to reflux, the temperature of the reaction solution was maintained at 115 to 120 ℃, and the reaction was continued for 6 hours, and the water formed was removed by evaporation.
(2) After the reaction, the reaction mixture obtained in step (1) was washed with a 5 wt% aqueous solution of sodium hydrogencarbonate and saturated aqueous solution of sodium chloride, respectively, and concentrated to give 4.36g of a pale yellow oily substance as dinonylphenol polyoxyethylene ether maleic diester (NP) containing 10 ethyleneoxy EO units10MA)。
Nuclear magnetic resonance hydrogen spectrum of the yellow oily substance obtained in this example (1HNMR,400MHz,CDCl3) As shown in fig. 1Chemical shifts delta (ppm)6.70-7.3(8H, hydrogen on benzene ring), 6.25(2H, hydrogen on double bond)HC＝CH) 3.0-4.5(80H, 20-OCH 2CH 2O-),0.5-2.2(38H, is alkyl hydrogen). NP conforming to formula (II)10The structural formula of MA.
The nuclear magnetic resonance hydrogen spectrum analysis confirms that the obtained product is dinonylphenol polyoxyethylene ether maleic diester (NP) containing 10 ethylene oxide EO units10MA)。
Example 2
The preparation method was the same as in example 1 except that: to step (1) were added nonylphenol polyoxyethylene ether (n ═ 6) containing 6 ethyleneoxy EO units (10.0000g,20.633mmol), maleic anhydride (0.9196g,9.378mmol) and p-toluenesulfonic acid (0.1973g,1.146 mmol).
The yellow oil obtained was dinonylphenol polyoxyethylene ether maleic diester (NP) containing 6 ethyleneoxy EO units6MA)7.90g。
The nuclear magnetic resonance hydrogen spectrum data are as follows:
1H NMR(400MHz,CDCl3) Delta (ppm)6.70-7.3(8H, hydrogen on benzene ring), 6.25(2H, hydrogen on double bond)HC＝CH) 3.0-4.5(48H, 12-OCH 2CH 2O-),0.5-2.2(38H, is alkyl hydrogen).
The nuclear magnetic resonance hydrogen spectrum analysis confirms that the obtained product is dinonylphenol polyoxyethylene ether maleic diester (NP) containing 6 ethylene oxide EO units6MA)。
Example 3
The preparation method is the same as example 1, except that: in step (1) di-tert-butylphenoxypolyoxyethylene ether (n-15) (10.0000g,11.533mmol) containing 15 ethyleneoxy EO units, maleic anhydride (0.3230g,3.294mmol) and p-toluenesulfonic acid (0.2064g,1.200mmol) were added.
The obtained yellow oily substance is di (di-tert-butyl phenoxy polyoxyethylene ether) maleic Diester (DPP) containing 15 ethylene oxide EO chain links15MA)4.76g。
The nuclear magnetic resonance hydrogen spectrum data are as follows:
1H NMR(400MHz,CDCl3) Delta (ppm)6.70-7.3(8H, hydrogen on benzene ring), 6.25(2H, hydrogen on double bond)HC＝CH) 3.0-4.5(120H, 30-OCH 2CH 2O-)0.5-2.2(36H, is tert-butylhydride).
The hydrogen spectrum analysis of nuclear magnetic resonance confirms that the obtained product is di (di-tert-butyl phenoxy polyoxyethylene ether) maleic Diester (DPP) containing 15 ethylene oxide EO chain links15MA)。
Example 4
(1) 0.2000g (0.14mmol) of dinonylphenol polyoxyethylene ether maleic diester (NP) containing 10 ethyleneoxy EO units was weighed out10MA) into 38mL of deionized water, adding 0.1300g (0.45mmol) of sodium dodecyl sulfate while stirring, stirring for 10min, then adding 7.8000g (108.24mmol) of acrylic acid and 2.0000g (9.65mmol) of 2-acrylamido-2-methylpropanesulfonic acid, stirring uniformly, adjusting the pH value of the solution to 7 with NaOH, bubbling with nitrogen gas to remove oxygen for 30min, and sealing.
(2) The temperature of the reaction solution in step (1) was raised to 30 ℃. Respectively preparing 0.0100g (0.037mmol) of potassium persulfate and 0.0192g (0.185mmol) of sodium bisulfite into 1mL of aqueous solution, respectively adding the aqueous solutions into the reaction solution once when the temperature is stabilized at 30 ℃, stirring for 5min, standing, observing the reaction solution to become sticky, and continuing to react for 8h to obtain a colloidal substance.
(3) Granulating, washing, drying, crushing and sieving the colloidal substance obtained in the step (2) to obtain the NP-containing material shown in the formula (I)109.66g of MA double-stranded polymer surfactant powder.
The infrared spectrum (FT-IR) spectrum of the polymeric surfactant prepared in this example is shown in FIG. 2, and is 3690-3161cm-1The broad peaks are the stretching vibration peaks of amide NH and residual-OH, 2928 and 2867cm-1In the form of alkyl, -CH2Stretching vibration peak of-and-CH-, 1715cm-1A stretching vibration peak of 1658cm for C ═ O-1Stretching vibration peak at NH-C ═ O, 1562 and 1451cm-1Is located at 1387cm and is a stretching vibration peak of a benzene ring-1Stretching vibration peak at-O-C ═ O, 1193cm-1Is treated with-SO3Characteristic absorption peak of Na, 1043cm-1Is represented by-CH2-O-CH2-characteristic peak of (a).
1H-NMR(400MHz,D2O) spectrum is shown in FIG. 3, the peak at chemical shift of 0.5-1.5ppm is alkyl hydrogen, and the peak at 1.5-2.8ppm is polymer skeleton-CH2Peaks of hydrogen atoms of-and-CH-, at 3.0 to 4.5ppm, — O-CH2CH2-O-and-CH2SO3Na has a hydrogen atom peak at 6.9-7.6ppm, and no CH is present between 5.0-7.0ppm2The peaks of hydrogen atoms of ═ CH-CO and-CH ═ CH-, indicate that no monomer remained in the polymer.
And (5) confirming that the obtained product is a target product through nuclear magnetic resonance hydrogen spectrum and infrared spectrum analysis.
The thermogravimetric analysis (TGA) spectrum is shown in fig. 4, and the thermal degradation temperature of the main chain can reach 390 ℃.
The double-stranded polymer surfactant obtained in this example was tested according to GB/T12005.10-1992 using an Ubbelohde viscometer (0.55mm pipe diameter) and had a viscosity-average molecular weight of 3.86X 106g/mol。
Example 5
The preparation method was the same as in example 4, except that: in the step (2), the amount of potassium persulfate was 0.0150g (0.0549mmol), and the amount of sodium bisulfite was 0.0289g (0.2777 mmol). Granulating, washing, oven drying, pulverizing, and sieving to obtain NP-containing material shown in formula (I)10MA polymer surfactant powder 9.18 g.
Infrared Spectrum (FT-IR) data for the polymer prepared in this example are as follows: upsilon ismax(cm-1)3640-3100(-NH, -OH),2930 and 2885 (alkyl, -CH)2-and-CH-), 1719(-C ═ O),1654(NH-C ═ O),1560 and 1452 (phenyl ring), 1339(-O-C ═ O),1118(-SO — (r) —3Na),1036(-CH2-O-CH2-)。
The nmr hydrogen spectra data are as follows:1H-NMR(400MHz,D2o) delta (ppm) of 0.5-1.5 (alkyl hydrogen atom), 1.5-2.8 (polymer skeleton hydrogen-CH)2-and-CH-), 3.0-4.5 (-OCH)2-CH2O-,-CH2SO3Na) 6.9-7.6 (hydrogen on benzene ring). And no CH appears between 5.0 and 7.0ppm2The peaks of hydrogen atoms of ═ CH-CO and-CH ═ CH-, indicate that no monomer remained in the polymer.
And (5) confirming that the obtained product is a target product through nuclear magnetic resonance hydrogen spectrum and infrared spectrum analysis.
The double-stranded polymer surfactant obtained in this example was tested according to GB/T12005.10-1992 using an Ubbelohde viscometer (0.55mm pipe diameter) and had a viscosity-average molecular weight of 4.11X 106g/mol。
Example 6
The preparation method was the same as in example 4, except that: the polymerizable surfactant monomer in the step (1) is dinonylphenoxy polyoxyethylene ether maleic diester (NP) containing 6 ethylene oxide EO units6MA), the charge amount was 0.2160g (0.206mmol), the charge amount of acrylic acid was 8.0000g (111.019mmol), and the charge amount of 2-acrylamido-2-methylpropanesulfonic acid was 1.7840g (8.610 mmol). Granulating, washing, oven drying, pulverizing, and sieving to obtain NP-containing material shown in formula (I)6MA, 8.76 g.
Infrared Spectrum (FT-IR) data for the polymer prepared in this example are as follows: upsilon ismax(cm-1)3640-3100(-NH, -OH),2930 and 2885 (alkyl, -CH)2-and-CH-), 1719(-C ═ O),1654(NH-C ═ O),1560 and 1452 (phenyl ring), 1339(-O-C ═ O),1118(-SO — (r) —3Na),1036(-CH2-O-CH2-)。
The nmr hydrogen spectra data are as follows:1H-NMR(400MHz,D2o) delta (ppm) of 0.5-1.5 (alkyl hydrogen atom), 1.5-2.8 (polymer skeleton hydrogen-CH)2-and-CH-), 3.0-4.5 (-OCH)2-CH2O-,-CH2SO3Na),6.9-7.6 (hydrogen on benzene ring). And no CH appears between 5.0 and 7.0ppm2The peaks of hydrogen atoms of ═ CH-CO and-CH ═ CH-, indicate that no monomer remained in the polymer.
And (5) confirming that the obtained product is a target product through nuclear magnetic resonance hydrogen spectrum and infrared spectrum analysis.
The method was carried out using a Ubbelohde viscometer (0.55mm tube diameter) in accordance with GB/T12005.10-1992The double-strand polymer surfactants obtained in the examples were tested to have a viscosity-average molecular weight of 3.57X 106g/mol。
Example 7
The preparation method was the same as in example 6, except that: in the step (2), the amount of potassium persulfate was 0.0150g (0.0549mmol), and the amount of sodium bisulfite was 0.0289g (0.2777 mmol). Granulating, washing, oven drying, pulverizing, and sieving to obtain NP-containing material shown in formula (I)6Powder of MA Polymer surfactant 9.08 g.
Infrared Spectrum (FT-IR) data for the polymer prepared in this example are as follows: upsilon ismax(cm-1)3640-3100(-NH, -OH),2930 and 2885 (alkyl, -CH)2-and-CH-), 1719(-C ═ O),1654(NH-C ═ O),1560 and 1452 (phenyl ring), 1339(-O-C ═ O),1118(-SO — (r) —3Na),1036(-CH2-O-CH2-)。
The nmr hydrogen spectra data are as follows:1H-NMR(400MHz,D2o) delta (ppm) of 0.5-1.5 (alkyl hydrogen atom), 1.5-2.8 (polymer skeleton hydrogen-CH)2-and-CH-), 3.0-4.5 (-OCH)2-CH2O-,-CH2SO3Na),6.9-7.6 (hydrogen on benzene ring). And no CH appears between 5.0 and 7.0ppm2The peaks of hydrogen atoms of ═ CH-CO and-CH ═ CH-, indicate that no monomer remained in the polymer.
And (5) confirming that the obtained product is a target product through nuclear magnetic resonance hydrogen spectrum and infrared spectrum analysis.
The double-stranded polymer surfactant obtained in this example was tested according to GB/T12005.10-1992 using an Ubbelohde viscometer (0.55mm pipe diameter) and had a viscosity-average molecular weight of 3.92X 106g/mol。
Example 8
The preparation method is the same as example 4, except that: in the step (1), the polymerizable monomer is di (di-tert-butyl phenoxy polyoxyethylene ether) maleic Diester (DPP) containing 15 ethylene oxide EO chain members15MA), the charge amount is 0.3000g (0.165mmol), the charge amount of acrylic acid is 7.8000g (108.24mmol), and the charge amount of 2-acrylamido-2-methylpropanesulfonic acid is 1.9000g (9.170 mmol). Granulating and washing the obtained colloidal substanceDrying, crushing and sieving to obtain DPP (dipeptidyl peptidase) shown in formula (I)15MA, 8.79 g.
Infrared Spectrum (FT-IR) data for the polymer prepared in this example are as follows: upsilon ismax(cm-1)3640-3100(-NH, -OH),2930 and 2885 (alkyl, -CH)2-and-CH-), 1719(-C ═ O),1654(NH-C ═ O),1560 and 1452 (phenyl ring), 1339(-O-C ═ O),1118(-SO — (r) —3Na),1036(-CH2-O-CH2-)。
The nmr hydrogen spectra data are as follows:1H-NMR(400MHz,D2o) delta (ppm) of 0.5-1.5 (alkyl hydrogen atom), 1.5-2.8 (polymer skeleton hydrogen-CH)2-and-CH-), 3.0-4.5 (-OCH)2-CH2O-,-CH2SO3Na),6.9-7.6 (hydrogen on benzene ring). And no CH appears between 5.0 and 7.0ppm2The peaks of hydrogen atoms of ═ CH-CO and-CH ═ CH-, indicate that no monomer remained in the polymer.
And (5) confirming that the obtained product is a target product through nuclear magnetic resonance hydrogen spectrum and infrared spectrum analysis.
The double-stranded polymer surfactant obtained in this example was tested according to GB/T12005.10-1992 using an Ubbelohde viscometer (0.55mm pipe diameter) and had a viscosity-average molecular weight of 3.17X 106g/mol。
Effects of the invention
(1) Interfacial activity test
The interface activity test conditions and steps are as follows: the surface tension of the aqueous solution was measured by the hanging strip method using a K-12 interfacial tensiometer from Kruss, Germany, at an experimental temperature of 25 ℃ and the results are shown in Table 1 below.
TABLE 1
(2) Viscosity reduction Performance test for thickened oils
The viscous oil viscosity reduction performance test experiment conditions and steps of the polymer type surfactant are as follows:
mixing thickened oil (Liaohe thickened oil) and water (containing 1000mg/L of the copolymer) in a mass ratio of 4:6Mixing at 50 deg.C to simulate low shear rate of stratum for 5-50s-1Forming a stable oil-in-water emulsion. The viscosity (50 ℃) of the thick oil and the oil-in-water emulsion is measured by an MCR301 type modular intelligent rheometer, and the results are shown in the following table 2 (the viscosity of the thick oil is 635 mPa.s).
TABLE 2
(3) Adhesion promotion Performance test
The polymeric surfactants prepared in examples were prepared into an aqueous solution (degree of mineralization: 1200mg/L) having a concentration of 1000mg/L, and the apparent viscosity at 25 ℃ was measured using a LVDV type II viscometer manufactured by Brookfield corporation, and the results are shown in Table 3 below.
TABLE 3
(4) Core oil displacement effect test
Experimental materials: the thick oil is Liaohe thick oil, and the viscosity of the thick oil is 635mPa.s at 50 ℃; the water is 1200mg/L simulated mineralized water; artificial core, 25mm by 300mm, air permeability 750 mD.
The oil displacement experimental method comprises the following steps: (1) the core was saturated with oil. Injecting thick oil into the rock core at the formation temperature of 50 ℃ until no water flows out from the outlet end of the rock core, stopping injecting oil, and calculating the saturated oil quantity and the initial oil saturation; (2) and (4) water-driving the core. Displacing the rock core with injected water at a formation temperature of 50 ℃ until the water content of the displacement liquid reaches 98%, stopping the experiment, and calculating the recovery ratio of water flooding; (3) polymer surfactant flooding core. And (3) after the water flooding is finished, displacing the rock core by using the polymer type surfactant aqueous solution until the water content of the displacement liquid reaches 98%, stopping the experiment, and calculating the viscosity reducer to improve the recovery ratio. (4) The recovery ratio of the polymer surfactant flooding, i.e., total recovery ratio-water flooding recovery ratio, is shown in table 4 below.
TABLE 4
Claims (19)
1. An aromatic group-containing double-stranded polymer surfactant, wherein the surfactant has a structure represented by the following formula (I):
in the formula (I), x/(x + y + z) x 100% is 0.1-0.5%, y/(x + y + z) x 100% is 90.8-93.3%, and z/(x + y + z) x 100% is 6.6-8.7%; r1And R2Each independently selected from C3～C10Linear or branched alkyl of (a); n is 6 to 15, and the viscosity average molecular weight of the surfactant is 2.1 × 106～4.5×106g/mol。
2. The double-pigtail polymeric surfactant of claim 1, wherein R1And R2Each independently selected from one of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.
3. The double-pigtail polymeric surfactant of claim 2, wherein the propyl group is an isopropyl group; the butyl is tert-butyl, sec-butyl or isobutyl; the amyl group is 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1-dimethylpropyl, 2-methylbutyl or neopentyl; the hexyl group is 1-methylpentyl, 2-ethylbutyl, 4-methylpentyl, 1, 3-dimethylbutyl, 2-methyl-1-ethylpropyl, 1-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, 1, 2-dimethylbutyl, 1-methyl-1-ethylpropyl, 2-ethylbutyl, 3-dimethylbutyl, 1,2, 2-trimethylpropyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl or 1,1, 2-trimethylpropyl.
4. A method for preparing the double-braid polymer surfactant as claimed in any one of claims 1 to 3, wherein the method comprises the following steps of taking diaryl polyoxyethylene ether maleic diester shown as a formula (II), acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid as raw materials, and carrying out polymerization reaction in the presence of a surfactant, an oxidant and a reducing agent to obtain the double-braid polymer surfactant:
R1、R2each independently selected from C3～C10One of linear or branched alkyl; n is 6-15;
the surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
5. The method according to claim 4, wherein the method comprises the steps of:
(1) dissolving diaryl polyoxyethylene ether maleic diester shown in formula (II), acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid and a surfactant in deionized water to obtain a mixed solution, and adding an alkaline agent to adjust the pH value of the solution to 6-9 to obtain a reaction solution;
(2) adjusting the temperature of the reaction solution obtained in the step (1) to 20-40 ℃, adding an oxidant and a reducing agent, and reacting to obtain a colloidal substance;
(3) and (3) carrying out post-treatment on the colloidal substance obtained in the step (2) to obtain the double-braid polymer surfactant containing diaryl polyoxyethylene ether maleic diester as shown in the formula (I).
6. The method according to claim 4 or 5, wherein the percentage of the mass of the diaryl polyoxyethylene ether maleate diester is 0.1% to 0.5% based on 100% of the total mass of the diaryl polyoxyethylene ether maleate diester, acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid; the mass percentage of the acrylic acid is 90.8 percent to 93.3 percent; the mass percentage of the 2-acrylamide-2-methyl propane sulfonic acid is 6.6-8.7%.
7. The method according to claim 4 or 5, wherein the surfactant is used in an amount of 1.2 to 2.6% by mass based on the total mass of the three reactive monomers.
8. The method according to claim 5, wherein the total mass concentration of the three reaction monomers in the mixed monomer aqueous solution in the step (1) is 15-30%.
9. The method according to claim 5, wherein the alkaline agent in step (1) is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate.
10. The method according to claim 5, wherein in the step (1), after the pH value of the solution is adjusted to 6-9 by adding the alkaline agent, nitrogen is introduced for 20-40 minutes, and then the solution is sealed to obtain the reaction solution.
11. The method according to claim 5, wherein the oxidant in step (2) is one or more selected from sodium persulfate, hydrogen peroxide, potassium persulfate and ammonium persulfate.
12. The method according to claim 5, wherein the mass amount of the oxidant used in the step (2) is 0.05-0.35% of the total mass of the three reaction monomers.
13. The method according to claim 5, wherein the reducing agent in step (2) is selected from one or more of sodium bisulfite, sodium sulfite, tetramethylethylenediamine and sodium thiosulfate.
14. The method according to claim 5, wherein the mass amount of the reducing agent in the step (2) is 0.11-0.5% of the total mass of the three reaction monomers.
15. The method according to claim 5, wherein the temperature of the reaction solution obtained in the step (1) is adjusted to 25-35 ℃ in the step (2).
16. The method according to claim 5, wherein the reaction time in the step (2) is 4-20 h.
17. The method according to claim 5, wherein the reaction time in the step (2) is 5-10 h.
18. The method of claim 5, wherein the post-treatment of step (3) comprises the steps of granulating, washing, drying, pulverizing and sieving.
19. A thickened oil viscosity reducer prepared from the polymer surfactant according to any one of claims 1 to 3 or the double-stranded polymer surfactant prepared by the method according to any one of claims 4 to 18.
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