CN111732722B - Polymer, preparation method thereof and application of polymer as or in preparation of sand control agent - Google Patents
Polymer, preparation method thereof and application of polymer as or in preparation of sand control agent Download PDFInfo
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- CN111732722B CN111732722B CN201910232027.6A CN201910232027A CN111732722B CN 111732722 B CN111732722 B CN 111732722B CN 201910232027 A CN201910232027 A CN 201910232027A CN 111732722 B CN111732722 B CN 111732722B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/56—Compositions for consolidating loose sand or the like around wells without excessively decreasing the permeability thereof
- C09K8/57—Compositions based on water or polar solvents
- C09K8/575—Compositions based on water or polar solvents containing organic compounds
- C09K8/5751—Macromolecular compounds
- C09K8/5755—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a polymer, the structural formula of which is shown in figure 1, and the preparation method comprises the following steps: (1) carrying out esterification reaction on reactants polyethylene oxide and phosphate under the action of a catalyst p-toluenesulfonic acid to obtain reaction liquid; (2) and (3) adjusting the reaction liquid to be weakly acidic, adding polyfurfuryl alcohol under normal pressure, and carrying out etherification reaction to obtain a reddish brown viscous liquid. The polymer of the invention can be used as or for preparing a sand control agent. The polymer is a novel nonionic phosphate coated sand control agent, phosphoric acid is used as a connecting group, and a polyethylene oxide chain segment is introduced through esterification reaction to obtain weak-acidic disubstituted phosphate; under the weak acidic condition, a polyfurfuryl alcohol chain segment with slow-control solidification is introduced, so that the effect of high-strength in-situ fixing stratum particles is realized.
Description
Technical Field
The invention relates to a polymer, a preparation method thereof and application thereof as or in preparation of a sand control agent, belonging to the technical field of preparation of sand control agents.
Background
In the middle and later period of development of oil fields, along with the increase of high mud quality, fine sand, aggregation and the like, the yield of the oil well after sand prevention is reduced quickly, the difficulty of extracting liquid is high, and the phenomenon of low liquid is obvious. How to effectively control the migration of particles such as clay, silt and the like in a reservoir and a filling zone becomes an effective means for solving the problems. The sand control agent commonly used at present mainly comprises inorganic salt, alkalies, inorganic polynuclear polymers and cationic polymers, and the cationic polymers are taken as main components. The cationic polymer can be dissolved and dissociated in water to generate polycation, and the polycation can adsorb and neutralize the electronegativity of the clay surface and adsorb between clay crystal layers to bridge the surface to inhibit the swelling of the clay and can bridge clay particles on the surface of the stratum to effectively inhibit the migration of the particles. However, cationic polymers have the following disadvantages: firstly, the water-soluble cationic polymer can be dissolved into the formation water again along with the prolonging of the production time, the effective components remained on the surface wall of the pore can be denatured and broken chains under the influence of the formation mineralization and the shearing action, and the descending is rapid so as to lead the sand inhibiting performance to be sharply reduced; secondly, the cationic polymer remained on the surface walls of the pores and the particles has weak sand inhibiting performance and low scouring resistance only by electrostatic adsorption and hydrogen bonding; thirdly, reservoir damage can be caused by improper use of the medium-low permeability reservoir. Therefore, in order to solve the problems of fast oil well yield reduction, large difficulty in extracting liquid, low liquid content and the like caused by the migration of stratum particles, the development of a sand control agent capable of generating a viscous film and fixing the stratum particles in situ is needed.
Disclosure of Invention
In view of the prior art, the invention provides a polymer, a preparation method thereof and application thereof as or in preparation of a sand control agent.
The invention is realized by the following technical scheme:
a polymer having the formula:
wherein m is 5 to 100, and n is 2 to 10.
The synthetic route of the polymer is as follows:
the preparation method of the polymer comprises the following steps:
(1) carrying out esterification reaction on reactants polyethylene oxide and phosphate under the action of a catalyst p-toluenesulfonic acid, wherein the reaction pressure is 0.8-1.0 MPa, the reaction temperature is 110-180 ℃, and the reaction time is 8-12 h, so as to obtain a reaction solution; the molecular weight of the polyethylene oxide is 220-4400 (m in the corresponding product is 5-100);
further, the molar ratio of polyethylene oxide to phosphate ester is 2: 1;
further, the p-toluenesulfonic acid is added in an amount of 0.1% by weight of the reactants (referring to the weight of the polyethylene oxide and the phosphate);
(2) adjusting the reaction liquid to be weakly acidic (pH is 4-6), adding polyfurfuryl alcohol under normal pressure, and carrying out etherification reaction at the reaction temperature of 50-70 ℃ for 4-6 h; the molecular weight of the polyfurfuryl alcohol is 196-980 (n in the corresponding product is 2-10); after the reaction, the obtained product is reddish brown viscous liquid, namely the polymer.
Further, the molar ratio of the polyfurfuryl alcohol to the polyethylene oxide in the step (1) is 1: 1.
The polymer can be used as a main agent of a sand control agent or used for preparing the sand control agent (such as a sand control agent emulsion) when being applied.
The invention also provides a phosphate coated sand control agent, and the preparation method comprises the following steps:
(1) carrying out esterification reaction on reactants polyethylene oxide and phosphate under the action of a catalyst p-toluenesulfonic acid, wherein the reaction pressure is 0.8-1.0 MPa, the reaction temperature is 110-180 ℃, and the reaction time is 8-12 h, so as to obtain a reaction solution; the molecular weight of the polyethylene oxide is 220-4400;
further, the molar ratio of polyethylene oxide to phosphate ester is 2: 1;
further, the p-toluenesulfonic acid is added in an amount of 0.1% by weight of the reactants (referring to the weight of the polyethylene oxide and the phosphate);
(2) adjusting the reaction liquid to be weakly acidic (pH is 4-6), adding polyfurfuryl alcohol under normal pressure, and carrying out etherification reaction at the reaction temperature of 50-70 ℃ for 4-6 h; the molecular weight of the polyfurfuryl alcohol is 196-980; after the reaction, the product was a reddish brown viscous liquid.
Further, the molar ratio of the polyfurfuryl alcohol to the polyethylene oxide in the step (1) is 1: 1.
The phosphate coated sand control agent can be used for preparing a sand control agent emulsion, such as a sand control agent emulsion with the mass concentration of 20%.
The polymer is a novel nonionic phosphate coated sand control agent, phosphoric acid is used as a connecting group, and a polyethylene oxide chain segment is introduced through esterification reaction to obtain weak-acidic disubstituted phosphate; under the weak acidic condition, a polyfurfuryl alcohol chain segment with slow-control solidification is introduced, so that the effect of high-strength in-situ fixing stratum particles is realized.
The polymer and phosphate coated sand control agent has the following advantages:
(1) the phosphoric acid in the polymer structure is used as a linking group on one hand and is also a catalyst for the curing reaction of the polyfurfuryl alcohol on the other hand.
(2) The polyethylene oxide temperature-sensitive chain segment is introduced, when the temperature rises and exceeds the cloud point (cloud point is 40-110 ℃) after the sand control agent is injected into a high-temperature oil well, the hydrogen bond between the polyethylene glycol chain segment and free water is destroyed, and the hydrophobicity of the polymer is enhanced, so that the sand control agent molecules can be adsorbed on the surface of sand grains, the sand control agent is conveniently contacted with the surface layer of the sand grains, and the solidification reaction is carried out.
(3) Under the acidic condition, hydroxyl (-CH) at the tail end of the sand control agent 2 -OH) and polar groups (Si-OH) on the surface of sand grains are easy to generate condensation reaction and are bonded through covalent bonds; at the same time, furfuryl alcoholThe chain segments can also generate cross-linking reaction to form a network polymer with a branched chain structure, and the network polymer can obviously enhance the bonding density and bonding strength among sand particles and enhance the sand fixing capacity of the sand control agent.
(4) The polymer contains a large amount of alkoxy and epoxy groups, the functional groups can form hydrogen bonds with polar groups (Si-OH) on the surface of sand grains after hydrolysis, and Si-O-Si covalent bonds are formed after heating, curing and dehydration, so that a layer of viscous film is formed on the surface of sand grains, the agglomeration effect among the sand grains is realized, and the aim of in-situ fixing of stratum particles is fulfilled.
In a word, the polymer and the sand control agent can be adsorbed on the surface of sand grains to perform a curing reaction with the sand grains, so that the bonding density and the bonding strength among the sand grains are stronger, a layer of viscous film can be formed on the surface of the sand grains, the agglomeration among the sand grains is realized, and the beneficial effect of in-situ fixing of stratum particles is achieved.
The various terms and phrases used herein have the ordinary meaning as is known to those skilled in the art.
Drawings
FIG. 1: the structural formula of the polymer of the invention.
FIG. 2: synthetic routes to the polymers of the invention.
FIG. 3: ir spectra of the polymers of the invention.
FIG. 4: nuclear magnetic resonance spectrum of the polymer of the invention.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
Example 1 preparation of Sand control Agents
Adding reactants polyethylene oxide and phosphate into a small high-temperature high-pressure reaction kettle, and carrying out esterification reaction under the catalytic action of p-toluenesulfonic acid to obtain reaction liquid; wherein the molar ratio of the polyethylene oxide (relative molecular weight is 440) to the phosphate is 2:1, the pressure in the reaction kettle is 0.8MPa, the reaction temperature is 180 ℃, the reaction time is 8h, and the addition of the p-toluenesulfonic acid is 0.1 percent of the total reaction mass; adjusting the reaction solution to be weakly acidic (pH is 4), adding polyfurfuryl alcohol (the relative molecular mass is 196) under normal pressure to carry out etherification reaction, wherein the amount of the polyfurfuryl alcohol is equal to that of the polyethylene oxide, reacting for 4h at 70 ℃, and obtaining a product which is a reddish brown viscous liquid and is a polymer with a structural formula shown in figure 1, wherein m is 10, n is 2, the synthetic route is shown in figure 2, the infrared spectrum is shown in figure 3, and the product is known to be 3150cm from figure 3 -1 The stretching vibration absorption peak of hydroxyl appears on the left and the right, and is 2843-3000 cm -1 The C-H bond stretching vibration peak and the bending vibration peak on methine and methylene are 1630-1659 cm -1 The peak appeared as a C ═ C bond stretching vibration absorption peak of furfuryl alcohol, 1390cm -1 A large amount of furfuryl alcohol hydroxyl absorption peaks are generated at 995-1050 cm -1 、1100～1200cm -1 Two groups of double shoulder peaks are caused by stretching vibration of C-O bonds of ethers, which indicates that the target product is successfully synthesized.
The structure of the product is further analyzed by a nuclear magnetic resonance spectrometer, and the testing solvent is D 2 As shown in FIG. 4, the results of O, as seen from FIG. 4, indicate that the peak values at. delta.3.52 to 4.31(aH) were strong and a dehydration condensation reaction of hydroxyl groups occurred, indicating that the sand-fixing agent contains polyether group-containing C-CH 2 And O-CH 2 ，δ4.47[P-OH(bH)]The proton peak of the unreacted alcoholic hydroxyl of phosphoric acid, two absorption peaks of delta 4.91(cH) and delta 6.19(eH) are generated and are proton peaks of furfuryl alcohol, which indicates that furfuryl alcohol is successfully grafted into the product, and delta 5.17(dH) belongs to a methyl proton peak in furfuryl alcohol, and the analysis of comprehensive IR and 1H-NMR can judge that the sand fixing agent contains a polyether group, a furfuryl alcohol hydroxyl group, a phosphoric acid hydroxyl group and a carbon-carbon double bond of furfuryl alcohol, and indicates that the target product is successfully prepared.
Example 2 preparation of Sand control Agents
Adding reactants polyethylene oxide and phosphate into a small high-temperature high-pressure reaction kettle, and carrying out esterification reaction under the catalytic action of p-toluenesulfonic acid to obtain reaction liquid; wherein, the molar ratio of the polyethylene oxide (the relative molecular mass is 4400) to the phosphate is 2:1, the pressure in a reaction kettle is 1.0MPa, the reaction temperature is 110 ℃, the reaction time is 12h, and the adding amount of the p-toluenesulfonic acid is 0.1 percent of the total reaction mass; adjusting the reaction liquid to be weakly acidic (pH is 6), adding polyfurfuryl alcohol (relative molecular mass is 980) under normal pressure to carry out etherification reaction, wherein the amount of polyfurfuryl alcohol is equal to that of polyethylene oxide, reacting for 6h at 50 ℃, and obtaining a product which is a dark brown viscous liquid and is a polymer with a structural formula shown in figure 1, wherein m is 100, and n is 10.
Example 3 preparation of Sand control Agents
Adding reactants polyethylene oxide and phosphate into a small high-temperature high-pressure reaction kettle, and carrying out esterification reaction under the catalytic action of p-toluenesulfonic acid to obtain reaction liquid; wherein, the molar ratio of the polyethylene oxide (the relative molecular mass is 1000) to the phosphate is 2:1, the pressure in the reaction kettle is 0.8MPa, the reaction temperature is 150 ℃, the reaction time is 10h, and the adding amount of the p-toluenesulfonic acid is 0.1 percent of the total reaction mass; adjusting the reaction liquid to be weakly acidic (pH is 6), adding polyfurfuryl alcohol (the relative molecular mass is 500) under normal pressure to carry out etherification reaction, wherein the mass amount of the polyfurfuryl alcohol is equal to that of the polyethylene oxide, reacting for 5h at 50 ℃, and obtaining a product which is a reddish brown viscous liquid and is a polymer with the structural formula shown in figure 1, wherein m is 23, and n is 5.
Example 4 preparation of Sand control Agents
Adding reactants polyethylene oxide and phosphate into a small high-temperature high-pressure reaction kettle, and carrying out esterification reaction under the catalytic action of p-toluenesulfonic acid to obtain reaction liquid; wherein the molar ratio of the polyethylene oxide (the relative molecular mass is 2000) to the phosphate is 2:1, the pressure in a reaction kettle is 1.0MPa, the reaction temperature is 150 ℃, the reaction time is 10h, and the addition of the p-toluenesulfonic acid is 0.1 percent of the total reaction mass; the reaction solution is adjusted to be weakly acidic (pH is 5), polyfurfuryl alcohol (the relative molecular mass is 700) is added under normal pressure for etherification, the amount of the polyfurfuryl alcohol is equal to that of polyethylene oxide, the reaction is carried out for 7 hours at 60 ℃, and the obtained product presents reddish brown viscous liquid and is a polymer with the structural formula shown in figure 1, wherein m is 46, and n is 7.
Experimental example 1 Sand control Performance test
The sand control agent is prepared in the above embodiment, a sand control agent aqueous emulsion (mass concentration is 20%) is prepared, a consolidation test is performed on a sand sample (the diameter of sand is 0.4-0.8 mm), and the sand control strength and permeability of the sand control agent to loose sand are tested. Respectively injecting the sand control agent emulsion solution into a mold filled with 100g of sand samples, wherein the specification of the mold is 250cm multiplied by 25mm, curing for 48 hours at 60 ℃, and then measuring the consolidation strength, the permeability and the porosity of each sand sample. Specific results are shown in table 1.
TABLE 1
| Examples | Sand control Strength (MPa) | Permeability (Darcy) |
| Example 1 | 3.02 | 4.07 |
| Example 2 | 2.98 | 5.87 |
| Example 3 | 4.67 | 6.73 |
| Examples4 | 2.26 | 7.03 |
As can be seen from Table 1, the sand control agents prepared in the above examples all have a sand control strength of greater than 2.0MPa to loose sand, and the permeability of the sand rod after sand control is greater than 4.0 Darcy.
Although the specific embodiments of the present invention have been described with reference to the examples, the scope of the present invention is not limited thereto, and those skilled in the art will appreciate that various modifications and variations can be made without inventive effort by those skilled in the art based on the technical solution of the present invention.
Claims (4)
1. A preparation method of phosphate coated sand control agent is characterized by comprising the following steps: the method comprises the following steps:
(1) carrying out esterification reaction on reactants of polyethylene oxide and phosphoric acid under the action of a catalyst p-toluenesulfonic acid, wherein the reaction pressure is 0.8-1.0 MPa, the reaction temperature is 110-180 ℃, and the reaction time is 8-12 h, so as to obtain a reaction solution; the molecular weight of the polyethylene oxide is 220-4400;
(2) adjusting the reaction liquid to be weakly acidic, adding polyfurfuryl alcohol under normal pressure, and reacting at the temperature of 50-70 ℃ for 4-6 h; the molecular weight of the polyfurfuryl alcohol is 196-980; after the reaction, the obtained product is reddish brown viscous liquid;
the molar ratio of polyethylene oxide to phosphoric acid is 2: 1; the addition amount of the p-toluenesulfonic acid is 0.1 percent of the weight of reactants; the molar ratio of the polyfurfuryl alcohol to the polyethylene oxide in the step (1) is 1: 1.
2. The phosphate coated sand control agent prepared by the preparation method of the phosphate coated sand control agent according to claim 1.
3. The use of the phosphate coated sand control agent of claim 2 in the preparation of a sand control agent emulsion.
4. A sand control agent emulsion is characterized in that: the mass concentration of the sand control agent is 20 percent; the sand control agent is the sand control agent of claim 2.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427069A (en) * | 1981-06-08 | 1984-01-24 | Getty Oil Company | Sand consolidation methods |
| CN1168407A (en) * | 1997-02-19 | 1997-12-24 | 辽河石油勘探局钻采工艺研究院 | Compounding process of high-temp foamed resin sand-fixing agent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427069A (en) * | 1981-06-08 | 1984-01-24 | Getty Oil Company | Sand consolidation methods |
| CN1168407A (en) * | 1997-02-19 | 1997-12-24 | 辽河石油勘探局钻采工艺研究院 | Compounding process of high-temp foamed resin sand-fixing agent |
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