CN110724235A - Copolymer containing polyphenyl polyether branched chain structure and preparation and application thereof - Google Patents
Copolymer containing polyphenyl polyether branched chain structure and preparation and application thereof Download PDFInfo
- Publication number
- CN110724235A CN110724235A CN201910952526.2A CN201910952526A CN110724235A CN 110724235 A CN110724235 A CN 110724235A CN 201910952526 A CN201910952526 A CN 201910952526A CN 110724235 A CN110724235 A CN 110724235A
- Authority
- CN
- China
- Prior art keywords
- polyphenyl
- polyether
- monomer
- structural unit
- branched chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyethers (AREA)
Abstract
The invention provides a copolymer containing a polyphenyl polyether branched chain structure, and preparation and application thereof. The copolymer contains a structural unit A shown in a formula (1), a lower ester structural unit B shown in a formula (2), a structural unit C shown in a formula (3) and a polyphenyl polyether branched chain structural unit D shown in a formula (4); and based on 100% of the total mass of structural units A, B, C and D in the copolymer containing the polyphenyl polyether branched chain structure, the content of the structural unit A is 12.0-98.0 wt%, the content of the structural unit B is 0.4-22.0 wt%, the content of the structural unit C is 0.1-28.0 wt%, and the content of the structural unit D is 0.5-58.0 wt%: the copolymer can highly disperse aggregates such as colloid, asphaltene, wax crystal and the like in thick oil, and hasThe viscosity and pour point of the thickened oil are obviously reduced, and the emulsifying effect is obvious, so that the fluidity of the thickened oil can be greatly improved.
Description
Technical Field
The invention relates to the field of petroleum and petrochemical industry, in particular to a copolymer containing a polyphenyl polyether branched chain structure, and preparation and application thereof, and especially relates to a copolymer containing a polyphenyl polyether branched chain structure, which is used for emulsification and viscosity reduction of thickened oil, chemical flooding for improving the crude oil recovery ratio, or used in the fields of drilling fluid, profile control and water shutoff, sewage and sludge treatment and the like.
Background
Thickened oil is an important strategic resource. With the decreasing production of conventional crude oil, the development of unconventional crude oil such as thick oil is increasingly important. However, the heavy oil has high content of heavy components such as colloid and asphaltene, high density, high viscosity and poor fluidity, so that the difficulty of exploitation, collection and transportation of the heavy oil is greatly increased compared with the conventional crude oil. The thickened oil thermal recovery technology has obvious effect of improving the recovery efficiency, is widely applied to thickened oil recovery, but has higher cost. In part of thick oil blocks, thick oil water flooding is also becoming an important oil recovery technology. However, the thick oil reservoir has strong heterogeneity, the thick oil has poor mobility in the stratum, low efficiency or ineffective circulation of injected water is easily caused, the water injection displacement effect is poor, and the crude oil recovery ratio is low. Therefore, the viscosity reduction of the thickened oil has important significance for improving the recovery ratio of the thickened oil and gathering and transporting the thickened oil.
The chemical viscosity reducing technology for thickened oil mainly comprises the steps of adding an oil-soluble viscosity reducing agent, demulsifying to reduce viscosity, emulsifying to reduce viscosity and the like, and has certain application in the improvement of the recovery efficiency of thickened oil and the gathering and transportation of thickened oil. In practical application, the oil-soluble viscosity reducer needs to use an aromatic hydrocarbon toxic solvent to increase the solubility of the oil-soluble viscosity reducer in thick oil, and is high in cost and harmful to the environment. The petroleum sulfonate surfactant can be used for emulsifying and reducing viscosity of thickened oil. For example, CN102618245A discloses an emulsifying viscosity-reducing agent, which is composed of petroleum benzene sulfonate, anionic surfactant and pH regulator, and can form an emulsion with thick oil. However, petroleum sulfonate surfactants are effective only for specific heavy oils, are too targeted and have poor salt resistance, and the formed O/W type emulsion has poor stability and is limited in application.
In order to realize high-efficiency emulsification and viscosity reduction of the thickened oil, an aggregate structure formed by heavy components such as colloid, asphaltene and wax in the thickened oil must be destroyed, so that the thickened oil is dispersed to form a fine oil-in-water emulsion and has certain stability. The heavy components in the thickened oil, such as colloid, asphaltene, wax and the like, are high in content, and the substances have high molecular weight and strong polarity, are easy to interact to form aggregates or are adsorbed to an oil-water interface film, and are important factors for causing the high viscosity of the thickened oil. The low molecular surfactant emulsifies faster, but the formed emulsion has poor stability and is easy to invert into high-viscosity water-in-oil emulsion, so that the viscosity of the crude oil is increased. The stability of the emulsion can be improved by compounding the low-molecular surfactant with alkali or a polymer, but the complex system has chromatographic separation during the migration in the stratum, so that the viscosity reducing effect of the emulsion is greatly reduced, and the alkali can bring adverse effects such as scaling of an injection and production system.
The invention relates to a copolymer containing polyphenyl polyether branched chain structure. The copolymer introduces a polyphenyl polyether branched chain, a lower ester branched chain and an alkyl sulfonate branched chain with surface activity on a polyacrylamide main chain structure, and the copolymer containing the active branched chain can quickly emulsify thick oil under a simulated stratum working condition to form a stable oil-in-water emulsion, greatly reduce the viscosity of the thick oil, improve the flowability of the crude oil, and can be used for emulsifying and viscosity reducing of the thick oil, improving the recovery ratio of the crude oil by chemical flooding or viscosity reducing and conveying the thick oil in a pipeline. The copolymer contains various active branched chains, has interfacial activity, emulsifying dispersion and certain thickening performance, and can be used in petroleum and petrochemical fields such as drilling fluid, plugging regulation, sewage and sludge treatment and the like.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a copolymer containing a polyphenyl polyether branched chain structure, and preparation and application thereof, wherein the copolymer can enable common crude oil, particularly thick oil, to be dispersed in water in the form of small oil drops to form an oil-in-water emulsion, greatly reduce the viscosity of the thick oil and improve the fluidity of the thick oil, and can be used for the fields of thick oil emulsification viscosity reduction, chemical flooding for improving the crude oil recovery ratio, drilling fluid, profile control and water plugging, sewage and sludge treatment and the like.
In order to achieve the above object, in one aspect, the present invention provides a copolymer containing a polyphenyl polyether branch structure, wherein the copolymer containing a polyphenyl polyether branch structure contains a structural unit a shown in formula (1), a lower ester structural unit B shown in formula (2), a structural unit C shown in formula (3), and a polyphenyl polyether branch structural unit D shown in formula (4); and based on 100% of the total mass of structural units A, B, C and D in the copolymer containing the polyphenyl polyether branched chain structure, the content of the structural unit A is 12.0-98.0 wt%, the content of the structural unit B is 0.4-22.0 wt%, the content of the structural unit C is 0.1-28.0 wt%, and the content of the structural unit D is 0.5-58.0 wt%:
wherein the content of the first and second substances,
R1is NH2ONa or OK; r2Is C1～C3An alkyl group; r3、R4Each independently is H or CH3。
The value range of m is 5-20, and the value range of n is 5-60.
The copolymer containing the polyphenyl polyether branched chain structure, provided by the invention, has the relative molecular mass (viscosity average molecular weight) of 160-2050 ten thousand.
In another aspect, the invention further provides a preparation method of the copolymer containing the polyphenyl polyether branch structure, wherein the method comprises a step of polymerizing a monomer mixture to obtain the copolymer containing the polyphenyl polyether branch structure, wherein the monomer mixture contains a monomer E shown in a formula (5), a lower unsaturated ester monomer F shown in a formula (6), a monomer G shown in a formula (7) and a polyphenyl terminated polyether monomer H shown in a formula (8). Based on 100 percent of the total mass of the monomer mixture (namely the monomer E shown in the formula (5), the monomer F shown in the formula (6), the monomer G shown in the formula (7) and the polyphenyl terminated polyether macromonomer H shown in the formula (8)), the content of the monomer E is 12.0 to 98.0 percent by weight, the content of the monomer F is 0.4 to 22.0 percent by weight, the content of the monomer G is 0.1 to 28.0 percent by weight, and the content of the monomer H is 0.5 to 58.0 percent by weight; the relative molecular mass of the copolymer obtained by the solution polymerization reaction is 160-2050 ten thousand,
wherein the content of the first and second substances,
R1is NH2ONa or OK; r2Is C1～C3An alkyl group; r3、R4Each independently is H or CH3。
The value range of m is 5-20, and the value range of n is 5-60.
According to some embodiments of the present invention, the method comprises polymerizing the monomer mixture in the presence of an aqueous medium, an initiator, and a polymerization aid to obtain the copolymer containing the polyphenyl polyether branch structure.
According to some embodiments of the invention, wherein the ratio of the mass of the monomer mixture to the total mass of the reaction system is (0.10 to 0.35): 1.
the reaction system comprises a monomer mixture, an aqueous medium, an initiator and a polymerization auxiliary agent; the total mass of the reaction system refers to the total mass including the monomer mixture, the aqueous medium, the initiator and the polymerization auxiliary agent.
According to some embodiments of the invention, wherein the initiator is selected from the group consisting of a redox initiator, a catalyst, and a mixture of one or more of azo-type initiators; when the initiators are respectively present, the initiators are respectively and independently used according to the total mass of the reaction system of 100 percent: 0.0010-0.0800% of redox agent, 0.0010-0.0400% of azo initiator and 0.0010-0.0600% of catalyst.
It is to be understood that the terms "present in each case" in the context of the invention mean that the particular constituents thereof are present in each case independently of one another. For example, the "presence of each initiator" means that one or more of a redox initiator, a catalyst and an azo-based initiator are present as the initiator, and for example, when a redox agent is present, it is used in an amount of 0.0010 to 0.0800%, and when an azo-based initiator is present, it is used in an amount of 0.0010 to 0.0400%. When the above components are present independently of each other, the amount ranges do not vary with the presence or absence of other components.
According to some embodiments of the invention, the redox initiator comprises an oxidizing agent and a reducing agent, wherein the molar ratio of the oxidizing agent to the reducing agent is (0.3-3.0): 1.
according to some embodiments of the invention, wherein the oxidizing agent is selected from at least one of potassium persulfate, ammonium persulfate, and sodium persulfate; the reducing agent is at least one selected from sodium bisulfite, sodium sulfite, sodium formaldehyde sulfoxylate and sodium thiosulfate.
According to some embodiments of the invention, the catalyst is selected from at least one of tetramethylethylenediamine, tetramethylbutanediamine, tetramethylpropanediamine, morpholine, and piperidine.
According to some embodiments of the present invention, the azo initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, 2-azobisisobutylamidine dihydrochloride, and azobisisobutyramidine hydrochloride (V-50).
According to some embodiments of the present invention, wherein the polymerization auxiliary agent is selected from at least one of an alkaline agent, a metal masking agent, a chain transfer agent, and other auxiliary agents; when the polymerization auxiliary agents are respectively and independently present, the dosage of the polymerization auxiliary agents is 100 percent of the total mass of the reaction system, and the dosage of the polymerization auxiliary agents is respectively and independently: 0.00-6.0% of alkaline agent, 0.0010-0.0700% of metal shielding agent, 0.0010-0.0800% of chain transfer agent and 0.0010-2.0000% of other auxiliary agents.
According to some embodiments of the invention, wherein the alkaline agent is selected from the group consisting of a mixture of one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the metal masking agent is selected from one or more of disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and sodium citrate; the chain transfer agent is one or a mixture of sodium formate, sodium hypophosphite and isopropanol; the other auxiliary agent is selected from one or a mixture of two of urea and lauryl sodium sulfate.
According to some embodiments of the present invention, the polymerization reaction comprises reacting at 3-20 ℃ for 1-10h, and then aging at 60-80 ℃ for 1-5h to obtain the copolymer containing the polyphenyl polyether branch structure.
According to some specific embodiments of the invention, the monomer mixture is subjected to a polymerization reaction in the presence of an aqueous medium, an initiator and a polymerization assistant to obtain the copolymer containing the polyphenyl polyether branched chain structure, and the method comprises the steps of adding the polymerization assistant into a solution of the monomer mixture and the aqueous medium at 3-20 ℃, introducing nitrogen for 20-40 min, then adding the initiator, continuously introducing nitrogen for 5-10 min, reacting for 1-10 hours after sealing, and then heating to 60-80 ℃ to cure for 1-5 hours to obtain the copolymer containing the polyphenyl polyether branched chain structure.
According to some embodiments of the present invention, the method comprises aging at 60-80 ℃ for 1-5h to obtain a gel product, and then granulating, drying, pulverizing and sieving the gel product to obtain solid particles of the copolymer containing polyphenyl polyether branch structure.
In still another aspect, the invention further provides an application of the copolymer containing the polyphenyl polyether branched chain structure in thick oil emulsification viscosity reduction, chemical flooding enhanced oil recovery and the like.
The embodiments of the present invention may be combined with each other arbitrarily without contradiction.
In conclusion, the invention provides a copolymer containing a polyphenyl polyether branched chain structure, and preparation and application thereof. The copolymer containing the polyphenyl polyether branched chain structure has the following advantages:
the copolymer structural unit contains a polyphenyl polyether branched chain structure, wherein polyphenyl at the tail end of a branched chain has very strong affinity with condensed ring aromatic hydrocarbons such as colloid, asphaltene and the like in the thick oil, and can permeate and be anchored into the thick oil through hydrogen bond action and the like; the polyphenyl has stronger function with the stacking aggregation structure of colloid and asphaltene in the thickened oil, and has stronger disassembling and dispersing functions on the aggregation structure, so that the sizes of the colloid and the asphaltene aggregate become smaller; the polyoxyethylene ether chain has the performances of hydrophile lipophile and reducing the tension of an oil-water interface, and the strong combination effect of the polyphenyl and the thick oil improves the wettability, the coating degree and the space effect of the polyoxyethylene branched chain on the surface of the thick oil, the dispersion capacity to the thick oil and the emulsion stability, and can ensure that the thick oil forms stable O/W emulsion in a copolymer solution, thereby reducing the viscosity of the thick oil. Because the polyphenyl and the polyether chain segment are positioned in the same side group, the synergistic effect of the polyphenyl and the polyether chain segment is obviously better than that of the polyphenyl and the polyether chain segment in different side groups. In addition, the polyether monomer of the polyphenyl end-capping structure does not contain active hydrogen, and free radical chain transfer effect does not exist, so that the polymerization activity and the copolymer performance of the polyether monomer are higher than those of the polyether monomer containing the active hydrogen. The polyether monomer and the anionic sulfonate monomer both have surface activity, the solubility and the polymerization capacity of the ester monomer in water can be improved by forming mixed micelles and the like, the additional emulsifier and the subsequent separation process are greatly reduced, and the performance and the quality of the obtained polymer are higher.
The short-chain ester branched chain structural unit in the copolymer molecule can be combined with-OH and-NH in colloid and source biomass molecules2When polar groups form hydrogen bonds, copolymer molecules can form a solvolysis layer on the surfaces of the colloid and asphaltene aggregates, so that the space shielding effect is achieved, the reaggregation of colloid and asphaltene lamellar structures is inhibited, and the viscosity reducing effect is achieved. The alkyl of the alkyl sulfonate branched chain reacts with wax crystals in the thick oil, so that the growth of the wax crystals is inhibited, the condensation point of the thick oil is reduced, and the flowing condition of the thick oil is improved. Therefore, the synergistic effect of the short-chain ester and the alkyl branched chain improves the viscosity reduction of the copolymer molecules on the thickened oilCoagulation effect.
Therefore, the copolymer molecule contains polyphenyl polyoxyethylene ether branched chains, ester groups and alkyl sulfonate with different lengths and ionic types, and the synergistic effect of different active branched chains greatly enhances the application performance of the copolymer molecule, improves the capability of disassembling and damaging colloids, asphaltenes, wax crystals and other aggregates in the thickened oil, promotes the thickened oil to be highly dispersed to form stable oil-in-water emulsion, realizes viscosity reduction and pour point depression of the thickened oil, and improves the fluidity of the thickened oil.
Drawings
FIG. 1 is an infrared spectrum of the products of examples 1, 2 and 3;
FIG. 2 is a micrograph of a fine oil-in-water emulsion of a thick oil in an aqueous solution of example 1 (b is a partial enlargement of a picture a).
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
The embodiment provides a copolymer containing a polyphenyl polyether branched chain structure, which comprises the following preparation steps and raw material proportions:
30.36g of monomer E (R) were weighed out1Is NH2I.e., acrylamide), 0.86g of a lower unsaturated ester monomer F (R)2Is CH3) 5.58G of monomer G (R)3H, m ═ 9), 0.96g of polyphenyl-terminated polyether monomer H (R)4H, n is 52), adding 104.60g of deionized water into a dissolver, adding 4.08g of sodium carbonate, stirring and dissolving, adjusting the temperature to 15 ℃, transferring the solution into a reactor, adding 2.88g of 3.0% disodium ethylene diamine tetraacetate, 2.4g of 1.5% sodium bisulfite, 1.28g of 6% sodium formate and other polymerization aids, introducing nitrogen for 30min, adding 4.8g of 0.7% potassium persulfate, 3.2g of 0.25% 2, 2-azobisisobutylamidine dihydrochloride, continuing introducing nitrogen for 10min, sealing the reactor, completing the reaction after 4H, heating the rubber block to 80 ℃, curing for 2H, and obtaining the polymer rubber block.
And taking out the obtained polymer gel block, and granulating, drying, crushing and screening to obtain the copolymer containing the polyphenyl polyether branched chain structure, wherein the molecular weight of the polymer is 1300.5 ten thousand.
The synthesized polymer was isolated, purified, and then subjected to infrared spectroscopic analysis by a tabletting method, and the results are shown in 1 of FIG. 1. Wherein the wave number is 3344cm-1The absorption peak is-OH absorption; wave number 2923cm-1And 1392cm-1Absorption peaks are respectively methylene-CH2-antisymmetric telescopic vibration and deformation absorption, indicating the presence of alkyl groups; wave number 1715cm-1The absorption peak is the stretching vibration absorption of carbonyl C ═ O; wave number of 1557cm-1The absorption peak is the vibration absorption of a benzene ring framework; wave number 1185cm-1The strong absorption peak nearby is the asymmetric stretching vibration of the polyoxyethylene C-O-C bond, 805cm-1The nearby absorption peak is the swing vibration of the polyoxyethylene plane; wave number 1160cm-1Strong absorption peak of (2) and 1042cm-1The nearby middle-strong narrow peak is sulfonate radical absorption. According to the judgment of absorption peaks of oxyethylene, alkyl, benzene ring, sulfonic group and the like on a spectrogram, the monomers all participate in polymerization to obtain a target product.
Example 2
The embodiment provides a copolymer containing a polyphenyl polyether branched chain structure, which comprises the following preparation steps and raw material ratio:
27.13g of monomer E (R) were weighed out1Is NH2I.e., acrylamide), 1.68g of a lower unsaturated ester monomer F (R)2Is CH3) 6.56G of monomer G (R)3H, m ═ 9), 1.61g of polyphenyl-terminated polyether monomer H (R)4H, n is 52), adding 103.2g of deionized water into a dissolver, adding 4.18g of sodium carbonate and 0.6g of sodium dodecyl sulfate, stirring and dissolving, adjusting the temperature to 13 ℃, transferring the solution into a reactor, adding 3.18g of 3.0% disodium ethylenediamine tetraacetate, 3.53g of 1.5% sodium bisulfite, 1.38g of 6% sodium hypophosphite and other polymerization aids, introducing nitrogen for 30min, adding 5.81g of 0.7% ammonium persulfate and 4.74g of 0.25% azobisisobutyrate hydrochloride, continuing introducing nitrogen for 10min, sealing the reactor, completing the reaction after 4H, heating the rubber block to 80 ℃, curing for 2H, and obtaining the polymer rubber block. The relative molecular mass of the polymer is 7306 ten thousand.
The synthesized polymer was isolated, purified, and then subjected to infrared spectroscopic analysis by the tabletting method, and the results are shown in 2 of FIG. 1. The absorption peak positions are 3421cm respectively-1、3196cm-1、2916cm-1、2862cm-1、1673cm-1、1558cm-1、1452cm-1、1423cm-1、1328cm-1、1196cm-1、1113cm-1、825cm-1、713cm-1The molecular structure of the synthetic polymer contains amide groups, methylene groups, carbonyl groups, phenyl groups, polyoxyethylene groups, sulfonic acid groups, and the like, and the obtained product is the target product.
Example 3
This example provides a copolymer containing polyphenyl polyether branch structure, the preparation steps are the same as example 1 (no alkali is added for neutralization), the raw material ratio is shown in example 3, and the molecular weight of the obtained polymer is 415.8 ten thousand.
The implementation provides a copolymer containing a polyphenyl polyether branched chain structure, and the preparation steps and the raw material ratio are as follows:
25.20g of monomer E (R) were weighed1Is ONa, i.e. acrylic acid), 2.10g of a lower unsaturated ester monomer F (R)2Is CH3) 7.11G of monomer G (R)3H, m ═ 9), 2.8g of polyphenyl-terminated polyether monomer H (R)4H, n is 32), adding 109.34g of deionized water into a dissolver, adding 1.2g of sodium dodecyl sulfate, stirring and dissolving, adjusting the temperature to 13 ℃, transferring the solution into a reactor, adding 2.88g of disodium ethylenediamine tetraacetic acid with the concentration of 3.0 percent, 4.3g of sodium formaldehyde sulfoxylate with the concentration of 1.5 percent, 1.6g of polymerization aids such as sodium formate with the concentration of 6 percent, introducing nitrogen for 30min, adding 6.2g of potassium persulfate with the concentration of 0.7 percent and 5.8g of azodiisobutyl hydrochloride with the concentration of 0.25 percent, continuously introducing nitrogen for 10min, sealing the reactor, completing the reaction after 4H, heating the rubber block to 80 ℃, curing for 2H, and obtaining the polymer rubber block. The relative molecular mass of the polymer was 426.2 ten thousand.
The synthesized polymer was isolated, purified, and then subjected to infrared spectroscopic analysis by a tabletting method, and the results are shown in 3 of FIG. 1. The absorption peaks were 3438cm in length-1、2928cm-1、2862cm-1、1661cm-1、1602cm-1、1549cm-1、1417cm-1、1192cm-1、1111cm-1、1075cm-1、706cm-1、673cm-1The molecular structure of the synthetic polymer contains carbonyl, amide, methylene, phenyl, polyoxyethylene, sulfonic acid, and the like groups, and the obtained product is the target product.
EXAMPLES evaluation
(1) Wetting and emulsifying effects of thickened oils
An appropriate amount of the copolymer prepared in the embodiments 1 to 3 of the invention is prepared into 0.1 percent solution by using oilfield field sewage, the solution is mixed with oilfield dehydrated crude oil (the viscosity is 961.6mPa.s at 50 ℃) according to the oil-water ratio of 4:6 (volume ratio, v/v), and the mixture is placed in a glass tube with a plug, and the low speed (the shear rate is 10 to 20S) is performed at 50 DEG-1) The mixture was sheared by shaking for 20min, the change in the volume of the aqueous phase was observed and recorded, and the water content of the emulsion (60% in the emulsion when completely emulsified) was calculated and shown in Table 1.
TABLE 1 emulsion phase Water content Change upon emulsification of oil-Water System in the Presence of different copolymers
| Time/min | Blank space | PAM commercially available | Example 1 | Example 2 | Example 3 |
| 0 | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ |
| 2 | 1.41％ | 3.57％ | 21.65％ | 6.25％ | 3.38％ |
| 6 | 1.41％ | 3.57％ | 27.27％ | 16.67％ | 7.74％ |
| 14 | 1.41％ | 3.57％ | 33.33％ | 21.05％ | 15.88％ |
| 30 | 1.41％ | 6.90％ | 46.67％ | 34.78％ | 24.74％ |
| 50 | 6.67％ | 15.63％ | 49.33％ | 37.50％ | 26.67％ |
| 95 | 8.50％ | 22.86％ | 52.50％ | 48.28％ | 42.80％ |
| 145 | 33.33％ | 41.30％ | 57.18％ | 54.55％ | 50.69％ |
| Emulsion type | W/O | W/O or W/O | O/W | O/W | O/W |
| Viscosity reduction ratio (50 ℃ C.) | / | <40％ | 90.1 | 92.2 | 80.2 |
A small amount of the emulsion was taken and observed under a microscope for microscopic morphology, as shown in FIG. 2 (viscosity reducer is example 1).
(2) Viscosity reducing effect of thickened oil
After complete emulsification the viscosity of the emulsion was measured using an MCR301 viscometer (see table 2).
TABLE 2 emulsifying and viscosity-reducing Effect of several viscosity-reducing Agents on thickened oils
Injecting micromolecular viscosity reducing agent which is polyethylene glycol octyl phenyl ether type nonionic surfactant; commercially available PAM (SK-18) is PAM containing nonionic hydrophobic monomer building blocks.
(3) Aqueous phase tackifying effect of copolymers
The polymer type prepared in example 2 was formulated into an aqueous solution having a concentration of 1200mg/L (degree of mineralization: 1200mg/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. It can be seen that when the polymer concentration is higher than 1400mg/L, the viscosity of the polymer solution exceeds 30mPa.s, which indicates that the polymer has stronger tackifying capability to the water phase.
Table 3 viscosity of polymer in example 2 aqueous solution at different concentrations
| Concentration (mg/L) | 400 | 800 | 1000 | 1200 | 1400 | 1600 |
| Viscosity (mPa.s) | 9.1 | 15.6 | 19.5 | 25 | 31 | 38 |
The embodiment evaluation results show that the copolymer containing the polyphenyl polyether branched chain structure can enable thick oil to be rapidly dispersed in water under experimental conditions, the viscosity reduction rate of the thick oil is high, and the copolymer has great application value in the technical fields of thick oil emulsifying viscosity reducers, chemical flooding and the like.
Claims (16)
1. A copolymer containing a polyphenyl polyether branched chain structure comprises a structural unit A shown in a formula (1), a lower ester structural unit B shown in a formula (2), a structural unit C shown in a formula (3) and a polyphenyl polyether branched chain structural unit D shown in a formula (4); and based on 100% of the total mass of structural units A, B, C and D in the copolymer containing the polyphenyl polyether branched chain structure, the content of the structural unit A is 12.0-98.0 wt%, the content of the structural unit B is 0.4-22.0 wt%, the content of the structural unit C is 0.1-28.0 wt%, and the content of the structural unit D is 0.5-58.0 wt%:
wherein the content of the first and second substances,
R1is NH2ONa or OK; r2Is C1～C3An alkyl group; r3、R4Each independently is H or CH3；
The value range of m is 5-20, and the value range of n is 5-60.
2. The polyphenyl polyether branch structure-containing copolymer according to claim 1, wherein the relative molecular mass of the polyphenyl polyether branch structure-containing copolymer is 160-2050 ten thousand.
3. A preparation method of the copolymer containing the polyphenyl polyether branched chain structure according to any one of claims 1 to 2, wherein the method comprises the step of carrying out polymerization reaction on a monomer mixture to obtain the copolymer containing the polyphenyl polyether branched chain structure, wherein the monomer mixture contains a monomer E shown in a formula (5), a lower unsaturated ester monomer F shown in a formula (6), a monomer G shown in a formula (7) and a polyphenyl terminated polyether monomer H shown in a formula (8); based on the total mass of the monomer mixture being 100%, the content of the monomer E is 12.0-98.0 wt%, the content of the monomer F is 0.4-22.0 wt%, the content of the monomer G is 0.1-28.0 wt%, and the content of the monomer H is 0.5-58.0 wt%; the relative molecular mass of the copolymer obtained by the polymerization reaction is 160-2050 ten thousand,
wherein the content of the first and second substances,
R1is NH2ONa or OK; r2Is C1～C3An alkyl group; r3、R4Each independently is H or CH3；
The value range of m is 5-20, and the value range of n is 5-60.
4. The preparation method of claim 3, wherein the method comprises the step of polymerizing the monomer mixture in the presence of an aqueous medium, an initiator and a polymerization assistant to obtain the copolymer containing the polyphenyl polyether branched chain structure.
5. The production method according to claim 4, wherein the ratio of the mass of the monomer mixture to the total mass of the reaction system is (0.10 to 0.35): 1.
6. the production method according to claim 4, wherein the initiator is selected from a mixture of one or more of a redox initiator, a catalyst and an azo-based initiator; when the initiators are respectively present, the initiators are respectively and independently used according to the total mass of the reaction system of 100 percent: 0.0010-0.0800% of redox agent, 0.0010-0.0400% of azo initiator and 0.0010-0.0600% of catalyst.
7. The production method according to claim 6, wherein the redox initiator comprises an oxidizing agent and a reducing agent in a molar ratio of (0.3-3.0): 1.
8. the production method according to claim 7, wherein the oxidizing agent is selected from at least one of potassium persulfate, ammonium persulfate, and sodium persulfate; the reducing agent is at least one selected from sodium bisulfite, sodium sulfite, sodium formaldehyde sulfoxylate and sodium thiosulfate.
9. The production method according to claim 8, wherein the catalyst is selected from at least one of tetramethylethylenediamine, tetramethylbutanediamine, tetramethylpropanediamine, morpholine, and piperidine.
10. The production method according to claim 9, wherein the azo-based initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, 2-azobisisobutylamidine dihydrochloride, and azobisisobutyramidine hydrochloride.
11. The production method according to claim 10, wherein the polymerization auxiliary agent is selected from at least one of an alkali agent, a metal masking agent, a chain transfer agent, and other auxiliary agents; when the polymerization auxiliary agents are respectively and independently present, the dosage of the polymerization auxiliary agents is 100 percent of the total mass of the reaction system, and the dosage of the polymerization auxiliary agents is respectively and independently: 0.00-6.0% of alkaline agent, 0.0010-0.0700% of metal shielding agent, 0.0010-0.0800% of chain transfer agent and 0.0010-2.0000% of other auxiliary agents.
12. The preparation method according to claim 11, wherein the alkaline agent is selected from a mixture of one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the metal masking agent is selected from one or more of disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and sodium citrate; the chain transfer agent is one or a mixture of sodium formate, sodium hypophosphite and isopropanol; the other auxiliary agent is selected from one or a mixture of two of urea, sodium dodecyl sulfate and polyoxyethylene ether laurate.
13. The preparation method of any one of claims 4 to 12, wherein the polymerization reaction comprises reacting at 3-20 ℃ for 1-10h, and then curing at 60-80 ℃ for 1-5h to obtain the copolymer containing the polyphenyl polyether branch structure.
14. The preparation method of claim 13, wherein the monomer mixture is subjected to a polymerization reaction in the presence of an aqueous medium, an initiator and a polymerization assistant to obtain the copolymer containing the polyphenyl polyether branched chain structure, and the method comprises the steps of adding the polymerization assistant into a solution of the monomer mixture and the aqueous medium at 3-20 ℃, introducing nitrogen for 20-40 min, then adding the initiator, continuously introducing nitrogen for 5-10 min, reacting for 1-10 hours after sealing, and then heating to 60-80 ℃ to age for 1-5 hours to obtain the copolymer containing the polyphenyl polyether branched chain structure.
15. The preparation method according to claim 13 or 14, wherein the method comprises aging at 60-80 ℃ for 1-5h to obtain a gel product, and then granulating, drying, crushing and sieving the gel product to obtain the solid granular copolymer containing the polyphenyl polyether branch structure.
16. The copolymer containing the polyphenyl polyether branch structure according to any one of claims 1 to 2, wherein the copolymer is applied to the aspects of emulsification viscosity reduction of common crude oil or thick oil, chemical flooding for improving the recovery rate of crude oil and the like, and the application of the copolymer in production processes of plugging control operation, drilling fluid or sewage sludge treatment and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910952526.2A CN110724235B (en) | 2019-10-09 | 2019-10-09 | Copolymer containing polyphenyl polyether branched chain structure and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910952526.2A CN110724235B (en) | 2019-10-09 | 2019-10-09 | Copolymer containing polyphenyl polyether branched chain structure and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110724235A true CN110724235A (en) | 2020-01-24 |
| CN110724235B CN110724235B (en) | 2022-08-30 |
Family
ID=69220858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910952526.2A Active CN110724235B (en) | 2019-10-09 | 2019-10-09 | Copolymer containing polyphenyl polyether branched chain structure and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110724235B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853958A (en) * | 2022-07-05 | 2022-08-05 | 山东科兴化工有限责任公司 | Supermolecule nano oil displacement agent for cold recovery of thick oil and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810933A (en) * | 2006-03-13 | 2006-08-02 | 辽宁奥克化学集团有限公司 | Thick oil demulsifier and its prepn |
| US20130005626A1 (en) * | 2011-06-28 | 2013-01-03 | Burkhard Breitzke | Surfactant compositions |
| CN104231160A (en) * | 2013-06-14 | 2014-12-24 | 中国石油化工股份有限公司 | Terpolymer used for resisting temperature and displacing oil and preparation method thereof |
-
2019
- 2019-10-09 CN CN201910952526.2A patent/CN110724235B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810933A (en) * | 2006-03-13 | 2006-08-02 | 辽宁奥克化学集团有限公司 | Thick oil demulsifier and its prepn |
| US20130005626A1 (en) * | 2011-06-28 | 2013-01-03 | Burkhard Breitzke | Surfactant compositions |
| CN104231160A (en) * | 2013-06-14 | 2014-12-24 | 中国石油化工股份有限公司 | Terpolymer used for resisting temperature and displacing oil and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853958A (en) * | 2022-07-05 | 2022-08-05 | 山东科兴化工有限责任公司 | Supermolecule nano oil displacement agent for cold recovery of thick oil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110724235B (en) | 2022-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110746550B (en) | Multi-component copolymer containing long-chain side group and preparation and application thereof | |
| CN110483687B (en) | Fracturing fluid thickening agent and preparation method thereof | |
| US4034809A (en) | Hydrolyzed polyacrylamide latices for secondary oil recovery | |
| CN105504182B (en) | A kind of nanoscale pickering emulsion type fracturing fluid and preparation method thereof | |
| US4525496A (en) | Self-inverting water-in-oil emulsions of water-soluble polymers | |
| US5362827A (en) | Solution process for preparation hydrophobically functionalized cationic polymers (C-2691) | |
| US20060237372A1 (en) | Separation of drilling mud emulsions | |
| CN107383273B (en) | A kind of viscous crude activator and preparation method thereof | |
| CN110591023B (en) | Amphiphilic polymer containing capped polyether structure and preparation and application thereof | |
| EP0464957A2 (en) | Hydrophobically functionalized cationic polymers | |
| CN110724235B (en) | Copolymer containing polyphenyl polyether branched chain structure and preparation and application thereof | |
| CN110746551B (en) | Copolymer containing double-polyoxyethylene-ether branched chain structure and preparation and application thereof | |
| CN113956856A (en) | Nano multifunctional cleanup additive for oil field drilling fluid and preparation method thereof | |
| CN108484839A (en) | A kind of amphipathic carboxylic dispersants and preparation method thereof | |
| CN111363089B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN115895634A (en) | Thick oil viscosity reducer composition and preparation method thereof | |
| CN111647106B (en) | Viscoelastic polymer emulsion and preparation method thereof, low-viscosity slippery water and high-viscosity sand-carrying fluid | |
| CN113652220B (en) | Resistance reducing agent, water-based fracturing fluid containing resistance reducing agent and application of water-based fracturing fluid | |
| Li et al. | Intrinsic viscosity, rheological property, and oil displacement of hydrophobically associating fluorinated polyacrylamide | |
| CN111363090B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN105622839A (en) | Environment-friendly nanometer emulsion fracturing fluid and preparation method thereof | |
| CN113429525B (en) | High-temperature-resistant oil-based drilling fluid cutting agent and preparation method and application thereof | |
| CN115304707B (en) | Polyacrylamide microsphere emulsion with adjustable particle size, and preparation method and application thereof | |
| CN115368885B (en) | Dual-stimulus response type polymer thickened oil emulsifying viscosity reducer and preparation method thereof | |
| CN111363087B (en) | Acrylamide copolymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |