Glycoside group-containing compound and use thereof

Abstract

A glycoside group-containing compound and a preparation method therefor and a use thereof. The glycoside group-containing compound has a structure represented by formula (1), and has a high emulsifying capability. The polymer obtained by polymerization of the glycoside group-containing compound can improve the water-flooding recovery rate of a conventional oil reservoir and a common heavy oil reservoir.

Description

Compounds containing glycoside groups and their applications

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent applications 202311522670.5 and 202311522771.2 filed on November 15, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to the field of preparation of new compounds, in particular to a compound containing a glycoside group, a preparation method and application thereof, and in particular to the development and application of new compounds suitable for the field of petroleum extraction. Background Art

[0004] Heavy oil accounts for approximately 70% of the world's proven oil resources. However, heavy oil has high viscosity and low drive efficiency. Thermal recovery is the primary method for its development, but this leads to problems such as large amounts of residual oil remaining between wells that cannot be recovered and high energy consumption. Cold recovery, which typically uses chemical methods to improve the fluidity of heavy oil, offers advantages such as simple extraction processes and low costs, making it a significant development trend.

[0005] Adding small molecule, water-soluble viscosity reducers can improve oil recovery by reducing viscosity. However, cold-production heavy oil reservoirs are generally highly heterogeneous, and small molecule viscosity reducer solutions have low viscosity, resulting in severe fingering and uneven displacement. While combining these with polymers can improve displacement, they suffer from chromatographic separation, hindering deep oil profile adjustment and oil washing. Furthermore, deep within reservoirs, the driving force is weak, and conventional viscosity reducers require strong agitation to emulsify heavy oil. Therefore, emulsification of heavy oil is difficult under reservoir flow dynamics.

[0006] Due to the high asphaltene and colloid content in heavy oil, its high viscosity makes it difficult to extract. Therefore, there is an urgent need to develop a functional polymer that can interact with heavy oil, replacing the weak hydrogen bonds between heavy oils, and at the same time, has the advantages of fluidity control, interfacial activity, and the ability to emulsify heavy oil at low power. This is of great significance for improving the recovery rate of heavy oil in cold production.

[0007] Summary of the Invention

[0008] The purpose of the present invention is to overcome the problems existing in the prior art and provide a compound containing a glycoside group and its application.

[0009] In order to achieve the above object, the present invention provides a compound containing a glycoside group, which has a structure shown in formula (1).

[0010] The present invention also provides a glycoside group-containing polymer, which includes a structural unit C represented by formula (C) and a structural unit D represented by formula (D).

[0011] The present invention also provides a method for preparing the polymer and the polymer prepared by the method.

[0012] The present invention also provides a method for reducing the viscosity of heavy oil, comprising contacting the polymer solution with the heavy oil.

[0013] In addition, the present invention also provides the use of the compound and polymer in reducing the viscosity of heavy oil.

[0014] The compounds of the present invention possess strong emulsifying ability, demonstrating prolonged emulsification times in heavy oil emulsification experiments. The polymers obtained by copolymerizing the compounds of the present invention with other monomers exhibit high salt tolerance and aqueous phase viscosification capabilities, improving the oil-water mobility ratio and adjusting reservoir heterogeneity during oil displacement. Specifically, under the low dynamic conditions of reservoirs with salinity ≤50,000 mg / L and temperature ≤70°C, the polymers exhibit a high viscosity reduction rate for heavy oil with a viscosity ≤3,000 mPa·s at reservoir temperature, potentially improving the recovery rate of conventional and standard heavy oil reservoirs.

[0015] In particular, compared to alkyl groups (the sum of n1 and n2 is 0), the introduction of alcohol ether groups (the sum of n1 and n2 is not 0) allows the structural units provided by the glycoside group-containing compound to significantly improve the aforementioned properties of the polymer at a lower content. Furthermore, the introduction of two specific alcohol ether groups can significantly improve the aforementioned properties of the polymer even at an even lower content of the structural units provided by the compounds. DETAILED DESCRIPTION

[0016] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0017] The first aspect of the present invention provides a compound containing a glycoside group (or a modified glycoside), wherein the compound has a structure as shown in formula (1):

[0018] In formula (1), R3 is a C4-C20 alkyl group (such as C5, C6, C8, C10, C12, C14, C16, C18, C20) or a C7-C20 alkylphenyl group (propylphenyl, butylphenyl, pentylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl), R4, R5, R6, R5' and R6' are each independently H or a C1-C4 alkyl group, X is O or NQ, Q is H or a C1-C4 alkyl group, and the sum of n1 and n2 is a natural number from 0 to 20.

[0019] In the present invention, when X is O, the sum of n1 and n2 is not equal to 0, that is, when X is O, the sum of n1 and n2 is a natural number of 1-20 (n1+n2=1-20); when X is NQ (such as imino, NH), the sum of n1 and n2 is a natural number of 0-20 (n1+n2=0-20).

[0020] Preferably, R3 is a C6-C18 normal alkyl group, a C6-C18 isomeric alkyl group or a C7-C18 alkylphenyl group, more preferably a n-hexyl group, a n-dodecyl group, a n-decyl group, a n-octyl group, a n-tetradecyl group, a 2-ethylhexyl group or a 11-methyldodecyl group.

[0021] Preferably, R4, R5, R6, R5' and R6' are each independently H or methyl.

[0022] Preferably, R5′ and R6′ are each independently H or methyl and R5′ and R6′ are different, and R5 and R6 are both H.

[0023] More preferably, R5' is methyl.

[0024] Preferably, R5 and R6 are each independently H or methyl, more preferably H.

[0025] More preferably, R5' is a methyl group, R6' is H, and R5 and R6 are both H. The compounds in the above preferred embodiments have more excellent properties.

[0026] Preferably, X is O or imino (-NH-).

[0027] Preferably, when X is O, n1 is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and n2 is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0028] Preferably, when X is NQ (e.g., -NH-), n1 is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and n2 is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0029] According to a preferred embodiment of the present invention, n2 / n1=1-10, more preferably, n2 / n1=1.5-5.5.

[0030] According to a preferred embodiment of the present invention, the compound has a structure as shown in formula (1-1) or formula (1-2):

[0031] Wherein, n is a natural number of 0-20 (preferably 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10); R3 and R4 are as described above.

[0032] The compound of the present invention has strong emulsifying ability and exhibits excellent interfacial activity. When adsorbed on the oil-water interface, it can reduce the oil-water interfacial tension and help form a surface tension gradient.

[0033] The present invention has no particular requirements for the specific preparation method of the compound described in the first aspect. A person skilled in the art can determine a suitable synthesis method based on the structural formula provided by the present invention in combination with known knowledge in the field of organic synthesis, or a person skilled in the art can also prepare the aforementioned compound based on the specific examples provided later in the present invention (with replacement of raw materials). However, in order to further improve the yield of the compound, the second aspect of the present invention provides a method for preparing the compound, comprising: mixing at least one of the glycoside compounds represented by formula (2) with at least one of the double bond-containing compounds represented by formula (3) to react:

[0034] Wherein, R is selected from H, trifluoromethanesulfonyl or p-toluenesulfonyl, X, R3, R4, R5, R6, R5', R6', n1 and n2 are as described above and will not be repeated here.

[0035] In the present invention, the natural fatty alcohol raw materials mostly exist in the form of mixed alcohols (such as the coexistence of C8 and C10, and the coexistence of C12 and C14). Therefore, when the natural fatty alcohol raw materials are used to prepare the glycoside compound represented by formula (2), the obtained product is also a mixed glycoside. The properties of this mixed glycoside are basically the same as those of the single glycoside, and both can react with the double bond-containing compound represented by formula (3). The corresponding product obtained is also a mixture. Obviously, this mixture also falls within the scope of protection of the present invention.

[0036] In the present invention, there is no particular limitation on the amount of each raw material used in the preparation of the compound. In some embodiments of the present invention, the amount of the glycoside compound used is 0.65-1.5 mol relative to 1 mol of the double bond-containing compound.

[0037] In some embodiments of the present invention, the reaction temperature may be 0-200° C. (such as below room temperature (0-25° C.) or 80-100° C.), preferably 20-150° C. The reaction time may be 5-12 h, preferably 6-10 h.

[0038] In some embodiments of the present invention, the mixing is carried out in the presence of an activator, and the activator can be selected from diisopropyl azodicarboxylate and / or triphenylphosphine, preferably diisopropyl azodicarboxylate and triphenylphosphine in a molar ratio of 0.5-1.5, and its effect is to activate hydroxyl groups, so that it is easily removed. Relative to 1mol of double bond-containing compound, the amount of the activator is preferably 2-5mol. The use of the activator is conducive to reducing the temperature (control room temperature) of the esterification. When using an activator, in order to avoid air oxidation, the esterification is carried out in an inert atmosphere, and the inert atmosphere can be provided by nitrogen and / or inert gas. In the context of the present invention, inert gas refers to the gaseous elemental substance corresponding to all 0 group elements on the periodic table, including helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) etc.

[0039] In some embodiments of the present invention, the mixing is carried out in the presence of trifluoromethanesulfonic acid, the main function of which is to activate the R group so that it is easier to remove. Relative to 1 mol of the double bond-containing compound, the amount of the trifluoromethanesulfonic acid is preferably 0.1-0.3 mol. The use of the trifluoromethanesulfonic acid is conducive to accelerating the reaction rate and promoting the reaction to proceed in the forward direction. When using trifluoromethanesulfonic acid, in order to avoid its hydrolysis, the reaction is carried out in an inert atmosphere, which can be provided by nitrogen and / or an inert gas.

[0040] In some embodiments of the present invention, the method may further include: performing purification after the reaction is completed. The purification method is not particularly limited. For example, purification may be performed by methods such as extraction and spin drying, recrystallization, and column chromatography. According to one embodiment of the present invention, the purification comprises: cooling the reaction system, and removing the solvent and unreacted double-bond-containing compound by vacuum distillation. In another embodiment of the present invention, the purification may further include: removing the solvent by vacuum distillation from the reaction system, and then separating the unreacted raw materials using a chromatographic column.

[0041] In the present invention, when X is O, according to a preferred embodiment of the present invention, the method comprises: contacting at least one of the double-bond-containing compounds (acrylic compounds) represented by formula (3a) with (at least one) glycoside compound represented by formula (2a) under esterification reaction conditions to obtain a modified glycoside product. Wherein, n is as described above.

[0042] The contact between the double bond-containing compound represented by formula (3a) and the glycoside compound represented by formula (2a) can be carried out in an organic solvent. The organic solvent can be various solvents that can dissolve the reaction substrate, such as C6-C10 benzene series and / or N,N-dialkylformamide. The alkyl group in N,N-dialkylformamide is preferably a C1-C3 alkyl group (such as methyl, ethyl, propyl or isopropyl). Preferably, the organic solvent is selected from at least one of toluene, xylene and N,N-dimethylformamide. There is no particular limitation on the amount of the organic solvent used, as long as it can mainly dissolve the glycoside compound and the double bond-containing compound. There is no particular requirement for the contact method of the double bond-containing compound represented by formula (3a) and the glycoside compound represented by formula (2a), and they can be contacted in the form of a solution. In some embodiments of the present invention, the preparation step comprises: adding the glycoside compound dissolved in the organic solvent to the solution of the double bond-containing compound, and then placing it under esterification reaction conditions. The esterification reaction of the double bond-containing compound represented by formula (3a) and the glycoside compound represented by formula (2a) can be carried out in the presence of an activator, and the activator is as described above. It is understood that by replacing the compound represented by formula (2a) with the compound represented by formula (2d) and contacting it with the double bond-containing compound represented by formula (3a) (repeating the above steps), more glycoside group-containing compounds with other structures can be obtained.

[0043] In the present invention, when X is NH, according to another preferred embodiment of the present invention, the method comprises: mixing and reacting at least one of the glycoside compounds represented by formula (2b) with at least one of the double bond-containing compounds (acrylamide compounds) represented by formula (3b) under amidation reaction conditions, wherein n is as described above.

[0044] The temperature of the amidation reaction can be 10-200°C (such as below room temperature (0-25°C) or 80-100°C). The amidation reaction time can be 5-12h, preferably 6-10h. When R is H, the amidation reaction temperature is preferably carried out below room temperature (0-25°C). In the present invention, in order to more conveniently separate the target product and further improve the yield of the target product, according to a preferred embodiment of the present invention, the method further includes contacting at least one of the glycoside compounds represented by formula (2a) with a sulfonating agent under esterification reaction conditions to obtain a glycoside sulfonate represented by formula (2c), and then mixing the glycoside sulfonate represented by formula (2c) with the double bond-containing compound represented by formula (3b) to react (amidation reaction). The sulfonating agent is p-toluenesulfonyl halide and / or trifluoromethanesulfonic anhydride. Using trifluoromethanesulfonic anhydride as the sulfonating agent makes product separation easier. By preparing the compound of the present invention through such a two-step reaction, only reduced pressure distillation is required to obtain the intermediate product or the target product, and the separation process is simpler, more efficient, and more practical.

[0045] In some embodiments of the present invention, the amount of the sulfonation reagent used is 0.8-1.5 mol relative to 1 mol of the glycoside compound.

[0046] In some embodiments of the present invention, the esterification reaction conditions of the glycoside compound represented by formula (2a) and the sulfonated reagent include: a reaction time of 5-12 hours, preferably 6-10 hours. The esterification reaction temperature of the glycoside compound represented by formula (2a) and the sulfonated reagent can be below room temperature (e.g., 0-25° C.).

[0047] In some embodiments of the present invention, an organic base is further introduced into the esterification reaction system of the glycoside compound shown in formula (2a) and the sulfonated reagent, that is, the esterification reaction is carried out in the presence of an organic base. The organic base can provide a reaction medium for the esterification reaction and an acid (such as hydrochloric acid) produced during the neutralization reaction. Preferably, the amount of the organic base is 10-50 mol relative to 1 mol of the glycoside compound. The organic base is preferably at least one of the nitrogen-containing heterocyclic compounds of C4-C10, and more preferably, the organic base is selected from at least one of pyridine, triethylamine, and piperidine. The esterification reaction of the glycoside compound shown in formula (2a) and the sulfonated reagent can be carried out in the presence of an activator, and the activator is as described above.

[0048] In some embodiments of the present invention, the conditions for mixing the glycoside sulfonate represented by formula (2c) with the double bond-containing compound include: temperature of 10-200° C., preferably 80-100° C.; time of 5-12 h, preferably 6-10 h.

[0049] In some embodiments of the present invention, to promote the reaction, the glycoside sulfonate represented by formula (2c) and the double bond-containing compound are mixed in the presence of sodium hydride. The amount of sodium hydride used can be 1-3 mol relative to 1 mol of the double bond-containing compound.

[0050] In some embodiments of the present invention, the glycoside sulfonate represented by formula (2c) and the double bond-containing compound are mixed in an organic solvent. Preferably, the organic solvent is selected from at least one of tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane. The amount of the organic solvent used is not particularly limited, as long as it can dissolve the glycoside sulfonate and the double bond-containing compound.

[0051] It can be understood that more glycoside group-containing compounds with other structures can be obtained by replacing the compound represented by formula (2b) with the compound represented by formula (2e) and contacting it with the double bond-containing compound represented by formula (3b) (repeating the above steps).

[0052] The third aspect of the present invention provides a glycoside group-containing polymer, characterized in that the polymer comprises a structural unit C represented by formula (C) (preferably formula (C')):

[0053] R3, R4, R5, R6, R5', R6', n1 and n2 and n are as described above, but the case where n=n1=n2=0 is also included in the scope of the polymer of the present invention, that is, n1+n2 in formula (C) or n in formula (C') is a natural number of 0-20, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0054] According to the present invention, the content of structural unit C is preferably 0.5 wt% or more of the total weight of the polymer, more preferably 1-10 wt% of the total weight of the polymer. According to a preferred embodiment of the present invention, when the polymer includes structural unit C represented by formula (C'), the content of structural unit C is 3 wt% or more. According to another preferred embodiment of the present invention, the polymer includes structural unit C represented by formula (C) and the content of structural unit C in formula (C) is Partial and The two moieties exist simultaneously but are different (correspondingly, the two moieties in formula (1) exist simultaneously but are different), and the content of the structural unit C is preferably less than 3% by weight, more preferably 1-2.5% by weight. The introduction of two specific alcohol ether groups can significantly improve the properties of the polymer while having a lower content of the structural unit provided by the compound.

[0055] According to the present invention, the polymer may further include structural units represented by formula (C-1) and / or formula (C-2):

[0056] Among them, R 11 and R 12 are each independently H or a C1-C4 alkyl group (preferably a methyl group); R 11 ' and R 12 ' are each independently H, a C1-C4 alkyl group (preferably methyl), a C2-C6 alkyl group substituted with SO3M (preferably -C(CH3)2CH2SO3M), or a C2-C6 alkyl group substituted with P(O)(OM)2 (preferably -C(CH3)2CH2P(O)(OM)2), wherein M is H or an alkali metal element. The content of the structural unit represented by formula (C-1) may account for more than 55 wt% of the total weight of the polymer, preferably 65-97 wt% (or the weight ratio with structural unit C is (1-1.8):(0.005-0.3), preferably (1-1.7):(0.006-0.15)). More preferably, the content of the structural unit represented by formula (C-2) may account for 1-10 wt% of the total weight of the polymer, preferably 1.5-5 wt%. Preferably, the structural unit represented by formula (C-1) is selected from structural unit A represented by formula (A) and / or structural unit represented by formula (B-2). Preferably, the structural unit represented by formula (C-2) is selected from the structural unit D represented by formula (D).

[0057] More preferably, the weight ratio of the structural unit C to the structural unit D is (5-300):(5-300), further preferably (6-150):(8-200), and most preferably 0.5-10 (0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 5.5, 6, 7, 8, 9 or 10).

[0058] According to a preferred embodiment of the present invention, the polymer comprises a structural unit A represented by formula (A), a structural unit B represented by formula (B-1) or (B-2), a structural unit C represented by formula (C), and a structural unit D represented by formula (D);

[0059] wherein R1, R2′, R2″, R7, and R8 are each independently H or a C1-C4 alkyl group, R2 is SO3M or P(O)(OM)2, and M and M′ are each independently H or an alkali metal element.

[0060] Preferably, R1, R2', R2", R7, and R8 are each independently H or methyl.

[0061] Preferably, M and M' are each independently H or Na.

[0062] Preferably, the weight ratio of the structural unit A, the structural unit B, the structural unit C, and the structural unit D is 1:(0.02-0.8):(0.005-0.3):(0.005-0.3), preferably 1:(0.03-0.7):(0.006-0.15):(0.008-0.2).

[0063] According to the present invention, the viscosity-average molecular weight of the polymer is 6 million to 18 million, for example, it can be 6.5 million, 7 million, 7.5 million, 8 million, 8.5 million, 9 million, 10 million, 11 million, 12 million, 12.5 million, 13 million, 13.2 million, 14 million, 15 million, 17.5 million, and the range formed by any two of the above values ​​and the value within the range, preferably 7 million to 15 million.

[0064] According to a more preferred embodiment of the present invention, the polymer includes structural unit A, structural unit B represented by formula (B-1), structural unit C and structural unit D, wherein R1 is H or a methyl group, R2' is H or a methyl group, M' is H or an alkali metal element (preferably Na), R7 is H, and R8 is H or a methyl group. In a preferred embodiment, based on the total weight of the polymer, the content of the structural unit A is 55-87 weight % (e.g., 55, 58, 60, 64, 70, 71, 73, 78, 80, 82, 83, 85 or 87 weight %); the content of the structural unit B is 10-25 weight % (e.g., 10, 15, 16, 17, 19.5, 20, 22 or 25 weight %); the content of the structural unit C is 1-10 weight % (e.g., 1, 1.3, 1.5, 2, 3, 4, 5, 6, 7, 7.5, 8, 9 or 10 weight %); and the content of the structural unit D is 1-10 weight % (e.g., 1, 1.5, 2, 3, 5, 6, 7, 7.5, 8, 9 or 10 weight %). The polymer in this preferred embodiment is more suitable for reducing the viscosity of heavy oil with a viscosity of ≤30000 mPa·s at reservoir temperature under salinity ≤30000 mg / L, temperature ≤70°C, and low dynamic reservoir environment (rotation speed 20-50 r / min).

[0065] According to another more preferred embodiment of the present invention, the polymer comprises structural unit A, structural unit B of formula (B-2), structural unit C and structural unit D, wherein R1 is H or methyl, R2 is SO3M or P(O)(OM)2 M is H or an alkali metal element (preferably Na), R2″ and R7 are H, and R8 is H or a methyl group. In a preferred embodiment, based on the total weight of the polymer, the content of the structural unit A is 60-87 wt % (e.g., 65, 68, 71, 74, 79, 80 or 85 wt %); the content of the structural unit B is 10-25 wt % (e.g., 12, 15, 17.5, 19.5, 20, 22, 23 or 25 wt %); and the content of the structural unit C is 1-10 wt % (e.g., 1, 1.3, 1.5, 2, 3, 4, 5, 6, 7, 8, 9 or 10 wt %). The content of the structural unit D is 1-5 wt% (e.g., 1, 1.2, 1.3, 1.5, 2, 2.5, 3, 4, or 5 wt%), preferably 1.3-6 wt%, and more preferably 1.5-4 wt%. The polymer in this preferred embodiment is more suitable for reducing the viscosity of heavy oil with a salinity of ≤50,000 mg / L, a calcium and magnesium ion concentration of ≤5,000 mg / L, a temperature of ≤70°C, and a viscosity of ≤3,000 mPa·s at reservoir temperature.

[0066] The present invention has no particular requirements for the specific method for preparing the aforementioned polymer. A person skilled in the art can determine a suitable method based on the structural units provided by the present invention in combination with known knowledge in the field of polymer synthesis, or a person skilled in the art can also prepare the aforementioned polymer according to the specific examples (replacing raw materials) provided later in the present invention. However, in order to further improve the conversion rate of the monomer, the fourth aspect of the present invention provides a method for preparing a polymer containing a glycoside group, characterized in that the method comprises: under solution polymerization reaction conditions, in the presence of an initiator, causing an alkenyl monomer in an alkenyl monomer solution to undergo polymerization reaction to obtain a polymer colloid; wherein the alkenyl monomer comprises a compound (monomer C') represented by formula (1), formula (1-1) or formula (1-2).

[0067] According to the present invention, the compound represented by formula (1) preferably accounts for more than 0.5 weight % of the total weight of the olefinic monomer, more preferably accounts for 1-10 weight % of the total weight of the olefinic monomer. Similarly, according to a preferred embodiment of the present invention, the compound represented by formula (1) accounts for more than 3 weight % of the total weight of the olefinic monomer. According to another preferred embodiment of the present invention, the olefinic monomer includes the compound represented by formula (1) and the compound represented by formula (1) Partial and The two alcohol ether groups are present simultaneously but are different, and the content of the compound represented by formula (1) is preferably less than 3% by weight, more preferably 1-2.5% by weight. The introduction of two specific alcohol ether groups can significantly improve the properties of the polymer while having a lower content of the structural units provided by the compounds.

[0068] According to the present invention, the alkenyl monomer may further include a monomer represented by formula (3-1) and / or formula (3-2):

[0069] Among them, R 11 、R 12 、R 11 ' and R 12 'As described above. The content of the monomer represented by formula (3-1) can account for more than 55 weight% of the total weight of the alkenyl monomer, preferably 65-97 weight% (or the weight ratio with monomer C' is (1-1.8): (0.005-0.3), preferably (1-1.7): (0.006-0.15)). More preferably, the content of the monomer represented by formula (3-2) can account for 1-10 weight% of the total weight of the alkenyl monomer, preferably 1-5 weight%. Preferably, the monomer represented by formula (3-1) is selected from monomer A' represented by formula (a) and / or monomer represented by formula (b-2). Preferably, the monomer represented by formula (3-2) is selected from monomer D' represented by formula (d).

[0070] More preferably, the weight ratio of the monomer C' to the monomer D' is (5-300):(5-300), further preferably (6-150):(8-200), and most preferably 0.5-10 (0.5, 1, 1.5, 2, 2.5, 3, 4, 5, 5.5, 6, 7, 8, 9 or 10).

[0071] According to a preferred embodiment of the present invention, the alkenyl monomer includes monomer A' represented by formula (a), monomer B' represented by formula (b-1) or (b-2), monomer C' represented by formula (1) and monomer D' represented by formula (d);

[0072] Among them, R1, R2, R2', M', R2", R7, and R8 are as described above and will not be repeated here.

[0073] Preferably, the weight ratio of monomer A', monomer B', monomer C' and monomer D' is 1:(0.02-0.8):(0.005-0.3):(0.005-0.3), preferably 1:(0.03-0.7):(0.006-0.15):(0.008-0.2).

[0074] According to a more preferred embodiment of the present invention, the alkenyl monomer includes monomer A', monomer B' shown in formula (b-1), monomer C' and monomer D', wherein R1 is H or a methyl group, R2' is H or a methyl group, M' is H or an alkali metal element (preferably Na), R7 is H, and R8 is H or a methyl group. In a preferred embodiment, based on the total weight of the olefinic monomers, the content of the monomer A' is 55-87 wt% (e.g., 55, 58, 60, 64, 70, 71, 73, 78, 80, 82, 83, 85 or 87 wt%); the content of the monomer B' is 10-25 wt% (e.g., 10, 15, 16, 17, 19.5, 20, 22 or 25 wt%); the content of the monomer C' is 1-10 wt% (e.g., 1, 1.3, 1.5, 2, 3, 4, 5, 6, 7, 7.5, 8, 9 or 10 wt%); and the content of the monomer D' is 1-10 wt% (e.g., 1, 1.5, 2, 3, 5, 6, 7, 7.5, 8, 9 or 10 wt%).

[0075] According to another more preferred embodiment of the present invention, the polymer comprises monomer A', monomer B', monomer C' and monomer D' shown in formula (b-2), wherein R1 is H or methyl, R2 is SO3M or P(O)(OM)2, M is H or an alkali metal element (preferably Na), R2" and R7 are H, and R8 is H or methyl. In a preferred embodiment, based on the total weight of the olefinic monomers, the content of the monomer A' is 60-87 wt% (e.g., 65, 68, 7 1, 74, 79, 80 or 85 weight %); the content of the monomer B' is 10-25 weight % (such as 12, 15, 17.5, 19.5, 20, 22, 23 or 25 weight %); the content of the monomer C' is 1-10 weight % (such as 1, 1.3, 1.5, 2, 3, 4, 5, 6, 7, 8, 9 or 10 weight %); the content of the monomer D' is 1-5 weight % (such as 1, 1.2, 1.3, 1.5, 2, 2.5, 3, 4 or 5 weight %).

[0076] According to the present invention, at the start of the solution polymerization reaction, the ratio between the weight of the olefinic monomer and the total weight of the solvent and the olefinic monomer is (0.1-0.4):1, preferably (0.15-0.3):1. The solvent is usually water.

[0077] According to the present invention, the solution polymerization reaction conditions can make the viscosity-average molecular weight of the obtained polymer fall within the range as described above. Preferably, the solution polymerization reaction conditions include: the starting temperature of the polymerization reaction is -10°C to 30°C, the time is 2-12 hours, and the pH value is 4-8. More preferably, the starting temperature of the polymerization reaction is -5°C to 10°C, the time is 3-10 hours, and the pH value is 5-7. In the present invention, the pH value of the polymerization reaction can be adjusted by using one or more of alkali metal hydroxides (such as sodium hydroxide, potassium hydroxide), acrylic acid, and 2-acrylamido-2-methylpropanesulfonic (phosphonic) acid. It is understood that by using alkali metal hydroxides (such as sodium hydroxide) to adjust the pH value, M and / or M' in the structural unit B (monomer B') can be converted from H to an alkali metal element (such as Na). Moreover, by controlling the amount of alkali metal hydroxide, the polymer of the present invention can also contain structural units in which M (M') is H and M (M') is an alkali metal element (such as Na).

[0078] According to the present invention, the initiator can be selected from various initiators commonly used in the art, for example, the initiator can be selected from an azo initiator and / or a redox initiator. The amount of the initiator can be 0.0001-0.5 wt % of the weight of the olefinic monomer. Preferably, the amount of the azo initiator is 0.0001-0.1 wt % of the weight of the olefinic monomer. Preferably, the amount of the redox initiator is 0.0002-0.3 wt % of the weight of the olefinic monomer.

[0079] According to the present invention, the azo initiator is preferably a water-soluble azo initiator. The redox initiator comprises an oxidizing agent and a reducing agent, wherein the reducing agent is an inorganic reducing agent and / or an organic reducing agent, and the weight ratio of the oxidizing agent to the reducing agent is preferably (0.1-1.2):1.

[0080] Preferably, the water-soluble azo initiator is selected from at least one of 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(2-imidazolinepropane) dihydrochloride, and 4,4'-azobis(4-cyanovaleric acid). Preferably, the oxidant is selected from at least one of benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5-dimethyl-2,5-bis(hydroperoxide)hexane, ammonium persulfate, sodium persulfate, and potassium persulfate. Preferably, the inorganic reducing agent is selected from at least one of ferrous sulfate, ferrous ammonium sulfate, cuprous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, sodium formaldehyde sulfoxylate (rongalite), and sodium bisulfite. Preferably, the organic reducing agent is at least one selected from N,N-dimethylethanolamine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylurea and N,N,N',N'-tetramethylethylenediamine.

[0081] According to the present invention, in order to better control the polymerization induction period and reduce the inhibitory effect of dissolved oxygen, the polymerization reaction is preferably carried out in an inert atmosphere, which can be provided by nitrogen and / or an inert gas.

[0082] According to the present invention, the method may further include: granulating, drying, crushing, and screening the polymer colloid to obtain a polymer product.

[0083] According to the present invention, the drying conditions include: a temperature of 40-70° C., preferably, a temperature of 45-65° C. In the present invention, the drying time is not specifically limited, and the product can be dried until the solid content reaches 85-95% by weight, preferably 88-90% by weight. Generally, the drying time is 2-24 hours.

[0084] The fifth aspect of the present invention provides a glycoside group-containing polymer obtained by the aforementioned preparation method.

[0085] The functional polymer provided by the present invention has both mobility control functions and spontaneous penetration and emulsification functions of heavy oil. It can achieve a high viscosity reduction rate for heavy oil with a viscosity of ≤3000 mPa·s at reservoir temperature under a salinity of ≤50000 mg / L (preferably ≤30000 mg / L), a calcium and magnesium ion concentration of ≤5000 mg / L, a temperature of ≤70°C, and a low-power reservoir environment (rotation speed of 20-50 r / min). It can achieve emulsification and dispersion of heavy oil under low-power conditions and can be used as a polymer for water-flooding and polymer flooding of heavy oil.

[0086] In the present invention, the content of each structural unit in the polymer can be tested by conventional methods in the prior art, such as infrared spectroscopy, nuclear magnetic resonance, and the amount of monomers fed during polymerization. Preferably, the amount of monomers fed is used to determine the content of each structural unit in the polymer. Specifically, the feed ratio of each monomer actually participating in the polymerization is determined by testing the content of unreacted monomers, thereby determining the content of each structural unit in the polymer. Furthermore, in the present invention, the content of each unreacted monomer in the tested polymer is less than 0.02% by weight, indicating that substantially all monomers participate in the polymerization reaction. Specifically, the content of the residual monomers can be measured using liquid chromatography.

[0087] A sixth aspect of the present invention provides a use of the aforementioned glycoside group-containing polymer in water-flooding heavy oil reservoir recovery. The polymer of the present invention is particularly suitable for water-flooding recovery of oil reservoirs with a viscosity of ≤3000 mPa·s at reservoir temperature.

[0088] In the present invention, water is used as the solvent and reaction medium in the polymer, and the present invention does not particularly limit the selection of water. The water can be natural water or artificial water. Natural water can be river, lake, atmospheric water, seawater, groundwater, etc. Artificial water can be tap water, distilled water, deionized water, or heavy water.

[0089] Generally speaking, in practical applications, the water used is often oilfield water (field water) or its corresponding simulated brine. Preferably, the water has a salinity of 1,000-50,000 mg / L (preferably 1,000-30,000 mg / L) and a calcium and magnesium ion content of 100-5,000 mg / L (preferably 100-3,000 mg / L).

[0090] A seventh aspect of the present invention provides a method for reducing the viscosity of heavy oil, characterized in that the method comprises: contacting a solution of the aforementioned polymer with the heavy oil. The polymer content in the polymer solution is preferably 1000-3000 mg / L. The amount of the polymer used is preferably 20-50 mg (e.g., 20, 25, 30, 35, 40, 45, or 50 mg) per 70 g of the heavy oil.

[0091] An eighth aspect of the present invention provides the use of the aforementioned compound or polymer in heavy oil viscosity reduction (or chemical flooding).

[0092] A ninth aspect of the present invention provides a method for recovering an oil reservoir, characterized in that the method comprises applying the aforementioned polymer to a low-efficiency water-flooded heavy oil reservoir, thereby recovering the heavy oil from the reservoir through polymer flooding, utilizing the polymer's ability to increase the viscosity of the displacement fluid and emulsify the heavy oil. The polymer is used in the form of a dry powder dissolved in water at a concentration of 1000-3000 mg / L.

[0093] The present invention will be described in detail below by way of examples. In the following examples and comparative examples:

[0094] Monomer A' was purchased from Dongying Baomo Environmental Engineering Co., Ltd.;

[0095] Monomer B' represented by formula (b-1) was purchased from Sigma-Aldrich Technology Co., Ltd.;

[0096] When R2 in the monomer B' represented by formula (b-2) is SO3M, it was purchased from Weifang Jinshi Environmental Protection Technology Co., Ltd. When R2 is P(O)(OM)2, it was prepared with reference to the synthesis method in "Improved Synthesis of AMPP via Ritter Reaction" (He Quanguo, Sun Yuanxi, Liu et al., Industrial Water Treatment, 2001, 21:26-28), wherein when M=Na, it was prepared by neutralizing the corresponding monomer with M=H with a base;

[0097] n-Hexyl glucoside, decyl glucoside, and dodecyl glucoside were purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd. The preparation method of alcohol ether glycosides was based on the "Preparation and Performance Study of Glycosylated Modified Alcohol Ethers" (Sun Gangjian, Yang Xiuquan, Yang Qingli, et al., Daily Chemicals, 2007, 37: 271-274), wherein the molar ratio of glucose to alcohol ether was controlled at 1:5. The alcohol ether represented by formula (2a) was purchased from Shanghai Jin Zijing Chemical Co., Ltd.; the alcohol ether represented by formula (2d) was purchased from Shanghai Bangao Chemical Co., Ltd.

[0098] Monomer D' was purchased from Sigma-Aldrich Technology Co., Ltd.;

[0099] Unless otherwise specified, the reagents and materials used in the following examples and comparative examples can be obtained commercially.

[0100] In the following examples and comparative examples, simulated brine was prepared according to the applicable reservoir environment. The salinity of the simulated brine was 30,000 mg / L or 50,000 mg / L, and the calcium and magnesium ion concentrations were 3,000 mg / L or 5,000 mg / L (it should be understood that the salinity is an approximate value). NMR analysis was performed using a Bruker 500 MHz NMR spectrometer.

[0101] The test methods for the properties of glycoside compounds and polymers are as follows:

[0102] 1) Viscosity determination method: Refer to Q / SH1020 1957-2008, "Technical Specifications for Active Polymers for Oil Displacement." Instrument: Brookfield DV-III viscometer, speed: 6 rpm.

[0103] 2) The molecular weight test method is as follows:

[0104] The viscosity average molecular weight of the polymer is calculated according to the method specified in GB / T 12005.10-92 using the formula M = ([η] / K) 1 / α To calculate, where K = 4.75 × 10 -3 , α = 0.8, [η] is the intrinsic viscosity; the intrinsic viscosity is measured according to the enterprise standard Q / SH1020 1572-2017 “Polyacrylamide for Oil Displacement” of Sinopec Shengli Petroleum Administration Bureau.

[0105] 3) The viscosity reduction test method refers to the "General Technical Requirements for Heavy Oil Viscosity Reducers" (Q / SH1020 1519-2016): The crude oil used in this experiment is an oil sample from a certain oil field block in my country (the surface degassed viscosity at 50°C is 1532mPa·s, 2389mPa·s, 1361mPa·s or 2620mPa·s). The initial viscosity μ0 of the test oil sample at 50°C is measured using a Brookfield DV-III viscometer. 70g of crude oil is taken and placed in a 100mL beaker. 30g of a functional polymer solution with a concentration of 1000mg / L is poured in. The solution is heated at a constant temperature of 50°C for 30min, and then stirred with a stirrer for 1min at a stirring rate of 20rpm (reservoir seepage dynamics). The viscosity of the emulsion is tested. Viscosity reduction Where: f is viscosity reduction rate, %; μ0 is initial viscosity of crude oil at 50℃, mPa·s; μ is viscosity of crude oil after viscosity reduction, mPa·s.

[0106] 4) The emulsification performance of the glycoside compound was characterized by emulsification time. The specific method was as follows: a 0.1 wt% glycoside compound solution was prepared. 20 mL of the glycoside compound solution and 20 mL of heavy oil (viscosity of 1532 mPa·s at 50°C, degassed on the ground) were added to a 100 mL stoppered graduated cylinder. The cylinder was capped and vigorously shaken up and down to mix thoroughly. The mixture was then allowed to stand. The time from the start of standing to the separation of 10 mL of the aqueous phase was recorded. The test was repeated three times under the same conditions, and the average value was taken. The longer the emulsification time, the stronger the emulsification ability. The emulsification time test results of the glycoside substrates used in the preparation examples and the resulting modified glycosides are shown in Table 1.

[0107] Preparation Example 1.1

[0108] This preparation example is intended to illustrate monomer C' (M1) and its preparation method.

[0109] Acrylic acid (130 mmol) was then added toluene (solvent) (300 mL), polyoxyethylene ether polyoxypropylene ether alcohol ether glycoside (100 mmol, structure shown in formula (2d), wherein R3 is 2-ethylhexyl, R5' is methyl, R5, R6, and R6' are H, n1 is 3, and n2 is 6), and trifluoromethanesulfonic acid (13 mmol) at room temperature. After the addition was complete, the temperature was raised to 120°C, refluxed, and the reaction was continued for 8 hours. After the reaction was complete, the temperature was lowered to room temperature, and the toluene and acid were removed by vacuum distillation to obtain the product, acrylic acid-modified alcohol ether glycoside. The yield of the product was 72.5% and the purity was 92.3%. The purity and yield were calculated using the internal standard NMR method. The yield was calculated as the actual yield of the target product / the amount of the target product produced × 100%, and the purity was calculated as the NMR-calculated yield / the actual NMR loading amount × 100% (the same below).

[0110] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1), wherein R3 is 2-ethylhexyl, R4 is H, X is O, R5' is methyl, R5, R6 and R6' are H, n1 is 3, and n2 is 6.

[0111] The specific NMR data are as follows: 6.40 (dd, J = 19.8, 4.6 Hz, 1H), 6.12 (dd, J = 33.5, 19.8 Hz, 1H), 5.82 (dd, J = 33.5, 4.6 Hz, 1H), 5.35–5.20 (m, 1H), 4.77 (dd, J = 24.2, 12.3 Hz, 1H), 4.29–3.86 (m, 7H), 3.84–3.30 (m, 32H), 3.16–3.05 (m, 1H), 1.86 (s, 1H), 1.62–1.35 (m, 6H), 1.33–1.29 (m, 10H), 1.29–1.20 (m, 4H), 0.98–0.85 (m, 6H).

[0112] Preparation Example 1.2

[0113] This preparation example is intended to illustrate monomer C' (M2) and its preparation method.

[0114] Acrylic acid (90 mmol) was then added toluene (300 mL), polyoxyethylene ether polyoxypropylene ether alcohol ether glycoside (100 mmol, structure shown in formula (2d), where R3 = normal C12 alkyl, R5' is methyl, R5, R6, and R6' are H, n1 is 6, and n2 is 9), and trifluoromethanesulfonic acid (20 mmol) at room temperature. After the addition was complete, the temperature was raised to 140°C, refluxed, and the reaction was continued for 10 hours. After the reaction was complete, the temperature was cooled to room temperature, and the toluene and acid were removed by vacuum distillation to obtain the product, acrylic acid-modified alcohol ether glycoside. The yield of the product was 61.5%, and the purity was 93.1%.

[0115] The structure of the product obtained by NMR analysis is shown in formula (1), wherein R3 is a normal C12 alkyl, R4 is H, X is O, R5' is a methyl group, R5, R6 and R6' are H, n1 is 6, and n2 is 9.

[0116] Preparation Example 1.3

[0117] This preparation example is intended to illustrate monomer C' (M3) and its preparation method.

[0118] A triphenylphosphine activator (150 mmol) and a polyoxyethylene ether polyoxypropylene ether alcohol ether glycoside (100 mmol, structure shown in formula (2d), where R3 is 11-methyldodecyl, R5' is methyl, R5, R6, and R6' are H, n1 is 2, and n2 is 11) were deoxygenated with nitrogen. N,N-dimethylformamide solvent (300 mL) and methacrylic acid (120 mmol) were added. The temperature was lowered to 0°C, and a diisopropyl azodicarboxylate activator (150 mmol) was slowly added dropwise. After addition, the temperature was raised to 25°C and the reaction was allowed to proceed for 8 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the crude product was separated by column chromatography (methylene chloride:methanol volume ratio = 9:1) to obtain a methacrylic acid-modified glycoside. The resulting product had a yield of 65.5% and a purity of 90.2%.

[0119] NMR detection shows that R3 is 11-methyldodecyl. Specifically, the structure of the product obtained by NMR analysis is shown in formula (1), wherein R3 is 11-methyldodecyl, R4 is methyl, X is O, R5' is methyl, R5, R6 and R6' are H, n1 is 2, and n2 is 11.

[0120] Preparation Example 1.4

[0121] This preparation example is intended to illustrate monomer C' (M4) and its preparation method.

[0122] Acrylic acid (130 mmol) was added to 300 mL of toluene (solvent), 100 mmol of n-hexyl glucoside, and 39 mmol of trifluoromethanesulfonic acid at room temperature. After the addition was complete, the temperature was raised to 120°C, refluxed, and the reaction continued for 8 hours. After the reaction was complete, the temperature was lowered to room temperature and the toluene and acid were removed by vacuum distillation to obtain the acrylic acid-modified glycoside. The yield was 75.1% and the purity was 91.9%.

[0123] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-1), wherein R3 is n-hexyl, R4 is H, and n=0.

[0124] The NMR data are as follows: 1H NMR (300MHz, DMSO-d6) δ: 6.41 (dd, J=19.9, 4.5Hz, 1H), 6.12 (dd, J=33.5, 19.8Hz, 1H), 5 .83(dd,J=33.5,4.4Hz,1H),4.60(d,J=15.4Hz,1H),4.45(dd,J=24.8,3.4Hz,1H),4.21 (dd,J=24.8,3.4Hz,1H),4.12–3.91(m,2H),3.58(dd,J=17.5,16.4Hz,1H),3.48(dt,J= 18.6,3.4Hz,1H),3.39–3.32(m,2H),1.63(s,3H),1.59–1.31(m,8H),0.94–0.84(m,3H).

[0125] Preparation Example 1.5

[0126] This preparation example is intended to illustrate monomer C' (M5) and its preparation method.

[0127] Acrylic acid (90 mmol) was added to toluene (300 mL), dodecyl glucoside (100 mmol), and trifluoromethanesulfonic acid (18 mmol) at room temperature. After the addition was complete, the temperature was raised to 140°C, refluxed, and the reaction was continued for 10 hours. After the reaction was complete, the temperature was lowered to room temperature and the toluene and acid were removed by vacuum distillation to obtain the product, an acrylic acid-modified glycoside. The yield was 58.0% and the purity was 93.1%.

[0128] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-1), wherein R3 is n-dodecyl, R4 is H, and n=0.

[0129] Preparation Example 1.6

[0130] This preparation example is intended to illustrate monomer C' (M6) and its preparation method.

[0131] Triphenylphosphine activator (150 mmol) and n-decyl glucoside (100 mmol) were deoxygenated with nitrogen, followed by the addition of N,N-dimethylformamide solvent (300 mL) and methacrylic acid (120 mmol). The temperature was lowered to 0°C, and diisopropyl azodicarboxylate activator (150 mmol) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was allowed to proceed for 8 hours. After the reaction, the solvent was removed by distillation under reduced pressure, and the crude product was separated by column chromatography (methylene chloride:methanol volume ratio = 9:1) to obtain the methacrylate-modified glycoside. The resulting product had a yield of 69.8% and a purity of 91.8%.

[0132] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-1), wherein R3 is n-decyl, R4 is methyl, and n=0.

[0133] Preparation Example 1.7

[0134] This preparation example is intended to illustrate monomer C' (M7) and its preparation method.

[0135] Acrylic acid (130 mmol) was then added toluene (300 mL), an alcohol ether glycoside (100 mmol, structure shown in formula (2a), R3 is a linear C8 alkyl group and a linear C10 alkyl group, n is 8), and trifluoromethanesulfonic acid (20 mmol) at room temperature. After the addition was complete, the temperature was raised to 120°C, refluxed, and the reaction was continued for 7 hours. After the reaction was complete, the temperature was lowered to room temperature, and the toluene and acid were removed by vacuum distillation to obtain the product, an acrylic acid-modified glycoside. The yield of the product was 82.9%, and the purity was 90.6%.

[0136] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-1), wherein R3 is a straight-chain C8 alkyl and a straight-chain C10 alkyl, R4 is H, and n is 8.

[0137] 1 H NMR (300MHz, DMSO-d6) δ6.41(dd,J=19.9,4.5Hz,2H),6.12(dd,J=33.5,19.8Hz,2H),5.83(dd,J=33.5,4.4Hz,2H),4.59(dd,J=24.8,13.8Hz,2H),4.52(d,J= 15.4Hz,2H),4.18–4.03(m,4H),3.77(dd,J=18.3,16.2Hz,2H),3.60–3.46(m,33+3 7H),3.44–3.28(m,6H),1.65–1.39(m,14H),1.34–1.20(m,16H),0.93–0.85(m,6H).

[0138] Preparation Example 1.8

[0139] This preparation example is intended to illustrate monomer C' (M8) and its preparation method.

[0140] Acrylic acid (150 mmol) was then added toluene (300 mL), an alcohol ether glycoside (100 mmol, structure shown in formula (2a), R3 is a linear C12 alkyl group and a linear C14 alkyl group, n is 4), and trifluoromethanesulfonic acid (15 mmol) at room temperature. After the addition was complete, the temperature was raised to 140°C, refluxed, and the reaction was continued for 10 hours. After the reaction was complete, the temperature was lowered to room temperature, and the toluene and acid were removed by vacuum distillation to obtain the product, an acrylic acid-modified glycoside. The yield of the product was 70.2%, and the purity was 87.7%.

[0141] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-1), wherein R3 is a straight-chain C12 alkyl and a straight-chain C14 alkyl, R4 is H, and n is 4.

[0142] Preparation Example 1.9

[0143] This preparation example is intended to illustrate monomer C' (M9) and its preparation method.

[0144] Triphenylphosphine (150 mmol) and an alcohol ether glycoside (100 mmol, structure shown in formula (2a), where R3 is a linear C12 alkyl group and a linear C14 alkyl group, and n is 7) were deoxygenated with nitrogen. N,N-dimethylformamide (300 mL) and acrylic acid (120 mmol) were added. The temperature was lowered to 0°C, and diisopropyl azodicarboxylate (150 mmol) was slowly added dropwise. After the addition was complete, the temperature was raised to 25°C and the reaction was allowed to proceed for 8 hours. After the reaction, the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography (dichloromethane:methanol volume ratio = 5:1) to obtain an acrylic acid-modified glycoside. The resulting product had a yield of 71.3% and a purity of 94.6%.

[0145] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-1), wherein R3 is a straight-chain C12 alkyl and a straight-chain C14 alkyl, R4 is H, and n is 7.

[0146] Preparation Example 1.10

[0147] The monomer was prepared in the same manner as in Preparation Example 1.4, except that an equal amount of maleic anhydride was used instead of acrylic acid to obtain maleic anhydride-modified alkyl glycoside (M10).

[0148] Preparation Example 1.11

[0149] The monomer was prepared in the same manner as in Preparation Example 1.1, except that the structure of the polyoxyethylene ether polyoxypropylene ether alcohol ether glycoside used was as shown in formula (2d), wherein R3 was 2-ethylhexyl, R5 was methyl, R6, R5' and R6' were H, n1 was 3, and n2 was 6, to obtain acrylic acid-modified alcohol ether glycoside (M11).

[0150] Preparation Example 2.1

[0151] This preparation example is intended to illustrate monomer C'(N1) and its preparation method.

[0152] (1) Polyoxyethylene ether polyoxypropylene ether alcohol ether glycoside (100 mmol, structure as shown in formula (2d), wherein R3 is 2-ethylhexyl, R5' is methyl, R5, R6 and R6' are H, n1 is 3, and n2 is 6) is taken, then nitrogen is passed through to deoxygenate, the temperature is lowered to 0°C, trifluoromethanesulfonic anhydride (90 mmol) and pyridine (3727 mmol) are added, and the temperature is maintained at 0°C for 6 hours after the addition is completed; after the raw materials react completely, the temperature is restored to room temperature, water is added to quench the reaction, and the organic phases are extracted three times with dichloromethane. The organic phases are combined and dried over anhydrous magnesium sulfate; the solvent and pyridine are then distilled off under reduced pressure to obtain the product alcohol ether glycoside sulfonate. The yield of the obtained product is 45.2% and the purity is 65.2%.

[0153] (2) Acrylamide (150 mmol) was added to alcohol ether glycoside sulfonate (100 mmol); nitrogen was then introduced to deoxygenate the mixture, and tetrahydrofuran (300 mL) and sodium hydride (200 mmol) were added at room temperature; after the addition was complete, the temperature was raised to 80°C and refluxed for 6 hours; after the reaction of the raw materials was complete, the temperature was lowered to room temperature, and a saturated ammonium chloride solution was added to quench the reaction. The mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous magnesium sulfate; the solvent and acrylamide were then distilled off under reduced pressure to obtain the product, acrylamide-modified glycoside. The yield of the obtained product was 70.1%, and the purity was 89.5%.

[0154] The structure of the product obtained by NMR analysis is shown in formula (1), wherein R3 is 2-ethylhexyl, R4 is H, X is NH, R5' is methyl, R5, R6 and R6' are H, n1 is 3, and n2 is 6. The specific NMR data are as follows: 1 H NMR(300MHz,DMSO-d6)δ6.19(dd,J=33.0,20.0Hz,1H),6.08–6.01(m,2H),5.6 9(dd,J=33.0,4.9Hz,1H),4.91(dd,J=3.6,1.8Hz,1H),4.77(d,J=1.8Hz,1H),4 .32(dd,J=8.6,3.6Hz,1H),4.00–3.76(m,5H),3.73–3.61(m,3H),3.57–2.95(m ,32H),1.76(s,1H),1.59–1.48(m,3H),1.45–1.20(m,16H),0.96–0.85(m,6H).

[0155] Preparation Example 2.2

[0156] This preparation example is intended to illustrate monomer C'(N2) and its preparation method.

[0157] (1) Polyoxyethylene ether polyoxypropylene ether alcohol ether glycoside (100 mmol, structure as shown in formula (2d), wherein R3 is a normal C12 alkyl group, R5' is a methyl group, R5, R6 and R6' are H, n1 is 6, and n2 is 9) is taken, and then nitrogen is passed through to deoxygenate. Trifluoromethanesulfonic anhydride (120 mmol) and pyridine (3727 mmol) are added, and the reaction is maintained at room temperature for 6 hours after the addition is completed. After the raw materials react completely, water is added to quench the reaction, and the mixture is extracted three times with dichloromethane. The organic phases are combined and dried over anhydrous magnesium sulfate. The solvent and pyridine are then distilled off under reduced pressure to obtain the product alcohol ether glycoside sulfonate. The yield of the obtained product is 48.5% and the purity is 72.3%.

[0158] (2) Acrylamide (200 mmol) was added to alcohol ether glycoside sulfonate (100 mmol); nitrogen was then passed through to deoxygenate the mixture, and tetrahydrofuran (300 mL) and sodium hydride (200 mmol) were added at room temperature; after the addition was complete, the temperature was raised to 100°C and refluxed for 8 hours; after the reaction of the raw materials was complete, the temperature was lowered to room temperature, and saturated ammonium chloride was added to quench the reaction. The mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous magnesium sulfate; the solvent and acrylamide were then distilled off under reduced pressure to obtain the product, acrylamide-modified glycoside. The yield of the obtained product was 74.2% and the purity was 90%.

[0159] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1), wherein R3 is a normal C12 alkyl group, R4 is H, X is NH, R5' is a methyl group, R5, R6 and R6' are H, n1 is 6, and n2 is 9.

[0160] Preparation Example 2.3

[0161] This preparation example is intended to illustrate monomer C'(N3) and its preparation method.

[0162] A triphenylphosphine activator (150 mmol) and a polyoxyethylene ether polyoxypropylene ether alcohol ether glycoside (100 mmol, structure shown in formula (2d), where R3 is 11-methyldodecyl, R5' is methyl, R5, R6, and R6' are H, n1 is 2, and n2 is 11) were deoxygenated with nitrogen. N,N-dimethylformamide solvent (3894 mmol) and methacrylamide (120 mmol) were added. The temperature was lowered to 0°C, and diisopropyl azodicarboxylate activator (150 mmol) was slowly added dropwise. After addition, the temperature was raised to 25°C and the reaction was allowed to proceed for 8 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the crude product was separated by column chromatography (methylene chloride:methanol volume ratio = 9:1) to obtain an acrylamide-modified glycoside. The resulting product had a yield of 58.1% and a purity of 91.0%.

[0163] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1), wherein R3 is 11-methyldodecyl, R4 is methyl, X is NH, R5' is methyl, R5, R6 and R6' are H, n1 is 2, and n2 is 11.

[0164] Preparation Example 2.4

[0165] This preparation example is intended to illustrate monomer C'(N4) and its preparation method.

[0166] (1) n-Hexyl glucoside (100 mmol) was taken, deoxygenated with nitrogen, cooled to 0°C, and p-toluenesulfonyl chloride (90 mmol) and pyridine (3727 mmol) were added. After the addition was complete, the reaction was maintained at 0°C for 6 hours. After the reaction was complete, the temperature was restored to room temperature, and water was added to quench the reaction. The reaction was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous magnesium sulfate. The solvent and pyridine were then distilled off under reduced pressure to obtain the product, glycoside sulfonate. The yield of the obtained product was 42.3%, and the purity was 60.8%.

[0167] (2) Acrylamide (150 mmol) was added to a glycoside sulfonate (100 mmol); nitrogen was then introduced to deoxygenate the mixture, and tetrahydrofuran (300 mL) and sodium hydride (200 mmol) were added at room temperature; after the addition was complete, the temperature was raised to 80°C and refluxed for 6 hours; after the reaction of the raw materials was complete, the temperature was lowered to room temperature, and a saturated ammonium chloride solution was added to quench the reaction. The mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous magnesium sulfate; the solvent and acrylamide were then removed by distillation under reduced pressure to obtain the product, acrylamide-modified glycoside. The yield of the obtained product was 68.9%, and the purity was 95.6%.

[0168] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-2), wherein R3 is n-hexyl, R4 is H, and n=0. 1 H NMR(300MHz,DMSO-d6)δ6.12(s,1H),6.05–5.92(m,2H),5.69(dd,J=30.8,7.1 Hz,1H),4.56(d,J=15.2Hz,1H),4.02–3.94(m,1H),3.62(dq,J=32.7,16.7Hz,2 H),3.48(dt,J=18.3,5.9Hz,1H),3.40–3.33(m,2H),3.27(dd,J=18.9,5.9Hz,1 H),3.02(dd,J=24.8,5.8Hz,1H),1.88(s,3H),1.57–1.30(m,8H),0.89(s,3H).

[0169] The reaction process of this preparation example is as follows:

[0170] Preparation Example 2.5

[0171] This preparation example is intended to illustrate monomer C'(N5) and its preparation method.

[0172] (1) Dodecyl glucoside (100 mmol) was taken and deoxygenated by nitrogen gas. p-Toluenesulfonyl chloride (120 mmol) and pyridine (3727 mmol) were added and the reaction was maintained at room temperature for 6 hours. After the reaction of the raw materials was complete, water was added to quench the reaction. The mixture was extracted three times with dichloromethane. The organic phases were combined and dried over anhydrous magnesium sulfate. The solvent and pyridine were then distilled off under reduced pressure to obtain the product, glycoside sulfonate. The yield of the obtained product was 69.3% and the purity was 92.3%.

[0173] (2) Acrylamide (200 mmol) was added to a glycoside sulfonate (100 mmol); nitrogen was then introduced to deoxygenate the mixture, and tetrahydrofuran (300 mL) and sodium hydride (200 mmol) were added at room temperature. After the addition was complete, the temperature was raised to 100°C and refluxed for 8 hours. After the reaction of the raw materials was complete, the temperature was lowered to room temperature, and saturated ammonium chloride was added to quench the reaction. The mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous magnesium sulfate. The solvent and acrylamide were then removed by distillation under reduced pressure to obtain the product, acrylamide-modified glycoside. The yield of the obtained product was 71.3%, and the purity was 96.9%.

[0174] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-2), wherein R3 is n-dodecyl, R4 is H, and n=0.

[0175] Preparation Example 2.6

[0176] This preparation example is intended to illustrate monomer C'(N6) and its preparation method.

[0177] A mixture of triphenylphosphine activator (150 mmol) and n-decyl glucoside (100 mmol) was deoxygenated with nitrogen, followed by the addition of N,N-dimethylformamide solvent (3894 mmol) and methacrylamide (120 mmol). The temperature was lowered to 0°C, and diisopropyl azodicarboxylate activator (150 mmol) was slowly added dropwise. After the addition was complete, the mixture was warmed to 25°C and allowed to react for 8 hours. After the reaction, the solvent was removed by distillation under reduced pressure, and the crude product was separated by column chromatography (methylene chloride:methanol volume ratio = 9:1) to obtain an acrylamide-modified glycoside. The yield of the product was 53.8%, and the purity was 91.8%.

[0178] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-2), wherein R3 is n-decyl, R4 is methyl, and n=0.

[0179] Preparation Example 2.7

[0180] This preparation example is intended to illustrate monomer C'(N7) and its preparation method.

[0181] (1) Take an alcohol ether glycoside (100 mmol, the structure is shown in formula (2a), wherein R3 is a linear C8 alkyl group and a linear C10 alkyl group, and n is 10), then pass nitrogen to deoxygenate, cool to 0°C, add p-toluenesulfonyl chloride (90 mmol) and pyridine (3727 mmol), and keep the temperature at 0°C for 6 hours after the addition is completed. After the raw materials react completely, return to room temperature, add water to quench the reaction, extract three times with dichloromethane, combine the organic phases and dry with anhydrous magnesium sulfate; then distill under reduced pressure to remove the solvent and pyridine to obtain the product alcohol ether glycoside sulfonate. The yield of the obtained product is 49.3%, and the purity is 72.9%.

[0182] (2) Acrylamide (150 mmol) was added to alcohol ether glycoside sulfonate (100 mmol); nitrogen was then introduced to deoxygenate the mixture, and tetrahydrofuran (300 mL) and sodium hydride (200 mmol) were added at room temperature; after the addition was complete, the temperature was raised to 80°C and refluxed for 8 hours; after the reaction of the raw materials was complete, the temperature was lowered to room temperature, saturated ammonium chloride was added to quench the reaction, and the mixture was extracted three times with dichloromethane. The organic phases were combined and dried over anhydrous magnesium sulfate; the solvent and acrylamide were then distilled off under reduced pressure to obtain the product, acrylamide-modified alcohol ether glycoside. The yield of the obtained product was 59.7% and the purity was 91.2%.

[0183] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-2), wherein R3 is a straight-chain C8 alkyl group and a straight-chain C10 alkyl group, R4 is H, and n is 10.

[0184] 1 H NMR(300MHz,DMSO-d6)δ6.11–6.03(m,4H),5.99(s,2H),5.69(dd,J=14.4,4.5Hz,2H), 4.60(d,J=7.7Hz,2H),4.12–4.06(m,2H),3.85–3.79(m,2H),3.62(t,J=8.5Hz,2H),3.5 9–3.48(m,45+49H),3.33(t,J=7.3Hz,4H),3.27(dd,J=12.5,6.2Hz,2H),3.02(dd,J=1 2.5,6.2Hz,2H),1.74(s,6H),1.58–1.43(m,8H),1.41–1.33(m,8H),0.92–0.86(m,6H).

[0185] Preparation Example 2.8

[0186] This preparation example is intended to illustrate monomer C'(N8) and its preparation method.

[0187] (1) An alcohol ether glycoside (100 mmol, structure as shown in formula (2a), wherein R3 is a linear C12 alkyl group and a linear C14 alkyl group, and n is 4) was prepared, and nitrogen was passed through to remove oxygen. p-Toluenesulfonyl chloride (120 mmol) and pyridine (3727 mmol) were added, and the mixture was kept at room temperature for 8 hours after the addition of the materials. After the reaction of the raw materials was complete, water was added to quench the reaction, and the mixture was extracted three times with dichloromethane. The organic phases were combined and dried over anhydrous magnesium sulfate. The solvent and pyridine were then distilled off under reduced pressure to obtain the product alcohol ether glycoside sulfonate. The yield of the obtained product was 69.8%, and the purity was 90.1%.

[0188] (2) Acrylamide (100 mmol) was added to alcohol ether glycoside sulfonate (100 mmol); nitrogen was then passed through to deoxygenate the mixture, and tetrahydrofuran (300 mL) and sodium hydride (200 mmol) were added at room temperature; after the addition was complete, the temperature was raised to 90°C and refluxed for 9.5 hours; after the reaction of the raw materials was complete, the temperature was lowered to room temperature, and saturated ammonium chloride was added to quench the reaction. The mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous magnesium sulfate; the solvent and acrylamide were then distilled off under reduced pressure to obtain the product, acrylamide-modified alcohol ether glycoside. The yield of the obtained product was 72.3%, and the purity was 97.1%.

[0189] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-2), wherein R3 is a straight-chain C12 alkyl and a straight-chain C14 alkyl, R4 is H, and n is 4.

[0190] Preparation Example 2.9

[0191] This preparation example is intended to illustrate monomer C'(N9) and its preparation method.

[0192] (1) Take an alcohol ether glycoside (100 mmol, the structure of which is shown in formula (2a), wherein R3 is a linear C12 alkyl group and a linear C14 alkyl group, and n is 7), then pass nitrogen gas to deoxygenate, add p-toluenesulfonyl chloride (150 mmol) and pyridine (3727 mmol), and keep the reaction at room temperature for 8 hours after the addition is completed; after the raw materials react completely, add water to quench the reaction, extract with dichloromethane three times, combine the organic phases and dry with anhydrous magnesium sulfate; then distill under reduced pressure to remove the solvent and pyridine to obtain the product alcohol ether glycoside sulfonate. The yield of the obtained product is 75.3% and the purity is 86.9%.

[0193] (2) Acrylamide (200 mmol) was added to alcohol ether glycoside sulfonate (100 mmol); nitrogen was then passed through to deoxygenate the mixture, and tetrahydrofuran (300 mL) and sodium hydride (200 mmol) were added at room temperature; after the addition was complete, the temperature was raised to 80°C and refluxed for 6 hours; after the reaction of the raw materials was complete, the temperature was lowered to room temperature, and saturated ammonium chloride was added to quench the reaction. The mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous magnesium sulfate; the solvent and acrylamide were then distilled off under reduced pressure to obtain the product, acrylamide-modified alcohol ether glycoside. The yield of the obtained product was 65.3%, and the purity was 88.1%.

[0194] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-2), wherein R3 is a straight-chain C12 alkyl and a straight-chain C14 alkyl, R4 is H, and n is 7.

[0195] Preparation Example 2.10

[0196] This preparation example is intended to illustrate monomer C'(N10) and its preparation method.

[0197] Triphenylphosphine (150 mmol) and an alcohol ether glycoside (100 mmol, structure shown in formula (2a), where R3 is a linear C8 alkyl group and a linear C10 alkyl group, and n is 5) were deoxygenated with nitrogen. N,N-dimethylformamide (3894 mmol) and acrylamide (130 mmol) were added after the mixture was cooled to 0°C and diisopropyl azodicarboxylate (150 mmol) was slowly added dropwise. After the addition was complete, the mixture was heated to room temperature (25°C) and reacted for 8 hours. After the reaction, the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography (dichloromethane:methanol volume ratio = 8:1) to obtain an acrylamide-modified alcohol ether glycoside. The yield of the product was 52.9% and the purity was 94.6%.

[0198] The structure of the product obtained by nuclear magnetic resonance analysis is shown in formula (1-2), wherein R3 is a straight-chain C8 alkyl and a straight-chain C10 alkyl, R4 is H, and n is 5.

[0199] The reaction process of this preparation example is as follows:

[0200] Preparation Example 2.11

[0201] The monomer was prepared in the same manner as in Preparation Example 2.1, except that the polyoxyethylene ether polyoxypropylene ether alcohol ether glycoside structure used was as shown in formula (2d), wherein R3 is 2-ethylhexyl, R5 is methyl, R6, R5' and R6' are H, n1 is 3, and n2 is 6) (N11).

[0202] Table 1 Emulsification time test results of compounds containing glycoside groups

[0203] By reacting the compound represented by formula (3) with the compound represented by formula (2), the emulsification performance of the compound represented by formula (2) on heavy oil can be significantly improved, and the improvement effect of the compound represented by formula (3) is better than that of maleic anhydride.

[0204] Example 1.1

[0205] (1) 46.32 g of monomer A′, 11.28 g of monomer B′, 1.2 g of monomer C′ (M1), and 1.2 g of monomer D′ were prepared, wherein the structure of monomer A′ is as shown in formula (a) (wherein R1 is H);

[0206] The structure of monomer B′ is shown in formula (b-1) (wherein R2′ is H and M′ is Na);

[0207] The structure of monomer D′ is shown in formula (d) (wherein R7 and R8 are H);

[0208] Dissolve in 240 g of deionized water, adjust the pH to 6 with sodium hydroxide solution, control the starting temperature at 10°C, bubble nitrogen into the system for 20 min to deoxygenate, then add 1.15 g of a 0.25 wt% aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt% aqueous solution of ammonium persulfate, and 1.25 g of a 0.3 wt% aqueous solution of sodium bisulfite to the system to initiate polymerization. After the system temperature rises by 0.5°C, stop bubbling nitrogen and continue the reaction for 4 hours;

[0209] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain a functional polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0210] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0211] Structural unit A (structure as shown in formula (A), wherein R1 is H);

[0212] Structural unit B (structure shown in formula (B-1), wherein R2' is H and M' is Na);

[0213] Structural unit C (structure as shown in formula (C), wherein R3 is 2-ethylhexyl, R4 is H, X is O, R5' is methyl, R5, R6 and R6' are H, n1 is 3, and n2 is 6);

[0214] Structural unit D (structure as shown in formula (D), wherein R7 and R8 are H);

[0215] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 77.2 wt %, the content of the structural unit B is 18.8 wt %, the content of the structural unit C is 2 wt %, and the content of the structural unit D is 2 wt %.

[0216] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0217] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0218] Example 1.2

[0219] (1) 55.65 g of monomer A′, 12.25 g of monomer B′, 1.05 g of monomer C′ (M2), and 1.05 g of monomer D′, wherein monomer A′ is the same as in Example 1.1; monomer B′ is the same as in Example 1.1; and the structure of monomer D′ is as shown in formula (d) (wherein R7 is H and R8 is methyl), are dissolved in 230 g of deionized water, and the pH value is adjusted to 6.0 with sodium hydroxide solution. The starting temperature is controlled at 12° C., and nitrogen is bubbled into the system for 20 min to remove oxygen. Then, 1.15 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.25 g of a 0.3 wt % aqueous solution of sodium bisulfite are added to the system to initiate polymerization. After the system temperature rises by 0.5° C., nitrogen bubbling is stopped and the reaction is continued for 4 hours.

[0220] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain a functional polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0221] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0222] Structural unit A (same as in Example 1.1);

[0223] Structural unit B (same as in Example 1.1);

[0224] Structural unit C (structure as shown in formula (C), wherein R3 is n-dodecyl, R4 is H, X is O, R6' is methyl, R5, R7, R6 and R7' are H, n1 is 6, and n2 is 9);

[0225] Structural unit D (structure as shown in formula (D), wherein R7 is H and R8 is methyl);

[0226] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 79.5 wt %, the content of the structural unit B is 17.5 wt %, the content of the structural unit C is 1.5 wt %, and the content of the structural unit D is 1.5 wt %.

[0227] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0228] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0229] Example 1.3

[0230] (1) 55.1 g of monomer A′, 13.7 g of monomer B′, 1.8 g of monomer C′ (M3), and 1.45 g of monomer D′ were taken, wherein monomer A′, monomer B′, and monomer D′ were the same as those in Example 1.1; dissolved in 228 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the initial temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.5 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped, and the reaction was continued for 4 hours;

[0231] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0232] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0233] Structural unit A (same as in Example 1.1);

[0234] Structural unit B (same as in Example 1.1);

[0235] Structural unit C (structure as shown in formula (C), wherein R3 is 11-methyldodecyl, R4 is methyl, X is O, R5' is methyl, R5, R6 and R6' are H, n1 is 2, and n2 is 11);

[0236] Structural unit D (same as in Example 1.1);

[0237] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 76.5 wt %, the content of the structural unit B is 19 wt %, the content of the structural unit C is 2.5 wt %, and the content of the structural unit D is 2 wt %.

[0238] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0239] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0240] Example 1.4

[0241] (1) 41 g of monomer A′, 10.8 g of monomer B′, 3.7 g of monomer C′ (M4), and 4.5 g of monomer D′ were prepared, wherein the structure of monomer A′ is as shown in formula (a) (wherein R1 is H);

[0242] The structure of monomer B′ is shown in formula (b-1) (wherein R2′ is H and M′ is Na);

[0243] The structure of monomer D′ is shown in formula (d) (wherein R7 and R8 are H);

[0244] Dissolve in 240 g of deionized water, adjust the pH to 6 with sodium hydroxide solution, control the starting temperature at 10°C, bubble nitrogen into the system for 20 min to deoxygenate, then add 1.15 g of a 0.25 wt% aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt% aqueous solution of ammonium persulfate, and 1.25 g of a 0.3 wt% aqueous solution of sodium bisulfite to the system to initiate polymerization. After the system temperature rises by 0.5°C, stop bubbling nitrogen and continue the reaction for 4 hours;

[0245] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain a functional polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0246] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0247] Structural unit A (structure as shown in formula (A), wherein R1 is H);

[0248] Structural unit B (structure shown in formula (B-1), wherein R2' is H and M' is Na);

[0249] Structural unit C (structure shown in formula (C'), wherein R3 is n-hexyl, R4, R5 and R6 are H, X is O, and n is 0);

[0250] Structural unit D (structure as shown in formula (D), wherein R7 and R8 are H);

[0251] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 68.3 wt %, the content of the structural unit B is 18 wt %, the content of the structural unit C is 6.2 wt %, and the content of the structural unit D is 7.5 wt %.

[0252] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0253] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0254] Example 1.5

[0255] (1) 46.2 g of monomer A′, 13.6 g of monomer B′, 5.3 g of monomer C′ (M5), and 4.9 g of monomer D′ were taken, wherein monomer A′ was the same as that in Example 1.4; monomer B′ was the same as that in Example 1.4; and the structure of monomer D′ was as shown in formula (d) (wherein R7 was H and R8 was methyl), and dissolved in 230 g of deionized water. The pH value was adjusted to 6.0 with sodium hydroxide solution, the starting temperature was controlled at 12° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.15 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.25 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped and the reaction was continued for 4 hours.

[0256] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain a functional polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0257] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0258] Structural unit A (same as in Example 1.4);

[0259] Structural unit B (same as in Example 1.4);

[0260] Structural unit C (structure shown in formula (C'), wherein R3 is n-dodecyl, R4, R5 and R6 are H, X is O, and n is 0);

[0261] Structural unit D (structure as shown in formula (D), wherein R7 is H and R8 is methyl);

[0262] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 66 weight %, the content of the structural unit B is 19.4 weight %, the content of the structural unit C is 7.6 weight %, and the content of the structural unit D is 7 weight %.

[0263] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0264] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0265] Example 1.6

[0266] (1) 49.9 g of monomer A′, 12.6 g of monomer B′, 5 g of monomer C′ (M6), and 4.5 g of monomer D′ were taken, wherein monomer A′, monomer B′, and monomer D′ were the same as those in Example 1.4; dissolved in 228 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.5 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped and the reaction was continued for 4 hours;

[0267] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0268] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0269] Structural unit A (same as in Example 1.4);

[0270] Structural unit B (same as in Example 1.4);

[0271] Structural unit C (structure shown in formula (C'), wherein R3 is n-decyl, R4 is methyl, R5 and R6 are H, X is O, and n is 0);

[0272] Structural unit D (same as in Example 1.4);

[0273] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 69.3 wt %, the content of the structural unit B is 17.5 wt %, the content of the structural unit C is 6.9 wt %, and the content of the structural unit D is 6.3 wt %.

[0274] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0275] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0276] Example 1.7

[0277] (1) 46.8 g of monomer A′, 11 g of monomer B′, 3.6 g of monomer C′ (M7), and 3.6 g of monomer D′ were taken, wherein monomer A′, monomer B′, and monomer D′ were the same as those in Example 1.4; dissolved in 237 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15°C, nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.1 g of a 0.25 wt% aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt% aqueous solution of ammonium persulfate, and 1.6 g of a 0.3 wt% aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5°C, nitrogen bubbling was stopped and the reaction was continued for 4 hours;

[0278] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0279] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0280] Structural unit A (same as in Example 1.4);

[0281] Structural unit B (same as in Example 1.4);

[0282] Structural unit C (structure as shown in formula (C'), wherein R3 is a linear C8 alkyl group and a linear C10 alkyl group, R4, R5 and R6 are H, X is O, and n is 8);

[0283] Structural unit D (same as in Example 1.4);

[0284] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 72 weight %, the content of the structural unit B is 17 weight %, the content of the structural unit C is 5.5 weight %, and the content of the structural unit D is 5.5 weight %.

[0285] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0286] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0287] Example 1.8

[0288] (1) 49.4 g of monomer A′, 11.3 g of monomer B′, 4 g of monomer C′ (M8), and 3.3 g of monomer D′ were taken, wherein monomer A′, monomer B′, and monomer D′ were the same as those in Example 1.4; dissolved in 232 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.1 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.6 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped and the reaction was continued for 4 hours;

[0289] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0290] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0291] Structural unit A (same as in Example 1.4);

[0292] Structural unit B (same as in Example 1.4);

[0293] Structural unit C (structure as shown in formula (C'), wherein R3 is a linear C12 alkyl group and a linear C14 alkyl group, R4, R5 and R6 are H, X is O, and n is 4);

[0294] Structural unit D (same as in Example 1.4);

[0295] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 72.6 wt %, the content of the structural unit B is 16.6 wt %, the content of the structural unit C is 5.9 wt %, and the content of the structural unit D is 4.9 wt %.

[0296] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0297] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0298] Example 1.9

[0299] (1) 63.3 g of monomer A′, 14.1 g of monomer B′, 3.8 g of monomer C′ (M9), and 3 g of monomer D′ were taken, wherein monomer A′, monomer B′, and monomer D′ were the same as those in Example 1.4; dissolved in 215.5 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.1 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.6 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped and the reaction was continued for 4 hours;

[0300] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0301] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0302] Structural unit A (same as in Example 1.4);

[0303] Structural unit B (same as in Example 1.4);

[0304] Structural unit C (structure as shown in formula (C'), wherein R3 is a linear C12 alkyl group and a linear C14 alkyl group, R4, R5 and R6 are H, X is O, and n is 7);

[0305] Structural unit D (same as in Example 1.4);

[0306] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 75.2 wt %, the content of the structural unit B is 16.7 wt %, the content of the structural unit C is 4.5 wt %, and the content of the structural unit D is 3.6 wt %.

[0307] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0308] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0309] Example 1.10

[0310] (1) 44.4 g of monomer A′, 16.5 g of monomer B′, 7.1 g of monomer C′, and 7 g of monomer D′ were taken, wherein monomer A′, monomer B′, monomer C′, and monomer D′ were the same as those in Example 1.4; dissolved in 225 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.1 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.6 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped, and the reaction was continued for 4 hours;

[0311] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0312] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0313] Structural unit A (same as in Example 1.4);

[0314] Structural unit B (same as in Example 1.4);

[0315] Structural unit C (same as in Example 1.4);

[0316] Structural unit D (same as in Example 1.4);

[0317] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 59.2 wt %, the content of the structural unit B is 22 wt %, the content of the structural unit C is 9.5 wt %, and the content of the structural unit D is 9.3 wt %.

[0318] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0319] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0320] Example 1.11

[0321] (1) 74.25 g of monomer A′, 13.5 g of monomer B′, 0.9 g of monomer C′, and 1.35 g of monomer D′ were taken, wherein monomer A′, monomer B′, monomer C′, and monomer D′ were the same as those in Example 1.2; dissolved in 234 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.1 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.6 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped, and the reaction was continued for 4 hours;

[0322] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0323] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0324] Structural unit A (same as in Example 1.2);

[0325] Structural unit B (same as in Example 1.2);

[0326] Structural unit C (same as in Example 1.2);

[0327] Structural unit D (same as in Example 1.2);

[0328] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 82.5 wt %, the content of the structural unit B is 15 wt %, the content of the structural unit C is 1 wt %, and the content of the structural unit D is 1.5 wt %.

[0329] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L, and the apparent viscosity at 50°C was measured.

[0330] The viscosity reduction rates of heavy oil samples with viscosities of 1532 mPa·s and 2389 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. The results are shown in Table 2.

[0331] Example 1.11a

[0332] The polymer was prepared in the same manner as in Example 1.11, except that monomer C' was replaced with an equimolar amount of monomer (M5) from Preparation Example 1.5.

[0333] Example 1.11b

[0334] The polymer was prepared in the same manner as in Example 1.11, except that monomer C' was replaced with an equimolar amount of the monomer (M7) from Preparation Example 1.7.

[0335] Example 1.11c

[0336] The polymer was prepared in the same manner as in Example 1.11, except that monomer C' was M11.

[0337] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0338] Structural unit A (same as in Example 1.11);

[0339] Structural unit B (same as in Example 1.11);

[0340] Structural unit C (structure as shown in formula (C), wherein R3 is 2-ethylhexyl, R4 is H, X is O, R5 is methyl, R6, R5' and R6' are H, n1 is 3, and n2 is 6);

[0341] Structural unit D (same as Example 1.11).

[0342] Comparative Example 1.1

[0343] The polymer was prepared in the same manner as in Example 1.4, except that monomer C' and monomer D' were not added.

[0344] According to the calculation determined based on the feed amount, the prepared polymer contains the same structural unit A and structural unit B as in Example 1.4; based on the total weight of the polymer, the content of the structural unit A is 79.2% by weight, and the content of the structural unit B is 20.8% by weight.

[0345] Comparative Example 1.2

[0346] The polymer was prepared in the same manner as in Example 1.11, except that no monomer D' was added.

[0347] According to the calculation determined based on the feed amount, the prepared polymer contains the same structural unit A, structural unit B, and structural unit C as in Example 1.11; based on the total weight of the polymer, the content of the structural unit A is 83.8% by weight, the content of the structural unit B is 15.2% by weight, and the content of the structural unit C is 1% by weight.

[0348] Comparative Example 1.3

[0349] The polymer was prepared in the same manner as in Example 1.4, except that no monomer C' was added.

[0350] According to the calculation determined based on the feed amount, the prepared polymer contains the same structural unit A, structural unit B, and structural unit D as in Example 1.4; based on the total weight of the polymer, the content of the structural unit A is 72.8% by weight, the content of the structural unit B is 19.2% by weight, and the content of the structural unit D is 8% by weight.

[0351] Comparative Example 1.4

[0352] The polymer was prepared in the same manner as in Example 1.11, except that monomer C' was replaced by an equimolar amount of M10.

[0353] Comparative Example 1.5

[0354] The polymer was prepared in the same manner as in Example 1.11, except that monomer D' was replaced by an equimolar amount of vinyl pyrrolidone.

[0355] Table 2 Viscosity average molecular weight, apparent viscosity and viscosity reduction test results

[0356] Example 1.12

[0357] The permeability is selected as 900×10 -3 μm 2 A core was saturated with simulated brine (mineralization 30,000 mg / L, calcium and magnesium ion content 3,000 mg / L) under vacuum for more than 2 hours. Crude oil with a viscosity of 1,532 mPa·s was then used to saturate the core at 50°C. The simulated brine was then flooded until the water cut at the core model outlet exceeded 98%, resulting in a waterflood recovery of 40.1%. The wastewater and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer described in Example 1.3 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached above 98%, resulting in a post-polymer injection recovery of 60.3%, an increase in oil displacement efficiency by 20.2%.

[0358] Example 1.13

[0359] The permeability is selected as 900×10 -3 μm 2 A core was saturated with simulated brine (mineralization 30,000 mg / L, calcium and magnesium ion content 3,000 mg / L) under vacuum for more than 2 hours. Crude oil with a viscosity of 1,532 mPa·s was then used to saturate the core at 50°C. The simulated brine was then flooded until the water cut at the core model outlet exceeded 98%, resulting in a waterflood recovery of 39.8%. The wastewater and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer described in Example 1.4 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached above 98%, resulting in a post-polymer injection recovery of 56.5%, an increase in oil displacement efficiency by 16.7%.

[0360] Example 1.14

[0361] The permeability is selected as 1000×10 -3 μm 2 A core was saturated with simulated brine (mineralization 30,000 mg / L, calcium and magnesium ion content 3,000 mg / L) under vacuum for more than 2 hours. The core was then saturated with crude oil with a viscosity of 2,389 mPa·s at 50°C. The simulated brine was then flooded until the water cut at the core model outlet reached above 98%, resulting in a water flooding recovery of 20.07%. The wastewater and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer described in Example 1.7 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached above 98%, resulting in a post-polymer injection recovery of 37.27%, an increase in oil displacement efficiency by 17.2%.

[0362] Example 1.15

[0363] The permeability is selected as 1000×10 -3 μm 2A core was saturated with simulated brine (mineralization 30,000 mg / L, calcium and magnesium ion content 3,000 mg / L) under vacuum for more than 2 hours. The core was then saturated with crude oil with a viscosity of 2,389 mPa·s at 50°C. The simulated brine was then flooded until the water cut at the core model outlet exceeded 98%, resulting in a waterflood recovery of 19.48%. The wastewater and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer described in Example 1.11 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached above 98%, resulting in a post-polymer injection recovery of 33.4%, an increase in oil displacement efficiency by 14.22%.

[0364] Comparative Example 1.6

[0365] The permeability is selected as 1000×10 -3 μm 2 The core was saturated with simulated brine (mineralization 30,000 mg / L, calcium and magnesium ion content 3,000 mg / L) by vacuuming for more than 2 hours. Crude oil with a viscosity of 2,389 mPa·s was then used to saturate the core at 50°C. The simulated brine was then used for water flooding until the water cut at the core model outlet reached 98% or more, resulting in a water flooding recovery of 34.51%. The waste liquid and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer of Comparative Example 1.1 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached 98% or more, resulting in a post-polymer injection recovery of 41.68%, an increase in oil displacement efficiency by 7.17%.

[0366] Comparative Example 1.7

[0367] The permeability is selected as 1000×10 -3 μm 2 The core was saturated with simulated brine (mineralization 30,000 mg / L, calcium and magnesium ion content 3,000 mg / L) by vacuuming for more than 2 hours. Crude oil with a viscosity of 2,389 mPa·s was then used to saturate the core at 50°C. The simulated brine was then used for water flooding until the water cut at the core model outlet exceeded 98%, resulting in a water flooding recovery of 32.41%. The waste liquid and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer of Comparative Example 1.2 with a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached above 98%, resulting in a post-polymer injection recovery of 42.4%, an increase in oil displacement efficiency by 9.99%.

[0368] Comparative Example 1.8

[0369] The permeability is selected as 1000×10 -3 μm 2The core was saturated with simulated brine (mineralization 30,000 mg / L, calcium and magnesium ion content 3,000 mg / L) by vacuuming for more than 2 hours. Crude oil with a viscosity of 2,389 mPa·s was then used to saturate the core at 50°C. The simulated brine was then used for water flooding until the water cut at the core model outlet reached 98% or more, resulting in a water flooding recovery of 30.45%. The waste liquid and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer of Comparative Example 1.3 with a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached 98% or more, resulting in a post-polymer injection recovery of 38.82%, an 8.37% increase in oil displacement efficiency.

[0370] Although not shown, under the same conditions, the polymers obtained in other examples can also improve the oil displacement effect by 14-21%, while the oil displacement effect of the polymers prepared in Comparative Examples 1.1 to 1-3 is improved by less than 10.5%.

[0371] The above results show that, compared with the comparative example, the functional polymer prepared from the compound of the present invention has good aqueous phase viscosifying function at 50°C in water with a salinity of 30,000 mg / L and a calcium and magnesium ion content of 3,000 mg / L. At the same time, under low dynamic conditions and at a concentration of 1,000 mg / L, the viscosity of heavy oil with a viscosity of 1,500-3,000 mPa·s at reservoir temperature can be reduced by more than 92%, which can significantly improve the water flooding recovery rate of heavy oil reservoirs.

[0372] Example 2.1

[0373] (1) 43.9 g of monomer A′, 11.14 g of monomer B′, 0.88 g of monomer C′(N1), and 1.12 g of monomer D′ were prepared, wherein the structure of monomer A′ is as shown in formula (a) (wherein R1 is H);

[0374] The structure of monomer B′ is shown in formula (b-2) (wherein, R2″ is H, R2 is SO3M, and M=Na);

[0375] The structure of monomer D′ is shown in formula (d) (wherein R7 and R8 are H);

[0376] Dissolve in 243 g of deionized water, adjust the pH to 6 with sodium hydroxide solution, control the starting temperature at 10°C, bubble nitrogen into the system for 20 min to deoxygenate, then add 1.15 g of a 0.25 wt% aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt% aqueous solution of ammonium persulfate, and 1.25 g of a 0.3 wt% aqueous solution of sodium bisulfite to the system to initiate polymerization. After the system temperature rises by 0.5°C, stop bubbling nitrogen and continue the reaction for 4 hours;

[0377] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain a functional polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0378] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0379] Structural unit A (structure as shown in formula (A), wherein R1 is H);

[0380] Structural unit B (structure as shown in formula (B-2), wherein R2″ is H, R2 is SO3M, and M=Na);

[0381] Structural unit C (structure as shown in formula (C), wherein R3 is 2-ethylhexyl, R4 is H, X is NH, R5' is methyl, R5, R6 and R6' are H, n1 is 3, and n2 is 6);

[0382] Structural unit D (structure as shown in formula (D), wherein R7 and R8 are H);

[0383] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 77 weight %, the content of the structural unit B is 19.5 weight %, the content of the structural unit C is 1.5 weight %, and the content of the structural unit D is 2 weight %.

[0384] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0385] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0386] Example 2.2

[0387] (1) 55 g of monomer A′, 12.6 g of monomer B′, 1.4 g of monomer C′(N2), and 1.05 g of monomer D′ were taken, wherein monomer A′ was the same as in Example 2.1; monomer B′ was the same as in Example 2.1; and the structure of monomer D′ was as shown in formula (d) (wherein, R7 was H and R8 was methyl), and dissolved in 230 g of deionized water. The pH value was adjusted to 6 using sodium hydroxide solution, the starting temperature was controlled at 12° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.15 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.8 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped and the reaction was continued for 4 hours.

[0388] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain a functional polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0389] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0390] Structural unit A (same as in Example 2.1);

[0391] Structural unit B (same as in Example 2.1);

[0392] Structural unit C (structure as shown in formula (C), wherein R3 is n-dodecyl, X is NH, R5' is methyl, R5, R6 and R6' are H, n1 is 6, and n2 is 9);

[0393] Structural unit D (structure as shown in formula (D), wherein R7 is H and R8 is methyl);

[0394] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 78.5 wt %, the content of the structural unit B is 18 wt %, the content of the structural unit C is 2 wt %, and the content of the structural unit D is 1.5 wt %.

[0395] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0396] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0397] Example 2.3

[0398] (1) 56.6 g of monomer A′, 15 g of monomer B′, 1.9 g of monomer C′ (N3), and 1.5 g of monomer D′ were taken, wherein monomer A′, monomer B′, and monomer D′ were the same as those in Example 2.1; dissolved in 225 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.7 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped, and the reaction was continued for 4 hours;

[0399] (2) After the polymerization is completed, the obtained colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed and sieved to obtain an acrylamide polymer dry powder product. The viscosity average molecular weight of the dry powder product is measured.

[0400] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0401] Structural unit A (same as in Example 2.1);

[0402] Structural unit B (same as Example 2.1);

[0403] Structural unit C (structure as shown in formula (C), wherein R3 is 11-methyldodecyl, R4 is methyl, X is NH, R5' is methyl, R5, R6 and R6' are H, n1 is 2, and n2 is 11);

[0404] Structural unit D (same as Example 2.1);

[0405] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 75.5 wt %, the content of the structural unit B is 20 wt %, the content of the structural unit C is 2.5 wt %, and the content of the structural unit D is 2 wt %.

[0406] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0407] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0408] Example 2.4

[0409] (1) 41.4 g of monomer A′, 9.5 g of monomer B′, 4.1 g of monomer C′ (N4), and 2 g of monomer D′ were prepared, wherein the structure of monomer A′ is as shown in formula (a) (wherein R1 is H);

[0410] The structure of monomer B′ is shown in formula (b-2) (wherein, R2″ is H, R2 is SO3M, and M=H);

[0411] The structure of monomer D′ is shown in formula (d) (wherein R7 and R8 are H);

[0412] Dissolve in 243 g of deionized water, adjust the pH to 6 with sodium hydroxide solution, control the starting temperature at 10°C, bubble nitrogen into the system for 20 min to deoxygenate, then add 1.15 g of a 0.25 wt% aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt% aqueous solution of ammonium persulfate, and 1.25 g of a 0.3 wt% aqueous solution of sodium bisulfite to the system to initiate polymerization. After the system temperature rises by 0.5°C, stop bubbling nitrogen and continue the reaction for 4 hours;

[0413] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain a functional polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0414] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0415] Structural unit A (structure as shown in formula (A), wherein R1 is H);

[0416] Structural unit B (structure as shown in formula (B-2), wherein R2″ is H, R2 is SO3M, and M=Na);

[0417] Structural unit C (structure shown in formula (C'), wherein R3 is n-hexyl, R4, R5 and R6 are H, X is NH, and n is 0);

[0418] Structural unit D (structure as shown in formula (D), wherein R7 and R8 are H);

[0419] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 72.6 wt %, the content of the structural unit B is 16.7 wt %, the content of the structural unit C is 7.2 wt %, and the content of the structural unit D is 3.5 wt %.

[0420] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0421] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0422] Example 2.5

[0423] (1) 52.5 g of monomer A′, 10.8 g of monomer B′, 4.6 g of monomer C′ (N5), and 2.1 g of monomer D′ were taken, wherein monomer A′ was the same as in Example 1; monomer B′ was the same as in Example 1; and the structure of monomer D′ was as shown in formula (d) (wherein, R7 was H and R8 was methyl), and dissolved in 230 g of deionized water. The pH value was adjusted to 6 using sodium hydroxide solution, the starting temperature was controlled at 12° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.15 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.8 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped and the reaction was continued for 4 hours.

[0424] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain a functional polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0425] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0426] Structural unit A (same as in Example 2.4);

[0427] Structural unit B (same as in Example 2.4);

[0428] Structural unit C (structure shown in formula (C'), wherein R3 is n-dodecyl, R4, R5 and R6 are H, X is NH, and n is 0);

[0429] Structural unit D (structure as shown in formula (D), wherein R7 is H and R8 is methyl);

[0430] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 75 weight %, the content of the structural unit B is 15.4 weight %, the content of the structural unit C is 6.6 weight %, and the content of the structural unit D is 3 weight %.

[0431] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0432] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0433] Example 2.6

[0434] (1) 56.2 g of monomer A′, 13.6 g of monomer B′, 3.5 g of monomer C′ (N6), and 1.73 g of monomer D′ were taken, wherein monomer A′, monomer B′, and monomer D′ were the same as those in Example 2.4; dissolved in 225 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.7 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped, and the reaction was continued for 4 hours;

[0435] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0436] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0437] Structural unit A (same as in Example 2.4);

[0438] Structural unit B (same as Example 2.4);

[0439] Structural unit C (structure shown in formula (C'), wherein R3 is n-decyl, R4 is methyl, R5 and R6 are H, X is NH, and n is 0);

[0440] Structural unit D (same as Example 2.4);

[0441] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 74.9 wt %, the content of the structural unit B is 18.1 wt %, the content of the structural unit C is 4.7 wt %, and the content of the structural unit D is 2.3 wt %.

[0442] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0443] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0444] Example 2.7

[0445] (1) Take 45.1g of monomer A', 12.3g of monomer B', 3.2g of monomer C'(N7), and 2.4g of monomer D', wherein monomer A' and monomer D' are the same as those in Example 2.4, and the structure of monomer B' is shown in formula (b-2) (wherein, R2" is H, R2 is P(O)(OM)2, and M=H); dissolve in 237g of deionized water, and adjust the pH value to 7 with sodium hydroxide solution, control the starting temperature to 15°C, and blow nitrogen gas into the system for 20min to deoxygenate, then add 1.1g of 0.25wt% aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2g of 0.2wt% aqueous solution of ammonium persulfate, and 1.6g of 0.3wt% aqueous solution of sodium bisulfite to the system to initiate polymerization. After the system temperature rises by 0.5°C, stop blowing nitrogen gas bubbles and continue the reaction for 4 hours;

[0446] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0447] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0448] Structural unit A (same as in Example 2.4);

[0449] Structural unit B (structure as shown in formula (B-2), R2″ is H, R2 is P(O)(OM)2, M=Na);

[0450] Structural unit C (structure as shown in formula (C'), wherein R3 is a linear C8 alkyl group and a linear C10 alkyl group, R4, R5 and R6 are H, X is NH, and n is 10);

[0451] Structural unit D (same as Example 2.4);

[0452] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 71.6 wt %, the content of the structural unit B is 19.5 wt %, the content of the structural unit C is 5.1 wt %, and the content of the structural unit D is 3.8 wt %.

[0453] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0454] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0455] Example 2.8

[0456] (1) Take 48.7g of monomer A', 11.6g of monomer B', 3.9g of monomer C' (N8), and 1.8g of monomer D', wherein monomer A', monomer B', and monomer D' are the same as those in Example 2.4; dissolve them in 240g of deionized water, and adjust the pH value to 6 with sodium hydroxide solution, control the starting temperature to 15°C, and blow nitrogen gas into the system for 20min to deoxygenate, then add 1.1g of 0.25wt% aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2g of 0.2wt% aqueous solution of ammonium persulfate, and 1.6g of 0.3wt% aqueous solution of sodium bisulfite to the system to initiate polymerization. After the system temperature rises by 0.5°C, stop blowing nitrogen bubbles and continue the reaction for 4 hours;

[0457] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0458] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0459] Structural unit A (same as in Example 2.4);

[0460] Structural unit B (same as Example 2.4);

[0461] Structural unit C (structure as shown in formula (C'), wherein R3 is a linear C12 alkyl group and a linear C14 alkyl group, R4, R5, R6 and R7 are H, X is NH, and n is 4);

[0462] Structural unit D (same as Example 2.4);

[0463] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 73.8 wt %, the content of the structural unit B is 17.6 wt %, the content of the structural unit C is 5.9 wt %, and the content of the structural unit D is 2.7 wt %.

[0464] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0465] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0466] Example 2.9

[0467] (1) 63.3 g of monomer A′, 16.8 g of monomer B′, 7 g of monomer C′ (N9), and 2.9 g of monomer D′ were taken, wherein monomer A′, monomer B′, and monomer D′ were the same as those in Example 2.4; dissolved in 234 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15°C, nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.1 g of a 0.25 wt% aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt% aqueous solution of ammonium persulfate, and 2 g of a 0.3 wt% aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5°C, nitrogen bubbling was stopped and the reaction was continued for 4 hours;

[0468] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0469] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0470] Structural unit A (same as in Example 2.4);

[0471] Structural unit B (same as Example 2.4);

[0472] Structural unit C (structure as shown in formula (C'), wherein R3 is a linear C12 alkyl group and a linear C14 alkyl group, R4, R5 and R6 are H, X is NH, and n is 7);

[0473] Structural unit D (same as Example 2.4);

[0474] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 70.3 wt %, the content of the structural unit B is 18.7 wt %, the content of the structural unit C is 7.8 wt %, and the content of the structural unit D is 3.2 wt %.

[0475] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0476] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0477] Example 2.10

[0478] (1) 44.3 g of monomer A′, 12 g of monomer B′, 2.5 g of monomer C′ (N10), and 1.2 g of monomer D′ were taken, wherein monomer A′, monomer B′, and monomer D′ were the same as those in Example 2.4; dissolved in 220 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the initial temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.1 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 1.6 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped, and the reaction was continued for 4 hours;

[0479] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0480] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0481] Structural unit A (same as in Example 2.4);

[0482] Structural unit B (same as Example 2.4);

[0483] Structural unit C (structure as shown in formula (C'), wherein R3 is a linear C8 alkyl group and a linear C10 alkyl group, R4, R5 and R6 are H, X is NH, and n is 5);

[0484] Structural unit D (same as Example 2.4);

[0485] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 73.8 wt %, the content of the structural unit B is 20 wt %, the content of the structural unit C is 4.2 wt %, and the content of the structural unit D is 2 wt %.

[0486] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0487] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0488] Example 2.11

[0489] (1) Take 43.6g of monomer A', 15.5g of monomer B', 5.9g of monomer C', and 1g of monomer D', wherein monomer A', monomer B', monomer C', and monomer D' are the same as those in Example 2.4; dissolve them in 234g of deionized water, and adjust the pH value to 6 with sodium hydroxide solution, control the starting temperature to 15°C, and blow nitrogen gas into the system for 20min to remove oxygen. Then, add 1.1g of 0.25wt% aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2g of 0.2wt% aqueous solution of ammonium persulfate, and 1.6g of 0.3wt% aqueous solution of sodium bisulfite to the system to initiate polymerization. After the system temperature rises by 0.5°C, stop blowing nitrogen gas bubbles and continue the reaction for 4 hours;

[0490] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0491] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0492] Structural unit A (same as in Example 2.4);

[0493] Structural unit B (same as Example 2.4);

[0494] Structural unit C (same as Example 2.4);

[0495] Structural unit D (same as Example 2.4);

[0496] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 66.1 wt %, the content of the structural unit B is 23.5 wt %, the content of the structural unit C is 8.9 wt %, and the content of the structural unit D is 1.5 wt %.

[0497] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0498] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0499] Example 2.12

[0500] (1) 71.55 g of monomer A′, 16.2 g of monomer B′, 0.9 g of monomer C′, and 1.35 g of monomer D′ were taken, wherein monomer A′, monomer B′, monomer C′, and monomer D′ were the same as those in Example 2.1; dissolved in 210 g of deionized water, and adjusted to pH 6 with sodium hydroxide solution, the starting temperature was controlled at 15° C., nitrogen was bubbled into the system for 20 min to remove oxygen, and then 1.15 g of a 0.25 wt % aqueous solution of 2,2-azobis(2-amidinopropane) dihydrochloride, 2 g of a 0.2 wt % aqueous solution of ammonium persulfate, and 2.2 g of a 0.3 wt % aqueous solution of sodium bisulfite were added to the system to initiate polymerization. After the system temperature rose by 0.5° C., nitrogen bubbling was stopped and the reaction was continued for 4 hours;

[0501] (2) After the polymerization is completed, the resulting colloid is granulated, dried at 50°C until the solid content reaches 89% by weight, crushed, and sieved to obtain an acrylamide polymer dry powder product. The viscosity-average molecular weight of the dry powder product is measured.

[0502] In addition, according to the calculation of the feeding amount, the functional polymer prepared contains:

[0503] Structural unit A (same as in Example 2.1);

[0504] Structural unit B (same as Example 2.1);

[0505] Structural unit C (same as Example 2.1);

[0506] Structural unit D (same as Example 2.1);

[0507] Wherein, based on the total weight of the functional polymer, the content of the structural unit A is 79.5 wt %, the content of the structural unit B is 18 wt %, the content of the structural unit C is 1 wt %, and the content of the structural unit D is 1.5 wt %.

[0508] A 2000 mg / L polymer solution was prepared using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5,000 mg / L, and the apparent viscosity at 50°C was measured.

[0509] The viscosity reduction rates of heavy oil samples with viscosities of 1361 mPa·s and 2630 mPa·s at 50°C were obtained by preparing a 1000 mg / L polymer solution using simulated brine with a salinity of 50,000 mg / L and a calcium and magnesium ion content of 5000 mg / L. The results are shown in Table 3.

[0510] Example 2.12a

[0511] The polymer was prepared in the same manner as in Example 2.12, except that monomer C' was replaced with an equimolar amount of the monomer from Preparation Example 2.5.

[0512] Example 2.12b

[0513] The polymer was prepared in the same manner as in Example 2.12, except that monomer C' was replaced with an equimolar amount of monomer (N7) from Preparation Example 2.7.

[0514] Example 2.12c

[0515] The polymer was prepared in the same manner as in Example 2.12, except that monomer C' used was N11.

[0516] Comparative Example 2.1

[0517] The polymer was prepared in the same manner as in Example 2.4, except that monomer C' and monomer D' were not added.

[0518] According to the calculation determined based on the feed amount, the prepared polymer contains the same structural unit A and structural unit B as in Example 2.4; based on the total weight of the polymer, the content of the structural unit A is 81.3% by weight, and the content of the structural unit B is 18.7% by weight.

[0519] Comparative Example 2.2

[0520] The polymer was prepared in the same manner as in Example 2.12, except that no monomer D' was added.

[0521] According to the calculation determined based on the feed amount, the prepared polymer contains the same structural unit A, structural unit B, and structural unit C as in Example 2.12; based on the total weight of the polymer, the content of the structural unit A is 80.7% by weight, the content of the structural unit B is 18.3% by weight, and the content of the structural unit C is 1% by weight.

[0522] Comparative Example 2.3

[0523] The polymer was prepared in the same manner as in Example 2.4, except that no monomer C' was added.

[0524] According to the calculation determined based on the feed amount, the prepared polymer contains the same structural unit A, structural unit B, and structural unit D as in Example 2.4; based on the total weight of the polymer, the content of the structural unit A is 78.3 weight%, the content of the structural unit B is 18 weight%, and the content of the structural unit D is 3.7 weight%.

[0525] Comparative Example 2.4

[0526] The polymer was prepared in the same manner as in Example 2.12, except that monomer C' was replaced with an equimolar amount of M10.

[0527] Comparative Example 2.5

[0528] The polymer was prepared in the same manner as in Example 2.12, except that monomer D was replaced with an equimolar amount of vinyl pyrrolidone.

[0529] Table 3 Viscosity average molecular weight, apparent viscosity and viscosity reduction test results

[0530] Example 2.13

[0531] The permeability is selected as 800×10 -3 μm 2 A core was saturated with simulated brine (mineralization 50,000 mg / L, calcium and magnesium ion content 5,000 mg / L) under vacuum for more than 2 hours. The core was then saturated with crude oil with a viscosity of 1,361 mPa·s at 50°C. The simulated brine was then flooded until the water cut at the core model outlet exceeded 98%, resulting in a water flooding recovery of 35.76%. The wastewater and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer described in Example 2.5 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached above 98%, resulting in a post-polymer injection recovery of 53.75%, an increase in oil displacement efficiency by 17.99%.

[0532] Example 2.14

[0533] The permeability is selected as 1000×10 -3 μm 2 The core was saturated with simulated brine (mineralization 50,000 mg / L, calcium and magnesium ion content 5,000 mg / L) by vacuuming for more than 2 hours. Crude oil with a viscosity of 2,630 mPa·s was then used to saturate the core at 50°C. The simulated brine was then flooded until the water cut at the core model outlet exceeded 98%, resulting in a water flooding recovery of 36.77%. The wastewater and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer described in Example 2.8 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached above 98%, resulting in a post-polymer injection recovery of 56.39%, an increase in oil displacement efficiency by 19.62%.

[0534] Example 2.15

[0535] The permeability is selected as 860×10 -3 μm 2 A core was saturated with simulated brine (mineralization 50,000 mg / L, calcium and magnesium ion content 5,000 mg / L) under vacuum for more than 2 hours. Crude oil with a viscosity of 1,361 mPa·s was then used to saturate the core at 50°C. The simulated brine was then flooded until the water cut at the core model outlet exceeded 98%, resulting in a waterflood recovery of 33.28%. The wastewater and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer described in Example 2.10 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached above 98%, resulting in a post-polymer injection recovery of 48.59%, an increase in oil displacement efficiency by 15.31%.

[0536] Comparative Example 2.6

[0537] The permeability is selected as 860×10 -3 μm 2 The core was saturated with simulated brine (mineralization 50,000 mg / L, calcium and magnesium ion content 5,000 mg / L) by vacuuming for more than 2 hours. Crude oil with a viscosity of 1,361 mPa·s was then used to saturate the core at 50°C. The simulated brine was then used for water flooding until the water cut at the core model outlet reached 98% or more, resulting in a water flooding recovery of 30.64%. The waste liquid and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer of Comparative Example 2.1 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached 98% or more, resulting in a post-polymer injection recovery of 37.85%, an increase in oil displacement efficiency by 7.21%.

[0538] Comparative Example 2.7

[0539] The permeability is selected as 860×10 -3 μm 2The core was saturated with simulated brine (mineralization 50,000 mg / L, calcium and magnesium ion content 5,000 mg / L) by vacuuming for more than 2 hours. The core was then saturated with crude oil with a viscosity of 1,361 mPa·s at 50°C. The simulated brine was then used for water flooding until the water cut at the core model outlet exceeded 98%, resulting in a water flooding recovery of 31.29%. The waste liquid and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer of Comparative Example 2.2 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached above 98%, resulting in a post-polymer injection recovery of 36.15%, an increase in oil displacement efficiency by 9.23%.

[0540] Comparative Example 2.8

[0541] The permeability is selected as 860×10 -3 μm 2 The core was saturated with simulated brine (mineralization 50,000 mg / L, calcium and magnesium ion content 5,000 mg / L) by vacuuming for more than 2 hours. Crude oil with a viscosity of 1,361 mPa·s was then used to saturate the core at 50°C. The simulated brine was then used for water flooding until the water cut at the core model outlet reached 98% or more, resulting in a water flooding recovery of 32.53%. The waste liquid and dead volume were then drained, and a 0.5 PV aqueous solution of the polymer of Comparative Example 2.3 at a concentration of 1,000 mg / L was injected. The flooding was continued until the water cut reached 98% or more, resulting in a post-polymer injection recovery of 41.12%, an 8.59% increase in oil displacement efficiency.

[0542] Although not shown, under the same conditions, the polymers obtained in other examples can also improve the oil displacement effect by 15-20%, while the oil displacement effect of the polymers prepared in Comparative Examples 2.1-2.3 is improved by less than 10%.

[0543] The above results show that, compared with the comparative example, the cold-adopting functional polymer prepared from the compound of the present invention has a good aqueous phase viscosifying function at 50°C in water with a salinity of ≤50,000 mg / L and a calcium and magnesium ion content of ≤5000 mg / L. At the same time, under low power conditions and at a concentration of 1000 mg / L, it can reduce the viscosity of heavy oil with a viscosity of 1500-3000 mPa·s in an oil reservoir environment by more than 91%, thereby significantly improving the water flooding recovery rate of heavy oil reservoirs.

[0544] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A compound containing a glycoside group, characterized in that The compound has a structure shown in formula (1): In formula (1), R3 is a C4-C20 alkyl group or a C7-C20 alkylphenyl group, R4, R5, R6, R5' and R6' are each independently H or a C1-C4 alkyl group, X is O or NQ, Q is H or a C1-C4 alkyl group, n1+n2=0-20, and when X is O, n1+n2≠0.

2. The compound according to claim 1, wherein R3 is a C6-C18 alkyl group; and / or, R4, R5, R6, R5' and R6' are each independently H or methyl; And / or, n1+n2≠0.

3. The compound according to claim 1 or 2, wherein R3 is n-hexyl, n-dodecyl, n-decyl, n-octyl, n-tetradecyl, 2-ethylhexyl or 11-methyldodecyl; and / or, R5' and R6' are each independently H or methyl and R5' and R6' are different, and R5 and R6 are both H; and / or, n1 and n2 are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

4. A polymer containing glycoside groups, characterized in that The polymer comprises a structural unit C represented by formula (C) and a structural unit D represented by formula (D): Wherein, R3 is a C4-C20 alkyl group or a C7-C20 alkylphenyl group, and R4, R5, R6, R5' and R6', R7 and R8 are X is independently H or C1-C4 alkyl, X is O or NQ, Q is H or C1-C4 alkyl, and n1+n2=0-20.

5. The polymer according to claim 4, wherein The weight ratio of the structural unit C to the structural unit D is (5-300):(5-300); And / or, R3 is a C6-C18 alkyl group; and / or, R4, R5, R6, R5', R6', R7, and R8 are each independently H or methyl; And / or, when X is O, n1+n2≠0.

6. The polymer according to claim 4 or 5, wherein The weight ratio of the structural unit C to the structural unit D is (6-150):(8-200); and / or, R3 is n-hexyl, n-dodecyl, n-decyl, n-octyl, n-tetradecyl, 2-ethylhexyl or 11-methyldodecyl; and / or, R5' and R6' are each independently H or methyl and R5' and R6' are different, and R5 and R6 are both H; and / or, n1+n2≠0; preferably, n1 and n2 are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

7. The polymer according to any one of claims 4 to 6, wherein The polymer also includes a structural unit represented by formula (C-1): Among them, R 11 is H or C1-C4 alkyl; R 11 ' is H, C1-C4 alkyl, C2-C6 alkyl substituted by SO3M, C2-C6 alkyl substituted by P(O)(OM)2, M is H or an alkali metal element; The weight ratio of the structural unit represented by formula (C-1) to the structural unit C is (1-1.8):(0.005-0.3), preferably (1-1.7):(0.006-0.15).

8. The polymer according to any one of claims 4 to 7, wherein The polymer comprises a structural unit A represented by formula (A), a structural unit B represented by formula (B-1) and / or (B-2), a structural unit C represented by formula (C) and a structural unit D represented by formula (D); Wherein, R1, R2', and R2" are each independently H or a C1-C4 alkyl group, R2 is SO3M or P(O)(OM)2, and M and M' are each independently H or an alkali metal element.

9. The polymer according to claim 8, wherein R1, R2', R2" are each independently H or methyl; and / or, M and M' are each independently H or Na. And / or, the weight ratio of the structural unit A, the structural unit B, the structural unit C, and the structural unit D is 1:(0.02-0.8):(0.005-0.3):(0.005-0.3), preferably 1:(0.03-0.7):(0.006-0.15):(0.008-0.2).

10. The polymer according to any one of claims 4 to 9, wherein The viscosity average molecular weight of the polymer is 6 million to 18 million.

11. The polymer according to any one of claims 4 to 9, wherein The viscosity average molecular weight of the polymer is 7 million to 15 million.

12. A method for preparing a polymer containing glycoside groups, characterized in that: The method comprises: under solution polymerization conditions and in the presence of an initiator, polymerizing an olefinic monomer in an olefinic monomer solution; wherein the olefinic monomer comprises a monomer C' represented by formula (1) and a monomer D' represented by formula (d); Wherein, R3 is a C4-C20 alkyl group or a C7-C20 alkylphenyl group, R4, R5, R6, R5' and R6', R7 and R8 are each independently H or a C1-C4 alkyl group, X is O or NQ, Q is H or a C1-C4 alkyl group, and n1+n2=0-20.

13. The method according to claim 12, wherein: The weight ratio of the monomer C' to the monomer D' is (5-300):(5-300); and / or, R3 is a C6-C18 alkyl group, and / or, R4, R5, R6, R5', R6', R7, R8 are each independently H or methyl; And / or, when X is O, n1+n2≠0.

14. The method according to claim 12 or 13, wherein: The weight ratio of the monomer C' to the monomer D' is (6-150):(8-200); and / or, R3 is n-hexyl, n-dodecyl, n-decyl, n-octyl, n-tetradecyl, 2-ethylhexyl or 11-methyldodecyl; and / or, R5' and R6' are each independently H or methyl and R5' and R6' are different, and R5 and R6 are both H; and / or, n1+n2≠0; preferably, n1 and n2 are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

15. The method according to any one of claims 12 to 14, wherein: The alkenyl monomer also includes a monomer represented by formula (3-1): Among them, R 11 is H or C1-C4 alkyl; R 11 ' is H, C1-C4 alkyl, C2-C6 alkyl substituted by SO3M, C2-C6 alkyl substituted by P(O)(OM)2, M is H or an alkali metal element; The weight ratio of the monomer represented by formula (3-1) to the monomer C' is (1-1.8):(0.005-0.3), preferably (1-1.7):(0.006-0.15).

16. The method according to any one of claims 12 to 15, wherein: The ethylenic monomer includes monomer A' represented by formula (a), monomer B' represented by formula (b-1) and / or (b-2), monomer C' represented by formula (1) and monomer D' represented by formula (d); Wherein, R1, R2', R2" are each independently H or a C1-C4 alkyl group, R2 is SO3M or P(O)(OM)2, and M and M' are each independently H or an alkali metal element; Preferably, the weight ratio of the monomer A', the monomer B', the monomer C' and the monomer D' is 1:(0.02-0.8):(0.005-0.3):(0.005-0.3), more preferably 1:(0.03-0.7):(0.006-0.15):(0.008-0.2).

17. The method according to any one of claims 12 to 16, wherein: The conditions of the solution polymerization reaction include: the starting temperature of the polymerization reaction is -10°C to 30°C, the time is 2-12 hours, and the pH value is 4-8.

18. A polymer obtained by the process of any one of claims 12 to 17.

19. A method for emulsifying and reducing the viscosity of heavy oil, characterized in that: The method comprises: contacting a solution of the polymer according to any one of claims 4 to 11 and 18 with heavy oil.

20. The method according to claim 19, wherein: The content of the polymer in the polymer solution is 1000-3000 mg / L; And / or, relative to 70 g of heavy oil, the amount of the polymer used is 20-50 mg.

21. Use of the compound according to any one of claims 1 to 3 or the polymer according to any one of claims 4 to 11 and 18 in chemical flooding.

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