Hyperbranched polymer and preparation method therefor and use thereof

Abstract

A hyperbranched polymer and a preparation method therefor and the use thereof. The hyperbranched polymer comprises a structural formula of formula 1, wherein R is selected from a substituted or unsubstituted C12-C18 alkyl. The hyperbranched polymer, which is used as a demulsifier for demulsifying crude oil emulsions, exhibits a high demulsification efficiency, a low usage amount, a low demulsification temperature, a high acid and alkali resistance, and a high salt resistance. The demulsifier has a high demulsification performance in oil-water emulsions with various properties.

Description

Hyperbranched polymer and preparation method and application thereof

[0001] The present application claims priority to the Chinese patent application No. 2024113187132 filed on September 20, 2024, and entitled "Hyperbranched polymer and preparation method and application thereof", the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] The present application belongs to the field of oil field chemical additives, and specifically relates to a hyperbranched polymer and a preparation method and application thereof. BACKGROUND

[0003] With the increase of crude oil demand, various technologies are used to improve the recovery of crude oil. However, the formation of a large amount of stable crude oil emulsion hinders the production of oil. Crude oil emulsion is thermodynamically unstable, but kinetically stable, and can even remain stable for several years. In the oil industry, emulsification usually occurs during transportation and extraction, and crude oil emulsification can cause pipeline and equipment corrosion, crude oil viscosity increase, and oil refining catalyst poisoning, etc. Therefore, crude oil emulsion needs to be demulsified before entering the refinery.

[0004] The method for demulsifying crude oil mainly adopts physical, chemical, biological and other simple and efficient demulsification methods and composite treatment methods. In the actual production process of oil fields, chemical demulsification method has always been the most commonly used demulsification technology. From the patents or research and application of demulsifiers at home and abroad, it can be known that the main synthesis method of demulsifiers at present is still the modification or compounding based on ethylene oxide and propylene oxide block polyether. For example, CN1283339C discloses a multifunctional demulsifier and a preparation method thereof, which uses organic amine as a starter, and polyether is generated by polymerization of ethylene oxide and propylene oxide, and then reacts with halogenated carboxylic acid to generate the target demulsifier. At present, mature demulsifiers usually use ethylene oxide, propylene oxide and other raw materials, which does not meet the development concept of green environmental protection. In addition, the synthesis of demulsifiers needs to be carried out under a certain pressure, and the reaction process has high requirements. With the use of various new crude oil production technologies, such as tertiary oil recovery technology, shale oil bulk fracturing technology, etc., the stability of oil-water emulsion is getting stronger and stronger, and conventional agents have been unable to meet the dehydration demand. Therefore, it is urgent for those skilled in the art to develop a demulsifier with low usage amount, high demulsification efficiency and strong environmental adaptability. SUMMARY

[0005] The present application provides a hyperbranched polymer, which is applied as a demulsifier, presents low usage amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance, high salt resistance, and can efficiently demulsify oil-water emulsions with different properties.

[0006] The application provides a demulsifier which is applied to a crude oil emulsion and has the advantages of low use amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance, high salt resistance, and wide application scenarios.

[0007] The application provides a crude oil emulsion demulsification method, and the demulsifier can demulsify the crude oil emulsion and has the advantages of high demulsification efficiency, low use amount, low demulsification temperature, high acid and alkali resistance, high salt resistance, and wide application scenarios.

[0008] The application provides a hyperbranched polymer, wherein the hyperbranched polymer has a structural formula shown in Formula 1.

[0009] In the formula, R is selected from C12-C18 alkyl.

[0010] The hyperbranched polymer as described above is prepared through the following steps.

[0011] The alkylphenol and the epichlorohydrin are subjected to a first reaction to obtain an alkylphenol glycidyl ether having a structural formula shown in Formula 2, and then the alkylphenol glycidyl ether is subjected to a ring-opening reaction with glycidol to obtain the hyperbranched polymer.

[0012] The application provides a preparation method of the hyperbranched polymer as described above, and the preparation method comprises the following steps.

[0013] 1) The alkylphenol and the epichlorohydrin are subjected to a first reaction to obtain an alkylphenol glycidyl ether having a structural formula shown in Formula 2.

[0014] 2) The alkylphenol glycidyl ether is subjected to a ring-opening reaction with glycidol to obtain the hyperbranched polymer.

[0015] The preparation method of the hyperbranched polymer as described above, wherein step 1) comprises the following steps.

[0016] After the alkylphenol and the epichlorohydrin are uniformly mixed, the mixture is reacted at 80-110 DEG C for 2-6 h, then cooled to 50-80 DEG C for a ring-closing reaction, and after the sodium hydroxide solution is completely added dropwise within 1-2 h, the mixture is reacted for 2-10 h to obtain the alkylphenol glycidyl ether.

[0017] The preparation method of the hyperbranched polymer as described above, wherein step 2) comprises the following steps.

[0018] The alkylphenol glycidyl ether and the glycidol are added to a solvent, uniformly mixed, and then subjected to the ring-opening reaction to obtain the hyperbranched polymer.

[0019] The reaction temperature of the ring-opening reaction is 80-120℃, and the reaction time is 4-10h.

[0020] The preparation method of the hyperbranched polymer as described above, wherein the alkyl phenol comprises at least one of 4-octadecyl phenol, 4-hexadecyl phenol, 4-tetradecyl phenol, and 4-dodecyl phenol; and the molar ratio of the alkyl phenol to the epichlorohydrin is 1:(3-10).

[0021] The mass percentage of the sodium hydroxide solution is 10-50%.

[0022] The molar ratio of the alkyl phenol glycidyl ether to the glycidol is 1:(2-15).

[0023] The preparation method of the hyperbranched polymer as described above, wherein the first reaction is carried out under the action of a first catalyst, the first catalyst comprises at least one of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, and trioctylmethylammonium chloride; and the molar ratio of the first catalyst to the alkyl phenol is (0.001-0.03):1.

[0024] The preparation method of the hyperbranched polymer as described above, wherein the ring-opening reaction is carried out under the action of a second catalyst, the second catalyst comprises at least one of sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide; and the molar ratio of the second catalyst to the alkyl phenol glycidyl ether is (0.01-0.05):1.

[0025] The solvent comprises at least one of methanol, chloroform, dioxane, N-methylpyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide.

[0026] The application provides a demulsifier comprising the hyperbranched polymer as described above.

[0027] The application provides a crude oil emulsion demulsification method, comprising the following steps:

[0028] The demulsifier as described above is dissolved in a solvent, and then the obtained demulsifier solution is mixed with the crude oil emulsion to demulsify.

[0029] The hyperbranched polymer provided in the application has a specific structural formula, the hyperbranched polymer has the structural formula shown in formula 1, one end is a hydrophobic long chain and a benzene ring structure, and the other end is a hydrophilic hyperbranched polyglycerol structure, so that the hyperbranched polymer exhibits excellent amphiphilicity and high interfacial activity, thereby being capable of greatly reducing the oil-water interfacial tension, promoting the occurrence of the demulsification process, enabling the hyperbranched polymer to perform efficient demulsification, and the hyperbranched polyglycerol structure is controllable, and can be adjusted according to different crude oil emulsions, so that the hyperbranched polymer can demulsify oil-water emulsions with different formation water properties, thereby expanding the application range

[0030] The hyperbranched polymer provided in the application has a specific structural formula, the hyperbranched polymer has the structural formula shown in formula 1, one end is a hydrophobic long chain and a benzene ring structure, and the other end is a hydrophilic hyperbranched polyglycerol structure, so that the hyperbranched polymer exhibits excellent amphiphilicity and high interfacial activity, thereby being capable of greatly reducing the oil-water interfacial tension, promoting the occurrence of the demulsification process, enabling the hyperbranched polymer to perform efficient demulsification, and the hyperbranched polyglycerol structure is controllable, and can be adjusted according to different crude oil emulsions, so that the hyperbranched polymer can demulsify oil-water emulsions with different formation water properties, thereby expanding the application range

[0031] The hyperbranched polymer provided in the application has a specific structural formula, the hyperbranched polymer has the structural formula shown in formula 1, one end is a hydrophobic long chain and a benzene ring structure, and the other end is a hydrophilic hyperbranched polyglycerol structure, so that the hyperbranched polymer exhibits excellent amphiphilicity and high interfacial activity, thereby being capable of greatly reducing the oil-water interfacial tension, promoting the occurrence of the demulsification process, enabling the hyperbranched polymer to perform efficient demulsification, and the hyperbranched polyglycerol structure is controllable, and can be adjusted according to different crude oil emulsions, so that the hyperbranched polymer can demulsify oil-water emulsions with different formation water properties, thereby expanding the application range

[0032] The hyperbranched polymer provided in the application has a specific structural formula, the hyperbranched polymer has the structural formula shown in formula 1, one end is a hydrophobic long chain and a benzene ring structure, and the other end is a hydrophilic hyperbranched polyglycerol structure, so that the hyperbranched polymer exhibits excellent amphiphilicity and high interfacial activity, thereby being capable of greatly reducing the oil-water interfacial tension, promoting the occurrence of the demulsification process, enabling the hyperbranched polymer to perform efficient demulsification, and the hyperbranched polyglycerol structure is controllable, and can be adjusted according to different crude oil emulsions, so that the hyperbranched polymer can demulsify oil-water emulsions with different formation water properties, thereby expanding the application range BRIEF DESCRIPTION OF DRAWINGS

[0033] FIG. 1 is an infrared spectrum of the hyperbranched polymer of Example 1. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical scheme and advantages of the application clearer, the technical scheme in the embodiments of the application will be clearly and completely described below in combination with the embodiments of the application. Obviously, the described embodiments are part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0035] The application provides a hyperbranched polymer, which has a structural formula shown in formula 1.

[0036] In the formula, R is selected from C12-C18 alkyl.

[0037] The hyperbranched polymer of the application has a structural formula shown in formula 1, wherein R is selected from C12-C18 alkyl. The substituted or unsubstituted C12-C18 alkyl of the application refers to alkyl with carbon atom number of 12-18. When a substituent is specified as a group with a specific carbon number, all geometric isomers with the carbon number are included. For example, R can be each independently selected from -(CH2) 11 CH3, -CH(CH3)(CH2)9CH3, -CH2CH(CH3)(CH2)8CH3, -CH2C(CH3)2(CH2)7CH3, -(CH2) 12 CH3, -(CH2) 13 CH3, -(CH2) 14 CH3, -(CH2) 15 CH3, and the like. The wave line connected to the oxygen atom in the compound shown in formula 1 of the application can be selected or hydrogen, the carbon atom at * in is connected to the oxygen atom in the compound of formula 1, and the wave line in can also be selected or hydrogen.

[0038] According to the above scheme provided by the application, the hyperbranched polymer is used as a demulsifier in crude oil emulsion demulsification, has low use amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance, high salt resistance, and can efficiently demulsify crude oil emulsions with different water contents. The applicant analyzes the principle and believes that the reason may be that the hyperbranched polymer has a structural formula shown in formula 1, one end is a hydrophobic long chain and a benzene ring structure, and the other end is a hydrophilic hyperbranched polyglycerol structure, so that the hyperbranched polymer exhibits excellent amphiphilicity and high interfacial activity, thereby greatly reducing the oil-water interfacial tension, replacing the active substances in the interfacial film, softening or destroying the interfacial film, promoting the occurrence of the demulsification process, enabling the hyperbranched polymer to demulsify efficiently, and the hyperbranched polyglycerol structure is controllable, which can be adjusted according to the properties of oil-water emulsions with different properties, so that it can demulsify oil-water emulsions with different formation water properties, and expand its application range.

[0039] Specifically, the hyperbranched polymer can be obtained by infrared absorption spectrum test.

[0040] In a specific embodiment, the hyperbranched polymer is prepared by the following steps:

[0041] The alkyl phenol, epichlorohydrin are subjected to a first reaction to obtain an alkyl phenol glycidyl ether having a structural formula shown in formula 2, and then the alkyl phenol glycidyl ether and glycidol are subjected to a ring-opening reaction to obtain a hyperbranched polymer:

[0042] Specifically, first, the alkyl phenol, epichlorohydrin are subjected to a first reaction to obtain an alkyl phenol glycidyl ether, and then the alkyl phenol glycidyl ether and glycidol are subjected to a ring-opening reaction to obtain a hyperbranched polymer.

[0043] The present application does not limit the specific parameter selection of the first reaction, which can be selected according to actual needs.

[0044] The present application does not limit the specific parameter selection of the ring-opening reaction, which can be selected according to actual needs.

[0045] The present application does not limit the addition ratio of the alkyl phenol and epichlorohydrin, which can be selected according to actual needs.

[0046] The present application does not limit the addition ratio of the alkyl phenol glycidyl ether and glycidol, which can be selected according to actual needs.

[0047] The present application, through the above preparation method, first, the alkyl phenol, epichlorohydrin are subjected to a first reaction to obtain an alkyl phenol glycidyl ether having a structural formula shown in formula 2, and then the alkyl phenol glycidyl ether and glycidol are subjected to a ring-opening reaction to obtain a hyperbranched polymer having a structural formula shown in formula 1. Through the preparation method, one end of the hyperbranched polymer is a hydrophobic long chain and a benzene ring structure, and the other end is a hydrophilic hyperbranched glycerol structure, so that the hyperbranched polymer presents amphiphilicity and high interfacial activity, the hyperbranched polymer presents low use amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance, high salt resistance, and the structure of the hyperbranched polymer can be regulated by controlling the addition ratio of the alkyl phenol glycidyl ether and glycidol, so that the hyperbranched polymer can efficiently demulsify oil-water emulsions with different properties.

[0048] The present application provides a preparation method of a hyperbranched polymer, comprising the following steps:

[0049] 1) The alkyl phenol, epichlorohydrin are subjected to a first reaction to obtain an alkyl phenol glycidyl ether having a structural formula shown in formula 2:

[0050] 2) The alkyl phenol glycidyl ether and glycidol are subjected to a ring-opening reaction to obtain a hyperbranched polymer.

[0051] Specifically, step 1) is a first reaction of the alkyl phenol and the epichlorohydrin to obtain an alkyl phenol glycidyl ether having a structural formula shown in formula 2.

[0052] The present application does not limit the specific parameter selection of the first reaction, which can be selected according to actual needs.

[0053] The present application does not limit the specific proportion of the alkyl phenol and the epichlorohydrin, which can be selected according to actual needs.

[0054] Step 2) is a ring-opening reaction of the alkyl phenol glycidyl ether and the glycidol to obtain the hyperbranched polymer.

[0055] The present application does not limit the specific parameter selection of the ring-opening reaction, which can be selected according to actual needs.

[0056] The present application does not limit the specific proportion of the alkyl phenol glycidyl ether and the glycidol, which can be selected according to actual needs.

[0057] The present application can prepare the hyperbranched polymer having the structural formula of formula 1 by the above preparation method. Through the preparation method, one end of the hyperbranched polymer is a hydrophobic long chain and a benzene ring structure, and the other end is a hydrophilic hyperbranched polyglycerol structure, so that the hyperbranched polymer presents amphiphilicity and high interfacial activity, and further presents low use amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance, high salt resistance, and the structure of the hyperbranched polymer is controllable, which is beneficial to the hyperbranched polymer to demulsify different properties of oil-water emulsions efficiently.

[0058] In one specific embodiment, step 1) comprises the following steps:

[0059] After the alkyl phenol and the epichlorohydrin are uniformly mixed, they are reacted at 80-110°C for 2-6h, then cooled to 50-80°C for a ring-closing reaction, and the sodium hydroxide solution is added dropwise within 1-2h, and then reacted for 2-10h to obtain the alkyl phenol glycidyl ether.

[0060] Specifically, first, the alkyl phenol and the epichlorohydrin are mixed, and after being uniformly mixed, the reaction is carried out at 80-110°C for 2-6h, for example, the temperature is 80°C, 85°C, 90°C, 95°C, 100°C, 105°C or 110°C, etc., and the time is 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, etc., after the reaction is completed, the temperature is lowered to 50-80°C, for example, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, etc., then the sodium hydroxide solution is added dropwise into the reaction system, and the sodium hydroxide solution is added dropwise within 1-2h, and then the ring closure reaction is carried out for 2-10h, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc., and then the solvent and impurities are removed to obtain the alkyl phenol glycidyl ether.

[0061] The application does not limit the specific operation of mixing the alkyl phenol and the epichlorohydrin, which can be selected according to actual needs.

[0062] The application does not limit the specific concentration of the sodium hydroxide solution, which can be selected according to actual needs.

[0063] The application does not limit the dropping speed of the sodium hydroxide solution, which can be selected according to actual needs.

[0064] The application does not limit the specific process of removing the impurities and the solvent, which can be selected according to actual needs.

[0065] The application can make the alkyl phenol and the epichlorohydrin react by the preparation method to obtain the alkyl phenol glycidyl ether with the structure of formula 2, and the preparation method is simple in operation, low in reaction temperature, low in preparation condition requirement, easy to obtain raw materials, and friendly to the environment.

[0066] In one specific embodiment, step 2) comprises the following steps:

[0067] The alkyl phenol glycidyl ether and the glycidol are added into the solvent, uniformly mixed, and then the ring opening reaction is carried out to obtain the hyperbranched polymer.

[0068] The reaction temperature of the ring opening reaction is 80-120°C, and the reaction time is 4-10h.

[0069] Specifically, the alkyl phenol glycidyl ether and the glycidol are added into the solvent to mix, and after being uniformly mixed, the ring opening reaction is carried out, the reaction temperature is 80-120°C, for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C or 120°C, etc., the reaction time is 4-10h, for example, 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc., after the reaction is completed, the impurities and the solvent are removed to obtain the hyperbranched polymer.

[0070] The present application does not limit the specific mixing parameters of the alkyl phenol glycidyl ether and glycidol in the solvent, which can be selected according to actual needs.

[0071] The present application can make the alkyl phenol glycidyl ether and glycidol perform efficient ring-opening reaction by the above method, realize the successful preparation of hyperbranched polymers. In addition, the preparation process of the preparation method is simple, the equipment requirement is low, the energy is saved, and the structure of the hyperbranched polymer can be effectively controlled by the preparation method, which is beneficial to the wide application of the hyperbranched polymer.

[0072] In a specific embodiment, the alkyl phenol includes at least one of 4-octadecyl phenol, 4-hexadecyl phenol, 4-tetradecyl phenol, and 4-dodecyl phenol; the molar ratio of the alkyl phenol to the epichlorohydrin is 1:(3-10), such as 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, etc. When the alkyl phenol is selected from the above compounds and the molar ratio is within the above range, the alkyl phenol of R can fully react with the epichlorohydrin to generate the alkyl phenol glycidyl ether having the structural formula of formula 2, which is beneficial to the subsequent preparation of hyperbranched polymers.

[0073] In a specific embodiment, the mass percentage content of the sodium hydroxide solution is 10-50%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, etc. When the mass percentage content of the sodium hydroxide solution is within the above range, the sodium hydroxide can neutralize the by-product hydrogen chloride generated by the reaction of the alkyl phenol with the epichlorohydrin, effectively prevent the occurrence of side reactions or reverse reactions, and is beneficial to the subsequent preparation of hyperbranched polymers.

[0074] In a specific embodiment, the molar ratio of the alkyl phenol glycidyl ether to the glycidol is 1:(2-15), such as 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, or 1:15, etc. When the molar ratio of the alkyl phenol glycidyl ether to the glycidol is within the above range, the alkyl phenol glycidyl ether and the glycidol can fully perform ring-opening reaction, which is beneficial to the preparation of the hyperbranched polyglycerol structure with hydrophilicity, and lays a foundation for the preparation of hyperbranched polymers.

[0075] In an embodiment, the first reaction is carried out in the presence of a first catalyst, the first catalyst comprising at least one of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride; the molar ratio of the first catalyst to the alkylphenol is (0.001-0.03):1, for example, 0.001:1, 0.005:1, 0.01:1, 0.015:1, 0.02:1, 0.025:1, or 0.03:1, etc. The alkylphenol and the epichlorohydrin of the present application are reacted in the presence of the first catalyst, and when the first catalyst is selected from the above compounds and the molar ratio is within the above range, the first catalyst can promote the rapid and sufficient reaction of the alkylphenol and the epichlorohydrin, laying a foundation for the efficient preparation of the hyperbranched polymer.

[0076] In an embodiment, the ring-opening reaction is carried out in the presence of a second catalyst, the second catalyst comprising at least one of sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide; the molar ratio of the second catalyst to the alkylphenol glycidyl ether is (0.01-0.05):1, for example, 0.01:1, 0.015:1, 0.02:1, 0.025:1, 0.03:1, 0.035:1, 0.04:1, 0.045:1, or 0.05:1, etc. The alkylphenol glycidyl ether and the glycidol of the present application are reacted in the presence of the second catalyst, and when the second catalyst is selected from the above compounds and the molar ratio is within the above range, the second catalyst can promote the ring-opening reaction of the alkylphenol glycidyl ether and the glycidol, facilitating the efficient preparation of the hyperbranched polymer.

[0077] In an embodiment, the solvent comprises at least one of methanol, chloroform, dioxane, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide. When the solvent is selected from the above compounds, the alkylphenol glycidyl ether and the glycidol can be fully dissolved in the solvent, facilitating the ring-opening reaction, and the components will not react with the solvent, avoiding the occurrence of side reactions, thereby ensuring the successful preparation of the hyperbranched polymer.

[0078] The present application provides a demulsifier comprising the above hyperbranched polymer. The demulsifier is prepared based on the hyperbranched polymer, and when the demulsifier is applied to a crude oil emulsion, the demulsifier exhibits low usage amount, high demulsification efficiency, low demulsification temperature, high acid and alkali resistance, high salt resistance, and can efficiently demulsify oil-water emulsions of different properties.

[0079] The application provides a crude oil emulsion demulsification method, comprising the following steps: dissolving the demulsifier in a solvent, and then mixing the obtained demulsifier solution with the crude oil emulsion uniformly to demulsify.

[0080] Hereinafter, the application is further described in detail through specific examples.

[0081] Example 1

[0082] The preparation process of the hyperbranched polymer provided in the example comprises the following steps:

[0083] 1. 31 mmol of 4-octadecylphenol, 93 mmol of epichlorohydrin and 0.1 mmol of tetrabutylammonium bromide are added to a reaction kettle, uniformly mixed, and then reacted at 90°C for 3h. Then, the temperature is lowered to 60°C for a ring closure reaction, 30 mmol of 30% sodium hydroxide solution is added dropwise within 2h, and then reacted for 5h. After removing the solvent and impurities, an alkylphenol glycidyl ether is obtained;

[0084] The molar ratio of 4-octadecylphenol to epichlorohydrin is 1:3, and the molar ratio of tetrabutylammonium bromide to 4-octadecylphenol is 0.0032:1;

[0085] 2. 31 mmol of 4-octadecylphenol glycidyl ether and 1.43 mmol of sodium methoxide are added to 25 mL of methanol, uniformly mixed, and then placed in a nitrogen atmosphere. Then, 279 mmol of glycidol is added dropwise to the above solution within 3.5h at 75°C, and then reacted at 100°C for 5h. After removing the solvent and impurities, an alkylphenol hyperbranched demulsifier is obtained;

[0086] The molar ratio of 4-octadecylphenol glycidyl ether to glycidol is 1:9, and the molar ratio of sodium methoxide to 4-octadecylphenol glycidyl ether is 0.046:1.

[0087] Example 2

[0088] The preparation process of the hyperbranched polymer provided in the example comprises the following steps:

[0089] 1. 31 mmol of 4-octadecylphenol, 93 mmol of epichlorohydrin and 0.1 mmol of tetrabutylammonium bromide are added to a reaction kettle, uniformly mixed, and then reacted at 100°C for 3h. Then, the temperature is lowered to 60°C for a ring closure reaction, 30 mmol of 30% sodium hydroxide solution is added dropwise within 2h, and then reacted for 5h. After removing the solvent and impurities, an alkylphenol glycidyl ether is obtained;

[0090] The molar ratio of 4-octadecylphenol to epichlorohydrin is 1:3, and the molar ratio of tetrabutylammonium bromide to 4-octadecylphenol is 0.0032:1.

[0091] 2. 31 mmol of 4-octadecylphenol glycidyl ether and 1.43 mmol of sodium methoxide are added to 25 mL of methanol, mixed uniformly, and then placed in a nitrogen atmosphere. Then, 93 mmol of glycidol is added dropwise to the above solution at 75°C within 3.5 h, and then reacted at 120°C for 5 h. The solvent and impurities are removed to obtain an alkylphenol hyperbranched demulsifier.

[0092] The molar ratio of 4-octadecylphenol glycidyl ether to glycidol is 1:6, and the molar ratio of sodium methoxide to 4-octadecylphenol glycidyl ether is 0.046:1.

[0093] Example 3

[0094] The preparation process of the hyperbranched polymer provided in this embodiment includes the following steps:

[0095] 1. 31 mmol of 4-octadecylphenol, 93 mmol of epichlorohydrin, and 0.1 mmol of tetrabutylammonium bromide are added to a reaction kettle, mixed uniformly, and then reacted at 90°C for 3 h. Then, the temperature is lowered to 60°C for a ring closure reaction. A 30% sodium hydroxide solution containing 30 mmol is added dropwise within 2 h, and then reacted for 5 h. The solvent and impurities are removed to obtain an alkylphenol glycidyl ether.

[0096] The molar ratio of 4-octadecylphenol to epichlorohydrin is 1:3, and the molar ratio of tetrabutylammonium bromide to 4-octadecylphenol is 0.0032:1.

[0097] 2. 31 mmol of 4-octadecylphenol glycidyl ether and 1.43 mmol of sodium methoxide are added to 25 mL of methanol, mixed uniformly, and then placed in a nitrogen atmosphere. Then, 93 mmol of glycidol is added dropwise to the above solution at 75°C within 3.5 h, and then reacted at 120°C for 5 h. The solvent and impurities are removed to obtain an alkylphenol hyperbranched demulsifier.

[0098] The molar ratio of 4-octadecylphenol glycidyl ether to glycidol is 1:3, and the molar ratio of sodium methoxide to 4-octadecylphenol glycidyl ether is 0.046:1.

[0099] Example 4

[0100] The preparation process of the hyperbranched polymer provided in this embodiment includes the following steps:

[0101] 1. 31 mmol of 4-tetradecylphenol, 93 mmol of epichlorohydrin and 0.1 mmol of tetrabutylammonium bromide are added to a reaction kettle, mixed uniformly and reacted at 100°C for 3h. Then, the temperature is lowered to 60°C for ring closure reaction. A 30% sodium hydroxide solution containing 30 mmol is added dropwise within 2h, and reacted for 5h. After removing the solvent and impurities, an alkylphenol glycidyl ether is obtained;

[0102] The molar ratio of 4-tetradecylphenol to epichlorohydrin is 1:3, and the molar ratio of tetrabutylammonium bromide to 4-octadecylphenol is 0.0032:1.

[0103] 2. 31 mmol of 4-tetradecylphenol glycidyl ether and 1.43 mmol of sodium methoxide are added to 25 mL of methanol, mixed uniformly, and then placed in a nitrogen atmosphere. Then, 279 mmol of glycidol is added dropwise to the above solution within 3.5h at 75°C, and reacted for 5h at 120°C. After removing the solvent and impurities, an alkylphenol hyperbranched demulsifier is obtained.

[0104] The molar ratio of 4-tetradecylphenol glycidyl ether to glycidol is 1:9, and the molar ratio of sodium methoxide to 4-tetradecylphenol glycidyl ether is 0.046:1.

[0105] Example 5

[0106] The preparation process of the hyperbranched polymer provided in this embodiment includes the following steps:

[0107] 1. 31 mmol of 4-tetradecylphenol, 93 mmol of epichlorohydrin and 0.1 mmol of tetrabutylammonium bromide are added to a reaction kettle, mixed uniformly and reacted at 100°C for 3h. Then, the temperature is lowered to 60°C for ring closure reaction. A 30% sodium hydroxide solution containing 30 mmol is added dropwise within 2h, and reacted for 5h. After removing the solvent and impurities, an alkylphenol glycidyl ether is obtained;

[0108] The molar ratio of 4-tetradecylphenol to epichlorohydrin is 1:3, and the molar ratio of tetrabutylammonium bromide to 4-octadecylphenol is 0.0032:1.

[0109] 2. 31 mmol of 4-tetradecylphenol glycidyl ether and 1.43 mmol of sodium methoxide are added to 25 mL of methanol, mixed uniformly, and then placed in a nitrogen atmosphere. Then, 279 mmol of glycidol is added dropwise to the above solution within 3.5h at 75°C, and reacted for 5h at 120°C. After removing the solvent and impurities, an alkylphenol hyperbranched demulsifier is obtained.

[0110] The molar ratio of 4-tetradecyl phenol glycidyl ether to glycidol is 1:6, and the molar ratio of sodium methoxide to 4-tetradecyl phenol glycidyl ether is 0.046:1.

[0111] Example 6

[0112] The preparation process of the hyperbranched polymer provided in the example includes the following steps:

[0113] 1. 31 mmol of 4-dodecyl phenol, 93 mmol of epichlorohydrin, and 0.1 mmol of tetrabutylammonium bromide were added to a reaction kettle, mixed uniformly, and then reacted at 90°C for 3h. Then, the temperature was lowered to 60°C for a ring closure reaction. A 30% sodium hydroxide solution containing 30 mmol was added dropwise within 2h, and then reacted for 5h. After removing the solvent and impurities, an alkyl phenol glycidyl ether was obtained;

[0114] The molar ratio of 4-dodecyl phenol to epichlorohydrin is 1:3, and the molar ratio of tetrabutylammonium bromide to 4-octadecyl phenol is 0.0032:1.

[0115] 2. 31 mmol of 4-dodecyl phenol glycidyl ether and 1.43 mmol of sodium methoxide were added to 25 mL of methanol, mixed uniformly, and then placed in a nitrogen atmosphere. Then, 93 mmol of glycidol was added dropwise to the above solution within 3.5h at 75°C. After that, the reaction was carried out at 100°C for 5h. After removing the solvent and impurities, an alkyl phenol hyperbranched demulsifier was obtained.

[0116] The molar ratio of 4-dodecyl phenol glycidyl ether to glycidol is 1:3, and the molar ratio of sodium methoxide to 4-dodecyl phenol glycidyl ether is 0.046:1.

[0117] Example 7

[0118] The preparation process of the hyperbranched polymer provided in the example is substantially the same as that of Example 1, except that 4-octadecyl phenol, epichlorohydrin, and tetrabutylammonium bromide were mixed uniformly, and then reacted at 80°C for 6h. Then, the temperature was lowered to 50°C for a ring closure reaction. A sodium hydroxide solution was added dropwise within 2h, and then reacted for 10h.

[0119] Example 8

[0120] The preparation process of the hyperbranched polymer provided in the example is substantially the same as that of Example 1, except that 4-octadecyl phenol, epichlorohydrin, and tetrabutylammonium bromide were mixed uniformly, and then reacted at 110°C for 2h. Then, the temperature was lowered to 80°C for a ring closure reaction. A sodium hydroxide solution was added dropwise within 1h, and then reacted for 2h.

[0121] Example 9

[0122] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of 4-octadecylphenol to epichlorohydrin is 1:6.

[0123] Embodiment 10

[0124] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of 4-octadecylphenol to epichlorohydrin is 1:10.

[0125] Embodiment 11

[0126] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of tetrabutylammonium bromide to 4-octadecylphenol is 0.001:1.

[0127] Embodiment 12

[0128] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of tetrabutylammonium bromide to 4-octadecylphenol is 0.01:1.

[0129] Embodiment 13

[0130] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of tetrabutylammonium bromide to 4-octadecylphenol is 0.03:1.

[0131] Embodiment 14

[0132] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the mass percentage content of the sodium hydroxide solution is 10%.

[0133] Embodiment 15

[0134] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the mass percentage content of the sodium hydroxide solution is 50%.

[0135] Embodiment 16

[0136] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the reaction temperature of the ring-opening reaction is 80°C, and the reaction time is 10h.

[0137] Embodiment 17

[0138] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the reaction temperature of the ring-opening reaction is 120°C, and the reaction time is 4h.

[0139] Embodiment 18

[0140] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of 4-octadecylphenol glycidyl ether to glycidol is 1:2.

[0141] Embodiment 19

[0142] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of 4-octadecylphenol glycidyl ether to glycidol is 1:15.

[0143] Embodiment 20

[0144] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of sodium methoxide to 4-octadecylphenol glycidyl ether is 0.01:1.

[0145] Embodiment 21

[0146] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of sodium methoxide to 4-octadecylphenol glycidyl ether is 0.05:1.

[0147] Embodiment 22

[0148] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that 4-octadecylphenol, epichlorohydrin and tetrabutylammonium bromide are uniformly mixed, and then reacted at 120°C for 7h, and then cooled to 90°C for ring closure reaction, and then sodium hydroxide solution is added dropwise within 0.5h, and then reacted for 11h.

[0149] Embodiment 23

[0150] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of 4-octadecylphenol to epichlorohydrin is 1:11.

[0151] Embodiment 24

[0152] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the molar ratio of tetrabutylammonium bromide to 4-octadecylphenol is 0.035:1.

[0153] Embodiment 25

[0154] The preparation process of the hyperbranched polymer provided in the embodiment is substantially the same as that in Embodiment 1, except that the mass percentage content of sodium hydroxide solution is 60%.

[0155] Embodiment 26

[0156] The preparation process of the hyperbranched polymer provided in this example is substantially the same as that of Example 1, except that the reaction temperature of the ring-opening reaction is 130°C, and the reaction time is 11 h.

[0157] Example 27

[0158] The preparation process of the hyperbranched polymer provided in this example is substantially the same as that of Example 1, except that the molar ratio of 4-octadecylphenol glycidyl ether to glycidol is 1:16.

[0159] Example 28

[0160] The preparation process of the hyperbranched polymer provided in this example is substantially the same as that of Example 1, except that the molar ratio of sodium methoxide to 4-octadecylphenol glycidyl ether is 0.06:1.

[0161] Comparative Example 1

[0162] This comparative example uses 4-octadecylphenol glycidyl ether prepared in Example 1 as a demulsifier.

[0163] Comparative Example 2

[0164] This comparative example uses a commercial demulsifier SA-003 purchased from Nantong Shina Water Treatment Reagent Co., Ltd.

[0165] Test Example 1

[0166] The infrared absorption spectrum test of the hyperbranched polymer of Example 1 is shown in Figure 1. The absorption peak at 3428 cm-1 is the stretching vibration absorption peak of -OH, the absorption peaks at 2931 cm-1 and 2858 cm-1 are the symmetric and asymmetric vibration absorption peaks of C-H, the absorption peak at 1600 cm-1 is the stretching vibration absorption peak of aromatic ring C=C, the absorption peak at 1457 cm-1 is the in-plane bending vibration absorption peak of -CH, the absorption peak at 1112 cm-1 is the C-O-C stretching vibration absorption peak, and the absorption peak at 750 cm-1 is attributed to the long-chain -(CH2)n characteristic peak, n > 4, so the hyperbranched polymer of Example 1 is successfully synthesized. -1 -1 -1 -1 -1 -1 -1 n

[0167] Test Example 2

[0168] ​​​​​​​​Crude oil (crude oil source is Changqing oil field, viscosity at 25℃: 7.6 mPa·s, asphaltene: 14wt%, resin: 6.03wt%, wax: 15.46%, water: 1.6wt%) was added to water in a mass ratio of 7 / 3, 1 / 1, 3 / 7, heated to 70℃, then stirred at a speed of 11000r / min for 20min, and this process was repeated three times until stable crude oil emulsion with different water content was obtained.

[0169] The hyperbranched polymers prepared in the examples and comparative examples were added to ethanol to prepare demulsifier solutions with a mass fraction of 0.6%.

[0170] 1 part by volume of the above demulsifier solution was added to 20 parts by volume of crude oil emulsion and mixed uniformly, then transferred to a 60℃ water bath and left to stand for 2h, and the dehydration rate was measured to characterize the demulsification efficiency, and the results are shown in Table 1.

[0171] Table 1

[0172] Test Example 3

[0173] Different amounts of hyperbranched polymers prepared in the examples and comparative examples were added to ethanol to prepare demulsifier solutions with a mass fraction of 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, respectively.

[0174] 1 part by volume of the above demulsifier solution was added to 20 parts by volume of crude oil emulsion and mixed uniformly, then transferred to a 60℃ water bath and left to stand for 2h, and the dehydration rate was measured, and the results are shown in Table 2.

[0175] Table 2

[0176] Test Example 4

[0177] The hyperbranched polymers prepared in the examples and comparative examples were added to ethanol to prepare demulsifier solutions with a mass fraction of 0.6%.

[0178] 1 part by volume of the above demulsifier solution was added to 20 parts by volume of crude oil emulsion and mixed uniformly, then transferred to a 60℃ water bath and left to stand for 2h, and the dehydration rate was measured, and the results are shown in Table 3.

[0179] Table 3

[0180] Test Example 5

[0181] The crude oil (crude oil source: Changqing oil field, viscosity at 25°C: 7.6 mPa-s, asphaltene: 14 wt%, resin: 6.03 wt%, wax: 15.46%, water: 1.6 wt%) was added to water in a mass ratio of 7 / 3, heated to 70°C, the pH value was adjusted by hydrochloric acid and sodium hydroxide, then stirred at a speed of 11000 r / min for 20 min, and the process was repeated three times until a stable crude oil emulsion was obtained.

[0182] The hyperbranched polymers prepared in the examples and comparative examples were added to ethanol to prepare a demulsifier solution with a mass fraction of 0.6%.

[0183] 1 part by volume of the above demulsifier solution was added to 20 parts by volume of crude oil emulsion with different pH values and mixed uniformly, then transferred to a 60°C water bath respectively and left to stand for 2 h, and the dehydration rate was measured, and the results are shown in Table 4.

[0184] Table 4

[0185] Test Example 6

[0186] The crude oil (crude oil source: Changqing oil field, viscosity at 25°C: 7.6 mPa-s, asphaltene: 14 wt%, resin: 6.03 wt%, wax: 15.46%, water: 1.6 wt%) was added to water in a mass ratio of 7 / 3, heated to 70°C, the salinity was adjusted by sodium chloride, then stirred at a speed of 11000 r / min for 20 min, and the process was repeated three times until a stable crude oil emulsion was obtained.

[0187] The hyperbranched polymers prepared in the examples and comparative examples were added to ethanol to prepare a demulsifier solution with a mass fraction of 0.6%.

[0188] 1 part by volume of the above demulsifier solution was added to 20 parts by volume of crude oil emulsion with different salinity and mixed uniformly, then transferred to a 60°C water bath respectively and left to stand for 2 h, and the dehydration rate was measured, and the results are shown in Table 5.

[0189] Table 5

[0190] As can be seen from Table 1, according to the comparison of Examples 1-28 and Comparative Examples 1-2, the hyperbranched polymer provided in the application can exhibit excellent demulsification performance as a demulsifier, while the demulsifier prepared in Comparative Example 1 cannot exhibit amphiphilicity due to the almost absence of hydrophilic structure in the molecular structure, resulting in no demulsification performance; as can be seen from Table 2, the hyperbranched polymer provided in the application can also have good demulsification performance in the crude oil emulsion at a lower concentration; as can be seen from Table 3, the hyperbranched polymer provided in the application has good demulsification performance above 50°C and low demulsification temperature; as can be seen from Table 4, the demulsification performance of the hyperbranched polymer provided in the application is less affected by pH, and has high demulsification efficiency in the range of pH 3-11; as can be seen from Table 5, the hyperbranched polymer provided in the application still has stable demulsification efficiency under high salinity conditions, indicating that the hyperbranched polymer has high salt resistance. In summary, the hyperbranched polymer provided in the application has the advantages of high demulsification efficiency, low use amount, low demulsification temperature, and excellent demulsification effect under high acid or alkaline conditions or high salinity conditions when applied as a demulsifier in the demulsification of crude oil emulsion.

[0191] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the application, and not to limit them; although the application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the application.

Claims

1. A hyperbranched polymer, wherein, The hyperbranched polymer has a structural formula shown in Formula 1: R is selected from C12-C18 alkyl.

2. The hyperbranched polymer of claim 1, wherein, The hyperbranched polymer is prepared by the following steps: alkylphenol, epichlorohydrin are subjected to a first reaction to obtain an alkylphenol glycidyl ether having a structural formula shown in Formula 2, and then the alkylphenol glycidyl ether is subjected to a ring-opening reaction with glycidol to obtain the hyperbranched polymer:

3. A process for the preparation of the hyperbranched polymer of claim 1 or 2, wherein, The method comprises the following steps: 1) subjecting the alkyl phenol, epichlorohydrin to a first reaction to obtain an alkyl phenol glycidyl ether having a structural formula shown in Formula 2: 2) ring-opening reaction of the alkylphenol glycidyl ether and glycidol to obtain the hyperbranched polymer.

4. The method for preparing the hyperbranched polymer as described in claim 3, wherein, Step 1) comprises the following steps: After the alkylphenol and epichlorohydrin are uniformly mixed, they are reacted at 80-110°C for 2-6h, then cooled to 50-80°C for ring-closing reaction, and after the sodium hydroxide solution is added dropwise in 1-2h, the reaction is carried out for 2-10h to obtain the alkylphenol glycidyl ether.

5. The method for preparing a hyperbranched polymer according to claim 3 or 4, wherein, Step 2) comprises the following steps: The alkylphenol glycidyl ether and glycidol are added to a solvent, uniformly mixed, and then subjected to the ring-opening reaction to obtain the hyperbranched polymer; The reaction temperature of the ring-opening reaction is 80-120°C, and the reaction time is 4-10h.

6. The method of preparing a hyperbranched polymer according to any one of claims 3 to 5, wherein, The alkylphenol comprises at least one of 4-octadecylphenol, 4-hexadecylphenol, 4-tetradecylphenol, and 4-dodecylphenol; the molar ratio of the alkylphenol to epichlorohydrin is 1:(3-10); And / or, the mass percentage content of the sodium hydroxide solution is 10-50%; And / or, the molar ratio of the alkylphenol glycidyl ether to glycidol is 1:(2-15).

7. The method of preparing a hyperbranched polymer according to any one of claims 3 to 6, wherein, The first reaction is carried out in the presence of a first catalyst, the first catalyst comprises at least one of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tetrabutylammonium hydrogen sulfate, and trioctylmethylammonium chloride; the molar ratio of the first catalyst to alkylphenol is (0.001-0.03):

1.

8. The method of preparing a hyperbranched polymer according to any one of claims 3 to 7, wherein, The ring-opening reaction is carried out in the presence of a second catalyst, the second catalyst comprises at least one of sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide; the molar ratio of the second catalyst to alkylphenol glycidyl ether is (0.01-0.05):1; And / or, the solvent comprises at least one of methanol, chloroform, dioxane, N-methylpyrrolidone, N,N-dimethylformamide, and dimethyl sulfoxide.

9. A demulsifier, wherein, The demulsifier comprises the hyperbranched polymer of claim 1 or 2.

10. A method of breaking an emulsion of a crude oil, wherein, The method comprises the following steps: The demulsifier of claim 9 is dissolved in a solvent, and then the obtained demulsifier solution is uniformly mixed with a crude oil emulsion for demulsification.

Images