Long-chain polyether, preparation method and application thereof, demulsifier raw material composition, demulsifier and preparation method of demulsifier

Abstract

The invention relates to the technical field of demulsifiers, in particular to long-chain polyether, a preparation method and application thereof, a demulsifier raw material composition, a demulsifier and a preparation method of the demulsifier. The long-chain polyether comprises a polyether chain segment and an end-capping group R2; the polyether chain segment contains at least two of an oxyvinyl structural unit, an oxypropenyl structural unit and an oxybutenyl structural unit; r2 is selected from the group consisting of X < 1 >, X < 2 >, X < 3 > and X < 4 > independently represent alkylene, a, b, c and d independently represent 0 or 1, and * represents a connection site. The long-chain polyether provided by the invention has excellent demulsification performance.

Description

Technical Field

[0001] This invention relates to the field of demulsifier technology, specifically to a long-chain polyether, its preparation method and application, as well as a demulsifier raw material composition and a demulsifier and its preparation method. Background Technology

[0002] Crude oil demulsification is a crucial physicochemical process in the oilfield industry. During oil extraction, crude oil and water form emulsions, severely impacting crude oil transportation and further refining. Therefore, crude oil demulsification is essential before centralized transportation. The use of surfactants as crude oil demulsifiers began to develop abroad in the 1920s; prior to this, simple sedimentation methods were used to dehydrate crude oil. With increased crude oil production and the application of water injection technology, the water content of crude oil increased, creating an urgent need for improved demulsification technology, thus promoting the research and development of crude oil demulsifiers. In the 1920s, caustic soda, common soaps (fatty acid soaps), naphthenic acid soaps, oxidized kerosene, and diesel oil were used for demulsification. These demulsifiers had low dehydration efficiency and could form insoluble salts with polyvalent metal ions in formation water, which could actually stabilize the emulsion. Subsequently, sulfonates began to be used as demulsifiers, and their demulsification performance was extensively studied. Various demulsifiers were prepared by sulfonation of unsaturated and saturated fatty acids and alkyl aromatics of different molecular weights. In the 1940s, the Soviet Union developed water-soluble sulfonates, which were neutralized with lime water, caustic soda, and ammonia water. Among these, sulfonate demulsifiers exhibited the best demulsifying properties. More complex sulfonate demulsifiers were produced by condensing aromatic hydrocarbons with aldehydes or ketones, such as dialkylbenzene with formaldehyde, followed by acid treatment. These demulsifiers were suitable for demulsifying asphalt-based water-containing crude oils. Since the 1940s, nonionic surfactants have been increasingly used as demulsifiers. Extensive research was conducted from the 1950s to the 1970s, resulting in numerous patents. In the 1970s, a few countries began exploring and developing new demulsifiers. The goal was to achieve low-temperature demulsification to save heat energy and rapid demulsification to improve equipment processing efficiency, expand the applicability of demulsifiers to crude oil, and overcome the weakness of excessive specialization in demulsifiers.

[0003] Conventional demulsifiers function by being added to crude oil emulsions, i.e., dissolved in water. Since the successful development of polyether demulsifiers in the 1970s, no new or more efficient crude oil demulsifiers have been introduced into application. Surface functionalization of materials provides a pathway for developing novel functional materials. Combining the demulsification function of crude oil emulsions with functional materials possessing other functions through surface modification can create new functional materials that can enhance the performance of crude oil demulsifiers or the original performance and application range of functional materials.

[0004] It is well known that crude oil has a negative impact on the natural environment, and crude oil spilled in the natural environment, such as crude oil on the sea surface, needs to be collected and treated centrally. A common method is to use porous materials to absorb the crude oil from the sea surface. Some researchers have also used surface-wettable mesh materials to quickly separate crude oil from seawater through filtration, enriching the crude oil for further processing. However, if the crude oil and seawater form an emulsion, the above methods will fail. Adding crude oil demulsifiers is also unsuitable in the open marine environment.

[0005] As mentioned above, crude oil emulsion demulsifiers are important oil recovery aids. Currently, oilfields commonly use various low-molecular-weight organic acid ester copolymers, alkylphenol resin polymers, hydrophobically associating trimers of acrylic acid series, and silicone-containing demulsifiers. For a specific crude oil emulsion, suitable demulsifiers can be screened from these conventional demulsifiers. However, due to limitations in the demulsification mechanism, the performance of these screened demulsifiers may not be high, and their universality may not be strong. Summary of the Invention

[0006] The inventors of this invention have discovered a polyether molecule with demulsifying function that is capped with chemically active groups. The polyether molecule with chemically active groups and demulsifying function has significant reactivity and can be chemically bonded to the active groups on the surface of various functional materials, thereby imparting the demulsifying function of crude oil emulsions to the material surface. It has a high efficiency in demulsification and is a crude oil demulsifier with a wide range of applications.

[0007] Based on this, a first aspect of the present invention provides a long-chain polyether comprising a polyether segment and a capping group R2; wherein the polyether segment contains at least two selected from oxyethylene structural units, oxypropylene structural units, and oxybutene structural units; and R2 is selected from... In this context, X1, X2, X3, and X4 are each independently alkylene groups, a, b, c, and d are each independently 0 or 1, and * indicates a linking site.

[0008] The second aspect of this invention provides a method for preparing the long-chain polyether described in the first aspect of this invention, the method comprising:

[0009] Under the action of a Lewis acid catalyst, the polyether raw material undergoes a first contact with epichlorohydrin, followed by a ring-closing reaction under the action of an alkali, and finally a first post-treatment; or

[0010] In the presence of an amination catalyst and hydrogen, the polyether feedstock undergoes a hydroamination reaction with an amine compound, followed by a second post-treatment; optionally, in the presence of a solvent and a carbonylation catalyst, the post-treated material undergoes a carbonylation reaction with dimethyl carbonate, followed by a third post-treatment; or

[0011] In the presence of amine catalysts and polymerization inhibitors, polyether raw materials undergo esterification with acryloyl chloride, followed by a fourth post-treatment.

[0012] The polyether raw material contains polyether segments and end-capping groups. Wherein O is an oxygen atom, X is an alkylene group, m is 0 or 1, and the polyether segment contains at least two of the following structural units: oxyvinyl group, oxypropylene group, and oxybutene group.

[0013] A third aspect of the present invention provides the application of the long-chain polyether described herein in a demulsifier.

[0014] A fourth aspect of the present invention provides a demulsifier raw material composition comprising: the long-chain polyether described in the present invention, and a solid-phase material having groups on its surface capable of reacting with end-capping group R2, wherein the definition of R2 is the same as the definition of R2 in the long-chain polyether of the present invention.

[0015] The fifth aspect of the present invention provides a method for preparing a demulsifier, the method comprising: contacting the raw material composition of the present invention in the presence of an inert solvent.

[0016] The sixth aspect of the present invention provides a demulsifier prepared by the above-described method for preparing the demulsifier.

[0017] Through the above technical solution, the long-chain polyether in this invention has excellent demulsification performance. When applied to the surface of various functional materials, it can easily impart excellent crude oil emulsion demulsification function to the material surface, effectively enhance the performance of functional materials, and expand the application range. Detailed Implementation

[0018] The endpoints and any values ​​of the ranges 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 endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0019] As mentioned above, existing crude oil demulsifiers may have limited performance and applicability. The inventors of this invention have discovered a long-chain polyether comprising polyether segments and end-capping groups R2; the polyether segments contain at least two of the following: oxyethylene structural units, oxypropylene structural units, and oxybutene structural units; R2 is selected from... In this context, X1, X2, X3, and X4 are each independently alkylene groups, a, b, c, and d are each independently 0 or 1, and * indicates a linking site.

[0020] The long-chain polyether in this invention, through the design of specific polyether segments and end-capping group R2, enables the long-chain polyether to have demulsification function and significant reactivity. It can be chemically bonded to the active groups on the surface of various functional materials, thereby imparting the crude oil emulsion demulsification function to the material surface, and exhibiting excellent demulsification performance during use.

[0021] According to a preferred embodiment of the present invention, R2 is selected from...

[0022] According to a particularly preferred embodiment of the present invention, R2 is selected from...

[0023] In this invention, when a is 0, it means that O-X1 is not present. Similarly, b, c and d have the same meaning. In this invention, it is preferred that a is 0.

[0024] In this invention, alkylene groups can be straight-chain or branched. According to a preferred embodiment of the invention, X1, X2, X3, and X4 are each independently C1-C1. 18 Alkylene.

[0025] In this invention, C1-C 18 Alkylene refers to a divalent saturated hydrocarbon chain containing 1-18 carbon atoms.

[0026] According to a particularly preferred embodiment of the present invention, X1 is a C1-C3 alkylene group, such as methylene, ethylene, or propylene. The long-chain polyethers described in the foregoing embodiments exhibit superior demulsifying properties when used as demulsifiers.

[0027] According to a particularly preferred embodiment of the present invention, X2 is C6-C. 18 The alkylene group, such as hexane, octane, 2,2-dimethyl-1,4-butylene, 3,6-dimethyl-1,6-hexane, etc., is preferably a C6 alkylene group. The long-chain polyethers described in the foregoing embodiments exhibit superior demulsifying properties when used as demulsifiers.

[0028] According to a particularly preferred embodiment of the present invention, X3 is a C3-C6 alkylene group, such as propylene, butylene, 2,2-dimethyl-1,4-butylene, hexylene, etc. The long-chain polyethers described in the foregoing embodiments exhibit superior demulsifying performance when used as demulsifiers.

[0029] According to a particularly preferred embodiment of the present invention, X4 is C6-C. 12The alkylene group, such as hexane, octane, 2,2-dimethyl-1,4-butylene, 3,6-dimethyl-1,6-hexane, etc., is preferably a C6 alkylene group. The long-chain polyethers described in the foregoing embodiments exhibit superior demulsifying properties when used as demulsifiers.

[0030] According to a preferred embodiment of the present invention, the number n of oxyethylene structural units ranges from 0 to 1000.

[0031] In this invention, when the number of oxyvinyl structural units n is 0, that is, there are no oxyvinyl structural units, the number of oxyvinyl structural units n that can be listed are 0, 20, 40, 80, 90, 100, 120, 130, 140, 160, 180, 200, 220, 240, 300, 320, 360, 400, 420, 500, 600, 800, 1000, and any range of any two of the above values.

[0032] According to a particularly preferred embodiment of the present invention, the number n of oxyethylene structural units is 5-200. The long-chain polyethers described in the foregoing embodiments exhibit superior demulsification performance when used as demulsifiers.

[0033] According to a particularly preferred embodiment of the present invention, the number m of oxypropylene structural units ranges from 0 to 1000.

[0034] In this invention, when the number m of oxypropylene structural units is 0, that is, when there are no oxypropylene structural units, the number of oxypropylene structural units m can be listed as 0, 80, 100, 160, 200, 240, 320, 400, 500, 600, 700, 800, 900, 1000, and any range of any two of the above values.

[0035] According to a particularly preferred embodiment of the present invention, the number of oxypropylene structural units m is 5-200. The long-chain polyethers described in the foregoing embodiments exhibit superior demulsifying performance when used as demulsifiers.

[0036] According to a particularly preferred embodiment of the present invention, the number p of oxybutene structural units ranges from 0 to 1000.

[0037] In this invention, when the number p of oxybutene structural units is 0, that is, when there are no oxybutene structural units, the number of oxybutene structural units that can be listed are 0, 80, 100, 160, 200, 240, 320, 400, 500, 600, 700, 800, 900, 1000, and any range of any two of the above values.

[0038] According to a particularly preferred embodiment of the present invention, the number p of oxybutene structural units is 5-200. The long-chain polyethers described in the foregoing embodiments exhibit superior demulsification performance when used as demulsifiers.

[0039] In this invention, the polyether segment contains at least two of the following structural units: oxyvinyl structural units, oxypropylene structural units, and oxybutene structural units. That is, at least two of the following structural units, n, m, and p, are not zero: preferably, the number of oxyvinyl structural units n, the number of oxypropylene structural units m, and / or the number of oxybutene structural units p, are not zero.

[0040] According to a particularly preferred embodiment of the present invention, m, n, and p are all non-zero.

[0041] In this invention, when m, n, and p are all non-zero, the polyether segment simultaneously contains oxyvinyl structural units, oxypropylene structural units, and oxybutene structural units.

[0042] In this invention, the number of each segment in the polyether chain is calculated according to the amount of raw material fed.

[0043] In this invention, each structural unit in the polyether segment can exist in a block form or a random form. In order to further increase its demulsification performance, it is preferred that the two ends of the polyether segment are oxyethylene structural units.

[0044] In this invention, when both ends of the polyether segment are oxyvinyl structural units, as long as the purpose of this invention can be achieved, the oxyvinyl structural units at both ends of the polyether segment can be selected as needed. Preferably, the number of oxyvinyl structural units at both ends of the polyether segment is 20-200 each.

[0045] In this invention, the long-chain polyether has two end-capping groups. To distinguish between the two end-capping groups, they are referred to as end-capping group R1 and end-capping group R2, respectively.

[0046] In this invention, the long-chain polyether has two end-capping groups, one or both of which are end-capping groups R2. Preferably, one end-capping group of the long-chain polyether is end-capping group R2, and one end-capping group R1 of the long-chain polyether is selected from alkyl, cycloalkyl, olefinic or aromatic groups.

[0047] According to a preferred embodiment of the present invention, R1 is selected from C1-C 18 Alkyl, C6-C 18 cycloalkyl, C2-C 18 olefinic or C6-C 24 Aromatic groups.

[0048] According to the invention, C1-C can be listed.18 The alkyl group includes methyl, ethyl, propyl, butyl, pentylhexyl, heptyl, octyl, dodecyl, and octadecyl. Preferably, R1 is selected from C1-C4 straight-chain alkyl groups.

[0049] According to the present invention, C6-C can be listed. 18 The cycloalkyl group includes cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl. Preferably, R1 is selected from C6 cycloalkyl groups.

[0050] According to the present invention, C6-C can be listed. 18 The aromatic group is phenyl, naphthyl, or biphenyl; preferably, R1 is selected from C6-C6. 18 Aromatic groups.

[0051] According to the present invention, C2-C can be listed. 18 The olefinic group includes vinyl, propenyl, butenyl, dodecenyl, and octadecenyl. Preferably, R1 is selected from C3-C6 straight-chain olefinic groups.

[0052] According to one embodiment of the present invention, the polyether is selected from A1-A18; among A1-A18, the long chain of the polyether has the general molecular formula as shown in formula (I);

[0053]

[0054] A1: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 80, m is 80, and p is 0;

[0055] A2: Methoxy polyoxyethylene ether (80) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 240, m is 320, and p is 0;

[0056] A3: Methoxy polyoxyethylene ether (60) polyoxypropylene (160) polyoxyethylene (80) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 140, m is 160, and p is 0;

[0057] A4: Propylene oxide polyoxyethylene ether (100) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is propyl, R2 is glycidyl, n is 260, m is 320, and p is 0.

[0058] A5: Butoxy polyoxyethylene ether (100) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is butyl, R2 is glycidyl, n is 260, m is 320, and p is 0.

[0059] A6: Allyl polyoxyethylene ether (80) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is allyl, R2 is glycidyl, n is 240, m is 320, and p is 0.

[0060] A7: Phenoxy polyoxyethylene ether (80) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is phenyl, R2 is glycidyl group, n is 240, m is 320, and p is 0;

[0061] A8: Phenoxy polyoxyethylene ether (80) polyoxybutylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is phenyl, R2 is glycidyl group, n is 240, m is 0, and p is 320.

[0062] A9: Cyclohexyloxy polyoxyethylene ether (80) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is cyclohexyl, R2 is glycidyl, n is 240, m is 320, and p is 0.

[0063] A10: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) amine, wherein R1 is methyl, R2 is amino, n is 80, m is 80, and p is 0;

[0064] A11: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) urethane, wherein R1 is methyl, R2 is urethane group, n is 80, m is 80, and p is 0;

[0065] A12: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) polyoxybutylene (20) urethane, wherein R1 is methyl, R2 is urethane group, n is 80, m is 80, and p is 20.

[0066] A13: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxybutene (20) polyoxyethylene (60) urethane, wherein R1 is methyl, R2 is urethane group, n is 80, m is 80, and p is 20.

[0067] A14: Methoxy polyoxyethylene ether (60) polyoxypropylene (160) polyoxybutene (20) polyoxyethylene (80) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 140, m is 160, and p is 20.

[0068] A15: Methoxy polyoxyethylene ether (120) polyoxypropylene (160) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 120, m is 160, and p is 0;

[0069] A16: Phenoxy polyoxyethylene ether (240) polyoxybutylene (320) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 240, m is 320, and p is 0;

[0070] A17: Methoxy polyoxyethylene ether (20) polyoxybutylene ether (1200) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 20, m is 0, and p is 1200;

[0071] A18: Methoxy polyoxyethylene ether (20) polyoxypropylene ether (1200) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 20, m is 1200, and p is 0.

[0072] According to the present invention, the preparation method of the long-chain polyether is not particularly limited as long as the purpose of the present invention can be achieved. Preferably, the second aspect of the present invention provides a method for preparing the long-chain polyether described in the first aspect of the present invention, the preparation method comprising:

[0073] Under the action of a Lewis acid catalyst, the polyether raw material undergoes a first contact with epichlorohydrin, followed by a ring-closing reaction under the action of an alkali, and finally a first post-treatment; or

[0074] In the presence of an amination catalyst and hydrogen, the polyether feedstock undergoes a hydroamination reaction with an amine compound, followed by a second post-treatment; optionally, in the presence of a solvent and a carbonylation catalyst, the post-treated material undergoes a carbonylation reaction with dimethyl carbonate, followed by a third post-treatment; or

[0075] In the presence of amine catalysts and polymerization inhibitors, polyether raw materials undergo esterification with acryloyl chloride, followed by a fourth post-treatment.

[0076] The polyether raw material contains polyether segments and end-capping groups. Wherein O is an oxygen atom, X is an alkylene group, m is 0 or 1, and the polyether segment contains at least two of the following structural units: oxyvinyl group, oxypropylene group, and oxybutene group.

[0077] In this invention, the long-chain polyether prepared by the preparation method of this invention has significant reactivity and can be chemically bonded to the active groups on the surface of various functional materials, thereby endowing the surface of the material with the function of demulsifying crude oil emulsions and exhibiting excellent demulsification performance during use.

[0078] According to the present invention, there is no particular limitation on the type of Lewis acid catalyst as long as the purpose of the present invention can be achieved. In a preferred embodiment, the Lewis acid catalyst is selected from at least one of boron trifluoride diethyl ether complex, boron trifluoride, sulfuric acid, and stannous dichloride.

[0079] According to a preferred embodiment of the present invention, the alkali is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, calcium hydroxide, and magnesium hydroxide.

[0080] According to a preferred embodiment of the present invention, the conditions for the first contact include: a temperature of 30°C to 100°C and a time of 3 to 7 hours.

[0081] In this invention, during the first contact, epichlorohydrin can be dripped into a Lewis acid catalyst and a polyether raw material for the first contact.

[0082] According to a preferred embodiment of the present invention, the conditions for the closed-loop reaction include: a temperature of 30°C to 100°C and a time of 5-8 hours.

[0083] In this invention, the purpose of the base in the closed-loop reaction is to participate in and promote the occurrence of the closed-loop reaction. During the reaction, the reaction solution may generate a temperature increase or cause side reactions. In order to reduce the intensity of the reaction and the probability of side reactions, the base can be added to the reaction system in batches. After the previous batch of base dissolves, the next batch of base is added. For example, it can be divided into three batches.

[0084] According to the present invention, the Lewis acid catalyst, as a catalyst, only promotes the reaction, and there is no special limitation on its amount added. For example, the mass ratio of the Lewis acid catalyst to the polyether raw material is 1:(100-2000), specifically 1:100, 1:200, 1:500, 1:800, 1:1000, 1:1500, and 1:2000.

[0085] According to the present invention, there is no particular limitation on the amount of epichlorohydrin added, which enables the end-capping groups of the polyether raw material to be determinated. Complete reaction is sufficient; for example, the mass ratio of epichlorohydrin to polyether raw material is 1:(20-200).

[0086] According to the present invention, there is no special limitation on the amount of alkali used, as long as it is sufficient to allow the end-capping groups after the polyether reaction to react fully with the alkali. For example, the mass ratio of epichlorohydrin to alkali is (1-5):1.

[0087] According to the present invention, the system may contain some inorganic salts after the ring-closing reaction, and post-treatment is required to remove these impurities. For example, the first post-treatment method includes: diluting with an inert solvent, then removing the inorganic salts by filtration through solid-liquid separation, and then evaporating the inert solvent to obtain the target product.

[0088] According to the present invention, the specific type of amine compound is not limited as long as the purpose of the present invention can be achieved. Preferably, the amine compound is liquid ammonia, methylamine, ethylamine or isopropylamine, preferably liquid ammonia.

[0089] According to the present invention, the amount of the amine compound added is generally in excess based on theoretical reaction calculations, and preferably the molar ratio of the amine compound to the polyether raw material is (3-10):1;

[0090] According to the present invention, the type of amination catalyst is not particularly limited as long as the purpose of the present invention can be achieved. Preferably, the amination catalyst is selected from at least one of Raney nickel, Raney copper, nickel-copper-chromium and nickel.

[0091] According to the present invention, the amination catalyst is used to promote the occurrence of the hydroamination reaction of the present invention, and the amount of the catalyst is preferably such that the hydroamination reaction can occur smoothly and in equilibrium. Preferably, the mass ratio of the amination catalyst to the polyether raw material is 1:(5-50).

[0092] According to the present invention, there is no special limitation on the amount of hydrogen used. Generally, hydrogen is added to a pressure of 2-5 MPa at the initial stage of the reaction.

[0093] According to a preferred embodiment of the present invention, the conditions for the hydroamination reaction include: a pressure of 12-25 MPa, a temperature of 150-250°C, and a reaction time of 1-3 hours.

[0094] The reaction system after the amination reaction may still contain ammonia, hydrogen and some other volatile components, as well as an amination catalyst. In this invention, ammonia, hydrogen and volatile components in the reaction system can be removed by depressurization, and the catalyst can be removed by filtration. If the product contains other byproducts, the target product can be obtained by separating them using conventional techniques in the art. This invention will not elaborate further on these aspects.

[0095] According to the present invention, in order to increase the reaction rate, the carbonylation reaction is generally carried out in the presence of a solvent and a carbonylation catalyst. The solvent is generally an inert solvent. Turpentine is used as an example of the solvent in the present invention to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0096] In the carbonylation reaction of this invention, the amount of polyether reaction raw material added in 1L of solvent is generally 300-2000g, and the amount of amine catalyst is 0.05-0.3wt% of the polyether reaction raw material.

[0097] According to a preferred embodiment of the present invention, the carbonylation catalyst is selected from at least one of lead octanoate, tetraphenyl titanate, tetramethyl titanate, triisopropanol, titanium tetrachloride, zinc carbonate, zinc oxide, zinc oxalate, zinc benzoate, triphenyltin acetate, tetrabutyltin maleate, aluminum / iodine / mercuric chloride, zinc acetate, lead oxide, and Pb3O4-ZnO.

[0098] According to the present invention, the conditions for the carbonylation reaction are not particularly limited as long as the purpose of the present invention can be achieved. For example, the conditions for the carbonylation reaction include: a temperature of 150-200°C and a time of 1-5 hours.

[0099] According to the present invention, the system after the carbonylation reaction contains a carbonylation catalyst and may also contain some unreacted raw materials. The present invention performs a third post-treatment to remove these components other than the target product. For example, the third post-treatment method is to filter to remove solid waste catalyst and to remove excess dimethyl carbonate by rotary evaporation.

[0100] According to the present invention, the specific type of amine catalyst is not particularly limited as long as the purpose of the present invention can be achieved. For example, the amine catalyst is selected from at least one of ethylamine, pyridine and N,N-diisopropylethylamine.

[0101] According to the present invention, polymerization may occur during the reaction process. In order to prevent polymerization, a polymerization inhibitor is often added. As long as the purpose of the present invention can be achieved, the type of polymerization inhibitor is not particularly limited. For example, the polymerization inhibitor is selected from at least one of p-tert-butylcatechol, 4-methoxyphenol, 2,6-di-tert-butyl-p-methylphenol and hydroquinone.

[0102] According to the present invention, there is no particular limitation on the amount of amine catalyst used, but preferably the mass of the amine catalyst is 0.5-5% of the mass of the polyether raw material.

[0103] According to the present invention, there is no particular limitation on the amount of polymerization inhibitor used, and the mass of the polymerization inhibitor is 0.01-0.1% of the mass of the polyether raw material.

[0104] According to a preferred embodiment of the present invention, the conditions for the esterification reaction include: a temperature of -5 to 5°C and a time of 0.5 to 2 hours.

[0105] The system after esterification may still contain some raw materials or catalysts, which can be removed by conventional methods in the art. For example, the fourth treatment method includes removing these components by evaporation.

[0106] The polyether raw material in this invention can be obtained commercially or prepared by conventional methods in the art. For example, in the presence of a copolymerization catalyst, the preparation method of the polyether raw material includes: copolymerizing the polyoxyethylene ether raw material of formula (A1) with propylene oxide and / or butane oxide in sequence, and optionally ethylene oxide, followed by acid neutralization, and optionally O-alkylation reaction, halogenation reaction, and hydrolysis reaction in sequence.

[0107]

[0108] In equation (A1), n1 is an integer between 5 and 200;

[0109] According to the present invention, preferably, the structure of formula (A1) is as follows: R1 is selected from alkyl, cycloalkyl, olefinic, and aromatic groups;

[0110] According to the present invention, preferably, the polyoxyethylene ether raw material represented by formula (A1) is copolymerized sequentially with, optionally, ethylene oxide A, propylene oxide, and ethylene oxide B; wherein, ethylene oxide A and ethylene oxide B both represent ethylene oxide, only to distinguish their order of addition.

[0111] According to the present invention, preferably, the copolymerization catalyst is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, calcium hydroxide, and magnesium hydroxide.

[0112] According to the present invention, preferably, the copolymerization conditions include a polymerization temperature of 130-160°C.

[0113] According to the present invention, the purpose of acid neutralization is to neutralize the copolymerization catalyst in the reaction solution, for example, by using phosphoric acid for neutralization.

[0114] According to the present invention, the hydroxyl alkylation reaction, halogenation reaction, and hydrolysis reaction are optionally carried out sequentially. This means that subsequent O-alkylation, halogenation, and hydrolysis reactions may or may not be carried out. The O-alkylation reaction refers to the reaction of replacing the hydrogen on the -OH terminal group of the polyether with an alkyl group to obtain a -O-alkyl terminal group through acid neutralization after copolymerization. The halogenation reaction refers to the reaction of replacing the H at the alkyl terminus of the -O-alkyl terminal group with a halogen to obtain an -O-alkylene-halogen. The hydrolysis reaction refers to the reaction of converting the -O-alkylene-halogen terminal group into a -O-alkylene-hydroxy terminal group. The O-alkylation, halogenation, and hydrolysis reactions are all conventional reactions in the art and will not be described in detail in this invention. In the preparation method of the present invention, some reactions can be post-processed as needed to obtain the corresponding target product, which will not be described in detail in this invention.

[0115] A third aspect of the present invention provides the application of the long-chain polyether described herein in a demulsifier.

[0116] The long-chain polyether provided in this invention has excellent demulsification properties.

[0117] According to the present invention, the long-chain polyether can be used alone as a demulsifier or in combination with other components as a demulsifier. In a preferred embodiment, the long-chain polyether and a solid material having groups on the surface that can react with the end-capping group R2 form a demulsifier with crude oil / water emulsion demulsification function, wherein the definition of R2 is the same as the definition of R2 in the long-chain polyether of the present invention.

[0118] In this invention, the demulsifier formed by combining the long-chain polyether of this invention with the material not only has excellent demulsification properties, but also excellent recyclability.

[0119] A fourth aspect of the present invention provides a demulsifier raw material composition comprising: the long-chain polyether described in the present invention, and a solid-phase material having groups on its surface capable of reacting with end-capping group R2, wherein the definition of R2 is the same as the definition of R2 in the long-chain polyether of the present invention.

[0120] The demulsifier raw material composition of this invention has excellent crude oil demulsification performance.

[0121] According to the present invention, there is no particular limitation on the specific selection of the solid material. Preferably, the solid material is selected from at least one of particulate materials, membrane materials and fiber materials, and is preferably a particulate material.

[0122] According to a preferred embodiment of the present invention, the particulate material is selected from at least one of magnetic nanoparticles, superparamagnetic Fe3O4 nanoparticles, and superparamagnetic γ-Fe2O3 nanoparticles.

[0123] According to a preferred embodiment of the present invention, the membrane material is selected from at least one of cellulose membranes and / or modified cellulose membranes.

[0124] According to a preferred embodiment of the present invention, the fiber material is selected from at least one of glass fiber, silicon carbide fiber, and polyacrylonitrile fiber.

[0125] According to a preferred embodiment of the present invention, when R2 is At that time, the surface of the solid material has amino groups.

[0126] According to a preferred embodiment of the present invention, when R2 is At that time, the surface of the solid material has epoxy groups and / or acrylate groups.

[0127] According to a preferred embodiment of the present invention, when R2 is When the solid material surface has at least one of amino groups, hydroxyl groups, and isocyanate, it is present in the solid phase material.

[0128] According to a preferred embodiment of the present invention, when R2 is At that time, the surface of the solid material has amino groups and / or thiol groups.

[0129] In this invention, the definitions of X1, X2, X3, X4, a, b, c, and d are the same as those in the long-chain polyethers of this invention, and will not be elaborated further here.

[0130] The fifth aspect of the present invention provides a method for preparing a demulsifier, the method comprising: contacting the raw material composition of the present invention in the presence of an inert solvent.

[0131] The demulsifier prepared by the method of the present invention has excellent crude oil demulsification function, and its demulsification performance does not decrease after repeated use.

[0132] According to the present invention, filtration after contact can remove the inert solvent, and the type of inert solvent is not particularly limited, including but not limited to ethanol.

[0133] The sixth aspect of the present invention provides a demulsifier prepared by the preparation method of the fifth aspect of the present invention.

[0134] The demulsifier in this invention not only has excellent demulsification performance, but also excellent reusability.

[0135] The present invention will be described in detail below through embodiments. Unless otherwise specified, the raw materials used in the following embodiments are all commercially available products.

[0136] Example 1

[0137] Add 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly heat to 80 °C and stir slowly until the potassium hydroxide dissolves. Vacuum the reactor (to 30 mmHg) and slowly introduce high-purity nitrogen to increase the pressure to 1 atmosphere. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly heat to 130 °C. Add 0 g of ethylene oxide, 464.6 g of propylene oxide, and 264.3 g of ethylene oxide in sequence. Control the rate of addition of epoxy raw materials so that the temperature of the reaction solution does not exceed 160 °C. After the reaction is complete, slowly lower the temperature of the reaction solution to room temperature and add 1.2 g of phosphoric acid to neutralize the potassium hydroxide in the reaction solution.

[0138] Then, under stirring conditions, 1.5 mL of boron trifluoride diethyl ether complex was added dropwise to the reaction vessel, the temperature was raised to 40 °C, and 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three equal batches. Each time NaOH was added, the mixture was stirred slowly until the NaOH dissolved before adding the next batch. The total reaction time was about 6 hours. After the reaction was completed, the temperature of the reaction solution was lowered to room temperature, and anhydrous ethanol was added for dilution and stirred evenly. The diluted reaction solution was transferred from the reaction vessel to a flask, and the inorganic salts precipitated in the reaction solution were removed by slow-speed filter paper filtration. The ethanol in the reaction solution was removed by rotary evaporation at 80 °C to obtain the target product methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) glycidyl ether.

[0139] Example 2

[0140] Add 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly heat to 80 °C and stir slowly until the potassium hydroxide dissolves. Vacuum the reactor (to 30 mmHg) and slowly introduce high-purity nitrogen to increase the pressure to 1 atmosphere. Repeat this process three times to replace the air in the reactor and reduce the pressure to 30 mmHg. Slowly heat to 130 °C and add 264.3 g of ethylene oxide, 1858.6 g of propylene oxide, and 704.8 g of ethylene oxide in sequence. Control the rate of addition of the epoxy raw materials so that the temperature of the reaction solution does not exceed 160 °C. After the reaction is completed, slowly lower the temperature of the reaction solution to room temperature and add 1.2 g of phosphoric acid to neutralize the potassium hydroxide in the reaction solution.

[0141] Then, under stirring conditions, boron trifluoride diethyl ether complex was added dropwise to the reaction vessel, the temperature was raised to 40°C, and 10 g of epichlorohydrin was slowly added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three equal batches. Each time NaOH was added, the mixture was stirred slowly until the NaOH dissolved before adding the next batch. The total reaction time was about 6 hours. After the reaction was completed, the temperature of the reaction solution was lowered to room temperature, and anhydrous ethanol was added for dilution and stirred evenly. The diluted reaction solution was transferred from the reaction vessel to a flask, and the inorganic salts precipitated in the reaction solution were removed by slow-speed filter paper filtration. The ethanol in the reaction solution was removed by rotary evaporation at 80°C to obtain the target product methoxy polyoxyethylene ether (80), polyoxypropylene (320), polyoxyethylene (160), and glycidyl ether.

[0142] Example 3

[0143] Add 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly raise the temperature to 80 °C and stir slowly until the potassium hydroxide dissolves. Evacuate the reactor (to 30 mmHg), and slowly introduce high-purity nitrogen to increase the pressure to 1 atm. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly raise the temperature to 130 °C. Add 176.2 g of ethylene oxide, 929.3 g of propylene oxide, and 352.4 g of ethylene oxide sequentially. Control the rate of addition of the epoxy raw materials to ensure that the reaction solution temperature does not exceed 160 °C. After the reaction is complete, slowly lower the reaction solution temperature to room temperature and add 1.2 g of phosphoric acid dropwise to neutralize the potassium hydroxide in the reaction solution. Then, under stirring conditions... Add boron trifluoride diethyl ether complex dropwise to the reaction vessel, heat to 40°C, add 10 g of epichlorohydrin dropwise, and after reacting for 5 hours, add 5 g of NaOH in three equal batches to the reaction vessel. Stir slowly after each addition of NaOH, and add the next batch after the NaOH dissolves. The total reaction time is about 6 hours. After the reaction is completed, cool the reaction solution to room temperature, add anhydrous ethanol to dilute, and stir evenly. Transfer the diluted reaction solution from the reaction vessel to a flask, filter it with slow filter paper to remove the inorganic salts precipitated in the reaction solution, and remove the ethanol in the reaction solution by rotary evaporation at 80°C to obtain the target product methoxy polyoxyethylene ether (60) polyoxypropylene (160) polyoxyethylene (80) glycidyl ether.

[0144] Example 4

[0145] Add 94 g of propoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly heat to 80 °C and stir slowly until the potassium hydroxide dissolves. Evacuate the reactor (to 30 mmHg), and slowly introduce high-purity nitrogen to increase the pressure to 1 atm. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly heat to 130 °C. Add 352.4 g of ethylene oxide, 1858.6 g of propylene oxide, and 704.8 g of ethylene oxide sequentially, controlling the rate of addition of the epoxy raw materials. The temperature of the reaction solution should not exceed 160 °C. After the reaction is complete, slowly lower the temperature of the reaction solution to room temperature and add 1.2 g of phosphoric acid dropwise to neutralize the potassium hydroxide in the reaction solution. Then, slowly add the solution dropwise under stirring. Add boron trifluoride diethyl ether complex to the reaction vessel, heat to 40℃, slowly add 10g of epichlorohydrin, and after reacting for 5 hours, add 5g of NaOH to the reaction vessel in three equal batches. Stir slowly after each addition of NaOH, and add the next batch after the NaOH dissolves. The total reaction time is about 6 hours. After the reaction is completed, cool the reaction solution to room temperature, add anhydrous ethanol to dilute, and stir evenly. Transfer the diluted reaction solution from the reaction vessel to a flask, filter it with slow filter paper to remove the inorganic salts precipitated in the reaction solution, and remove the ethanol from the reaction solution by rotary evaporation at 80℃ to obtain the target products propoxy polyoxyethylene ether (100), polyoxypropylene (320), polyoxyethylene (160), and glycidyl ether.

[0146] Example 5

[0147] Add 95.3 g of butoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly raise the temperature to 80 °C and stir slowly until the potassium hydroxide dissolves. Evacuate the reactor (to 30 mmHg) and slowly introduce high-purity nitrogen to increase the pressure to 1 atm. Repeat this process three times to replace the air in the reactor, then reduce the pressure to 30 mmHg. Slowly raise the temperature to 130 °C and add 352.4 g of ethylene oxide, 1858.6 g of propylene oxide, and 704.8 g of ethylene oxide sequentially, controlling the rate of addition of the epoxy raw materials. The temperature of the reaction solution should not exceed 160 °C. After the reaction is complete, slowly lower the temperature of the reaction solution to room temperature. Add 1.2 g of phosphoric acid to neutralize the potassium hydroxide in the reaction solution; then, under stirring, add boron trifluoride diethyl ether complex to the reaction vessel, heat to 40°C, add 10 g of epichlorohydrin, and after reacting for 5 hours, add 5 g of NaOH in three equal batches to the reaction vessel, stirring slowly after each addition of NaOH, and adding the next batch after the NaOH has dissolved. The total reaction time is about 6 hours. After the reaction is completed, cool the reaction solution to room temperature, add anhydrous ethanol to dilute, and stir evenly. Transfer the diluted reaction solution from the reaction vessel to a flask, and filter it with slow-speed filter paper to remove the precipitated inorganic salts. Remove the ethanol from the reaction solution by rotary evaporation at 80°C to obtain the target products: butoxy polyoxyethylene ether (100), polyoxypropylene (320), polyoxyethylene (160), and glycidyl ether.

[0148] Example 6

[0149] Add 93.8 g of allyl polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly heat to 80 °C and stir slowly until the potassium hydroxide dissolves. Evacuate the reactor (to 30 mmHg), and slowly introduce high-purity nitrogen to increase the pressure to 1 atmosphere. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly heat to 130 °C. Then, add 352.4 g of ethylene oxide, 1858.6 g of propylene oxide, and 704.8 g of ethylene oxide sequentially, controlling the amount of epoxy raw materials. The reaction solution temperature was kept below 160°C by adding phosphoric acid at a controlled rate. After the reaction was complete, the temperature was slowly lowered to room temperature, and 1.2 g of phosphoric acid was added dropwise to neutralize the potassium hydroxide in the reaction solution. Then, under stirring, boron trifluoride diethyl ether complex was added dropwise to the reaction vessel, the temperature was raised to 40°C, and 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three batches, with slow stirring after each addition of NaOH. The next batch was added only after the NaOH had dissolved. The total reaction time was approximately 6 hours. After the reaction was complete, the temperature of the reaction solution was lowered to room temperature, and anhydrous ethanol was added for dilution and stirred until homogeneous. The diluted reaction solution was transferred from the reaction vessel to a flask, and the inorganic salts precipitated in the reaction solution were removed by slow-speed filter paper filtration. The ethanol in the reaction solution was removed by rotary evaporation at 80°C to obtain the target product: allyl polyoxyethylene ether (80), polyoxypropylene (320), polyoxyethylene (160), and glycidyl ether.

[0150] Example 7

[0151] 97.4 g of phenoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide were added to a 5 L reactor. The temperature was slowly raised to 80 °C, and the mixture was slowly stirred until the potassium hydroxide dissolved. The reactor was evacuated (to 30 mmHg), and high-purity nitrogen was slowly introduced to increase the pressure to 1 atm. The air in the reactor was replaced three times, and the pressure was reduced to 30 mmHg. The temperature was slowly raised to 130 °C, and 264.3 g of ethylene oxide, 1858.6 g of propylene oxide, and 704.8 g of ethylene oxide were added sequentially. The rate of addition of the epoxy raw materials was controlled so that the temperature of the reaction solution did not exceed 160 °C. After the reaction was completed, the temperature of the reaction solution was slowly lowered to room temperature, and 1.2 g of phosphoric acid was added dropwise to neutralize the potassium hydroxide in the reaction solution. Then, the reaction was carried out under stirring conditions. Boron trifluoride diethyl ether complex was slowly added dropwise to the reaction vessel, the temperature was raised to 40°C, and 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three equal batches. Each time NaOH was added, the mixture was stirred slowly until the NaOH dissolved before adding the next batch. The total reaction time was about 6 hours. After the reaction was completed, the temperature of the reaction solution was lowered to room temperature, and anhydrous ethanol was added to dilute it and stirred evenly. The diluted reaction solution was transferred from the reaction vessel to a flask, and the inorganic salts precipitated in the reaction solution were removed by slow-speed filter paper filtration. The ethanol in the reaction solution was removed by rotary evaporation at 80°C to obtain the target product phenoxy polyoxyethylene ether (80), polyoxypropylene (320), polyoxyethylene (160), and glycidyl ether.

[0152] Example 8

[0153] Add 97.4 g of phenoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly raise the temperature to 80 °C and stir slowly until the potassium hydroxide dissolves. Evacuate the reactor (to 30 mmHg), and slowly introduce high-purity nitrogen to increase the pressure to 1 atm. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly raise the temperature to 130 °C. Then, add 264.3 g of ethylene oxide, 2243.9 g of ethylene oxide, and 704.8 g of ethylene oxide in sequence, controlling the rate of addition of the epoxy raw materials to ensure that the temperature of the reaction solution does not exceed 16 °C. At 0℃, after the reaction was completed, the temperature of the reaction solution was slowly lowered to room temperature, and 1.2 g of phosphoric acid was added dropwise to neutralize the potassium hydroxide in the reaction solution. Then, under stirring, boron trifluoride diethyl ether complex was added dropwise to the reaction vessel, the temperature was raised to 40℃, and 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three equal batches. After each addition of NaOH, the mixture was stirred slowly until the NaOH dissolved before adding the next batch. The total reaction time was about 6 hours. After the reaction was completed, the temperature of the reaction solution was lowered to room temperature, and anhydrous ethanol was added for dilution and stirred evenly. The diluted reaction solution was transferred from the reaction vessel to a flask, and the inorganic salts precipitated in the reaction solution were removed by slow-speed filter paper filtration. The ethanol in the reaction solution was removed by rotary evaporation at 80℃ to obtain the target product phenoxy polyoxyethylene ether (80) polyoxybutylene (320) polyoxyethylene (160) glycidyl ether.

[0154] Example 9

[0155] Add 98g of cyclohexyloxyethylene ether (20) and 1g of potassium hydroxide to a 5L reactor. Slowly heat to 80°C and stir slowly until the potassium hydroxide dissolves. Vacuum the reactor (to 30mmHg) and slowly introduce high-purity nitrogen to increase the pressure to 1 atmosphere. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30mmHg and slowly heat to 130°C. Add 264.3g of ethylene oxide, 1858.6g of propylene oxide, and 704.8g of ethylene oxide in sequence. Control the rate of addition of epoxy raw materials so that the temperature of the reaction solution does not exceed 160°C. After the reaction is complete, slowly lower the temperature of the reaction solution to room temperature and add 1.2g of phosphoric acid to neutralize the potassium hydroxide in the reaction solution.

[0156] Then, under stirring, boron trifluoride diethyl ether complex was added dropwise to the reaction vessel, the temperature was raised to 40°C, and 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three equal batches. After each addition of NaOH, the mixture was stirred slowly until the NaOH dissolved before adding the next batch. The total reaction time was approximately 6 hours. After the reaction was completed, the temperature of the reaction solution was lowered to room temperature, and anhydrous ethanol was added for dilution and stirred evenly. The diluted reaction solution was transferred from the reaction vessel to a flask, and the inorganic salts precipitated in the reaction solution were removed by slow-speed filter paper filtration. The ethanol in the reaction solution was removed by rotary evaporation at 80°C to obtain the target product cyclohexyloxyethylene ether (80), polyoxypropylene (320), polyoxyethylene (160), and glycidyl ether.

[0157] Example 10

[0158] 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide were added to a 5 L reactor. The temperature was slowly raised to 80°C and stirred slowly until the potassium hydroxide dissolved. The reactor was evacuated (to 30 mmHg). High-purity nitrogen was slowly introduced to increase the pressure to 1 atmosphere. The air in the reactor was replaced three times. The pressure was reduced to 30 mmHg and the temperature was slowly raised to 130°C. 0 g of ethylene oxide, 464.6 g of propylene oxide and 264.3 g of ethylene oxide were added in sequence. The rate of addition of the epoxy raw materials was controlled so that the temperature of the reaction solution did not exceed 160°C. After the reaction was completed, the temperature of the reaction solution was slowly reduced to room temperature. 1.2 g of phosphoric acid was added dropwise to neutralize the potassium hydroxide in the reaction solution to obtain the polyether raw material system.

[0159] The reaction solution was then transferred to a high-pressure reactor and heated to 100°C. The pressure was reduced to a triple vacuum, and the solution was stirred to remove moisture. The air in the reactor was replaced three times with nitrogen. Then, 30 g Raney nickel catalyst was added. While stirring, liquid ammonia (molar ratio of liquid ammonia to polyether was 5:1) and hydrogen were added to the high-pressure reactor until the pressure reached 3 MPa. The temperature was raised to 200°C ± 20°C and the reaction was carried out for 2 hours, maintaining the reactor pressure between 12 and 25 MPa during the reaction. Afterward, the reaction solution was cooled to room temperature, and the ammonia, hydrogen, and volatile components in the reaction system were removed under reduced pressure. The reaction solution was filtered to remove the catalyst. HPLC analysis showed that 76% of the polyether was converted to polyetheramine, of which 71% was converted to the target product polyetheramine, and 5% was converted to dietheramine. The polyetheramine was the target product: methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) amine.

[0160] Example 11

[0161] Add 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly heat to 80 °C and stir slowly until the potassium hydroxide dissolves. Vacuum the reactor (to 30 mmHg) and slowly introduce high-purity nitrogen to increase the pressure to 1 atmosphere. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly heat to 130 °C. Add 0 g of ethylene oxide, 464.6 g of propylene oxide, and 264.3 g of ethylene oxide in sequence. Control the rate of addition of epoxy raw materials so that the temperature of the reaction solution does not exceed 160 °C. After the reaction is complete, slowly lower the temperature of the reaction solution to room temperature and add 1.2 g of phosphoric acid to neutralize the potassium hydroxide in the reaction solution.

[0162] The reaction solution was then transferred to a high-pressure reactor and heated to 100°C. The pressure was reduced to a triple vacuum, and the solution was stirred to remove moisture. The air in the reactor was replaced three times with nitrogen. Then, 30 g Raney nickel catalyst was added. While stirring, liquid ammonia (molar ratio of liquid ammonia to polyether was 5:1) and hydrogen were added to the high-pressure reactor until the pressure reached 3 MPa. The temperature was raised to 200°C ± 20°C and the reaction was carried out for 2 hours, maintaining the reactor pressure between 12 and 25 MPa during the reaction. Afterward, the reaction solution was cooled to room temperature, and the ammonia, hydrogen, and volatile components in the reaction system were removed under reduced pressure. The reaction solution was filtered to remove the catalyst. HPLC analysis showed that 76% of the polyether was converted to polyetheramine, of which 71% was converted to the target product polyetheramine, and 5% was converted to dietheramine. The polyetheramine was the target product: methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) amine.

[0163] The final polyetheramine was transferred to a high-pressure reactor, 1L of turpentine was added, and the mixture was stirred evenly. Then, 2.3g of lead octanoate and 429g of dimethyl carbonate were added and stirred evenly. The mixture was then reacted at 180℃ for 2 hours. After that, the mixture was cooled to room temperature, the solid waste catalyst was removed by filtration, and the excess dimethyl carbonate was removed by rotary evaporation to obtain the target product methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) urethane.

[0164] Example 12

[0165] Add 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly heat to 80 °C and stir slowly until the potassium hydroxide dissolves. Vacuum the reactor (to 30 mmHg) and slowly introduce high-purity nitrogen to increase the pressure to 1 atmosphere. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly heat to 130 °C. Add 0 g of ethylene oxide, 464.6 g of propylene oxide, 264.3 g of ethylene oxide, and 144.2 g of butane oxide in sequence. Control the rate of addition of epoxy raw materials so that the temperature of the reaction solution does not exceed 160 °C. After the reaction is complete, slowly lower the temperature of the reaction solution to room temperature and add 1.2 g of phosphoric acid to neutralize the potassium hydroxide in the reaction solution.

[0166] The reaction solution was then transferred to a high-pressure reactor and heated to 100°C. The pressure was reduced to a triple vacuum, and the solution was stirred to remove moisture. The air in the reactor was replaced three times with nitrogen. Then, 30 g Raney nickel catalyst was added. While stirring, liquid ammonia (molar ratio of liquid ammonia to polyether was 5:1) and hydrogen were added to the high-pressure reactor until the pressure reached 3 MPa. The temperature was raised to 200°C ± 20°C and the reaction was carried out for 2 hours, maintaining the reactor pressure between 12 and 25 MPa during the reaction. Afterward, the reaction solution was cooled to room temperature, and the ammonia, hydrogen, and volatile components in the reaction system were removed under reduced pressure. The reaction solution was filtered to remove the catalyst. HPLC analysis showed that 76% of the polyether was converted to polyetheramine, of which 71% was converted to the target product polyetheramine, and 5% was converted to dietheramine. The polyetheramine was the target product: methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) amine.

[0167] The final polyetheramine was then transferred to a high-pressure reactor, 1L of turpentine was added, and the mixture was stirred until homogeneous. Then, 2.3g of lead octanoate and 429g of dimethyl carbonate were added and stirred until homogeneous. The mixture was then reacted at 180℃ for 2 hours. After that, the mixture was cooled to room temperature, the solid waste catalyst was removed by filtration, and the excess dimethyl carbonate was removed by rotary evaporation to obtain the target product methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) polyoxybutylene (20) urethane.

[0168] Example 13

[0169] Add 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly heat to 80 °C and stir slowly until the potassium hydroxide dissolves. Vacuum the reactor (to 30 mmHg) and slowly introduce high-purity nitrogen to increase the pressure to 1 atmosphere. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly heat to 130 °C. Add 0 g of ethylene oxide, 464.6 g of propylene oxide, 144.2 g of butane oxide, and 264.3 g of ethylene oxide in sequence. Control the rate of addition of epoxy raw materials so that the temperature of the reaction solution does not exceed 160 °C. After the reaction is complete, slowly lower the temperature of the reaction solution to room temperature and add 1.2 g of phosphoric acid to neutralize the potassium hydroxide in the reaction solution.

[0170] The reaction solution was then transferred to a high-pressure reactor and heated to 100°C. The pressure was reduced to a triple vacuum, and the solution was stirred to remove moisture. The air in the reactor was replaced three times with nitrogen. Then, 30 g Raney nickel catalyst was added. While stirring, liquid ammonia (molar ratio of liquid ammonia to polyether was 5:1) and hydrogen were added to the high-pressure reactor until the pressure reached 3 MPa. The temperature was raised to 200°C ± 20°C and the reaction was carried out for 2 hours, maintaining the reactor pressure between 12 and 25 MPa during the reaction. Afterward, the reaction solution was cooled to room temperature, and the ammonia, hydrogen, and volatile components in the reaction system were removed under reduced pressure. The reaction solution was filtered to remove the catalyst. HPLC analysis showed that 76% of the polyether was converted to polyetheramine, of which 71% was converted to the target product polyetheramine, and 5% was converted to dietheramine. The polyetheramine was the target product: methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) amine.

[0171] The final polyetheramine was then transferred to a high-pressure reactor. 1L of turpentine was added and stirred until homogeneous. Then, 2.3g of lead octanoate and 429g of dimethyl carbonate were added and stirred until homogeneous. The mixture was then reacted at 180°C for 2 hours. After that, the mixture was cooled to room temperature, filtered to remove the solid waste catalyst, and the excess dimethyl carbonate was removed by rotary evaporation to obtain the target product: methoxy polyoxyethylene ether (20), polyoxypropylene (80), polyoxybutene (20), polyoxyethylene (60), and carbamate.

[0172] Example 14

[0173] Add 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly heat to 80 °C and stir slowly until the potassium hydroxide dissolves. Evacuate the reactor (to 30 mmHg) and slowly introduce high-purity nitrogen to increase the pressure to 1 atmosphere. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly heat to 130 °C. Add 176.2 g of ethylene oxide, 929.3 g of propylene oxide, 144.2 g of butane oxide, and 352.4 g of ethylene oxide in sequence. Control the rate of addition of epoxy raw materials so that the temperature of the reaction solution does not exceed 160 °C. After the reaction is complete, slowly lower the temperature of the reaction solution to room temperature and add 1.2 g of phosphoric acid dropwise to neutralize the potassium hydroxide in the reaction solution.

[0174] Then, under stirring conditions, boron trifluoride diethyl ether complex was added dropwise to the reaction vessel, the temperature was raised to 40°C, and 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three equal batches. Each time NaOH was added, the mixture was stirred slowly until the NaOH dissolved before adding the next batch. The total reaction time was about 6 hours. After the reaction was completed, the temperature of the reaction solution was lowered to room temperature, and anhydrous ethanol was added for dilution and stirred evenly. The diluted reaction solution was transferred from the reaction vessel to a flask, and the inorganic salts precipitated in the reaction solution were removed by slow-speed filter paper filtration. The ethanol in the reaction solution was removed by rotary evaporation at 80°C to obtain the target product methoxy polyoxyethylene ether (60), polyoxypropylene (160), polyoxybutene (20), polyoxyethylene (80), and glycidyl ether.

[0175] Example 15

[0176] Add 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly raise the temperature to 80 °C and stir slowly until the potassium hydroxide dissolves. Evacuate the reactor (to 30 mmHg), and slowly introduce high-purity nitrogen to increase the pressure to 1 atm. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly raise the temperature to 130 °C. Add 440.5 g of ethylene oxide and 928.8 g of propylene oxide sequentially, controlling the rate of addition of the epoxy raw materials to ensure that the reaction solution temperature does not exceed 160 °C. After the reaction is complete, slowly lower the reaction solution temperature to room temperature and add 1.2 g of phosphoric acid dropwise to neutralize the potassium hydroxide in the reaction solution. Then, under stirring conditions, slowly... Add boron trifluoride diethyl ether complex dropwise to the reaction vessel, heat to 40°C, add 10 g of epichlorohydrin dropwise, and after reacting for 5 hours, add 5 g of NaOH in three equal batches to the reaction vessel. Stir slowly after each addition of NaOH, and add the next batch after the NaOH has dissolved. The total reaction time is about 6 hours. After the reaction is completed, cool the reaction solution to room temperature, add anhydrous ethanol to dilute, and stir evenly. Transfer the diluted reaction solution from the reaction vessel to a flask, filter it with slow filter paper to remove the precipitated inorganic salts in the reaction solution, and remove the ethanol in the reaction solution by rotary evaporation at 80°C to obtain the target product methoxy polyoxyethylene ether (120) polyoxypropylene (160) glycidyl ether.

[0177] Example 16

[0178] Add 97.4 g of phenoxy polyoxyethylene ether (20) and 1 g of potassium hydroxide to a 5 L reactor. Slowly raise the temperature to 80 °C and stir slowly until the potassium hydroxide dissolves. Evacuate the reactor (to 30 mmHg), and slowly introduce high-purity nitrogen to increase the pressure to 1 atm. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly raise the temperature to 130 °C. Add 969.1 g of ethylene oxide and 2312 g of epoxide sequentially, controlling the rate of addition of the epoxy raw materials to ensure that the reaction solution temperature does not exceed 160 °C. After the reaction is complete... After the reaction, the temperature of the reaction solution was slowly lowered to room temperature, and 1.2 g of phosphoric acid was added dropwise to neutralize the potassium hydroxide in the reaction solution. Then, under stirring, boron trifluoride diethyl ether complex was added dropwise to the reaction vessel, the temperature was raised to 40°C, and 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three equal batches. After each addition of NaOH, the mixture was stirred slowly until the NaOH dissolved before adding the next batch. The total reaction time was about 6 hours. After the reaction was completed, the temperature of the reaction solution was lowered to room temperature, and anhydrous ethanol was added for dilution and stirred evenly. The diluted reaction solution was transferred from the reaction vessel to a flask, and the inorganic salts precipitated in the reaction solution were removed by slow-speed filter paper filtration. The ethanol in the reaction solution was removed by rotary evaporation at 80°C to obtain the target product phenoxy polyoxyethylene ether (240) polyoxybutylene (320) glycidyl ether.

[0179] Example 17

[0180] Add 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of DMC to a 5 L reactor. Slowly raise the temperature to 80 °C and stir slowly until potassium hydroxide dissolves. Evacuate the reactor (to 30 mmHg) and slowly introduce high-purity nitrogen to increase the pressure to 1 atm. Repeat this process three times to replace the air in the reactor. Reduce the pressure to 30 mmHg and slowly raise the temperature to 130 °C. Add 8652.7 g of epoxide sequentially, controlling the rate of addition of the epoxy raw materials to ensure that the temperature of the reaction solution does not exceed 160 °C. After the reaction is complete, slowly lower the temperature of the reaction solution to room temperature and add 1.2 g of phosphoric acid dropwise to neutralize the potassium hydroxide in the reaction solution. Then, under stirring conditions, slowly add boron trifluoride. The ether complex was added to the reactor and heated to 40°C. 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reactor in three equal batches. Each time NaOH was added, the mixture was stirred slowly until it dissolved before adding the next batch. The total reaction time was about 6 hours. After the reaction was completed, the temperature of the reaction solution was lowered to room temperature and diluted with anhydrous ethanol. The solution was stirred evenly. The diluted reaction solution was transferred from the reactor to a flask and filtered with slow filter paper to remove the inorganic salts precipitated in the reaction solution. The ethanol in the reaction solution was removed by rotary evaporation at 80°C to obtain the target product methoxy polyoxyethylene ether (20) polyoxybutylene ether (1200) glycidyl ether.

[0181] Example 18

[0182] 91.2 g of methoxy polyoxyethylene ether (20) and 1 g of DMC were added to a 5 L reactor. The temperature was slowly raised to 80 °C, and the mixture was slowly stirred until the potassium hydroxide dissolved. The reactor was evacuated (to 30 mmHg), and high-purity nitrogen was slowly introduced to increase the pressure to 1 atm. The air in the reactor was replaced three times, and the pressure was reduced to 30 mmHg. The temperature was slowly raised to 130 °C, and 6971 g of propylene oxide was added sequentially. The addition rate of the epoxy raw materials was controlled so that the temperature of the reaction solution did not exceed 160 °C. After the reaction was completed, the temperature of the reaction solution was slowly lowered to room temperature, and 1.2 g of phosphoric acid was added dropwise to neutralize the potassium hydroxide in the reaction solution. Then, boron trifluoride ether was slowly added dropwise under stirring. The complex was added to the reaction vessel and heated to 40°C. 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three equal batches. Each time NaOH was added, the mixture was stirred slowly until it dissolved before adding the next batch. The total reaction time was about 6 hours. After the reaction was completed, the temperature of the reaction solution was lowered to room temperature and diluted with anhydrous ethanol. The solution was stirred evenly. The diluted reaction solution was transferred from the reaction vessel to a flask and filtered with slow filter paper to remove the inorganic salts precipitated in the reaction solution. The ethanol in the reaction solution was removed by rotary evaporation at 80°C to obtain the target product methoxy polyoxyethylene ether (20) polyoxypropylene ether (1200) glycidyl ether.

[0183] Comparative Example 1

[0184] Currently, the crude oil emulsion demulsifier that has been widely used in oil and gas fields is: ethylene polyamine polyoxyethylene polyoxypropylene ether (demulsifier AE series) 121, denoted as DF1.

[0185] Comparative Example 2

[0186] 883 g of methoxy polyoxyethylene ether (200) was added to a reaction vessel. Under stirring, 1 g of boron trifluoride diethyl ether complex was added dropwise to the reaction vessel. The temperature was raised to 40°C, and 10 g of epichlorohydrin was added dropwise. After reacting for 5 hours, 5 g of NaOH was added to the reaction vessel in three equal batches. Each time NaOH was added, the mixture was stirred slowly until dissolved before adding the next batch. The total reaction time was approximately 6 hours. After the reaction was complete, the reaction solution was cooled to room temperature, diluted with anhydrous ethanol, and stirred until homogeneous. The diluted reaction solution was transferred from the reaction vessel to a flask, and the precipitated inorganic salts were removed by slow-speed filter paper filtration. Ethanol was removed from the reaction solution by rotary evaporation at 80°C to obtain the target product, methoxy polyoxyethylene ether (200) glycidyl ether.

[0187] Example 1 of Crude Oil Emulsion Demulsifier Preparation

[0188] 100g of amino-modified magnetic nano-iron oxide particles were dispersed in 100ml of ethanol, and then 5g of long-chain polyether samples (the long-chain polyethers in Examples 1-9, 14-18, and Comparative Example 1, respectively) were slowly added. After stirring at room temperature for 3 hours, the ethanol was removed by rotary evaporation at 80℃ to obtain water-soluble crude oil emulsion demulsifiers that could respond to the magnetic field, which were designated as A1-A9, A14-A18, and DF2, respectively.

[0189] Example 2: Preparation of crude oil emulsion demulsifier

[0190] 100g of amino-modified glass fiber was dispersed in 100ml of ethanol, and then 5g of the prepared long-chain polyether samples (the long-chain polyethers in Examples 1-9) were slowly added. After stirring at room temperature for 3 hours, the ethanol was removed by filtering with filter paper to obtain glass fiber with crude oil emulsion demulsification properties, which were designated as B1-B9.

[0191] Example 3: Preparation of crude oil emulsion demulsifier

[0192] 100g of magnetic iron oxide nanoparticles modified with silane coupling agent containing epoxy groups were dispersed in 100ml of ethanol. Then, 5g of the prepared long-chain polyether sample (the long-chain polyether in Example 10) was slowly added and stirred at room temperature for 3 hours. The ethanol was removed by filtering with filter paper to obtain glass fiber with crude oil emulsion demulsification properties, denoted as C10.

[0193] Example 4: Preparation of crude oil emulsion demulsifier

[0194] 100g of isocyanate-modified magnetic iron oxide nanoparticles were dispersed in 100ml of ethanol, and then 5g of the prepared long-chain polyether sample (the long-chain polyether in Examples 11-13) was slowly added. The mixture was stirred at room temperature for 3 hours, and the ethanol was removed by filtration with filter paper to obtain glass fibers with crude oil emulsion demulsification properties, which were designated as D11-D13.

[0195] Test case

[0196] Preparation of crude oil emulsion: Crude oil from Jiangsu Oilfield Sha-7, Sha-7 formation water and a displacement surfactant prepared in our laboratory were mixed in a volume ratio of 200:780:20 and stirred rapidly to form a crude oil emulsion.

[0197] (1) Add 0.1 g of crude oil emulsion demulsifiers A1-A9, A14-A18, C10, and D11-D13 to 100 ml of the above crude oil emulsion and stir evenly. Place a U-shaped magnet nearby and observe that the emulsion breaks down rapidly and separates into crude oil and clear water phase. Record the separation time. The volume of the crude oil phase is about 20-21 ml and the volume of the water phase is about 79-80 ml.

[0198] (2) Add 0.1 g of the demulsifier (DF1) from Comparative Example 1 to 100 ml of the above crude oil emulsion. After stirring, allow the emulsion to stand until the crude oil and clear aqueous phases are initially separated. Record the initial separation time as approximately 20 minutes. The crude oil phase volume is approximately 25 ml, the aqueous phase is approximately 74.5 ml, and approximately 0.5 ml is in the middle layer. This indicates that the crude oil separated from the emulsion contains a significant amount of water that has not been separated, and the demulsifier cannot be recycled.

[0199] (3) 0.1 g of crude oil emulsion demulsifier B1-B9 was added to 100 ml of the above crude oil emulsion. After stirring and standing, the emulsion was observed to separate into crude oil and clear aqueous phases. The separation time was recorded. The glass fiber settled to the bottom of the container. The upper crude oil and lower aqueous phases were separated by pouring. Then, 100 ml of crude oil emulsion was added to the container and stirred. After standing, the emulsion was found to have demulsified and separated into crude oil and clear aqueous phases. The crude oil phase had a volume of approximately 22-23 ml, and the aqueous phase had a volume of approximately 77-78 ml. The crude oil emulsion demulsifier settled to the bottom. This process was repeated. The glass fiber modified with the polyether sample always had the demulsification function, could be reused, and was easily separated from the system.

[0200] The stratification time is shown in Table 1.

[0201] Table 1

[0202]

[0203]

[0204] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A long-chain polyether, characterized in that, This long-chain polyether comprises polyether segments and end-capping group R2; The polyether segment contains at least two of the following: oxyvinyl structural units, oxypropylene structural units, and oxybutene structural units; R2 is selected from In this context, X1, X2, X3, and X4 are each independently alkylene groups, a, b, c, and d are each independently 0 or 1, and * indicates a linking site.

2. The long-chain polyether according to claim 1, wherein, X1, X2, X3, and X4 are each independently C1-C 18 Alkylene; preferably, X1 is a C1-C3 alkylene group; and / or X2 is C6-C 18 Alkylene, preferably C6 alkylene; and / or X3 is a C3-C6 alkylene group; and / or X4 is C6-C 12 alkylene groups; and / or R2 is selected from Preferred selection 3. The long-chain polyether according to claim 1 or 2, wherein, The number n of the oxyethylene structural units ranges from 0 to 1000, preferably from 5 to 200; and / or The number m of the oxypropylene structural units ranges from 0 to 1000, preferably from 5 to 200; and / or The number p of the oxybutene structural units ranges from 0 to 1000, preferably from 5 to 200; and / or The number n of the oxyvinyl structural units, the number m of the oxypropylene structural units, and / or the number p of the oxybutene structural units are not 0, preferably m, n, and p are all not 0.

4. The long-chain polyether according to any one of claims 1-3, wherein, The polyether segment has oxyethylene structural units at both ends, preferably 20-200 oxyethylene structural units at each end of the polyether segment; and / or One of the end-capping groups R1 of the long-chain polyether is selected from alkyl, cycloalkyl, olefinic or aromatic groups; Preferably, R1 is selected from C1-C 18 Alkyl, C6-C 18 cycloalkyl, C2-C 18 olefinic or C6-C 24 The aromatic group is preferably selected from C1-C4 straight-chain alkyl, C6 cycloalkyl, C6 cycloalkyloxy, C3-C6 straight-chain olefin or C6-C 18 Aromatic groups.

5. The long-chain polyether according to any one of claims 1-4, wherein, The polyether is selected from one of A1-A18; among A1-A18, the general molecular formula of the long chain of the polyether is shown in formula (I); A1: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 80, m is 80, and p is 0; A2: Methoxy polyoxyethylene ether (80) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 240, m is 320, and p is 0; A3: Methoxy polyoxyethylene ether (60) polyoxypropylene (160) polyoxyethylene (80) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 140, m is 160, and p is 0; A4: Propylene oxide polyoxyethylene ether (100) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is propyl, R2 is glycidyl, n is 260, m is 320, and p is 0. A5: Butoxy polyoxyethylene ether (100) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is butyl, R2 is glycidyl, n is 260, m is 320, and p is 0. A6: Allyl polyoxyethylene ether (80) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is allyl, R2 is glycidyl, n is 240, m is 320, and p is 0. A7: Phenoxy polyoxyethylene ether (80) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is phenyl, R2 is glycidyl group, n is 240, m is 320, and p is 0; A8: Phenoxy polyoxyethylene ether (80) polyoxybutylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is phenyl, R2 is glycidyl group, n is 240, m is 0, and p is 320. A9: Cyclohexyloxy polyoxyethylene ether (80) polyoxypropylene (320) polyoxyethylene (160) glycidyl ether, wherein R1 is cyclohexyl, R2 is glycidyl, n is 240, m is 320, and p is 0. A10: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) amine, wherein R1 is methyl, R2 is amino, n is 80, m is 80, and p is 0; A11: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) urethane, wherein R1 is methyl, R2 is urethane group, n is 80, m is 80, and p is 0; A12: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxyethylene (60) polyoxybutylene (20) urethane, wherein R1 is methyl, R2 is urethane group, n is 80, m is 80, and p is 20. A13: Methoxy polyoxyethylene ether (20) polyoxypropylene (80) polyoxybutene (20) polyoxyethylene (60) urethane, wherein R1 is methyl, R2 is urethane group, n is 80, m is 80, and p is 20. A14: Methoxy polyoxyethylene ether (60) polyoxypropylene (160) polyoxybutene (20) polyoxyethylene (80) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 140, m is 160, and p is 20. A15: Methoxy polyoxyethylene ether (120) polyoxypropylene (160) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 120, m is 160, and p is 0; A16: Phenoxy polyoxyethylene ether (240) polyoxybutylene (320) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 240, m is 320, and p is 0; A17: Methoxy polyoxyethylene ether (20) polyoxybutylene ether (1200) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 20, m is 0, and p is 1200; A18: Methoxy polyoxyethylene ether (20) polyoxypropylene ether (1200) glycidyl ether, wherein R1 is methyl, R2 is glycidyl group, n is 20, m is 1200, and p is 0.

6. A method for preparing the long-chain polyether according to any one of claims 1-5, characterized in that, The preparation method includes: Under the action of a Lewis acid catalyst, the polyether raw material undergoes a first contact with epichlorohydrin, followed by a ring-closing reaction under the action of an alkali, and finally a first post-treatment; or In the presence of an amination catalyst and hydrogen, the polyether feedstock undergoes a hydroamination reaction with an amine compound, followed by a second post-treatment; optionally, in the presence of a solvent and a carbonylation catalyst, the post-treated material undergoes a carbonylation reaction with dimethyl carbonate, followed by a third post-treatment; or In the presence of amine catalysts and polymerization inhibitors, polyether raw materials undergo esterification with acryloyl chloride, followed by a fourth post-treatment. The polyether raw material contains polyether segments and end-capping groups. Wherein O is an oxygen atom, X is an alkylene group, m is 0 or 1, and the polyether segment contains at least two of the following structural units: oxyvinyl group, oxypropylene group, and oxybutene group.

7. The preparation method according to claim 6, wherein, The Lewis acid catalyst is selected from at least one of boron trifluoride diethyl ether complex, boron trifluoride, sulfuric acid, and stannous dichloride; The alkali is selected from at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, calcium hydroxide, and magnesium hydroxide; and / or The conditions for the first contact include: a temperature of 30°C to 100°C, and / or a time of 3-7 hours; and / or The conditions for the closed-loop reaction include: a temperature of 30℃ to 100℃, and / or a time of 5-8 hours; and / or The amine compound is liquid ammonia, methylamine, ethylamine, or isopropylamine; and / or The amination catalyst is selected from at least one of Raney nickel, Raney copper, nickel-copper-chromium, and nickel; and / or The conditions for the hydroamination reaction include: a pressure of 12-25 MPa, and / or a temperature of 150-250 °C, and / or a reaction time of 1-3 hours.

8. The preparation method according to claim 6, wherein, The carbonylation catalyst is selected from at least one of lead octanoate, tetraphenyl titanate, tetramethyl titanate, triisopropanol, titanium tetrachloride, zinc carbonate, zinc oxide, zinc oxalate, zinc benzoate, triphenyltin acetate, tetrabutyltin maleate, aluminum / iodine / mercuric chloride, zinc acetate, lead oxide, and Pb3O4-ZnO; and / or The conditions for the carbonylation reaction include: a temperature of 150-200°C and / or a time of 1-5 hours; and / or The amine catalyst is selected from at least one of ethylamine, pyridine, and N,N-diisopropylethylamine; The polymerization inhibitor is selected from at least one of p-tert-butylcatechol, 4-methoxyphenol, 2,6-di-tert-butyl-p-methylphenol, and hydroquinone. The conditions for the esterification reaction include a temperature of -5 to 5°C and / or a time of 0.5 to 2 hours.

9. The use of the long-chain polyether according to any one of claims 1-5 in a demulsifier; Preferably, the long-chain polyether and a solid-phase material having groups on its surface capable of reacting with the end-capping group R2 form a demulsifier with crude oil / water emulsion demulsification function, wherein, The definition of R2 is the same as the definition of R2 in any one of claims 1-5.

10. A demulsifier raw material composition, characterized in that, The raw material composition includes: The long-chain polyether according to any one of claims 1-5, and the solid-phase material having groups on its surface capable of reacting with end-capping group R2, wherein the definition of R2 is the same as the definition of R2 in any one of claims 1-5; Preferably, the solid material is selected from at least one of particulate materials, membrane materials, and fiber materials; More preferably, the particulate material is selected from at least one of magnetic nanoparticles, superparamagnetic Fe3O4 nanoparticles, and superparamagnetic γ-Fe2O3 nanoparticles; and / or The membrane material is selected from at least one of cellulose membranes and / or modified cellulose membranes; and / or The fiber material is selected from at least one of glass fiber, silicon carbide fiber and polyacrylonitrile fiber.

11. The composition according to claim 10, wherein, When R2 is At that time, the surface of the solid material has amino groups; When R2 is At that time, the surface of the solid material has epoxy groups and / or acrylate groups; When R2 is When the solid material surface has at least one of amino groups, hydroxyl groups, and isocyanate; When R2 is At that time, the surface of the solid material has amino groups and / or thiol groups; The definitions of X1, X2, X3, X4, a, b, c, and d are the same as those of any one of claims 1-5.

12. A method for preparing a demulsifier, characterized in that, The preparation method includes: The raw material composition of claim 10 or 11 is contacted in the presence of an inert solvent.

13. The demulsifier prepared by the method of claim 12.

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