CN110452376B - Polyamide-amine hyperbranched polymer and preparation method and application thereof - Google Patents

Polyamide-amine hyperbranched polymer and preparation method and application thereof Download PDF

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CN110452376B
CN110452376B CN201910684663.2A CN201910684663A CN110452376B CN 110452376 B CN110452376 B CN 110452376B CN 201910684663 A CN201910684663 A CN 201910684663A CN 110452376 B CN110452376 B CN 110452376B
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polyamide
hyperbranched polymer
amine
demulsifier
demulsification
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CN110452376A (en
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米远祝
匡家哲
李平
刘适
叶泛
江夏
黄志明
张泽俊
袁怀奎
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Yangtze University
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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    • C08G73/028—Polyamidoamines
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract

The invention discloses a polyamide-amine hyperbranched polymer and a preparation method and application thereof, and relates to the technical field of petroleum additives. The polyamide-amine hyperbranched polymer is a polyamide-amine hyperbranched polymer with 4,4' -diaminodiphenylmethane as a reaction center and an amino group as an end group. The preparation method is simple and comprises the following steps: 4,4 '-diaminodiphenylmethane and methyl acrylate react for 24 hours at normal temperature to prepare 0.5G ester taking 4,4' -diaminodiphenylmethane as a core; and adding ethylenediamine and methyl acrylate in stoichiometric ratio, and performing normal-temperature reaction, segmented heating reaction and other steps to obtain the polyamide-amine demulsifier with the hyperbranched structure. The polyamide-amine hyperbranched polymer is used as a demulsifier, can rapidly demulsify an oil-in-water emulsion at 50-70 ℃, realizes effective oil-water separation, has demulsification efficiency of 99.5% when the amount of the demulsifier is 50mg/L, and has the characteristics of high demulsification rate, low amount, high demulsification efficiency and the like.

Description

Polyamide-amine hyperbranched polymer and preparation method and application thereof
Technical Field
The invention relates to the technical field of petroleum additives, in particular to a polyamide-amine hyperbranched polymer and a preparation method and application thereof.
Background
Crude oil is produced in the form of water-in-oil (W/O) or oil-in-water (O/W) emulsions, and in recent years water-polymer flooding techniques used for Enhanced Oil Recovery (EOR) have been rapidly developed, resulting in a substantial increase in the number of oil-in-water (O/W) emulsions. The presence of a dense film of natural interfacial active material at the oil/water interface makes the O/W aqueous emulsion highly stable, thereby severely impacting petroleum transportation and subsequent refining processes. Therefore, the demulsification research of the O/W emulsion has very important significance.
Chemical demulsification is the purpose of demulsification by adding a certain amount of chemical agents into emulsion. Demulsifiers can be classified into cationic, anionic and nonionic. Compared with the ionic demulsifier, the nonionic demulsifier is not easily affected by the electrolyte because of having an amphiphilic structure. The chemical demulsifier is the key of chemical demulsification, and the traditional demulsifier has the problems of low demulsification efficiency, large using amount of the demulsifier, overlong demulsification time, unclearly water phase and the like, is sensitive to the environment and the like, and is easy to cause environmental pollution.
Hyperbranched polymers are highly branched nonionic demulsifiers with geometric and topological structures, which can be easily adsorbed to the oil-water interface to replace the original interface active substances, and thus have great potential for demulsification. Branched molecules having the same polyamine backbone but different numbers of generations and end groups have completely different demulsifying properties. Research shows that the performance of the amine dendritic polymer is obviously superior to that of the existing commercial demulsifier.
The polyamide-amine hyperbranched polymer is a more mature hyperbranched polymer. However, when the existing polyamide-amine hyperbranched polymer is used for demulsifying oil-in-water emulsions, the problems of low demulsification efficiency, large amount of demulsifiers or long demulsification time still exist.
The existing polyamidoamine hyperbranched polymer usually uses ethylenediamine as a core, for example, Chinese patent CN105601941B discloses an application of polyamidoamine hyperbranched polymer as a demulsifier, wherein the hyperbranched polymer has ethylenediamine as a center and amino as an end group, and the molecular weight is 6000-12000. The oil-in-water emulsion with diesel oil as oil phase is demulsified at the concentration of 80mg/L, and the oil removal rate is 87% when the oil is settled and reduced at 60 ℃ for 30 min. The amount of demulsifier used is still to be further reduced.
In the journal Fuel No. 226, Life Zhang et al published a Hyperbranched poly (amidoamine) oligomers with ethylene diamine/1, 3-propanediol as an initiator for oil-in-water emulsions, wherein the application of a polyamide-amine Hyperbranched polymer with ethylenediamine/1, 3-propylenediamine as a core in an oil-in-water emulsion is disclosed, and it is found that an emulsion breaker with 1, 3-propylenediamine as a core has a high emulsion breaking performance, and that the emulsion breaking efficiency is 92% as measured by an ultraviolet test method when the emulsion breaker sinks at 60 ℃ for 30min at a concentration of 40 mg/L. However, the inventor of the present application synthesized the demulsifier centered on propylenediamine by the same method, and tested the demulsifying effect at the concentration of 40mg/L, and found that the light transmittance of the water phase is only 58.6% when the water phase is reduced for 30min at 60 ℃, which indicates that the demulsifying efficiency still needs to be improved.
Disclosure of Invention
The invention aims to solve the problems of the prior art and provides a novel polyamide-amine hyperbranched polymer and a preparation method and application thereof, the polyamide-amine hyperbranched polymer takes 4,4' -diaminodiphenylmethane as a core, the preparation method is simple, and the polyamide-amine hyperbranched polymer used as a demulsifier has the advantages of high demulsification rate, small dosage, high demulsification efficiency and the like.
In order to achieve the above object, the present invention provides a method for preparing a polyamide-amine hyperbranched polymer, comprising the steps of:
s1, dissolving 4,4' -diaminodiphenylmethane in a solvent, and then dropwise adding propane into the solvent
Fully reacting methyl enoate at room temperature under stirring to obtain a mixture;
s2, adding ethylenediamine and methyl acrylate into the mixture obtained in the step S1, continuously stirring and reacting for 20-30h at room temperature, and then removing the solvent under reduced pressure to obtain a mixed solution;
s3, the mixed solution obtained in the step S2 is subjected to gradient temperature rise reaction for 8-10h from 60-140 ℃ under the reduced pressure condition, is naturally cooled to room temperature, is precipitated by ethyl ether, and is dried in vacuum to obtain a bright yellow product.
Preferably, the molar ratio of the 4,4' -diaminodiphenylmethane to the amount of methyl acrylate added in step S1 is 1: 4.
Preferably, the molar ratio of the amount of ethylenediamine added in step S2 to the amount of 4,4' -diaminodiphenylmethane added in step S1 is 1: 28.
Preferably, the molar ratio of the total amount of methyl acrylate added to the amount of ethylenediamine added in steps S1 and S2 is 1: 1.
Preferably, the solvent is methanol.
Preferably, the gradient temperature reaction process in step S3 includes: the reaction is carried out for 1h at 60 ℃, 1h at 80 ℃, 2h at 100 ℃, 2h at 120 ℃ and 2h at 140 ℃.
Preferably, the stirring rate is 300 r/min.
The invention also provides a polyamide-amine hyperbranched polymer prepared by the preparation method of any one of claims 1 to 7, wherein the polyamide-amine hyperbranched polymer takes 4,4' -diaminodiphenylmethane as the center and the terminal group is an amine group.
The invention also provides a demulsifier, which contains the polyamide-amine hyperbranched polymer.
The invention also provides an application of the polyamide-amine hyperbranched polymer in a demulsifier, wherein the demulsifier is used for demulsifying an oil-in-water emulsion, after the demulsifier is added into the emulsion, the concentration of the polyamide-amine hyperbranched polymer in the emulsion is 30-70 mg/L, the demulsification temperature is 50-70 ℃, and the demulsification time is 30-120 min.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method comprises the steps of firstly reacting 4,4 '-diaminodiphenylmethane with methyl acrylate, synthesizing 0.5G ester taking 4,4' -diaminodiphenylmethane as the center at normal temperature, then adding ethylenediamine and methyl acrylate in stoichiometric ratio, and preparing the polyamide-amine hyperbranched polymer through the steps of normal-temperature reaction, segmented heating reaction and the like.
(2) The polyamide-amine hyperbranched polymer takes 4,4' -diaminodiphenylmethane as a reaction center and an amino group as an end group as a demulsifier, can rapidly demulsify an oil-in-water emulsion at 50-70 ℃, realizes effective oil-water separation, and has the characteristics of high demulsification rate, small dosage, high demulsification efficiency and the like, and the demulsification efficiency can reach 99.5% when the dosage of the demulsifier is 50 mg/L.
Drawings
Fig. 1 is a schematic molecular structure diagram of a polyamide-amine hyperbranched polymer according to example 1 of the present invention.
FIG. 2 shows a process for preparing a polyamidoamine hyperbranched polymer according to example 1 of the present invention1H NMR chart.
FIG. 3 is a schematic diagram showing the demulsifying effect of the demulsifier with different concentrations prepared from the polyamide-amine hyperbranched polymer of example 1 of the present invention.
FIG. 4 is an IR spectrum of a polyamidoamine hyperbranched polymer of example 1 of the present invention.
Reference numerals: the H's at different positions in the molecular structure are indicated by lower case letters a-p in fig. 1, and correspondingly, the different peak positions from different H's in the molecular structure are also indicated by lower case letters in fig. 2.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad invention, and that the described embodiments are merely illustrative of some, but not all, of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the polyamide-amine hyperbranched polymer mainly comprises the following steps:
s1.5.34 g (0.02mol) of 4,4' -diaminodiphenylmethane were dissolved in 30ml of methanol, 6.88g (0.08mol) of methyl acrylate was added dropwise thereto, and the mixture was stirred at 300r/min at room temperature (25 ℃ C.) for 24 hours.
S2.33.6 g (0.56mol) of ethylenediamine and 41.28g (0.48mol) of methyl acrylate were added to S1, and the reaction was continued at room temperature for 24 hours, after which the solvent methanol was removed under reduced pressure.
And S3, reacting the mixed solution at 60 ℃ for 1h under reduced pressure, at 80 ℃ for 1h, at 100 ℃ for 2h, at 120 ℃ for 2h, at 140 ℃ for 2h, naturally cooling to room temperature, precipitating with diethyl ether, and vacuum drying to obtain a bright yellow product.
By adopting the 4,4' -diaminodiphenylmethane in the embodiment as the core, controlling the metering ratio of each reactant and adopting a specific stirring speed and a gradient heating mode, fewer reaction byproducts can be produced, the product result is more controllable, and the polyamide-amine hyperbranched polymer can be rapidly prepared at room temperature. The preparation method of this embodiment is a preferred preparation method of the present invention, and other methods for preparing the polyamide-amine hyperbranched polymer with 4,4' -diaminodiphenylmethane as the core also fall within the protection scope of the present invention.
The theoretical molecular structure of the product obtained in this example is schematically shown in FIG. 1, and the product obtained in this example is subjected to1HNMR analysis, the test results of which are shown with reference to FIG. 2. It can be seen from the respective peak positions in fig. 2 that they coincide with the H positions at different positions in fig. 1. As can be seen from the infrared test results of FIG. 4, it is located at 3280.15cm-1The broad peak of (A) is-NH2Typical vibration region, located at 1638.46cm-1The peak at (B) corresponds to the stretching vibration peak of C ═ O, 1550.51cm-1The peak at the position corresponds to a coupling peak formed by N-H bending vibration and C-N stretching vibration, 1238.09cm-1The absorption peak at (A) is a typical C-N vibration peak, and thus it can be confirmed that N-CH exists in the polymer2-。1740cm-1The absence of a typical absorption band in the vicinity indicates that no ester-terminated intermediate product is present in the product. 2939.29 and 2846.60cm-1The left and right absorption peaks are respectively corresponding to-CH2Asymmetric and symmetric expansion and contraction of 825.80cm-1The absorption peak is from para-substituted benzene. The infrared and nuclear magnetic results combined confirm that this example 1 successfully synthesizes the polyamidoamine hyperbranched polymer shown in fig. 1.
The polyamide-amine hyperbranched polymer of example 1 was formulated into a demulsifier, and an emulsion demulsification experiment was performed to test the demulsification efficiency, which was obtained by TOC comparative testing of the organic carbon content of the aqueous phase and the organic carbon content of the emulsion.
The preparation method of the oil-in-water emulsion comprises the following steps: 50g of diesel oil, 0.09g of span 80, 0.91g of tween 80 and 450ml of distilled water were thoroughly mixed and then 11000 r.min-1Stirring at high speed for 20min to obtain milky white diesel oil/water emulsion of 10 wt%.
Example 2
2mL of aqueous solution of a demulsifier with the concentration of polyamide-amine hyperbranched polymer of 1000mg/L is added into 38mL of diesel oil/water emulsion, the concentration of the polyamide-amine hyperbranched polymer in the emulsion is 50mg/L (50ppm), the mixture is uniformly mixed by rapid oscillation, and then the mixture is kept stand at 60 ℃ for 30min, and then the light transmittance of the water phase is measured to be 82.7 percent, and the demulsification efficiency is 95.4 percent. After standing at 60 ℃ for 60min, the light transmittance of the water phase is determined to be 84%, and the demulsification efficiency is determined to be 95.9%. After standing at 60 ℃ for 120min, the light transmittance of the water phase is measured to be 87.1%, and the demulsification efficiency is measured to be 99.5%.
Example 3
2mL of aqueous solution of a demulsifier with the concentration of polyamide-amine hyperbranched polymer of 1000mg/L is added into 38mL of diesel oil/water emulsion, the concentration of the polyamide-amine hyperbranched polymer in the emulsion is 50mg/L (50ppm), the mixture is uniformly mixed by rapid oscillation, and then the mixture is kept stand at 50 ℃ for 60min, and then the light transmittance of the water phase is determined to be 80.1 percent, and the demulsification efficiency is 93.7 percent.
Example 4
Adding 2mL of aqueous solution of a demulsifier with the concentration of polyamide-amine hyperbranched polymer of 1000mg/L into 38mL of diesel oil/water emulsion, wherein the concentration of the polyamide-amine hyperbranched polymer in the emulsion is 50mg/L (50ppm), uniformly mixing the polyamide-amine hyperbranched polymer and the aqueous solution by rapid oscillation, standing the mixture at 70 ℃ for 120min, and measuring the light transmittance of the aqueous phase to be 86.9% and the demulsification efficiency to be 99.3%.
Example 5
Adding 2mL of aqueous solution of a demulsifier with the concentration of polyamide-amine hyperbranched polymer of 800mg/L into 38mL of diesel oil/water emulsion, wherein the concentration of the polyamide-amine hyperbranched polymer in the emulsion is 40mg/L (40ppm), uniformly mixing the polyamide-amine hyperbranched polymer and the aqueous solution by rapid oscillation, standing the mixture at 60 ℃ for 30min, and then measuring the light transmittance of the aqueous phase to be 76.6% and the demulsification efficiency to be 88.2%. Then standing at 60 ℃ for 60min, and measuring that the light transmittance of the water phase is 78.4% and the demulsification efficiency is 90.4%. Then standing at 120 ℃ for 30min, and measuring the light transmittance of the water phase to be 78.8% and the demulsification efficiency to be 92.1%.
Example 6
2mL of aqueous solution of demulsifier with polyamide-amine hyperbranched polymer concentration of 800mg/L is added into 38mL of diesel oil/water emulsion, the concentration of polyamide-amine hyperbranched polymer in the emulsion is 40mg/L (40ppm), the mixture is uniformly mixed by rapid oscillation, and then the mixture is kept stand at 50 ℃ for 60min, and then the light transmittance of the water phase is determined to be 79.1%, and the demulsification efficiency is 91.5%.
Example 7
2mL of aqueous solution of demulsifier with polyamide-amine hyperbranched polymer concentration of 800mg/L is added into 38mL of diesel oil/water emulsion, the concentration of polyamide-amine hyperbranched polymer in the emulsion is 40mg/L (40ppm), the mixture is uniformly mixed by rapid oscillation, and then the mixture is kept stand at 70 ℃ for 120min, and then the light transmittance of the water phase is measured to be 85.4%, and the demulsification efficiency is 98.3%.
Example 8
2mL of aqueous solution of a demulsifier with the concentration of the polyamide-amine hyperbranched polymer of 600mg/L is added into 38mL of diesel oil/water emulsion, the concentration of the polyamide-amine hyperbranched polymer in the emulsion is 30mg/L (30ppm), the mixture is uniformly mixed by rapid oscillation, and then the mixture is kept stand at 60 ℃ for 30min, and then the light transmittance of the water phase is measured to be 75.8 percent, and the demulsification efficiency is 86.6 percent. Standing at 60 deg.C for 60min, and measuring the light transmittance of water phase to be 76.9% and the demulsification efficiency to be 88.7%. After standing at 60 ℃ for 120min, the light transmittance of the water phase is measured to be 78.3%, and the demulsification efficiency is measured to be 90.1%.
Example 9
2mL of aqueous emulsion breaker solution with the concentration of the polyamide-amine hyperbranched polymer of 600mg/L is added into 38mL of diesel oil/water emulsion, the concentration of the polyamide-amine hyperbranched polymer in the emulsion is 30mg/L (30ppm), the mixture is uniformly mixed by rapid oscillation, and then the mixture is kept stand at 70 ℃ for 120min, and then the light transmittance of a water phase is measured to be 76.8 percent, and the emulsion breaking efficiency is 88.7 percent.
Example 10
2mL of aqueous emulsion breaker solution with the concentration of the polyamide-amine hyperbranched polymer of 600mg/L is added into 38mL of diesel oil/water emulsion, the concentration of the polyamide-amine hyperbranched polymer in the emulsion is 30mg/L (30ppm), the mixture is uniformly mixed by rapid oscillation, and then the mixture is kept stand at 50 ℃ for 120min, and then the light transmittance of a water phase is measured to be 75.5 percent, and the emulsion breaking efficiency is 86.5 percent.
FIG. 3 is a schematic diagram showing the demulsification effect of the emulsion after being added with different contents of the polyamidoamine hyperbranched polymer of the embodiment 1 of the invention and placed at 60 ℃ for 30 min. From left to right, 0, 10, 20, 30, 40, 50mg/L (ppm) of the polyamide-amine hyperbranched polymer is added in the experimental bottle in sequence, and from figure 3, it can be seen that the demulsification effect of the polyamide-amine hyperbranched polymer with different addition amounts of 10-50 ppm is remarkable.
The data of the embodiment show that the addition amount of the polyamide-amine hyperbranched polymer in the oil-in-water emulsion is 30-70 mg/L, and the demulsification efficiency can exceed 85%, namely, the better demulsification efficiency can be achieved with a smaller addition amount. The addition amount only needs to reach 40mg/L concentration, the demulsification efficiency can reach 88.2 percent when the emulsion is settled down for 30min at 60 ℃, and the oil removal rate of the polymer taking ethylene diamine as the center in the patent CN105601941B at the concentration of 80mg/L is already exceeded. In the embodiment, when the concentration of the demulsifier in the polyamide-amine hyperbranched polymer is 50mg/L, the demulsification rate of the demulsifier can reach more than 95% after 30min of sedimentation at 60-70 ℃, and the demulsification efficiency of the demulsifier can reach 99.5% after 2 h. In conclusion, the polyamide-amine hyperbranched polymer used as the demulsifier has the characteristics of high demulsification rate, low consumption, high demulsification efficiency and the like.
Comparative example 1
Adding 22.4g (0.3mol) of 1,3-propane diamine into 30mL of methanol, then adding 25.83g (0.3mol) of methyl acrylate, stirring the mixture at 25 ℃ for 48 hours, then distilling at 25 ℃ under reduced pressure to remove excessive methanol, then heating at 60 ℃ under vacuum program to react for 1 hour, reacting at 80 ℃ for 1 hour, reacting at 100 ℃ for 2 hours, reacting at 120 ℃ for 2 hours, reacting at 140 ℃ for 2 hours, precipitating the obtained crude product with diethyl ether for three times, and then drying under reduced pressure for 24 hours to obtain the hyperbranched polymer taking propane diamine as the center.
Comparative examples 2, 5 and 8 hyperbranched polymers centering on propylenediamine were prepared into demulsifiers according to examples 2, 5 and 8, respectively, and an emulsion demulsification experiment was performed and the transmittance of a water phase after demulsification was measured, in the same manner as in examples.
Comparative example 2
2mL of a demulsifier aqueous solution with a propylenediamine-centered hyperbranched polymer concentration of 1000mg/L was added to 38mL of a diesel/water emulsion in which the propylenediamine-centered hyperbranched polymer concentration in the emulsion was 50mg/L (50ppm), the mixture was uniformly mixed by rapid oscillation, and then left to stand at 60 ℃ for 30min, and the light transmittance of the water phase was measured to be 74.9%. After standing at 60 ℃ for 60min, the light transmittance of the aqueous phase was determined to be 79%. After standing at 60 ℃ for 120min, the light transmittance of the aqueous phase was measured to be 84.1%.
Comparative example 5
Adding 2mL of demulsifier aqueous solution with the concentration of the hyperbranched polymer taking the propylene diamine as the center being 800mg/L into 38mL of diesel oil/water emulsion, wherein the concentration of the hyperbranched polymer taking the propylene diamine as the center in the emulsion is 40mg/L (40ppm), uniformly mixing the mixture by rapid oscillation, standing the mixture at 60 ℃ for 30min, and measuring the light transmittance of the water phase to be 54.2%. Then, after standing at 60 ℃ for 60min, the light transmittance of the aqueous phase was measured to be 58.6%. Then, after standing at 60 ℃ for 120min, the light transmittance of the aqueous phase was measured to be 70.4%.
Comparative example 8
2mL of demulsifier aqueous solution with propylene diamine-centered hyperbranched polymer concentration of 600mg/L is added into 38mL of diesel oil/water emulsion, the propylene diamine-centered hyperbranched polymer concentration in the emulsion is 30mg/L (30ppm), the mixture is uniformly mixed by rapid oscillation, and then the mixture is kept stand at 60 ℃ for 30min, and then the light transmittance of the water phase is measured to be 40.3%. After standing at 60 ℃ for 60min, the light transmittance of the aqueous phase was measured to be 46.9%. After standing at 60 ℃ for 120min, the light transmittance of the aqueous phase was measured to be 55.7%.
It can be seen from the comparison of examples 2, 5 and 8 with comparative examples 2, 5 and 8 that the demulsifying agent has higher demulsifying efficiency than the propylene diamine-centered hyperbranched polymer of comparative example 1 at the same addition amount and the same temperature and demulsifying time, and the difference between the two is particularly significant under the conditions of lower addition amount or shorter standing time. For example, when the emulsion is added in an amount of 30mg/L (30ppm), the light transmittance of the aqueous phase can reach 75.8% after the emulsion is broken at 60 ℃/30min in example 8, and the light transmittance of the aqueous phase is only 40.3% at 60 ℃/30min in comparative example 8. The higher the light transmittance of the water phase is, the better the demulsification effect is proved, which shows that the demulsification efficiency of the polyamide-amine hyperbranched polymer in example 1 at low addition is obviously higher than that of the hyperbranched polymer taking propylene diamine as the center in comparative example 1. This shows that the polyamidoamine hyperbranched polymer of the present example is used as a demulsifier, has better demulsification efficiency, and is used in a lower amount.
Various modifications and variations of the embodiments of the present invention may be made by those skilled in the art, and they are also within the scope of the present invention, provided they are within the scope of the claims of the present invention and their equivalents. What is not described in detail in the specification is prior art that is well known to those skilled in the art.

Claims (4)

1. The preparation method of the polyamide-amine hyperbranched polymer is characterized by comprising the following steps:
s1, dissolving 5.34g of 4,4' -diaminodiphenylmethane in 30ml of methanol, then dropwise adding 6.88g of methyl acrylate into the solution, and stirring the mixture at room temperature and 25 ℃ at the speed of 300r/min for reaction for 24 hours;
s2, adding 33.6g of ethylenediamine and 41.28g of methyl acrylate to the mixture obtained in the step S1, continuing the stirring reaction at room temperature for 24 hours, and then removing methanol under reduced pressure to obtain a mixed solution;
s3, reacting the mixed solution obtained in the step S2 for 1 hour at 60 ℃, 1 hour at 80 ℃, 2 hours at 100 ℃, 2 hours at 120 ℃, 2 hours at 140 ℃, naturally cooling to room temperature, precipitating with diethyl ether, and drying in vacuum to obtain a bright yellow product, namely the polyamide-amine hyperbranched polymer.
2. A polyamide-amine hyperbranched polymer, which is prepared by the preparation method of claim 1, and is characterized in that the polyamide-amine hyperbranched polymer takes 4,4' -diaminodiphenylmethane as the center and the end group is an amine group.
3. A demulsifier comprising the polyamidoamine hyperbranched polymer of claim 2.
4. The application of the polyamide-amine hyperbranched polymer in demulsification is characterized in that the demulsifier is used for demulsification of oil-in-water emulsions, and after the demulsifier of claim 3 is added into the emulsion, the concentration of the polyamide-amine hyperbranched polymer in the emulsion is 40mg/L, the temperature for demulsification is 60 ℃, and the time for demulsification is 30 min.
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