CN109503833B - Amphiphilic hyperbranched polymer and preparation and application thereof - Google Patents
Amphiphilic hyperbranched polymer and preparation and application thereof Download PDFInfo
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- 229920000587 hyperbranched polymer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920000962 poly(amidoamine) Polymers 0.000 claims abstract description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims description 10
- 238000007112 amidation reaction Methods 0.000 claims description 9
- 239000007764 o/w emulsion Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Preparation (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to an amphiphilic hyperbranched polymer, and a preparation method and an application thereof, wherein the inner core of the amphiphilic hyperbranched polymer is hyperbranched polyamidoamine with strong hydrophilicity, and part of terminal amino groups and NH of the hyperbranched polyamidoamine2(CH2)5CONH(CH2)5The carboxyl groups on COOH are grafted by amide bonds. Because the external amino is partially replaced by a straight chain structure which takes a long-chain carbon skeleton as a main body and takes the amino as an end group, the shell simultaneously contains strong hydrophilic group amino and a hydrophobic group long-chain carbon skeleton, certain water solubility of the shell is ensured, the shell can quickly reach an oil-water interface to damage an oil-water interface membrane, and meanwhile, the external oleophilic group has strong adsorption capacity and can adsorb more oil drops, so that the oil drops are coalesced and float upwards to finally achieve oil-water separation, and quick demulsification can be realized under the condition of less addition amount.
Description
Technical Field
The invention relates to the technical field of petroleum additives, in particular to an amphiphilic hyperbranched polymer and preparation and application thereof.
Background
Hyperbranched Polyamidoamines (HPAMAM) are a class of hyperbranched polymers (hyper-branched polymers) which are well researched, low in price and industrially produced at present. HPAMAM has low viscosity in solvent, good thermal stability compared with other high molecular polymers, good solubility and a large amount of amino groups at the tail end of a branched chain, and does not decompose at the temperature of lower than 300 ℃ in air as shown by thermogravimetric analysis.
Due to the novel structure, unique performance and potential application prospect, the polymer is generally concerned by the scientific and industrial fields once coming out, due to the characteristic of multi-amino at the tail end of a branched chain, a small molecular substance with certain functions is grafted, so that the hyperbranched polymer meeting the requirements of people can be synthesized, and compared with other branched polymers, the hyperbranched polymer has the advantage of being unique in the aspect of preparing novel functional materials.
With the continuous deepening of oil field exploitation technology, each large oil field enters a tertiary oil recovery stage successively, oil resources are reduced day by day, crude oil extracted from an oil well is converted into oil-in-water (O/W) type emulsion from water-in-oil (W/O) type emulsion at the initial development stage, the stability of the crude oil emulsion is gradually enhanced due to the wide application of a chemical oil displacement method, the produced liquid treatment becomes a technical problem in the production of a plurality of oil fields, the demulsification difficulty is increased more and more, and the requirement on the performance of a demulsifier is highest.
Statistical research shows that most of the demulsifiers used on site at present belong to high molecular polymers. The molecular morphology thereof can be roughly classified into linear (straight-chain) and branched (branched or branched).
Linear demulsifiers, which are generally polyethers, are generally obtained by adjusting the block length of a certain repeating unit in the molecular chain to obtain different molecular weights. Because different linear demulsifiers have block distribution of different functional groups, the molecular structure of the demulsifiers can generally form a wider HLB value, the demulsifiers have wider performance and application range, generally do not dissociate in water, and ether bonds and water have strong capability of forming hydrogen bonds, high stability and are not easily influenced by electrolyte.
The branched demulsifier mainly comprises a branched macromolecule, wherein three or more than three sub-chains are generally connected in the branched macromolecule, some sub-chains are also side chains or are part of a main chain, and the side chains with different lengths are randomly distributed along the main chain and the side chains. Branched demulsifiers have many unique advantages: the structure can be accurately controlled, can be changed and adjusted, has high order, good monodispersity and good water solubility, contains a large amount of functional groups in the interior and at the tail end of a molecule, has better hydrophilic capacity, wettability and permeation effect compared with a linear demulsifier, can quickly reach an oil-water interface, has less consumption of the branched demulsifier, and has better integral demulsification effect compared with the linear demulsifier. However, the demulsification efficiency of the existing branched demulsifiers is still to be further improved.
Disclosure of Invention
The invention aims to provide an amphiphilic hyperbranched polymer aiming at the defects of the prior art, and the amphiphilic hyperbranched polymer can realize rapid demulsification under the condition of less addition amount when being used as a demulsifying agent.
The technical scheme provided by the invention is as follows:
an amphiphilic hyperbranched polymer, the inner core of which is hyperbranched polyamidoamine with strong hydrophilicity, and part of terminal amino groups and NH of the hyperbranched polyamidoamine2(CH2)5CONH(CH2)5The carboxyl groups on COOH are grafted by amide bonds.
Wherein NH2(CH2)5CONH(CH2)5The structural formula of COOH is as follows:
by using NH in the invention2(CH2)5CONH(CH2)5COOH modifies partial end group of the hyperbranched polyamidoamine to obtain hyperbranched polymer HPAMAM-br-C with an amphiphilic structure12. The modification is based on increasing a certain carbon long chain outside the HPAMAM, so that the terminal group is still kept as a hydrophilic group amino. The structure can enable the demulsifier to be dispersed in an emulsion system more quickly and uniformly, molecular chains can be fully unfolded, so that demulsifier molecules can be quickly adsorbed to an oil-water interface at multiple points, original surfactant substances are effectively punctured and replaced, the strength of an interface film is reduced, oil drop collision, coalescence and combination are accelerated, and oil-water separation is further achieved, so that the novel hyperbranched polymer demulsifier is used as a novel hyperbranched polymer demulsifier.
Preferably, the NH is2(CH2)5CONH(CH2)5The mass ratio of COOH to hyperbranched polyamidoamine is 0.5-1.7.
The invention provides a preparation method of an amphiphilic hyperbranched polymerThe method comprises the following steps: reacting NH2(CH2)5CONH(CH2)5Performing amidation reaction on the COOH and the hyperbranched polyamidoamine to obtain an amphiphilic hyperbranched polymer; the NH2(CH2)5CONH(CH2)5The mass ratio of COOH to hyperbranched polyamidoamine is 0.5-1.7.
In the present invention, NH is used2(CH2)5CONH(CH2)5The COOH carries out amidation modification on partial amino at the outer end of the hyperbranched polyamidoamine to obtain amphiphilic hyperbranched polyamidoamine HPAMAM-br-C12. The modified amphiphilic hyperbranched polyamidoamine has the advantages that the external amino group is partially substituted into a linear structure which takes a long-chain carbon skeleton as a main body and takes the amino group as an end group, the shell simultaneously contains a strong hydrophilic group amino group and a hydrophobic group long-chain alkyl group, the hydrophobic group long-chain alkyl group can effectively adsorb oil drops, the amino group at the tail end of the hydrophobic group long-chain alkyl group can still keep good water solubility, amphiphilic polymers with different substitution degrees and a core-shell structure are formed, and the number average molecular weight distribution of the amphiphilic polyamidoamine is 10000-20000.
Secondly, by controlling NH2(CH2)5CONH(CH2)5The modified structure of the COOH and the hyperbranched polyamidoamine has higher interfacial activity, can be quickly dispersed in an oil-water emulsion to quickly reach an oil-water interface while ensuring good water solubility, destroys an oil-water interface film, has stronger adsorption capacity due to long carbon chains, can adsorb more oil drops, enables the oil drops to coalesce and float, and finally achieves oil-water separation, and can realize quick demulsification under the condition of less addition amount.
The amidation reaction in the present invention includes:
1) dissolving hyperbranched polyamidoamine in organic solvent, adding catalyst N, N' -carbonyldiimidazole, and then dropwise adding NH dissolved in the same organic solvent2(CH2)5CONH(CH2)5Performing amidation reaction on COOH at 40-100 ℃ for 3-24 h to obtain a crude product;
2) concentrating the crude product obtained in the step 1), separating acetone, and performing rotary evaporation to obtain the amphiphilic hyperbranched polymer.
Preferably, the temperature of the amidation reaction is 55-65 ℃, and the time is 8-10 h.
NH described in the invention2(CH2)5CONH(CH2)5The mass ratio of COOH to hyperbranched polyamidoamine is 0.5-1.7.
The mass ratio of the N, N' -carbonyldiimidazole to the hyperbranched polyamidoamine is 0.3-1.4.
The organic solvent is trichloromethane or methanol.
The invention also provides a method for demulsifying the oil-in-water type emulsion by using the amphiphilic hyperbranched polymer, which is used for demulsifying by dispersing the amphiphilic hyperbranched polymer into the oil-in-water type emulsion.
The addition amount of the amphiphilic hyperbranched polymer in the oil-in-water emulsion is 5-20 mg/L. The addition amount is less than 5mg/L, and the demulsification effect is poor; the addition amount is more than 20mg/L, the demulsification effect is not changed greatly, but the economic cost is increased greatly.
The temperature of demulsification is 25-65 ℃, and the settling time is 30-90 min.
The oil phase in the oil-in-water emulsion of the present invention is a simulated oil or an actual oil.
Preferably, the simulated oil is n-dodecane, n-tridecane, n-tetradecane, or n-hexadecane.
Preferably, the actual oil is kerosene, diesel oil or gasoline.
The mineralization degree of a water phase in the oil-in-water type emulsion is 0-20000 mg/L, wherein NaCl and CaCl in the water phase2The mass ratio of (A) to (B) is 0.1 to 1.5.
Compared with the prior art, the invention has the beneficial effects that:
according to the amphiphilic hyperbranched polymer, the external amino group is partially substituted into a straight-chain structure which takes a long-chain carbon skeleton as a main body and takes the amino group as an end group, and the shell simultaneously contains a strong hydrophilic group amino group and a hydrophobic group long-chain carbon skeleton, so that the amphiphilic hyperbranched polymer can quickly reach an oil-water interface to destroy an oil-water interface membrane while ensuring certain water solubility, and meanwhile, the external lipophilic group has strong adsorption capacity and can adsorb more oil drops to enable the oil drops to coalesce and float upwards to finally achieve oil-water separation, and quick demulsification can be realized under the condition of less addition amount.
Drawings
FIG. 1 shows the amphiphilic hyperbranched polymer HPAMAM-br-C of the present invention12Schematic structural diagram of (1).
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1: NH (NH)2(CH2)5CONH(CH2)5Preparation of COOH
(1) Dissolving 3g of the compound shown in the formula (a) in DMF, adding 4.9g of potassium carbonate, and dropwise adding 2g of methanol for reacting overnight to obtain a compound shown in the formula (b);
(2) the product obtained in the step (1) is dissolved in methanol again after being dried in a spinning mode, a certain amount of Pd/C is added, the mixture stays overnight under the protection of hydrogen, and the compound shown in the formula (C) can be obtained after suction filtration;
(3) then 3g of the compound shown as the formula (a) is taken to be dissolved in chloroform, 1.5g of the compound shown as the formula (C) is added to react for 3 hours at 70 ℃, the solution is evaporated to dryness, the solution is dissolved in a mixed solution of water and tetrahydrofuran, a small amount of LiOH is added to react for 6 hours, dilute HCl is added dropwise to adjust the pH value to acidity, and then Pd/C is used for hydrogenation reduction to obtain a product NH2(CH2)5CONH(CH2)5COOH。
The structural formula is as follows:
example 2: amphiphilic hyperbranched polymer (HPAMAM-br-C)12) Preparation of
Take 4.81g NH2(CH2)5CONH(CH2)5COOH was dissolved in 30mL of methanol, 3.39g of CDI was weighed and added to the reaction system, and after it was dissolved by stirring, a mixed solution was obtained. Dissolving 3g of HPAMAM in 10mL of methanol, then dropwise adding the solution into the mixed solution, and carrying out amidation reaction at 55 ℃ for 9h to obtain a crude product with high polymerization degree; cooling the crude product to room temperature, pouring into 250mL acetone, stirring for 60min, allowing yellow transparent viscous liquid to precipitate in the lower layer, removing the upper layer acetone, repeating the precipitation for 2 times, and rotary steaming at 50 deg.C under vacuum to obtain HPAMAM-br-C12。
Amphiphilic hyperbranched polymer (HPAMAM-br-C)12) As shown in fig. 1, it should be noted that the hyperbranched structure is variable and complex, and the structure shown is only an example.
Examples 3 to 8
The amphiphilic hyperbranched polymer is prepared by referring to example 2, and the specific process parameters are shown in table 1, so that the amphiphilic hyperbranched polymer can be obtained. NH (NH)2(CH2)5CONH(CH2)5COOH is denoted as a in the table below.
Table 1: comparison of preparation Process parameters of examples 2 to 8
Application example 1
Weighing HPAMAM-br-C of example 212(number average molecular weight distribution: 10000 to 20000) and dissolved in an oil-in-water emulsion containing n-hexadecane as an oil phase and having a degree of mineralization of 7500mg/L, with stirring at a concentration of 10 mg/L. The oil removal efficiency was measured at 25 ℃ for settling times of 1min, 10min, 20min and 30min, respectively. The results show that HPAMAM-br-C12The oil removal efficiency at these settling times is respectively improved by 3 percentTo 59%, 75%, 84% and 90%.
Application examples 2 to 10
The test was conducted with reference to application example 1, and the specific process parameters and the results of the oil removal efficiency of the aqueous phase are shown in table 2.
Table 2: comparison of technological parameters and water phase oil removal efficiency of application examples 2-10
Claims (9)
1. The amphiphilic hyperbranched polymer is characterized in that the inner core of the amphiphilic hyperbranched polymer is hyperbranched polyamidoamine with strong hydrophilicity, and part of terminal amino groups and NH of the hyperbranched polyamidoamine2(CH2)5CONH(CH2)5Grafting carboxyl on COOH through amido bond; the NH2(CH2)5CONH(CH2)5The mass ratio of COOH to hyperbranched polyamidoamine is 0.5-1.7.
2. A method for preparing an amphiphilic hyperbranched polymer, which is characterized by comprising the following steps: reacting NH2(CH2)5CONH(CH2)5Performing amidation reaction on the COOH and the hyperbranched polyamidoamine to obtain an amphiphilic hyperbranched polymer; the NH2(CH2)5CONH(CH2)5The mass ratio of COOH to hyperbranched polyamidoamine is 0.5-1.7.
3. The method of claim 2, wherein the amidation reaction comprises:
1) dissolving hyperbranched polyamidoamine in organic solvent, adding catalyst N, N' -carbonyldiimidazole, and dropwise addingNH dissolved in the same organic solvent2(CH2)5CONH(CH2)5Performing amidation reaction on COOH at 40-100 ℃ for 3-24 h to obtain a crude product;
2) concentrating the crude product obtained in the step 1), separating acetone, and performing rotary evaporation to obtain the amphiphilic hyperbranched polymer.
4. The method for preparing the amphiphilic hyperbranched polymer according to claim 3, wherein the mass ratio of the N, N' -carbonyldiimidazole to the hyperbranched polyamidoamine is 0.3-1.4.
5. The method of claim 3, wherein the organic solvent is chloroform or methanol.
6. A method of breaking an oil-in-water emulsion using the amphiphilic hyperbranched polymer of claim 1, wherein the amphiphilic hyperbranched polymer is dispersed in the oil-in-water emulsion to break the emulsion.
7. The method for demulsifying an oil-in-water emulsion by using an amphiphilic hyperbranched polymer as claimed in claim 6, wherein the amphiphilic hyperbranched polymer is added in the oil-in-water emulsion in an amount of 5-20 mg/L.
8. The method for demulsifying an oil-in-water emulsion by using an amphiphilic hyperbranched polymer as claimed in claim 6, wherein the temperature for demulsification is 25-65 ℃ and the settling time is 30-90 min.
9. The method of claim 6, wherein the oil phase of the oil-in-water emulsion is a simulated oil or a real oil.
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| US4558120A (en) * | 1983-01-07 | 1985-12-10 | The Dow Chemical Company | Dense star polymer |
| CN105601941A (en) * | 2016-01-15 | 2016-05-25 | 浙江大学 | Application of polyamidoamine hyperbranched polymer as demulsifying agent |
| CN106367103A (en) * | 2016-10-23 | 2017-02-01 | 中海油天津化工研究设计院有限公司 | Preparation method of non-polyether heavy oil demulsifier |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4558120A (en) * | 1983-01-07 | 1985-12-10 | The Dow Chemical Company | Dense star polymer |
| CN105601941A (en) * | 2016-01-15 | 2016-05-25 | 浙江大学 | Application of polyamidoamine hyperbranched polymer as demulsifying agent |
| CN106367103A (en) * | 2016-10-23 | 2017-02-01 | 中海油天津化工研究设计院有限公司 | Preparation method of non-polyether heavy oil demulsifier |
Non-Patent Citations (3)
| Title |
|---|
| Hyperbranched poly(amido amine) demulsifiers with ethylenediamine/1,3-propanediamine as an initiator for oil-in-water emulsions with microdroplets;Lifeng Zhang et al.;《Fuel》;20180411;第226卷;第381-388页 * |
| Lifeng Zhang et al..Hyperbranched poly(amido amine) as an effective demulsifier for oil-in-water emulsions of microdroplets.《Fuel》.2017,第211卷第197-205页. * |
| 改性树状大分子W－PAMAM 的合成及破乳性能研究;王雪敏 等;《精细石油化工进展》;20150728;第16卷(第4期);第30-32页 * |
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