CN109503833A - A kind of Ambident hyperbranched polymer and its preparation and application - Google Patents
A kind of Ambident hyperbranched polymer and its preparation and application Download PDFInfo
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- CN109503833A CN109503833A CN201811425386.5A CN201811425386A CN109503833A CN 109503833 A CN109503833 A CN 109503833A CN 201811425386 A CN201811425386 A CN 201811425386A CN 109503833 A CN109503833 A CN 109503833A
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- hyperbranched polymer
- oil
- ambident hyperbranched
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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
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- 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
Abstract
The present invention relates to a kind of Ambident hyperbranched polymer and its preparation and application, the kernel of Ambident hyperbranched polymer is the over-branched polyamidoamine with strongly hydrophilic, the portions end amino and NH of the over-branched polyamidoamine2(CH2)5CONH(CH2)5Carboxyl on COOH is grafted by amido bond.Since external amino is partially substituted by based on long-chain carbon skeleton, amino is the linear chain structure of end group, shell contains strongly hydrophilic group amino and hydrophobic grouping long-chain carbon skeleton simultaneously, guarantee its it is certain it is water-soluble simultaneously, oil-water interfaces can quickly be reached, destroy oil-water interfacial film, external lipophilic group possesses stronger adsorption capacity simultaneously, more oil droplets can be adsorbed, keep it poly- simultaneously, it floats, is finally reached water-oil separating, fast emulsion breaking may be implemented in the case where less additive amount.
Description
Technical field
The present invention relates to petroleum additive technical fields, and in particular to a kind of Ambident hyperbranched polymer and its preparation and
Using.
Background technique
Over-branched polyamidoamine (HPAMAM) is that one kind is studied more mature, cheap, at present industrial metaplasia
The dissaving polymer (Hyperamanched polymers) of production.HPAMAM viscosity very little in a solvent, with other macromolecules
Polymer phase ratio, it has good thermal stability, and thermogravimetric analysis shows and do not decompose lower than 300 DEG C in air, has preferably
Dissolubility, branch terminals have a large amount of amino.
Due to its novel structure, unique performance and potential application prospect, this quasi polymer once come out just by
The common concern of scientific circles and industry, the characteristics of due to its branch terminals polyamino, by the small molecule object with certain function
In matter grafting, dissaving polymer needed for meeting people can be synthesized, other are compared in terms of preparing new function material
Fluidized polymer has advantageous advantage.
As oilfield exploitation technically deepens continuously, each elephant has subsequently entered tertiary phase, petroleum resources day
Benefit is reduced, and oil well produced crude oil is changed into oil-in-water (O/W) type lotion by the Water-In-Oil of initial stage of development (W/O) type emulsion,
And due to the extensive use of chemical displacement of reservoir oil method, the stability of emulsion of crude oil is gradually increased, and Produced Liquid is processed into order to very much
Technical problem in the production of oil field, demulsification difficulty is increasing, and highest is also got in the requirement of demulsifier performance.
Statistical research, the demulsifier overwhelming majority that current scene uses belong to high molecular polymer.From its molecular conformation
On can be roughly divided into line style (straight chain type) and branch type (branching type, branched chain type).
Line style demulsifier generally obtains different points by adjusting the block length of certain repetitive unit in strand with this
Son amount, such demulsifier are generally polyethers.Since synteny demulsifier does not have the block distributed of different functional groups, so should
Class molecular structure can generally form wider HLB value, and demulsifier performance and the scope of application are wider, will not generally occur in water
Dissociation, and the ability of ehter bond and water generation hydrogen bond is strong, and stability is high, not vulnerable to Influence of Electrolyte.
Branching type demulsifier mainly contains branched polymer, and three or three or more sons are generally connected in branched polymer
Chain, some subchains are also a part of side chain or main chain simultaneously, and the side chain of different length is random along main chain and side chain
Distribution.Branching type demulsifier has many unique superiority: structure accurately controls, and can be changed and adjusts, high-sequential,
Monodispersity is good and good water solubility, while generally speaking a large amount of functional groups are contained in intramolecule and end, branched chain type demulsifier
There is better hydrophilic ability, wettability and osmotic effect than line style demulsifier, oil-water interfaces can be rapidly reached, propped up simultaneously
Chain demulsifier dosage is less, and whole demulsification is better than line style demulsifier.But the demulsification of existing branching type demulsifier
It still needs further improvement for efficiency.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to a kind of Ambident hyperbranched polymer be provided, as broken
Fast emulsion breaking may be implemented in the case where less additive amount when emulsion.
Technical solution provided by the present invention are as follows:
A kind of Ambident hyperbranched polymer, the kernel of the Ambident hyperbranched polymer are super with strongly hydrophilic
Branched polyamide amine, the portions end amino and NH of the over-branched polyamidoamine2(CH2)5CONH(CH2)5Carboxyl on COOH
It is grafted by amido bond.
Wherein, NH2(CH2)5CONH(CH2)5The structural formula of COOH is as follows:
The present invention uses NH2(CH2)5CONH(CH2)5COOH is modified over-branched polyamidoamine part end group, obtains
Dissaving polymer HPAMAM-br-C with amphipathic structure12.This is modified in the base for increasing certain carbon long-chain outside HPAMAM
On plinth, end group is made still to remain hydrophilic radical amino.The structure can make its faster, more evenly be dispersed in emulsion liquid
In system, strand can sufficiently unfold, and enable demulsification agent molecule quickly, multiple spot to be adsorbed onto oil-water interfaces, effectively pierce through
With the original surfactant materials of substitution, interfacial film strength is reduced, accelerates oil droplet collision, coalescence and merging, further reaches
Water-oil separating, in this, as novel hyperbranched polymer demulsifier.
Preferably, the NH2(CH2)5CONH(CH2)5The mass ratio of COOH and over-branched polyamidoamine is 0.5~1.7.
The present invention provides a kind of preparation method of Ambident hyperbranched polymer, comprising: by NH2(CH2)5CONH(CH2)5COOH and over-branched polyamidoamine obtain Ambident hyperbranched polymer by amidation process；The NH2(CH2)5CONH
(CH2)5The mass ratio of COOH and over-branched polyamidoamine is 0.5~1.7.
NH is used in the present invention2(CH2)5CONH(CH2)5COOH carries out amide to over-branched polyamidoamine outer end portion amino
Change and be modified, obtains Ambident hyperbranched daiamid HPAMAM-br-C12.Modified Ambident hyperbranched daiamid due to
External amino is partially substituted by based on long-chain carbon skeleton, and amino is the linear chain structure of end group, and shell contains strong parent simultaneously
Aqueous group amino and hydrophobic grouping chain alkyl, hydrophobic grouping chain alkyl can effectively adsorb oil droplet, the amino of end
Its good water solubility can be still kept, the different degree of substitution amphiphilic polymer with core-shell structure is formed, number is divided equally
Son amount is distributed as 10000~20000.
Secondly, passing through control NH2(CH2)5CONH(CH2)5The mass ratio of COOH and over-branched polyamidoamine, modified knot
Structure makes it have higher interfacial activity, guarantee its it is good it is water-soluble simultaneously, it can be made to be dispersed in grease faster
In emulsion, oil-water interfaces are rapidly reached, destroy oil-water interfacial film, while Long carbon chain has stronger adsorption capacity, it can
More oil droplets are adsorbed, keeps it poly- simultaneously, floats, be finally reached water-oil separating, may be implemented in the case where less additive amount fast
Speed demulsification.
Heretofore described amidation process includes:
1) over-branched polyamidoamine is dissolved in organic solvent, catalyst n is added, then N '-carbonyl dimidazoles add dropwise
Enter the NH for being dissolved in identical organic solvent2(CH2)5CONH(CH2)5COOH, at 40~100 DEG C by 3~amidation for 24 hours is anti-
It answers, obtains crude product；
2) crude product for obtaining step 1) rotates by concentration, acetone separation, obtains Ambident hyperbranched polymer.
Preferably, the temperature of the amidation process is 55~65 DEG C, time 8-10h.
Heretofore described NH2(CH2)5CONH(CH2)5The mass ratio of COOH and over-branched polyamidoamine is 0.5~1.7.
The mass ratio of heretofore described N, N '-carbonyl dimidazoles and over-branched polyamidoamine is 0.3~1.4.
Heretofore described organic solvent is chloroform or methanol.
Oil-in-water emulsion is carried out brokenly using such as above-mentioned Ambident hyperbranched polymer the present invention also provides a kind of
The method of cream, Ambident hyperbranched polymer is distributed in oil-in-water emulsion and is demulsified.
Additive amount of the heretofore described Ambident hyperbranched polymer in oil-in-water emulsion is 5~20mg/L.
Additive amount is less than 5mg/L, and demulsification is bad；Additive amount is greater than 20mg/L, and demulsification variation is little, but economic cost increases
Very much.
The temperature of heretofore described demulsification is 25~65 DEG C, and the sedimentation time is 30~90min.
Oil in heretofore described oil-in-water emulsion is mutually simulation oil or practical oil.
Preferably, the simulation oil is n-dodecane, n-tridecane, n-tetradecane or hexadecane.
Preferably, the practical oil is kerosene, bavin Water Oil Or Gas.
The salinity of water phase in heretofore described oil-in-water emulsion is 0~20000mg/L, wherein in water phase
NaCl and CaCl2Mass ratio be 0.1~1.5.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
Ambident hyperbranched polymer is partially substituted by based on long-chain carbon skeleton due to external amino in the present invention,
Amino is the linear chain structure of end group, and shell contains strongly hydrophilic group amino and hydrophobic grouping long-chain carbon skeleton simultaneously, guaranteeing
Its it is certain it is water-soluble can quickly reach oil-water interfaces simultaneously, destroy oil-water interfacial film, while external lipophilic group
Group possesses stronger adsorption capacity, can adsorb more oil droplets, keeps it poly- simultaneously, floats, water-oil separating is finally reached, less
Fast emulsion breaking may be implemented in the case where additive amount.
Detailed description of the invention
Fig. 1 is Ambident hyperbranched polymer HPAMAM-br-C in the present invention12Structural schematic diagram.
Specific embodiment
Below with reference to specific embodiment, present invention will be explained in further detail.
Embodiment 1:NH2(CH2)5CONH(CH2)5The preparation of COOH
(1) it takes 3g formula (a) compound to be dissolved in DMF, 4.9g potassium carbonate is added, the reaction of 2g methanol is added dropwise overnight, can obtain
To formula (b) compound；
(2) it is again dissolved in methanol after being spin-dried for for the product in step (1), a certain amount of Pd/C is added, in the guarantor of hydrogen
Shield is lower overnight, and formula (c) compound can be obtained after suction filtration；
(3) 3g formula (a) compound is then taken to be dissolved in chloroform, addition 1.5g formula (c) compound reacts 3h at 70 DEG C, will be molten
Liquid is evaporated, and is dissolved in that a small amount of LiOH is added in the mixed solution of water and tetrahydrofuran, and after reacting 6h, dilute HCl is added dropwise by pH tune
To acidity, Pd/C hydrogenating reduction is used immediately, product NH can be obtained2(CH2)5CONH(CH2)5COOH。
Its structural formula is as follows:
Embodiment 2: Ambident hyperbranched polymer (HPAMAM-br-C12) preparation
Take 4.81g NH2(CH2)5CONH(CH2)5COOH is dissolved in 30mL methanol, weighs 3.39g CDI and reactant is added
System, stirring obtain mixed liquor after its dissolution.3g HPAMAM is dissolved in 10mL methanol, mixing is then added dropwise to
In liquid, amidation process is carried out at 55 DEG C, reaction time 9h obtains the crude product of high polymerization degree；Then, crude product is cooling
It is poured into after to room temperature in 250mL acetone and stirs 60min, the thick liquid that yellow transparent can be observed is sunken to lower layer, discards upper layer
Acetone, repeats precipitating 2 times, and HPAMAM-br-C can be obtained in the lower 50 DEG C of revolvings of vacuum12。
Ambident hyperbranched polymer (HPAMAM-br-C12) structural schematic diagram, as shown in Figure 1, it should be noted that
Since dissaving structure is changeable and complicated, shown structure is merely illustrative.
Embodiment 3~8
Reference implementation example 2 carries out preparing Ambident hyperbranched polymer, and specific process parameter is as shown in table 1, can obtain
Ambident hyperbranched polymer.NH2(CH2)5CONH(CH2)5COOH is denoted as a in the following table.
Table 1: the preparation technology parameter of embodiment 2~8 compares
Application examples 1
Weigh the HPAMAM-br-C in embodiment 212(number average molecular weight distribution is 10000~20000), with 10mg/L's
For concentration stirring and dissolving in being oily phase with hexadecane, salinity is the oil-in-water emulsion of 7500mg/L.At 25 DEG C respectively
Survey the oil removal efficiency that the sedimentation time is 1min, 10min, 20min and 30min.The result shows that HPAMAM-br-C12In these sedimentations
Oil removal efficiency under time is respectively increased by 3% to 59%, 75%, 84% and 90%.
Application examples 2~10
It is tested with reference to application examples 1, the results are shown in Table 2 for specific process parameter and water phase oil removal efficiency.
Table 2: the technological parameter and water phase oil removal efficiency of application examples 2~10 compare
Claims (10)
1. a kind of Ambident hyperbranched polymer, which is characterized in that the kernel of the Ambident hyperbranched polymer is with strong
Hydrophilic over-branched polyamidoamine, the portions end amino and NH of the over-branched polyamidoamine2(CH2)5CONH(CH2)5Carboxyl on COOH is grafted by amido bond.
2. Ambident hyperbranched polymer according to claim 1, which is characterized in that the NH2(CH2)5CONH(CH2)5The mass ratio of COOH and over-branched polyamidoamine is 0.5~1.7.
3. a kind of preparation method of Ambident hyperbranched polymer characterized by comprising by NH2(CH2)5CONH(CH2)5COOH and over-branched polyamidoamine obtain Ambident hyperbranched polymer by amidation process；The NH2(CH2)5CONH
(CH2)5The mass ratio of COOH and over-branched polyamidoamine is 0.5~1.7.
4. the preparation method of Ambident hyperbranched polymer according to claim 3, which is characterized in that the amidation is anti-
Should include:
1) over-branched polyamidoamine is dissolved in organic solvent, catalyst n is added, then N '-carbonyl dimidazoles are added dropwise molten
In the NH of identical organic solvent2(CH2)5CONH(CH2)5COOH, at 40~100 DEG C by 3~amidation process for 24 hours, obtain
To crude product；
2) crude product for obtaining step 1) rotates by concentration, acetone separation, obtains Ambident hyperbranched polymer.
5. the preparation method of Ambident hyperbranched polymer according to claim 4, which is characterized in that the N, N '-carbonyl
The mass ratio of base diimidazole and over-branched polyamidoamine is 0.3~1.4.
6. the preparation method of Ambident hyperbranched polymer according to claim 4, which is characterized in that the organic solvent
For chloroform or methanol.
7. a kind of be demulsified to oil-in-water emulsion using Ambident hyperbranched polymer as claimed in claim 1 or 2
Method, which is characterized in that Ambident hyperbranched polymer is distributed in oil-in-water emulsion and is demulsified.
8. the side according to claim 7 being demulsified using Ambident hyperbranched polymer to oil-in-water emulsion
Method, which is characterized in that additive amount of the Ambident hyperbranched polymer in oil-in-water emulsion is 5~20mg/L.
9. the side according to claim 7 being demulsified using Ambident hyperbranched polymer to oil-in-water emulsion
Method, which is characterized in that the temperature of the demulsification is 25~65 DEG C, and the sedimentation time is 30~90min.
10. the side according to claim 7 being demulsified using Ambident hyperbranched polymer to oil-in-water emulsion
Method, which is characterized in that the oil in the oil-in-water emulsion is mutually simulation oil or practical oil.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040154A (en) * | 2019-12-24 | 2020-04-21 | 中海油天津化工研究设计院有限公司 | Demulsification and water purification integrated medicament modified hyperbranched polyamidoamine polymer |
| CN115785990A (en) * | 2022-12-22 | 2023-03-14 | 南阳腾远石油工程技术服务有限公司 | Crude oil demulsifier and preparation method thereof |
| CN115785990B (en) * | 2022-12-22 | 2024-05-17 | 南阳腾远石油工程技术服务有限公司 | Crude oil demulsifier and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040154A (en) * | 2019-12-24 | 2020-04-21 | 中海油天津化工研究设计院有限公司 | Demulsification and water purification integrated medicament modified hyperbranched polyamidoamine polymer |
| CN115785990A (en) * | 2022-12-22 | 2023-03-14 | 南阳腾远石油工程技术服务有限公司 | Crude oil demulsifier and preparation method thereof |
| CN115785990B (en) * | 2022-12-22 | 2024-05-17 | 南阳腾远石油工程技术服务有限公司 | Crude oil demulsifier and preparation method thereof |
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