CN106317399A - Hydrophobically associating polymer and preparation method thereof - Google Patents
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Abstract
The invention provides a hydrophobically associating polymer and a preparation method thereof. The hydrophobically associating polymer is of a structure represented by the formula I (shown in the specification), wherein the molecular weight of a polyethylene glycol chain section is 200 to 2,000. As the chemical structure of pyrene is a conjugated aromatic nucleus, pyrene is more compact than straight-chain paraffin, and the hydrophobicity is higher; and therefore, the effects of reducing the oil-water interface tension and solubilizing crude oil can be better achieved, and the harvesting rate of an oil field is increased.
Description
Technical field
The present invention relates to oil-gas field development field, be specifically related to a kind of use new hydrophobic associated polymer flooding and carry
The method of high recovery rate.
Background technology
Hydrophobic associated polymer refers to a small amount of hydrophobic group (molar fraction < 5%) to be covalently bonded to water
The polymer formed on the molecular backbone of soluble polymer.Hydrophobic associated polymer water soluble, but
Aqueous solution can show the rheological property of uniqueness.Under the effect of hydrophobic association, reach to dredge during certain concentration
Water base group forms dynamic three-dimensional net structure by intermolecular association, thus forms the biggest oversubscription subchain
Aggregation, increases the hydrodynamic volume of polymer, and significantly increases the viscosity of solution.In high shear
Under effect, the dynamic physical cross-linked network structure that hydrophobic association is formed is destroyed, and solution viscosity declines, and shears
The association crosslinking that effect reduces or elimination post-consumer polymer chain is intersegmental re-forms, and viscosity will be recovered again.Just by
In the rheological equationm of state that it is unique in aqueous, hydrophobic associated polymer can be applied in many fields, than
As tertiary oil recovery improves recovery ratio, pharmacy, cosmetics, coating, water process and drag reducer etc..
The hydrophilic monomer that the hydrophobic associated polymer utilizing process for copolymerization to prepare is commonly used is acrylamide (AM),
Properly prepare the water-soluble polymer of high molecular due to AM and be widely used in each elephant as three times
The chemical pouring agent recovered the oil, after introducing hydrophobic group, viscosity improves further, and can form the micro-of solubilising crude oil
See micelle core, can reach more preferably raising recovery ratio effect.Conventional hydrophobic group is mainly carbon atom quantity
From the straight or branched alkane of 12-20, although can reach the effect of thickening, but due to its single property, no
It is beneficial to the intermolecular interaction from Molecular level study hydrophobic associated polymer, thus cannot form for hydrophobic
The improvement closing polymer is effectively instructed with exploitation offer.
Summary of the invention
It is an object of the invention to overcome the shortcoming and defect of above-mentioned prior art, use one to possess hydrophobicity
The fluorescent chromophore pyrene (Py) of matter replaces traditional alkane hydrophobic group, is connected to Polyethylene Glycol (PEG)
Strand two ends form most basic new hydrophobic association polymer.This polymer may be used for detection by quantitative
The hydrophobically modified rate of PEG chain segment, the microcosmic such as quantitative study hydrophobic polymer form in aqueous and composition
Parameter, thus be conducive to synthesis technique and operation principle and the effect etc. of hydrophobic associated polymer are entered one
The research of step and improvement.
The present invention provides a kind of hydrophobic associated polymer, and this hydrophobic associated polymer has knot shown in formula I
Structure,
Wherein, the molecular weight of Polyethylene Glycol segment is 200-20000；It is preferably 500-5000.
The present invention also provides for the preparation method of a kind of hydrophobic associated polymer, it is characterised in that the method includes
Following steps:
(1) in the presence of noble gas and the first organic solvent, under weak basic condition, utilize toluene sulphur
The terminal hydroxyl of Polyethylene Glycol is activated by acyl chlorides, obtains activated polyethylene glycol solution；
(2) in the presence of noble gas and the second organic solvent, pyrene methanol is mixed with sodium hydride, obtains pyrene
Methanol solution；
(3) the pyrene methanol solution that activated polyethylene glycol solution step (1) obtained and step (2) obtain
Hybrid reaction, obtains hydrophobic associated polymer shown in formula I；
Wherein, Polyethylene Glycol is 1:8-10 with the consumption mol ratio of pyrene methanol,
The molecular weight of Polyethylene Glycol is 200-20000；It is preferably 500-5000.
Due to the aromatic rings that the chemical constitution of Py is conjugation, more more compact than linear paraffin, hydrophobicity is higher, from
And can preferably reduce oil water interfacial tension and the effect of solubilising crude oil, improve the recovery ratio in oil field.
This polymer can also be used for the hydrophobically modified rate of detection by quantitative PEG chain segment, quantitative study hydrophobic polymer simultaneously
The micro-parameter such as form in aqueous and composition.Described quantitative study can be real by the method for Fluorescent Characterization
Existing, owing to pyrene is a kind of fluorescent chromophore, and fluorescence method has high Molecular Detection sensitivity, therefore may be used
To use steady-state fluorescence spectrographic method or Dynamic Fluorescence strength retrogression's method to distinguish the pyrene molecule of free state and by dredging
Water association association pyrene molecule together.
Accompanying drawing explanation
By combining accompanying drawing, disclosure illustrative embodiments is described in more detail, the disclosure above-mentioned
And other purpose, feature and advantage will be apparent from.
Fig. 1 shows the molecule shape that the hydrophobic associated polymer of the present invention interacts in aqueous with oil droplet
State schematic diagram.
Fig. 2 shows the preparation method of the hydrophobic associated polymer according to a kind of detailed description of the invention of the present invention
Chemical constitution schematic diagram.
Fig. 3 shows the gel chromatography figure of the hydrophobic associated polymer according to a kind of detailed description of the invention of the present invention,
A represents hydrophobic associated polymer product, and B represents PyMe.
Fig. 4 shows that the ultraviolet-visible of the hydrophobic associated polymer according to a kind of detailed description of the invention of the present invention divides
Light spectrogram.
Detailed description of the invention
The present invention provides a kind of hydrophobic associated polymer, and this hydrophobic associated polymer has knot shown in formula I
Structure,
Wherein, the molecular weight of Polyethylene Glycol segment is 200-20000, more preferably 500-5000.This gathers
Main chain in compound is hydrophilic segment, and two groups at two ends are hydrophobic group.
The present invention also provides for the preparation method of a kind of hydrophobic associated polymer, and the method comprises the following steps:
(1) in the presence of noble gas and the first organic solvent, under weak basic condition, utilize toluene sulphur
The terminal hydroxyl of Polyethylene Glycol (PEG) is activated by acyl chlorides (TsCl), obtains activated polyethylene glycol solution；Its
In, the effect of above-mentioned paratoluensulfonyl chloride is activated polyethylene glycol terminal hydroxyl, and its addition is to meet end
The effect of terminal hydroxy group activation is advisable, it is preferable that the mol ratio of PEG Yu TsCl is 1:1-2；First organic solvent
Consumption can be popular response solvent load, the weight ratio of such as PEG and the first organic solvent is 1:10-50；
(2) in the presence of noble gas and the second organic solvent, by pyrene methanol (PyMe) and sodium hydride (NaH)
Mixing, obtains pyrene methanol solution；The effect of sodium hydride is activation pyrene methanol, and its consumption can be this area
Conventional amount used, it is preferable that the weight ratio of PyMe Yu NaH is 8-12:1；The consumption of the second organic solvent is permissible
For popular response solvent load, it is preferable that the weight ratio of PyMe Yu DMF is 1:10-50.
(3) the pyrene methanol solution that activated polyethylene glycol solution step (1) obtained and step (2) obtain
Hybrid reaction, obtains hydrophobic associated polymer shown in formula I；
Wherein, described pyrene methanol is relative to PEG excess, pyrene methanol and the mol ratio of PEG in step (1)
For 8-10:1.
According to one preferred implementation of the present invention, in step (1), the condition of described activation includes: stirring,
Temperature is-4 to 5 DEG C, and the time is 12-20 hour.
According to one preferred implementation of the present invention, in step (1), described first organic solvent is preferably two
Chloromethanes.
According to one preferred implementation of the present invention, in step (1), described weak basic condition is preferably by adding
Enter triethylamine to realize.The above-mentioned addition bringing alkaline compound can be the amount of being routinely added to of this area,
Such as, PEG is 1:5-20 with the weight ratio bringing weakly alkaline compound.
According to one preferred implementation of the present invention, in step (2), described second organic solvent is preferably two
Methylformamide.
According to one preferred implementation of the present invention, in step (2), the method for described mixing includes, by institute
State pyrene methanol to be dissolved in described second organic solvent, after being completely dissolved, be slowly added to sodium hydride, stir 0.5-3
Hour.
According to one preferred implementation of the present invention, in step (3), the condition of described hybrid reaction includes:
Stirring, temperature is 50-80 DEG C, and the time is 12-20 hour.
According to one preferred implementation of the present invention, the method also includes carrying step (3) products therefrom
Pure, the method for described purification includes: rotary evaporation removes part reaction solution, is dropwise precipitated by surplus solution
In ether, being dissolved in methanol, be placed in dry ice after being filtered by precipitate, hydrophobic associated polymer product is analysed
It is collected by filtration after going out.This step preferably repeats 2-3 time to remove the impurity in product and unreacted chemistry examination
Agent.The Polyethylene Glycol product of the pyrene hydrophobically modified obtained can be dried under vacuum.
According to one preferred implementation of the present invention, step (1) also includes activated polyethylene glycol product is entered
Row purifies, and the method for described purification includes: rotary evaporation removes part reaction solution, by surplus solution dropwise
It is deposited in ether, repeats precipitation 2-3 time after being filtered by precipitate with the impurity and unreacted in removing product
Chemical reagent.Finally it is vacuum dried.
In the present invention, the polymer of synthesis is the PEG using Py to carry out hydrophobically modified.Fig. 1 shows the present invention
Hydrophobic associated polymer in aqueous with oil droplet interact molecular conformation schematic diagram.In polymer
Hydrophobic group can form intermolecular crosslinking thus increase viscosity, and hydrophobic group associates with oil droplet simultaneously,
Bulk remaining oil is gradually resolved into little oil droplet, finally crude oil molecule is gradually dissolved in formed microcosmic glue
In bundle core, reach the purpose of molten crude oil.
According to one detailed description of the invention of the present invention, the preparation method of hydrophobic associated polymer such as Fig. 2 reaction stream
Shown in journey figure, specifically include following steps:
(1) under conditions of 0 DEG C and noble gas, quantitative PEG is dissolved in dichloromethane (DCM),
The weight ratio of PEG Yu DCM is 1:20, adds excess to toluene by amount after adding appropriate triethylamine (TEA)
Sulfonic acid chloride (TsCl), the weight ratio of PEG Yu TEA be the weight ratio of 1:10, TEA and TsCl be 10:1,
Carry out magnetic agitation.Dropwise precipitate after reaction solution being removed part solution by rotary evaporation after 12-20 hour
In the ether of 0 DEG C, repeat precipitation process 2-3 time after being collected by filtration by precipitate with the impurity in removing product
With unreacted chemical reagent.Last product is vacuum dried at 40-50 DEG C.
(2) under conditions of noble gas, the pyrene methanol (PyMe) of excess is dissolved in dimethylformamide
(DMF) in, the weight ratio of PyMe Yu DMF is 1:15, gradually adds appropriate hydrogenation after being completely dissolved
Sodium (NaH), the weight ratio of PyMe Yu NaH is 10:1, carries out magnetic agitation in flask.After one hour
The product that the first step is reacted gained adds flask, and mixed solution is warming up to the 60-70 DEG C of bar at noble gas
Continue reaction 12-20 hour under part, subsequently reaction solution is removed part solution by rotary evaporation, dropwise sink
Form sediment in the ether of 0 DEG C.It is dissolved in methanol after being collected by filtration by precipitate, then methanol solution is positioned over-78 DEG C
Dry ice in, product is collected by filtration after separating out, and repeats this process 2-3 time with the impurity in removing product.Finally
Product be the PEG of Py hydrophobically modified, be vacuum dried at 40-50 DEG C.
Then utilizing nuclear magnetic resonance, NMR, gel chromatography, the means of testing such as ultraviolet-visible spectrophotometer characterizes poly-
After the parameters such as the molecular structure of compound forms, molecular weight, critical micelle concentration (CMC), investigate it and making
The indexs such as profit character when using for oil displacement agent, rheological property, flow conductivity energy and oil displacement efficiency.
Embodiment 1
(1) quantitative PEG2000 is dissolved in dichloromethane (DCM) under conditions of 0 DEG C and noble gas
In, the weight ratio of PEG Yu DCM is 1:20, adds excess to toluene by amount after adding triethylamine (TEA)
Sulfonic acid chloride (TsCl), the weight ratio of PEG Yu TEA be the weight ratio of 1:10, TEA and TsCl be 10:1,
Carry out magnetic agitation.Dropwise it is deposited in after reaction solution being removed part solution by rotary evaporation after 12 hours
In the ether of 0 DEG C, repeat after precipitate is collected by filtration precipitation process 2-3 time with the impurity that removes in product with
Unreacted chemical reagent.Last product is vacuum dried at 40 DEG C.
(2) under conditions of noble gas, the pyrene methanol (PyMe) of excess is dissolved in dimethylformamide
(DMF) in, the weight ratio of PyMe Yu DMF is 1:15, gradually adds appropriate hydrogenation after being completely dissolved
Sodium (NaH), the weight ratio of PyMe Yu NaH be the mol ratio of 10:1, PyMe and PEG be 9:1,
Flask carries out magnetic agitation.The product that the first step was reacted after one hour gained adds flask, will mix molten
Liquid is warming up to 60 DEG C and continues reaction 12 hours under conditions of noble gas, subsequently by reaction solution by rotating
Evaporation removes part solution, is dropwise deposited in the ether of 0 DEG C.Methanol it is dissolved in after being collected by filtration by precipitate,
Then being positioned in the dry ice of-78 DEG C by methanol solution, product is collected by filtration after separating out, and repeats this process 2-3
Secondary to remove the impurity in product.Last product is the PEG of Py hydrophobically modified, carries out at 40 DEG C
Vacuum drying, obtains hydrophobic associated polymer product A.
Utilizing nuclear magnetic resonance, NMR, gel chromatography, product A is characterized by ultraviolet-visible spectrophotometer.?
To gel chromatography as it is shown on figure 3, spectrophotometry spectrogram as shown in Figure 4.Gel chromatography figure shows
The molecular weight of product significantly increases compared with pyrene methanol, and without unreacted pyrene methanol completely in product,
By using the polystyrene sample correction of standard molecular weight can obtain the concrete molecular weight of product, (particular number takes
Certainly in n value).Spectrophotometry spectrogram shows the absorbance of a certain amount of product, passes through
Beer-Lambert law can calculate the concrete molecular weight (particular number depends on n value) of product, with PEG
The molecular weight of raw material is consistent with the molecular weight of pyrene methanol.The position of hydrogen atom in nmr spectrum display product,
Consistent with the end product molecular structure shown in Fig. 2.By various mensuration, it was demonstrated that obtain polymeric articles A.
Embodiment 2
(1) quantitative PEG500 is dissolved in dichloromethane (DCM) under conditions of-4 DEG C and noble gas
In, the weight ratio of PEG Yu DCM is 1:10, adds excess to toluene by amount after adding triethylamine (TEA)
Sulfonic acid chloride (TsCl), the weight ratio of PEG Yu TEA be the weight ratio of 1:5, PEG and TsCl be 1:1.5,
Carry out magnetic agitation.Dropwise it is deposited in after reaction solution being removed part solution by rotary evaporation after 20 hours
In the ether of 0 DEG C, repeat after precipitate is collected by filtration precipitation process 2-3 time with the impurity that removes in product with
Unreacted chemical reagent.Last product is vacuum dried at 40 DEG C.
(2) under conditions of noble gas, the pyrene methanol (PyMe) of excess is dissolved in dimethylformamide
(DMF) in, the weight ratio of PyMe Yu DMF is 1:10, gradually adds appropriate hydrogenation after being completely dissolved
Sodium (NaH), the weight ratio of PyMe Yu NaH be the mol ratio of 8:1, PyMe and PEG be 8:1.?
Flask carries out magnetic agitation.The product that the first step was reacted after one hour gained adds flask, will mix molten
Liquid is warming up to 50 DEG C and continues reaction 20 hours under conditions of noble gas, subsequently by reaction solution by rotating
Evaporation removes part solution, is dropwise deposited in the ether of 0 DEG C.Methanol it is dissolved in after being collected by filtration by precipitate,
Then being positioned in the dry ice of-78 DEG C by methanol solution, product is collected by filtration after separating out, and repeats this process 2-3
Secondary to remove the impurity in product.Last product is the PEG of Py hydrophobically modified, carries out at 40 DEG C
Vacuum drying, obtains hydrophobic associated polymer product B.
Embodiment 3
(1) quantitative PE5000 is dissolved in dichloromethane (DCM) under conditions of 5 DEG C and noble gas
In, the weight ratio of PEG Yu DCM is 1:50, adds excess to toluene by amount after adding triethylamine (TEA)
Sulfonic acid chloride (TsCl), the weight ratio of PEG Yu TEA be the weight ratio of 1:20, PEG and TsCl be 1:2,
Carry out magnetic agitation.Dropwise it is deposited in after reaction solution being removed part solution by rotary evaporation after 16 hours
In the ether of 0 DEG C, repeat after precipitate is collected by filtration precipitation process 2-3 time with the impurity that removes in product with
Unreacted chemical reagent.Last product is vacuum dried at 40 DEG C.
(2) under conditions of noble gas, the pyrene methanol (PyMe) of excess is dissolved in dimethylformamide
(DMF) in, the weight ratio of PyMe Yu DMF is 1:30, gradually adds appropriate hydrogenation after being completely dissolved
Sodium (NaH), the weight ratio of PyMe Yu NaH be the mol ratio of 12:1, PyMe and PEG be 10:1.
Magnetic agitation is carried out in flask.The product that the first step was reacted after one hour gained adds flask, will mixing
Solution is warming up to 80 DEG C and continues reaction 16 hours under conditions of noble gas, subsequently by reaction solution by rotation
Turn evaporation and remove part solution, be dropwise deposited in the ether of 0 DEG C.Methanol it is dissolved in after being collected by filtration by precipitate,
Then being positioned in the dry ice of-78 DEG C by methanol solution, product is collected by filtration after separating out, and repeats this process 2-3
Secondary to remove the impurity in product.Last product is the PEG of Py hydrophobically modified, carries out at 40 DEG C
Vacuum drying, obtains hydrophobic associated polymer products C.
Adopting and be measured the performance of hydrophobic associated polymer A-C with the following method, following assay method is
This area conventional determining method.
1, oil water interfacial tension performance study: based on simulating water, measures the oil of polymer under variable concentrations
Water interfacial tension change and viscosity B coefficent.It is gradually increased concentration until interfacial tension can reach ultralow
(1×10-3mN/m)。
2, anti-salt property evaluation: be separately added into a certain amount of Ca in the polymer solution of variable concentrations2+With
Mg2+, observe liquid situation of change (whether having the phenomenon such as precipitation, flocculation to occur), mensuration interfacial tension and molten
Fluid viscosity also contrasts with the data not adding ion.
3, emulsifiability research: aqueous solutions of polymers and crude oil are mixed according to different proportion and puts into dosing container
In, measure profit volume ratio after mix homogeneously, after standing a period of time, again measure profit volume ratio.
4, rheological behavior research: configuration higher concentration polymer solution, uses flow graph to be swept by shear rate
Retouch and frequency scan the viscosity of both of which research system and the situation of change of modulus.
5, the flow conductivity in porous media can be studied: the polymer solution configured is injected artificial core
Or fill out in sand tube, along journey inspection measuring pressure change.
6, Displacement Efficiency: investigated the oil displacement efficiency of polymer solution by rock core displacement test.
Comprising hydrophobic group in hydrophobic associated polymer, the formation that can flock together in aqueous is nonpolar
Microcosmic oleophylic environment, the most of component in oil is alkane or aromatic hydrocarbon structure, is dissolvable in water hydrophobic association
In the micro environment that polymer is formed, reach the effect of molten crude oil.Therefore, the most permissible based on this
Finding out, the intrinsic amphiphilic attribute of hydrophobic associated polymer can produce the effect of displacement of reservoir oil conventional surfactants,
I.e. it is attached on oil-water interfaces thus reduces oil water interfacial tension, in general can use hydrophobic associated polymer
Improve the recovery ratio in oil field.
Claims (10)
1. a hydrophobic associated polymer, it is characterised in that this hydrophobic associated polymer has shown in formula I
Structure,
Wherein, the molecular weight of Polyethylene Glycol segment is 200-20000.
Hydrophobic associated polymer the most according to claim 1, wherein, the molecular weight of Polyethylene Glycol segment
For 500-5000.
3. the preparation method of a hydrophobic associated polymer, it is characterised in that the method comprises the following steps:
(1) in the presence of noble gas and the first organic solvent, under weak basic condition, utilize toluene sulphur
The terminal hydroxyl of Polyethylene Glycol is activated by acyl chlorides, obtains activated polyethylene glycol solution；
(2) in the presence of noble gas and the second organic solvent, pyrene methanol is mixed with sodium hydride, obtains pyrene
Methanol solution；
(3) the pyrene methanol solution that activated polyethylene glycol solution step (1) obtained and step (2) obtain
Hybrid reaction, obtains hydrophobic associated polymer shown in formula I；
Wherein, Polyethylene Glycol is 1:8-10 with the consumption mol ratio of pyrene methanol,
The molecular weight of described Polyethylene Glycol is 200-20000；
Method the most according to claim 3, wherein, the molecular weight of described Polyethylene Glycol is 500-5000.
Method the most according to claim 3, wherein, in step (1), the condition bag of described activation
Include: stirring, temperature is-4 to 5 DEG C, and the time is 12-20 hour.
Method the most according to claim 4, wherein, in step (1), described first organic solvent
For dichloromethane.
7. according to the method described in any one in claim 4-6, wherein, in step (1), described weak
Alkalescence condition realizes by adding triethylamine.
Method the most according to claim 3, wherein, in step (2), described second organic solvent
For dimethylformamide.
9. according to the method described in claim 3,4 or 8, wherein, in step (2), described mixing
Method includes, is dissolved in described second organic solvent by described pyrene methanol, is slowly added to hydrogen after being completely dissolved
Change sodium, stir 0.5-3 hour.
Method the most according to claim 3, wherein, in step (3), the bar of described hybrid reaction
Part includes: stirring, temperature is 50-80 DEG C, and the time is 12-20 hour.
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| CN107817196A (en) * | 2017-10-31 | 2018-03-20 | 重庆科技学院 | A kind of method for judging that ternary hydrophobic associated polymer possesses drag reduction and increasing stick performance using microstructure |
| CN109575902A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | A kind of novel heavy crude thinner and preparation method thereof |
| CN109713157A (en) * | 2018-12-10 | 2019-05-03 | 云谷（固安）科技有限公司 | Display panel and preparation method thereof and display device |
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