CN106008839B - A kind of preparation method of fluorine-containing water-soluble dissaving polymer oil displacement agent - Google Patents
A kind of preparation method of fluorine-containing water-soluble dissaving polymer oil displacement agent Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer.This method comprises the following steps：(1) under an inert atmosphere, the cyclodextrin polymer of the end group hydroxyl is reacted with redox initiator, obtains reaction solution 1；(2) acrylamide monomer, fluorine-containing hydrophobic monomer, both sexes multijaw type hydrophobic function monomer are slowly added to successively into the reaction solution 1 and carries out graft copolymerization；(3) sodium hydroxide is added into the reaction system of step (2), reaction is hydrolyzed to get the polymer；The structural formula of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is as shown in formula I.The fluorine-containing water-soluble dissaving polymer oil displacement agent of the present invention is according to monomer type difference, series of products can be obtained, and building-up process normal temperature and pressure, step are simply amplified, water phase free radical polymerization green non-pollution, and with the thickening and anti-shear performance better than plain polypropylene amide polymer.
Description
Technical field
The present invention relates to a kind of preparation methods of fluorine-containing water-soluble dissaving polymer oil displacement agent, belong to high molecular material neck
Domain.
Background technology
It is poly- to drive one of the important technology that raising recovery efficiency technique is production and steady oil control water in the increasing the storage of oil field.Polymer flooding oil body
System is basis and the core of poly- drive technology, and application at present is as extensive for partially hydrolyzed polyacrylamide (PHPA) Type of Collective object.One side
In oil displacement process mechanical degradation, thermal degradation, microbial degradation and chemistry often occur for face, polyacrylamide polymer
Degradation etc., causes solution viscosity to decline, and oil displacement efficiency reduces, and wherein mechanical shearing degradation is particularly acute, and has been reported that display, is injected
The high speed shear of mechanical pump can be such that solution viscosity declines up to 70% or more, viscosity retention ratio only 30%.On the other hand, with technology
It is increasingly mature, the oil reservoir of poly- drive technology application also by a kind of oil reservoir, gradually to condition it is poor two, three classes oil reservoir expand, to poly-
Close also increasingly increasing for object stability.It designs and prepares the polymer with good thickening and anti-shear performance to improving polymer
Oil displacement efficiency has a very important significance.
Invention content
The object of the present invention is to provide a kind of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide Type of Collective oil displacement agent objects
Preparation method, fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer oil displacement agent provided by the invention have higher viscous
Degree and stronger anti-shear performance.
The preparation method of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer provided by the present invention, including such as
Lower step：
(1) under an inert atmosphere, the cyclodextrin polymer of end group hydroxyl is reacted with redox initiator, is reacted
Liquid 1；
(2) acrylamide monomer, fluorine-containing hydrophobic monomer, both sexes multijaw type is slowly added to successively into the reaction solution 1 to dredge
Water function monomer carries out graft copolymerization；
(3) sodium hydroxide is added into the reaction system of step (2), reaction is hydrolyzed to get the polymer；
The structural formula of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is as shown in formula I：
Wherein, core A is the cyclodextrin polymer of end group hydroxyl；
Arm B is to be dredged by acrylic amide-acrylic sodium random copolymer segment, poly- fluorine-containing hydrophobic segment and poly- both sexes multijaw type
The copolymer that water function segment is in turn connected to form, and the other end of the acrylic amide-acrylic sodium random copolymer segment
It is grafted on the core A.
The viscosity average molecular weigh of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is 3,000,000~1000
Ten thousand, such as 10,000,000；
The degree of hydrolysis of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is 20%~40%, such as
27%；
The core A, the acrylic amide-acrylic sodium random copolymer segment, described gather fluorine-containing hydrophobic segment and described
The mass ratio of poly- both sexes multijaw type hydrophobic function segment can be 1：220~350：5~15：6~18, concretely 1：280：8.4
~8.5：10.5~10.6,1：280：8.5：10.6 or 1：280：8.4：10.5.
The poly- fluorine-containing hydrophobic segment is polymerize to obtain by fluorine-containing hydrophobic monomer；
The fluorine-containing hydrophobic monomer can be hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, methacrylic acid 13
At least one of fluorine monooctyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate and trifluoroethyl methacrylate；
The poly- both sexes multijaw type hydrophobic function can be acrylic acid bromo shown in acrylic acid glycine betaine or formula III shown in formula II
Quaternary ammonium salt：
In formula II, n is the number between 1~8；
In formula III, p is the number between 11~17.
In above-mentioned preparation method, the cyclodextrin polymer of the end group hydroxyl is prepared according to the method included the following steps：
Under alkaline condition, cyclodextrin is reacted with epoxychloropropane to obtain the final product；
The cyclodextrin is beta-cyclodextrin.
In above-mentioned preparation method, the mass ratio of the cyclodextrin and the epoxychloropropane can be 1：0.2~0.3, tool
Body can be 1：0.24；
The temperature of the reaction can be 45~55 DEG C, and the time can be 5~8 hours, be reacted 6 hours such as at 50 DEG C；
The alkaline condition transfers in capable regulation and control by sodium hydrate aqueous solution, and the quality percentage of the sodium hydrate aqueous solution contains
Amount is 0.5~2%.
In above-mentioned preparation method, in step (1), the redox initiator can be selected from following at least one：Nitric acid
Cerium ammonium, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate and hydrogen peroxide；
The redox initiator participates in reacting in the form of its aqueous solution, in the aqueous solution, the redox
The mass percent concentration of initiator can be 0.5%~3%, concretely 1.5%；
The mass ratio of the redox initiator and the cyclodextrin polymer of the end group hydroxyl can be 1.5~3：1, specifically
Can be 2.4：1；
The temperature of the reaction can be 30~50 DEG C, and the time can be 30~60min, can specifically be reacted under conditions of 40 DEG C
40min。
In above-mentioned preparation method, in step (2), the acrylamide monomer is in the form of acrylamide monomer aqueous solution
It being added, the mass percent concentration of the acrylamide monomer aqueous solution can be 20~30%, concretely 25%；
The fluorine-containing hydrophobic monomer is added in the form of emulsion, the emulsion using lauryl sodium sulfate and water into
Row is prepared, and in the emulsion, the mass percent concentration of the fluorine-containing hydrophobic monomer can be 2~10%, and concretely 5%；
The both sexes multijaw type hydrophobic function monomer is added in the form of both sexes multijaw type hydrophobic function monomer solution, institute
The mass concentration for stating both sexes multijaw type hydrophobic function monomer solution can be 2~10%, concretely 5%.
In above-mentioned preparation method, the cyclodextrin polymer of the end group hydroxyl, described fluorine-containing is dredged the acrylamide monomer
The mass ratio of aqueous monomer and the both sexes multijaw type hydrophobic function monomer can be 1 successively：250~400：8~20：8~20, specifically
Can be 1：300：10：12；
The temperature of the graft copolymerization can be 45~75 DEG C, and the time can be 5~10h, such as anti-under conditions of 55 DEG C
Answer 6h.
In above-mentioned preparation method, in step (3), the additive amount of the sodium hydroxide can be the quality of acrylamide monomer
10%~20%, concretely 16.7%；
The temperature of the hydrolysis can be 90 DEG C~120 DEG C, and the time can be 1~3 hour, and it is small that 3 are carried out such as at 120 DEG C
When.
The fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer can be used as oil displacement agent for field polymers
In the displacement of reservoir oil, compound concentration ranging from 1200~3000mg/L, such as 1750mg/L.
The present invention has following beneficial aspects：
The fluorine-containing water-soluble dissaving polymer oil displacement agent of the present invention can obtain series of products, and close according to monomer type difference
At process normal temperature and pressure, step is simply amplified, water phase free radical polymerization green non-pollution, and with better than plain polypropylene
The thickening and anti-shear performance of amide polymer.
Description of the drawings
Fig. 1 is the thickening property figure of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer prepared by the present invention.
Fig. 2 is the anti-shear performance of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer prepared by the present invention
Figure.
Fig. 3 is the HNMR nuclear-magnetism figures of acrylic acid glycine betaine monomer.
Fig. 4 is the HNMR nuclear-magnetism figures of acrylic acid bromo quaternary ammonium salt monomer.
Specific implementation mode
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
HCD employed in following embodiments is prepared as steps described below：
25% NaOH solution and 15mL water of 5.0g β-CD, 7.5mL is added, stirs 1 hour, is slowly added dropwise very much
The epoxychloropropane of 1.0mL (1.18g) after being added dropwise, is stirred to react 6h, system 100mL third energetically at a temperature of 50 DEG C
Ketone precipitates, obtained white solid, the water of crude product 100mL：Ethyl alcohol=1:It is unreacted that 2 mixed solution cleans removing repeatedly
CD and propylene oxide class monomer, last white solid is with obtaining the product in a vacuum and drying environment HCD.
Acrylic acid glycine betaine monomer (n=1) employed in following embodiments is prepared by the following method：5.0mL is added
1, the 3- propane sultones containing 2.6mL are added dropwise in the acetone of monomer 2- (dimethylamino) ethylmethyl acrylate, 25.0mL
Acetone soln 10mL.After being added dropwise, 40 DEG C are warming up to, is stirred to react 10 hours, system generates a large amount of white solids, after cooling
Filtering, crude product are cleaned with the acetone of 20mL and remove unreacted monomer and sultones repeatedly, and last white solid is dry with vacuum
Dry to obtain product, HNMR nuclear-magnetism figures are as shown in Figure 3.
Acrylic acid bromo quaternary ammonium salt monomer (n=16) employed in following embodiments is prepared by the following method：It is added
The bromo n-octadecane containing 9.9g is added dropwise in the acetone of 5.0mL monomers 2- (dimethylamino) ethylmethyl acrylate, 40.0mL
Acetone soln 10mL.After being added dropwise, 40 DEG C are warming up to, is stirred to react 10-20 hours several, a large amount of white solids of system generation,
Cooled and filtered, crude product are cleaned with the acetone of 100mL and remove unreacted monomer and bromo n-octadecane repeatedly, and last white is solid
For body with obtaining the product in a vacuum and drying environment, HNMR nuclear-magnetism figures are as shown in Figure 4.
Dodecafluoroheptyl methacrylate employed in following embodiments is to avenge good fluorine chemistry of silicones Products, reagent contracting
DFBMA is write, CAS registration numbers are 2261-99-6.
Embodiment 1 prepares fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
By 30mg parent nucleus HCD, 95mL H2O is placed in three-necked flask, stirring and dissolving, is passed through nitrogen deoxygenation 45min, then
Ammonium ceric nitrate aqueous solution (72mg ammonium ceric nitrates are dissolved in 4.7mL water) is added under nitrogen protection, is stirred to react at 40 DEG C
30min is slowly added to acrylamide aqueous solution (9.0g acrylamides are dissolved in 27mL water), metering system into reaction solution successively
(300mg dodecafluoroheptyl methacrylate monomers are emulsifiable in 5.7mL water sour ten difluoro heptyl ester monomer emulsions, and emulsifier is
Dodecyl sodium sulfate 300mg), (360mg acrylic acid glycine betaine monomers are dissolved in 6.8mL water to acrylic acid glycine betaine monomer solution
In), it is then warming up to 55 DEG C and reacts 6 hours, 1.5g NaOH are added into reaction solution, are hydrolyzed 2 hours at 120 DEG C, dry,
Up to 1# water-soluble ultrabranching polymer, viscosity average molecular weigh is 10,000,000 or so, degree of hydrolysis 27%.
In 1# water-soluble ultrabranchings polymer manufactured in the present embodiment, HCD, acrylic amide-acrylic sodium random copolymer
The mass ratio of segment, ten difluoro heptyl ester segment of polymethylacrylic acid and polyacrylic acid glycine betaine segment is 1：280：8.5：10.6.
Embodiment 2 prepares fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
By 30mg parent nucleus HCD, 95mL H2O is placed in three-necked flask, stirring and dissolving, is passed through nitrogen deoxygenation 45min, then
Ammonium ceric nitrate aqueous solution (72mg ammonium ceric nitrates are dissolved in 4.7mL water) is added under nitrogen protection, is stirred to react at 40 DEG C
30min is slowly added to acrylamide aqueous solution (9.0g acrylamides are dissolved in 27mL water), metering system into reaction solution successively
(300mg dodecafluoroheptyl methacrylate monomers are emulsifiable in 5.7mL water sour ten difluoro heptyl ester monomer emulsions, and emulsifier is
Dodecyl sodium sulfate 300mg), (360mg acrylic acid bromo quaternary ammonium salt monomers are dissolved in acrylic acid bromo quaternary ammonium salt monomer aqueous solution
In 6.8mL water), it is then warming up to 55 DEG C and reacts 6 hours, 1.5g NaOH are added into reaction solution, it is small that 2 are hydrolyzed at 120 DEG C
When, drying is to get 2# water-soluble ultrabranching polymer, and viscosity average molecular weigh is 10,000,000 or so, degree of hydrolysis 27%.
In 2# water-soluble ultrabranchings polymer manufactured in the present embodiment, HCD, acrylic amide-acrylic sodium random copolymer
The mass ratio of segment, ten difluoro heptyl ester segment of polymethylacrylic acid and polyacrylic acid bromo quaternary ammonium salt segment is 1：280：8.4：
10.5。
The performance test of embodiment 3, fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
The performance of the 1# and 2# water-soluble ultrabranching polymer of the invention prepared is evaluated, evaluation method and result
As follows, wherein unaltered portion hydrolyzed polyacrylamide (i.e. " general polymer ") is industrialization product, and marque is
FP6050, is purchased from SNF companies of France, and structure is linear straight chain type.
(1) thickening property：A certain amount of polymer is taken, under 45 DEG C of water bath conditions, various concentration is prepared with deionized water
Polymer solution, the relationship of test polymer viscosity and concentration evaluates the thickening property of polymer, and the results are shown in Figure 1, and
It is compared with unaltered portion hydrolyzed polyacrylamide performance.
As shown in Figure 1：With the increase of concentration, the viscosity of the fluorine-containing dissaving polymer aqueous solutions of 1# and 2# dramatically increases,
As a concentration of 2000mg/L, 1# and the fluorine-containing dissaving polymer solution viscosities of 2# may be up to 120 and 135mPas, remote high
In the 65.8mPas of unaltered portion hydrolyzed polyacrylamide.
(2) anti-shear performance：It is the polymer solution of 1500mg/L to take aimed concn, with the 1 grade of shearing of Rhein blender
20s measures its apparent viscosity before and after polymeric shear at different temperatures, calculates viscosity retention ratio, and the results are shown in Figure 2,
And it is compared with unaltered portion hydrolyzed polyacrylamide performance.
As shown in Figure 2：In concentrated water, after 1# and the fluorine-containing dissaving polymer solution of 2# are clipped, viscosity retains
Rate is maintained at 55% or so, is higher than 40% or so of unaltered portion hydrolyzed polyacrylamide.
(3) Oil Displacing Capacity：It is the polymer solution of 1750mg/L, one grade of shearing 20s of Waring blenders to take aimed concn
It is spare afterwards.Use for laboratory artificial core, gas permeability are respectively 500,2000 and 4000mD from top to bottom.With Bohai Sea oil field
Simulation oil is compounded after comprehensive oil sample dehydration with kerosene, 65 DEG C of viscosity are 70mPas.First carry out water drive, it is aqueous up to 98% or more when
Turn polymer flooding.Polymer and water drive velocity are 3m/d, and polymer solution injected slurry volume is 0.3PV.The experimental results showed that 1#
With the oil-recovering rate of the fluorine-containing water-soluble dissaving polymer solution of 2# 10 are can be improved than unaltered portion hydrolyzed polyacrylamide
~15%.
In conclusion fluorine-containing water-soluble dissaving polymer provided by the invention is demonstrated by and gathers better than unaltered portion hydrolysis
The viscosifying of acrylamide, anti-shearing and Oil Displacing Capacity, are expected to be used for polymer displacement of reservoir oil.
Claims (1)
1. the preparation method of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer, includes the following steps：
(1) under an inert atmosphere, the cyclodextrin polymer of the end group hydroxyl is reacted with redox initiator, is reacted
Liquid 1；
Oxidant in the redox initiator is selected from following at least one：Ammonium ceric nitrate, potassium peroxydisulfate, ammonium persulfate,
Sodium peroxydisulfate and hydrogen peroxide；
The redox initiator participates in reacting in the form of its aqueous solution, in the aqueous solution, the Redox Initiator
The mass percent concentration of agent is 0.5%~3%；
The mass ratio of the redox initiator and the cyclodextrin polymer of the end group hydroxyl is 1.5~3：1；
The temperature of the reaction is 30~50 DEG C, and the time is 30~60min；
(2) acrylamide monomer, fluorine-containing hydrophobic monomer, the hydrophobic work(of both sexes multijaw type are slowly added to successively into the reaction solution 1
It can monomer progress graft copolymerization；
Cyclodextrin polymer, the acrylamide monomer, the fluorine-containing hydrophobic monomer and the both sexes multijaw of the end group hydroxyl
The mass ratio of type hydrophobic function monomer is followed successively by 1：250~400：8~20：8~20；
The temperature of the graft copolymerization is 45~75 DEG C, and the time is 5~10h；
The acrylamide monomer is added in the form of acrylamide monomer aqueous solution, the matter of the acrylamide monomer aqueous solution
It is 20~30% to measure percent concentration；
The fluorine-containing hydrophobic monomer is added in the form of emulsion, and the emulsion is matched using lauryl sodium sulfate and water
It makes, in the emulsion, the mass percent concentration of the fluorine-containing hydrophobic monomer is 2~10%；
The both sexes multijaw type hydrophobic function monomer is added in the form of both sexes multijaw type hydrophobic function monomer solution, and described two
Property multijaw type hydrophobic function monomer solution mass concentration can be 2~10%；
(3) sodium hydroxide is added into the reaction system of step (2), reaction is hydrolyzed to get the polymer；
The additive amount of the sodium hydroxide is the 10%~20% of the quality of acrylamide monomer；
The temperature of the hydrolysis is 90 DEG C~120 DEG C, and the time is 1~3 hour；
The structural formula of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is as shown in formula I：
Core A：● arm B：
Wherein, core A is the cyclodextrin polymer of end group hydroxyl；
The cyclodextrin polymer of the end group hydroxyl is prepared according to the method included the following steps：
Under alkaline condition, cyclodextrin is reacted with epoxychloropropane to obtain the final product；
The cyclodextrin is beta-cyclodextrin；
The mass ratio of the cyclodextrin and the epoxychloropropane is 1：0.2~0.3；
The temperature of the reaction is 45~55 DEG C, and the time is 5~8 hours；
Arm B is by acrylic amide-acrylic sodium random copolymer segment, gathers fluorine-containing hydrophobic segment and the poly- hydrophobic work(of both sexes multijaw type
The copolymer that energy segment is in turn connected to form, and the other end grafting of the acrylic amide-acrylic sodium random copolymer segment
Onto the core A；
The core A, the acrylic amide-acrylic sodium random copolymer segment, the poly- fluorine-containing hydrophobic segment and described poly- two
Property multijaw type hydrophobic function segment mass ratio be 1：220~350：5~15：6~18；
The poly- fluorine-containing hydrophobic segment is polymerize to obtain by fluorine-containing hydrophobic monomer；
The fluorine-containing hydrophobic monomer be hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, ten trifluoro monooctyl ester of methacrylic acid,
At least one of dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate and trifluoroethyl methacrylate；
The poly- both sexes multijaw type hydrophobic function is acrylic acid bromo quaternary ammonium salt shown in acrylic acid glycine betaine or formula III shown in formula II：
In formula II, n is the number between 1~8；
In formula III, p is the number between 11~17；
The viscosity average molecular weigh of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is 3,000,000~10,000,000；
The degree of hydrolysis of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is 20%~40%.
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