CN106117427B - A kind of preparation method of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer - Google Patents
A kind of preparation method of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer 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 end group hydroxyl is reacted with redox initiator, obtains reaction solution 1；(2) acrylamide monomer, fluorine-containing hydrophobic monomer, amphoteric ion choline 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 ultrabranching multi-arm polyacrylamide polymers synthesis technology of the present invention is simply amplified, water phase free radical polymerization green non-pollution, the product of Series Molecules amount and structure can be obtained, and its thickening and shear resistant are significantly better than that conventional linear polyacrylamide polymer, have field use foreground.
Description
Technical field
The present invention relates to a kind of preparation methods of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer, belong to high
Molecular material field.
Background technology
Polymer displacement of reservoir oil tech is one of the technical way that oil field development improves oil recovery factor, has good increasing
Produce stable yields effect.The excellent thickening property of polymer can reduce water phase permeability and water-oil mobility ratio, expand sweep efficiency, reduce
Residual oil saturation, to improve oil recovery factor.
Partially hydrolyzed polyacrylamide (PHPA) Type of Collective object or its modified product are the polymer displacement of reservoir oil being most widely used at present
Agent.Although the extensive use of polymer, polymer is gradually spilt cruelly in the defect of application process.Polymer is in preparation (stirring
Device), conveying (pump, pipeline, valve), inject (casing borehole) and flow through during pore media by strong mechanical shear
It cuts so that molecular chain rupture, molecular structure are destroyed, and molecular chain length reduces, drastically so as to cause polymer solution viscosity
It reduces, oil displacement efficiency declines.Polymer is carried out structure and composition to be modified being the main means for improving polymer anti-shear performance.
Invention content
The object of the present invention is to provide a kind of preparation sides of fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
Method, the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer prepared by the present invention have higher viscosity 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, amphoteric ion choline are slowly added to successively into the reaction solution 1
Class 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 by acrylic amide-acrylic sodium random copolymer segment, gathers fluorine-containing hydrophobic segment and poly- amphoteric ion choline
The copolymer that function segment is in turn connected to form, and another termination of the acrylic amide-acrylic sodium random copolymer segment
On branch to the core A.
The viscosity average molecular weigh of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer can be 3,500,000~1000
Ten thousand, such as 10,000,000；
The degree of hydrolysis of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer can be 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- amphoteric ion choline function segment can be 1：200~350：5~18：6~20, concretely 1：300：8.2~
8.3：7.2~12.4,1：300：8.3：7.2 or 1：300：8.2：12.4.
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- amphoteric ion choline function segment is polymerize to obtain by amphoteric ion choline function monomer；
The amphoteric ion choline function monomer can be shown in methylacryloyl phosphocholine or formula III shown in formula II
Methacryl yl carboxylic acid choline：
In formula III, n is the number between 1~3.
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 0.5%；
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 2：1；
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 2~15%, and concretely 5%；
The amphoteric ion choline function monomer is added in the form of amphoteric ion choline function monomer aqueous solution, institute
The mass concentration for stating amphoteric ion choline function monomer aqueous solution can be 2~15%, 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 amphoteric ion choline function monomer can be 1 successively：220~420：9~25：7~23, specifically
Can be 1：320：18：15；
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 is the quality of acrylamide monomer
10%~20%, concretely 15%；
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.
Fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer prepared by the present invention can be used as oil displacement agent and be used for oil
In the polymer displacement of reservoir oil of field, compound concentration range can be 1200~3000mg/L, such as 1750mg/L.
The present invention has following beneficial aspects：
The fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymers synthesis technology of the present invention is simply amplified, and water phase is certainly
Green non-pollution is polymerize by base, the product of Series Molecules amount and structure can be obtained, and its thickening and shear resistant are significantly better than that often
Gage line polyacrylamide polymer has field use foreground.
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.
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：
The NaOH solution and 15mL water of the 25wt% 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.
Acryloyl group phosphorylcholine-monomer employed in following embodiments is the production of drug Co., Ltd of Sigma of the U.S.
Product, reagent abbreviation MPC, CAS accession number is 67881-98-5.
The product of drug Co., Ltd of Sigma of the acryloyl group carboxylic acid choline U.S. employed in following embodiments, reagent
Abridge CBMA, and CAS accession number is 24249-95-4, wherein n=1.
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 25mg 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 (50mg ammonium ceric nitrates are dissolved in 10mL water) is added under nitrogen protection, 30min is stirred to react at 40 DEG C,
It is slowly added to acrylamide aqueous solution (8.0g acrylamides are dissolved in 24mL water), methacrylic acid 12 successively into reaction solution
(450mg dodecafluoroheptyl methacrylate monomers are emulsifiable in 8.6mL water fluorine heptyl ester monomer emulsion, and emulsifier is dodecane
Base sodium sulfonate 450mg), acryloyl group ethyoxyl phosphorylcholine-monomer aqueous solution (375mg acryloyl group ethyoxyl phosphocholine lists
Body is dissolved in 7.1mL water), it is then warming up to 55 DEG C and reacts 6 hours, 1.2g NaOH, the water at 120 DEG C are added into reaction solution
Solution 2 hours, drying is to get the fluorine-containing water-soluble ultrabranching multiarm polymers of 1#, and viscosity average molecular weigh is 10,000,000 or so, degree of hydrolysis
It is 27%.
In the fluorine-containing water-soluble ultrabranching multiarm polymers of 1# manufactured in the present embodiment, HCD, acrylic amide-acrylic sodium without
The mass ratio for advising copolymer segment, ten difluoro heptyl ester segment of polymethylacrylic acid and polypropylene acyl group phosphocholine segment is 1：
300：8.3：7.2.
Embodiment 2, fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
By 25mg 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 (50mg ammonium ceric nitrates are dissolved in 10mL water) is added under nitrogen protection, 30min is stirred to react at 40 DEG C,
It is slowly added to acrylamide aqueous solution (8.0g acrylamides are dissolved in 24mL water), methacrylic acid 12 successively into reaction solution
(450mg dodecafluoroheptyl methacrylate monomers are emulsifiable in 8.6mL water fluorine heptyl ester monomer emulsion, and emulsifier is dodecane
Base sodium sulfonate 450mg), (375mg acrylic acid carboxylic acid choline monomers are dissolved in 7.1mL water to acrylic acid carboxylic acid choline monomer solution
In), be then warming up to 55 DEG C reaction 6h, into reaction solution be added 1.2g NaOH, hydrolyze 2 hours at 120 DEG C, dry to get
The fluorine-containing water-soluble ultrabranching multiarm polymers of 2#, viscosity average molecular weigh are 10,000,000 or so, degree of hydrolysis 27%.
In the fluorine-containing water-soluble ultrabranching multiarm polymers of 2# manufactured in the present embodiment, HCD, acrylic amide-acrylic sodium without
The mass ratio for advising copolymer segment, ten difluoro heptyl ester segment of polymethylacrylic acid and polyacrylic acid carboxylic acid choline segment is 1：300：
8.2：12.4.
The performance test of embodiment 3, fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer
Performance progress to 1# and the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymers of 2# prepared by the present invention
Evaluation, evaluation method and result are as follows, and wherein unaltered portion hydrolyzed polyacrylamide (i.e. " general polymer ") is industry
Change product, marque 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 1# and the fluorine-containing water-soluble ultrabranching multiarm polymers aqueous solutions of 2#
Dramatically increase, as a concentration of 2000mg/L, 1# and 2# water-soluble ultrabranching aqueous polymer solution viscosities may be up to 113.6 and
129.3mPas is far above 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.
As shown in Figure 2, in concentrated water, the fluorine-containing water-soluble ultrabranching multiarm polymers solution of 1# and 2# is clipped
Afterwards, viscosity retention ratio is maintained at 58% 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# 11 are can be improved than unaltered portion hydrolyzed polyacrylamide
~13%.
In conclusion fluorine-containing water-soluble ultrabranching multiarm polymers provided by the invention are demonstrated by better than unaltered portion water
Thickening, salt resistance, the anti-shearing and Oil Displacing Capacity for solving polyacrylamide, can be applied to 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 end group hydroxyl is reacted with redox initiator, obtains reaction solution 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, amphoteric ion choline work(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 amphoteric ion of the end group hydroxyl
The mass ratio of choline function monomer is followed successively by 1：220~420：9~25：7~23；
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 2~15%；
The amphoteric ion choline function monomer is added in the form of amphoteric ion choline function monomer aqueous solution, and described two
Property ion choline function monomer aqueous solution mass concentration can be 2~15%；
(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 poly- amphoteric ion choline function
The copolymer that segment is in turn connected to form, and the other end of the acrylic amide-acrylic sodium random copolymer segment is grafted to
On 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 ion choline function segment mass ratio be 1：200~350：5~18：6~20；
The poly- fluorine-containing hydrophobic segment is polymerize to obtain by the 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- amphoteric ion choline function segment is polymerize to obtain by the amphoteric ion choline function monomer；
The amphoteric ion choline function monomer is glycine betaine shown in methylacryloyl phosphocholine or formula III shown in formula II
Class monomer：
In formula III, n is the number between 1~3；
The viscosity average molecular weigh of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is 3,500,000~10,000,000；
The degree of hydrolysis of the fluorine-containing water-soluble ultrabranching multi-arm polyacrylamide polymer is 20%~40%.
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| EP2604636A1 (en) * | 2011-12-15 | 2013-06-19 | Stichting Dutch Polymer Institute | Enhanced oil recovery using polyacrylamides |
| CN104844760A (en) * | 2015-05-18 | 2015-08-19 | 中国海洋石油总公司 | Water-soluble hyper-branched polymer oil displacement agent and preparation method thereof |
| CN104877079A (en) * | 2015-05-18 | 2015-09-02 | 中国海洋石油总公司 | Water-soluble hyperbranched multi-arm polyacrylamide polymer and preparation method thereof |
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2016
- 2016-06-23 CN CN201610464323.5A patent/CN106117427B/en active Active
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|---|---|---|---|---|
| CN101519473A (en) * | 2009-03-31 | 2009-09-02 | 山东大学 | Method for preparing fluorine-containing modified amphoteric water-soluble polymer |
| EP2604636A1 (en) * | 2011-12-15 | 2013-06-19 | Stichting Dutch Polymer Institute | Enhanced oil recovery using polyacrylamides |
| CN104844760A (en) * | 2015-05-18 | 2015-08-19 | 中国海洋石油总公司 | Water-soluble hyper-branched polymer oil displacement agent and preparation method thereof |
| CN104877079A (en) * | 2015-05-18 | 2015-09-02 | 中国海洋石油总公司 | Water-soluble hyperbranched multi-arm polyacrylamide polymer and preparation method thereof |
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