CN106866881A - Hydrophobic association acrylamide copolymer emulsion and preparation method thereof - Google Patents
Hydrophobic association acrylamide copolymer emulsion and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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Abstract
The present invention relates to a kind of hydrophobic association acrylamide copolymer emulsion and preparation method thereof, mainly solve more than hydrophobic associated polymer in the prior art using micella or aqueous solution polymerization, the tediously long complicated, energy consumption of equipment, technique is higher, and the displacement of reservoir oil construction for the particularly marine oil reservoir of Oil Field application brings some difficult problems.The present invention uses inverse emulsion polymerization method, using the nonionic surfactant of commercialization as emulsifying agent in oil-water system, by the addition speed for controlling initiator, obtain solid content hydrophobic associated polymer emulsion higher, can rapid dispersion in water, convenient scene online injection carries out displacement of reservoir oil operation, use in terms of emulsion parts by weight, comprising 10~50 parts of oil phase, 1~10 part of emulsifying agent and assistant for emulsifying agent, the technical scheme of 40~80 parts of the water phase containing comonomer, preferably resolve the problem, can be used for the scene application that terrestrial facies or the marine displacement of reservoir oil etc. improve recovery ratio.
Description
Technical field
The present invention relates to a kind of hydrophobic association acrylamide copolymer emulsion and preparation method thereof.
Background technology
Hydrophobic associated water-soluble polymer refers to a small amount of hydrophobic grouping one on polymer hydrophilicity macromolecular chain
Class water-soluble polymer.Due to the SOLUTION PROPERTIES such as the thickening of its uniqueness, salt resistance, anti-shearing, as new polymers
Oil displacement agent is applied to harsh oil reservoir development and has a good application prospect.
It is difficult hydrophilic monomer because hydrophilic monomer is larger with hydrophobic monomer polarity spectrum, therefore in building-up process
It is sufficiently mixed with hydrophobic monomer.Typically there are two kinds of thinkings in the synthesis of hydrophobic associated polymer, one kind is will be hydrophobic
Monomer is directly connected to the copolymerization method on water-soluble polymer chain, and product is mainly the copolymer of acrylic amide, separately
A kind of macromolecular reaction method for being first combined polymerization and then being functionalized again, is mainly used in the hydrophobically modified of macromolecular.
With the development of research, such as emulsion polymerization, active ion polymerization, radical polymerization, super is have also appeared
The new method such as sonic method and supercritical CO 2 medium method.Again with micell polymerization method to prepare macromolecule in copolymerization method
A kind of common method of hydrophobic polymer is measured, this method dissolves hydrophobic list by adding surfactant in water
Body, enters hydrophobic monomer and is polymerized in the micella that surfactant molecule is formed.McCormick et al.
(Mccormick C L,Johnson C B.Water-soluble copolymers.29.Ampholytic copolymers
of sodium 2-acrylamido-2-methylpropanesulfonate with(2-acrylamido-2-methylpropyl)
dimethylammonium chloride:solution properties[J].Macromolecules,1988,21(3):
Micell polymerization method 694-699.) is utilized, with N- alkyl acrylamides as hydrophobic monomer, has synthesized bipolymer
AM/N- alkyl acrylamides.It was found that hydrophobic grouping carbochain is more long, the water solubility of bipolymer is poorer, and with
The increase of hydrophobic monomer ratio, the apparent viscosity of polymer solution becomes big to the dependence of solution concentration.Guo Ruiwei
(micell polymerization method of hydrophobically modified polyacrylamide prepares and characterizes progress [J] chemical industry progress 2006,25 (1)：
25~30) the detailed overview progress of the micell polymerization method of hydrophobic associated polymer HMPAM in recent years, is situated between
Continued the principle and synthesis condition of micell polymerization method, including monomer, surfactant, initiator, polymerization temperature and
The characterizing method of the relative molecular mass and composition of polymerization time and HMPAM.Zhong Chuanrong (hydrophobic associations third
The synthesis of acrylamide copolymer and performance and in the solution research [D] the Chengdu of structural form：Sichuan University, 2004
Year), Jiang Liding (synthesis of new family's hydrophobic association polyacrylamide and its rheological property [D] the Taiyuan of the aqueous solution：
Northcentral University, 2007), Feng Zhiqiang (research [J] of hydrophobic association type AM/DBA copolymers used for tertiary oil recovery should
With chemistry 2004, (21) 6:556~560) etc. hydrophobic associated polymer is all prepared for using micellar copolymerization method.Feng Ru
Gloomy (CN1793189A), Zhong Chuanrong (CN101293944A, CN 101148582A), Ou Yangjian
(CN1317501), hole beautiful jade etc. (CN1528734, CN1528797) and BASF AG (CN102471415
103328602 A of A, CN of A, CN 103339220) etc. relate to hydrophobic associated polymer glue in the patent delivered
The synthesis of beam method.
In micella copolymerization, with molecular state it is soluble in water be water-soluble monomer, be solubilized into micella or and surface
What activating agent formed mixed micelle is hydrophobic monomer.Mean concentration in system is far below hydrophobic monomer in micella microcell
Local concentration.Therefore, micellar copolymerization is different with homogeneous polymerization, the direct shadow of Microinhomogeneity of this monomer distribution
The Copolymerization behavior between two class monomers is rung, and has affected the structure of the hydrophobic associated polymer for ultimately forming.Although
Micellar copolymerization is to prepare the conventional polymerization of hydrophobic associated polymer, but needs to add when adopting this method polymerization
Substantial amounts of surfactant (such as SDS) makes hydrophobic monomer solubilising in micella, but adds in the course of the polymerization process a large amount of
Surfactant have significant impact to the association behavior of polymer, these surfactants in polymerizate with
Hydrophobic segment interacts, and deteriorates the performance of hydrophobic associated water-soluble polymer.If removing the work of these surfaces
Property agent, can increase separate and purifying etc. last handling process complexity.In order to simplify last handling process and strengthen polymerization
The dissolubility of thing, can be using the inherently hydrophobic monomer with surface-active.This kind of monomer contains hydrophobic group simultaneously
Group and hydrophilic radical, surfactant need not be it is possible to additionally incorporate in combined polymerization, can directly use traditional free radical
Aqueous solution polymerization, and can make that hydrophobic monomer is highly unordered to be irregularly introduced into copolymer.Xia Yanmin etc.
Be relate in the patent of (CN201310435308.4, CN201310435350.6, CN201310435366.7)
Aqueous process prepares the hydrophobic associated polymer of resisting high temperature, high salt, and still needing to dry composition during product use sets
It is standby, can cause certain difficulty for offshore applications.
For problem above, the preparation for carrying out hydrophobic associated polymer using emulsion polymerization is increasingly taken seriously.
Emulsion method has more ripe mechanism of polymerization, but for water-soluble monomer, typically using antiphase emulsifiable method
To prepare polymer, mechanism of polymerization has larger difference with positive phase emulsion, at present relatively generally acknowledge have Micellar nucleation mechanism,
Monomer droplet mechanism of nucleation and two kinds of mechanism are simultaneously deposited.Abroad, water-soluble polymer latex (emulsion) product has been
Through carrying out industrialized production and being widely used in many fields, and the reversed-phase emulsion of domestic industry water solubility latex is produced
Product not yet turn into main flow.Inverse emulsion polymerization water-soluble monomer is provided can have high gathering as conventional emulsion polymerization
Close the polymerization of speed and relative molecular mass product high.Additionally, inverse emulsion polymerization can also make water-soluble monomer
Effectively be polymerized powdering or milky product, and polymerizing condition relaxes, and side reaction is few, convenient use, therefore anti-phase breast
Liquid polymerization is rapidly developed as a supplement of emulsion polymerization.Existing some researchers in the country are ground
Study carefully, such as Zhao Yong (synthesis of hydrophobically associated polyacrylamide and its performance study [J] high scores in reverse micro emulsion
Sub- journal, 2000,1 (5)：Hydrophobically associated polyacrylamide 550-553.) is synthesized in Reverse Microemulsion System
(HAPAM) HAPAM for, determining its water soluble energy and being prepared with classical micellar polymerization compares.Knot
Fruit shows that the HAPAM of conversed phase micro emulsion copolymerization method synthesis has more superior salt tolerant and anti-shear performance, and this is main
Because on its macromolecular chain hydrophobic comonomer in random distribution rather than in block distributed, its hydrophobic molecule chain with
It is intermolecular rather than based on Intramolecular association.In Hongjiang etc., (reverse microemulsion process synthesizes the Heat Resistant and Salt Tolerant Polymer displacement of reservoir oil
Agent [J] Chemical Engineers, 2009,10:47-50), Feng Yujun etc. (CN 101343339, CN 101372525A)
Emulsifier content is higher during hydrophobic associated polymer, but microemulsion has been obtained with reverse microemulsion process, for being produced into
This and later stage application may bring some problems, and Yuan Junhai (A of CN 102453191) is contained with control hydrophobic monomer
The preparation method that amount increases the inverse emulsion polymer of salt-resistance has obtained hydrophobic associated polymer, when hydrophobic monomer is
When 0.6%, the polymer solution of 2000mg/L obtains viscosity higher in the NaCl solution that concentration is 10%
Retention rate, but without dated test temperature.
The present invention is polymerized for acrylamide hydrophobically associating to antiphase emulsifiable method comparing various polymerizations
The synthesis of thing, structural characterization and properties are carried out extensively, on the basis of in-depth study, there is provided a kind of hydrophobic to form
Acrylamide copolymer emulsion and preparation method thereof is closed, mainly solves to adopt hydrophobic associated polymer in the prior art more
With micella or aqueous solution polymerization, the process such as need to cut, crush, dry, crushing again through blob of viscose and obtaining dry powder formulations,
One is that the more tediously long complicated, energy consumption of production procedure is higher, two be hydrophobic associated polymer dry composition need it is special
Equipment, need to be through processes such as high-speed stirred dissolving, curings, this drive for the particularly marine oil reservoir of Oil Field application
Oil construction brings some difficult.The present invention uses inverse emulsion polymerization method, using commercialization in oil-water system
Nonionic surfactant as emulsifying agent, by controlling the addition speed of initiator, obtain solid content it is higher dredge
Water associative polymer emulsion, in water can rapid dispersion, convenient scene online injection carries out displacement of reservoir oil operation.With emulsion
Parts by weight meter, the oil phase comprising 10~50 parts, 1~10 part of emulsifying agent and assistant for emulsifying agent, 40~80 parts containing copolymerization
The technical scheme of the water phase of monomer, preferably resolves the problem, obtained hydrophobic association acrylamide copolymer
The scene that emulsion directly or after being compounded with other oil field chemicals improves recovery ratio for road phase or the marine displacement of reservoir oil etc. should
With.
The content of the invention
One of technical problems to be solved by the invention are used hydrophobic associated polymer present in prior art more
Micella or aqueous solution polymerization, the process such as need to cut through blob of viscose, crush, dry, crushing again and obtaining dry powder formulations, one
It is that the more tediously long complicated, energy consumption of production procedure is higher, two is that the dry composition of hydrophobic associated polymer needs special setting
It is standby, need to be through processes such as high-speed stirred dissolving, curings, this displacement of reservoir oil for the particularly marine oil reservoir of Oil Field application
Construction brings some difficult.A kind of hydrophobic association acrylamide copolymer emulsion is provided, product solid content is higher,
Disperse rapidly in water, can preferably solve the above problems.
The two of the technical problems to be solved by the invention are to provide a kind of hydrophobic association solved in one of technical problem
The preparation method of acrylamide copolymer emulsion.
The three of the technical problems to be solved by the invention are to provide a kind of hydrophobic association third for solving one of technical problem
Application of the acrylamide polymer emulsion in tertiary oil production in oil field.
One of in order to solve the above-mentioned technical problem, the present invention is as follows using following technical scheme：A kind of hydrophobic association third
Acrylamide polymer emulsion and preparation method thereof, the emulsion system is obtained by inverse emulsion polymerization method；With weight
Number meter, described copolymerization component is included：
A) 10~50 parts of oil phase；
B) 1~10 part of emulsifying agent and assistant for emulsifying agent；
C) 40~80 parts of the water phase containing comonomer.
In above-mentioned technical proposal, the oil-dissolving solvent is selected from aliphatic hydrocarbon, aromatic hydrocarbons, halogenated hydrocarbons etc., such as toluene, neighbour
One kind or many in dimethylbenzene, isomery paraffin, isoparaffin, thiacyclohexane, heptane, octane, white oil and kerosene etc.
Mixture is planted, consumption accounts for the 10~50% of whole system.
In above-mentioned technical proposal, the emulsifying agent is by oil soluble surfactant and water soluble surfactant active's compounding
Into mostly nonionic emulsifier, such as polyoxyethylene carboxylate, alkyl acid APEO, fatty alcohol polyoxy
Vinethene etc., the mass ratio of two class surfactants is 20:1~2:1 so that hydrophilic lipophilic balance is between 4~7；
In order to increase the stability of system, can also add some lower molecular weights polymer such as PVP,
Used as assistant for emulsifying agent, both account for the 1~10% of whole system by total consumption to polyvinyl alcohol etc..
In above-mentioned technical proposal, described comonomer includes following components：
A) nonionic water-soluble monomers of 5~99.9w.t.%；
B) anionic monomer or/and cationic monomer of 0~50w.t.%；
C) hydrophobic monomer of 0.1~10w.t.%.
In above-mentioned technical proposal, described nonionic water-soluble monomers are selected from water-soluble vinyl monomer, the ethene
Base monomer is selected from least one in the monomer shown in formula (1), formula (2), formula (3) or formula (4)：
Wherein, R1、R4、R5、R6It is independently chosen from hydrogen, C1~C4Alkyl；R2、R3Be independently chosen from hydrogen,
C1~C4Alkyl or hydroxyl substituted alkyl group.
In above-mentioned technical proposal, described anionic monomer be selected from 2- acrylamide-2-methylpro panesulfonic acids, acrylic acid,
Methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylbenzenesulfonic acid, vinyl sulfonic acid, second
In alkenyl phosphonic acid, allyl sulphonic acid, allyl phosphonic acid and/or its water-soluble alkali, alkaline-earth metal and ammonium salt extremely
Few one kind；Described cationic monomer is selected from dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl chlorination
In ammonium, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides
It is at least one.
In above-mentioned technical proposal, described hydrophobic monomer is Long carbon chain ionic surfactant monomer, esters of acrylic acid
One or more mixtures in hydrophobic monomer, the hydrophobic monomer containing many membered cyclic compounds.Further carbon wherein long
Chain ionic surfactant monomer can be cation or cationic, and carbon chain lengths are 8~22, such as vinyl carbochain number
It is 8~18 acrylamide azanyl sodium sulfonate, the allyl alkyl ammonium chloride that vinyl carbochain number is 12~22 etc.,
The atomic number of alkyl carbon of esters of acrylic acid can be 4~18, and many yuan of rings in many membered cyclic compounds can be five yuan or six
Unit.
In above-mentioned technical proposal, the initiator can be all kinds of initiators well-known to those skilled in the art, this
Art personnel can carry out conventional selection, for example but do not limit selected from water-soluble oxide, water soluble oxidized-
The composition of one or more in reduction system, azo compound etc.；Wherein water-soluble oxide is selected from over cure
The persulfates such as sour potassium, sodium peroxydisulfate, ammonium persulfate, water soluble oxidized-reduction system is selected from above-mentioned water-soluble over cure
The compound of the composition such as hydrochlorate and water-soluble reducing agent such as sulphite or acid sulphite, azo compound choosing
From azo diisobutyl amidine hydrochloride, 2,2'- azos [2- (2- imidazoline -2- bases) propane] dihydrochloride, the isobutyl of azo two
Nitrile, ABVN etc..
In order to solve the above-mentioned technical problem two, the present invention is as follows using technical scheme：A kind of acrylic amide is hydrophobic
The preparation method of associative polymer emulsion, including following steps：
A) comonomer is dissolved in the water and obtains water phase I；
B) add assistant for emulsifying agent to be well mixed in above-mentioned water phase I, and pH value is adjusted to 5~9, obtain water phase II；
C) it is oil phase and emulsifier for mixing is uniform, as continuous phase；
D) by water soluble starter with finite concentration wiring solution-forming soluble in water, by oil-soluble initiator with a small amount of second
The dissolving such as alcohol or ethyl acetate is made into certain density solution；
E) by continuous phase put into reactor in and open stirring, by water phase II point, 2~3 batches are slowly added to continuous phase,
And high-speed stirred is emulsified to uniform；Reactor temperature is controlled at 10~30 DEG C, then first adds oxidant
The aqueous solution, can also add oil-soluble initiator in addition, and reducing agent aqueous solution, control drop are then instilled again
Acceleration ensures that polymerization system programming rate is 0.5~2.0 DEG C/min；The highest temperature is controlled at 40~70 DEG C,
Stop that reducing agent is added dropwise；
F) system temperature is maintained at 40~70 DEG C by adjusting bath temperature, continues to react 3~8 hours, obtain white
The opaque hydrophobic association acrylamide copolymer emulsion of color；
In above-mentioned technical proposal, auxiliary agent, such as complexing agent, example can also be added in the aqueous phase system in step (a)
Such as disodium ethylene diamine tetraacetate or diethylene triamine pentacetic acid (DTPA) sodium with eliminate metal ion to react influence, consumption
Account for the 0.01~1% of copolymerization component.
In order to solve the above-mentioned technical problem three, the technical solution adopted by the present invention is as follows：A kind of above-mentioned technical proposal
In application of any described acrylamide hydrophobically associating polymer emulsion in tertiary oil production in oil field.
In above-mentioned technical proposal, the application can be incited somebody to action using conventional technical means well-known to those skilled in the art
Described acrylamide hydrophobically associating polymer emulsion is used in tertiary oil production in oil field, for example, dredge acrylic amide
Water associative polymer emulsion directly or in acrylamide hydrophobically associating polymer emulsion adds surfactant to stir
Mix uniform, the system just can be used for the live of the raising recovery ratio such as tertiary oil production in oil field terrestrial facies or the marine displacement of reservoir oil and answer
In.
Acrylamide hydrophobically associating polymer emulsion of the present invention and preparation method thereof, due to selecting anti-phase breast
The method of liquid polymerization, reaction is easily controlled, and product can obtain solid content acrylamide higher without post processing
Hydrophobically associating polymer emulsion.Use acrylamide hydrophobically associating obtained in preparation technology provided by the present invention
Polymer emulsion, in all kinds of water quality can rapid dispersion, directly or with other oil field chemicals compounding after for oil
Field terrestrial facies used for tertiary oil recovery or the marine displacement of reservoir oil etc. improve the scene application of recovery ratio.
Below by specific embodiment, the present invention will be further elaborated.
Specific embodiment
【Embodiment 1】
In a kettle. first add 186g5 white oils, 30g Span60,4g Tween60, HLB value=5.9 are stirred
Mix to being mixed thoroughly, control temperature in the kettle for 21 DEG C, speed of agitator is 200rpm.In other container
First add 168g deionized waters, disodium ethylene diamine tetraacetate (EDTA) 0.12g, 2- acrylamido -2- methyl-props
Sulfonic acid (AMPS) 38.4g, acrylamide (AM) 152g, 2- acrylamido sodium cetanesulfonate 1.5g,
Stirring to being mixed thoroughly, with being neutralized with the equimolar NaOH of AMPS (NaOH) and by pH
7 are adjusted to, PVP (PVP) 2.18g that the trade mark is K30 (molecular weight about 40000) is added
And stir standby as aqueous phase solution to being mixed thoroughly.During this solution slowly put into reactor, stirring is risen
Up to rotating speed 1000rpm emulsifies 30min, and rotating speed then is down into 300rpm, first instills the mistake that concentration is 10%
1% sodium hydrogensulfite (MBS) aqueous solution 10.8g is slowly dropped into after ammonium sulfate (APS) aqueous solution 3.5g, 5min,
Reaction temperature is raised slowly to 56 DEG C during this, and bath temperature is risen into 50 DEG C carries out insulation reaction, after 4 hours
Discharging, product is White-opalescent emulsion form system, can stablize and deposit more than half a year.
Take in the absolute ethyl alcohol that 10g or so polymer emulsions are added dropwise in about 300ml stirrings, there are a large amount of white solids
Separate out, suction filtration drying much filtrate after standing a few hours, it is 32.5% to be measured with weight method and can separate out solid content；
Emulsion is directly used into total salinity 180000mg/L (wherein Ca2++Mg2+Salt solution 5000mg/L) is made into 0.15%
Solution, stirring several minutes can obtain homogeneous solution, at 90 DEG C use Brookfield viscometer, shear rate 7.34s-1
Under the apparent viscosity that measures be 39mPas, 90 DEG C of viscosity retention ratios after aging 30 days are 91.8%.
【Embodiment 2】
In a kettle. first add 190g hexamethylenes, 28g Span80,3.2g Tween80, HLB value=5.4 are stirred
Mix to being mixed thoroughly, control temperature in the kettle for 21 DEG C, speed of agitator is 200rpm.In other container
First add 162g deionized waters, disodium ethylene diamine tetraacetate (EDTA) 0.16g, 2- acrylamido -2- methyl-props
Sulfonic acid (AMPS) 42g, acrylamide (AM) 148g, hexadecyldimethyl benzyl ammonium allyl ammonium chloride 1.2g,
Stirring to being mixed thoroughly, with being neutralized with the equimolar NaOH of AMPS (NaOH) and by pH
7 are adjusted to, the trade mark are added for polyvinyl alcohol (PVA) 1.26g of 1788 (molecular weight about 80000) and is stirred extremely
It is mixed thoroughly standby as aqueous phase solution.During this solution slowly put into reactor, stirring is increased to rotating speed
1000rpm emulsifies 30min, and rotating speed then is down into 300rpm, first instills the ammonium persulfate that concentration is 10%
(APS) 1% sodium hydrogensulfite (MBS) aqueous solution 19.8g is slowly dropped into after aqueous solution 3.2g, 5min, this
During reaction temperature be raised slowly to 52 DEG C, bath temperature is risen into 50 DEG C carries out insulation reaction, goes out after 5 hours
Material, product is White-opalescent emulsion form system, can stablize and deposit more than half a year.
Take in the absolute ethyl alcohol that 10g or so polymer emulsions are added dropwise in about 300ml stirrings, there are a large amount of white solids
Separate out, suction filtration drying much filtrate after standing a few hours, it is 31.8% to be measured with weight method and can separate out solid content；
Emulsion is directly used into total salinity 180000mg/L (wherein Ca2++Mg2+Salt solution 5000mg/L) is made into 0.15%
Solution, stirring several minutes can obtain homogeneous solution, at 90 DEG C use Brookfield viscometer, shear rate 7.34s-1
Under the apparent viscosity that measures be 36mPas, 90 DEG C of viscosity retention ratios after aging 30 days are 93.2%.
【Embodiment 3】
In a kettle. first add 180g120 solvent naphthas, 26g Span85,4.2g Tween80, HLB value=5.8,
Stirring controls temperature in the kettle for 21 DEG C to being mixed thoroughly, and speed of agitator is 200rpm.In other container
It is middle first to add 172g deionized waters, disodium ethylene diamine tetraacetate (EDTA) 0.16g, 2- acrylamido -2- methyl
Propane sulfonic acid (AMPS) 52g, acrylamide (AM) 178g, 2- acrylamido myristyl sodium sulfonate 1.6g,
Stirring to being mixed thoroughly, with being neutralized with the equimolar NaOH of AMPS (NaOH) and by pH
7 are adjusted to, PVP (PVP) 1.1g that the trade mark is K60 (molecular weight about 200000) is added
And stir standby as aqueous phase solution to being mixed thoroughly.During this solution slowly put into reactor, stirring is risen
Up to rotating speed 1000rpm emulsifies 30min, and rotating speed then is down into 300rpm, first instills the mistake that concentration is 10%
1% sodium hydrogensulfite (MBS) aqueous solution 13.5g is slowly dropped into after ammonium sulfate (APS) aqueous solution 4.7g, 5min,
Reaction temperature is raised slowly to 62 DEG C during this, and bath temperature is risen into 60 DEG C carries out insulation reaction, after 5 hours
Discharging, product is White-opalescent emulsion form system, can stablize and deposit more than half a year.
Take in the absolute ethyl alcohol that 10g or so polymer emulsions are added dropwise in about 300ml stirrings, there are a large amount of white solids
Separate out, suction filtration drying much filtrate after standing a few hours, it is 43.2% to be measured with weight method and can separate out solid content；
Emulsion is directly used into total salinity 180000mg/L (wherein Ca2++Mg2+Salt solution 5000mg/L) is made into 0.15%
Solution, stirring several minutes can obtain homogeneous solution, at 90 DEG C use Brookfield viscometer, shear rate 7.34s-1
Under the apparent viscosity that measures be 45mPas, 90 DEG C of viscosity retention ratios after aging 30 days are 92.3%.
【Embodiment 4】
180g7 white oils, 30g Span80,3.8g OP10, HLB value=5.4,3.8g are first added in a kettle.
T-butyl styrene, stirs to being mixed thoroughly, and controls temperature in the kettle for 21 DEG C, and speed of agitator is 200rpm.
163g deionized waters, disodium ethylene diamine tetraacetate (EDTA) 0.15g, 2- propylene are first added in other container
Amide groups -2- methyl propane sulfonic acid (AMPS) 38.4g, acrylamide (AM) 152g, stirring are equal to being thoroughly mixed
It is even, with being neutralized with the equimolar NaOH of AMPS (NaOH) and pH being adjusted into 7, add hydroxyl second
Base cellulose (HEC) 2.8g is simultaneously stirred standby as aqueous phase solution to being mixed thoroughly.This solution is slowly thrown
Enter in reactor, stirring be increased to rotating speed 1000rpm emulsification 30min, rotating speed is then down to 300rpm,
First instill concentration be 10% ammonium persulfate (APS) aqueous solution 4.5g, 5min after be slowly dropped into 1% sulfurous acid
Hydrogen sodium (MBS) aqueous solution 12.8g, reaction temperature is raised slowly to 71 DEG C during this, and bath temperature is risen to
60 DEG C carry out insulation reaction, are discharged after 4 hours, and product is White-opalescent emulsion form system, can stablize storage half
More than year.
Take in the absolute ethyl alcohol that 10g or so polymer emulsions are added dropwise in about 300ml stirrings, there are a large amount of white solids
Separate out, suction filtration drying much filtrate after standing a few hours, it is 33.9% to be measured with weight method and can separate out solid content；
Emulsion is directly used into total salinity 180000mg/L (wherein Ca2++Mg2+Salt solution 5000mg/L) is made into 0.15%
Solution, stirring several minutes can obtain homogeneous solution, at 90 DEG C use Brookfield viscometer, shear rate 7.34s-1
Under the apparent viscosity that measures be 41mPas, 90 DEG C of viscosity retention ratios after aging 30 days are 89.6%.
【Embodiment 5】
In a kettle. first add 172g200 solvent naphthas, 30g Span80,6.2g AEO9, HLB value=5.9,
Stirring controls temperature in the kettle for 21 DEG C to being mixed thoroughly, and speed of agitator is 200rpm.In other container
It is middle first to add 168g deionized waters, disodium ethylene diamine tetraacetate (EDTA) 0.15g, 2- acrylamido -2- methyl
Propane sulfonic acid (AMPS) 38.4g, acrylamide (AM) 152g, solution property 1.5g,
Stirring to being mixed thoroughly, with being neutralized with the equimolar NaOH of AMPS (NaOH) and by pH
7 are adjusted to, carboxymethylcellulose calcium (CMC) 2.9g are added and is stirred standby as aqueous phase solution to being mixed thoroughly
With.During this solution slowly put into reactor, stirring is increased to rotating speed 1000rpm emulsification 30min, then will
Rotating speed is down to 300rpm, delays after first instilling ammonium persulfate (APS) aqueous solution 3.6g, 5min that concentration is 10%
Sodium hydrogensulfite (MBS) aqueous solution 11.2g of slow instillation 1%, reaction temperature is raised slowly to 54 DEG C during this,
Bath temperature is risen into 50 DEG C carries out insulation reaction, is discharged after 7 hours, and product is White-opalescent emulsion form system,
Can stablize and deposit more than half a year.
Take in the absolute ethyl alcohol that 10g or so polymer emulsions are added dropwise in about 300ml stirrings, there are a large amount of white solids
Separate out, suction filtration drying much filtrate after standing a few hours, it is 34.6% to be measured with weight method and can separate out solid content；
Emulsion is directly used into total salinity 180000mg/L (wherein Ca2++Mg2+Salt solution 5000mg/L) is made into 0.15%
Solution, stirring several minutes can obtain homogeneous solution, at 90 DEG C use Brookfield viscometer, shear rate 7.34s-1
Under the apparent viscosity that measures be 41mPas, 90 DEG C of viscosity retention ratios after aging 30 days are 90.3%.
【Embodiment 6】
192g kerosene, 32g Span80,4.2g Tween80, HLB value=5.5, propylene are first added in a kettle.
Sour octadecyl ester 2.6g, AIBN0.5g, stir to being mixed thoroughly, and control temperature in the kettle for 21 DEG C, and stirring turns
Speed is 200rpm.168g deionized waters, disodium ethylene diamine tetraacetate (EDTA) are first added in other container
0.1g, 2- acrylamide-2-methylpro panesulfonic acid (AMPS) 29.3g, acrylamide (AM) 152g, acryloyl
Oxy-ethyl-trimethyl salmiac 12g, stirring to being mixed thoroughly, with the equimolar NaOH of AMPS
(NaOH) neutralized and pH is adjusted to 7, added the poly- second that the trade mark is K30 (molecular weight about 40000)
Vinyl pyrrolidone (PVP) 1.92g is simultaneously stirred standby as aqueous phase solution to being mixed thoroughly.This solution is delayed
In slow input reactor, stirring is increased to rotating speed 1000rpm emulsification 30min, rotating speed is then down to 300rpm,
First instill concentration be 10% ammonium persulfate (APS) aqueous solution 4.1g, 5min after be slowly dropped into 1% sulfurous acid
Hydrogen sodium (MBS) aqueous solution 12.3g, reaction temperature is raised slowly to 56 DEG C during this, and bath temperature is risen to
50 DEG C carry out insulation reaction, are discharged after 4 hours, and product is White-opalescent emulsion form system, can stablize storage half
More than year.
Take in the absolute ethyl alcohol that 10g or so polymer emulsions are added dropwise in about 300ml stirrings, there are a large amount of white solids to analyse
Go out, suction filtration drying much filtrate after standing a few hours, it is 34.6% to be measured with weight method and can separate out solid content；Will
Emulsion directly uses total salinity 180000mg/L (wherein Ca2++Mg2+Salt solution 5000mg/L) is made into 0.15%
Solution, stirring several minutes can obtain homogeneous solution, at 90 DEG C use Brookfield viscometer, shear rate 7.34s-1
Under the apparent viscosity that measures be 43mPas, 90 DEG C of viscosity retention ratios after aging 30 days are 93.2%.
【Embodiment 7】
In a kettle. first add 190g hexamethylenes, 24.14g Span80,7.06g Tween60, HLB value=6.7,
Stirring controls temperature in the kettle for 21 DEG C to being mixed thoroughly, and speed of agitator is 200rpm.In other container
It is middle first to add 162g deionized waters, disodium ethylene diamine tetraacetate (EDTA) 0.16g, 2- acrylamido -2- first
Base propane sulfonic acid (AMPS) 42g, acrylamide (AM) 148g, hexadecyldimethyl benzyl ammonium allyl ammonium chloride 1.2g,
Stirring to being mixed thoroughly, with being neutralized with the equimolar NaOH of AMPS (NaOH) and by pH
7 are adjusted to, the trade mark are added for polyvinyl alcohol (PVA) 1.26g of 1788 (molecular weight about 80000) and is stirred extremely
It is mixed thoroughly standby as aqueous phase solution.During this solution slowly put into reactor, stirring is increased to rotating speed
1000rpm emulsifies 30min, and rotating speed then is down into 300rpm, first instills the ammonium persulfate that concentration is 10%
(APS) 1% sodium hydrogensulfite (MBS) aqueous solution 19.8g is slowly dropped into after aqueous solution 3.2g, 5min, this
During reaction temperature be raised slowly to 54 DEG C, bath temperature is risen into 55 DEG C carries out insulation reaction, goes out after 5 hours
Material, product is White-opalescent emulsion form system, can stablize and deposit more than half a year.
Take in the absolute ethyl alcohol that 10g or so polymer emulsions are added dropwise in about 300ml stirrings, there are a large amount of white solids
Separate out, suction filtration drying much filtrate after standing a few hours, it is 29.6% to be measured with weight method and can separate out solid content；
Emulsion is directly used into total salinity 180000mg/L (wherein Ca2++Mg2+Salt solution 5000mg/L) is made into 0.15%
Solution, stirring several minutes can obtain homogeneous solution, at 90 DEG C use Brookfield viscometer, shear rate 7.34s-1
Under the apparent viscosity that measures be 39mPas, 90 DEG C of viscosity retention ratios after aging 30 days are 95.2%.
【Comparative example 1】
First add 190g hexamethylenes in a kettle., 31.2g Span40, HLB value=6.7, stirring is to being thoroughly mixed
Uniformly, control temperature in the kettle for 21 DEG C, speed of agitator is 200rpm.162g is first added to go in other container
Ionized water, disodium ethylene diamine tetraacetate (EDTA) 0.16g, 2- acrylamide-2-methylpro panesulfonic acid (AMPS)
42g, acrylamide (AM) 148g, hexadecyldimethyl benzyl ammonium allyl ammonium chloride 1.2g, stirring is to being thoroughly mixed
Uniformly, with being neutralized with the equimolar NaOH of AMPS (NaOH) and pH being adjusted into 7, board is added
Number for polyvinyl alcohol (PVA) 1.26g of 1788 (molecular weight about 80000) and stirring is to being mixed thoroughly work
For aqueous phase solution is standby.During this solution slowly put into reactor, stirring is increased to rotating speed 1000rpm emulsifications
30min, is then down to 300rpm by rotating speed, first instills ammonium persulfate (APS) aqueous solution that concentration is 10%
1% sodium hydrogensulfite (MBS) aqueous solution 19.8g, reaction temperature during this are slowly dropped into after 3.2g, 5min
52 DEG C are raised slowly to, bath temperature is risen into 50 DEG C carries out insulation reaction, are discharged after 5 hours, product is white
Opaque emulsion shape system, but it is placed into more obvious layering occurred within second day.
Taken after polymer emulsion is stirred in the absolute ethyl alcohol that 10g or so is added dropwise in about 300ml stirrings, had
A large amount of white solids are separated out, suction filtration drying much filtrate after standing a few hours, and being measured with weight method can separate out solid content and contain
Measure is 26.3%；Emulsion is directly used into total salinity 180000mg/L (wherein Ca2++Mg2+5000mg/L)
Salt solution is made into 0.15% solution, and stirring several minutes can obtain homogeneous solution, Brookfield viscometer is used at 90 DEG C,
Shear rate 7.34s-1Under the apparent viscosity that measures be 17mPas, 90 DEG C of viscosity retention ratios after aging 30 days are respectively
75.6%.
Comparative example 1 is emulsifying agent with the difference of embodiment 7, and embodiment 7 is Compositional type, and comparative example 1 is single
One type, from terms of the outward appearance and performance evaluation of polymer emulsion product, product stability prepared by single type emulsifying agent is poor,
Solution viscosity and aging retention rate are also below Compositional type emulsifying agent.
Claims (9)
1. a kind of hydrophobic association acrylamide copolymer emulsion and preparation method thereof, the emulsion system is obtained by inverse emulsion polymerization method；In terms of parts by weight, described copolymerization component is included：
A) 10~50 parts of oil phase；
B) 1~10 part of emulsifying agent and assistant for emulsifying agent；
C) 40~80 parts of the water phase containing comonomer.
2. hydrophobic association acrylamide copolymer emulsion according to claim 1, it is characterised in that the oil phase is selected from one or more the mixture in aliphatic hydrocarbon, aromatic hydrocarbons, halogenated hydrocarbons etc., consumption accounts for the 10~50% of whole copolymerization component.
3. hydrophobic association acrylamide copolymer emulsion according to claim 1, it is characterized in that the emulsifying agent is nonionic emulsifier, hydrophilic lipophilic balance is between 4~7, formed by oil soluble surfactant and water soluble surfactant active's compounding, the mass ratio of oil soluble surfactant and water soluble surfactant active is 20:1~2:1.
4. the online injection type oil displacement agent containing hydrophobic associated polymer emulsion according to claim 1, it is characterised in that the emulsifying agent also includes the polymer selected from low-molecular-weight as assistant for emulsifying agent, and the total consumption of emulsifying agent accounts for the 1~10% of whole copolymerization component.
5. hydrophobic association acrylamide copolymer emulsion according to claim 1, it is characterised in that described comonomer includes following components：
A) nonionic water-soluble monomers of 5~99.9w.t.%；
B) anionic monomer or/and cationic monomer of 0~50w.t.%；
C) hydrophobic monomer of 0.1~10w.t.%.
6. hydrophobic association acrylamide copolymer emulsion according to claim 4, it is characterized in that described nonionic water-soluble monomers are selected from water-soluble vinyl monomer, the vinyl monomer is selected from least one in the monomer shown in formula (1), formula (2), formula (3) or formula (4)：
Wherein, R1、R4、R5、R6It is independently chosen from hydrogen, C1~C4Alkyl；R2、R3It is independently chosen from hydrogen, C1~C4Alkyl or hydroxyl substituted alkyl group.
7. hydrophobic association acrylamide copolymer emulsion according to claim 4, it is characterised in that described anionic monomer is selected from least one in 2- acrylamide-2-methylpro panesulfonic acids, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylbenzenesulfonic acid, vinyl sulfonic acid, vinyl phosphonate, allyl sulphonic acid, allyl phosphonic acid and/or its water-soluble alkali, alkaline-earth metal and ammonium salt；Described cationic monomer is selected from least one in dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides；Described hydrophobic monomer is one or more the mixture in Long carbon chain ionic surfactant monomer, esters of acrylic acid hydrophobic monomer, the hydrophobic monomer containing many membered cyclic compounds, wherein Long carbon chain ionic surfactant monomer can be cation or cationic, carbon chain lengths are 8~16, the atomic number of alkyl carbon of esters of acrylic acid can be 4~18, and many yuan of rings in many membered cyclic compounds can be five yuan or hexa-atomic.
8. any described hydrophobic association acrylamide copolymer emulsion preparation method of claim 1~7, including following steps：
A) comonomer is dissolved in the water and obtains water phase I；
B) add assistant for emulsifying agent to be well mixed in above-mentioned water phase, and pH value is adjusted to 5~9, obtain water phase II；
C) it is oil phase and emulsifier for mixing is uniform, as continuous phase；
D) oil-soluble initiator is made into certain density solution by water soluble starter with finite concentration wiring solution-forming soluble in water with the dissolving such as a small amount of ethanol or ethyl acetate；
E) continuous phase is put into reactor and opens stirring, water phase II point 2~3 batches is slowly added to continuous phase, and high-speed stirred is emulsified to uniform；Reactor temperature is controlled at 10~30 DEG C, then first adds aqueous oxidizing agent solution, and oil-soluble initiator can be also added in addition, and reducing agent aqueous solution is then instilled again, controls rate of addition to ensure that polymerization system programming rate is 0.5~2.0 DEG C/min；The highest temperature is controlled at 40~70 DEG C, stops that reducing agent is added dropwise；
F) system temperature is maintained at 40~70 DEG C by adjusting bath temperature, continues to react 3~8 hours, obtain the hydrophobic association acrylamide copolymer emulsion of White-opalescent.
9. application of any described hydrophobic association acrylamide copolymer emulsion of claim 1~7 in tertiary oil production in oil field.
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