CN107759727B - A kind of Polymer Used For Oil Displacement and its preparation method and application with surface-active - Google Patents
A kind of Polymer Used For Oil Displacement and its preparation method and application with surface-active Download PDFInfo
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- CN107759727B CN107759727B CN201610675066.XA CN201610675066A CN107759727B CN 107759727 B CN107759727 B CN 107759727B CN 201610675066 A CN201610675066 A CN 201610675066A CN 107759727 B CN107759727 B CN 107759727B
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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
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—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 surfactants
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Abstract
The present invention relates to oil recovering fields, disclose a kind of Polymer Used For Oil Displacement and its preparation method and application with surface-active, the polymer contains structural unit A, structural unit B and structural unit C, wherein, the structural unit A is the structural unit with structure shown in formula (1), the structural unit B is the structural unit with structure shown in formula (2), and the structural unit C is the structural unit with structure shown in formula (3).A kind of novel table living polymerization object has been prepared by introducing hydrophobic monomer and hydrophilic monomer together in the macromolecular chain of polyacrylamide in the present invention, and resulting Novel clock living polymerization object has the tackifying improved, emulsifiability and reduces the performances such as surface and interface tension.
Description
Technical field
The present invention relates to oil recovering fields, and in particular, to a kind of Polymer Used For Oil Displacement with surface-active, one kind
The displacement of reservoir oil with surface-active for preparing the method for the Polymer Used For Oil Displacement with surface-active and being prepared by this method
Use polymer, the Polymer Used For Oil Displacement with surface-active as oil displacement agent application.
Background technique
It is referred to as table living polymerization object with the active functional polymer of certain surface, table living polymerization object refers in its high score
Hydrophilic radical and lipophilic group are existed simultaneously in minor structure, make its aqueous solution that there is a kind of active new type functional of excellent surface
Polymer generally obtains table living polymerization object using precipitation from aqueous solution or micellar co-polymerization mode, that is, passes through certain temperature and draw
Cause comonomer polymerization under the action of hair agent to obtain.
Table living polymerization object and conventional high molecular surfactant have very big difference.The property of high molecular surfactant
It is more likely to Small molecular surfactant, and table living polymerization object then more shows the property of polymer.
The relative molecular mass of high molecular surfactant is not high, general < 2,000,000, tackifying is not strong；And table living polymerization object
Relative molecular mass be usually above 8,000,000, even more than 15,000,000, there is stronger tackifying and viscoplasticity, while can be with
Grease surface and interface tension is effectively reduced and with certain emulsification washing oil ability, can achieve one multi-purpose effect, therefore table
Living polymerization object has more broad application prospect as a kind of novel oil displacement agent, in tertiary oil recovery field.
Use table living polymerization object as oil displacement agent, is applied to tertiary oil recovery field, it is living with polymer flooding and polymer/surface
Property agent binary combination flooding compared to having great advantages.
Single polymers drive only has the function of improving displacing fluid swept volume, without having the characteristic of emulsification washing oil；It is poly-
Chromatographic isolation phenomenon can be occurred during reservoir formation porous media is migrated by closing object/surfactant binary combination flooding, be dropped
Low oil displacement efficiency.
Table living polymerization object is the macromolecular structure of one-component, during use can be to avoid above-mentioned as oil displacement agent
Problem more can effectively play the characteristics such as itself tackifying, viscoplasticity, emulsification, increase-volume, can not only expand swept volume, and
And displacement efficiency can be improved.
At present is in the table living polymerization object research of the displacement of reservoir oil development in laboratory stage, domestic and international pertinent literature report is very
It is few.Such functional polymer will also promote few in chemical combined flooding oil systems use or without surfactant, and reduction
The investment of live filing provision greatly reduces displacement of reservoir oil cost.
Table living polymerization object can be copolymerized by acrylamide monomer and surface active monomer or hydrophobic monomer/hydrophilic monomer
It is obtained after conjunction.Surface active monomer polymerization activity is lower, and price is more expensive, is unfavorable for large-scale industrial production and answers
With；The features such as suitable hydrophobic monomer and hydrophilic monomer have polymerization activity moderate, and the polymer molecular weight of preparation is higher, can use
In the combined polymerization of acrylamide monomers, thus the displacement of reservoir oil being had excellent performance table living polymerization object.
Therefore hydrophobic monomer and hydrophilic monomer are collectively incorporated on the macromolecular chain of polyacrylamide, are a kind of to prepare table
Living polymerization object and the important channel for improving temperature-resistant and anti-salt type flooding polymers comprehensive performance, while also being created for inefficient well under low oil price
Beneficial synergy provides behave, improves oil well productivity for ultra-high water cut stage and provides technical support.
Summary of the invention
There is good tackifying, emulsifiability the object of the present invention is to provide one kind and reduce the performances such as surface and interface tension
Novel clock living polymerization object.
It to achieve the goals above, should in a first aspect, the present invention provides a kind of Polymer Used For Oil Displacement with surface-active
Polymer contains structural unit A, structural unit B and structural unit C, wherein the structural unit A is with knot shown in formula (1)
The structural unit of structure, the structural unit B are the structural unit with structure shown in formula (2), and the structural unit C is with formula
(3) structural unit of structure shown in；Wherein, on the basis of the weight of the polymer, the content of the structural unit A is 70-
The content of 99.98 weight %, the structural unit B is 0.01-10 weight %, and the content of the structural unit C is 0.01-20 weight
% is measured, and the viscosity average molecular weigh of the polymer is 15,000,000-3,000 ten thousand；
Wherein, R1、R2And R3It is each independently the alkyl of H or C1-C4；M is H, Na or K；P is the integer of 7-20, and m is
The integer of 2-10, n and y are each independently the integer of 0-4.
Second aspect, the present invention provide a kind of method for preparing the Polymer Used For Oil Displacement with surface-active, this method packet
It includes: in initiator, emulsifier, promotor and in the presence of as the water of solvent, monomer D, monomer E and monomer F being made to carry out solution
Polymerization reaction, wherein the monomer D is the monomer with structure shown in formula (4), and the monomer E is with structure shown in formula (5)
Monomer, the monomer F be the monomer with structure shown in formula (6), wherein the dosage of the monomer D, monomer E and monomer F make
The content of structural unit A is 70-99.98 weight % in the polymer that must be prepared, and the content of structural unit B is 0.01-10
The content of weight %, structural unit C are 0.01-20 weight %, and make the viscosity average molecular weigh of the polymer being prepared to be
15000000-3,000 ten thousand；The structural unit A be the structural unit with structure shown in formula (1), the structural unit B be with
The structural unit of structure shown in formula (2), the structural unit C are the structural unit with structure shown in formula (3),
Wherein, R1、R2And R3It is each independently the alkyl of H or C1-C4；M is H, Na or K；P is the integer of 7-20, and m is
The integer of 2-10, n and y are each independently the integer of 0-4.
The third aspect, the present invention provide a kind of displacement of reservoir oil polymerization with surface-active being prepared by preceding method
Object.
Fourth aspect, the present invention provide application of the aforementioned Polymer Used For Oil Displacement with surface-active as oil displacement agent.
The present invention by introducing hydrophobic monomer in the macromolecular chain of polyacrylamide and hydrophilic monomer is prepared together
A kind of novel table living polymerization object, resulting Novel clock living polymerization object have the tackifying improved, emulsifiability and reduce table
The performances such as interfacial tension.
Polymer Used For Oil Displacement and preparation method thereof of the present invention with surface-active, compared with prior art,
Also have the advantages that in detail below and effect in MOLECULE DESIGN synthesis and performance:
The present invention is the hydrophobic monomer and hydrophilic monomer for introducing long-chain together in the macromolecular structure of polyacrylamide, together
When joined emulsifier and promotor in polymerization system, on the one hand can form stable micella, on the other hand significantly improve
The polymerization activity of hydrophobic monomer and hydrophilic monomer, and then improve the molecular weight and aqueous copolymers solution of polymeric articles
Surface-active makes it have excellent tackifying and heat and salt resistance.
In addition, in copolymer molecule chain hydrophobic monomer structural unit introducing, make to contain one in its copolymer macromolecular chain
The saturated alkyl of measured length, and then the heat resistance and salt tolerance of copolymer molecule interchain is enhanced, make aqueous copolymers solution in high temperature
Higher viscosity is still able to maintain under with high salt.
Particular, it is important that the present invention can also adjust copolymer structure list according to geology reservoir and oil property
The ratio of hydrophobic structure unit and hydrophilic structural unit in member, the different table living polymerization object of design composition sequence structure, to meet
Demand of the different reservoir conditions to flooding polymers.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, the alkyl of the C1-C4 refers to that carbon atom number is the alkyl of 1-4.
The integer of 7-20 includes 7,8,9,10,11,12,13,14,15,16,17,18,19 and 20.
The integer of 2-10 includes 2,3,4,5,6,7,8,9 and 10.
The integer of 0-4 includes 0,1,2,3 and 4.
According to the present invention, the alkyl of the C1-C4 can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, just
Butyl, sec-butyl, isobutyl group and tert-butyl.
First aspect, the present invention provides a kind of Polymer Used For Oil Displacement with surface-active, which contains structure
Unit A, structural unit B and structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (1), institute
Stating structural unit B is the structural unit with structure shown in formula (2), and the structural unit C is the knot with structure shown in formula (3)
Structure unit；Wherein, on the basis of the weight of the polymer, the content of the structural unit A is 70-99.98 weight %, described
The content of structural unit B is 0.01-10 weight %, and the content of the structural unit C is 0.01-20 weight %, and the polymer
Viscosity average molecular weigh be 15,000,000-3,000 ten thousand；
Wherein, R1、R2And R3It is each independently the alkyl of H or C1-C4；M is H, Na or K；P is the integer of 7-20, and m is
The integer of 2-10, n and y are each independently the integer of 0-4.
The present invention by introducing hydrophobic monomer and hydrophilic monomer obtains with surface-active together in macromolecular chain
The performances such as tackifying, emulsifiability and the reduction surface and interface tension of Polymer Used For Oil Displacement are more excellent.
Preferably, on the basis of the weight of the polymer, the content of the structural unit A is 85-99.8 weight %, institute
The content for stating structural unit B is 0.1-5 weight %, and the content of the structural unit C is 0.1-10 weight %, and the polymer
Viscosity average molecular weigh is 20,000,000-2,800 ten thousand.
According to the present invention, under the first preferable case, structure shown in the structural unit of the structure shown in formula (1), formula (2)
Structural unit and formula (3) shown in structure structural unit in, R1、R2And R3Be each independently H, methyl, ethyl, n-propyl,
Isopropyl, normal-butyl；M is H, Na or K；P is the integer of 7-20, and m is the integer of 2-10, and n and y are each independently the whole of 0-3
Number.
According to the present invention, under second of preferable case, structure shown in the structural unit of the structure shown in formula (1), formula (2)
Structural unit and formula (3) shown in structure structural unit in, R1、R2And R3It is each independently H, methyl, ethyl, n-propyl；
M is H, Na or K；P is the integer of 8-18, and m is the integer of 4-8, and n and y are each independently the integer of 0-2.
According to the present invention, under the third preferable case, structure shown in the structural unit of the structure shown in formula (1), formula (2)
Structural unit and formula (3) shown in structure structural unit in, R1、R2And R3It is each independently H or methyl；M is Na or K；p
For the integer of 9-17, m is the integer of 4-8, and n and y are each independently the integer of 0-2.
The present inventor has found under study for action, by following specific structural unit A, structural unit B and structural unit C
The polymer of composition has more excellent tackifying, emulsifiability and reduces surface and interface tension.The structural unit A be with
The structural unit of structure shown in formula (7), the structural unit B are structural unit and the knot with structure shown in formula (8)
Structure unit C is the structural unit with structure shown in formula (9),
Wherein, M is Na or K；P is the integer of 9-17, and m 4,6 or 8, n and y are each independently 0 or 1.
Second aspect, the present invention provides a kind of method for preparing the Polymer Used For Oil Displacement with surface-active, this method
It include: to carry out monomer D, monomer E and monomer F molten in initiator, emulsifier, promotor and in the presence of as the water of solvent
Liquid polymerization reaction, wherein the monomer D is the monomer with structure shown in formula (4), and the monomer E is with knot shown in formula (5)
The monomer of structure, the monomer F are the monomer with structure shown in formula (6), wherein the dosage of the monomer D, monomer E and monomer F
So that the content of structural unit A is 70-99.98 weight % in the polymer being prepared, the content of structural unit B is 0.01-
The content of 10 weight %, structural unit C are 0.01-20 weight %, and make the viscosity average molecular weigh of polymer being prepared
It is 15,000,000-3,000 ten thousand；The structural unit A is the structural unit with structure shown in formula (1), and the structural unit B is tool
There is the structural unit of structure shown in formula (2), the structural unit C is the structural unit with structure shown in formula (3),
Wherein, R1、R2And R3It is each independently the alkyl of H or C1-C4；M is H, Na or K；P is the integer of 7-20, and m is
The integer of 2-10, n and y are each independently the integer of 0-4.
The monomer F can be commercially available or synthesize to obtain using the method for the prior art.For example, of the invention
The monomer F that embodiment part uses is all from commercially available.And there is the displacement of reservoir oil of surface-active to polymerize for the preparation of the invention
Polymerization reaction involved in the method for object is carried out using random copolymerization mode.
In the present invention, the structural unit of structure shown in the formula (1), the structural unit of structure shown in formula (2), formula (3)
The list of structure shown in the monomer and formula (6) of structure shown in the monomer of structure shown in the structural unit of shown structure, formula (4), formula (5)
The related definition and substance classes of substituent group in body are identical as correspondence noted earlier of the invention, and the present invention is no longer superfluous herein
It states, those skilled in the art should not be construed as the limitation to technical solution of the present invention.
In the present invention, it should be noted that the one body approximation is fully converted to have the displacement of reservoir oil use of surface-active poly-
The corresponding structural unit that object contains is closed, what the dosage of the monomer and the Polymer Used For Oil Displacement with surface-active contained
The content of corresponding structural unit can be consistent.
Preferably, the dosage of the monomer D, monomer E and monomer F make structural unit A in the polymer being prepared
Content is 85-99.8 weight %, and the content of structural unit B is 0.1-5 weight %, and the content of structural unit C is 0.1-10 weight
% is measured, and the viscosity average molecular weigh for the polymer being prepared is made to be 20,000,000-2,800 ten thousand.
Preferably, monomer D, monomer E and monomer F are formed into aqueous solution in presence of water；It is further preferred that in the water
In solution, the total concentration of monomer D, monomer E and monomer F are 20-40 weight %.
Preferably, the monomer D is the monomer with structure shown in formula (10)；The monomer E is with shown in formula (11)
The monomer of structure；The monomer F is the monomer with structure shown in formula (12),
Wherein, M is Na or K；P is the integer of 9-17, and m 4,6 or 8, n and y are each independently 0 or 1.
According to the method for the present invention, the solution polymerization preferably carries out under conditions of pH value is 6-10.The pH
Value can be obtained by the way that pH adjusting agent is added into polymerization system, and the pH adjusting agent can be the various of this field routine
PH adjusting agent, such as can be at least one of sodium hydroxide, sodium carbonate, potassium carbonate and ammonium hydroxide, preferably sodium hydroxide
And/or sodium carbonate.
According to the method for the present invention, chelating agent being added can prevent metal ion from having an impact to polymerization reaction, therefore, excellent
In the case of choosing, the solution polymerization carries out in the presence of chelating agent.The chelating agent can be ethylenediamine tetra-acetic acid two
Sodium, aminotriacetic acid or ammonium citrate, preferably disodium ethylene diamine tetraacetate.The present invention is to the dosage of the chelating agent without spy
Other restriction can change in a wider scope, on the basis of the total amount of the monomer D, the monomer E and the monomer F,
The dosage of the chelating agent can be 0.01-0.1 weight %.The chelating agent can be that concentration is the water-soluble of 0.1-5 weight %
Liquid form.
The emulsifier is preferably lauryl sulfate, particularly, the emulsifier be selected from lauryl sodium sulfate and
At least one of dodecyl sulphate potassium.
Preferably, the dosage of the emulsifier is the 0.05-1 weight % of total dosage of monomer D, monomer E and monomer F.
The promotor is preferably selected from pentamethyl-diethylenetriamine, tetramethylethylenediamine and N, N, N ', in N '-tetramethylguanidine
At least one；It is further preferred that the promotor is pentamethyl-diethylenetriamine.
Preferably, the dosage of the promotor is the 0.02-0.2 weight % of total dosage of monomer D, monomer E and monomer F.
The solution polymerization can also carry out in the presence of protective gas, and the protective gas preferably can be nitrogen
Gas.
It preferably, further include that aqueous solution of urea is added into reaction system in the solution polymerization, the urea
Dosage can be the 0.01-0.1 weight % of total dosage of monomer D, monomer E and monomer F.For example, the aqueous solution of urea
Concentration can be 0.1-5 weight %.
It is polymeric colloid by the product mixtures obtained after the solution polymerization, it is of the present invention in order to obtain
The Polymer Used For Oil Displacement finished product with surface-active, method of the invention can also include that the polymeric colloid that will obtain carries out
It is granulated, is dry, crush, obtaining the Polymer Used For Oil Displacement finished product with surface-active after screening.
Preferably, it is 0-30 DEG C, more preferably 0-20 DEG C that the condition of the solution polymerization, which includes: temperature,；Time is
2-15h, more preferably 5-10h.
Preferably, the initiator includes azo-initiator, peroxide type initiators and redox type initiators
At least one of；The azo-initiator is selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo two
Formamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano formamide, azo diisopropyl imidazoline hydrochloride, azo dicyan
At least one in base valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile
Kind；The peroxide type initiators be selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide and
At least one of benzoyl peroxide；The redox type initiators are selected from persulfate-sulphite, over cure
At least one of hydrochlorate-thiocarbamide, persulfate-organic salt and ammonium persulfate-fatty amine.
Preferably, the initiator is redox type initiators；It is further preferred that the redox type initiators are
The oxidation-reduction trigger system being made of persulfate oxidation agent and sulfite reducing agent.Under the preferable case, persulfuric acid
The dosage of salt oxidizing agent is the 0.01-0.1 weight % of total dosage of monomer D, monomer E and monomer F；The use of sulfite reducing agent
Amount is the 0.005-0.05% of total dosage of monomer D, monomer E and monomer F.For example, the oxygen in the redox type initiators
Agent can be the persulfate aqueous solution of 0.2 weight % and/or the ammonium persulfate aqueous solution of 0.2 weight %；The oxidation is also
Reducing agent in former class initiator can be the bisulfite aqueous solutions of potassium of 0.1 weight % and/or the bisulfite of 0.1 weight %
Sodium water solution.
According to a kind of preferred embodiment, the preparation method packet of the Polymer Used For Oil Displacement with surface-active
Include following steps:
Step 1: being added in polymerisation bottle by monomer D and monomer F and be configured to aqueous solution, adjusts the aqueous solution with alkali
PH value is 6-10；
Step 2: monomer E, chelating agent, emulsifier and promotor being added into the aqueous solution of step 1, stir evenly make its at
For stable micellar solution；
Step 3: at a temperature of 0-30 DEG C, after blasting nitrogen 5-60min, being added initiator into the micellar solution of step 2,
And make it after mixing blasting nitrogen, sealing polymerization 2-15h obtains polymeric colloid；
Step 4: taking out the polymeric colloid, and alkaline matter is added after being granulated, after mixing, in 50-120 DEG C of temperature
It is hydrolyzed under degree 0.5-8 hours；
Step 5: take out colloid be granulated, dried again, being crushed, sieve after obtain having the displacement of reservoir oil polymerization of surface-active
Object finished product.
In the step 1, the alkali used can be selected from least one of sodium hydroxide and sodium carbonate.
In the step 4, the alkaline matter used can be sodium hydroxide grain alkali.
The third aspect, the present invention provides the Polymer Used For Oil Displacements with surface-active being prepared by preceding method.
Fourth aspect, application the present invention provides the aforementioned Polymer Used For Oil Displacement with surface-active as oil displacement agent.
In application of the above-mentioned Polymer Used For Oil Displacement with surface-active as oil displacement agent, specific application method is this
Technology known to the technical staff of field.
The present invention will be described in detail by way of examples below.
Polymerized monomer used below is purchased from Aladdin reagent (Shanghai) Co., Ltd..
In following embodiment, the test method being related to is as follows:
The viscosity average molecular weigh of polymer is tested using one point method using Ubbelohde viscometer；In nominative testing temperature
Apparent viscosity under (85 DEG C) with Brookfield viscosimeter measurement polymer solution in the case where salinity is 33000mg/L；Referring to
Determine the aqueous solution surface tension under test temperature (25 DEG C) with DCAT-21 surface tension instrument measurement polymer under pure water.
Embodiment 1: the Polymer Used For Oil Displacement with surface-active is prepared
1, by 17.0g acrylamide (the 85 weight % for accounting for monomer total amount), 2.0g formula (12) shown in hydrophilic monomer
(m=6, n=0, y=0 account for 10 weight % of monomer total amount) is added in heat preservation polymerisation bottle (i.e. polymerization bottle), and addition is gone
Ionized water 60.0g dissolution is made into aqueous solution, and adding sodium hydroxide and adjusting pH is 6.0；
2, hydrophobic monomer shown in the formula (11) of 1.0g (p=9 accounts for 5 weight % of monomer total amount), 0.2g are sequentially added
Lauryl sodium sulfate, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, pentamethyl two
Ethylene triamine 20.0mg is sufficiently stirred to obtain stable micella；
3, the temperature of aqueous solution is controlled at 10 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.2 weight %
The aqueous solution of sodium bisulfite 2.0g of aqueous solution 2.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min, close
Polymerization reaction of being honored as a queen 6 hours；
4, it takes out blob of viscose to be granulated, 0.4g sodium hydroxide grain alkali is added after granulation and carries out water at 85 DEG C after mixing
Solution 3 hours；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular surface-active at 60 DEG C
Polymer samples.
The viscosity average molecular weigh of polymer is 21,000,000 after tested, apparent viscosity 30.6mPas, and surface tension is
29.2mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 2: the Polymer Used For Oil Displacement with surface-active is prepared
1, by 17.98g acrylamide (the 89.9 weight % for accounting for monomer total amount), 2.0g formula (12) shown in hydrophily list
Body (m=4, n=1, y=1 account for 10 weight % of monomer total amount) is added in heat preservation polymerisation bottle (i.e. polymerization bottle), is added
Deionized water 60.0g dissolution is made into aqueous solution, and adding sodium hydroxide and adjusting pH is 7.0；
2, sequentially add hydrophobic monomer shown in the formula (11) of 0.02g (p=13 accounts for 0.1 weight % of monomer total amount),
The lauryl sodium sulfate of 0.1g, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, five first
Base diethylenetriamine 40.0mg is sufficiently stirred to obtain stable micella；
3, the temperature of aqueous solution is controlled at 5 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.2 weight %
The aqueous solution of sodium bisulfite 3.0g of aqueous solution 3.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min, close
Polymerization reaction of being honored as a queen 6 hours；
4, it takes out blob of viscose to be granulated, 0.45g sodium hydroxide grain alkali is added after granulation and is carried out at 80 DEG C after mixing
Hydrolysis 4 hours；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular surface-active at 60 DEG C
Polymer samples.
The viscosity average molecular weigh of polymer is 23,000,000 after tested, apparent viscosity 39.8mPas, and surface tension is
29.3mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 3: the Polymer Used For Oil Displacement with surface-active is prepared
1, by 19.96g acrylamide (the 99.8 weight % for accounting for monomer total amount), 0.02g formula (12) shown in hydrophily
Monomer (m=8, n=0, y=0 account for 0.1 weight % of monomer total amount) is added in heat preservation polymerisation bottle (i.e. polymerization bottle), is added
Enter deionized water 60.0g dissolution and be made into aqueous solution, adding sodium hydroxide and adjusting pH is 10.0；
2, sequentially add hydrophobic monomer shown in the formula (11) of 0.02g (p=17 accounts for 0.1 weight % of monomer total amount),
The lauryl sodium sulfate of 0.2g, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, five first
Base diethylenetriamine 40.0mg is sufficiently stirred to obtain stable micella；
3, the temperature of aqueous solution is controlled at 20 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.2 weight %
The aqueous solution of sodium bisulfite 4.0g of aqueous solution 4.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min, close
Polymerization reaction of being honored as a queen 8 hours；
4, it takes out blob of viscose to be granulated, 0.5g sodium hydroxide grain alkali is added after granulation and carries out water at 90 DEG C after mixing
Solution 2 hours；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular surface-active at 60 DEG C
Polymer samples.
The viscosity average molecular weigh of polymer is 25,000,000 after tested, apparent viscosity 44.1mPas, and surface tension is
29.3mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 4: the Polymer Used For Oil Displacement with surface-active is prepared
1, by 18.5g acrylamide (the 92.5 weight % for accounting for monomer total amount), 1.0g formula (12) shown in hydrophily list
Body (m=6, n=1, y=1 account for 5 weight % of monomer total amount) is added in heat preservation polymerisation bottle (i.e. polymerization bottle), and addition is gone
Ionized water 60.0g dissolution is made into aqueous solution, and adding sodium hydroxide and adjusting pH is 10.0；
2, sequentially add hydrophobic monomer shown in the formula (11) of 0.5g (p=17 accounts for 2.5 weight % of monomer total amount),
The lauryl sodium sulfate of 0.1g, the EDTA-2Na aqueous solution 1.0g of 1 weight %, the aqueous solution of urea 0.5g of 1 weight %, five first
Base diethylenetriamine 40.0mg is sufficiently stirred to obtain stable micella；
3, the temperature of aqueous solution is controlled at 15 DEG C, is led to nitrogen flooding oxygen after 30 minutes, is added the potassium peroxydisulfate of 0.2 weight %
The aqueous solution of sodium bisulfite 10.0g of aqueous solution 10.0g and 0.1 weight %, initiation reaction stop after continuing logical nitrogen 5min,
Sealing post-polymerization 6 hours；
4, it takes out blob of viscose to be granulated, 0.45g sodium hydroxide grain alkali is added after granulation and is carried out at 85 DEG C after mixing
Hydrolysis 2.5 hours；
5, taking-up micelle is granulated again, drying to constant weight, crushing, sieving obtains white granular surface-active at 60 DEG C
Polymer samples.
The viscosity average molecular weigh of polymer is 23,000,000 after tested, apparent viscosity 40.8mPas, and surface tension is
30.2mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 5: the Polymer Used For Oil Displacement with surface-active is prepared
The present embodiment is carried out using method similar to Example 1, except that:
The dosage of acrylamide in the present embodiment is 18.99g (the 94.95 weight % for accounting for monomer total amount), formula (12) institute
The dosage of the hydrophilic monomer (m=6, n=0, y=0) shown is 0.01g (the 0.05 weight % for accounting for monomer total amount), formula (11) institute
The dosage of the hydrophobic monomer (p=9) shown is 1.0g (the 5 weight % for accounting for monomer total amount).
Remaining is in the same manner as in Example 1.
Obtain white granular surface-active polymer sample.
The viscosity average molecular weigh of polymer is 19,000,000 after tested, apparent viscosity 25.3mPas, and surface tension is
26.5mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 6: the Polymer Used For Oil Displacement with surface-active is prepared
The present embodiment is carried out using method similar to Example 1, except that:
The dosage of acrylamide in the present embodiment is 16.0g (the 80 weight % for accounting for monomer total amount), shown in formula (12)
The dosage of hydrophilic monomer (m=6, n=0, y=0) is 3.0g (the 15 weight % for accounting for monomer total amount), hydrophobic shown in formula (11)
Property monomer (p=9) dosage be 1.0g (the 5 weight % for accounting for monomer total amount).
Remaining is in the same manner as in Example 1.
Obtain white granular surface-active polymer sample.
The viscosity average molecular weigh of polymer is 18,000,000 after tested, apparent viscosity 21.6mPas, and surface tension is
27.0mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 7: the Polymer Used For Oil Displacement with surface-active is prepared
The present embodiment is carried out using method similar to Example 2, except that:
The dosage of acrylamide in the present embodiment is 17.99g (the 89.95 weight % for accounting for monomer total amount), formula (12) institute
The dosage of the hydrophilic monomer (m=4, n=1, y=1) shown is 2.0g (the 10 weight % for accounting for monomer total amount), shown in formula (11)
The dosage of hydrophobic monomer (p=13) is 0.01g (the 0.05 weight % for accounting for monomer total amount).
Remaining is in the same manner as in Example 2.
Obtain white granular surface-active polymer sample.
The viscosity average molecular weigh of polymer is 19,000,000 after tested, apparent viscosity 26.1mPas, and surface tension is
26.8mN/m shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 8: the Polymer Used For Oil Displacement with surface-active is prepared
The present embodiment is carried out using method similar to Example 2, except that:
The dosage of acrylamide in the present embodiment is 16.4g (the 82 weight % for accounting for monomer total amount), shown in formula (12)
The dosage of hydrophilic monomer (m=4, n=1, y=1) is 2.0g (the 10 weight % for accounting for monomer total amount), hydrophobic shown in formula (11)
Property monomer (p=13) dosage be 1.6g (the 8 weight % for accounting for monomer total amount).
Remaining is in the same manner as in Example 2.
Obtain white granular surface-active polymer sample.
The viscosity average molecular weigh of polymer is 17,000,000 after tested, apparent viscosity 20.9mPas, and surface tension is
27.0mN/m shows excellent surface-active and resisting high temperature, high salt performance.
It can be seen that the viscous of the Polymer Used For Oil Displacement provided by the invention with surface-active from the result of above-described embodiment
Average molecular weight is 17,000,000 or more, also, apparent viscosity is higher, and surface tension value is lower.Illustrate, it is provided by the invention to have
The Polymer Used For Oil Displacement of surface-active all has excellent surface-active and resisting high temperature, high salt performance.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (15)
1. a kind of Polymer Used For Oil Displacement with surface-active, which is characterized in that the polymer contains structural unit A, structure list
First B and structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (1), the structural unit B
For the structural unit with structure shown in formula (2), the structural unit C is the structural unit with structure shown in formula (3)；Its
In, on the basis of the weight of the polymer, the content of the structural unit A is 70-99.98 weight %, the structural unit B
Content be 0.01-10 weight %, the content of the structural unit C is 0.01-20 weight %, and the viscous equal molecule of the polymer
Amount is 15,000,000-3,000 ten thousand；
Wherein, R1、R2And R3It is each independently the alkyl of H or C1-C4；M is H, Na or K；P is the integer of 7-20, m 2-10
Integer, n and y are each independently the integer of 0-4.
2. polymer according to claim 1, wherein on the basis of the weight of the polymer, the structural unit A's
Content is 85-99.8 weight %, and the content of the structural unit B is 0.1-5 weight %, and the content of the structural unit C is
0.1-10 weight %, and the viscosity average molecular weigh of the polymer is 20,000,000-2,800 ten thousand.
3. polymer according to claim 1 or 2, wherein the structural unit A is the knot with structure shown in formula (7)
Structure unit, the structural unit B are that the structural unit and the structural unit C with structure shown in formula (8) are with formula
(9) structural unit of structure shown in,
Wherein, M is Na or K；P is the integer of 9-17, and m 4,6 or 8, n and y are each independently 0 or 1.
4. a kind of method for preparing the Polymer Used For Oil Displacement with surface-active, this method comprises: in initiator, emulsifier, rush
In the presence of into agent and as the water of solvent, monomer D, monomer E and monomer F is set to carry out solution polymerization, wherein the monomer
D be the monomer with structure shown in formula (4), the monomer E be the monomer with structure shown in formula (5), the monomer F be with
The monomer of structure shown in formula (6), wherein the dosage of the monomer D, monomer E and monomer F to tie in the polymer being prepared
The content of structure unit A is 70-99.98 weight %, and the content of structural unit B is 0.01-10 weight %, the content of structural unit C
For 0.01-20 weight %, and the viscosity average molecular weigh for the polymer being prepared is made to be 15,000,000-3,000 ten thousand；The structure
Unit A is the structural unit with structure shown in formula (1), and the structural unit B is the structure list with structure shown in formula (2)
Member, the structural unit C are the structural unit with structure shown in formula (3),
Wherein, R1、R2And R3It is each independently the alkyl of H or C1-C4；M is H, Na or K；P is the integer of 7-20, m 2-10
Integer, n and y are each independently the integer of 0-4.
5. according to the method described in claim 4, wherein, what the dosage of the monomer D, monomer E and monomer F to be prepared
The content of structural unit A is 85-99.8 weight % in polymer, and the content of structural unit B is 0.1-5 weight %, structural unit C
Content be 0.1-10 weight %, and make the polymer being prepared viscosity average molecular weigh be 20,000,000-2,800 ten thousand.
6. method according to claim 4 or 5, wherein the monomer D is the monomer with structure shown in formula (10)；Institute
Stating monomer E is the monomer with structure shown in formula (11)；The monomer F is the monomer with structure shown in formula (12),
Wherein, M is Na or K；P is the integer of 9-17, and m 4,6 or 8, n and y are each independently 0 or 1.
7. method according to claim 4 or 5, wherein the emulsifier is lauryl sulfate.
8. method according to claim 4 or 5, wherein the dosage of the emulsifier is monomer D, monomer E and monomer F
The 0.05-1 weight % of total dosage.
9. method according to claim 4 or 5, wherein the promotor is selected from pentamethyl-diethylenetriamine, tetramethyl second
Diamines and N, N, N ', at least one of N '-tetramethylguanidine.
10. method according to claim 4 or 5, wherein the dosage of the promotor is monomer D, monomer E and monomer F
The 0.02-0.2 weight % of total dosage.
11. method according to claim 4 or 5, wherein the condition of the solution polymerization includes: that temperature is 0-30
℃；Time is 2-15h.
12. according to the method for claim 11, wherein the condition of the solution polymerization includes: that temperature is 0-20 DEG C；
Time is 5-10h.
13. method according to claim 4 or 5, wherein the initiator includes azo-initiator, peroxide
At least one of initiator and redox type initiators；The azo-initiator be selected from azo-bis-iso-dimethyl,
Azo-bis-isobutyrate hydrochloride, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano formamide,
Azo diisopropyl imidazoline hydrochloride, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile
At least one of with azobisisoheptonitrile；The peroxide type initiators are selected from hydrogen peroxide, ammonium persulfate, persulfuric acid
At least one of sodium, potassium peroxydisulfate, benzoyl peroxide and benzoyl peroxide；The redox type initiators
In persulfate-sulphite, persulfate-thiocarbamide, persulfate-organic salt and ammonium persulfate-fatty amine at least
It is a kind of.
14. the Polymer Used For Oil Displacement with surface-active that method described in any one of claim 4-13 is prepared.
15. the Polymer Used For Oil Displacement described in any one of claim 1-3 and 14 with surface-active is as oil displacement agent
Using.
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