CN106478868A - A kind of polymer of tool surface active function and its preparation method and application - Google Patents
A kind of polymer of tool surface active function and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to polymer arts, disclose a kind of polymer of tool surface active function and its preparation method and application, this polymer contains construction unit A, construction unit B and construction unit C, wherein, described construction unit A is the construction unit with structure shown in formula (1), described construction unit B is the construction unit with structure shown in formula (2), and described construction unit C is the construction unit with structure shown in formula (3).The polymer of the tool surface active function that the present invention provides has good surface activity, viscous water media capabilities and temperature-resistant anti-salt ability concurrently.
Description
Technical field
A kind of the present invention relates to polymer arts, in particular it relates to polymerization of tool surface active function
Thing, a kind of preparation method of polymer of tool surface active function and the tool being prepared by the method
The polymer of surface active function, a kind of polymer of tool surface active function is as polymer oil-displacing agent
Application.
Background technology
Heatproof, anti-salt property in order to solve the problems, such as Polymer Used For Oil Displacement are poor, and researcher proposes
Introduce function monomer in the molecule and improve the method for polymer molecular weight to improve aqueous solutions of polymers
Apparent viscosity and temperature-resistant anti-salt performance, thus have developed hydrophobic associated polymer, comb shape polymerization
Thing, Heat Resistant and Salt Tolerant Polymer etc., but this kind of polymer does not have surface activity and washing oil ability.
In tertiary oil recovery technology, ternary combined chemical flooding technology is capable of the ultralow interface of profit and opens
Power, keeps the viscosity of injection fluid simultaneously, increases substantially recovery ratio.But, different component chemistry
The performance characteristics such as absorption, diffusion and migration in reservoir of porous medium for the mixture of agent differ greatly,
Lead to produce " chromatographic fractionation effect " during the displacement of reservoir oil in reservoir pore.Surfactant is in displacement simultaneously
During waste increase, recovery ratio and economic benefit reduce.When additionally using highly basic auxiliary agent, extraction
During all too many levels produce serious scale, bring difficulty to production management.
Oil displacement system to be ensured has sufficiently high viscosity under high salinity and higher temperature conditions simultaneously
With ultralow interfacial tension it is necessary to break through the restriction utilizing polymer/surfactant compound system in the past.
In conjunction with the surface activity of high molecular tackifying ability and low-molecular-weight surfactant, macromolecular chain draws
Enter to have the functional group of good surface activity, reach the effect not only viscosifying but also reducing interfacial tension, make
Obtain a kind of material and simultaneously work as polymer and the effect of surfactant bi-material, therefore such have
The macromolecule oil-displacing agent of surface activity will solve polymer-surfactant combination flooding to a certain extent to be existed
Chromatographic fractionation effect problem, simultaneously because having the thickening property of surface active function polymer, it
Also there is the effect of stable foam, in foam flooding and polynary foam composite flooding, may act as foam stabilizer,
These superior functions make it have broad application prospects in tertiary oil recovery.
Survey data in recent years shows, low-permeability oil deposit has become the important of China's In Oil Field Exploration And Development
Field, ended for the end of the year 2008, accumulative 28,700,000,000 tons of the verified oil oil in place in the whole nation, wherein hyposmosis
Petroleum-in-place is 14,100,000,000 tons, accounts for 49.2%.Raising with degree of prospecting and petroleum resources are needed
The continuous growth asked, no matter from residual petroleum resource, or developing trend analysis, low-permeability oil deposit will
It is the main object of China's future In Oil Field Exploration And Development.Carry out Polymer Flooding in low-permeability oil deposit to set
Timing is it is necessary to the matching relationship of prior Study Polymer Melts relative molecular mass and reservoir permeability.Poly-
Drive block relative molecular mass preferred when, on the one hand to consider to select polymer phase as high as possible to point
Protonatomic mass, thus obtaining more preferable polymer displacement of reservoir oil performance, on the other hand polymer molecule to be considered with
The matching relationship of different permeability oil reservoirs, as increases polymer solution enterable oil reservoir hole empty as possible
Between, improve polymer flooding control extent, thus obtaining more preferable polymer flooding effect.Researcher passes through interior
Flowing experiment research obtains low permeability pay and can carry out polymer flooding, Polymer Molecular Weight with
There is certain relation in the matching between low permeability pay permeability, if circled round with polymer molecule
Between radius and hole duct radius, relation is reflecting that then matching relationship can be expressed as matching relationship：For
Low-permeability oil reservoir, when the ratio of pore constriction radius and polymer molecule radius of gyration is more than 5 times, note
Enter low relative molecular mass polymer will not block, during less than 5 times, blocking occur, obtained with
The close result of major oil reservoir.If with comparing of permeability square root and polymer molecule radius of gyration
Experimental result carries out stating, and can be expressed as permeability square root big with the ratio of polymer molecule radius of gyration
Oil reservoir will not be blocked when 1.5.Accordingly, it is considered to ooze to Polymer Molecular Weight with low permeability pay
Thoroughly there is certain relation in the coupling between rate, should synthesize the polymer of certain molecular weight scope to meet
Matching with low-permeability oil deposit.
With people, the research of tool surface active function polymer is deepened continuously, develop new kind and
New synthetic method is also the focus of current research.But due to recognizing not to relation between structure and property
Enough, the macromolecular aqueous solution system being related to physicochemical properties is again extremely complex, up to the present has a table
The progress in face this field of active function polymer is slow, with regard to the tool table of middle and low permeable reservoir
The research of face active function polymer does not almost have.Therefore study its relation be- tween structure and properties, synthesis
The copolymer with high surface of certain molecular weight scope, has important theory and application valency
Value.
It is respectively adopted alkyl or alkyl phenol polyoxy second in US4138381, US4463151 and EP426864
Alkene ether acrylate surface activated monomer and acrylamide monomers copolymerization, mainly use surface activity
Association in water for the hydrophobic group of monomer, so that the viscosity of copolymer increases substantially, contains
The copolymer having surface active monomer component has more preferable salt tolerance, but amphipathic polymeric monomer component exists
It is difficult in bipolymer to interface aggregates, therefore, synthesized copolymer surface activity is bad.
In CN1178802A, by acrylamide monomers, surface-active macromonomers and ionic comonomer altogether
Gather and obtain terpolymer, this copolymer viscosity is higher but surface activity is poor.Southwest Petroleum Institute
Sun Lili et al. adopts homogeneous polymerization process, has synthesized a kind of novel high polymer surfactant (PS1),
This high molecular surfactant is acrylamide, acrylic acid, methyl methacrylate copolymer,
This high molecular surfactant reduces capillary ability not as good as low-molecular-weight surfactant, its with no
Machine salt compounds, and due to cooperative effect, can produce the compound property better than single surfactant, make
Surface tension is even lower, but the temperature-resistant anti-salt performance of this high molecular surfactant is poor.The Chinese Academy of Sciences
The gold of Chengdu organic chemistry institute brave et al. with toluene di-isocyanate(TDI) and polyethers as primary raw material, close
A class has been become to carry the non-iron polymerizable polyurethane high molecular surfactant of double bond, this macromolecule
Surfactant can make solution surface tension be down to 37.6mN/m when concentration is for 0.06mol/L
(25 DEG C), still can keep good surface activity under very low concentrations simultaneously, in addition, this can gather
Close nonionic polyurethane high molecular surfactant and reduce capillary ability with hydrophobic segment institute
The increase of accounting example and increase, but this non-iron polymerizable polyurethane high molecular surfactant is poly-
Close active poor, heat resistance is poor simultaneously.
Content of the invention
The invention aims to it is good to overcome high, medium and low infiltration oil reservoir polymer at present can not have concurrently
The shortcoming of good surface activity, viscous water media capabilities and temperature-resistant anti-salt ability, provides one kind to have concurrently well
Surface activity, the polymer of tool surface active function of viscous water media capabilities and temperature-resistant anti-salt ability and
The preparation method and application of this polymer.
To achieve these goals, in a first aspect, the present invention provides a kind of the poly- of tool surface active function
Compound, this polymer contains construction unit A, construction unit B and construction unit C, wherein, described knot
Structure unit A is the construction unit with structure shown in formula (1), and described construction unit B is to have formula (2)
The construction unit of shown structure, described construction unit C is the construction unit with structure shown in formula (3)；
Wherein, on the basis of the weight of described polymer, the content of described construction unit A is 45-89 weight
The content of amount %, described construction unit B is 10-40 weight %, and the content of described construction unit C is
1-15 weight %, the viscosity-average molecular weight of described polymer is 5,000,000-2,000 ten thousand；
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3Alkylene for C1-C14
Base；R4And R5It is each independently the alkyl of H or C1-C4, and R4And R5It is asynchronously H；M
For H, Na or K；R6Alkyl for H or C1-C4；R7Alkyl for C1-C16.
Second aspect, the present invention provides a kind of preparation method of the polymer of tool surface active function, should
Method includes：In the presence of in initiator with as the water of solvent, make monomer D, monomer E and monomer F
Carry out solution polymerization, wherein, described monomer D is the monomer with structure shown in formula (4), institute
Stating monomer E is the monomer with structure shown in formula (5), and described monomer F is to have knot shown in formula (6)
The monomer of structure, wherein, the consumption of described monomer D, monomer E and monomer F makes the polymerization preparing
In thing, the content of construction unit A is 45-89 weight %, and the content of construction unit B is 10-40 weight %,
The content of construction unit C is 1-15 weight %, and so that the viscous equal molecule of the polymer preparing
Measure as 5,000,000-2,000 ten thousand；Described construction unit A is the construction unit with structure shown in formula (1),
Described construction unit B is the construction unit with structure shown in formula (2), and described construction unit C is tool
There is the construction unit of structure shown in formula (3),
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3Alkylene for C1-C14
Base；R4And R5It is each independently the alkyl of H or C1-C4, and R4And R5It is asynchronously H；M
For H, Na or K；R6Alkyl for H or C1-C4；R7Alkyl for C1-C16.
The third aspect, the present invention provides the polymerization of the tool surface active function being prepared by preceding method
Thing.
Fourth aspect, the present invention provides the polymer of aforementioned tool surface active function as polymer displacement of reservoir oil
The application of agent.
The polymer of the tool surface active function that the present invention provides has good surface activity, viscous water concurrently
Media capabilities and temperature-resistant anti-salt ability.
The present invention, from the angle of MOLECULE DESIGN, improves polymerization by introducing surface active monomer F
The surface activity of thing, in molecular structure, active carbon-carbon double bond makes it have very high reactivity, pole
Easily generate different functional polymers from other various vinyl monomer copolymerizations, in molecular structure, contain epistasis
Anion and hydrophilic functional group's sulfonic group, have anti-precipitated cationic performance well.
Heretofore described tool surface active function polymer molecular weight control within the specific limits with
Meet the matching from different permeability oil reservoir, in combination with high molecular tackifying and low molecular weight surfactant
The surface activity of activating agent, has the advantages that fluidity control and reduction oil/water interfacial tension act on, one
The problems such as determine the chromatographic fractionation effect that the presence of polymer-surfactant combination flooding is solved on degree.Separately
Outward, also efficiently solve the problem of existing oil displacement system temperature-resistant anti-salt performance difference.Additionally, the present invention
Tool surface active function polymer also there is good ageing resistace.Therefore such polymer flooding
Oil preparation is applied to high, medium and low infiltration oil reservoir, high-temperature oil reservoir, the unconventional oil such as high temperature and high salt oil deposit
Hide, oil recovery factor can be improved in tertiary oil recovery further.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part
Bright.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description,
It is used for explaining the present invention together with detailed description below, but do not constitute the limit to the present invention
System.In the accompanying drawings：
Fig. 1 be the present invention test case 1 in polymer P 5 solution, polymer P 7 solution, polymer
The apparent viscosity of P8 solution and acrylamide polymer (FP6030) solution and KYP solution is with temperature
Change curve.
Fig. 2 be the present invention test case 2 in polymer P 5 solution, polymer P 7 solution, polymer
The surface tension of P8 solution and acrylamide polymer (FP6030) solution and KYP solution is with concentration
Change curve.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place
The specific embodiment of description is merely to illustrate and explains the present invention, is not limited to the present invention.
In a first aspect, the invention provides a kind of polymer of tool surface active function, this polymer contains
There are construction unit A, construction unit B and construction unit C, wherein, described construction unit A is to have formula
(1) construction unit of structure shown in, described construction unit B is the structure with structure shown in formula (2)
Unit, described construction unit C is the construction unit with structure shown in formula (3)；Wherein, with described
On the basis of the weight of polymer, the content of described construction unit A is 45-89 weight %, described structure list
The content of first B is 10-40 weight %, and the content of described construction unit C is 1-15 weight %, described poly-
The viscosity-average molecular weight of compound is 5,000,000-2,000 ten thousand；
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3Alkylene for C1-C14
Base；R4And R5It is each independently the alkyl of H or C1-C4, and R4And R5It is asynchronously H；M
For H, Na or K；R6Alkyl for H or C1-C4；R7Alkyl for C1-C16.
In the present invention, the alkyl of described C1-C4 refers to the alkyl that carbon number is 1-4；Described
The alkylidene of C1-C14 refers to the alkylidene that carbon number is 1-14；The alkyl of described C1-C16 refers to
Carbon number is the alkyl of 1-16.
According to the present invention, the alkyl of described C1-C4 can include but is not limited to：Methyl, ethyl, just
Propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
According to the present invention, the alkylidene of described C1-C14 can be straight or branched, described C1-C14
Alkylidene can include but is not limited to：Methylene, ethylidene, sub- n-pro-pyl, isopropylidene, Asia
Normal-butyl, sub- sec-butyl, isobutylidene, the sub- tert-butyl group, sub- n-pentyl, isoamylidene, sub- uncle penta
Base, sub- neopentyl, sub- n-hexyl, sub- n-heptyl, sub- n-octyl, sub- n-nonyl, sub- positive decyl,
Sub- positive hendecyl, sub- positive dodecyl, sub- positive tritriacontyl and sub- positive tetradecyl, preferably methylene.Institute
State alkylidene refer to alkane lose two hydrogen atoms after residue, described two hydrogen atoms can be same
Two hydrogen atoms on individual carbon atom, it is also possible to two hydrogen atoms on different carbon atom, can be straight
Chain or side chain, for example, described ethylidene can be-CH2CH2- or
-CH(CH3)-.
According to the present invention, the alkyl of described C1-C16 can be straight or branched, described C1-C16
Alkyl can include but is not limited to：Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, Zhong Ding
Base, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, positive heptan
Base, n-octyl, n-nonyl, positive decyl, positive hendecyl, positive dodecyl, positive tritriacontyl, positive 14
Base, positive pentadecyl and positive palmityl.
According to the invention it is preferred in the case of, in the construction unit of structure shown in formula (1), formula (2) institute
Show in the construction unit and the construction unit of structure shown in formula (3) of structure, R1And R2It is each independently
H, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl；R3For methylene, ethylidene, Asia positive third
Base, sub- normal-butyl, sub- n-pentyl, sub- n-hexyl；R4And R5It is each independently H, methyl, second
Base, n-pro-pyl, isopropyl, normal-butyl, and R4And R5It is asynchronously H；M is H, Na or K；
R6For H, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl；R7For normal-butyl, sec-butyl,
Isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl,
N-octyl, n-nonyl, positive decyl, positive hendecyl, positive dodecyl.
According to the invention it is preferred in the case of, in the construction unit of structure shown in formula (1), formula (2) institute
Show in the construction unit and the construction unit of structure shown in formula (3) of structure, R1And R2It is each independently
H, methyl, ethyl, n-pro-pyl；R3For methylene, ethylidene, sub- n-pro-pyl, sub- normal-butyl；R4
And R5It is each independently H, methyl, ethyl, n-pro-pyl, and R4And R5It is asynchronously H；M is
Na or K；R6For H, methyl, ethyl, n-pro-pyl；R7For normal-butyl, n-pentyl, n-hexyl,
N-heptyl, n-octyl, n-nonyl, positive decyl, positive hendecyl, positive dodecyl.
According to the invention it is preferred in the case of, in the construction unit of structure shown in formula (1), formula (2) institute
Show in the construction unit and the construction unit of structure shown in formula (3) of structure, R1And R2It is each independently
H, methyl；R3For methylene；R4And R5It is each independently H, methyl, ethyl, and R4And R5
It is asynchronously H；M is Na or K；R6For H, methyl, ethyl；R7For normal-butyl, n-pentyl,
N-hexyl, n-octyl, positive decyl, positive dodecyl.
The present inventor finds under study for action, by specific construction unit A, construction unit B and knot
The polymer of structure unit C composition is used for obtain preferable oil displacement efficiency during oil displacement agent.For example, according to
A kind of preferred embodiment of the present invention, described construction unit A is to have knot shown in formula (7)
The construction unit of structure, described construction unit B is the construction unit with structure shown in formula (8), and
Described construction unit C is to have the construction unit of structure shown in formula (9), have knot shown in formula (10)
The construction unit of structure and at least one having in the construction unit of structure shown in formula (11),
In the case of more preferably, in the present invention, on the basis of the weight of described polymer, described knot
The content of structure unit A is 50-75 weight %, and the content of described construction unit B is 15-40 weight %,
The content of described construction unit C is 5-10 weight %, and the viscosity-average molecular weight of described polymer is 5,000,000
- 1,600 ten thousand.
According to the present invention, the intrinsic viscosity η of the polymer of described tool surface active function can be
1000-3300mL/g；The polymer of described tool surface active function is dissolved in salinity is
When being configured to the solution that concentration is 1500mg/L in the saline of 10000mg/L, the surface tension of this solution
Can be 32-40mN/m.Under preferable case, the characteristic of the polymer of described tool surface active function is glued
Number η is 1000-2650mL/g；The polymer of described tool surface active function is dissolved in salinity is
When being configured to the solution that concentration is 1500mg/L in the saline of 10000mg/L, the surface tension of this solution
For 32-36.5mN/m.
In the present invention, the polyacrylamide intrinsic viscosity that intrinsic viscosity specifies according to GB12005.1-89
Assay method is measured, and measures the NaCl solution of 10 weight % at 25 DEG C with Ubbelohde viscometer.Table
Face tension force is measured using Dataphysics DCAT21 surface tension instrument.Salinity in the present invention
Refer to Na in simulated formation water+、K+、Ca2+、Mg2+、Cl-、SO4 2-、CO3 2-Contain Deng inorganic ionss
The summation of amount.
Second aspect, the invention provides a kind of preparation method of the polymer of tool surface active function,
The method includes：In the presence of in initiator with as the water of solvent, make monomer D, monomer E and monomer
F carries out solution polymerization, and wherein, described monomer D is the monomer with structure shown in formula (4),
Described monomer E is the monomer with structure shown in formula (5), and described monomer F is to have shown in formula (6)
The monomer of structure, wherein, the consumption of described monomer D, monomer E and monomer F makes prepare to gather
In compound, the content of construction unit A is 45-89 weight %, and the content of construction unit B is 10-40 weight
The content of amount %, construction unit C is 1-15 weight %, and makes gluing all of the polymer preparing
Molecular weight is 5,000,000-2,000 ten thousand；Described construction unit A is the structure with structure shown in formula (1)
Unit, described construction unit B is the construction unit with structure shown in formula (2), described construction unit
C is the construction unit with structure shown in formula (3),
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3Alkylene for C1-C14
Base；R4And R5It is each independently the alkyl of H or C1-C4, and R4And R5It is asynchronously H；M
For H, Na or K；R6Alkyl for H or C1-C4；R7Alkyl for C1-C16.
In the present invention, the construction unit of structure shown in described formula (1), the knot of structure shown in formula (2)
Structure unit, the construction unit of structure shown in formula (3), the monomer of structure shown in formula (4), formula (5)
The related definition of substituent group in the monomer of shown structure and the monomer of structure shown in formula (6) and material kind
Class is noted earlier corresponding identical with the present invention's, and the present invention will not be described here, those skilled in the art
Should not be construed as the restriction to technical scheme.
According to the present invention, the consumption of described monomer can change, with described monomer in wider scope
Total amount on the basis of, the consumption of described monomer D can be 45-89 weight %, preferably 50-75 weight
Amount %.
According to the present invention, the consumption of described monomer can change, with described monomer in wider scope
Total amount on the basis of, the consumption of described monomer E can be 10-40 weight %, preferably 15-40 weight
Amount %.
According to the present invention, the consumption of described monomer can change, with described monomer in wider scope
Total amount on the basis of, the consumption of described monomer F can be 1-15 weight %, preferably 5-10 weight %.
In the present invention, it should be noted that described one body approximation is fully converted to have surface activity work(
The corresponding construction unit that the polymer of energy contains, the consumption of described monomer and described tool surface activity work(
The content of the corresponding construction unit that the polymer of energy contains can be consistent.
According to the invention it is preferred to what the consumption of described monomer D, monomer E and monomer F made to prepare
In polymer, the content of construction unit A is 50-75 weight %, and the content of construction unit B is 15-40 weight
The content of amount %, construction unit C is 5-10 weight %, and makes gluing all of the polymer preparing
Molecular weight is 5,000,000-1,600 ten thousand.
The present inventor finds under study for action, is carried out by specific monomer D, monomer E and monomer F
The polymer obtaining during reaction is used for obtain preferable oil displacement efficiency during oil displacement agent.For example, according to
A kind of specific preferred implementation of the present invention, described monomer D is to have structure shown in formula (12)
Monomer；Described monomer E is the monomer with structure shown in formula (13)；Described monomer F is to have formula (14)
The monomer of shown structure, there is the monomer of structure shown in formula (15) and have structure shown in formula (16)
At least one in monomer,
The method according to the invention, the total amount of described monomer D, described monomer E and described monomer F does not have
Special limit, can change in wider scope, using as the water of solvent and described monomer D,
On the basis of the total amount of described monomer E and described monomer F, described monomer D, described monomer E and described list
The total content of body F can be 15-35 weight %, preferably 20-30 weight %.
The method according to the invention, the condition of described solution polymerization can be the conventional bar in this area
Part, for example described polyreaction is carried out in the presence of an inert gas.
Under preferable case, in the present invention, described solution polymerization condition can include：Polymerization temperature
Spend for 0-30 DEG C, preferably 0-20 DEG C；Polymerization time is 2-15 hour, preferably 5-10 hour.
For save energy and reduces cost, described polyreaction is preferably carried out under adiabatic conditions.Institute
Stating noble gases is the gas not reacted with raw material and product, for example can be conventional for this area
At least one in group 0 element gas in nitrogen or the periodic table of elements, preferably nitrogen and/or argon
Gas.
The method according to the invention, described solution polymerization preferably enters under conditions of pH value is for 6-10
OK.Described pH value can be obtained by adding pH value regulator in polymerization system, and described pH value is adjusted
Section agent can be the conventional various pH value regulator in this area, for example, can be sodium hydroxide, carbonic acid
At least one in sodium, potassium carbonate and ammonia, preferably sodium hydroxide.
The method according to the invention, there is no particular limitation for the consumption of described initiator, can be wider
In the range of change, on the basis of the total amount of described monomer D, described monomer E and described monomer F, institute
The consumption stating initiator is 0.01-0.1 weight %.
The method according to the invention, described initiator can be the conventional various initiators in this area, example
As being any two kinds in radical polymerization initiator：Described radical polymerization initiator bag
Include azo-initiator, peroxide type initiators and redox type initiators.Described azo draws
Send out agent and be selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azodicarbonamide, idol
Nitrogen diisopropyl imidazoline hydrochloride, azo isobutyl cyano group Methanamide, azo diisopropyl imidazoline hydrochloride, idol
Nitrogen dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and idol
At least one in the different heptonitrile of nitrogen two；Described peroxide type initiators are selected from hydrogen peroxide, persulfuric acid
In ammonium, sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester at least
A kind of；Described redox type initiators are selected from sulfate-sulphite, persulfate-thiourea, over cure
At least one in hydrochlorate-organic salt and Ammonium persulfate .-fatty amine.
The method according to the invention, adds chelating agen can prevent metal ion from producing shadow to polyreaction
Ring, it is therefore preferable that in the case of, described solution polymerization is carried out in the presence of chelating agen.Described chela
Mixture can be disodiumedetate, aminotriacetic acid or ammonium citrate, preferably ethylenediamine tetrem
Acid disodium.There is no particular limitation for the consumption to described chelating agen for the present invention, can be in wider scope
Change, on the basis of the total amount of described monomer D, described monomer E and described monomer F, described chelating agen
Consumption can be 0.1-0.3 weight %.
The method according to the invention, adds auxiliary agent can improve the dissolubility of polymer, it is therefore preferable that feelings
Under condition, described solution polymerization is carried out in the presence of auxiliary agent.Described auxiliary agent can for carbamide, thiourea and
At least one in ammonia, preferably carbamide.There is no particular limitation for the consumption to described auxiliary agent for the present invention,
Can change in wider scope, the total amount with described monomer D, described monomer E and described monomer F is
Benchmark, the consumption of described auxiliary agent can be 0.01-0.1 weight %.
The method according to the invention, adds molecular weight regulator can synthesize the polymer of different molecular weight,
It is therefore preferable that in the case of, described polyreaction is carried out in the presence of molecular weight regulator.Described molecular weight
Regulator can be isopropanol, ammonia, N, in N '-methylene-bisacrylamide and dimethyl sulfourea extremely
Few one kind.The consumption of described molecular weight regulator can be selected according to the conventional amount used of this area.Example
As, on the basis of the total amount of described monomer D, described monomer E and described monomer F, described molecular-weight adjusting
The consumption of agent can be 0.001-0.1 weight %.
The third aspect, the invention provides the tool surface active function being prepared by preceding method is poly-
Compound.
Fourth aspect, the invention provides the polymer of aforementioned tool surface active function is as polymer flooding
The application of oil preparation.
Above-mentioned tool surface active function polymer as in the application of polymer oil-displacing agent, specifically
The technology that application process is well known to those skilled in the art.
The polymer of the described tool surface active function of the present invention can serve as polymer oil-displacing agent, can fit
For high, medium and low infiltration oil reservoir and high-temperature oil reservoir and high temperature and high salt oil deposit, enter in tertiary oil recovery
One step improves oil recovery factor.
Hereinafter will be described the present invention by embodiment.
In following examples, the method for testing being related to is as follows：
The dissolution time of polymer is measured by the method that GB12005.8-89 specifies.
The polyacrylamide Intrinsic Viscosity Measurements that the intrinsic viscosity η of polymer is specified by GB12005.1-89
Method is measured, and measures 10 weight %NaCl solution with Ubbelohde viscometer at 25 DEG C.
Viscosity molecular weight is according to formula M=([η]/K)1/αIt is calculated, wherein K=4.75 × 10-3,
α=0.80.
The apparent viscosity of polymer solution is tested with Brookfield DV-III viscometer, and rotating speed is
6r·min-1.
Surface tension adopts Dataphysics DCAT21 surface tension instrument to measure, and test temperature is
30℃.
In following examples, the apparent viscosity conservation rate of aqueous solutions of polymers of tool surface active function
Method of testing includes：Polymer is dissolved in the salt of salinity 10000mg/L with the concentration of 1500mg/L
In water, solution deoxygenation to oxygen content is less than 1mg/L, by the aqueous solution obtaining aging 1 at 90 DEG C
After month, measure 25 DEG C of above-mentioned aqueous solution of apparent viscosity with Brookfield viscometer, use below equation
Calculate apparent viscosity conservation rate：
In following examples, used reagent is commercially available chemically pure reagent, uses in test case
Polymer samples are FP6030 and KYP.Wherein, FP6030 is the trade mark that French SNF company produces
Acrylamide polymer for FP6030, the viscosity-average molecular weight of FP6030 is 18,000,000；KYP is oil
Field provide with sample, KYP contains acrylamide construction unit and 2- methyl -2- acrylamido third
Sulfonic acid structures unit, on the basis of the weight of KYP, the content of acrylamide construction unit is 75 weights
Amount %, the content of 2- methyl -2- acryamidopropanesulfonic acid construction unit is 25 weight %, and KYP's is viscous
Average molecular weight is 10,100,000, and intrinsic viscosity is 1915mL/g.
Embodiment 1
The present embodiment is used for polymer of tool surface active function of the present invention and preparation method thereof is described.
Using aqueous solution polymerization method, add in the adiabatic polymerisation reactor have surface thermocouple
0.375g structures alone MAS-1 (Dandong Jin Hai Fine Chemical Co., Ltd) conduct as shown in formula (14)
Water-soluble surface-active monomer, 33.375g acrylamide, the 2- acrylamido -2- methyl-prop of 3.75g
Sulfonic acid and distilled water, on the basis of the total content of monomer and distilled water, the total content of monomer is 15 weights
Amount %, the solution being stirred well in polymerisation bottle is changed into clear solution.It is subsequently adding 50mg auxiliary agent
Carbamide, 75mg disodiumedetate, 1mL ammonia and 10mg isopropanol, use hydroxide simultaneously
Sodium regulation system pH value, to 6, is passed through the high pure nitrogen that volumetric concentration is 99.99% 30 minutes to remove
Oxygen in polymerisation bottle.Then 20mg Ammonium persulfate., 15mg sodium sulfite are sequentially added,
Continue to be passed through high pure nitrogen 10 minutes, polymerization temperature is 25 DEG C, react 3 hours, obtain transparent having
The polymer of viscosity, obtains the polymer having surface active function through pelletize, drying, pulverizing, screening
P1.
Consumption according to acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and structures alone MAS-1
Can calculate and learn, in the polymer P 1 of tool surface active function, the structure of derived from acrylamides
The content of unit is about 89 weight %, the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acid
Content be about 10 weight %, the content of the construction unit derived from structures alone MAS-1 is about 1 weight
Amount %.
The intrinsic viscosity of the polymer P 1 of tool surface active function is 1088mL/g, and viscosity-average molecular weight is
5010000, the simulated formation water prepared polymer solution being 10000mg/L with oil field salinity, in polymerization
Thing solution concentration is 1500mg/L, and the surface tension of this solution is 39.6mN/m.With oil field salinity it is
The simulated formation water prepared polymer solution of 10000mg/L, in polymer solution concentration be
1500mg/L, shear rate is 7.34s-1Under conditions of, the apparent viscosity when 25 DEG C for the polymer solution
For 16.9mPa s, the apparent viscosity when 85 DEG C is 8.1mPa s, and polymer solution is at 90 DEG C
After aging 1 month in substantially free of environment, apparent viscosity conservation rate is 92.2%, shows the tool table obtaining
The polymer of face active function has preferable surface activity, temperature-resistant anti-salt ability, good viscous water
Media capabilities and good ageing resistace.
Embodiment 2
The present embodiment is used for polymer of tool surface active function of the present invention and preparation method thereof is described.
Using aqueous solution polymerization method, add in there is the polymer reactor of thermal insulation of surface thermocouple
5g as shown in formula (14) structures alone MAS-1 (Dandong Jin Hai Fine Chemical Co., Ltd) as water
Soluble surfactant's monomer, 25g acrylamide, the 2- acrylamide-2-methylpro panesulfonic acid of 20g and steaming
Distilled water, on the basis of the total content of monomer and distilled water, the total content of monomer is 20 weight %, fully
The solution stirring to polymerisation bottle is changed into clear solution.Be subsequently adding 50mg auxiliary agent carbamide,
75mg disodiumedetate, 1mL ammonia, simultaneously with sodium hydroxide regulation system pH value to 7,
It is passed through the high pure nitrogen that volumetric concentration is 99.99% 30 minutes to remove the oxygen in polymerisation bottle.So
After sequentially add 10mg Ammonium persulfate., 10mg sodium sulfite, continue to be passed through 10 points of high pure nitrogen
Clock, polymerization temperature is 15 DEG C, reacts 5 hours, obtains the transparent polymer with viscosity, through making
Grain, be dried, pulverize, screening obtain have surface active function polymer P 2.
Consumption according to acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and structures alone MAS-1
Can calculate and learn, in the polymer P 2 of tool surface active function, the structure of derived from acrylamides
The content of unit is about 50 weight %, the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acid
Content be about 40 weight %, the content of the construction unit derived from structures alone MAS-1 is about 10
Weight %.
The intrinsic viscosity of the polymer P 2 of tool surface active function is 1278mL/g, and viscosity-average molecular weight is
6120000, the simulated formation water prepared polymer solution being 10000mg/L with oil field salinity, in polymerization
Thing solution concentration is 1500mg/L, and the surface tension of this solution is 32.3mN/m.With oil field salinity it is
The simulated formation water prepared polymer solution of 10000mg/L, in polymer solution concentration be
1500mg/L, shear rate is 7.34s-1Under conditions of, the apparent viscosity when 25 DEG C for the polymer solution
For 18.3mPa s, the apparent viscosity when 85 DEG C is 9.0mPa s, and polymer solution is at 90 DEG C
After aging 1 month in substantially free of environment, apparent viscosity conservation rate is 93.7%, shows the tool table obtaining
The polymer of face active function has good surface activity, temperature-resistant anti-salt ability, good viscous water
Media capabilities and good ageing resistace.
Embodiment 3
The present embodiment is used for polymer of tool surface active function of the present invention and preparation method thereof is described.
Using aqueous solution polymerization method, add in the adiabatic polymerisation reactor have surface thermocouple
9.375g structures alone MAS-1 (Dandong Jin Hai Fine Chemical Co., Ltd) conduct as shown in formula (14)
Water-soluble surface-active monomer, 28.125g acrylamide, the 2- acrylamido -2- methyl-prop sulphur of 25g
Acid and distilled water, on the basis of the total content of monomer and distilled water, the total content of monomer is 25 weights
Amount %, the solution being stirred well in polymerisation bottle is changed into clear solution.It is subsequently adding 75mg auxiliary agent
Carbamide, 100mg disodiumedetate, 1mL ammonia and 5mgN, N- methylene bisacrylamide acyl
Amine, uses sodium hydroxide regulation system pH value to 8 simultaneously, is passed through the High Purity Nitrogen that volumetric concentration is 99.99%
Gas 30 minutes is to remove the oxygen in polymerisation bottle.Then sequentially add 15mg Ammonium persulfate.,
10mg sodium sulfite, continues to be passed through high pure nitrogen 10 minutes, and polymerization temperature is 10 DEG C, reacts 5
Hour, obtain the transparent polymer with viscosity, obtain tool table through pelletize, drying, pulverizing, screening
The polymer P 3 of face active function.
Consumption according to acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and structures alone MAS-1
Can calculate and learn, in the polymer P 3 of tool surface active function, the structure of derived from acrylamides
The content of unit is about 45 weight %, the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acid
Content be about 40 weight %, the content of the construction unit derived from structures alone MAS-1 is about 15
Weight %.
The intrinsic viscosity of the polymer P 3 of tool surface active function is 1433mL/g, and viscosity-average molecular weight is
7070000, the simulated formation water prepared polymer solution being 10000mg/L with oil field salinity, in polymerization
Thing solution concentration is 1500mg/L, and the surface tension of this solution is 32.1mN/m.With oil field salinity it is
The simulated formation water prepared polymer solution of 10000mg/L, in polymer solution concentration be
1500mg/L, shear rate is 7.34s-1Under conditions of, the apparent viscosity when 25 DEG C for the polymer solution
For 21.5mPa s, the apparent viscosity when 85 DEG C is 11.7mPa s, and polymer solution is at 90 DEG C
After aging 1 month in substantially free of environment, apparent viscosity conservation rate is 93.1%, shows the tool table obtaining
The polymer of face active function has good surface activity, temperature-resistant anti-salt ability, good viscous water
Media capabilities and good ageing resistace.
Embodiment 4
The present embodiment is used for polymer of tool surface active function of the present invention and preparation method thereof is described.
Using aqueous solution polymerization method, add in the adiabatic polymerisation reactor have surface thermocouple
4.25g structures alone MAS-1 (Dandong Jin Hai Fine Chemical Co., Ltd) conduct as shown in formula (14)
Water-soluble surface-active monomer, 42.0g acrylamide, the 2- acrylamido -2- methyl-prop sulphur of 16.25g
Acid and distilled water, on the basis of the total content of monomer and distilled water, the total content of monomer is 25 weights
Amount %, the solution being stirred well in polymerisation bottle is changed into clear solution.It is subsequently adding 75mg auxiliary agent
Carbamide, 100mg disodiumedetate, 2mL ammonia and 10mgN, N- methylene bisacrylamide acyl
Amine, uses sodium hydroxide regulation system pH value to 8 simultaneously, is passed through the High Purity Nitrogen that volumetric concentration is 99.99%
Gas 30 minutes is to remove the oxygen in polymerisation bottle.Then sequentially add 15mg Ammonium persulfate.,
20mg sodium sulfite, continues to be passed through high pure nitrogen 10 minutes, and polymerization temperature is 10 DEG C, reacts 10
Hour, obtain the transparent polymer with viscosity, obtain tool table through pelletize, drying, pulverizing, screening
The polymer P 4 of face active function.
Consumption according to acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and structures alone MAS-1
Can calculate and learn, in the polymer P 4 of tool surface active function, the structure of derived from acrylamides
The content of unit is about 67.2 weight %, the structure list derived from 2- acrylamide-2-methylpro panesulfonic acid
The content of unit is about 26 weight %, and the content of the construction unit derived from structures alone MAS-1 is about 6.8
Weight %.
The intrinsic viscosity of the polymer P 4 of tool surface active function is 1623mL/g, and viscosity-average molecular weight is
8260000, the simulated formation water prepared polymer solution being 10000mg/L with oil field salinity, in polymerization
Thing solution concentration is 1500mg/L, and the surface tension of this solution is 35.7mN/m.With oil field salinity it is
The simulated formation water prepared polymer solution of 10000mg/L, in polymer solution concentration be
1500mg/L, shear rate is 7.34s-1Under conditions of, the apparent viscosity when 25 DEG C for the polymer solution
For 23.8mPa s, the apparent viscosity when 85 DEG C is 13.5mPa s, and polymer solution is at 90 DEG C
After aging 1 month in substantially free of environment, apparent viscosity conservation rate is 95.0%, shows the tool table obtaining
The polymer of face active function has good surface activity, temperature-resistant anti-salt ability, good viscous water
Media capabilities and good ageing resistace.
Embodiment 5
The present embodiment is used for polymer of tool surface active function of the present invention and preparation method thereof is described.
Using aqueous solution polymerization method, add in the adiabatic polymerisation reactor have surface thermocouple
3.75g structures alone MAS-2 (Dandong Jin Hai Fine Chemical Co., Ltd) conduct as shown in formula (15)
Water-soluble surface-active monomer, 43.75g acrylamide, the 2- acrylamide-2-methylpro panesulfonic acid of 15g
And distilled water, on the basis of the total content of monomer and distilled water, the total content of monomer is 25 weight %,
The solution being stirred well in polymerisation bottle is changed into clear solution.Be subsequently adding 75mg auxiliary agent carbamide,
The N,N methylene bis acrylamide of 150mg disodiumedetate, 2mL ammonia and 20mg, with
When with sodium hydroxide regulation system pH value to 8, be passed through the high pure nitrogen 30 that volumetric concentration is 99.99%
Minute is to remove the oxygen in polymerisation bottle.Then 15mg Ammonium persulfate., 30mg Asia are sequentially added
Sodium bisulfate, continues to be passed through high pure nitrogen 10 minutes, and polymerization temperature is 10 DEG C, reacts 15 hours, obtains
To the transparent polymer with viscosity, obtain having surface activity work(through pelletize, drying, pulverizing, screening
The polymer P 5 of energy.
Consumption according to acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and structures alone MAS-2
Can calculate and learn, in the polymer P 5 of tool surface active function, the structure of derived from acrylamides
The content of unit is about 70 weight %, the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acid
Content be about 24 weight %, the content of the construction unit derived from structures alone MAS-2 is about 6 weights
Amount %.
The intrinsic viscosity of the polymer P 5 of tool surface active function is 1910mL/g, and viscosity-average molecular weight is
10130000, the simulated formation water prepared polymer solution being 10000mg/L with oil field salinity, poly-
Polymer solution concentration is 1500mg/L, and the surface tension of this solution is 35.9mN/m.Use oil field salinity
Simulated formation water prepared polymer solution for 10000mg/L, in polymer solution concentration be
1500mg/L, shear rate is 7.34s-1Under conditions of, the apparent viscosity when 25 DEG C for the polymer solution
For 28.6mPa s, the apparent viscosity when 85 DEG C is 15.1mPa s, and polymer solution is at 90 DEG C
After aging 1 month in substantially free of environment, apparent viscosity conservation rate is 92.9%, shows the tool table obtaining
The polymer of face active function has good surface activity, temperature-resistant anti-salt ability, good viscous water
Media capabilities and good ageing resistace.
Embodiment 6
The present embodiment is used for polymer of tool surface active function of the present invention and preparation method thereof is described.
Using aqueous solution polymerization method, add in the adiabatic polymerisation reactor have surface thermocouple
6.25g structures alone MAS-3 (Dandong Jin Hai Fine Chemical Co., Ltd) conduct as shown in formula (16)
Water-soluble surface-active monomer, 46.875g acrylamide, the 2- acrylamido -2- methyl-prop of 9.375g
Sulfonic acid and distilled water, on the basis of the total content of monomer and distilled water, the total content of monomer is 25 weight %,
The solution being stirred well in polymerisation bottle is changed into clear solution.Be subsequently adding 75mg auxiliary agent carbamide,
150mg disodiumedetate, 2mL ammonia and 5mg dimethyl sulfourea, use sodium hydroxide simultaneously
Regulation system pH value, to 8, is passed through the high pure nitrogen that volumetric concentration is 99.99% and is gathered with removing for 30 minutes
Close the oxygen in reaction bulb.Then sequentially add 15mg Ammonium persulfate., 15mg sodium sulfite, continue
Continuous be passed through high pure nitrogen 10 minutes, polymerization temperature is 5 DEG C, reacts 10 hours, obtain transparent have viscous
The polymer of degree, obtains the polymer P 6 having surface active function through pelletize, drying, pulverizing, screening.
Consumption according to acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and structures alone MAS-3
Can calculate and learn, in the polymer P 6 of tool surface active function, the structure of derived from acrylamides
The content of unit is about 75 weight %, the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acid
Content be about 15 weight %, the content of the construction unit derived from structures alone MAS-3 is about 10
Weight %.
The intrinsic viscosity of the polymer P 6 of tool surface active function is 2330mL/g, and viscosity-average molecular weight is
12950000, the simulated formation water prepared polymer solution being 10000mg/L with oil field salinity, poly-
Polymer solution concentration is 1500mg/L, and the surface tension of this solution is 34.0mN/m.Use oil field salinity
Simulated formation water prepared polymer solution for 10000mg/L, in polymer solution concentration be
1500mg/L, shear rate is 7.34s-1Under conditions of, the apparent viscosity when 25 DEG C for the polymer solution
For 31.6mPa s, the apparent viscosity when 85 DEG C is 15.8mPa s, and polymer solution is at 90 DEG C
After aging 1 month in substantially free of environment, apparent viscosity conservation rate is 95.0%, shows the tool table obtaining
The polymer of face active function has good surface activity, temperature-resistant anti-salt ability, good viscous water Jie
Mass-energy power and good ageing resistace.
Embodiment 7
The present embodiment is used for polymer of tool surface active function of the present invention and preparation method thereof is described.
Using aqueous solution polymerization method, add in the adiabatic polymerisation reactor have surface thermocouple
7.35g structures alone MAS-2 (Dandong Jin Hai Fine Chemical Co., Ltd) conduct as shown in formula (15)
Water-soluble surface-active monomer, 45.15g acrylamide, the 2- acrylamide-2-methylpro panesulfonic acid of 35g
And distilled water, on the basis of the total content of monomer and distilled water, the total content of monomer is 35 weight %,
The solution being stirred well in polymerisation bottle is changed into clear solution.Be subsequently adding 75mg auxiliary agent carbamide,
100mg disodiumedetate, 2mL ammonia and 5mg dimethyl sulfourea, use sodium hydroxide simultaneously
Regulation system pH value, to 10, is passed through the high pure nitrogen that volumetric concentration is 99.99% and is gathered with removing for 30 minutes
Close the oxygen in reaction bulb.Then sequentially add 15mg Ammonium persulfate., 30mg sodium sulfite, continue
Continuous be passed through high pure nitrogen 10 minutes, polymerization temperature is 0 DEG C, reacts 8 hours, obtains transparent thering is viscosity
Polymer, obtain the polymer P 7 having surface active function through pelletize, drying, pulverizing, screening.
Consumption according to acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and structures alone MAS-2
Can calculate and learn, in the polymer P 7 of tool surface active function, the structure of derived from acrylamides
The content of unit is about 51.6 weight %, the structure list derived from 2- acrylamide-2-methylpro panesulfonic acid
The content of unit is about 40 weight %, and the content of the construction unit derived from structures alone MAS-2 is about 8.4
Weight %.
The intrinsic viscosity of the polymer P 7 of tool surface active function is 2415mL/g, and viscosity-average molecular weight is
13570000, the simulated formation water prepared polymer solution being 10000mg/L with oil field salinity, poly-
Polymer solution concentration is 1500mg/L, and the surface tension of this solution is 33.9mN/m.Use oil field salinity
Simulated formation water prepared polymer solution for 10000mg/L, in polymer solution concentration be
1500mg/L, shear rate is 7.34s-1Under conditions of, the apparent viscosity when 25 DEG C for the polymer solution
For 34.3mPa s, the apparent viscosity when 85 DEG C is 18.5mPa s, and polymer solution is at 90 DEG C
After aging 1 month in substantially free of environment, apparent viscosity conservation rate is 93.0%, shows the tool table obtaining
The polymer of face active function has good surface activity, temperature-resistant anti-salt ability, good viscous water
Media capabilities and good ageing resistace.
Embodiment 8
The present embodiment is used for polymer of tool surface active function of the present invention and preparation method thereof is described.
Using aqueous solution polymerization method, add in the adiabatic polymerisation reactor have surface thermocouple
3.75g structures alone MAS-2 (Dandong Jin Hai Fine Chemical Co., Ltd) conduct as shown in formula (15)
Water-soluble surface-active monomer, 56.25g acrylamide, the 2- acrylamide-2-methylpro panesulfonic acid of 15g
And distilled water, on the basis of the total content of monomer and distilled water, the total content of monomer is 30 weight %,
The solution being stirred well in polymerisation bottle is changed into clear solution.Be subsequently adding 75mg auxiliary agent carbamide,
100mg disodiumedetate, 2mL ammonia and 20mg dimethyl sulfourea, use sodium hydroxide simultaneously
Regulation system pH value, to 9, is passed through the high pure nitrogen that volumetric concentration is 99.99% and is gathered with removing for 30 minutes
Close the oxygen in reaction bulb.Then sequentially add 15mg Ammonium persulfate., 15mg sodium sulfite, continue
Continuous be passed through high pure nitrogen 10 minutes, polymerization temperature is 0 DEG C, reacts 10 hours, obtain transparent have viscous
The polymer of degree, obtains the polymer P 8 having surface active function through pelletize, drying, pulverizing, screening.
Consumption according to acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and structures alone MAS-2
Can calculate and learn, in the polymer P 8 of tool surface active function, the structure of derived from acrylamides
The content of unit is about 75 weight %, the construction unit derived from 2- acrylamide-2-methylpro panesulfonic acid
Content be about 20 weight %, the content of the construction unit derived from structures alone MAS-2 is about 5 weights
Amount %.
The intrinsic viscosity of the polymer P 8 of tool surface active function is 2631mL/g, and viscosity-average molecular weight is
15110000, the simulated formation water prepared polymer solution being 10000mg/L with oil field salinity, poly-
Polymer solution concentration is 1500mg/L, and the surface tension of this solution is 36.5mN/m.Use oil field salinity
Simulated formation water prepared polymer solution for 10000mg/L, in polymer solution concentration be
1500mg/L, shear rate is 7.34s-1Under conditions of, the apparent viscosity when 25 DEG C for the polymer solution
For 38.9mPa s, the apparent viscosity when 85 DEG C is 22.6mPa s, and polymer solution is at 90 DEG C
After aging 1 month in substantially free of environment, apparent viscosity conservation rate is 94.4%, shows the tool table obtaining
The polymer of face active function has good surface activity, temperature-resistant anti-salt ability, good viscous water
Media capabilities and good ageing resistace.
Test case 1
By comparative sample FP6030 (French SNF company) and KYP (oil field offer) and polymer P 5,
Polymer P 7 and polymer P 8 contrast, and (concentration is to observe aqueous solutions of polymers under different temperatures
1500mg/L, salinity is 10000mg/L) apparent viscosity, result is as shown in Figure 1.
It will be seen from figure 1 that being existed according to the polymer P 5 of the present invention, polymer P 7 and polymer P 8
85 DEG C still have higher apparent viscosity, the aqueous solution of polymer P 5, polymer P 7 and polymer P 8
Apparent viscosity can reach 15.1-22.6mPa s, and the trade mark that French SNF company produces is FP6030
Acrylamide polymer and the aqueous solution of acrylamide polymer that the code name that provides of oil field is KYP
Apparent viscosity is only 8.9-12.6mPa s, shows the polymer of the tool surface active function according to the present invention
There is good temperature-resistant anti-salt performance.
Test case 2
By comparative sample FP6030 (French SNF company) and KYP (oil field offer) and polymer P 5,
Polymer P 7 and polymer P 8 contrast, and observation salinity is that the simulated formation water of 10000mg/L is prepared
Variable concentrations (Cp) surface tension (γ) at 30 DEG C for the aqueous solutions of polymers, result such as Fig. 2
Shown.
Figure it is seen that with the increase of concentration, according to polymer P 5, the polymer P 7 of the present invention
It is gradually reduced with the surface tension of the aqueous solution of polymer P 8, when concentration is 1500mg/L, polymer
The surface tension of the aqueous solution of P5, polymer P 7 and polymer P 8 between 33.9-36.5N/m, table
Reveal good surface activity.The surface tension of the aqueous solution of comparative sample FP6030 and KYP is with concentration
Increase and decline, surface tension is between 60-70mN/m.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in embodiment, in the range of the technology design of the present invention, can be to the skill of the present invention
Art scheme carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention no longer separately illustrates to various possible compound modes.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as
, without prejudice to the thought of the present invention, it equally should be considered as content disclosed in this invention for it.
Claims (10)
1. a kind of polymer of tool surface active function is it is characterised in that this polymer contains structure list
First A, construction unit B and construction unit C, wherein, described construction unit A is for having formula (1) institute
Show the construction unit of structure, described construction unit B is the construction unit with structure shown in formula (2),
Described construction unit C is the construction unit with structure shown in formula (3)；Wherein, with described polymer
Weight on the basis of, the content of described construction unit A is 45-89 weight %, described construction unit B's
Content is 10-40 weight %, and the content of described construction unit C is 1-15 weight %, described polymer
Viscosity-average molecular weight is 5,000,000-2,000 ten thousand；
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3Alkylene for C1-C14
Base；R4And R5It is each independently the alkyl of H or C1-C4, and R4And R5It is asynchronously H；M
For H, Na or K；R6Alkyl for H or C1-C4；R7Alkyl for C1-C16.
2. polymer according to claim 1, wherein, with the weight of described polymer as base
Standard, the content of described construction unit A is 50-75 weight %, and the content of described construction unit B is 15-40
Weight %, the content of described construction unit C is 5-10 weight %, and the viscosity-average molecular weight of described polymer is
5000000-1,600 ten thousand.
3. polymer according to claim 1, wherein, described construction unit A is to have formula (7)
The construction unit of shown structure, described construction unit B is the construction unit with structure shown in formula (8),
And described construction unit C is for having the construction unit of structure shown in formula (9), having formula (10) institute
The construction unit showing structure and at least one having in the construction unit of structure shown in formula (11),
4. a kind of preparation method of the polymer of tool surface active function, the method includes：In initiator
In the presence of the water as solvent, monomer D, monomer E and monomer F is made to carry out solution polymerization,
Wherein, described monomer D is the monomer with structure shown in formula (4), and described monomer E is to have formula (5)
The monomer of shown structure, described monomer F is the monomer with structure shown in formula (6), wherein, described
The consumption of monomer D, monomer E and monomer F makes containing of construction unit A in the polymer preparing
Measure as 45-89 weight %, the content of construction unit B is 10-40 weight %, the content of construction unit C
For 1-15 weight %, and the viscosity-average molecular weight of the polymer preparing is made to be 5,000,000-2000
Ten thousand；Described construction unit A is the construction unit with structure shown in formula (1), described construction unit B
For having the construction unit of structure shown in formula (2), described construction unit C is to have knot shown in formula (3)
The construction unit of structure,
Wherein, R1And R2It is each independently the alkyl of H or C1-C4；R3Alkylene for C1-C14
Base；R4And R5It is each independently the alkyl of H or C1-C4, and R4And R5It is asynchronously H；M
For H, Na or K；R6Alkyl for H or C1-C4；R7Alkyl for C1-C16.
5. method according to claim 4, wherein, described monomer D, monomer E and monomer F
Consumption make construction unit A in the polymer preparing content be 50-75 weight %, structure list
The content of first B is 15-40 weight %, and the content of construction unit C is 5-10 weight %, and makes system
The viscosity-average molecular weight of the standby polymer obtaining is 5,000,000-1,600 ten thousand.
6. method according to claim 4, wherein, described monomer D is for having formula (12) institute
Show the monomer of structure；Described monomer E is the monomer with structure shown in formula (13)；Described monomer F is
There is the monomer of structure shown in formula (14), there is the monomer of structure shown in formula (15) and there is formula (16)
At least one in the monomer of shown structure,
7. the method according to any one in claim 4-6, wherein, described polymerisation in solution is anti-
The condition answered includes：Temperature is 0-30 DEG C, preferably 0-20 DEG C；Time is 2-15h, preferably 5-10h.
8. the method according to any one in claim 4-6, wherein, described initiator includes
At least one in azo-initiator, peroxide type initiators and redox type initiators；Described
Azo-initiator is selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo two formyl
Amine, azo dicyclohexyl formonitrile HCN hydrochlorate, azo isobutyl cyano group Methanamide, azo diisopropyl imidazoline hydrochloride,
Azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and idol
At least one in the different heptonitrile of nitrogen two；Described peroxide type initiators be selected from hydrogen peroxide, Ammonium persulfate.,
At least one in sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester；
Described redox type initiators be selected from sulfate-sulphite, persulfate-thiourea, persulfate-
At least one in organic salt and Ammonium persulfate .-fatty amine.
9. the tool surface active function that in claim 4-8, the method described in any one prepares
Polymer.
10. the polymer conduct of the tool surface active function described in any one in claim 1-3 and 9
The application of polymer oil-displacing agent.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4138381A (en) * | 1975-04-14 | 1979-02-06 | E. I. Du Pont De Nemours And Company | Polymeric thickeners, processes for their preparation and uses thereof |
| US4463151A (en) * | 1982-12-29 | 1984-07-31 | Exxon Research And Engineering Co. | Process for the formation of novel acrylamide acrylate copolymers |
| CN1178802A (en) * | 1995-11-24 | 1998-04-15 | 四川联合大学 | Polymer surfactant and preparation method thereof |
| WO2012069942A1 (en) * | 2010-11-24 | 2012-05-31 | Basf Se | Use of hydrophobically associating copolymer as additive in specific oilfield applications |
| CN104693351A (en) * | 2013-12-09 | 2015-06-10 | 中国石油化工股份有限公司 | Functional polymer with surface activity as well as preparation method and application thereof |
-
2015
- 2015-08-28 CN CN201510542915.XA patent/CN106478868A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4138381A (en) * | 1975-04-14 | 1979-02-06 | E. I. Du Pont De Nemours And Company | Polymeric thickeners, processes for their preparation and uses thereof |
| US4463151A (en) * | 1982-12-29 | 1984-07-31 | Exxon Research And Engineering Co. | Process for the formation of novel acrylamide acrylate copolymers |
| CN1178802A (en) * | 1995-11-24 | 1998-04-15 | 四川联合大学 | Polymer surfactant and preparation method thereof |
| WO2012069942A1 (en) * | 2010-11-24 | 2012-05-31 | Basf Se | Use of hydrophobically associating copolymer as additive in specific oilfield applications |
| CN104693351A (en) * | 2013-12-09 | 2015-06-10 | 中国石油化工股份有限公司 | Functional polymer with surface activity as well as preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 姚志钢等: "双子表面活性剂——二元醇双琥珀酸双酯磺酸钠（GMI-01）的合成与性能研究", 《精细化工》 * |
| 张振华等: "十二烷基烯丙基琥珀酸酯磺酸钠的合成", 《南华大学学报（自然科学版）》 * |
| 胡艾希等: "琥珀酸双酯磺酸钠类反应型表面活性剂的合成", 《精细化工》 * |
| 葛虹等: "反应型表面活性剂的研究进展", 《日用化学工业》 * |
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