CN106496406B - A kind of polymer and its preparation method and application of tool surface active function - Google Patents
A kind of polymer and its preparation method and application of tool surface active function Download PDFInfo
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Abstract
The present invention relates to polymer arts, disclose a kind of polymer and its preparation method and application of tool surface active function, the polymer of the tool surface active function 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)；On the basis of the weight of the polymer of the tool surface active function, the content that content that the content of the structural unit A is 50 85 weight %, the structural unit B is 10 40 weight %, the structural unit C is 1 10 weight %.The polymer of tool surface active function provided by the invention has both good surface-active, viscous water media capabilities and temperature-resistant anti-salt ability.
Description
Technical field
The present invention relates to polymer arts, and in particular, to a kind of tool polymer of surface active function, a kind of tool surface
Polymer, a kind of tool of the preparation method of the polymer of active function and the tool surface active function being prepared by this method
Application of the polymer of surface active function as oil displacement agent.
Background technology
Heatproof, anti-salt property to solve the problems, such as Polymer Used For Oil Displacement is poor, and researcher proposes to be drawn in the molecule
Enter function monomer and improve the method for polymer molecular weight to improve the apparent viscosity and temperature-resistant anti-salt performance of aqueous solutions of polymers,
Thus hydrophobic associated polymer, comb polymer, Heat Resistant and Salt Tolerant Polymer etc. are had developed, but this kind of polymer does not have table
Face activity and washing oil ability.
In tertiary oil recovery technology, ternary combined chemical flooding technology can realize grease ultralow interfacial tension, protect simultaneously
Injected fluid viscosity is held, recovery ratio is increased substantially.But the mixture of different component chemical agent is in reservoir of porous medium
The performance characteristics such as absorption, diffusion and migration differ greatly, and lead to " chromatographic fractionation effect " when the displacement of reservoir oil in reservoir pore.Simultaneously
Surfactant waste in displacement process increases, and recovery ratio and economic benefit reduce.When in addition using highly basic auxiliary agent, extraction
All too many levels generate serious scale in the process, and difficulty is brought to production management.
Ensure oil displacement system under high salinity and higher temperature conditions while there is sufficiently high viscosity and ultralow boundary
Face tension, it is necessary to break through the previous circle for utilizing polymer/surfactant compound system.In conjunction with high molecular tackifying ability with
The surface-active of low-molecular-weight surfactant, being introduced on macromolecular chain has the active functional group of good surface, reaches both
Thickening reduces the effect of interfacial tension again, and a kind of material plays the role of two kinds of materials of polymer and surfactant simultaneously, because
This such macromolecule oil-displacing agent with surface-active will be solved to a certain extent existing for polymer-surfactant combination flooding
Chromatographic fractionation effect problem, simultaneously because the thickening property with surface active function polymer, it also has stable foam
Effect, may act as foam stabilizer, these superior functions make it have in tertiary oil recovery in foam flooding and polynary foam composite flooding
Have broad application prospects.
Survey data in recent years shows that low-permeability oil deposit has become the key areas of China's In Oil Field Exploration And Development, cut-off
In 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, is accounted for
49.2%.No matter raising with degree of prospecting and the continuous growth to petroleum resources demand still open from residual petroleum resource
Send out trend analysis, low-permeability oil deposit by be China's future In Oil Field Exploration And Development main object.It is polymerize in low-permeability oil deposit
When object drives mining site design, it is necessary to the matching relationship of prior Study Polymer Melts relative molecular mass and reservoir permeability.In the areas Ju Qu
When block relative molecular mass is preferred, on the one hand to consider to select Polymer Molecular Weight as high as possible, to obtain more
Good polymer displacement of reservoir oil performance, on the other hand will consider the matching relationship of polymer molecule and different permeability oil reservoirs, as far as possible
Increase the enterable oil reservoir interstitial space of polymer solution, polymer flooding control extent is improved, to obtain better polymer flooding effect.Section
Polymer flooding, Polymer Molecular Weight can be carried out by grinding worker and obtaining low permeability pay by indoor moveable experimental study
There are certain relationships for matching between low permeability pay permeability, if shouted with hole with polymer molecule radius of gyration
Relationship reflects that then matching relationship can be expressed as matching relationship between road radius：For low-permeability oil reservoir, when pore constriction half
When the ratio between diameter and polymer molecule radius of gyration are more than 5 times, injection low relative molecular mass polymer will not block, and be less than
It will appear blocking at 5 times, obtained and result similar in major oil reservoir.If circled round with permeability square root and polymer molecule
The comparison experimental result of radius is stated, and can be expressed as the ratio between permeability square root and polymer molecule radius of gyration and is more than
Oil reservoir will not be blocked when 1.5.Accordingly, it is considered to be deposited to the matching between Polymer Molecular Weight and low permeability pay permeability
In certain relationship, the polymer of certain molecular weight range should be synthesized to meet the matching with low-permeability oil deposit.
As people deepen continuously to the research for having surface active function polymer, new kind and new synthesis side are developed
Method is also the hot spot of current research.But it is inadequate due to recognizing relation between structure and property, it is related to big point of physicochemical properties
Sub- water solution system again it is extremely complex, up to the present have this field of surface active function polymer progress it is slow,
For middle and low permeable reservoir tool surface active function polymer research almost without.Therefore its structure and performance are studied
Relationship synthesizes the copolymer with high surface of certain molecular weight range, has important theory and application value.
Alkyl or alkyl phenol polyoxyethylene ether acrylate are respectively adopted in US4138381, US4463151 and EP426864
Surface active monomer is copolymerized with acrylamide monomers, mainly utilizes the association of the hydrophobic grouping of surface active monomer in water
Effect, to make the viscosity of copolymer increase substantially, the copolymer containing surface active monomer component has better salt tolerant
Property, but amphipathic polymeric monomer component is difficult in bipolymer to interface aggregates, therefore, synthesized copolymer surface-active
It is bad.
In CN1178802A, it is copolymerized acrylamide monomers, surface-active macromonomers and ionic comonomer to obtain ternary
Copolymer, the copolymer viscosity is higher but surface-active is poor.Sun Lili of Southwest Petroleum Institute et al. uses homogeneous polymerization process,
A kind of novel high polymer surfactant (PS1) is synthesized, which is acrylamide, acrylic acid, methyl
Methyl acrylate terpolymer, the high molecular surfactant reduce the ability of surface tension not as good as low molecular surfactant activity
Agent compounds with inorganic salts, due to synergistic effect, will produce out the compound property better than single surfactant, makes surface
Power is even lower, but the temperature-resistant anti-salt performance of the high molecular surfactant is poor.Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences
It is poly- to have synthesized a kind of non-iron polymerizable with double bond using toluene di-isocyanate(TDI) and polyethers as primary raw material by Jin Yong et al.
Urethane high molecular surfactant, the high molecular surfactant can be such that solution surface tension drops in a concentration of 0.06mol/L
To 37.6mN/m (25 DEG C), while good surface-active can be still kept under very low concentrations, in addition, this it is polymerizable it is non-from
The ability that subtype polyurethane high molecule surfactant reduces surface tension increases with the increase of hydrophobic segment proportion,
But the polymerization activity of the non-iron polymerizable polyurethane high molecular surfactant is poor, while heat resistance is poor.
Invention content
The purpose of the present invention is overcome current high, medium and low infiltration oil reservoir polymer cannot have both good surface-active,
The shortcomings that viscous water media capabilities and temperature-resistant anti-salt ability, provides one kind and having both good surface-active, viscous water media capabilities
With temperature-resistant anti-salt ability tool surface active function polymer, the preparation method of the polymer of the tool surface active function, by
The polymer of the polymer for the tool surface active function that this method is prepared and the tool surface active function is as polymerization
The application of object oil displacement agent.
To achieve the goals above, in a first aspect, the present invention provides a kind of polymer of tool surface active function, the tool table
The polymer of face active function contains structural unit A, structural unit B and structural unit C, wherein the structural unit A be with
The structural unit of structure shown in formula (1), the structural unit B are the structural unit with structure shown in formula (2), the structure list
First C is the structural unit with structure shown in formula (3)；On the basis of the weight of the polymer of the tool surface active function, institute
The content for stating structural unit A is that the content of 50-85 weight %, the structural unit B are 10-40 weight %, the structural unit C
Content be 1-10 weight %, the viscosity average molecular weigh of the polymer of the tool surface active function is 5,000,000-2,000 ten thousand；
Wherein, R1And R2It is each independently H or C1-C4Alkyl；R3For C1-C14Alkylidene；R4And R5It is respectively independent
Ground is H or C1-C4Alkyl, and R4And R5It is asynchronously H；M in formula (2) and formula (3) is each independently H, Na or K；R6For
H or CH3；R7For C1-C18Alkyl；R8For C1-C18Alkyl；N is the integer selected from 3-10.
Second aspect, the present invention provide a kind of preparation method of the polymer of tool surface active function, and this method includes：
Initiator and as the water of solvent in the presence of, so that monomer D, monomer E and monomer F is carried out solution polymerization, wherein the list
Body D is the monomer with structure shown in formula (4), and the monomer E is the monomer with structure shown in formula (5), and the monomer F is tool
There is the monomer of structure shown in formula (6), wherein the dosage of the monomer D, monomer E and monomer F make in the polymer being prepared
It is the content of 10-40 weight %, structural unit C is 1- that the content of structural unit A, which is the content of 50-85 weight %, structural unit B,
10 weight %, and so that the viscosity average molecular weigh for the polymer being prepared is 5,000,000-2,000 ten thousand；The structural unit A is tool
It is the structural unit with structure shown in formula (2), the structure to have the structural unit of structure shown in formula (1), the structural unit B
Unit C is the structural unit with structure shown in formula (3),
Wherein, R1And R2It is each independently H or C1-C4Alkyl；R3For C1-C14Alkylidene；R4And R5It is respectively independent
Ground is H or C1-C4Alkyl, and R4And R5It is asynchronously H；M in formula (2) and formula (3) and formula (5) and formula (6) is respectively independent
Ground is H, Na or K；R6For H or CH3；R7For C1-C18Alkyl；R8For C1-C18Alkyl；N is the integer selected from 3-10.
The third aspect, the present invention provide the polymer for the tool surface active function being prepared by preceding method.
Fourth aspect, the present invention provide application of the polymer of aforementioned tool surface active function as polymer oil-displacing agent.
It is provided by the invention tool surface active function polymer have both good surface-active, viscous water media capabilities and
Temperature-resistant anti-salt ability.
The present invention is lived by introducing surface active monomer F to provide the surface of polymer from the angle of MOLECULE DESIGN
Property, the double bond of allyl has very high copolyreaction activity in molecular structure, is easily given birth to various other vinyl monomer copolymerizations
At different functional polymers, in addition, also containing strong cation and hydrophilic functional group's sulfonate radical in the molecular structure of monomer F
Ion has good dissolubility and anti-precipitated cationic performance, also contains polyethers non-ionic group in molecular structure, have good
Good water solubility and anti-cationic properties.
It is heretofore described tool surface active function polymer molecular weight control in a certain range with meet with not
Have in combination with the surface-active of high molecular tackifying and low-molecular-weight surfactant with the matching of permeability oil reservoir
The advantages that fluidity control and reduction oil/water interfacial tension effect, it is compound to solve polymer-surfactant to a certain extent
The problems such as driving existing chromatographic fractionation effect.In addition, also efficiently solving asking for existing oil displacement system temperature-resistant anti-salt performance difference
Topic.
In addition, the polymer of the tool surface active function of the present invention also has good anti-aging property.Therefore this is birdsed of the same feather flock together
It closes object oil displacement agent and is suitable for the nontraditional reservoirs such as high, medium and low infiltration oil reservoir, high-temperature oil reservoir, high temperature and high salt oil deposit, it can be three times
Oil recovery factor is further increased in oil recovery.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 be the present invention test case 1 in 3 solution of polymer P, 5 solution of polymer P, 6 solution of polymer P and acryloyl
The apparent viscosity variation with temperature curve graph of amine polymer (FP6030) solution and KYP solution.
Fig. 2 be the present invention test case 2 in 3 solution of polymer P, 5 solution of polymer P, 6 solution of polymer P and acryloyl
The surface tension of amine polymer (FP6030) solution and KYP solution with concentration change curve.
Specific implementation mode
The specific implementation mode of the present invention is described in detail 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.
In a first aspect, the present invention provides a kind of polymer of tool surface active function, which gathers
It closes object and contains structural unit A, structural unit B and structural unit C, wherein the structural unit A is with structure shown in formula (1)
Structural unit, the structural unit B be the structural unit with structure shown in formula (2), the structural unit C be with formula
(3) structural unit of structure shown in；On the basis of the weight of the polymer of the tool surface active function, the structural unit A
Content be the content of 50-85 weight %, the structural unit B be the content of 10-40 weight %, the structural unit C be 1-
10 weight %, the viscosity average molecular weigh of the polymer of the tool surface active function is 5,000,000-2,000 ten thousand；
Wherein, R1And R2It is each independently H or C1-C4Alkyl；R3For C1-C14Alkylidene；R4And R5It is respectively independent
Ground is H or C1-C4Alkyl, and R4And R5It is asynchronously H；M in formula (2) and formula (3) is each independently H, Na or K；R6For H
Or CH3；R7For C1-C18Alkyl；R8For C1-C18Alkyl；N is the integer selected from 3-10.
According to the present invention, the C1-C4Alkyl can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, just
Butyl, sec-butyl, isobutyl group and tertiary butyl.
According to the present invention, the C1-C14Alkylidene can be linear chain or branched chain, the C1-C14Alkylidene can be with
Including but not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, isobutylidene, sub- uncle
Butyl, sub- n-pentyl, isoamylidene, sub- tertiary pentyl, 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.The alkylidene refers to that alkane loses
Residue after two hydrogen atoms, described two hydrogen atoms can be two hydrogen atoms on the same carbon atom, can also be different
Two hydrogen atoms on carbon atom, can be straight chains, can also be branch, for example, the ethylidene can be-CH2CH2-
Or-CH (CH3)-。
According to the present invention, the C1-C18Alkyl can be linear chain or branched chain, the C1-C18Alkyl may include
But it is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl,
Tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive hendecyl, positive dodecyl, positive tritriacontyl,
Positive tetradecyl, positive pentadecyl, positive palmityl, n-octadecane base.
According to the present invention, the integer of the 3-10 may include 3,4,5,6,7,8,9 and 10.
In the case of, according to the invention it is preferred to, the structure list of structure shown in the structural unit of structure, formula (2) shown in formula (1)
In the structural unit of structure shown in member and formula (3), R1And R2It is each independently H, methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, sec-butyl, isobutyl group or tertiary butyl；R3For methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, Asia Zhong Ding
Base, isobutylidene, sub- tertiary butyl, sub- n-pentyl, isoamylidene, sub- tertiary pentyl, sub- neopentyl, sub- n-hexyl, sub- n-heptyl, Asia
N-octyl, sub- n-nonyl, sub- positive decyl, sub- positive dodecyl or sub- positive tetradecyl；R4And R5Be each independently H, methyl, ethyl,
N-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or tertiary butyl, and R4And R5It is asynchronously H；M in formula (2) and formula (3)
It is each independently H, Na or K；R6For H or CH3；R7For methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl
Base, tertiary butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive ten
Diyl, positive tetradecyl, positive palmityl or n-octadecane base；R8For methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group, tertiary butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl,
Positive dodecyl, positive tetradecyl, positive palmityl or n-octadecane base；N is the integer selected from 3-10.
According to the present invention, in the case of more preferred, the knot of structure shown in the structural unit of structure, formula (2) shown in formula (1)
In the structural unit of structure shown in structure unit and formula (3), R1And R2Be each independently H, methyl, ethyl, n-propyl, isopropyl,
Normal-butyl or tertiary butyl；R3For methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- n-pentyl, it is sub- just oneself
Base, sub- n-heptyl, sub- n-octyl, sub- n-nonyl or sub- positive decyl；R4And R5Be each independently H, methyl, ethyl, n-propyl,
Isopropyl, normal-butyl, sec-butyl, isobutyl group or tertiary butyl, and R4And R5It is asynchronously H；M in formula (2) and formula (3) is respectively only
It is on the spot H or Na；R6For H or CH3；R7For methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl or n-octyl；R8For methyl, ethyl, n-propyl, different
Propyl, normal-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or
Positive dodecyl；N is the integer selected from 3-10.
According to the present invention, in the case of more preferred, the knot of structure shown in the structural unit of structure, formula (2) shown in formula (1)
In the structural unit of structure shown in structure unit and formula (3), R1And R2Be each independently H, methyl, ethyl, n-propyl, isopropyl,
Normal-butyl or tertiary butyl；R3For methylene, ethylidene, sub- n-propyl or isopropylidene；R4And R5Be each independently H, methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or tertiary butyl, and R4And R5It is asynchronously H；Formula (2) and formula (3)
In M be each independently H or Na；R6For H；R7For n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl, just
Amyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl or n-octyl；R8For n-pentyl, isopentyl, tertiary pentyl, new penta
Base, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl or positive dodecyl；N is the integer selected from 3-10.
The present inventor has found under study for action, is made of specific structural unit A, structural unit B and structural unit C
Polymer be used for oil displacement agent when can obtain preferable oil displacement efficiency.For example, a kind of preferred specific implementation according to the present invention
Mode, the structural unit A are the structural unit with structure shown in formula (7), and the structural unit B is with shown in formula (8)
The structural unit of structure and the structural unit C are with the structural unit of structure shown in formula (9), with shown in formula (10)
The structural unit of structure and at least one of the structural unit with structure shown in formula (11),
In the case of more preferably, in the present invention, on the basis of the weight of the polymer, the structural unit A's contains
Amount is that the content of 50-75 weight %, the structural unit B are that the content of 20-45 weight %, the structural unit C are heavy for 1-5
% is measured, the viscosity average molecular weigh of the polymer is 5,000,000-1,600 ten thousand.
According to the present invention, the intrinsic viscosity η of the polymer of the tool surface active function can be 1000-3300mL/g；
It is a concentration of to be configured in the brine of 10000mg/L that the polymer of the tool surface active function is dissolved in salinity
When the solution of 1500mg/L, the surface tension of the solution can be 31-40mN/m.Under preferable case, the tool surface-active work(
The intrinsic viscosity η of the polymer of energy is 1100-2650mL/g；The polymer of the tool surface active function is dissolved in salinity
When to be configured to the solution of a concentration of 1500mg/L in the brine of 10000mg/L, the surface tension of the solution is 31-36mN/m.
In the present invention, intrinsic viscosity is according to polyacrylamide Intrinsic Viscosity Measurements method as defined in GB12005.1-89
It is measured, measures the NaCl solution of 10 weight % at 25 DEG C with Ubbelohde viscometer.Surface tension uses Dataphysics
DCAT21 surface tension instruments are measured.Salinity in the present invention refers to Na in simulated formation water+、K+、Ca2+、Mg2+、Cl-、
SO4 2-、CO3 2-The summation of equal inorganic ion contents.
Second aspect, the present invention provides a kind of preparation method of the polymer of tool surface active function, this method includes：
In initiator and in the presence of as the water of solvent, monomer D, monomer E and monomer F is set to carry out solution polymerization, wherein described
Monomer D is the monomer with structure shown in formula (4), and the monomer E is the monomer with structure shown in formula (5), and the monomer F is
Monomer with structure shown in formula (6), wherein the dosage of the monomer D, monomer E and monomer F make the polymer being prepared
The content of middle structural unit A is that the content of 50-85 weight %, structural unit B are 10-40 weight %, and the content of structural unit C is
1-10 weight %, and so that the viscosity average molecular weigh for the polymer being prepared is 5,000,000-2,000 ten thousand；The structural unit A is
Structural unit with structure shown in formula (1), the structural unit B are the structural unit with structure shown in formula (2), the knot
Structure unit C is the structural unit with structure shown in formula (3),
Wherein, R1And R2It is each independently H or C1-C4Alkyl；R3For C1-C14Alkylidene；R4And R5It is respectively independent
Ground is H or C1-C4Alkyl, and R4And R5It is asynchronously H；M in formula (2) and formula (3) and formula (5) and formula (6) is respectively independent
Ground is H, Na or K；R6For H or CH3；R7For C1-C18Alkyl；R8For C1-C18Alkyl；N is the integer selected from 3-10.
In the present invention, the structural unit of structure, formula (3) shown in the structural unit of structure, formula (2) shown in the formula (1)
The list of structure shown in the monomer of structure and formula (6) shown in the monomer of structure, formula (5) shown in the structural unit of shown structure, formula (4)
The related definition and substance classes of substituent group in body are identical as the correspondence noted earlier of the present 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 scheme of the present invention.
According to the present invention, the dosage of the monomer can change in a wider scope, using the total amount of the monomer as base
The dosage of standard, the monomer D can be 50-85 weight %, preferably 50-75 weight %.
According to the present invention, the dosage of the monomer can change in a wider scope, using the total amount of the monomer as base
The dosage of standard, the monomer E can be 10-50 weight %, preferably 20-45 weight %.
According to the present invention, the dosage of the monomer can change in a wider scope, using the total amount of the monomer as base
The dosage of standard, the monomer F can be 1-10 weight %, preferably 1-5 weight %.
In the present invention, it should be noted that the one body approximation is fully converted to the polymer of tool surface active function
The corresponding structural unit contained, the corresponding knot that the dosage of the monomer contains with the polymer of the tool surface active function
The content of structure unit can be consistent.
, according to the invention it is preferred to which the dosage of the monomer D, monomer E and monomer F make structure in the polymer being prepared
The content of unit A is that the content of 50-75 weight %, structural unit B are that the content of 20-45 weight %, structural unit C are heavy for 1-5
% is measured, and so that the viscosity average molecular weigh for the polymer being prepared is 5,000,000-1,600 ten thousand.
The present inventor has found under study for action, is obtained when being reacted by specific monomer D, monomer E and monomer F
Polymer is used to that when oil displacement agent preferable oil displacement efficiency can be obtained.For example, a kind of specific preferred implementation according to the present invention
Mode, the monomer D are the monomer with structure shown in formula (12)；The monomer E is the monomer with structure shown in formula (13)；
The monomer F is with the monomer of structure shown in formula (14), with the monomer of structure shown in formula (15) and with shown in formula (16)
At least one of monomer of structure,
According to the method for the present invention, there is no particular limitation for the total amount of the monomer D, the monomer E and the monomer F,
It can change in a wider scope, the total amount using water and the monomer D, the monomer E and the monomer F as solvent is
The total content of benchmark, the monomer D, the monomer E and the monomer F can be 15-35 weight %, preferably 20-30 weights
Measure %.
According to the method for the present invention, the condition of the solution polymerization can be the condition of this field routine, such as institute
Polymerisation is stated to carry out in the presence of an inert gas.
Under preferable case, in the present invention, the solution polymerization condition may include：Polymerization temperature is 0-30 DEG C,
Preferably 0-25 DEG C；Polymerization time is 2-20 hours, preferably 3-15 hours.
In order to save the energy and reduce cost, the polymerisation preferably carries out under adiabatic conditions.The inert gas
For the gas not reacted with raw material and product, such as it can be zero group in the nitrogen or the periodic table of elements of this field routine
At least one of elemental gas, preferably nitrogen and/or argon gas.
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.
According to the method for the present invention, there is no particular limitation for the dosage of the initiator, can become in a wider scope
Dynamic, on the basis of the total amount of the monomer D, the monomer E and the monomer F, the dosage of the initiator is 0.01-0.1 weights
Measure %.
According to the method for the present invention, the initiator can be the various initiators of this field routine, such as can be choosing
From arbitrary two kinds in radical polymerization initiator：The radical polymerization initiator includes azo-initiator, peroxide
Class initiator and redox type initiators.The azo-initiator is selected from azo-bis-iso-dimethyl, two isobutyl of azo
Amidine hydrochloride, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano formamide, two hexamethylene of azo
Base formonitrile HCN, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and azo two are different
At least one of heptonitrile；The peroxide type initiators are selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate,
At least one of benzoyl peroxide and the benzoyl peroxide tert-butyl ester；The redox type initiators are selected from sulfate-
At least one of sulphite, persulfate-thiocarbamide, persulfate-organic salt and ammonium persulfate-fatty amine.
According to the method for the present invention, chelating agent being added can prevent metal ion from being had an impact to polymerisation, 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 0.1-0.3 weight %.
According to the method for the present invention, the dissolubility of polymer can be improved by auxiliary agent being added, it is therefore preferable that in the case of, it is described
Solution polymerization carries out in the presence of auxiliary agent.The auxiliary agent can be at least one of urea, thiocarbamide and ammonium hydroxide, preferably
Urea.There is no particular limitation for dosage of the present invention to the auxiliary agent, can change in a wider scope, with the monomer D,
On the basis of the total amount of the monomer E and the monomer F, the dosage of the auxiliary agent can be 0.01-0.1 weight %.
According to the method for the present invention, the polymer of different molecular weight can be synthesized by molecular weight regulator being added, it is therefore preferable that
In the case of, the polymerisation carries out in the presence of molecular weight regulator.The molecular weight regulator can be isopropanol, ammonia
Water, N, at least one of N '-methylene-bisacrylamides and dimethyl sulfourea.The dosage of the molecular weight regulator can root
It is selected according to the conventional amount used of this field.For example, on the basis of the total amount of the monomer D, the monomer E and the monomer F,
The dosage of the molecular weight regulator can be 0.001-0.1 weight %.
The third aspect, the present invention provides the polymer for the tool surface active function being prepared by preceding method.
Fourth aspect, the present invention provides polymer the answering as polymer oil-displacing agent of aforementioned tool surface active function
With.
Above-mentioned tool surface active function polymer as in the application of polymer oil-displacing agent, specific application process is
Technology well-known to those skilled in the art.
The polymer of the tool surface active function of the present invention may be used as polymer oil-displacing agent, can be suitably used for it is high, in,
Low-permeability oil deposit and high-temperature oil reservoir and high temperature and high salt oil deposit, further increase oil recovery factor in tertiary oil recovery.
The present invention will be described in detail by way of examples below.
In following embodiment, the test method being related to is as follows：
The dissolution time of polymer is measured by method as defined in GB12005.8-89.
The intrinsic viscosity η of polymer is surveyed by polyacrylamide Intrinsic Viscosity Measurements method as defined in GB12005.1-89
It is fixed, 10 weight %NaCl solution are measured at 25 DEG C with Ubbelohde viscometer.
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 viscosimeters, rotating speed 6rmin-1。
Surface tension is measured using Dataphysics DCAT21 surface tension instruments, and test temperature is 30 DEG C.
In following embodiment, has the test method of the apparent viscosity conservation rate of the aqueous solutions of polymers of surface active function
Including：Polymer is dissolved in the concentration of 1500mg/L in the brine of salinity 10000mg/L, by solution deoxygenation to oxygen content
Less than 1mg/L, after aging 1 month, above-mentioned aqueous solution is measured into Brookfield viscosimeters at 90 DEG C for obtained aqueous solution
25 DEG C of apparent viscosity, calculate apparent viscosity retention with following formula：
Used reagent is commercially available chemically pure reagent, the polymer samples used in test case in following embodiment
For FP6030 and KYP.Wherein, FP6030 is the acrylamide polymer that the trade mark of French SNF companies production is FP6030,
The viscosity average molecular weigh of FP6030 is 18,000,000；KYP be oil field provide with sample, KYP contain acrylamide structural unit and
2- methyl -2- acryamidopropanesulfonic acid structural units, on the basis of the weight of KYP, the content of acrylamide structural unit is
The content of 75 weight %, 2- methyl -2- acryamidopropanesulfonic acid structural units is that the viscosity average molecular weigh of 25 weight %, KYP is
10100000, intrinsic viscosity 1915mL/g.
Embodiment 1
The present embodiment is used to illustrate the polymer and preparation method thereof of the tool surface active function of the present invention.
Using aqueous solution polymerization method, 1.875g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(14) structures alone MNRS-1 shown in (Shanghai Jinshan longitude and latitude Chemical Co., Ltd.) is as water-soluble surface-active monomer, 18.75g
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 16.875g, the total content with monomer and distilled water are
The total content of benchmark, monomer is 15 weight %, and the solution being stirred well in polymerisation bottle becomes clear solution.Then it is added
150mg auxiliary agents urea, 100mg disodium ethylene diamine tetraacetates, 2mL ammonium hydroxide, while with sodium hydroxide regulation system pH value to 6, leading to
Enter the high pure nitrogen 30 minutes that volumetric concentration is 99.99% to remove the oxygen in polymerisation bottle.Then 20mg is sequentially added
Ammonium persulfate, 15mg sodium hydrogensulfites continue to be passed through high pure nitrogen 10 minutes, and polymerization temperature is 25 DEG C, reacts 3 hours, obtains
The transparent polymer with viscosity obtains the polymer P 1 of tool surface active function through granulation, drying, crushing, screening.
It can be calculated according to the dosage of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and structures alone MNRS-1
It learns, in the polymer P 1 of tool surface active function, the content of the structural unit of derived from acrylamides is about 50 weight %,
The content of structural unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 45 weight %, is derived from structures alone
The content of the structural unit of MNRS-1 is about 5 weight %.
The intrinsic viscosity for having the polymer P 1 of surface active function is 1130mL/g, and viscosity average molecular weigh is 5,290,000, uses oil field
Salinity is the simulated formation water prepared polymer solution of 10000mg/L, is 1500mg/L, the solution in polymer solution concentration
Surface tension be 31.6mN/m.The simulated formation water prepared polymer solution for being 10000mg/L with oil field salinity, is polymerizeing
Object solution concentration is 1500mg/L, shear rate 7.34s-1Under conditions of, apparent viscosity of the polymer solution at 25 DEG C is
17.5mPas, the apparent viscosity at 85 DEG C are 8.8mPas, and polymer solution is old in substantially free of environment at 90 DEG C
Apparent viscosity conservation rate is 96.7% after changing 1 month, and the polymer of the tool surface active function shown has preferable table
Face activity, temperature-resistant anti-salt ability, good viscous water media capabilities and good anti-aging property.
Embodiment 2
The present embodiment is used to illustrate the polymer and preparation method thereof of the tool surface active function of the present invention.
Using aqueous solution polymerization method, 0.5g such as formulas are added in the adiabatic polymer reactor with surface thermocouple
(14) structures alone MNRS-1 shown in (Shanghai Jinshan longitude and latitude Chemical Co., Ltd.) is as water-soluble surface-active monomer, 27.5g
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 22g, on the basis of the total content of monomer and distilled water,
The total content of monomer is 20 weight %, and the solution being stirred well in polymerisation bottle becomes clear solution.Then 150mg is added
Auxiliary agent urea, 100mg disodium ethylene diamine tetraacetates, 1mL ammonium hydroxide and 10mg isopropanols, while with sodium hydroxide regulation system pH value
To 7, high pure nitrogen that volumetric concentration is 99.99% is passed through 30 minutes to remove the oxygen in polymerisation bottle.Then add successively
Enter 10mg ammonium persulfates, 10mg sodium hydrogensulfites, continue to be passed through high pure nitrogen 10 minutes, polymerization temperature is 15 DEG C, and reaction 5 is small
When, the transparent polymer with viscosity is obtained, the polymer of tool surface active function is obtained through granulation, drying, crushing, screening
P2。
It can be calculated according to the dosage of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and structures alone MNRS-1
It learns, in the polymer P 2 of tool surface active function, the content of the structural unit of derived from acrylamides is about 55 weight %,
The content of structural unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 44 weight %, is derived from structures alone
The content of the structural unit of MNRS-1 is about 1 weight %.
The intrinsic viscosity for having the polymer P 2 of surface active function is 1285mL/g, and viscosity average molecular weigh is 6,160,000, uses oil field
Salinity is the simulated formation water prepared polymer solution of 10000mg/L, is 1500mg/L, the solution in polymer solution concentration
Surface tension be 35.3mN/m.The simulated formation water prepared polymer solution for being 10000mg/L with oil field salinity, is polymerizeing
Object solution concentration is 1500mg/L, shear rate 7.34s-1Under conditions of, apparent viscosity of the polymer solution at 25 DEG C is
18.8mPas, the apparent viscosity at 85 DEG C are 9.3mPas, and polymer solution is old in substantially free of environment at 90 DEG C
Apparent viscosity conservation rate is 95.8% after changing 1 month, and the polymer of the tool surface active function shown has good table
Face activity, temperature-resistant anti-salt ability, good viscous water media capabilities and good anti-aging property.
Embodiment 3
The present embodiment is used to illustrate the polymer and preparation method thereof of the tool surface active function of the present invention.
Using aqueous solution polymerization method, 1.25g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(14) structures alone MNRS-1 shown in (Shanghai Jinshan longitude and latitude Chemical Co., Ltd.) is as water-soluble surface-active monomer, 37.5g
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 23.75g, using the total content of monomer and distilled water as base
The total content of standard, monomer is 25 weight %, and the solution being stirred well in polymerisation bottle becomes clear solution.Then it is added
150mg auxiliary agents urea, 100mg disodium ethylene diamine tetraacetates, 1mL ammonium hydroxide and 5mgN, N- methylene-bisacrylamide, are used simultaneously
Sodium hydroxide regulation system pH value is passed through high pure nitrogen that volumetric concentration is 99.99% 30 minutes to remove polymerisation bottle to 8
In oxygen.Then 15mg ammonium persulfates, 10mg sodium hydrogensulfites are sequentially added, continues to be passed through high pure nitrogen 10 minutes, is polymerize
Temperature is 10 DEG C, reacts 5 hours, obtains the transparent polymer with viscosity, and tool surface is obtained through granulation, drying, crushing, screening
The polymer P 3 of active function.
It can be calculated according to the dosage of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and structures alone MNRS-1
It learns, in the polymer P 3 of tool surface active function, the content of the structural unit of derived from acrylamides is about 60 weight %,
The content of structural unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 38 weight %, is derived from structures alone
The content of the structural unit of MNRS-1 is about 2 weight %.
The intrinsic viscosity for having the polymer P 3 of surface active function is 1445mL/g, and viscosity average molecular weigh is 7,130,000, uses oil field
Salinity is the simulated formation water prepared polymer solution of 10000mg/L, is 1500mg/L, the solution in polymer solution concentration
Surface tension be 34.1mN/m.The simulated formation water prepared polymer solution for being 10000mg/L with oil field salinity, is polymerizeing
Object solution concentration is 1500mg/L, shear rate 7.34s-1Under conditions of, apparent viscosity of the polymer solution at 25 DEG C is
25.0mPas, the apparent viscosity at 85 DEG C is 112.9mPas, and polymer solution is at 90 DEG C in substantially free of environment
Apparent viscosity conservation rate is 95.3% after aging 1 month, and the polymer of the tool surface active function shown is with good
Surface-active, temperature-resistant anti-salt ability, good viscous water media capabilities and good anti-aging property.
Embodiment 4
The present embodiment is used to illustrate the polymer and preparation method thereof of the tool surface active function of the present invention.
Using aqueous solution polymerization method, 1.875g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(14) structures alone MNRS-1 shown in (Shanghai Jinshan longitude and latitude Chemical Co., Ltd.) as water-soluble surface-active monomer,
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of 40.625g acrylamides, 20g, with the total content of monomer and distilled water
On the basis of, the total content of monomer is 25 weight %, and the solution being stirred well in polymerisation bottle becomes clear solution.Then plus
Enter 150mg auxiliary agents urea, 100mg disodium ethylene diamine tetraacetates, 2mL ammonium hydroxide and 10mgN, N- methylene-bisacrylamide, simultaneously
With sodium hydroxide regulation system pH value to 8, high pure nitrogen that volumetric concentration is 99.99% is passed through 30 minutes to remove polymerisation
Oxygen in bottle.Then 15mg ammonium persulfates, 20mg sodium hydrogensulfites are sequentially added, continues to be passed through high pure nitrogen 10 minutes, is gathered
It is 10 DEG C to close temperature, reacts 10 hours, obtains the transparent polymer with viscosity, had through granulation, drying, crushing, screening
The polymer P 4 of surface active function.
It can be calculated according to the dosage of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and structures alone MNRS-1
It learns, in the polymer P 4 of tool surface active function, the content of the structural unit of derived from acrylamides is about 65 weight %,
The content of structural unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 32 weight %, is derived from structures alone
The content of the structural unit of MNRS-1 is about 3 weight %.
The intrinsic viscosity for having the polymer P 4 of surface active function is 1590mL/g, and viscosity average molecular weigh is 8,040,000, uses oil field
Salinity is the simulated formation water prepared polymer solution of 10000mg/L, is 1500mg/L, the solution in polymer solution concentration
Surface tension be 33.2mN/m.The simulated formation water prepared polymer solution for being 10000mg/L with oil field salinity, is polymerizeing
Object solution concentration is 1500mg/L, shear rate 7.34s-1Under conditions of, apparent viscosity of the polymer solution at 25 DEG C is
26.2mPas, the apparent viscosity at 85 DEG C is 15.1mPas, and polymer solution is at 90 DEG C in substantially free of environment
Apparent viscosity conservation rate is 99.0% after aging 1 month, and the polymer of the tool surface active function shown is with good
Surface-active, temperature-resistant anti-salt ability, good viscous water media capabilities and good anti-aging property.
Embodiment 5
The present embodiment is used to illustrate the polymer and preparation method thereof of the tool surface active function of the present invention.
Using aqueous solution polymerization method, 1.875g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(15) structures alone MNRS-2 shown in (Shanghai Jinshan longitude and latitude Chemical Co., Ltd.) is as water-soluble surface-active monomer, 43.75g
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 16.875g, the total content with monomer and distilled water are
The total content of benchmark, monomer is 25 weight %, and the solution being stirred well in polymerisation bottle becomes clear solution.Then it is added
300mg auxiliary agents urea, 150mg disodium ethylene diamine tetraacetates, 2mL ammonium hydroxide and 20mgN, N- methylene-bisacrylamide, are used simultaneously
Sodium hydroxide regulation system pH value is passed through high pure nitrogen that volumetric concentration is 99.99% 30 minutes to remove polymerisation bottle to 8
In oxygen.Then 15mg ammonium persulfates, 30mg sodium hydrogensulfites are sequentially added, continues to be passed through high pure nitrogen 10 minutes, is polymerize
Temperature is 10 DEG C, reacts 15 hours, obtains the transparent polymer with viscosity, tool table is obtained through granulation, drying, crushing, screening
The polymer P 5 of face active function.
It can be calculated according to the dosage of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and structures alone MNRS-2
It learns, in the polymer P 5 of tool surface active function, the content of the structural unit of derived from acrylamides is about 70 weight %,
The content of structural unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 27 weight %, is derived from structures alone
The content of the structural unit of MNRS-2 is about 3 weight %.
The intrinsic viscosity for having the polymer P 5 of surface active function is 2040mL/g, and viscosity average molecular weigh is 11,070,000, with oil
Field salinity is the simulated formation water prepared polymer solution of 10000mg/L, is 1500mg/L in polymer solution concentration, this is molten
The surface tension of liquid is 32.5mN/m.The simulated formation water prepared polymer solution for being 10000mg/L with oil field salinity, poly-
Polymer solution a concentration of 1500mg/L, shear rate 7.34s-1Under conditions of, apparent viscosity of the polymer solution at 25 DEG C
For 29.9mPas, the apparent viscosity at 85 DEG C is 17.1mPas, polymer solution substantially free of environment at 90 DEG C
Apparent viscosity conservation rate is 93.9% after middle aging 1 month, and the polymer of the tool surface active function shown has well
Surface-active, temperature-resistant anti-salt ability, good viscous water media capabilities and good anti-aging property.
Embodiment 6
The present embodiment is used to illustrate the polymer and preparation method thereof of the tool surface active function of the present invention.
Using aqueous solution polymerization method, 3.125g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(15) structures alone MNRS-2 shown in (Shanghai Jinshan longitude and latitude Chemical Co., Ltd.) is as water-soluble surface-active monomer, 43.75g
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 15.625g, the total content with monomer and distilled water are
The total content of benchmark, monomer is 25 weight %, and the solution being stirred well in polymerisation bottle becomes clear solution.Then it is added
300mg auxiliary agents urea, 150mg disodium ethylene diamine tetraacetates, 2mL ammonium hydroxide and 5mg dimethyl sulfoureas, while being adjusted with sodium hydroxide
System pH is passed through high pure nitrogen that volumetric concentration is 99.99% 30 minutes to remove the oxygen in polymerisation bottle to 8.So
After sequentially add 15mg ammonium persulfates, 15mg sodium hydrogensulfites, continue to be passed through high pure nitrogen 10 minutes, polymerization temperature be 5 DEG C, instead
It answers 10 hours, obtains the transparent polymer with viscosity, the poly- of tool surface active function is obtained through granulation, drying, crushing, screening
Close object P6.
It can be calculated according to the dosage of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and structures alone MNRS-2
It learns, in the polymer P 6 of tool surface active function, the content of the structural unit of derived from acrylamides is about 70 weight %,
The content of structural unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 25 weight %, is derived from structures alone
The content of the structural unit of MNRS-2 is about 5 weight %.
The intrinsic viscosity for having the polymer P 6 of surface active function is 2335mL/g, and viscosity average molecular weigh is 12,980,000, with oil
Field salinity is the simulated formation water prepared polymer solution of 10000mg/L, is 1500mg/L in polymer solution concentration, this is molten
The surface tension of liquid is 31.0mN/m.The simulated formation water prepared polymer solution for being 10000mg/L with oil field salinity, poly-
Polymer solution a concentration of 1500mg/L, shear rate 7.34s-1Under conditions of, apparent viscosity of the polymer solution at 25 DEG C
For 32.3mPas, the apparent viscosity at 85 DEG C is 17.9mPas, polymer solution substantially free of environment at 90 DEG C
Apparent viscosity conservation rate is 96.4% after middle aging 1 month, and the tool surface active function polymer shown has good
Surface-active, temperature-resistant anti-salt ability, good viscous water media capabilities and good anti-aging property.
Embodiment 7
The present embodiment is used to illustrate the polymer and preparation method thereof of the tool surface active function of the present invention.
Using aqueous solution polymerization method, 1.75g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(16) structures alone MNRS-3 shown in (Shanghai Jinshan longitude and latitude Chemical Co., Ltd.) as water-soluble surface-active monomer,
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of 65.625g acrylamides, 20.125g, with the total of monomer and distilled water
On the basis of content, the total content of monomer is 35 weight %, and the solution being stirred well in polymerisation bottle becomes clear solution.So
300mg auxiliary agents urea, 100mg disodium ethylene diamine tetraacetates, 2mL ammonium hydroxide and 5mg dimethyl sulfoureas are added afterwards, while using hydroxide
Sodium regulation system pH value is passed through high pure nitrogen that volumetric concentration is 99.99% 30 minutes to remove in polymerisation bottle to 10
Oxygen.Then 15mg ammonium persulfates, 30mg sodium hydrogensulfites are sequentially added, continues to be passed through high pure nitrogen 10 minutes, polymerization temperature
It is 0 DEG C, reacts 8 hours, obtain the transparent polymer with viscosity, tool surface-active is obtained through granulation, drying, crushing, screening
The polymer P 7 of function.
It can be calculated according to the dosage of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and structures alone MNRS-3
It learns, in the polymer P 7 of tool surface active function, the content of the structural unit of derived from acrylamides is about 75 weight %,
The content of structural unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 23 weight %, is derived from structures alone
The content of the structural unit of MNRS-3 is about 2 weight %.
The intrinsic viscosity for having the polymer P 7 of surface active function is 2490mL/g, and viscosity average molecular weigh is 14,150,000, with oil
Field salinity is the simulated formation water prepared polymer solution of 10000mg/L, is 1500mg/L in polymer solution concentration, should
The surface tension of solution is 33.8mN/m.The simulated formation water prepared polymer solution for being 10000mg/L with oil field salinity,
Polymer solution concentration is 1500mg/L, shear rate 7.34s-1Under conditions of, polymer solution is apparent viscous at 25 DEG C
Degree is 35.1mPas, and the apparent viscosity at 85 DEG C is 19.3mPas, polymer solution substantially free of ring at 90 DEG C
Apparent viscosity conservation rate is 92.2% after aging 1 month in border, and the polymer of the tool surface active function shown has good
Good surface-active, temperature-resistant anti-salt ability, good viscous water media capabilities and good anti-aging property.
Embodiment 8
The present embodiment is used to illustrate the polymer and preparation method thereof of the tool surface active function of the present invention.
Using aqueous solution polymerization method, 3.75g such as formulas are added in the adiabatic polymerisation reactor with surface thermocouple
(15) structures alone MNRS-2 shown in (Shanghai Jinshan longitude and latitude Chemical Co., Ltd.) is as water-soluble surface-active monomer, 56.25g
The 2- acrylamide-2-methylpro panesulfonic acids and distilled water of acrylamide, 15g, on the basis of the total content of monomer and distilled water,
The total content of monomer is 30 weight %, and the solution being stirred well in polymerisation bottle becomes clear solution.Then 300mg is added
Auxiliary agent urea, 100mg disodium ethylene diamine tetraacetates, 2mL ammonium hydroxide and 20mg dimethyl sulfoureas, while with sodium hydroxide regulation system
PH value is passed through high pure nitrogen that volumetric concentration is 99.99% 30 minutes to remove the oxygen in polymerisation bottle to 9.Then according to
Secondary addition 15mg ammonium persulfates, 15mg sodium hydrogensulfites, continue to be passed through high pure nitrogen 10 minutes, and polymerization temperature is 0 DEG C, reaction 10
Hour, the transparent polymer with viscosity is obtained, the polymer of tool surface active function is obtained through granulation, drying, crushing, screening
P8。
It can be calculated according to the dosage of acrylamide, 2- acrylamide-2-methylpro panesulfonic acids and structures alone MNRS-2
It learns, in the polymer P 8 of tool surface active function, the content of the structural unit of derived from acrylamides is about 75 weight %,
The content of structural unit derived from 2- acrylamide-2-methylpro panesulfonic acids is about 20 weight %, is derived from structures alone
The content of the structural unit of MNRS-2 is about 5 weight %.
The intrinsic viscosity for having the polymer P 8 of surface active function is 2650mL/g, and viscosity average molecular weigh is 15,070,000, with oil
Field salinity is the simulated formation water prepared polymer solution of 10000mg/L, is 1500mg/L in polymer solution concentration, this is molten
The surface tension of liquid is 31.2mN/m.The simulated formation water prepared polymer solution for being 10000mg/L with oil field salinity, poly-
Polymer solution a concentration of 1500mg/L, shear rate 7.34s-1Under conditions of, apparent viscosity of the polymer solution at 25 DEG C
For 38.9mPas, the apparent viscosity at 85 DEG C is 22.6mPas, polymer solution substantially free of environment at 90 DEG C
Apparent viscosity conservation rate is 97.3% after middle aging 1 month, and the polymer of the tool surface active function shown has well
Surface-active, temperature-resistant anti-salt ability, good viscous water media capabilities and good anti-aging property.
Test case 1
By contrast sample FP6030 (French SNF companies) and KYP (oil field offer) and polymer P 3, polymer P 5 and it polymerize
Object P6 comparisons are observed the apparent of aqueous solutions of polymers (a concentration of 1500mg/L, salinity 10000mg/L) under different temperatures and are glued
Degree, the results are shown in Figure 1.
It will be seen from figure 1 that polymer P 3 according to the present invention, polymer P 5 and polymer P 6 85 DEG C still have it is higher
Apparent viscosity, the aqueous solution apparent viscosity of polymer P 3, polymer P 5 and polymer P 6 can reach 12.9-17.9mPa
S, and the propylene that the code name that the acrylamide polymer and oil field that the trade mark of SNF companies of France production is FP6030 provide is KYP
The apparent viscosity of the aqueous solution of amide polymer is only 8.9-12.6mPas, shows tool surface active function according to the present invention
Polymer have good temperature-resistant anti-salt performance.
Test case 2
By contrast sample FP6030 (French SNF companies) and KYP (oil field offer) and polymer P 3, polymer P 5 and it polymerize
Object P6 comparisons, the aqueous solutions of polymers for the various concentration (Cp) that observation is prepared with the simulated formation water that salinity is 10000mg/L
Surface tension (γ) at 30 DEG C, as a result as shown in Fig. 2.
Figure it is seen that with the increase of concentration, polymer P 3 according to the present invention, polymer P 5 and polymer P 6
The surface tension of aqueous solution is gradually reduced, when a concentration of 1500mg/L, polymer P 3, polymer P 5 and polymer P 6 aqueous solution
Surface tension between 31.0-34.1N/m, show good surface-active.Contrast sample FP6030's and KYP is water-soluble
The surface tension with the increase of concentration of liquid and decline, but fall very little, surface tension is between 60-70mN/m.
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 can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, 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 of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
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 (11)
1. a kind of polymer of tool surface active function, the polymer of the tool surface active function contain 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)；With institute
On the basis of the weight for stating the polymer of tool surface active function, the content of the structural unit A is 50-85 weight %, the knot
The content of structure unit B is that the content of 10-50 weight %, the structural unit C are 1-10 weight %, the tool surface active function
Polymer viscosity average molecular weigh be 5,000,000-2,000 ten thousand；
Wherein, R1And R2It is each independently H or C1-C4Alkyl；R3For C1-C14Alkylidene；R4And R5It is each independently H
Or C1-C4Alkyl, and R4And R5It is asynchronously H；M in formula (2) and formula (3) is each independently H, Na or K；R6For H or
CH3；R7For C1-C18Alkyl；R8For C1-C18Alkyl；N is the integer selected from 3-10.
2. polymer according to claim 1, wherein on the basis of the weight of the polymer, the structural unit A's
Content is that the content of 50-75 weight %, the structural unit B are that the content of 20-45 weight %, the structural unit C are heavy for 1-5
% is measured, the viscosity average molecular weigh of the polymer is 5,000,000-1,600 ten thousand.
3. polymer according to claim 1, wherein the structural unit A is the structure list with structure shown in formula (7)
Member, the structural unit B are with the structural unit of structure shown in formula (8) and the structural unit C for formula (9) institute
Show the structural unit of structure, with the structural unit of structure shown in formula (10) and in the structural unit of structure shown in formula (11)
At least one,
4. a kind of preparation method of the polymer of tool surface active function, this method include：In initiator and as the water of solvent
In the presence of, so that monomer D, monomer E and monomer F is carried out solution polymerization, wherein the monomer D is with knot shown in formula (4)
The monomer of structure, the monomer E are the monomer with structure shown in formula (5), and the monomer F is the list with structure shown in formula (6)
Body, wherein the dosage of the monomer D, monomer E and monomer F so that the content of structural unit A in the polymer being prepared is
The content of 50-85 weight %, structural unit B are that the content of 10-50 weight %, structural unit C are 1-10 weight %, and are made
The viscosity average molecular weigh for the polymer being prepared is 5,000,000-2,000 ten thousand；The structural unit A is with structure shown in formula (1)
Structural unit, the structural unit B are the structural unit with structure shown in formula (2), and the structural unit C is with formula (3)
The structural unit of shown structure,
Wherein, R1And R2It is each independently H or C1-C4Alkyl；R3For C1-C14Alkylidene；R4And R5It is each independently H
Or C1-C4Alkyl, and R4And R5It is asynchronously H；M in formula (2) and formula (3) and formula (5) and formula (6) is each independently
H, Na or K；R6For H or CH3；R7For C1-C18Alkyl；R8For C1-C18Alkyl；N is the integer selected from 3-10.
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
It is 20-45 weight % that the content of structural unit A, which is the content of 50-75 weight %, structural unit B, in polymer, structural unit C's
Content is 1-5 weight %, and so that the viscosity average molecular weigh for the polymer being prepared is 5,000,000-1,600 ten thousand.
6. according to the method described in claim 4, wherein, the monomer D is the monomer with structure shown in formula (12)；The list
Body E is the monomer with structure shown in formula (13)；The monomer F is with the monomer of structure shown in formula (14), with formula (15)
The monomer of shown structure and at least one of the monomer with structure shown in formula (16),
7. according to the method described in any one of claim 4-6, wherein the condition of the solution polymerization includes：Temperature
Degree is 0-30 DEG C；Time is 2-20h.
8. according to the method described in claim 7, wherein, the condition of the solution polymerization includes：Temperature is 0-25 DEG C；When
Between be 3-15h.
9. according to the method described in claim 8, wherein, the initiator includes azo-initiator, peroxide initiation
At least one of agent and redox type initiators；The azo-initiator is selected from azo-bis-iso-dimethyl, azo
Two NSC 18620 hydrochlorides, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano formamide, azo
Dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and idol
At least one of two different heptonitrile of nitrogen；The peroxide type initiators are selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, mistake
At least one of potassium sulfate, benzoyl peroxide and benzoyl peroxide tert-butyl ester；The redox type initiators are selected from
At least one of persulfate-sulphite, persulfate-thiocarbamide and ammonium persulfate-fatty amine.
10. the polymer for the tool surface active function that the method described in any one of claim 4-9 is prepared.
11. the polymer of the tool surface active function described in any one of claim 1-3 and 10 is as polymer oil-displacing agent
Application.
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| CN104693374A (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 |
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