CN106317302A - Polymer with surface active function and preparation method and application thereof - Google Patents
Polymer with surface active function and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polymer with a surface active function and a preparation method and an application thereof. The polymer with the surface active function consists of a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a structural unit of a formula (1) as shown in the specification; the structural unit B is a structural unit of a formula (2) as shown in the specification; the structural unit C is a structural unit of a formula (3) as shown in the specification; based on the weight of the polymer with the surface active function, the content of the structural unit A is 5-60wt%, the content of the structural unit B is 30-90wt%, and the content of the structural unit C is 0.1-10wt%; the viscosity average molecular weight of the polymer is 12000000-30000000. The polymer disclosed by the invention has the advantages of being good in water solubility, viscosifying ability, heat resistance and salt tolerance and surface activity, so that the polymer is good in oil absorption effects, and can be used as an oil-displacement polymer for reservoirs with low to medium permeability.
Description
Technical field
The present invention relates to a kind of polymer with surface active function, a kind of have surface active function
The preparation method of polymer, the method the polymer with surface active function prepared, and
The described polymer application as oil displacement agent with surface active function.
Background technology
At present, China's major part oilfield exploitation has been enter into middle and late stage, and carrying out tertiary oil recovery has become raising and adopt
Yield and the important measures of maintenance field output, polymer flooding occupies particularly significant in tertiary oil recovery simultaneously
Status.In polymer flooding, main application is partially hydrolyzed polyacrylamide (PHPA), its have molecular weight high,
The features such as good water solubility, but under the reservoir condition of high temperature and high salt, partially hydrolyzed polyacrylamide (PHPA) is in property
Obvious defect can be gone up, as poor, degradable in heatproof, saline-alkaline tolerance etc..It is not enough for the above,
Researcher is in order to improve the heat and salt resistance of polyacrylamide solution both at home and abroad, the increasing to polymer oil-displacing agent
The structure of the viscous mechanism of action, thermal degradation and salt tolerance and polymer and heatproof, the relation work of salt resistant character
Numerous studies, developing the temperature-resistant and anti-salt type polymer oil-displacing agent of function admirable.
But, along with continuing to increase of conventional oil reservoir recovery percent of reserves, the drastically minimizing of recoverable reserves, employ
Middle LOW PERMEABILITY RESERVOIR is extremely the most urgent.But owing to low-molecular-weight flooding polymers can not meet oil field performance
Index request, and high molecular flooding polymers occurs that under the conditions of middle and low permeable reservoir oil reservoir space is blocked up
Plug, the phenomenons such as injection pressure is higher, the development progress causing middle and low permeable reservoir is slower.Therefore,
The research tool carrying out middle and low permeable reservoir displacement of reservoir oil new polymers is of great significance.
Can be applied to the polymer of middle and low permeable reservoir must be fulfilled for that dissolubility is good, molecular weight is the highest, with
Time still there is under the conditions of high temperature and high salt the conditions such as viscosity higher, thus to the displacement of reservoir oil that can be used for middle hyposmosis
Polymer is had higher requirement.
Summary of the invention
It is an object of the invention to provide a kind of polymer with surface active function, one has surface and lives
The preparation method of the polymer of sexual function, the method the polymerization with surface active function prepared
Thing, and described in there is the polymer application as oil displacement agent of surface active function.The present invention provides
Polymer has that good water solubility, tackifying be strong and temperature-resistant anti-salt performance and the good advantage of surface activity,
So that this polymer has good washing oil effect, can be polymerized as the displacement of reservoir oil of middle and low permeable reservoir
Thing.
The present invention is to introduce one in acrylamide copolymer not only to have surface activity but also contain polymerizable
The function monomer of vinyl, thus it is anti-to improve the surface activity of polyacrylamide solution, tackifying and heatproof
Salt.This is possibly due to: saturated or undersaturated alkyl the introducing of this function monomer terminal long-chain strengthens
The heat resistance and salt tolerance of copolymer, makes the aqueous solutions of polymers with surface active function of formation at height
Remain to keep higher viscosity under temperature high salt conditions；The introducing of the most highly polar sulfonic acid group, is greatly increased
Anti-bivalent metal ion ability, and its strongest hydrophilic interaction makes polymer have with electrostatic repulsion forces
Good water solublity, also greatly increases the hydrodynamic volume of strand, shows good thickening
Effect and heat and salt resistance, improve the swept volume of polymer flooding；It addition, introduce on macromolecular chain
There is the polymerisable monomer of surface activity, be substantially reduced surface tension and the interfacial tension of polymer solution,
Polymer is made to have good surface activity, by increase-volume emulsifying and reduction surface tension, so that
This polymer has good washing oil ability, and then improves oil recovery factor.
The present invention provides a kind of polymer with surface active function, and wherein, this has surface activity merit
The polymer of energy contains construction unit A, construction unit B and construction unit C, and described construction unit A is
Construction unit shown in formula (1), described construction unit B is the construction unit shown in formula (2), described
Construction unit C is the construction unit shown in formula (3), with the described polymer with surface active function
Weight on the basis of, the content of described construction unit A is 5-60 weight %, described construction unit B's
Content is 30-90 weight %, and the content of described construction unit C is 0.1-10 weight %；Described polymer
Viscosity-average molecular weight be 12,000,000-3,000 ten thousand；
Wherein, R1、R5And R6It is each independently the alkyl of H or C1-C4, R2Asia for C1-C4
Alkyl, R3、R4And R8It is each independently the alkyl of H or C1-C4, and R3And R4It is asynchronously
H, M1And M2It is each independently H, Na or K, R7For the saturated of C8-C18 or undersaturated hydrocarbon
Base.
Present invention also offers the preparation method of a kind of polymer with surface active function, the method bag
Include: initiator and as the water of solvent in the presence of, make monomer D, monomer E and monomer F carry out molten
Liquid polyreaction, wherein, described monomer D is for having the monomer of structure, described monomer shown in formula (4)
E is for having the monomer of structure shown in formula (5), and described monomer F is for having the list of structure shown in formula (6)
Body, on the basis of the total amount of described monomer D, described monomer E and described monomer F, described monomer D
Consumption be 5-60 weight %, the consumption of described monomer E is 30-90 weight %, the use of described monomer F
Amount is 0.1-10 weight %；The condition of described solution polymerization makes resulting polymers after polyreaction
Viscosity-average molecular weight is 12,000,000-3,000 ten thousand；
Wherein, R1、R5And R6It is each independently the alkyl of H or C1-C4, R2Asia for C1-C4
Alkyl, R3、R4And R8It is each independently the alkyl of H or C1-C4, and R3And R4It is asynchronously
H, M1And M2It is each independently H, Na or K, R7For the saturated of C8-C18 or undersaturated hydrocarbon
Base.
Present invention also offers the polymer with surface active function prepared by said method.
Present invention also offers the above-mentioned polymer application as oil displacement agent with surface active function.
The polymer with surface active function that the present invention provides has good water solublity, good increasing
Viscosity, excellent heat and salt resistance and excellent surface activity.Specifically, by embodiment 1 to embodiment
The polymer with surface active function of 5 preparations is dissolved in the saline that salinity is 25000mg/L joins
The apparent viscosity (80 DEG C) making the solution that concentration is 1500mg/L is 28-49mPa s, by embodiment
The polymer with surface active function of 1 to embodiment 5 preparation is dissolved in pure water and is configured to concentration and is
During the solution of 1500mg/L, the surface tension of this solution is 31-37mN/m.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of polymer with surface active function, and wherein, this has surface activity merit
The polymer of energy contains construction unit A, construction unit B and construction unit C, and described construction unit A is
Construction unit shown in formula (1), described construction unit B is the construction unit shown in formula (2), described
Construction unit C is the construction unit shown in formula (3), with the described polymer with surface active function
Weight on the basis of, the content of described construction unit A is 5-60 weight %, described construction unit B's
Content is 30-90 weight %, and the content of described construction unit C is 0.1-10 weight %；Described polymer
Viscosity-average molecular weight be 12,000,000-3,000 ten thousand；
Wherein, R1、R5And R6It is each independently the alkyl of H or C1-C4, R2Asia for C1-C4
Alkyl, R3、R4And R8It is each independently the alkyl of H or C1-C4, and R3And R4It is asynchronously
H, M1And M2It is each independently H, Na or K, R7For the saturated of C8-C18 or undersaturated hydrocarbon
Base.
The present invention uses acrylamide and with surface active groups and the function containing polymerizable vinyl
Monomer carries out copolymerization, introduces hydrophilic group and lipophilic group by copolymerization, so that what the present invention provided
Polymer not only has the tackifying of water-soluble polymer, on the other hand, surface active function polymerizable list
The introducing of body so that this type of novel high molecular polymer has certain surface activity, by emulsifying increase-volume
With reduce the characteristic such as surface and interface tension force, thus increase the washing oil effect of polymer.It is above-mentioned that the present invention provides
Polymer has that good water solubility, tackifying be strong and temperature-resistant anti-salt performance and the good advantage of surface activity,
Can be as the Polymer Used For Oil Displacement of middle and low permeable reservoir.
Preferably, R1、R5And R6It is each independently H or methyl, R2For methylene, R3And R4
It is each independently methyl, R7For the saturated of C10-C16 or undersaturated straight-chain alkyl, the most excellent
Elect the straight chained alkyl of C10-C16 or the straight-chain alkenyl of C10-C16, R as8For H.
According to the present invention, the saturated or undersaturated alkyl of C8-C18 can be straight or branched, can
To include but not limited to: n-octyl, iso-octyl, n-nonyl, positive decyl, positive hendecyl, positive 12
Base, positive tritriacontyl, positive tetradecyl, Pentadecane base, positive octenyl, isooctene base, decene base.
In the present invention, described undersaturated straight-chain alkyl can contain at least one thiazolinyl.
According to the present invention, the alkylidene of described C1-C4 can be straight or branched, can include but not
It is limited to: methylene, ethylidene, sub-n-pro-pyl, isopropylidene, sub-normal-butyl, sub-sec-butyl, sub-different
Butyl and the sub-tert-butyl group.
Described alkylidene refer to alkane lose two hydrogen atoms after residue, said two hydrogen atom can be
Two hydrogen atoms on same carbon atom, it is also possible to two hydrogen atoms on different carbon atoms, Ke Yishi
Straight chain, it is also possible to be side chain, such as, described ethylidene can be-CH2CH2-or-CH (CH3)-。
According to the present invention, the alkyl of described C1-C4 can be straight or branched, can include but not
It is limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
In order to have the polymer of surface active function described in making, there is more excellent tackifying, temperature-resistant anti-salt
Performance and surface activity, under preferable case, with the weight of the described polymer with surface active function
On the basis of, the content of described construction unit A is 10-40 weight %, and the content of described construction unit B is
55-89.9 weight %, the content of described construction unit C is 0.1-5 weight %；Gluing all of described polymer
Molecular weight is 15,000,000-2,500 ten thousand.
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 can obtain preferable oil displacement efficiency when oil displacement agent.Such as, described knot
Structure unit A can be for having the construction unit of structure shown in formula (1-1), and described construction unit B is permissible
For having the construction unit of structure shown in formula (2-1), described construction unit C can be to have formula (3-1)
The construction unit of shown structure,
Wherein, M1And M2It is each independently H, Na or K, preferably Na；R7For C10-C16
Saturated or undersaturated straight-chain alkyl, the more preferably straight chained alkyl of C10-C16 or C10-C16
Straight-chain alkenyl.
Present invention also offers the preparation method of a kind of polymer with surface active function, the method bag
Include: initiator and as the water of solvent in the presence of, make monomer D, monomer E and monomer F carry out molten
Liquid polyreaction, wherein, described monomer D is for having the monomer of structure, described monomer shown in formula (4)
E is for having the monomer of structure shown in formula (5), and described monomer F is for having the list of structure shown in formula (6)
Body, on the basis of the total amount of described monomer D, described monomer E and described monomer F, described monomer D
Consumption be 5-60 weight %, the consumption of described monomer E is 30-90 weight %, the use of described monomer F
Amount is 0.1-10 weight %；The condition of described solution polymerization makes resulting polymers after polyreaction
Viscosity-average molecular weight is 12,000,000-3,000 ten thousand；
Wherein, R1、R5And R6It is each independently the alkyl of H or C1-C4, R2Asia for C1-C4
Alkyl, R3、R4And R8It is each independently the alkyl of H or C1-C4, and R3And R4It is asynchronously
H, M1And M2It is each independently H, Na or K, R7For the saturated of C8-C18 or undersaturated hydrocarbon
Base.
Preferably, R1、R5And R6It is each independently H or methyl, R2For methylene, R3And R4
It is each independently methyl, R7For the saturated of C10-C16 or undersaturated straight-chain alkyl, the most excellent
Elect the straight chained alkyl of C10-C16 or the straight-chain alkenyl of C10-C16, R as8For H.
The method according to the invention, in order to make had surface active function by what said method prepared
Polymer has more excellent tackifying, temperature-resistant anti-salt performance and surface activity, under preferable case, with
On the basis of the total amount of described monomer D, described monomer E and described monomer F, the consumption of described monomer D
For 10-40 weight %, the consumption of described monomer E is 55-89.9 weight %, and the consumption of described monomer F is
0.1-5 weight %；After the condition of described solution polymerization makes polyreaction, the viscous of resulting polymers is divided equally
Son amount is 15,000,000-2,500 ten thousand.
In the present invention, it should be noted that described one body approximation be fully converted to described in have surface live
The corresponding construction unit contained in the polymer of sexual function, the consumption of described monomer has surface with described
The content of the corresponding construction unit contained in the polymer of active function is consistent.
The present inventor finds under study for action, specific monomer D, monomer E and monomer F carry out
The polymer obtained during reaction can obtain preferable oil displacement efficiency when oil displacement agent.Such as, described list
Body D can be for having the monomer of structure shown in formula (4-1), and shown monomer E can be to have formula (5-1)
Shown in the monomer of structure, shown monomer F can for having the monomer of structure shown in formula (6-1),
Wherein, M1For H, Na or K, R7For the saturated of C10-C16 or undersaturated straight-chain alkyl,
The more preferably straight chained alkyl of C10-C16 or the straight-chain alkenyl of C10-C16.
The method according to the invention, the condition of described solution polymerization can be the bar that this area is conventional
Part, the most described solution polymerization is carried out under an inert atmosphere, described inert atmosphere be not with raw material and
The gas that product reacts, such as, can be zero group in the conventional nitrogen in this area or the periodic table of elements
At least one in elemental gas, preferably nitrogen and/or argon.
The method according to the invention, the condition of described solution polymerization can be the bar that this area is conventional
Part.Such as, described polymeric reaction condition may include that polymerization temperature is 0-80 DEG C, and polymerization time is
2-15 hour, pH value was 6-10.
The method according to the invention, described pH value is adjusted by adding acid or alkali, and described acid is preferred
For mineral acid, described mineral acid can be at least one in hydrochloric acid, sulphuric acid, sulfonic acid, nitric acid and phosphoric acid；
Described alkali can be inorganic base or organic amine compound, as being selected from sodium hydroxide, sodium carbonate, hydrogen
At least one in potassium oxide, ammonia, methylamine, ethamine, ethanolamine and triethanolamine, preferably carbonic acid
Sodium and/or sodium hydroxide.
The present inventor finds under study for action, takes following condition can improve polymer further
Molecular weight: i.e., it is preferable that described solution polymerization includes two stages carried out successively: the first rank
The reaction condition of section includes: temperature is 0-25 DEG C, preferably 0-10 DEG C, and the time is 2.5-12 hour, excellent
Elect 6-8 hour as；The reaction condition of second stage includes: temperature is 30-80 DEG C, preferably 50-70 DEG C,
Time is 2.5-10 hour, preferably 5-8 hour.
The method according to the invention, the total amount of described monomer D, described monomer E and described monomer F does not has
Particularly limit, can change in wider scope, using as the water of solvent and described monomer D, institute
On the basis of stating the total amount of monomer E and described monomer F, described monomer D, described monomer E and described monomer
Total consumption of F can be 10-50 weight %, preferably 20-40 weight %.
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, described
The consumption of initiator is 0.001-0.2 weight %, preferably 0.01-0.15 weight %.
According to the inventive method, described initiator is preferably oxidoreduction series initiators, described oxidoreduction
Series initiators includes Oxidizing and Reducing Agents, and described oxidant is selected from Ammonium persulfate., potassium peroxydisulfate, over cure
At least one in acid sodium and hydrogen peroxide；Described reducing agent selected from sodium sulfite, Potassium acid sulfite,
Sodium sulfite, potassium sulfite, rongalite, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite and ascorbic acid
In at least one.Under preferable case, described oxidant is Ammonium persulfate., potassium peroxydisulfate and sodium peroxydisulfate
In at least one；Described reducing agent is sodium sulfite, Potassium acid sulfite, sodium sulfite and sulfurous acid
At least one in potassium.In the present invention, oxidant and the reduction of described oxidoreduction series initiators are constituted
Agent such as can provide as a solution, such as: the preferred described oxidant of the present invention be concentration be 0.1
The persulfate aqueous solution of weight % or the ammonium persulfate aqueous solution that concentration is 0.1 weight %；Preferably institute
State reducing agent be concentration be the bisulfite aqueous solutions of potassium of 0.1 weight % or the Asia that concentration is 0.1 weight %
Sodium bisulphate solution.
The method according to the invention, the consumption of described Oxidizing and Reducing Agents can be become in wider scope
Dynamic, the most described oxidant can be 1-10:1, preferably 1-5:1 with the weight ratio of described reducing agent.
The method according to the invention, adds chelating agent and is possible to prevent metal ion that polyreaction is produced shadow
Ring, it is therefore preferable that in the case of, described solution polymerization is carried out in the presence of chelating agent.Described network
Mixture can be disodiumedetate, triethylenediamine pentaacetic acid, citric acid, citrate and poly-hydroxyl
At least one in base acrylic acid, preferably disodiumedetate.The present invention is to described chelating agent
There is no particular limitation for consumption, can change, with described monomer D, described monomer in wider scope
On the basis of the total amount of E and described monomer F, the consumption of described chelating agent can be 0.001-0.15 weight %,
It is preferably 0.01-0.1 weight %.To the type of service of described chelating agent, there is no particular limitation, such as may be used
To use with pure solution form, use in solid form, or use with the solution form being diluted.Excellent
Selection condition, described chelating agent can be concentration be the EDTA-2Na aqueous solution of 1-5 weight %.
The method according to the invention, adds auxiliary agent and can improve the dissolubility of polymer, it is therefore preferable that feelings
Under condition, described polyreaction is carried out in the presence of auxiliary agent.Described auxiliary agent can be carbamide, sodium formate, different
At least one in propanol and sodium hypophosphite, preferably carbamide.The consumption of described auxiliary agent is not had by the present invention
Particularly limit, can change in wider scope, with described monomer D, described monomer E and described
On the basis of the total amount of monomer F, the consumption of described auxiliary agent can be 0.001-0.15 weight %, is preferably
0.005-0.1 weight %.In method of the present invention, the most special to the offer form of described auxiliary agent
Restriction, such as can provide with pure solution form, provide in solid form, or molten be diluted
Liquid form provides.The most in the present invention, when the auxiliary agent used is carbamide, carbamide can be with water-soluble
Liquid form provides, and to the concentration of its solution, there is no particular limitation.In the inventive solutions, excellent
Select described chelating agent can be such as concentration be the aqueous solution of urea of 1-5 weight %.
According to one preferred implementation of the present invention, described in there is the preparation of polymer of surface active function
Method comprises the following steps:
(1) under conditions of pH value is 6-10, shown in the monomer shown in formula (4), formula (5)
Monomer contact with water with the monomer shown in formula (6), obtain mixture solution；
(2) described mixture solution is contacted with chelating agent and auxiliary agent, obtain solution to be polymerized；
(3) under the polymerization conditions, described solution to be polymerized is connect under nitrogen protection with initiator
Touching, wherein, described polyreaction includes carrying out two stages successively, and the reaction condition of first stage includes:
Temperature is 0-25 DEG C, and the time is 2.5-12 hour；The reaction condition of second stage includes: temperature is
30-80 DEG C, the time is 2.5-10 hour.
The method according to the invention, described in there is surface active function the preparation method of polymer all right
Including: carry out the blob of viscose obtained after aggregated reaction successively cutting, pelletize, pulverize and sieve and obtain institute
State the polymer end product with surface active function.
The present invention to described cutting, pelletize, pulverize and the method sieved there is no particular limitation, this area
Technical staff reasonably can select according to this area usual manner.
Present invention also offers the above-mentioned polymer application as oil displacement agent with surface active function.Tool
The technology that the application process of body is well known to those skilled in the art.The described tool surface activity merit of the present invention
The polymer of energy can serve as polymer oil-displacing agent, is particularly suited for middle and low permeable reservoir, in tertiary oil recovery
In can improve oil recovery factor further.
Hereinafter will be described the present invention by embodiment.
In following example and comparative example, in case of no particular description, the various reagent used
It is from the chemically pure reagent being purchased.
In following example, dissolution time is measured by GB12500.8-89 that (sample quality is all by sample
Straight polymer quality meter in product), record prepared powdered samples dissolution time and be respectively less than 2 hours；
In the examples below, Ubbelohde viscometer is used to use one point method that the viscosity-average molecular weight of polymer is entered
Row test；
Measure the apparent viscosity of polymer solution with Brookfield viscometer under test temperature (80 DEG C),
Method particularly includes: the polymer with surface active function is dissolved in the salt that salinity is 25000mg/L
Water is configured to the solution that concentration is 1500mg/L, measures the apparent viscosity of this polymer solution, wherein,
Salinity refers to Na in simulated formation water+、Ca2+、Mg2+And Cl-Summation Deng inorganic ion content.Its
In, Ca2+And Mg2+Ion concentration sum be 800mg/L, remaining is Na+And Cl-；
Polymer is measured in pure water by DCAT-21 surface tension instrument under test temperature (25 DEG C)
The surface tension of aqueous solution, the concentration of polymer is 1500mg/L.
In embodiments of the invention and comparative example, 2-acrylamide-2-methylpro panesulfonic acid is prosperous purchased from Weifang spring
Chemical Co., Ltd..
The monomer of structure shown in formula (6-1) is with reference to (Bistline R.G, Synthetic detergents from
animal fats.Ⅵ.Polymerizable ester of alpha-sulfonated fatty acids.Journal of the
American Oil Chemists Society, 1956,33 (1): 44-45) prepared by the method described in.
Embodiment 1
The present embodiment is for polymer with surface active function that the present invention is described and preparation method thereof.
(1) by the acrylamide of 11.8g, the 2-acrylamide-2-methylpro panesulfonic acid of 8.0g and 0.2g
Formula (6-1) shown in the function monomer (R of structure7For-CH2(CH2)8CH3) join polyreaction bottle
In (i.e. polymerization bottle), add deionized water 60.0g dissolving and be made into aqueous solution, add solid hydrogen oxidation
Sodium regulation pH value is 6.0, obtains mixture solution；
(2) be sequentially added in above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 1.0g,
The aqueous solution of urea 0.5g of 1 weight %, stirs, and obtains solution to be polymerized；
(3) putting in water bath with thermostatic control by polyreaction bottle, logical nitrogen flooding oxygen, after 30 minutes, adds 0.1
The persulfate aqueous solution 3.0g of weight % and the aqueous solution of sodium bisulfite 1.5g of 0.1 weight %, in 0 DEG C
Initiation reaction, continues logical nitrogen and stops after five minutes, under nitrogen protection, and polyreaction 6 hours；So
After be warming up to 50 DEG C continue reaction 8 hours, obtain blob of viscose；
(4) take out step (3) blob of viscose that obtains, carry out successively cutting, pelletize, pulverize, sieve
White temperature-resistant anti-salt Polymer Used For Oil Displacement A1.
After tested, the molecular weight of polymer A 1 is 23,000,000, and apparent viscosity (80 DEG C) is 45.1mPa s,
Surface tension is 36.42mN/m, shows surface activity and the resisting high temperature, high salt performance of excellence.
Comparative example 1
Method same as in Example 1 is used to prepare polymer, except that, in step (1)
It is added without the function monomer of structure shown in formula (6-1), forms reference polymer DA1.
After tested, the molecular weight of polymer DA1 is 27,000,000, and apparent viscosity (80 DEG C) is
30.2mPa s, surface tension is 68.5mN/m.
Comparative example 2
Method same as in Example 1 is used to prepare polymer, except that, in step (1)
The function monomer 5g of structure shown in addition formula (6-1), forms reference polymer DA2.
After tested, the molecular weight of polymer DA2 is 14,000,000, and apparent viscosity (80 DEG C) is
17.5mPa s, surface tension is 36.9mN/m.
Embodiment 2
The present embodiment is used for the polymer with surface active function and the preparation thereof that the present invention provides is described
Method.
(1) by the acrylamide of 11.0g, the 2-acrylamide-2-methylpro panesulfonic acid of 8.0g and 1.0g
Formula (6-1) shown in the function monomer (R of structure7For-CH2(CH2)11CH=CH2) join polymerization instead
Answer in bottle, add deionized water 60.0g dissolving and be made into aqueous solution, add solid sodium hydroxide regulation pH
Value is 7.8, obtains mixture solution；
(2) be sequentially added in above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 1.0g,
The aqueous solution of urea 1.0g of 1 weight %, stirs, and obtains solution to be polymerized；
(3) putting in water bath with thermostatic control by polyreaction bottle, logical nitrogen flooding oxygen, after 30 minutes, adds 0.1
The ammonium persulfate aqueous solution 6.0g of weight % and the bisulfite aqueous solutions of potassium 3.0g of 0.1 weight %, in 5 DEG C
Initiation reaction, continues logical nitrogen and stops after five minutes, under nitrogen protection, and polyreaction 6 hours；So
After be warming up to 55 DEG C continue reaction 7 hours, obtain blob of viscose；
(4) take out step (3) blob of viscose that obtains, carry out successively cutting, pelletize, pulverize, sieve
White temperature-resistant anti-salt Polymer Used For Oil Displacement A2.
After tested, the molecular weight of polymer A 2 is 15,000,000, and apparent viscosity (80 DEG C) is 28.4mPa s,
Surface tension is 31.45mN/m, shows surface activity and the resisting high temperature, high salt performance of excellence.
Embodiment 3
The present embodiment is for polymer with surface active function that the present invention is described and preparation method thereof.
(1) by the acrylamide of 17.95g, the 2-acrylamide-2-methylpro panesulfonic acid of 2.0g and 0.05g
Formula (6-1) shown in the function monomer (R of structure7For-CH2(CH2)14CH3) join polyreaction bottle
In, add deionized water 60.0g dissolving and be made into aqueous solution, add solid sodium hydroxide regulation pH value
It is 10.0, obtains mixture solution；
(2) be sequentially added in above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 2.0g,
The aqueous solution of urea 0.5g of 1 weight %, stirs, and obtains solution to be polymerized；
(3) putting in water bath with thermostatic control by polyreaction bottle, logical nitrogen flooding oxygen, after 30 minutes, adds 0.1
The ammonium persulfate aqueous solution 10.0g of weight % and the aqueous solution of sodium bisulfite 5.0g of 0.1 weight %, in
10 DEG C of initiation reactions, continue logical nitrogen and stop after five minutes, under nitrogen protection, and polyreaction 8 hours；
It is warming up to 70 DEG C and continues reaction 5 hours, obtain blob of viscose；
(4) take out step (3) blob of viscose that obtains, carry out successively cutting, pelletize, pulverize, sieve
White temperature-resistant anti-salt Polymer Used For Oil Displacement A3.
After tested, the molecular weight of polymer A 3 is 22,000,000, and apparent viscosity (80 DEG C) is 42.6mPa s,
Surface tension is 36.24mN/m, shows surface activity and the resisting high temperature, high salt performance of excellence.
Embodiment 4
The present embodiment is for polymer with surface active function that the present invention is described and preparation method thereof.
(1) by the acrylamide of 11.98g, the 2-acrylamide-2-methylpro panesulfonic acid of 8.0g and 0.02g
Formula (6-1) shown in the function monomer (R of structure7For-CH2(CH2)14CH3) join polyreaction bottle
In, add deionized water 60.0g dissolving and be made into aqueous solution, adding solid sodium carbonate regulation pH value is
8.0, obtain mixture solution；
(2) be sequentially added in above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 0.2g,
The aqueous solution of urea 0.2g of 1 weight %, stirs, and obtains solution to be polymerized；
(3) putting in water bath with thermostatic control by polyreaction bottle, logical nitrogen flooding oxygen, after 30 minutes, adds 0.1
The ammonium persulfate aqueous solution 4.0g of weight % and the aqueous solution of sodium bisulfite 2.0g of 0.1 weight %, in 10 DEG C
Initiation reaction, continues logical nitrogen and stops after five minutes, under nitrogen protection, and polyreaction 7 hours；So
After be warming up to 60 DEG C continue reaction 6 hours, obtain blob of viscose；
(4) take out step (3) blob of viscose that obtains, carry out successively cutting, pelletize, pulverize, sieve
White temperature-resistant anti-salt Polymer Used For Oil Displacement A4.
After tested, the molecular weight of polymer A 4 is 25,000,000, and apparent viscosity (80 DEG C) is 48.5mPa s,
Surface tension is 34.41mN/m, shows surface activity and the resisting high temperature, high salt performance of excellence.
Embodiment 5
The present embodiment is for polymer with surface active function that the present invention is described and preparation method thereof.
(1) by the acrylamide of 13.8g, the 2-acrylamide-2-methylpro panesulfonic acid of 6.0g and 0.2g
Formula (6-1) shown in the function monomer (R of structure7For-CH2(CH2)14CH3) join polyreaction bottle
In (i.e. polymerization bottle), add deionized water 50.0g dissolving and be made into aqueous solution, add solid hydrogen oxidation
Sodium regulation pH value is 8.0, obtains mixture solution；
(2) be sequentially added in above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 0.2g,
The aqueous solution of urea 2.0g of 1 weight %, stirs, and obtains solution to be polymerized；
(3) putting in water bath with thermostatic control by polyreaction bottle, logical nitrogen flooding oxygen, after 30 minutes, adds 0.1
The persulfate aqueous solution 20.0g of weight % and the aqueous solution of sodium bisulfite 10.0g of 0.1 weight %, in
0 DEG C of initiation reaction, continues logical nitrogen and stops after five minutes, under nitrogen protection, and polyreaction 6.5 hours；
Then heat to 65 DEG C and continue reaction 5.5 hours, obtain blob of viscose；
(4) take out step (3) blob of viscose that obtains, carry out successively cutting, pelletize, pulverize, sieve
White temperature-resistant anti-salt Polymer Used For Oil Displacement A5.
After tested, the viscosity-average molecular weight of polymer A 5 is 18,000,000, and apparent viscosity is 35.6mPa s,
Surface tension is 33.69mN/m, shows surface activity and the resisting high temperature, high salt performance of excellence.
Embodiment 6
Method same as in Example 1 is used to prepare polymer, except that, in step (1)
Function monomer (the R of structure shown in addition formula (6-1)7For-CH2(CH2)3CH=CH (CH2)3CH3),
Obtain polymer A 6.
The molecular weight of polymer A 6 is 16,000,000 after tested, and apparent viscosity (80 DEG C) is 30.3mPa s,
Surface tension is 32.2mN/m, shows surface activity and the resisting high temperature, high salt performance of excellence.
By the result of embodiment 1-6 and comparative example 1 and comparative example 2 it can be seen that use the present invention
The method provided prepares the polymer with surface active function of the present invention and has good
Tackifying, excellent surface activity and resisting high temperature, high salt performance.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a polymer with surface active function, it is characterised in that this has surface activity merit
The polymer of energy contains construction unit A, construction unit B and construction unit C, and described construction unit A is
Construction unit shown in formula (1), described construction unit B is the construction unit shown in formula (2), described
Construction unit C is the construction unit shown in formula (3), with the described polymer with surface active function
Weight on the basis of, the content of described construction unit A is 5-60 weight %, described construction unit B's
Content is 30-90 weight %, and the content of described construction unit C is 0.1-10 weight %；Described polymer
Viscosity-average molecular weight be 12,000,000-3,000 ten thousand；
Wherein, R1、R5And R6It is each independently the alkyl of H or C1-C4, R2Asia for C1-C4
Alkyl, R3、R4And R8It is each independently the alkyl of H or C1-C4, and R3And R4It is asynchronously
H, M1And M2It is each independently H, Na or K, R7For the saturated of C8-C18 or undersaturated hydrocarbon
Base.
The polymer with surface active function the most according to claim 1, wherein, R1、R5
And R6It is each independently H or methyl, R2For methylene, R3And R4It is each independently methyl,
R7For the saturated of C10-C16 or undersaturated straight-chain alkyl, R8For H.
The polymer with surface active function the most according to claim 1 and 2, wherein, with
On the basis of the weight of the described polymer with surface active function, the content of described construction unit A is
10-40 weight %, the content of described construction unit B is 55-89.9 weight %, described construction unit C's
Content is 0.1-5 weight %；The viscosity-average molecular weight of described polymer is 15,000,000-2,500 ten thousand.
4. having a preparation method for the polymer of surface active function, the method includes: causing
Agent and as the water of solvent in the presence of, make monomer D, monomer E and monomer F carry out solution polymerization,
Wherein, described monomer D is for having the monomer of structure shown in formula (4), and described monomer E is for having formula (5)
The monomer of shown structure, described monomer F is for having the monomer of structure shown in formula (6), with described monomer
On the basis of the total amount of D, described monomer E and described monomer F, the consumption of described monomer D is 5-60 weight
Amount %, the consumption of described monomer E is 30-90 weight %, and the consumption of described monomer F is 0.1-10 weight %；
After the condition of described solution polymerization makes polyreaction, the viscosity-average molecular weight of resulting polymers is 1200
Ten thousand-3,000 ten thousand；
Wherein, R1、R5And R6It is each independently the alkyl of H or C1-C4, R2Asia for C1-C4
Alkyl, R3、R4And R8It is each independently the alkyl of H or C1-C4, and R3And R4It is asynchronously
H, M1And M2It is each independently H, Na or K, R7For the saturated of C8-C18 or undersaturated hydrocarbon
Base.
Method the most according to claim 4, wherein, R1、R5And R6Be each independently H or
Methyl, R2For methylene, R3And R4It is each independently methyl, R7For the saturated of C10-C16 or not
Saturated straight-chain alkyl, R8For H.
Method the most according to claim 4, wherein, described initiator is that redox system causes
Agent, on the basis of the total amount of described monomer D, described monomer E and described monomer F, described initiator
Consumption is 0.001-0.2 weight %；Described oxidoreduction series initiators includes Oxidizing and Reducing Agents, described
Oxidant is 1-10:1 with the weight ratio of described reducing agent, and described oxidant is selected from Ammonium persulfate., over cure
At least one in acid potassium, sodium peroxydisulfate and hydrogen peroxide, described reducing agent is selected from sodium sulfite, Asia
At least one in sodium sulfate, rongalite, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite and ascorbic acid.
Method the most according to claim 4, wherein, with described water and described monomer D, described
On the basis of the total amount of monomer E and described monomer F, described monomer D, described monomer E and described monomer F
Total consumption be 10-50 weight %.
Method the most according to claim 4, wherein, described solution polymerization at chelating agent and
Carry out in the presence of auxiliary agent, on the basis of the total amount of described monomer D, described monomer E and described monomer F,
The consumption of described chelating agent is 0.001-0.15 weight %, and the consumption of described auxiliary agent is 0.001-0.15 weight
Amount %；Described chelating agent is selected from disodiumedetate, triethylenediamine pentaacetic acid, citric acid, Fructus Citri Limoniae
At least one in hydrochlorate and poly-hydroxy acrylic acid, described auxiliary agent selected from carbamide, sodium formate, isopropanol and
At least one in sodium hypophosphite.
9. according to the method described in claim 4 or 8, wherein, the condition of described solution polymerization
Including: described solution polymerization is carried out under an inert atmosphere, and polymerization temperature is 0-80 DEG C, polymerization time
For 2-15 hour, pH value was 6-10.
Method the most according to claim 9, wherein, described solution polymerization includes entering successively
In two stages of row, the reaction condition of first stage includes: temperature is 0-25 DEG C, and the time is that 2.5-12 is little
Time；The reaction condition of second stage includes: temperature is 30-80 DEG C, and the time is 2.5-10 hour.
11. are had surface activity by what the method described in any one in claim 4-10 prepared
The polymer of function.
The polymer with surface active function described in any one or right in 12. claim 1-3
Require the polymer application as oil displacement agent with surface active function described in 11.
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| 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 |
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| 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 |
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| CN116063622A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Fracturing fluid thickener, oil displacement fracturing fluid and application |
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