CN105440203B - A kind of polymer with surface active function and preparation method thereof - Google Patents
A kind of polymer with surface active function and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polymer with surface active function and preparation method thereof, the polymer contains construction unit A, construction unit B and construction unit C, the construction unit A is the construction unit shown in formula (1), the construction unit B is the construction unit shown in formula (2), the construction unit C is the construction unit shown in formula (3), on the basis of total consumption molal quantity of construction unit in the polymer, the content of the construction unit A is 8 45 moles of %, the content of the construction unit B is 50 91 moles of %, the content of the construction unit C is 0.001 5 moles of %；The viscosity average molecular weigh of the polymer is 12,000,000 2,500 ten thousand；The polymer of the present invention can as middle and low permeable reservoir flooding polymers, have the advantages that good water solubility, tackifying strong and temperature-resistant anti-salt performance and surface-active are good, so that the polymer has good washing oil effect.
Description
Technical field
Oil recovering is improved the present invention relates to the water miscible polymer with surface active function and Polymer Used For Oil Displacement
The research field of rate, in particular it relates to a kind of polymer with surface active function and preparation method thereof.Especially
Refer to Polymer Used For Oil Displacement with surface active function and preparation method thereof.
Background technology
Polymer Used For Oil Displacement should have excellent performance and good water solubility, tackifying strong, adapt to inject the environment of oil reservoir
Condition (such as reservoir temperature and salinity), is not susceptible to degraded, and ageing resistace is good.Usual polymer oil-displacing agent has synthesis poly-
Compound, biopolymer, the modified product three major types of natural polymer.At present, the displacement of reservoir oil mainly applied in tertiary oil production in oil field
Polymer is partially hydrolyzed polyacrylamide (PHPA), the features such as it has high molecular weight, good water solubility.But in high temperature and high salt oil deposit bar
Under part, partially hydrolyzed polyacrylamide (PHPA) has obvious defect in performance, and such as heatproof, saline-alkaline tolerance is poor.For the above
Deficiency, domestic and international researcher is in order to improve the heat and salt resistance of polyacrylamide solution to develop function admirable temperature-resistant and anti-salt type
Polymer oil-displacing agent, the structure of viscosifying action mechanism, thermal degradation and salt tolerance and polymer to polymer oil-displacing agent with it is resistance to
Temperature, the relation of salt resistant character have made numerous studies.
However, continuing to increase with conventional oil reservoir recovery percent of reserves, the drastically reduction of recoverable reserves, employ middle LOW PERMEABILITY RESERVOIR
It is extremely urgent.But it is due to that low molecule amount flooding polymers can not meet oil field performance indications requirement, and HMW drives
There is the blocking of oil reservoir space under the conditions of middle and low permeable reservoir in oil polymer, the injection phenomenon such as pressure is higher, causes middle hyposmosis
The development progress of oil reservoir is slower.Therefore, the research of development middle and low permeable reservoir displacement of reservoir oil new polymers has particularly significant
Meaning.
The polymer that middle and low permeable reservoir can be applied to must be fulfilled for that dissolubility is good, and molecular weight is not high, while in high temperature
Still there is viscosity higher under high salt, thus the flooding polymers available for middle hyposmosis are proposed with higher requirement.
The content of the invention
It is an object of the invention to provide a kind of polymer with surface active function, the polymer of the invention can conduct
The flooding polymers of middle and low permeable reservoir are good with good water solubility, strong tackifying and temperature-resistant anti-salt performance and surface-active
Advantage so that the polymer has good washing oil effect.
In the polymer of the present invention, introduce end and contain the function monomer of Dialkylamino, so as to improve polymer
Anti-hydrolytic performance, aqueous solutions of polymers is kept higher viscosity under high salt.In ageing process, the steric hindrance of rigid phenyl group
Effect, makes molecular motion resistance big, reduces molecule chain break, improves the chronic anti-aging performance of polymer solution；It is simultaneously strong
The introducing of polarity sulfonic acid group, considerably increases the ability of anti-bivalent metal ion, and its very strong hydrophilic interaction and electrostatic
Repulsive force makes polymer have good water solubility, also greatly increases the hydrodynamic volume of strand, shows good
Viscosifying action and heat and salt resistance.Introducing-the SO in acrylamide polymer3 -Group, polymer will show good
The performance of the anti-divalence of heatproof and multivalent metal cation.Due to highly polar sulfonic acid group, its very strong hydrophilic interaction and electrostatic
Repulsive force makes polymer have good water solubility, the hydrodynamic volume of strand is also greatly increased, with good
Viscosifying action, it is often more important that polymer has outstanding heat and salt resistance and surface-active.
To achieve these goals, on the one hand, the present invention provides a kind of polymer with surface active function, the polymerization
It is the construction unit shown in formula (1) that thing, which contains construction unit A, construction unit B and construction unit C, the construction unit A, described
Construction unit B is the construction unit shown in formula (2), and the construction unit C is the construction unit shown in formula (3), with the polymerization
In thing on the basis of the total mole number of construction unit, the content of the construction unit A is 8-45 moles of %, the construction unit B's
Content is 50-91 moles of %, and the content of the construction unit C is 0.001-5 moles of %；The viscosity average molecular weigh of the polymer is
12000000-2,500 ten thousand；
Wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H or C1-C3 alkyl；A, m are identical with n
Or it is different, it is each independently 0 or 1-8 integer, R6And R7It is identical or different, it is various independently to be substituted or unsubstituted C1-
C10 alkyl；M in formula (1) and formula (3) is respectively one kind in Li, Na, K or H.
On the other hand, the present invention also provides a kind of preparation method of the polymer with surface active function, this method bag
Include：PH value be 6-10 under conditions of, under the polymerization conditions, will as the monomer shown in formula (4), the monomer shown in formula (5),
Monomer, water, complexing agent shown in formula (6) and the solution of auxiliary agent formation are contacted with initiator, with the polymer monomer it is total
On the basis of consumption molal quantity, the consumption of the monomer shown in the formula (4) is 8-45 moles of %, the monomer shown in the formula (5)
Consumption is 50-91 moles of %, and the consumption of the monomer shown in the formula (6) is 0.001-5 moles of %；The condition of the polymerisation
So that the viscosity average molecular weigh of resulting polymers is 12,000,000-2,500 ten thousand after polymerisation；
Wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H or C1-C3 alkyl；A, m are identical with n
Or it is different, it is each independently 0 or 1-8 integer, R6And R7It is identical or different, it is various independently to be substituted or unsubstituted C1-
C10 alkyl；M in formula (4) and formula (6) is respectively one kind in Li, Na, K or H.
A kind of polymer with surface active function that the present invention is provided introduces one kind in macromolecular chain and contains two hydrocarbon
The function monomer with surface active function of base amino so that on the one hand polyacrylamide has high molecular weight water soluble polymer
Tackifying and viscoplasticity, and thus improve sweep efficiency；The introducing of another aspect surface active function polymerisable monomer so that
Such novel high polymer oil displacement agent has certain surface-active, by emulsifying the characteristic such as increase-volume and reduction surface and interface tension force, from
And increase the washing oil effect of polymer.The present invention the polymer can as middle and low permeable reservoir flooding polymers, with water
Dissolubility is good, tackifying is strong and temperature-resistant anti-salt performance and the good advantage of surface-active.
It is the major way for preparing the polymer with surface active function of the present invention using the method for polymerization, that is,
Say and polymerize using acrylamide with the function monomer with surface active groups, hydrophilic radical and oleophylic are introduced by polymerizeing
Group, so that polymer has higher surface-active, while having the characteristic of general water-soluble polymer.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of polymer with surface active function, it is characterised in that the polymer contains
It is the construction unit shown in formula (1), the structure to have construction unit A, construction unit B and construction unit C, the construction unit A
Unit B is the construction unit shown in formula (2), and the construction unit C is the construction unit shown in formula (3), with the polymer
On the basis of the total mole number of construction unit, the content of the construction unit A is 8-45 moles of %, the content of the construction unit B
For 50-91 moles of %, the content of the construction unit C is 0.001-5 moles of %；The viscosity average molecular weigh of the polymer is 1200
Ten thousand -2,500 ten thousand；
Wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H or C1-C3 alkyl；A, m are identical with n
Or it is different, it is each independently 0 or 1-8 integer, R6And R7It is identical or different, it is various independently to be substituted or unsubstituted C1-
C10 alkyl；M in formula (1) and formula (3) is respectively one kind in Li, Na, K or H.
A kind of polymer with surface active function that the present invention is provided introduces one kind in macromolecular chain and contains two hydrocarbon
The function monomer with surface active function of base amino so that on the one hand polyacrylamide has high molecular weight water soluble polymer
Tackifying and viscoplasticity, and thus improve sweep efficiency；The introducing of another aspect surface active function polymerisable monomer so that
Such novel high polymer oil displacement agent has certain surface-active, by emulsifying the characteristic such as increase-volume and reduction surface and interface tension force, from
And increase the washing oil effect of polymer.The present invention the polymer can as middle and low permeable reservoir flooding polymers, with water
Dissolubility is good, tackifying is strong and temperature-resistant anti-salt performance and the good advantage of surface-active.
Under preferable case, in the polymer of the present invention with surface active function, R1、R2、R3、R4And R5It is identical
Or it is different, H, methyl, ethyl, n-propyl or isopropyl can be each independently；A, m and n are identical or different, can be each only
It is on the spot 1-8 integer, R6And R7It is identical or different, the various alkyl for independently being unsubstituted C1-C10.In the present invention,
The alkyl of the unsubstituted C1-C10 includes the alkyl that unsubstituted carbon number is 1-10, specifically, of the present invention
Method in, the alkyl that the unsubstituted carbon number is 1-10 can be methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, isobutyl group, the tert-butyl group, amyl group, cyclopenta, hexyl, cyclohexyl, heptyl, octyl group, nonyl or certain herbaceous plants with big flowers base.
Preferably, in the polymer of the present invention with surface active function, the m can be 1-4 integer,
N can be 2-8 integer, R6And R7It is identical or different, the various alkyl for independently being unsubstituted C1-C6.Specifically, at this
In invention, the integer of the 1-4 includes 1,2,3 and 4；The integer of the 2-8 includes 2,3,4,5,6,7 and 8；It is described unsubstituted
C1-C6 alkyl includes methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, cyclopenta, hexyl
And cyclohexyl.
In the polymer of the present invention with surface active function, preferably described construction unit A is formula (1-1) institute
The construction unit shown, the construction unit B is the construction unit shown in formula (2-1), and the construction unit C is shown in formula (3-1)
Construction unit,
Wherein, m is 1-4 integer, and n is 2-8 integer, R6And R7It is identical or different, it is various independently be methyl, ethyl,
N-propyl or isopropyl；M in formula (1-1) and formula (3-1) is respectively one kind in Li, Na, K or H.
According to the polymer of the present invention with surface active function, wherein, preferably described construction unit A content
Can be 9-29 moles of %, the content of the construction unit B can be 70-90 moles of %, the content of the construction unit C can be with
For 0.01-1 moles of %；The viscosity average molecular weigh of the polymer can be 15,000,000-2,200 ten thousand.
According to the polymer of the present invention with surface active function, wherein, the most preferably construction unit A's contains
Amount can be 10-20 moles of %, and the content of the construction unit B can be 79.6-89.8 moles of %, the construction unit C's
Content can be 0.02-0.40 moles of %.
Present invention also offers a kind of preparation method of the polymer with surface active function, this method includes：In pH
It is worth under conditions of 6-10, under the polymerization conditions, will be as the monomer shown in formula (4), the monomer shown in formula (5), formula (6) institute
The solution of monomer, water, complexing agent and the auxiliary agent formation shown is contacted with initiator, with total consumption mole of monomer in the polymer
On the basis of number, the consumption of the monomer shown in the formula (4) is 8-45 moles of %, and the consumption of the monomer shown in the formula (5) is 50-
91 moles of %, the consumption of the monomer shown in the formula (6) is 0.001-5 moles of %；The condition of the polymerisation causes polymerization
The viscosity average molecular weigh of resulting polymers is 12,000,000-2,500 ten thousand after reaction；Wherein, R1、R2、R3、R4And R5It is identical or different, each
It independently is H or C1-C3 alkyl；A, m and n are identical or different, are each independently 0 or 1-8 integer, R6And R7It is identical
Or different, the various alkyl for independently being substituted or unsubstituted C1-C10；M in formula (4) and formula (6) is respectively Li, Na, K
Or one kind in H,
In the above method of the present invention, the water is used to dissolve monomer involved in method of the invention, and conduct
Reaction dissolvent is used, and those skilled in the art, can be using other feasible molten after technical scheme has been understood
Agent is replaced, as long as enabling to polymerisation to carry out.And water of the present invention can be deionized water.
In method of the present invention, the condition of the polymerisation is aqueous solution polymerization condition, and the aqueous solution gathers
Conjunction condition can understanding of technical scheme for conventional use of various conditions in the art, those skilled in the art
After can be selected as needed in normal condition, the present invention will not be repeated here.And the present invention preferably polymerization
Reaction is carried out in the presence of protective gas.
In the above method of the present invention, the pH value can be used for 6-10 condition by using routine in the art
Various acidic materials or alkaline matter be adjusted, adjusted present invention preferably uses such as sodium hydroxide and/or sodium carbonate
Section.
In the case of more preferably, the preparation method of the polymer with surface active function of the invention is 8-10's in pH value
Under the conditions of carry out.
Under preferable case, in the preparation method of the polymer of the present invention with surface active function, R1、R2、
R3、R4And R5It is identical or different, it is each independently H, methyl, ethyl, n-propyl or isopropyl；A, m and n are identical or different, respectively
From the integer for independently being 1-8, R6And R7It is identical or different, the various alkyl for independently being unsubstituted C1-C10.
In the case of more preferably, in the preparation method of the polymer of the present invention with surface active function, m is 1-
4 integer, n is 2-8 integer, R6And R7It is identical or different, the various alkyl for independently being unsubstituted C1-C6.
In the preparation method of the polymer of the present invention with surface active function, shown in preferably described formula (4)
Monomer can be the compound shown in formula (4-1), the monomer shown in the formula (5) can be the compound shown in formula (5-1),
Monomer shown in the formula (6) can be the compound shown in formula (6-1),
Wherein, m is 1-4 integer, and n is 2-8 integer；M in formula (4-1) and formula (6-1) is respectively Li, Na, K or H
In one kind.
In the preparation method of the polymer of the present invention with surface active function, shown in preferably described formula (4)
The consumption of monomer can be 9-29 moles of %, the consumption of the monomer shown in the formula (5) can be 70-90 moles of %, described
The consumption of monomer shown in formula (6) can be 0.01-1 moles of %；The condition of the polymerisation causes gained after polymerisation
The viscosity average molecular weigh of polymer can be 15,000,000-2,200 ten thousand.
In the preparation method of the polymer of the present invention with surface active function, most preferably described formula (4) institute
The consumption of the monomer shown can rub for 10-20 moles of %, the consumption of the monomer shown in the formula (5) for 79.6-89.8
You are %, and the consumption of the monomer shown in the formula (6) can be 0.02-0.40 moles of %.
The preparation method of the polymer with surface active function provided according to the present invention, wherein, shown in the formula (4)
Monomer, the consumption of the monomer shown in formula (5) and the monomer shown in formula (6) cause monomer shown in the formula (4), formula (5) institute
Total consumption of the monomer shown in monomer and formula (6) shown is as the monomer shown in the formula (4), the monomer shown in formula (5), formula
(6) concentration in the solution that monomer, water, complexing agent and auxiliary agent shown in are formed can be 5-60 weight %；Preferably 10-40 weights
Measure %.In the range of the above-mentioned concentration values of the present invention one can be used as per the weight % of increasing or decreasing 1 or 0.5 weight %
The embodiment that can be selected.
The preparation method of the polymer with surface active function provided according to the present invention, wherein, shown in the formula (4)
Monomer, the monomer shown in formula (5) and the total consumption and complexing agent of the monomer shown in formula (6) and the consumption weight ratio of auxiliary agent be
100：0.005-0.12：0.001-0.15；Preferably 100：0.01-0.1：0.005-0.1.
The preparation method of the polymer with surface active function provided according to the present invention, wherein, the complexing agent can
Think at least one of disodium ethylene diamine tetraacetate, citric acid, citrate and poly- hydroxy acrylic acid, more preferably described complexing
Agent is disodium ethylene diamine tetraacetate.In method of the present invention, the offer form to the complexing agent is not limited particularly
It is fixed, it can for example be provided, provided in solid form with pure solution form, or provided with the solution form being diluted.In this hair
In bright method, preferably described complexing agent can be the EDTA-2Na aqueous solution that concentration is 1 weight %.
The preparation method of the polymer with surface active function provided according to the present invention, wherein, the auxiliary agent can be with
For selected from least one of urea, sodium formate, isopropanol and sodium hypophosphite, more preferably described auxiliary agent is urea.In the present invention
In described method, to the offer form of the auxiliary agent, there is no particular limitation, for example, can be provided with pure solution form, with solid
Body form is provided, or is provided with the solution form being diluted.For example in the present invention, when used auxiliary agent is urea,
Urea can be provided as an aqueous solution, and to the concentration of its solution, there is no particular limitation.In the inventive solutions, it is excellent
It for example can be the aqueous solution of urea that concentration is 1 weight % to select the complexing agent.
The preparation method of the polymer with surface active function provided according to the present invention, wherein, the initiator can
Think redox series initiators.
The preparation method of the polymer with surface active function provided according to the present invention, wherein, the redox
Series initiators include Oxidizing and Reducing Agents, and the oxidant is selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and peroxidating
At least one of hydrogen；The reducing agent is white selected from sodium hydrogensulfite, potassium bisulfite, sodium sulfite, potassium sulfite, carving
At least one of powder, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite, ascorbic acid and urea.Under most preferred case, in the present invention
In the preparation method of the described polymer with surface active function, the oxidant is ammonium sulfate, potassium peroxydisulfate and over cure
At least one of sour sodium；The reducing agent be sodium hydrogensulfite, potassium bisulfite, sodium sulfite and potassium sulfite at least
It is a kind of.In the present invention, the Oxidizing and Reducing Agents for constituting the redox series initiators for example can be as a solution
There is provided, for example：The preferably oxidant of the invention is that persulfate aqueous solution or concentration that concentration is 0.1 weight % are 0.1
Weight % ammonium persulfate aqueous solution；It is preferred that bisulfite aqueous solutions of potassium that it is 0.1 weight % that the reducing agent, which is concentration, or
Concentration is 0.1 weight % aqueous solution of sodium bisulfite.
The preparation method of the polymer with surface active function provided according to the present invention, wherein, preferably described oxidation
The consumption of reduction series initiators is total with the monomer shown in the monomer shown in the formula (4), the monomer shown in formula (5) and formula (6)
The weight ratio of consumption can be 0.005-0.2：100, more preferably 0.01-0.15：100.
The preparation method of the polymer with surface active function provided according to the present invention, wherein, preferably described oxidation
The weight ratio of agent and the reducing agent can be 1-25：1, more preferably 5-20：1.
The preparation method of the polymer with surface active function provided according to the present invention, wherein, the polymerisation
Method can be included in the presence of protective gas, first polymerize 2.5-12h at 0-25 DEG C, 30-80 DEG C is then warming up to again
Lower polymerization 2.5-10h.
The preparation method of the polymer with surface active function provided according to the present invention, preferably described polymerisation can
To be carried out under being acted in gas shield, such as being protected nitrogen.
According to a preferred embodiment of the invention, the preparation method of the polymer with surface active function, tool
Body may comprise steps of：
1) under conditions of pH value is 6-10, by shown in the monomer shown in formula (4), the monomer shown in formula (5) and formula (6)
Monomer is contacted with water, obtains mixture solution；
2) mixture solution is contacted with complexing agent and auxiliary agent, obtains solution to be polymerized；
3) under the polymerization conditions, the solution to be polymerized is contacted under nitrogen protection with initiator, wherein, it is described
The method of polymerisation can preferably include first polymerizeing 2.5-12h at 0-25 DEG C, be then warming up at 30-80 DEG C and polymerize again
2.5-10h。
According to another preferred embodiment of the present invention, the preparation side of the polymer with surface active function
Method can also include：The blob of viscose obtained after aggregated reaction is cut, granulates, crushes and sieved successively to be had described in obtaining
The polymer end product of surface active function.
There is no particular limitation to the method cut, granulate, crush and sieved by the present invention, and those skilled in the art can
To be carried out according to conventional use of various methods in the art.
Above-mentioned polymer with surface active function of the present invention and preparation method thereof, compared with prior art, is dividing
There is advantages below and effect in son design and synthesis：
The present invention is to introduce a kind of not only with surface-active but also containing polymerizable vinyl in acrylamide polymer
Function monomer, so as to improve the surface-active of polyacrylamide solution, tackifying and heat and salt resistance.In acrylamide polymer
Middle introducing-SO3 -Group, polymer will show the anti-divalence of good heatproof and the performance of multivalent metal cation.Due to strong
The sulfonic acid group of polarity, its very strong hydrophilic interaction makes polymer have good water solubility with electrostatic repulsion forces, also greatly
The hydrodynamic volume of strand is increased, with good viscosifying action, it is often more important that polymer has outstanding heatproof
Salt-resistance and surface-active.In ageing process, due to the steric effect of the rigid phenyl group of the monomer with surface active function,
Make molecular motion resistance big, reduce molecule chain break, improve the chronic anti-aging performance of polymer solution；While highly polar sulphur
The introducing of acid groups, considerably increases anti-bivalent metal ion ability, and its very strong hydrophilic interaction makes with electrostatic repulsion forces
Polymer has good water solubility, also greatly increases the hydrodynamic volume of strand, shows good thickening and makees
With and heat and salt resistance.
The present invention will be described in detail by way of examples below.In following examples, in the feelings being not particularly illustrated
Under condition, used various reagents are from commercially available chemically pure reagent.
In the examples below, the viscosity average molecular weigh of polymer is tested using one point method using Ubbelohde viscometer；
It is 25000mg/L (its in salinity to determine polymer solution with Brookfield viscosimeters at nominative testing temperature (80 DEG C)
Middle calcium ions and magnesium ions be 800mg/L (high salt)) under apparent viscosity；With DCAT-21 surfaces at nominative testing temperature (25 DEG C)
Power instrument determines aqueous solution surface tension of the polymer under pure water.
Monomer shown in embodiments of the invention Chinese style (4) is purchased from Weifang company of Quan Xin Chemical Co., Ltd.s.
The synthesis of monomer：The method synthesis that monomer shown in following embodiment Chinese styles (6) can be provided using prior art,
The synthetic method of the monomer shown in the formula (6) in embodiment 1 is exemplarily listed in the preparation example 1 of the present invention, remaining implementation
Different monomers in example are synthesized by using different raw materials and using the method similar with preparation example 1, and the present invention is herein not
Repeat again.
Preparation example 1
This preparation example is used for the synthetic method for illustrating the monomer shown in the formula (6) in embodiment 1：
100mL tetrahydrofuran is added in 250mL there-necked flask, in the brine bath for being positioned over minus 10 DEG C, in stirring
Lower addition 0.1mol to benzene divinyl, then pass to SO3(0.1mol), after question response is complete, then is added dropwise N, N- dimethyl second
Insulation reaction 1h again after the RMgBr (0.1mol) of base magnesium chloride, completion of dropping, then adding n-hexane separates out product, most
Washed more than three times with n-hexane afterwards, that is, obtain the monomer shown in the Chinese style of embodiment 1 (6).
Embodiment 1
The method that the present embodiment is provided using the present invention prepares the polymer with surface active function that the present invention is provided
1-A, wherein, the monomer described in formula (4) is 2- acrylamide-2-methylpro panesulfonic acids；Monomer described in formula (5) is acryloyl
Amine；M=1, n=2, R in monomer (hereinafter also referred to function monomer) described in formula (6)6And R7It is CH3, R5For H, M is H, point
Son amount is 283.
Specifically, the present embodiment is adopted is carried out with the following method：
1) by acrylamide (166.2mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.6mmol) and function monomer
(0.7mmol) is added in polymerisation bottle (i.e. polymerization bottle), is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds
Sodium hydroxide adjusts pH value to 8.0, obtains mixture solution；
2) added into above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 1.0g, 1 weight % urea it is water-soluble
Liquid 0.5g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, leads to after nitrogen flooding oxygen, add 0.1 weight % potassium peroxydisulfate water
Solution 4.0g and 0.1 weight % aqueous solution of sodium bisulfite 2.0g, in 10 DEG C of initiation reactions, continue logical nitrogen and stop after five minutes
Only, under nitrogen protection, polymerisation 4 hours；50 DEG C are then heated to continue to react 6 hours；
4) take out step 3) in obtained blob of viscose, cut, granulated, crushed, sieved successively, obtain white temperature-resistant anti-salt
Polymer Used For Oil Displacement 1-A.
After tested, polymer 1-A viscosity average molecular weigh is 22,000,000, and apparent viscosity is 45.6mPas, surface tension
For 31.78mN/m, excellent surface-active and resisting high temperature, high salt performance is shown.
Embodiment 2
The method that the present embodiment is provided using the present invention prepares the polymer with surface active function that the present invention is provided
2-A, wherein, the monomer described in formula (4) is 2- acrylamide-2-methylpro panesulfonic acids；Monomer described in formula (5) is acryloyl
Amine；M=1, n=4, R in monomer (hereinafter also referred to function monomer) described in formula (6)6And R7It is CH3, R5For H, M is H, point
Son amount is 311.
Specifically, the present embodiment is adopted is carried out with the following method：
1) by acrylamide (167.6mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.6mmol) and function monomer
(0.35mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium hydroxide tune
PH value is saved to 9.0, mixture solution is obtained；
2) added into above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 1.0g, 1 weight % urea it is water-soluble
Liquid 1.0g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, leads to after nitrogen flooding oxygen, add 0.1 weight % ammonium persulfate water
Solution 5.0g and 0.1 weight % bisulfite aqueous solutions of potassium 2.5g, in 11 DEG C of initiation reactions, continues logical nitrogen and stops after five minutes
Only, under nitrogen protection, polymerisation 6 hours；55 DEG C are then heated to continue to react 6 hours；
4) take out step 3) in obtained blob of viscose, cut, granulated, crushed, sieved successively, obtain white temperature-resistant anti-salt
Polymer Used For Oil Displacement 2-A.
After tested, polymer 2-A viscosity average molecular weigh is 18,000,000, and apparent viscosity is 42.4mPas, and surface tension is
31.73mN/m, shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 3
The method that the present embodiment is provided using the present invention prepares the polymer with surface active function that the present invention is provided
3-A, wherein, the monomer described in formula (4) is 2- acrylamide-2-methylpro panesulfonic acids；Monomer described in formula (5) is acryloyl
Amine；M=1, n=4, R in monomer (hereinafter also referred to function monomer) described in formula (6)6And R7It is CH3, R5For H, M is H, point
Son amount is 311.
Specifically, the present embodiment is adopted is carried out with the following method：
1) by acrylamide (196.5mmol), 2- acrylamide-2-methylpro panesulfonic acids (29.0mmol) and function monomer
(0.18mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium hydroxide tune
PH value is saved to 10.0, mixture solution is obtained；
2) added into above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 2.0g, 1 weight % urea it is water-soluble
Liquid 0.5g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, led to after nitrogen flooding oxygen, the ammonium persulfate for adding 0.1 weight % is water-soluble
Liquid 10.0g and 0.1 weight % aqueous solution of sodium bisulfite 5.0g, in 15 DEG C of initiation reactions, continue logical nitrogen and stop after five minutes
Only, under nitrogen protection, polymerisation 8 hours；60 DEG C are then heated to continue to react 5 hours；
4) take out step 3) in obtained blob of viscose, cut, granulated, crushed, sieved successively, obtain white temperature-resistant anti-salt drive
Oil uses polymer 3-A.
After tested, polymer 3-A viscosity average molecular weigh is 17,000,000, and apparent viscosity is 41.6mPas, surface tension
For 32.52mN/m, excellent surface-active and resisting high temperature, high salt performance is shown.
Embodiment 4
The method that the present embodiment is provided using the present invention prepares the polymer with surface active function that the present invention is provided
4-A, wherein, the monomer described in formula (4) is 2- acrylamide-2-methylpro panesulfonic acids；Monomer described in formula (5) is acryloyl
Amine；M=1, n=8, R in monomer (hereinafter also referred to function monomer) described in formula (6)6And R7It is CH3, R5For H, M is H, point
Son amount is 367.
Specifically, the present embodiment is adopted is carried out with the following method：
1) by acrylamide (168.7mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.6mmol) and function monomer
(0.07mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium carbonate regulation
PH value obtains mixture solution to 8.0；
2) added into above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 0.2g, 1 weight % urea it is water-soluble
Liquid 0.2g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, leads to after nitrogen flooding oxygen, add 0.1 weight % ammonium persulfate water
Solution 4.0g and 0.1 weight % aqueous solution of sodium bisulfite 2.0g, in 12 DEG C of initiation reactions, continue logical nitrogen and stop after five minutes
Only, under nitrogen protection, polymerisation 7 hours；60 DEG C are then heated to continue to react 4 hours；
4) take out step 3) in obtained blob of viscose, cut, granulated, crushed, sieved successively, obtain white temperature-resistant anti-salt
Polymer Used For Oil Displacement 4-A.
After tested, polymer 4-A viscosity average molecular weigh is 25,000,000, and apparent viscosity is 46.9mPas, and surface tension is
31.83mN/m, shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 5
The method that the present embodiment is provided using the present invention prepares the polymer with surface active function that the present invention is provided
5-A, wherein, the monomer described in formula (4) is 2- acrylamide-2-methylpro panesulfonic acids；Monomer described in formula (5) is acryloyl
Amine；M=2, n=4, R in monomer (hereinafter also referred to function monomer) described in formula (6)6And R7It is CH3, R5For H, M is H, point
Son amount is 325.
Specifically, the present embodiment is adopted is carried out with the following method：
1) by acrylamide (169.0mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.2mmol) and function monomer
(0.35mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium hydroxide tune
PH value is saved to 8.0, mixture solution is obtained；
2) added into above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 0.2g, 1 weight % urea it is water-soluble
Liquid 2.0g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, leads to after nitrogen flooding oxygen, add 0.1 weight % potassium peroxydisulfate water
Solution 20.0g and 0.1 weight % aqueous solution of sodium bisulfite 10.0g, in 15 DEG C of initiation reactions, continue logical nitrogen after five minutes
Stop, under nitrogen protection, polymerisation 5 hours；45 DEG C are then heated to continue to react 5 hours；
4) take out step 3) in obtained blob of viscose, cut, granulated, crushed, sieved successively, obtain white temperature-resistant anti-salt drive
Oil uses polymer 5-A.
After tested, polymer 5-A viscosity average molecular weigh is 15,000,000, and apparent viscosity is 40.2mPas, surface tension
For 33.95mN/m, excellent surface-active and resisting high temperature, high salt performance is shown.
Embodiment 6
The method that the present embodiment is provided using the present invention prepares the polymer with surface active function that the present invention is provided
6-A, wherein, the monomer described in formula (4) is 2- acrylamide-2-methylpro panesulfonic acids；Monomer described in formula (5) is acryloyl
Amine；M=4, n=6, R in monomer (hereinafter also referred to function monomer) described in formula (6)6And R7It is CH3, R5For H, M is H, point
Son amount is 381.
Specifically, the present embodiment is adopted is carried out with the following method：
1) by acrylamide (169.0mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.2mmol) and function monomer
(0.35mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium carbonate regulation
PH value obtains mixture solution to 9.0；
2) added into above-mentioned mixture solution 1 weight % EDTA-2Na aqueous solution 2.0g, 1 weight % urea it is water-soluble
Liquid 0.2g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, leads to after nitrogen flooding oxygen, add 0.1 weight % potassium peroxydisulfate water
Solution 3.0g and 0.1 weight % aqueous solution of sodium bisulfite 1.5g, in 10 DEG C of initiation reactions, continue logical nitrogen and stop after five minutes
Only, under nitrogen protection, polymerisation 4 hours；50 DEG C are then heated to continue to react 6 hours；
4) take out step 3) in obtained blob of viscose, cut, granulated, crushed, sieved successively, obtain white temperature-resistant anti-salt
Polymer Used For Oil Displacement 6-A.
After tested, polymer 6-A viscosity average molecular weigh is 20,000,000, and apparent viscosity is 42.9mPas, and surface tension is
31.67mN/m, shows excellent surface-active and resisting high temperature, high salt performance.
Embodiment 7
The present embodiment prepares the polymerization with surface active function that the present invention is provided using method same as Example 1
Thing 7-A, wherein, except that, the R in the monomer described in formula (4)1And R2For H, R3For CH3, a is that 4, M is H.
After tested, polymer 7-A viscosity average molecular weigh is 17,000,000, and apparent viscosity is 41.3mPas, surface tension
For 32.58mN/m, excellent surface-active and resisting high temperature, high salt performance is shown.
Embodiment 8
The present embodiment prepares the polymerization with surface active function that the present invention is provided using method same as Example 2
Thing 8-A, wherein, except that, m=4, n=8, R in the monomer described in formula (6)6For CH3, R7For CH2CH3, R5It is for H, M
H, molecular weight is 423.
After tested, polymer 8-A viscosity average molecular weigh is 19,000,000, and apparent viscosity is 42.5mPas, surface tension
For 31.11mN/m, excellent surface-active and resisting high temperature, high salt performance is shown.
Embodiment 9
The present embodiment prepares the polymerization with surface active function that the present invention is provided using method same as Example 3
Thing 9-A, wherein, except that, m=1, n=1, R in the monomer described in formula (6)6For isopropyl, R7For normal-butyl, R5For
H, M are H, and molecular weight is 339.
After tested, polymer 9-A viscosity average molecular weigh is 21,000,000, and apparent viscosity is 44.3mPas, surface tension
For 31.41mN/m, excellent surface-active and resisting high temperature, high salt performance is shown.
Embodiment 10
The present embodiment prepares the polymerization with surface active function that the present invention is provided using method same as Example 4
Thing 10-A, wherein, except that, m=1, n=2, R in the monomer described in formula (6)6For CH3、R7For cyclohexyl, R5For CH3,
M is Na, and molecular weight is 387.
After tested, polymer 10-A viscosity average molecular weigh is 25,000,000, and apparent viscosity is 46.5mPas, surface tension
For 30.05mN/m, excellent surface-active and resisting high temperature, high salt performance is shown.
Embodiment 11
The present embodiment prepares the polymerization with surface active function that the present invention is provided using method same as Example 6
Thing 11-A, wherein, except that, in step 1) middle addition 200g deionized waters.
After tested, polymer 11-A viscosity average molecular weigh is 12,000,000, and apparent viscosity is 30.2mPas, surface tension
For 36.03mN/m, more excellent surface-active and resisting high temperature, high salt performance is shown.
Embodiment 12
The present embodiment prepares the polymerization with surface active function that the present invention is provided using method same as Example 1
Thing 12-A, wherein, except that, the amount of the monomer described in the formula (6) of addition is 4.3mmol.
After tested, polymer 12-A viscosity average molecular weigh is 15,000,000, and apparent viscosity is 31.1mPas, surface tension
For 36.16mN/m, preferable surface-active and resisting high temperature, high salt performance are shown.
Comparative example 1
This comparative example prepares the polymer 1-B with surface active function using method same as Example 1, wherein,
Except that, the amount of the monomer described in the formula (6) of addition is 12.87mmol.
After tested, polymer 1-B viscosity average molecular weigh is 10,000,000, and apparent viscosity is 15.1mPas, surface tension
For 46.01mN/m, surface-active and resisting high temperature, high salt performance are bad.
The method provided using the present invention is can be seen that by comparative example 1-12 and comparative example 1 result to prepare
Obtaining the polymer of the present invention with surface active function has excellent surface-active and resisting high temperature, high salt performance.
Therefore, the above-mentioned polymer with surface active function that provides of the present invention due to the introducing containing rigid phenyl group so that
The hydrophobic effect between polymer molecule is improved, hydrophobic grouping is carried out orderly arrangement on surface, aqueous solutions of polymers is reduced
Surface tension so that aqueous solutions of polymers can keep higher viscosity under high temperature and high salt.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, 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 equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of polymer with surface active function, it is characterised in that the polymer contains construction unit A, construction unit B
With construction unit C, the construction unit A is the construction unit shown in formula (1), and the construction unit B is the structure shown in formula (2)
Unit, the construction unit C is the construction unit shown in formula (3), using the total mole number of construction unit in the polymer as base
Standard, the content of the construction unit A is 8-45 moles of %, and the content of the construction unit B is 50-91 moles of %, the structure
Unit C content is 0.001-5 moles of %；The viscosity average molecular weigh of the polymer is 12,000,000-2,500 ten thousand；
Wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H or C1-C3 alkyl；A, m are identical with n or not
Together, 0 or 1-8 integer, R are each independently6And R7It is identical or different, it is various independently to be substituted or unsubstituted C1-C10
Alkyl；M in formula (1) and formula (3) is respectively one kind in Li, Na, K or H.
2. polymer according to claim 1, wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H, first
Base, ethyl, n-propyl or isopropyl；A, m and n are identical or different, are each independently 1-8 integer, R6And R7It is identical or not
Together, the various alkyl for independently being unsubstituted C1-C10.
3. polymer according to claim 2, wherein, m is 1-4 integer, and n is 2-8 integer, R6And R7It is identical or not
Together, the various alkyl for independently being unsubstituted C1-C6.
4. polymer according to claim 1, wherein, the construction unit A is the construction unit shown in formula (1-1), institute
It is the construction unit shown in formula (2-1) to state construction unit B, and the construction unit C is the construction unit shown in formula (3-1),
Wherein, m is 1-4 integer, and n is 2-8 integer, R6And R7It is identical or different, it is various independently to be methyl, ethyl, positive third
Base or isopropyl；M in formula (1-1) and formula (3-1) is respectively one kind in Li, Na, K or H.
5. the polymer according to any one in claim 1-4, wherein, the content of the construction unit A is rubbed for 9-29
You are %, and the content of the construction unit B is 70-90 moles of %, and the content of the construction unit C is 0.01-1 moles of %；It is described
The viscosity average molecular weigh of polymer is 15,000,000-2,200 ten thousand.
6. a kind of preparation method of the polymer with surface active function, it is characterised in that this method includes：It is 6- in pH value
, under the polymerization conditions, will be as the monomer shown in formula (4), the monomer shown in formula (5), the list shown in formula (6) under conditions of 10
Body, water, complexing agent and the solution of auxiliary agent formation are contacted with initiator, and total consumption molal quantity using monomer in the polymer is base
Standard, the consumption of the monomer shown in the formula (4) is 8-45 moles of %, and the consumption of the monomer shown in the formula (5) rubs for 50-91
You are %, and the consumption of the monomer shown in the formula (6) is 0.001-5 moles of %；The condition of the polymerisation causes polymerisation
The viscosity average molecular weigh of resulting polymers is 12,000,000-2,500 ten thousand afterwards；
Wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H or C1-C3 alkyl；A, m are identical with n or not
Together, 0 or 1-8 integer, R are each independently6And R7It is identical or different, it is various independently to be substituted or unsubstituted C1-C10
Alkyl；M in formula (4) and formula (6) is respectively one kind in Li, Na, K or H.
7. method according to claim 6, wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H, first
Base, ethyl, n-propyl or isopropyl；A, m and n are identical or different, are each independently 1-8 integer, R6And R7It is identical or not
Together, the various alkyl for independently being unsubstituted C1-C10.
8. method according to claim 7, wherein, m is 1-4 integer, and n is 2-8 integer, R6And R7It is identical or different,
The various alkyl for independently being unsubstituted C1-C6.
9. method according to claim 6, wherein, the monomer shown in the formula (4) is the compound shown in formula (4-1),
Monomer shown in the formula (5) is the compound shown in formula (5-1), and the monomer shown in the formula (6) is the change shown in formula (6-1)
Compound,
Wherein, m is 1-4 integer, and n is 2-8 integer；M in formula (4-1) and formula (6-1) is respectively in Li, Na, K or H
It is a kind of.
10. the method according to any one in claim 6-9, wherein, the consumption of the monomer shown in the formula (4) is 9-
29 moles of %, the consumption of the monomer shown in the formula (5) is 70-90 moles of %, and the consumption of the monomer shown in the formula (6) is
0.01-1 moles of %；The condition of the polymerisation cause the viscosity average molecular weighs of resulting polymers after polymerisation for 15,000,000-
22000000.
11. the method according to any one in claim 6-9, wherein, shown in the monomer, formula (5) shown in the formula (4)
Monomer and formula (6) shown in the consumption of monomer cause the monomer shown in the formula (4), the monomer shown in formula (5) and formula (6) institute
Total consumption of the monomer shown is as the monomer shown in the formula (4), the monomer shown in formula (5), the monomer shown in formula (6), water, network
Concentration in mixture and the solution of auxiliary agent formation is 5-60 weight %.
12. method according to claim 11, wherein, monomer shown in monomer, formula (5) and formula shown in the formula (4)
(6) the consumption weight ratio of total consumption of the monomer shown in and complexing agent and auxiliary agent is 100：0.005-0.12：0.001-0.15.
13. method according to claim 12, wherein, the complexing agent is disodium ethylene diamine tetraacetate, citric acid, lemon
At least one of hydrochlorate and poly- hydroxy acrylic acid；The auxiliary agent is in urea, sodium formate, isopropanol and sodium hypophosphite
It is at least one.
14. the method according to any one in claim 6-9, wherein, the initiator is redox series initiators,
Shown in monomer, the monomer shown in formula (5) and formula (6) shown in the consumption and the formula (4) of the redox series initiators
The weight ratio of total consumption of monomer is 0.005-0.2：100；The redox series initiators include Oxidizing and Reducing Agents, institute
The weight for stating oxidant and the reducing agent compares 1-25：1, the oxidant is selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate
At least one of with hydrogen peroxide；The reducing agent be selected from sodium hydrogensulfite, sodium sulfite, rongalite, sodium thiosulfate,
At least one of ferrous sulfate, sodium hydrosulfite and ascorbic acid.
15. the method according to any one in claim 6-9, wherein, the method for the polymerisation is included in protection
In the presence of gas, first it polymerize 2.5-12h at 0-25 DEG C, then heats at 30-80 DEG C and polymerize 2.5-10h.
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| CN102030852A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Polymer for tertiary oil recovery and preparation method thereof |
| CN102050917A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Macromolecular compound containing aliphatic tertiary amine group as well as preparation method thereof and application in oil displacement agent |
| CN102408517A (en) * | 2010-09-25 | 2012-04-11 | 中国石油化工股份有限公司 | Degradation-resistant polymer for tertiary oil recovery and preparation method thereof |
| CN103965855A (en) * | 2014-05-21 | 2014-08-06 | 江南大学 | Compound oil displacement agent containing double-long-chain-alkyl sulphobetaine and application thereof |
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| CN102030852A (en) * | 2009-09-25 | 2011-04-27 | 中国石油化工股份有限公司 | Polymer for tertiary oil recovery and preparation method thereof |
| CN102050917A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Macromolecular compound containing aliphatic tertiary amine group as well as preparation method thereof and application in oil displacement agent |
| CN102408517A (en) * | 2010-09-25 | 2012-04-11 | 中国石油化工股份有限公司 | Degradation-resistant polymer for tertiary oil recovery and preparation method thereof |
| CN103965855A (en) * | 2014-05-21 | 2014-08-06 | 江南大学 | Compound oil displacement agent containing double-long-chain-alkyl sulphobetaine and application thereof |
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