CN105440206B - 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 dosage 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 2,800 ten thousand；The present invention the polymer can as the flooding polymers of middle and low permeable reservoir, have good water solubility, tackifying by force and temperature-resistant anti-salt performance and surface-active it is good the advantages of so that the polymer has good washing oil effect.
Description
Technical field
The present invention relates to the water miscible polymer with surface active function and Polymer Used For Oil Displacement to improve oil recovering
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 degrade, 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), and it has the characteristics that molecular weight height, good water solubility.But in high temperature and high salt oil deposit bar
Under part, partially hydrolyzed polyacrylamide (PHPA) is having the defects of obvious in performance, as heatproof, saline-alkaline tolerance are 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 because low molecule amount flooding polymers can not meet oil field performance indications requirement, and HMW drives
Phenomena such as blocking of oil reservoir space occurs under the conditions of middle and low permeable reservoir in oil polymer, and injection 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, thus to proposing higher requirement available for the flooding polymers of middle hyposmosis under high salt.
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, have good water solubility, tackifying strong and temperature-resistant anti-salt performance and surface-active good
The advantages of, so that the polymer has good washing oil effect.
The present inventor is based on completion technical scheme considered below：In water-soluble polymer,
Hydrophobic grouping is introduced, the heat resistance and salt tolerance using hydrophobic grouping is the important channel for improving polymer heat-resistant salt-resistant performance.And
Rigid phenyl group has relatively low cohesive energy just, increases polymerization so as to be more beneficial for hydrophobic grouping formation Interpolymer Association effect
The hydrodynamic volume of thing molecule, the viscosity of solution is exponentially increased with the increase of polymer concentration, or even polymer is in salt solution
In ratio of viscosities pure water in it is higher.In addition, the ordered arrangement of hydrophobic grouping can also effectively reduce the surface and interface of polymer solution
Tension force and the emulsifiability for improving polymer.On the one hand sulfonic acid group can increase the water solubility of polymer, separately as water-wet side
On the one hand the temperature-resistant anti-salt performance of polymer can also be improved.In polymer ageing process, because the steric hindrance of rigid phenyl group is imitated
Should, make molecular motion resistance big, reduce macromolecule chain break, improve the ageing resistance of polymer.In acrylamide polymerization
Introducing-SO in thing3 -Group, polymer will show the anti-divalence of good heatproof and the performance of multivalent metal cation.Due to
Highly polar sulfonic acid group, its very strong hydrophilic interaction make polymer have good water solubility with electrostatic repulsion forces, also greatly
Ground increases the hydrodynamic volume of strand, has good viscosifying action, it is often more important that polymer has remarkably resistance to
Warm salt-resistance and surface-active.According to this thinking, the present inventor had not only been contained phenyl using selection but also had contained sulfonic group
The surface active monomer of group is as the major measure for improving flooding polymers heat and salt resistance.
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
12000000-2,800 ten thousand；
Wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H or C1-C3 alkyl；A, m and n is identical
Or it is different, it is each independently 0 or 1-6 integer, R is substituted or unsubstituted C1-C10 alkyl, in formula (1) and formula (3)
M be 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),
The solution that monomer, water, complexing agent shown in formula (6) and auxiliary agent are formed contacts with initiator, with the polymer monomer it is total
On the basis of dosage molal quantity, the dosage of the monomer shown in the formula (4) is 8-45 moles of %, the monomer shown in the formula (5)
Dosage is 50-91 moles of %, and the dosage 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 12,000,000-2,800 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 and n is identical
Or it is different, it is each independently 0 or 1-6 integer, R is substituted or unsubstituted C1-C10 alkyl, in formula (4) and formula (6)
M be respectively one kind in Li, Na, K or H.
A kind of polymer with surface active function provided by the invention introduces a kind of containing rigidity in macromolecular chain
The function monomer with surface active function of phenyl group so that on the one hand polyacrylamide has water soluble polymer polymerization
The tackifying and viscoplasticity of thing, and thus improve sweep efficiency；The introducing of another aspect surface active function polymerisable monomer, makes
Obtaining such novel high polymer oil displacement agent has certain surface-active, by emulsifying increase-volume and reducing the characteristics such as surface and interface tension force,
So as to increase the washing oil effect of polymer.The polymer of the present invention can have as the flooding polymers of middle and low permeable reservoir
The advantages of good water solubility, tackifying are by force and temperature-resistant anti-salt performance and surface-active is good.
Method using polymerization is to prepare the major way of the polymer with surface active function of the present invention, 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 there is the characteristic of general water-soluble polymer.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is 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 -2,800 ten thousand；
Wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H or C1-C3 alkyl；A, m and n is identical
Or it is different, it is each independently 0 or 1-6 integer, R is substituted or unsubstituted C1-C10 alkyl, in formula (1) and formula (3)
M be respectively one kind in Li, Na, K or H.
A kind of polymer with surface active function provided by the invention introduces a kind of containing rigidity in macromolecular chain
The function monomer with surface active function of phenyl 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 this
Class novel high polymer oil displacement agent has certain surface-active, by emulsifying increase-volume and reducing the characteristics such as surface and interface tension force, so as to
Increase the washing oil effect of polymer.The polymer of the present invention can have water-soluble as the flooding polymers of middle and low permeable reservoir
The advantages of property is good, tackifying is strong and temperature-resistant anti-salt performance and surface-active is good.
Under preferable case, of the present invention with the polymer of 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 1-6 integer, R can be unsubstituted C1-C10 alkyl.In the present invention, the hydrocarbon of the unsubstituted C1-C10
Base includes the alkyl that unsubstituted carbon number is 1-10, specifically, in method of the present invention, the unsubstituted carbon
The alkyl that atomicity is 1-10 can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, ring
Amyl group, hexyl, cyclohexyl, heptyl, octyl group, nonyl or certain herbaceous plants with big flowers base.
Preferably, of the present invention with the polymer of surface active function, the m can be 1-4 integer,
N can be 1-6 integer, and R can be unsubstituted C1-C6 alkyl.Specifically, in the present invention, the integer bag of the 1-4
Include 1,2,3 and 4；The integer of the 1-6 includes 1,2,3,4,5 and 6；The alkyl of the unsubstituted C1-C6 includes methyl, second
Base, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, cyclopenta, hexyl and cyclohexyl.
Of the present invention with the polymer of surface active function, preferably described construction unit A is formula (1-1) institute
The construction unit shown, the construction unit B are 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 1-6 integer；M in formula (1-1) and formula (3-1) is respectively Li, Na, K or H
In one kind.
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 %, and 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 16,000,000-2,300 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 that monomer, water, complexing agent and the auxiliary agent shown is formed contacts with initiator, with total dosage mole of monomer in the polymer
On the basis of number, the dosage of the monomer shown in the formula (4) is 8-45 moles of %, and the dosage of the monomer shown in the formula (5) is 50-
91 moles of %, the dosage of the monomer shown in the formula (6) is 0.001-5 moles of %；The condition of the polymerisation to polymerize
The viscosity average molecular weigh of resulting polymers is 12,000,000-2,800 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 1-6 integer, R for substitution or
Unsubstituted C1-C10 alkyl, the M in formula (4) and formula (6) are respectively one kind in Li, Na, K or 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 uses, and those skilled in the art can use 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 be conventional use of various conditions in the art, and those skilled in the art understanding of technical scheme
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 condition that the pH value is 6-10 can be by using conventional use in the art
Various acidic materials or alkaline matter be adjusted, present invention preferably uses such as sodium hydroxide and/or sodium carbonate to be adjusted
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 1-6, R is unsubstituted C1-C10 alkyl.
In the case of more preferably, in the preparation method of the polymer of the present invention with surface active function, m 1-
4 integer, n are 1-6 integer, and R is unsubstituted C1-C6 alkyl.
In the preparation method of the polymer of the present invention with surface active function, shown in preferably described formula (4)
Monomer can be compound shown in formula (4-1), 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 1-6 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 dosage of monomer can be 9-29 moles of %, the dosage of the monomer shown in the formula (5) can be 70-90 moles of %, described
The dosage 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 16,000,000-2,300 ten thousand.
In the preparation method of the polymer of the present invention with surface active function, most preferably described formula (4) institute
The dosage of the monomer shown can be 10-20 moles of %, and the dosage of the monomer shown in the formula (5) can rub for 79.6-89.8
You are %, and the dosage of the monomer shown in the formula (6) can be 0.02-0.40 moles of %.
According to the preparation method of the polymer provided by the invention with surface active function, wherein, shown in the formula (4)
Monomer, the dosage 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 dosage 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 %.One can be used as per the weight % of increasing or decreasing 1 or 0.5 weight % in the range of the above-mentioned concentration values of the present invention
The embodiment that can be selected.
According to the preparation method of the polymer provided by the invention with surface active function, wherein, shown in the formula (4)
Monomer, the total dosage and the dosage weight ratio of complexing agent and auxiliary agent of the monomer shown in formula (5) and the monomer shown in formula (6) be
100：0.005-0.12：0.001-0.15；Preferably 100：0.01-0.1：0.005-0.1.
According to the preparation method of the polymer provided by the invention with surface active function, 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 does not limit particularly
It is fixed, such as can be provided with pure solution form, provide in solid form, or the solution form to be diluted provides.In this hair
In bright method, preferably described complexing agent can be the EDTA-2Na aqueous solution that concentration is 1 weight %.
According to the preparation method of the polymer provided by the invention with surface active function, 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, there is no particular limitation for the offer form to the auxiliary agent, such as can be provided with pure solution form, with solid
Body form provides, or the solution form to be diluted provides.Such as in the present invention, when used auxiliary agent is urea,
Urea can provide 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.
According to the preparation method of the polymer provided by the invention with surface active function, wherein, the initiator can
Think redox series initiators.
According to the preparation method of the polymer provided by the invention with surface active function, 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 forming the redox series initiators for example can be as a solution
There is provided, such as：The preferably oxidant of the invention is the persulfate aqueous solution that concentration is 0.1 weight % or concentration is 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.
According to the preparation method of the polymer provided by the invention with surface active function, wherein, preferably described oxidation
The dosage of reduction series initiators is total with the monomer shown in the formula (4), the monomer shown in formula (5) and the monomer shown in formula (6)
The weight ratio of dosage can be 0.005-0.2：100, more preferably 0.01-0.15：100.
According to the preparation method of the polymer provided by the invention with surface active function, wherein, preferably described oxidation
Agent and the weight ratio of the reducing agent can be 1-25：1, more preferably 5-20：1.
According to the preparation method of the polymer provided by the invention with surface active function, wherein, the polymerisation
Method can be included in the presence of protective gas, first polymerize 2.5-12h at 0-25 DEG C, be then warming up to 30-80 DEG C again
Lower polymerization 2.5-10h.
According to the preparation method of the polymer provided by the invention with surface active function, preferably described polymerisation can
To be carried out in the case where gas shield acts on, such as nitrogen protection etc..
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 contacts 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, be granulated, crushed and sieved to obtain successively described to be had
The polymer end product of surface active function.
There is no particular limitation to the method cut, be granulated, 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, dividing
There is advantages below and effect in son design and synthesis：
The present invention is to introduce a kind of not only to have 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.Due to drawing for rigid phenyl group
Enter, so as to improve the hydrophobic effect between polymer molecule, to make hydrophobic grouping to carry out orderly arrangement on surface, reduce polymer
The surface tension of the aqueous solution, and then increase the emulsification washing oil ability of polymer, while make aqueous solutions of polymers in high temperature and high salt
It is lower to keep higher viscosity.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；Highly polar sulphur simultaneously
The introducing of acid groups, anti-bivalent metal ion ability is considerably increased, 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 to determine polymer solution in salinity with Brookfield viscosimeters at nominative testing temperature (80 DEG C)
Middle calcium ions and magnesium ions are 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：Monomer shown in following embodiment Chinese styles (6) can use the method synthesis that prior art provides,
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, is positioned in minus 10 DEG C of brine bath, is being stirred
Lower addition 0.1mol to benzene divinyl, then pass to SO3(0.1mol), after question response is complete, then it is added dropwise to ethylbenzyl
The RMgBr (0.1mol) of magnesium chloride, insulation reaction 1h again after being added dropwise, then adding n-hexane separates out product, finally
Washed with n-hexane more than three times, that is, obtain the monomer shown in the Chinese style of embodiment 1 (6).
Embodiment 1
The present embodiment prepares the polymer provided by the invention with surface active function using method provided by the invention
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=1, R CH in monomer (hereinafter also referred to function monomer) described in formula (6)3, R5It is for H, M H, molecular weight
330。
Specifically, the present embodiment is carried out with the following method：
1) by acrylamide (166.2mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.6mmol) and function monomer
(0.6mmol) 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) EDTA-2Na aqueous solution 1.0g, the 1 weight % urea that 1 weight % is added into above-mentioned mixture solution are water-soluble
Liquid 0.5g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, after leading to nitrogen flooding oxygen, adds 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；Then heat to 50 DEG C and continue reaction 6 hours；
4) blob of viscose obtained in step 3) is taken out, is cut, be 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, apparent viscosity 45.9mPas, surface tension
For 31.76mN/m, excellent surface-active and resisting high temperature, high salt performance are shown.
Embodiment 2
The present embodiment prepares the polymer provided by the invention with surface active function using method provided by the invention
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=2, R CH in monomer (hereinafter also referred to function monomer) described in formula (6)3, R5It is for H, M H, molecular weight
344。
Specifically, the present embodiment is carried out with the following method：
1) by acrylamide (167.6mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.6mmol) and function monomer
(0.3mmol) 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, obtains mixture solution；
2) EDTA-2Na aqueous solution 1.0g, the 1 weight % urea that 1 weight % is added into above-mentioned mixture solution are water-soluble
Liquid 1.0g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, after leading to nitrogen flooding oxygen, adds 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, continue logical nitrogen and stop after five minutes
Only, under nitrogen protection, polymerisation 6 hours；Then heat to 55 DEG C and continue reaction 6 hours；
4) blob of viscose obtained in step 3) is taken out, is cut, be 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 20,000,000, apparent viscosity 43.2mPas, and surface tension is
31.99mN/m, show excellent surface-active and resisting high temperature, high salt performance.
Embodiment 3
The present embodiment prepares the polymer provided by the invention with surface active function using method provided by the invention
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=5, R CH in monomer (hereinafter also referred to function monomer) described in formula (6)3, R5It is for H, M H, molecular weight
372。
Specifically, the present embodiment is carried out with the following method：
1) by acrylamide (196.5mmol), 2- acrylamide-2-methylpro panesulfonic acids (29.0mmol) and function monomer
(0.15mmol) 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, obtains mixture solution；
2) EDTA-2Na aqueous solution 2.0g, the 1 weight % urea that 1 weight % is added into above-mentioned mixture solution are water-soluble
Liquid 0.5g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, after leading to 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；Then heat to 60 DEG C and continue reaction 5 hours；
4) blob of viscose obtained in step 3) is taken out, is cut, be granulated, crushed, sieved successively, white temperature-resistant anti-salt is obtained and drives
Oil uses polymer 3-A.
After tested, polymer 3-A viscosity average molecular weigh is 18,000,000, apparent viscosity 40.9mPas, surface tension
For 32.02mN/m, excellent surface-active and resisting high temperature, high salt performance are shown.
Embodiment 4
The present embodiment prepares the polymer provided by the invention with surface active function using method provided by the invention
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=6, R CH in monomer (hereinafter also referred to function monomer) described in formula (6)3, R5It is for H, M H, molecular weight
390。
Specifically, the present embodiment is carried out with the following method：
1) by acrylamide (168.7mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.6mmol) and function monomer
(0.06mmol) 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) EDTA-2Na aqueous solution 0.2g, the 1 weight % urea that 1 weight % is added into above-mentioned mixture solution are water-soluble
Liquid 0.2g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, after leading to nitrogen flooding oxygen, adds 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；Then heat to 60 DEG C and continue reaction 4 hours；
4) blob of viscose obtained in step 3) is taken out, is cut, be 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 23,000,000, apparent viscosity 41.7mPas, and surface tension is
32.13mN/m, show excellent surface-active and resisting high temperature, high salt performance.
Embodiment 5
The present embodiment prepares the polymer provided by the invention with surface active function using method provided by the invention
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 CH in monomer (hereinafter also referred to function monomer) described in formula (6)3, R5It is for H, M H, molecular weight
386。
Specifically, the present embodiment is carried out with the following method：
1) by acrylamide (169.0mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.2mmol) and function monomer
(0.3mmol) 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, obtains mixture solution；
2) EDTA-2Na aqueous solution 0.2g, the 1 weight % urea that 1 weight % is added into above-mentioned mixture solution are water-soluble
Liquid 2.0g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, after leading to nitrogen flooding oxygen, adds 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；Then heat to 45 DEG C and continue reaction 5 hours；
4) blob of viscose obtained in step 3) is taken out, is cut, be granulated, crushed, sieved successively, white temperature-resistant anti-salt is obtained and drives
Oil uses polymer 5-A.
After tested, polymer 5-A viscosity average molecular weigh is 16,000,000, apparent viscosity 37.3mPas, surface tension
For 34.25mN/m, excellent surface-active and resisting high temperature, high salt performance are shown.
Embodiment 6
The present embodiment prepares the polymer provided by the invention with surface active function using method provided by the invention
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=4, R CH in monomer (hereinafter also referred to function monomer) described in formula (6)3, R5It is for H, M H, molecular weight
414。
Specifically, the present embodiment is carried out with the following method：
1) by acrylamide (169.0mmol), 2- acrylamide-2-methylpro panesulfonic acids (38.2mmol) and function monomer
(0.3mmol) 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) EDTA-2Na aqueous solution 2.0g, the 1 weight % urea that 1 weight % is added into above-mentioned mixture solution are water-soluble
Liquid 0.2g, stirs, and obtains solution to be polymerized；
3) polymerisation bottle is put into water bath with thermostatic control, after leading to nitrogen flooding oxygen, adds 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；Then heat to 50 DEG C and continue reaction 6 hours；
4) blob of viscose obtained in step 3) is taken out, is cut, be 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 23,000,000, apparent viscosity 43.4mPas, and surface tension is
32.78mN/m, show excellent surface-active and resisting high temperature, high salt performance.
Embodiment 7
The present embodiment prepares the polymerization provided by the invention with surface active function 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 4, M H.
After tested, polymer 7-A viscosity average molecular weigh is 17,000,000, apparent viscosity 37.6mPas, surface tension
For 33.73mN/m, excellent surface-active and resisting high temperature, high salt performance are shown.
Embodiment 8
The present embodiment prepares the polymerization provided by the invention with surface active function using method same as Example 2
Thing 8-A, wherein, except that, m=6, n=8, R CH in the monomer described in formula (6)3, R5It is for H, M H, molecular weight
498。
After tested, polymer 8-A viscosity average molecular weigh is 19,000,000, apparent viscosity 40.7mPas, surface tension
For 32.21mN/m, excellent surface-active and resisting high temperature, high salt performance are shown.
Embodiment 9
The present embodiment prepares the polymerization provided by the invention with surface active function using method same as Example 3
Thing 9-A, wherein, except that, the m=5 in the monomer described in formula (6), n=0, R are isopropyl, R5For H, M H, molecule
Measure as 400.
After tested, polymer 9-A viscosity average molecular weigh is 22,000,000, apparent viscosity 44.2mPas, surface tension
For 31.91mN/m, excellent surface-active and resisting high temperature, high salt performance are shown.
Embodiment 10
The present embodiment prepares the polymerization provided by the invention with surface active function using method same as Example 4
Thing 10-A, wherein, except that, the m=1 in the monomer described in formula (6), n=2, R are cyclohexyl, R5For CH3, M Na, point
Son amount is 463.
After tested, polymer 10-A viscosity average molecular weigh is 28,000,000, apparent viscosity 46.1mPas, surface tension
For 31.15mN/m, excellent surface-active and resisting high temperature, high salt performance are shown.
Embodiment 11
The present embodiment prepares the polymerization provided by the invention with surface active function using method same as Example 6
Thing 11-A, wherein, except that, 200g deionized waters are added in step 1).
After tested, polymer 11-A viscosity average molecular weigh is 12,000,000, apparent viscosity 31.9mPas, surface tension
For 36.32mN/m, excellent surface-active and resisting high temperature, high salt performance are shown.
Embodiment 12
The present embodiment prepares the polymerization provided by the invention with surface active function 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 13,000,000, apparent viscosity 32.5mPas, surface tension
For 37.69mN/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 7,000,000, apparent viscosity 12.3mPas, and surface tension is
48.01mN/m, surface-active and resisting high temperature, high salt performance are bad.
It can be seen that by comparative example 1-12 and comparative example 1 result and prepared using method provided by the invention
The polymer of the present invention with surface active function is obtained with excellent surface-active and resisting high temperature, high salt performance.
Therefore, the above-mentioned polymer with surface active function provided by the invention due to the introducing containing rigid phenyl group so as to
The hydrophobic effect between polymer molecule is improved, hydrophobic grouping is carried out orderly arrangement on surface, reduces aqueous solutions of polymers
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 are 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 12,000,000-2,800 ten thousand；
Wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H or C1-C3 alkyl；A, m and n is identical or not
Together, it is each independently 0 or 1-6 integer, R is substituted or unsubstituted C1-C10 alkyl, and the M in formula (1) and formula (3) is each
One kind from for 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 1-6 integer, and R is unsubstituted C1-
C10 alkyl.
3. polymer according to claim 1, wherein, m is 1-4 integer, and n is 1-6 integer, and R is unsubstituted C1-
C6 alkyl.
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 1-6 integer；M in formula (1-1) and formula (3-1) is respectively in Li, Na, K or H
It is a kind of.
5. according to the polymer described in 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 16,000,000-2,300 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
The solution that body, water, complexing agent and auxiliary agent are formed contacts with initiator, using total dosage molal quantity of monomer in the polymer as base
Standard, the dosage of the monomer shown in the formula (4) is 8-45 moles of %, and the dosage of the monomer shown in the formula (5) is rubbed for 50-91
You are %, and the dosage 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 12,000,000-2,800 ten thousand afterwards；
Wherein, R1、R2、R3、R4And R5It is identical or different, it is each independently H or C1-C3 alkyl；A, m and n is identical or not
Together, it is each independently 0 or 1-6 integer, R is substituted or unsubstituted C1-C10 alkyl, and the M in formula (4) and formula (6) is each
One kind from for Li, Na, K or H.
7. the method according to claim 11, 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 1-6 integer, and R is unsubstituted C1-
C10 alkyl.
8. according to the method for claim 7, wherein, m is 1-4 integer, n is 1-6 integer, and R is unsubstituted C1-C6
Alkyl.
9. according to the method for 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 1-6 integer；M in formula (4-1) and formula (6-1) is respectively in Li, Na, K or H
It is a kind of.
10. according to the method described in any one in claim 6-9, wherein, the dosage of the monomer shown in the formula (4) is 9-
29 moles of %, the dosage of the monomer shown in the formula (5) is 70-90 moles of %, and the dosage 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 16,000,000-
23000000.
11. according to the method described in 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 dosage of monomer cause the monomer shown in the formula (4), the monomer shown in formula (5) and formula (6) institute
Total dosage 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 the solution that mixture and auxiliary agent are formed is 5-60 weight %.
12. the method according to claim 11, wherein, the monomer and formula shown in monomer, formula (5) shown in the formula (4)
(6) total dosage of the monomer shown in is 100 with the dosage weight ratio of complexing agent and auxiliary agent：0.005-0.12：0.001-0.15.
13. according to the method for 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. according to the method described in any one in claim 6-9, wherein, the initiator is redox series initiators,
Shown in monomer shown in the dosage and the formula (4) of the redox series initiators, the monomer shown in formula (5) and formula (6)
The weight ratio of total dosage 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. according to the method described in 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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| US4584358A (en) * | 1985-06-12 | 1986-04-22 | University Of Southern Mississippi | Calcium-tolerant N-substituted acrylamides as thickeners for aqueous systems |
| CN1542031A (en) * | 2003-11-07 | 2004-11-03 | 四川大学 | Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof |
| CN101274974A (en) * | 2008-04-29 | 2008-10-01 | 成都理工大学 | Temperature-resistant water-soluble copolymer, preparation and use thereof |
| CN102050914A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Ultra-high molecular weight sulfonic acid type acrylamide and preparation method thereof |
| CN102433107A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Low-molecular-weight polymer type filtrate loss reducer for drilling fluid and preparation method for same |
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| US4584358A (en) * | 1985-06-12 | 1986-04-22 | University Of Southern Mississippi | Calcium-tolerant N-substituted acrylamides as thickeners for aqueous systems |
| CN1542031A (en) * | 2003-11-07 | 2004-11-03 | 四川大学 | Viscosity highly increased water-soluble hydrophobic association copolymer and preparation method and use thereof |
| CN101274974A (en) * | 2008-04-29 | 2008-10-01 | 成都理工大学 | Temperature-resistant water-soluble copolymer, preparation and use thereof |
| CN102050914A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Ultra-high molecular weight sulfonic acid type acrylamide and preparation method thereof |
| CN102433107A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Low-molecular-weight polymer type filtrate loss reducer for drilling fluid and preparation method for same |
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