CN105440205B - 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
- Publication number
- CN105440205B CN105440205B CN201410397268.3A CN201410397268A CN105440205B CN 105440205 B CN105440205 B CN 105440205B CN 201410397268 A CN201410397268 A CN 201410397268A CN 105440205 B CN105440205 B CN 105440205B
- Authority
- CN
- China
- Prior art keywords
- formula
- construction unit
- polymer
- monomer
- moles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 8,000,000 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 polymer ageing process, due to macromolecular side base or the steric effect of rigid side base, make molecular motion resistance
Greatly, reduce macromolecule chain break, improve the ageing resistance of polymer.Introducing-the SO in acrylamide polymer3 -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 makes polymer have good water solubility with electrostatic repulsion forces, also greatly increases the stream of strand
Hydrodynamic volume, with good viscosifying action, it is often more important that polymer has outstanding heat and salt resistance and surface-active.
According to this thinking, the present inventor not only containing long-chain saturated alkyl or unsaturated alkane but also had contained sulfonic group using selection
The surface active monomer of group is used 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
8000000-2,500 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, 0 or 1-6 integer is each independently, R is C11-C24 alkyl, and D is methylene, imido grpup, oxygen or sulphur, formula
And the M in formula (3) is respectively one kind in Li, Na, K or H (1).
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：Under conditions of pH value is 6-10, under the polymerization conditions, by the monomer shown in formula (4), the monomer shown in formula (5), formula
(6) monomer, water, complexing agent, auxiliary agent shown in 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 8,000,000-2,500 ten thousand afterwards；Wherein, R1、 R2、R3、R4And R5It is identical or different, it is each independent
Ground is H or C1-C3 alkyl；A, m and n are identical or different, are each independently 0 or 1-6 integer, and R is C11-C24's
Alkyl, D is methylene, imido grpup, oxygen or sulphur, and the 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 a kind of with surface in macromolecular chain
Active function and the function monomer containing polymerizable vinyl 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 the characteristic such as increase-volume and reduction surface and interface tension force,
So as to increase the washing oil effect of polymer.The present invention the polymer can as middle and low permeable reservoir flooding polymers, have
Good water solubility, tackifying be 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.
In the present invention, the alkyl of the C11-C24 can include the alkyl that carbon number is 11-24, specifically, at this
In the described method of invention, the alkyl of the C11-C24 can include saturation or undersaturated alkyl, for example, the C11-C24
Alkyl can for C11-C24 straight or branched saturated hydrocarbyl and C11-C24 straight or branched unsaturated alkyl in
Any one.The alkyl of the C11-C24 can include C11 alkyl, C12 alkyl, C13 alkyl, C14 alkyl,
C15 alkyl, C16 alkyl, C17 alkyl, C18 alkyl, C19 alkyl, C20 alkyl, C21 alkyl, C22
Any one in alkyl, C23 alkyl, C24 alkyl.
In the present invention, at least one alkenyl can be contained in the undersaturated straight-chain alkyl.
On the one hand, the invention provides a kind of polymer with surface active function, the polymer contains construction unit
A, construction unit B and construction unit C, the construction unit A are the construction unit shown in formula (1), and the construction unit B is formula
(2) construction unit shown in, the construction unit C is the construction unit shown in formula (3), with construction unit in the polymer
On the basis of total mole number, the content of the construction unit A is 8-45 moles of %, and the content of the construction unit B is rubbed for 50-91
You are %, and the content of the construction unit C is 0.001-5 moles of %；The viscosity average molecular weigh of the polymer is 8,000,000-2500
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, 0 or 1-6 integer is each independently, R is C11-C24 alkyl, and D is methylene, imido grpup, oxygen or sulphur, formula
And the M in formula (3) is respectively one kind in Li, Na, K or H (1).
The above-mentioned polymer with surface active function that the present invention is provided introduces a kind of with surface in macromolecular chain
Active function and the function monomer containing polymerizable vinyl 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 the characteristic such as increase-volume and reduction surface and interface tension force,
So as to increase the washing oil effect of polymer.The displacement of reservoir oil that the above-mentioned polymer that the present invention is provided can serve as middle and low permeable reservoir gathers
Compound, has the advantages that strong good water solubility, tackifying and temperature-resistant anti-salt performance and surface-active are good.
Under preferable case, in the polymer of the present invention with surface active function, R1、R2、 R3、R4And R5Phase
It is same or different, it is each independently H, methyl, ethyl, n-propyl or isopropyl；A, m and n are identical or different, independently of one another
For 0,1,2,4 or saturation that 6, R are C11-C24 or undersaturated straight-chain alkyl, D is methylene or imido grpup.
In the case of more preferably, in the polymer of the present invention with surface active function, n is 2 or 6, and D is
Imido grpup.
In the polymer of the present invention with surface active function, preferably described construction unit A can be formula (1-
1) construction unit shown in, the construction unit B is the construction unit shown in formula (2-1), and the construction unit C is formula (3-1)
Shown construction unit,
Wherein, m is 1-4 integer, n is 2 or 6, R are C11-C24 saturation or undersaturated straight-chain alkyl；Formula (1-1)
One kind in Li, Na, K or H is respectively with the M in formula (3-1).
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 10,000,000-2,200 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 79.6-89.9 moles of %, the construction unit C's
Content can be 0.01-0.40 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
The viscosity average molecular weigh of resulting polymers is 8,000,000-2,500 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 and n are identical or different, are each independently 0 or 1-6 integer, and R is
C11-C24 alkyl, D is that the M in methylene, imido grpup, oxygen or sulphur, formula (4) and formula (6) is respectively in Li, Na, K or H
One kind,
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 in pH values
Under 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 independently be 0,1,2,4 or 6, R for C11-C24 saturation or undersaturated straight-chain alkyl, D be methylene or imido grpup.
In the case of more preferably, in the preparation method of the polymer of the present invention with surface active function, n can be with
For 2 or 6, and D is imido grpup.
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 can be 1-4 integer, and n can be 2 or 6, R can be C11-C24 saturation or undersaturated straight chain
Alkyl；M in formula (4-1) and formula (6-1) can be respectively one kind in Li, Na, K or H.
According to preparation method of the present invention, wherein, the consumption of the monomer shown in preferably described formula (4) can be 9-29
Mole %, the consumption of the monomer shown in the formula (5) can be 70-90 moles of %, and the consumption of the monomer shown in the formula (6) can
Think 0.01-1 moles of %；The condition of the polymerisation allows the viscosity average molecular weigh of resulting polymers after polymerisation to be
10000000-2,200 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 content of the monomer shown in the formula (5) for 79.6-89.9
You are %, and the content of the monomer shown in the formula (6) can be 0.01-0.40 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.Due to long-chain saturated alkyl
Or the introducing of unsaturated alkane makes hydrophobic grouping be carried out in order on surface so as to improve the hydrophobic effect between polymer molecule
Arrangement, reduces the surface tension of aqueous solutions of polymers, and then increases the emulsification washing oil ability of polymer, while making polymer water-soluble
Liquid keeps higher viscosity under high temperature and high salt.In ageing process, due to the rigidity of the monomer with surface active function
The steric effect of phenyl, makes molecular motion resistance big, reduces molecule chain break, improves the chronic anti-aging property of polymer solution
Energy；The introducing of highly polar sulfonic acid group, considerably increases anti-bivalent metal ion ability simultaneously, and its very strong hydrophilic interaction
Make polymer that there is good water solubility with electrostatic repulsion forces, also greatly increase the hydrodynamic volume of strand, show
Go out good viscosifying action 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：
The first step：First 100mL tetrahydrofuran is added in 250mL there-necked flask, in the water-bath for being positioned over 50 DEG C,
Stirring is lower to add laurate (0.1mol) and ethylenediamine (0.1mol), and dichloromethane (0.1mol) is added after completion of the reaction, and
The KI of catalytic amount is added, the compound shown in formula (I) is obtained with ethyl alcohol recrystallization.By gained compound (I) and magnesium metal
Stir to prepare the RMgBr shown in formula (II) in absolute ether.
Second step：100mL tetrahydrofuran is added in 250mL there-necked flask, in the brine bath for being positioned over minus 10 DEG C,
Under agitation add 0.1mol to benzene divinyl, then pass to SO3(0.1mol), after question response is complete, then is added dropwise formula (II)
Insulation reaction 1h again after shown RMgBr (0.1mol), completion of dropping, then adding n-hexane separates out product, finally uses
N-hexane is washed more than three times, that is, obtains 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 in monomer (hereinafter also referred to function monomer) described in formula (6), n=2, R is CH2(CH2)9CH3, R5For H, D is NH,
M is H, and molecular weight is 466.
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 list
Body (0.4mmol) is added in polymerisation bottle (i.e. polymerization bottle), is added deionized water 50.0g dissolvings and is made into the aqueous solution, then adds
Enter sodium hydroxide and adjust pH value to 8.0, obtain 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 20,000,000, and apparent viscosity is 38.6mPas, surface tension
For 32.26mN/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 in monomer (hereinafter also referred to function monomer) described in formula (6), n=6, R is CH2(CH2)9CH3, R5For H, D is NH,
M is H, and molecular weight is 522.
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 list
Body (0.2mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium hydroxide
PH value is adjusted 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 35.1mPas, and surface tension is
33.74mN/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=4 in monomer (hereinafter also referred to function monomer) described in formula (6), n=2, R is CH2(CH2)14CH=CH2, R5For H, D
For NH, M is H, and molecular weight is 590.
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 list
Body (0.08mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium hydroxide
PH value is adjusted 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 15,000,000, and apparent viscosity is 33.6mPas, surface tension
For 33.47mN/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=4 in monomer (hereinafter also referred to function monomer) described in formula (6), n=2, R is CH2(CH2)15CH3, R5It is for H, D
NH, M are H, and molecular weight is 592.
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 list
Body (0.03mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium carbonate 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 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 19,000,000, and apparent viscosity is 37.7mPas, and surface tension is
35.82mN/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 in monomer (hereinafter also referred to function monomer) described in formula (6), n=2, R is CH2(CH2)9CH3, R5For H, D is NH,
M is H, and molecular weight is 480.
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 list
Body (0.2mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium hydroxide
PH value is adjusted 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 14,000,000, and apparent viscosity is 32.0mPas, surface tension
For 35.68mN/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 in monomer (hereinafter also referred to function monomer) described in formula (6), n=6, R is CH2(CH2)9CH3, R5For H, D is NH,
M is H, and molecular weight is 564.
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 list
Body (0.2mmol) is added in polymerisation bottle, is added deionized water 50.0g dissolvings and is made into the aqueous solution, adds sodium carbonate 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 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 40.8mPas, and surface tension is
32.41mN/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 13,000,000, and apparent viscosity is 31.2mPas, surface tension
For 36.26mN/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, the m=3 in the monomer described in formula (6), n=3, R is CH2(CH2)13CH3, R5It is for H, D
NH, M are H, and molecular weight is 564.
After tested, polymer 8-A viscosity average molecular weigh is 10,000,000, and apparent viscosity is 29.2mPas, surface tension
For 39.46mN/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, the m=4 in the monomer described in formula (6), n=2, R is CH2(CH2)14CH=CH2, R5For H,
D is O, and M is H, and molecular weight is 591.
After tested, polymer 9-A viscosity average molecular weigh is 22,000,000, and apparent viscosity is 39.3mPas, surface tension
For 32.06mN/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, the m=4 in the monomer described in formula (6), n=2, R is CH2(CH2)15CH3, R5It is for H, D
S, M are H, and molecular weight is 607.
After tested, polymer 10-A viscosity average molecular weigh is 25,000,000, and apparent viscosity is 40.7mPas, surface tension
For 33.02mN/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 5
Thing 11-A, wherein, except that, the monomer described in formula (4) is that sodium-salt form, i.e. M are Na.
After tested, polymer 11-A viscosity average molecular weigh is 14,500,000, and apparent viscosity is 32.1mPas, surface tension
For 38.02mN/m, 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 6
Thing 12-A, wherein, except that, in step 1) middle addition 200g deionized waters.
After tested, polymer 12-A viscosity average molecular weigh is 12,000,000, and apparent viscosity is 31.1mPas, surface tension
For 37.02mN/m, excellent surface-active and resisting high temperature, high salt performance is shown.
Embodiment 13
The present embodiment prepares the polymerization with surface active function that the present invention is provided using method same as Example 1
Thing 13-A, wherein, except that, the quality of the monomer described in the formula (6) of addition is 4.3mmol.
After tested, polymer 13-A viscosity average molecular weigh is 8,000,000, and apparent viscosity is 28.1mPas, surface tension
For 40.02mN/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 6,000,000, and apparent viscosity is 15.1mPas, and surface tension is
50.37mN/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 1-13 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 the present invention is provided is due to long-chain saturated alkyl or unsaturation
The introducing of alkane makes hydrophobic grouping carry out orderly arrangement, drop on surface so as to improve the hydrophobic effect between polymer molecule
The surface tension of the low polymer aqueous solution 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 8,000,000-2,500 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, be each independently 0 or 1-6 integer, R is C11-C24 alkyl, D is methylene, imido grpup, oxygen or sulphur, formula (1) and
M in 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 0,1,2,4 or 6, R satisfying for C11-C24
And/or undersaturated straight-chain alkyl, D is methylene or imido grpup.
3. polymer according to claim 2, wherein, n is 2 or 6, D are imido grpup.
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, n is 2 or 6, R are C11-C24 saturation or undersaturated straight-chain alkyl；Formula (1-1) and formula
M in (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 10,000,000-2,200 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 8,000,000-2,500 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, be each independently 0 or 1-6 integer, R is C11-C24 alkyl, D is methylene, imido grpup, oxygen or sulphur, formula (4) and
M in 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, be each independently 0,1,2,4 or 6, R for C11-C24
Saturation or undersaturated straight-chain alkyl, D are methylene or imido grpup.
8. method according to claim 7, wherein, n is 2 or 6, D are imido grpup.
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, n is 2 or 6, R are C11-C24 saturation or undersaturated straight-chain alkyl；Formula (4-1) and formula
M in (6-1) is respectively one kind in Li, Na, K or H.
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 10,000,000-
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, ascorbic acid and urea.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410397268.3A CN105440205B (en) | 2014-08-13 | 2014-08-13 | A kind of polymer with surface active function and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410397268.3A CN105440205B (en) | 2014-08-13 | 2014-08-13 | A kind of polymer with surface active function and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105440205A CN105440205A (en) | 2016-03-30 |
| CN105440205B true CN105440205B (en) | 2017-09-29 |
Family
ID=55550882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410397268.3A Active CN105440205B (en) | 2014-08-13 | 2014-08-13 | A kind of polymer with surface active function and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105440205B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437291B (en) * | 2020-11-05 | 2023-02-24 | 中国石油化工股份有限公司 | Acrylamide surface active polymer and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-08-13 CN CN201410397268.3A patent/CN105440205B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105440205A (en) | 2016-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107033293B (en) | A kind of double tail hydrophobic associated polymers with surface-active and preparation method thereof | |
| CN104650301B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN105646772B (en) | A kind of hydrophobic associated polymer and preparation method thereof | |
| CN105505364A (en) | Oil displacing agent for increasing oil recovery in high temperature high salt mid-low permeability oil reservoir, preparation method and applications thereof | |
| CN101157741A (en) | Synthesis technology of high molecular weight temperature-tolerant anti-salt polyacrylamide | |
| CN105566560B (en) | A kind of structure directing type composite initiator system and acrylamide polymer and its preparation method and application | |
| CN105566515B (en) | A kind of structure directing type composite initiator agent system and acrylamide polymer and its preparation method and application | |
| CN105440205B (en) | A kind of polymer with surface active function and preparation method thereof | |
| CN106317308B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN104672408A (en) | Rigid-core-shell-structure water-soluble oil-displacing polymer and preparation method thereof | |
| CN105440204B (en) | A kind of polymer with surface active function and preparation method thereof | |
| CN107245126A (en) | A kind of flooding polymers containing silicate sturcture and application | |
| CN105440203B (en) | A kind of polymer with surface active function and preparation method thereof | |
| CN105440206B (en) | A kind of polymer with surface active function and preparation method thereof | |
| CN107759728B (en) | A kind of Polymer Used For Oil Displacement and its preparation method and application with surface-active | |
| CN107226884B (en) | A kind of polymer and its preparation method and application with surface active function | |
| CN106317311B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN107226887B (en) | A kind of polymer and its preparation method and application with surface active function | |
| CN107226886B (en) | A kind of polymer and its preparation method and application with surface active function | |
| CN107236092A (en) | One kind contains silicate sturcture monomer and preparation method and application | |
| CN108503748A (en) | A kind of temperature-resistant anti-salt functional form polymer and preparation method thereof | |
| CN107759727B (en) | A kind of Polymer Used For Oil Displacement and its preparation method and application with surface-active | |
| CN104448129B (en) | High-temperature-resistant hydrolyzed copolymer for oilfields, and preparation method and application thereof | |
| CN103409125B (en) | A kind of Water-soluble quadripolymer oil-displacing agent and synthetic method thereof | |
| CN106317310B (en) | A kind of acrylamide copolymer and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |