CN108003278A - Polymer with water plugging and profile controlling performance and its preparation method and application - Google Patents
Polymer with water plugging and profile controlling performance and its preparation method and application Download PDFInfo
- Publication number
- CN108003278A CN108003278A CN201610929230.5A CN201610929230A CN108003278A CN 108003278 A CN108003278 A CN 108003278A CN 201610929230 A CN201610929230 A CN 201610929230A CN 108003278 A CN108003278 A CN 108003278A
- Authority
- CN
- China
- Prior art keywords
- construction unit
- monomer
- polymer
- weight
- content
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to oil field profile control and water plugging field, disclose polymer with water plugging and profile controlling performance and its preparation method and application, polymer contains construction unit A, construction unit B and construction unit C, construction unit A is provided by acrylamide monomer, construction unit B is provided by N vinylpyrrolidone monomers, and construction unit C is provided by the monomer with formula (1) structure；On the basis of the weight of polymer, the content that content that the content of construction unit A is 60 98 weight %, the construction unit B is 1 39 weight %, the construction unit C is 1 39 weight %；In formula (1), R1、R2、R3It is each independently the substituted or unsubstituted aryl of H, the alkyl of C1 C12, C6 C12；R4The substituted or unsubstituted cycloalkyl of alkyl, C6 C12 for C1 C12, the substituted or unsubstituted aryl of C6 C12.
Description
Technical field
The present invention relates to oil recovering field, and in particular, to a kind of polymer with water plugging and profile controlling performance, a kind of system
The method of the standby polymer with water plugging and profile controlling performance and the polymerization with water plugging and profile controlling performance being prepared by this method
Thing, have the polymer of water plugging and profile controlling performance in water plugging and profile controlling and prepare the application being used in the product of water plugging and profile controlling.
Background technology
China's land oil 80% is above is by waterflooding extraction.One oil reservoir is often made of multiple oil reservoirs.Due to each
The difference of reservoir permeability, injection water will advance by leaps and bounds along high permeability zone, cause the too early water of oil well to cover.Therefore for waterflooding extraction
Oilfield for, water outlet is a common problem.The major measure for solving the problems, such as this is profile control and water plugging.Profile control and water plugging is arranged
The cumulative water-oil ratio of oil well can be reduced by applying, and improve oil production；Increase oil-producing interval thickness, reduce high aquifer formation thickness, improve oil well
Produce liquid bevel；The utilization rate of injection water is improved, improves displacement in flooding effect；Improve the intake profile of water injection well.So as to from entirety
Upper improvement waterflooding development effect.China oil field generally uses waterflooding extraction mode, since formation heterogeneity is serious, reservoir geology
Complexity, later stage rate of water cut increase under development are accelerated.Oil well production is average aqueous up to more than 80% at present.Eastern region
Some old fileds are aqueous up to more than 90%.Therefore, it is very necessary come decreasing water cut and increasing oil using profile control and water plugging.
For China's chemical water shutoff in oilfield technology from the fifties, application at the scene has the history of 60 years so far.It is initially to use
Oil based cement, milk of lime, resin, viscous crude etc. are developed after cement mortar water blockoff；The sixties is based on resin；The seventies is water-soluble
Property polymer and its gel start in field use.From this, Water in Water Shutoff in Oil Field technology enters a new developing stage, blocking agent product
Kind increases sharply, and processing well time increases, and economic effect also significantly improves.
Existing water plugging profile control agent is primarily present two problems：1st, the operating distance of water plugging profile control agent is short, only to nearly well
Band is effectively；2nd, the plastic reactivity of water plugging profile control agent is uncontrollable, often results in the blocking of near wellbore zone；3rd, water plugging profile control agent is more
For multiple agent, i.e. A, B agent system, chromatographic isolation occurs in the migration process of stratum, simultaneously for the construction of water plugging and profile controlling measure
Design causes uncertainty.
For existing water plugging profile control agent system there are the problem of, the present invention provides a kind of retardance self-crosslinking of one-pack type
Water-soluble polymer, can realize controllable water plugging and profile controlling in remote well area.
The content of the invention
The defects of the purpose of the present invention is overcoming the prior art, there is provided a kind of polymer with water plugging and profile controlling performance and its
Preparation method and application, the polymer provided by the invention with water plugging and profile controlling performance can be realized slow in the range of longer time
Slow thickening plastic, system are not required to additionally add delayed crosslinker, and the self-crosslinking Weak Gels aging formed retains viscosity height, fits
Close the deep water plugging and profile controlling for carrying out remote well area.
To achieve these goals, in a first aspect, the present invention provides a kind of polymer with water plugging and profile controlling performance, its
In, which contains construction unit A, construction unit B and construction unit C, wherein, construction unit A is carried by acrylamide monomer
For construction unit B is provided by n-vinyl pyrrolidone monomer, and construction unit C is carried as the monomer of the structure shown in formula (1)
For；Wherein, on the basis of the weight of the polymer, the content of construction unit A is 60-98 weight %, the construction unit B's
Content is that the content of 1-39 weight %, the construction unit C are 1-39 weight %；
Wherein, in formula (1), R1、R2、R3It is each independently the alkyl of H, C1-C12, the substituted of C6-C12 or not
Substituted aryl；R4The substituted or unsubstituted cycloalkyl of alkyl, C6-C12 for C1-C12, C6-C12 it is substituted
Or unsubstituted aryl.
Second aspect, the present invention provides a kind of preparation method of the polymer with water plugging and profile controlling performance, wherein, the party
Method includes：In the presence of initiator and as the water of solvent, and under atmosphere of inert gases, make monomer D, monomer E and monomer F
Carry out solution polymerization；Wherein, the monomer D is acrylamide monomer, and the monomer E is n-vinyl pyrrolidone list
Body, the monomer F are the monomer with structure shown in formula (1)；Wherein, the dosage of the monomer D, monomer E and monomer F to make
In standby obtained polymer, the content of construction unit A be that the content of 60-98 weight %, construction unit B are 1-39 weight %, is tied
The content of structure unit C is 1-39 weight %；
Wherein, in formula (1), R1、R2、R3It is each independently the alkyl of H, C1-C12, the substituted of C6-C12 or not
Substituted aryl；R4The substituted or unsubstituted cycloalkyl of alkyl, C6-C12 for C1-C12, C6-C12 it is substituted
Or unsubstituted aryl.
The third aspect, the present invention provide the polymer with water plugging and profile controlling performance being prepared by preceding method.
Fourth aspect, the present invention provide the foregoing polymer with water plugging and profile controlling performance and are applied in Water in Water Shutoff in Oil Field profile control.
5th aspect, the present invention provide the foregoing polymer with water plugging and profile controlling performance in Water in Water Shutoff in Oil Field profile control agent is prepared
Using.
Technical solution using the present invention, in the polymer with construction unit A, construction unit B and construction unit C,
Construction unit C (70-90 DEG C) under formation temperature conditions is hydrolyzed, and produces N- methylol propionyl amine structures and active hydrogen.Institute
Product is obtained Mannich Mannich reactions further occur with construction unit A and form crosslinking.Due to construction unit C in the earth formation
Hydrolysis be a more slow progressive process.Water plugging profile control agent is allowd to be transported to the remote slow plastic in well area.Therefore,
Polymer provided by the invention with water plugging and profile controlling performance can realize slowly thickening plastic, system in the range of longer time
It is not required to additionally add delayed crosslinker, and the self-crosslinking Weak Gels aging formed retains viscosity height, is appropriate for remote well area
Deep water plugging and profile controlling.
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.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of polymer with water plugging and profile controlling performance, wherein, which contains structure
Unit A, construction unit B and construction unit C, wherein, construction unit A is provided by acrylamide monomer, and construction unit B is by N- ethene
Base pyrrolidone monomeric provides, and construction unit C is provided as the monomer of the structure shown in formula (1)；Wherein, with the polymer
Weight on the basis of, the content of construction unit A is that the content of 60-98 weight %, the construction unit B are 1-39 weight %, institute
The content for stating construction unit C is 1-39 weight %；
Wherein, in formula (1), R1、R2、R3It is each independently the alkyl of H, C1-C12, the substituted of C6-C12 or not
Substituted aryl；R4The substituted or unsubstituted cycloalkyl of alkyl, C6-C12 for C1-C12, C6-C12 it is substituted
Or unsubstituted aryl.
The present inventor has found there is construction unit A, construction unit provided by the invention in the course of the study
In the polymer of B and construction unit C, construction unit C (70-90 DEG C) under formation temperature conditions is hydrolyzed, and produces N- hydroxyl first
Base propionyl amine structure and active hydrogen.Products therefrom further occurs Mannich Mannich reactions with construction unit A and forms friendship
Connection.Since the hydrolysis of construction unit C in the earth formation is a more slow progressive process.Water plugging profile control agent is conveyed
To the remote slow plastic in well area.Therefore, the polymer provided by the invention with water plugging and profile controlling performance can be in longer time model
Enclosing interior realization, slowly thickening plastic, system are not required to additionally add delayed crosslinker, and the self-crosslinking Weak Gels aging formed is protected
Stay viscosity high, be appropriate for the deep water plugging and profile controlling in remote well area, so as to complete the present invention.
Preferably, on the basis of the weight of the polymer, the content of the construction unit A is 75-90 weight %, described
The content of construction unit B is that the content of 5-20 weight %, the construction unit C are 4-20 weight %.
According to the present invention, in the case of no conversely explanation, term " alkyl of C1-C12 " can be straight or branched
, the alkyl of the C1-C12 for example including：Methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, the last of the ten Heavenly stems
Base, undecyl and dodecyl.
" C6-C12 " in term " the substituted or unsubstituted cycloalkyl of C6-C12 " refers to the total of all carbon atoms
Number, when containing substituent in cycloalkyl, the substituent is preferably direct-connected or side chain the alkyl or alkylidene of C1-C4,
For example, alkyl can include methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group, alkylidene
It can include the substructure of as above alkyl.The substituent can also be the cycloalkyl of C2, C3 or C4." the quilt of C6-C12
The agent structure of substitution or unsubstituted cycloalkyl ", such as can be cyclohexyl, suberyl or cyclooctyl.
" C6-C12 " in term " the substituted or unsubstituted aryl of C6-C12 " refers to the total of all carbon atoms
Number, when containing substituent in aryl, the substituent is preferably direct-connected or side chain the alkyl or alkylidene of C1-C4, example
Such as, alkyl can include methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group, and alkylidene can
To include the substructure of as above alkyl.The substituent can also be the cycloalkyl of C2, C3 or C4." C6-C12's is substituted
Or unsubstituted aryl " agent structure for example, can be phenyl or naphthyl.
According to the present invention, it is further preferred that in formula (1), R1、R2、R3Be each independently H, C1-C4 alkyl,
The alkyl of C12, the substituted or unsubstituted aryl of C6-C10；R4The alkyl of alkyl, C12 for C1-C4, C6-C10
The cycloalkyl of substituted or unsubstituted aryl, C6-C8.
According to the present invention, in the case of no conversely explanation, term " alkyl of C1-C4 " can be straight or branched
, for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group；Term " the quilt of C6-C10
" C6-C10 " in substitution or unsubstituted aryl " refers to the sum of all carbon atoms, when containing substituent in aryl,
The substituent is preferably direct-connected or side chain the alkyl or alkylidene of C1-C4, for example, alkyl can include methyl, ethyl,
N-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group, alkylidene can include the substructure of as above alkyl.Institute
State the cycloalkyl that substituent can also be C2, C3 or C4.The main body knot of " the substituted or unsubstituted aryl of C6-C10 "
Structure is for example, can be phenyl or naphthyl.
According to the present invention, it is further preferred that R1、R2、R3Be each independently H, methyl, ethyl, n-propyl, isopropyl,
Normal-butyl, isobutyl group, dodecyl, phenyl, naphthyl, benzyl or ethylphenyl, more preferably methyl, ethyl or isopropyl；
R4For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, dodecyl, phenyl, naphthyl, benzyl, ethylphenyl,
Cyclohexyl, suberyl or cyclooctyl, more preferably methyl, ethyl, isopropyl, cyclohexyl or suberyl.
According to the present invention, it is conversely illustrate in the case of, construction unit that polymer of the invention includes by
Corresponding monomer is opened by carbon-carbon double bond to be obtained.
Second aspect, the present invention provides a kind of preparation method of the polymer with water plugging and profile controlling performance, wherein, the party
Method includes：In the presence of initiator and as the water of solvent, and under atmosphere of inert gases, make monomer D, monomer E and monomer F
Carry out solution polymerization；Wherein, the monomer D is acrylamide monomer, and the monomer E is n-vinyl pyrrolidone
(NVP) monomer, the monomer F are the monomer with structure shown in formula (1)；Wherein, the use of the monomer D, monomer E and monomer F
For amount so that in the polymer that is prepared, the content of construction unit A be that the content of 60-98 weight %, construction unit B are that 1-39 is weighed
% is measured, the content of construction unit C is 1-39 weight %；
Wherein, in formula (1), R1、R2、R3It is each independently the alkyl of H, C1-C12, the substituted of C6-C12 or not
Substituted aryl；R4The substituted or unsubstituted cycloalkyl of alkyl, C6-C12 for C1-C12, C6-C12 it is substituted
Or unsubstituted aryl.
The monomer F can be commercially available or synthesize to obtain using the method for the prior art.For example, the present invention
The monomer F that embodiment part uses is all from commercially available.And the preparation of the present invention has the polymer of water plugging and profile controlling performance
Method involved in polymerisation carried out using random copolymerization mode.
In the present invention, have formula (1) shown in structure monomer in substituent related definition and substance classes with
The correspondence noted earlier of the present invention is identical, and details are not described herein by the present invention, and those skilled in the art should not be construed as to the present invention
Technical solution limitation.
It should be noted that in polymerisation in the present invention, used one body approximation is fully converted to have stifled
The corresponding construction unit that the polymer of water profile control performance contains, the dosage of the monomer is with described with water plugging and profile controlling performance
The content for the corresponding construction unit that polymer contains can be consistent.
Preferably, the dosage of the monomer D, monomer E and monomer F cause in the polymer that is prepared, the structure list
The content of first A is that the content of 75-90 weight %, the construction unit B are 5-20 weight %, and the content of the construction unit C is
4-20 weight %.
According to the present invention, monomer D, monomer E and monomer F are formed into aqueous solution in presence of water；It is further preferred that institute
State in aqueous solution, the ratio between the dosage of water and the dosage of monomer D, monomer E and monomer F are 1000：150-245：2.5-97.5：2.5-
97.5；More preferably 1000：187.5-225：12.5-50：12.5-50.Herein it should be noted that the monomer D, monomer E
Aqueous solution can be configured to respectively with monomer F, and when use is mixed according still further to ratio as above, directly can also be pressed them
It is added to according to ratio as above and predetermined mixed monomer solution is configured in aqueous solution.
According to the present invention, the inert atmosphere refers in the presence of an inert gas, wherein inert gas for not with raw material and
The gas that product reacts, for example, can be this area routine nitrogen or the periodic table of elements in group 0 element (helium, neon,
At least one of argon, krypton, xenon) gas；It is preferred that the inert gas is nitrogen.
The method according to the invention, inert atmosphere passes through following optional approach in the solution polymerization condition of the alkene
Realize：Inert gas is continuously passed through during the solution polymerization of the alkene；Or the polymerisation in solution in the alkene
Reaction is passed through the inert gas scheduled time into the aqueous solution for be mixed with monomer mixture before starting, and it is anti-then to seal polymerisation in solution
Answer space；It is preferred that the scheduled time is 5-60min, more preferably 20-40min.
The method according to the invention, the solution polymerization is 8-10 preferably in pH value, under conditions of preferably 8.5-9.5
Carry out.The pH value can be obtained by adding pH adjusting agent into polymerization system, and the pH adjusting agent can be ability
The various pH adjusting agents of domain routine, such as can be at least one of sodium hydroxide, sodium carbonate, potassium carbonate and ammonium hydroxide, it is excellent
Elect sodium hydroxide and/or sodium carbonate as.
Preferably, the time of the solution polymerization is 5-10h, when being preferably 6-7 small.
Preferably, the initiator can be this area routine initiator, for example, can be azo-initiator with/
Or redox type initiators；The azo-initiator is preferably selected from 2,2- azos (2- (2- imidazoline -2- bases) propane) two
Hydrochloride (alias VA-044), 2,2- azos (2- methyl-N- (2- hydroxyethyls) propionamides (alias VA-086) and 2,2- azos
Double (the 2- methyl-props amidine) hydrochloric acid of at least one of double (2- methyl-props amidine) hydrochlorides (alias V50), more preferably 2,2- azos
Salt；In the redox type initiators, oxidant is preferably potassium peroxydisulfate and/or ammonium persulfate, and reducing agent is preferably sulfurous
Sour sodium and/or sodium hydrogensulfite, it is furthermore preferred that oxidant is ammonium persulfate, reducing agent is sodium hydrogensulfite.
Preferably, the dosage of the initiator can be the dosage of this area routine, as long as enabling to monomer D, monomer E
Sufficiently polymerization is carried out with monomer F to form the polymer with water plugging and profile controlling performance of the present invention.For example, with 1000 weights
On the basis of measuring the water in the solution of part, the dosage of the initiator can be 0.001-0.05 parts by weight, be preferably
0.005-0.02 parts by weight.
In the preparation process in accordance with the present invention, when the initiator selects azo-initiator, the temperature of the polymerisation
Degree is preferably 40-70 DEG C, more preferably 45-60 DEG C；It is described poly- when the initiator selects redox type initiators
The temperature for closing reaction is preferably 15-30 DEG C, more preferably 15-20 DEG C.
According to the present invention, the method preferably first adjusts the pH value of the aqueous solution of monomer D, monomer E and monomer F, Ran Houzai
The inert gas is passed through, still further preferably, after initiator is added, stopping is passed through nitrogen.
It is polymeric colloid by the product mixtures obtained after the solution polymerization, it is of the present invention in order to obtain
The polymer end product with water plugging and profile controlling performance, method of the invention can also include the polymeric colloid of acquisition is made
The polymer end product with water plugging and profile controlling performance is obtained after grain, dry, crushing, screening.
A kind of preferred embodiment according to the present invention, the preparation side of the polymer with water plugging and profile controlling performance
Method comprises the following steps：
1st step：Monomer D, monomer E and monomer F are added in polymer reactor and are configured to aqueous solution, described in alkali is adjusted
The pH value of aqueous solution is passed through after nitrogen 5-60min to remove oxygen therein to 8-10；
2nd step：Initiator is added into the aqueous solution of the 1st step and is uniformly mixed, while stops being passed through nitrogen and sealing, is gathered
When conjunction reaction 5-10 is small, gum polymers aqueous solution is obtained；Wherein, it is described poly- when the initiator is azo-initiator
The temperature for closing reaction is 40-70 DEG C；When the initiator selects redox type initiators, the temperature of the polymerisation is
15-30℃；
3rd step：Take out colloid be granulated, dry again, being crushed, sieve after obtain of the invention there is water plugging and profile controlling performance
Polymer end product.Wherein, the granulation, method that is dry, crushing, sieve are known to those skilled in the art, herein
No longer it is described in detail.
The third aspect, the present invention provides the polymer with water plugging and profile controlling performance being prepared by preceding method.
Fourth aspect, should in Water in Water Shutoff in Oil Field profile control the present invention provides the foregoing polymer with water plugging and profile controlling performance
With.
5th aspect, the present invention provides the foregoing polymer with water plugging and profile controlling performance to prepare Water in Water Shutoff in Oil Field profile control agent
Middle application.
The above-mentioned polymer with water plugging and profile controlling performance is in Water in Water Shutoff in Oil Field profile control and in Water in Water Shutoff in Oil Field profile control agent is prepared
In application, the technology that specific application process is well known to those skilled in the art, the present invention are no longer discussed in detail herein.
Described polymer with water plugging and profile controlling performance of the present invention and its preparation method and application is with following specific
Advantage：
1) in the polymer with construction unit A, construction unit B and construction unit C, construction unit C is in formation temperature
Under the conditions of (70-90 DEG C) hydrolyze, produce N- methylol propionyl amine structures and active hydrogen.Products therefrom further with structure list
First A occurs Mannich Mannich reactions and forms crosslinking.Since the hydrolysis of construction unit C in the earth formation is one more slow
Progressive process.Water plugging profile control agent is allowd to be transported to the remote slow plastic in well area.Therefore, it is provided by the invention that there is water blockoff
The polymer of profile control performance can realize slowly thickening plastic in the range of longer time, and the deep for being appropriate for remote well area is blocked up
Water profile control.
2) system is not required to additionally add delayed crosslinker.
The present invention will be described in detail by way of examples below.It is it should be appreciated that described herein specific real
The mode of applying is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Embodiment 1
The present embodiment is used to illustrate polymer provided by the invention with water plugging and profile controlling performance and preparation method thereof
(1) by the acrylamide (AM) of 225 parts of mass fraction, 50 parts of n-vinyl pyrrolidone (NVP) and 12.5 parts
The acrylamide group methyl carboxylate as shown in formula (2), be dissolved under stirring in 1000 parts of water, adjusted using sodium hydroxide
Solution ph is to 9.2, and at room temperature, after aqueous solution is led to nitrogen deoxygenation 30 minutes.
(2) 0.02 part of initiator 2, double (the 2- methyl-props amidine) hydrochlorides (AIBA) of 2- azos are added, while stop being passed through
Nitrogen, when 50 DEG C of isothermal reactions 6 of normal pressure are small under air-proof condition, obtains gum polymers solution product.
(3) product obtains the polymer A1 with water plugging and profile controlling performance of the present invention, institute through drying, granulation, crushing, screening
Obtain in polymer, the content of construction unit A is 78 weight %, and the content of construction unit B is 17 weight %, and construction unit C's contains
Measure and be shown in Table 1 for 5 weight %, the molecular weight and solid content of gained polymerization.
Embodiment 2
The present embodiment is used to illustrate polymer provided by the invention with water plugging and profile controlling performance and preparation method thereof
(1) by the acrylamide (AM) of 200 parts of mass fraction, 25 parts of n-vinyl pyrrolidone (NVP) and 25 parts such as
Acrylamide group methyl carboxylate shown in formula (3), is dissolved in 1000 parts of water under stirring, uses sodium hydrate regulator solution
PH value is to 9, and at room temperature, after aqueous solution is led to nitrogen deoxygenation 30 minutes.
(2) add 0.01 part ammonium persulfate and 0.01 part of sodium hydrogensulfite as redox initiation system, at the same time
Stopping is passed through nitrogen, when 20 DEG C of isothermal reactions 7 of normal pressure are small under air-proof condition, obtains gum polymers solution product.
(3) product obtains the polymer A2 with water plugging and profile controlling performance of the present invention, institute through drying, granulation, crushing, screening
Obtain in polymer, the content of construction unit A is 80 weight %, and the content of construction unit B is 10 weight %, and construction unit C's contains
Measure and be shown in Table 1 for 10 weight %, the molecular weight and solid content of gained polymerization.
Embodiment 3
The present embodiment is used to illustrate polymer provided by the invention with water plugging and profile controlling performance and preparation method thereof
(1) by the acrylamide (AM) of 187.5 parts of mass fraction, 12.5 parts of n-vinyl pyrrolidone (NVP) and 50
Acrylamide group methyl carboxylate of the part as shown in formula (4), is dissolved in 1000 parts of water under stirring, is adjusted using sodium hydroxide
Solution ph is to 8.5, and at room temperature, after aqueous solution is led to nitrogen deoxygenation 30 minutes.
(2)) 0.015 part of initiator 2, double (the 2- methyl-props amidine) hydrochlorides (AIBA) of 2- azos are added, while are stopped logical
Enter nitrogen, when 45 DEG C of isothermal reactions 6 of normal pressure are small under air-proof condition, obtain gum polymers solution product.
(3) product obtains the polymer A3 with water plugging and profile controlling performance of the present invention, institute through drying, granulation, crushing, screening
In polymer, the content of construction unit A is 75 weight %, and the content of construction unit B is 5 weight %, the content of construction unit C
For 20 weight %, the molecular weight and solid content of gained polymerization are shown in Table 1.
Embodiment 4
The present embodiment is used to illustrate polymer provided by the invention with water plugging and profile controlling performance and preparation method thereof
Method according to embodiment 3 carries out the preparation of the polymer A4 with water plugging and profile controlling performance, unlike, used
Initiator be 2,2- azos (2- (2- imidazoline -2- bases) propane) dihydrochloride (VA-044), the molecular weight of gained polymerization and
Solid content is shown in Table 1.
Embodiment 5
The present embodiment is used to illustrate polymer provided by the invention with water plugging and profile controlling performance and preparation method thereof
Method according to embodiment 3 carries out the preparation of the polymer A5 with water plugging and profile controlling performance, unlike, acryloyl
The dosage of amine (AM) is 150 parts by weight, and the dosage of n-vinyl pyrrolidone (NVP) is 97.5 parts by weight, the list shown in formula (4)
The dosage of body is 2.5 parts by weight, and the pH value of reaction is 8.0.
In resulting polymers, the content of construction unit A is 60 weight %, and the content of construction unit B is 39 weight %, structure
The content of unit C is 1 weight %, and the molecular weight and solid content of gained polymerization are shown in Table 1.
Embodiment 6
The present embodiment is used to illustrate polymer provided by the invention with water plugging and profile controlling performance and preparation method thereof
Method according to embodiment 3 carries out the preparation of the polymer A6 with water plugging and profile controlling performance, unlike, formula (4)
In phenyl substituted with cyclohexyl, gained polymerization molecular weight and solid content be shown in Table 1.
Comparative example 1
This comparative example is used to illustrate polymer with water plugging and profile controlling performance of reference and preparation method thereof
Method according to embodiment 3 carries out the preparation of the polymer D1 with water plugging and profile controlling performance, unlike, without using
Monomer shown in formula (4), the molecular weight and solid content of gained polymerization are shown in Table 1.
Comparative example 2
This comparative example is used to illustrate polymer with water plugging and profile controlling performance of reference and preparation method thereof
Method according to embodiment 3 carries out the preparation of the polymer D2 with water plugging and profile controlling performance, unlike, acryloyl
The dosage of amine (AM) is 100 parts by weight, and the dosage of n-vinyl pyrrolidone (NVP) is 25 parts by weight, the monomer shown in formula (4)
Dosage be 100 parts by weight.
In resulting polymers, the content of construction unit A is 44.4 weight %, and the content of construction unit B is 11.2 weight %,
The content of construction unit C is 44.4 weight %, and the molecular weight and solid content of gained polymerization are shown in Table 1.
Comparative example 3
This comparative example is used to illustrate polymer with water plugging and profile controlling performance of reference and preparation method thereof
Method according to embodiment 3 carries out the preparation of the polymer D3 with water plugging and profile controlling performance, unlike, step
(1) be not passed through nitrogen in, and polymerisation no longer seal under conditions of carry out, the molecular weight and solid content of gained polymerization are shown in Table 1.
Test case
(1) (the use of salinity is 10000mg/L by the aqueous solution of obtained water plugging profile control agent product configuration into 1500mg/L
Water prepared), deoxygenation sealing, carry out 80 DEG C at heat ageing.Measure (test condition：Shearing 7.34/S) it is different old
Change the solution viscosity under the time, acquired results are shown in Table 1.
Table 1
(viscosity unit mPas)
(2) (the use of salinity is 10000mg/L by the aqueous solution of obtained water plugging profile control agent product configuration into 1500mg/L
Water prepared), deoxygenation sealing, carry out 90 DEG C at heat ageing.Measure (test condition：Shearing 7.34/S) it is different old
Change the solution viscosity under the time, acquired results are shown in Table 2.
Table 2
(viscosity unit mPas)
Test result shows that the water-soluble polymer of one-pack type retardance self-crosslinking provided by the invention can be longer
Slowly thickening plastic is realized in time range.System is not required to additionally add delayed crosslinker.The self-crosslinking Weak Gels formed are old
Change and retain viscosity height, be appropriate for the deep water plugging and profile controlling in remote well area.And polymer in the preferred range as
Upper performance is more preferably.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
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 (12)
1. a kind of polymer with water plugging and profile controlling performance, it is characterised in that the polymer contains construction unit A, construction unit B
With construction unit C, wherein, construction unit A is provided by acrylamide monomer, and construction unit B is by n-vinyl pyrrolidone monomer
There is provided, construction unit C is provided as the monomer of the structure shown in formula (1)；Wherein, on the basis of the weight of the polymer,
The content of construction unit A is that the content of 60-98 weight %, the construction unit B are 1-39 weight %, the construction unit C's
Content is 1-39 weight %；
Wherein, in formula (1), R1、R2、R3It is each independently the alkyl of H, C1-C12, the substituted of C6-C12 or is not taken
The aryl in generation；R4The substituted or unsubstituted cycloalkyl of alkyl, C6-C12 for C1-C12, the substituted of C6-C12 or
Unsubstituted aryl.
2. polymer according to claim 1, wherein, on the basis of the weight of the polymer, the construction unit A's
Content be 75-90 weight %, the construction unit B content be 5-20 weight %, the construction unit C content be 4-20 weight
Measure %.
3. polymer according to claim 1 or 2, wherein, in formula (1), R1、R2、R3It is each independently H, C1-C4
Alkyl, alkyl, the substituted or unsubstituted aryl of C6-C10 of C12；R4The alkyl of alkyl, C12 for C1-C4,
The substituted or unsubstituted aryl of C6-C10；
Preferably, R1、R2、R3Be each independently H, methyl, ethyl, propyl group, butyl, dodecyl, phenyl, naphthyl, benzyl or
Ethylphenyl；R4For methyl, ethyl, propyl group, butyl, dodecyl, phenyl, naphthyl, benzyl, ethylphenyl, cyclohexyl, cycloheptyl
Base or cyclooctyl.
4. a kind of preparation method of the polymer with water plugging and profile controlling performance, it is characterised in that this method includes：In initiator and
In the presence of the water of solvent, and under atmosphere of inert gases, monomer D, monomer E and monomer F is set to carry out solution polymerization；
Wherein, the monomer D is acrylamide monomer, and the monomer E is n-vinyl pyrrolidone monomer, the monomer F be with
The monomer of structure shown in formula (1)；Wherein, the dosage of the monomer D, monomer E and monomer F cause in the polymer that is prepared,
The content of construction unit A is that the content of 60-98 weight %, construction unit B are that the content of 1-39 weight %, construction unit C is 1-
39 weight %；
Wherein, in formula (1), R1、R2、R3It is each independently the alkyl of H, C1-C12, the substituted of C6-C12 or is not taken
The aryl in generation；R4The substituted or unsubstituted cycloalkyl of alkyl, C6-C12 for C1-C12, the substituted of C6-C12 or
Unsubstituted aryl.
5. preparation method according to claim 4, wherein, the dosage of the monomer D, monomer E and monomer F to be prepared into
To polymer in, the content of the construction unit A is that the content of 75-90 weight %, the construction unit B are 5-20 weights
% is measured, the content of the construction unit C is 4-20 weight %.
6. preparation method according to claim 4 or 5, wherein, in formula (1), R1、R2、R3It is each independently H, C1-
The alkyl of C4, the alkyl of C12, the substituted or unsubstituted aryl of C6-C10；R4The alkane of alkyl, C12 for C1-C4
The substituted or unsubstituted aryl of base, C6-C10；
Preferably, R1、R2、R3Be each independently H, methyl, ethyl, propyl group, butyl, dodecyl, phenyl, naphthyl, benzyl or
Ethylphenyl, R4For methyl, ethyl, propyl group, butyl, dodecyl, phenyl, naphthyl, benzyl, ethylphenyl, cyclohexyl, cycloheptyl
Base or cyclooctyl.
7. according to the preparation method described in any one in claim 4-6, wherein, the inert gas is nitrogen.
8. according to the preparation method described in any one in claim 4-6, wherein, the condition bag of the solution polymerization
Include：PH value is 8-10；Temperature is 15-70 DEG C, when the time is 5-10 small.
9. preparation method according to claim 4, wherein, the initiator includes azo-type initiator and/or oxidation also
Prototype initiator；
Preferably, the azo-type initiator is 2,2- azos (2- (2- imidazoline -2- bases) propane) dihydrochloride, 2,2- azos
(at least one of 2- methyl-N- (2- hydroxyethyls) propionamides and double (the 2- methyl-props amidine) hydrochlorides of 2,2- azo, are preferably
Double (the 2- methyl-props amidine) hydrochlorides of 2,2- azos；In the redox type initiator, oxidant is potassium peroxydisulfate and/or over cure
Sour ammonium, reducing agent are sodium sulfite and/or sodium hydrogensulfite, it is preferred that in redox type initiator, oxidant is persulfuric acid
Ammonium, reducing agent are sodium hydrogensulfite；
Preferably, the initiator is azo-type initiator, 40-70 DEG C of the temperature of the solution polymerization；
Preferably, the initiator is redox type initiator, and the temperature of the polymerisation is 15-30 DEG C.
10. the polymer with water plugging and profile controlling performance that the method in claim 4-9 described in any one is prepared.
11. the polymer with water plugging and profile controlling performance in claim 1-3 and 10 described in any one is in Water in Water Shutoff in Oil Field profile control
Middle application.
12. the polymer with water plugging and profile controlling performance in claim 1-3 and 10 described in any one is preparing Water in Water Shutoff in Oil Field
Applied in profile control agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610929230.5A CN108003278B (en) | 2016-10-31 | 2016-10-31 | Polymer with water shutoff profile control performance and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610929230.5A CN108003278B (en) | 2016-10-31 | 2016-10-31 | Polymer with water shutoff profile control performance and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108003278A true CN108003278A (en) | 2018-05-08 |
| CN108003278B CN108003278B (en) | 2020-04-03 |
Family
ID=62047808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610929230.5A Active CN108003278B (en) | 2016-10-31 | 2016-10-31 | Polymer with water shutoff profile control performance and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108003278B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231164A (en) * | 2013-06-20 | 2014-12-24 | 中国石油化工股份有限公司 | Acrylamide copolymer as well as preparation method and application of acrylamide copolymer |
| CN104610490A (en) * | 2013-11-04 | 2015-05-13 | 中国石油化工股份有限公司 | Acrylamide copolymer and preparation method and application thereof |
-
2016
- 2016-10-31 CN CN201610929230.5A patent/CN108003278B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231164A (en) * | 2013-06-20 | 2014-12-24 | 中国石油化工股份有限公司 | Acrylamide copolymer as well as preparation method and application of acrylamide copolymer |
| CN104610490A (en) * | 2013-11-04 | 2015-05-13 | 中国石油化工股份有限公司 | Acrylamide copolymer and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 桜田一郎等: ""高分子スルホン酸触媒による高分子エステルの加水分解"", 《高分子化学》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108003278B (en) | 2020-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106883357B (en) | A kind of pre-crosslinked gel delays swollen microballoon profile control agent and its preparation method and application | |
| CN101914182B (en) | The synthetic method of base underground crosslinked thickening agent | |
| CN101775275B (en) | Novel viscoelastic particle oil displacement agent and preparation method thereof | |
| CN106675540A (en) | Temperature-resistant salt-resistant profile control plugging agent and preparation method thereof | |
| CN104371682A (en) | AA-AM-AMPS-DAC (acrylic acid-acrylamide-2-acrylamido-methylpropanesulfonic acid-acryloyloxyethyl ammonium chloride) polymer gel plugging agent and synthesis method thereof | |
| CN105368423B (en) | One kind is recovered the oil and uses Chrome-free compound resin gel-like profile control agent and preparation method and purposes | |
| CN109735315A (en) | A kind of environment-friendly type oil recovery delay crosslinking profile control agent and preparation method and purposes | |
| CN106479463A (en) | Retarded crosslinking high intensity frozen glue profile-controlling and plugging agent | |
| CN107793529A (en) | A kind of high temperature resistant acid fracturing polymer and preparation method | |
| CN103923629A (en) | Plugging agent | |
| CN102492414B (en) | Synthesis of thickening agent for methanol-based fracturing fluid | |
| MX2012010146A (en) | Ammonium halide as gelation retarder for crosslinkable polymer compositions. | |
| CN104371692A (en) | Deep coating composite gel modifying and flooding agent for oil recovery and preparation method of deep coating composite gel modifying and flooding agent | |
| CN108017754A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN108017753A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN108003276A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN108003278A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN108003283A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN108017756A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN102559156B (en) | High temperature high salinity fluid loss agent for drilling fluid and preparation method thereof | |
| CN108003280A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN108003281A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN108003279A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN108017752A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application | |
| CN108017755A (en) | Polymer with water plugging and profile controlling performance and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |