CN106317311A - Acrylamide copolymer, preparation method therefor and application of acrylamide copolymer - Google Patents
Acrylamide copolymer, preparation method therefor and application of acrylamide copolymer Download PDFInfo
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Abstract
The invention discloses an acrylamide copolymer, a preparation method therefor and an application of the acrylamide copolymer. The acrylamide copolymer contains a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a unit with a structure represented by a formula (1) shown in the description, the structural unit B is at least one of units with structures represented by formulae (2 to 5) shown in the description, the structural unit C is a unit with a structure represented by a formula (6) shown in the description, the weight ratio of the structural unit A to the structural unit B to the structural unit C is 1 to (0.001 to 10) to (0.001 to 10), and the viscosity average molecular weight of the acrylamide copolymer is 30,000,000 to 36,000,000. The acrylamide copolymer disclosed by the invention has the characteristics of good water solubility, low residual monomer content and high molecular weight; and particularly, under high-temperature and high-salt conditions, the apparent viscosity of a solution of the acrylamide copolymer is improved greatly compared with that of the conventional polyacrylamide, so that the acrylamide copolymer can serve as an oil displacement agent for tertiary oil recovery of high-temperature and high-salt oil reservoirs.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer, the preparation method of a kind of acrylamide copolymer, by
Acrylamide copolymer prepared by the method and the application of described acrylamide copolymer.
Background technology
Polymer flooding, mainly by injecting the polymer solution of certain scale, increases displacing fluid viscosity, fall
Low oil-reservoir water phase permeability reduces mobility ratio, adjusts intake profile, to reach to improve displacing phase volume
Purpose, and then improve recovery ratio.
As main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (PHPA) (HPAM) is at conventional oil reservoir
In tertiary oil recovery (EOB) technology, large-scale promotion and application are obtained, for oilfield stable production and volume increase
Play important function.Along with the minimizing of conventional reservoir reserve, high temperature and high salt oil deposit makes answering of HPAM
With being faced with many difficult problems, in high temperature, high salt and solution when being mainly reflected in exploitation high temperature and high salt oil deposit
The compound action that dissolved oxygen produces makes HPAM solution viscosity be greatly reduced, and causes the HPAM displacement of reservoir oil to be imitated
Fruit is the most notable.Research shows, when temperature is higher than 70 DEG C, and the acylamino-hydrolysis of HPAM generates carboxyl
Notable aggravation, when degree of hydrolysis reaches more than 40%, carboxyl is just easy to and Ca in solution2+、Mg2+Ion
Generate precipitation, make solution viscosity lose.Additionally, at high temperature, there is dissolving in oxygen and solution in air
During oxygen, main polymer chain fracture also can be caused to make solution viscosity be remarkably decreased.
In order to improve the temperature-resistant anti-salt performance of polyacrylamide, carry out a large amount of tackling key problem research both at home and abroad, main
To carry out greatly around the chain yardstick of polymer, chain size distribution, construction unit composition, micro-sequential structure
Amount correlational study work, as temperature-resistant anti-salt monomer-polymer, hydrophobic associated polymer, amphiphilic polymers,
Composite polymer, comb polymer, template polymer and surface-active polymer etc..As entitled
" the low temperature synthesis of AMPS/AM copolymer and performance " (Chang Zhiying, polymer material science and engineering,
1997,13,16) with acrylamide (AM) and heat-resistant salt-resistant monomer 2-acrylamido-2-methyl-prop sulphur
Acid (AMPS) copolymerization bipolymer.A kind of comb-type structure activity as open in CN101260171A
Polymer and preparation technology thereof and application, by monomers such as polyurethanes surface-active macromonomer and acrylamides altogether
Aggregate into and there is tackifying and reduce interfacial tension target product.The polymer that above two method obtains is each
Have its feature, some performance such as temperature tolerance, salt-resistance, shear resistant and surface activity index relatively pass
The polyacrylamide of system increases really, but technological operation is relatively cumbersome, and it is little to obtain molecular weight of product
(less than 20,000,000), causes the application of polymer to be restricted.
Summary of the invention
It is an object of the invention to overcome the drawbacks described above of prior art, it is provided that a kind of acrylamide copolymer
And its preparation method and application.
The present invention provides a kind of acrylamide copolymer, and wherein, this acrylamide copolymer contains structure list
Unit A, construction unit B and construction unit C, wherein, described construction unit A is for having formula (1) institute
Showing the unit of structure, described construction unit B is for having in the unit of structure shown in formula (2)-formula (5)
At least one, described construction unit C is for having the unit of structure shown in formula (6), and described structure
The weight ratio of unit A, described construction unit B and described construction unit C is 1:0.001-10:0.001-10,
The viscosity-average molecular weight of described acrylamide copolymer is 30,000,000-3,600 ten thousand,
Wherein, R1、R2、R6、R7、R10And R11It is each independently the alkyl of hydrogen or C1-C4,
R3For the alkylidene of C1-C14, R4And R5It is each independently the alkyl of hydrogen or C1-C15, R8With
R9It is each independently the alkyl of C1-C4, R12For the alkyl of C1-C3, n is the most whole in 6-22
Number, M1And M2It is each independently H, Na or K.
It was found by the inventors of the present invention that the main chain of the acrylamide copolymer strand of the present invention is mainly by third
The construction unit of acrylamide is constituted with the construction unit of temperature-resistant anti-salt monomer, is ensureing that polymeric water-soluble is same
Time, the temperature-resistant anti-salt performance of polymer molecule can be improved.Addition block copolymer side chain is by surface active function
The construction unit of monomer is constituted, and has generation Interpolymer Association effect, increases the slack time of molecular motion,
Improve solution viscoelasticity and reduce the effect of oil water interfacial tension.
The present invention also provides for the preparation method of a kind of acrylamide copolymer, and this preparation method includes: molten
Under liquid polymeric reaction condition, in the presence of initiator, a kind of monomer mixture is made to carry out polymerization in water anti-
Should, wherein, described monomer mixture contains monomer E, monomer F and monomer G, and described monomer E is tool
Having the monomer of structure shown in formula (8), described monomer F is for having structure shown in formula (9)-formula (12)
Monomer at least one, described monomer G is for having the monomer of structure shown in formula (13) and described
The weight ratio of monomer E, described monomer F and described monomer G is 1:0.001-10:0.001-10；Described
After solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is 30,000,000-3600
Ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently the alkyl of hydrogen or C1-C4,
R3' it is the alkylidene of C1-C14, R4' and R5' it is each independently the alkyl of hydrogen or C1-C15, R8' and
R9' it is each independently the alkyl of C1-C4, R12' it is the alkyl of C1-C3, n ' is arbitrary in 6-22
Integer, M1' and M2' it is each independently H, Na or K.
Present invention also offers the acrylamide copolymer prepared by said method.
Additionally, present invention also offers the application as oil displacement agent of the aforesaid propylene amide copolymer.
The acrylamide copolymer that the present invention provides has that good water solubility, residual monomer content be low, molecular weight
High feature, particularly under conditions of high temperature and high salt, the more conventional polyacrylamide of apparent viscosity of solution
Amine is substantially improved.Specifically, the acrylamide copolymer molecular weight of the present invention reaches as high as 34,000,000,
Particularly under conditions of high salinity 32000mg/L and high temperature 95 DEG C, the apparent viscosity of solution is the highest
Up to 25.0mPa s, and the molecular weight of commercially available high molecular weight polyacrylamide is only about 26,000,000, molten
The apparent viscosity of liquid is only 8.9mPa s, compared with commercially available prod, and the acrylamide copolymer tool of the present invention
There is significantly thickening advantage, can be as high temperature and high salt oil deposit Flooding Agent for EOR.
The preparation method step of the acrylamide copolymer that the present invention provides is simple, prepares acrylamide copolymerization
The feature that thing has good water solubility, residual monomer content is low, molecular weight is high, particularly in high temperature and high salt
Under the conditions of, the more conventional polyacrylamide of apparent viscosity of solution is substantially improved, can be as high temperature and high salt
Oil reservoir Flooding Agent for EOR.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of acrylamide copolymer, and wherein, this acrylamide copolymer contains structure list
Unit A, construction unit B and construction unit C, wherein, described construction unit A is for having formula (1) institute
Showing the unit of structure, described construction unit B is for having in the unit of structure shown in formula (2)-formula (5)
At least one, described construction unit C is for having the unit of structure shown in formula (6), and described structure
The weight ratio of unit A, described construction unit B and described construction unit C is 1:0.001-10:0.001-10,
It is preferably 1:0.01-1.5:0.01-0.2, more preferably 1:0.01-1:0.01-0.1；Described propylene
The viscosity-average molecular weight of amide copolymer is 30,000,000-3,600 ten thousand, preferably 32,000,000-3,500 ten thousand；
Wherein, R1、R2、R6、R7、R10And R11It is each independently the alkyl of hydrogen or C1-C4,
R3For the alkylidene of C1-C14, R4And R5It is each independently the alkyl of hydrogen or C1-C15, R8With
R9It is each independently the alkyl of C1-C4, R12For the alkyl of C1-C3, n is the most whole in 6-22
Number, M1And M2It is each independently H, Na or K.
In the present invention, the alkyl of described C1-C4 can be straight chain, it is also possible to be side chain.Described
The example of the alkyl of C1-C4 may include that methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, secondary
Butyl, isobutyl group and the tert-butyl group.
In the present invention, the alkylidene of described C1-C14 can be straight or branched, described C1-C14
The example of alkylidene can include but not limited to: methylene, ethylidene, sub-n-pro-pyl, isopropylidene,
Sub-normal-butyl, sub-sec-butyl, isobutylidene and the sub-tert-butyl group, sub-n-pentyl, isoamylidene, sub-uncle penta
Base, sub-neopentyl, sub-n-hexyl, sub-n-heptyl, sub-n-octyl, sub-n-nonyl, sub-positive decyl,
Sub-positive hendecyl, sub-positive dodecyl, sub-positive tritriacontyl and the positive tetradecyl in Asia.Described alkylidene refers to alkane
Hydrocarbon loses the residue after two hydrogen atoms, and said two hydrogen atom can be two on same carbon atom
Hydrogen atom, it is also possible to two hydrogen atoms on different carbon atoms, can be straight chains, it is also possible to be side chain
, such as, described ethylidene can be-CH2CH2-or-CH (CH3)-。
In the present invention, the alkyl of described C1-C15 can be straight chain, it is also possible to be side chain.Institute
The example of the alkyl stating C1-C15 can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, just
Hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, just
Tridecyl, n-tetradecane base, Pentadecane base.
In the present invention, although if containing construction unit A, construction unit B and construction unit C and
Meet aforementioned proportion relation and can realize the purpose of the present invention, but under preferable case, with described acrylamide
On the basis of the total amount of copolymer, the content of described construction unit A is 30-99 weight %.
According to the present invention, in order to make acrylamide copolymer have good viscoelasticity, under preferable case,
Described construction unit B for have at least one in the unit of structure shown in formula (2)-formula (4) and
The unit of structure shown in formula (7):
Wherein, M3For K or Na, preferably Na；R1As hereinbefore defined.
The content of the unit of structure shown in formula (7) is not specially required by the present invention, for instance, it is preferred that
In the unit of structure shown in the unit of structure shown in formula (1), formula (2)-formula (4) at least one,
Shown in the unit of structure shown in formula (6) and formula (7), the weight ratio of the unit of structure is 1:0.001-10:
0.001-10:0.1-1, more preferably 1:0.01-1.5:0.01-0.2:0.1-1, more preferably 1:
0.01-1:0.01-0.1:0.1-1.
Preferably, the acrylates construction unit shown in described formula (7) can be former by acrylate monomers
Material carries out polymerization and obtains or led to by the construction unit shown in some acrylamide construction unit i.e. formula (1)
Cross hydrolysis to obtain, it is further preferred that the construction unit shown in formula (7) is by some acrylamide structure
Construction unit shown in unit i.e. formula (1) is obtained by hydrolysis.Those skilled in the art could be aware that
, the process of hydrolysis includes reacting hydrolytic reagent with acrylamide copolymer, it is preferable that described hydrolysis
The consumption of agent makes the degree of hydrolysis of acrylamide copolymer be 10-30%.
In the present invention, the condition of described hydrolysis is not particularly limited, under preferable case, and described hydrolysis
Condition include: temperature is 50-110 DEG C, preferably 70-90 DEG C；Time is 0.5-6 hour, is preferably
1-4 hour.
In the present invention, described degree of hydrolysis refers to that the molal quantity of acrylates construction unit accounts for the third of the present invention
The percentage ratio of the total mole number of the construction unit of acrylamide copolymer.Described degree of hydrolysis is by water of the present invention
The consumption solving agent determines.
In the present invention, hydrolytic reagent is the various inorganic alkalines being capable of above-mentioned purpose commonly used in the art
Compound, can be selected from one or more in sodium hydroxide, potassium hydroxide and sodium carbonate.Described hydrolysis
The consumption of agent can carry out suitable selection according to the degree of hydrolysis of acrylamide copolymer, so that acrylamide
The degree of hydrolysis of copolymer meets use requirement and is as the criterion.
Those skilled in the art could be aware that, by regulating the consumption of inorganic alkaline compound, and can
To obtain the acrylamide copolymer of different degree of hydrolysis.In the present invention, described inorganic alkaline compound
Molal quantity is equal to the molal quantity of acrylates construction unit.
The present inventor finds under study for action, by specific construction unit A, construction unit B, knot
It is good that the polymer of structure unit C composition can obtain preferable oil displacement efficiency when oil displacement agent.For example, it is preferable to
Ground, R2And R7It is each independently hydrogen or methyl, R6For hydrogen, R3For the alkylidene of C1-C4, more excellent
Elect methylene as；R4And R5It is each independently methyl, R8And R9It is each independently methyl or ethyl,
M1For hydrogen；In described construction unit C, R8And R9It is each independently methyl or ethyl, M1For hydrogen；
In described construction unit C, R12For methyl, n is 16 or 18, it is further preferred that described in there is knot
Structure unit C for having the unit shown in formula (14),
In formula (14), n is 16 or 18.
The present invention also provides for the preparation method of a kind of acrylamide copolymer, and this preparation method includes: molten
Under liquid polymeric reaction condition, in the presence of initiator, a kind of monomer mixture is made to carry out polymerization in water anti-
Should, wherein, described monomer mixture contains monomer E, monomer F and monomer G, and described monomer E is tool
Having the monomer of structure shown in formula (8), described monomer F is for having structure shown in formula (9)-formula (12)
Monomer at least one, described monomer G is for having the monomer of structure shown in formula (13) and described
The weight ratio of monomer E, described monomer F and described monomer G is 1:0.001-10:0.001-10, more excellent
Elect 1:0.01-1.5:0.01-0.2 as, most preferably 1:0.01-1:0.01-0.1；Described polymerisation in solution is anti-
After answering condition to make polyreaction, the viscosity-average molecular weight of resulting polymers is 30,000,000-3,600 ten thousand, is preferably
32000000-3,500 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently the alkyl of hydrogen or C1-C4,
R3' it is the alkylidene of C1-C14, R4' and R5' it is each independently the alkyl of hydrogen or C1-C15, R8' and
R9' it is each independently the alkyl of C1-C4, R12' it is the alkyl of C1-C3, n ' is arbitrary in 6-22
Integer, M1' and M2' it is each independently H, Na or K.
In the present invention, the content of monomer E is preferably 30-99 weight % of monomer mixture gross mass.
In the present invention, described monomer F is temperature-resistant anti-salt monomer, the example of described monomer F can be but
It is not limited to: acrylic acid, 2-acrylamide-2-methylpro panesulfonic acid, N, N-DMAA, N, N-
Acrylamide, N-vinyl pyrrolidone, 2-acrylamido-dodecane sulfonic acid, 2-acryloyl
One or more in amido-tetradecane sulfonic acid and 2-acrylamido-hexadecane sulfonic acid.
The present inventor finds under study for action, when selecting specific monomer E, monomer F and monomer G
When reacting, it is possible to improve the oil displacement efficiency of the polymer of gained further.For instance, it is preferred that institute
Stating monomer F is at least one in the monomer of structure shown in formula (9)-formula (11), and R2' and R7’
It is each independently hydrogen or methyl, R6' it is hydrogen, R3' it is the alkylidene of C1-C4, more preferably methylene；
R4' and R5' it is each independently methyl, R8' and R9' it is each independently methyl or ethyl, M1' it is hydrogen；
In described monomer G, R12' it is methyl, n ' is 16 or 18.It is further preferred that described monomer G is
There is the monomer of structure shown in formula (15),
In formula (15), n ' is 16 or 18.
In the present invention, described monomer G can be prepared according to the conventional method of this area, such as root
According to document: Xinyang Normal College's journal: natural science edition, described in 2013,26 (2): 270-272
Method prepare.
According to the present invention, described solution polymerization is carried out in water, when described solution polymerization starts,
There is no particular limitation for the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture,
Can change in wider scope, under preferable case, the weight of described monomer mixture and water and monomer
The ratio of the gross weight of mixture is 0.15-0.4:1, more preferably 0.2-0.3:1.
In the present invention, described initiator can be the various initiator in this area.Such as, described initiator
Azo series initiators and/or redox system initiator, preferably azo series initiators and oxygen can be selected from
Change reduction system initiator.The consumption of described azo series initiators is the gross weight of monomer in monomer mixture
0.0001-0.1 weight %, preferably 0.001-0.05 weight %；Described oxidoreduction series initiators
Consumption is 0.0002-0.3 weight % of the gross weight of monomer in monomer mixture, preferably 0.002-0.15
Weight %.Described azo series initiators is preferably water-soluble azo series initiators, and described redox system draws
Send out agent and include that Oxidizing and Reducing Agents, described reducing agent are inorganic reducing agent and/or organic reducing agent, and institute
The weight ratio stating oxidant and described reducing agent is 0.1-1:1.
In the present invention, described water-soluble azo series initiators is preferably 2, and 2 '-azo is double (2-amidine propane)
In double (the 2-imidazoline propane) dihydrochloride of dihydrochloride, 2,2 '-azo and 4,4'-azo double (4-cyanopentanoic acid)
At least one, further preferred 2, double (2-amidine propane) dihydrochloride of 2 '-azo.
In the present invention, described oxidant can be selected from acyl peroxide, hydroperoxides and persulfate
At least one, preferably benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, 2,5-diformazan
Base-2, at least one in double (hydrogen peroxide) hexane of 5-, Ammonium persulfate., sodium peroxydisulfate and potassium peroxydisulfate,
More preferably Ammonium persulfate. and/or potassium peroxydisulfate.
In the present invention, described reducing agent can be inorganic reducing agent and/or organic reducing agent, is preferably
Inorganic reducing agent and organic reducing agent.Described inorganic reducing agent can be selected from ferrous sulfate, Ferrous ammonium sulfate,
Cu-lyt., potassium sulfite, sodium sulfite, ammonium bisulfite, Potassium acid sulfite, sodium thiosulfate,
At least one in Potassium hyposulfite., rongalite and sodium sulfite, preferably sodium sulfite；Described
Organic reducing agent is preferably amine reducing agent, described amine reducing agent be preferably N, N-dimethylethanolamine,
N, N '-dimethyl piperazine, N, N, N ', N '-tetramethylurea element and N, N, N ' and, in N '-tetramethylethylenediamine extremely
Few one, more preferably N, N, N ', N '-tetramethylethylenediamine.
In the preferred embodiment of the present invention, described initiator is 2, double (the 2-amidino groups third of 2 '-azo
Alkane) dihydrochloride, Ammonium persulfate., sodium sulfite and N, N, N ', N '-tetramethylethylenediamine.
According to the present invention, the condition of described solution polymerization can be the condition that this area is conventional.Such as,
Described polyreaction is carried out under an inert atmosphere, and described solution polymerization condition may include that polymerization is anti-
The initial temperature answered is-10 DEG C to 20 DEG C, preferably 5 DEG C to 15 DEG C；Time is 2-12 hour, preferably 4-8
Hour；PH value is 4-12, preferably 5-10.
Described inert atmosphere is the gas not reacted with raw material and product, such as, can be that this area is normal
At least one in group 0 element gas, preferably nitrogen in the nitrogen of rule or the periodic table of elements.
Described pH value can obtain by adding pH adjusting agent in polymerization system, described pH adjusting agent
Can be various acidic ph modifiers and/or alkaline pH adjusting agent, the described alkaline pH of this area routine
Regulator can be in inorganic alkaline compound, such as sodium hydroxide, potassium hydroxide and sodium carbonate at least
One, preferably sodium hydroxide；Described acidic ph modifier can be in hydrochloric acid, sulphuric acid and nitric acid
One or more.
In accordance with the present invention it is preferred that, described monomer F is for having structure shown in formula (9)-formula (11)
During at least one in monomer, described method also include being hydrolyzed resulting polymers after polyreaction and
Being dried, after described hydrolysis makes polyreaction, the degree of hydrolysis of resulting polymers can be 10-30%.Ability
The technical staff in territory could be aware that, the process of hydrolysis includes hydrolytic reagent and polymer reaction.Pass through
Hydrolysis, the construction unit shown in some acrylamide construction unit i.e. formula (1) is transformed into acrylates knot
Structure unit, i.e. the unit of structure shown in formula (7).
In the present invention, the condition of described hydrolysis is not particularly limited, under preferable case, and described hydrolysis
Condition include: temperature is 50-110 DEG C, preferably 70-90 DEG C；Time is 0.5-6 hour, is preferably
1-4 hour.
In the present invention, the definition of described degree of hydrolysis is same as above, does not repeats them here.Described hydrolysis
Degree is determined by the inventory of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent is the various inorganic alkalines being capable of above-mentioned purpose commonly used in the art
Compound, can be selected from one or more in sodium hydroxide, potassium hydroxide and sodium carbonate.Described hydrolysis
The consumption of agent can carry out suitable selection according to the degree of hydrolysis of acrylamide copolymer, so that acrylamide
The degree of hydrolysis of copolymer meets use requirement and is as the criterion.
Those skilled in the art could be aware that, by regulating the consumption of inorganic alkaline compound, and can
To obtain the acrylamide copolymer of different degree of hydrolysis.
In the present invention, the molal quantity of described inorganic alkaline compound rubbing equal to acrylates construction unit
That number.
According to the present invention, the present invention is to drying condition without particular/special requirement, and described drying means can use heat
Wind seasoning, described hot air drying temperature can be 40-120 DEG C, preferably 70-90 DEG C；Time is 0.2-4
Hour, preferably 0.5-2 hour.
Additionally, the preparation method of the present invention also includes the product being dried to obtain is pulverized and sieved, institute
State the condition pulverized and sieve reasonably to select according to prior art, do not repeat them here.
The present invention one preferred embodiment in, the preparation method bag of described acrylamide copolymer
Include following steps:
(1) acrylamide monomer, temperature-resistant anti-salt monomer, surface active function monomer and water are mixed shape
Become comonomer aqueous solution, regulate pH to 4-12 with inorganic alkaline compound, control solution polymerization
Initial temperature be-10 DEG C to 20 DEG C；
(2) in comonomer aqueous solution, logical nitrogen carries out deoxygenation, deoxygenation more than 30 minutes；
(3) under logical condition of nitrogen gas, add composite initiation system to monomer solution, carry out adiabatic poly-
Close, obtain copolymer gel；
(4) copolymer gel is carried out a pelletize, hydrolysis, secondary granulation, is dried, pulverizes and sieves
Get the acrylamide copolymer product of temperature-resistant anti-salt.
According to the present invention, in step (1), described temperature-resistant anti-salt monomer is monomer F of the present invention,
Described surface active function monomer is monomer G of the present invention, and described inorganic alkaline compound is used for adjusting
The pH value of the joint aqueous solution containing acrylamide, temperature-resistant anti-salt monomer and surface active monomer.Described nothing
Machine alkali compounds can be at least one in sodium hydroxide, potassium hydroxide and sodium carbonate, preferably hydrogen
Sodium oxide.
Present invention also offers the acrylamide copolymer prepared according to said method.
Additionally, present invention also offers the application in oil displacement agent of the described acrylamide copolymer.The present invention
The acrylamide copolymer provided is particularly useful as high temperature and high salt oil deposit Flooding Agent for EOR.
In following example, the performance test of product uses following methods to carry out:
1, solid content is measured according to the method for regulation in GB12005.2-89；
2, dissolution time is measured according to the method for regulation in GB12005.8-89；
3, intrinsic viscosity is measured according to the method for regulation in GB12005.1-89；
4, formula M=([η]/K) is used according to the method for regulation in GB12005.10-921/αCalculate polymerization
The viscosity-average molecular weight of thing, wherein, K=4.75 × 10-3, α=0.80, [η] is intrinsic viscosity；
5, the apparent viscosity of polymer solution is to be made into by polymer with the saline of salinity 32000mg/L
The solution of 1500mg/L, with Brookfield viscometer at 95 DEG C, 7.34s-1Under the conditions of measure.
6, survey according to Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation's company standard Q/SH10201572-2006
Determine filtration ratio and the AM residual monomer content of the aqueous solution of polymer.
In following example, commercially available from Beijing victory triumphant reach bulk material equipment company limited model be
Carry out pelletize on the comminutor of SLG (J)-120, reach bulk material equipment company limited commercially available from Beijing victory is triumphant
The pulverizer that model is DGF on pulverize.
In following example, acrylamide is commercially available from Bao Mo biochemical industry limited company, 2-acryloyl
Amido-2-methyl propane sulfonic acid commercially available from Xiamen Changtian Enterprise Co., Ltd., NVP, 2,2 '-
Double (2-amidine propane) dihydrochloride of azo is commercially available from Aldrich.
Embodiment 1
The preparation method of the acrylamide copolymer that the present embodiment provides for the present invention is described.
1000 grams of acrylamides (AM), 10 grams of 2-acrylamido-2-methyl-prop sulphurs are added in beaker
Acid and 10 grams of structures as shown in formula (15) surface active function monomer G (n ' be 16, according to document:
Xinyang Normal College's journal: natural science edition, the method system described in 2013,26 (2): 270-272
, the most identical), 4080 grams of deionized waters, under stirring, control solution temperature with chilled brine
5 DEG C, add sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle, adds 10.2
Milligram double (2-amidine propane) dihydrochlorides of water-soluble azo initiator 2,2 '-azo and 10.2 milligrams of amines
N, N, N ', N '-tetramethylethylenediamine, logical high pure nitrogen deoxygenation 0.5 hour, add 10.2 milligrams of sulfurous acids
Hydrogen sodium and 10.2 milligrams of Ammonium persulfate .s, continue logical nitrogen until thermocouple starts to warm up in polymerization bottle, reaction
8 hours time.Colloid is taken out, is become the copolymer micelle of 4-6 millimeter by granulator granulation.Will
The copolymer micelle arrived and the sodium hydroxide grain alkali kneading contact of 113.2 grams, hydrolyze 0.5 at temperature 90 DEG C
Hour, after secondary granulation, it is dried, by crushing and screening the product obtaining 20-80 mesh.Obtain
The performance of acrylamide copolymer be shown in Table 1.
Embodiment 2
The preparation method of the acrylamide copolymer that the present embodiment provides for the present invention is described.
1000 grams of acrylamides (AM), 1000 grams of 2-acrylamido-2-methyl-prop are added in beaker
The surface active function monomer G of sulfonic acid and 100 grams of structures as shown in formula (15) (n ' be 16), 4900
Gram deionized water, under stirring, controls solution temperature 15 DEG C with chilled brine, adds sodium hydroxide and adjusts
Joint pH to 7.Monomer solution is transferred in polymerization bottle, add 1.05 grams of water-soluble azo initiators 2,2 '-
Double (2-amidine propane) dihydrochloride of azo and 1.05 donaxine classes N, N, N ', N '-tetramethylethylenediamine, logical height
Pure nitrogen gas deoxygenation 0.5 hour, adds 1.05 grams of sodium sulfitees and 1.05 grams of Ammonium persulfate .s, continues logical nitrogen
Gas until in polymerization bottle thermocouple start to warm up, 4 hours response time.Colloid is taken out, passes through pelletize
Machine is a granulated into the copolymer micelle of 4-6 millimeter.By the copolymer micelle obtained and the hydroxide of 153.8 grams
Sodium grain alkali mediates contact, hydrolyzes 4 hours, after secondary granulation, be dried under temperature 70 C, logical
Cross and crush and screen the product obtaining 20-80 mesh.The performance of the acrylamide copolymer obtained is shown in Table 1.
Embodiment 3
The preparation method of the acrylamide copolymer that the present embodiment provides for the present invention is described.
1000 grams of acrylamides (AM) (14.069mol), 100 grams of 2-acrylamides are added in beaker
The surface active function monomer G of base-2-methyl propane sulfonic acid and 50 grams of structures as shown in formula (15) (n ' be
16), 3450 grams of deionized waters, under stirring, control solution temperature 10 DEG C with chilled brine, add
Sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle, adds 115 milligrams of water solublity
Double (2-amidine propane) dihydrochloride of azo initiator 2,2 '-azo and 115 milligrams of amine N, N, N ', N '-four
Methyl ethylenediamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium sulfitees and 115 millis
Gram Ammonium persulfate., continues logical nitrogen until thermocouple starts to warm up in polymerization bottle, 6 hours response time.
Colloid is taken out, is become the copolymer micelle of 4-6 millimeter by granulator granulation.The copolymer glue that will obtain
The grain sodium hydroxide grain alkali with 117.7 grams is mediated and is contacted, and hydrolyzes 2 hours, through secondary at temperature 80 DEG C
After pelletize, it is dried, by crushing and screening the product obtaining 20-80 mesh.The acrylamide obtained is altogether
The performance of polymers is shown in Table 1.
Embodiment 4
The preparation method of the acrylamide copolymer that the present embodiment provides for the present invention is described.
1000 grams of acrylamides (AM), 100 grams of 2-acrylamido-2-methyl-prop are added in beaker
The surface active function monomer G of sulfonic acid and 50 grams of structures as shown in formula (15) (n ' it is 18, according to literary composition
Offer: Xinyang Normal College's journal: natural science edition, the side described in 2013,26 (2): 270-272
Method prepares), 3450 grams of deionized waters, under stirring, control solution temperature 10 DEG C with chilled brine,
Add sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle, adds 115 milligrams of water
Double (2-amidine propane) dihydrochlorides of soluble azo initiator 2,2 '-azo and 115 milligrams of amines
N, N, N ', N '-tetramethylethylenediamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sulfurous acids
Hydrogen sodium and 115 milligrams of Ammonium persulfate .s, continue logical nitrogen until thermocouple starts to warm up in polymerization bottle, reaction
6 hours time.Colloid is taken out, is become the copolymer micelle of 4-6 millimeter by granulator granulation.Will
The copolymer micelle arrived and the sodium hydroxide grain alkali kneading contact of 117.6 grams, hydrolyze 2 at temperature 80 DEG C
Hour, after secondary granulation, it is dried, by crushing and screening the product obtaining 20-80 mesh.Obtain
The performance of acrylamide copolymer be shown in Table 1.
Embodiment 5
The preparation method of the acrylamide copolymer that the present embodiment provides for the present invention is described.
1000 grams of acrylamides (AM), 50 grams of 2-acrylamido-2-methyl-prop sulphurs are added in beaker
Acid, 50 grams of N, N-DMAAs and 50 grams of surface active functions of structure as shown in formula (15)
Monomer G (n ' be 16), 3450 grams of deionized waters, under stirring, control solution temperature with chilled brine
Spend 10 DEG C, add sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle, adds 115
Milligram double (2-amidine propane) dihydrochlorides of water-soluble azo initiator 2,2 '-azo and 115 milligrams of amines
N, N, N ', N '-tetramethylethylenediamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sulfurous acids
Hydrogen sodium and 115 milligrams of Ammonium persulfate .s, continue logical nitrogen until thermocouple starts to warm up in polymerization bottle, reaction
6 hours time.Colloid is taken out, is become the copolymer micelle of 4-6 millimeter by granulator granulation.Will
The copolymer micelle arrived and the sodium hydroxide grain alkali kneading contact of 119.8 grams, hydrolyze 2 at temperature 80 DEG C
Hour, after secondary granulation, it is dried, by crushing and screening the product obtaining 20-80 mesh.Obtain
The performance of acrylamide copolymer be shown in Table 1.
Embodiment 6
The preparation method of the acrylamide copolymer that the present embodiment provides for the present invention is described.
1000 grams of acrylamides (AM), 50 grams of 2-acrylamido-2-methyl-prop sulphurs are added in beaker
Acid, 50 grams of N-vinyl pyrrolidones and 50 grams of surface active function lists of structure as shown in formula (15)
Body G (n ' be 16), 3450 grams of deionized waters, under stirring, control solution temperature with chilled brine
10 DEG C, add sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle, adds 115
Milligram double (2-amidine propane) dihydrochlorides of water-soluble azo initiator 2,2 '-azo and 115 milligrams of amines
N, N, N ', N '-tetramethylethylenediamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sulfurous acids
Hydrogen sodium and 115 milligrams of Ammonium persulfate .s, continue logical nitrogen until thermocouple starts to warm up in polymerization bottle, reaction
6 hours time.Colloid is taken out, is become the copolymer micelle of 4-6 millimeter by granulator granulation.Will
The copolymer micelle arrived and the sodium hydroxide grain alkali kneading contact of 119.4 grams, hydrolyze 2 at temperature 80 DEG C
Hour, after secondary granulation, it is dried, by crushing and screening the product obtaining 20-80 mesh.Obtain
The performance of acrylamide copolymer be shown in Table 1.
Embodiment 7
The preparation method of the acrylamide copolymer that the present embodiment provides for the present invention is described.
Method same as in Example 2 is used to prepare acrylamide copolymer, except for the difference that, without water
Solve, the most do not carry out being mediated with sodium hydroxide grain alkali by the copolymer micelle obtained in embodiment 2 and contact,
The step of 4 hours is hydrolyzed at 70 DEG C.The performance of the acrylamide copolymer obtained is shown in Table 1.
Comparative example 1
Use method same as in Example 1 to prepare acrylamide copolymer, be except for the difference that added without such as formula
The surface active function monomer G of structure shown in (15) (n ' be 16), the reference acrylamide obtained is altogether
The performance of polymers is shown in Table 1.
Table 1
Data in conjunction with table 1 understand, and the acrylamide copolymer viscosity-average molecular weight that embodiment 1 obtains is permissible
Reach 34,000,000, and the viscosity-average molecular weight that comparative example 1 obtains acrylamide copolymer be only 28,000,000,
Embodiment 1 molecular weight of copolymer that relatively comparative example 1 obtains improves nearly 6,000,000, and at corresponding 95 DEG C
Apparent viscosity improves 11mPa s.Illustrate that in the present invention, the introducing of surface active function monomer is more beneficial for carrying
The apparent viscosity of copolymer solution under the viscosity-average molecular weight of high copolymer and hot conditions.
By embodiment 2 compared with Example 7, embodiment 7 obtains the viscous of acrylamide copolymer to divide equally
Son amount be the corresponding meter observing viscosity at 30,200,000,95 DEG C be 16.8mPa s, be below the finger of embodiment 2
Mark result.Illustrate that being suitably introduced into sodium acrylate construction unit in copolymer structure is more beneficial for improving copolymerization
The apparent viscosity of the copolymer solution under the molecular weight of thing and hot conditions.
As a example by embodiment 1, the temperature-resistant anti-salt acrylamide copolymer that the present invention obtains is in high salinity
Under the conditions of 32000mg/L and high temperature 95 DEG C, solution apparent viscosity is up to 25.0mPa s, and commercially available high score
The apparent viscosity of sub-weight polyacrylamide solution is only 8.9mPa s, compared with commercially available prod, the present invention's
Acrylamide copolymer has significantly thickening advantage.Accordingly, it is known that the acrylamide copolymerization that the present invention provides
Thing has good temperature-resistant anti-salt performance.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. an acrylamide copolymer, it is characterised in that this acrylamide copolymer contains structure list
Unit A, construction unit B and construction unit C, wherein, described construction unit A is for having formula (1) institute
Showing the unit of structure, described construction unit B is for having in the unit of structure shown in formula (2)-formula (5)
At least one, described construction unit C is for having the unit of structure shown in formula (6), and described structure
The weight ratio of unit A, described construction unit B and described construction unit C is 1:0.001-10:0.001-10,
The viscosity-average molecular weight of described acrylamide copolymer is 30,000,000-3,600 ten thousand,
Wherein, R1、R2、R6、R7、R10And R11It is each independently the alkyl of hydrogen or C1-C4,
R3For the alkylidene of C1-C14, R4And R5It is each independently the alkyl of hydrogen or C1-C15, R8With
R9It is each independently the alkyl of C1-C4, R12For the alkyl of C1-C3, n is the most whole in 6-22
Number, M1And M2It is each independently H, Na or K.
Acrylamide copolymer the most according to claim 1, wherein, described construction unit B is
There is structure shown at least one in the unit of structure shown in formula (2)-formula (4) and formula (7)
Unit:
Wherein, M3For K or Na.
Acrylamide copolymer the most according to claim 2, wherein, structure shown in formula (1)
In the unit of structure shown in unit, formula (2)-formula (4) at least one, structure shown in formula (6)
Shown in unit and formula (7), the weight ratio of the unit of structure is 1:0.001-10:0.001-10:0.1-1,
It is preferably 1:0.01-1.5:0.01-0.2:0.1-1；The viscosity-average molecular weight of described acrylamide copolymer is
32000000-3,500 ten thousand.
4. according to the acrylamide copolymer described in any one in claim 1-3, wherein, R2With
R7It is each independently hydrogen or methyl, R6For hydrogen, R3For the alkylidene of C1-C4, R4And R5The most solely
It is on the spot methyl, R8And R9It is each independently methyl or ethyl, M1For hydrogen；Described construction unit C
In, R12For methyl, n is 16 or 18.
5. a preparation method for acrylamide copolymer, this preparation method includes: anti-in polymerisation in solution
Under the conditions of Ying, in the presence of initiator, making a kind of monomer mixture carry out polyreaction in water, it be special
Levying and be, described monomer mixture contains monomer E, monomer F and monomer G, and described monomer E is for having
The monomer of structure shown in formula (8), described monomer F is for having structure shown in formula (9)-formula (12)
At least one in monomer, described monomer G is for having the monomer of structure shown in formula (13), and described list
The weight ratio of body E, described monomer F and described monomer G is 1:0.001-10:0.001-10；Described molten
After liquid polymeric reaction condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is 30,000,000-3600
Ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently the alkyl of hydrogen or C1-C4,
R3' it is the alkylidene of C1-C14, R4' and R5' it is each independently the alkyl of hydrogen or C1-C15, R8' and
R9' it is each independently the alkyl of C1-C4, R12' it is the alkyl of C1-C3, n ' is arbitrary in 6-22
Integer, M1' and M2' it is each independently H, Na or K.
Method the most according to claim 5, wherein, described monomer F is for having formula (9)-formula
(11) at least one in the monomer of structure shown in, and R2' and R7' it is each independently hydrogen or methyl,
R6' it is hydrogen, R3' it is the alkylidene of C1-C4, R4' and R5' it is each independently methyl, R8' and R9' each
From independently be methyl or ethyl, M1' it is hydrogen；In described monomer G, R12' be methyl, n ' be 16 or
18。
Method the most according to claim 5, wherein, when described solution polymerization starts, institute
Stating the weight of monomer mixture with the ratio of water and the gross weight of monomer mixture is 0.15-0.4:1, preferably
For 0.2-0.3:1.
Method the most according to claim 5, wherein, described initiator is selected from azo series initiators
With oxidoreduction series initiators, the consumption of described azo series initiators is the gross weight of monomer in monomer mixture
0.0001-0.1 weight % of amount, the consumption of described oxidoreduction series initiators is monomer in monomer mixture
0.0002-0.3 weight % of gross weight；Described azo series initiators is water-soluble azo series initiators,
Described oxidoreduction series initiators include Oxidizing and Reducing Agents, described reducing agent be inorganic reducing agent and/
Or organic reducing agent, and the weight ratio of described oxidant and described reducing agent is 0.1-1:1；Preferably,
Described water-soluble azo series initiators is selected from 2,2 '-azo double (2-amidine propane) dihydrochloride, 2,2 '-azo
At least one in double (2-imidazoline propane) dihydrochlorides and 4,4 '-azo double (4-cyanopentanoic acid)；Described oxygen
Agent is selected from benzoyl peroxide, hydrogen peroxide, tert-butyl hydroperoxide, the double (mistake of 2,5-dimethyl-2,5-
Hydrogen oxide) hexane, Ammonium persulfate., at least one in sodium peroxydisulfate and potassium peroxydisulfate；Described inorganic also
Former dose is selected from ferrous sulfate, Ferrous ammonium sulfate, Cu-lyt., potassium sulfite, sodium sulfite, sulfurous acid
In hydrogen ammonium, Potassium acid sulfite, sodium thiosulfate, Potassium hyposulfite., rongalite and sodium sulfite extremely
Few one；Described organic reducing agent be selected from N, N-dimethylethanolamine, N, N '-dimethyl piperazine,
N, N, N ', N '-tetramethylurea element and N, N, N ', at least one in N '-tetramethylethylenediamine.
Method the most according to claim 5, wherein, described solution polymerization is at inert atmosphere
Under carry out, described solution polymerization condition includes: the initial temperature of polyreaction is-10 DEG C to 20 DEG C；
Time is 2-12 hour；PH value is 4-112.
10. according to the method described in any one in claim 5-9, wherein, described monomer F is tool
When having at least one in the monomer of structure shown in formula (9)-formula (11), described method also includes poly-
After closing reaction, resulting polymers is hydrolyzed and is dried, and described hydrolysis makes resulting polymers after polyreaction
Degree of hydrolysis be 10-30%；Preferably, described hydrolysising condition includes: temperature is 50-110 DEG C, the time
For 0.5-6 hour；Described dry condition includes: temperature is 40-120 DEG C, and the time is 0.2-4 hour.
The acrylamide copolymer that in 11. claim 5-10, method described in any one prepares.
In 12. claim 1-4 and 11, the acrylamide copolymer described in any one is as oil displacement agent
Application.
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| CN108424493A (en) * | 2017-02-14 | 2018-08-21 | 中国石油化工股份有限公司 | A kind of acrylamide copolymer and its preparation method and application |
| CN114437292A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Acrylamide surface active polymer and preparation method and application thereof |
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| CN108424493A (en) * | 2017-02-14 | 2018-08-21 | 中国石油化工股份有限公司 | A kind of acrylamide copolymer and its preparation method and application |
| CN114437292A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Acrylamide surface active polymer and preparation method and application thereof |
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