CN106317314B - A kind of acrylamide copolymer and its preparation method and application - Google Patents
A kind of acrylamide copolymer and its preparation method and application Download PDFInfo
- Publication number
- CN106317314B CN106317314B CN201510363538.3A CN201510363538A CN106317314B CN 106317314 B CN106317314 B CN 106317314B CN 201510363538 A CN201510363538 A CN 201510363538A CN 106317314 B CN106317314 B CN 106317314B
- Authority
- CN
- China
- Prior art keywords
- formula
- monomer
- independently
- unit
- construction unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of acrylamide copolymer and its preparation method and application, the acrylamide copolymer contains construction unit A, construction unit B and construction unit C, wherein, construction unit A is the unit with structure shown in formula (1), construction unit B is with least one of unit of structure shown in formula (2) formula (5), construction unit C is the unit with structure shown in formula (6), and construction unit A, construction unit B and construction unit C weight ratio are 1：0.001‑10：0.001 10, the viscosity average molecular weigh of the acrylamide copolymer is 30,000,000 3,800 ten thousand, the acrylamide copolymer of the present invention has the characteristics of good water solubility, residual monomer content are low, molecular weight is high, particularly under high temperature and high salt conditions, the more conventional polyacrylamide of apparent viscosity of solution is substantially improved, and can be used as high temperature and high salt oil deposit Flooding Agent for EOR.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer, a kind of preparation method of acrylamide copolymer, by party's legal system
The application of standby acrylamide copolymer and the acrylamide copolymer.
Background technology
Polymer flooding is mainly the polymer solution by injecting certain scale, increases displacement fluid viscosity, reduces oil-reservoir water
Phase permeability come reduce mobility ratio, adjustment intake profile, with reach improve displacement phase volume purpose, and then improve recovery ratio.
As main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (PHPA) (HPAM) is in conventional oil reservoir tertiary oil recovery
(EOB) in technology, large-scale promotion and application have been obtained, important function has been played for oilfield stable production and volume increase.With routine
The reduction of reservoir reserve, high temperature and high salt oil deposit cause HPAM application to be faced with many problems, and it is high to be mainly reflected in exploitation high temperature
Compound action caused by dissolved oxygen causes HPAM solution viscosities to be greatly reduced in high temperature, high salt and solution during salt oil deposit, causes
HPAM oil displacement efficiencies are not notable.Research shows that, when temperature is higher than 70 DEG C, HPAM acylamino- hydrolysis generation carboxyl significantly adds
Play, when degree of hydrolysis reaches more than 40%, carboxyl is just easy to and Ca in solution2+、Mg2+Ion generation precipitation, damages solution viscosity
Lose.In addition, at high temperature, when dissolved oxygen be present in oxygen and solution in air, main polymer chain fracture can be also caused to glue solution
Degree is remarkably decreased.
In order to improve the temperature-resistant anti-salt performance of polyacrylamide, a large amount of tackling key problem researchs have been carried out both at home and abroad, mainly around poly-
Chain yardstick, chain size distribution, construction unit composition, the micro-sequential structure of compound carry out a large amount of correlative study work, such as heatproof
Salt resistance monomer-polymer, hydrophobic associated polymer, amphiphilic polymers, composite polymer, comb polymer, template polymer and
Surface-active polymer etc..Such as entitled " the low temperature synthesis of AMPS/AM copolymers and performance " (Chang Zhiying, polymer material science
With engineering, 1997,13,16) with acrylamide (AM) and heat-resistant salt-resistant monomer 2- acrylamide-2-methylpro panesulfonic acids (AMPS)
Copolymerization bipolymer.As CN101260171A discloses a kind of comb-type structure activity polymer and its preparation technology with answering
With being synthesized by polyurethanes surface-active macromonomer with monomer copolymerizations such as acrylamides with tackifying and reduce interfacial tension target
Product.The polymer that above two method obtains respectively has its feature, some performances for example temperature tolerance, salt-resistance, shear resistant and
More traditional polyacrylamide increases really in surface-active index, but technological operation is relatively cumbersome, and obtains product point
Son amount is small (being no more than 20,000,000), causes the applicable of polymer to be restricted.
The content of the invention
It is an object of the invention to overcome the drawbacks described above of prior art, there is provided a kind of acrylamide copolymer, Yi Zhongbing
The preparation method of acrylamide copolymer, by this method prepare acrylamide copolymer and the acrylamide copolymer should
With.
The present invention provides a kind of acrylamide copolymer, wherein, the acrylamide copolymer contains construction unit A, structure
Unit B and construction unit C, wherein, the construction unit A is the unit with structure shown in formula (1), and the construction unit B is
With formula (2)-at least one of unit of structure shown in formula (5), the construction unit C is with structure shown in formula (6)
Unit, and the construction unit A, the construction unit B and the construction unit C weight ratio are 1：0.001-10：0.001-
10, the viscosity average molecular weigh of the acrylamide copolymer is 30,000,000-3,800 ten thousand,
Wherein, R1、R2、R6、R7、R10And R11It is each independently hydrogen or C1-C4 alkyl, R3For C1-C14 alkylidene,
R4And R5It is each independently hydrogen or C1-C15 alkyl, R8And R9It is each independently C1-C4 alkyl, R12、R13、R14、R15
And R16It is each independently C1-C3 alkylidene, R17、R18And R19C1-C3 alkyl is each independently, n is any in 1-15
Integer, 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 acrylamide
The construction unit of construction unit and temperature-resistant anti-salt monomer is formed, and is being ensured polymeric water-soluble simultaneously, can improved polymer point
The temperature-resistant anti-salt performance of son.In addition, copolymer side chain is made up of the construction unit of surface active function monomer, has and produce molecule
Between association, increase slack time of molecular motion, improve solution viscoplasticity and reduce the effect of oil water interfacial tension.
The present invention also provides a kind of preparation method of acrylamide copolymer, and the preparation method includes：It is anti-in polymerisation in solution
Under the conditions of answering, in the presence of initiator, a kind of monomer mixture is set to carry out polymerisation in water, wherein, the monomer mixing
Thing contains monomer E, monomer F and monomer G, the monomer E are the monomer with structure shown in formula (8), and the monomer F is with formula
(9) at least one of monomer of structure shown in-formula (12), the monomer G are the monomer with structure shown in formula (13), and institute
The weight ratio for stating monomer E, the monomer F and the monomer G is 1：0.001-10：0.001-10；The solution polymerization bar
Part make it that the viscosity average molecular weigh of resulting polymers after polymerisation is 30,000,000-3,800 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently hydrogen or C1-C4 alkyl, R3' for C1-C14's
Alkylidene, R4' and R5' it is each independently hydrogen or C1-C15 alkyl, R8' and R9' C1-C4 alkyl is each independently,
R12’、R13’、R14’、R15' and R16' it is each independently C1-C3 alkylidene, R17’、R18' and R19' it is each independently C1-
C3 alkyl, n ' be 1-15 in arbitrary integer, M1' and M2' it is each independently H, Na or K.
Present invention also offers the acrylamide copolymer prepared by the above method.
In addition, present invention also offers application of the aforesaid propylene amide copolymer as oil displacement agent.
Acrylamide copolymer provided by the invention has the characteristics of good water solubility, residual monomer content are low, molecular weight is high,
Particularly under conditions of high temperature and high salt, the more conventional polyacrylamide of apparent viscosity of solution is substantially improved.Specifically, originally
The acrylamide copolymer molecular weight of invention reaches as high as 34,500,000, particularly in 95 DEG C of high salinity 32000mg/L and high temperature
Under conditions of, the apparent viscosity of solution reaches as high as 26.0mPas, and the molecular weight of commercially available high molecular weight polyacrylamide is only
26,000,000 or so, the apparent viscosity of solution is only 8.9mPas, compared with commercially available prod, acrylamide of the invention copolymerization
Thing, which has, significantly thickens advantage, can be used as high temperature and high salt oil deposit Flooding Agent for EOR.
The preparation method step of acrylamide copolymer provided by the invention is simple, and obtained acrylamide copolymer has water
The characteristics of dissolubility is good, residual monomer content is low, molecular weight is high, particularly under conditions of high temperature and high salt, contain the present invention's
The more conventional polyacrylamide of apparent viscosity of the solution of acrylamide copolymer is substantially improved, and can be used as high temperature and high salt oil deposit
Flooding Agent for EOR.
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 present invention provides a kind of acrylamide copolymer, wherein, the acrylamide copolymer contains construction unit A, structure
Unit B and construction unit C, wherein, the construction unit A is the unit with structure shown in formula (1), and the construction unit B is
With formula (2)-at least one of unit of structure shown in formula (5), the construction unit C is with structure shown in formula (6)
Unit, and the construction unit A, the construction unit B and the construction unit C weight ratio are 1：0.001-10：0.001-
10, preferably 1：0.01-1.5：0.01-0.2, more preferably 1：0.01-1：0.01-0.1；The acrylamide copolymer
Viscosity average molecular weigh be 30,000,000-3,800 ten thousand, preferably 32,000,000-3,500 ten thousand；
Wherein, R1、R2、R6、R7、R10And R11It is each independently hydrogen or C1-C4 alkyl, R3For C1-C14 alkylidene,
R4And R5It is each independently hydrogen or C1-C15 alkyl, R8And R9It is each independently C1-C4 alkyl, R12、R13、R14、R15
And R16It is each independently C1-C3 alkylidene, R17、R18And R19C1-C3 alkyl is each independently, n is any in 1-15
Integer, M1And M2Each stand alone as H, Na or K.
In the present invention, the alkyl of the C1-C4 can be straight chain or side chain.The alkyl of the C1-C4
Example can include：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
In the present invention, the alkylidene of the C1-C14 can be straight or branched, the reality of the alkylidene of the C1-C14
Example can include but is not limited to：Methylene, ethylidene, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, isobutylidene
With the sub- tert-butyl group, sub- n-pentyl, isoamylidene, sub- tertiary pentyl, sub- neopentyl, sub- n-hexyl, sub- n-heptyl, sub- n-octyl, Asia
N-nonyl, sub- positive decyl, sub- positive hendecyl, sub- positive dodecyl, sub- positive tritriacontyl and sub- positive tetradecyl.The alkylidene refers to alkane
Hydrocarbon loses the residue after two hydrogen atoms, and described two hydrogen atoms can be two hydrogen atoms on same carbon atom, also may be used
Can be straight chain or side chain with two hydrogen atoms on different carbon atoms, for example, the ethylidene can be-
CH2CH2- or-CH (CH3)-。
In the present invention, the alkyl of the C1-C15 can be straight chain or side chain.The alkane of the C1-C15
The example of base can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group,
N-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, just
Dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base.
In the present invention, although as long as containing construction unit A, construction unit B and construction unit C and meeting aforementioned proportion pass
The purpose of the present invention can be achieved in system, but under preferable case, on the basis of the total amount of the acrylamide copolymer, the structure
Unit A content is 30-99 weight %.
According to the present invention, in order that acrylamide copolymer has good viscoplasticity, under preferable case, the structure list
First B be with formula (2)-unit of structure shown at least one of unit of structure shown in formula (4) and formula (7)：
Wherein, M2For K or Na, preferably Na；R1As hereinbefore defined.
The present invention does not specially require to the content of the unit of structure shown in formula (7), for instance, it is preferred that being tied shown in formula (1)
Unit, formula (2)-at least one of unit of structure shown in formula (4), the unit of structure shown in formula (6) and the formula (7) of structure are shown
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 the formula (7) can be polymerize by acrylate monomers raw material
Obtain or obtained as the construction unit shown in some acrylamide construction unit i.e. formula (1) by hydrolysis, it is further preferred that
Construction unit shown in formula (7) is that construction unit shown in formula (1) is obtained by hydrolysis as some acrylamide construction unit.This
The technical staff in field could be aware that the process of hydrolysis includes reacting hydrolytic reagent and acrylamide copolymer, it is preferable that
The dosage of the hydrolytic reagent make it that the degree of hydrolysis of acrylamide copolymer is 10-30%.
In the present invention, the condition of the hydrolysis is not particularly limited, under preferable case, the condition bag of the hydrolysis
Include：Temperature is 50-110 DEG C, preferably 70-90 DEG C；Time is 0.5-6 hours, preferably 1-4 hours.
In the present invention, the degree of hydrolysis refers to that the molal quantity of acrylates construction unit accounts for acrylamide of the invention and is total to
The percentage of the total mole number of the construction unit of polymers.The degree of hydrolysis is determined by the inventory of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent is the various inorganic alkaline compounds that can realize above-mentioned purpose commonly used in the art,
Can be selected from the one or more in sodium hydroxide, potassium hydroxide and sodium carbonate.The dosage of the hydrolytic reagent can be according to propylene
The degree of hydrolysis of amide copolymer carries out appropriate selection, so that the degree of hydrolysis of acrylamide copolymer meets that requirement is defined.
Those skilled in the art could be aware that, by adjusting the dosage of inorganic alkaline compound, can obtain not
With the acrylamide copolymer of degree of hydrolysis.In the present invention, the molal quantity of the inorganic alkaline compound is equal to shown in formula (7) and tied
The molal quantity of the acrylates construction unit of structure.
The present inventor has found under study for action, is made up of specific construction unit A, construction unit B, construction unit C
Polymer be used to that during oil displacement agent preferable oil displacement efficiency can be obtained it is good.For instance, it is preferred that R2And R7Be each independently hydrogen or
Methyl；R6For hydrogen；R3For C1-C4 alkylidene, R4And R5It is each independently methyl；R8And R9It is each independently methyl or second
Base, M1For hydrogen；In the construction unit C, R12、R13、R14、R15And R16It is each independently methylene, R17、R18And R19Each solely
It is on the spot methyl, n is arbitrary integer in 1-11, it is further preferred that described have construction unit C for formula (14) Suo Shi
Unit,
The present invention also provides a kind of preparation method of acrylamide copolymer, and the preparation method includes：It is anti-in polymerisation in solution
Under the conditions of answering, in the presence of initiator, a kind of monomer mixture is set to carry out polymerisation in water, wherein, the monomer mixing
Thing contains monomer E, monomer F and monomer G, the monomer E are the monomer with structure shown in formula (8), and the monomer F is with formula
(9) at least one of monomer of structure shown in-formula (12), the monomer G are the monomer with structure shown in formula (13), and institute
The weight ratio for stating monomer E, the monomer F and the monomer G is 1：0.001-10：0.001-10, more preferably 1：0.01-1.5：
0.01-0.2, most preferably 1：0.01-1：0.01-0.1；Gained polymerize after the solution polymerization condition causes polymerisation
The viscosity average molecular weigh of thing is 30,000,000-3,800 ten thousand, preferably 32,000,000-3,500 ten thousand,
Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently hydrogen or C1-C4 alkyl, R3' for C1-C14's
Alkylidene, R4' and R5' it is each independently hydrogen or C1-C15 alkyl, R8' and R9' C1-C4 alkyl is each independently,
R12’、R13’、R14’、R15' and R16' it is each independently C1-C3 alkylidene, R17’、R18' and R19' it is each independently C1-
C3 alkyl, n ' be 1-15 in arbitrary integer, M1' and M2' it is each independently H, Na or K.
In the present invention, monomer E is preferably the 30-99 weight % of monomer mixture gross mass.
In the present invention, the monomer F is temperature-resistant anti-salt monomer, and the example of the monomer F can be but be not limited to：Propylene
Acid, 2- acrylamide-2-methylpro panesulfonic acids, N, N- DMAAs, N, N- acrylamides, N- vinylpyridines
Press against alkanone, 2- acrylamidos-dodecane sulfonic acid, 2- acrylamidos-tetradecane sulfonic acid, 2- acrylamidos-hexadecane sulphur
One or more in acid.
The present inventor has found under study for action, when selecting specific monomer E, monomer F and monomer G to be reacted,
The oil displacement efficiency of the polymer of gained can further be improved.For instance, it is preferred that the monomer F is shown in formula (9)-formula (11)
At least one of monomer of structure, and R2' and R7' it is each independently hydrogen or methyl, R6' it is hydrogen, R3' be C1-C4 alkylene
Base, R4' and R5' it is each independently methyl, R8' and R9' it is each independently methyl or ethyl, M1' it is hydrogen；In the monomer G,
R12’、R13’、R14’、R15' and R16' it is each independently methylene, R17’、R18' and R19' methyl is each independently, n ' is 1-
Arbitrary integer in 11.It is further preferred that the monomer G is the monomer with structure shown in formula (15),
In the present invention, the monomer G can be prepared according to the conventional method of this area, such as according to document
Percec,V.；Cho,W.D.；Mosier,P.E.；Ungar,G.；Yeardley,D.J.P.J.Am.Chem.Soc.1998,
Method in 120,11061-11070 is reacted by Williamson to be synthesized.
According to the present invention, the solution polymerization is carried out in water, when the solution polymerization starts, the monomer
There is no particular limitation for the ratio of the weight and water of mixture and the gross weight of monomer mixture, can become in wider scope
Dynamic, under preferable case, the ratio of the weight and water of the monomer mixture and the gross weight of monomer mixture is 0.15-0.4：1,
More preferably 0.2-0.3：1.
In the present invention, the initiator can be the various initiators in this area.For example, the initiator can be selected from occasionally
Nitrogen series initiators and/or redox system initiator, preferably azo series initiators and redox system initiator.It is described
The dosage of azo series initiators is 0.0001-0.1 the weight %, preferably 0.001- of the gross weight of monomer in monomer mixture
0.05 weight %；The dosage of the redox series initiators is the 0.0002-0.3 weights of the gross weight of monomer in monomer mixture
Measure %, preferably 0.002-0.15 weight %.The azo series initiators are preferably water-soluble azo series initiators, the oxidation
Reduction series initiators include Oxidizing and Reducing Agents, and the reducing agent is inorganic reducing agent and/or organic reducing agent, and the oxygen
Agent and the weight ratio of the reducing agent are 0.1-1:1.
In the present invention, the water-soluble azo series initiators are preferably 2, double (2- amidine propanes) two hydrochloric acid of 2 '-azo
Salt, 2, at least one of double (the 2- imidazolines propane) dihydrochlorides of 2 '-azo and 4,4'- azo double (4- cyanopentanoic acids), enter
One step is preferably 2,2 '-azo (2- amidine propanes) dihydrochloride.
In the present invention, the oxidant can be in acyl peroxide, hydroperoxides and persulfate at least one
Kind, preferably benzoyl peroxide, hydrogen peroxide, TBHP, 2,5- dimethyl -2,5- double (hydrogen peroxide) oneself
At least one of alkane, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate, more preferably ammonium persulfate and/or potassium peroxydisulfate.
In the present invention, the reducing agent can be inorganic reducing agent and/or organic reducing agent, preferably inorganic reducing agent
And organic reducing agent.The inorganic reducing agent can be selected from ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sulfurous
At least one in sour sodium, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium hydrogensulfite
Kind, preferably sodium hydrogensulfite；The organic reducing agent is preferably amine reducing agent, and the amine reducing agent is preferably N, N- bis-
Methylethanolamine, N, N '-dimethyl piperazine, N, N, N ', N '-tetramethylurea element and N, N, N ', in N '-tetramethylethylenediamine extremely
Few one kind, more preferably N, N, N ', N '-tetramethylethylenediamine.
In the preferred embodiment of the present invention, the initiator is 2, double (2- amidine propanes) disalts of 2 '-azo
Hydrochlorate, ammonium persulfate, sodium hydrogensulfite and N, N, N ', N '-tetramethylethylenediamine.
According to the present invention, the condition of the solution polymerization can be the conventional condition in this area.For example, the polymerization
Reaction is carried out in the presence of an inert gas, and the polymeric reaction condition can include：The initial temperature of polymerisation be -10 DEG C extremely
20 DEG C, preferably 5 DEG C to 15 DEG C；Time is 2-12 hours, preferably 4-8 hours；PH value is 4-12, preferably 5-10.
The inert gas is the gas not reacted with raw material and product, such as can be the conventional nitrogen in this area
Or at least one of group 0 element gas in the periodic table of elements, preferably nitrogen.
The pH value can be obtained by adding pH adjusting agent into polymerization system, and the pH adjusting agent can be this area
Conventional various acidic ph modifiers and/or alkaline pH adjusting agent, the alkaline pH adjusting agent can be inorganic alkaline compound,
Such as at least one of sodium hydroxide, potassium hydroxide and sodium carbonate, preferably sodium hydroxide；The acidic ph modifier can be with
For the one or more in hydrochloric acid, sulfuric acid and nitric acid.
In accordance with the present invention it is preferred that the monomer F is with least one in formula (9)-monomer of structure shown in formula (11)
During kind, methods described also includes resulting polymers after polymerisation are hydrolyzed and dried, and the hydrolysis causes polymerisation
The degree of hydrolysis of resulting polymers can be 10-30% afterwards.Those skilled in the art could be aware that the process of hydrolysis includes
By hydrolytic reagent and polymer reaction.By hydrolysis, some acrylamide construction unit is that the construction unit shown in formula (1) is transformed into
Acrylates construction unit, i.e. the unit of structure shown in formula (7).
In the present invention, the condition of the hydrolysis is not particularly limited, under preferable case, the condition bag of the hydrolysis
Include：Temperature is 50-110 DEG C, preferably 70-90 DEG C；Time is 0.5-6 hours, preferably 1-4 hours.
In the present invention, the degree of hydrolysis refers to that the molal quantity of acrylates construction unit accounts for acrylamide of the invention and is total to
The percentage of the total mole number of the construction unit of polymers.The degree of hydrolysis is determined by the inventory of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent is the various inorganic alkaline compounds that can realize above-mentioned purpose commonly used in the art,
Can be selected from the one or more in sodium hydroxide, potassium hydroxide and sodium carbonate.The dosage of the hydrolytic reagent can be according to propylene
The degree of hydrolysis of amide copolymer carries out appropriate selection, so that the degree of hydrolysis of acrylamide copolymer meets that requirement is defined,
It is preferred that the dosage of inorganic alkaline compound make it that the degree of hydrolysis of acrylamide copolymer is 10-30%.
Those skilled in the art could be aware that, by adjusting the dosage of inorganic alkaline compound, can obtain not
With the acrylamide copolymer of degree of hydrolysis.
In the present invention, the molal quantity of the inorganic alkaline compound is equal to the molal quantity of acrylates construction unit.
According to the present invention, the present invention can use hot-air seasoning to drying condition without particular/special requirement, the drying means,
The heated-air drying temperature can be 40-120 DEG C, preferably 70-90 DEG C；Time is 0.2-4 hours, preferably 0.5-2 hours.
In addition, the present invention preparation method also include the product being dried to obtain is crushed and sieved, it is described crushing and
The condition of screening can reasonably be selected according to prior art, will not be repeated here.
In a kind of preferred embodiment of the present invention, the preparation method of the acrylamide copolymer includes following step
Suddenly：
(1) acrylamide monomer, temperature-resistant anti-salt monomer, surface active function monomer and water are mixed to form comonomer water
Solution, pH to 4-12 is adjusted with inorganic alkaline compound, the initial temperature for controlling polymerisation in solution is -10 DEG C to 20 DEG C；
(2) lead to nitrogen into the comonomer aqueous solution and carry out deoxygenation, deoxygenation more than 30 minutes；
(3) under logical condition of nitrogen gas, composite initiation system is added to monomer solution, adiabatic polymerisation is carried out, is copolymerized
Thing gel；
(4) by copolymer gel progress, once granulation, hydrolysis, secondary granulation, drying, crushing and screening obtain temperature-resistant anti-salt
Acrylamide copolymer product.
According to the present invention, in step (1), the temperature-resistant anti-salt monomer is monomer F of the present invention, the surface-active work(
Energy monomer is monomer G of the present invention, and the inorganic alkaline compound is used to adjust containing acrylamide, temperature-resistant anti-salt monomer
With the pH value of the aqueous solution of surface active monomer.The inorganic alkaline compound can be sodium hydroxide, potassium hydroxide and carbonic acid
At least one of sodium, preferably sodium hydroxide.
Present invention also offers the acrylamide copolymer according to made from the above method.
In addition, the application present invention also offers the acrylamide copolymer in oil displacement agent.Provided by the invention third
Acrylamide copolymer is particularly useful as high temperature and high salt oil deposit Flooding Agent for EOR.The method of application is referred to existing skill
Art, it will not be repeated here.
In following examples, the performance test of product is carried out using following methods：
1st, the method according to specified in GB12005.2-89 determines solid content；
2nd, method determines dissolution time according to specified in GB12005.8-89；
3rd, the method according to specified in GB12005.1-89 determines intrinsic viscosity；
4th, method uses formula M=([η]/K) according to specified in GB12005.10-921/αTo calculate the viscous equal of polymer
Molecular weight, wherein, K=4.75 × 10-3, α=0.80, [η] is intrinsic viscosity；
5th, the apparent viscosity of polymer solution is that polymer is made into 1500mg/L's with salinity 32000mg/L salt solution
Solution, with Brookfield viscosimeters at 95 DEG C, 7.34s-1Under the conditions of determine.
6th, polymer is determined according to Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard Q/SH10201572-2006
Filtration ratio, insolubles content and the AM residual monomer contents of the aqueous solution.
In following examples, winning the triumphant model SLG's (J) -120 up to bulk material equipment Co., Ltd commercially available from Beijing
It is granulated on comminutor, it is enterprising in the pulverizer for winning the triumphant model DGF up to bulk material equipment Co., Ltd commercially available from Beijing
Row crushes.
In following examples, acrylamide is commercially available from Bao Mo biochemical industries limited company, 2- acrylamido -2- first
Base propane sulfonic acid is commercially available from Xiamen Changtian Enterprise Co., Ltd., NVP, 2,2 '-azo (2- amidine propanes) disalt
Hydrochlorate is commercially available from Aldrich.Monomer reference literature Percec, V. shown in the formula (15)；Cho,W.D.；Mosier,
P.E.；Ungar,G.；Yeardley, D.J.P.J.Am.Chem.Soc.1998,120,11061-11070 method pass through
It is prepared by Williamson reactions.
Embodiment 1
The present embodiment is used for the preparation method for illustrating acrylamide copolymer provided by the invention
1000 grams of acrylamides (AM), 10 grams of 2- acrylamide-2-methylpro panesulfonic acids and 10 grams are added in beaker such as
The surface active function monomer of structure shown in formula (15), 4080 grams of deionized waters, under stirring, solution is controlled with chilled brine
5 DEG C of temperature, add sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle, adds 10.2 milligrams of water-soluble azos
Initiator 2, double (2- amidine propanes) dihydrochlorides of 2 '-azo and 10.2 milligrams of amines N, N, N ', N '-tetramethylethylenediamine, lead to
High pure nitrogen deoxygenation 0.5 hour, 10.2 milligrams of sodium hydrogensulfites and 10.2 milligrams of ammonium persulfates are added, continue logical nitrogen until poly-
Close thermocouple in bottle to start to warm up, 8 hours reaction time.Colloid is taken out, the copolymer of 4-6 millimeters is granulated into by comminutor
Micelle.Obtained copolymer micelle is mediated with 113 grams of sodium hydroxide grain alkali and contacted, is hydrolyzed 0.5 hour at 90 DEG C of temperature,
After secondary granulation, it is dried, by crushing and screening to obtain the product of 20-80 mesh.The property of obtained acrylamide copolymer
It can be listed in Table 1 below.
Embodiment 2
The present embodiment is used for the preparation method for illustrating acrylamide copolymer provided by the invention
1000 grams of acrylamides (AM) of addition, 1000 grams of 2- acrylamide-2-methylpro panesulfonic acids and 100 grams in beaker
The surface active function monomer of structure as shown in formula (15), 4900 grams of deionized waters, under stirring, controlled with chilled brine molten
15 DEG C of liquid temperature degree, add sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle, it is even to add 1.05 grams of water solubilitys
Nitrogen initiator 2, double (2- amidine propanes) dihydrochlorides of 2 '-azo and 1.05 donaxine class N, N, N ', N '-tetramethylethylenediamine, lead to
High pure nitrogen deoxygenation 0.5 hour, 1.05 grams of sodium hydrogensulfites and 1.05 grams of ammonium persulfates are added, continue logical nitrogen until polymerization bottle
Middle thermocouple starts to warm up, 4 hours reaction time.Colloid is taken out, the copolymer glue of 4-6 millimeters is granulated into by comminutor
Grain.Obtained copolymer micelle is mediated with 151.9 grams of sodium hydroxide grain alkali and contacted, is hydrolyzed 4 hours under temperature 70 C, is passed through
After secondary granulation, it is dried, by crushing and screening to obtain the product of 20-80 mesh.The performance of obtained acrylamide copolymer
It is listed in Table 1 below.
Embodiment 3
The present embodiment is used for the preparation method for illustrating acrylamide copolymer provided by the invention
1000 grams of acrylamides (AM), 100 grams of 2- acrylamide-2-methylpro panesulfonic acids and 50 grams are added in beaker such as
The surface active function monomer of structure shown in formula (15), 3450 grams of deionized waters, under stirring, solution is controlled with chilled brine
10 DEG C of temperature, add sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle, adds 115 milligrams of water-soluble azos
Initiator 2, double (2- amidine propanes) dihydrochlorides of 2 '-azo and 115 milligrams of amines N, N, N ', N '-tetramethylethylenediamine, lead to height
Pure nitrogen gas deoxygenation 0.5 hour, 115 milligrams of sodium hydrogensulfites and 115 milligrams of ammonium persulfates are added, continue logical nitrogen until polymerization bottle
Middle thermocouple starts to warm up, 6 hours reaction time.Colloid is taken out, the copolymer glue of 4-6 millimeters is granulated into by comminutor
Grain.Obtained copolymer micelle is mediated with 116.8 grams of sodium hydroxide grain alkali and contacted, hydrolyze 2 hours at 80 DEG C of temperature, warp
After secondary granulation, it is dried, by crushing and screening to obtain the product of 20-80 mesh.The performance of obtained acrylamide copolymer
It is listed in Table 1 below.
Embodiment 4
1000 grams of acrylamides (AM), 50 grams of 2- acrylamide-2-methylpro panesulfonic acids, 50 grams of N, N- are added in beaker
The surface active function monomer of DMAA (0.504mol) and 50 grams of structures as shown in formula (15), 3450 grams of deionizations
Water, under stirring, 10 DEG C of solution temperature is controlled with chilled brine, add sodium hydroxide regulation pH to 7.Monomer solution is shifted
Into polymerization bottle, 115 milligrams of water-soluble azo initiators 2, double (2- amidine propanes) dihydrochlorides of 2 '-azo and 115 millis are added
Donaxine class N, N, N ', N '-tetramethylethylenediamine, lead to high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium hydrogensulfites and 115
Milligram ammonium persulfate, continue logical nitrogen until thermocouple starts to warm up in polymerization bottle, 6 hours reaction time.Colloid is taken out, led to
Cross the copolymer micelle that comminutor is granulated into 4-6 millimeters.Obtained copolymer micelle is pinched with 118.9 grams of sodium hydroxide grain alkali
Splice grafting touches, and hydrolyzes 2 hours, after secondary granulation, is dried, by crushing and screening to obtain 20-80 purposes at 80 DEG C of temperature
Product.The performance of obtained acrylamide copolymer is listed in Table 1 below.
Embodiment 5
1000 grams of acrylamides (AM), 50 grams of 2- acrylamide-2-methylpro panesulfonic acids, 50 grams of N- second are added in beaker
The surface active function monomer of alkenyl pyrrolidone and 50 grams of structures as shown in formula (15), 3450 grams of deionized waters, stirring
Under, 10 DEG C of solution temperature is controlled with chilled brine, adds sodium hydroxide regulation pH to 7.Monomer solution is transferred in polymerization bottle,
Double (2- amidine propanes) dihydrochlorides of 115 milligrams of water-soluble azo initiator 2,2 '-azos and 115 milligrams of amines N, N are added,
N ', N '-tetramethylethylenediamine, leads to high pure nitrogen deoxygenation 0.5 hour, adds 115 milligrams of sodium hydrogensulfites and 115 milligrams of persulfuric acid
Ammonium, continue logical nitrogen until thermocouple starts to warm up in polymerization bottle, 6 hours reaction time.Colloid is taken out, made by comminutor
Copolymer micelle of the grain into 4-6 millimeters.Obtained copolymer micelle is mediated with 118.4 grams of sodium hydroxide grain alkali and contacted,
Hydrolyze 2 hours at 80 DEG C of temperature, after secondary granulation, be dried, by crushing and screening to obtain the product of 20-80 mesh.Obtain
The performance of acrylamide copolymer be listed in Table 1 below.
Embodiment 6
Acrylamide copolymer is prepared using method same as Example 2, unlike, without hydrolysis, that is, do not have
Carry out mediating obtained copolymer micelle with sodium hydroxide grain alkali in embodiment 2 to contact, the step of 4 hours is hydrolyzed at 70 DEG C
Suddenly.The performance of obtained acrylamide copolymer is listed in Table 1 below.
Comparative example 1
Acrylamide copolymer is prepared using method same as Example 1, unlike, it is added without as shown in formula (15)
The surface active function monomer of structure, the performance of obtained acrylamide copolymer are listed in Table 1 below.
Table 1
Understand that the acrylamide copolymer molecular weight that embodiment 1 obtains can reach 34,500,000 with reference to the data of table 1, and
It is only 28,000,000 that comparative example 1, which obtains acrylamide copolymer molecular weight product, and embodiment 1 is compared with the copolymer point that comparative example 1 obtains
Son amount improves nearly 6,500,000, and corresponding 95 DEG C of apparent viscosities improve 12mPas.Illustrate drawing for surface active function monomer in the present invention
Enter the apparent viscosity of copolymer solution under the molecular weight for being more beneficial for improving copolymer and hot conditions.
By embodiment 2 compared with Example 6, the molecular weight that acrylamide copolymer is obtained in embodiment 6 is 30,500,000,95
DEG C corresponding meter observing viscosity is 17.0mPas, is below the index result of embodiment 2.Illustrate to be suitably introduced into copolymer structure
PAA construction unit is more beneficial for improving the molecular weight of copolymer and the apparent viscosity of the copolymer solution under hot conditions.
By taking embodiment 1 as an example, the obtained temperature-resistant anti-salt acrylamide copolymer of the present invention in high salinity 32000mg/L,
Under the conditions of 95 DEG C of high temperature, solution sees viscosity up to 26.0mPas, and commercially available high molecular weight polyacrylamide solution apparent viscosity
Only 8.9mPas, compared with commercially available prod, acrylamide copolymer of the invention, which has, significantly thickens advantage.Accordingly, it is known that
Acrylamide copolymer provided by the invention has good temperature-resistant anti-salt performance.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.It is further to note that described in above-mentioned embodiment
Each particular technique feature, in the case of reconcilable, can be combined by any suitable means.In order to avoid not
Necessary repetition, the present invention no longer separately illustrate to various combinations of possible ways.
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 (16)
- A kind of 1. acrylamide copolymer, it is characterised in that the acrylamide copolymer contain construction unit A, construction unit B and Construction unit C, wherein, the construction unit A is the unit with structure shown in formula (1), and the construction unit B is with formula (2) at least one of unit of structure shown in-formula (5), the construction unit C are the unit with structure shown in formula (6), and The construction unit A, the construction unit B and the construction unit C weight ratio are 1：0.001-10：0.001-10, it is described The viscosity average molecular weigh of acrylamide copolymer is 30,000,000-3,800 ten thousand,Wherein, R1、R2、R6、R7、R10And R11It is each independently hydrogen or C1-C4 alkyl, R3For C1-C14 alkylidene, R4With R5It is each independently hydrogen or C1-C15 alkyl, R8And R9It is each independently C1-C4 alkyl, R12、R13、R14、R15And R16 It is each independently C1-C3 alkylidene, R17、R18And R19C1-C3 alkyl is each independently, n is arbitrary whole in 1-15 Number, M1And M2It is each independently H, Na or K.
- 2. acrylamide copolymer according to claim 1, wherein, the construction unit B is with formula (2)-formula (4) institute Show the unit of structure shown at least one of unit of structure and formula (7)：Wherein, M3For K or Na.
- 3. acrylamide copolymer according to claim 2, wherein, the unit of structure shown in formula (1), formula (2)-formula (4) The weight ratio of the unit of structure is shown in the unit of structure shown at least one of unit of shown structure, formula (6) and formula (7) 1：0.001-10：0.001-10：0.1-1, the viscosity average molecular weigh of the acrylamide copolymer is 32,000,000-3,500 ten thousand.
- 4. acrylamide copolymer according to claim 2, wherein, the unit of structure shown in formula (1), formula (2)-formula (4) The weight ratio of the unit of structure is shown in the unit of structure shown at least one of unit of shown structure, formula (6) and formula (7) 1：0.01-1.5：0.01-0.2：0.1-1.
- 5. according to the acrylamide copolymer described in any one in claim 1-4, wherein, R2And R7It is each independently hydrogen Or methyl, R6For hydrogen, R3For C1-C4 alkylidene, R4And R5It is each independently methyl, R8And R9Be each independently methyl or Ethyl, M1For hydrogen；In the construction unit C, R12、R13、R14、R15And R16It is each independently methylene, R17、R18And R19Each Methyl independently is, n is arbitrary integer in 1-11.
- 6. a kind of preparation method of acrylamide copolymer, the preparation method include：Under the conditions of solution polymerization, triggering In the presence of agent, a kind of monomer mixture is set to carry out polymerisation in water, it is characterised in that the monomer mixture contains monomer E, monomer F and monomer G, the monomer E are the monomer with structure shown in formula (8), and the monomer F is with formula (9)-formula (12) At least one of monomer of shown structure, the monomer G are the monomer with structure shown in formula (13), and the monomer E, institute The weight ratio for stating the monomer F and monomer G is 1：0.001-10：0.001-10；The solution polymerization condition to polymerize The viscosity average molecular weigh of resulting polymers is 30,000,000-3,800 ten thousand after reaction,Wherein, R1’、R2’、R6’、R7’、R10' and R11' it is each independently hydrogen or C1-C4 alkyl, R3' be C1-C14 alkylene Base, R4' and R5' it is each independently hydrogen or C1-C15 alkyl, R8' and R9' it is each independently C1-C4 alkyl, R12’、 R13’、R14’、R15' and R16' it is each independently C1-C3 alkylidene, R17’、R18' and R19' it is each independently C1-C3 alkane Base, n ' be 1-15 in arbitrary integer, M1' and M2' it is each independently H, Na or K.
- 7. according to the method for claim 6, wherein, the monomer F be with formula (9)-monomer of structure shown in formula (11) At least one of, and R2' and R7' it is each independently hydrogen or methyl, R6' it is hydrogen, R3' be C1-C4 alkylidene, R4' and R5’ It is each independently methyl, R8' and R9' it is each independently methyl or ethyl, M1' it is hydrogen；In the monomer G, R12’、R13’、 R14’、R15' and R16' it is each independently methylene, R17’、R18' and R19' methyl is each independently, n ' is any in 1-11 Integer.
- 8. the method according to claim 11, wherein, when the solution polymerization starts, the weight of the monomer mixture Amount and the ratio of water and the gross weight of monomer mixture are 0.15-0.4：1.
- 9. the method according to claim 11, wherein, when the solution polymerization starts, the weight of the monomer mixture Amount and the ratio of water and the gross weight of monomer mixture are 0.2-0.3：1.
- 10. according to the method for claim 6, wherein, the initiator is selected from azo series initiators and redox system draws Send out agent, the dosages of the azo series initiators is the 0.0001-0.1 weight % of the gross weight of monomer in monomer mixture, described The dosage of redox series initiators is the 0.0002-0.3 weight % of the gross weight of monomer in monomer mixture；The azo system Initiator is water-soluble azo series initiators, and the redox series initiators include Oxidizing and Reducing Agents, the reducing agent For inorganic reducing agent and/or organic reducing agent, and the weight ratio of the oxidant and the reducing agent is 0.1-1：1.
- 11. according to the method for claim 10, wherein, the water-soluble azo series initiators are selected from 2, the double (2- of 2 '-azo Amidine propane) dihydrochloride, double (the 2- imidazolines propane) dihydrochlorides of 2,2 '-azo and 4,4 '-azo pair (4- cyanopentanoic acids) At least one of；The oxidant is selected from benzoyl peroxide, hydrogen peroxide, TBHP, 2,5- dimethyl -2, At least one of 5- double (hydrogen peroxide) hexane, ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfates；The inorganic reducing agent is selected from Ferrous sulfate, iron ammonium sulfate, stannous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, thiosulfuric acid At least one of sodium, potassium thiosulfate, rongalite and sodium hydrogensulfite；The organic reducing agent is selected from N, N- dimethyl ethanols Amine, N, N '-dimethyl piperazine, N, N, N ', N '-tetramethylurea element and N, N, N ', at least one of N '-tetramethylethylenediamine.
- 12. according to the method for claim 6, wherein, the solution polymerization is carried out under an inert atmosphere, the solution Polymeric reaction condition includes：The initial temperature of polymerisation is -10 DEG C to 20 DEG C, and the time is 2-12 hours, pH value 4-12.
- 13. according to the method described in any one in claim 6-12, wherein, the monomer F is with formula (9)-formula (11) During at least one of monomer of shown structure, methods described also includes resulting polymers after polymerisation are hydrolyzed and done Dry, the hydrolysis is so that the degree of hydrolysis of resulting polymers is 10-30% after polymerisation.
- 14. according to the method for claim 13, wherein, the hydrolysising condition includes：Temperature is 50-110 DEG C, and the time is 0.5-6 hours；The condition of the drying includes：Temperature is 40-120 DEG C, and the time is 0.2-4 hours.
- 15. acrylamide copolymer made from the method in claim 6-14 described in any one.
- 16. application of the acrylamide copolymer as oil displacement agent in claim 1-5 and 15 described in any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510363538.3A CN106317314B (en) | 2015-06-26 | 2015-06-26 | A kind of acrylamide copolymer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510363538.3A CN106317314B (en) | 2015-06-26 | 2015-06-26 | A kind of acrylamide copolymer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106317314A CN106317314A (en) | 2017-01-11 |
| CN106317314B true CN106317314B (en) | 2018-04-10 |
Family
ID=57722235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510363538.3A Active CN106317314B (en) | 2015-06-26 | 2015-06-26 | A kind of acrylamide copolymer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106317314B (en) |
-
2015
- 2015-06-26 CN CN201510363538.3A patent/CN106317314B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106317314A (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104650301B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN104628944B (en) | Acrylamide copolymer, as well as preparation method and application thereof | |
| CN104448127B (en) | Polymer mobility control agent suitable for special high salinity reservoirs and preparation method thereof | |
| CN106866878B (en) | Polymer-type profile control agent and preparation method thereof suitable for high temperature and high salt harshness oil reservoir | |
| CN106317308B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN104628943B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN106317311B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN105566515A (en) | Structure-oriented composite initiator system and acrylamide polymer and preparation method and application thereof | |
| CN106317314B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN106317313B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN106317310B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN106317312B (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN107759728A (en) | A kind of Polymer Used For Oil Displacement with surface-active and its preparation method and application | |
| CN107759727B (en) | A kind of Polymer Used For Oil Displacement and its preparation method and application with surface-active | |
| CN107226886A (en) | A kind of polymer with surface active function and its preparation method and application | |
| CN109232810A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232809A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN109232803A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN107964067A (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN108424490A (en) | A kind of acrylamide copolymer and its preparation method and application | |
| CN109232797B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN106317339A (en) | Acrylamide copolymer, and preparation method and application thereof | |
| CN109232801A (en) | Acrylamide copolymer and the preparation method and application thereof | |
| CN102050916A (en) | Tertiary aliphatic amine group-contained macromolecule as well as preparation method and application thereof | |
| CN109232799A (en) | Acrylamide copolymer and the preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |