CN106543022B - Amphoteric ion copolymer cationic monomer and preparation method thereof and amphoteric ion copolymer and its preparation method and application - Google Patents
Amphoteric ion copolymer cationic monomer and preparation method thereof and amphoteric ion copolymer and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to copolymer fields, disclose a kind of amphoteric ion copolymer cationic monomer and preparation method thereof and amphoteric ion copolymer and its preparation method and application, amphoteric ion copolymer provided by the invention has structure shown in formula (1) with cationic monomer, wherein R1For the alkyl of H or C1 C3；R2For at least one of H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element；R3And R4It is each independently the alkyl of H or C1 C4；X is halogen element；The integer that n is 3 13.Acrylamide amphoteric ion copolymer provided by the invention due to introduce cation group, surface of stratum have stronger adsorptivity, improve polymer surface of stratum abrasion resistance.The heat-resistant salt-resistant performance for improving polymer in molecule due to existing simultaneously amphoteric ion, can be used for high temperature and high salinity oil reservoir.
Description
Technical field
The present invention relates to copolymer fields, and in particular, to a kind of amphoteric ion copolymer cationic monomer and its system
Preparation Method, a kind of acrylamide amphoteric ion copolymer, a kind of preparation method of acrylamide amphoteric ion copolymer with
And be prepared by this method acrylamide amphoteric ion copolymer, acrylamide amphoteric ion copolymer is in water blockoff tune
Application in cuing open.
Background technology
With the increasingly exploitation in oil field, water proportion in the oil exploited is increasing.Well water will be direct
The decline of yield is caused, the intensity of loss and the water filling of stratum energy increases and the harm such as the corrosion of equipment pipe network aggravation, makes
Development benefit is by serious influence.In order to reduce this unnecessary waste, Water in Water Shutoff in Oil Field exists as the means of water and oil control
It is extremely important in oil extraction process.China's water plugging and profiling technology passes through development in more than 40 years, is played in oilfield development process
Important function.
Selective water-plugging used in oilwell water shutoff is mostly by water-soluble polymerics such as polyacrylamide and its derivatives at present
Object generates gel in stratum or frozen glue blocks water flooding, or is met water plastic with oil base blocking agent or cured closure water breakthrough and led to
Road is realized, but due to existing blocking agent poor selectivity, also be will be greatly reduced oleic permeability while water blockoff, caused
Low liquid after stifled, constrains the application of water shutoff in oil well.Therefore a kind of novel highly selective water shutoff material is developed, realizes oil reservoir
The not stifled oil of water blockoff, improves oil well productivity to ultra-high water cut stage and has great importance.
Amphoteric ion polymer due on strand simultaneous with anions and canons group, because of its unique molecular structure
With good application performance, at home and abroad gradually promoted and applied in oil-gas mining, for example, water plugging profile control agent, strengthen oil displacement agent,
Novel fluid loss additive, visbreaking agent, shale control agent, additive for drilling fluid, cementing extra-agent, fracturing fluid additive etc..Its
Prepare and application process related art mainly have CN103509154A, CN103694394A, CN104558405A,
CN101412785A, CN1861654A, CN1386769A etc..
Amphoteric ion polymer have certain salt thickening property, in the environment of water flooding saliferous, amphoteric polymer and its
The ability for forming gel blocking pore throat is stronger, this is the advantage not available for other gel profile control agents.When poly- using amphoteric ion
When closing object for profile-controlling and plugging agent, since surface of stratum is negativity interface, the cation group in amphoteric ion polymer can be strong
Strong is adsorbed on surface of stratum, increases the abrasion resistance of profile-controlling and plugging agent.In addition, water soluble amphoteric ion polymerize in aqueous solution
Anion on object strand and cation, since electrostatic attraction acts on, in strand and molecule interchain generates bonding action,
Its strand is caused to shrink, molecular conformation is more close, and viscosity is small.And in saline solution, since this bonding action is small
The shielding of molecule salt destroys, and macromolecule-solvent interaction ability enhancing, molecular conformation becomes to unfold, and viscosity increases, and is presented ten
Divide apparent anti-polyelectrolyte solution behavior, there is the salt tolerance for improving polymer to zwitterionic.
However, the amphoteric ion polymer generally existing selectivity of above-mentioned prior art offer is not high, heat resistance is poor
Disadvantage.
Therefore, a kind of new amphoteric ion copolymer of exploitation is of great significance for water plugging and profile controlling.
Invention content
The purpose of the present invention is overcoming the defect that the amphoteric ion copolymer of the prior art is selectively low, heat resistance is poor,
Rigid radical phenyl ring is introduced in polymer molecular structure, to provide a kind of new high selectivity, heat resistance better third
Acrylamide system amphoteric ion copolymer.
It to achieve the goals above, should in a first aspect, the present invention provides a kind of amphoteric ion copolymer cationic monomer
Monomer has structure shown in formula (1),
Wherein, R1For the alkyl of H or C1-C3；R2For in H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element at least
It is a kind of；R3And R4It is each independently the alkyl of H or C1-C4；X is halogen element；N is the integer of 3-13.
Second aspect, the present invention provide the preparation method of aforementioned amphoteric ion copolymer cationic monomer, this method packet
It includes：
(1) under alkaline condition, monomer shown in formula (2) and formula (3) compound represented are carried out in organic solvent
Haptoreaction；
(2) product that step (1) obtains will be passed through and carry out hybrid reaction with formula (4) compound represented；
Wherein, R1、R2、R3、R4, X and the n such as present invention it is aforementioned define.
The third aspect, the present invention provide a kind of amphoteric ion terpolymer, which contains structural unit A, structure
Unit B and structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (5), the structural unit
B is the structural unit with structure shown in formula (6), and the structural unit C is selected from knot shown in structure, formula (8) shown in formula (7)
Structural unit in structure shown in structure and formula (10) shown in structure, formula (9)；Weight with the amphoteric ion terpolymer is
Benchmark, the content of the structural unit A are that the content of 15-90 weight %, the structural unit B are 5-70 weight %, the knot
The content of structure unit C is 5-60 weight %, and the viscosity average molecular weigh of the amphoteric ion terpolymer is 300-1500 ten thousand；
Wherein, R1For the alkyl of H or C1-C3；R2For in H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element at least
It is a kind of；R3And R4It is each independently the alkyl of H or C1-C4；R5For the alkyl of H or C1-C4；X is halogen element；N is the whole of 3-13
Number；M in formula (7), formula (9) and formula (10) is each independently H, Na or K.
Fourth aspect, the present invention provide a kind of preparation method of amphoteric ion terpolymer, and this method includes：Causing
Agent and as the water of solvent in the presence of, so that monomer D, monomer E and monomer F is carried out solution polymerization, wherein the monomer D
For the monomer with structure shown in formula (11), the monomer E is the monomer with structure shown in formula (1), the monomer F be selected from
The monomer of structure shown in structure and formula (15) shown in structure, formula (14) shown in structure, formula (13) shown in formula (12), wherein described
The dosage of monomer D, monomer E and monomer F so that the content of structural unit A in the copolymer being prepared is 15-90 weight %, knot
The content of structure unit B is that the content of 5-70 weight %, structural unit C are 5-60 weight %, and make the polymerization being prepared
The viscosity average molecular weigh of object is 300-1500 ten thousand；The structural unit A is the structural unit with structure shown in formula (5), the knot
Structure unit B is the structural unit with structure shown in formula (6), and the structural unit C is selected from structure shown in formula (7), formula (8) institute
Show the structural unit in structure shown in structure and formula (10) shown in structure, formula (9),
Wherein, R1For the alkyl of H or C1-C3；R2For in H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element at least
It is a kind of；R3And R4It is each independently the alkyl of H or C1-C4；R5For the alkyl of H or C1-C4；X is halogen element；N is the whole of 3-13
Number；M in formula (7) and formula (12), formula (9) and formula (14) and formula (10) and formula (15) is each independently H, Na or K.
5th aspect, the present invention provide the amphoteric ion terpolymer that preceding method is prepared.
6th aspect, the present invention provide application of the aforementioned amphoteric ion terpolymer in water plugging and profile controlling.
The present invention provides a kind of novel polymerizable cationic monomer, which has good heat resistance.
It is total that the cationic monomer can obtain acrylamide amphoteric ion with acrylamides, anionic monomer polymerisation
Polymers.
Acrylamide amphoteric ion copolymer obtained above has due to introducing cation group in surface of stratum
Stronger adsorptivity, improve polymer surface of stratum abrasion resistance.It is improved in molecule due to existing simultaneously amphoteric ion
The heat-resistant salt-resistant performance of polymer, can be used for high temperature and high salinity oil reservoir.The copolymer is used as having when water plugging profile control agent good
Good oil-water selectivity.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In a first aspect, the present invention provides a kind of amphoteric ion copolymer cationic monomer, which has formula (1) institute
The structure shown,
Wherein, R1For the alkyl of H or C1-C3；R2For in H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element at least
It is a kind of；R3And R4It is each independently the alkyl of H or C1-C4；X is halogen element；N is the integer of 3-13.
In the present invention, the R of phenyl is connected2It can be one, two or more.
The alkyl of the C1-C3 can include but is not limited to：Methyl, ethyl, n-propyl and isopropyl.
The alkyl of the C1-C4 can include but is not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding
Base, isobutyl group and tertiary butyl.
The halogen element can include but is not limited to：Fluorine, chlorine, bromine, iodine.
The integer of the 3-13 may include：3,4,5,6,7,8,9,10,11,12 and 13.
In the present invention, in formula (1), the preferably described R1For H, methyl, ethyl, n-propyl or normal-butyl；R2For H, first
At least one of base, ethyl, methoxyl group, ethyoxyl, chlorine and bromine；R3And R4It is each independently H, methyl, ethyl, n-propyl
Or normal-butyl；X is chlorine or bromine；N is the integer of 3-13.
In the present invention, in formula (1), the more preferred R1、R2、R3And R4It is methyl, X is bromine；N is 3-13's
Integer.
Second aspect, the present invention provides the preparation method of aforementioned amphoteric ion copolymer cationic monomer, this method
Including：
(1) under alkaline condition, monomer shown in formula (2) and formula (3) compound represented are carried out in organic solvent
Haptoreaction；
(2) product that step (1) obtains will be passed through and carry out hybrid reaction with formula (4) compound represented；
Wherein, R1、R2、R3、R4, X and the n such as present invention it is aforementioned define.
According to the present invention, the amphoteric ion copolymer in the preparation method of amphoteric ion copolymer cationic monomer is used
The related definition of the cationic monomer such as present invention is noted earlier, and in order to avoid repeating, details are not described herein by the present invention.
In step (1), the catalytic condition may include：Temperature is 5-30 DEG C, time 20-240min.
In step (1), the dosage molar ratio of monomer shown in formula (2) and formula (3) compound represented can be 1：3-
0.3。
In step (1), the alkaline condition can by be added into reaction system the alkaline matters such as sodium hydroxide come
It realizes, for example, the present invention is realized by using the sodium hydroxide solution of a concentration of 2-10mol/L.It is preferred that of the present invention
The pH value of alkaline condition is 8-11.
In step (1), to the type of the organic solvent, there is no particular limitation, and the organic solvent can be dichloro
At least one of methane, ether, ethyl acetate, chloroform and isopropyl ether.The method of the present invention does not have the dosage of organic solvent
Special to limit, those skilled in the art can select according to common quantity of solvent, the preferably described organic solvent of the present invention
Dosage be 2-20 times of dosage (weight) of formula (3) compound represented.
Monomer shown in the formula (2) can synthesize to obtain by method that is commercially available or using the prior art to provide.This
The method that invention illustratively provides synthesizing methyl acryloyl chloride (one kind in monomer shown in formula (2))：
Using monomer shown in the reaction bulb synthesis formula (2) with distilling apparatus and dropping funel.It is added into reaction bulb
Chlorobenzoyl chloride, methacrylic acid and polymerization inhibitor are equipped with methacrylic acid in dropping funel.Under the conditions of vacuum (0.01-0.05MPa)
Reaction mass in heating stirring reaction bulb starts to be added dropwise with dropping funel when temperature, which has risen to methacrylic chloride, to be steamed
Methacrylic acid.Wherein, polymerization inhibitor can be in hydroquinone, p-tert-Butylcatechol, stannous chloride and butter of tin
At least one.The polymerization inhibitor is the 0.05-2% of reaction solution gross mass in reaction bulb.The amount of the substance of the chlorobenzoyl chloride
Amount ratio with the total material of methacrylic acid is 3-0.3：1.The quality of methacrylic acid in reaction bulb is that methacrylic acid is total
The 5-20% of quality.Reaction temperature is 50-85 DEG C, reaction time 20-120min.
In step (1), the haptoreaction can carry out in the presence of inert gas such as nitrogen.
Those skilled in the art may be used what conventional use of post-processing means in the art were obtained to passing through step (1)
Reaction mixture is post-processed.Such as following steps may be used to after the reaction mixture that step (1) obtains carries out
Processing：The reaction mixture that separation is obtained by step (1) obtains organic layer, removes solvent, is added into obtained concentrate
Then polymerization inhibitor is depressurized (vacuum degree 50Pa) distillation, collect 90-100 DEG C to get the product obtained by step (1).Its
In, the type of the polymerization inhibitor is as previously described.The quality of polymerization inhibitor is the 0.01-5% of the quality of concentrate.
In step (2), the condition of the hybrid reaction may include：Temperature is 20-100 DEG C, time 2-10h.
In step (2), preferably described formula (3) compound represented and the dosage molar ratio of monomer shown in formula (2) are
0.3-3：1.
Further include mixing the product obtained by step (1) with formula (4) compound represented in step (2)
The step of the step of mix products obtained after reaction are post-processed, the post-processing may include：The mix products are used
Ether washs, and it is 1 that volume ratio, which is used in combination,：1 acetone and the mixture of ether are recrystallized, will recrystallize obtained product into
Row is dry to get to amphoteric ion copolymer cationic monomer of the present invention.
The amphoteric ion ternary that polymerization is formed is participated in using amphoteric ion copolymer provided by the invention cationic monomer
Copolymer high selectivity can be used as water plugging profile control agent application.
The third aspect, the present invention provides a kind of amphoteric ion terpolymer, which contains structural unit A, knot
Structure unit B and structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (5), the structure list
First B is the structural unit with structure shown in formula (6), and the structural unit C is selected from knot shown in structure, formula (8) shown in formula (7)
Structural unit in structure shown in structure and formula (10) shown in structure, formula (9)；Weight with the amphoteric ion terpolymer is
Benchmark, the content of the structural unit A are that the content of 15-90 weight %, the structural unit B are 5-70 weight %, the knot
The content of structure unit C is 5-60 weight %, and the viscosity average molecular weigh of the amphoteric ion terpolymer is 300-1500 ten thousand；
Wherein, R1For the alkyl of H or C1-C3；R2For in H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element at least
It is a kind of；R3And R4It is each independently the alkyl of H or C1-C4；R5For the alkyl of H or C1-C4；X is halogen element；N is the whole of 3-13
Number；M in formula (7), formula (9) and formula (10) is each independently H, Na or K.
In the present invention, the structural unit of structure shown in the formula (6) is corresponding with structures alone shown in formula (1), preceding
State corresponding definition of the definition to structures alone shown in formula (1) suitable for the structural unit of structure shown in formula (6), this hair
It is bright that details are not described herein.
In the structural unit of structure shown in formula (5), the R5It can be the alkyl of H or C1-C4；It is preferred that the R5For H,
Methyl, ethyl, n-propyl or normal-butyl；The more preferable R5For H, methyl or ethyl；The particularly preferred R5For H or methyl.
The knot of structure shown in the structural unit of structure and formula (10) shown in the structural unit of structure, formula (9) shown in formula (7)
M in structure unit is each independently H, Na or K；It is preferred that the M is each independently H or Na；The particularly preferred M is
Na。
According to a kind of preferred embodiment, amphoteric ion terpolymer of the present invention contains structural unit
A, structural unit B and structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (5), the knot
Structure unit B is the structural unit with structure shown in formula (6), and the structural unit C is selected from structure shown in formula (7), formula (8) institute
Show the structural unit in structure shown in structure and formula (10) shown in structure, formula (9)；Wherein, R1For H, methyl, ethyl or positive third
Base；R2For at least one of H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element；R3And R4Be each independently H, methyl,
Ethyl, n-propyl or normal-butyl；R5For H, methyl, ethyl, n-propyl or normal-butyl；X is chlorine or bromine；N is the integer of 3-13；
M in formula (7), formula (9) and formula (10) is each independently H or Na.
According to another preferred embodiment, amphoteric ion terpolymer of the present invention contains structure list
First A, structural unit B and structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (5), described
Structural unit B is the structural unit with structure shown in formula (6), and the structural unit C is selected from structure, formula (8) shown in formula (7)
Structural unit in structure shown in structure and formula (10) shown in shown structure, formula (9)；Wherein, R1For H or methyl；R2For H, first
At least one of base, ethyl；R3And R4It is each independently H, methyl or ethyl；R5For H, methyl or ethyl；X is chlorine or bromine；
N is the integer of 3-13；M in formula (7), formula (9) and formula (10) is each independently H or Na.
According to another preferred embodiment, amphoteric ion terpolymer of the present invention contains structure list
First A, structural unit B and structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (5), described
Structural unit B is the structural unit with structure shown in formula (6), and the structural unit C is selected from structure, formula (8) shown in formula (7)
Structural unit in structure shown in structure and formula (10) shown in shown structure, formula (9)；Wherein, R1For H or methyl；R2For H；R3With
R4It is methyl；R5For H or methyl；X is chlorine or bromine；N is the integer of 3-13；M in formula (7), formula (9) and formula (10) is respectively only
It is on the spot H or Na.
In the case of more preferably, in the present invention, on the basis of the weight of the amphoteric ion terpolymer, the knot
The content of structure unit A is that the content of 30-90 weight %, the structural unit B are 5-50 weight %, and the structural unit C's contains
Amount is 5-50 weight %, and the viscosity average molecular weigh of the amphoteric ion terpolymer is 500-1000 ten thousand.
Fourth aspect, the present invention provides a kind of preparation method of amphoteric ion terpolymer, this method includes：Drawing
Send out agent and as the water of solvent in the presence of, so that monomer D, monomer E and monomer F is carried out solution polymerization, wherein the monomer
D is the monomer with structure shown in formula (11), and the monomer E is the monomer with structure shown in formula (1), and the monomer F is choosing
From the monomer of structure shown in structure and formula (15) shown in structure, formula (14) shown in structure, formula (13) shown in formula (12), wherein institute
The dosage for stating monomer D, monomer E and monomer F so that the content of structural unit A in the copolymer being prepared is 15-90 weight %,
The content of structural unit B is that the content of 5-70 weight %, structural unit C are 5-60 weight %, and to be prepared poly-
The viscosity average molecular weigh for closing object is 300-1500 ten thousand；The structural unit A is the structural unit with structure shown in formula (5), described
Structural unit B is the structural unit with structure shown in formula (6), and the structural unit C is selected from structure, formula (8) shown in formula (7)
Structural unit in structure shown in structure and formula (10) shown in shown structure, formula (9),
Wherein, R1For the alkyl of H or C1-C3；R2For in H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element at least
It is a kind of；R3And R4It is each independently the alkyl of H or C1-C4；R5For the alkyl of H or C1-C4；X is halogen element；N is the whole of 3-13
Number；M in formula (7) and formula (12), formula (9) and formula (14) and formula (10) and formula (15) is each independently H, Na or K.
The knot of structure shown in the structural unit of structure, formula (7) shown in the structural unit of structure, formula (6) shown in the formula (5)
The structure list of structure shown in the structural unit of structure, formula (10) shown in the structural unit of structure, formula (9) shown in structure unit, formula (8)
The definition of the related group of the structural unit of structure shown in member and formula (1) is identical as related definition above-mentioned respectively, and the present invention exists
This is repeated no more.Moreover, structure shown in the monomer of structure, formula (13) shown in the monomer of structure, formula (12) shown in the formula (11)
Monomer, structure shown in formula (14) monomer and formula (15) shown in structure monomer be respectively structure shown in formula (5) structure list
Member, the structural unit of structure shown in formula (7), the structural unit of structure shown in formula (8), structure shown in formula (9) structural unit and
Monomer corresponding to the structural unit of structure shown in formula (10), therefore, for shown in the monomer of structure, formula (12) shown in formula (11)
In the monomer of structure shown in the monomer of structure and formula (15) shown in the monomer of structure, formula (14) shown in the monomer of structure, formula (13)
Related group the related definition defined in corresponding monomer it is identical.
Meanwhile the amphoteric ion ternary being prepared involved in the preparation method of the amphoteric ion terpolymer is total
The preferred embodiment of polymers is identical as the aforementioned preferred embodiment of amphoteric ion terpolymer, in order to avoid
It repeats, details are not described herein by the present invention.
The condition of the solution polymerization preferably includes：Temperature is 5-50 DEG C；Time is 1-15h.
According to the method for the present invention, there is no particular limitation for the dosage of the initiator, can become in a wider scope
Dynamic, on the basis of the total amount of the monomer D, the monomer E and the monomer F, the dosage of the initiator is 0.01-0.1 weights
Measure %.
According to the method for the present invention, the initiator can be the various initiators of this field routine, such as can be choosing
From arbitrary two kinds in radical polymerization initiator：The radical polymerization initiator includes azo-initiator, peroxide
Class initiator and redox type initiators.The azo-initiator is selected from azo-bis-iso-dimethyl, two isobutyl of azo
Amidine hydrochloride, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano formamide, two hexamethylene of azo
Base formonitrile HCN, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and azo two are different
At least one of heptonitrile；The peroxide type initiators are selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate,
At least one of benzoyl peroxide and the benzoyl peroxide tert-butyl ester；The redox type initiators are selected from sulfate-
At least one of sulphite, persulfate-thiocarbamide, persulfate-organic salt and ammonium persulfate-fatty amine.
According to the method for the present invention, chelating agent being added can prevent metal ion from being had an impact to polymerisation, therefore, excellent
In the case of choosing, the solution polymerization carries out in the presence of chelating agent.The chelating agent can be ethylenediamine tetra-acetic acid two
Sodium, aminotriacetic acid or ammonium citrate, preferably disodium ethylene diamine tetraacetate.The present invention is to the dosage of the chelating agent without spy
Other restriction can change in a wider scope, on the basis of the total amount of the monomer D, the monomer E and the monomer F,
The dosage of the chelating agent can be 0.1-0.3 weight %.
According to the method for the present invention, the dissolubility of polymer can be improved by auxiliary agent being added, it is therefore preferable that in the case of, it is described
Solution polymerization carries out in the presence of auxiliary agent.The auxiliary agent can be at least one of urea, thiocarbamide and ammonium hydroxide, preferably
Urea.There is no particular limitation for dosage of the present invention to the auxiliary agent, can change in a wider scope, with the monomer D,
On the basis of the total amount of the monomer E and the monomer F, the dosage of the auxiliary agent can be 0.01-0.1 weight %.
According to the method for the present invention, the polymer of different molecular weight can be synthesized by molecular weight regulator being added, it is therefore preferable that
In the case of, the polymerisation carries out in the presence of molecular weight regulator.The molecular weight regulator can be isopropanol, ammonia
Water, N, at least one of N '-methylene-bisacrylamides and dimethyl sulfourea.The dosage of the molecular weight regulator can root
It is selected according to the conventional amount used of this field.For example, on the basis of the total amount of the monomer D, the monomer E and the monomer F,
The dosage of the molecular weight regulator can be 0.001-0.1 weight %.
5th aspect, the present invention provides the amphoteric ion terpolymers that preceding method is prepared.
6th aspect, the present invention provides application of the aforementioned amphoteric ion terpolymer in water plugging and profile controlling.
Amphoteric ion terpolymer product of the present invention can be used as highly selective water plugging profile control agent be used in recovered the oil
Cheng Zhong.As water plugging profile control agent in use, blocking up oily high selectivity with resistance to erosion, temperature-resistant anti-salt, water blockoff, to oleic permeability shadow
Ring small advantage.As water plugging profile control agent in Oil Field in use, it is preferred that the mass concentration of amphoteric ion terpolymer is
0.01-0.5%.
The present invention will be described in detail by way of examples below.
The intrinsic viscosity η of polymer is surveyed by polyacrylamide Intrinsic Viscosity Measurements method as defined in GB12005.1-89
It is fixed, 10 weight %NaCl solution are measured at 25 DEG C with Ubbelohde viscometer.
Viscosity molecular weight is according to formula M=([η]/K)1/αIt is calculated, wherein K=4.75 × 10-3, α=0.80.
Used reagent is commercially available chemically pure reagent in following embodiment.
Preparation example 1
This preparation example is used to prepare methacrylic chloride (one kind in monomer shown in formula (2))：
Blender, still, dropping funel, thermometer are loaded onto on four-hole boiling flask, are loaded onto with vacuum after condenser pipe
The receiving bottle that tail is taken over.Chlorobenzoyl chloride, the methacrylic acid of 0.3mol and the protochloride of 0.7g of 3.0mol are added in flask
Copper.The methacrylic acid of 2.7mol is added in dropping funel.It is 0.2MPa to start vacuum pump control vacuum degree.Heating stirring is to temperature
Degree is 75 DEG C, has methacrylic chloride to distillate in receiving bottle.Meanwhile methacrylic acid is added dropwise with dropping funel.Heating stirring is anti-
Answer 60min.It is for use to obtain methacryl chlorine products.
Preparation example 2
This preparation example is used to prepare amphoteric ion copolymer cationic monomer (bromination dimethyl dodecyl base (2- methyl
Acrylamido is to phenyl) ammonium)：
(1) in the three neck round bottom flask equipped with blender and logical nitrogen pipe, the 4- of 250mL dichloromethane, 0.3mol is added
Amino-N, N-dimethylaniline and 9mol/L sodium hydroxide solutions 40mL.It is passed through nitrogen, at 5 DEG C stirring and dissolving.It is leaked with dropping liquid
Bucket is added dropwise to the methacrylic chloride that the 0.3mol preparation examples 1 dissolved by 50mL dichloromethane are prepared.It is stirred to react
90min.Isolated organic layer, is distilled off solvent, obtains 50.9g products.0.08g phenthazine will be added in products therefrom,
Vacuum distillation.90-100 DEG C, the fraction of vacuum degree 50Pa are collected, products therefrom is Methacrylamide to pheiiyldimetliyl
Amine；
(2) Methacrylamide for obtaining 0.1mol steps (1) is to phenyl dimethyl amine, 0.15mol bromododecanes
After being stirred in reaction bulb with 4g pyridines, logical nitrogen reacts 4h at 50 DEG C.It is washed, is dried with ether after product is cooled down
Afterwards by 1：The acetone of 1 (v/v) and the mixture recrystallization of ether.Bromination dimethyl 12 will be obtained after product drying after purification
Alkyl (2- methacryl amidos are to phenyl) ammonium.
Preparation example 3
This preparation example is used to prepare amphoteric ion copolymer cationic monomer (bromination dimethyl undecyl (2- methyl
Acrylamido is to phenyl) ammonium)：
(1) in the three neck round bottom flask equipped with blender and logical nitrogen pipe, the 4- of 250mL dichloromethane, 0.3mol is added
Amino-N, N-dimethylaniline and 9mol/L sodium hydroxide solutions 60mL.It is passed through nitrogen, the stirring and dissolving at 8 DEG C.It is leaked with dropping liquid
Bucket is added dropwise to the methacrylic chloride that the 0.5mol preparation examples 1 dissolved by 60mL dichloromethane are prepared.It is stirred to react
90min.Isolated organic layer, is distilled off solvent, obtains 52.5g products.0.07g phenthazine will be added in products therefrom,
Vacuum distillation.90-100 DEG C, the fraction of vacuum degree 50Pa are collected, products therefrom is Methacrylamide to pheiiyldimetliyl
Amine；
(2) Methacrylamide for obtaining 0.1mol steps (1) is to phenyl dimethyl amine, 0.15mol bromoundecanes
After being stirred in reaction bulb with 4g pyridines, logical nitrogen reacts 5h at 60 DEG C.It is washed, is dried with ether after product is cooled down
Afterwards by 1：The acetone of 1 (v/v) and the mixture recrystallization of ether.Bromination dimethyl 11 will be obtained after product drying after purification
Alkyl (2- methacryl amidos are to phenyl) ammonium.
Preparation example 4
This preparation example is used to prepare amphoteric ion copolymer cationic monomer (bromination dimethylhexanyl (2- metering systems
Amide groups is to phenyl) ammonium)：
(1) in the three neck round bottom flask equipped with blender and logical nitrogen pipe, the 4- ammonia of 250mL ether, 0.35mol is added
Base-N, accelerine and 9mol/L sodium hydroxide solutions 75mL.It is passed through nitrogen, the stirring and dissolving at 10 DEG C.It is leaked with dropping liquid
Bucket is added dropwise to the methacrylic chloride that the 0.45mol preparation examples 1 dissolved by 60mL dichloromethane are prepared.It is stirred to react
90min.Isolated organic layer, is distilled off solvent, obtains 56.3g products.0.10g phenthazine will be added in products therefrom,
Vacuum distillation.90-100 DEG C, the fraction of vacuum degree 50Pa are collected, products therefrom is Methacrylamide to pheiiyldimetliyl
Amine；
(2) Methacrylamide for obtaining 0.1mol steps (1) to phenyl dimethyl amine, 0.18mol bromos hexane and
After 6g pyridines are stirred in reaction bulb, logical nitrogen reacts 4h at 70 DEG C.It is washed with ether after product is cooled down, after drying
By 1：The acetone of 1 (v/v) and the mixture recrystallization of ether.Bromination dimethylhexanyl will be obtained after product drying after purification
(2- methacryl amidos are to phenyl) ammonium.
Embodiment 1
The present embodiment is used to prepare amphoteric ion terpolymer of the present invention：
20g acrylamides are added in reaction bulb, the bromination dimethyl dodecyl base (2- that 5.0g preparation examples 2 are prepared
Methacryl amido is to phenyl) ammonium, 3.0g 2- acrylamide-2-methylpro panesulfonic acids sodium, 100g distilled water, stirring it is molten
Solution.Dropwise addition mass concentration is that 20% sodium hydrate aqueous solution adjusting pH is 9.Sodium hydrogensulfite 10mg and ammonium persulfate is added
15mg leads to nitrogen reaction 5h at 25 DEG C, obtains acrylamide/bromination dimethyl dodecyl base (2- methacryl amidos pair
Phenyl) ammonium/2- acrylamide-2-methylpro panesulfonic acid sodium terpolymer crude products.Crude product is dried in vacuo at 50 DEG C,
Acrylamide/bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium/2- acrylamides is obtained after crushing
Base -2- methyl propane sulfonic acid sodium terpolymer products.It measures using viscosimetry to obtain its relative molecular mass with Ubbelohde viscometer
It is 7,500,000.
Embodiment 2
The present embodiment is used to prepare amphoteric ion terpolymer of the present invention：
23g acrylamides are added in reaction bulb, the bromination dimethyl undecyl (2- that 3.0g preparation examples 3 are prepared
Methacryl amido is to phenyl) ammonium, 3.0g acrylic acid, 100g distilled water, stirring and dissolving.Dropwise addition mass concentration is 20% hydrogen-oxygen
It is 9 to change sodium water solution to adjust pH.Sodium hydrogensulfite 10mg and ammonium persulfate 20mg is added, nitrogen is led at 20 DEG C and reacts 5h, is obtained
It is slightly produced to acrylamide/bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium/acrylic ternary copolymer
Product.Crude product is dried in vacuo at 50 DEG C, acrylamide/bromination dimethyl undecyl (2- metering systems are obtained after crushing
Amide groups is to phenyl) ammonium/acrylic ternary copolymer product.It measures using viscosimetry to obtain its average molecular with Ubbelohde viscometer
Quality is 6,500,000.
Embodiment 3
The present embodiment is used to prepare amphoteric ion terpolymer of the present invention：
25g acrylamides are added in reaction bulb, bromination dimethylhexanyl (the 2- methyl that 4.5g preparation examples 4 are prepared
Acrylamido is to phenyl) ammonium, 3.2g propene sulfonic acids, 100g distilled water, stirring and dissolving.Dropwise addition mass concentration is 20% hydroxide
It is 9 that sodium water solution, which adjusts pH,.Sodium hydrogensulfite 10mg and ammonium persulfate 20mg is added, nitrogen is led at 30 DEG C and reacts 4h, is obtained
Acrylamide/bromination dimethylhexanyl (2- methacryl amidos are to phenyl) ammonium/propene sulfonic acid terpolymer crude product.It will
Crude product is dried in vacuo at 50 DEG C, and acrylamide/bromination dimethylhexanyl is obtained after crushing, and (2- methacryl amidos are to benzene
Base) ammonium/propene sulfonic acid terpolymer product.With Ubbelohde viscometer use viscosimetry measure to obtain its relative molecular mass for
6800000.
Embodiment 4
The present embodiment is used to prepare amphoteric ion terpolymer of the present invention：
Bromination dimethyl dodecyl base (the 2- Methacrylamides being prepared in 4g preparation examples 2 are added in reaction bulb
Base is to phenyl) ammonium, 20g acrylamides, 4g vinylbenzenesulfonic acids, 100g distilled water, stirring and dissolving.It is 20% that mass concentration, which is added dropwise,
It is 9 that sodium hydrate aqueous solution, which adjusts pH,.Sodium hydrogensulfite 10mg and ammonium persulfate 15mg is added, it is anti-that nitrogen constant temperature is led at 20 DEG C
5h is answered, acrylamide/bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium/vinylbenzenesulfonic acid three is obtained
Membered copolymer crude product.Crude product is dried in vacuo at 50 DEG C, acrylamide/bromination dimethyl dodecyl base is obtained after crushing
(2- methacryl amidos are to phenyl) ammonium/vinylbenzenesulfonic acid terpolymer product.Viscosimetry is used with Ubbelohde viscometer
It is 8,200,000 that measurement, which obtains its relative molecular mass,.
Embodiment 5
Bromination dimethyl undecyl (the 2- methacryl amidos that 5g preparation examples 3 are prepared are added in reaction bulb
To phenyl) ammonium, 20g acrylamides, 4g propene sulfonic acids, 100g distilled water, stirring and dissolving.20% sodium hydroxide of mass concentration is added dropwise
It is 9 that aqueous solution, which adjusts pH,.Sodium hydrogensulfite 10mg and ammonium persulfate 20mg is added, nitrogen is led at 20 DEG C and reacts 5h, obtains third
Acrylamide/bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium/propene sulfonic acid terpolymer crude product.
Crude product is dried in vacuo at 50 DEG C, acrylamide/bromination dimethyl undecyl (2- Methacrylamides are obtained after crushing
Base is to phenyl) ammonium/propene sulfonic acid terpolymer product.It measures using viscosimetry to obtain its average molecular matter with Ubbelohde viscometer
Amount is 5,700,000.
Test case 1
This test case is used to illustrate the terpolymer product synthesized by embodiment 1-5 respectively to the sealing characteristics of oil, water.
The sealing ratiod of polymeric articles is investigated using rock core displacement test, sealing ratiod is by measuring rock core envelope
The variation of front and back permeability is blocked up to determine.
(1) experimental article
Artificial core：The long 8-10cm of rock core, internal diameter 2.3cm, end face is polished, and is dried at 90 DEG C；
Simulate oil sample：The weight ratio of crude oil and neutral kerosene is 1：0.9, crude oil and neutral kerosene come from Shengli Oil Field；
Simulated formation water (high salinity)：Salinity is 32868mg/L, and group becomes Mg2+177mg/L, Ca2+700mg/L, K+
+Na+11668mg/L, Cl-20323mg/L。
Terpolymer aqueous solution：Test sample is formulated as mass concentration 500mg/L with high salinity simulated formation water
Aqueous solution.
(2) test method
Artificial core is evacuated, under the conditions of 90 DEG C, is saturated with simulated formation water (high salinity).It is surveyed with simulation oil displacement
Fixed its oleic permeability KO1, with simulated formation water drive for its water phase permeability of measurement KW1, inject the terpolymer of aforementioned preparation
Aqueous solution, then measure water phase permeability K with the positive anti-row of simulated formation waterW2, with simulation oil, positive anti-row measures oleic permeability
KO2.Data processing is finally carried out, water plugging rate and oil plugging rate are calculated, to assess water plugging effect and selectivity, as a result such as 1 institute of table
Show.Wherein, raw material sources：Polyacrylamide (HPAM；Beijing Heng Ju groups company).
Table 1
| Sample | Water plugging rate (%) | Oil plugging rate (%) |
| Embodiment 1 | 97.8 | 6.7 |
| Embodiment 2 | 95.7 | 9.1 |
| Embodiment 3 | 98.1 | 9.0 |
| Embodiment 4 | 95.9 | 5.3 |
| Embodiment 5 | 96.3 | 4.9 |
| Polyacrylamide | 80.2 | 17.6 |
Amphoteric ion terpolymer provided by the invention is can be seen that in high temperature height from the result of the test case of the present invention
When being used as water plugging profile control agent under the conditions of salinity, there is good oil-water selectivity, water plugging effect is good, can improve individual well production
Energy.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of amphoteric ion copolymer cationic monomer, which is characterized in that the monomer has structure shown in formula (1),
Wherein, R1For the alkyl of H or C1-C3；R2For at least one of H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element；
R3And R4It is each independently the alkyl of H or C1-C4；X is halogen element；N is the integer of 3-13.
2. monomer according to claim 1, wherein R1For H or methyl；R2For H；R3And R4It is methyl；X is chlorine or bromine；n
For the integer of 3-13.
3. the preparation method of amphoteric ion copolymer cationic monomer as claimed in claim 1 or 2, this method include：
(1) under alkaline condition, monomer shown in formula (2) is contacted in organic solvent with formula (3) compound represented
Reaction；
(2) product that step (1) obtains will be passed through and carry out hybrid reaction with formula (4) compound represented；
Wherein, R1、R2、R3、R4, X and n such as claims 1 or 2 defined.
4. according to the method described in claim 3, wherein, in step (1), the catalytic condition includes：Temperature is
5-30 DEG C, time 20-240min.
5. according to the method described in claim 3, wherein, in step (1), monomer shown in formula (2) is changed with shown in formula (3)
The dosage molar ratio for closing object is 1：3-0.3.
6. according to the method described in claim 3, wherein, in step (2), the condition of the hybrid reaction includes：Temperature is
20-100 DEG C, time 2-10h.
7. a kind of amphoteric ion terpolymer, which is characterized in that the copolymer contains structural unit A, structural unit B and structure
Unit C, wherein the structural unit A is the structural unit with structure shown in formula (5), and the structural unit B is with formula
(6) structural unit of structure shown in, the structural unit C is selected from structure, formula (9) institute shown in structure, formula (8) shown in formula (7)
Show the structural unit in structure shown in structure and formula (10)；It is described on the basis of the weight of the amphoteric ion terpolymer
The content of structural unit A is that the content of 15-90 weight %, the structural unit B are 5-70 weight %, the structural unit C's
Content is 5-60 weight %, and the viscosity average molecular weigh of the amphoteric ion terpolymer is 300-1500 ten thousand；
Wherein, R1For the alkyl of H or C1-C3；R2For at least one of H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element；
R3And R4It is each independently the alkyl of H or C1-C4；R5For the alkyl of H or C1-C4；X is halogen element；N is the integer of 3-13；Formula
(7), the M in formula (9) and formula (10) is each independently H, Na or K.
8. copolymer according to claim 7, wherein R1For H or methyl；R2For H；R3And R4It is methyl；R5For H or first
Base；X is chlorine or bromine；N is the integer of 3-13；M in formula (7), formula (9) and formula (10) is each independently H or Na.
9. a kind of preparation method of amphoteric ion terpolymer, this method include：In depositing for initiator and water as solvent
Under, monomer D, monomer E and monomer F is made to carry out solution polymerization, wherein the monomer D is with structure shown in formula (11)
Monomer, the monomer E be the monomer with structure shown in formula (1), the monomer F be selected from structure, formula shown in formula (12)
(13) monomer of structure shown in structure and formula (15) shown in structure, formula (14) shown in, wherein the monomer D, monomer E and monomer F
Dosage so that the content that the content of structural unit A in the copolymer being prepared is 15-90 weight %, structural unit B is 5-
The content of 70 weight %, structural unit C are 5-60 weight %, and so that the viscosity average molecular weigh for the polymer being prepared is
300-1500 ten thousand；The structural unit A is the structural unit with structure shown in formula (5), and the structural unit B is with formula
(6) structural unit of structure shown in, the structural unit C is selected from structure, formula (9) institute shown in structure, formula (8) shown in formula (7)
Show the structural unit in structure shown in structure and formula (10),
Wherein, R1For the alkyl of H or C1-C3；R2For at least one of H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element；
R3And R4It is each independently the alkyl of H or C1-C4；R5For the alkyl of H or C1-C4；X is halogen element；N is the integer of 3-13；Formula
(7) and the M in formula (12), formula (9) and formula (14) and formula (10) and formula (15) is each independently H, Na or K.
10. according to the method described in claim 9, wherein, the condition of the solution polymerization includes：Temperature is 5-50 DEG C；
Time is 1-15h.
11. according to the method described in claim 9, wherein, the initiator includes azo-initiator, peroxide initiation
At least one of agent and redox type initiators；The azo-initiator is selected from azo-bis-iso-dimethyl, azo
Two NSC 18620 hydrochlorides, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano formamide, azo
Dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, azobisisovaleronitrile and idol
At least one of two different heptonitrile of nitrogen；The peroxide type initiators are selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, mistake
At least one of potassium sulfate, benzoyl peroxide and benzoyl peroxide tert-butyl ester；The redox type initiators are selected from
At least one of sulfate-sulphite, persulfate-thiocarbamide, persulfate-organic salt and ammonium persulfate-fatty amine.
12. the amphoteric ion terpolymer that the method described in any one of claim 9-11 is prepared.
13. the application of claim 7-8, the amphoteric ion terpolymer described in any one of 12 in water plugging and profile controlling.
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| CN101612537A (en) * | 2009-07-28 | 2009-12-30 | 上海美亚企业集团能源发展有限公司 | A kind of functional macromolecule surfactant and uses thereof |
| CN104098746A (en) * | 2014-07-02 | 2014-10-15 | 西南石油大学 | Adamantyl contained hydrophobic association zwitter-ion starch and preparation method thereof |
| CN104558403A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Cross-linked gradient swelling polymeric microsphere and preparation method thereof |
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| CN101612537A (en) * | 2009-07-28 | 2009-12-30 | 上海美亚企业集团能源发展有限公司 | A kind of functional macromolecule surfactant and uses thereof |
| CN104558403A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Cross-linked gradient swelling polymeric microsphere and preparation method thereof |
| CN104098746A (en) * | 2014-07-02 | 2014-10-15 | 西南石油大学 | Adamantyl contained hydrophobic association zwitter-ion starch and preparation method thereof |
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