CN106543022A - 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 field, disclose a kind of amphoteric ion copolymer cationic monomer and preparation method thereof and amphoteric ion copolymer and its preparation method and application, the amphoteric ion copolymer cationic monomer that the present invention is provided has the structure shown in formula (1), wherein, R1For the alkyl of H or C1-C3;R2For at least one in 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;Integers of the n for 3-13.The acrylamide amphoteric ion copolymer that the present invention is provided has stronger adsorptivity in surface of stratum, improves abrasion resistance of the polymer in surface of stratum due to introducing cation group.Due to there is the heat-resistant salt-resistant performance that amphion improves polymer simultaneously in molecule, can be used for high temperature and high salinity oil reservoir.
Description
Technical field
The present invention relates to copolymer field, in particular it relates to a kind of application of a kind of amphoteric ion copolymer cationic monomer and preparation method thereof, acrylamide amphoteric ion copolymer, a kind of preparation method of acrylamide amphoteric ion copolymer and the acrylamide amphoteric ion copolymer, acrylamide amphoteric ion copolymer that are prepared by the method in water plugging and profile controlling.
Background technology
With the increasingly exploitation in oil field, water proportion in the oil exploited is increasing.Well water will directly contribute the harm such as the decline of yield, the intensity increasing of the loss and water filling of stratum energy, and the corrosion aggravation of equipment pipe network, make development benefit be subject to serious impact.In order to reduce this unnecessary waste, Water in Water Shutoff in Oil Field is extremely important in oil extraction process as the means of water and oil control.China's water plugging and profiling technology is played an important role in oilfield development process through the development of more than 40 years.
The at present selective water-plugging used by oilwell water shutoff is to generate gel by water-soluble polymers such as polyacrylamide and its derivants in stratum or frozen glue is blocked to stratum water mostly, or meet water plastic or solidification closure water breakthrough passage to realize with oil base blocking agent, but due to existing blocking agent poor selectivity, oleic permeability can be also greatly lowered while water blockoff, low liquid after causing to block up, constrains the application of water shutoff in oil well.Therefore a kind of new high selectivity water shutoff material is developed, realizes that the water blockoff of oil reservoir does not block up oil, oil well productivity is improved to ultra-high water cut stage and is had great importance.
Amphoteric ion polymer due on strand simultaneous with anions and canons group, because of its unique molecular structure and good application performance, progressively popularization and application in oil-gas mining at home and abroad, such as water plugging profile control agent, reinforcing oil displacement agent, new fluid loss additive, visbreaking agent, shale control agent, additive for drilling fluid, cementing extra-agent, fracturing fluid additive etc..Which is prepared and the related art of application process mainly has CN103509154A, CN103694394A, CN104558405A, CN101412785A, CN1861654A, CN1386769A etc..
Amphoteric ion polymer has certain salt thickening property, and in the environment of the water saliferous of stratum, the ability of amphiphilic polymers and its formation gel blocking pore throat is higher, and this is the advantage not available for other gel profile control agents.When profile-controlling and plugging agent is used for using amphoteric ion polymer, as surface of stratum is negativity interface, the absorption that the cation group in amphoteric ion polymer can be strong increased the abrasion resistance of profile-controlling and plugging agent in surface of stratum.Additionally, the anion and cation in aqueous solution on water soluble amphoteric ion polymer molecular chain, as electrostatic attraction is acted on, in strand produces bonding action with molecule interchain, cause its strand to shrink, molecular conformation is more tight, and viscosity is little.And in saline solution, as this bonding action is by small molecule salt shielding, destruction, macromolecule-solvent interaction ability strengthens, molecular conformation becomes to unfold, viscosity increases, and fairly obvious anti-polyelectrolyte solution behavior is presented, and there is the salt tolerance that improve polymer so as to zwitterionic.
However, amphoteric ion polymer generally existing selectivity that above-mentioned prior art is provided is high, the shortcoming that heat resistance is poor.
Therefore, develop a kind of new amphoteric ion copolymer significant for water plugging and profile controlling.
The content of the invention
The purpose of the present invention is the defect that amphoteric ion copolymer selectivity is low, heat resistance is poor for overcoming prior art, rigid radical phenyl ring is introduced in polymer molecular structure, so as to provide a kind of new selectivity height, the more preferable acrylamide amphoteric ion copolymer of heat resistance.
To achieve these goals, in a first aspect, the present invention provides a kind of amphoteric ion copolymer cationic monomer, the monomer has the structure shown in formula (1),
Wherein, R1For the alkyl of H or C1-C3;R2For at least one in 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;Integers of the n for 3-13.
Second aspect, the present invention provide the preparation method of aforementioned amphoteric ion copolymer cationic monomer, and the method includes:
(1) in the basic conditions, the monomer shown in formula (2) is carried out into haptoreaction in organic solvent with the compound shown in formula (3);
(2) product obtained through step (1) is carried out into hybrid reaction with the compound shown in formula (4);
Wherein, R1、R2、R3、R4, the X and n such as present invention it is aforementioned define.
The third aspect, the present invention provides a kind of amphion terpolymer, the copolymer contains construction unit A, construction unit B and construction unit C, wherein, the construction unit A is the construction unit with structure shown in formula (5), the construction unit B is the construction unit with structure shown in formula (6), and the construction unit C is the construction unit in structure shown in formula (7), structure shown in formula (8), structure and structure shown in formula (10) shown in formula (9);On the basis of the weight of the amphion terpolymer, the content of the construction unit A is 15-90 weight %, the content of the construction unit B is 5-70 weight %, the content of the construction unit C is 5-60 weight %, and the viscosity-average molecular weight of the amphion terpolymer is 300-1500 ten thousand;
Wherein, R1For the alkyl of H or C1-C3;R2For at least one in 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;Integers of the n for 3-13;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 amphion terpolymer, and the method includes:In the presence of initiator and the water as solvent, make monomer D, monomer E and monomer F carry out solution polymerization, wherein, the monomer D is the monomer with structure shown in formula (11), the monomer E is the monomer with structure shown in formula (1), the monomer F is selected from structure shown in formula (12), structure shown in formula (13), the monomer of structure shown in formula (14) and structure shown in formula (15), wherein, the monomer D, it is 15-90 weight % that the consumption of monomer E and monomer F causes the content of construction unit A in the copolymer for preparing, the content of construction unit B is 5-70 weight %, the content of construction unit C is 5-60 weight %, and the viscosity-average molecular weight of the polymer for causing to prepare is 300-1500 ten thousand;The construction unit A is the construction unit with structure shown in formula (5), the construction unit B is the construction unit with structure shown in formula (6), the construction unit C is the construction unit in structure shown in formula (7), structure shown in formula (8), structure and structure shown in formula (10) shown in formula (9)
Wherein, R1For the alkyl of H or C1-C3;R2For at least one in 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;Integers of the n for 3-13;Formula (7) and formula (12), formula (9) and formula (14) and the M in formula (10) and formula (15) are each independently H, Na or K.
In terms of 5th, the present invention provides the amphion terpolymer that preceding method is prepared.
In terms of 6th, the present invention provides application of the aforementioned amphion terpolymer in water plugging and profile controlling.
The invention provides a kind of novel polymerizable cationic monomer, the cationic monomer has good heat resistance.The cationic monomer can obtain acrylamide amphoteric ion copolymer with acrylamides, anionic monomer polyreaction.
Acrylamide amphoteric ion copolymer obtained above has stronger adsorptivity in surface of stratum, improves abrasion resistance of the polymer in surface of stratum due to introducing cation group.Due to there is the heat-resistant salt-resistant performance that amphion improves polymer simultaneously in molecule, can be used for high temperature and high salinity oil reservoir.The copolymer be used as water plugging profile control agent when with good oil-water selectivity.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that specific embodiment described herein is merely to illustrate and explains the present invention, the present invention is not limited to.
In a first aspect, the invention provides a kind of amphoteric ion copolymer cationic monomer, the monomer has the structure shown in formula (1),
Wherein, R1For the alkyl of H or C1-C3;R2For at least one in 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;Integers of the n for 3-13.
In the present invention, connect the R of phenyl2Can for one, it is two or more.
The alkyl of the C1-C3 can be including but not limited to:Methyl, ethyl, n-pro-pyl and isopropyl.
The alkyl of the C1-C4 can be including but not limited to:Methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
The halogen element can be including but not limited to:Fluorine, chlorine, bromine, iodine.
The integer of the 3-13 can include:3rd, 4,5,6,7,8,9,10,11,12 and 13.
In the present invention, in formula (1), the preferably R1For H, methyl, ethyl, n-pro-pyl or normal-butyl;R2For at least one in H, methyl, ethyl, methoxyl group, ethyoxyl, chlorine and bromine;R3And R4It is each independently H, methyl, ethyl, n-pro-pyl or normal-butyl;X is chlorine or bromine;Integers of the n for 3-13.
In the present invention, in formula (1), the more preferably R1、R2、R3And R4Methyl is, X is bromine;Integers of the n for 3-13.
Second aspect, the invention provides the preparation method of aforementioned amphoteric ion copolymer cationic monomer, the method includes:
(1) in the basic conditions, the monomer shown in formula (2) is carried out into haptoreaction in organic solvent with the compound shown in formula (3);
(2) product obtained through step (1) is carried out into hybrid reaction with the compound shown in formula (4);
Wherein, R1、R2、R3、R4, the X and n such as present invention it is aforementioned define.
According to the present invention, noted earlier to the related definition such as present invention of the amphoteric ion copolymer cationic monomer in the preparation method of amphoteric ion copolymer cationic monomer, in order to avoid repeating, the present invention will not be described here.
In step (1), the catalytic condition can include:Temperature is 5-30 DEG C, and the time is 20-240min.
In step (1), the monomer shown in formula (2) can be 1 with the consumption mol ratio of the compound shown in formula (3):3-0.3.
In step (1), the alkalescence condition can be realized by the alkaline matter such as sodium hydroxide is added in reaction system, for example, the present invention by adopt concentration for 2-10mol/L sodium hydroxide solution realizing.It is preferred that the pH value of alkalescence condition of the present invention is 8-11.
In step (1), to the species of the organic solvent, there is no particular limitation, and the organic solvent can be at least one in dichloromethane, ether, ethyl acetate, chloroform and diisopropyl ether.There is no particular limitation for consumption of the method for the present invention to organic solvent, those skilled in the art can be selected according to conventional quantity of solvent, and the consumption of the present invention preferably organic solvent is 2-20 times of the consumption (weight) of the compound shown in formula (3).
Monomer shown in the formula (2) can be obtained by method synthesis that is commercially available or being provided using prior art.The method that the present invention exemplarily provides synthesizing methyl acryloyl chloride (one kind in monomer shown in formula (2)):
Using the monomer shown in the reaction bulb synthesis type (2) with distilling apparatus and Dropping funnel.Benzenecarbonyl chloride., methacrylic acid and polymerization inhibitor are added in reaction bulb, methacrylic acid is housed in Dropping funnel.Reaction mass under the conditions of vacuum (0.01-0.05MPa) in heated and stirred reaction bulb, when temperature has risen to methacrylic chloride to be steamed, starts with Dropping funnel Deca methacrylic acid.Wherein, polymerization inhibitor can be selected from least one in hydroquinone, p-tert-Butylcatechol, Cu-lyt. and butter of tin.The polymerization inhibitor is the 0.05-2% of reactant liquor gross mass in reaction bulb.The amount of the material of the Benzenecarbonyl chloride. is 3-0.3 with the amount ratio of the total material of methacrylic acid:1.5-20% of the quality of the methacrylic acid in reaction bulb for methacrylic acid gross mass.Reaction temperature is 50-85 DEG C, and the response time is 20-120min.
In step (1), the haptoreaction can be carried out in the presence of noble gases such as nitrogen.
Those skilled in the art can carry out post processing to the reactant mixture obtained through step (1) using conventional use of post processing means in the art.For example post processing can be carried out to the reactant mixture obtained through step (1) using following steps:The reactant mixture that separation is obtained through step (1), obtains organic layer, removes solvent, polymerization inhibitor is added in the concentrated solution for obtaining, then reduced pressure (vacuum 50Pa) distillation, collect 90-100 DEG C, obtain final product the product obtained through step (1).Wherein, the species of the polymerization inhibitor is as previously mentioned.0.01-5% of the quality of polymerization inhibitor for the quality of concentrated solution.
In step (2), the condition of the hybrid reaction can include:Temperature is 20-100 DEG C, and the time is 2-10h.
In step (2), the compound preferably shown in the formula (3) is 0.3-3 with the consumption mol ratio of the monomer shown in formula (2):1.
In step (2), also include that the step of the step of mix products obtained after the product that step (1) is obtained carries out hybrid reaction with the compound shown in formula (4) are carried out post processing, post processing can include:The mix products are washed with ether, and is 1 with volume ratio:1 acetone and the mixture of ether carry out recrystallization, and the product obtained by recrystallization is dried, that is, obtain amphoteric ion copolymer cationic monomer of the present invention.
The amphoteric ion copolymer provided using the present invention is high with the amphion terpolymer selectivity that cationic monomer participates in polymerization formation, can be used as water plugging profile control agent application.
The third aspect, the invention provides a kind of amphion terpolymer, the copolymer contains construction unit A, construction unit B and construction unit C, wherein, the construction unit A is the construction unit with structure shown in formula (5), the construction unit B is the construction unit with structure shown in formula (6), and the construction unit C is the construction unit in structure shown in formula (7), structure shown in formula (8), structure and structure shown in formula (10) shown in formula (9);On the basis of the weight of the amphion terpolymer, the content of the construction unit A is 15-90 weight %, the content of the construction unit B is 5-70 weight %, the content of the construction unit C is 5-60 weight %, and the viscosity-average molecular weight of the amphion terpolymer is 300-1500 ten thousand;
Wherein, R1For the alkyl of H or C1-C3;R2For at least one in 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;Integers of the n for 3-13;M in formula (7), formula (9) and formula (10) is each independently H, Na or K.
In the present invention, shown in the formula (6), the construction unit of structure is corresponding with the structures alone shown in formula (1), corresponding definition of the definition of the aforementioned structures alone to shown in formula (1) suitable for the construction unit of structure shown in formula (6), the present invention will not be described here.
In the construction 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-pro-pyl or normal-butyl;More preferably described R5For H, methyl or ethyl;The particularly preferably R5For H or methyl.
M in the construction unit of structure shown in formula (7), the construction unit of structure and the construction unit of structure shown in formula (10) shown in formula (9) is each independently H, Na or K;It is preferred that the M is each independently H or Na;The particularly preferably M is Na.
According to a kind of preferred embodiment, amphion terpolymer of the present invention contains construction unit A, construction unit B and construction unit C, wherein, the construction unit A is the construction unit with structure shown in formula (5), the construction unit B is the construction unit with structure shown in formula (6), and the construction unit C is the construction unit in structure shown in formula (7), structure shown in formula (8), structure and structure shown in formula (10) shown in formula (9);Wherein, R1For H, methyl, ethyl or n-pro-pyl;R2For at least one in H, methyl, ethyl, methoxyl group, ethyoxyl and halogen element;R3And R4It is each independently H, methyl, ethyl, n-pro-pyl or normal-butyl;R5For H, methyl, ethyl, n-pro-pyl or normal-butyl;X is chlorine or bromine;Integers of the n for 3-13;M in formula (7), formula (9) and formula (10) is each independently H or Na.
According to another kind of preferred embodiment, amphion terpolymer of the present invention contains construction unit A, construction unit B and construction unit C, wherein, the construction unit A is the construction unit with structure shown in formula (5), the construction unit B is the construction unit with structure shown in formula (6), and the construction unit C is the construction unit in structure shown in formula (7), structure shown in formula (8), structure and structure shown in formula (10) shown in formula (9);Wherein, R1For H or methyl;R2For at least one in H, methyl, ethyl;R3And R4It is each independently H, methyl or ethyl;R5For H, methyl or ethyl;X is chlorine or bromine;Integers of the n for 3-13;M in formula (7), formula (9) and formula (10) is each independently H or Na.
According to another kind of preferred embodiment, amphion terpolymer of the present invention contains construction unit A, construction unit B and construction unit C, wherein, the construction unit A is the construction unit with structure shown in formula (5), the construction unit B is the construction unit with structure shown in formula (6), and the construction unit C is the construction unit in structure shown in formula (7), structure shown in formula (8), structure and structure shown in formula (10) shown in formula (9);Wherein, R1For H or methyl;R2For H;R3And R4It is methyl;R5For H or methyl;X is chlorine or bromine;Integers of the n for 3-13;M in formula (7), formula (9) and formula (10) is each independently H or Na.
In the case of more preferably, in the present invention, on the basis of the weight of the amphion terpolymer, the content of the construction unit A is 30-90 weight %, the content of the construction unit B is 5-50 weight %, the content of the construction unit C is 5-50 weight %, and the viscosity-average molecular weight of the amphion terpolymer is 500-1000 ten thousand.
Fourth aspect, the invention provides a kind of preparation method of amphion terpolymer, the method includes:In the presence of initiator and the water as solvent, make monomer D, monomer E and monomer F carry out solution polymerization, wherein, the monomer D is the monomer with structure shown in formula (11), the monomer E is the monomer with structure shown in formula (1), the monomer F is selected from structure shown in formula (12), structure shown in formula (13), the monomer of structure shown in formula (14) and structure shown in formula (15), wherein, the monomer D, it is 15-90 weight % that the consumption of monomer E and monomer F causes the content of construction unit A in the copolymer for preparing, the content of construction unit B is 5-70 weight %, the content of construction unit C is 5-60 weight %, and the viscosity-average molecular weight of the polymer for causing to prepare is 300-1500 ten thousand;The construction unit A is the construction unit with structure shown in formula (5), the construction unit B is the construction unit with structure shown in formula (6), the construction unit C is the construction unit in structure shown in formula (7), structure shown in formula (8), structure and structure shown in formula (10) shown in formula (9)
Wherein, R1For the alkyl of H or C1-C3;R2For at least one in 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;Integers of the n for 3-13;Formula (7) and formula (12), formula (9) and formula (14) and the M in formula (10) and formula (15) are each independently H, Na or K.
The definition of the construction unit of structure shown in the formula (5), the construction unit of structure shown in formula (6), the construction unit of structure shown in formula (7), the construction unit of structure shown in formula (8), the construction unit of structure shown in formula (9), the construction unit of structure shown in formula (10) and the related group of the construction unit of structure shown in formula (1) is identical with aforesaid related definition respectively, and the present invention will not be described here.And, the monomer of structure shown in the formula (11), the monomer of structure shown in formula (12), the monomer of structure shown in formula (13), the monomer of the monomer of structure shown in formula (14) and structure shown in formula (15) is respectively the construction unit of structure shown in formula (5), the construction unit of structure shown in formula (7), the construction unit of structure shown in formula (8), the construction unit of structure shown in formula (9) and the monomer shown in formula (10) corresponding to the construction unit of structure, therefore, for the monomer of structure shown in formula (11), the monomer of structure shown in formula (12), the monomer of structure shown in formula (13), the monomer of structure shown in formula (14) is identical to the related definition defined in corresponding monomer of the related group in the monomer of structure shown in formula (15).
Simultaneously, the amphion terpolymer for preparing being related in the preparation method of the amphion terpolymer it is preferred embodiment identical with the preferred embodiment of aforementioned amphion terpolymer, in order to avoid repeating, the present invention will not be described here.
The condition of the solution polymerization is preferably included:Temperature is 5-50 DEG C;Time is 1-15h.
The method according to the invention, there is no particular limitation for the consumption of the initiator, can change in wider scope, and on the basis of the total amount of the monomer D, the monomer E and the monomer F, the consumption of the initiator is 0.01-0.1 weight %.
The method according to the invention, the initiator can be the conventional various initiators in this area, for example, can be any two kinds in radical polymerization initiator:The radical polymerization initiator includes azo-initiator, peroxide type initiators and redox type initiators.At least one of the azo-initiator in azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azodicarbonamide, azo dicyclohexyl formonitrile HCN hydrochlorate, azo isobutyl cyano group Methanamide, azo diisopropyl imidazoline hydrochloride, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile);The peroxide type initiators are selected from hydrogen peroxide, Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate, at least one in benzoyl peroxide and the benzoyl peroxide tert-butyl ester;At least one of the redox type initiators in sulfate-sulphite, persulfate-thiourea, persulfate-organic salt and Ammonium persulfate .-fatty amine.
The method according to the invention, adds chelating agen prevent metal ion from producing impact to polyreaction, it is therefore preferable that in the case of, the solution polymerization is carried out in the presence of chelating agen.The chelating agen can be disodiumedetate, aminotriacetic acid or ammonium citrate, preferably disodiumedetate.There is no particular limitation for consumption of the present invention to the chelating agen, can change in wider scope, and on the basis of the total amount of the monomer D, the monomer E and the monomer F, the consumption of the chelating agen can be 0.1-0.3 weight %.
The method according to the invention, adds auxiliary agent improve the dissolubility of polymer, it is therefore preferable that in the case of, the solution polymerization is carried out in the presence of auxiliary agent.The auxiliary agent can be at least one in carbamide, thiourea and ammonia, preferably carbamide.There is no particular limitation for consumption of the present invention to the auxiliary agent, can change in wider scope, and on the basis of the total amount of the monomer D, the monomer E and the monomer F, the consumption of the auxiliary agent can be 0.01-0.1 weight %.
The method according to the invention, adds molecular weight regulator synthesize the polymer of different molecular weight, it is therefore preferable that in the case of, the polyreaction is carried out in the presence of molecular weight regulator.The molecular weight regulator can be isopropanol, ammonia, N, at least one in N '-methylene-bisacrylamide and dimethyl sulfourea.The consumption of the molecular weight regulator can be selected according to the conventional amount used of this area.For example, on the basis of the total amount of the monomer D, the monomer E and the monomer F, the consumption of the molecular weight regulator can be 0.001-0.1 weight %.
In terms of 5th, the invention provides the amphion terpolymer that preceding method is prepared.
In terms of 6th, the invention provides application of the aforementioned amphion terpolymer in water plugging and profile controlling.
Amphion terpolymer product of the present invention can be used in oil recovery process as high selectivity water plugging profile control agent.When using as water plugging profile control agent, have the advantages that the stifled oil selectivity of resistance to erosion, temperature-resistant anti-salt, water blockoff is high, affect little to oleic permeability.As water plugging profile control agent when Oil Field is used, the mass concentration of preferred amphion terpolymer is 0.01-0.5%.
Hereinafter will be described the present invention by embodiment.
The intrinsic viscosity η of polymer is measured by the polyacrylamide Intrinsic Viscosity Measurements method that GB12005.1-89 specifies, determines 10 weight %NaCl solution with Ubbelohde viscometer at 25 DEG C.
Viscosity molecular weight is according to formula M=([η]/K)1/ αIt is calculated, wherein K=4.75 × 10-3, α=0.80.
In following examples, used reagent is commercially available chemically pure reagent.
Preparation example 1
This preparation example is used to prepare methacrylic chloride (one kind in monomer shown in formula (2)):
Agitator, dephlegmator, Dropping funnel, thermometer are loaded onto on four-hole boiling flask, the receiving bottle with the adapter of vacuum tail is loaded onto after condensing tube.The Cu-lyt. of the Benzenecarbonyl chloride., the methacrylic acid of 0.3mol and 0.7g of 3.0mol is added in flask.The methacrylic acid of 2.7mol is added in Dropping funnel.Start vacuum pump vacuum is controlled for 0.2MPa.Heated and stirred is 75 DEG C to temperature, has methacrylic chloride to distillate in receiving bottle.Meanwhile, with Dropping funnel Deca methacrylic acid.Heated and stirred reacts 60min.Obtain methacryl chlorine products stand-by.
Preparation example 2
This preparation example is used to prepare amphoteric ion copolymer cationic monomer (bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium):
(1) in the three neck round bottom flask equipped with agitator and logical nitrogen pipe, 250mL dichloromethane, the 4- amino-DMA of 0.3mol and 9mol/L sodium hydroxide solution 40mL are added.Nitrogen is passed through, the stirring and dissolving at 5 DEG C.The methacrylic chloride prepared by the 0.3mol preparation examples 1 that 50mL dichloromethane dissolves is added dropwise to Dropping funnel.Stirring reaction 90min.Isolated organic layer, is distilled off solvent, obtains 50.9g products.0.08g phenothiazine, vacuum distillation will be added in products therefrom.90-100 DEG C, the fraction of vacuum 50Pa are collected, products therefrom is Methacrylamide to phenyl dimethyl amine;
(2), after the Methacrylamide for obtaining 0.1mol steps (1) stirs mixing in reaction bulb to phenyl dimethyl amine, 0.15mol bromododecanes and 4g pyridines, logical nitrogen reacts 4h at 50 DEG C.Washed with ether after product is cooled down, by 1 after drying:The mixture recrystallization of the acetone and ether of 1 (v/v).Bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium will be obtained after product drying after purification.
Preparation example 3
This preparation example is used to prepare amphoteric ion copolymer cationic monomer (bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium):
(1) in the three neck round bottom flask equipped with agitator and logical nitrogen pipe, 250mL dichloromethane, the 4- amino-DMA of 0.3mol and 9mol/L sodium hydroxide solution 60mL are added.Nitrogen is passed through, the stirring and dissolving at 8 DEG C.The methacrylic chloride prepared by the 0.5mol preparation examples 1 that 60mL dichloromethane dissolves is added dropwise to Dropping funnel.Stirring reaction 90min.Isolated organic layer, is distilled off solvent, obtains 52.5g products.0.07g phenothiazine, vacuum distillation will be added in products therefrom.90-100 DEG C, the fraction of vacuum 50Pa are collected, products therefrom is Methacrylamide to phenyl dimethyl amine;
(2), after the Methacrylamide for obtaining 0.1mol steps (1) stirs mixing in reaction bulb to phenyl dimethyl amine, 0.15mol bromoundecanes and 4g pyridines, logical nitrogen reacts 5h at 60 DEG C.Washed with ether after product is cooled down, by 1 after drying:The mixture recrystallization of the acetone and ether of 1 (v/v).Bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium will be obtained after product drying after purification.
Preparation example 4
This preparation example is used to prepare amphoteric ion copolymer cationic monomer (bromination dimethylhexanyl (2- methacryl amidos are to phenyl) ammonium):
(1) in the three neck round bottom flask equipped with agitator and logical nitrogen pipe, 250mL ether, the 4- amino-DMA of 0.35mol and 9mol/L sodium hydroxide solution 75mL are added.Nitrogen is passed through, the stirring and dissolving at 10 DEG C.The methacrylic chloride prepared by the 0.45mol preparation examples 1 that 60mL dichloromethane dissolves is added dropwise to Dropping funnel.Stirring reaction 90min.Isolated organic layer, is distilled off solvent, obtains 56.3g products.0.10g phenothiazine, vacuum distillation will be added in products therefrom.90-100 DEG C, the fraction of vacuum 50Pa are collected, products therefrom is Methacrylamide to phenyl dimethyl amine;
(2), after the Methacrylamide for obtaining 0.1mol steps (1) stirs mixing in reaction bulb to phenyl dimethyl amine, 0.18mol bromos hexane and 6g pyridines, logical nitrogen reacts 4h at 70 DEG C.Washed with ether after product is cooled down, by 1 after drying:The mixture recrystallization of the acetone and ether of 1 (v/v).Bromination dimethylhexanyl (2- methacryl amidos are to phenyl) ammonium will be obtained after product drying after purification.
Embodiment 1
The present embodiment is used to prepare amphion terpolymer of the present invention:
Bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium, the 2- acrylamide-2-methylpro panesulfonic acid sodium of 3.0g, 100g distilled water that 20g acrylamides, 5.0g preparation examples 2 prepare, stirring and dissolving are added in reaction bulb.Deca mass concentration is that 20% sodium hydrate aqueous solution adjusts pH for 9.Add sodium sulfite 10mg and Ammonium persulfate. 15mg, lead to nitrogen reaction 5h at 25 DEG C, obtain acrylamide/bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium/2- acrylamide-2-methylpro panesulfonic acid sodium terpolymer crude products.Crude product is vacuum dried at 50 DEG C, acrylamide/bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium/2- acrylamide-2-methylpro panesulfonic acid sodium terpolymer products after crushing, are obtained.Adopt viscosimetry to determine with Ubbelohde viscometer its relative molecular mass is obtained as 7,500,000.
Embodiment 2
The present embodiment is used to prepare amphion terpolymer of the present invention:
Bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium, 3.0g acrylic acid, 100g distilled water that 23g acrylamides, 3.0g preparation examples 3 prepare, stirring and dissolving are added in reaction bulb.Deca mass concentration is that 20% sodium hydrate aqueous solution adjusts pH for 9.Sodium sulfite 10mg and Ammonium persulfate. 20mg is added, is led to nitrogen reaction 5h at 20 DEG C, is obtained acrylamide/bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium/acrylic ternary copolymer crude product.Crude product is vacuum dried at 50 DEG C, acrylamide/bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium/acrylic ternary copolymer product after crushing, is obtained.Adopt viscosimetry to determine with Ubbelohde viscometer its relative molecular mass is obtained as 6,500,000.
Embodiment 3
The present embodiment is used to prepare amphion terpolymer of the present invention:
Bromination dimethylhexanyl (2- methacryl amidos are to phenyl) ammonium, 3.2g propene sulfonic acids, 100g distilled water that 25g acrylamides, 4.5g preparation examples 4 prepare, stirring and dissolving are added in reaction bulb.Deca mass concentration is that 20% sodium hydrate aqueous solution adjusts pH for 9.Sodium sulfite 10mg and Ammonium persulfate. 20mg is added, is led to nitrogen reaction 4h at 30 DEG C, is obtained acrylamide/bromination dimethylhexanyl (2- methacryl amidos are to phenyl) ammonium/propene sulfonic acid terpolymer crude product.Crude product is vacuum dried at 50 DEG C, acrylamide/bromination dimethylhexanyl (2- methacryl amidos are to phenyl) ammonium/propene sulfonic acid terpolymer product after crushing, is obtained.Adopt viscosimetry to determine with Ubbelohde viscometer its relative molecular mass is obtained as 6,800,000.
Embodiment 4
The present embodiment is used to prepare amphion terpolymer of the present invention:
Add in reaction bulb prepare in 4g preparation examples 2 bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium, 20g acrylamides, 4g vinylbenzenesulfonic acids, 100g distilled water, stirring and dissolving.Deca mass concentration is that 20% sodium hydrate aqueous solution adjusts pH for 9.Sodium sulfite 10mg and Ammonium persulfate. 15mg is added, is led to nitrogen isothermal reaction 5h at 20 DEG C, is obtained acrylamide/bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium/vinylbenzenesulfonic acid terpolymer crude product.Crude product is vacuum dried at 50 DEG C, acrylamide/bromination dimethyl dodecyl base (2- methacryl amidos are to phenyl) ammonium/vinylbenzenesulfonic acid terpolymer product after crushing, is obtained.Adopt viscosimetry to determine with Ubbelohde viscometer its relative molecular mass is obtained as 8,200,000.
Embodiment 5
Bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium, 20g acrylamides, 4g propene sulfonic acids, 100g distilled water that 5g preparation examples 3 prepare, stirring and dissolving are added in reaction bulb.It is 9 that 20% sodium hydrate aqueous solution of Deca mass concentration adjusts pH.Sodium sulfite 10mg and Ammonium persulfate. 20mg is added, is led to nitrogen reaction 5h at 20 DEG C, is obtained acrylamide/bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium/propene sulfonic acid terpolymer crude product.Crude product is vacuum dried at 50 DEG C, acrylamide/bromination dimethyl undecyl (2- methacryl amidos are to phenyl) ammonium/propene sulfonic acid terpolymer product after crushing, is obtained.Adopt viscosimetry to determine with Ubbelohde viscometer its relative molecular mass is obtained as 5,700,000.
Test case 1
This test case is used to illustrate terpolymer product synthesized by embodiment 1-5 respectively to oil, the sealing characteristics of water.
The sealing ratiod of polymeric articles is investigated using rock core displacement test, sealing ratiod is by determining the change of permeability before and after reservoir core plugging determining.
(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;
Simulation oil sample:Crude oil is 1 with the weight ratio of neutral kerosene:0.9, crude oil and neutral kerosene are from Shengli Oil Field;
Simulated formation water (high salinity):Salinity is 32868mg/L, consists of Mg2+177mg/L, Ca2+700mg/L, K++Na+11668mg/L, Cl-20323mg/L。
Terpolymer aqueous solution:Test sample is formulated as the aqueous solution of mass concentration 500mg/L with high salinity simulated formation water.
(2) method of testing
Artificial core is evacuated, under the conditions of 90 DEG C, with simulated formation water (high salinity) saturation.Its oleic permeability K is determined with simulation oil displacementO1, with simulated formation water drive for measure its water phase permeability KW1, the terpolymer aqueous solution of aforementioned preparation is injected, then water phase permeability K is determined with the positive anti-row of simulated formation waterW2, with simulation oil, positive anti-row determines oleic permeability KO2.Data processing is finally carried out, water plugging rate and oil plugging rate is calculated, so as to assess water plugging effect and selectivity, as a result as shown in table 1.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 |
When the amphion terpolymer that present invention offer be can be seen that from the result of the test case of the present invention is used as water plugging profile control agent under the conditions of high temperature and high salinity, with good oil-water selectivity, water plugging effect is good, it is possible to increase single well productivity.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the range of the technology design of the present invention; various simple variants can be carried out to technical scheme, these simple variants belong to protection scope of the present invention.
It is further to note that, each particular technique feature described in above-mentioned specific embodiment, in the case of reconcilable, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is no longer separately illustrated to various possible compound modes.
Additionally, combination in any can also be carried out between a variety of embodiments of the present invention, as long as which is without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of amphoteric ion copolymer cationic monomer, it is characterised in that the monomer has formula (1)
Shown structure,
Wherein, R1For the alkyl of H or C1-C3;R2For H, methyl, ethyl, methoxyl group, ethoxy
At least one in base and halogen element;R3And R4It is each independently the alkyl of H or C1-C4;X is
Halogen element;Integers of the n for 3-13.
2. monomer according to claim 1, wherein, R1For H or methyl;R2For H;R3
And R4It is methyl;X is chlorine or bromine;Integers of the n for 3-13.
3. the preparation method of the amphoteric ion copolymer cationic monomer described in claim 1 or 2,
The method includes:
(1) in the basic conditions, the monomer shown in formula (2) is existed with the compound shown in formula (3)
Haptoreaction is carried out in organic solvent;
(2) product obtained through step (1) and the compound shown in formula (4) are carried out mixing anti-
Should;
Wherein, R1、R2、R3、R4, X and n such as claim 1 or 2 defined.
4. method according to claim 3, wherein, in step (1), the haptoreaction
Condition include:Temperature is 5-30 DEG C, and the time is 20-240min;It is preferred that
Monomer shown in formula (2) is 1 with the consumption mol ratio of the compound shown in formula (3):3-0.3.
5. method according to claim 3, wherein, in step (2), the hybrid reaction
Condition include:Temperature is 20-100 DEG C, and the time is 2-10h;It is preferred that
Compound shown in the formula (3) is 0.3-3 with the consumption mol ratio of the monomer shown in formula (2):
1。
6. a kind of amphion terpolymer, it is characterised in that the copolymer contains construction unit
A, construction unit B and construction unit C, wherein, the construction unit A is with formula (5) Suo Shi
The construction unit of structure, the construction unit B is the construction unit with structure shown in formula (6), institute
It is selected from knot shown in structure shown in formula (7), structure shown in formula (8), formula (9) to state construction unit C
Construction unit in structure and structure shown in formula (10);Weight with the amphion terpolymer is
Benchmark, the content of the construction unit A is 15-90 weight %, and the content of the construction unit B is
5-70 weight %, the content of the construction unit C is 5-60 weight %, the amphion ternary polymerization
The viscosity-average molecular weight of thing is 300-1500 ten thousand;
Wherein, R1For the alkyl of H or C1-C3;R2For H, methyl, ethyl, methoxyl group, ethoxy
At least one in base and halogen element;R3And R4It is each independently the alkyl of H or C1-C4;R5
For the alkyl of H or C1-C4;X is halogen element;Integers of the n for 3-13;Formula (7), formula (9)
H, Na or K are each independently with the M in formula (10).
7. copolymer according to claim 6, wherein, R1For H or methyl;R2For H;R3
And R4It is methyl;R5For H or methyl;X is chlorine or bromine;Integers of the n for 3-13;Formula (7),
M in formula (9) and formula (10) is each independently H or Na.
8. a kind of preparation method of amphion terpolymer, the method include:In initiator and work
In the presence of for the water of solvent, monomer D, monomer E and monomer F is made to carry out solution polymerization, its
In, the monomer D is the monomer with structure shown in formula (11), and the monomer E is with formula (1)
The monomer of shown structure, the monomer F be selected from structure shown in formula (12), structure shown in formula (13),
The monomer of structure shown in formula (14) and structure shown in formula (15), wherein, the monomer D, monomer E
It is 15-90 weights with the content that the consumption of monomer F causes construction unit A in the copolymer for preparing
The content of amount %, construction unit B is 5-70 weight %, and the content of construction unit C is 5-60 weight %,
And the viscosity-average molecular weight of the polymer for causing to prepare is 300-1500 ten thousand;The construction unit A
It is the construction unit with structure shown in formula (5), the construction unit B is to tie with formula (6) Suo Shi
The construction unit of structure, the construction unit C be selected from structure shown in formula (7), structure shown in formula (8),
Construction unit in structure and structure shown in formula (10) shown in formula (9),
Wherein, R1For the alkyl of H or C1-C3;R2For H, methyl, ethyl, methoxyl group, ethoxy
At least one in base and halogen element;R3And R4It is each independently the alkyl of H or C1-C4;R5
For the alkyl of H or C1-C4;X is halogen element;Integers of the n for 3-13;Formula (7) and formula (12),
Formula (9) and formula (14) and the M in formula (10) and formula (15) are each independently H, Na
Or K.
9. method according to claim 8, wherein, the condition of the solution polymerization includes:
Temperature is 5-50 DEG C;Time is 1-15h.
10. according to method according to claim 8, wherein, the initiator includes that azo draws
Send out at least one in agent, peroxide type initiators and redox type initiators;The azo
Initiator selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azodicarbonamide,
Azo dicyclohexyl formonitrile HCN hydrochlorate, azo isobutyl cyano group Methanamide, azo diisopropyl imidazoline hydrochloride,
Azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and
At least one in 2,2'-Azobis(2,4-dimethylvaleronitrile);The peroxide type initiators are selected from hydrogen peroxide, over cure
In sour ammonium, sodium peroxydisulfate, potassium peroxydisulfate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester extremely
Few one kind;The redox type initiators are selected from sulfate-sulphite, persulfate-thiourea, mistake
At least one in sulfate-organic salt and Ammonium persulfate .-fatty amine.
The amphion ternary that method in 11. claim 8-10 described in any one is prepared is altogether
Polymers.
12. claim 6-7, the amphion terpolymer in 11 described in any one are adjusted in water blockoff
Application in cuing open.
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