CN106588754B - Styrene compound and acrylamide copolymer and its preparation method and application - Google Patents
Styrene compound and acrylamide copolymer and its preparation method and application Download PDFInfo
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- CN106588754B CN106588754B CN201510684472.8A CN201510684472A CN106588754B CN 106588754 B CN106588754 B CN 106588754B CN 201510684472 A CN201510684472 A CN 201510684472A CN 106588754 B CN106588754 B CN 106588754B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D211/74—Oxygen atoms
- C07D211/76—Oxygen atoms attached in position 2 or 6
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The present invention relates to field of petroleum exploitation, disclose a kind of styrene compound, which has structure shown in Formulas I.The invention also discloses it is a kind of containing compound shown in Formulas I provide structural unit and intrinsic viscosity be 17-30dl/g acrylamide copolymer and preparation method thereof, this method is included in the presence of solution polymerization condition and initiator, and monomer mixture is made to carry out polymerization reaction in aqueous solution；The monomer mixture contains styrene compound monomer and acrylamide monomers shown in Formulas I, on the basis of the total weight of monomer mixture, the content of styrene compound monomer is 1-99 weight %, and the weight ratio of styrene compound monomer and acrylamide monomers is 100:1-100.The invention also discloses the acrylamide copolymers to prepare the application in oil displacement agent.Styrene compound provided by the invention and acrylamide copolymerization can be obtained compared with high salinity and at a temperature of be still able to maintain the water solubility copolymer of higher apparent viscosity.
Description
Technical field
The present invention relates to field of petroleum exploitation, and in particular, to a kind of styrene suitable for preparing water solubility copolymer
Class compound and acrylamide copolymer and its preparation method and application.
Background technique
Important component of the water-soluble polymer as Oilfield Chemicals, in drilling well, well cementation, acidification and tertiary oil recovery, all
It plays a very important role.Polymer displacement of reservoir oil is one of the important method in tertiary oil recovery technology, it is molten using polymer
The high viscosity and residual resistance factor of liquid adjust intake profile, improve oil and water mobility ratio, improve oil recovery to reach
Purpose.It is therefore desirable to aqueous solutions of polymers viscosity with higher, and can be under conditions of high salinity and high temperature, still
The viscosity of high value can so be kept.Applied to improve recovery ratio water-soluble polymer there are two main classes: one kind is propylene
Amide polymer, another kind of is biopolymer (such as xanthan gum).In contrast, wide, cheap with source due to the former,
The advantages that dissolubility and good tackifying, substantially exceeds biopolymer in the use ratio improved in oil recovery, but third
Acrylamide polymer, facing, reservoir media is severe, such as in the condition of high temperature and high salinity condition, is easy degradation, heat is steady
Qualitative, salt tolerance is poor, at this moment has to use biopolymer in large quantities.
At this stage, China Petroleum is faced with the mining problem of high temperature and high salt oil deposit, the energy ring based on current sternness
How border exploits the oil reservoir under harsh geological environment, becomes the huge challenge of petroleum industry.Prepare high molecular weight and temperature-resistant anti-salt
It is main challenge direction that type acrylamide polymer type oil recovery auxiliary agent, which substitutes bio-based polymers,.
Summary of the invention
Monomer is suitable as the purpose of the present invention is overcoming the deficiencies of the prior art and provide one kind and prepares temperature-resistant anti-salt water
Styrene compound and acrylamide copolymer of soluble copolymer and its preparation method and application.
To achieve the goals above, in a first aspect, the present invention provides a kind of styrene compounds, wherein the chemical combination
Object has structure shown in following formula I:
Wherein, R1And R2It is each independently selected from H or C1-20Alkyl, m=1 or 2.
Second aspect, the present invention provides a kind of acrylamide copolymers, wherein the acrylamide copolymer contains Formulas I a
Shown in structural unit B shown in structural unit A and Formula V a, it is described on the basis of the total weight of the acrylamide copolymer
The content of structural unit A is that the weight ratio of 1-99 weight %, the structural unit A and structural unit B are 100:1-100, described
The intrinsic viscosity of acrylamide copolymer is 17-30dl/g,
Wherein, R1、R2And R3It is each independently selected from H or C1-20Alkyl, m=1 or 2.
The third aspect, the present invention provides a kind of method for preparing acrylamide copolymer, it is poly- that this method is included in solution
It closes under reaction condition, in the presence of initiator or in the presence of reagent and additive in polymerization and initiator, makes monomer mixture in water
Polymerization reaction, the intrinsic viscosity 17-30dl/g for the copolymer that the condition of polymerization reaction makes are carried out in solution；The monomer
Mixture contains acrylamide monomers shown in styrene compound monomer and Formula V shown in Formulas I, with monomer mixing
On the basis of the total weight of object, the content of the styrene compound monomer is 1-99 weight %, the styrene compound
The weight ratio of monomer and acrylamide monomers is 100:1-100,
Wherein, R1、R2And R3It is each independently selected from H or C1-20Alkyl, m=1 or 2.
Fourth aspect, the present invention provides acrylamide copolymers made from the method described in the third aspect.
5th aspect, the present invention provides acrylamide copolymers described in second aspect or fourth aspect in the preparation displacement of reservoir oil
Application in agent.
Styrene compound provided by the invention have benzene ring structure and lactam structure, can keep at high temperature compared with
High thermal stability, while there is good water solubility again, it can be obtained with acrylamide copolymerization compared with high salinity and temperature
Under be still able to maintain the water solubility copolymer of higher apparent viscosity, temperature-resistant anti-salt performance is strong.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments 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.
Styrene compound provided by the invention has structure shown in following formula I:
Wherein, R1And R2It is each independently selected from H or C1-20Alkyl (C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、
C12、C13、C14、C15、C16、C17、C18、C19、C20Or the alkyl between above-mentioned any carbon atom number), m=1 or 2.Of the invention
In preferred embodiment, R1And R2It is each independently selected from H or methyl, it is highly preferred that m=1.
In Formulas I,Ortho position, the meta or para position of vinyl can be connected in.R1And R2It is identical or different.
In the present invention, the C1-20Alkyl can be straight chain, be also possible to branch.The C1-20Alkyl
Example can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, positive penta
Base, isopentyl, tertiary pentyl, neopentyl, n-hexyl, 2- methyl amyl, 3- methyl amyl, 4- methyl amyl, 1,2- dimethyl butyrate
Base, 1,3- dimethylbutyl, 2,3- dimethylbutyl, 1,1- dimethylbutyl, 2,2- dimethylbutyl, 3,3- dimethyl butyrate
Base, 1,1,2- thmethylpropyl, 1,2,2- thmethylpropyl, 1- ethyl-butyl, 2- ethyl-butyl, 1- Ethyl-2-Methyl propyl,
N-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, positive ten
Five alkyl, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base and n-eicosane base.
Most preferred embodiment according to the present invention, the styrene compound are one of following compounds:
The preparation method of above-mentioned styrene compound provided by the invention may include: by lactams shown in Formula II
And/or its salt is mixed with alkaline agent, and by vinyl benzyl chloride haptoreaction, reselection shown in obtained mixture and formula III
Property in the presence of alkylating reagent, the alkylation of the product that obtains haptoreaction,
(m=1 or 2, preferably m=1)
Wherein, the salt of lactams shown in Formula II can be the salt of the common various lactams in this field, including but unlimited
In hydrochloride, sulfate and acetate.Vinyl benzyl chloride shown in formula III can be for vinyl benzyl chloride, vinyl benzyl chloride
At least one of with adjacent vinyl benzyl chloride, preferably to vinyl benzyl chloride.
In the present invention, to lactams shown in Formula II and/or its salt, alkaline agent, vinyl benzyl chloride and alkylating reagent
Dosage does not require particularly, as long as Formulas I compound represented can be obtained.
Preferably, lactams shown in the Formula II relative to every mole and/or its salt, the dosage of the alkaline agent are 1-
5mol, more preferably 1-1.2mol.
Preferably, lactams shown in the Formula II relative to every mole and/or its salt, the dosage of the vinyl benzyl chloride
For 1-2mol, more preferably 1.1-1.3mol.
Preferably, lactams shown in the Formula II relative to every mole and/or its salt, the dosage of the alkylating reagent
For 1-10mol, more preferably 2.1-2.3mol.
In the present invention, the alkaline agent is that common various can react to obtain the object of lactams anion with lactams
Matter (usually can produce the substance of alkali) in water.Preferably, the alkaline agent is alkali metal, the hydride of alkali metal, alkali metal
Hydroxide and at least one of the salt of alkali metal, it is highly preferred that the alkali metal is sodium and/or potassium, further preferably
Ground, the alkaline agent are metallic sodium, metallic potassium, sodium hydride, hydrofining, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, carbon
At least one of sour hydrogen sodium and saleratus.
In the present invention, the mixed time is not required particularly, as long as can react and obtain with lactams
To lactams anion.Under preferable case, the mixed time is 25-60min.
In the present invention, the catalytic time is not required particularly, as long as change shown in formula IV can be obtained
Close object.Under preferable case, the catalytic time is 80-150min.
In the present invention, alkylated operation is selectively carried out and can be conventionally alkylated.Example
Such as, the alkylating reagent used can include but is not limited to halogenated hydrocarbons, dialkyl sulfate etc..Under preferable case, the alkyl
The condition of change includes: to react 3.5-6h at 0-10 DEG C, reacts 20-30h at 15-40 DEG C.
Wherein, those skilled in the art will know that: R can be obtained using different alkylating reagents1Or R2Different benzene
Ethylene compounds, and by using " protection-NH2In H, deprotection, be alkylated using different alkylating reagents "
Mode can be obtained R1And R2Respectively different styrene compound.
In the present invention, the mixing, haptoreaction and alkylation can in the presence of a solvent and this field skill
Art personnel can select solvent, for example, the example of the solvent includes but is not limited to chlorohydrocarbon (such as methylene chloride), chlorine
For benzene, dimethylformamide (DMF), dimethyl acetamide (DMAc), N-Methyl pyrrolidone, tetrahydrofuran and dioxane.
In the present invention, in order to keep the compound of the present invention easily stored, under preferable case, the method further includes
Above-mentioned reaction products therefrom is washed, extracted and dried.The washing, extraction and drying can be conventional using this field
Method, details are not described herein.
Acrylamide copolymer provided by the invention contains structural unit shown in structural unit A and Formula V a shown in Formulas I a
B, on the basis of the total weight of the acrylamide copolymer, the content of the structural unit A is 1-99 weight %, preferably 9-
The weight ratio of 30 weight %, the structural unit A and structural unit B is 100:(1-100), preferably 100:(10-45), described
The intrinsic viscosity of acrylamide copolymer be 17-30dl/g, preferably 19-24dl/g,
Wherein, R1、R2And R3It is each independently selected from H or C1-20Alkyl (as previously described), m=1 or 2.
In a preferred embodiment of the invention, R1And R2It is each independently selected from H or methyl, R3More preferably H, it is more excellent
Selection of land, m=1.
Most preferred embodiment according to the present invention, the structural unit A are at least one of following:
The structural unit C that the acrylamide copolymer can also be provided containing another monomer (temperature-resistant anti-salt monomer)
(formation of carbon-carbon double bond participation acrylamide copolymer).The weight ratio of the structural unit B and the structural unit C can be
1:(0.1-10), preferably 1:(0.25-1).The another kind monomer can be selected from: 2- acrylamide-2-methylpro panesulfonic acid,
N-vinyl pyrrolidone, Dimethylaminoethyl Methacrylate, dimethylamino ethyl acrylate, acrylic acid diethylin second
At least one of ester, diethylaminoethyl base ethyl ester and N,N-DMAA, are preferably selected from: 2- acrylamide
At least one of base -2- methyl propane sulfonic acid, n-vinyl pyrrolidone and N, N- dimethacrylamide.
In a preferred embodiment of the invention, the acrylamide copolymer is by structural unit A and structural unit B group
It is formed at or by structural unit A, structural unit B and structural unit C.
The preparation method of acrylamide copolymer provided by the invention includes: to cause under the conditions of solution polymerization
In the presence of agent or in the presence of reagent and additive in polymerization and initiator, monomer mixture is made to carry out polymerization reaction in aqueous solution,
The intrinsic viscosity 17-30dl/g (preferably 19-24dl/g) for the copolymer that the condition of polymerization reaction makes；The monomer mixing
Object contains acrylamide monomers shown in styrene compound monomer and Formula V shown in Formulas I, with the monomer mixture
On the basis of total weight, the content of the styrene compound monomer is 1-99 weight %, preferably 9-30 weight %, the benzene
The weight ratio of ethylene compounds monomer and acrylamide monomers is 100:(1-100), preferably 100:(10-45),
Wherein, R1、R2And R3It is each independently selected from H or C1-20Alkyl (as previously described), m=1 or 2.
In a preferred embodiment of the invention, R1And R2It is each independently selected from H or methyl, R3More preferably H, it is more excellent
Selection of land, m=1.
Correspondingly, most preferred embodiment according to the present invention, styrene compound monomer shown in Formulas I is followingization
Close at least one of object:
Inventive point of the invention, which essentially consists in, uses the styrene compound to prepare acrylamide copolymerization as monomer
Object is referred to initiator and polymeric reaction condition etc. the conventional method of this field, for example, 104558407 A of CN.
Wherein, the ratio between the weight of the monomer mixture and the total weight of water and monomer mixture is preferably
(0.05-0.5): 1.
Wherein, the ratio between the weight of the initiator and the monomer mixture total weight is preferably 1:(2 × 103-
106), preferably 1:(7 × 103-105).The initiator can be redox initiator, the redox initiator by
Oxidizing and Reducing Agents composition；The oxidant is ammonium persulfate and/or potassium peroxydisulfate；The reducing agent is iron ammonium sulfate
And/or sodium hydrogensulfite；The weight ratio of the oxidant and the reducing agent is usually 1:(0.2-5).Alternatively, the initiator
For redox initiator and azo initiator, the azo initiator is azodiisobutyronitrile and/or azo diisobutyl amidine
Hydrochloride；The weight ratio of the redox initiator and the azo initiator is usually 1:(0.1-10).
Wherein, as previously mentioned, the polymerization reaction can also carry out in the presence of reagent and additive in polymerization and initiator.For example,
The reagent and additive in polymerization can be disodium ethylene diamine tetraacetate and/or urea.The weight of the reagent and additive in polymerization is mixed with the monomer
Ratio between object total weight can be 1:(5 × 103-106)。
Wherein, the pH value of the reaction system of the polymerization reaction is preferably 7-9.It generally, can be using alkaline matter (such as
At least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate) adjust reaction system pH value.
Wherein, the polymerization reaction preferably carries out in an inert atmosphere.The inert atmosphere refer to not with reactants and products
Any one gas or admixture of gas chemically reacted, as in nitrogen, helium and periodic table of elements zero group gas extremely
Few one kind.Keep the method for inert atmosphere can be above-mentioned anti-with reactants and products generation chemistry to be passed through into reaction system
Any one gas or admixture of gas answered.
Wherein, the condition of the polymerization reaction preferably includes: reaction temperature is 0-80 DEG C, and the reaction time is 2-20 hours.
The mode of the polymerization reaction is preferred are as follows: reacts 4-12 hours at 0-20 DEG C, reacts 1-2 hours at 60-80 DEG C.
In addition, the present invention also provides acrylamide copolymers prepared by the above method.
Since acrylamide copolymer of the invention has good heat and salt resistance, the temperature-resistant and anti-salt type displacement of reservoir oil can be used as
Agent.Therefore, the present invention also provides above-mentioned acrylamide copolymers to prepare the application in oil displacement agent.It is total to the acrylamide
The dosage of polymers does not require particularly, it is preferable that the weight of the total weight of the oil displacement agent and the acrylamide copolymer
Between ratio be (500-5000): 1.The oil displacement agent can also with containing alkaline matter, surfactant etc., thus conduct
Binary composite oil displacement agent or ternary composite driving finish use.
The present invention will be described in detail by way of examples below.
In following embodiment, intrinsic viscosity is referring to GB12005.1-89 acrylamide copolymer Intrinsic Viscosity Measurements side
Method；Viscosity average molecular weigh can be measured according to GB12005.10-92 acrylamide copolymer molecular weight determination-viscosimetry, by formula M
=([η]/K)1/α, wherein K=4.75 × 10-3, the calculating of α=0.8；The weight being related to is in terms of butt, that is, dry at 105 DEG C
To constant weight per hour weight change be no more than 0.02g when weight.
Prepare embodiment 1
The alpha-amido valerolactam of 11.4g is dissolved in 100m anhydrous tetrahydro furan, 2.4g metallic sodium, reaction is added
After 30min, 16g is dissolved in 10ml anhydrous tetrahydro furan vinyl benzyl chloride, is added drop-wise in above-mentioned solution, drop in 30min
It adds complete.After the reaction was continued 60min, chloroform dissolution is added after removing solvent in revolving, is washed with deionized organic phase 3 times, is added
Enter Anhydrous potassium carbonate to be dried.After dry removal solvent, compound 1 is obtained20g.Through X
Ray fluorescence spectrometer measures the chemical composition of the compound are as follows: C, 72.98, N, 12.09, O, 6.97 (theoretical value: C, 73.01；
N, 12.16；O, 6.95).
24.6g compound 1 is dissolved in anhydrous methylene chloride, the potassium carbonate of 15g is added, under conditions of ice bath, slowly
Iodomethane 30g is added dropwise.After 4 hours are added dropwise, be warming up to room temperature (25 DEG C), the reaction was continued product is distilled off afterwards for 24 hours it is molten
Liquid and unreacted substance iodomethane, are then again dissolved product using methylene chloride, and washing, organic to be added to desiccant anhydrous
Sodium sulphate is dried, and desiccant is filtered out after dry, and revolving obtains compound A after removing solvent
15g.The chemical composition of the compound is measured through Xray fluorescence spectrometer are as follows: C, 74.41；N, 10.80；O, 6.24 (theoretical value:
C, 74.38；N, 10.84；O, 6.19).
Prepare embodiment 2
23.0g compound 1 is dissolved in dimethylformamide, 15g Anhydrous potassium carbonate is added, 100g bromo 18 is added
Alkane after reacting 8h at 100 DEG C, stops reaction.After solvent and unreacted bromo-octadecane is removed under reduced pressure, product methylene chloride
Dissolution is added anhydrous sodium sulfate and organic phase is dried, filter out desiccant after dry, rotated after distillation washing 3 times
Except obtaining compound B after solventIt is measured through Xray fluorescence spectrometer
The chemical composition of the compound are as follows: C, 81.70, N, 3.77, O, 2.10 (theoretical value: C, 81.68；N, 3.81；O, 2.18).
Embodiment 1
7.1g acrylamide and 0.71g compound A are dissolved in 30g water, nitrogen, deoxygenation 20 are passed through into reaction vessel
Minute.Be added 0.0007g azo diisobutyl amidine hydrochloride, ammonium persulfate 0.002g, disodium ethylene diamine tetraacetate 0.006g and
Urea 0.012g.PH is adjusted to 7.5 with solid sodium hydroxide, is transferred in polymerization bottle, logical nitrogen deoxygenation is depressurized after twenty minutes
Pump drainage deoxidation, then logical nitrogen 20 minutes, sodium hydrogensulfite 0.002g is added afterwards repeatedly for three times, after 8 DEG C are reacted 6 hours, heating
It is reacted 2 hours to 70 DEG C, obtains gluey copolymer 1.
Comparative example 1
By 7.1g acrylamide, deoxygenation 20 minutes.0.0007g azo diisobutyl amidine hydrochloride, ammonium persulfate is added
0.002g, disodium ethylene diamine tetraacetate 0.006g and urea 0.012g.PH is adjusted to 7.5 with solid sodium hydroxide, is transferred to
In polymerization bottle, pump drainage deoxidation, then logical nitrogen 20 minutes are depressurized in logical nitrogen deoxygenation after twenty minutes, and bisulfite is added afterwards repeatedly for three times
Sodium 0.002g is warming up to 70 DEG C and reacts 2 hours, obtain gluey copolymer A after 8 DEG C are reacted 6 hours.
Embodiment 2
7.1g acrylamide and 3.04g compound A are dissolved in 30g water, nitrogen, deoxygenation 20 are passed through into reaction vessel
Minute.Be added 0.0007g azo diisobutyl amidine hydrochloride, ammonium persulfate 0.002g, disodium ethylene diamine tetraacetate 0.006g and
Urea 0.012g.PH is adjusted to 7.5 with solid sodium hydroxide, is transferred in polymerization bottle, logical nitrogen deoxygenation is depressurized after twenty minutes
Pump drainage deoxidation, then logical nitrogen 20 minutes, sodium hydrogensulfite 0.002g is added afterwards repeatedly for three times, after 8 DEG C are reacted 6 hours, heating
It is reacted 2 hours to 70 DEG C, obtains gluey copolymer 2.
Embodiment 3
7.1g acrylamide and 3.04g compound A are dissolved in 30g water, nitrogen, deoxygenation 20 are passed through into reaction vessel
Minute.Be added 0.0007g azo diisobutyl amidine hydrochloride, ammonium persulfate 0.002g, disodium ethylene diamine tetraacetate 0.006g and
Urea 0.012g.PH is adjusted to 9 with solid sodium hydroxide, is transferred in polymerization bottle, pumping is depressurized in logical nitrogen deoxygenation after twenty minutes
Venting oxygen, then logical nitrogen 20 minutes, sodium hydrogensulfite 0.002g is added afterwards repeatedly for three times, after 8 DEG C are reacted 6 hours, is warming up to
70 DEG C are reacted 2 hours, and gluey copolymer 3 is obtained.
Embodiment 4
By 8.2g acrylamide, N,N-DMAA (being purchased from Aldrich) dissolution of 3.04g compound A and 5g
In 30g water, it is passed through nitrogen into reaction vessel, deoxygenation 20 minutes.0.0005g azo diisobutyl amidine hydrochloride, mistake is added
Ammonium sulfate 0.002g, disodium ethylene diamine tetraacetate 0.006g and urea 0.012g.PH is adjusted to 9 with solid sodium hydroxide, is turned
It moves on in polymerization bottle, pump drainage deoxidation, then logical nitrogen 20 minutes are depressurized in logical nitrogen deoxygenation after twenty minutes, and sulfurous is added afterwards repeatedly for three times
Sour hydrogen sodium 0.002g is warming up to 70 DEG C and reacts 2 hours, obtain gluey copolymer 4 after 8 DEG C are reacted 6 hours.
Embodiment 5
The n-vinyl pyrrolidone (being purchased from Aldrich) of 8.2g acrylamide, 3.04g compound A and 5g is dissolved in
In 30g water, it is passed through nitrogen into reaction vessel, deoxygenation 20 minutes.0.0005g azo diisobutyl amidine hydrochloride, over cure is added
Sour ammonium 0.002g, disodium ethylene diamine tetraacetate 0.006g and urea 0.012g.PH is adjusted to 9 with solid sodium hydroxide, transfer
Into polymerization bottle, pump drainage deoxidation, then logical nitrogen 20 minutes are depressurized in logical nitrogen deoxygenation after twenty minutes, and sulfurous acid is added afterwards repeatedly for three times
Hydrogen sodium 0.002g is warming up to 70 DEG C and reacts 2 hours, obtain gluey copolymer 5 after 8 DEG C are reacted 6 hours.
Embodiment 6
By 11.3g acrylamide, the 2- acrylamide-2-methylpro panesulfonic acid and 2.04g compound A of 4g is dissolved in 19g
In water, it is passed through nitrogen into reaction vessel, deoxygenation 20 minutes.0.0005g azo diisobutyl amidine hydrochloride, ammonium persulfate is added
0.002g, disodium ethylene diamine tetraacetate 0.006g and urea 0.012g.PH is adjusted to 7.5 with solid sodium hydroxide, is transferred to
In polymerization bottle, pump drainage deoxidation, then logical nitrogen 20 minutes are depressurized in logical nitrogen deoxygenation after twenty minutes, and bisulfite is added afterwards repeatedly for three times
Sodium 0.002g is warming up to 70 DEG C and reacts 2 hours, obtain gluey copolymer 6 after 8 DEG C are reacted 6 hours.
Embodiment 7
Copolymer is prepared according to the method for embodiment 6, unlike, it uses " compound 1 " replacement " compound A ", obtains
Gluey copolymer 7.
Embodiment 8
7.1g acrylamide and 3.02g compound B are dissolved in 30g water, nitrogen, deoxygenation 20 are passed through into reaction vessel
Minute.Be added 0.0007g azo diisobutyl amidine hydrochloride, ammonium persulfate 0.002g, disodium ethylene diamine tetraacetate 0.006g and
Urea 0.012g.PH is adjusted to 7.5 with solid sodium hydroxide, is transferred in polymerization bottle, logical nitrogen deoxygenation is depressurized after twenty minutes
Pump drainage deoxidation, then logical nitrogen 20 minutes, sodium hydrogensulfite 0.002g is added afterwards repeatedly for three times, after 8 DEG C are reacted 6 hours, heating
It is reacted 2 hours to 70 DEG C, obtains gluey copolymer 8.
Comparative example 2
11.3g acrylamide is dissolved in 19g water, is passed through nitrogen into reaction vessel, deoxygenation 20 minutes.It is added
0.0005g azo diisobutyl amidine hydrochloride, ammonium persulfate 0.002g, disodium ethylene diamine tetraacetate 0.006g and urea
0.012g.PH is adjusted to 7.5 with solid sodium hydroxide, is transferred in polymerization bottle, pump drainage is depressurized in logical nitrogen deoxygenation after twenty minutes
Deoxidation, then logical nitrogen 20 minutes, sodium hydrogensulfite 0.002g is added afterwards repeatedly for three times, after 8 DEG C are reacted 6 hours, is warming up to 70
DEG C reaction 2 hours, obtain gluey copolymer B.
Test case 1
Copolymer 1-8, copolymer A and copolymer B is tested to glue with apparent under the conditions of different salinities at different temperatures
Degree.
Using sodium chloride solution as simulation mineral reserve water, the concentration of the sodium chloride solution is mineralising angle value；Respectively with not
It by copolymer 1-8, copolymer A and copolymer B compound concentration is being total to for 1500mg/L that simulation mineral reserve water with salinity, which is solvent,
Copolymer solution stirs 2 hours at 25 DEG C；The apparent viscosity of copolymer solution at different temperatures is measured, copolymer solution is investigated
The case where apparent viscosity changes with the change of temperature and salinity.Apparent viscosity passes through the DV- III of BROOKFIELD company
It is measured on ULTRA type rotational viscometer, it is 7.34s that shear rate is constant when measurement-1。
When measuring apparent viscosity, after completely dissolution with water by copolymer, by G2 funnel, in the embodiment of the present invention or survey
Under conditions of trying example, gained copolymer all has good dissolubility, is not copolymerized that object is insoluble to cause filterability to be deteriorated
The case where.Namely illustrate that copolymer of the invention has good water solubility.
The following table 1 is copolymer 1-8, the intrinsic viscosity of copolymer A and copolymer B and above-mentioned copolymer solution in copolymer
Concentration is 1500mg/L, under different salinity, 25 DEG C when apparent viscosity measurement result.
Table 1
It can be seen that compared with copolymer A and copolymer B from the data of table 1, copolymer 1-8 is in salinity 30000mg/L
When, viscosity higher is still kept, illustrates that copolymer provided by the present invention has excellent anti-salt property.
The following table 2 be copolymer 1-8, copolymer A and copolymer B solution copolymer concentration be 1500mg/L, salinity
For the apparent viscosity measurement result under 30000mg/L, different temperatures.
Table 2
It can be seen that in 25-90 DEG C of Range of measuring temp from the data of table 2, the apparent viscosity of copolymer 1-8 is high always
In copolymer A, copolymer B, illustrate that there is good heat resistance through copolymer provided by the invention.
It can be seen from the results above that the obtained acrylamide copolymer of the present invention copolymer concentration be 1500mg/L,
Salinity is 30000mg/L and temperature be apparent viscosity at 90 DEG C is 9-13mPas, and only prepared by acrylamide
The apparent viscosity of acrylamide copolymer under the same conditions is only 4.7mPas.Therefore, copolymer prepared by the present invention is more existing
Some temperature-resistant anti-salt acrylamide copolymers have better temperature-resistant anti-salt performance, so as to improve Flooding Agent for EOR
Comprehensive performance.
Therefore, copolymer provided by the invention has good anti-salt temperature-resistant performance, therefore can be used as temperature-resistant and anti-salt type
Oil displacement agent.
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 within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, 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 where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
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 (22)
1. a kind of styrene compound, which is characterized in that the compound has structure shown in following formula I:
Wherein, R1And R2It is each independently selected from H or C1-20Alkyl, m=1 or 2.
2. compound according to claim 1, wherein R1And R2It is each independently selected from H or methyl.
3. compound according to claim 1 or 2, wherein m=1.
4. compound according to claim 1, wherein the compound is one of following compounds:
5. a kind of acrylamide copolymer, which is characterized in that the acrylamide copolymer contain structural unit A shown in Formulas I a and
Structural unit B shown in Formula V a, on the basis of the total weight of the acrylamide copolymer, the content of the structural unit A is
The weight ratio of 1-99 weight %, the structural unit A and structural unit B are 100:1-100, the spy of the acrylamide copolymer
Property viscosity number be 17-30dl/g,
Wherein, R1、R2And R3It is each independently selected from H or C1-20Alkyl, m=1 or 2.
6. acrylamide copolymer according to claim 5, wherein the content of the structural unit A is 9-30 weight %.
7. acrylamide copolymer according to claim 5 or 6, wherein the weight of the structural unit A and structural unit B
Amount is than being 100:10-45.
8. acrylamide copolymer according to claim 5, wherein R1And R2It is each independently selected from H or methyl.
9. the acrylamide copolymer according to claim 5 or 8, wherein R3For H.
10. acrylamide copolymer according to claim 5, wherein m=1.
11. acrylamide copolymer according to claim 5, wherein the structural unit A is in following structural units
It is at least one:
12. a kind of method for preparing acrylamide copolymer, which is characterized in that this method is included in solution polymerization condition
Under, in the presence of initiator or in the presence of reagent and additive in polymerization and initiator, carry out monomer mixture in aqueous solution
Polymerization reaction, the intrinsic viscosity 17-30dl/g for the copolymer that the condition of polymerization reaction makes；The monomer mixture contains
Acrylamide monomers shown in styrene compound monomer and Formula V shown in Formulas I, with the total weight of the monomer mixture
On the basis of, the content of the styrene compound monomer is 1-99 weight %, the styrene compound monomer and propylene
The weight ratio of acid amide type monomer is 100:1-100,
Wherein, R1、R2And R3It is each independently selected from H or C1-20Alkyl, m=1 or 2.
13. according to the method for claim 12, wherein the content of the styrene compound monomer is 9-30 weight
Measure %.
14. method according to claim 12 or 13, wherein the styrene compound monomer and acid/acrylic amide type list
The weight ratio of body is 100:10-45.
15. according to the method for claim 12, wherein R1And R2It is each independently selected from H or methyl.
16. method described in 2 or 15 according to claim 1, wherein R3For H.
17. according to the method for claim 12, wherein m=1.
18. according to the method for claim 12, wherein the weight of the monomer mixture and water and monomer mixture it is total
Ratio between weight is 0.05-0.5:1；Ratio between the weight of the initiator and the monomer mixture total weight is
1:2 × 103-106；Ratio between the weight of the reagent and additive in polymerization and the monomer mixture total weight is 1:5 × 103-106；
The pH value of the reaction system of the polymerization reaction is 7-9；The polymerization reaction carries out in an inert atmosphere；The polymerization is anti-
The condition answered includes: that reaction temperature is 0-80 DEG C, and the reaction time is 2-20 hours.
19. method described in 2 or 18 according to claim 1, wherein the mode of the polymerization reaction are as follows: reacted at 0-20 DEG C
It 4-12 hours, is reacted 1-2 hours at 60-80 DEG C.
20. acrylamide copolymer made from method described in any one of claim 12-19.
21. acrylamide described in acrylamide copolymer described in any one of claim 5-11 or claim 20 is total
Polymers is preparing the application in oil displacement agent.
22. application according to claim 21, wherein the total weight of the oil displacement agent and the acrylamide copolymer
Ratio between weight is 500-5000:1.
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| CN102775710A (en) * | 2011-05-13 | 2012-11-14 | 中国石油化工股份有限公司 | Oil-displacing agent composition and preparation method thereof |
| CN104558407A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant water-soluble polymer, and preparation and application method thereof |
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| CN102775710A (en) * | 2011-05-13 | 2012-11-14 | 中国石油化工股份有限公司 | Oil-displacing agent composition and preparation method thereof |
| CN104558407A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant water-soluble polymer, and preparation and application method thereof |
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