CN103570864B - A kind of acrylamide terpolymer and its preparation method and application - Google Patents
A kind of acrylamide terpolymer and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of acrylamide terpolymer and its preparation method and application, this acrylamide terpolymer contains construction unit A, construction unit B and construction unit C, wherein, described construction unit A is for having the construction unit of structure shown in formula (1), described construction unit B is for having the construction unit of structure shown in formula (2), and described construction unit C is for having the construction unit of structure shown in formula (3). Acrylamide terpolymer of the present invention has improved the dissolubility with alcohol and clay inhibitor, has higher drag reducing efficiency as drag reducer under high salinity condition, and has good drag-reduction effect in the scope that is 4-10 at pH.
Description
Technical field
The present invention relates to a kind of acrylamide terpolymer and preparation method thereof, and described acryloylAmine is the application of terpolymer as drag reducer.
Background technology
As unconventional petroleum resources utilize Typical Representative---the exploitation of shale gas (oil) resource becomesFor a revolution in global unconventional petroleum resources field, the development and utilization of shale gas has at present become generationVarious countries of boundary pay close attention to emphatically the focus technology with development. Because the ultimate attainment close oil-gas reservoirs such as shale gas reservoir have infiltrationThe feature that rate extremely low (being generally less than 0.5mD), frac pressure be high, easily cause formation damage. Must adoptExploit by " drag reduction water (slippery water) pressure break " technique.
" drag reduction water (slippery water) pressure break " is the one of fracturing, (changes with current conventional pressure break systemProperty guar gum cross-linking system) compare, drag reduction water (slippery water) pressure break is not to rely on high viscosity colloid to take sand,But take sand with high infusion discharge capacity, realize the final purpose that reservoir fracturing is reticulated to crack. Drag reduction waterThe more conventional pressure break system of (slippery water) pressure break has greater advantage on cost, to the injury on stratum simultaneouslyLittle.
Drag reduction water fracturing fluid core auxiliary agent is water-based drag reducer, in practice of construction, and the adding of water-based drag reducerEnter to overcome the frictional resistance of working solution in pipeline, ensured the raising of infusion discharge capacity, make pressure maximum limitDegree ground acts on and presses off stratum and extend formation fracture, and what can be used as at present water-based drag reducer mainly contains melon thatGlue and derivative thereof, cellulose derivative, acrylamide copolymer.
At present, adopt guar gum, cellulose and derivative thereof the drag reducer in splitting as drag reduction hydraulic pressure certainIn degree, improved infusion discharge capacity, reduced the frictional resistance in pipeline (US5697444,US5271466), but still cannot meet the requirement that drag reduction hydraulic pressure splits, deposit mainly due to above-mentioned boiomacromoleculeIn following shortcoming: 1. resistance reducing performance is limited, obviously not as good as acrylamide copolymer; 2. due to guar gum,Cellulose and derivative thereof have a small amount of insoluble matter and very easily stratum are damaged. 3. dissolution time is longer.
In drag reduction water pressing crack construction, adopt acrylamide copolymer (substantially to adopt partial hydrolysis third moreAlkene acid amides or anionic acrylamide copolymer) as the drag reducer in drag reduction water fracturing fluid, very great ChengOn degree, improve infusion discharge capacity, reduced the frictional resistance in pipeline, but as shale gas reservoir drag reduction hydraulic pressureThe drag reducer that splits liquid uses, and has following major defect: 1. in order to reduce " the water-sensitive effect in fracturing processShould ", the hydration swelling of inhibition shale medium clay soil component, helps the of the fracturing fluid row of returning of drag reduction water, reduces " waterStifled ", must in fracturing fluid, add part alcohol. Partial hydrolysis acrylamide or anionic acrylamideThe compatibility of copolymer and product emulsion thereof and alcohol is poor, very easily produces precipitation. 2. partial hydrolysis acryloylWhen amine or anionic acrylamide copolymer use as the of the fracturing fluid drag reducer of shale gas reservoir drag reduction water,Anti-filtration property is poor, this kind of drag reduction water fracturing fluid very easily leak-off in the middle of stratum. 3. temperature-resistant anti-saltPoor, especially, under high salinity (high divalent ion content) condition, molecular structure is unstable, drag reductionEffect declines very fast.
US20090298721A1 discloses the of the fracturing fluid formula of a kind of drag reduction water: to 1000 gallons go fromIn sub-water, add 0.5 gallon of acrylic acidcoacrylamide thing (FR-56TM) etc. anionic acryloylAmine copolymer thing emulsion is as drag reducer, then adds the complexing agents such as 0.15wt.% sodium carbonate or EDTA-2Na.This drag reduction water fracturing fluid has good resistance reducing performance, and indoor average drag reducing efficiency reaches 65.0%, salt tolerance(the especially tolerance to divalent calcium ion) had improvement to a certain degree, but this kind of drag reduction hydraulic pressure splits bodySystem is used as shale gas drag reduction water fracturing fluid, and there are the following problems: 1. poor with the compatibility of alcohol, withThe alcohol effects such as methyl alcohol very easily produce precipitation. 2. anti-filtration property is poor, and this kind of drag reduction water fracturing fluid very easily filteredLose in the middle of stratum. 3. in practice of construction, " water-sensitive effect " is remarkable. 4. very easily produce " water blocking ".5. resistance to high speed shear poor performance, under high speed shear effect, drag reducing efficiency declines very fast; 6. heat-resistant salt-resistantPoor, especially, under high salinity (high divalent ion content) condition, molecular structure is unstable, subtractsResistance effect declines very fast.
The acrylamide copolymer of cationic high-molecular amount also has report as drag reducer (US3868328)Road, compared with above-mentioned partial hydrolysis acrylamide or anionic acrylamide copolymer, this kind of structure altogetherThe compatibility of polymers and alcohol is better, better with clay inhibitor (as KCl) compatibility, " water-sensitive effect " noSignificantly, be difficult for " water blocking ".
How further to improve the resistance to high speed shear performance of drag reducer, improve the inhibition of fracturing fluid to clay andAnti-leak-off makes the stability raising of drag reducing efficiency be still one still under high temperature, high salt, shear conditionsAn open question.
Summary of the invention
The object of this invention is to provide that a kind of super high molecular weight, drag reducing efficiency are high, good water solubility, press down with clayPreparation and subtract blocking agent and have good compatibility, and the short acrylamide terpolymer of dissolution time, withAnd the preparation method and application of this acrylamide terpolymer.
The invention provides a kind of acrylamide terpolymer, wherein, this acrylamide ternary polymerizationThing contains construction unit A, construction unit B and construction unit C, and wherein, described construction unit A is toolHave the construction unit of structure shown in formula (1), described construction unit B has structure shown in formula (2)Construction unit, described construction unit C is the construction unit with structure shown in formula (3), and with describedIn acrylamide terpolymer, the total mole number of construction unit is benchmark, and described construction unit A containsAmount is 5-95 % by mole, and the content of described construction unit B is 2.5-90 % by mole, described construction unit CContent be 0.5-90 % by mole; Preferably, the content of described construction unit A is 10-70 % by mole,The content of described construction unit B is 20-50 % by mole, and the content of described construction unit C is that 10-40 rubsYou are %; The viscosity average molecular weigh of described acrylamide terpolymer is 1,500 ten thousand-2,500 ten thousand, is preferably1800 ten thousand-2,200 ten thousand;
Wherein, R1For hydrogen atom or methyl; R2For being total between nitrogen-atoms on tertiary carbon atom and imidazole ringValence link, or be C1-C4Alkylidene; R3For C1-C20Straight chained alkyl or C3-C20Branched alkyl;R4-R6Independent is separately hydrogen atom, methyl or ethyl; X-For Cl–、Br-、I-、SCN-、OrN is the integer of 1-20.
The present invention also provides a kind of preparation method of acrylamide terpolymer, and the method is included in alkeneUnder the solution polymerization condition of hydrocarbon, under initator exists, make monomer mixture in water, carry out polymerizationReaction, described monomer mixture contains monomer D, monomer E and monomer F, and described monomer D is for having formula(11) monomer of structure shown in, described monomer E is the monomer with structure shown in formula (12), described inMonomer F is for having the monomer of structure shown in formula (13), and always rubbing with monomer in described monomer mixtureYour number is benchmark, and the content of described monomer D is 5-95 % by mole, and the content of described monomer E is 2.5-90% by mole, the content of described monomer F is 0.5-90 % by mole; Preferably, the content of described monomer D is10-70 % by mole, the content of described monomer E is 20-50 % by mole, the content of described monomer F is 10-40% by mole; The condition of described polymerisation makes the viscosity average molecular weigh of resulting polymers after polymerisation be1500 ten thousand-2,500 ten thousand, be preferably 1,800 ten thousand-2,200 ten thousand;
Wherein, R1-R6And X-Identical with above-mentioned definition.
In addition, the invention provides the acrylamide terpolymer of preparing by said method.
It is the application of terpolymer as drag reducer that the present invention also provides aforesaid propylene acid amides.
The present invention by by polymerizable functional monomer by the method for ternary polymerization, be incorporated into and contain propyleneOn the macromolecular chain of acid amides, cationic monomer, obtain the ternary of super high molecular weight by controlling polymerizing conditionCopolymer. This terpolymer has kept the excellent viscoplasticity of linear macromolecule, and has high temperature resistant, resistance toThe performance of salt and resistance to high shear, by this terpolymer for drag reducer, can improve high temperature, high salt,Drag reducing efficiency under shear conditions; Due to alcohol (for example: methyl alcohol, ethanol) and clay inhibitor (exampleAs NaCl or KCl) compatibility improve, thereby improve inhibition and the anti-filtration property to clay,Reduce the generation of water-sensitive effect and water blocking phenomenon, can ensure that thus high infusion discharge capacity takes sand, realize and will store upLamination is cleaved into the final purpose of chicken-wire cracking. With the guar gum drag reducer, the cation that use in prior artAcrylamide copolymer (DP2) and binary acrylamide polymer (DP1) are compared, and the present invention carriesThe acrylamide terpolymer P1-P3 of confession has improved the dissolubility with alcohol and clay inhibitor, asDrag reducer has the drag reducing efficiency that exceedes 60% under high salinity condition, and in the scope that is 4-10 at pHThere is high drag reducing efficiency.
Detailed description of the invention
The invention provides a kind of acrylamide terpolymer, wherein, this acrylamide ternary polymerizationThing contains construction unit A, construction unit B and construction unit C, and wherein, described construction unit A is toolHave the construction unit of structure shown in formula (1), described construction unit B has structure shown in formula (2)Construction unit, described construction unit C is the construction unit with structure shown in formula (3), and with describedIn acrylamide terpolymer, the total mole number of construction unit is benchmark, and described construction unit A containsAmount is 5-95 % by mole, and the content of described construction unit B is 2.5-90 % by mole, described construction unit CContent be 0.5-90 % by mole; Preferably, the content of described construction unit A is 10-70 % by mole,The content of described construction unit B is 20-50 % by mole, and the content of described construction unit C is that 10-40 rubsYou are %; More preferably, the content of described construction unit A is 50-70 % by mole, described construction unit BContent be 20-30 % by mole, the content of described construction unit C is 10-20 % by mole; Described propyleneAcid amides is that the viscosity average molecular weigh of terpolymer is 1,500 ten thousand-2,500 ten thousand, is preferably 1,800 ten thousand-2,200 ten thousand;
Wherein, R1For hydrogen atom or methyl; R2For being total between nitrogen-atoms on tertiary carbon atom and imidazole ringValence link, or be C1-C4Alkylidene; R3For C1-C20Straight chained alkyl or C3-C20Branched alkyl;R4-R6Independent is separately hydrogen atom, methyl or ethyl; X-For Cl-、Br-、I-、SCN-、OrN is the integer of 1-20.
Acrylamide terpolymer of the present invention, in the preferred case, R3For C1-C4StraightAlkyl group or C3-C4Branched alkyl; X-For Cl-、Br-、I-OrN is 1-10Integer.
In the present invention, described alkylidene refers to that alkane loses two residues after hydrogen atom, described two hydrogenAtom can be two hydrogen atoms on same carbon atom, and two hydrogen on also can different carbon atoms are formerSon; Can be straight chain, can be also side chain, and for example, described ethylidene can be-CH2CH2-Or-CH (CH3)-. C described in the present invention1-C4Alkylidene can include but not limited to methane, ethane,In propane, normal butane or iso-butane, lose two alkyl after hydrogen atom. Described C1-C20Straight chain orThe alkyl of chain can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, Zhong DingBase, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl,N-octyl, positive decyl, dodecyl, cetyl or eicosyl.
The present inventor finds under study for action, by specific construction unit A, construction unit B and knotThe ter-polymers of structure unit C composition can be obtained fabulous drag-reduction effect.
In the preferred case, described construction unit A is the construction unit with structure shown in formula (4),Described construction unit B is for having the construction unit of structure shown in formula (5) and/or formula (6), described knotStructure unit C is for having at least one in the construction unit of structure shown in formula (7)-(10),
The present invention also provides a kind of preparation method of acrylamide terpolymer, and the method is included in alkeneUnder the solution polymerization condition of hydrocarbon, under initator exists, a kind of monomer mixture is carried out in waterPolymerisation, described monomer mixture contains monomer D, monomer E and monomer F, and described monomer D is toolHave the monomer of structure shown in formula (11), described monomer E is the monomer with structure shown in formula (12),Described monomer F is for having the monomer of structure shown in formula (13), and with monomer in described monomer mixtureTotal mole number is benchmark, and the content of described monomer D is 5-95 % by mole, and the content of described monomer E is2.5-90 % by mole, the content of described monomer F is 0.5-90 % by mole; Preferably, described monomer DContent is 10-70 % by mole, and the content of described monomer E is 20-50 % by mole, and described monomer F containsAmount is 10-40 % by mole; More preferably, the content of described monomer D is 50-70 % by mole, described listThe content of body E is 20-30 % by mole, and the content of described monomer F is 10-20 % by mole; Described polymerizationThe condition of reaction makes the viscosity average molecular weigh of resulting polymers after polymerisation be 1,500 ten thousand-2,500 ten thousand, excellentElect 1,800 ten thousand-2,200 ten thousand as;
Wherein, described R1-R6、X-With the elaboration of n and preferable case with describe above identical, at this notRepeat.
The method according to this invention, the weight of monomer mixture can be chosen in a big way, as long as protectCard water can fully distribute the heat that polymerisation produces, for example: and when described polymerisation starts,The ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.05-0.5:1, excellentElect 0.15-0.4:1 as, more preferably 0.2-0.4:1.
The method according to this invention, can be used all kinds of initators for polymerisation in solution in polymerisation,Wherein, can use separately a class initator, also can be used in combination initators more than two classes. ExcellentChoosing situation under, described initator is selected from azo initiator and redox initiator, in mole, instituteThe consumption of stating azo series initiators can be the 0-10 % by mole of the total mole number of monomer in monomer mixture,The consumption of described redox series initiators can be the 0-10 of the total mole number of monomer in monomer mixture% by mole, and the consumption of described initator is the 0.0001-10 of the total mole number of monomer in monomer mixture% by mole.
In the method for the invention, described azo initiator can be selected from azodiisobutyronitrile, 4,4 '-azoTwo (4-cyanopentanoic acids), 2,2 '-azo diisobutyl amidine hydrochloride and azo diimidazole quinoline base propane two hydrochloric acidAt least one in salt.
In the method for the invention, described redox initiator comprises Oxidizing and Reducing Agents, described oxygenThe mol ratio of agent and described reducing agent can be 0.1-10:1. Described oxidant can be selected from persulfuric acidAt least one in ammonium, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide. Described reducing agent can be inorganicReducing agent and/or organic reducing agent, for example, described inorganic reducing agent be selected from sodium hydrogensulfite, sodium sulfite,At least one in rongalite, sodium thiosulfate, ferrous sulfate and sodium hydrosulfite; Described organic reducing agent choosingFrom N, N '-dimethyl-ethylenediamine, N, N '-dimethyl-1,3-propane diamine, N, N, N ', N '-tetramethylethylenediamine,N, at least one in N-dimethyl amine and 3-methylamino propylamine.
The method according to this invention, described polymerisation can also be carried out under various auxiliary agents exist, described inAuxiliary agent can be selected from one or more in chelating agent, chain extender and other auxiliary agents. Mix with described monomerIn thing, the total mole number of monomer is benchmark, and the consumption of described auxiliary agent can be 0.0001-6 % by mole. Wherein,Taking the total mole number of monomer in described monomer mixture as benchmark, the consumption of described chelating agent can be 0-2% by mole, be preferably 0.0001-2 % by mole; The consumption of described chain extender can be 0-2 % by mole, excellentElect 0.0001-2 % by mole as; The consumption of described other auxiliary agents can be 0-2 % by mole, is preferably 0.0001-2% by mole.
Described chelating agent can be selected from ethylenediamine tetra-acetic acid and salt (as EDTA-2Na) thereof, triethylenediamineAt least one in pentaacetic acid, citric acid, citrate and poly-hydroxy acrylic acid, more preferablyEDTA and/or citrate, described citrate can be potassium citrate, natrium citricum, calcium citrateWith at least one in ammonium citrate.
Described chain extender can be selected from N, N '-dimethyl-ethylenediamine, N, and N, N ', N '-tetramethylethylenediamine,N, N-dimethyl amine, 3-methylamino propylamine, N, N '-dimethyl-1,3-propane diamine, 1-(dimethylamino)-2-At least one in propylamine and diethylenetriamines. In the preferred case, described chain extender is N, N '-Dimethyl-ethylenediamine, N, N '-dimethyl-1,3-propane diamine, N, N, N ', N '-tetramethylethylenediamine and N, N-One or more in dimethyl amine.
Described other auxiliary agents can be selected from least one in urea, sodium formate, isopropyl alcohol and sodium hypophosphite,Be preferably urea and/or sodium formate.
The present inventor finds, exists at the same time under the condition of above-mentioned initator and auxiliary agent, can obtainTo the very high polymer of viscosity average molecular weigh.
The method according to this invention, the condition of described polymerisation can be conventional solution polymerization barPart. For example, described polymerisation is carried out under inert gas exists, and described polymeric reaction condition can wrapDraw together: temperature is 0-80 DEG C, the time is 1-24 hour, and pH value is 5-13; Under preferable case, temperature is0-60 DEG C, the time is 8-24 hour, pH value is 6-11. In the time that needs add sour regulation system pH value,Described acid is preferably inorganic acid, and described inorganic acid can be in hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and phosphoric acidAt least one. In the time that needs add alkali regulation system pH value, described alkali can be inorganic base or organicAminated compounds, as being selected from NaOH, potassium hydroxide, ammoniacal liquor, methylamine, ethamine, monoethanolamineWith at least one in triethanolamine, be preferably NaOH.
The present inventor finds under study for action, takes following condition can further improve polymerMolecular weight:, preferably, described polymerisation comprises the three phases carrying out successively: the first stageReaction condition comprises: temperature is 0-10 DEG C, be preferably 0-5 DEG C, and the time is 1-15 hour, be preferably 3-10Hour; The reaction condition of second stage comprises: temperature is 15-30 DEG C, is preferably 20-30 DEG C, and the time is3-8 hour, be preferably 3-6 hour; The reaction condition of phase III comprises: temperature is 35-60 DEG C, excellentElect 40-55 DEG C as, the time is 2-14 hour, be preferably 4-12 hour.
In addition, the present inventor finds under study for action, when select specific monomer D, monomer E withWhen monomer F reacts, can further improve the drag-reduction effect of the polymer of gained.
In the preferred case, monomer D is for having the monomer of structure shown in formula (14), described monomer EFor having the monomer of structure shown in formula (15) and/or formula (16), described monomer F is for having formula (17)To at least one in the monomer of structure shown in formula (20),
The present invention also provides the acrylamide making according to said method terpolymer.
In addition, the present invention also provides the application of described acrylamide terpolymer as drag reducer.
Below, by following examples, the present invention will be described in more detail.
In embodiment, the monomer shown in formula used (21), formula (23) and formula (25) is all purchased from Sigma-AldrichCompany, in addition, unless specified otherwise, the polymer of using in embodiment, comparative example and test caseWith reagent etc. all by commercially available.
Intrinsic viscosity is surveyed according to GB12005.1-89 polyacrylamide For Intrinsic Viscosity Measurements methodFixed; Viscosity average molecular weigh is according to formula Mv＝（[η]/K）1/α, wherein K=4.5 × 10-3, α=0.80Calculate; Dissolution time is measured by GB12500.8-89, and the dissolution time recording is all less than 2 hours;Molecular structure and composition adopt IR spectroscopic assay; Water insoluble matter content is pressed SY/T5862-1993 and is measured;Indoor drag reducing efficiency is pressed SY/T6376-1998 and is measured.
Embodiment 1
Under room temperature, by monomer and 26g shown in 35.6g acrylamide (AM), 55.2g formula (21)Acrylic acid-2-methoxyl group ethyl ester joins in reaction bulb, adds deionized water 272.5g, stirs and makes monomer completeCL, and stir. Respectively to the EDTA aqueous solution 5.5g that adds 1 % by weight in flask, 1% by weight azo diisobutyl amidine hydrochloride aqueous solution 2.1g, chain extender N, N '-dimethyl-ethylenediamine0.166g, urea 0.12g, fully stirs it is mixed. With the sodium hydroxide solution of 1 % by weightPH to 7.5. Hierarchy of control initial temperature to 4 DEG C, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weightAmmonium persulfate aqueous solution 1.1g, and continue letting nitrogen in and deoxidizing 20 minutes. Reactor is airtight, remain on 4DEG C, react after 10 hours, after being risen to 20 DEG C, temperature reacts 5 hours, then temperature is risen to 50 DEG CReact 5 hours, the gluey product obtaining is taken out, through granulation, dry, pulverizing acquisition acrylamideTerpolymer P1.
P1 is carried out to IR spectroscopic assay, 1730cm in IR spectrum-1There is belonging to acrylic acid-2-first in placeThe C=O stretching vibration of oxygen base ethyl ester unit; 1660cm-1And 1635cm-1There is respectively belonging to acid amides in placeThe amide Ⅰ absworption peak (C=O stretching vibration) of base and acid amides II band absworption peak (N-H flexural vibrations); ?1430cm-1There is the stretching vibration absworption peak of C-N in place; 1356 and 1401cm-1There is typical methylSymmetric curvature vibration absorption peak; 3100cm-1Place's small peak belongs to the stretching vibration of C=C-H on imidazole ring;2923cm-1、2852cm-1The belong to respectively-CH that locates out peak2-、-CH3C-H stretching vibration;1508-1654cm-1Go out peak and belong to C=C stretching vibration on imidazole ring; 1467cm-1Going out peak belongs to-CH2-、-CH3C-H flexural vibrations; 1034-1229cm-1Going out peak belongs to C=N on imidazole ring and stretchesContracting vibration; 1260cm-1Go out peak and belong to C-O stretching vibration on ester bond; 625-911cm-1Go out peak ownershipVibrate in imidazole ring Ar-H out-of plane bending. Can determine and obtain by characteristic peak in above-mentioned IR spectrumCopolymer molecule has the structure shown in formula (22), records its viscosity average molecular weigh Mv to be by viscosimetry1840 ten thousand, monomer conversion is more than 99.9%. Wherein, formula (22) and x, y and z only representGo out type and the number of construction unit, and do not represent the connected mode of construction unit. X, y and z's is concreteNumerical value is determined by inventory.
Comparative example 1
Method according to embodiment 1 is prepared acrylamide polymer, and different is not add acrylic acid firstThe addition of ester and acrylamide is that the addition of the monomer shown in 44.5g, formula (21) is 69g,Obtain acrylamide bipolymer DP1, sticky the dividing equally of this acrylamide bipolymer DP1Son amount is 1,800 ten thousand. By IR spectrum analysis, except lacking, acrylic acid-2-methoxyl group ethyl ester hasCharacteristic peak, the characteristic peak that the construction unit in DP1 shows go out peak position and knot identical in P1The characteristic peak that structure unit shows to go out peak position similar.
Comparative example 2
According to the method for embodiment 1, different is synthetic 38.1g acrylamide and 42.1g (3-acryloylAmido-3-methyl) the copolymer DP2 of butyl trimethyl ammonium chloride, record the viscosity average molecular weigh of this copolymerBe 1,810 ten thousand.
Embodiment 2
By monomer and 71.2g methoxypolyethylene glycol methyl-prop shown in 42.7gAM, 70.7g formula (23)Olefin(e) acid ester (have the structure shown in formula (19), number-average molecular weight is 475) joins in reaction bulb,Add 550g deionized water, stir monomer is dissolved completely, in flask, add 1 quality %'s respectivelyEDTA aqueous solution 4.65g, adds 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 1.23g, addsEnter chain extender N, N '-dimethyl-ethylenediamine 0.12g, adds 0.1% solution of sodium bisulfite 1.13g, addsUrea 0.11g, fully stirs it is mixed. Hierarchy of control initial temperature to 4 DEG C, logical nitrogen deoxygenationAfter 30 minutes, add 1 % by weight ammonium persulfate aqueous solution 1.0g and continue letting nitrogen in and deoxidizing 10 minutes. WillReactor is airtight, remains on 2 DEG C, reacts after 8 hours, is warming up to 25 DEG C, reacts after 6 hours, risesWarm to 50 DEG C of reactions 12 hours, the gluey product obtaining is taken out, through granulation, dry, pulverizing acquisitionAcrylamide terpolymer P2.
P2 is carried out to IR spectroscopic assay, 1730cm in IR spectrum-1There is belonging to polyethylene glycol first in placeThe C=O stretching vibration of ether metacrylic acid ester unit; 1660cm in IR spectrum-1And 1635cm-1Place respectivelyOccur belonging to the amide Ⅰ absworption peak (C=O stretching vibration) of amide groups and acid amides II band absworption peak (N-H flexural vibrations); At 1430cm-1There is the stretching vibration absworption peak of C-N in place; 1310cm-1Locate littlePeak belongs to the stretching vibration of C=C-H on imidazole ring; 2923cm-1、2852cm-1Locating out peak belongs to respectivelyIn-CH2-、-CH3C-H stretching vibration; 1508-1654cm-1Go out peak and belong to C=C on imidazole ringStretching vibration; 1467cm-1Belong to-the CH that goes out peak2-、-CH3C-H flexural vibrations; 1034-1229cm-1Go out peak and belong to C=N stretching vibration on imidazole ring; 1260cm-1Going out peak, to belong on ester bond C-O flexibleVibration; 625-911cm-1Go out peak and belong to the vibration of imidazole ring Ar-H out-of plane bending. By above-mentioned IR lightCharacteristic peak in spectrum can determine that the copolymer molecule obtaining has the structure shown in formula (24), by stickyIt is 2,013 ten thousand that degree method records its viscosity average molecular weigh Mv, and monomer conversion is more than 99.9%. Wherein, formula(24) and x2, y2 and z2 only express type and the number of construction unit, and do not represent structure listThe connected mode of unit. The concrete numerical value of x2, y2 and z2 is determined by inventory.
Embodiment 3
Under room temperature, by the monomer 37.5g shown in 59.6g Methacrylamide, 56.5g formula (25) poly-(thirdGlycol) methacrylate (have the structure shown in formula (20), number-average molecular weight is 375) to reactionIn bottle, add 235g deionized water, stir monomer is dissolved completely, in flask, add 1 weight respectivelyThe EDTA aqueous solution 7.56g of amount %, adds the 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution2.13g, adds chain extender N, and N '-dimethyl-ethylenediamine 0.01g adds 0.1 % by weight sodium hydrogensulfite moltenLiquid 2.13g, adds urea 0.20g, fully stirs it is mixed. Hierarchy of control initial temperature to 2DEG C, logical nitrogen deoxygenation, after 30 minutes, adds 1% ammonium persulfate aqueous solution 3.0g and continues letting nitrogen in and deoxidizing10 minutes. Reactor is airtight, remain on 2 DEG C, react after 8 hours, be warming up to 30 DEG C, reaction 5After hour, be warming up to 50 DEG C of reactions 4 hours, the gluey product obtaining taken out, through granulation, dry,Pulverize and obtain acrylamide terpolymer P3.
P3 is carried out to IR spectroscopic assay, 1730cm in IR spectrum-1There is belonging to poly-(propane diols) in placeMethacrylate unit C=O stretching vibration; 1660cm in IR spectrum-1And 1635cm-1Place goes out respectivelyNow belong to amide Ⅰ absworption peak (C=O stretching vibration) and the acid amides II band absworption peak (N-H of amide groupsFlexural vibrations); At 1430cm-1There is the stretching vibration absworption peak of C-N in place; 1310cm-1Place's small peak is returnedBelong to the stretching vibration of C=C-H on imidazole ring; 2923cm-1、2852cm-1Locating out peak belongs to respectively-CH2-、-CH3C-H stretching vibration; 1508 ~ 1654cm-1Going out peak belongs to C=C on imidazole ring and stretchesContracting vibration; 1467cm-1Belong to-the CH that goes out peak2-、-CH3C-H flexural vibrations; 1034-1229cm-1Go out peak and belong to C=N stretching vibration on imidazole ring; 625-911cm-1Going out peak, to belong to imidazole ring Ar-H flatOut-of-plane bending vibration. Can be determined the copolymer p 3 molecule tools that obtain by the characteristic peak in above-mentioned IR spectrumHave the structure shown in formula (26), recording its viscosity average molecular weigh Mv by viscosimetry is 1,945 ten thousand, singleTransformation rate is more than 99.9%. Wherein, formula (26) and x3, y3 and z3 only express structure listType and the number of unit, and do not represent the connected mode of construction unit. The concrete numerical value of x3, y3 and z3Determined by inventory.
Test case 1
Water insoluble matter content is to measure according to the method specifying in SY/T5862-1993. By P1-P3,DP1-DP2 and hydroxypropyl guar gum (JXY wellfracturing hydroxypropyl melon rubber powder, the poly-limited public affairs of prosperous chemical industry in ShandongDepartment, below identical) carry out water-soluble mensuration, result is as shown in table 1.
Table 1
As can be seen from Table 1, in P1-P3, water insoluble matter content is starkly lower than HPG, saysThe bright acrylamide terpolymer P1-P3 being prepared by method provided by the invention is as shale gas pressure breakWith drag reducer, compared with hydroxypropyl guar gum, low to the injury on stratum.
Test case 2
Under 2500rpm shear rate, respectively by P1-P3, DP1-DP2 and partial hydrolysis polyacrylamide(HPAM, Zibo Tian Jian Chemical Co., Ltd., trade mark TJY-3, viscosity average molecular weigh are 1800-2000 to amineTen thousand, lower with) slowly to join respectively separately volume ratio be water/alcohol (this test of 80/20,60/40In example, using methyl alcohol) in solution, the consumption of P1-P3, DP1-DP2 and HPAM is water/alcoholic solution0.01 % by weight, dissolution time is 30min, result is as shown in table 2.
Table 2
As can be seen from Table 2, the acrylamide terpolymer that prepared by method provided by the inventionP1-P3 is as shale gas pressure break drag reducer, compared with partially hydrolyzed polyacrylamide (PHPA), with the compatibility of alcoholProperty is good.
Test case 3
Be under the condition of 25 DEG C, by P1-P3, DP1-DP2, HPAM and HPG in temperatureBeing dissolved in respectively pure water and concentration is 2 % by weight, 4 % by weight, 8 % by weight, 10 % by weight, 12 % by weightNaCl or KCl solution in, the 500mg/L being mixed with and the solution of 1000mg/L, thenOn GLM-1 pipeline frictional resistance determinator, measure above-mentioned according to the method specifying in SY/T6376-1998Drag reducing efficiency (the test condition: the internal diameter of test section pipeline is 8mm, and the length of test section pipeline is of solution9m, infusion discharge capacity is 30L/min), result is as shown in Table 3 and Table 4.
Table 3
Table 4
From table 3 and table 4, can find out, acrylamide ternary prepared by method provided by the invention altogetherPolymers P1, as shale gas pressure break drag reducer, compared with hydroxypropyl guar gum, HPAM, presses down with clayPreparation (as, NaCl or KCl) compatibility is good, anti-salt property excellence.
Test case 4
Drag reducing efficiency is to measure according to the method specifying in SY/T6376-1998. By P1-P3, DP1-DP2Be dissolved in respectively pure water, be mixed with the solution of 500mg/L, by adding HCl or NaOH, regulateThe pH value of system changes between 2.5 ~ 10, and result is as shown in table 5.
Table 5
| PH | 2.5 | 3.0 | 4.0 | 5.0 | 6.0 | 7.0 | 8.0 | 9.0 | 10.0 |
| P1（500mg/L） | 38% | 55% | 69% | 70% | 69% | 72% | 71% | 68% | 66% |
| P2（500mg/L） | 40% | 58% | 71% | 71% | 72% | 74% | 72% | 70% | 69% |
| P3（500mg/L） | 40% | 57% | 69% | 70% | 71% | 73% | 71% | 69% | 67% |
| DP1（500mg/L） | 34% | 53% | 65% | 65% | 66% | 66% | 66% | 65% | 63% |
| DP2（500mg/L） | 25% | 37% | 57% | 58% | 59% | 60% | 58% | 50% | 45% |
As can be seen from Table 5, the acrylamide terpolymer that prepared by method provided by the inventionP1-P3 has good drag reduction effect within the scope of very large pH value with drag reducer as shale gas pressure breakReally.
Above-mentioned test result illustrates that acrylamide terpolymer provided by the invention has good waterDissolubility is low to the injury on stratum; And can be dissolved in completely in water/alcoholic solution, good with the compatibility of alcohol;Owing to improving with the compatibility of alcohol and clay inhibitor (NaCl or KCl), make the moisture in pressure break waterBe difficult for running off, improved anti-filtration property; And still there is height under high salt, wider pH value conditionDrag reducing efficiency. In addition, the preparation method of acrylamide terpolymer provided by the invention has easyAnd the advantage that monomer conversion is high.
Claims (18)
1. an acrylamide terpolymer, is characterized in that, this acrylamide ternary polymerizationThing contains construction unit A, construction unit B and construction unit C, and wherein, described construction unit A is toolHave the construction unit of structure shown in formula (1), described construction unit B has structure shown in formula (2)Construction unit, described construction unit C is the construction unit with structure shown in formula (3), and with describedIn acrylamide terpolymer, the total mole number of construction unit is benchmark, and described construction unit A containsAmount is 5-95 % by mole, and the content of described construction unit B is 2.5-90 % by mole, described construction unit CContent be 0.5-90 % by mole; The viscosity average molecular weigh of described acrylamide terpolymer is 1500Ten thousand-2,500 ten thousand;
Wherein, R1For hydrogen atom or methyl; R2For being total between nitrogen-atoms on tertiary carbon atom and imidazole ringValence link, or be C1-C4Alkylidene; R3For C1-C20Straight chained alkyl or C3-C20Branched alkyl;R4-R6Independent is separately hydrogen atom, methyl or ethyl; X–For Cl–、Br–、I–、SCN–、 N is the integer of 1-20.
2. acrylamide terpolymer according to claim 1, wherein, with described propyleneAcid amides is that the total mole number of construction unit in terpolymer is benchmark, and the content of described construction unit A is10-70 % by mole, the content of described construction unit B is 20-50 % by mole, described construction unit C'sContent is 10-40 % by mole.
3. acrylamide terpolymer according to claim 1, wherein, described acryloylAmine is that the viscosity average molecular weigh of terpolymer is 1,800 ten thousand-2,200 ten thousand.
4. acrylamide terpolymer according to claim 1, wherein, R3For C1-C4Straight chained alkyl or C3-C4Branched alkyl; X–For Cl–、Br–、I–OrN is 1-10Integer.
5. acrylamide terpolymer according to claim 4, wherein, described structure listThe A of unit is for having the construction unit of structure shown in formula (4), and described construction unit B is for having formula (5)And/or the construction unit of structure shown in formula (6), described construction unit C is for having formula (7)-(10)Shown at least one in the construction unit of structure,
6. a preparation method for acrylamide terpolymer, the method is included in the solution of alkeneUnder polymeric reaction condition, under initator exists, make monomer mixture in water, carry out polymerisation, instituteState monomer mixture and contain monomer D, monomer E and monomer F, described monomer D is for having formula (11) instituteShow the monomer of structure, described monomer E is for having the monomer of structure shown in formula (12), and described monomer F isThere is the monomer of structure shown in formula (13), and taking the total mole number of monomer in described monomer mixture as baseStandard, the content of described monomer D is 5-95 % by mole, the content of described monomer E is 2.5-90 % by mole,The content of described monomer F is 0.5-90 % by mole; The condition of described polymerisation makes institute after polymerisationThe viscosity average molecular weigh that obtains polymer is 1,500 ten thousand-2,500 ten thousand;
Wherein, R1-R6, n and X–As defined in the claims 1 or 4.
7. method according to claim 6, wherein, total with monomer in described monomer mixtureMolal quantity is benchmark, and the content of described monomer D is 10-70 % by mole, and the content of described monomer E is 20-50% by mole, the content of described monomer F is 10-40 % by mole.
8. method according to claim 6, wherein, the condition of described polymerisation makes polymerizationAfter reaction, the viscosity average molecular weigh of resulting polymers is 1,800 ten thousand-2,200 ten thousand.
9. method according to claim 6, wherein, when described polymerisation starts, described listThe ratio of the gross weight of the weight of body mixture and water and monomer mixture is 0.05-0.5:1.
10. method according to claim 9, wherein, when described polymerisation starts, described listThe ratio of the gross weight of the weight of body mixture and water and monomer mixture is 0.15-0.4:1.
11. according to the method described in any one in claim 6-10, wherein, and described initator choosingFrom azo initiator and redox initiator, the consumption of described azo series initiators is in monomer mixtureThe 0-10 % by mole of the total mole number of monomer, the consumption of described redox series initiators is monomer mixtureThe 0-10 % by mole of the total mole number of middle monomer, and the consumption of described initator is monomer in monomer mixtureThe 0.0001-10 % by mole of total mole number; Described azo initiator is selected from azodiisobutyronitrile, 4,4 '-Azo two (4-cyanopentanoic acid), 2,2 '-azo diisobutyl amidine hydrochloride and azo diimidazole quinoline base propane twoAt least one in hydrochloride; Described redox initiator comprises Oxidizing and Reducing Agents, described oxidationThe mol ratio of agent and described reducing agent is 0.1-10:1, described oxidant be selected from ammonium persulfate, potassium peroxydisulfate,At least one in sodium peroxydisulfate and hydrogen peroxide, described reducing agent is inorganic reducing agent and/or organic reducingAgent, described inorganic reducing agent is selected from sodium hydrogensulfite, sodium sulfite, rongalite, sodium thiosulfate, sulphurAt least one in acid ferrous iron and sodium hydrosulfite, described organic reducing agent is selected from N, N '-dimethyl-ethylenediamine,N, N '-dimethyl-1,3-propane diamine, N, N, N ', N '-tetramethylethylenediamine, N, N-dimethyl amine and 3-At least one in methylamino propylamine.
12. according to the method described in any one in claim 6-10, wherein, and described polymerisationUnder auxiliary agent exists, carry out, described auxiliary agent is selected from a kind of or many in chelating agent, chain extender and other auxiliary agentsKind; Taking the total mole number of monomer in described monomer mixture as benchmark, the consumption of described chelating agent is 0-2% by mole, the consumption of described chain extender is 0-2 % by mole, the consumption of described other auxiliary agents is 0-2 % by mole,And taking the total mole number of monomer in described monomer mixture as benchmark, the consumption of described auxiliary agent is 0.0001-6% by mole; Described chelating agent is selected from disodium ethylene diamine tetraacetate, triethylenediamine pentaacetic acid, citric acid, lemonAt least one in lemon hydrochlorate and poly-hydroxy acrylic acid; Described chain extender is selected from N, N '-dimethyl-ethylenediamine,N, N '-dimethylated propyl diethylenetriamine, N, N, N ', N '-tetramethylethylenediamine, N, N-dimethyl amine, 3-methylaminoPropylamine, N, N '-dimethyl-1, in 3-propane diamine, 1-(dimethylamino)-2-propylamine and diethylenetriaminesAt least one; Described other auxiliary agents are selected from least one in urea, sodium formate, isopropyl alcohol and sodium hypophosphiteKind.
13. methods according to claim 12, wherein, with monomer in described monomer mixtureTotal mole number is benchmark, and the consumption of described chelating agent is 0.0001-2 % by mole, the consumption of described chain extenderFor 0.0001-2 % by mole, the consumption of described other auxiliary agents is 0.0001-2 % by mole.
14. according to the method described in any one in claim 6-10, wherein, and described polymerisationUnder inert gas exists, carry out, the condition of described polymerisation comprises: temperature is 0-80 DEG C, and the time is1-24 hour, pH value is 5-13.
15. methods according to claim 14, wherein, described polymerisation comprises successively carries outThree phases, the reaction condition of first stage comprises: temperature is 0-10 DEG C, the time is 1-15 hour;The reaction condition of second stage comprises: temperature is 15-30 DEG C, and the time is 3-8 hour; Phase IIIReaction condition comprises: temperature is 35-60 DEG C, and the time is 2-14 hour.
16. according to the method described in any one in claim 6-10, and wherein, monomer D is for havingThe monomer of structure shown in formula (14), described monomer E is for having shown in formula (15) and/or formula (16)The monomer of structure, described monomer F for have formula (17) in the monomer of structure shown in formula (20) extremelyIt is few a kind of,
The 17. acrylamide ternarys of preparing according to the method described in any one in claim 6-16Copolymer.
Acrylamide terpolymer conduct in 18. claim 1-5 and 17 described in any oneThe application of drag reducer.
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