CN104250338B - A kind of acrylamide based copolymer and its preparation method and application - Google Patents
A kind of acrylamide based copolymer and its preparation method and application Download PDFInfo
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- CN104250338B CN104250338B CN201310267842.9A CN201310267842A CN104250338B CN 104250338 B CN104250338 B CN 104250338B CN 201310267842 A CN201310267842 A CN 201310267842A CN 104250338 B CN104250338 B CN 104250338B
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Abstract
The invention discloses a kind of acrylamide based copolymer and its preparation method and application. Described acrylamide based copolymer contains construction unit A, construction unit B, construction unit C and construction unit D, wherein, described construction unit A is the construction unit shown in formula (1), described construction unit B is the construction unit shown in formula (2), described construction unit C is the construction unit shown in the construction unit shown in formula (3) and/or formula (4), and described construction unit D is the construction unit shown in formula (5); The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000-1,500 ten thousand. Acrylamide based copolymer drag reducing efficiency provided by the invention is high, salt tolerance is high, anti-high shear performance is good, good water solubility, with clay stabilizer have good compatibility and low to formation damage.
Description
Technical field
The present invention relates to two kinds of preparation methods and described third of a kind of acrylamide based copolymer, acrylamide based copolymerAlkene acid amides based copolymer is as the application of drag reducer.
Background technology
It is non-that the exploitation of the Typical Representative utilizing as unconventional petroleum resources---shale gas (oil) resource has become the whole worldA revolution of conventional gas and oil resources domain, the development and utilization of shale gas at present has become countries in the world and has paid close attention to emphatically and send outThe focus technology of exhibition. Because the ultimate attainment close oil-gas reservoirs such as shale gas reservoir have permeability extremely low (being generally less than 0.5mD), pressure breakThe feature that pressure is high, easily cause formation damage. Must adopt the exploitation of " drag reduction water (slippery water) pressure break " technique.
" drag reduction water (slippery water) pressure break " is the one of fracturing. (modifyed guar gum is handed over current conventional pressure break systemConjuncted system) to compare, drag reduction water (slippery water) pressure break is not to rely on high viscosity colloid to take sand, but with high infusion discharge capacityTake sand, realize the final purpose that reservoir fracturing is reticulated to crack. Compared with conventional pressure break system, drag reduction water (slippery water)Pressure break has in greater advantage less to the injury on stratum on cost.
Drag reduction water fracturing fluid core auxiliary agent is water-based drag reducer, in practice of construction, water-based drag reducer add the work of overcomingThe frictional resistance of liquid in pipeline, has ensured the raising of infusion discharge capacity, pressure is acted on to greatest extent press off stratum andExtend formation fracture, what can be used as at present water-based drag reducer mainly contains guanidine glue and derivative thereof, cellulose derivative, propyleneAcylamide polymer.
At present, adopt guanidine glue, cellulose and derivative thereof the drag reducer in splitting as drag reduction hydraulic pressure to improve to a certain extentInfusion discharge capacity, reduce the frictional resistance (US5697444, US5271466) in pipeline, but still cannot meet drag reduction water, there is following shortcoming mainly due to above-mentioned boiomacromolecule in the requirement of pressure break: (1) resistance-reducing performance is limited; (2) due to guanidineGlue, 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 (partial hydrolysis acrylamide or anionic third moreAlkene amide copolymer) friction reducer in splitting as drag reduction hydraulic pressure, has improved to a great extent infusion discharge capacity, has reduced pipelineIn frictional resistance, but the drag reducer splitting as shale gas reservoir drag reduction hydraulic pressure use, there is following major defect: (1) isReduce " the water-sensitive effect " in fracturing process, suppress the hydration swelling of shale medium clay soil component, must in fracturing fluid, addEnter little molecular cation clay stabilizer (as potassium chloride, tetramethyl ammonium chloride etc.). Partial hydrolysis acrylamide or anionThe compatibility of type acrylamide copolymer and product emulsion thereof and above-mentioned clay stabilizer is poor, very easily produces precipitation; (2)The drag reducer that partial hydrolysis acrylamide or anionic acrylamide copolymer split as shale gas reservoir drag reduction hydraulic pressure uses 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-salt is poor, especially existsUnder high salinity high divalent ion content condition, molecular structure is unstable, and resistance reducing effect declines very fast.
Patent US20090298721A1 discloses the of the fracturing fluid formula of a kind of drag reduction water: in 1000 gallons of deionized watersAdd 0.5 gallon of acrylic acidcoacrylamide thing (FR-56TM) etc. the conduct of anionic acrylamide copolymer emulsionDrag reducer, then add the complexing agents such as 0.15wt% sodium carbonate or EDTA-2Na, this drag reduction water fracturing fluid has good fallingResistive energy, indoor average resistance-reducing yield reaches 65.0%, and salt tolerance (the especially tolerance to divalent calcium ion) has been had to oneDetermine the improvement of degree, use as shale gas drag reduction water fracturing fluid but this kind of drag reduction hydraulic pressure splits system, there are the following problems: (1)Poor with the compatibility of clay stabilizer (as potassium chloride, tetramethyl ammonium chloride etc.) and alcohol, with the alcohol effects such as methyl alcohol very easilyProduce precipitation; (2) anti-filtration property is poor, this kind of drag reduction water fracturing fluid very easily leak-off in the middle of stratum; (3) in realityIn construction, " water-sensitive effect " is remarkable; (4) very easily produce " water blocking "; (5) resistance to high speed shear poor performance, in high speed shearEffect is lower unstable, and resistance-reducing yield declines very fast; (6) heat-resistant salt-resistant is poor, especially contains at high salinity high divalent ionUnder amount condition, molecular structure is unstable, and resistance reducing effect declines very fast; (7) be difficult for degraded, easily to extremely fine and close pagePermanent type injury is caused on rock stratum, pollutes stratum, then affects oil and gas production.
Compared with above-mentioned partial hydrolysis acrylamide or anionic acrylamide copolymer, third of cationic high-molecular amountAlkene amide copolymer also has report as drag reducer (US356226, US3868328), and this kind of structure copolymer, with stickySoil stabilizer (as KCl) compatibility is better, better with the compatibility of alcohol, and " water-sensitive effect " is not remarkable, be difficult for " water blocking ",But the large molecule of this type of friction reducer is also difficult for degraded, easily fine and close shale is caused to possible permanent damage.
Therefore, how further to improve the resistance to high speed shear performance of drag reducer, improve the inhibition of fracturing fluid to clay and anti-Leak-off, the stability that improves the drag reducing efficiency under high salt shear conditions has degradability simultaneously, reduces polymer pairThe injury on stratum is still a still an open question.
Summary of the invention
The object of the invention is to overcome the defect of prior art, provide that a kind of drag reducing efficiency is high, salt tolerance is high, anti-high shearCan be good, good water solubility, there is good compatibility with clay stabilizer, there is degradability, and to formation damage little thirdAlkene acid amides based copolymer and its preparation method and application.
The invention provides a kind of acrylamide based copolymer, wherein, described acrylamide based copolymer contain construction unit A,Construction unit B, construction unit C and construction unit D, wherein, described construction unit A is the structure shown in formula (1)Unit, described construction unit B is the construction unit shown in formula (2), described construction unit C is the knot shown in formula (3)Construction unit shown in structure unit and/or formula (4), described construction unit D is the construction unit shown in formula (5); And withIn described acrylamide based copolymer, the total mole number of construction unit is benchmark, and the content of described construction unit A is that 5-95 rubsThat %, the content of described construction unit B is 2.5-90 % by mole, the content of described construction unit C is 0.5-90 % by mole,The content of described construction unit D is 0.0001-1 % by mole; The viscosity average molecular weigh of described acrylamide based copolymer is 500Ten thousand-1,500 ten thousand;
Wherein, R1、R2、R7、R10、R12And R12' be the alkyl of H or C1-C4 independently of one another; R3For C1-C4Straight or branched alkylidene; R4、R5、R6、R13、R14、R13' and R14' be the alkyl of C1-C4 independently of one another;R8And R9Be the straight or branched alkyl of H or C1-C20 independently of one another, and R8And R9When different, be H; R11For the straight chain branched alkyl of C1-C20; X-For Cl-，Br-，I-，SCN-，
The present invention also provides a kind of preparation method of acrylamide based copolymer, and the solution that this preparation method is included in alkene gathersClose under reaction condition, under initator exists, make a kind of monomer mixture in water, carry out polymerisation, wherein, described inMonomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the monomer shown in formula (6),Described monomer F is the monomer shown in formula (7), and described monomer G is shown in the monomer shown in formula (8) and/or formula (9)Structure monomer, described monomer H is the monomer shown in formula (10), with the total mole number of monomer in described monomer mixtureFor benchmark, the content of described monomer E is 5-95 % by mole, and the content of described monomer F is 2.5-90 % by mole, described listThe content of body G is 0.5-90 % by mole, and the content of described monomer H is 0.0001-1 % by mole; Described solution polymerizationCondition to make the viscosity average molecular weigh of resulting polymers after polymerisation be 5,000,000-1,500 ten thousand,
Wherein, R1、R2、R7、R10、R12And R12' be the alkyl of H or C1-C4 independently of one another; R3For C1-C4Straight or branched alkylidene; R4、R5、R6、R13、R14、R13' and R14' be the alkyl of C1-C4 independently of one another;R8And R9Be the straight or branched alkyl of H or C1-C20 independently of one another, and R8And R9When different, be H; R11For the straight chain branched alkyl of C1-C20; X-is Cl-，Br-，I-，SCN-，
In addition, the present invention also provides a kind of preparation method of acrylamide based copolymer, this preparation method comprise water andOil phase is mixed to form reversed-phase emulsion, then under emulsion polymerization condition, under the existence of initator, by this anti-phase breastLiquid carries out polymerisation, and described water is the aqueous solution that contains monomer mixture, and described oil phase contains organic solvent and emulsificationAgent, wherein, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is above-mentionedMonomer shown in formula (6), described monomer F is the monomer shown in above-mentioned formula (7), described monomer G is above-mentioned formula (8)Structure monomer shown in shown monomer and/or above-mentioned formula (9), described monomer H is the monomer shown in above-mentioned formula (10),Taking the total mole number of monomer in described monomer mixture as benchmark, the content of described monomer E is 5-95 % by mole, described listThe content of body F is 2.5-90 % by mole, and the content of described monomer G is 0.5-90 % by mole, and the content of described monomer H is0.0001-1 % by mole; The condition of described emulsion polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisation be5000000-1,500 ten thousand.
In addition, the present invention also provides the application of described acrylamide based copolymer as drag reducer.
In described acrylamide based copolymer provided by the invention, by the construction unit that contains azo group is passed through altogetherPoly-method, is incorporated on the macromolecular chain that contains acrylamide construction unit and cationic monomer construction unit, by controlPolymerizing condition processed obtains the copolymer of suitable molecular weight, makes this acrylamide based copolymer have self-degradation, lowerFormation temperature under (being generally greater than 60 DEG C) can realize from degraded, can reduce the injury to stratum, simultaneously this acryloylAmine based copolymer has higher drag reducing efficiency under high salt shear conditions, and with clay stabilizer (as KCl and NaCl)There is higher compatibility. Thereby obtain the present invention.
And acrylamide based copolymer of the present invention water insoluble matter content when as drag reducer is obviously lower; With the row of helpingAgent (as methyl alcohol) has good compatibility.
The viscosity average molecular weigh of the acrylamide based copolymer making in embodiment 1-6 particularly, all can reach 500-1500 ten thousand;Insolubles content in water is only 0.01 % by weight; Under the shear rate of 2500rpm, this polymer is at water/alcoholic solutionDo not produce precipitation, can dissolve completely; It is 2 weights that the acrylamide based copolymer making in embodiment 1-6 is dissolved in to concentrationIn the NaCl or KCl solution of amount %, 4 % by weight, 8 % by weight, 10 % by weight, 12 % by weight, be mixed with 500mg/LWith the solution of 1000mg/L, drag reducing efficiency all can reach more than 60%; At the lower formation temperature bar of (being greater than 60 DEG C)Under part, this polymer can carry out, from degraded, the injury on stratum being less than to 10%.
In addition the preparation method of acrylamide based copolymer provided by the invention (solution polymerization process and reversed emulsion polymerization),Have advantages of easy and monomer conversion is high.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that concrete reality described hereinThe mode of executing, only for description and interpretation the present invention, is not limited to the present invention.
(1) acrylamide based copolymer
The invention provides a kind of acrylamide based copolymer, wherein, described acrylamide based copolymer contain construction unit A,Construction unit B, construction unit C and construction unit D, wherein, described construction unit A is the structure shown in formula (1)Unit, described construction unit B is the construction unit shown in formula (2), described construction unit C is the knot shown in formula (3)Construction unit shown in structure unit and/or formula (4), described construction unit D is the construction unit shown in formula (5); And withIn described acrylamide based copolymer, the total mole number of construction unit is benchmark, and the content of described construction unit A can be5-95 % by mole, is preferably 10-70 % by mole, more preferably 50-70 % by mole; The content of described construction unit B is 2.5-90% by mole, be preferably 5-60 % by mole, more preferably 20-40 % by mole; The content of described construction unit C is 0.5-90% by mole, be preferably 5-30 % by mole, more preferably 5-20 % by mole, the content of described construction unit D is 0.0001-1% by mole, be preferably 0.001-0.5 % by mole, more preferably 0.005-0.2 % by mole; Described acrylamide based copolymerViscosity average molecular weigh is 5,000,000-1,500 ten thousand, is preferably 5,000,000-1,000 ten thousand,
Wherein, R1、R2、R7、R10、R12And R12' be the alkyl of H or C1-C4 independently of one another, preferable caseUnder, R1And R2Be H or methyl independently of one another, R7And R10Be H independently of one another, R12And R12' independent separatelyGround is methyl; R3For the straight or branched alkylidene of C1-C4, be preferably ethylidene (as ,-CH2CH2-）；R4、R5、R6、R13、R14、R13' and R14' be the alkyl of C1-C4 independently of one another, be preferably methyl; R8And R9Independent separatelyGround is the straight or branched alkyl of H or C1-C20, and R8And R9When different, be H, under preferable case, R8And R9Be the straight or branched alkyl of H or C1-C5 independently of one another, and R8And R9When different, be H, further preferred feelingsUnder condition, R8And R9Be H, methyl, ethyl, isopropyl or the tert-butyl group independently of one another, and R8And R9When different, beH；R11For the straight chain branched alkyl of C1-C20, be preferably the straight or branched alkyl of C1-C5, more preferably firstBase, ethyl, isopropyl or the tert-butyl group; X-is Cl-，Br-，I-，SCN-，ExcellentElect Cl as-。
In the present invention, the example of the alkyl of described C1-C4 can include but not limited to: methyl, ethyl, n-pro-pyl, differentPropyl group, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
Described alkylidene refers to that alkane loses two residues after hydrogen atom, and described two hydrogen atoms can be that same carbon is formerTwo hydrogen atoms on son, two hydrogen atoms on also can different carbon atoms, can be straight chains, can be also side chains, for example, described ethylidene can be-CH2CH2-or-CH (CH3)-。
In the present invention, described alkylidene can be straight chain, can be also side chain. The straight or branched of described C1-C4The example of alkylidene can include but not limited to: methylene, ethylidene, sub-n-pro-pyl, isopropylidene, sub-normal-butyl,Sub-sec-butyl, isobutylidene, the sub-tert-butyl group.
The present inventor finds under study for action, by specific construction unit A, construction unit B, construction unit C withThe acrylamide quadripolymer of construction unit D composition can be obtained fabulous resistance reducing effect. For example, preferably, R1WithR2Be H or methyl independently of one another, R3For ethylidene, R7And R10Be H independently of one another; R8And R9Only separatelyBe on the spot the straight or branched alkyl of H or C1-C5, and R8And R9When different, be H; R11For the straight chain of C1-C5Or branched alkyl; R4、R5、R6、R12、R12’、R13、R14、R13' and R14' be methyl independently of one another; X-For Cl-。That is, described construction unit A is the construction unit shown in formula (1), wherein, and R1For H or methyl, described construction unitB is the construction unit shown in formula (11), and described construction unit C is formula (12), formula (13), formula (14) and formula (15)One in shown construction unit, described construction unit D is the construction unit shown in formula (16),
Wherein, R2For the alkyl of H or C1-C4, under preferable case, R2For H or methyl; R3For C1-C4Straight or branched alkylidene, be preferably ethylidene (as ,-CH2CH2-）。
(2) solution polymerization process
In addition, the present invention also provides a kind of preparation method of acrylamide based copolymer, and this preparation method is included in alkeneUnder solution polymerization condition, under initator exists, make a kind of monomer mixture in water, carry out polymerisation, wherein,Described monomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the list shown in formula (6)Body, described monomer F is the monomer shown in formula (7), described monomer G is the monomer shown in formula (8) and/or formula (9)Shown structure monomer, described monomer H is the monomer shown in formula (10), and total with monomer in described monomer mixtureMolal quantity is benchmark, and the content of described monomer E is 5-95 % by mole, is preferably 10-70 % by mole, more preferably 50-70% by mole; The content of described monomer F is 2.5-90 % by mole, is preferably 5-60 % by mole, more preferably 20-40 % by mole;The content of described monomer G is 0.5-90 % by mole, is preferably 5-30 % by mole, more preferably 5-20 % by mole, described listThe content of body H is 0.0001-1 % by mole, is preferably 0.001-0.5 % by mole, more preferably 0.005-0.2 % by mole; InstituteIt is 5,000,000-1,500 ten thousand that the condition of stating solution polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisation, preferablyBe 5,000,000-1,000 ten thousand;
Wherein, R1、R2、R7、R10、R12And R12' be the alkyl of H or C1-C4 independently of one another, preferable caseUnder, R1And R2Be H or methyl independently of one another, R7And R10Be H independently of one another, R12And R12' independent separatelyGround is methyl; R3For the straight or branched alkylidene of C1-C4, be preferably ethylidene (as ,-CH2CH2-）；R4、R5、 R6、R13、R14、R13' and R14' be the alkyl of C1-C4 independently of one another, be preferably methyl; R8And R9Independent separatelyGround is the straight or branched alkyl of H or C1-C20, and R8And R9When different, be H, under preferable case, R8And R9Be the straight or branched alkyl of H or C1-C5 independently of one another, and R8And R9When different, be H, further preferred feelingsUnder condition, R8And R9Be H, methyl, ethyl, isopropyl or the tert-butyl group independently of one another, and R8And R9When different, beH；R11For the straight chain branched alkyl of C1-C20, be preferably the straight or branched alkyl of C1-C5, more preferably firstBase, ethyl, isopropyl or the tert-butyl group; X-For Cl-，Br-，I-，SCN-，ExcellentElect Cl as-。
According to the present invention, when described polymerisation starts, the weight of described monomer mixture and water and monomer mixture totalThe ratio of weight is various ratio known in those skilled in the art, usually, and the weight of described monomer mixture and waterWith the ratio of the gross weight of monomer mixture can be 0.05-0.5:1, be preferably 0.15-0.4:1.
According to the present invention, described initator can be the various initators in this area. For example, be selected from azo series initiators and oxygenChange reduction series initiators. Taking the total mole number of monomer in described monomer mixture as benchmark, the use of described azo series initiatorsAmount is 0-10 % by mole, and the consumption of described redox series initiators is 0-10 % by mole, and described azo initiator and oxygenTotal consumption of changing reduction initator preferably meets: total consumption of described initator is the total mole number of monomer in monomer mixture0.0001-10 % by mole.
In the present invention, preferably, described azo series initiators is for being selected from 2,2 '-azo diisobutyl amidine hydrochloride and/or 2,2 '-Azo two [2-(2-imidazoline-2-propane)-dihydrochloride].
Described redox series initiators comprises Oxidizing and Reducing Agents, preferably, and described oxidant and described reducing agentMol ratio is 0.5-3.5:1, meets under the condition of aforementioned proportion, and the consumption of described oxidant can be single in monomer mixtureThe 0.0001-0.01 % by mole of the total mole number of body, is preferably the 0.001-0.008 of the total mole number of monomer in monomer mixture% by mole; Under preferable case, described oxidant is selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxideAt least one, more preferably ammonium persulfate and/or potassium peroxydisulfate; The consumption of described reducing agent can be monomer mixtureThe 0.0001-0.005 % by mole of the total mole number of middle monomer, is preferably the total mole number of monomer in monomer mixture0.001-0.004 % by mole; Described reducing agent can be inorganic reducing agent (helping reducing agent), preferably, and described inorganic reductionAgent is for being selected from sodium hydrogensulfite, sodium sulfite, rongalite, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite, ascorbic acidWith at least one in urea, more preferably sodium hydrogensulfite and/or sodium thiosulfate.
In the present invention, need to particularly point out ground, described monomer H plays the effect of chain extender in polymerization process simultaneously,This is because two the two key groups that have in described monomer H can participate in polymerisation, likeness in form " bridge formation ".
In addition, the acrylamide based copolymer provided by the invention over the ground injury of layer reduces, and this may be due to this polymerIn there is azo group, easily under lower formation temperature, (be greater than 60 DEG C) and occur from degradation reaction.
According to the present invention, described solution polymerization can also carry out under various auxiliary agents exist, and described auxiliary agent can be selected fromAt least one in chelating agent and other auxiliary agents; Taking the total mole number of monomer in described monomer mixture as benchmark, described chelaThe consumption of mixture is 0-2 % by mole, is preferably 0.0001-1 % by mole, more preferably 0.0001-0.05 % by mole, instituteThe consumption of stating other auxiliary agents can be 0-2 % by mole, is preferably 0.0001-1 % by mole, more preferably 0.0001-0.2% by mole; Preferably, the consumption of described chelating agent and other auxiliary agents makes: with always rubbing of monomer in described monomer mixtureYour number is benchmark, and the consumption of described auxiliary agent is 0.0001-4 % by mole.
According to the present invention, described chelating agent can for be selected from disodium ethylene diamine tetraacetate (EDTA), triethylenediamine pentaacetic acid,At least one in citric acid, citrate and poly-hydroxy acrylic acid, more preferably EDTA, citrate and threeAt least one in ethylenediamine pentaacetic acid, described citrate can be potassium citrate, natrium citricum, calcium citrate and lemonLemon acid ammonium etc.
According to the present invention, described other auxiliary agents can be for being selected from urea, sodium formate, isopropyl alcohol, dodecyl trimethyl bromineChange at least one in ammonium and sodium hypophosphite, be preferably urea and/or sodium formate.
The present inventor finds, has at the same time under the condition of above-mentioned various initator and auxiliary agent solution polymerization process energyAccess the controlled acrylamide based copolymer of viscosity average molecular weigh.
According to the present invention, the condition of described solution polymerization can be the condition of this area routine. For example, described solutionPolymerisation is carried out under inert gas exists, and polymeric reaction condition can comprise: temperature is 0-50 DEG C, and the time is 1-24Hour, pH value is 5-13; Under preferable case, temperature is 4-45 DEG C, and the time is 4-24 hour, and pH value is 5-9. InstituteStating pH value can be by adding acid or alkali to regulate, and described acid is preferably inorganic acid, described inorganic acid be preferably hydrochloric acid,At least one in sulfuric acid, sulfonic acid, nitric acid and phosphoric acid; Described alkali can be inorganic base or organic amine compound, for exampleCan be selected from least one in NaOH, potassium hydroxide, ammoniacal liquor, methylamine, ethamine, monoethanolamine and triethanolamine,Be preferably NaOH.
The present inventor finds under study for action, takes following condition can further improve the molecular weight of polymer:,Preferably, the process of described solution polymerization comprises the three phases carrying out successively: the reaction condition of first stage comprises:Temperature is 0-10 DEG C, is preferably 4-10 DEG C, and the time is 1-15 hour, is preferably 3-10 hour; The reaction of second stageCondition comprises: temperature is 15-30 DEG C, is preferably 20-30 DEG C, and the time is 3-8 hour, is preferably 3-5 hour; The 3rdThe reaction condition in stage comprises: temperature is 35-50 DEG C, is preferably 35-45 DEG C, and the time is 2-14 hour, is preferably 2-12Hour.
In addition, the present inventor finds under study for action, when selecting specific monomer E, monomer F, monomer G and listWhen body H reacts, can further improve the resistance reducing effect of the polymer of gained.
For example, preferably, R1And R2Be H or methyl independently of one another, R3For ethylidene, R7And R10Only separatelyBe on the spot H; R8And R9Be the straight or branched alkyl of H or C1-C5 independently of one another, and R8And R9When differentFor H; R11For the straight or branched alkyl of C1-C5; R4、R5、R6、R12、R12’、R13、R14、R13' and R14’Be methyl independently of one another; X-is Cl-. That is, described monomer E is the monomer shown in formula (6), wherein, and R1For H orMethyl, described monomer F is the monomer shown in formula (17), described monomer G is formula (18), formula (19), formula (20)And one in the monomer shown in formula (21), described monomer H is the monomer shown in formula (22),
Wherein, R2For the alkyl of H or C1-C4, under preferable case, R2For H or methyl; R3For C1-C4Straight or branched alkylidene, be preferably ethylidene (as ,-CH2CH2-）。
(3) reversed emulsion polymerization
In addition, the present invention also provides a kind of preparation method of acrylamide based copolymer, this preparation method comprise water andOil phase is mixed to form reversed-phase emulsion, then under emulsion polymerization condition, under the existence of initator, by this anti-phase breastLiquid carries out polymerisation, and described water is the aqueous solution that contains monomer mixture, and described oil phase contains organic solvent and emulsificationAgent, wherein, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is above-mentionedMonomer shown in formula (6), described monomer F is the monomer shown in above-mentioned formula (7), described monomer G is above-mentioned formula (8)Structure monomer shown in shown monomer and/or formula (9), described monomer H is the monomer shown in above-mentioned formula (10), andTaking the total mole number of monomer in described monomer mixture as benchmark, the content of described monomer E is 5-95 % by mole, is preferably10-70 % by mole, more preferably 50-70 % by mole; The content of described monomer F is 2.5-90 % by mole, is preferably 5-60% by mole, more preferably 20-40 % by mole; The content of described monomer G is 0.5-90 % by mole, is preferably 5-30 mole%, more preferably 5-20 % by mole, the content of described monomer H is 0.0001-1 % by mole, is preferably 0.001-0.5 mole%, more preferably 0.005-0.2 % by mole; The condition of described polymerisation makes all sticky of resulting polymers after polymerisationMolecular weight is 5,000,000-1,500 ten thousand, is preferably 5,000,000-1,000 ten thousand; The selection of monomer shown in formula (6)-Shi (10) withDescribe identically above, do not repeat them here.
According to the present invention, described water is the aqueous solution that contains monomer mixture. The weight of described monomer mixture and water andThe selection of the ratio of the gross weight of monomer mixture with describe identically above, do not repeat herein.
According to the present invention, the part by weight of described water and oil phase is had no particular limits, as long as make described water and oilBe thoroughly mixed to form mutually reversed-phase emulsion, under preferable case, the part by weight of described water and oil phase is 1:0.1-2,More preferably 1:0.3-0.8.
According to the present invention, described organic solvent can be this area various for emulsion polymerisation with the mutual exclusive non-utmost point of waterProperty or the little organic solvent of polarity, can be for example toluene, dimethylbenzene, hexane, cyclohexane, normal heptane, isomery paraffin,At least one in isoparaffin, gasoline, kerosene and white oil, under preferable case, described organic solvent for be selected from toluene,At least one in dimethylbenzene, normal heptane, isoparaffin, cyclohexane and kerosene.
According to the present invention, described oil phase contains organic solvent and emulsifying agent. Not special to the consumption of described organic solventRequirement can change in wider scope, as long as described organic solvent and emulsifying agent are mixed to form oil phase, preferablyIn situation, taking the gross weight of described emulsion as benchmark, the consumption of described organic solvent can be 10-60 % by weight, furtherBe preferably 20-35 % by weight.
According to the present invention, described emulsifying agent can be the various nonionic emulsifier for emulsion polymerisation in this area, for exampleCan be sorbitan fatty acid ester, APES, isomery alcohol APEO, lauryl alcohol polyethylene glycol oxideEther, methyl glycol fatty acid ester, laureth, benzylphenol oxygen APEO, phenethyl phenol polyethenoxy ether, polyoxyEthene anhydrous sorbitol fatty acid ester, sorbitan fatty acid ester ethylene oxide adduct, benzyl dimethyl phenol polyoxy secondAt least one in alkene ether, AEO and aliphatic amine polyoxyethylene ether. Under preferable case, described emulsifying agentBe selected from sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, NPE, octyl phenolAPEO, benzylphenol oxygen APEO, phenethyl phenol polyethenoxy ether, isomerous tridecanol polyoxyethylene ether, the moonAt least one in cinnamic alcohol APEO and benzyl dimethyl phenol polyethenoxy ether, more preferably by above-mentioned two kinds orThe compound emulsifying agent that the hydrophilic lipophilic balance of two or more emulsifying agent compositions is 5-9 can be for example anhydrous sorbitolFatty acid ester and NPE.
According to the present invention, the consumption of described emulsifying agent is not particularly limited, can in wider scope, change, onlyWant described emulsifying agent and described organic solvent to be mixed to form oil phase, under preferable case, taking the gross weight of described emulsion asBenchmark, the consumption of described emulsifying agent can be 1-15 % by weight, more preferably 2-10 % by weight.
According to the present invention, described initator can be various initators in this area, the selection of described initator with retouch aboveState identically, repeat no more herein.
In the present invention, under preferable case, can first azo series initiators be added to water, then be mixed to form anti-phase breast with oil phaseLiquid, then contacts reversed-phase emulsion, by redox initiator initiated polymerization with redox series initiators.
According to the present invention, described polymerisation can also be carried out under various auxiliary agents exist, and described auxiliary agent can be selected from chelatingAt least one in agent and other auxiliary agents, the selection of described auxiliary agent with describe identically above, repeat no more herein.
According to the present invention, to there is no special requirement the reinforced opportunity of described chelating agent, as long as make chelating agent and metal fromThere is chelation so that copolymer is played to static stabilization in son, can be chosen in that water adds or in oil phaseAdd, under preferable case, in order to make the chelating agent effect of playing stably more fully, can be chosen in and in water, add chelatingAgent.
According to the present invention, the selection of described chelating agent with describe identically above, repeat no more herein.
Equally, the present inventor finds, has at the same time under the condition of above-mentioned various initator and auxiliary agent anti-phase breastLiquid polymerization can obtain the acrylamide based copolymer that viscosity average molecular weigh is controlled and dissolution velocity is fast.
According to the present invention, the condition of described emulsion polymerization can be the condition of this area routine. Described polymerisation barThe selection of part with describe identically above, repeat no more herein.
Equally, the present inventor finds under study for action, takes following condition can further improve the molecule of polymerAmount:, preferably, the process of described emulsion polymerization comprises two stages of carrying out successively: the reaction of first stageCondition comprises: temperature is 0-20 DEG C, is preferably 5-10 DEG C, and the time is 1-15 hour, is preferably 1-5 hour; Second-orderThe reaction condition of section comprises: temperature is 20-50 DEG C, is preferably 25-45 DEG C, and the time is 2-8 hour, is preferably 2-5 littleTime.
According to the present invention, the method after being also included in described polymerisation connects described polymerisation products therefrom and phase inversion agentTouch, so that described polymerisation products therefrom dissolves fast in fracturing fluid application in water. Described phase inversion agent is passableFor this area is for the various phase inversion agent of emulsion polymerisation, as long as make the water-soluble increase of described polymerisation products therefrom,Can be for example polyoxyethylene sorbitan fatty acid ester, NPE, OPEO, benzylBase phenol polyethenoxy ether, phenethyl phenol polyethenoxy ether, isomery ten alcohol APEOs, isomery undecyl alcohol APEO,At least one in the nonionic emulsifier of isomerous tridecanol polyoxyethylene ether and aliphatic amine polyoxyethylene ether, preferable caseUnder, described phase inversion agent is for being selected from polyoxyethylene sorbitan fatty acid ester, isomery ten alcohol APEOs, isomery 11In alcohol APEO, isomerous tridecanol polyoxyethylene ether, NPE and OPEO extremelyFew a kind of.
According to the present invention, the consumption of described phase inversion agent is not had to special requirement, as long as can make described polymerisation gainedProduct dissolves fast in fracturing fluid application in water, and the consumption of described phase inversion agent makes: with the gross weight of described emulsionAmount is benchmark, and the consumption of described phase inversion agent can be 0.5-10 % by weight, is preferably 1-4 % by weight.
In addition, the present inventor finds under study for action, when selecting specific monomer E, monomer F, monomer G and listWhen body H reacts, can further improve the resistance reducing effect of the polymer of gained. For example, preferably, R1And R2Be H or methyl independently of one another, R3For ethylidene, R7And R10Be H independently of one another; R8And R9Independent separatelyGround is the straight or branched alkyl of H or C1-C5, and R8And R9When different, be H; R11For the straight chain of C1-C5 orBranched alkyl; R4、R5、R6、R12、R12’、R13、R14、R13' and R14' be methyl independently of one another; X-For Cl-。That is, described monomer E is the monomer shown in formula (6), wherein, and R1For H or methyl, described monomer F is formula (17)Shown monomer, described monomer G is one in the monomer shown in formula (18), formula (19), formula (20) and formula (21)Kind, described monomer H is the monomer shown in formula (22), the selection of monomer shown in formula (6), formula (17)-Shi (22) withDescribe identically above, do not repeat them here.
In addition, the present invention also provides the application of described acrylamide based copolymer in drag reducer. Employing the invention providesDescribed acrylamide based copolymer as fracturing fluid drag reducer, can obtain high and stable drag reducing efficiency, concrete applicationThe technology that method is well known to those skilled in the art.
Below will describe the present invention by embodiment. Should be understood that concrete enforcement described hereinMode only, for description and interpretation the present invention, is not limited to the present invention.
Intrinsic viscosity is measured according to GB12005.1-89 polyacrylamide For Intrinsic Viscosity Measurements method; Sticky equal moleculeAmount is according to formula Mv=（[η]/K）1\α, wherein K=4.5 × 10-3, calculate α=0.80; Dissolution time is pressed GB12500.8-89Measure (sample quality is all by straight polymer quality in sample), the powdered samples dissolution time recording is all less than20min, samples of latex dissolution time is all less than 5min; The composition of molecular structure and construction unit adopt IR spectrum and13C-NMR measures; Water insoluble matter content is pressed SY/T5862-1993 and is measured; Indoor drag reducing efficiency is pressed SY/T6376-2008Measure.
Monomer M 3 shown in monomer M 1 shown in following embodiment Chinese style (23) and formula (27) is purchased from Sigma-AldrichCompany, in addition, unless specified otherwise, the reagent of using in embodiment, comparative example and test case etc. is commercially available product.
Embodiment 1
The present embodiment is used for illustrating that solution polymerization process provided by the invention prepares acrylamide based copolymer.
Under room temperature, by M1 monomer, 17.55g shown in the formula (23) of the acrylamide of 4.26g (AM), 69.66gN,N-DMAA (purchased from Sigma-Aldrich company, below identical) and the formula (24) of 1.16g shown inThe method of M2 monomer (the method preparation of recording according to embodiment in JP08217755A 1, below identical) make,Join in polymerization bottle, add deionized water 524.9g, stir monomer is dissolved completely, and stir. Respectively to burningIn bottle, add the EDTA aqueous solution 5.5g of 1 % by weight, 2 of 1 % by weight, 2 '-azo diisobutyl amidine hydrochloride aqueous solution2.1g, adds the solution of sodium bisulfite 1.1g of 0.1 % by weight, and urea 0.12g fully stirs it is mixed. With 1The sodium hydroxide solution of % by weight regulates pH to 7.5. Hierarchy of control initial temperature to 4 DEG C, led to nitrogen deoxygenation after 30 minutes,Add 1 % by weight ammonium persulfate aqueous solution 0.45g, and continue letting nitrogen in and deoxidizing 20 minutes. Reactor is airtight, remain on 4DEG C, react after 8 hours, after being risen to 20 DEG C, temperature reacts 5 hours, then temperature is risen to 45 DEG C of reactions 2 hours,The gluey product obtaining is taken out, through granulation, dry, pulverize and can receive acrylamide copolymer p 1.
P1 is carried out to various mensuration, 1660cm in IR spectrum-1And 1635cm-1There is respectively belonging to the acyl of amide groups in placeAmine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is C-N in placeStretching vibration absworption peak, 1170cm-1There is M2 monomer CH3-C-CH3Skeletal vibration feature stretching vibration peak,1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak, can determine the copolymer molecule obtainingHave the structure shown in formula (25), recording its viscosity-average molecular weight Mv by viscosity method is 7,350,000, and monomer conversion isMore than 99.9%. Wherein, formula (25) and x1、x2、y1、y2、z1、z2Only express the type of construction unit with uAnd number, and do not represent the connected mode of construction unit. x1、x2、y1、y2、z1、z2With the concrete numerical value of u by feeding intakeAmount is definite, and the composition of molecular structural formula and construction unit adopts quantitatively13C composes mensuration, wherein, and (x1+x2)：(y1+y2)：(z1+z2)：u=1：6：2.95：0.05。
Comparative example 1
Prepare acrylamide based copolymer according to the method for embodiment 1, different, do not add M1 monomer, N, N-bis-Methacrylamide and M2 monomer, (3-acrylamido-3-methyl) the butyl trimethyl by acrylamide with identical molal quantityAmmonium chloride carries out polymerisation, thereby obtains bipolymer DP1, records its viscosity average molecular weigh MvBe 1,150 ten thousand.
Embodiment 2
The present embodiment is used for illustrating that solution polymerization process provided by the invention prepares acrylamide based copolymer.
By the M1 monomer shown in the formula of the AM of 29.85g, 5.81g (23), the NIPA of 16.84gM2 monomer shown in the formula (24) of (purchased from Sigma-Aldrich company, below identical) and 0.46g joins polymerizationIn bottle, add 123.57g deionized water, stir monomer is dissolved completely, respectively to the EDTA that adds 1 % by weight in flaskAqueous solution 4.65g, adds 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 1.23g, adds 0.1 % by weight sulfurous acidHydrogen sodium water solution 1.15g, adds urea 0.11g, fully stirs it is mixed, molten with the NaOH of 10 % by weightLiquid regulates pH to 7.1. 10 DEG C of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight over cureAcid aqueous ammonium 0.45g, and continue letting nitrogen in and deoxidizing 10 minutes. Reactor is airtight, remain on 10 DEG C, react 3 hoursAfter, be warming up to 30 DEG C, react after 3 hours, be warming up to 35 DEG C of reactions 12 hours, the gluey product obtaining is taken out,Through granulation, dry, pulverize and can receive acrylamide copolymer p 2.
P2 is carried out to various mensuration, 1660cm in IR spectrum-1And 1635cm-1There is respectively belonging to the acyl of amide groups in placeAmine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is C-N in placeStretching vibration absworption peak, 1170cm-1There is M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration,1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak. Can determine the copolymer molecule obtainingHave the structure shown in formula (26), recording its viscosity-average molecular weight Mv by viscosity method is 5,850,000, and monomer conversion isMore than 99.9%. Wherein, formula (26) and x1、x2、y1、y2、z1、z2Only express the type of construction unit with uAnd number, and do not represent the connected mode of construction unit. x1、x2、y1、y2、z1、z2With the concrete numerical value of u by feeding intakeAmount is definite, and the composition of molecular structural formula and construction unit adopts quantitatively13C composes mensuration, wherein, and (x1+x2)：(y1+y2)：(z1+z2)：u=1：0.07：0.35：0.003。
Embodiment 3
The present embodiment is used for illustrating that solution polymerization process provided by the invention prepares acrylamide based copolymer.
Under room temperature, by the M3 monomer shown in the formula of the Methacrylamide of 25.53g, 54.77g (27), 4.58gShown in the formula (24) of N tert butyl acrylamide (purchased from Sigma-Aldrich company, below identical) and 0.002gM2 monomer joins in polymerization bottle, adds 127.32g deionized water, stirs monomer is dissolved completely, respectively in flaskAdd the EDTA aqueous solution 11.63g of 1 % by weight, add 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 2.13g,Add 0.1 % by weight solution of sodium bisulfite 1.13g, add urea 0.20g, DTAB 0.01g,Fully stir it is mixed. With the sodium hydroxide solution adjusting pH to 7.3 of 10 % by weight. Hierarchy of control initial temperatureTo 8 DEG C, logical nitrogen deoxygenation, after 30 minutes, adds 1% ammonium persulfate aqueous solution 0.4g, and continues letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, remain on 8 DEG C, react after 10 hours, be warming up to 25 DEG C, react after 4 hours, be warming up to 45DEG C reaction 7 hours, takes out the gluey product obtaining, through granulation, dry, pulverize and can receive acrylamide copolymerizationThing P3.
P3 is carried out to various mensuration, 1660cm in IR spectrum-1And 1635cm-1There is respectively belonging to the acyl of amide groups in placeAmine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is C-N in placeStretching vibration absworption peak, 1170cm-1There is M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration,1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak. Can determine the copolymer molecule obtainingHave the structure shown in formula (28), recording its viscosity-average molecular weight Mv by viscosity method is 8,430,000, and monomer conversion isMore than 99.9%. Wherein, formula (28) and x1、x2、y1、y2、z1、z2Only express the type of construction unit with uAnd number, and do not represent the connected mode of construction unit. x1、x2、y1、y2、z1、z2With the concrete numerical value of u by feeding intakeAmount is definite, and the composition of molecular structural formula and construction unit adopts quantitatively13C composes mensuration, wherein, and (x1+x2)：(y1+y2)：(z1+z2)：u=1：0.88：0.12：0.00002。
Embodiment 4
The present embodiment is used for illustrating that reversed emulsion polymerization provided by the invention prepares acrylamide based copolymer.
(1) by the M1 monomer shown in the formula of the Methacrylamide of 5.11g, 69.66g (23), the N of 17.55g, N-M2 monomer shown in the formula (24) of DMAA and 1.16g joins in configuration bottle, add 152.52g go fromSub-water, stirs monomer is dissolved completely, to the EDTA aqueous solution 14.61g that adds 1 % by weight in flask, adds 1 respectively2 of % by weight, 2 '-azo diisobutyl amidine hydrochloride aqueous solution 1.03g, adds urea 0.15g, fully stirs and makes its mixingEvenly, with the sodium hydroxide solution adjusting pH to 7.1 of 10 % by weight, obtain water.
(2) by sorbitan fatty acid ester (span60, Sigma-Aldrich company, below identical) 40g, alkylPhenol polyethenoxy ether (IgepalCA720, Sigma-Aldrich company, below identical) 4.5g, 164.93g kerosene mixBecome oil phase, and the water obtaining in step (1) is joined in whole oil phases, mix formation reversed-phase emulsion by high speed and addEnter in reactor.
(3) 5 DEG C of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight sodium hydrogensulfite water-solubleLiquid 0.25g, then add 1 % by weight ammonium persulfate aqueous solution 1.0g and continue letting nitrogen in and deoxidizing 10 minutes. Reactor is airtight,Remain on 5 DEG C, react after 5 hours, be warming up to 45 DEG C, react 2 hours. After question response temperature cool to room temperature, addEnter 18.85g NPE (Sigma-Aldrich company, below identical), obtain with 80 order filter-cloth filteringsEmulsion form product. After reversed-phase emulsion product is precipitated out with acetone and methyl alcohol mixed solvent, can obtain acrylamideCopolymer p 4.
P4 is carried out to various mensuration, 1660cm in IR spectrum-1And 1635cm-1There is respectively belonging to the acyl of amide groups in placeAmine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is C-N in placeStretching vibration absworption peak, 1170cm-1There is M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration,1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak. Can determine the copolymer molecule obtainingHave the structure shown in formula (29), recording its viscosity average molecular weigh Mv by viscosity method is 6,500,000, and monomer conversion isMore than 99.9%. Wherein, formula (29) and x1、x2、y1、y2、z1、z2Only express the type of construction unit with uAnd number, and do not represent the connected mode of construction unit. x1、x2、y1、y2、z1、z2With the concrete numerical value of u by feeding intakeAmount is definite, and the composition of molecular structural formula and construction unit adopts quantitatively13C composes mensuration, wherein, and (x1+x2)：(y1+y2)：(z1+z2)：u=1：6：2.95：0.05。
Comparative example 2
Prepare acrylamide based copolymer according to the method for embodiment 4, different, do not add M1 monomer, N, N-bis-Methacrylamide and M2 monomer, (3-acrylamido-3-methyl) butyl three by Methacrylamide with identical molal quantityAmmonio methacrylate carries out polymerisation, thereby obtains bipolymer DP2, records its viscosity average molecular weigh MvBe 9,500,000.
Embodiment 5
The present embodiment is used for illustrating that reversed emulsion polymerization provided by the invention prepares acrylamide based copolymer.
(1) by the M1 monomer shown in the formula of the Methacrylamide of 35.74g, 5.81g (23), the N-of 16.84gM2 monomer shown in the formula (24) of N-isopropylacrylamide and 0.46g joins in preparation bottle, add 235.4g go fromSub-water, stirs monomer is dissolved completely, to the EDTA aqueous solution 7.63g that adds 1 % by weight in flask, adds 1 respectively% by weight azo diisobutyl amidine hydrochloride aqueous solution 2.03g, adds urea 0.10g, and fully stir it is mixed,With the sodium hydroxide solution adjusting pH to 7.0 of 15 % by weight, obtain water.
(2) by sorbitan fatty acid ester (span60) 30g, APES (IgepalCA720) 8g,114.01g kerosene is mixed into oil phase, and the water obtaining in step (1) is all joined in oil phase, mixes by high speedEven formation reversed-phase emulsion joins in reactor.
(3) 10 DEG C of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight sodium hydrogensulfite waterSolution 0.13g, then add 1 % by weight ammonium persulfate aqueous solution 0.63g, and continue letting nitrogen in and deoxidizing 10 minutes. By reactorAirtight, remain on 10 DEG C, react after 1 hour, be warming up to 25 DEG C, react question response temperature cool to room temperature 5 hoursAfter, add 9.12g NPE, obtain emulsion form product with 80 order filter-cloth filterings. By reversed-phase emulsion productAfter being precipitated out with acetone and methyl alcohol mixed solvent, can obtain acrylamide copolymer p 5.
P5 is carried out to various mensuration, 1660cm in IR spectrum-1And 1635cm-1There is respectively belonging to the acyl of amide groups in placeAmine I band absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is C-N in placeStretching vibration absworption peak, 1170cm-1There is M2 monomer CH3-C-CH3The feature stretching vibration peak of skeletal vibration,1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak. Can determine the copolymer molecule obtainingHave the structure shown in formula (30), recording its viscosity average molecular weigh Mv by viscosity method is 5,410,000, and monomer conversion isMore than 99.9%. Wherein, formula (30) and x1、x2、y1、y2、z1、z2Only express the type of construction unit with uAnd number, and do not represent the connected mode of construction unit. x1、x2、y1、y2、z1、z2With the concrete numerical value of u by feeding intakeAmount is definite, and the composition of molecular structural formula and construction unit adopts quantitatively13C composes mensuration, wherein, and (x1+x2)：(y1+y2)：(z1+z2)：u=1：0.07：0.35：0.003。
Embodiment 6
The present embodiment is used for illustrating that reversed emulsion polymerization provided by the invention prepares acrylamide based copolymer.
(1) by the M3 monomer shown in the formula of the acrylamide of 21.32g, 54.77g (27), the N-tert-butyl group of 4.58gM2 monomer shown in the formula (24) of acrylamide and 0.002g joins in configuration bottle, adds 454.31g deionized water,Stirring is dissolved monomer completely, to the EDTA aqueous solution 8.5g that adds 1 % by weight in flask, adds 1 % by weight respectivelyAzo diisobutyl amidine hydrochloride aqueous solution 2.1g, adds urea 0.08g, and DTAB 0.01g, fillsDivide to stir it is mixed, with the sodium hydroxide solution adjusting pH to 7.1 of 10 % by weight, obtain water.
(2) by sorbitan fatty acid ester (span60) 11.81g, APES (IgepalCA720,Sigma-Aldrich company, below identical) 10g, 141.74g kerosene is mixed into oil phase, and will in step (1), obtain waterBe added in oil phase, mix formation reversed-phase emulsion by high speed and join in reactor.
(3) 8 DEG C of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight sodium hydrogensulfite water-solubleLiquid 0.18g, then add 1 % by weight ammonium persulfate aqueous solution 1.3g, and continue letting nitrogen in and deoxidizing 10 minutes. Reactor is closeClose, remain on 8 DEG C, react after 3 hours, be warming up to 40 DEG C, react 4 hours, after question response temperature cool to room temperature,Add 7.09 NPEs, obtain emulsion form product with 100 order filter-cloth filterings. By reversed-phase emulsion product with thirdAfter ketone and methyl alcohol mixed solvent are precipitated out, can obtain acrylamide copolymer p 6.
P6 is carried out to various mensuration, in IR spectrum, 1660cm-1And 1635cm-1There is respectively belonging to amide groups in placeAmide Ⅰ absworption peak (C=O stretching vibration) and acid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1Place occursThe stretching vibration absworption peak of C-N, 1170cm-1There is M2 monomer CH3-C-CH3The feature stretching vibration of skeletal vibrationPeak, 1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak. Can determine the copolymer obtainingMolecule has the structure shown in formula (31), and recording its viscosity average molecular weigh Mv by viscosity method is 7,850,000, and monomer transformsRate is more than 99.9%. Wherein, formula (31) and x1、x2、y1、y2、z1、z2Only express construction unit with uType and number, and do not represent the connected mode of construction unit. x1、x2、y1、y2、z1、z2With the concrete numerical value of u byInventory is definite, and the composition of molecular structural formula and construction unit adopts quantitatively13C composes mensuration, wherein, and (x1+x2)：(y1+y2)：(z1+z2)：u=1：0.88：0.12：0.00002。
Test case 1
Water-insoluble is to measure according to the method specifying in SY/T5862-1993. By P1-P6, DP1, DP2 and hydroxypropylBase melon glue (JXY wellfracturing hydroxypropyl melon rubber powder, Shandong Juxin Chemical Co., Ltd., below identical) carry out water-solubleMeasure, result is as shown in table 1.
Table 1
As can be seen from Table 1, in the acrylamide copolymer p 1-P6 that prepared by two kinds of methods provided by the invention, water is notMolten thing content is starkly lower than the conventional hydroxypropyl guar gum that cooks drag reducer in site operation, and this explanation and hydroxypropyl guar gum ratio, makeLow to the injury on stratum as shale gas pressure break drag reducer with P1-P6.
Test case 2
Under 2500rpm shear rate, respectively by P1-P6, DP1, DP2, partially hydrolyzed polyacrylamide (PHPA) (HPAM,Zibo Tian Jian Chemical Co., Ltd., trade mark TJY-1, viscosity average molecular weigh is 1000-1300 ten thousand, lower same) and separately respectivelySlowly join volume ratio and be in water/alcoholic solution (using methyl alcohol in this test case) of 80/20 and 60/40, P1-P6, DP1,The consumption of DP2 and partially hydrolyzed polyacrylamide (PHPA) is that (sample quality is by simple polymerisation in sample for 0.01 % by weight of water/alcoholic solutionAmount meter), dissolution time is 30min, result is as shown in table 2.
Table 2
As can be seen from Table 2, the acrylamide copolymer p 1-P6 that prepared by two kinds of methods provided by the invention is as pageRock air pressure splits with drag reducer, compared with partially hydrolyzed polyacrylamide (PHPA), good with the compatibility of alcohol.
Test case 3
Be, under the condition of 25 DEG C, P1-P6, DP1, DP2, HPAM and hydroxypropyl guar gum to be dissolved in respectively to pure water in temperatureWith concentration be in the NaCl or KCl solution of 2 % by weight, 4 % by weight, 8 % by weight, 10 % by weight, 12 % by weight,The 500mg/L being mixed with and the solution of 1000mg/L (sample quality is by straight polymer quality in sample), then rootOn GLM-1 pipeline frictional resistance determinator, measure the drag reducing efficiency of above-mentioned solution according to the method specifying in SY/T6376-2008,(test condition: the internal diameter of test section pipeline is 8mm, the length of test section pipeline is 9m, infusion discharge capacity is 30L/min),Result as shown in Table 3 and Table 4.
Table 3
Table 4
From table 3 and table 4, can find out acrylamide copolymer p 1-P6 prepared by two kinds of methods provided by the inventionAs shale gas pressure break drag reducer, compare with hydroxypropyl guar gum, HPAM, DP1 and DP2, with clay stabilizer (as,KCl and NaCl) compatibility is good, anti-salt property excellence.
Test case 4
Friction reducer to the nocuity of rock core, by oil and gas industry standard SY/T5107-2005, " comment by aqueous fracturing fluid performanceValency method " in fracturing fluid filtrate to rock core matrix permeability infringement experiment carry out, in the formation damage test of American core companyOn instrument (FDS-800), test, the matrix permeability of rock core is 2md.
P1-P6, DP1 and DP2 are dissolved in respectively to pure water, and (sample quality is by sample to be mixed with the solution of 1000mg/LStraight polymer quality meter in product), be to preserve 24hr under the condition of 65 DEG C at probe temperature, at American core company formation damageUpper its nocuity to rock core of testing of test macro (FDS-800), result is as shown in table 5.
Table 5
As can be seen from Table 5, the acrylamide copolymer p 1-P6 that prepared by two kinds of methods provided by the invention is to rock coreInjury be starkly lower than in site operation the conventional comparative sample of cooking drag reducer, this explanation is used P1-P6 as shale air pressureSplit with drag reducer low to the injury on stratum.
Above-mentioned test result explanation, the insolubles content of acrylamide based copolymer provided by the invention in water is only0.01%; Under the shear rate of 2500rpm, can be dissolved in completely in water/alcoholic solution, good with the compatibility of alcohol; Due toImprove with the compatibility of alcohol and clay stabilizer (NaCl or KCl), improved anti-filtration property; And at high salt and heightUnder the condition of shearing, still there is high drag reducing efficiency; Under the lower formation temperature condition of (being greater than 60 DEG C), have from fallingXie Xing is low to the injury on stratum. In addition, the preparation method of acrylamide based copolymer provided by the invention have easy andThe advantage that monomer conversion is high.
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited in above-mentioned embodimentDetail, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention,These simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characterictic described in above-mentioned detailed description of the invention, in contradiction notSituation under, can combine by any suitable mode. For fear of unnecessary repetition, the present invention is to variousThe explanation no longer separately of possible combination.
In addition, between various embodiment of the present invention, also can be combined, as long as it is without prejudice to thisBright thought, it should be considered as content disclosed in this invention equally.
Claims (23)
1. an acrylamide based copolymer, is characterized in that, described acrylamide based copolymer containsConstruction unit A, construction unit B, construction unit C and construction unit D, wherein, described construction unitA is the construction unit shown in formula (1), and described construction unit B is the construction unit shown in formula (2),Described construction unit C is the construction unit shown in the construction unit shown in formula (3) and/or formula (4),Described construction unit D is the construction unit shown in formula (5); And in described acrylamide based copolymerThe total mole number of construction unit is benchmark, and the content of described construction unit A is 5-95 % by mole, described inThe content of construction unit B is 2.5-90 % by mole, and the content of described construction unit C is 0.5-90 % by mole,The content of described construction unit D is 0.0001-1 % by mole; The sticky of described acrylamide based copolymer divided equallySon amount is 5,000,000-1,500 ten thousand;
Wherein, R1、R2、R7、R10、R12And R12' be the alkyl of H or C1-C4 independently of one another;R3For the straight or branched alkylidene of C1-C4; R4、R5、R6、R13、R14、R13' and R14' separatelyBe the alkyl of C1-C4 independently; R8And R9Be independently of one another H or C1-C20 straight chain orAlkyl group, and R8And R9When different, be H; R11For the straight or branched alkyl of C1-C20; X-For Cl-、 Br-、I-、SCN-、
2. acrylamide based copolymer according to claim 1, wherein, with described acrylamideIn based copolymer, the total mole number of construction unit is benchmark, and the content of described construction unit A is that 10-70 rubsThat %, the content of described construction unit B is 5-60 % by mole, the content of described construction unit C is 5-30% by mole, the content of described construction unit D is 0.001-0.5 % by mole, described acrylamide based copolymerViscosity average molecular weigh be 5,000,000-1,000 ten thousand.
3. acrylamide based copolymer according to claim 1, wherein, R1And R2Independent separatelyGround is H or methyl, R3For ethylidene, R7And R10Be H independently of one another; R8And R9Only separatelyBe on the spot the straight or branched alkyl of H or C1-C5, and R8And R9When different, be H; R11For C1-C5Straight or branched alkyl; R4、R5、R6、R12、R12’、R13、R14、R13' and R14' independent separatelyGround is methyl; X-For Cl-。
4. a preparation method for acrylamide based copolymer, this preparation method is included in the solution of alkeneUnder polymeric reaction condition, under initator exists, make a kind of monomer mixture in water, carry out polymerisation,Wherein, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, described monomer EFor the monomer shown in formula (6), described monomer F is the monomer shown in formula (7), and described monomer G is formula(8) the structure monomer shown in the monomer shown in and/or formula (9), described monomer H is formula (10) instituteThe monomer showing, taking the total mole number of monomer in described monomer mixture as benchmark, the content of described monomer EFor 5-95 % by mole, the content of described monomer F is 2.5-90 % by mole, and the content of described monomer G is0.5-90 % by mole, the content of described monomer H is 0.0001-1 % by mole; Described solution polymerizationIt is 5,000,000-1,500 ten thousand that condition makes the viscosity average molecular weigh of resulting polymers after polymerisation,
Wherein, R1、R2、R7、R10、R12And R12' be the alkyl of H or C1-C4 independently of one another;R3For the straight or branched alkylidene of C1-C4; R4、R5、R6、R13、R14、R13' and R14' separatelyBe the alkyl of C1-C4 independently; R8And R9Be independently of one another H or C1-C20 straight chain orAlkyl group, and R8And R9When different, be H; R11For the straight or branched alkyl of C1-C20; X-For Cl-、Br-、I-、SCN-、
5. a preparation method for acrylamide based copolymer, this preparation method comprises water and oil phaseBe mixed to form reversed-phase emulsion, then under emulsion polymerization condition, under the existence of initator, shouldReversed-phase emulsion carries out polymerisation, and described water is the aqueous solution that contains monomer mixture, and described oil phase containsHave organic solvent and emulsifying agent, wherein, described monomer mixture contains monomer E, monomer F, monomer GWith monomer H, described monomer E is the monomer shown in formula (6), and described monomer F is shown in formula (7)Monomer, described monomer G is the structure monomer shown in the monomer shown in formula (8) and/or formula (9), instituteStating monomer H is the monomer shown in formula (10), taking the total mole number of monomer in described monomer mixture as baseStandard, the content of described monomer E is 5-95 % by mole, the content of described monomer F is 2.5-90 % by mole,The content of described monomer G is 0.5-90 % by mole, and the content of described monomer H is 0.0001-1 % by mole;It is 5,000,000 that the condition of described emulsion polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisation-1,500 ten thousand,
Wherein, R1、R2、R7、R10、R12And R12' be the alkyl of H or C1-C4 independently of one another;R3For the straight or branched alkylidene of C1-C4; R4、R5、R6、R13、R14、R13' and R14' separatelyBe the alkyl of C1-C4 independently; R8And R9Be independently of one another H or C1-C20 straight chain orAlkyl group, and R8And R9When different, be H; R11For the straight or branched alkyl of C1-C20; X-For Cl-、Br-、I-、SCN-、
6. preparation method according to claim 5, wherein, the weight ratio of described water and oil phaseFor 1:0.1-2.
7. preparation method according to claim 6, wherein, the weight ratio of described water and oil phaseFor 1:0.3-0.8.
8. preparation method according to claim 5, wherein, taking the gross weight of described emulsion as baseStandard, the consumption of described organic solvent is 10-60 % by weight, the consumption of described emulsifying agent is 1-15 % by weight.
9. preparation method according to claim 8, wherein, taking the gross weight of described emulsion as baseStandard, the consumption of described organic solvent is 20-35 % by weight, the consumption of described emulsifying agent is 2-10 % by weight.
10. preparation method according to claim 5, wherein, the method is also included in described polymerizationAfter reaction, described polymerisation products therefrom is contacted with phase inversion agent.
11. preparation methods according to claim 10, wherein, taking the gross weight of described emulsion asBenchmark, the consumption of described phase inversion agent is 0.5-10 % by weight.
12. preparation methods according to claim 11, wherein, taking the gross weight of described emulsion asBenchmark, the consumption of described phase inversion agent is 1-4 % by weight.
13. according to the preparation method described in claim 4 or 5, wherein, and in described monomer mixtureThe total mole number of monomer is benchmark, and the content of described monomer E is 10-70 % by mole, described monomer F'sContent is 5-60 % by mole, and the content of described monomer G is 5-30 % by mole, the content of described monomer HFor 0.001-0.5 % by mole; The condition of described polymerisation makes all sticky of resulting polymers after polymerisationMolecular weight is 5,000,000-1,000 ten thousand.
14. according to the preparation method described in claim 4 or 5, wherein, and R1And R2Independently of one anotherFor H or methyl, R3For ethylidene, R7And R10Be H independently of one another; R8And R9Independent separatelyGround is the straight or branched alkyl of H or C1-C5, and R8And R9When different, be H; R11For C1-C5Straight or branched alkyl; R4、R5、R6、R12、R12’、R13、R14、R13' and R14' independent separatelyGround is methyl; X-For Cl-。
15. according to the preparation method described in claim 4 or 5, wherein, and the weight of described monomer mixtureThe ratio of the gross weight of amount and water and monomer mixture is 0.05-0.5:1.
16. preparation methods according to claim 15, wherein, the weight of described monomer mixtureWith the ratio of the gross weight of water and monomer mixture be 0.15-0.4:1.
17. according to the preparation method described in claim 4 or 5, and wherein, described initator is selected from azoSeries initiators and redox series initiators, taking the total mole number of monomer in described monomer mixture as baseStandard, the consumption of described azo series initiators is 0-10 % by mole, the consumption of described redox series initiatorsFor 0-10 % by mole, and total consumption of described initator is 0.0001-10 % by mole; Described azo is to drawSend out agent and be selected from 2,2 '-azo diisobutyl amidine hydrochloride and/or 2, the two [2-(2-imidazoline-2-yl) third of 2 '-azoAlkane] dihydrochloride, described redox series initiators comprises Oxidizing and Reducing Agents, described oxidant withThe mol ratio of described reducing agent is 0.5-3.5:1, described oxidant for be selected from ammonium persulfate, potassium peroxydisulfate,At least one in sodium peroxydisulfate and hydrogen peroxide; Described reducing agent is inorganic reducing agent, rongalite, anti-At least one in bad hematic acid and urea, described inorganic reducing agent for be selected from sodium hydrogensulfite, sodium sulfite,At least one in sodium thiosulfate, ferrous sulfate and sodium hydrosulfite.
18. according to the preparation method described in claim 4 or 5, and wherein, described polymerisation is at auxiliary agentUnder existence, carry out, described auxiliary agent is at least one being selected from chelating agent and other auxiliary agents; With described monomerThe total mole number of mixture is benchmark, and the consumption of described chelating agent is 0-2 % by mole, described other auxiliary agentsConsumption be 0-2 % by mole, and taking the total mole number of monomer in described monomer mixture as benchmark, described inTotal consumption of auxiliary agent is 0.0001-4 % by mole; Described chelating agent is for being selected from disodium ethylene diamine tetraacetate, twoAt least one in second pentaacetic acid, citric acid, citrate and poly-hydroxy acrylic acid, described otherAuxiliary agent is to be selected from urea, sodium formate, isopropyl alcohol, DTAB and sodium hypophosphiteAt least one.
19. preparation methods according to claim 4, wherein, described solution polymerization is in inertiaGas carries out under existing, and polymeric reaction condition comprises: temperature is 0-50 DEG C, and the time is 1-24 hour,PH value is 5-13.
20. preparation methods according to claim 5, wherein, described emulsion polymerization is in inertiaGas carries out under existing, and polymeric reaction condition comprises: temperature is 0-50 DEG C, and the time is 1-24 hour,PH value is 5-13.
21. according to the preparation method described in claim 4 or 19, wherein, and described solution polymerizationProcess comprise the three phases carrying out successively, the reaction condition of first stage comprises: temperature is 0-10 DEG C,Time is 1-15 hour; The reaction condition of second stage comprises: temperature is 15-30 DEG C, and the time is 3-8Hour; The reaction condition of phase III comprises: temperature is 35-50 DEG C, and the time is 2-14 hour.
22. according to the preparation method described in claim 5 or 20, wherein, and described emulsion polymerizationProcess comprise two stages of carrying out successively, the reaction condition of first stage comprises: temperature is 0-20 DEG C,Time is 1-15 hour; The reaction condition of second stage comprises: temperature is 20-50 DEG C, and the time is 2-8Hour.
Acrylamide based copolymer in 23. claim 1-3 described in any one or by claimThe acrylamide based copolymer that method in 4-22 described in any one prepares should as drag reducerWith.
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| CN102050926A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof |
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| CN103131404A (en) * | 2013-02-17 | 2013-06-05 | 中国石油化工股份有限公司 | Amphoteric ionic polymer water base fracturing fluid thickening agent and preparation method thereof |
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| JPH08217755A (en) * | 1995-02-15 | 1996-08-27 | Asahi Chem Ind Co Ltd | Production of an azo compound and a graft polymer |
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| US3868328A (en) * | 1972-03-09 | 1975-02-25 | Calgon Corp | Friction reducing compounds for use in hydraulic fracturing fluids |
| CN102050926A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof |
| CN102351976A (en) * | 2011-07-22 | 2012-02-15 | 武汉工程大学 | Synthetic method of salt tolerant quadripolymer superabsorbent resin |
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