CN104250357B - 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
- Publication number
- CN104250357B CN104250357B CN201310268816.8A CN201310268816A CN104250357B CN 104250357 B CN104250357 B CN 104250357B CN 201310268816 A CN201310268816 A CN 201310268816A CN 104250357 B CN104250357 B CN 104250357B
- Authority
- CN
- China
- Prior art keywords
- monomer
- construction unit
- mole
- formula
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 and construction unit C, wherein, described construction unit A is the construction unit shown in formula (1), and described construction unit B is the construction unit shown in formula (2), and described construction unit C is the construction unit shown in formula (3); And taking the total mole number of construction unit in described acrylamide based copolymer as benchmark, the content of described construction unit A is 5-95 % by mole, and the content of described construction unit B is 2.5-90 % by mole, and the content of described construction unit C is 0.5-90 % by mole; The viscosity average molecular weigh of described acrylamide based copolymer is 2,000,000-1,500 ten thousand. Acrylamide based copolymer drag reducing efficiency provided by the invention is high, heat-resisting and high, the anti-high shear performance of salt tolerance is good, good water solubility, have good compatibility, viscosity average molecular weigh low and little to the nocuity on stratum with clay stabilizer (alcohol).
Description
Technical field
The present invention relates to a kind of acrylamide based copolymer, acrylamide based copolymer two kinds of preparation methods and described inAcrylamide based copolymer is as the application of drag reducer.
Background technology
As unconventional petroleum resources utilize Typical Representative---the exploitation of shale gas (oil) resource has become the whole worldA revolution in unconventional petroleum resources field, 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), frac pressureHigh, easily to cause formation damage feature. 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 crosslinked with current conventional pressure break systemSystem) to compare, drag reduction water (slippery water) pressure break is not to rely on high viscosity colloid to take sand, but takes sand with high infusion discharge capacity, realNow reservoir fracturing is reticulated to the final purpose in crack. Compared with conventional pressure break system, drag reduction water (slippery water) pressure break is at costOn less to the injury on stratum when having greater advantage.
Drag reduction water fracturing fluid core auxiliary agent is water-based drag reducer, and in practice of construction, adding of water-based drag reducer overcomes workMake the frictional resistance of liquid in pipeline, 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, acrylamideBase 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, reduced the frictional resistance (US5697444, US5271466) in pipeline, split but still cannot meet drag reduction hydraulic pressureRequirement, there is following shortcoming mainly due to above-mentioned boiomacromolecule: (1) resistance-reducing performance is limited; (2) due to guanidine glue, celluloseAnd derivative has a small amount of insoluble matter and very easily stratum is damaged; (3) dissolution time is longer.
In drag reduction water pressing crack construction, adopt acrylamide copolymer (partial hydrolysis acrylamide or anionic moreAcrylamide copolymer) friction reducer in splitting as drag reduction hydraulic pressure, has improved to a great extent infusion discharge capacity, has reduced in pipelineFrictional resistance, but the drag reducer splitting as shale gas reservoir drag reduction hydraulic pressure use, there is following major defect: (1) is in order to reduce" water-sensitive effect " in fracturing process, the hydration swelling of inhibition shale medium clay soil component must add little molecule in fracturing fluidCationic clay stabilizing agent (as potassium chloride, tetramethyl ammonium chloride etc.). Partial hydrolysis acrylamide or anionic acrylamideThe compatibility of copolymer and product emulsion thereof and above-mentioned clay stabilizer is poor, very easily produces precipitation; (2) partial hydrolysis acryloylThe drag reducer that amine or anionic acrylamide copolymer split as shale gas reservoir drag reduction hydraulic pressure uses anti-filtration property poor, thisKind of drag reduction water fracturing fluid very easily leak-off in the middle of stratum; (3) temperature-resistant anti-salt is poor, especially contains at high salinity high divalent ionUnder amount 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. anionic acrylamide copolymer emulsion as subtractingResist, then add the complexing agents such as 0.15wt% sodium carbonate or EDTA-2Na, this drag reduction water fracturing fluid has good resistance-reducing performance,Indoor average resistance-reducing yield reaches 65.0%, and salt tolerance (the especially tolerance to divalent calcium ion) has been had to improvement to a certain degree,But this kind of drag reduction hydraulic pressure splits system to be used as shale gas drag reduction water fracturing fluid, and there are the following problems: (1) and clay stabilizer andThe compatibility of alcohol is poor, very easily produces precipitation; (2) anti-filtration property is poor, this kind of drag reduction water fracturing fluid very easily leak-off to stratumIn the middle of; (3) in practice of construction, " water-sensitive effect " is remarkable; (4) very easily produce " water blocking "; (5) resistance to high speed shear poor performance, at heightUnstable under speed shear action, resistance-reducing yield declines very fast; (6) heat-resistant salt-resistant is poor, especially at high salinity high divalent ionUnder content condition, molecular structure is unstable, and resistance reducing effect declines very fast; (7) be difficult for degraded, easily to extremely fine and close shale groundLayer causes permanent type injury, pollutes stratum, then affects oil and gas production.
Compared with above-mentioned partial hydrolysis acrylamide or anionic acrylamide copolymer, cationic high-molecular amountAcrylamide copolymer also has report as drag reducer (US356226, US3868328), the compatibility of this kind of structure copolymer and alcoholProperty is better, and better with little molecule clay stabilizer (as KCl, tetramethyl ammonium chloride etc.) compatibility, " water-sensitive effect " is not remarkable, noEasily " water blocking ", polymer itself has the effect of certain inhibition hydration and expansion of clay. But this type of friction reducer molecular weight is higher, noEasily degraded, easily causes possible permanent damage to fine and close shale.
Therefore, 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, the stability that improves the drag reducing efficiency under high temperature and high salt shear conditions reduces the injury of polymer to stratum simultaneouslyBe 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 viscosity average molecular weigh is low, drag reducing efficiency is high, heat-resisting andHigh, the anti-high shear performance of salt tolerance is good, good water solubility, with clay stabilizer have good compatibility 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 contains construction unitA, construction unit B and construction unit C, wherein, described construction unit A is the construction unit shown in formula (1), described construction unit BFor the construction unit shown in formula (2), described construction unit C is the construction unit shown in formula (3); And with described acrylamide altogetherIn polymers, the total mole number of construction unit is benchmark, and the content of described construction unit A is 5-95 % by mole, described construction unit B'sContent is 2.5-90 % by mole, and the content of described construction unit C is 0.5-90 % by mole; Gluing all of described acrylamide based copolymerMolecular weight is 2,000,000-1,500 ten thousand;
Wherein, R1And R2Be the straight or branched alkyl of H or C1-C4 independently of one another; R3For connecting key or C1-C6Straight or branched alkylidene; R4For the alkyl of H or C1-C2; R5For oxygen atom or-NH-; R6For the straight chain of C1-C10 orBranched alkylidene; R7And R8Be the straight or branched alkyl of C1-C4 independently of one another; X-For Cl-，Br-，I-，SCN-，
The present invention also provides a kind of preparation method of acrylamide based copolymer, and 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 listBody mixture contains monomer D, monomer E and monomer F, and described monomer D is the monomer shown in formula (6), and described monomer E is formula (7) instituteThe monomer showing, described monomer F is the monomer shown in formula (8), taking the total mole number of monomer in described monomer mixture as benchmark, instituteThe content of stating monomer D is 5-95 % by mole, and the content of described monomer E is 2.5-90 % by mole, and the content of described monomer F is 0.5-90% by mole; It is 2,000,000-1500 that the condition of described solution polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisationTen thousand,
Wherein, R1And R2Be the straight or branched alkyl of H or C1-C4 independently of one another; R3For connecting key or C1-C6Straight or branched alkylidene; R4For the alkyl of H or C1-C2; R5For oxygen atom or-NH-; R6For C1-C10Straight chain orChain alkylidene; R7And R8Be the straight or branched alkyl of C1-C4 independently of one another; X-For Cl-，Br-，I-，SCN-，
In addition, the present invention also provides a kind of preparation method of acrylamide based copolymer, and this preparation method comprises waterBe mixed to form reversed-phase emulsion with oil phase, then under emulsion polymerization condition, under the existence of initator, by this reversed-phase emulsionCarry out polymerisation, described water is the aqueous solution that contains monomer mixture, and described oil phase contains organic solvent and emulsifying agent, itsIn, described monomer mixture contains monomer D, monomer E and monomer F, and described monomer D is the monomer shown in above-mentioned formula (6), described listBody E is the monomer shown in above-mentioned formula (7), and described monomer F is the monomer shown in above-mentioned formula (8), with single in described monomer mixtureThe total mole number of body 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, instituteThe content of stating monomer F is 0.5-90 % by mole; The condition of described emulsion polymerization makes the sticky of resulting polymers after polymerisationAverage molecular weight is 2,000,000-1,500 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 triphenyl phosphonium salt system shown in introduction-type (2)Hydrophobic structure unit shown in hydrophobic structure unit and formula (3), and control relatively low viscosity average molecular weigh, make this thirdAlkene acid amides based copolymer has higher drag reducing efficiency under high temperature and high salt shear conditions, and with clay stabilizer (as KCl,NaCl) there is higher compatibility.
And acrylamide based copolymer of the present invention water insoluble matter content when as drag reducer is obviously lower; With helpRow's agent (as methyl alcohol) has good compatibility; Low to formation damage.
The viscosity average molecular weigh of the acrylamide based copolymer making in embodiment 1-6 particularly, all can reach 1,500 ten thousand withUnder; 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 % by weight, 4 that the acrylamide based copolymer making in embodiment 1-6 is dissolved in to concentrationIn the NaCl or KCl solution of % by weight, 8 % by weight, 10 % by weight, 12 % by weight, be mixed with the molten of 500mg/L and 1000mg/LLiquid, the drag reducing efficiency at 25 DEG C all can reach more than 60%, and the drag reducing efficiency under the condition of 60 DEG C also can reach more than 50%; ThisOutward, the acrylamide based copolymer making in the embodiment 1-6 over the ground injury of layer is less than 10%.
In addition the preparation method of acrylamide based copolymer provided by the invention (solution polymerization process and inverse emulsion polymerization,Method) 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, described herein concreteEmbodiment 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 contains construction unitA, construction unit B and construction unit C, wherein, described construction unit A is the construction unit shown in formula (1), described construction unit BFor the construction unit shown in formula (2), described construction unit C is the construction unit shown in formula (3); And with described acrylamide altogetherIn polymers, the total mole number of construction unit is benchmark, and the content of described construction unit A can be 5-95 % 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, is preferably 20-50 % by mole, moreBe preferably 20-30 % by mole; The content of described construction unit C is 0.5-90 % by mole, is preferably 10-40 % by mole, more preferably10-20 % by mole; The viscosity average molecular weigh of described acrylamide based copolymer is 2,000,000-1,500 ten thousand, is preferably 2,000,000-6,000,000,
Wherein, R1For the alkyl of H or C1-C4, be preferably H or methyl; R2For the straight or branched alkane of H or C1-C4Base, under preferable case, R2For H; R3For the straight or branched alkylidene of connecting key or C1-C6, be preferably connecting key or methyleneBase; R4For the alkyl of H or C1-C2, be preferably H or methyl; R5For oxygen atom or-NH-; R6For the straight chain of C1-C10 orBranched alkylidene; R7And R8Be the straight or branched alkyl of C1-C4 independently of one another, be preferably methyl; X-For Cl-，Br-，I-，SCN-，Be preferably Br-。
In the present invention, the example of the alkyl of described C1-C4 can include but not limited to: methyl, ethyl, n-pro-pyl, isopropylBase, 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 same carbonTwo hydrogen atoms on atom, 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-C10The example of alkylidene can include but not limited to: methylene, ethylidene, sub-n-pro-pyl, isopropylidene, sub-normal-butyl, sub-Zhong DingBase, isobutylidene, the sub-tert-butyl group, sub-n-pentyl, isoamylidene, sub-tertiary pentyl, sub-neopentyl, sub-n-hexyl, sub-n-heptyl, AsiaN-octyl, sub-positive decyl.
The present inventor finds under study for action, is made up of specific construction unit A, construction unit B and construction unit CAcrylamide ter-polymers can obtain fabulous resistance reducing effect. Preferably, R1For H or methyl, R2For H, R3For connectingKey or methylene, X-For Br-, that is, described construction unit A is the construction unit shown in formula (1), wherein, and R1For H or methyl, instituteStating construction unit B is the construction unit shown in the construction unit shown in formula (9) and/or formula (10), and described construction unit C is formula(4) construction unit shown in the construction unit shown in and/or formula (5),
Wherein, R4For the alkyl of H or C1-C2, under preferable case, R4For H or methyl; N and p are 1-independently of one another10 integer, under preferable case, n and p are the integer of 1-5 independently of one another.
(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 alkeneSolution polymerization condition under, initator exist under, make a kind of monomer mixture in water, carry out polymerisation, wherein,Described monomer mixture contains monomer D, monomer E and monomer F, and described monomer D is the monomer shown in formula (6), and described monomer E is formula(7) monomer shown in, described monomer F is the monomer shown in formula (8), and taking the total mole number of monomer in described monomer mixture asBenchmark, the content of described monomer D is 5-95 % by mole, is preferably 10-70 % by mole, more preferably 50-70 % by mole; Described monomer EContent be 2.5-90 % by mole, be preferably 20-50 % by mole, more preferably 20-30 % by mole; The content of described monomer F is 0.5-90 % by mole, be preferably 10-40 % by mole, more preferably 10-20 % by mole; The condition of described solution polymerization makes polymerization anti-The viscosity average molecular weigh of resulting polymers is 2,000,000-1,500 ten thousand afterwards, is preferably 2,000,000-6,000,000;
Wherein, R1For the alkyl of H or C1-C4, be preferably H or methyl; R2For the straight or branched alkane of H or C1-C4Base, under preferable case, R2For H; R3For the straight or branched alkylidene of connecting key or C1-C6, be preferably connecting key or methyleneBase; R4For the alkyl of H or C1-C2, be preferably H or methyl; R5For oxygen atom or-NH-; R6For the straight chain of C1-C10 orBranched alkylidene; R7And R8Be the straight or branched alkyl of C1-C4 independently of one another, be preferably methyl; X-For Cl-，Br-，I-，SCN-，Be preferably Br-。
According to the present invention, when described polymerisation starts, the weight of described monomer mixture and water and monomer mixtureThe ratio of gross 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 consumption of described azo series initiatorsFor 0-10 % by mole, the consumption of described redox series initiators is 0-10 % by mole, and described azo initiator and redoxTotal consumption of 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 azodiisobutyronitrile, ABVN, azoTwo methylpent hydrochlorates, 2,2 '-azo diisobutyl amidine hydrochloride and 2,2 '-azo two [2-(2-imidazoline-2-propane)-disaltHydrochlorate] at least one, more preferably 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 be 0.5-3.5:1, meet under the condition of aforementioned proportion, 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 least one in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxideKind, more preferably ammonium persulfate and/or potassium peroxydisulfate; The consumption of described reducing agent can be monomer in monomer mixtureThe 0.0001-0.005 % by mole of total mole number, the 0.001-0.004 that is preferably the total mole number of monomer in monomer mixture rubsYou are %; Described reducing agent can be inorganic reducing agent (helping reducing agent) and/or organic reducing agent (chain extender), preferably, and described nothingMachine reducing agent 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; Described organic reducing agent is for being selected from N,N '-dimethyl-ethylenediamine, N, N '-dimethyl-1,3-propane diamine, N, N, N ', N '-tetramethylethylenediamine, N, N-dimethyl amine,3-methylamino propylamine, Dimethylaminoethyl Methacrylate, N-(3-dimethylamino-propyl) Methacrylamide, 1-(dimethylAmino) at least one in-2-propylamine and diethylenetriamines, more preferably N, N '-dimethyl-ethylenediamine, N, N '-bis-Methyl isophthalic acid, 3-propane diamine and N, N, N ', at least one in N '-tetramethylethylenediamine.
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 chelaAt least one in mixture and other auxiliary agents; Taking the total mole number of monomer in described monomer mixture as benchmark, described chelating agentConsumption be 0-2 % by mole, be preferably 0.0001-1 % by mole, more preferably 0.0001-0.05 % by mole, described other helpThe consumption of agent can be 0-2 % by mole, is preferably 0.0001-1 % by mole, more preferably 0.0001-0.2 % by mole; PreferablyGround, the consumption of described chelating agent and other auxiliary agents makes: taking the total mole number of monomer in described monomer mixture as benchmark, described inThe consumption of 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 triethylenediamineAt least one in pentaacetic acid, described citrate can be potassium citrate, natrium citricum, calcium citrate and ammonium citrate etc.
According to the present invention, described other auxiliary agents can be for being selected from urea, sodium formate, isopropyl alcohol and sodium hypophosphite at leastOne, is 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 processCan obtain 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 0-80 DEG C, and the time is that 1-24 is littleTime, pH value is 5-13; Under preferable case, temperature is 4-60 DEG C, and the time is 4-24 hour, and pH value is 5-9. Described pH value can be led toCross and add acid or alkali to regulate, described acid is preferably inorganic acid, described inorganic acid be preferably hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid andAt least one in phosphoric acid; Described alkali can be inorganic base or organic amine compound, for example, can be selected from NaOH, hydrogen-oxygenChange at least one in potassium, 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 bag of first stageDraw together: temperature is 0-10 DEG C, is preferably 4-10 DEG C, the time is 1-15 hour, is preferably 3-10 hour; The reaction condition of second stageComprise: temperature is 15-30 DEG C, is preferably 20-30 DEG C, the time is 3-8 hour, is preferably 3-5 hour; The reaction bar of phase IIIPart comprises: temperature is 35-60 DEG C, is preferably 45-55 DEG C, and the time is 2-14 hour, is preferably 2-12 hour.
In addition, the present inventor finds under study for action, when selecting specific monomer D, monomer E and monomer F to carry out insteadAt once, can further improve the resistance reducing effect of the polymer of gained. Preferably, R1For H or methyl, R2For H, R3For connectingKey or methylene, X-For Br-, that is, preferably, described monomer D is the monomer shown in formula (6), wherein, and R1For H or methyl, instituteStating monomer E is the monomer shown in the monomer shown in formula (11) and/or formula (12), described monomer F be the monomer shown in formula (9) and/Or the monomer shown in formula (10),
Wherein, R4For the alkyl of H or C1-C2, under preferable case, R4For H or methyl; N and p are 1-independently of one another10 integer, under preferable case, n and p are the integer of 1-5 independently of one another. Wherein, having the monomer of structure shown in formula (9) canWith by with acryloyl chloride (or methacrylic chloride) and the amine with structure shown in general formula A under methanol solution and alkali conditionReaction obtains. The monomer with structure shown in formula (10) can and have logical by methyl acrylate (or methyl methacrylate)The ester exchange under the existence of catalyst (isopropyl titanate etc.) and polymerization inhibitor (phenthazine etc.) of the alkanolamine of structure shown in formula B is anti-Should obtain (referring to " isopropyl titanate catalytic transesterification synthesizing dimethylaminoethyl methacrylate ", Zhang Guangxu etc., oilWork, 2008,27(11): 1160-1165).
(3) reversed emulsion polymerization
In addition, the present invention also provides a kind of preparation method of acrylamide based copolymer, and this preparation method comprises waterBe mixed to form reversed-phase emulsion with oil phase, then under emulsion polymerization condition, under the existence of initator, by this reversed-phase emulsionCarry out polymerisation, described water is the aqueous solution that contains monomer mixture, and described oil phase contains organic solvent and emulsifying agent, itsIn, described monomer mixture contains monomer D, monomer E and monomer F, and described monomer D is the monomer shown in above-mentioned formula (6), described listBody E is the monomer shown in above-mentioned formula (7), and described monomer F is the monomer shown in above-mentioned formula (8). Monomer shown in formula (6)-Shi (8)Select and describe identically above, not repeating them here.
According to the present invention, described water is the aqueous solution that contains monomer mixture. The weight of described monomer mixture and waterWith the 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 withOil phase is thoroughly mixed to form reversed-phase emulsion, and under preferable case, the part by weight of described water and oil phase is 1:0.1-2, entersOne step is preferably 1:0.3-0.8.
According to the present invention, described organic solvent can be various mutual exclusive non-with water for emulsion polymerisation in this areaThe organic solvent that polarity or polarity are little can be for example toluene, dimethylbenzene, hexane, cyclohexane, normal heptane, isomery paraffin, isomeryAt least one in alkane, gasoline, kerosene and white oil, under preferable case, described organic solvent is for being selected from toluene, dimethylbenzene, justAt least one in 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 in wider scope, change, as long as described organic solvent and emulsifying agent are mixed to form oil phase, preferred feelingsUnder condition, taking the gross weight of described emulsion as benchmark, the consumption of described organic solvent can be 10-60 % by weight, more preferably20-35 % by weight.
According to the present invention, described emulsifying agent can be the various nonionic emulsifier for emulsion polymerisation in this area, exampleAs being 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, polyoxyethylene loseWater sorbitan fatty acid fat, sorbitan fatty acid ester ethylene oxide adduct, benzyl dimethyl phenol polyethenoxy ether, fatAt least one in alcohol APEO and aliphatic amine polyoxyethylene ether. Under preferable case, described emulsifying agent is selected from dehydration sorbAlcohol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, NPE, OPEO, benzylPhenol oxygen APEO, phenethyl phenol polyethenoxy ether, isomerous tridecanol polyoxyethylene ether, ethoxylated dodecyl alcohol and benzylAt least one in dimethyl phenol APEO, is more preferably made up of above-mentioned two or more emulsifying agentHydrophilic lipophilic balance is the compound emulsifying agent of 5-9, for example, can be sorbitan fatty acid ester and Nonyl phenoEther.
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 as baseStandard, 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, and the selection of described initator is with aboveDescribe 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 chelaAt least one in mixture 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 metalIon generation chelation is so that play static stabilization to copolymer, 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 chelating agent.
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 polymerisationThe selection of condition with describe identically above, repeat no more herein.
Equally, the present inventor finds under study for action, takes following condition can further improve dividing of polymerSon amount:, preferably, the process of described emulsion polymerization comprises two stages of carrying out successively: the reaction bar of first stagePart 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; The reaction of second stageCondition comprises: temperature is 20-60 DEG C, is preferably 25-55 DEG C, and the time is 2-8 hour, is preferably 2-5 hour.
According to the present invention, the method is also included in after described polymerisation described polymerisation products therefrom and phase inversion agentContact, 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, benzylphenolAPEO, phenethyl phenol polyethenoxy ether, isomery ten alcohol APEOs, isomery undecyl alcohol APEO, isomery tenAt least one in the nonionic emulsifier of triol APEO and aliphatic amine polyoxyethylene ether, under preferable case, described inPhase inversion agent is for being selected from polyoxyethylene sorbitan fatty acid ester, isomery ten alcohol APEOs, isomery undecyl alcohol polyoxyethyleneAt least one in ether, isomerous tridecanol polyoxyethylene ether, NPE and OPEO.
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 instituteObtain product and in water, dissolve fast in fracturing fluid application, 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 D, monomer E and monomer F to carry out insteadAt once, can further improve the resistance reducing effect of the polymer of gained. Preferably, R1For H or methyl, R2For H, R3For connectingKey or methylene, X-For Br-, that is, described monomer D is the monomer shown in formula (6), described monomer E is the monomer shown in formula (11)And/or the monomer shown in formula (12), described monomer F is the monomer shown in the monomer shown in formula (9) and/or formula (10), formula (6),The selection of monomer shown in formula (9)-Shi (12) with describe identically above, do not repeat them here.
In addition, the present invention also provides the application of described acrylamide based copolymer as drag reducer. Employing the present invention carryThe described acrylamide based copolymer of confession, 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 reality described hereinThe mode of executing, 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 dividing equallySon amount 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 surveysFixed; Water insoluble matter content is pressed SY/T5862-1993 and is measured; Indoor drag reducing efficiency is pressed SY/T6376-2008 and is measured.
Monomer M 1 shown in following embodiment Chinese style (13) is purchased from Sigma-Aldrich company; Monomer shown in formula (15)M2 is according to document (Synthesisoftriphenylmethyl-substitutedconjugateddienesvi aWittigreaction, HuaxueShiji, 2011,33 (9), 782-784) in the method recorded make.
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 the M1 monomer shown in the formula (13) of the acrylamide of 21.32g (AM), 66.40g and the N-of 20.43g(3-dimethylamino-propyl) Methacrylamide joins in reaction bulb, adds deionized water 612.85g, stirs and makes monomer completeDissolve, and stir. Respectively to the EDTA aqueous solution 5.5g that adds 1 % by weight in flask, 1 % by weight azo diisobutyl amidine saltAcid salt aqueous solution 2.1g, chain extender N ', N-dimethyl-ethylenediamine 0.002g, adds 0.1% solution of sodium bisulfite 1.1g, urea0.12g, fully stirs it is mixed. With the sodium hydroxide solution adjusting pH to 7.5 of 1 % by weight. Hierarchy of control initial temperatureTo 4 DEG C, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight ammonium persulfate aqueous solution 0.75g, and continues letting nitrogen in and deoxidizing 20 minutes.Reactor is airtight, remain on 4 DEG C, react after 8 hours, after being risen to 20 DEG C, temperature reacts 5 hours, then temperature is risen to 50DEG C reaction 2 hours, takes out the gluey product obtaining, 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 stretching of C-N in placeContracting vibration absorption peak; 1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak, 1506,1577,1600cm-1Go out peak and belong to the stretching vibration of C=C on phenyl ring; 1437cm-1Go out peak and belong to Ar-P stretching vibration; 691,724,747cm-1Go out peak and belong to Ar-H out-of plane bending vibration on phenyl ring. Can determine that the copolymer molecule obtaining has formula (14) instituteThe structure of showing, recording its viscosity-average molecular weight Mv by viscosity method is 3,500,000, monomer conversion is more than 99.9%. Wherein, formula(14) and x, y and z only express type and the number of construction unit, and do not represent the connected mode of construction unit. Molecule knotThe composition of structure formula and construction unit adopts quantitatively13C-NMR composes mensuration, obtains x:y:z=1:0.6:0.4.
Comparative example 1
Prepare acrylamide based copolymer according to the method for embodiment 1, different, by acrylamide and identical molal quantity(3-acrylamido-3-methyl) butyl trimethyl ammonium chloride carry out polymerisation, thereby obtain bipolymer DP1, surveyObtaining its viscosity average molecular weigh Mv is 1,450 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 N-of the monomer M 2 shown in the formula of the AM of 29.85g, 45.94g (15) and 10.26g (4-dimethylamino butyl) thirdOlefin(e) acid ester joins in polymerization bottle, adds 200.78g deionized water, stirs monomer is dissolved completely, adds 1 respectively in flaskThe EDTA aqueous solution 4.65g of % by weight, adds 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 1.23g, adds chain extender N,N '-dimethyl-ethylenediamine 0.002g, adds 0.1% solution of sodium bisulfite 1.15g, adds urea 0.11g, fully stirs and makes itMix. With the sodium hydroxide solution adjusting pH to 7.1 of 1 % by weight. Hierarchy of control initial temperature to 10 DEG C, logical nitrogen deoxygenationAfter 30 minutes, add 1 % by weight ammonium persulfate aqueous solution 0.6g, and continue letting nitrogen in and deoxidizing 10 minutes. Reactor is airtight, keepAt 10 DEG C, react after 3 hours, be warming up to 30 DEG C, react after 3 hours, be warming up to 55 DEG C of reactions 12 hours, the glue obtaining is producedThing takes out, through granulation, dry, pulverize and can receive acrylamide copolymer p 2.
P2 is carried out to various mensuration, 1730cm in IR spectrum-1There is belonging to acrylic ester unit C=O stretching vibration in place,1660cm in IR spectrum-1And 1635cm-1Place occur respectively belonging to amide groups amide Ⅰ absworption peak (C=O stretching vibration) andAcid amides II band absworption peak (N-H flexural vibrations), at 1430cm-1There is the stretching vibration absworption peak of C-N in place; 1356cm-1With1401cm-1There is typical methyl symmetric curvature vibration absorption peak, 1506,1577,1600cm-1Go out peak and belong to C=C on phenyl ringStretching vibration; 1437cm-1Go out peak and belong to Ar-P stretching vibration; 691,724,747cm-1Go out peak and belong to Ar-H on phenyl ringOut-of plane bending vibration. Can determine that the copolymer molecule obtaining has the structure shown in formula (16), records it by viscosity methodViscosity-average molecular weight Mv is 4,130,000, and monomer conversion is more than 99.9%. Wherein, formula (16) and x, y and z only express structure listType and the number of unit, and do not represent the connected mode of construction unit. The composition of molecular structural formula and construction unit adopts quantitatively13C-NMR composes mensuration, obtains x:y:z=1:0.3:0.14.
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 N-(5-of the M1 monomer 47.52g shown in the formula of the Methacrylamide of 5.11g, 110.66g (13)Dimethylamino amyl group) Methacrylamide in polymerization bottle, add 244.94g deionized water, stir monomer is dissolved completely, pointNot, to the EDTA aqueous solution 11.63g that adds 1 % by weight in flask, do not add the 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution2.13g, adds chain extender N ', and N-dimethyl-ethylenediamine 0.001g adds 0.1 % by weight solution of sodium bisulfite 1.13g, addsUrea 0.20g, fully stirs it is mixed. With the sodium hydroxide solution adjusting pH to 7.3 of 1 % by weight. The hierarchy of control is initialTemperature to 2 DEG C, logical nitrogen deoxygenation, after 30 minutes, adds 1% ammonium persulfate aqueous solution 0.8g, and continues letting nitrogen in and deoxidizing 10 minutes. WillReactor is airtight, remains on 8 DEG C, reacts after 10 hours, is warming up to 25 DEG C, reacts after 4 hours, is warming up to 45 DEG C of reactions 7 hours,The gluey product obtaining is taken out, through granulation, dry, pulverize and can receive acrylamide copolymer p 3.
P3 is carried out to various mensuration, in IR spectrum, 1660cm-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 stretching of C-N in placeContracting vibration absorption peak; 1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak, 1506,1577,1600cm-1Go out peak and belong to the stretching vibration of C=C on phenyl ring; 1437cm-1Go out peak and belong to Ar-P stretching vibration; 691,724,747cm-1Go out peak and belong to Ar-H out-of plane bending vibration on phenyl ring. Can determine that the copolymer molecule obtaining has formula (17) instituteThe structure of showing, recording its viscosity-average molecular weight Mv by viscosity method is 5,430,000, monomer conversion is more than 99.9%. Wherein, formula(17) and x, y and z only express type and the number of construction unit, and do not represent the connected mode of construction unit. Molecule knotThe composition of structure formula and construction unit adopts quantitatively13C-NMR composes mensuration, obtains x:y:z=1:5:4.
Embodiment 4
The present embodiment is used for illustrating that reversed emulsion polymerization provided by the invention prepares acrylamide based copolymer.
(1) by the N-(3-bis-of the M1 monomer shown in the formula of the Methacrylamide of 5.11g, 110.66g (13), 40.86gMethylamino propyl group) Methacrylamide joins in configuration bottle, adds 255.55g deionized water, and stir monomer is dissolved completely,Respectively to the EDTA aqueous solution 14.61g that adds 1 % by weight in flask, chain extender N ', N-dimethyl-ethylenediamine 0.001g, adds 1% by weight azo diisobutyl amidine hydrochloride aqueous solution 1.03g, adds urea 0.15g, fully stirs it is mixed, with 10The sodium hydroxide solution of % by weight regulates pH to 7.1, obtains water.
(2) by sorbitan fatty acid ester (span60, Sigma-Aldrich company, below identical) 15g, alkyl phenolAPEO (IgepalCA720, Sigma-Aldrich company, below identical) 62.04g, 265.34g kerosene is mixed into oilPhase, and the water obtaining in step (1) is joined in whole oil phases, mix formation reversed-phase emulsion by high speed and join reactionIn device.
(3) 5 DEG C of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight aqueous solution of sodium bisulfite0.25g, 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 5DEG C, react after 5 hours, be warming up to 55 DEG C, react 2 hours. After question response temperature cool to room temperature, add 15.41g nonyl phenol poly-Oxygen vinethene (Sigma-Aldrich company, below identical), obtains emulsion form product with 80 order filter-cloth filterings. By reversed-phase emulsionProduct can obtain acrylamide copolymer p 4 after being precipitated out with acetone and methyl alcohol mixed solvent.
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 stretching of C-N in placeContracting vibration absorption peak; 1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak, 1506,1577,1600cm-1Go out peak and belong to the stretching vibration of C=C on phenyl ring; 1437cm-1Go out peak and belong to Ar-P stretching vibration; 691,724,747cm-1Go out peak and belong to Ar-H out-of plane bending vibration on phenyl ring. Can determine that the copolymer molecule obtaining has formula (18) instituteThe structure of showing, recording its viscosity average molecular weigh Mv by viscosity method is 4,430,000, monomer conversion is more than 99.9%. Wherein, formula(18) and x, y and z only express type and the number of construction unit, and do not represent the connected mode of construction unit. X, y and zConcrete numerical value determined by inventory, the composition of molecular structural formula and construction unit adopts quantitatively13C-NMR composes mensuration, obtains x:y：z=1：5：4。
Comparative example 2
Prepare acrylamide based copolymer according to the method for embodiment 4, different, Methacrylamide is rubbed with identicalYou carry out polymerisation, thereby obtain bipolymer by (3-acrylamido-3-methyl) butyl trimethyl ammonium chloride of numberDP2, recording its viscosity average molecular weigh Mv is 9,550,000.
Embodiment 5
The present embodiment is used for illustrating that reversed emulsion polymerization provided by the invention prepares acrylamide based copolymer.
(1) by the N-(4-bis-of the M2 monomer shown in the formula of the Methacrylamide of 35.74g, 45.94g (15) and 10.26gMethylamino butyl) acrylate joins in configuration bottle, adds 367.76g deionized water, and stir monomer is dissolved completely, respectivelyTo the EDTA aqueous solution 7.63g that adds 1 % by weight in flask, chain extender N ', N-dimethyl-ethylenediamine 0.001g, adds 1 % by weightAzo diisobutyl amidine hydrochloride aqueous solution 2.03g, adds urea 0.10g, fully stirs it is mixed, and uses 15 % by weightSodium hydroxide solution regulate pH to 7.0, obtain water.
(2) by sorbitan fatty acid ester (span60) 48g, APES (IgepalCA720)16.68g, 170.05g kerosene is mixed into oil phase, and the water obtaining in step (1) is all joined in oil phase, by high speedMixing 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 aqueous solution of sodium bisulfite0.13g, then add 1 % by weight ammonium persulfate aqueous solution 0.63g, and continue letting nitrogen in and deoxidizing 10 minutes. Reactor is airtight, keepAt 10 DEG C, react after 1 hour, be warming up to 30 DEG C, react 5 hours, after question response temperature cool to room temperature, add 21.13g nonylPhenol polyethenoxy ether, obtains emulsion form product with 80 order filter-cloth filterings. By acetone and methyl alcohol mixed solvent for reversed-phase emulsion productAfter being precipitated out, 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 stretching of C-N in placeContracting vibration absorption peak, 1729cm-1There is the feature stretching vibration peak of ester carbonyl group, 1356cm-1And 1401cm-1Occur typicalMethyl symmetric curvature vibration absorption peak, 2923cm-1、2852cm-1The belong to respectively-CH that locates out peak2-、-CH3Flexible the shaking of C-HMoving, 1506,1577,1600cm-1Go out peak and belong to the stretching vibration of C=C on phenyl ring; 1437cm-1Going out peak, to belong to Ar-P flexibleVibration; 691,724,747cm-1Go out peak and belong to Ar-H out-of plane bending vibration on phenyl ring. Can determine that the copolymer obtaining dividesSon has the structure shown in formula (19), and recording its viscosity average molecular weigh Mv by viscosity method is 5,100,000, and monomer conversion is 99.9%Above. Wherein, formula (19) and x, y and z only express type and the number of construction unit, and do not represent the connection of construction unitMode. The concrete numerical value of x, y and z determined by inventory, and the composition of molecular structural formula and construction unit adopts quantitatively13C-NMR spectrumMeasure, obtain x:y:z=1:0.29:0.14.
Embodiment 6
The present embodiment is used for illustrating that reversed emulsion polymerization provided by the invention prepares acrylamide based copolymer.
(1) by N-(the 5-diformazan ammonia of the M1 monomer shown in the formula of the acrylamide of 19.19g, 66.40g (13) and 29.7gBase amyl group) Methacrylamide joins in configuration bottle, adds 653.31g deionized water, and stir monomer is dissolved completely, respectivelyTo the EDTA aqueous solution 8.5g that adds 1 % by weight in flask, chain extender N ', N-dimethyl-ethylenediamine 0.001g, adds 1 % by weight evenNitrogen diisobutyl amidine hydrochloride aqueous solution 2.1g, adds urea 0.08g, fully stirs it is mixed, with the hydrogen of 10 % by weightSodium hydroxide solution regulates pH to 7.1, obtains water.
(2) by sorbitan fatty acid ester (span60) 20g, APES (IgepalCA720,Sigma-Aldrich company, below identical) 11.17g, 202.61g kerosene is mixed into oil phase, and will in step (1), obtain waterJoin 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 aqueous solution of sodium bisulfite0.18g, then add 1 % by weight ammonium persulfate aqueous solution 1.3g and continue letting nitrogen in and deoxidizing 10 minutes. Reactor is airtight, remain on 8DEG C, react after 3 hours, be warming up to 40 DEG C, react 4 hours, after question response temperature cool to room temperature, add 10.13g nonyl phenol poly-Oxygen vinethene, obtains emulsion form product with 100 order filter-cloth filterings. By acetone and methyl alcohol mixed solvent precipitation for reversed-phase emulsion productOut, can obtain the acrylamide copolymer p 6 of HMW.
P6 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 stretching of C-N in placeContracting vibration absorption peak, 1356cm-1And 1401cm-1There is typical methyl symmetric curvature vibration absorption peak, 2923cm-1、2852cm-1The belong to respectively-CH that locates out peak2-、-CH3C-H stretching vibration, 1506,1577,1600cm-1Go out peak and belong to benzeneThe stretching vibration of C=C on ring; 1437cm-1Go out peak and belong to Ar-P stretching vibration; 691,724,747cm-1Go out peak and belong to phenyl ringUpper Ar-H out-of plane bending vibration. Can determine that the copolymer molecule obtaining has the structure shown in formula (20), passes through viscosity methodRecording its viscosity average molecular weigh Mv is 3,600,000, and monomer conversion is more than 99.9%. Wherein, formula (20) and x, y and z only expressThe type of construction unit and number, and do not represent the connected mode of construction unit. The concrete numerical value of x, y and z determined by inventory,The composition of molecular structural formula and construction unit adopts quantitatively13C composes mensuration, obtains x:y:z=1:0.67:0.56.
Test case 1 water-insoluble is to measure according to the method specifying in SY/T5862-1993. By P1-P6, DP1 and DP2And in site operation the conventional hydroxypropyl guar gum that cooks drag reducer (JXY wellfracturing hydroxypropyl melon rubber powder, the poly-prosperous chemical industry in Shandong hasLimit company, below identical) carry out water-soluble mensuration, result is as shown in table 1. Table 1
As can be seen from Table 1, the water in the acrylamide copolymer p 1-P6 that prepared by two kinds of methods provided by the inventionInsolubles content is starkly lower than in site operation the conventional hydroxypropyl guar gum that cooks drag reducer, and this illustrates compared with hydroxypropyl guar gum,Use P1-P6 as shale gas pressure break drag reducer, lower to the injury on stratum.
Test case 2
Under 2500rpm shear rate, respectively by P1-P6, DP1, DP2 and partial hydrolysis polypropylene amine (HPAM, sky, ZiboStrong Chemical Co., Ltd., trade mark TJY-1, viscosity average molecular weigh is 1000-1300 ten thousand) slowly join respectively volume ratio 80/20 HeIn water/alcoholic solution (using methyl alcohol in this test case) of 60/40, the use of P1-P6, DP1, DP2 and partially hydrolyzed polyacrylamide (PHPA)Amount is 0.01 % by weight (sample quality is by straight polymer quality in sample) of water/alcoholic solution, and dissolution time is 30min, resultAs shown in table 2.
Table 2
As can be seen from Table 2, use P1-P6 prepared by two kinds of methods provided by the invention as shale gas pressure break with subtractingResist is compared with partially hydrolyzed polyacrylamide (PHPA), good with the compatibility of cleanup additive (taking methyl alcohol as example).
Test case 3
Be at 25 DEG C in temperature, P1-P6, DP1, DP2, HPAM and hydroxypropyl guar gum be dissolved in respectively to pure water and concentration is 2In the NaCl or KCl solution of % by weight, 4 % by weight, 8 % by weight, 10 % by weight, 12 % by weight, the 500mg/L being mixed with andThe solution (sample quality is by straight polymer quality in sample) of 1000mg/L, then according to specifying in SY/T6376-2008Method is measured the drag reducing efficiency (test condition: the internal diameter of test section pipeline is of above-mentioned solution on GLM-1 pipeline frictional resistance determinator8mm, the length of test section pipeline is 9m, infusion discharge capacity is 30L/min), result is as shown in Table 3 and Table 4.
At the temperature of 60 DEG C, by P1-P6, DP1, D2 and HPAM be dissolved in respectively pure water and concentration be 2 % by weight, 4 % by weight,In the NaCl solution of 8 % by weight, 10 % by weight, 12 % by weight, the 500mg/L being mixed with and the solution of 1000mg/L, according toThe method (condition determination is identical with at above-mentioned 25 DEG C) specifying in SY/T6376-2008, measurement result is in table 5.
Table 3
Table 4
Table 5
From table 3-table 5, can find out, with the conventional hydroxypropyl guar gum that cooks drag reducer in site operation, HAPM, DP1 andDP2 compares, and acrylamide copolymer P1-P6 prepared by method provided by the invention is as shale air pressure drag reducer, with clayStabilizing agent (as, KCl and NaCl) compatibility is better, and anti-salt property is more excellent; In addition acrylamide copolymerization provided by the invention,The drag reducing efficiency of thing at 25 DEG C all can reach more than 60%, and the drag reducing efficiency at 60 DEG C also can reach more than 50%, and the present invention is describedThe acrylamide based copolymer providing still has higher drag reducing efficiency under high temperature, high salt, shear conditions.
Test case 4
Friction reducer is pressed oil and gas industry standard SY/T5107-2005 " aqueous fracturing fluid performance to the nocuity of rock coreEvaluation 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/LInterior straight polymer quality meter), above test its injury to rock core at American core company formation damage test macro (FDS-800)Property, result is as shown in table 6.
Table 6
As can be seen from Table 6, 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 gas pressure breakLow to the injury on stratum with drag reducer.
Above-mentioned test result explanation, the insolubles content of acrylamide based copolymer of the present invention in water is only 0.01 weightAmount %; Under the shear rate of 2500rpm, can be dissolved in completely in water/alcoholic solution, good with the compatibility of alcohol; Due to alcohol and stickyThe compatibility of soil stabilizer (NaCl or KCl) improves, and has improved anti-filtration property; And tool still under the condition of high salt and high temperatureThere is high drag reducing efficiency, and there is relatively low viscosity average molecular weigh, low to formation damage. In addition acryloyl provided by the invention,The preparation method of amine based copolymer has advantages of easy and 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, thisA little 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, at lance notIn the situation of shield, can combine by any suitable mode. For fear of unnecessary repetition, the present invention to various canThe combination explanation no longer separately of energy.
In addition, between various embodiment of the present invention, also can be combined, as long as it is without prejudice to thisThe thought of invention, it should be considered as content disclosed in this invention equally.
Claims (25)
1. an acrylamide based copolymer, is characterized in that, described acrylamide based copolymer contains construction unit A, structureUnit B and construction unit C, wherein, described construction unit A is the construction unit shown in formula (1), described construction unit B is formula (2)Shown construction unit, described construction unit C is the construction unit shown in formula (3); 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, the content of described construction unit BFor 2.5-90 % by mole, the content of described construction unit C is 0.5-90 % by mole; The sticky of described acrylamide based copolymer divided equallySon amount is 2,000,000-1,500 ten thousand;
Wherein, R1And R2Be the straight or branched alkyl of H or C1-C4 independently of one another; R3Straight for connecting key or C1-C6Chain or branched alkylidene; R4For the alkyl of H or C1-C2; R5For oxygen atom or-NH-; R6For the straight or branched of C1-C10Alkylidene; R7And R8Be the straight or branched alkyl of C1-C4 independently of one another; X-For Cl-、Br-、I-、SCN-、
2. acrylamide based copolymer according to claim 1, wherein, with structure list in described acrylamide based copolymerThe total mole number of unit is benchmark, and the content of described construction unit A is 10-70 % by mole, and the content of described construction unit B is 20-50 % by mole, the content of described construction unit C is 10-40 % by mole, and the viscosity average molecular weigh of described acrylamide based copolymer is2000000-6,000,000.
3. acrylamide based copolymer according to claim 1, wherein, R1For H or methyl, R2For H, R3For connecting keyOr methylene, X-For Br-。
4. acrylamide based copolymer according to claim 1, wherein, described construction unit C is the structure shown in formula (4)Construction unit shown in unit and/or formula (5),
Wherein, R4For the alkyl of H or C1-C2; N and p are the integer of 1-10 independently of one another.
5. a preparation method for acrylamide based copolymer, this preparation method is included in the solution polymerization condition of alkeneUnder, under initator exists, make a kind of monomer mixture in water, carry out polymerisation, wherein, described monomer mixture containsMonomer D, monomer E and monomer F, described monomer D is the monomer shown in formula (6), described monomer E is the monomer shown in formula (7), described inMonomer F is the monomer shown in formula (8), taking the total mole number of monomer in described monomer mixture as benchmark, and the content of described monomer DFor 5-95 % by mole, the content of described monomer E is 2.5-90 % by mole, and the content of described monomer F is 0.5-90 % by mole; DescribedIt is 2,000,000-1,500 ten thousand that the condition of solution polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisation,
Wherein, R1And R2Be the straight or branched alkyl of H or C1-C4 independently of one another; R3Straight for connecting key or C1-C6Chain or branched alkylidene; R4For the alkyl of H or C1-C2; R5For oxygen atom or-NH-; R6For the straight or branched of C1-C10Alkylidene; R7And R8Be the straight or branched alkyl of C1-C4 independently of one another; X-For Cl-、Br-、I-、SCN-、
6. a preparation method for acrylamide based copolymer, this preparation method comprises water and oil phase is mixed to form to anti-phase breastLiquid, then, under emulsion polymerization condition, under the existence of initator, carries out polymerisation by this reversed-phase emulsion, described waterThe aqueous solution for containing monomer mixture mutually, described oil phase contains organic solvent and emulsifying agent, and wherein, described monomer mixture containsHave monomer D, monomer E and monomer F, described monomer D is the monomer shown in formula (6), and described monomer E is the monomer shown in formula (7), instituteStating monomer F is the monomer shown in formula (8), and taking the total mole number of monomer in described monomer mixture as benchmark, described monomer D containsAmount is 5-95 % by mole, and the content of described monomer E is 2.5-90 % by mole, and the content of described monomer F is 0.5-90 % by mole; InstituteIt is 2,000,000-1,500 ten thousand that the condition of stating emulsion polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisation,
Wherein, R1And R2Be the straight or branched alkyl of H or C1-C4 independently of one another; R3Straight for connecting key or C1-C6Chain or branched alkylidene; R4For the alkyl of H or C1-C2; R5For oxygen atom or-NH-; R6For the straight or branched of C1-C10Alkylidene; R7And R8Be the straight or branched alkyl of C1-C4 independently of one another; X-For Cl-、Br-、I-、SCN-、
7. preparation method according to claim 6, wherein, the weight ratio of described water and oil phase is 1:0.1-2.
8. preparation method according to claim 7, wherein, the weight ratio of described water and oil phase is 1:0.3-0.8.
9. preparation method according to claim 6, wherein, taking the gross weight of described emulsion as benchmark, described organic solventConsumption be 10-60 % by weight, the consumption of described emulsifying agent is 1-15 % by weight.
10. preparation method according to claim 9, wherein, taking the gross weight of described emulsion as benchmark, described organic solventConsumption be 20-35 % by weight, the consumption of described emulsifying agent is 2-10 % by weight.
11. preparation methods according to claim 6, wherein, the method is gathered described after being also included in described polymerisationClosing reaction products therefrom contacts with phase inversion agent.
12. preparation methods according to claim 11, wherein, taking the gross weight of described emulsion as benchmark, described phase inversion agentConsumption be 0.5-10 % by weight
13. preparation methods according to claim 12, wherein, taking the gross weight of described emulsion as benchmark, described phase inversion agentConsumption be 1-4 % by weight.
14. according to the preparation method described in claim 5 or 6, wherein, taking the total mole number of monomer in described monomer mixture asBenchmark, the content of described monomer D 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; It is 200 that the condition of described polymerisation makes the viscosity average molecular weigh of resulting polymers after polymerisationTen thousand-6,000,000.
15. according to the preparation method described in claim 5 or 6, wherein, and R1For H or methyl, R2For H, R3For connecting key orMethylene, X-For Br-。
16. according to the preparation method described in claim 5 or 6, and wherein, described monomer F is monomer and/or the formula shown in formula (9)(10) monomer shown in,
Wherein, R4For the alkyl of H or C1-C2; N and p are the integer of 1-10 independently of one another.
17. according to the preparation method described in claim 5 or 6, and wherein, the weight of described monomer mixture is mixed with water and monomerThe ratio of the gross weight of thing is 0.05-0.5:1.
18. preparation methods according to claim 17, wherein, the weight of described monomer mixture and water and monomer mixtureThe ratio of gross weight be 0.15-0.4:1.
19. according to the preparation method described in claim 5 or 6, and wherein, described initator is selected from azo series initiators and oxidation is gone backFormer series initiators, taking the total mole number of monomer in described monomer mixture as benchmark, the consumption of described azo series initiators is 0-10 % by mole, the consumption of described redox series initiators is 0-10 % by mole, and total consumption of described initator is 0.0001-10 % by mole; Described azo series initiators is for being selected from azodiisobutyronitrile, ABVN, 2,2 '-azo diisobutyl amidineHydrochloride and 2, at least one in two [2-(2-imidazoline-2-yl) propane] dihydrochlorides of 2 '-azo, described redox systemInitator comprises Oxidizing and Reducing Agents, and the mol ratio of described oxidant and described reducing agent is 0.5-3.5:1, described oxidantFor being selected from least one in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide; Described reducing agent is inorganic reducing agentAnd/or organic reducing agent, described inorganic reducing agent for be selected from sodium hydrogensulfite, sodium sulfite, sodium thiosulfate, ferrous sulfate andAt least one in sodium hydrosulfite, described organic reducing agent is for being selected from rongalite, ascorbic acid, urea, N, N '-dimethyl-ethylenediamine,N, N '-dimethyl-1,3-propane diamine, N, N, N ', N '-tetramethylethylenediamine, N, N-dimethyl amine, 3-methylamino propylamine, firstBase dimethylaminoethyl acrylate, N-(3-dimethylamino-propyl) Methacrylamide, 1-(dimethylamino)-2-propylamine and twoAt least one in ethylidene triamine.
20. according to the preparation method described in claim 5 or 6, and wherein, described polymerisation is carried out under auxiliary agent exists, described inAuxiliary agent is at least one being selected from chelating agent and other auxiliary agents; Taking the total mole number of described monomer mixture as benchmark, described inThe consumption of chelating agent is 0-2 % by mole, and the consumption of described other auxiliary agents is 0-2 % by mole, and with single in described monomer mixtureThe total mole number of body is benchmark, and total consumption of described auxiliary agent is 0.0001-4 % by mole; Described chelating agent is for being selected from ethylenediamine tetraaceticAt least one in acetic acid disodium, diethylenetriamine pentaacetic acid, citric acid, citrate and poly-hydroxy acrylic acid, described other helpAgent is at least one being selected from urea, sodium formate, isopropyl alcohol and sodium hypophosphite.
21. preparation methods according to claim 5, wherein, described solution polymerization carries out under inert gas exists,Polymeric reaction condition comprises: temperature is 0-80 DEG C, and the time is 1-24 hour, and pH value is 5-13.
22. preparation methods according to claim 6, wherein, described emulsion polymerization carries out under inert gas exists,Polymeric reaction condition comprises: temperature is 0-80 DEG C, and the time is 1-24 hour, and pH value is 5-13.
23. according to the preparation method described in claim 5 or 21, and wherein, the process of described solution polymerization comprises successivelyThe three phases of row, the reaction condition of first stage comprises: temperature is 0-10 DEG C, the time is 1-15 hour; Second stage anti-The condition of answering comprises: temperature is 15-30 DEG C, and the time is 3-8 hour; The reaction condition of phase III comprises: temperature is 35-60 DEG C,Time is 2-14 hour.
24. according to the preparation method described in claim 6 or 22, and wherein, the process of described emulsion polymerization comprises successivelyIn two stages of row, the reaction condition of first stage comprises: temperature is 0-20 DEG C, and the time is 1-15 hour; Second stage anti-The condition of answering comprises: temperature is 20-60 DEG C, and the time is 2-8 hour.
Acrylamide based copolymer in 25. claim 1-4 described in any one or by claim 5-24 any oneThe acrylamide based copolymer that method described in prepares is as the application of drag reducer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310268816.8A CN104250357B (en) | 2013-06-28 | 2013-06-28 | A kind of acrylamide based copolymer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310268816.8A CN104250357B (en) | 2013-06-28 | 2013-06-28 | A kind of acrylamide based copolymer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104250357A CN104250357A (en) | 2014-12-31 |
| CN104250357B true CN104250357B (en) | 2016-05-25 |
Family
ID=52185626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310268816.8A Active CN104250357B (en) | 2013-06-28 | 2013-06-28 | A kind of acrylamide based copolymer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104250357B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857658A (en) * | 2009-04-09 | 2010-10-13 | 北京佛瑞克技术发展有限公司 | Copolymer for acid fracturing retarded gel acid and preparation method thereof |
| 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 |
-
2013
- 2013-06-28 CN CN201310268816.8A patent/CN104250357B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857658A (en) * | 2009-04-09 | 2010-10-13 | 北京佛瑞克技术发展有限公司 | Copolymer for acid fracturing retarded gel acid and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104250357A (en) | 2014-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103788289B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN105646772B (en) | A kind of hydrophobic associated polymer and preparation method thereof | |
| CN103788293B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250348B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250339B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN103570867B (en) | A kind of Acrylamide terpolymer and its preparation method and application | |
| CN105646775B (en) | A kind of hydrophobic associated polymer and preparation method thereof | |
| CN104250345B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250354B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250343B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN103788292B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250357B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN103570864B (en) | A kind of acrylamide terpolymer and its preparation method and application | |
| CN104250356B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250337B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250336B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN103788290B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250351B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN103788291B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250347B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250352B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN103772601B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250338B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250353B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN104250355B (en) | A kind of acrylamide based copolymer and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |