CN104250347B - A kind of acrylamide based copolymer and its preparation method and application - Google Patents

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), 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/or formula (4); 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

A kind of acrylamide based copolymer and its preparation method and application

Technical field

The present invention relates to two kinds of preparation methods of a kind of acrylamide based copolymer, acrylamide based copolymerAnd described acrylamide based copolymer is as the application of drag reducer.

Background technology

As unconventional petroleum resources utilize Typical Representative---the exploitation of shale gas (oil) resourceBecome a revolution in global unconventional petroleum resources field, the development and utilization of shale gas at present becomesThe focus technology with development is paid close attention to emphatically in countries in the world. Because having, the ultimate attainment close oil-gas reservoirs such as shale gas reservoir oozeThoroughly high, the feature that easily causes formation damage of rate extremely low (being generally less than 0.5mD), frac pressure. NecessaryAdopt the exploitation of " drag reduction water (slippery water) pressure break " technique.

" drag reduction water (slippery water) pressure break " is the one of fracturing. (change with current conventional pressure break systemProperty melon glue cross-linking system) compare, drag reduction water (slippery water) pressure break is not to rely on high viscosity colloid to take sand,But take sand with high infusion discharge capacity, realize the final purpose that reservoir fracturing is reticulated to crack. With routinePressure break system is compared, and drag reduction water (slippery water) pressure break has in greater advantage stratum on costInjure less.

Drag reduction water fracturing fluid core auxiliary agent is water-based drag reducer, in practice of construction, and the adding of water-based drag reducerEnter to overcome the frictional resistance of working solution in pipeline, ensured the raising of infusion discharge capacity, make pressure maximum limitDegree ground acts on and presses off stratum and extension formation fracture, and what can be used as at present water-based drag reducer mainly contains guanidine glueAnd derivative, cellulose derivative, acrylamide copolymer.

At present, adopt guanidine glue, cellulose and derivative thereof the certain journey of drag reducer in splitting as drag reduction hydraulic pressureOn degree, improve infusion discharge capacity, reduced the frictional resistance (US5697444, US5271466) in pipeline,But still cannot meet the requirement that drag reduction hydraulic pressure splits, there is following shortcoming mainly due to above-mentioned boiomacromolecule:(1) resistance-reducing performance is limited; (2) because guanidine glue, cellulose and derivative thereof have a small amount of insoluble matter utmost pointEasily stratum is damaged; (3) dissolution time is longer.

In drag reduction water pressing crack construction, adopt more acrylamide copolymer (partial hydrolysis acrylamide orAnionic acrylamide copolymer) friction reducer in splitting as drag reduction hydraulic pressure, has improved to a great extentInfusion discharge capacity, reduce the frictional resistance in pipeline, but the drag reducer splitting as shale gas reservoir drag reduction hydraulic pressureUse, have following major defect: (1), in order to reduce " the water-sensitive effect " in fracturing process, suppressesThe hydration swelling of shale medium clay soil component must add little molecular cation clay stabilizer in fracturing fluid(as potassium chloride, tetramethyl ammonium chloride etc.). Partial hydrolysis acrylamide or anionic acrylamide are altogetherThe compatibility of polymers and product emulsion thereof and above-mentioned clay stabilizer is poor, very easily produces precipitation; (2) portionWhat point hydrolysis acrylamide or anionic acrylamide copolymer split as shale gas reservoir drag reduction hydraulic pressure subtractsResist is used anti-filtration property poor, this kind of drag reduction water fracturing fluid very easily leak-off in the middle of stratum; (3) resistance toTemperature salt-resistance is poor, and especially, under high salinity high divalent ion content condition, molecular structure is unstable,Resistance reducing effect declines very fast.

Patent US20090298721A1 discloses the of the fracturing fluid formula of a kind of drag reduction water: to 1000 gallonsIn deionized water, add 0.5 gallon of acrylic acidcoacrylamide thing (FR-56^TM) etc. anionic thirdAlkene amide copolymer emulsion is as drag reducer, then adds the complexings such as 0.15wt% sodium carbonate or EDTA-2NaAgent, this drag reduction water fracturing fluid has good resistance-reducing performance, and indoor average resistance-reducing yield reaches 65.0%, rightSalt tolerance (the especially tolerance to divalent calcium ion) has had improvement to a certain degree, but this kind of drag reduction waterPressure break system is used as shale gas drag reduction water fracturing fluid, and there are the following problems: (1) and clay stabilizerPoor with the compatibility of alcohol, very easily produce precipitation; (2) anti-filtration property is poor, and this kind of drag reduction hydraulic pressure splitsLiquid very easily leak-off in the middle of stratum; (3) in practice of construction, " water-sensitive effect " is remarkable; (4) very easily produceRaw " water blocking "; (5) resistance to high speed shear poor performance, unstable under high speed shear effect, under resistance-reducing yieldFall very fast; (6) heat-resistant salt-resistant is poor, especially, under high salinity high divalent ion content condition, dividesMinor structure is unstable, and resistance reducing effect declines very fast; (7) be difficult for degraded, easily to extremely fine and close shalePermanent type injury is caused on stratum, pollutes stratum, then affects oil and gas production.

Compared with above-mentioned partial hydrolysis acrylamide or anionic acrylamide copolymer, cationic heightThe acrylamide copolymer of molecular weight also has report as drag reducer (US356226, US3868328),The compatibility of this kind of structure copolymer and alcohol is better, with little molecule clay stabilizer (as KCl, tetramethylAmmonium chloride etc.) compatibility is better, and " water-sensitive effect " is not remarkable, is difficult for " water blocking " tool of polymer ownThere is the effect of certain inhibition hydration and expansion of clay. But this type of friction reducer molecular weight is higher, be 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 fracturing fluid to clayInhibition and anti-leak-off, the stability that improves the drag reducing efficiency under high temperature and high salt shear conditions subtracts simultaneouslyFew polymer is still a still an open question to the injury on stratum.

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 efficiencyHigh, the anti-high shear performance of high, heat-resisting and salt tolerance is good, good water solubility, have well with clay stabilizerCompatibility and to little acrylamide based copolymer of formation damage and its preparation method and application.

The invention provides a kind of acrylamide based copolymer, wherein, described acrylamide based copolymer containsConstruction unit A, construction unit B and construction unit C, wherein, described construction unit A is formula (1)Shown construction unit, described construction unit B is the construction unit shown in formula (2), described structure listThe C of unit is the construction unit shown in the construction unit shown in formula (3) and/or formula (4); And with described thirdIn alkene acid amides based copolymer, the total mole number of construction unit is benchmark, and the content of described construction unit A is5-95 % by mole, the content of described construction unit B is 2.5-90 % by mole, described construction unit C containsAmount is 0.5-90 % by mole; The viscosity average molecular weigh of described acrylamide based copolymer is 2,000,000-1,500 ten thousand;

Wherein, R₁、R₂、R₄And R₇Be the straight or branched alkyl of H or C1-C4 independently of one another;R₃For the straight or branched alkylidene of connecting key or C1-C6; R₅And R₆Be independently of one another H orThe straight or branched alkyl of C1-C20, and R₅And R₆When different, be H; R₈For the straight chain of C1-C20 props upAlkyl group; 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 alkeneUnder the solution polymerization condition of hydrocarbon, under initator exists, a kind of monomer mixture is carried out in waterPolymerisation, wherein, described monomer mixture contains monomer D, monomer E and monomer F, described monomerD is the monomer shown in formula (5), and described monomer E is the monomer shown in formula (6), and described monomer F isMonomer shown in monomer shown in formula (7) and/or formula (8), total with monomer in described monomer mixtureMolal quantity is benchmark, and the content of described monomer D is 5-95 % by mole, and the content of described monomer E is 2.5-90% by mole, the content of described monomer F is 0.5-90 % by mole; The condition of described solution polymerization makesAfter polymerisation, the viscosity average molecular weigh of resulting polymers is 2,000,000-1,500 ten thousand,

Wherein, R₁、R₂、R₄And R₇Be the straight or branched alkyl of H or C1-C4 independently of one another;R₃For the straight or branched alkylidene of connecting key or C1-C6; R₅And R₆Be independently of one another H orThe straight or branched alkyl of C1-C20, and R₅And R₆When different, be H; R₈For the straight chain of C1-C20 props upAlkyl group; X^-For Cl^-，Br^-，I^-，SCN^-，

The present invention also provides a kind of preparation method of acrylamide based copolymer, and this preparation method comprises waterPhase and oil phase are mixed to form reversed-phase emulsion, then under emulsion polymerization condition, in the existence of initatorUnder, this reversed-phase emulsion is carried out to polymerisation, described water is the aqueous solution that contains monomer mixture, instituteState oil phase and contain organic solvent and emulsifying agent, wherein, described monomer mixture contains monomer D, monomer EWith monomer F, described monomer D is the monomer shown in above-mentioned formula (5), and described monomer E is above-mentioned formula (6)Shown monomer, described monomer F is the list shown in the monomer shown in above-mentioned formula (7) and/or formula (8)Body, taking the total mole number of monomer in described monomer mixture as benchmark, the content of described monomer D is 5-95% by mole, the content of described monomer E is 2.5-90 % by mole, the content of described monomer F is that 0.5-90 rubsYou are %; The condition of described emulsion polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisation be2000000-1,500 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 three shown in introduction-type (2)Ben Ji phosphonium salt is the hydrophobic structure unit of hydrophobic structure unit and formula (3), and controls relatively lowViscosity average molecular weigh, make this acrylamide based copolymer under high temperature and high salt shear conditions, have higherDrag reducing efficiency, and there is higher compatibility with clay stabilizer (as KCl, NaCl).

And acrylamide based copolymer of the present invention at water insoluble matter content when the drag reducer obviouslyLow; There is good compatibility with cleanup additive (as methyl alcohol); Low to formation damage.

The viscosity average molecular weigh of the acrylamide based copolymer making in embodiment 1-6 particularly, all can reachBelow 1500 ten thousand; Insolubles content in water is only 0.01 % by weight; In the shearing speed of 2500rpmUnder rate, this polymer does not produce precipitation at water/alcoholic solution, can dissolve completely; To in embodiment 1-6, makeAcrylamide based copolymer be dissolved in concentration be 2 % by weight, 4 % by weight, 8 % by weight, 10 % by weight,In the NaCl of 12 % by weight or KCl solution, be mixed with the solution of 500mg/L and 1000mg/L,Drag reducing efficiency at 25 DEG C all can reach more than 60%, and in addition, the drag reducing efficiency under the condition of 60 DEG C alsoCan reach more than 50%; In addition the acrylamide based copolymer making in embodiment 1-6, is the wound of layer over the groundEvil is less than 10%.

In addition the preparation method of acrylamide based copolymer provided by the invention (solution polymerization process and anti-phase,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, retouch in this placeThe detailed description of the invention of stating 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 containsConstruction unit A, construction unit B and construction unit C, wherein, described construction unit A is formula (1)Shown construction unit, described construction unit B is the construction unit shown in formula (2), described structure listThe C of unit is the construction unit shown in the construction unit shown in formula (3) and/or formula (4); And with described thirdIn alkene acid amides based copolymer, the total mole number of construction unit is benchmark, and the content of described construction unit A is passableFor 5-95 % by mole, be preferably 10-70 % by mole, more preferably 50-70 % by mole; Described structure listThe content of the B of unit is 2.5-90 % by mole, is preferably 20-50 % by mole, more 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 preferably 10-20% by mole; The viscosity average molecular weigh of described acrylamide based copolymer is 2,000,000-1,500 ten thousand, is preferably 200Ten thousand-6,000,000,

Wherein, R₁For the alkyl of H or C1-C4, be preferably H or methyl; R₂、R₄And R₇Be the straight or branched alkyl of H or C1-C4 independently of one another, be preferably H; R₃For connecting key orThe straight or branched alkylidene of person C1-C6, is preferably connecting key or methylene; R₅And R₆Only separatelyBe on the spot the straight or branched alkyl of H or C1-C20, and R₅And R₆When different, be H, preferably feelingsUnder condition, R₅And R₆Be the straight or branched alkyl of H or C1-C5 independently of one another, and R₅And R₆When different, be H, under further preferable case, R₅And R₆Be independently of one another H, methyl, ethyl,Isopropyl or the tert-butyl group, and R₅And R₆When different, be H; R₈For the straight or branched alkane of C1-C20Base, is preferably the straight or branched alkyl of C1-C5, more preferably methyl, ethyl, isopropyl orPerson's tert-butyl group; X^-For Cl^-，Br^-，I^-，SCN^-，Be preferably Br^-。

The present inventor finds under study for action, by specific construction unit A, construction unit B and knotThe acrylamide ter-polymers of structure unit C composition can be obtained fabulous resistance reducing effect. Preferably,R₁For H or methyl, R₂、R₄And R₇Be H independently of one another, R₃For connecting key or methylene; R₅And R₆Be the straight or branched alkyl of H or C1-C5 independently of one another, and R₅And R₆When different, beH；R₈For the straight or branched alkyl of C1-C5; X^-For Br^-, that is, described construction unit A is formula (1)Shown construction unit, wherein, R₁For H or methyl; Described construction unit B is shown in formula (9)Construction unit and/or formula (10) shown in construction unit, described construction unit C is formula (11), formula(12) at least one, in the construction unit shown in formula (13) and formula (14),

In the present invention, the example of the alkyl of described C1-C4 can include but not limited to: methyl, ethyl,N-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.

In the present invention, described alkyl can be straight chain, can be also side chain. Described C1-C20'sThe example of straight or branched alkyl can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl,Normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, justHexyl, n-heptyl, n-octyl, positive decyl, dodecyl, cetyl and eicosyl.

Described alkylidene refers to that alkane loses two residues after hydrogen atom, and described two hydrogen atoms can beTwo hydrogen atoms on same carbon atom, two hydrogen atoms on also can different carbon atoms, Ke YishiStraight chain can be also side chain, and for example, described ethylidene can be-CH₂CH₂-or-CH (CH₃)-。

In the present invention, the example of the alkylidene of described C1-C4 can include but not limited to: methylene, AsiaEthyl, sub-n-pro-pyl, isopropylidene, sub-normal-butyl, sub-sec-butyl, isobutylidene and the sub-tert-butyl group.

(2) solution polymerization process

In addition, the present invention also provides a kind of preparation method of acrylamide based copolymer, this preparation method's bagDraw together under the solution polymerization condition of alkene, under initator exists, make a kind of monomer mixture at waterIn carry out polymerisation, wherein, described monomer mixture contains monomer D, monomer E and monomer F, instituteStating monomer D is the monomer shown in formula (5), and described monomer E is the monomer shown in formula (6), described inMonomer F is the monomer shown in the monomer shown in formula (7) and/or formula (8), and mixes with described monomerIn thing, the total mole number of monomer is benchmark, and the content of described monomer D is 5-95 % by mole, is preferably 10-70% by mole, more preferably 50-70 % by mole; The content of described monomer E is 2.5-90 % by mole, preferablyFor 20-50 % by mole, more preferably 20-30 % by mole; The content of described monomer F is 0.5-90 mole%, is preferably 10-40 % by mole, more preferably 10-20 % by mole; The condition of described solution polymerizationMaking the viscosity average molecular weigh of resulting polymers after polymerisation is 2,000,000-1,500 ten thousand, is preferably 2,000,000-600 ten thousand;

Wherein, R₁For the alkyl of H or C1-C4, be preferably H or methyl; R₂、R₄And R₇Be the straight or branched alkyl of H or C1-C4 independently of one another, be preferably H; R₃For connecting key orThe straight or branched alkylidene of person C1-C6, is preferably connecting key or methylene; R₅And R₆Only separatelyBe on the spot the straight or branched alkyl of H or C1-C20, and R₅And R₆When different, be H, preferably feelingsUnder condition, R₅And R₆Be the straight or branched alkyl of H or C1-C5 independently of one another, and R₅And R₆When different, be H, under further preferable case, R₅And R₆Be independently of one another H, methyl, ethyl,Isopropyl or the tert-butyl group, and R₅And R₆When different, be H; R₈For the straight or branched alkane of C1-C20Base, is preferably the straight or branched alkyl of C1-C5, more preferably methyl, ethyl, isopropyl orPerson's tert-butyl group; 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 monomerThe ratio of the gross weight of mixture is various ratio known in those skilled in the art, usually, described inThe ratio of the gross weight of the weight of monomer mixture and water and monomer mixture can be 0.05-0.5:1, excellentElect 0.15-0.4:1 as.

According to the present invention, described initator can be the various initators in this area. For example, be selected from azo systemInitator and redox 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, and the consumption of described redox series initiators is0-10 % by mole, and total consumption of described azo initiator and redox initiator preferably meets: described inTotal consumption of initator is the 0.0001-10 % by mole of the total mole number of monomer in monomer mixture.

In the present invention, preferably, described azo series initiators for being selected from azodiisobutyronitrile, azo two is differentHeptonitrile, the two methylpent hydrochlorates, 2 of azo, 2 '-azo diisobutyl amidine hydrochloride and 2,2 '-azo two [2-(2-Imidazoline-2-propane)-dihydrochloride] at least one, more preferably 2,2 '-azo diisobutylAmidine 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 instituteThe mol ratio of stating reducing agent is 0.5-3.5:1, meets under the condition of aforementioned proportion the use of described oxidantAmount can be the 0.0001-0.01 % by mole of the total mole number of monomer in monomer mixture, is preferably monomer mixedThe 0.001-0.008 % by mole of the total mole number of monomer in compound; Under preferable case, described oxidant is selected fromAt least one in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide, more preferably mistakeAmmonium sulfate and/or potassium peroxydisulfate; The consumption of described reducing agent can be total mole of monomer in monomer mixtureThe 0.0001-0.005 % by mole of number, 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) and/or organic going backFormer dose (chain extender), preferably, described inorganic reducing agent for be selected from sodium hydrogensulfite, sodium sulfite,At least one in rongalite, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite, ascorbic acid and urea, entersOne step is preferably sodium hydrogensulfite and/or sodium thiosulfate; Described organic reducing agent is for being selected from N, N '-diformazanBase ethylenediamine, N, N '-dimethyl-1,3-propane diamine, N, N, N ', N '-tetramethylethylenediamine, N, N-dimethylEthamine, 3-methylamino propylamine, Dimethylaminoethyl Methacrylate, N-(3-dimethylamino-propyl) methylAt least one in acrylamide, 1-(dimethylamino)-2-propylamine and diethylenetriamines, further excellentElect N as, N '-dimethyl-ethylenediamine, N, N '-dimethyl-1,3-propane diamine and N, N, N ', N '-tetramethyl second twoAt least one in amine.

According to the present invention, described polymerisation can also be carried out under various auxiliary agents exist, and described auxiliary agent canTo be selected from least one in chelating agent and other auxiliary agents; With total mole of monomer in described monomer mixtureNumber is benchmark, and the consumption of described chelating agent is 0-2 % by mole, is preferably 0.0001-1 % by mole, enters oneStep is preferably 0.0001-0.05 % by mole, and the consumption of described other auxiliary agents can be 0-2 % by mole, preferablyFor 0.0001-1 % by mole, more preferably 0.0001-0.2 % by mole; Preferably, described chelating agentMake with the consumption of other auxiliary agents: 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 be for being selected from disodium ethylene diamine tetraacetate (EDTA), three secondAt least one in two triamine pentaacetic acids, citric acid, citrate and poly-hydroxy acrylic acid, further preferredFor at least one in EDTA, citrate and triethylenediamine pentaacetic acid, described citrate can bePotassium 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, dodecaneAt least one in base trimethylammonium bromide and sodium hypophosphite, is preferably urea and/or sodium formate.

The present inventor finds, exists at the same time under the condition of above-mentioned various initator and auxiliary agent, moltenLiquid polymerization can obtain the controlled acrylamide based copolymer of viscosity average molecular weigh.

According to the present invention, the condition of described polymerisation can be the condition of this area routine. For example, instituteState solution polymerization and carry out under inert gas exists, polymeric reaction condition can comprise: temperature is0-80 DEG C, the time is 1-24 hour, pH value is 5-13; Under preferable case, temperature is 4-60 DEG C, timeBetween be 4-24 hour, pH value is 5-9. Described pH value can be by adding acid or alkali to regulate, instituteState acid and be preferably inorganic acid, described inorganic acid is preferably in hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and phosphoric acidAt least one; Described alkali can be inorganic base or organic amine compound, for example can be selected from NaOH,At least one in potassium hydroxide, ammoniacal liquor, methylamine, ethamine, monoethanolamine and triethanolamine, is preferably hydrogenSodium oxide molybdena.

The present inventor finds under study for action, takes following condition can further improve polymerMolecular weight:, 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 that 1-15 is littleTime, be preferably 3-10 hour; The reaction condition of second stage comprises: temperature is 15-30 DEG C, is preferably20-30 DEG C, the time is 3-8 hour, is preferably 3-5 hour; The reaction condition of phase III comprises: temperatureDegree, for 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 select specific monomer D, monomer E withWhen monomer F reacts, can further improve the resistance reducing effect of the polymer of gained. Preferably, R₁For H or methyl, R₂、R₄And R₇Be H independently of one another, R₃For connecting key or methylene; R₅WithR₆Be the straight or branched alkyl of H or C1-C5 independently of one another, and R₅And R₆When different, be H;R₈For the straight or branched alkyl of C1-C5; X^-For Br^-, that is, described monomer D is shown in formula (5)Monomer, wherein, R₁For H or methyl; Described monomer E be the monomer shown in formula (15) and/orMonomer shown in formula (16), described monomer F is formula (17), formula (18), formula (19) and formula (20)At least one in shown monomer,

(3) reversed emulsion polymerization

In addition, the present invention also provides a kind of preparation method of acrylamide based copolymer, this preparation method's bagDraw together water and oil phase are mixed to form to reversed-phase emulsion, then under emulsion polymerization condition, at initatorExistence under, this reversed-phase emulsion is carried out to polymerisation, described water is contain monomer mixture water-solubleLiquid, described oil phase contains organic solvent and emulsifying agent, wherein, described monomer mixture contain monomer D,Monomer E and monomer F, described monomer D is the monomer shown in above-mentioned formula (5), described monomer E is upperState the monomer shown in formula (6), described monomer F is shown in the monomer shown in formula (7) and/or formula (8)Monomer. The selection of monomer shown in formula (5)-Shi (8) with describe identically above, do not repeat them here.

According to the present invention, described water is the aqueous solution that contains monomer mixture. Described monomer mixtureWeight and the selection of the ratio of the gross weight of water and monomer mixture with describe identically above, do not do superfluous hereinState.

According to the present invention, the part by weight of described water and oil phase is had no particular limits, as long as make instituteState water and oil phase is thoroughly mixed to form reversed-phase emulsion, under preferable case, described water and oil phasePart by weight 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 water mutually notCompatible nonpolar or organic solvent that polarity is little can be for example toluene, dimethylbenzene, hexane, hexamethyleneAt least one in alkane, normal heptane, isomery paraffin, isoparaffin, gasoline, kerosene and white oil, preferablyIn situation, described organic solvent for be selected from toluene, dimethylbenzene, normal heptane, isoparaffin, cyclohexane andAt least one in kerosene.

According to the present invention, described oil phase contains organic solvent and emulsifying agent. To the consumption of described organic solventThere is no special requirement, can in wider scope, change, as long as described organic solvent and emulsifying agent are mixedClose and form oil phase, under preferable case, taking the gross weight of described emulsion as benchmark, described organic solventConsumption can be 10-60 % by weight, more preferably 20-35 % by weight.

According to the present invention, described emulsifying agent can be the various nonionic breasts for emulsion polymerisation in this areaAgent can be for example sorbitan fatty acid ester, APES, isomery alcohol polyoxy secondAlkene ether, ethoxylated dodecyl alcohol, methyl glycol fatty acid ester, laureth, benzylphenol oxygen polyoxy secondAlkene ether, phenethyl phenol polyethenoxy ether, polyoxyethylene sorbitan fatty acid ester, anhydrous sorbitol fatFat acid esters ethylene oxide adduct, benzyl dimethyl phenol polyethenoxy ether, AEO and fatAt least one in fat amine APEO. Under preferable case, described emulsifying agent is selected from anhydrous sorbitol fatFat acid esters, polyoxyethylene sorbitan fatty acid ester, NPE, octyl phenol polyoxy secondAlkene ether, benzylphenol oxygen APEO, phenethyl phenol polyethenoxy ether, isomerous tridecanol polyoxyethylene ether,At least one in ethoxylated dodecyl alcohol and benzyl dimethyl phenol polyethenoxy ether, more preferablyThe composite emulsifying that the hydrophilic lipophilic balance being made up of above-mentioned two or more emulsifying agent is 5-9Agent can be for example sorbitan fatty acid ester and NPE.

According to the present invention, the consumption of described emulsifying agent is not particularly limited, can be in wider scopeInterior variation, as long as described emulsifying agent and described organic solvent are mixed to form oil phase, under preferable case,Taking the gross weight of described emulsion as benchmark, the consumption of described emulsifying agent can be 1-15 % by weight, furtherBe preferably 2-10 % by weight.

According to the present invention, described initator can be various initators in this area, the choosing of described initatorSelect and describe identically above, repeating no more herein.

In the present invention, under preferable case, can first azo series initiators be added to water, then mix with oil phaseForm reversed-phase emulsion, then reversed-phase emulsion is contacted with redox series initiators, draw by redoxSend out agent initiated polymerization.

According to the present invention, described polymerisation can also be carried out under various auxiliary agents exist, and described auxiliary agent canTo be selected from least one in chelating agent and other auxiliary agents, the selection of described auxiliary agent with describe above identical,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 chelatingAgent and metal ion generation chelation so that copolymer is played to static stabilization, can be chosen inWater adds or adds in oil phase, under preferable case, for chelating agent is played stably more fullyEffect, 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 the condition of above-mentioned various initator and auxiliary agentUnder, reversed emulsion polymerization can obtain the acrylamide that viscosity average molecular weigh is controlled and dissolution velocity is fast and be total toPolymers.

According to the present invention, the condition of described emulsion polymerization can be the condition of this area routine. DescribedThe selection of polymeric reaction condition with describe identically above, repeat no more herein.

Equally, the present inventor finds under study for action, takes following condition further to improve poly-The molecular weight of compound:, preferably, the process of described emulsion polymerization comprises two that carry out successivelyIn the stage: the reaction condition of first stage comprises: temperature is 0-20 DEG C, is preferably 5-10 DEG C, the time is1-15 hour, is preferably 1-5 hour; The reaction condition of second stage comprises: temperature is 20-60 DEG C,Be preferably 25-55 DEG C, 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 therefromContact with phase inversion agent, so that described polymerisation products therefrom dissolves fast in fracturing fluid application in water. Described phase inversion agent can be for this area be for the various phase inversion agent of emulsion polymerisation, as long as make described poly-The water-soluble increase of closing reaction products therefrom can be for example polyoxyethylene sorbitan aliphatic acidEster, NPE, OPEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenolAPEO, isomery ten alcohol APEOs, isomery undecyl alcohol APEO, isomerous tridecanol gatherAt least one in the nonionic emulsifier of oxygen vinethene and aliphatic amine polyoxyethylene ether, preferable caseUnder, described phase inversion agent for be selected from polyoxyethylene sorbitan fatty acid ester, isomery ten alcohol APEOs,Isomery undecyl alcohol APEO, isomerous tridecanol polyoxyethylene ether, NPE and octyl groupAt least one in phenol polyethenoxy ether.

According to the present invention, the consumption of described phase inversion agent is not had to special requirement, as long as can make described poly-Close reaction products therefrom and in water, dissolve fast in fracturing fluid application, the consumption of described phase inversion agent makes: taking the gross weight of described emulsion as benchmark, the consumption of described phase inversion agent can be 0.5-10 % by weight,Be preferably 1-4 % by weight.

In addition, the present inventor finds under study for action, when select specific monomer D, monomer E withWhen monomer F reacts, can further improve the resistance reducing effect of the polymer of gained. Preferably, R₁For H or methyl, R₂、R₄And R₇Be H independently of one another, R₃For connecting key or methylene; R₅WithR₆Be the straight or branched alkyl of H or C1-C5 independently of one another, and R₅And R₆When different, be H; R₈For the straight or branched alkyl of C1-C5; X^-For Br^-, that is, described monomer D is shown in formula (5)Monomer, described monomer E is the monomer shown in the monomer shown in formula (15) and/or formula (16), instituteState monomer F and be at least one in the monomer shown in formula (17), formula (18), formula (19) and formula (20)Kind, the selection of monomer shown in formula (5), formula (15)-Shi (20) with describe above identical, at this notRepeat again.

In addition, the present invention also provides the application of described acrylamide based copolymer in drag reducer. AdoptDescribed acrylamide based copolymer provided by the invention, as fracturing fluid drag reducer, can obtain high and stableDrag reducing efficiency, the technology that concrete application process is well known to those skilled in the art.

Below will describe the present invention by embodiment. Should be understood that, described hereinDetailed description of the invention only for description and interpretation the present invention, be not limited to the present invention.

Intrinsic viscosity is surveyed according to GB12005.1-89 polyacrylamide For Intrinsic Viscosity Measurements methodFixed; Viscosity average molecular weigh is according to formula M_v=（[η]/K）^1\α, wherein K=4.5 × 10^-3, α=0.80Calculate; Dissolution time measures by GB12500.8-89 that (sample quality is all by simple polymerisation material in sampleAmount meter), the powdered samples dissolution time recording is all less than 20min, and samples of latex dissolution time is all littleIn 5min; The composition of molecular structure and construction unit adopt IR spectrum and¹³C-NMR measures; Water is insolubleThing 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 (21) is purchased from Sigma-Aldrich company; Formula (23)Shown monomer M 2 is according to document (Synthesisoftriphenylmethyl-substitutedconjugatedDienesviaWittigreaction, HuaxueShiji, 2011,33 (9), 782-784) the middle method system of recording.

In addition,, unless specified otherwise, the reagent of using in embodiment, comparative example and test case etc. are equalFor 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 shown in the formula (21) of the acrylamide of 21.32g (AM), 66.40gThe N,N-DMAA of monomer and 11.90g joins in reaction bulb, adds deionized water564.48g, stirs monomer is dissolved completely, and stir. Respectively to adding 1 % by weight in flaskEDTA aqueous solution 5.5g, 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 2.1g, chain extender N ', N-Dimethyl-ethylenediamine 0.002g, adds 0.1% solution of sodium bisulfite 1.1g, and urea 0.11g, fully stirsMix it is mixed. With the sodium hydroxide solution adjusting pH to 7.5 of 1 % by weight. The hierarchy of control is initialTemperature to 4 DEG C, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight ammonium persulfate aqueous solution 0.75g,And continue letting nitrogen in and deoxidizing 20 minutes. Reactor is airtight, remain on 4 DEG C, react after 8 hours, by temperatureAfter degree rises to 20 DEG C, react 5 hours, then temperature is risen to 50 DEG C of reactions 2 hours, by the glue obtainingShape product takes out, through granulation, dry, pulverize and can receive acrylamide copolymer p 1.

P1 is carried out to various mensuration, in IR spectrum, 1660cm^-1And 1635cm^-1There is respectively ownership in placeIn the amide Ⅰ absworption peak (C=O stretching vibration) of amide groups and acid amides II band absworption peak, (N-H bending is shakenMoving), at 1430cm^-1There is the stretching vibration absworption peak of C-N in place; 1356cm^-1And 1401cm^-1Go outNow typical methyl symmetric curvature vibration absorption peak, 1506,1577,1600cm^-1Peak, place belongs to phenyl ringThe stretching vibration of upper C=C; 1437cm^-1Peak, place belongs to Ar-P stretching vibration; 691,724,747cm^-1Peak, place belongs to Ar-H out-of plane bending vibration on phenyl ring. Can determine that the copolymer molecule obtaining hasStructure shown in formula (22), recording its viscosity-average molecular weight Mv by viscosity method is 4,200,000, monomer turnsRate is more than 99.9%. Wherein, formula (22) and x, y and z only express the type of construction unitAnd 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-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 with(3-acrylamido-3-methyl) butyl trimethyl ammonium chloride of identical molal quantity carries out polymerisation, therebyObtain bipolymer DP1, recording its viscosity average molecular weigh Mv is 1,050 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 M2 monomer shown in the formula of the AM of 29.85g, 45.94g (23) and the N-isopropyl of 6.79gBase acrylamide joins in polymerization bottle, adds 192.69g deionized water, and stir monomer is dissolved completely,To the EDTA aqueous solution 4.65g that adds 1 % by weight in flask, add 1 % by weight azo two isobutyls respectivelyBase amidine hydrochloride aqueous solution 1.23g, adds chain extender N, and N '-dimethyl-ethylenediamine 0.002g, adds 0.1%Solution of sodium bisulfite 1.15g, adds urea 0.11g, fully stirs it is mixed. Use 1 weightThe sodium hydroxide solution of % regulates pH to 7.1. 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, remain on 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 gluey product obtaining taken out, through granulation, dry, pulverizeCan receive acrylamide copolymer p 2.

P2 is carried out to various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Belonging to appears respectively in place(N-H bending is shaken for the amide Ⅰ absworption peak (C=O stretching vibration) of amide groups and acid amides II band absworption peakMoving), at 1430cm^-1There is the stretching vibration absworption peak of C-N in place; 2923,2852cm^-1Peak, place respectivelyBelong to-CH₂-、-CH₃C-H stretching vibration, 1506,1577,1600cm^-1Peak, place belongs to benzeneThe stretching vibration of C=C on ring; 1437cm^-1Peak, place belongs to Ar-P stretching vibration; 691,724,747cm^-1Peak, place belongs to Ar-H out-of plane bending vibration on phenyl ring. Can determine that the copolymer molecule obtaining hasStructure shown in formula (24), recording its viscosity-average molecular weight Mv by viscosity method is 5,430,000, monomer turnsRate is more than 99.9%. Wherein, formula (24) and x, y and z only express the type of construction unitAnd 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-NMR composes mensuration, obtains x:y:z=1:0.3：0.14。

Embodiment 3

Under room temperature, by the M1 monomer shown in the formula of the Methacrylamide of 5.11g, 110.66g (21)Join in polymerization bottle with the N tert butyl acrylamide of 30.52g, add 219.44g deionized water,Stirring is dissolved monomer completely, respectively to the EDTA aqueous solution 11.63g that adds 1 % by weight in flask,Add 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 2.13g, add chain extender N ', N-dimethylEthylenediamine 0.001g, adds 0.1 % by weight solution of sodium bisulfite 1.13g, adds urea 0.20g,, tenDialkyl group trimethylammonium bromide 0.01g, fully stirs it is mixed. With the hydroxide of 1 % by weightSodium solution regulates pH to 7.3. Hierarchy of control initial temperature to 2 DEG C, led to nitrogen deoxygenation after 30 minutes,Add 1% ammonium persulfate aqueous solution 0.8g, and continue letting nitrogen in and deoxidizing 10 minutes. Reactor is airtight, protectBe held in 8 DEG C, react after 10 hours, be warming up to 25 DEG C, react after 4 hours, be warming up to 45 DEG C of reactions7 hours, the gluey product obtaining is taken out, through granulation, dry, pulverize and can receive acrylamideCopolymer p 3.

P3 is carried out to various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Belonging to appears respectively in place(N-H bending is shaken for the amide Ⅰ absworption peak (C=O stretching vibration) of amide groups and acid amides II band absworption peakMoving), at 1430cm^-1There is the stretching vibration absworption peak of C-N in place; 2923,2852cm^-1Locating out peak dividesDo not belong to-CH₂-、-CH₃C-H stretching vibration, 1506,1577,1600cm^-1Going out peak belongs toThe 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 obtaining dividesSon has the structure shown in formula (25), and recording its viscosity-average molecular weight Mv by viscosity method is 3,600,000,Monomer conversion is more than 99.9%. Wherein, formula (25) and x, y and z only express construction unitType and number, and do not represent the connected mode of construction unit. The concrete numerical value of x, y and z is by feeding intakeAmount is definite, and the composition of molecular structural 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 copolymerizationThing.

(1) by the M1 monomer shown in the formula of the Methacrylamide of 5.11g, 110.66g (21),The N,N-DMAA of 23.79g joins in configuration bottle, adds 227.7g deionized water, stirsMix monomer is dissolved completely, respectively to the EDTA aqueous solution 14.61g that adds 1 % by weight in flask, expandChain agent N ', N-dimethyl-ethylenediamine 0.001g, adds 1 % by weight azo diisobutyl amidine hydrochloride water-solubleLiquid 1.03g, adds urea 0.15g, fully stirs it is mixed, with the hydroxide of 10 % by weightSodium solution regulates pH to 7.1, obtains water.

(2) by sorbitan fatty acid ester (span60, Sigma-Aldrich company, below identical)45g, APES (IgepalCA720, Sigma-Aldrich company, below identical)23.95g, 237.49g kerosene is mixed into oil phase, and the water obtaining in step (1) is joined allIn oil phase, mix formation reversed-phase emulsion by high speed and join in reactor.

(3) 5 DEG C of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight AsiaNiter cake aqueous solution 0.25g, then add 1 % by weight ammonium persulfate aqueous solution 1.0g and continue logical nitrogen and removeOxygen 10 minutes. Reactor is airtight, remain on 5 DEG C, react after 5 hours, be warming up to 55 DEG C, anti-Answer 2 hours. After question response temperature cool to room temperature, add 13.79g NPE(Sigma-Aldrich company, below identical), obtains emulsion form product with 80 order filter-cloth filterings. Will be anti-Phase emulsion product can obtain acrylamide based copolymer after being precipitated out with acetone and methyl alcohol mixed solvent P4。

P4 is carried out to various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Belonging to appears respectively in place(N-H bending is shaken for the amide Ⅰ absworption peak (C=O stretching vibration) of amide groups and acid amides II band absworption peakMoving), at 1430cm^-1There is the stretching vibration absworption peak of C-N in place; 1356cm^-1And 1401cm^-1OccurTypical methyl symmetric curvature vibration absorption peak, 1506,1577,1600cm^-1Going out peak belongs on phenyl ringThe stretching vibration of C=C; 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 hasStructure shown in formula (26), recording its viscosity average molecular weigh Mv by viscosity method is 3,780,000, monomer turnsRate is more than 99.9%. Wherein, formula (26) and x, y and z only express the type of construction unitAnd 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-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, by methacrylAmine carries out polymerisation with (3-acrylamido-3-methyl) butyl trimethyl ammonium chloride of identical molal quantity,Thereby obtain bipolymer DP2, recording its viscosity average molecular weigh Mv is 9,250,000.

Embodiment 5

The present embodiment is used for illustrating that emulsion polymerization provided by the invention prepares acrylamide based copolymer.

(1) by the M2 monomer shown in the formula of the Methacrylamide of 35.74g, 45.94g (23) andThe NIPA of 6.79g joins in configuration bottle, adds 353.88g deionized water, stirsMonomer is dissolved completely, respectively to the EDTA aqueous solution 7.63g that adds 1 % by weight in flask, chain extensionAgent N ', N-dimethyl-ethylenediamine 0.001g, adds the 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution2.03g, adds urea 0.10g, fully stirs it is mixed, molten with the NaOH of 15 % by weightLiquid regulates pH to 7.0, obtains water.

(2) by sorbitan fatty acid ester (span60) 35g, APES (IgepalCA720) 21.52g, 169.54g kerosene is mixed into oil phase, and by full the water obtaining in step (1)Portion joins in oil phase, mixes formation reversed-phase emulsion join in reactor by high speed.

(3) 10 DEG C of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight AsiaNiter cake aqueous solution 0.13g, then add 1 % by weight ammonium persulfate aqueous solution 0.63g and continue logical nitrogen and removeOxygen 10 minutes. Reactor is airtight, remain on 10 DEG C, react after 1 hour, be warming up to 30 DEG C, anti-Answer 5 hours, after question response temperature cool to room temperature, add 20.35g NPE, use80 order filter-cloth filterings obtain emulsion form product. By acetone and methyl alcohol mixed solvent precipitation for reversed-phase emulsion productOut, can obtain acrylamide copolymer p 5.

P5 is carried out to various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Belonging to appears respectively in place(N-H bending is shaken for the amide Ⅰ absworption peak (C=O stretching vibration) of amide groups and acid amides II band absworption peakMoving), at 1430cm^-1There is the stretching vibration absworption peak of C-N in place; 1356cm^-1And 1401cm^-1Go outNow typical methyl symmetric curvature vibration absorption peak, 1506,1577,1600cm^-1Go out peak and belong to phenyl ringThe stretching vibration of upper C=C; 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 hasStructure shown in formula (27), recording its viscosity average molecular weigh Mv by viscosity method is 4,630,000, monomer turnsRate is more than 99.9%. Wherein, formula (27) and x, y and z only express the type of construction unitAnd 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-NMR composes mensuration, obtains x:y:z=1:0.29：0.14。

Embodiment 6

The present embodiment is used for illustrating that emulsion polymerization provided by the invention prepares acrylamide based copolymer.

(1) by M1 monomer and 19.08g shown in the formula of the acrylamide of 19.19g, 66.40g (21)N tert butyl acrylamide join in configuration bottle, add 593.13g deionized water, stir and make monomerDissolve completely, respectively to 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 azo diisobutyl amidine hydrochloride aqueous solution 2.1g, addsEnter urea 0.08g, DTAB 0.01g, 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) 10g, APES (IgepalCA720, Sigma-Aldrich company, below identical) 18.34g, 184.2g kerosene is mixed into oil phase,And join in oil phase obtaining water in step (1), mix formation reversed-phase emulsion by high speed and addIn reactor.

(3) 8 DEG C of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight AsiaNiter cake aqueous solution 0.18g, then add 1 % by weight ammonium persulfate aqueous solution 1.3g, and continue logical nitrogenDeoxygenation 10 minutes. Reactor is airtight, 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 9.21g NPE, use100 order filter-cloth filterings obtain emulsion form product. Reversed-phase emulsion product is heavy with acetone and methyl alcohol mixed solventAfter forming sediment out, can obtain acrylamide copolymer p 6.

P6 is carried out to various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Belonging to appears respectively in place(N-H bending is shaken for the amide Ⅰ absworption peak (C=O stretching vibration) of amide groups and acid amides II band absworption peakMoving), 2923,2852cm^-1The belong to respectively-CH of peak of place₂-、-CH₃C-H stretching vibration, 1506,1577、1600cm^-1Peak, place belongs to the stretching vibration of C=C on phenyl ring; 1437cm^-1Peak, place belongs toAr-P stretching vibration; 691,724,747cm^-1Peak, place belongs to Ar-H out-of plane bending vibration on phenyl ring.Can determine that the copolymer molecule obtaining has the structure shown in formula (28), record it by viscosity method and glueAverage molecular weight Mv is 5,600,000, and monomer conversion is more than 99.9%. Wherein, formula (28) 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,The concrete numerical value of y and z determined by inventory, and the composition of molecular structural formula and construction unit adopts quantitatively¹³CSpectrum is measured, and 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, DP1With conventional hydroxypropyl guar gum (the JXY wellfracturing hydroxypropyl that cooks drag reducer in DP2 and site operationMelon glue powder, Shandong Juxin Chemical Co., Ltd., below identical) carry out water-soluble mensuration, result is as table 1Shown in.

Table 1

As can be seen from Table 1, the acrylamide based copolymer that prepared by two kinds of methods provided by the inventionWater insoluble matter content in P1-P6 is starkly lower than the conventional hydroxypropyl guar gum that cooks drag reducer in site operation,This illustrates compared with hydroxypropyl guar gum, uses P1-P6 as shale gas pressure break drag reducer, to stratumInjure lower.

Test case 2

Under 2500rpm shear rate, respectively by P1-P6, DP1, DP2 and partial hydrolysis polypropyleneAmine (HPAM, Zibo Tian Jian Chemical Co., Ltd., trade mark TJY-1, viscosity average molecular weigh is 1000-1300Ten thousand) water/alcoholic solution that slowly joins respectively volume ratio 80/20 and 60/40 (uses first in this test caseAlcohol) in, the consumption of P1-P6, DP1, DP2 and partially hydrolyzed polyacrylamide (PHPA) is water/alcoholic solution 0.01% by weight (sample quality is by straight polymer quality in sample), dissolution time is 30min, result is as tableShown in 2.

Table 2

As can be seen from Table 2, use P1-P6 prepared by two kinds of methods provided by the invention as shaleAir pressure splits with drag reducer, compared with partially hydrolyzed polyacrylamide (PHPA), with cleanup additive (taking methyl alcohol as example)Compatibility is good.

Test case 3

Be at 25 DEG C in temperature, P1-P6, DP1, DP2, HPAM and hydroxypropyl guar gum is molten respectivelyBe the NaCl of 2 % by weight, 4 % by weight, 8 % by weight, 10 % by weight, 12 % by weight in pure water and concentrationOr in KCl solution, (sample quality is by sample for the 500mg/L being mixed with and the solution of 1000mg/LStraight polymer quality meter in product), then according to the method specifying in SY/T6376-2008 at GLM-1On pipeline frictional resistance determinator, measure the drag reducing efficiency (test condition: the internal diameter of test section pipeline of above-mentioned solutionFor 8mm, the length of test section pipeline is 9m, and infusion discharge capacity is 30L/min), result is as table 3 and tableShown in 4.

At the temperature of 60 DEG C, P1-P6, DP1, D2 and HPAM are dissolved in respectively to pure water and concentrationBe in the NaCl solution of 2 % by weight, 4 % by weight, 8 % by weight, 10 % by weight, 12 % by weight, willThe 500mg/L that it is mixed with and the solution of 1000mg/L, according to the side specifying in SY/T6376-2008Method (condition determination is identical with at above-mentioned 25 DEG C), 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 compare with DP2, acrylamide copolymer P1-P6 prepared by method provided by the inventionAs shale air pressure drag reducer, with clay stabilizer (as, KCl and NaCl) compatibility is better, anti-Salt performance is more excellent; In addition, the drag reducing efficiency of acrylamide based copolymer provided by the invention at 25 DEG C is equalCan reach more than 60%, the drag reducing efficiency at 60 DEG C also can reach more than 50%, illustrates at high temperature and high saltUnder shear conditions, acrylamide based copolymer provided by the invention still has higher drag reducing efficiency.

Test case 4

Friction reducer is pressed oil and gas industry standard SY/T5107-2005 " water base pressure to the nocuity of rock coreSplit liquid method of evaluating performance " in fracturing fluid filtrate to rock core matrix permeability infringement experiment carry out, in the U.S.On rock core company formation injury tester device (FDS-800), test, the matrix permeability of rock core is2md。

P1-P6, DP1 and DP2 are dissolved in respectively to pure water, are mixed with the solution (sample of 1000mg/LProduct quality is by straight polymer quality in sample), at American core company formation damage test macro(FDS-800) upper its nocuity to rock core of testing, result is as shown in table 6.

Table 6

As can be seen from Table 6, the acrylamide based copolymer that prepared by two kinds of methods provided by the inventionP1-P6 is starkly lower than the conventional comparative sample of cooking drag reducer in site operation, this explanation to the injury of rock coreUse P1-P6 low to the injury on stratum with drag reducer as shale gas pressure break.

Above-mentioned test result explanation, the insolubles content of acrylamide based copolymer of the present invention in water onlyIt is 0.01 % by weight; Under the shear rate of 2500rpm, can be dissolved in completely in water/alcoholic solution, withThe compatibility of alcohol is good; Owing to improving with the compatibility of alcohol and clay stabilizer (NaCl or KCl), improveAnti-filtration property; And under the condition of high salt and high temperature, still there is high drag reducing efficiency, and there is phaseTo low viscosity average molecular weigh, low to formation damage, and there is relatively low viscosity average molecular weigh, to stratumInjury low. In addition, the preparation method of acrylamide based copolymer provided by the invention has easy and singleThe advantage that transformation rate is high.

More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited to above-mentioned realityExecute the detail in mode, within the scope of technical conceive of the present invention, can be to technical side of the present inventionCase is carried out multiple simple variant, and these simple variant all belong to protection scope of the present invention.

It should be noted that in addition each the concrete technology spy described in above-mentioned detailed description of the inventionLevy, in reconcilable situation, can combine by any suitable mode, for fear of needn'tThe repetition of wanting, the present invention is to the explanation no longer separately of various possible combinations.

In addition, between various embodiment of the present invention, also can be combined, as long as itsWithout prejudice to thought of the present invention, 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 and construction unit C, wherein, described construction unit A is formula (1)Shown construction unit, described construction unit B is the construction unit shown in formula (2), described structure listThe C of unit is the construction unit shown in the construction unit shown in formula (3) and/or formula (4); And with described thirdIn alkene acid amides based copolymer, the total mole number of construction unit is benchmark, and the content of described construction unit A is5-95 % by mole, the content of described construction unit B is 2.5-90 % by mole, described construction unit C containsAmount is 0.5-90 % by mole; The viscosity average molecular weigh of described acrylamide based copolymer is 2,000,000-1,500 ten thousand;

Wherein, R₁、R₂、R₄And R₇Be the straight or branched alkyl of H or C1-C4 independently of one another;R₃For the straight or branched alkylidene of connecting key or C1-C6; R₅And R₆Be independently of one another H orThe straight or branched alkyl of C1-C20, and R₅And R₆When different, be H; R₈For the straight chain of C1-C20 orBranched alkyl; 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 20-50 % by mole, the content of described construction unit C is 10-40% by mole, the viscosity average molecular weigh of described acrylamide based copolymer is 2,000,000-6,000,000.

3. acrylamide based copolymer according to claim 1, wherein, R₁For H or methyl,R₂、R₄And R₇Be H independently of one another, R₃For connecting key or methylene; R₅And R₆Independently of one anotherFor the straight or branched alkyl of H or C1-C5, and R₅And R₆When different, be H; R₈For C1-C5Straight or branched alkyl; X^-For Br^-。

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 D, monomer E and monomer F, and described monomer D is formula (5)Shown monomer, described monomer E is the monomer shown in formula (6), described monomer F is shown in formula (7)Monomer and/or formula (8) shown in monomer, taking the total mole number of monomer in described monomer mixture as baseStandard, the content of described monomer D is 5-95 % by mole, the content of described monomer E is 2.5-90 % by mole,The content of described monomer F is 0.5-90 % by mole; The condition of described solution polymerization makes polymerisationThe viscosity average molecular weigh of rear resulting polymers is 2,000,000-1,500 ten thousand,

Wherein, R₁、R₂、R₄And R₇Be the straight or branched alkyl of H or C1-C4 independently of one another;R₃For the straight or branched alkylidene of connecting key or C1-C6; R₅And R₆Be independently of one another H orThe straight or branched alkyl of C1-C20, and R₅And R₆When different, be H; R₈For the straight chain of C1-C20 orBranched alkyl; 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 D, monomer E and monomer F,Described monomer D is the monomer shown in formula (5), and described monomer E is the monomer shown in formula (6), instituteStating monomer F is the monomer shown in the monomer shown in formula (7) and/or formula (8), mixes with described monomerIn thing, the total mole number of monomer is benchmark, and the content of described monomer D is 5-95 % by mole, described monomer EContent be 2.5-90 % by mole, the content of described monomer F is 0.5-90 % by mole; Described emulsion polymerisationIt is 2,000,000-1,500 ten thousand that the condition of reaction makes the viscosity average molecular weigh of resulting polymers after polymerisation,

Wherein, R₁、R₂、R₄And R₇Be the straight or branched alkyl of H or C1-C4 independently of one another;R₃For the straight or branched alkylidene of connecting key or C1-C6; R₅And R₆Be independently of one another H orThe straight or branched alkyl of C1-C20, and R₅And R₆When different, be H; R₈For the straight chain of C1-C20 orBranched alkyl; 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 D is 10-70 % by mole, described monomer E'sContent is 20-50 % by mole, and the content of described monomer F is 10-40 % by mole; Described polymerisationIt is 2,000,000-6,000,000 that condition makes the viscosity average molecular weigh of resulting polymers after polymerisation.

14. according to the preparation method described in claim 4 or 5, wherein, and R₁For H or methyl,R₂、R₄And R₇Be H independently of one another, R₃For connecting key or methylene; R₅And R₆Be independently of one anotherThe straight or branched alkyl of H or C1-C5, and R₅And R₆When different, be H; R₈Straight for C1-C5Chain or branched alkyl; X^-For Br^-。

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 for being selected from azodiisobutyronitrile, ABVN, 2,2 '-azo diisobutyl amidine hydrochloride with2, at least one in 2 '-azo two [2-(2-imidazoline-2-yl) propane] dihydrochloride, 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 oxidant is to be selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide at leastA kind of; Described reducing agent is inorganic reducing agent and/or organic reducing agent, and described inorganic reducing agent is for being selected from AsiaAt least one in niter cake, sodium sulfite, sodium thiosulfate, ferrous sulfate and sodium hydrosulfite, described inOrganic reducing agent is for being selected from rongalite, ascorbic acid, urea, N, N '-dimethyl-ethylenediamine, N, N '-diformazanBase-1,3-propane diamine, N, N, N ', N '-tetramethylethylenediamine, N, N-dimethyl amine, 3-methylamino propylamine,Dimethylaminoethyl methacrylate, N-(3-dimethylamino-propyl) Methacrylamide, 1-(dimethylaminoBase) at least one in-2-propylamine and diethylenetriamines.

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, lemonAt least one in lemon acid, citrate and poly-hydroxy acrylic acid, described other auxiliary agents for be selected from urea,At least one in sodium formate, isopropyl alcohol, DTAB and sodium hypophosphite.

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 0-80 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 0-80 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 35-60 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 20-60 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.