CN104250348B

CN104250348B - A kind of acrylamide based copolymer and its preparation method and application

Info

Publication number: CN104250348B
Application number: CN201310269900.1A
Authority: CN
Inventors: 杜凯; 祝纶宇
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2013-06-28
Filing date: 2013-06-28
Publication date: 2016-08-17
Anticipated expiration: 2033-06-28
Also published as: CN104250348A

Abstract

The invention discloses a kind of acrylamide based copolymer and its preparation method and application.Described acrylamide based copolymer contains construction unit A, construction unit B, construction unit C and construction unit D, wherein, described construction unit A is the construction unit shown in formula (1), described construction unit B is the construction unit shown in formula (2), described construction unit C is the construction unit shown in formula (3) and/or the construction unit shown in formula (4), and described construction unit D is the construction unit shown in formula (5)；The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000 1,500 ten thousand.The acrylamide based copolymer drag reducing efficiency that the present invention provides is high, salt tolerance high shear performance high, anti-is good, good water solubility and clay stabilizer have good compatibility and low to formation damage.

Description

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

Technical field

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

Background technology

Exploitation as Typical Representative shale gas (oily) resource of unconventional petroleum resources utilization has become as the whole world One revolution in unconventional petroleum resources field, the development and utilization of current shale gas has become countries in the world and has paid close attention to emphatically and send out The focus technology of exhibition.Owing to the ultimate attainment close oil-gas reservoirs such as shale gas reservoir have permeability extremely low (generally less than 0.5mD), frac pressure High, easily cause the feature of formation damage." drag reduction water (slippery water) pressure break " technique must be used to exploit.

" drag reduction water (slippery water) pressure break " is the one of fracturing.(modifyed guar gum cross-links with the most conventional pressure break system System) to compare, drag reduction water (slippery water) pressure break does not relies on high viscosity colloid and takes sand, but takes sand with high infusion discharge capacity, real Now reservoir fracturing is reticulated the final purpose in crack.Compared with conventional pressure break system, drag reduction water (slippery water) pressure break is at cost On have greater advantage while less to the injury on stratum.

Drag reduction water fracturing fluid core auxiliary agent is water-based drag reducer, and in practice of construction, the addition of water-based drag reducer overcomes work Make liquid frictional resistance in pipeline, it is ensured that the raising of infusion discharge capacity, make pressure act on to greatest extent press off stratum and Extend formation fracture, currently available make water-based drag reducer mainly have guanidine glue and derivative, cellulose derivative, acrylamide Base polymer.

At present, guanidine glue, drag reducer during cellulose and its derivates splits as drag reduction hydraulic pressure is used to improve to a certain extent Infusion discharge capacity, the frictional resistance (US5697444, US5271466) reduced in pipeline, but still drag reduction hydraulic pressure cannot be met split Requirement, have the disadvantage in that (1) resistance-reducing performance is limited mainly due to above-mentioned boiomacromolecule；(2) due to guanidine glue, cellulose And derivative has a small amount of insoluble matter and easily damages stratum；(3) dissolution time is longer.

In drag reduction water pressing crack construction, use acrylamide copolymer (partial hydrolysis acrylamide or anionic more Acrylamide copolymer) split as drag reduction hydraulic pressure in friction reducer, greatly enhance infusion discharge capacity, reduce in pipeline Frictional resistance, but the drag reducer split as shale gas reservoir drag reduction hydraulic pressure uses, and there is following major defect: (1) is in order to reduce " water-sensitive effect " in fracturing process, the hydration swelling of clay composition in suppression shale, it is necessary to add little molecule in fracturing fluid Cationic clay stabilizer (such as potassium chloride, tetramethyl ammonium chloride etc.).Partial hydrolysis acrylamide or anionic acrylamide Copolymer and product emulsion thereof are poor with the compatibility of above-mentioned clay stabilizer, easily produce precipitation；(2) partial hydrolysis acryloyl Amine or anionic acrylamide copolymer use anti-filtration property poor as the drag reducer that shale gas reservoir drag reduction hydraulic pressure splits, this Kind of drag reduction water fracturing fluid easily leak-off is in the middle of stratum；(3) heat and salt resistance is poor, especially contains at high salinity high divalent ion Under the conditions of amount, molecular structure is unstable, and resistance reducing effect declines very fast.

Patent US20090298721A1 discloses the formula of a kind of drag reduction water fracturing fluid: in 1000 gallons of deionized water Add 0.5 gallon of acrylic acidcoacrylamide thing (FR-56^TM) etc. anionic acrylamide copolymer emulsion as subtracting Resist, adds the complexing agents such as 0.15wt% sodium carbonate or EDTA-2Na, and this drag reduction water fracturing fluid has excellent resistance-reducing performance, Indoor average resistance-reducing yield reaches 65.0%, and salt tolerance (the especially tolerance to divalent calcium ions) has been had a certain degree of improvement, But this kind of drag reduction hydraulic pressure splits system and uses as shale gas drag reduction water fracturing fluid, and there are the following problems: (1) is stable with organic clay The compatibility of agent (such as tetramethyl ammonium chloride etc.) and alcohol is poor, easily produces precipitation；(2) anti-filtration property is poor, this kind of drag reduction Water fracturing fluid easily leak-off is in the middle of stratum；(3) in practice of construction, " water-sensitive effect " is notable；(4) easily " water blocking " is produced； (5) resistance to high speed shear poor performance, unstable under high speed shear effect, resistance-reducing yield declines quickly；(6) heat-resistant salt-resistant is poor, Especially under the conditions of high salinity high divalent ion content, molecular structure is unstable, and resistance reducing effect declines very fast；(7) it is difficult to fall Solve, easily cause permanent type to injure the finest and close shale formation, pollute stratum, then affect oil and gas production.

Compared with above-mentioned partial hydrolysis acrylamide or anionic acrylamide copolymer, cationic high-molecular amount Acrylamide copolymer also has been reported that as drag reducer (US356226, US3868328), and this kind of structure copolymer is with steady with clay Determining agent (such as KCl) compatibility preferable, preferable with the compatibility of alcohol, " water-sensitive effect " be not notable, is difficult to " water blocking ", but this type of fall resistance The big molecule of agent is not easy to degraded, easily fine and close shale is caused possible permanent damage.

Therefore, improve the resistance to high speed shear performance of drag reducer the most further, improve fracturing fluid to the inhibition of clay and Anti-leak-off, the stability improving the drag reducing efficiency under high salt shear conditions has degradability simultaneously, reduces polymer pair The injury on stratum is still a yet unresolved issue.

Summary of the invention

It is an object of the invention to overcome the defect of prior art, it is provided that a kind of drag reducing efficiency is high, salt tolerance high shear high, anti- Good, the good water solubility of energy and clay stabilizer have good compatibility, have degradability and acrylamide little to formation damage Copolymer and its preparation method and application.

The present invention provides a kind of acrylamide based copolymer, and wherein, described acrylamide based copolymer contains construction unit A, construction unit B, construction unit C and construction unit D, wherein, described construction unit A is the construction unit shown in formula (1), described Construction unit B is the construction unit shown in formula (2), and described construction unit C is the construction unit shown in formula (3) and/or formula (4) institute The construction unit shown, described construction unit D is the construction unit shown in formula (5)；And so that described acrylamide based copolymer to be tied On the basis of the total mole number of structure unit, the content of described construction unit A is 5-95 mole of %, and the content of described construction unit B is 2.5-90 mole of %, the content of described construction unit C is 0.5-90 mole of %, and the content of described construction unit D is that 0.0001-1 rubs You are %；The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000-1,500 ten thousand；

Wherein, R₁、R₂、R₅、R₈、R₁₀And R₁₀' it is each independently the alkyl of H or C1-C4；R₃Alkylidene for C1-C4 Or connecting key；R₄Straight or branched alkylidene for C1-C20；R₆And R₇Be each independently H or C1-C20 straight chain or Branched alkyl, and R₆And R₇It is asynchronously H；R₉Straight chain branched alkyl for C1-C20；R₁₁、R₁₂、R₁₁' and R₁₂' independently of one another Straight or branched alkyl for C1-C4；X^-For Cl^-, Br^-, I^-, SCN^-Or

The present invention also provides for the preparation method of a kind of acrylamide based copolymer, and this preparation method is included in the solution of alkene Under polymeric reaction condition, in the presence of initiator, a kind of monomer mixture is made to carry out polymerisation, wherein, described list in water Body mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the monomer shown in formula (6), and described monomer F is formula (7) monomer shown in, described monomer G is the monomer shown in formula (8) and/or the structures alone shown in formula (9), and described monomer H is Monomer shown in formula (10), in described monomer mixture on the basis of the total mole number of monomer, the content of described monomer E is 5-95 Mole %, the content of described monomer F is 2.5-90 mole of %, and the content of described monomer G is 0.5-90 mole of %, and described monomer H contains Amount is 0.0001-1 mole of %；The condition of described solution polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisation It is 5,000,000-1,500 ten thousand,

Additionally, the present invention also provides for the preparation method of a kind of acrylamide based copolymer, this preparation method includes aqueous phase It is mixed to form reversed-phase emulsion, then under the conditions of emulsion polymerization, in the presence of initiator, by this reversed-phase emulsion with oil phase Carrying out polymerisation, described aqueous phase is the aqueous solution containing monomer mixture, and described oil phase contains organic solvent and emulsifying agent, its In, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the monomer shown in above-mentioned formula (6), Described monomer F is the monomer shown in above-mentioned formula (7), and described monomer G is the monomer shown in above-mentioned formula (8) and/or above-mentioned formula (9) institute The structures alone shown, described monomer H is the monomer shown in above-mentioned formula (10), with the total mole number of monomer in described monomer mixture On the basis of, the content of described monomer E is 5-95 mole of %, and the content of described monomer F is 2.5-90 mole of %, and described monomer G contains Amount is 0.5-90 mole of %, and the content of described monomer H is 0.0001-1 mole of %；The condition of described emulsion polymerization makes polymerization After reaction, the viscosity average molecular weigh of resulting polymers is 5,000,000-1,500 ten thousand.

Additionally, present invention also offers the application as drag reducer of the described acrylamide based copolymer.

In the described acrylamide based copolymer that the present invention provides, by the construction unit containing azo group is passed through The method of copolymerization, is incorporated on the macromolecular chain containing acrylamide construction unit and cationic monomer construction unit, by control Polymerizing condition processed obtains the copolymer of suitable molecular weight so that this acrylamide based copolymer has self-degradation, relatively low Under formation temperature, (generally higher than 60 DEG C) can realize from degrading, it is possible to decrease the injury to stratum, and this acrylamide is altogether simultaneously Polymers has higher drag reducing efficiency under high salt shear conditions, and has higher with clay stabilizer (such as KCl and NaCl) Compatibility.Thus obtain the present invention.

And, the acrylamide based copolymer of present invention water insoluble matter content when as drag reducer is the most less；With help Row's agent (such as methyl alcohol) has preferable compatibility.

Specifically, the viscosity average molecular weigh of the acrylamide based copolymer prepared in embodiment 1-6 can reach 500-1500 ten thousand； Insolubles content in water is only 0.01 weight %；Under the shear rate of 2500rpm, this polymer does not produces at water/alcoholic solution Raw precipitation, can be completely dissolved；The acrylamide based copolymer prepared in embodiment 1-6 is dissolved in concentration is 2 weight %, 4 weights Measure in NaCl or the KCl solution of %, 8 weight %, 10 weight %, 12 weight %, be configured to the molten of 500mg/L and 1000mg/L Liquid, drag reducing efficiency all can reach more than 60%；Under conditions of lower ground layer temperature (more than 60 DEG C), this polymer can be carried out certainly Degraded, the injury to stratum is less than 10%.

Additionally, preparation method (solution polymerization process and the emulsion polymerization) tool of the acrylamide based copolymer of present invention offer There are simplicity and the high advantage of monomer conversion.

Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.

Detailed description of the invention

Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.

(1) acrylamide based copolymer

The present invention provides a kind of acrylamide based copolymer, and wherein, described acrylamide based copolymer contains construction unit A, construction unit B, construction unit C and construction unit D, wherein, described construction unit A is the construction unit shown in formula (1), described Construction unit B is the construction unit shown in formula (2), and described construction unit C is the construction unit shown in formula (3) and/or formula (4) institute The construction unit shown, described construction unit D is the construction unit shown in formula (5)；And so that described acrylamide based copolymer to be tied On the basis of the total mole number of structure unit, the content of described construction unit A can be 5-95 mole of %, preferably 10-70 mole %, more It is preferably 50-70 mole of %；The content of described construction unit B is 2.5-90 mole of %, preferably 5-60 mole %, more preferably 20- 40 moles of %；The content of described construction unit C is 0.5-90 mole of %, preferably 5-30 mole %, more preferably 5-20 mole %, institute The content stating construction unit D is 0.0001-1 mole of %, preferably 0.001-0.5 mole %, more preferably 0.005-0.2 mole %； The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000-1,500 ten thousand, preferably 5,000,000-1,000 ten thousand,

Wherein, R₁、R₂、R₅、R₈、R₁₀And R₁₀' it is each independently the alkyl of H or C1-C4, under preferable case, R₁For H Or methyl, R₂、R₅And R₈It is each independently H, R₁₀And R₁₀' it is methyl；R₃For alkylidene or the connecting key of C1-C4, preferably For connecting key or methylene；R₄For the straight or branched alkylidene of C1-C20, under preferable case, R₄For C1-C5 straight chain or Chain alkylidene, more preferably ethylidene, such as-CH₂CH₂-；R₆And R₇It is each independently the straight or branched alkane of H or C1-C20 Base, and R₆And R₇It is asynchronously H, under preferable case, R₆And R₇It is each independently the straight or branched alkyl of H or C1-C5, And R₆And R₇Be asynchronously H, further preferably in the case of, R₆And R₇It is each independently H, methyl, ethyl, isopropyl or uncle Butyl, and R₆And R₇It is asynchronously H；R₉For the straight or branched alkyl of C1-C20, the straight or branched alkyl of preferably C1-C5, More preferably methyl, ethyl, isopropyl or the tert-butyl group；R₁₁、R₁₂、R₁₁' and R₁₂' it is each independently the straight chain of C1-C4 Or branched alkyl, preferably methyl；X^-For Cl^-, Br^-, I^-, SCN^-OrIt is preferably Br^-。

In the present invention, described R₃For the nitrogen-atoms on the imidazole ring in connecting key expression (2) directly with InGroup connects.

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 Base, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.

Described alkylidene refer to alkane lose two hydrogen atoms after residue, said two hydrogen atom can be same carbon Two hydrogen atoms on atom, it is also possible to two hydrogen atoms on different carbon atoms, can be straight chains, it is also possible to be side chain , such as, described ethylidene can be-CH₂CH₂-or-CH (CH₃)-。

In the present invention, described alkylidene can be straight chain, it is also possible to be side chain.The straight or branched of described C1-C20 The example of alkylidene can include but not limited to: methylene, ethylidene, sub-n-pro-pyl, isopropylidene, sub-normal-butyl, sub-Zhong Ding Base, isobutylidene, the sub-tert-butyl group, sub-n-pentyl, isoamylidene, sub-tertiary pentyl, sub-neopentyl, sub-n-hexyl, sub-n-heptyl, Asia N-octyl, sub-positive decyl, sub-dodecyl, sub-cetyl and alkylene eicosyl.

The present inventor finds under study for action, by specific construction unit A, construction unit B, construction unit C and knot The acrylamide quadripolymer of structure cells D composition can obtain fabulous resistance reducing effect.Preferably, R is worked as₁For H or methyl, R₂、R₅And R₈It is each independently H, R₃For connecting key or methylene, R₆And R₇It is each independently the straight chain of H or C1-C5 Or branched alkyl, and R₆And R₇It is asynchronously H, R₉Straight or branched alkyl for C1-C5；R₁₀、R₁₀’、R₁₁、R₁₂、R₁₁' and R₁₂’ It is each independently methyl；X^-For Br^-.That is, described construction unit A is the construction unit shown in formula (1), wherein, R₁For H or first Base, described construction unit B is the construction unit shown in formula (11) and/or the construction unit shown in formula (12), described construction unit C For the one in formula (13), formula (14), formula (15) and the construction unit shown in formula (16), described construction unit D is formula (17) institute The construction unit shown,

Wherein, R⁴For the straight or branched alkylidene of C1-C5, more preferably ethylidene, such as-CH₂CH₂-。

(2) solution polymerization process

Additionally, the present invention also provides for the preparation method of a kind of acrylamide based copolymer, this preparation method is included in alkene Solution polymerization under the conditions of, in the presence of initiator, make a kind of monomer mixture carry out polymerisation in water, wherein, Described monomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the monomer shown in formula (6), described list Body F is the monomer shown in formula (7), and described monomer G is the monomer shown in formula (8) and/or the structures alone shown in formula (9), described Monomer H is the monomer shown in formula (10), and in described monomer mixture on the basis of the total mole number of monomer, described monomer E's Content is 5-95 mole of %, preferably 10-70 mole %, more preferably 50-70 mole %；The content of described monomer F is that 2.5-90 rubs You are %, preferably 5-60 mole %, more preferably 20-40 mole %；The content of described monomer G is 0.5-90 mole of %, preferably 5- 30 moles of %, more preferably 5-20 mole %, the content of described monomer H is that 0.0001-1 mole of %, preferably 0.001-0.5 rub You are %, more preferably 0.005-0.2 mole %；After the condition of described polymerisation makes polymerisation, the viscous of resulting polymers is divided equally Son amount is 5,000,000-1,500 ten thousand, preferably 5,000,000-1,000 ten thousand；

According to the present invention, when described polymerisation starts, the weight of described monomer mixture and water and monomer mixture The various ratios that the ratio of gross weight is known to those skilled in the art, usually, the weight of described monomer mixture and water Can be 0.05-0.5:1, preferably 0.15-0.4:1 with the ratio of the gross weight of monomer mixture.

According to the present invention, described initiator can be the various initiator in this area.Such as, selected from azo series initiators and oxygen Change reduction series initiators.In described monomer mixture on the basis of the total mole number of monomer, the consumption of described azo series initiators For 0-10 mole of %, the consumption of described redox series initiators is 0-10 mole of %, and described azo initiator and redox Total consumption of initiator is the most satisfied: total consumption of described initiator is the total mole number of monomer in monomer mixture 0.0001-10 mole of %.

In the present invention, it is preferable that described azo series initiators be selected from 2,2 '-azo diisobutyl amidine hydrochloride and/or 2, 2 '-azo two [2-(2-imidazoline-2-propane)-dihydrochloride].

Described redox series initiators includes Oxidizing and Reducing Agents, it is preferable that described oxidant and described reducing agent Mol ratio be 0.5-3.5:1, under conditions of meeting aforementioned proportion, the consumption of described oxidant can be single in monomer mixture 0.0001-0.01 mole of % of the total mole number of body, the preferably 0.001-0.008 of the total mole number of monomer in monomer mixture Mole %；Under preferable case, described oxidant is selected from least in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide Kind, more preferably ammonium persulfate and/or potassium peroxydisulfate；The consumption of described reducing agent can be monomer in monomer mixture 0.0001-0.005 mole of % of total mole number, preferably in monomer mixture, the 0.001-0.004 of the total mole number of monomer rubs You are %；Described reducing agent can be inorganic reducing agent (helping reducing agent), it is preferable that described inorganic reducing agent is selected from bisulfite At least one in sodium, sodium sulfite, rongalite, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite, ascorbic acid and urea, further It is preferably sodium hydrogensulfite and/or sodium thiosulfate.

In the present invention, needing to particularly point out ground, described monomer H simultaneously works as the effect of chain extender in the course of the polymerization process, This is because two the double bond groups that have in described monomer H may participate in polymerisation, it is similar to " bridge formation ".

It addition, the injury of the acrylamide based copolymer layer over the ground of present invention offer reduces, this is likely due to this polymerization Thing has azo group, easily occurs from degradation reaction (more than 60 DEG C) at a temperature of relatively low stratum.

According to the present invention, described solution polymerization can also be carried out in the presence of various auxiliary agents, and described auxiliary agent can select At least one in chelating agent and other auxiliary agents；In described monomer mixture on the basis of the total mole number of monomer, described chela The consumption of mixture is 0-2 mole of %, preferably 0.0001-1 mole %, more preferably 0.0001-0.05 mole of %, described its The consumption of his auxiliary agent can be 0-2 mole of %, preferably 0.0001-1 mole %, more preferably 0.0001-0.2 mole of %；Excellent The consumption of selection of land, described chelating agent and other auxiliary agents makes: in described monomer mixture on the basis of the total mole number of monomer, institute The consumption stating auxiliary agent is 0.0001-4 mole of %.

According to the present invention, described chelating agent can 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 triethylenediamine At least one in pentaacetic acid, described citrate can be potassium citrate, sodium citrate, calcium citrate and ammonium citrate etc..

According to the present invention, other auxiliary agents described can be selected from urea, sodium formate, isopropanol, trimethyl bromine Change at least one in ammonium and sodium hypophosphite, preferably urea and/or sodium formate.

It was found by the inventors of the present invention that under conditions of existing concurrently with above-mentioned various initiator and auxiliary agent, solution polymerization process The acrylamide based copolymer that viscosity average molecular weigh is controlled can be obtained.

According to the present invention, the condition of described solution polymerization can be the condition that this area is conventional.Such as, described solution Polymerisation is carried out in the presence of an inert gas, and polymeric reaction condition may include that temperature is 0-50 DEG C, and the time is that 1-24 is little Time, pH value is 5-13；Under preferable case, temperature is 4-45 DEG C, and the time is 4-24 hour, and pH value is 5-9.Described pH value can be led to Cross addition acid or alkali be adjusted, described acid is preferably inorganic acid, described inorganic acid be preferably hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and At least one in phosphoric acid；Described alkali can be inorganic base or organic amine compound, such as, can be selected from NaOH, hydrogen-oxygen Change at least one in potassium, ammoniacal liquor, methylamine, ethamine, monoethanolamine and triethanolamine, preferably NaOH.

The present inventor finds under study for action, takes following condition can improve the molecular weight of polymer further: I.e., it is preferable that the process of described solution polymerization includes the three phases carried out successively: the reaction condition bag of first stage Including: temperature is 0-10 DEG C, preferably 4-10 DEG C, the time is 1-15 hour, preferably 3-10 hour；The reaction condition of second stage Including: temperature is 15-30 DEG C, preferably 20-30 DEG C, and the time is 3-8 hour, preferably 3-5 hour；The reaction bar of phase III Part includes: temperature is 35-50 DEG C, preferably 35-45 DEG C, and the time is 2-14 hour, preferably 2-12 hour.

Additionally, the present inventor finds under study for action, when selecting specific monomer E, monomer F, monomer G and monomer H When reacting, it is possible to improve the resistance reducing effect of the polymer of gained further.Preferably, R is worked as₁For H or methyl, R₂、R₅With R₈It is each independently H, R₃For connecting key or methylene, R₆And R₇It is each independently the straight or branched of H or C1-C5 Alkyl, and R₆And R₇It is asynchronously H；R₉Straight or branched alkyl for C1-C5；R₁₀、R₁₀’、R₁₁、R₁₂、R₁₁' and R₁₂' the most only It it is on the spot methyl；X^-For Br^-.That is, described monomer E is the monomer shown in formula (6), wherein, R₁For H or methyl, described monomer F is Monomer shown in formula (18) and/or the monomer shown in formula (19), described monomer G is formula (20), formula (21), formula (22) and formula (23) The shown one in monomer, described monomer H is the monomer shown in formula (24),

Wherein, R₄For the straight or branched alkylidene of C1-C20, under preferable case, R₄Straight or branched alkylene for C1-C5 Base, more preferably ethylidene, such as-CH₂CH₂-。

(3) reversed emulsion polymerization

Additionally, the present invention also provides for the preparation method of a kind of acrylamide based copolymer, this preparation method includes aqueous phase It is mixed to form reversed-phase emulsion, then under the conditions of emulsion polymerization, in the presence of initiator, by this reversed-phase emulsion with oil phase Carrying out polymerisation, described aqueous phase is the aqueous solution containing monomer mixture, and described oil phase contains organic solvent and emulsifying agent, its In, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, and described monomer E is the monomer shown in above-mentioned formula (6), Described monomer F is the monomer shown in above-mentioned formula (7), and described monomer G is shown in the monomer shown in above-mentioned formula (8) and/or formula (9) Structures alone, described monomer H is the monomer shown in above-mentioned formula (10), and with the total mole number of monomer in described monomer mixture is Benchmark, the content of described monomer E is 5-95 mole of %, preferably 10-70 mole %, more preferably 50-70 mole %；Described monomer F Content be 2.5-90 mole of %, preferably 5-60 mole %, more preferably 20-40 mole %；The content of described monomer G is 0.5- 90 moles of %, preferably 5-30 mole %, more preferably 5-20 mole %, the content of described monomer H is 0.0001-1 mole of %, preferably For 0.001-0.5 mole of %, more preferably 0.005-0.2 mole %；The condition of described polymerisation makes gained after polymerisation The viscosity average molecular weigh of polymer is 5,000,000-1,500 ten thousand, preferably 5,000,000-1,000 ten thousand；The choosing of monomer shown in formula (6)-formula (10) Select identical with described above, do not repeat them here.

According to the present invention, described aqueous phase is the aqueous solution containing monomer mixture.The weight of described monomer mixture and water Selection with the ratio of the gross weight of monomer mixture is identical with described above, does not repeats.

According to the present invention, the part by weight of described aqueous phase and oil phase is had no particular limits, if make described aqueous phase with Oil phase is thoroughly mixed to form reversed-phase emulsion, and under preferable case, the part by weight of described aqueous phase and oil phase is 1:0.1-2, enters One step is preferably 1:0.3-0.8.

According to the present invention, described organic solvent can be this area various for emulsion polymerization mutual exclusive with water non- Polarity or the little organic solvent of polarity, such as, can be toluene, dimethylbenzene, hexane, hexamethylene, normal heptane, isomery paraffin, isomery At least one in alkane, gasoline, kerosene and white oil, under preferable case, described organic solvent is selected from toluene, dimethylbenzene, just At least one in heptane, isoparaffin, hexamethylene and kerosene.

According to the present invention, described oil phase contains organic solvent and emulsifying agent.The most special to the consumption of described organic solvent Requirement, can change in wider scope, as long as described organic solvent and emulsifying agent are mixed to form oil phase, preferably feelings Under condition, on the basis of the gross weight of described emulsion, the consumption of described organic solvent can be 10-60 weight %, more preferably 20-35 weight %.

According to the present invention, described emulsifying agent can be the various nonionic emulsifier for emulsion polymerization in this area, example As being sorbitan fatty acid ester, APES, isomeric alcohol polyethenoxy ether, lauryl alcohol polyethylene glycol oxide Ether, methyl glycol fatty acid ester, laureth, benzylphenol oxygen APEO, phenethyl phenol polyethenoxy ether, polyoxyethylene lose Water sorbitan fatty acid fat, sorbitan fatty acid ester ethylene oxide adduct, benzyl dimethyl phenol polyethenoxy ether, fat At least one in alcohol APEO and aliphatic amine polyoxyethylene ether.Under preferable case, described emulsifying agent is selected from Sorbitan Alcohol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, NPE, OPEO, benzyl Phenol oxygen APEO, phenethyl phenol polyethenoxy ether, isomerous tridecanol polyoxyethylene ether, ethoxylated dodecyl alcohol and benzyl At least one in dimethyl phenol APEO, is further preferably be made up of above two or two or more emulsifying agents Hydrophilic lipophilic balance is the compound emulsifying agent of 5-9, such as, can be sorbitan fatty acid ester and Nonyl pheno Ether.

According to the present invention, the consumption of described emulsifying agent is not particularly limited, can change in wider scope, only Described emulsifying agent and described organic solvent is wanted to be mixed to form oil phase, under preferable case, with the gross weight of described emulsion as base Standard, the consumption of described emulsifying agent can be 1-15 weight %, more preferably 2-10 weight %.

According to the present invention, described initiator can be various initiators in this area, and the selection of described initiator is with above Describing identical, here is omitted.

In the present invention, under preferable case, first azo series initiators can be added aqueous phase, then be mixed to form anti-phase breast with oil phase Liquid, then contacts reversed-phase emulsion with redox series initiators, by redox initiator initiated polymerization.

According to the present invention, described polymerisation can also be carried out in the presence of various auxiliary agents, and described auxiliary agent can be selected from chela At least one in mixture and other auxiliary agents, the selection of described auxiliary agent is identical with described above, and here is omitted.

According in the present invention, the charging not particularly requirement on opportunity to described chelating agent, as long as making chelating agent and metal Ion generation chelation, so that copolymer is played static stabilization, can select to add or in oil phase at aqueous phase Add, under preferable case, in order to make chelating agent play stably more fully effect, addition chelating agent in aqueous phase can be selected.

According to the present invention, the selection of described chelating agent is identical with described above, and here is omitted.

Equally, it was found by the inventors of the present invention that under conditions of existing concurrently with above-mentioned various initiator and auxiliary agent, anti-phase breast Liquid 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 that this area is conventional.Described polymerisation The selection of condition is identical with described above, and here is omitted.

Equally, the present inventor finds under study for action, takes following condition can improve dividing of polymer further Son amount: i.e., it is preferable that the process of described emulsion polymerization includes two stages carried out successively: the reaction bar of first stage Part includes: temperature is 0-20 DEG C, preferably 5-10 DEG C, and the time is 1-15 hour, preferably 1-5 hour；The reaction of second stage Condition includes: temperature is 20-50 DEG C, preferably 25-45 DEG C, and the time is 2-8 hour, preferably 2-5 hour.

According to the present invention, the method is additionally included in described polymerisation products therefrom and phase inversion agent after described polymerisation Contact, so that described polymerisation products therefrom quickly dissolves in fracturing fluid is applied in water.Described phase inversion agent is permissible The various phase inversion agent being polymerized for emulsion for this area, as long as making the water solubility of described polymerisation products therefrom increase, Can be such as polyoxyethylene sorbitan fatty acid ester, NPE, OPEO, benzylphenol APEO, phenethyl phenol polyethenoxy ether, isomery ten alcohol APEO, isomery undecyl alcohol APEO, isomery ten At least one in the nonionic emulsifier of triol APEO and aliphatic amine polyoxyethylene ether, under preferable case, described Phase inversion agent is selected from polyoxyethylene sorbitan fatty acid ester, isomery ten alcohol APEO, isomery undecyl alcohol polyoxyethylene At least one in ether, isomerous tridecanol polyoxyethylene ether, NPE and OPEO.

According to the present invention, the consumption not particularly requirement to described phase inversion agent, as long as described polymerisation institute can be made Obtaining product quickly to dissolve in water in fracturing fluid is applied, the consumption of described phase inversion agent makes: with the gross weight of described emulsion On the basis of amount, the consumption of described phase inversion agent can be 0.5-10 weight %, preferably 1-4 weight %.

Additionally, the present inventor finds under study for action, when selecting specific monomer E, monomer F, monomer G and monomer H When reacting, it is possible to improve the resistance reducing effect of the polymer of gained further.For instance, it is preferred that work as R₁For H or methyl, R₃ For connecting key or methylene, R₂、R₅And R₈It is each independently H, R₆And R₇Be each independently H or C1-C5 straight chain or Branched alkyl, and R₆And R₇It is asynchronously H；R₉Straight or branched alkyl for C1-C5；R₁₀、R₁₀’、R₁₁、R₁₂、R₁₁' and R₁₂' each From independently be methyl；X^-For Br^-.That is, described monomer E is the monomer shown in formula (6), wherein, R₁For H or methyl, described monomer F is the monomer shown in formula (18) and/or the monomer shown in formula (19), and described monomer G is formula (20), formula (21), formula (22) and formula (23) one in the monomer shown in, described monomer H is the monomer shown in formula (24), single shown in formula (6), formula (18)-formula (24) The selection of body is identical with described above, does not repeats them here.

Additionally, present invention also offers the application in drag reducer of the described acrylamide based copolymer.Employing is the present invention carry The described acrylamide based copolymer of confession is as fracturing fluid drag reducer, it is possible to obtain high and stable drag reducing efficiency, concrete application The technology that method is well known to those skilled in the art.

Hereinafter will be described the present invention by embodiment.It should be appreciated that concrete reality described herein The mode of executing is merely to illustrate and explains the present invention, is not limited to the present invention.

Intrinsic viscosity is measured according to GB12005.1-89 polyacrylamide Intrinsic Viscosity Measurements method；Glue and divide equally Son amount is according to formula M_v=([η]/K)^1\α, wherein K=4.5 × 10^-3, α=0.80 calculates；Dissolution time presses GB12500.8-89 Being measured (sample quality is all based on straight polymer quality in sample), the powdered samples dissolution time recorded is respectively less than 20min, samples of latex dissolution time is respectively less than 5min；The composition of molecular structure and construction unit use IR spectrum and¹³C-NMR surveys Fixed；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 M1 shown in following embodiment Chinese style (25) is according to document (Efficient fixation of CO₂into cyclic carbonates catalyzed by hydroxyl-functionalized poly(ionic liquids), RSCAdvances, 2013,3 (11), 3726-3732) described in method prepare, the monomer M3 shown in formula (28) is according to patent Prepared by the method that WO2010033014A2 embodiment 3 is recorded.

Monomer M1 shown in following embodiment Chinese style (25) and the monomer M3 shown in formula (28) is public purchased from Sigma-Aldrich Department, in addition, unless specifically indicated, the reagent etc. used in embodiment, comparative example and test case is commercially available product.

Embodiment 1

The present embodiment is for illustrating that the solution polymerization process that the present invention provides prepares acrylamide based copolymer.

Under room temperature, by the acrylamide (AM) of 4.26g, 77.04g formula (25) shown in M1 monomer, the N of 17.55g, N- The M2 monomer shown in formula (26) of DMAA (purchased from Sigma-Aldrich company) and 1.16g (according to Prepared by the method that in JP08217755A, embodiment 1 is recorded, the most identical), join in reaction bulb, add deionized water 566.72g, stirring makes monomer be completely dissolved, and stirs.The EDTA aqueous solution 5.5g of 1 weight % is added respectively in flask, The 2 of 1 weight %, 2 '-azo diisobutyl amidine hydrochloride aqueous solution 2.1g, add the solution of sodium bisulfite 1.1g of 0.1 weight %, Urea 0.12g, is sufficiently stirred for making it mix.Regulate to 7.5 with the sodium hydroxide solution pH of 10 weight %.At the beginning of control system Beginning temperature, to 4 DEG C, after leading to nitrogen deoxygenation 30 minutes, adds 1 weight % ammonium persulfate aqueous solution 0.45g, and continues letting nitrogen in and deoxidizing 20 Minute.Reactor is airtight, it is maintained at 4 DEG C, after reacting 8 hours, reacts 5 hours after temperature is risen to 20 DEG C, then by temperature Rise to 45 DEG C react 2 hours, the gum-like product that obtain is taken out, through granulation, be dried, pulverize and can receive acrylamide copolymerization Thing P1.

P1 is carried out various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Place occurs belonging to the acyl of amide groups respectively Amine 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 place Contracting vibration absorption peak；1170cm^-1Occur in that M2 monomer CH₃-C-CH₃The feature stretching vibration peak of skeletal vibration, 1356cm^-1With 1401cm^-1Typical methyl symmetric curvature vibration absorption peak, 3100cm occur^-1Place's small peak belongs to stretching of C=C-H on imidazole ring Contracting vibration, 2923,2852cm^-1Place goes out peak and is respectively belonging to-CH₂-、-CH₃C-H stretching vibration, 1508-1654cm^-1Go out peak to return Belong to C=C stretching vibration on imidazole ring, 1467cm^-1Go out peak and belong to-CH₂-、-CH₃C-H flexural vibrations, 1034-1229cm^-1 Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm^-1Go out peak and belong to the vibration of imidazole ring Ar-H out-of plane bending.Can To determine that the copolymer molecule obtained has the structure shown in formula (27), recording its viscosity-average molecular weight Mv by viscosity method is 670 Ten thousand, monomer conversion is more than 99.9%.Wherein, formula (27) and x₁、x₂、y₁、y₂、z₁、z₂Construction unit is only represented with u Type and number, and do not indicate that the connected mode of construction unit.x₁、x₂、y₁、y₂、z₁、z₂True by inventory with the concrete numerical value of u Fixed, the composition of molecular structural formula and construction unit uses quantitatively¹³C composes mensuration, wherein, (x₁+x₂): (y₁+y₂): (z₁+z₂): u=1: 6:2.95:0.05.

Comparative example 1

Prepare acrylamide based copolymer according to the method for embodiment 1, except for the difference that, be added without M1 monomer, N, N-diformazan Base acrylamide and M2 monomer, by (3-acrylamido-3-methyl) butyl trimethyl chlorine of acrylamide Yu identical molal quantity Change ammonium and carry out polymerisation, thus obtain bipolymer DP1, record its viscosity average molecular weigh M_vIt is 14,010,000.

Embodiment 2

By M3 monomer, the isopropyl ester of 16.96g and the 0.46g shown in the formula (28) of AM, 6.99g of 29.85g The M2 monomer shown in formula (26) join in polymerization bottle, add 126.61g deionized water, stirring make monomer be completely dissolved, point In flask, do not add the EDTA aqueous solution 4.65g of 1 weight %, add the 2 of 1 weight %, 2 '-azo diisobutyl amidine hydrochloric acid salt solution Solution 1.23g, adds 0.1% solution of sodium bisulfite 1.15g, adds urea 0.11g, is sufficiently stirred for making it mix.With 10 The sodium hydroxide solution regulation pH to 7.1 of weight %.Control system initial temperature is to 10 DEG C, after leading to nitrogen deoxygenation 30 minutes, adds 1 weight % ammonium persulfate aqueous solution 0.45g, and continue letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, it is maintained at 10 DEG C, reacts 3 After hour, it is warming up to 30 DEG C, after reacting 3 hours, is warming up to 35 DEG C and reacts 12 hours, the gum-like product obtained is taken out, through making Grain, be dried, pulverize can receive acrylamide copolymer p 2.

P2 is carried out various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Place occurs belonging to the acyl of amide groups respectively Amine 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 place Contracting vibration absorption peak；1170cm^-1Occur in that M2 monomer CH₃-C-CH₃The feature stretching vibration peak of skeletal vibration；1310cm^-1Locate little Peak belongs to the stretching vibration of C=C-H on imidazole ring, and 2923,2852cm^-1Place goes out peak and is respectively belonging to-CH₂-、-CH₃C-H stretch Contracting vibration, 1508-1654cm^-1Go out peak and belong to C=C stretching vibration on imidazole ring, 1467cm^-1Go out peak and belong to-CH₂-、-CH₃ C-H flexural vibrations, 1034-1229cm^-1Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm^-1Go out peak to belong to Imidazole ring Ar-H out-of plane bending vibrates.May determine that the copolymer molecule obtained has the structure shown in formula (29), by glutinous It is 5,700,000 that degree method records its viscosity-average molecular weight Mv, and monomer conversion is more than 99.9%.Wherein, formula (29) and x₁、x₂、y₁、 y₂、z₁、z₂Only represent type and the number of construction unit with u, and do not indicate that the connected mode of construction unit.x₁、x₂、y₁、y₂、 z₁、z₂Determining by inventory with the concrete numerical value of u, the composition of molecular structural formula and construction unit uses quantitatively¹³C composes mensuration, its In, x₁、x₂、y₁、y₂、z₁、z₂、u₁And u₂Numerical value be respectively (x₁+x₂): (y₁+y₂): (z₁+z₂): u=1:0.07:0.35: 0.003。

Embodiment 3

Under room temperature, by the Methacrylamide of 25.53g, 57.79g formula (25) shown in M1 monomer, uncle N-of 4.58g The M2 monomer shown in formula (26) of butylacrylamide and 0.002g joins in polymerization bottle, adds 131.85g deionized water, stirs Mix and make monomer be completely dissolved, in flask, add the EDTA aqueous solution 11.63g of 1 weight % respectively, add the 2 of 1 weight %, 2 '-idol Nitrogen diisobutyl amidine hydrochloride aqueous solution 2.13g, adds 0.1 weight % solution of sodium bisulfite 1.13g, adds urea 0.20g, DTAB 0.01g, is sufficiently stirred for making it mix.PH is regulated with the sodium hydroxide solution of 10 weight % To 7.3.Control system initial temperature, to 8 DEG C, after leading to nitrogen deoxygenation 30 minutes, adds 1% ammonium persulfate aqueous solution 0.4g, and continues Continuous letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, it is maintained at 8 DEG C, after reacting 10 hours, is warming up to 25 DEG C, after reacting 4 hours, It is warming up to 40 DEG C react 7 hours, the gum-like product that obtain is taken out, through granulation, be dried, pulverize and can receive acrylamide altogether Polymers P3.

P3 is carried out various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Place occurs belonging to the acyl of amide groups respectively Amine 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 place Contracting vibration absorption peak；1170cm^-1Occur in that M2 monomer CH₃-C-CH₃The feature stretching vibration peak of skeletal vibration, 1310cm^-1Locate little Peak belongs to the stretching vibration of C=C-H on imidazole ring, and 2923,2852cm^-1Place goes out peak and is respectively belonging to-CH₂-、-CH₃C-H stretch Contracting vibration, 1508-1654cm^-1Go out peak and belong to C=C stretching vibration on imidazole ring, 1467cm^-1Go out peak and belong to-CH₂-、-CH₃ C-H flexural vibrations, 1034-1229cm^-1Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm^-1Go out peak to belong to Imidazole ring Ar-H out-of plane bending vibrates.May determine that the copolymer molecule obtained has the structure shown in formula (30), by glutinous It is 8,150,000 that degree method records its viscosity-average molecular weight Mv, and monomer conversion is more than 99.9%.Wherein, formula (30) and x₁、x₂、y₁、 y₂、z₁、z₂Only represent type and the number of construction unit with u, and do not indicate that the connected mode of construction unit.x₁、x₂、y₁、y₂、 z₁、z₂Determining by inventory with the concrete numerical value of u, the composition of molecular structural formula and construction unit uses quantitatively¹³C composes mensuration, its In, (x₁+x₂): (y₁+y₂): (z₁+z₂): u=1:0.88:0.12:0.00002.

Embodiment 4

The present embodiment is for illustrating that the reversed emulsion polymerization that the present invention provides prepares acrylamide based copolymer.

(1) by the Methacrylamide of 5.11g, 77.04g formula (25) shown in M1 monomer, the N of 17.55g, N-diformazan The M2 monomer shown in formula (26) of base acrylamide and 1.16g joins in configuration bottle, adds 164.56g deionized water, stirring Make monomer be completely dissolved, in flask, add the EDTA aqueous solution 14.61g of 1 weight % respectively, add the 2 of 1 weight %, 2 '-azo Diisobutyl amidine hydrochloride aqueous solution 1.03g, adds urea 0.15g, is sufficiently stirred for making it mix, with the hydrogen of 10 weight % Sodium hydroxide solution regulation pH to 7.1, obtains aqueous phase.

(2) by sorbitan fatty acid ester (span60, Sigma-Aldrich company, the most identical) 37.81g, alkyl Phenol polyethenoxy ether (Igepal CA720, Sigma-Aldrich company, the most identical) 10g, 177.16g kerosene is mixed into oil Phase, and the aqueous phase obtained in step (1) is joined in whole oil phase, form reversed-phase emulsion by mixing at a high speed and join reaction In device.

(3) control system initial temperature 5 DEG C, after leading to nitrogen deoxygenation 30 minutes, add 1 weight % aqueous solution of sodium bisulfite 0.25g, adds 1 weight % ammonium persulfate aqueous solution 1.0g and continues letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, it is maintained at 5 DEG C, after reacting 5 hours, it is warming up to 45 DEG C, reacts 2 hours.After question response temperature is cooled to room temperature, adds 20.25g nonyl phenol and gather Oxygen vinethene (Sigma-Aldrich company, the most identical), obtains emulsion-formulated products with 80 mesh filter-cloth filterings.By reversed-phase emulsion After product acetone and methanol mixed solvent are precipitated out, acrylamide copolymer p 4 can be obtained.

P4 is carried out various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Place occurs belonging to the acyl of amide groups respectively Amine 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 place Contracting vibration absorption peak, 1170cm^-1Occur in that M2 monomer CH₃-C-CH₃The feature stretching vibration peak of skeletal vibration, 1356cm^-1With 1401cm^-1Typical methyl symmetric curvature vibration absorption peak, 3100cm occur^-1Place's small peak belongs to stretching of C=C-H on imidazole ring Contracting vibration, 2923,2852cm^-1Place goes out peak and is respectively belonging to-CH₂-、-CH₃C-H stretching vibration, 1508-1654cm^-1Go out peak to return Belong to C=C stretching vibration on imidazole ring, 1467cm^-1Go out peak and belong to-CH₂-、-CH₃C-H flexural vibrations, 1034-1229cm^-1 Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm^-1Go out peak and belong to the vibration of imidazole ring Ar-H out-of plane bending.Can To determine that the copolymer molecule obtained has the structure shown in formula (31), recording its viscosity average molecular weigh Mv by viscosity method is 710 Ten thousand, monomer conversion is more than 99.9%.Wherein, formula (31) and x₁、x₂、y₁、y₂、z₁、z₂Construction unit is only represented with u Type and number, and do not indicate that the connected mode of construction unit.x₁、x₂、y₁、y₂、z₁、z₂True by inventory with the concrete numerical value of u Fixed, the composition of molecular structural formula and construction unit uses quantitatively¹³C composes mensuration, wherein, (x₁+x₂): (y₁+y₂): (z₁+z₂): u=1: 6:2.95:0.05.

Comparative example 2

Prepare acrylamide based copolymer according to the method for embodiment 4, except for the difference that, be added without M1 monomer, N, N-diformazan Base acrylamide and M2 monomer, by (3-acrylamido-3-methyl) butyl front three of Methacrylamide Yu identical molal quantity Ammonium chloride carries out polymerisation, thus obtains bipolymer DP2, records its viscosity average molecular weigh M_vIt is 9,250,000.

Embodiment 5

(1) by the Methacrylamide of 35.74g, 6.99g formula (28) shown in M3 monomer, 16.96g acrylic acid different The M2 monomer shown in formula (26) of propyl diester and 0.46g joins in preparation bottle, adds 240.6g deionized water, and stirring makes monomer It is completely dissolved, in flask, adds the EDTA aqueous solution 7.63g of 1 weight % respectively, add 1 weight % azo diisobutyl amidine hydrochloric acid Saline solution 2.03g, adds urea 0.10g, is sufficiently stirred for making it mix, and regulates with the sodium hydroxide solution of 15 weight % PH to 7.0, obtains aqueous phase.

(2) by sorbitan fatty acid ester (span60) 28.82g, APES (Igepal CA720) 10g, 116.44g kerosene is mixed into oil phase, and is all joined in oil phase by the aqueous phase obtained in step (1), by the most mixed Even formation reversed-phase emulsion joins in reactor.

(3) control system initial temperature 10 DEG C, after leading to nitrogen deoxygenation 30 minutes, add 1 weight % aqueous solution of sodium bisulfite 0.13g, adds 1 weight % ammonium persulfate aqueous solution 0.63g, and continues letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, keep At 10 DEG C, after reacting 1 hour, it is warming up to 25 DEG C, reacts 5 hours, after question response temperature is cooled to room temperature, add 9.31g nonyl Phenol polyethenoxy ether, obtains emulsion-formulated products with 80 mesh filter-cloth filterings.By reversed-phase emulsion product acetone and methanol mixed solvent After being precipitated out, acrylamide copolymer p 5 can be obtained.

P5 is carried out various mensuration, 1660cm in IR spectrum^-1And 1635cm^-1Place occurs belonging to the acyl of amide groups respectively Amine 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 place Contracting vibration absorption peak, 1170cm^-1Occur in that M2 monomer CH₃-C-CH₃The feature stretching vibration peak of skeletal vibration, 1310cm^-1Locate little Peak belongs to the stretching vibration of C=C-H, 1356cm on imidazole ring^-1And 1401cm^-1Occur that the vibration of typical methyl symmetric curvature is inhaled Receive peak, 2923,2852cm^-1Place goes out peak and is respectively belonging to-CH₂-、-CH₃C-H stretching vibration, 1508-1654cm^-1Go out peak ownership C=C stretching vibration on imidazole ring, 1467cm^-1Go out peak and belong to-CH₂-、-CH₃C-H flexural vibrations, 1034-1229cm^-1Go out Peak belongs to C=N stretching vibration on imidazole ring, 1260cm^-1Go out peak and belong to C-O stretching vibration on ester bond, 625-911cm^-1Go out Peak belongs to the vibration of imidazole ring Ar-H out-of plane bending.May determine that the copolymer molecule obtained has the knot shown in formula (32) Structure, recording its viscosity average molecular weigh Mv by viscosity method is 5,450,000, and monomer conversion is more than 99.9%.Wherein, formula (32) and x₁、x₂、y₁、y₂、z₁、z₂Only represent type and the number of construction unit with u, and do not indicate that the connected mode of construction unit.x₁、 x₂、y₁、y₂、z₁、z₂Determining by inventory with the concrete numerical value of u, the composition of molecular structural formula and construction unit uses quantitatively¹³C composes Measure, wherein, (x₁+x₂): (y₁+y₂): (z₁+z₂): u=1:0.07:0.35:0.003.

Embodiment 6

(1) by the acrylamide of 21.32g, 57.79g formula (25) shown in M1 monomer, the N-tert-butyl group propylene of 4.58g The M2 monomer shown in formula (26) of acid amides and 0.002g joins in preparation bottle, adds 474.26g deionized water, and stirring makes monomer It is completely dissolved, in flask, adds the EDTA aqueous solution 8.5g of 1 weight % respectively, add 1 weight % azo diisobutyl amidine hydrochloric acid Saline solution 2.1g, adds urea 0.08g, DTAB 0.01g, is sufficiently stirred for making it mix, and uses The sodium hydroxide solution regulation pH to 7.1 of 10 weight %, obtains aqueous phase.

(2) by sorbitan fatty acid ester (span60) 12.75g, APES (Igepal CA720, Sigma-Aldrich company, the most identical) 10g, 147.84g kerosene is mixed into oil phase, and adds obtaining aqueous phase in step (1) Enter in oil phase, form reversed-phase emulsion by mixing at a high speed and join in reactor.

(3) control system initial temperature 8 DEG C, after leading to nitrogen deoxygenation 30 minutes, add 1 weight % aqueous solution of sodium bisulfite 0.18g, adds 1 weight % ammonium persulfate aqueous solution 1.3g and continues letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, it is maintained at 8 DEG C, after reacting 3 hours, it is warming up to 40 DEG C, reacts 4 hours, after question response temperature is cooled to room temperature, adds 7.39g nonyl phenol and gather Oxygen vinethene, obtains emulsion-formulated products with 100 mesh filter-cloth filterings.Reversed-phase emulsion product acetone and methanol mixed solvent are precipitated After out, acrylamide copolymer p 6 can be obtained.

P6 is carried out various mensuration, in IR spectrum, 1660cm^-1And 1635cm^-1Place occurs belonging to the acyl of amide groups respectively Amine 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 place Contracting vibration absorption peak, 1170cm^-1Occur in that M2 monomer CH₃-C-CH₃The feature stretching vibration peak of skeletal vibration, 1310cm^-1Locate little Peak belongs to the stretching vibration of C=C-H on imidazole ring, and 2923,2852cm^-1Place goes out peak and is respectively belonging to-CH₂-、-CH₃C-H stretch Contracting vibration, 1508-1654cm^-1Go out peak and belong to C=C stretching vibration on imidazole ring, 1467cm^-1Go out peak and belong to-CH₂-、-CH₃ C-H flexural vibrations, 1034-1229cm^-1Go out peak and belong to C=N stretching vibration on imidazole ring, 625-911cm^-1Go out peak to belong to Imidazole ring Ar-H out-of plane bending vibrates.May determine that the copolymer molecule obtained has the structure shown in formula (33), by glutinous It is 7,600,000 that degree method records its viscosity average molecular weigh Mv, and monomer conversion is more than 99.9%.Wherein, formula (33) and x₁、x₂、y₁、 y₂、z₁、z₂Only represent type and the number of construction unit with u, and do not indicate that the connected mode of construction unit.x₁、x₂、y₁、y₂、 z₁、z₂Determining by inventory with the concrete numerical value of u, the composition of molecular structural formula and construction unit uses quantitatively¹³C composes mensuration, its In, (x₁+x₂): (y₁+y₂): (z₁+z₂): u=1:0.88:0.12:0.00002.

Test case 1

Water-insoluble is to measure according to the method for regulation in SY/T5862-1993.By P1-P6, DP1, DP2 and hydroxypropyl Guar gum (JXY wellfracturing hydroxypropyl melon rubber powder, Shandong Juxin Chemical Co., Ltd., the most identical) carry out water-soluble mensuration, knot Fruit is as shown in table 1.

Table 1

From table 1 it follows that in the acrylamide copolymer p 1-P6 for preparing of two kinds of methods that provides of the present invention water is not Molten thing content is the conventional hydroxypropyl guar gum cooking drag reducer significantly lower than in site operation, this explanation and hydroxypropyl guar gum ratio, uses P1-P6 is low to the injury on stratum as shale gas pressure break drag reducer.

Test case 2

Under 2500rpm shear rate, respectively by P1-P6, DP1, DP2, partially hydrolyzed polyacrylamide (PHPA) (HPAM, Zibo Tian Jian Chemical Co., Ltd., trade mark TJY-1, viscosity average molecular weigh is 1000-1300 ten thousand, lower same) and be each slowly added to respectively In water/alcoholic solution (using methyl alcohol in this test case) that volume ratio is 80/20 and 60/40, P1-P6, DP1, DP2 and part water Solve the 0.01 weight %(sample quality that consumption is water/alcoholic solution of polyacrylamide based on straight polymer quality in sample), dissolve Time is 30min, and result is as shown in table 2.

Table 2

From Table 2, it can be seen that acrylamide copolymer p 1-P6 prepared by two kinds of methods that the present invention provides is as page Rock air pressure splits with drag reducer, compared with partially hydrolyzed polyacrylamide (PHPA), good with the compatibility of alcohol.

Test case 3

Under conditions of temperature is 25 DEG C, P1-P6, DP1, DP2, HPAM and hydroxypropyl guar gum are dissolved in respectively pure water and dense Degree is in NaCl or the KCl solution of 2 weight %, 4 weight %, 8 weight %, 10 weight %, 12 weight %, the 500mg/L being configured to With the solution (sample quality is based on straight polymer quality in sample) of 1000mg/L, then specify according in SY/T6376-2008 Method on GLM-1 pipeline frictional resistance determinator, measure the drag reducing efficiency of above-mentioned solution, (test condition: test section pipeline interior Footpath is 8mm, a length of 9m of test section pipeline, and infusion discharge capacity is 30L/min), result is as shown in Table 3 and Table 4.

Table 3

Table 4

It can be seen that the acrylamide copolymer p 1-P6 for preparing of two kinds of methods that provides of the present invention from table 3 and table 4 As shale gas pressure break drag reducer, compared with hydroxypropyl guar gum, HPAM, DP1 and DP2, with clay stabilizer (e.g., KCl and NaCl) compatibility is good, and anti-salt property is excellent.

Test case 4

The nocuity of rock core is pressed oil and gas industry standard SY/T5107-2005 " aqueous fracturing fluid performance by friction reducer Evaluation method " in fracturing fluid filtrate matrix permeability of rock core infringement experiment is carried out, in the test of American core company formation damage Testing on instrument (FDS-800), the matrix permeability of rock core is 2md.

P1-P6, DP1 and DP2 are dissolved in pure water respectively, and (sample quality is by sample to be configured to the solution of 1000mg/L Interior straight polymer quality meter), under conditions of test temperature is 65 DEG C, preserve 24hr, in the formation damage test of American core company System (FDS-800) is upper tests its nocuity to rock core, and result is as shown in table 5.

Table 5

As can be seen from Table 5, acrylamide copolymer p 1-P6 prepared by two kinds of methods that the present invention provides is to rock core Injury significantly lower than in site operation the conventional comparative sample cooking drag reducer, this explanation uses P1-P6 as shale gas pressure break Low to the injury on stratum with drag reducer.

Above-mentioned test result illustrates, the acrylamide based copolymer that the present invention provides insolubles content in water is only 0.01%；Under the shear rate of 2500rpm, can be dissolved completely in water/alcoholic solution, good with the compatibility of alcohol；Due to alcohol and The compatibility of clay stabilizer (NaCl or KCl) improves, and improves anti-filtration property；And under conditions of high salt and high shear Still there is high drag reducing efficiency；Under conditions of lower ground layer temperature (more than 60 DEG C), there is self-degradation, the injury to stratum Low.Additionally, the preparation method of acrylamide based copolymer that the present invention provides has simplicity and the high advantage of monomer conversion.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this A little simple variant belong to protection scope of the present invention.

It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can The combination of energy illustrates the most separately.

Additionally, can also be combined between the various different embodiment of the present invention, as long as it is without prejudice to this The thought of invention, it should be considered as content disclosed in this invention equally.

Claims

1. an acrylamide based copolymer, it is characterised in that described acrylamide based copolymer contains construction unit A, structure Unit B, construction unit C and construction unit D, wherein, described construction unit A is the construction unit shown in formula (1), described structure list 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 the knot shown in formula (4) Structure unit, described construction unit D is the construction unit shown in formula (5)；And with construction unit in described acrylamide based copolymer Total mole number on the basis of, the content of described construction unit A is 5-95 mole of %, and the content of described construction unit B is 2.5-90 Mole %, the content of described construction unit C is 0.5-90 mole of %, and the content of described construction unit D is 0.0001-1 mole of %； The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000-1,500 ten thousand；

Wherein, R₁、R₂、R₅、R₈、R₁₀And R₁₀' it is each independently the alkyl of H or C1-C4；R₃For C1-C4 alkylidene or Connecting key；R₄Straight or branched alkylidene for C1-C20；R₆And R₇It is each independently the straight or branched of H or C1-C20 Alkyl, and R₆And R₇It is asynchronously H；R₉Straight or branched alkyl for C1-C20；R₁₁、R₁₂、R₁₁' and R₁₂' be each independently The straight or branched alkyl of C1-C4；X^-For Cl^-、Br^-、I^-、SCN^-Or

Acrylamide based copolymer the most according to claim 1, wherein, with structure list in described acrylamide based copolymer On the basis of the total mole number of unit, the content of described construction unit A is 10-70 mole of %, and the content of described construction unit B is 5-60 Mole %, the content of described construction unit C is 5-30 mole of %, and the content of described construction unit D is 0.001-0.5 mole of %, The viscosity average molecular weigh of described acrylamide based copolymer is 5,000,000-1,000 ten thousand.

Acrylamide based copolymer the most according to claim 1, wherein, R₁For H or methyl, R₂、R₅And R₈The most independent Ground is H, R₃For connecting key or methylene, R₆And R₇It is each independently the straight or branched alkyl of H or C1-C5, and R₆With R₇It is asynchronously H, R₉For the straight or branched alkyl of C1-C5, R₁₀、R₁₀’、R₁₁、R₁₂、R₁₁' and R₁₂' it is each independently methyl, X^-For Br^-。

4. a preparation method for acrylamide based copolymer, this preparation method is included in the solution polymerization condition of alkene Under, in the presence of initiator, make a kind of monomer mixture carry out polymerisation in water, wherein, described monomer mixture contains Monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in formula (6), and described monomer F is the list shown in formula (7) Body, described monomer G is the monomer shown in formula (8) and/or the structures alone shown in formula (9), and described monomer H is shown in formula (10) Monomer, in described monomer mixture on the basis of the total mole number of monomer, the content of described monomer E is 5-95 mole of %, described The content of monomer F is 2.5-90 mole of %, and the content of described monomer G is 0.5-90 mole of %, and the content of described monomer H is 0.0001-1 mole of %；After the condition of described solution polymerization makes polymerisation, the viscosity average molecular weigh of resulting polymers is 5000000-1,500 ten thousand,

5. a preparation method for acrylamide based copolymer, this preparation method includes aqueous phase and oil phase are mixed to form anti-phase breast Liquid, then under the conditions of emulsion polymerization, in the presence of initiator, carries out polymerisation, described water by this reversed-phase emulsion Being the aqueous solution containing monomer mixture mutually, described oil phase contains organic solvent and emulsifying agent, and wherein, described monomer mixture contains Having monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in formula (6), and described monomer F is shown in formula (7) Monomer, described monomer G is the monomer shown in formula (8) and/or the structures alone shown in formula (9), and described monomer H is shown in formula (10) Monomer, in described monomer mixture on the basis of the total mole number of monomer, the content of described monomer E is 5-95 mole of %, institute The content stating monomer F is 2.5-90 mole of %, and the content of described monomer G is 0.5-90 mole of %, and the content of described monomer H is 0.0001-1 mole of %；After the condition of described emulsion polymerization makes polymerisation, the viscosity average molecular weigh of resulting polymers is 5000000-1,500 ten thousand,

Preparation method the most according to claim 5, wherein, described aqueous phase is 1:0.1-2 with the weight ratio of oil phase.

Preparation method the most according to claim 6, wherein, described aqueous phase is 1:0.3-0.8 with the weight ratio of oil phase.

Preparation method the most according to claim 5, wherein, on the basis of the gross weight of described emulsion, described organic solvent Consumption be 10-60 weight %, the consumption of described emulsifying agent is 1-15 weight %.

Preparation method the most according to claim 8, wherein, on the basis of the gross weight of described emulsion, described organic solvent Consumption be 20-35 weight %, the consumption of described emulsifying agent is 2-10 weight %.

Preparation method the most according to claim 5, wherein, the method is gathered described after being additionally included in described polymerisation Close reaction products therefrom to contact with phase inversion agent.

11. preparation methods according to claim 10, wherein, on the basis of the gross weight of described emulsion, described phase inversion agent Consumption be 0.5-10 weight %.

12. preparation methods according to claim 11, wherein, on the basis of the gross weight of described emulsion, described phase inversion agent Consumption be 1-4 weight %.

13. according to the preparation method described in claim 4 or 5, wherein, with the total mole number of monomer in described monomer mixture is Benchmark, the content of described monomer E is 10-70 mole of %, and the content of described monomer F is 5-60 mole of %, the content of described monomer G For 5-30 mole of %, the content of described monomer H is 0.001-0.5 mole of %；The condition of described polymerisation makes polymerisation The viscosity average molecular weigh of rear resulting polymers is 5,000,000-1,000 ten thousand.

14. according to the preparation method described in claim 4 or 5, wherein, R₁For H or methyl, R₂、R₅And R₈It is each independently H, R₃For connecting key or methylene, R₆And R₇It is each independently the straight or branched alkyl of H or C1-C5, and R₆And R₇No It is H, R simultaneously₉Straight or branched alkyl for C1-C5；R₁₀、R₁₀’、R₁₁、R₁₂、R₁₁' and R₁₂' it is each independently methyl each Independently be methyl；X^-For Br^-。

15. according to the preparation method described in claim 4 or 5, and wherein, the weight of described monomer mixture mixes with water and monomer The ratio of the gross weight of thing is 0.05-0.5:1.

16. preparation methods according to claim 15, wherein, the weight of described monomer mixture and water and monomer mixture The ratio of gross weight be 0.15-0.4:1.

17. according to the preparation method described in claim 4 or 5, and wherein, described initiator is gone back selected from azo series initiators and oxidation Former series initiators, in described monomer mixture on the basis of the total mole number of monomer, the consumption of described azo series initiators is 0- 10 moles of %, the consumption of described redox series initiators is 0-10 mole of %, and total consumption of described initiator is 0.0001- 10 moles of %；Described azo series initiators is selected from the double [2-(2-of 2,2 '-azo diisobutyl amidine hydrochloride and/or 2,2 '-azo Imidazoline-2-base) propane] dihydrochloride, described redox series initiators includes Oxidizing and Reducing Agents, described oxidant with The mol ratio of described reducing agent is 0.5-3.5:1, and described oxidant is selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and mistake At least one in hydrogen oxide；Described reducing agent is at least one in inorganic reducing agent, rongalite, ascorbic acid and urea, institute Stating inorganic reducing agent is at least in sodium hydrogensulfite, sodium sulfite, sodium thiosulfate, ferrous sulfate and sodium hydrosulfite Kind.

18. according to the preparation method described in claim 4 or 5, and wherein, described polymerisation is carried out in the presence of auxiliary agent, described Auxiliary agent is at least one in chelating agent and other auxiliary agents；On the basis of the total mole number of described monomer mixture, described The consumption of chelating agent is 0-2 mole of %, and the consumption of other auxiliary agents described is 0-2 mole of %, and with single in described monomer mixture On the basis of the total mole number of body, total consumption of described auxiliary agent is 0.0001-4 mole of %；Described chelating agent is selected from ethylenediamine tetraacetic At least one in acetic acid disodium, diethylenetriamine pentaacetic acid, citric acid, citrate and poly-hydroxy acrylic acid, described other help Agent is at least one in urea, sodium formate, isopropanol, DTAB and sodium hypophosphite.

19. preparation methods according to claim 4, wherein, described solution polymerization is carried out in the presence of an inert gas, Polymeric reaction condition includes: temperature is 0-50 DEG C, and the time is 1-24 hour, and pH value is 5-13.

20. preparation methods according to claim 5, wherein, described emulsion polymerization is carried out in the presence of an inert gas, Polymeric reaction condition includes: temperature is 0-50 DEG C, and the time is 1-24 hour, and pH value is 5-13.

21. according to the preparation method described in claim 4 or 19, and wherein, the process of described solution polymerization includes entering successively The three phases of row, the reaction condition of first stage includes: temperature is 0-10 DEG C, and the time is 1-15 hour；Second stage anti- Answering condition to include: temperature is 15-30 DEG C, the time is 3-8 hour；The reaction condition of phase III includes: temperature is 35-50 DEG C, Time is 2-14 hour.

22. according to the preparation method described in claim 5 or 20, and wherein, the process of described emulsion polymerization includes entering successively In two stages of row, the reaction condition of first stage includes: temperature is 0-20 DEG C, and the time is 1-15 hour；Second stage anti- Answering condition to include: temperature is 20-50 DEG C, the time is 2-8 hour.

Acrylamide based copolymer described in any one or by any one in claim 4-22 in 23. claims 1-3 The acrylamide based copolymer that method described in Xiang prepares is as the application of drag reducer.