CN103788293A - Acrylamide series copolymer, preparation method thereof and applications thereof - Google Patents

Acrylamide series copolymer, preparation method thereof and applications thereof Download PDF

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CN103788293A
CN103788293A CN201210422133.9A CN201210422133A CN103788293A CN 103788293 A CN103788293 A CN 103788293A CN 201210422133 A CN201210422133 A CN 201210422133A CN 103788293 A CN103788293 A CN 103788293A
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CN103788293B (en
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杜凯
赵方园
刘希
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract

The invention discloses an acrylamide series copolymer, a preparation method thereof and applications thereof. The acrylamide series copolymer comprises a structure unit A, a structure unit B, a structure unit C and a structure unit D, wherein the structure unit A is a structure unit shown as the formula (1) and/or a structure unit shown as the formula (2); the structure unit B is at least one structural unit shown as the formula (3), the formula (4), the formula (5) and the formula (6); the structure unit C is a structure unit shown as the formula (7) and/or a structure unit shown as the formula (8); the structure unit D is a structure unit shown as the formula (9) and/or a structure unit shown as the formula (10); and the viscosity average molecular weight of the acrylamide series copolymer is two million to eighteen million. The acrylamide series copolymer has high drag reduction efficiency, good heat resistance, good salt resistance, good high-shear resistance, good water solubility, good compatibleness with clay inhibitors (alcohols) and low damage to stratums.

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 and its preparation method and application.
Background technology
Utilize as unconventional petroleum resources Typical Representative---the exploitation of shale gas (oil) resource has become a revolution in global unconventional petroleum resources field, the at present development and utilization of shale gas has become countries in the world and has paid close attention to emphatically and the focus technology of development.Because the ultimate attainment close hydrocarbon-bearing pools such as shale gas reservoir have the advantages that rate of permeation extremely low (being generally less than 0.5mD), frac pressure are high, easily cause formation damage.Must adopt the exploitation of " drag reduction water (slippery water) pressure break " technique.
" drag reduction water (slippery water) pressure break " is the one of waterfrac treatment.Compared with current conventional pressure break system (modifyed guar gum cross-linking system), drag reduction water (slippery water) pressure break is not to rely on high viscosity colloid to take sand, but takes sand with high infusion discharge capacity, realizes the final purpose that reservoir fracturing is reticulated to crack.The more conventional pressure break system of drag reduction water (slippery water) pressure break has in greater advantage less to the injury on stratum on cost.
Drag reduction water fracturing liquid core auxiliary agent is water base friction reducer, in practice of construction, adding of water-based drag reducer overcomes the friction resistance of working fluid in pipeline, guarantee the raising of infusion discharge capacity, pressure acted on to greatest extent press off stratum and extend formation fracture, what can be used as at present water base friction reducer mainly contains guanidine glue and derivative thereof, derivatived cellulose, acrylamide copolymer.
At present, flow improver during employing guanidine glue and derivative, Mierocrystalline cellulose and derivative thereof split as drag reduction hydraulic pressure has improved to a certain extent infusion discharge capacity, has reduced (the US 5697444 of the friction resistance in pipeline, US 5271466), but still cannot meet the requirement that drag reduction hydraulic pressure splits, there is following shortcoming mainly due to above-mentioned biopolymer: (1) resistance-reducing performance is limited; (2) because having a small amount of insolubles, guanidine glue and derivative, Mierocrystalline cellulose and derivative thereof very easily stratum is damaged; (3) dissolution time is longer.
In drag reduction water pressing crack construction, flow improver during many employing acrylamide copolymers (partially hydrolyzed polyacrylamide) split as drag reduction hydraulic pressure, improve to a great extent infusion discharge capacity, reduce the friction resistance in pipeline, but the flow improver splitting as shale gas reservoir drag reduction hydraulic pressure uses, there is following major defect: (1) is in order to reduce " the water-sensitive effect " in fracturing process, suppress the hydration swelling of shale medium clay soil component, help the of the fracturing fluid row of returning to reduce " water blocking ", must in fracturing liquid, add part alcohol, but the compatibleness of partial hydrolysis acrylamide and product emulsion thereof and alcohol is poor, very easily produce precipitation, (2) flow improver that partially hydrolyzed polyacrylamide splits as shale gas reservoir drag reduction hydraulic pressure uses anti-filtration property poor, this kind of drag reduction water fracturing liquid very easily leak-off in the middle of stratum, (3) temperature resistant antisalt is poor, and especially, under high salinity high divalent ion content condition, molecular structure is unstable, and resistance reducing effect declines very fast, (4) acrylamide copolymer of traditional high molecular weight is difficult for degraded, easily extremely fine and close shale formation is caused to permanent type injury.
Patent US 20090298721A1 discloses the of the fracturing fluid formula of a kind of drag reduction water: in 1000 gallons of deionized waters, add 0.5 gallon of acrylic acidcoacrylamide thing (FR-56 tM) etc. anionic acrylamide copolymer emulsion as flow improver, add again the complexing agents such as 0.15wt% sodium carbonate or EDTA-2Na, this drag reduction water fracturing liquid has good resistance-reducing performance, indoor average resistance-reducing yield reaches 65.0%, salt tolerance (the especially tolerance to divalent calcium ion) has been had to improvement to a certain degree, but this kind of drag reduction hydraulic pressure splits system and uses as shale gas drag reduction water fracturing liquid, there are the following problems: the compatibleness of (1) and alcohol is poor, very easily produces precipitation with the alcohol effect such as methyl alcohol; (2) anti-filtration property is poor, this kind of drag reduction water fracturing liquid very easily leak-off in the middle of stratum; (3) in practice of construction, " water-sensitive effect " is remarkable; (4) very easily produce " water blocking "; (5) resistance to high speed shear poor performance, unstable under high speed shear effect, and resistance-reducing yield declines very fast; (6) heat-resistant salt-resistant is poor, and especially, under high salinity high divalent ion content condition, molecular structure is unstable, and resistance reducing effect declines very fast; (7) be difficult for degraded, easily extremely fine and close shale formation caused to permanent type injury, pollute stratum, then affect oil and gas production.
Compared with above-mentioned partially hydrolyzed polyacrylamide, the acrylamide copolymer of cationic high-molecular amount also has report as flow improver (US 356226, US 3868328).US 3868328 discloses a kind of polymkeric substance, and this polymkeric substance contains (3-acrylamido-3-methyl) butyl trimethyl ammonium chloride and/or reductive agent, adds or acid adding not.The compatibleness of this kind of structure copolymer and alcohol is better, better with clay inhibitor (as KCl) consistency, " water-sensitive effect " is not remarkable, is difficult for " water blocking ", but this type of friction reducer macromole is also difficult for degraded, easily extremely fine and close shale formation is caused to permanent type injury.
But how further to improve the resistance to high speed shear performance of flow improver, improve inhibition and the anti-leak-off of fracturing liquid to clay, the stability that improves the drag reducing efficiency under high temperature and high salt shear conditions has degradability simultaneously, reduce the injury of polymkeric substance to stratum, be still a problem of needing solution badly.
Summary of the invention
The object of the invention is to overcome the defect of above-mentioned prior art, provide that a kind of high molecular, drag reducing efficiency are high, good water solubility, have good compatibleness with clay inhibitor, there is degradability, little to formation damage, and the short acrylamide based copolymer of dissolution time, and the preparation method and application of this acrylamide based copolymer.
The inventor is through research, be surprised to find that, polymerizable functional monomer, by the method for copolymerization, is incorporated into and is contained on acrylamide macromolecular chain, obtain the multipolymer of high molecular by controlling polymerizing condition, can improve the drag reducing efficiency under high temperature and high salt shear conditions simultaneously, the compatibleness of raising and clay inhibitor, reduces the generation of water-sensitive and water blocking phenomenon, has degradability, can reduce the injury to stratum, thereby obtain the present invention.
The invention provides a kind of acrylamide based copolymer, wherein, described acrylamide based copolymer contains structural unit A, structural unit B, structural unit C and structural unit D, wherein, described structural unit A is the structural unit shown in the structural unit shown in formula (1) and/or formula (2), described structural unit B is formula (3), formula (4), at least one in structural unit shown in formula (5) and formula (6), described structural unit C is the structural unit shown in the structural unit shown in formula (7) and/or formula (8), described structural unit D is the structural unit shown in the structural unit shown in formula (9) and/or formula (10), and take the total mole number of structural unit in described acrylamide based copolymer as benchmark, the content of described structural unit A is 5-95 % by mole, the content of described structural unit B is 2.5-90 % by mole, the content of described structural unit C is 0.5-90 % by mole, and the content of described structural unit D is 0.0001-1 % by mole, preferably, the content of described structural unit A is 10-70 % by mole, and the content of described structural unit B is 20-50 % by mole, and the content of described structural unit C is 5-40 % by mole, and the content of described structural unit D is 0.001-0.5 % by mole, the viscosity-average molecular weight of described acrylamide based copolymer is 2,000,000-1,800 ten thousand, is preferably 4,000,000-1,500 ten thousand,
Figure BDA00002321758200021
formula (1), formula (2),
Figure BDA00002321758200023
formula (3), formula (4),
Figure BDA00002321758200031
formula (5),
Figure BDA00002321758200032
formula (6),
Figure BDA00002321758200033
formula (7), formula (8),
Figure BDA00002321758200035
formula (9),
Figure BDA00002321758200036
formula (10),
Wherein, R 1, R 4, R 1' and R 4' be the alkylidene group of C1-C4 independently of one another; R 2, R 3, R 2', R 3', R 5, R 6, R 7, R 8, R 9, R 11, R 14, R 15, R 5', R 6', R 7', R 8', R 9', R 11', R 14' and R 15' be the alkyl of C1-C4 independently of one another; R 10, R 12, R 13, R 10', R 12' and R 13' be the straight or branched alkylidene group of C1-C20 independently of one another; M is at least one in H, K and Na; X -for Cl -, Br -, I -, SCN -,
Figure BDA00002321758200037
Figure BDA00002321758200041
The present invention also provides a kind of preparation method of acrylamide based copolymer, this preparation method comprises, under the solution polymerization condition of alkene, under initiator exists, make a kind of monomer mixture in water, carry out polyreaction, wherein, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in the monomer shown in formula (15) and/or formula (16), described monomer F is formula (17), formula (18), at least one in monomer shown in formula (19) and formula (20), described monomer G is the monomer shown in the monomer shown in formula (21) and/or formula (22), described monomer H is the monomer shown in the monomer shown in formula (23) and/or formula (24),
Figure BDA00002321758200042
formula (15),
Figure BDA00002321758200043
formula (16),
formula (17),
Figure BDA00002321758200045
formula (18),
Figure BDA00002321758200046
formula (19),
Figure BDA00002321758200047
formula (20),
Figure BDA00002321758200048
formula (21),
Figure BDA00002321758200049
formula (22),
formula (23),
Figure BDA00002321758200052
formula (24),
Wherein, R 1, R 4, R 1' and R 4' be the alkylidene group of C1-C4 independently of one another; R 2, R 3, R 2', R 3', R 5, R 6, R 7, R 8, R 9, R 11, R 14, R 15, R 5', R 6', R 7', R 8', R 9', R 11', R 14' and R 15' be the alkyl of C1-C4 independently of one another; R 10r 12, R 13, R 10', R 12' and R 13' be the straight or branched alkylidene group of C1-C20 independently of one another; M is at least one in H, K and Na; X -for Cl -, Br -, I -, SCN -,
Figure BDA00002321758200053
In addition, the present invention also provides a kind of preparation method of acrylamide based copolymer, this preparation method comprises water and oil phase is mixed to form to reversed-phase emulsion, then under emulsion polymerization condition, this reversed-phase emulsion is contacted with initiator, described water is the aqueous solution that contains monomer mixture, described oil phase contains oil and emulsifying agent, the condition of contact makes monomer mixture polymerization reaction take place, wherein, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in the monomer shown in above-mentioned formula (15) and/or formula (16), described monomer F is above-mentioned formula (17), formula (18), at least one in monomer shown in formula (19) and formula (20), described monomer G is the monomer shown in the monomer shown in above-mentioned formula (21) and/or formula (22), described monomer H is the monomer shown in the monomer shown in above-mentioned formula (23) and/or formula (24).
In addition, the present invention also provides the acrylamide preparing by aforesaid method based copolymer, and the application of described acrylamide based copolymer in flow improver.
Acrylamide based copolymer of the present invention has high viscosity-average molecular weight, and the viscosity-average molecular weight of the multipolymer making in embodiment 1-6 all can reach more than 4,000,000; Insolubles content in water is only 0.01 % by weight; Be in the NaCl of 2 % by weight, 4 % by weight, 8 % by weight, 10 % by weight, 12 % by weight or KCl solution and in pH value under the condition at 2.5-10 in concentration, drag reducing efficiency all can reach more than 60%; Under the shearing rate of 2500rpm, this polymkeric substance does not produce precipitation at water/alcoholic solution, can dissolve completely; In the time that pH value is less than under 2.5 condition, this polymkeric substance can be degraded, and the injury on stratum is less than to 10%.Illustrate that acrylamide based copolymer of the present invention still has high drag reducing efficiency under high salt, shear conditions, have good consistency with expansion-resisting agent (as KCl), cleanup additive (as methyl alcohol) conventional in fracturing liquid formula, and to the low injury in stratum.In addition, two of acrylamide based copolymer provided by the invention kinds of preparation methods (solution polymerization process and reversed emulsion polymerization) have advantages of easy and monomer conversion is high.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein 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, it is characterized in that, described acrylamide based copolymer contains structural unit A, structural unit B, structural unit C and structural unit D, wherein, described structural unit A is the structural unit shown in the structural unit shown in formula (1) and/or formula (2), described structural unit B is formula (3), formula (4), at least one in structural unit shown in formula (5) and formula (6), described structural unit C is the structural unit shown in the structural unit shown in formula (7) and/or formula (8), described structural unit D is the structural unit shown in the structural unit shown in formula (9) and/or formula (10), and take the total mole number of structural unit in described acrylamide based copolymer as benchmark, the content of described structural unit A is 5-95 % by mole, the content of described structural unit B is 2.5-90 % by mole, the content of described structural unit C is 0.5-90 % by mole, and the content of described structural unit D is 0.0001-1 % by mole, preferably, the content of described structural unit A is 10-70 % by mole, and the content of described structural unit B is 20-50 % by mole, and the content of described structural unit C is 5-40 % by mole, and the content of described structural unit D is 0.001-0.5 % by mole, more preferably, the content of described structural unit A is 50-70 % by mole, and the content of described structural unit B is 20-40 % by mole, and the content of described structural unit C is 5-20 % by mole, and the content of described structural unit D is 0.005-0.2 % by mole, the viscosity-average molecular weight of described acrylamide based copolymer is 2,000,000-1,800 ten thousand, is preferably 4,000,000-1,500 ten thousand,
Figure BDA00002321758200061
formula (1), formula (2),
Figure BDA00002321758200063
formula (3),
Figure BDA00002321758200064
formula (4),
Figure BDA00002321758200065
formula (5),
Figure BDA00002321758200066
formula (6),
Figure BDA00002321758200067
formula (7),
Figure BDA00002321758200068
formula (8),
Figure BDA00002321758200071
formula (9),
Figure BDA00002321758200072
formula (10),
Wherein, R 1and R 1' be the alkylidene group of C1-C4 independently of one another, be preferably methylene radical; R 4and R 4' be the alkylidene group of C1-C4 independently of one another, be preferably sub-n-propyl, more preferably-CH 2cH 2cH 2-; R 2, R 3, R 2', R 3', R 5, R 6, R 7, R 8, R 9, R 11, R 14, R 15, R 5', R 6', R 7', R 8', R 9', R 11', R 14' and R 15' be the alkyl of C1-C4 independently of one another, be preferably methyl; R 10and R 10' be the straight or branched alkylidene group of C1-C20 independently of one another, be preferably the straight or branched alkylidene group of C1-C10, more preferably methylene radical; R 12, R 13, R 12' and R 13' be the straight or branched alkylidene group of C1-C20 independently of one another, be preferably the straight or branched alkylidene group of C1-C3, more preferably ethylidene, most preferably is-CH 2cH 2-; M is at least one in H, K and Na, is preferably H; X -for Cl -, Br -, I -, SCN -,
Figure BDA00002321758200073
be preferably Cl -.
The present inventor finds under study for action, and the quadripolymer being made up of specific structural unit A, structural unit B, structural unit C and structural unit D can be obtained fabulous resistance reducing effect.
For example, described structural unit B is the structural unit shown in the structural unit shown in formula (11) and/or formula (12), and described structural unit C is the structural unit shown in formula (13), and described structural unit D is the structural unit shown in formula (14),
Figure BDA00002321758200074
formula (11),
Figure BDA00002321758200075
formula (12),
Figure BDA00002321758200076
formula (13),
Figure BDA00002321758200081
formula (14),
Wherein, R 1for the alkylidene group of C1-C4, be preferably methylene radical; R 4for the alkylidene group of C1-C4, be preferably sub-n-propyl, more preferably-CH 2cH 2cH 2-; R 10for the straight or branched alkylidene group of C1-C20, be preferably the straight or branched alkylidene group of C1-C10, more preferably methylene radical; R 12' and R 13' be the straight or branched alkylidene group of C1-C20, be preferably the straight or branched alkylidene group of C1-C3, more preferably ethylidene, most preferably is-CH 2cH 2-.
In the present invention, the example of the alkyl of described C1-C4 can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl.
Described alkylidene group refers to that alkane loses two residues after hydrogen atom, and described two hydrogen atoms can be two hydrogen atoms on same carbon atom, two hydrogen atoms on also can different carbon atoms, it can be straight chain, also can be side chain, for example, described ethylidene can be-CH 2cH 2-or-CH (CH 3)-.
In the present invention, described alkylidene group can be straight chain, can be also side chain.The example of the straight or branched alkylidene group of described C1-C20 can include but not limited to: methylene radical, ethylidene, sub-n-propyl, isopropylidene, sub-normal-butyl, sub-sec-butyl, isobutylidene, the sub-tertiary butyl, sub-n-pentyl, isopentylidene, sub-tert-pentyl, sub-neo-pentyl, sub-n-hexyl, sub-n-heptyl, sub-n-octyl, sub-positive decyl, sub-dodecyl, sub-hexadecyl and sub-eicosyl.
(2) solution polymerization process
The present invention also provides a kind of preparation method of acrylamide based copolymer, this preparation method comprises, under the solution polymerization condition of alkene, under initiator exists, make a kind of monomer mixture in water, carry out polyreaction, wherein, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in the monomer shown in formula (15) and/or formula (16), described monomer F is formula (17), formula (18), at least one in monomer shown in formula (19) and formula (20), described monomer G is the monomer shown in the monomer shown in formula (21) and/or formula (22), described monomer H is the monomer shown in the monomer shown in formula (23) and/or formula (24), and take the total mole number of monomer in described monomer mixture as benchmark, the content of described monomer E is 5-95 % by mole, and the content of described monomer F is 2.5-90 % by mole, and the content of described monomer G is 0.5-90 % by mole, and the content of described monomer H is 0.0001-1 % by mole, preferably, the content of described monomer E is 10-70 % by mole, and the content of described monomer F is 20-50 % by mole, and the content of described monomer G is 5-40 % by mole, and the content of described monomer H is 0.001-0.5 % by mole, more preferably, the content of described monomer E is 50-70 % by mole, and the content of described monomer F is 20-40 % by mole, and the content of described monomer G is 5-20 % by mole, and the content of described monomer H is 0.005-0.2 % by mole, it is 2,000,000-1,800 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of resulting polymers after polyreaction, is preferably 4,000,000-15,000,000,
Figure BDA00002321758200082
formula (15),
Figure BDA00002321758200083
formula (16),
Figure BDA00002321758200091
formula (17),
Figure BDA00002321758200092
formula (18),
Figure BDA00002321758200093
formula (19),
Figure BDA00002321758200094
formula (20),
Figure BDA00002321758200095
formula (21),
Figure BDA00002321758200096
formula (22),
formula (23),
Figure BDA00002321758200098
formula (24),
Wherein, R 1and R 1' be the alkylidene group of C1-C4 independently of one another, be preferably methylene radical; R 4and R 4' be the alkylidene group of C1-C4 independently of one another, be preferably sub-n-propyl, more preferably-CH 2cH 2cH 2-; R 2, R 3, R 2', R 3', R 5, R 6, R 7, R 8, R 9, R 11, R 14, R 15, R 5', R 6', R 7', R 8', R 9', R 11', R 14' and R 15' be the alkyl of C1-C4 independently of one another, be preferably methyl; R 10and R 10' be the straight or branched alkylidene group of C1-C20 independently of one another, be preferably the straight or branched alkylidene group of C1-C10, more preferably methylene radical; R 12, R 13, R 12' and R 13' be the straight or branched alkylidene group of C1-C20 independently of one another, be preferably the straight or branched alkylidene group of C1-C3, more preferably ethylidene, most preferably is-CH 2cH 2-; M is at least one in H, K and Na, is preferably H; X -for Cl -, Br -, I -, SCN -,
Figure BDA00002321758200101
be preferably Cl -.
According to the present invention, when described polyreaction starts, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is various ratio known in those skilled in the art, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is preferably 0.05-0.5:1, more preferably 0.15-0.4:1, most preferably is 0.2-0.35:1.
According to the present invention, described initiator can be the various initiators in this area.For example, be selected from azo series initiators and redox series initiators.Take the total mole number of monomer in described monomer mixture as benchmark, the consumption of described azo series initiators is 0-10 % by mole, the consumption of described redox series initiators is 0-10 % by mole, and total consumption of described azo series initiators and redox series initiators preferably meets: total consumption of described initiator 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 is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the two methylpent hydrochlorates, 2 of azo, 2 '-azo diisobutyl amidine hydrochloride and 2, at least one in 2 '-azo two [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride], more preferably 2,2 '-azo diisobutyl amidine hydrochloride and 2, at least one in 2 '-azo two [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride].Described redox series initiators comprises Oxidizing and Reducing Agents, preferably, the mol ratio of described oxygenant and described reductive agent is 0.5-2:1, meet under the condition of aforementioned proportion, the consumption of described oxygenant is preferably the 0.0001-0.01 % by mole of the total mole number of monomer in monomer mixture, more preferably 0.001-0.008 % by mole; Under preferable case, described oxygenant is selected from least one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide, more preferably at least one in ammonium persulphate, Potassium Persulphate and Sodium Persulfate; The consumption of described reductive agent is preferably the 0.0001-0.005 % by mole of the total mole number of monomer in monomer mixture, is preferably the 0.001-0.004 % by mole of the total mole number of monomer in monomer mixture; Described reductive agent can be inorganic reducing agent (helping reductive agent), preferably, described inorganic reducing agent is selected from least one in sodium bisulfite, S-WAT, rongalite, Sulfothiorine, ferrous sulfate, vat powder, xitix and urea, more preferably sodium bisulfite and/or Sulfothiorine.
In the present invention, need to particularly point out ground, described monomer H plays the effect of chainextender and organic reducing agent in polymerization process simultaneously, need in polymerization process, not add again organic reducing agent, this may be that when can participating in polyreaction because of the two key groups in described monomer H, the tertiary amine group of end can participate in redox initiation reaction, produces free radical endways on methyl, then on terminal methyl, continue trigger monomer polymerization, likeness in form " bridge formation ".
In addition, the acrylamide based copolymer provided by the invention over the ground injury of layer reduces, and this may be owing to having ester carbonyl group in this polymkeric substance, easily under acidic conditions, DeR occurs.
According to the present invention, described polyreaction can also be carried out under various auxiliary agents exist, and described auxiliary agent can be selected from sequestrant and/or other auxiliary agents; Take the total mole number of monomer in described monomer mixture as benchmark, the consumption of described sequestrant is 0-2 % by mole, be preferably 0.0001-1 % by mole, more preferably 0.0001-0.05 % by mole, the consumption of described other auxiliary agents can be 0-2 % by mole, be preferably 0.0001-1 % by mole, more preferably 0.0001-0.2 % by mole; Preferably, the consumption of described sequestrant and other auxiliary agents makes: take the total mole number of monomer in described monomer mixture as benchmark, the consumption of described auxiliary agent is 0.0001-4 % by mole.
Described sequestrant can be selected from least one in disodium ethylene diamine tetraacetate (EDTA), Triethylene Diamine pentaacetic acid, citric acid, Citrate trianion and poly-hydroxyl acrylic, more preferably one or more in EDTA, Citrate trianion and Triethylene Diamine pentaacetic acid, described Citrate trianion can be Tripotassium Citrate, Trisodium Citrate, citrate of lime and ammonium citrate etc.
Described other auxiliary agents can be selected from least one in urea, sodium formiate, Virahol and sodium hypophosphite, are preferably urea and/or sodium formiate.
The present inventor's discovery, exists under the condition of above-mentioned various initiator and auxiliary agent at the same time, and solution polymerization process can obtain the acrylamide based copolymer that viscosity-average molecular weight is very high.
According to the present invention, the condition of described polyreaction can be the condition of this area routine.For example, described polyreaction is carried out under rare gas element exists, and described polymeric reaction condition can comprise: temperature is 0-80 ℃, and the time is 1-24 hour, and pH value is 5-13; Under preferable case, temperature is 4-60 ℃, and the time is 4-36 hour, and pH value is 5-9, and described pH value is by adding acid or alkali to regulate, and described acid is preferably mineral acid, and described mineral acid is preferably at least one in hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and phosphoric acid; Described alkali can be mineral alkali or organic amine compound, as being selected from least one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, methylamine, ethamine, thanomin and trolamine, is preferably sodium hydroxide.
The present inventor finds under study for action, take following condition can further improve the molecular weight of polymkeric substance:, preferably, described polyreaction comprises the three phases carrying out successively: the reaction conditions of first stage comprises: temperature is 0-10 ℃, be preferably 4-10 ℃, time is 1-15 hour, is preferably 3-10 hour; The reaction conditions of subordinate phase comprises: temperature is 15-30 ℃, is preferably 20-30 ℃, and the time is 3-8 hour, is preferably 3-5 hour; The reaction conditions of phase III comprises: temperature is 35-60 ℃, is preferably 45-55 ℃, and the time is 2-14 hour, is preferably 2-12 hour.
In addition, the present inventor finds under study for action, in the time selecting specific monomer F, monomer G to react with monomer H, can further improve the resistance reducing effect of the polymkeric substance of gained.For example, preferably, described monomer F is the monomer shown in the monomer shown in formula (25) and/or formula (26), and described monomer G is the monomer shown in formula (27), and described monomer H is the monomer shown in formula (28),
Figure BDA00002321758200111
formula (25),
Figure BDA00002321758200112
formula (26),
Figure BDA00002321758200113
formula (27), formula (28),
Wherein, R 1for the alkylidene group of C1-C4, be preferably methylene radical; R 4for the alkylidene group of C1-C4, be preferably sub-n-propyl, more preferably-CH 2cH 2cH 2-; R 10for the straight or branched alkylidene group of C1-C20, be preferably the straight or branched alkylidene group of C1-C10, more preferably methylene radical; R 12' and R 13' be the straight or branched alkylidene group of C1-C20, be preferably the straight or branched alkylidene group of C1-C3, more preferably ethylidene, most preferably is-CH 2cH 2-.
(3) reversed emulsion polymerization
In addition, the present invention also provides a kind of preparation method of acrylamide based copolymer, this preparation method comprises water and oil phase is mixed to form to reversed-phase emulsion, then under emulsion polymerization condition, this reversed-phase emulsion is contacted with initiator, described water is the aqueous solution that contains monomer mixture, described oil phase contains oil and emulsifying agent, the condition of contact makes monomer mixture polymerization reaction take place, wherein, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in the monomer shown in formula (15) and/or formula (16), described monomer F is formula (17), formula (18), at least one in monomer shown in formula (19) and formula (20), described monomer G is the monomer shown in the monomer shown in formula (21) and/or formula (22), described monomer H is the monomer shown in the monomer shown in formula (23) and/or formula (24), and take the total mole number of monomer in described monomer mixture as benchmark, the content of described monomer E is 5-95 % by mole, and the content of described monomer F is 2.5-90 % by mole, and the content of described monomer G is 0.5-90 % by mole, and the content of described monomer H is 0.0001-1 % by mole, preferably, the content of described monomer E is 10-70 % by mole, and the content of described monomer F is 20-50 % by mole, and the content of described monomer G is 5-40 % by mole, and the content of described monomer H is 0.001-0.5 % by mole, more preferably, the content of described monomer E is 50-70 % by mole, and the content of described monomer F is 20-40 % by mole, and the content of described monomer G is 5-20 % by mole, and the content of described monomer H is 0.005-0.2 % by mole, it is 2,000,000-1,800 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of resulting polymers after polyreaction, is preferably 4,000,000-15,000,000.
The elaboration of monomer and preferable case shown in formula (15)-Shi (24) with describe identically above, do not repeat them here.
According to the present invention, described water is the aqueous solution that contains monomer mixture.Elaboration and the preferable case of the weight of described monomer mixture and the ratio of the gross weight of water and monomer mixture and describe identically above do not repeat herein.
According to the present invention, part by weight to described water and oil phase has no particular limits, as long as make described water and oil phase be thoroughly mixed to form reversed-phase emulsion, under preferable case, the part by weight of described water and oil phase can be 1:0.1-2, more preferably 1:0.3-0.8.
According to the present invention, described oil can be this area various for letex polymerization with the mutual exclusive nonpolar or organic solvent that polarity is little of water, can be for example at least one in toluene, dimethylbenzene, hexane, hexanaphthene, normal heptane, isomery paraffin, isoparaffin, gasoline, kerosene and white oil, under preferable case, at least one in toluene, dimethylbenzene, normal heptane, isoparaffin, hexanaphthene and kerosene of described grease separation.
According to the present invention, described oil phase contains oil and emulsifying agent.The consumption of described oil is not had to special requirement, can in wider scope, change, as long as described oil and emulsifying agent are mixed to form oil phase, under preferable case, take the gross weight of described emulsion as benchmark, the consumption of described oil 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 emulsifier for letex polymerization in this area, for example, can be sorbitan fatty acid ester, alkylphenol polyoxyethylene, isomery polyoxyethylenated alcohol, ethoxylated dodecyl alcohol, propylene glycol fatty acid ester, laureth, benzylphenol oxygen Soxylat A 25-7, styroyl phenol polyethenoxy ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester ethylene oxide adduct, benzyl dimethyl phenol polyethenoxy ether, at least one in fatty alcohol-polyoxyethylene ether and aliphatic amine polyoxyethylene ether, under preferable case, described emulsifying agent is selected from sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, benzylphenol oxygen Soxylat A 25-7, styroyl phenol polyethenoxy ether, isomerous tridecanol polyoxyethylene ether, at least one in ethoxylated dodecyl alcohol and benzyl dimethyl phenol polyethenoxy ether, the compound emulsifying agent that the hydrophile-lipophile balance value being more preferably made up of above-mentioned two or more emulsifying agent is 5-9 can be for example sorbitan fatty acid ester and polyoxyethylene nonylphenol ether.
According to the present invention, consumption to described emulsifying agent is not particularly limited, can in wider scope, change, as long as described emulsifying agent and oil are mixed to form oil phase, under preferable case, take the gross weight of described emulsion as benchmark, the consumption of described emulsifying agent can be 1-10 % by weight, more preferably 2-9 % by weight.
According to the present invention, described initiator can be various initiators in this area, the elaboration of described initiator and preferable case with describe identically above, repeat no more herein.
In the present invention, under preferable case, can first azo series initiators be added to water, then be mixed to form reversed-phase emulsion with oil phase, then reversed-phase emulsion be contacted with redox series initiators, by redox initiator initiated polymerization.
According to the present invention, described polyreaction can also be carried out under various auxiliary agents exist, and described auxiliary agent can be selected from sequestrant and/or other auxiliary agents, the elaboration of described auxiliary agent and preferable case with describe identically above, repeat no more herein.
According to the present invention, to there is no special requirement the reinforced opportunity of described sequestrant, as long as make sequestrant and metal ion generation sequestering action so that multipolymer is played to static stabilization, can be chosen in water adds or adds in oil phase, under preferable case, in order to make the sequestrant effect of playing stably more fully, can be chosen in and in water, add sequestrant.
According to the present invention, the elaboration of described sequestrant and preferable case with describe identically above, repeat no more herein.
Equally, the present inventor finds under study for action, take following condition can further improve the molecular weight of polymkeric substance:, preferably, described polyreaction comprises two stages of carrying out successively: the reaction conditions of first stage comprises: temperature is 0-20 ℃, be preferably 5-10 ℃, the time is 1-15 hour, is preferably 1-5 hour; The reaction conditions of subordinate phase comprises: temperature is 20-60 ℃, is preferably 25-55 ℃, and the time is 2-8 hour, is preferably 2-5 hour.
According to the present invention, the method contacts described polyreaction products therefrom after being also included in described polyreaction with phase inversion agent.Described phase inversion agent can be for this area be for the various phase inversion agent of letex polymerization, as long as described polyreaction products therefrom is dissolved fast in fracturing liquid application in water, it can be for example polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, Ben-zylphenol Polyoxyethyl Ether, styroyl phenol polyethenoxy ether, isomery ten polyoxyethylenated alcohol, isomery undecyl alcohol Soxylat A 25-7, at least one in the nonionic emulsifier of isomerous tridecanol polyoxyethylene ether and aliphatic amine polyoxyethylene ether, under preferable case, described phase inversion agent is selected from polyoxyethylene sorbitan fatty acid ester, isomery ten polyoxyethylenated alcohol, isomery undecyl alcohol Soxylat A 25-7, isomerous tridecanol polyoxyethylene ether, at least one in polyoxyethylene nonylphenol ether and polyoxyethylene octylphenol 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 polyreaction products therefrom dissolve in water fast in fracturing liquid application, the consumption of described phase inversion agent makes: take the gross weight of described emulsion as benchmark, the consumption of described phase inversion agent can be 0.5-10 % by weight, is preferably 1-4 % by weight.
In addition, the present inventor finds under study for action, in the time selecting specific monomer F, monomer G to react with monomer H, can further improve the resistance reducing effect of the polymkeric substance of gained.For example, preferably, described monomer F is the monomer shown in the monomer shown in formula (25) and/or formula (26), described monomer G is the monomer shown in formula (27), described monomer H is the monomer shown in formula (28), the elaboration of monomer and preferable case shown in formula (25)-Shi (28) with describe identically above, do not repeat them here.
The present invention also provides the acrylamide based copolymer making according to above-mentioned two kinds of methods.
In addition, the present invention also provides the application of described acrylamide based copolymer in flow improver.Adopt described acrylamide based copolymer provided by the invention as fracturing liquid flow improver, can obtain high and stable drag reducing efficiency, the technology that concrete application method is well known to those skilled in the art.
By the following examples the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
Intrinsic viscosity is measured according to GB12005.1-89 polyacrylamide For Intrinsic Viscosity Measurements method; Viscosity-average molecular weight is according to formula M v([η]/K) 1 α, wherein K=4.5 × 10 -3, calculate α=0.80; Dissolution time is measured by GB12500.8-89, and (sample quality is all by straight polymer quality in sample), the powdered samples dissolution time recording is all less than 20min, and samples of latex dissolution time is all less than 5min; The composition of molecular structure and structural unit adopt IR spectrum and 13c-NMR measures; Water insoluble matter content is pressed SY/T 5862-1993 and is measured; Indoor drag reducing efficiency is pressed SY/T 6376-2008 and is measured; Friction reducer carries out rock core matrix permeability infringement experiment by fracturing liquid filtrate in oil and gas industry standard SY/T 5107-2005 " aqueous fracturing fluid method of evaluating performance " the nocuity of rock core.
Monomer M 3 shown in monomer M 1 shown in following embodiment Chinese style (29) and formula (33) is all purchased from Sigma-Aldrich company, and in addition, unless specified otherwise, polymkeric substance and the reagent etc. of using in embodiment, comparative example and test case is all 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 M2 monomer shown in monomer M 1, the diacetone-acryloamide(DAA) of 5.98g and the formula of 0.41g (30) shown in the formula (29) of the acrylamide of 36.8g (AM), 37.6g (according to document Macromolecular Bioscience, 2006,6 (7), the method of 540-554 makes, below identical) join in reaction flask, add deionized water 149.28g, stirring is dissolved monomer completely, and stirs.Respectively to the EDTA aqueous solution 17.94g that adds 1 % by weight in flask, 1 % by weight 2,2 '-azo diisobutyl amidine hydrochloride aqueous solution 2.1g, urea 0.12g, fully stirs it is mixed.With the sodium hydroxide solution pH to 7.5 of 1 % by weight, add 0.5 % by weight sodium sulfite solution 0.62g, hierarchy of control initial temperature to 4 ℃, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight ammonium persulfate aqueous solution 0.62g, and continues letting nitrogen in and deoxidizing 20 minutes.Reactor is airtight, remain on 4 ℃, react after 8 hours, after being risen to 20 ℃, temperature reacts 5 hours, then temperature is risen to 50 ℃ of reactions 2 hours, the gluey product obtaining is taken out, through granulation, dry, pulverize and can obtain high molecular weight acrylamide based copolymer P1.
P1 is carried out to IR spectrometry, in IR spectrum, 1660cm -1and 1635cm -1there is respectively belonging to amide Ⅰ absorption peak (C=O stretching vibration) and the acid amides II band absorption peak (N-H flexural vibration) of amide group in place, at 1546cm -1, 1449cm -1, 1364cm -1there is diacetone-acryloamide(DAA) C=O absorption peak in place, at 1430cm -1there is the stretching vibration absorption peak of C-N, 1729cm in place -1there is the feature stretching vibration peak of M2 monomeric ester carbonyl, 1356 and 1401cm -1there is typical methyl symmetric curvature vibration absorption peak, 2792cm -1for the methyl C-H asymmetrical stretching vibration absorption peak of quaternary ammonium group.Can determine that the copolymer molecule obtaining has the structure shown in formula (31), recording its viscosity-average molecular weight Mv by viscosity method is 8,000,000, and monomer conversion is more than 99.9%.Wherein, formula (31) and x 1, x 2, y 1, y 2, z 1, z 2only express type and the number of structural unit with u, and do not represent the mode of connection of structural unit.X 1, x 2, y 1, y 2, z 1, z 2determined by charging capacity with the concrete numerical value of u, the composition of molecular structural formula and structural unit adopts quantitatively 13c composes mensuration, obtains (x 1+ x 2): (y 1+ y 2): (z 1+ z 2): u=1:0.38:0.07:0.003.
formula (29),
Figure BDA00002321758200142
formula (30),
Comparative example 1
Prepare acrylamide based copolymer according to the method for embodiment 1, different, do not add diacetone-acryloamide(DAA) and M2 monomer, thereby obtain multipolymer DP1, record its viscosity-average molecular weight M vbe 1,010 ten thousand.
Comparative example 2
Prepare acrylamide based copolymer according to the method for embodiment 1, different is, acrylamide is carried out to polyreaction with (3-acrylamido-3-methyl) butyl trimethyl ammonium chloride of identical mole number, thereby obtain copolymer DP2, record its viscosity-average molecular weight M vbe 1,180 ten thousand.
Figure BDA00002321758200151
formula (31).
Embodiment 2
The present embodiment is used for illustrating that solution polymerization process provided by the invention prepares acrylamide based copolymer.
Under room temperature, M2 monomer shown in monomer M 1 shown in the formula of the Methacrylamide of 38.60g, 74.07g (29), the diacetone-acryloamide(DAA) of 15.6g and the formula of 0.01g (30) is added in polymerization bottle, add 346.8g deionized water, stir monomer is dissolved completely.To the sodium citrate aqueous solution 0.24g that adds 0.1 % by weight in flask, add 1 % by weight 2.2 '-azo diisobutyl amidine hydrochloride aqueous solution 2.13g respectively, add urea 0.08g, fully stir it is mixed.With the sodium hydroxide solution pH to 8 of 1 % by weight, add 0.1 % by weight sodium sulfite solution 2.53g, hierarchy of control initial temperature to 10 ℃, logical nitrogen deoxygenation, after 30 minutes, adds 1% ammonium persulfate aqueous solution 1g and continues letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, remain on 10 ℃, react after 3 hours, be warming up to 30 ℃, react after 3 hours, be warming up to 55 ℃ of reactions 7 hours, the gluey product obtaining is taken out, through granulation, dry, pulverize the acrylamide copolymer p 2 that can obtain high molecular.
P2 is carried out to IR spectrometry, 1660cm in IR spectrum -1and 1635cm -1there is respectively belonging to amide Ⅰ absorption peak (C=O stretching vibration) and the acid amides II band absorption peak (N-H flexural vibration) of amide group in place, at 1546cm -1, 1449cm -1, 1364cm -1there is diacetone-acryloamide(DAA) C=O absorption peak in place, at 1430cm -1there is the stretching vibration absorption peak of C-N, 1729cm in place -1there is the feature stretching vibration peak of M2 monomeric ester carbonyl, 2923,2852cm -1the belong to respectively-CH that locates out peak 2-,-CH 3c-H stretching vibration, 2792cm -1for the methyl C-H asymmetrical stretching vibration absorption peak of quaternary ammonium group.1467cm -1belong to-the CH that goes out peak 2-,-CH 3c-H flexural vibration.Can determine that the copolymer molecule obtaining has the structure shown in formula (32), recording its viscosity-average molecular weight Mv by viscosity method is 1,320 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (32) and x 1, x 2, y 1, y 2, z 1, z 2only express type and the number of structural unit with u, and do not represent the mode of connection of structural unit.X 1, x 2, y 1, y 2, z 1, z 2determined by charging capacity with the concrete numerical value of u, the composition of molecular structural formula and structural unit adopts quantitatively 13c composes mensuration, obtains (x 1+ x 2): (y 1+ y 2): (z 1+ z 2): u=1:0.79:0.20:0.0001.
Figure BDA00002321758200161
formula (32).
Embodiment 3
The present embodiment is used for illustrating that solution polymerization process provided by the invention prepares acrylamide based copolymer.
Under room temperature, by the acrylamide of 38.38g (AM), the M2 monomer shown in the monomer M 3 shown in the formula (33) of 37.31g, the diacetone-acryloamide(DAA) of 30.46g and the formula of 0.21g (30) joins in reaction flask, adds deionized water 424.6g, stirring is dissolved monomer completely, and stirs.Respectively to the EDTA aqueous solution 10.03g that adds 1 % by weight in flask, 1 % by weight 2.2 '-azo diisobutyl amidine hydrochloride aqueous solution 4.87g, urea 0.03g, fully stirs it is mixed.PH is adjusted to 7.5 with solid sodium hydroxide.Add 0.5 % by weight sodium sulfite solution 1.1g, hierarchy of control initial temperature to 8 ℃, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight ammonium persulfate aqueous solution 1.1g, and continues letting nitrogen in and deoxidizing 20 minutes.Reactor is airtight, remain on 8 ℃, react after 10 hours, after being risen to 20 ℃, temperature reacts 4 hours, then temperature is risen to 45 ℃ of reactions 12 hours, the gluey product obtaining is taken out, through granulation, dry, pulverize and can obtain high molecular weight acrylamide based copolymer P3.
P3 is carried out to IR spectrometry, in IR spectrum, 1660cm -1and 1635cm -1there is respectively belonging to amide Ⅰ absorption peak (C=O stretching vibration) and the acid amides II band absorption peak (N-H flexural vibration) of amide group in place, at 1546cm -1, 1449cm -1, 1364cm -1there is diacetone-acryloamide(DAA) C=O absorption peak in place, at 1430cm -1there is the stretching vibration absorption peak of C-N in place, at 1040cm -1there is the stretching vibration absorption peak of O-S in place, at 601cm -1there is the stretching vibration absorption peak of C-S, 1729cm in place -1there is the feature stretching vibration peak of M2 monomeric ester carbonyl.Can determine that the copolymer molecule obtaining has the structure shown in formula (34), recording its viscosity-average molecular weight Mv by viscosity method is 1,420 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (34) and x 1, x 2, y 1, y 2, z 1, z 2only express type and the number of structural unit with u, and do not represent the mode of connection of structural unit.X 1, x 2, y 1, y 2, z 1, z 2determined by charging capacity with the concrete numerical value of u, the composition of molecular structural formula and structural unit adopts quantitatively 13c composes mensuration, obtains (x 1+ x 2): (y 1+ y 2): (z 1+ z 2): u=1:0.33:0.33:0.002.
Figure BDA00002321758200171
formula (33),
Figure BDA00002321758200172
formula (34).
Embodiment 4
The present embodiment is used for illustrating that emulsion polymerization provided by the invention prepares acrylamide based copolymer.
(1) by the Methacrylamide of 40.85g, M2 monomer shown in monomer M 3 shown in the formula (33) of 33.16g, the diacetone-acryloamide(DAA) of 27.07g and the formula of 0.21g (30) joins in configuration bottle, add 187.72g deionized water, stirring is dissolved monomer completely, respectively to the EDTA aqueous solution 14.61g that adds 1 quality % in flask, add 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 1.03g, add urea 0.09g, fully stir it is mixed, pH is adjusted to 7.1 with solid sodium hydroxide, obtains water.
(2) by sorbitan fatty acid ester (span60, Sigma-Aldrich company, identical below) 10.66g, alkylphenol polyoxyethylene (Igepal CA720, Sigma-Aldrich company, identical below) 6.67g, 127.07g kerosene be mixed into oil phase, and all joins in oil phase obtaining water in step (1), and mix and form reversed-phase emulsion and join in reactor by high speed.
(3) 5 ℃ of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight aqueous solution of sodium bisulfite 0.7g, then adds 1 % by weight ammonium persulfate aqueous solution 1.0g and continue letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, remain on 5 ℃, react after 5 hours, be warming up to 55 ℃, react 2 hours.After question response temperature cool to room temperature, add 4.45g polyoxyethylene nonylphenol ether (Sigma-Aldrich company, below identical), obtain emulsion form product with 80 order filter-cloth filterings.After using acetone and methanol mixed solvent deposition out reversed-phase emulsion product, can obtain the acrylamide copolymer p 4 of high molecular.
P4 is carried out to IR spectrometry, 1660cm in IR spectrum -1and 1635cm -1there is respectively belonging to amide Ⅰ absorption peak (C=O stretching vibration) and the acid amides II band absorption peak (N-H flexural vibration) of amide group in place, at 1546cm -1, 1449cm -1, 1364cm -1there is diacetone-acryloamide(DAA) C=O absorption peak in place, at 1430cm -1there is the stretching vibration absorption peak of C-N, 1729cm in place -1there is the feature stretching vibration peak of M2 monomeric ester carbonyl, at 1040cm -1there is the stretching vibration absorption peak of O-S in place, at 601cm -1there is the stretching vibration absorption peak of C-S, 2936cm in place -1appearance-CH 3absorption peak.Can determine that the copolymer molecule obtaining has the structure shown in formula (35), recording its viscosity-average molecular weight Mv by viscosity method is 1,345 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (35) and x 1, x 2, y 1, y 2, z 1, z 2only express type and the number of structural unit with u, and do not represent the mode of connection of structural unit.X 1, x 2, y 1, y 2, z 1, z 2determined by charging capacity with the concrete numerical value of u, the composition of molecular structural formula and structural unit adopts quantitatively 13c composes mensuration, obtains x 1, x 2, y 1, y 2, z 1, z 2and u=1:0.33:0.33:0.002.
Figure BDA00002321758200181
formula (35).
Comparative example 3
Prepare acrylamide based copolymer according to the method for embodiment 4, different, do not add diacetone-acryloamide(DAA) and M2 monomer, thereby obtain multipolymer DP3, record its viscosity-average molecular weight M vbe 1,050 ten thousand.
Comparative example 4
Prepare acrylamide based copolymer according to the method for embodiment 4, different is, Methacrylamide is carried out to polyreaction with (3-acrylamido-3-methyl) butyl trimethyl ammonium chloride of identical mole number, thereby obtain copolymer DP4, record its viscosity-average molecular weight M vbe 1,140 ten thousand.
Embodiment 5
The present embodiment is used for illustrating that emulsion polymerization provided by the invention prepares acrylamide based copolymer.
(1) by the Methacrylamide of 41.70g, M2 monomer shown in monomer M 1 shown in the formula (29) of 36.17g, the diacetone-acryloamide(DAA) of 5.92g and the formula of 0.008g (30) joins in configuration bottle, add 335.19g deionized water, stirring is dissolved monomer completely, respectively to the EDTA aqueous solution 7.83g that adds 1 quality % in flask, add 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 2.03g, add urea 0.10g, fully stir it is mixed, with the sodium hydroxide solution pH to 7.1 of 1 % by weight, obtain water.
(2) by sorbitan fatty acid ester (span60) 30.22g, alkylphenol polyoxyethylene (Igepal CA720) 30g, 263.96g kerosene is mixed into oil phase, and the water obtaining in step (1) is all joined in oil phase, mix formation reversed-phase emulsion by high speed and join in reactor.
(3) 10 ℃ of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight aqueous solution of sodium bisulfite 0.73g, then adds 1 % by weight ammonium persulfate aqueous solution 1.3g and continue letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, remain on 10 ℃, react after 1 hour, be warming up to 25 ℃, react 5 hours.After question response temperature cool to room temperature, add 30.16g polyoxyethylene nonylphenol ether, obtain emulsion form product with 100 order filter-cloth filterings.After using acetone and methanol mixed solvent deposition out reversed-phase emulsion product, can obtain the acrylamide copolymer p 5 of high molecular.
P5 is carried out to IR spectrometry, 1660cm in IR spectrum -1and 1635cm -1there is respectively belonging to amide Ⅰ absorption peak (C=O stretching vibration) and the acid amides II band absorption peak (N-H flexural vibration) of amide group in place, at 1546cm -1, 1449cm -1, 1364cm -1there is diacetone-acryloamide(DAA) C=O absorption peak in place, at 1430cm -1there is the stretching vibration absorption peak of C-N, 1729cm in place -1there is the feature stretching vibration peak of M2 monomeric ester carbonyl, 2792cm -1for the methyl C-H asymmetrical stretching vibration absorption peak of quaternary ammonium group, 2923,2852cm -1the belong to respectively-CH that locates out peak 2-,-CH 3c-H stretching vibration, 1467cm -1belong to-the CH that goes out peak 2-,-CH 3c-H flexural vibration.Can determine that the copolymer molecule obtaining has the structure shown in formula (36), recording its viscosity-average molecular weight Mv by viscosity method is 1,380 ten thousand, and monomer conversion is more than 99.9%.Wherein, formula (36) and x 1, x 2, y 1, y 2, z 1, z 2only express type and the number of structural unit with u, and do not represent the mode of connection of structural unit.X 1, x 2, y 1, y 2, z 1, z 2determined by charging capacity with the concrete numerical value of u, the composition of molecular structural formula and structural unit adopts quantitatively 13c composes mensuration, obtains (x 1+ x 2): (y 1+ y 2): (z 1+ z 2): u=1:0.36:0.07:0.0001.
Embodiment 6
The present embodiment is used for illustrating that emulsion polymerization provided by the invention prepares acrylamide based copolymer.
(1) by the AM of 33.76g, M2 monomer shown in monomer M 1 shown in the formula (29) of 78.55g and the diacetone-acryloamide(DAA) of 16.07g and the formula of 0.5g (30) joins in configuration bottle, add 385.14g deionized water, stirring is dissolved monomer completely, respectively to the EDTA aqueous solution 8.5g that adds 1 quality % in flask, add 1 % by weight azo diisobutyl amidine hydrochloride aqueous solution 2.1g, add urea 0.08g, fully stir it is mixed, with the sodium hydroxide solution pH to 7.1 of 1 % by weight, obtain water.
(2) by sorbitan fatty acid ester (span60) 10.54g, alkylphenol polyoxyethylene (Igepal CA720) 10g, 133.52g kerosene is mixed into oil phase, and the water obtaining in step (1) is all joined in oil phase, mix formation reversed-phase emulsion by high speed and join in reactor.
(3) 8 ℃ of hierarchy of control initial temperatures, logical nitrogen deoxygenation, after 30 minutes, adds 1 % by weight aqueous solution of sodium bisulfite 0.98g, then adds 1 % by weight ammonium persulfate aqueous solution 1.3g and continue letting nitrogen in and deoxidizing 10 minutes.Reactor is airtight, remain on 8 ℃, react after 3 hours, be warming up to 40 ℃, react 4 hours.After question response temperature cool to room temperature, add 13.35g polyoxyethylene nonylphenol ether, obtain emulsion form product with 80 order filter-cloth filterings.After using acetone and methanol mixed solvent deposition out reversed-phase emulsion product, can obtain the acrylamide copolymer p 6 of high molecular.
P6 is carried out to IR spectrometry, 1660cm in IR spectrum -1and 1635cm -1there is respectively belonging to amide Ⅰ absorption peak (C=O stretching vibration) and the acid amides II band absorption peak (N-H flexural vibration) of amide group in place, at 1546cm -1, 1449cm -1, 1364cm -1there is diacetone-acryloamide(DAA) C=O absorption peak in place, at 1430cm -1there is the stretching vibration absorption peak of C-N, 1729cm in place -1there is the feature stretching vibration peak of M2 monomeric ester carbonyl, 2792cm -1for the methyl C-H asymmetrical stretching vibration absorption peak of quaternary ammonium group.Can determine that the copolymer molecule obtaining has the structure shown in formula (37), recording its viscosity-average molecular weight Mv by viscosity method is 7,600,000, and monomer conversion is more than 99.9%.Wherein, formula (37) and x 1, x 2, y 1, y 2, z 1, z 2only express type and the number of structural unit with u, and do not represent the mode of connection of structural unit.X 1, x 2, y 1, y 2, z 1, z 2determined by charging capacity with the concrete numerical value of u, the composition of molecular structural formula and structural unit adopts quantitatively 13c composes mensuration, obtains (x 1+ x 2): (y 1+ y 2): (z 1+ z 2): u=1:0.8:0.2:0.005.
Figure BDA00002321758200201
formula (36).
Figure BDA00002321758200202
formula (37).
Test case 1
Water-insoluble is to measure according to the method stipulating in SY/T 5862-1993.By P1-P6, DP1-DP4 and hydroxypropyl guar gum (JXY wellfracturing hydroxypropyl melon rubber powder, Shandong Ju Xin Chemical Co., Ltd., below identical) carry out water-soluble mensuration, result is as shown in table 1.
Table 1
Figure BDA00002321758200211
As can be seen from the above table, in acrylamide copolymer p 1-P6 prepared by two kinds of methods provided by the invention, water-insoluble is starkly lower than the conventional hydroxypropyl guar gum that cooks flow improver in site operation, this illustrates compared with hydroxypropyl guar gum, uses P1-P6 provided by the invention low to the injury on stratum as shale gas pressure break flow improver.
Test case 2
Under 2500rpm shearing rate, respectively by P1-P6, DP1-DP4 and partially hydrolyzed polyacrylamide (HPAM, Zibo Tian Jian Chemical Co., Ltd., trade mark TJY-1, viscosity-average molecular weight are 1000-1300 ten thousand, lower with) slowly to join respectively separately volume ratio be in water/alcoholic solution (using methyl alcohol in this test case) of 80/20 and 60/40, the consumption of P1-P6, DP1-DP4 and partially hydrolyzed polyacrylamide is 0.01 % by weight (sample quality is by straight polymer quality in sample) of water/alcoholic solution, dissolution time is 30min, and result is as shown in table 2.
Table 2
Figure BDA00002321758200212
As can be seen from Table 2, acrylamide copolymer p 1-P6 prepared by two kinds of methods provided by the invention is as shale gas pressure break flow improver, compared with partially hydrolyzed polyacrylamide, good with the compatibleness of alcohol.
Test case 3
Be under the condition of 25 ℃ in temperature, by P1-P6, DP1-DP4, HPAM and hydroxypropyl guar gum are dissolved in respectively pure water and concentration is 2 % by weight, 4 % by weight, 8 % by weight, 10 % by weight, in the NaCl of 12 % by weight or KCl solution, the 500mg/L being mixed with and the solution of 1000mg/L (sample quality is by straight polymer quality in sample), then on GLM-1 pipeline frictional resistance determinator, measure the drag reducing efficiency of above-mentioned solution according to the method stipulating in SY/T 6376-2008, (test condition: the internal diameter of test section pipeline is 8mm, the length of test section pipeline is 9m, infusion discharge capacity is 30L/min) result is as shown in Table 3 and Table 4.
Table 3
Figure BDA00002321758200222
Figure BDA00002321758200231
Table 4
Figure BDA00002321758200241
From table 3 and table 4, can find out, acrylamide copolymer p 1-P6 prepared by two kinds of methods provided by the invention, as shale gas pressure break flow improver, compares with hydroxypropyl guar gum, HPAM and DP1-DP4, with clay inhibitor (as, KCl) compatibleness is good, anti-salt property excellence.
Test case 4
Drag reducing efficiency is to measure according to the method stipulating in SY/T 6376-2008.P1-P6, DP1-DP4 are dissolved in respectively to pure water, are mixed with the solution (sample quality is by straight polymer quality in sample) of 500mg/L, by adding HCl or NaOH, the pH value of regulation system changes between 2.5-10, and result is as shown in table 5.
Table 5
Figure BDA00002321758200252
As can be seen from Table 5, the acrylamide copolymer p 1-P6 that prepared by two kinds of methods provided by the invention has good resistance reducing effect as shale gas pressure break flow improver within the scope of very large pH value.
Test case 5
Friction reducer carries out rock core matrix permeability infringement experiment by fracturing liquid filtrate in oil and gas industry standard SY/T 5107-2005 " aqueous fracturing fluid method of evaluating performance " the nocuity of rock core, on American core company formation injury tester (model is FDS-800), test, the matrix permeability of rock core is 2md.
P1-P6, DP1-DP4 are dissolved in respectively to pure water, be mixed with the solution (sample quality is by straight polymer quality in sample) of 1000mg/L, by adding HCl, the pH value of regulator solution is 2, at upper its nocuity to rock core of testing of American core company formation injury tester (model is FDS-800), result is as shown in table 6.
Table 6
Figure BDA00002321758200261
As can be seen from the above table, acrylamide copolymer p 1-P6 prepared by two kinds of methods provided by the invention is starkly lower than the conventional comparative sample of cooking flow improver in site operation for the injury of rock core, and this explanation is used P1-P6 low to the injury on stratum with flow improver as shale gas pressure break.
The explanation of above-mentioned test result, acrylamide based copolymer provided by the invention has good water-soluble, low to the injury on stratum; And can be dissolved in completely in water-alcohol solution, good with the compatibleness of alcohol; Owing to improving with the compatibleness of alcohol and clay inhibitor (NaCl or KCl), improve anti-filtration property; And still there is high drag reducing efficiency under high salt, wider pH value condition; There is degradability, be less than 2.5 o'clock degradables in pH value, low to the injury on stratum.In addition, the preparation method of acrylamide based copolymer provided by the invention has advantages of easy and monomer conversion is high.

Claims (18)

1. an acrylamide based copolymer, it is characterized in that, described acrylamide based copolymer contains structural unit A, structural unit B, structural unit C and structural unit D, wherein, described structural unit A is the structural unit shown in the structural unit shown in formula (1) and/or formula (2), described structural unit B is formula (3), formula (4), at least one in structural unit shown in formula (5) and formula (6), described structural unit C is the structural unit shown in the structural unit shown in formula (7) and/or formula (8), described structural unit D is the structural unit shown in the structural unit shown in formula (9) and/or formula (10), and take the total mole number of structural unit in described acrylamide based copolymer as benchmark, the content of described structural unit A is 5-95 % by mole, the content of described structural unit B is 2.5-90 % by mole, the content of described structural unit C is 0.5-90 % by mole, and the content of described structural unit D is 0.0001-1 % by mole, preferably, the content of described structural unit A is 10-70 % by mole, and the content of described structural unit B is 20-50 % by mole, and the content of described structural unit C is 5-40 % by mole, and the content of described structural unit D is 0.001-0.5 % by mole, the viscosity-average molecular weight of described acrylamide based copolymer is 2,000,000-1,800 ten thousand, is preferably 4,000,000-1,500 ten thousand,
formula (1), formula (2),
Figure FDA00002321758100013
formula (3),
Figure FDA00002321758100014
formula (4),
Figure FDA00002321758100015
formula (5),
formula (6),
Figure FDA00002321758100017
formula (7),
Figure FDA00002321758100018
formula (8),
Figure FDA00002321758100021
formula (9),
Figure FDA00002321758100022
formula (10),
Wherein, R 1, R 4, R 1' and R 4' be the alkylidene group of C1-C4 independently of one another; R 2, R 3, R 2', R 3', R 5, R 6, R 7, R 8, R 9, R 11, R 14, R 15, R 5', R 6', R 7', R 8', R 9', R 11', R 14' and R 15' be the alkyl of C1-C4 independently of one another; R 10, R 12, R 13, R 10', R 12' and R 13' be the straight or branched alkylidene group of C1-C20 independently of one another; M is at least one in H, K and Na; X -for Cl -, Br -, I -, SCN -,
Figure FDA00002321758100023
Figure FDA00002321758100024
2. acrylamide based copolymer according to claim 1, wherein, described structural unit B is the structural unit shown in the structural unit shown in formula (11) and/or formula (12), described structural unit C is the structural unit shown in formula (13), described structural unit D is the structural unit shown in formula (14)
formula (11),
Figure FDA00002321758100026
formula (12),
Figure FDA00002321758100027
formula (13),
Figure FDA00002321758100031
formula (14),
Wherein, R 1and R 4for the alkylidene group of C1-C4; R 10, R 12' and R 13' be the straight or branched alkylidene group of C1-C20.
3. the preparation method of an acrylamide based copolymer, this preparation method comprises, under the solution polymerization condition of alkene, under initiator exists, make a kind of monomer mixture in water, carry out polyreaction, it is characterized in that, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in the monomer shown in formula (15) and/or formula (16), described monomer F is formula (17), formula (18), at least one in monomer shown in formula (19) and formula (20), described monomer G is the monomer shown in the monomer shown in formula (21) and/or formula (22), described monomer H is the monomer shown in the monomer shown in formula (23) and/or formula (24),
Figure FDA00002321758100032
formula (15),
Figure FDA00002321758100033
formula (16),
Figure FDA00002321758100034
formula (17), formula (18),
Figure FDA00002321758100036
formula (19),
Figure FDA00002321758100041
formula (20),
Figure FDA00002321758100042
formula (21),
Figure FDA00002321758100043
formula (22),
Figure FDA00002321758100044
formula (23),
Figure FDA00002321758100045
formula (24),
Wherein, R 1, R 4, R 1' and R 4' be the alkylidene group of C1-C4 independently of one another; R 2, R 3, R 2', R 3', R 5, R 6, R 7, R 8, R 9, R 11, R 14, R 15, R 5', R 6', R 7', R 8', R 9', R 11', R 14' and R 15' be the alkyl of C1-C4 independently of one another; R 10r 12, R 13, R 10', R 12' and R 13' be the straight or branched alkylidene group of C1-C20 independently of one another; M is at least one in H, K and Na; X-is Cl -, Br -, I -, SCN -,
Figure FDA00002321758100046
4. the preparation method of an acrylamide based copolymer, this preparation method comprises water and oil phase is mixed to form to reversed-phase emulsion, then under emulsion polymerization condition, this reversed-phase emulsion is contacted with initiator, described water is the aqueous solution that contains monomer mixture, described oil phase contains oil and emulsifying agent, the condition of contact makes monomer mixture polymerization reaction take place, wherein, described monomer mixture contains monomer E, monomer F, monomer G and monomer H, described monomer E is the monomer shown in the monomer shown in formula described in claim 3 (15) and/or formula (16), described monomer F is formula described in claim 3 (17), formula (18), at least one in monomer shown in formula (19) and formula (20), described monomer G is the monomer shown in the monomer shown in formula described in claim 3 (21) and/or formula (22), described monomer H is the monomer shown in the monomer shown in formula described in claim 3 (23) and/or formula (24).
5. preparation method according to claim 4, wherein, the weight ratio of described water and oil phase is 1:0.1-2, is preferably 1:0.3-0.8.
6. preparation method according to claim 4, wherein, take the gross weight of described emulsion as benchmark, the consumption of described oil is 10-60 % by weight, and the consumption of described emulsifying agent is 1-10 % by weight, preferably, the consumption of described oil is 20-35 % by weight, and the consumption of described emulsifying agent is 2-9 % by weight.
7. preparation method according to claim 4, wherein, the method contacts described polyreaction products therefrom after being also included in described polyreaction with phase inversion agent.
8. preparation method according to claim 7, wherein, take the gross weight of described emulsion as benchmark, the consumption of described phase inversion agent is 0.5-10 % by weight, is preferably 1-4 % by weight.
9. according to the preparation method described in claim 3 or 4, wherein, take the total mole number of monomer in described monomer mixture as benchmark, the content of described monomer E is 5-95 % by mole, the content of described monomer F is 2.5-90 % by mole, the content of described monomer G is 0.5-90 % by mole, and the content of described monomer H is 0.0001-1 % by mole; Preferably, the content of described monomer E is 10-70 % by mole, and the content of described monomer F is 20-50 % by mole, and the content of described monomer G is 5-40 % by mole, and the content of described monomer H is 0.001-0.5 % by mole; It is 2,000,000-1,800 ten thousand that the condition of described polyreaction makes the viscosity-average molecular weight of resulting polymers after polyreaction, is preferably 4,000,000-15,000,000
10. according to the preparation method described in claim 3 or 4, wherein, described monomer F is the monomer shown in the monomer shown in formula (25) and/or formula (26), and described monomer G is the monomer shown in formula (27), and described monomer H is the monomer shown in formula (28),
Figure FDA00002321758100051
formula (25),
Figure FDA00002321758100052
formula (26),
Figure FDA00002321758100053
formula (27),
Figure FDA00002321758100054
formula (28),
Wherein, R 1and R 4for the alkylidene group of C1-C4; R 10, R 12' and R 13' be the straight or branched alkylidene group of C1-C20.
11. according to the preparation method described in claim 3 or 4, and wherein, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.05-0.5:1, is preferably 0.15-0.4:1.
12. according to the preparation method described in claim 3 or 4, wherein, described initiator is selected from azo series initiators and redox series initiators, take the total mole number of monomer in described monomer mixture as benchmark, the consumption of described azo series initiators is 0-10 % by mole, the consumption of described redox series initiators is 0-10 % by mole, and total consumption of described initiator is 0.001-10 % by mole; Described azo series initiators is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the two methylpent hydrochlorates, 2 of azo, 2 '-azo diisobutyl amidine hydrochloride and 2, at least one in 2 '-azo two [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride], described redox series initiators comprises Oxidizing and Reducing Agents, the mol ratio of described oxygenant and described reductive agent is 0.5-2:1, and described oxygenant is selected from least one in ammonium persulphate, Potassium Persulphate, Sodium Persulfate and hydrogen peroxide; Described reductive agent is inorganic reducing agent, and described inorganic reducing agent is selected from least one in sodium bisulfite, S-WAT, rongalite, Sulfothiorine, ferrous sulfate, vat powder, xitix and urea.
13. according to the preparation method described in claim 3 or 4, and wherein, described polyreaction is carried out under auxiliary agent exists, and described auxiliary agent is selected from least one in sequestrant and other auxiliary agents; Take the total mole number of described monomer mixture as benchmark, the consumption of described sequestrant is 0-2 % by mole, the consumption of described other auxiliary agents is 0-2 % by mole, and take the total mole number of monomer in described monomer mixture as benchmark, total consumption of described auxiliary agent is 0.0001-4 % by mole; Described sequestrant is selected from least one in disodium ethylene diamine tetraacetate, Triethylene Diamine pentaacetic acid, citric acid, Citrate trianion and poly-hydroxyl acrylic, and described other auxiliary agents are selected from least one in urea, sodium formiate, Virahol and sodium hypophosphite.
14. according to the preparation method described in any one in claim 3-13, and wherein, described polyreaction is carried out under rare gas element exists, and described polymeric reaction condition comprises: temperature is 0-80 ℃, and the time is 1-24 hour, and pH value is 5-13.
15. preparation methods according to claim 3, wherein, described polyreaction comprises the three phases carrying out successively, and the reaction conditions of first stage comprises: temperature is 0-10 ℃, and the time is 1-15 hour; The reaction conditions of subordinate phase comprises: temperature is 15-30 ℃, and the time is 3-8 hour; The reaction conditions of phase III comprises: temperature is 35-60 ℃, and the time is 2-14 hour
16. preparation methods according to claim 4, wherein, described polyreaction comprises two stages of carrying out successively, and the reaction conditions of first stage comprises: temperature is 0-20 ℃, and the time is 1-15 hour; The reaction conditions of subordinate phase comprises: temperature is 20-60 ℃, and the time is 2-8 hour.
The 17. acrylamide based copolymers that make according to the preparation method described in any one in claim 3-16.
The application of acrylamide based copolymer in 18. claim 1-2 and 17 described in any one in flow improver.
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