CN104250343B - A kind of acrylamide based copolymer and its preparation method and application - Google Patents
A kind of acrylamide based copolymer and its preparation method and application Download PDFInfo
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- CN104250343B CN104250343B CN201310268115.4A CN201310268115A CN104250343B CN 104250343 B CN104250343 B CN 104250343B CN 201310268115 A CN201310268115 A CN 201310268115A CN 104250343 B CN104250343 B CN 104250343B
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Abstract
The invention discloses a kind of acrylamide based copolymer and its preparation method and application.Described acrylamide based copolymer contains construction unit A, construction unit B and construction unit C, wherein, described construction unit A is the construction unit shown in formula (1), and described construction unit B is the construction unit shown in formula (2), and described construction unit C is the construction unit shown in formula (3)；And in described acrylamide based copolymer on the basis of the total mole number of construction unit, the content of described construction unit A is 5 95 moles of %, the content of described construction unit B is 2.5 90 moles of %, and the content of described construction unit C is 0.5 90 moles of %；The viscosity average molecular weigh of described acrylamide based copolymer is 2,000,000 1,500 ten thousand.The acrylamide based copolymer drag reducing efficiency that the present invention provides is high, heat-resisting and salt tolerance high shear performance high, anti-is good, good water solubility and clay stabilizer (alcohol) have good compatibility, viscosity average molecular weigh is low and little to the nocuity on stratum.
Description
Technical field
The present invention relates to two kinds of preparation methods of a kind of acrylamide based copolymer, acrylamide based copolymer
And described acrylamide based copolymer is as the application of drag reducer.
Background technology
As unconventional petroleum resources utilize Typical Representative shale gas (oily) resource exploitation
Becoming a revolution in unconventional petroleum resources field, the whole world, the development and utilization of current shale gas becomes
Countries in the world are paid close attention to emphatically and the focus technology of development.Ooze owing to the ultimate attainment close oil-gas reservoirs such as shale gas reservoir have
Thoroughly rate extremely low (generally less than 0.5mD), frac pressure is high, easily cause the feature of formation damage.Necessary
Use the exploitation of " drag reduction water (slippery water) pressure break " technique.
" drag reduction water (slippery water) pressure break " is the one of fracturing.(change with the most conventional pressure break system
Property guar gum cross-linking system) to compare, drag reduction water (slippery water) pressure break does not relies on high viscosity colloid and takes sand,
But take sand with high infusion discharge capacity, it is achieved reservoir fracturing is reticulated the final purpose in crack.With routine
Pressure break system is compared, and drag reduction water (slippery water) pressure break has while greater advantage stratum on cost
Injure less.
Drag reduction water fracturing fluid core auxiliary agent is water-based drag reducer, in practice of construction, and adding of water-based drag reducer
Enter the frictional resistance overcoming working solution in pipeline, it is ensured that the raising of infusion discharge capacity, make pressure maximum limit
Degree ground acts on and presses off stratum and extension formation fracture, currently available make water-based drag reducer mainly have guanidine glue
And derivative, cellulose derivative, acrylamide copolymer.
At present, the certain journey of drag reducer in using guanidine glue, cellulose and its derivates to split as drag reduction hydraulic pressure
The frictional resistance (US5697444, US5271466) improve infusion discharge capacity on degree, reducing in pipeline,
But still the requirement that drag reduction hydraulic pressure splits cannot be met, have the disadvantage in that mainly due to above-mentioned boiomacromolecule
(1) resistance-reducing performance is limited；(2) due to guanidine glue, cellulose and its derivates, there is a small amount of insoluble matter pole
Easily stratum is damaged；(3) dissolution time is longer.
In drag reduction water pressing crack construction, use more acrylamide copolymer (partial hydrolysis acrylamide or
Anionic acrylamide copolymer) split as drag reduction hydraulic pressure in friction reducer, greatly enhance
Infusion discharge capacity, the frictional resistance reduced in pipeline, but the drag reducer split as shale gas reservoir drag reduction hydraulic pressure
Use, there is following major defect: (1) is for " the water-sensitive effect " that reduce in fracturing process, suppression
The hydration swelling of clay composition in shale, it is necessary to add little molecular cation clay stabilizer in fracturing fluid
(such as potassium chloride, tetramethyl ammonium chloride etc.).Partial hydrolysis acrylamide or anionic acrylamide are altogether
Polymers and product emulsion thereof are poor with the compatibility of above-mentioned clay stabilizer, easily produce precipitation；(2) portion
Divide hydrolyzed acrylamide or anionic acrylamide copolymer as subtracting that shale gas reservoir drag reduction hydraulic pressure splits
Resist uses anti-filtration property poor, in the middle of this kind of drag reduction water fracturing fluid easily leak-off to stratum；(3) resistance to
Temperature salt-resistance is poor, and especially under the conditions of high salinity high divalent ion content, molecular structure is unstable,
Resistance reducing effect declines very fast.
Patent US20090298721A1 discloses the formula of a kind of drag reduction water fracturing fluid: to 1000 gallons
Deionized water adds 0.5 gallon of acrylic acidcoacrylamide thing (FR-56TM) etc. anionic third
Acrylamide copolymer emulsion, as drag reducer, adds the complexings such as 0.15wt% sodium carbonate or EDTA-2Na
Agent, this drag reduction water fracturing fluid has an excellent resistance-reducing performance, and indoor average resistance-reducing yield reaches 65.0%, right
Salt tolerance (the especially tolerance to divalent calcium ions) has had a certain degree of improvement, but this kind of drag reduction water
Pressure break system uses as shale gas drag reduction water fracturing fluid, and there are the following problems: (1) and clay stabilizer
Poor with the compatibility of alcohol, easily produce precipitation；(2) anti-filtration property is poor, and this kind of drag reduction hydraulic pressure splits
Liquid easily leak-off is in the middle of stratum；(3) in practice of construction, " water-sensitive effect " is notable；(4) easily produce
Raw " water blocking "；(5) resistance to high speed shear poor performance, unstable, under resistance-reducing yield under high speed shear effect
Fall is quickly；(6) heat-resistant salt-resistant is poor, especially under the conditions of high salinity high divalent ion content, point
Minor structure is unstable, and resistance reducing effect declines very fast；(7) the most degradable, easily to the finest and close shale
Stratum causes permanent type to injure, and pollutes stratum, then affects oil and gas production.
Compared with above-mentioned partial hydrolysis acrylamide or anionic acrylamide copolymer, cationic is high
The acrylamide copolymer of molecular weight also has been reported that as drag reducer (US356226, US3868328),
This kind of structure copolymer is preferable, with little molecule clay stabilizer (such as KCl, tetramethyl with the compatibility of alcohol
Ammonium chloride etc.) compatibility is preferable, and " water-sensitive effect " is notable, is difficult to " water blocking ", polymer tool itself
There is the effect of certain suppression hydration and expansion of clay.But this type of friction reducer molecular weight is higher, the most degradable,
Easily fine and close shale is caused possible permanent damage.
But improve the resistance to high speed shear performance of drag reducer the most further, improve fracturing fluid and clay is pressed down
Property processed and anti-leak-off, the stability improving the drag reducing efficiency under high temperature and high salt shear conditions reduces simultaneously
Polymer is still a yet unresolved issue to the injury on stratum.
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 viscosity average molecular weigh is low, drag reducing efficiency
High, heat-resisting and salt tolerance high shear performance high, anti-is good, good water solubility and clay stabilizer have well
Compatibility and the acrylamide based copolymer little to formation damage 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 and construction unit C, wherein, described construction unit A is formula (1)
Shown construction unit, described construction unit B is the construction unit shown in formula (2), described structure list
Unit C is the construction unit shown in formula (3)；And with construction unit in described acrylamide based copolymer
On the basis of total mole number, the content of described construction unit A is 5-95 mole of %, described construction unit B
Content be 2.5-90 mole of %, the content of described construction unit C is 0.5-90 mole of %；Described propylene
The viscosity average molecular weigh of acid amides based copolymer is 2,000,000-1,500 ten thousand；
Wherein, R1、R2And R4It is each independently the alkyl of H or C1-C4；R3For connecting key or
The straight or branched alkylidene of person C1-C6；R7Straight or branched alkylidene for C1-C20；R5、R6
And R8It is each independently the alkyl of 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 alkene
Under the conditions of the solution polymerization of hydrocarbon, in the presence of initiator, a kind of monomer mixture is made to carry out in water
Polymerisation, wherein, described monomer mixture contains monomer D, monomer E and monomer F, described monomer
D is the monomer shown in formula (4), and described monomer E is the monomer shown in formula (5), and described monomer F is
Monomer shown in formula (6), in described monomer mixture on the basis of the total mole number of monomer, described list
The content of body D is 5-95 mole of %, and the content of described monomer E is 2.5-90 mole of %, described monomer F
Content be 0.5-90 mole of %；The condition of described solution polymerization makes gained polymerization after polymerisation
The viscosity average molecular weigh of thing is 2,000,000-1,500 ten thousand,
Wherein, R1、R2And R4It is each independently the alkyl of H or C1-C4；R3For connecting key or
The straight or branched alkylidene of person C1-C6；R7Straight or branched alkylidene for C1-C20；R5、R6
And R8It is each independently the alkyl of C1-C4；X-For Cl-, Br-, I-, SCN-,Or
Additionally, the present invention also provides for the preparation method of a kind of acrylamide based copolymer, this preparation method bag
Include and aqueous phase and oil phase are mixed to form reversed-phase emulsion, then under the conditions of emulsion polymerization, at initiator
In the presence of, this reversed-phase emulsion is carried out polymerisation, described aqueous phase is water-soluble containing monomer mixture
Liquid, described oil phase contains organic solvent and emulsifying agent, wherein, described monomer mixture contain monomer D,
Monomer E and monomer F, described monomer D are the monomer shown in above-mentioned formula (4), and described monomer E is upper
Stating the monomer shown in formula (5), described monomer F is the monomer shown in above-mentioned formula (6), with described monomer
In mixture on the basis of the total mole number of monomer, the content of described monomer D is 5-95 mole of %, described
The content of monomer E is 2.5-90 mole of %, and the content of described monomer F is 0.5-90 mole of %；Described molten
After the condition of liquid polymerisation makes polymerisation, the viscosity average molecular weigh of resulting polymers is 2,000,000-1500
Ten thousand.
It addition, present invention also offers the acrylamide based copolymer prepared by said method.
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 three shown in introduction-type (2)
Hydrophobic structure unit shown in phenyl salt system's hydrophobic structure unit and formula (3), and control relatively
Relatively low viscosity average molecular weigh so that this acrylamide based copolymer has under high temperature and high salt shear conditions
Higher drag reducing efficiency, and with clay stabilizer (such as KCl, NaCl), there is higher compatibility.
And, the acrylamide based copolymer of present invention water insoluble matter content when as drag reducer is obvious the most relatively
Low；Preferable compatibility is had with cleanup additive (such as methyl alcohol)；Low to formation damage.
Specifically, the viscosity average molecular weigh of the acrylamide based copolymer prepared in embodiment 1-6 all can reach
Less than 15000000；Insolubles content in water is only 0.01 weight %；Shearing speed at 2500rpm
Under rate, this polymer does not produce precipitation at water/alcoholic solution, can be completely dissolved；Embodiment 1-6 will be made
Acrylamide based copolymer be dissolved in concentration be 2 weight %, 4 weight %, 8 weight %, 10 weight %,
In NaCl or the KCl solution of 12 weight %, it is configured to the solution of 500mg/L and 1000mg/L,
Drag reducing efficiency at 25 DEG C all can reach more than 60%, the drag reducing efficiency at 60 DEG C also can reach 50% with
On；Additionally, the injury of the acrylamide based copolymer layer over the ground prepared in embodiment 1-6 is less than 10%.
Additionally, the preparation method (solution polymerization process and anti-phase of acrylamide based copolymer that the present invention provides
Emulsion polymerization) there is 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 this place is retouched
The detailed description of the invention stated 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 and construction unit C, wherein, described construction unit A is formula (1)
Shown construction unit, described construction unit B is the construction unit shown in formula (2), described structure list
Unit C is the construction unit shown in formula (3)；And with construction unit in described acrylamide based copolymer
On the basis of total mole number, the content of described construction unit A can be 5-95 mole of %, preferably 10-70
Mole %, more preferably 50-70 mole %；The content of described construction unit B is 2.5-90 mole of %,
It is preferably 20-50 mole of %, more preferably 20-30 mole %；The content of described construction unit C is 0.5-90
Mole %, preferably 10-40 mole %, more preferably 10-20 mole %；Described acrylamide copolymerization
The viscosity average molecular weigh of thing is 2,000,000-1,500 ten thousand, preferably 2,000,000-600 ten thousand,
Wherein, R1、R2And R4It is each independently the alkyl of H or C1-C4, under preferable case,
R1For H or methyl, R2And R4It is each independently H；R3For connecting key or the straight chain of C1-C6
Or branched alkylidene, preferably connecting key or methylene；R7Straight or branched alkylene for C1-C20
Base, preferably methylene or ethylidene, more preferably methylene；R5、R6And R8It is each independently
The alkyl of C1-C4, preferably methyl；X-For Cl-, Br-, I-, SCN-,Or
It is preferably Br-。
In the present invention, the example of the alkyl of described C1-C4 can include but not limited to: methyl, ethyl,
N-pro-pyl, isopropyl, 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
Two hydrogen atoms on same carbon atom, it is also possible to two hydrogen atoms on different carbon atoms, Ke Yishi
Straight chain, 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.Described C1-C20
The example of straight or branched alkylidene can include but not limited to: methylene, ethylidene, sub-n-pro-pyl,
Isopropylidene, sub-normal-butyl, sub-sec-butyl, isobutylidene, the sub-tert-butyl group, sub-n-pentyl, sub-isoamyl
Base, sub-tertiary pentyl, sub-neopentyl, sub-n-hexyl, sub-n-heptyl, sub-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 and knot
The acrylamide ter-polymers of structure unit C composition can obtain fabulous resistance reducing effect.Preferably,
R1For H or methyl, R2And R4It is each independently H, R3For connecting key or methylene, R5、
R6And R8It is each independently methyl, X-For Br-.That is, described construction unit A is shown in formula (1)
Construction unit, wherein, R1For methyl or H, described construction unit B is the knot shown in formula (7)
Construction unit shown in structure unit and/or formula (8), described construction unit C is the knot shown in formula (9)
Structure unit,
Wherein, R7For the straight or branched alkylidene of C1-C20, preferably methylene or ethylidene, more
It is preferably methylene.
(2) solution polymerization process
Additionally, the present invention also provides for the preparation method of a kind of acrylamide based copolymer, this preparation method bag
Include under the conditions of the solution polymerization of alkene, in the presence of initiator, make a kind of monomer mixture at water
In carry out polymerisation, wherein, described monomer mixture contains monomer D, monomer E and monomer F, institute
Stating monomer D is the monomer shown in formula (4), and described monomer E is the monomer shown in formula (5), described
Monomer F is the monomer shown in formula (6), and with the total mole number of monomer in described monomer mixture as base
Standard, the content of described monomer D is 5-95 mole of %, preferably 10-70 mole %, more preferably 50-70
Mole %；The content of described monomer E is 2.5-90 mole of %, preferably 20-50 mole %, more preferably
For 20-30 mole of %；The content of described monomer F is 0.5-90 mole of %, preferably 10-40 mole %,
More preferably 10-20 mole of %；The condition of described solution polymerization makes gained polymerization after polymerisation
The viscosity average molecular weigh of thing is 2,000,000-1,500 ten thousand, preferably 2,000,000-600 ten thousand；
Wherein, R1、R2And R4It is each independently the alkyl of H or C1-C4, under preferable case,
R1For H or methyl, R2And R4It is each independently H；R3For connecting key or the straight chain of C1-C6
Or branched alkylidene, preferably connecting key or methylene；R7Straight or branched alkylene for C1-C20
Base, preferably methylene or ethylidene, more preferably methylene；R5、R6And R8It is each independently
The alkyl of C1-C4, preferably methyl；X-For Cl-, Br-, I-, SCN-,Or
It is preferably Br-。
According to the present invention, when described polymerisation starts, the weight of described monomer mixture and water and monomer
The various ratios that the ratio of the gross weight of mixture is known to those skilled in the art, usually, described
The weight of monomer mixture can be 0.05-0.5:1 with the ratio of water and the gross weight of monomer mixture, excellent
Elect 0.15-0.4:1 as.
According to the present invention, described initiator can be the various initiator in this area.Such as, selected from azo system
Initiator and redox 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 mole of %, and the consumption of described redox series initiators is
0-10 mole of %, and total consumption of described azo initiator and redox initiator is the most satisfied: described
The 0.0001-10 mole of % that total consumption is the total mole number of monomer in monomer mixture of initiator.
In the present invention, it is preferable that described azo series initiators is different selected from azodiisobutyronitrile, azo two
The double methylpent hydrochlorate of heptonitrile, azo, 2,2 '-azo diisobutyl amidine hydrochloride and 2,2 '-azo two [2-(2-
Imidazoline-2-propane)-dihydrochloride] at least one, more preferably 2,2 '-azo diisobutyl
Amidine hydrochloride and/or 2,2 '-azo two [2-(2-imidazoline-2-propane)-dihydrochloride].
Described redox series initiators includes Oxidizing and Reducing Agents, it is preferable that described oxidant and institute
The mol ratio stating reducing agent is 0.5-3.5:1, under conditions of meeting aforementioned proportion, and the use of described oxidant
Amount can be that 0.0001-0.01 mole of % of the total mole number of monomer in monomer mixture, preferably monomer are mixed
0.001-0.008 mole of % of the total mole number of monomer in compound；Under preferable case, described oxidant is selected from
At least one in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide, more preferably mistake
Ammonium sulfate and/or potassium peroxydisulfate；The consumption of described reducing agent can be total mole of monomer in monomer mixture
0.0001-0.005 mole of % of number, the preferably total mole number of monomer in monomer mixture
0.001-0.004 mole of %；Described reducing agent can be inorganic reducing agent (helping reducing agent) and/or organic also
Former dose (chain extender), it is preferable that described inorganic reducing agent be selected from sodium hydrogensulfite, sodium sulfite,
At least one in rongalite, sodium thiosulfate, ferrous sulfate, sodium hydrosulfite, ascorbic acid and urea, enters
One step is preferably sodium hydrogensulfite and/or sodium thiosulfate；Described organic reducing agent is selected from N, N '-diformazan
Base ethylenediamine, N, N '-dimethyl-1,3-propane diamine, N, N, N ', N '-tetramethylethylenediamine, N, N-dimethyl
Ethamine, 3-methylamino propylamine, Dimethylaminoethyl Methacrylate, N-(3-dimethylamino-propyl) methyl
At least one in acrylamide, 1-(dimethylamino)-2-propylamine and diethylenetriamines, the most excellent
Elect N, N '-dimethyl ethylenediamine, N, N '-dimethyl-1,3-propane diamine and N, N, N as ', N '-tetramethyl second two
At least one in amine.
According to the present invention, described polymerisation can also be carried out in the presence of various auxiliary agents, and described auxiliary agent can
With at least one in chelating agent and other auxiliary agents；With in described monomer mixture total mole of monomer
On the basis of number, the consumption of described chelating agent is 0-2 mole of %, and preferably 0.0001-1 mole % enters one
Step is preferably 0.0001-0.05 mole of %, and the consumption of other auxiliary agents described can be 0-2 mole of %, preferably
For 0.0001-1 mole of %, more preferably 0.0001-0.2 mole of %；Preferably, described chelating agent
Make with the consumption of other auxiliary agents: in described monomer mixture on the basis of the total mole number of monomer, described
The consumption of 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), three second
At least one in two triamine pentaacetic acids, citric acid, citrate and poly-hydroxy acrylic acid, further preferably
For at least one in EDTA, citrate and triethylenediamine 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 and sodium hypophosphite
In at least one, 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, molten
Liquid polymerization can obtain the acrylamide based copolymer that viscosity average molecular weigh is controlled.
According to the present invention, the condition of described polymerisation can be the condition that this area is conventional.Such as, institute
Stating solution polymerization to carry out in the presence of an inert gas, polymeric reaction condition may include that temperature is
0-80 DEG C, the time is 1-24 hour, and pH value is 5-13；Under preferable case, temperature is 4-60 DEG C, time
Between be 4-24 hour, pH value is 5-9.Described pH value can be adjusted by adding acid or alkali, institute
Stating acid and be preferably inorganic acid, described inorganic acid is preferably in hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and phosphoric acid
At least one；Described alkali can be inorganic base or organic amine compound, such as can be selected from NaOH,
At least one in potassium hydroxide, ammoniacal liquor, methylamine, ethamine, monoethanolamine and triethanolamine, preferably hydrogen
Sodium oxide molybdena.
The present inventor finds under study for action, takes following condition can improve polymer further
Molecular weight: i.e., it is preferable that the process of described solution polymerization includes the three phases carried out successively:
The reaction condition of first stage includes: temperature is 0-10 DEG C, preferably 4-10 DEG C, and the time is that 1-15 is little
Time, preferably 3-10 hour；The reaction condition of second stage includes: temperature is 15-30 DEG C, is preferably
20-30 DEG C, the time is 3-8 hour, preferably 3-5 hour；The reaction condition of phase III includes: temperature
Degree is for 35-60 DEG C, and preferably 45-55 DEG C, the time is 2-14 hour, preferably 2-12 hour.
Additionally, the present inventor finds under study for action, when select specific monomer D, monomer E with
When monomer F reacts, it is possible to improve the resistance reducing effect of the polymer of gained further.Preferably, R1
For methyl or H, R2And R4It is each independently H, R3For connecting key or methylene, R5、R6
And R8It is each independently methyl, X-For Br-.That is, described monomer D is the monomer shown in formula (7),
Wherein, R1For methyl or H, described monomer E is the monomer shown in formula (10) and/or formula (11)
Shown monomer, described monomer F is the monomer shown in formula (12),
Wherein, R7For the straight or branched alkylidene of C1-C20, preferably methylene or ethylidene, more
It is preferably methylene.
(3) reversed emulsion polymerization
Additionally, the present invention also provides for the preparation method of a kind of acrylamide based copolymer, this preparation method bag
Include and aqueous phase and oil phase are mixed to form reversed-phase emulsion, then under the conditions of emulsion polymerization, at initiator
In the presence of, this reversed-phase emulsion is carried out polymerisation, described aqueous phase is water-soluble containing monomer mixture
Liquid, described oil phase contains organic solvent and emulsifying agent, wherein, described monomer mixture contain monomer D,
Monomer E and monomer F, described monomer D are the monomer shown in above-mentioned formula (4), and described monomer E is upper
Stating the monomer shown in formula (5), described monomer F is the monomer shown in above-mentioned formula (6).Formula (4)-formula
(6) selection of monomer shown in is identical with described above, does not repeats them here.
According to the present invention, described aqueous phase is the aqueous solution containing monomer mixture.Described monomer mixture
Weight and the selection of water and the ratio of the gross weight of monomer mixture are identical with described above, the most do not do superfluous
State.
According to the present invention, the part by weight of described aqueous phase and oil phase is had no particular limits, as long as making institute
State aqueous phase and oil phase and be thoroughly mixed to form reversed-phase emulsion, under preferable case, described aqueous phase and oil phase
Part by weight is 1:0.1-2, more preferably 1:0.3-0.8.
According to the present invention, described organic solvent can be this area various for emulsion polymerization with water mutually the most not
The organic solvent that compatible nonpolar or polarity is little, such as, can be toluene, dimethylbenzene, hexane, hexamethylene
At least one in alkane, normal heptane, isomery paraffin, isoparaffin, gasoline, kerosene and white oil, preferably
In the case of, described organic solvent be selected from toluene, dimethylbenzene, normal heptane, isoparaffin, hexamethylene and
At least one in kerosene.
According to the present invention, described oil phase contains organic solvent and emulsifying agent.Consumption to described organic solvent
Particularly requirement, can not change in wider scope, as long as described organic solvent mixes with emulsifying agent
Close and form oil phase, under preferable case, on the basis of the gross weight of described emulsion, described organic solvent
Consumption can be 10-60 weight %, more preferably 20-35 weight %.
According to the present invention, described emulsifying agent can be the various nonionic breast for emulsion polymerization in this area
Agent, such as, can be sorbitan fatty acid ester, APES, isomery alcohol polyoxy second
Alkene ether, ethoxylated dodecyl alcohol, methyl glycol fatty acid ester, laureth, benzylphenol oxygen polyoxy second
Alkene ether, phenethyl phenol polyethenoxy ether, polyoxyethylene sorbitan fatty acid ester, Sorbitan alcohol ester
Fat acid ester ethylene oxide addition product, benzyl dimethyl phenol polyethenoxy ether, AEO and fat
At least one in fat amine APEO.Under preferable case, described emulsifying agent is selected from Sorbitan alcohol ester
Fat acid esters, polyoxyethylene sorbitan fatty acid ester, NPE, octyl phenol polyoxy second
Alkene ether, benzylphenol oxygen APEO, phenethyl phenol polyethenoxy ether, isomerous tridecanol polyoxyethylene ether,
At least one in ethoxylated dodecyl alcohol and benzyl dimethyl phenol polyethenoxy ether, more preferably
The composite emulsifying that hydrophilic lipophilic balance is 5-9 being made up of above two or two or more emulsifying agents
Agent, such as, can be sorbitan fatty acid ester and NPE.
According to the present invention, the consumption of described emulsifying agent is not particularly limited, can be in wider scope
Interior variation, as long as described emulsifying agent and described organic solvent are mixed to form oil phase, under preferable case,
On the basis of the gross weight of described emulsion, the consumption of described emulsifying agent can be 1-15 weight %, further
It is preferably 2-10 weight %.
According to the present invention, described initiator can be various initiators in this area, the choosing of described initiator
Selecting identical with described above, here is omitted.
In the present invention, under preferable case, first azo series initiators can be added aqueous phase, then mix with oil phase
Form reversed-phase emulsion, then reversed-phase emulsion is contacted with redox series initiators, drawn by redox
Send out agent 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
With at least one in chelating agent and other auxiliary agents, the selection of described auxiliary agent is identical with described above,
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
Aqueous phase adds or adds in oil phase, under preferable case, in order to make chelating agent play stably more fully
Effect, can select to add chelating agent in aqueous phase.
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 exist concurrently with above-mentioned various initiator and the condition of auxiliary agent
Under, reversed emulsion polymerization can obtain the acrylamide that viscosity average molecular weigh is controlled and dissolution velocity is fast and be total to
Polymers.
According to the present invention, the condition of described emulsion polymerization can be the condition that this area is conventional.Described
The selection of polymeric reaction condition is identical with described above, and here is omitted.
Equally, the present inventor finds under study for action, takes following condition to improve further poly-
The molecular weight of compound: i.e., it is preferable that the process of described emulsion polymerization includes two carried out successively
In the stage: the reaction condition of first stage includes: temperature is 0-20 DEG C, preferably 5-10 DEG C, the time is
1-15 hour, preferably 1-5 hour；The reaction condition of second stage includes: temperature is 20-60 DEG C,
Being preferably 25-55 DEG C, 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 after described polymerisation
Contact with phase inversion agent, so that described polymerisation products therefrom quickly dissolves in fracturing fluid is applied in water
?.Described phase inversion agent can be this area various phase inversion agent for emulsion polymerization, as long as making described poly-
The water solubility closing reaction products therefrom increases, such as, can be polyoxyethylene sorbitan aliphatic acid
Ester, NPE, OPEO, Ben-zylphenol Polyoxyethyl Ether, phenethyl phenol
APEO, isomery ten alcohol APEO, isomery undecyl alcohol APEO, isomerous tridecanol are poly-
At least one in the nonionic emulsifier of oxygen vinethene and aliphatic amine polyoxyethylene ether, preferable case
Under, described phase inversion agent be selected from polyoxyethylene sorbitan fatty acid ester, isomery ten alcohol APEO,
Isomery undecyl alcohol APEO, isomerous tridecanol polyoxyethylene ether, NPE and octyl group
At least one in phenol polyethenoxy ether.
According to the present invention, the consumption not particularly requirement to described phase inversion agent, as long as can make described poly-
Closing reaction products therefrom quickly to dissolve in water in fracturing fluid is applied, the consumption of described phase inversion agent makes
: on the basis of the gross weight of described emulsion, the consumption of described phase inversion agent can be 0.5-10 weight %,
It is preferably 1-4 weight %.
Additionally, the present inventor finds under study for action, when select specific monomer D, monomer E with
When monomer F reacts, it is possible to improve the resistance reducing effect of the polymer of gained further.Preferably, R1
For H or methyl, R2And R4It is each independently H, R3For connecting key or methylene, R5、R6
And R8It is each independently methyl, X-For Br-.That is, described monomer D is the monomer shown in formula (7),
Described monomer E is the monomer shown in formula (10) and/or the monomer shown in formula (11), described monomer F
For the monomer shown in formula (12), shown in formula (7)-formula (12), the selection of monomer is identical with described above,
Do not repeat them here.
Additionally, present invention also offers the application as drag reducer of the described acrylamide based copolymer.Use
The described acrylamide based copolymer that the present invention provides is as fracturing fluid drag reducer, it is possible to obtain high and stablize
Drag reducing efficiency, the technology that concrete application process is well known to those skilled in the art.
Hereinafter will be described the present invention by embodiment.It should be appreciated that it is described herein
Detailed description of the invention be merely to illustrate and explain the present invention, be not limited to the present invention.
Intrinsic viscosity is surveyed according to GB12005.1-89 polyacrylamide Intrinsic Viscosity Measurements method
Fixed；Viscosity average molecular weigh is according to formula Mv=([η]/K)1\α, wherein K=4.5 × 10-3, α=0.80 is counted
Calculate；Dissolution time is measured by GB12500.8-89 that (sample quality is all by simple polymerisation material in sample
Gauge), the powdered samples dissolution time recorded is respectively less than 20min, and samples of latex dissolution time is the least
In 5min；The composition of molecular structure and construction unit use IR spectrum and13C-NMR measures；Water is insoluble
Thing 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 (13) is purchased from Sigma-Aldrich company；Formula (15)
Shown monomer M2 is according to document (Synthesis of triphenylmethyl-substituted conjugated
Dienes via Wittig reaction, Huaxue Shiji, 2011,33 (9), 782-784) described in method system
?.
In addition, unless specifically indicated, the reagent used in embodiment, comparative example and test case etc. are equal
For 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 21.32g, 66.40g formula (13) shown in M1
The DAAM (purchased from Sigma-Aldrich company, the most identical) of monomer and 20.3g adds
In reaction bulb, adding deionized water 612.11g, stirring makes monomer be completely dissolved, and stirs.
The EDTA aqueous solution 5.5g of 1 weight %, 1 weight % azo diisobutyl amidine is added respectively in flask
Hydrochloride aqueous solution 2.1g, chain extender N ', N-dimethyl-ethylenediamine 0.002g, add 0.1% bisulfite
Sodium solution 1.1g, urea 0.12g, be sufficiently stirred for making it mix.NaOH by 1 weight %
Solution regulation pH to 7.5.Control system initial temperature, to 4 DEG C, after leading to nitrogen deoxygenation 30 minutes, adds
Enter 1 weight % ammonium persulfate aqueous solution 0.75g, and continue letting nitrogen in and deoxidizing 20 minutes.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 liter
React 2 hours to 50 DEG C, the gum-like product that obtain is taken out, through granulation, be dried, pulverize and can receive
Acrylamide copolymer p 1.
P1 is carried out various mensuration, in IR spectrum, 1660cm-1And 1635cm-1Place occurs belonging to respectively
(N-H bending is shaken for the amide Ⅰ absworption peak (C=O stretching vibration) of amide groups and acid amides II band absworption peak
Dynamic), at 1546cm-1、1449cm-1、1364cm-1There is DAAM C=O absworption peak in place,
At 1430cm-1There is the stretching vibration absworption peak of C-N in place, 1506,1577,1600cm-1Go out peak to belong to
The stretching vibration of C=C on phenyl ring；1437cm-1Go out peak and belong to Ar-P stretching vibration；691、724、747cm-1
Go out peak and belong to Ar-H out-of plane bending vibration on phenyl ring.May determine that the copolymer molecule obtained has formula
(14) structure shown in, recording its viscosity-average molecular weight Mv by viscosity method is 4,200,000, monomer conversion
It is more than 99.9%.Wherein, formula (14) and x, y and z only represent type and the number of construction unit,
And do not indicate that the connected mode of construction unit.The concrete numerical value of x, y and z is determined by inventory, and molecule is tied
The composition of structure formula and construction unit uses quantitatively13C-NMR composes mensuration, obtains x:y:z=1:0.6:0.4.
Comparative example 1
Prepare acrylamide based copolymer according to the method for embodiment 1, except for the difference that, by acrylamide with
(3-acrylamido-3-methyl) butyl trimethyl ammonium chloride of identical molal quantity carries out polymerisation, thus
Obtaining bipolymer DP1, recording its viscosity average molecular weigh Mv is 12,500,000.
Embodiment 2
The present embodiment is for illustrating that the solution polymerization process that the present invention provides prepares acrylamide based copolymer.
By the M2 monomer shown in the formula (15) of AM, 45.94g of 29.85g and the diacetone of 10.15g
Acrylamide joins in polymerization bottle, adds 200.53g deionized water, and stirring makes monomer be completely dissolved,
In flask, add the EDTA aqueous solution 4.65g of 1 weight % respectively, add 1 weight % azo two isobutyl
Base amidine hydrochloride aqueous solution 1.23g, adds chain extender N, N '-dimethyl ethylenediamine 0.002g, adds 0.1%
Solution of sodium bisulfite 1.15g, adds urea 0.11g, is sufficiently stirred for making it mix.Use 1 weight
The sodium hydroxide solution regulation pH to 7.1 of %.Control system initial temperature, to 10 DEG C, leads to nitrogen deoxygenation
After 30 minutes, add 1 weight % ammonium persulfate aqueous solution 0.8g and continue letting nitrogen in and deoxidizing 10 minutes.Will
Reactor is airtight, is maintained at 10 DEG C, after reacting 3 hours, is warming up to 30 DEG C, after reacting 3 hours,
It is warming up to 55 DEG C react 12 hours, the gum-like product that obtain is taken out, through granulation, be dried, pulverize i.e.
The acrylamide copolymer p 2 that can receive.
P2 is carried out various mensuration, in IR spectrum, 1660cm-1And 1635cm-1Place occurs belonging to respectively
(N-H bending is shaken for the amide Ⅰ absworption peak (C=O stretching vibration) of amide groups and acid amides II band absworption peak
Dynamic), at 1546cm-1、1449cm-1、1364cm-1There is DAAM C=O absworption peak in place,
At 1430cm-1There is the stretching vibration absworption peak of C-N in place, 1506,1577,1600cm-1Go out peak to belong to
The stretching vibration of C=C on phenyl ring；1437cm-1Go out peak and belong to Ar-P stretching vibration；691、724、747cm-1
Go out peak and belong to Ar-H out-of plane bending vibration on phenyl ring.May determine that the copolymer molecule obtained has formula
(16) structure shown in, recording its viscosity-average molecular weight Mv by viscosity method is 3,170,000, monomer conversion
It is more than 99.9%.Wherein, formula (16) and x, y and z only represent type and the number of construction unit,
And do not indicate that the connected mode of construction unit.The concrete numerical value of x, y and z is determined by inventory, and molecule is tied
The composition of structure formula and construction unit uses quantitatively13C-NMR composes mensuration, obtains x:y:z=1:0.29:0.14.
Embodiment 3
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 Methacrylamide of 5.11g, 110.66g formula (13) shown in M1 monomer
With in the DAAM of 40.61g to polymerization bottle, adding 234.57g deionized water, stirring makes list
Body is completely dissolved, and adds the EDTA aqueous solution 7.56g of 1 weight % respectively, add 1 weight in flask
Amount % azo diisobutyl amidine hydrochloride aqueous solution 2.13g, adds chain extender N ', N-dimethyl-ethylenediamine
0.001g, adds 0.1 weight % solution of sodium bisulfite 1.13g, adds urea 0.20g, is sufficiently stirred for
Make it mix.PH to 7.3 is regulated with the sodium hydroxide solution of 1 weight %.Control system is the warmest
Degree is to 8 DEG C, after leading to nitrogen deoxygenation 30 minutes, adds 1% ammonium persulfate aqueous solution 0.9g and continues logical nitrogen
Deoxygenation 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, be warming up to 45 DEG C and react 7 hours, the gum-like product that obtain is taken out, through granulation,
Be dried, pulverizing can receive acrylamide copolymer p 3.
P3 is carried out various mensuration, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to acyl respectively
The amide Ⅰ absworption peak (C=O stretching vibration) of amido and acid amides II band absworption peak (N-H flexural vibrations),
At 1430cm-1There is the stretching vibration absworption peak of C-N in place, at 1546cm-1、1449cm-1、1364cm-1
There is DAAM C=O absworption peak in place, at 1430cm-1Place occurs that the stretching vibration of C-N absorbs
Peak, 1506,1577,1600cm-1Go out peak and belong to the stretching vibration of C=C on phenyl ring；1437cm-1Go out
Peak belongs to Ar-P stretching vibration；691、724、747cm-1Go out peak and belong to Ar-H plane excurvation on phenyl ring
Qu Zhendong.May determine that the copolymer molecule obtained has the structure shown in formula (17), pass through viscosity method
Recording its viscosity-average molecular weight Mv is 5,030,000, and monomer conversion is more than 99.9%.Wherein, formula (17)
And x, y and z only represent type and the number of construction unit, and do not indicate that the connection side of construction unit
Formula.The concrete numerical value of x, y and z is determined by inventory, and the composition of molecular structural formula and construction unit uses
Quantitatively13C-NMR composes mensuration, obtains x:y:z=1:5:4.
Embodiment 4
The present embodiment is for illustrating that the reversed emulsion polymerization that the present invention provides prepares acrylamide copolymerization
Thing.
(1) by the Methacrylamide of 5.11g, 110.66g formula (13) shown in M1 monomer,
The DAAM of 40.61g joins in configuration bottle, adds 290.42g deionized water, and stirring makes
Monomer is completely dissolved, and adds the EDTA aqueous solution 14.61g of 1 weight %, chain extender respectively in flask
N ', N-dimethyl-ethylenediamine 0.001g, adds the 1 weight % azo diisobutyl amidine hydrochloride aqueous solution
1.03g, adds urea 0.09g, is sufficiently stirred for making it mix, and the NaOH by 10 weight % is molten
Liquid regulation pH to 7.1, obtains aqueous phase.
(2) by sorbitan fatty acid ester (span60, Sigma-Aldrich company, the most identical)
70g, APES (Igepal CA720, Sigma-Aldrich company, the most identical)
13.26g, 286.76g kerosene is mixed into oil phase, and is joined all by the aqueous phase obtained in step (1)
In oil phase, form reversed-phase emulsion by mixing at a high speed and join in reactor.
(3) control system initial temperature 5 DEG C, after leading to nitrogen deoxygenation 30 minutes, add 1 weight % sub-
Sodium bisulphate solution 0.25g, adds 1 weight % ammonium persulfate aqueous solution 1.0g and the logical nitrogen of continuation removes
Oxygen 10 minutes.Reactor is airtight, it is maintained at 5 DEG C, after reacting 5 hours, is warming up to 55 DEG C, instead
Answer 2 hours.After question response temperature is cooled to room temperature, add 16.65g NPE
(Sigma-Aldrich company, the most identical), obtains emulsion-formulated products with 80 mesh filter-cloth filterings.Will be anti-
After phase emulsion product acetone and methanol mixed solvent are precipitated out, acrylamide based copolymer can be obtained
P4。
P4 is carried out various mensuration, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to acyl respectively
The amide Ⅰ absworption peak (C=O stretching vibration) of amido and acid amides II band absworption peak (N-H flexural vibrations),
1546cm-1、1449cm-1、1364cm-1There is DAAM C=O absworption peak in place, at 1430cm-1
There is the stretching vibration absworption peak of C-N in place, 1506,1577,1600cm-1Go out peak and belong to C=C on phenyl ring
Stretching vibration；1437cm-1Go out peak and belong to Ar-P stretching vibration；691、724、747cm-1Go out peak to return
Belong to Ar-H out-of plane bending vibration on phenyl ring.May determine that the copolymer molecule obtained has formula (18)
Shown structure, recording its viscosity average molecular weigh Mv by viscosity method is 3,640,000, and monomer conversion is 99.9%
Above.Wherein, formula (18) and x, y and z only represent type and the number of construction unit, and not
Represent the connected mode of construction unit.The concrete numerical value of x, y and z is determined by inventory, molecular structural formula
Use quantitatively with the composition of construction unit13C-NMR composes mensuration, obtains x:y:z=1:5:4.
Comparative example 2
Acrylamide based copolymer is prepared, except for the difference that, by methacryl according to the method for embodiment 4
Amine carries out polymerisation with (3-acrylamido-3-methyl) butyl trimethyl ammonium chloride of identical molal quantity,
Thus obtain bipolymer DP2, recording its viscosity average molecular weigh Mv is 9,250,000.
Embodiment 5
The present embodiment is for illustrating that the reversed emulsion polymerization that the present invention provides prepares acrylamide copolymerization
Thing.
(1) by the Methacrylamide of 35.74g, 45.94g formula (15) shown in M2 monomer and
The DAAM of 10.15g joins in configuration bottle, adds 367.32g deionized water, and stirring makes
Monomer is completely dissolved, and adds the EDTA aqueous solution 7.83g of 1 weight %, chain extender respectively in flask
N ', N-dimethyl-ethylenediamine 0.001g, adds the 1 weight % azo diisobutyl amidine hydrochloride aqueous solution
2.03g, adds urea 0.10g, is sufficiently stirred for making it mix, and the NaOH by 15 weight % is molten
Liquid regulation pH to 7.0, obtains aqueous phase.
(2) by sorbitan fatty acid ester (span60) 48g, APES (Igepal
CA720) 8.29g, 178.26g kerosene is mixed into oil phase, and by whole for the aqueous phase that obtains in step (1)
Join in oil phase, form reversed-phase emulsion by mixing at a high speed and join in reactor.
(3) control system initial temperature 10 DEG C, after leading to nitrogen deoxygenation 30 minutes, add 1 weight % sub-
Sodium bisulphate solution 0.13g, adds 1 weight % ammonium persulfate aqueous solution 0.63g and the logical nitrogen of continuation removes
Oxygen 10 minutes.Reactor is airtight, it is maintained at 10 DEG C, after reacting 1 hour, is warming up to 30 DEG C, instead
Answer 5 hours, after question response temperature is cooled to room temperature, add 21.11g NPE, use
80 mesh filter-cloth filterings obtain emulsion-formulated products.Reversed-phase emulsion product acetone and methanol mixed solvent are precipitated
After out, acrylamide copolymer p 5 can be obtained.
P5 is carried out various mensuration, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to acyl respectively
The amide Ⅰ absworption peak (C=O stretching vibration) of amido and acid amides II band absworption peak (N-H flexural vibrations),
1546cm-1、1449cm-1、1364cm-1There is DAAM C=O absworption peak in place, at 1430cm-1
There is the stretching vibration absworption peak of C-N in place, 1506,1577,1600cm-1Go out peak and belong to C=C on phenyl ring
Stretching vibration；1437cm-1Go out peak and belong to Ar-P stretching vibration；691、724、747cm-1Go out peak to return
Belong to Ar-H out-of plane bending vibration on phenyl ring.May determine that the copolymer molecule obtained has formula (19)
Shown structure, recording its viscosity average molecular weigh Mv by viscosity method is 5,170,000, and monomer conversion is 99.9%
Above.Wherein, formula (19) and x, y and z only represent type and the number of construction unit, and not
Represent the connected mode of construction unit.The concrete numerical value of x, y and z is determined by inventory, molecular structural formula
Use quantitatively with the composition of construction unit13C-NMR composes mensuration, obtains x:y:z=1:0.29:0.14.
Embodiment 6
The present embodiment is for illustrating that the reversed emulsion polymerization that the present invention provides prepares acrylamide copolymerization
Thing.
(1) by the acrylamide of 19.19g, 66.40g formula (13) shown in M1 monomer and 25.38g
DAAM join configuration bottle in, add 628.83g deionized water, stirring make monomer complete
CL, adds the EDTA aqueous solution 8.5g, chain extender N ', N-bis-of 1 weight % respectively in flask
Methyl ethylenediamine 0.001g, adds the 2 of 1 weight %, 2 '-azo diisobutyl amidine hydrochloride aqueous solution 2.1g,
Add urea 0.08g, be sufficiently stirred for making it mix, regulate with the sodium hydroxide solution of 10 weight %
PH to 7.1, obtains aqueous phase.
(2) by sorbitan fatty acid ester (span60) 20g, APES (Igepal
CA720, Sigma-Aldrich company, the most identical) 10.02g, 195.12g kerosene is mixed into oil phase,
And join in oil phase by step (1) obtains aqueous phase, form reversed-phase emulsion by mixing at a high speed and add
In reactor.
(3) control system initial temperature 8 DEG C, after leading to nitrogen deoxygenation 30 minutes, add 1 weight % sub-
Sodium bisulphate solution 0.18g, adds 1 weight % ammonium persulfate aqueous solution 1.3g and the logical nitrogen of continuation removes
Oxygen 10 minutes.Reactor is airtight, it is maintained at 8 DEG C, after reacting 3 hours, is warming up to 40 DEG C, instead
Answer 4 hours, after question response temperature is cooled to room temperature, add 7.5g NPE, with 100
Mesh filter-cloth filtering obtains emulsion-formulated products.Reversed-phase emulsion product acetone and methanol mixed solvent are settled out
After Laiing, acrylamide copolymer p 6 can be obtained.
P6 is carried out various mensuration, 1660cm in IR spectrum-1And 1635cm-1Place occurs belonging to acyl respectively
The amide Ⅰ absworption peak (C=O stretching vibration) of amido and acid amides II band absworption peak (N-H flexural vibrations),
1546cm-1、1449cm-1、1364cm-1There is DAAM C=O absworption peak in place, at 1430cm- 1There is the stretching vibration absworption peak of C-N in place, 1506,1577,1600cm-1Go out peak and belong to C=C on phenyl ring
Stretching vibration；1437cm-1Go out peak and belong to Ar-P stretching vibration；691、724、747cm-1Go out peak to return
Belong to Ar-H out-of plane bending vibration on phenyl ring.May determine that the copolymer molecule obtained has formula (20)
Shown structure, recording its viscosity average molecular weigh Mv by viscosity method is 4,600,000, and monomer conversion is 99.9%
Above.Wherein, formula (20) and x, y and z only represent type and the number of construction unit, and not
Represent the connected mode of construction unit.The concrete numerical value of x, y and z is determined by inventory, molecular structural formula
Use quantitatively with the composition of construction unit13C composes mensuration, obtains x:y:z=1:0.67:0.56.
Test case 1
Water-insoluble is to measure according to the method for regulation in SY/T5862-1993.By P1-P6, DP1
Conventional hydroxypropyl guar gum (the JXY wellfracturing hydroxypropyl cooking drag reducer with in DP2 and site operation
Melon glue powder, Shandong Juxin Chemical Co., Ltd., the most identical) carry out water-soluble mensuration, result such as table 1
Shown in.
Table 1
From table 1 it follows that acrylamide based copolymer prepared by two kinds of methods that the present invention provides
Water insoluble matter content in P1-P6 is the conventional hydroxypropyl guar gum cooking drag reducer significantly lower than in site operation,
This explanation is compared with hydroxypropyl guar gum, and P1-P6 is as shale gas pressure break drag reducer, to stratum in use
Injure lower.
Test case 2
Under 2500rpm shear rate, respectively by P1-P6, DP1, DP2 and partial hydrolysis polypropylene
(HPAM, Zibo Tian Jian Chemical Co., Ltd., trade mark TJY-1, molecular weight is 1000-1300 to acid amides
Ten thousand) water/alcoholic solution being respectively added slowly to volume ratio 80/20 and 60/40 (uses first in this test case
Alcohol) in, the consumption of P1-P6, DP1 and DP2 and partially hydrolyzed polyacrylamide (PHPA) is the 0.01 of water/alcoholic solution
Weight %(sample quality is based on straight polymer quality in sample), dissolution time is 30min, result such as table
Shown in 2.
Table 2
From Table 2, it can be seen that P1-P6 prepared by the two kinds of methods using the present invention to provide is as shale
Air pressure splits with drag reducer, compared with partially hydrolyzed polyacrylamide (PHPA), with cleanup additive (as a example by methyl alcohol)
Compatibility is good.
Test case 3
At a temperature of 25 DEG C, P1-P6, DP1, D2, HPAM and hydroxypropyl guar gum are dissolved in respectively
Pure water and concentration are 2 weight %, 4 weight %, 8 weight %, 10 weight %, the NaCl of 12 weight %
Or in KCl solution, (sample quality is by sample for the solution of 500mg/L and 1000mg/L being configured to
Straight polymer quality meter in product), then according to the method for regulation in SY/T6376-2008 at GLM-1
Drag reducing efficiency (the test condition: the internal diameter of test section pipeline of above-mentioned solution is measured on pipeline frictional resistance determinator
For 8mm, a length of 9m of test section pipeline, infusion discharge capacity is 30L/min), result such as table 3 and table
Shown in 4.
At a temperature of 60 DEG C, P1-P6, DP1, D2 and HPAM are dissolved in respectively pure water and concentration
It is in the NaCl solution of 2 weight %, 4 weight %, 8 weight %, 10 weight %, 12 weight %, will
The solution of its 500mg/L and 1000mg/L being configured to, according to the side of regulation in SY/T6376-2008
Method (condition determination with above-mentioned 25 DEG C at identical), measurement result is shown in Table 5.
Table 3
Table 4
Table 5
From table 3-table 5 it can be seen that with site operation conventional cook drag reducer hydroxypropyl guar gum,
HAPM, DP1 compare with DP2, acrylamide copolymer P1-P6 prepared by the method that the present invention provides
It is as shale air pressure drag reducer, more preferable with clay stabilizer (e.g., KCl and NaCL) compatibility,
Anti-salt property is more excellent；Additionally, the drag reducing efficiency that the acrylamide based copolymer of present invention offer is at 25 DEG C
All can reach more than 60%, the drag reducing efficiency at 60 DEG C also can reach more than 50%, illustrates at high temperature high
The acrylamide based copolymer that under salt shear conditions, the present invention provides still has higher drag reducing efficiency.
Test case 4
The nocuity of rock core is pressed oil and gas industry standard SY/T5107-2005 " water base pressure by friction reducer
Split liquid method of evaluating performance " in fracturing fluid filtrate to matrix permeability of rock core infringement experiment carry out, in the U.S.
Testing in rock core company formation injury tester device (FDS-800), the matrix permeability of rock core is
2md。
P1-P6, DP1 and DP2 are dissolved in respectively pure water, are configured to the solution (sample of 1000mg/L
Quality is based on straight polymer quality in sample), in American core company formation damage test system
(FDS-800) upper its nocuity to rock core of test, result is as shown in table 6.
Table 6
As can be seen from Table 6, acrylamide based copolymer prepared by two kinds of methods that the present invention provides
Rock core is injured the conventional comparative sample cooking drag reducer, this explanation significantly lower than in site operation by P1-P6
Use P1-P6 low to the injury on stratum as shale gas pressure break drag reducer.
Above-mentioned test result illustrates, the acrylamide based copolymer of present invention insolubles content in water is only
It is 0.01 weight %；Under the shear rate of 2500rpm, can be dissolved completely in water/alcoholic solution, with
The compatibility of alcohol is good；Owing to the compatibility with alcohol and clay stabilizer (NaCl or KCl) improves, improve
Anti-filtration property；And still there is under conditions of high salt and high temperature high drag reducing efficiency；And there is phase
To low viscosity average molecular weigh, the injury to stratum is low.Additionally, the acrylamide copolymerization that the present invention provides
The preparation method of thing 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 to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible combinations are illustrated by the present invention the most separately.
Additionally, can also be combined between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (23)
1. an acrylamide based copolymer, it is characterised in that described acrylamide based copolymer contains
Construction unit A, construction unit B and construction unit C, wherein, described construction unit A is formula (1)
Shown construction unit, described construction unit B is the construction unit shown in formula (2), described structure list
Unit C is the construction unit shown in formula (3)；And with construction unit in described acrylamide based copolymer
On the basis of total mole number, the content of described construction unit A is 5-95 mole of %, described construction unit B
Content be 2.5-90 mole of %, the content of described construction unit C is 0.5-90 mole of %；Described propylene
The viscosity average molecular weigh of acid amides based copolymer is 2,000,000-1,500 ten thousand；
Wherein, R1、R2And R4It is each independently the alkyl of H or C1-C4；R3For connecting key or
The straight or branched alkylidene of person C1-C6；R7Straight or branched alkylidene for C1-C20；R5、R6
And R8It is each independently the alkyl of C1-C4；X-For Cl-、Br-、I-、SCN-、Or
Acrylamide based copolymer the most according to claim 1, wherein, with described acrylamide
In based copolymer on the basis of the total mole number of construction unit, the content of described construction unit A is that 10-70 rubs
You are %, and the content of described construction unit B is 20-50 mole of %, and the content of described construction unit C is 10-40
Mole %, the viscosity average molecular weigh of described acrylamide based copolymer is 2,000,000-600 ten thousand.
Acrylamide based copolymer the most according to claim 1, wherein, R1For H or methyl,
R2And R4It is each independently H, R3For connecting key or methylene, R5、R6And R8Independently of one another
For methyl, X-For Br-。
4. a preparation method for acrylamide based copolymer, 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 in water,
Wherein, described monomer mixture contains monomer D, monomer E and monomer F, and described monomer D is formula (4)
Shown monomer, described monomer E is the monomer shown in formula (5), and described monomer F is shown in formula (6)
Monomer, in described monomer mixture on the basis of the total mole number of monomer, the content of described monomer D is
5-95 mole of %, the content of described monomer E is 2.5-90 mole of %, and the content of described monomer F is 0.5-90
Mole %；The condition of described solution polymerization makes the viscosity average molecular weigh of resulting polymers after polymerisation
It is 2,000,000-1,500 ten thousand,
Wherein, R1、R2And R4It is each independently the alkyl of H or C1-C4；R3For connecting key or
The straight or branched alkylidene of person C1-C6；R7Straight or branched alkylidene for C1-C20；R5、R6
And R8It is each independently the alkyl of C1-C4；X-For Cl-、Br-、I-、SCN-、Or
5. a preparation method for acrylamide based copolymer, this preparation method includes aqueous phase and oil phase
It is mixed to form reversed-phase emulsion, then under the conditions of emulsion polymerization, in the presence of initiator, should
Reversed-phase emulsion carries out polymerisation, and described aqueous phase is the aqueous solution containing monomer mixture, and described oil phase contains
Having organic solvent and emulsifying agent, wherein, described monomer mixture contains monomer D, monomer E and monomer F,
Described monomer D is the monomer shown in formula (4), and described monomer E is the monomer shown in formula (5), institute
Stating monomer F is the monomer shown in formula (6), and in described monomer mixture, the total mole number of monomer is as base
Standard, the content of described monomer D is 5-95 mole of %, and the content of described monomer E is 2.5-90 mole of %,
The content of described monomer F is 0.5-90 mole of %；The condition of described emulsion polymerization makes polymerisation
The viscosity average molecular weigh of rear resulting polymers is 2,000,000-1,500 ten thousand,
Wherein, R1、R2And R4It is each independently the alkyl of H or C1-C4；R3For connecting key or
The straight or branched alkylidene of person C1-C6；R7Straight or branched alkylidene for C1-C20；R5、R6
And R8It is each independently the alkyl of C1-C4；X-For Cl-、Br-、I-、SCN-、Or
Preparation method the most according to claim 5, wherein, described aqueous phase and the weight ratio of oil phase
For 1:0.1-2.
Preparation method the most according to claim 6, wherein, described aqueous phase and the weight ratio of oil phase
For 1:0.3-0.8.
Preparation method the most according to claim 5, wherein, with the gross weight of described emulsion as base
Standard, the consumption of described organic solvent is 10-60 weight %, and the consumption of described emulsifying agent is 1-15 weight %.
Preparation method the most according to claim 8, wherein, with the gross weight of described emulsion as base
Standard, the consumption of described organic solvent is 20-35 weight %, and the consumption of described emulsifying agent is 2-10 weight %.
Preparation method the most according to claim 5, wherein, the method is additionally included in described polymerization
After reaction, described polymerisation products therefrom is contacted with phase inversion agent.
11. preparation methods according to claim 10, wherein, with the gross weight of described emulsion be
Benchmark, the consumption of described phase inversion agent is 0.5-10 weight %.
12. preparation methods according to claim 11, wherein, with the gross weight of described emulsion be
Benchmark, the consumption of described phase inversion agent is 1-4 weight %.
13. according to the preparation method described in claim 4 or 5, wherein, with in described monomer mixture
On the basis of the total mole number of monomer, the content of described monomer D is 10-70 mole of %, described monomer E's
Content is 20-50 mole of %, and the content of described monomer F is 10-40 mole of %；Described polymerisation
After condition makes polymerisation, the viscosity average molecular weigh of resulting polymers is 2,000,000-600 ten thousand.
14. according to the preparation method described in claim 4 or 5, wherein, R1For H or methyl,
R2And R4It is each independently H, R3For connecting key or methylene, R5、R6And R8Independently of one another
For methyl, X-For Br-。
15. according to the preparation method described in claim 4 or 5, wherein, and the weight of described monomer mixture
Amount is 0.05-0.5:1 with the ratio of water and the gross weight of monomer mixture.
16. preparation methods according to claim 15, wherein, the weight of described monomer mixture
It is 0.15-0.4:1 with the ratio of water and the gross weight of monomer mixture.
17. according to the preparation method described in claim 4 or 5, and wherein, described initiator is selected from azo
Series initiators and redox series initiators, in described monomer mixture, the total mole number of monomer is as base
Standard, the consumption of described azo series initiators is 0-10 mole of %, the consumption of described redox series initiators
For 0-10 mole of %, and total consumption of described initiator is 0.0001-10 mole of %；Described azo system draws
Send out agent selected from azodiisobutyronitrile, ABVN, 2,2 '-azo diisobutyl amidine hydrochloride and 2,2 '
At least one in double [2-(2-imidazoline-2-base) propane] dihydrochloride of-azo, described redox system draws
Send out agent and include that Oxidizing and Reducing Agents, described oxidant are 0.5-3.5:1 with the mol ratio of described reducing agent,
Described oxidant is at least one in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide；
Described reducing agent is inorganic reducing agent and/or organic reducing agent, and described inorganic reducing agent is selected from bisulfite
At least one in sodium, sodium sulfite, sodium thiosulfate, ferrous sulfate and sodium hydrosulfite, described organic also
Former dose is selected from rongalite, ascorbic acid, urea, N, N '-dimethyl ethylenediamine, N, N '-dimethyl-1,3-third
Diamines, N, N, N ', N '-tetramethylethylenediamine, N, N-dimethyl amine, 3-methylamino propylamine, methyl-prop
Olefin(e) acid dimethylaminoethyl, N-(3-dimethylamino-propyl) Methacrylamide, 1-(dimethylamino)-2-
At least one in propylamine and diethylenetriamines.
18. according to the preparation method described in claim 4 or 5, and wherein, described polymerisation is at auxiliary agent
In the presence of carry out, described auxiliary agent is at least one in chelating agent and other auxiliary agents；With described monomer
On the basis of the total mole number of mixture, the consumption of described chelating agent is 0-2 mole of %, other auxiliary agents described
Consumption be 0-2 mole of %, and in described monomer mixture on the basis of the total mole number of monomer, described
Total consumption of auxiliary agent is 0.0001-4 mole of %；Described chelating agent is selected from disodium ethylene diamine tetraacetate, diethyl
At least one in pentaacetic acid, citric acid, citrate and poly-hydroxy acrylic acid, described other help
At least one in urea, sodium formate, isopropanol and sodium hypophosphite of agent.
19. preparation methods according to claim 4, wherein, described solution polymerization is in inertia
Carrying out in the presence of gas, polymeric reaction condition includes: temperature is 0-80 DEG C, and the time is 1-24 hour,
PH value is 5-13.
20. preparation methods according to claim 5, wherein, described emulsion polymerization is in inertia
Carrying out in the presence of gas, polymeric reaction condition includes: temperature is 0-80 DEG C, and the time is 1-24 hour,
PH value is 5-13.
21. according to the preparation method described in claim 4 or 19, wherein, and described solution polymerization
Process include the three phases that carries out successively, the reaction condition of first stage includes: temperature is 0-10 DEG C,
Time is 1-15 hour；The reaction condition of second stage includes: temperature is 15-30 DEG C, and the time is 3-8
Hour；The reaction condition of phase III includes: temperature is 35-60 DEG C, and the time is 2-14 hour.
22. according to the preparation method described in claim 5 or 20, wherein, and described emulsion polymerization
Process include two stages carrying out successively, the reaction condition of first stage includes: temperature is 0-20 DEG C,
Time is 1-15 hour；The reaction condition of second stage includes: temperature is 20-60 DEG C, and the time is 2-8
Hour.
Acrylamide based copolymer described in any one or by claim in 23. claims 1-3
The acrylamide based copolymer that in 4-22, method described in any one prepares as drag reducer should
With.
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| CN102050926A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof |
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| CN102050926A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof |
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