CN106317318B - Acrylamide terpolymer and pressure break drag reducer and their preparation method - Google Patents
Acrylamide terpolymer and pressure break drag reducer and their preparation method Download PDFInfo
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Abstract
The present invention relates to shale gas exploitation fracturing yield increasing fields, disclose Acrylamide terpolymer and pressure break drag reducer and their preparation method, the Acrylamide terpolymer contains structural unit A, structural unit B and structural unit C, the structural unit A is the structural unit with structure shown in formula (1), the structural unit B is the structural unit with structure shown in formula (2), and the structural unit C is the structural unit with structure shown in formula (3).The shale gas pressure break drag reducer drag reduction efficiency and anti-shear performance of the present invention is high, and viscosity is low, good fluidity, solution rate are fast and environmental protection.Formula (1)Formula (2)
Description
Technical field
The present invention relates to shale gas exploitation fracturing yield increasing fields, and in particular, to a kind of Acrylamide terpolymer
And preparation method thereof, a kind of shale gas pressure break drag reducer and preparation method thereof.
Background technology
Shale gas resource is very abundant, however since the permeability of shale matrix is very low (being generally less than 1mD), development technique
Difficult, 90% or more shale gas well needs that more satisfactory yield could be obtained by fracturing reform.
Currently, shale gas fracture stimulation operations carry out fracture stimulation operations frequently with drag reduction water.It is in water that drag reduction hydraulic pressure, which is split,
The middle fracturing work that the additives such as a small amount of fracturing fluid drag reducer, cleanup additive, fungicide are added and are carried out as fracturing fluid.With gel pressure
Liquid difference is split, drag reduction hydraulic pressure, which is split, can be substantially reduced pressure break cost, reduce formation damage, and can obtain gel fracture cannot be real
Existing volume fracturing, to improve the exploitation yield of shale gas.
Since natural polymer loses resistance reducing performance because of degradation in acid condition, drag reducer used at present is mainly
Some synthesising macromolecule copolymers, CN103820099A disclose a kind of acid solution drag reducer and preparation method thereof, it is by propylene
Amide, 2- acrylamide-2-methylpro panesulfonic acids and long chain cation monomer polymerize, dry, crushing preparation in aqueous solution,
In application, drag reducer dissolution time is up to 1-2h, shale gas pressure break huge discharge, the needs that big flow is prepared online are cannot be satisfied.
CN103694984A discloses a kind of shale gas acid fracturing drag reducer and preparation method thereof, which passes through anti-
Prepared by phase emulsion method, a large amount of organic solvent and surfactant, this fracturing fluid drag reducer injection are contained in reversed-phase emulsion
The pollution that underground water can be caused behind stratum cannot be satisfied the requirement of environmental protection.
CN102977877A also discloses that a kind of shale gas pressure break drag reducer and preparation method thereof, it is in saline solution
In, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids sodium and acrylic acid are caused by free radical under the protection of dispersant
Three kinds of monomers of sodium carry out the shale gas pressure break drag reducer and preparation method thereof that random copolymerization obtains, and this method is without organic molten
Agent, it is environmentally friendly, but lead to since effective content is low to need to reach 0.2% using concentration that just there is preferable resistance-reducing performance,
And 2- acrylamide-2-methylpro panesulfonic acid sodium has certain dissolubility to cause the emulsion viscosity prepared big in brine,
It is unfavorable for practical application.
Therefore, there is an urgent need for find a kind of new shale gas pressure break drag reduction that can overcome prior art defect in the art
Agent.
Invention content
The purpose of the present invention is overcoming the deficiencies of existing technologies, a kind of drag reduction efficiency is provided and anti-shear performance is high, viscosity
The fast and environmentally friendly new shale gas pressure break drag reducer of low, good fluidity, solution rate.
To achieve the goals above, in a first aspect, the present invention provides a kind of Acrylamide terpolymer, the acryloyl
Amine system terpolymer contains structural unit A, structural unit B and structural unit C, wherein the structural unit A is with formula
(1) structural unit of structure shown in, the structural unit B are the structural unit with structure shown in formula (2), the structural unit
C is the structural unit with structure shown in formula (3), and with the total moles of structural unit in the Acrylamide terpolymer
On the basis of number, the content of the structural unit A is 60-75 moles of %, and the content of the structural unit B is 10-20 moles of %, institute
The content for stating structural unit C is 5-30 moles of %；The viscosity average molecular weigh of the Acrylamide terpolymer be 3,000,000 to
15000000；
Wherein, in formula (1), R1For H, methyl, ethyl, n-propyl or isopropyl；
In formula (2), M Li, Na, K, Rb or Cs；
In formula (3), R2For the alkyl of C1-C5, R3For H, methyl, ethyl, n-propyl or isopropyl, m is the integer of 1-3.
Second aspect, the present invention provide a kind of preparation method of Acrylamide terpolymer, and this method is included in alkene
Under the conditions of the solution polymerization of hydrocarbon, in the presence of initiator, so that monomer mixture is carried out polymerisation, the monomer in water
It is the monomer with structure shown in formula (4) that mixture, which contains monomer D, monomer E and monomer F, the monomer D, and the monomer E is tool
It is the monomer with structure shown in formula (6) to have the monomer of structure shown in formula (5), the monomer F, and in the monomer mixture
On the basis of the total mole number of monomer, the content of the monomer D is 60-75 moles of %, and the content of the monomer E is rubbed for 10-20
You are %, and the content of the monomer F is 5-30 moles of %；The condition of the polymerisation makes gained copolymer after polymerisation
Viscosity average molecular weigh is 3,000,000 to 15,000,000；
Wherein, R1-R3And the m and M such as present invention is defined before.
The third aspect, the present invention provide a kind of shale gas pressure break drag reducer, contain acrylamide three in the drag reducer
Membered copolymer, stabilizer, inorganic salts and water, the Acrylamide terpolymer are the foregoing acrylamide of the present invention
It is terpolymer or the acrylamide to be prepared by the preparation method of the Acrylamide terpolymer of the present invention
It is terpolymer；It is preferred that
On the basis of the total weight of the drag reducer, the content of the Acrylamide terpolymer is 10-30 weights
% is measured, the content of the stabilizer is 0.5-2 weight % and the content of the inorganic salts is 15-30 weight %.
Fourth aspect, the present invention provide a kind of preparation method of shale gas pressure break drag reducer, and this method includes：This method
Including：Under the conditions of the solution polymerization of alkene, in the presence of initiator, by the monomer containing monomer D, monomer E and monomer F
Mixture, stabilizer and inorganic salts carry out hybrid reaction, wherein the monomer D is the monomer with structure shown in formula (4), institute
It is the monomer with structure shown in formula (5) to state monomer E, and the monomer F is the monomer with structure shown in formula (6),
Wherein, R1-R3And the m and M such as present invention is defined before.
Drag reducer provided by the invention introduces functional monomer in conventional polypropylene amide drag reduction agent molecule, improves and subtracts
The drag reduction efficiency and anti-shear performance of resist, and drag reducer viscosity is low, good fluidity, solution rate is fast, organic molten due to being free of
Agent has good environmental-protecting performance.The method for preparing drag reducer of the present invention utilizes water-water polymerization technique, the drag reduction prepared
Agent is water-soluble polymer milky aqueous dispersion lotion, can online prepare and use directly in pressing crack construction.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, the structural unit A be the structural unit with structure shown in formula (1), the monomer D be with
The monomer of structure shown in formula (4)：
Wherein, in formula (1) and formula (4), R1For H, methyl, ethyl, n-propyl or isopropyl.
In the present invention, the structural unit B be the structural unit with structure shown in formula (2), the monomer E be with
The monomer of structure shown in formula (5)：
Wherein, in formula (2) and formula (5), M Li, Na, K, Rb or Cs.
In the present invention, the structural unit C be the structural unit with structure shown in formula (3), the monomer F be with
The monomer of structure shown in formula (6)：
Wherein, in formula (3) and formula (6), R2For the alkyl of C1-C5, R3For H, methyl, ethyl, n-propyl or isopropyl, m
It is 1,2 or 3；The alkyl of the C1-C5 includes methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, new butyl, positive penta
Base, isopentyl and cyclopenta.
In a first aspect, the present invention provides a kind of Acrylamide terpolymer, the Acrylamide terpolymer
Contain structural unit A, structural unit B and structural unit C, wherein the structural unit A is the knot with structure shown in formula (1)
Structure unit, the structural unit B are the structural unit with structure shown in formula (2), and the structural unit C is with formula (3) institute
Show the structural unit of structure, and on the basis of the total mole number of structural unit in the Acrylamide terpolymer, it is described
The content of structural unit A is 60-75 moles of %, and the content of the structural unit B is 10-20 moles of %, the structural unit C's
Content is 5-30 moles of %；The viscosity average molecular weigh of the Acrylamide terpolymer is 3,000,000 to 15,000,000；
Wherein, in formula (1), R1For H, methyl, ethyl, n-propyl or isopropyl；
In formula (2), M Li, Na, K, Rb or Cs；
In formula (3), R2For the alkyl of C1-C5, R3For H, methyl, ethyl, n-propyl or isopropyl, m is the integer of 1-3.
Under preferable case, in the present invention, in formula (1), R1For H, methyl or ethyl；And/or
In formula (2), M Li, Na or K；And/or
In formula (3), R2For methyl, ethyl, n-propyl or isopropyl, R3For H, methyl or ethyl, m is 1 or 2.
In the case of more preferably, in the present invention, in formula (1), R1For H or methyl；And/or
In formula (2), M is Li or Na；And/or
In formula (3), R2For methyl, ethyl or n-propyl, R3For H, methyl or ethyl, m 1.
In the case of particularly preferably, in the present invention, in formula (1), R1For H；And/or
In formula (2), M Na；And/or
In formula (3), R2And R3It is methyl, m 1.
Second aspect, the present invention provides a kind of preparation method of Acrylamide terpolymer, this method is included in
Under the conditions of the solution polymerization of alkene, in the presence of initiator, so that monomer mixture is carried out polymerisation, the list in water
It is the monomer with structure shown in formula (4) that body mixture, which contains monomer D, monomer E and monomer F, the monomer D, and the monomer E is
Monomer with structure shown in formula (5), the monomer F are the monomer with structure shown in formula (6), and with the monomer mixture
On the basis of the total mole number of middle monomer, the content of the monomer D is 60-75 moles of %, and the content of the monomer E is rubbed for 10-20
You are %, and the content of the monomer F is 5-30 moles of %；The condition of the polymerisation makes gained copolymer after polymerisation
Viscosity average molecular weigh is 3,000,000 to 15,000,000；
Wherein, R1-R3And the m and M such as present invention is defined before.
In the present invention, it is preferred to which the polymerisation is reacted for random copolymerization.
In the present invention, it should be strongly noted that involved in the preparation method of the Acrylamide terpolymer
Acrylamide terpolymer related definition with the present invention aforementioned definitions it is identical, in order to avoid repeat, the present invention
Details are not described herein.
In the present invention, the initiator is selected from azo initiator and redox initiator；The azo initiator choosing
From azodiisobutyronitrile, 4,4 '-azos bis- (4- cyanopentanoic acids), 2,2 '-azo diisobutyl amidine hydrochlorides and azo diimidazole
At least one of quinoline base propane dihydrochloride；The redox initiator includes Oxidizing and Reducing Agents, the oxidant
Molar ratio with the reducing agent is 0.1-10:1, the oxidant is selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and peroxide
Change at least one of hydrogen, the reducing agent is inorganic reducing agent and/or organic reducing agent, and the inorganic reducing agent is selected from sulfurous
At least one of sour hydrogen sodium, sodium sulfite, rongalite, sodium thiosulfate, ferrous sulfate and sodium hydrosulfite, the organic reducing agent
Selected from N, N '-dimethyl ethylenediamine, N, N '-dimethyl -1,3- propane diamine, N, N, N ', N '-tetramethylethylenediamines, N, N- diformazans
At least one of base ethamine and 3- methylamino propylamine.
In the present invention, it is preferred to which the polymerisation carries out in the presence of auxiliary agent, the auxiliary agent is selected from chelating agent, chain extender
With it is one or more in other auxiliary agents；The chelating agent is selected from disodium ethylene diamine tetraacetate, triethylenediamine pentaacetic acid, lemon
At least one of acid, citrate and poly- hydroxy acrylic acid；The chain extender is selected from N, N '-dimethyl ethylenediamine, N, N, N ',
N '-tetramethylethylenediamines, N, N- dimethyl amines, 3- methylaminos propylamine, N, N '-dimethyl -1,3- propane diamine, 1- (dimethyl
Amino) at least one of -2- propylamine and diethylenetriamines；Other auxiliary agents are selected from urea, sodium formate, isopropanol and secondary
At least one of sodium phosphate.
In the present invention, it is preferred to the polymerisation carries out in the presence of an inert gas, the condition packet of the polymerisation
It includes：Temperature is 30-50 DEG C, and the time is 2-8 hour, and pH value is 6-8 when needing that sour regulation system pH value is added, and the acid is preferred
For inorganic acid, the inorganic acid can be at least one of hydrochloric acid, sulfuric acid, sulfonic acid, nitric acid and phosphoric acid.When need be added alkali tune
When saving system pH, the alkali can be inorganic base or organic amine compound, can such as be selected from sodium hydroxide, potassium hydroxide,
At least one of ammonium hydroxide, methylamine, ethamine, ethanol amine and triethanolamine, preferably sodium hydroxide.
The third aspect contains acrylamide the present invention provides a kind of shale gas pressure break drag reducer in the drag reducer
Terpolymer, stabilizer, inorganic salts and water, the Acrylamide terpolymer are the foregoing acryloyl of the present invention
Amine system terpolymer or for by the acryloyl that is prepared of preparation method of the Acrylamide terpolymer of the present invention
Amine system terpolymer.
Under preferable case, in the present invention, on the basis of the total weight of the drag reducer, the acrylamide ternary is total
The content of polymers is 10-30 weight %, and the content of the stabilizer is 0.5-2 weight % and the content of the inorganic salts is
15-30 weight %.
In the case of more preferably, in the present invention, on the basis of the total weight of the drag reducer, the acrylamide three
The content of membered copolymer is 15-25 weight %, and the content of the stabilizer is the content of 0.5-1 weight % and the inorganic salts
For 18-25 weight %.
In the present invention, the stabilizer is the water-soluble low-molecular with certain solubility property in inorganic salt solution
Weight polymers, the Acrylamide terpolymer obtained by monomer D, the monomer E and monomer F random copolymerizations of the present invention exist
It is precipitated in inorganic salt solution, becomes polymer billet, a stabilizer part is adsorbed on its surface, another portion by physical action
Divide and stretch in aqueous solution, to be formed on its surface aquation adsorption layer, by electrical charge rejection and space steric effect, protection is poly-
It closes object micelle not coalesce, so that polymer billet is steadily suspended in aqueous solution, form milky aqueous dispersion lotion.
In the case of in the present invention, it is preferred to, the stabilizer is to contain the structural unit A's and structural unit G
Bipolymer, wherein the structural unit A is the structural unit with structure shown in formula (1), and the structural unit G is tool
There is the structural unit of structure shown in formula (7), and on the basis of the total weight of the stabilizer, the content of the structural unit A is
The content of 0.1-10 weight %, the structural unit G are 90-99.9 weight %, and the viscosity average molecular weigh of the stabilizer is 300,000
To 800,000,
Wherein, in formula (1), R1For H, methyl, ethyl, n-propyl or isopropyl；And/or
In formula (7), R5And R6It is each independently the alkyl of H or C1-C4, R4For H, methyl, ethyl, n-propyl or different
Propyl, n are the integer of 1-4, M Li, Na, K, Rb or Cs.
In the case of more preferably, in the present invention, the stabilizer is to contain the structural unit A and the structural unit
The bipolymer of G, the structural unit A be the structural unit with structure shown in formula (1), the structural unit G be with
The structural unit of structure shown in formula (7), in formula (1), R1For H；In formula (7), R4、R5And R6It is methyl, n 1, M are
Na。
In the present invention, it is preferred to which the inorganic salts include Na2SO4、NaH2PO4、K2CO3、(NH4)2HPO4, NaCl and (NH4)2SO4At least one of.
Acrylamide terpolymer of the present invention can be soluble in water, but in the inorganic salt solution of the present invention
It is insoluble.
Fourth aspect, the present invention provides a kind of preparation method of shale gas pressure break drag reducer, this method includes：The party
Method includes：Under the conditions of the solution polymerization of alkene, in the presence of initiator, by the list containing monomer D, monomer E and monomer F
Body mixture, stabilizer and inorganic salts carry out hybrid reaction, wherein and the monomer D is the monomer with structure shown in formula (4),
The monomer E is the monomer with structure shown in formula (5), and the monomer F is the monomer with structure shown in formula (6),
Wherein, R1-R3And the m and M such as present invention is defined before.
Under preferable case, in the present invention, with the total weight of the monomer mixture, the dosage of the monomer D is 40-
The dosage of 75 weight %, the monomer E is that the dosage of 5-30 weight %, the monomer F are 5-50 weight %.
Under preferable case, in the present invention, on the basis of the total weight for the shale gas pressure break drag reducer being prepared, institute
The dosage for stating monomer mixture is 10-35 weight %, more preferably 15-25 weight %；The dosage of the inorganic salts is 10-35 weights
Measure %, more preferably 18-25 weight %；The dosage of the stabilizer is 0.01-5 weight %, preferably 0.5-1 weight %.
In the present invention, the initiator, inorganic salts, the type such as present invention of stabilizer are noted earlier.
In the present invention, it is preferred to which the condition of the hybrid reaction includes：Temperature is 30-50 DEG C, and the time is 2-8 hours, pH
Value is 6-8.
In the case of more preferably, the condition of the hybrid reaction includes：Temperature is 35-45 DEG C, and the time is 4-6 hours, pH
Value is 6-8.
In the case of in the present invention, it is preferred to, on the basis of the total weight for the shale gas pressure break drag reducer being prepared, institute
The dosage for stating initiator is that the dosage of initiator is 0.0001-0.05 weight %, preferably 0.001-0.01 weight %, more preferably
For 0.005-0.008 weight %.
The present invention will be described in detail by way of examples below.
According to the present invention, in following embodiment, the resistance reducing performance test condition of pressure break drag reducer is as follows：Fracturing fluid drag reduction
The resistance reducing performance test of agent is measured by fracturing fluid drag reducer measurement device, and condition is as follows：Under room temperature, fracturing fluid drag reducer is added molten
Tank is solved, after ten minutes, solution enters test section by pump conveying outflow through spinner flowmeter for stirring.It is measured and is flowed with spinner flowmeter
Amount, uninterrupted measure pressure drop of the solution by test section by Frequency Converter Control.Test pipe diameter 0.635cm tests pipeline section
Length is 3m, a concentration of 0.1 weight % of fracturing fluid drag reducer in deionized water, and drag reducing efficiency (DR) is calculated as follows：
Wherein, Δ P0For deionized water pressure drop, unit Pa；Δ P be fracturing fluid dreg reducer solution with water-soluble liquid phase
Pressure drop under same Reynolds constant, unit Pa.
Acrylamide used in the present invention, chemistry is pure, is purchased from Shandong Polymer Bio-Chemicals Co., Ltd.；Made
N- (2- hydroxypropyls) Methacrylamide, analysis is pure, is purchased from Sinopharm Chemical Reagent Co., Ltd.；Used sulfuric acid
Ammonium, hydrochloric acid, chemistry is pure, purchased from Tianjin recovery fine chemistry industry research institute；Used 2- acrylamide-2-methylpro panesulfonic acids
The double methylpent hydrochlorates of sodium, two isobutyl imidazoline hydrochloride of azo, 2,2 '-azo diisobutyl amidine hydrochlorides and azo are purchased from
aldrich。
Preparation example 1
This preparation example is used to prepare stabilizer used in the present invention.
In the 1.5L polymeric kettles equipped with thermometer, stirring rod and condenser pipe, acrylamide 10g, 2- acrylamide is added
Base -2- methyl propane sulfonic acid sodium 190g and deionized water 800g, are warming up to 60 DEG C, after being completely dissolved, and lead to nitrogen deoxygenation, and azo is added
Two isobutyl imidazoline hydrochloride 0.2g stop reaction after being stirred to react 6 hours, drying crushes, and it is spare to obtain stabilizer W.
Preparation example 2
This preparation example is used to prepare Acrylamide terpolymer of the present invention.
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Deionized water 595g, acrylamide 134.6g, sodium acrylate 47.4g, N- (2- hydroxypropyls) Methacrylamide 18g is added, stirs
It mixes and is warming up to 40 DEG C after so that solid is completely dissolved；2,2 '-azo diisobutyl amidine hydrochlorides are added in logical nitrogen after twenty minutes
0.02g obtains the Acrylamide terpolymer that viscosity average molecular weigh is 55.7 ten thousand, to this after continuing logical nitrogen gas stirring reaction 3h
Acrylamide terpolymer carries out IR spectroscopic assays, 1660cm in IR spectrum-1And 1635cm-1Place belongs to respectively
The amide Ⅰ absorption peak (C=O stretching vibrations) and amide II of amide groups are with absorption peak (N-H bending vibrations)；In 1430cm-1Place
There is the stretching vibration absworption peak of C-N；1356 and 1401cm-1There is typical methyl symmetric curvature vibration absorption peak；2923cm-1、2852cm-1Place's appearance is respectively belonging to-CH2-、-CH3C-H stretching vibrations；1467cm-1Appearance belongs to-CH2-、-CH3
C-H bending vibrations；3321cm-1Appearance belongs to the stretching vibration peak of CO-NH and C-OH.Characteristic peak in above-mentioned IR spectrum can
To determine that obtained copolymer molecule is the copolymer with formula：
Wherein, x, y and z only represent the type and number of structural unit, and do not indicate that the connection type of structural unit.x、
The concrete numerical value of y and z is determined by inventory.
Embodiment 1
The present embodiment is used to illustrate the preparation method of shale gas pressure break drag reducer of the present invention and prepares the present invention
The shale gas pressure break drag reducer.
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Deionized water 595g, ammonium sulfate 200g, acrylamide 134.6g, sodium acrylate 47.4g, N- (2- hydroxypropyls) metering system is added
Amide 18g, stabilizer W 5g, stirring are warming up to 35 DEG C after so that solid is completely dissolved；Logical nitrogen is after 30 minutes；It is even to be added 2,2 '-
Nitrogen diisobutyl amidine hydrochloride 0.05g obtains the milky that apparent viscosity is 275mPa.s after continuing logical nitrogen gas stirring reaction 4h
Dispersion liquid, at room temperature can be 12 months with storage-stable.
Comparative example 1
The method that this comparative example prepares fracturing fluid drag reducer with embodiment 1 is identical, and institute is the difference is that the preparation method
In N- (2- hydroxypropyls) Methacrylamide change 2- acrylamide-2-methylpro panesulfonic acid sodium into；As a result apparent viscosity is obtained
For the milky viscous fluid of 5600mPa.s.
Embodiment 2
The present embodiment is used to illustrate the preparation method of shale gas pressure break drag reducer of the present invention and prepares the present invention
The shale gas pressure break drag reducer.
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Deionized water 550g, ammonium sulfate 250g, acrylamide 89.8g, sodium acrylate 19.8g, N- (2- hydroxypropyls) metering system is added
Amide 90.4g, stabilizer W 10g, stirring are warming up to 45 DEG C after so that solid is completely dissolved；Logical nitrogen is after 30 minutes；It is added 2,2 '-
Azo diisobutyl amidine hydrochloride 0.08g obtains apparent viscosity as the milky white of 270mPa.s after continuing logical nitrogen gas stirring reaction 6h
Color dispersion liquid, at room temperature can be 12 months with storage-stable.
Embodiment 3
The present embodiment is used to illustrate the preparation method of shale gas pressure break drag reducer of the present invention and prepares the present invention
The shale gas pressure break drag reducer.
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Deionized water 572g, ammonium sulfate 220g, acrylamide 124.2g, sodium acrylate 41g, N- (2- hydroxypropyls) methacryl is added
Amine 34.8g, stabilizer A 8g, stirring are warming up to 35 DEG C after so that solid is completely dissolved；Logical nitrogen is after 30 minutes；It is even to be added 2,2 '-
Nitrogen diisobutyl amidine hydrochloride 0.05g obtains the milky that apparent viscosity is 272mPa.s after continuing logical nitrogen gas stirring reaction 4h
Dispersion liquid, at room temperature can be 12 months with storage-stable.
Embodiment 4
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Deionized water 595g, ammonium sulfate 300g, acrylamide 134.6g, sodium acrylate 47.4g, N- (2- hydroxypropyls) metering system is added
Amide 18g, stabilizer W 5g, stirring are warming up to 35 DEG C after so that solid is completely dissolved；Logical nitrogen is after 30 minutes；It is even to be added 2,2 '-
Nitrogen diisobutyl amidine hydrochloride 0.05g obtains the milky that apparent viscosity is 311mPa.s after continuing logical nitrogen gas stirring reaction 4h
Dispersion liquid, at room temperature can be 12 months with storage-stable.
Embodiment 5
In the 1.5L four-hole bottles equipped with condenser pipe, temperature controller, constant speed mechanical agitator, nitrogen inlet and constant pressure addition device
Deionized water 550g, ammonium sulfate 150g, acrylamide 89.8g, sodium acrylate 19.8g, N- (2- hydroxypropyls) metering system is added
Amide 90.4g, stabilizer W 10g, stirring are warming up to 45 DEG C after so that solid is completely dissolved；Logical nitrogen is after 30 minutes；It is added 2,2 '-
Azo diisobutyl amidine hydrochloride 0.08g obtains apparent viscosity as the milky white of 302mPa.s after continuing logical nitrogen gas stirring reaction 6h
Color dispersion liquid, at room temperature can be 12 months with storage-stable.
Testing example
This testing example is illustrating that the fracturing fluid drag reducer that 1-5 of the embodiment of the present invention and comparative example 1 are prepared exists
Drag-reduction effect in deionized water.
The drag reducing efficiency (DR%) for the fracturing fluid drag reducer being prepared in testing example 1-5 and comparative example 1 respectively, knot
Fruit is as shown in table 1.
Table 1
It was found from the data in table 1：In embodiment 1-5, fracturing fluid drag reducer prepared by the present invention of 0.2 weight % exists
Drag reducing efficiency in deionized water is up to 77.6%, and in concentration to be only 0.1 weight % still have higher resistance-reducing efficiency；And it is right
Ratio 1, since obtained product is sticky, dissolve still has part undissolved in deionized water after ten minutes, and resistance-reducing yield is only
60.5%, but when using a concentration of 0.1 weight %, resistance-reducing yield declines rapidly, only 35.5%, there is apparent concentration dependant
Property is restricted in commercial Application.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of Acrylamide terpolymer, which is characterized in that the Acrylamide terpolymer contains structural unit
A, structural unit B and structural unit C, wherein the structural unit A is the structural unit with structure shown in formula (1), the knot
Structure unit B is the structural unit with structure shown in formula (2), and the structural unit C is the structure list with structure shown in formula (3)
Member, and on the basis of the total mole number of structural unit in the Acrylamide terpolymer, the content of the structural unit A
Content for 60-75 moles of %, the structural unit B is 10-20 moles of %, and the content of the structural unit C is rubbed for 5-30
You are %；The viscosity average molecular weigh of the Acrylamide terpolymer is 3,000,000 to 15,000,000；
Wherein, in formula (1), R1For H, methyl, ethyl, n-propyl or isopropyl；
In formula (2), M Li, Na, K, Rb or Cs；
In formula (3), R2For the alkyl of C1-C5, R3For H, methyl, ethyl, n-propyl or isopropyl, m is the integer of 1-3.
2. copolymer according to claim 1, wherein in formula (1), R1For H；And/or
In formula (2), M Na；And/or
In formula (3), R2And R3It is methyl, m 1.
3. a kind of preparation method of Acrylamide terpolymer, wherein this method is included in the solution polymerization of alkene
Under the conditions of, in the presence of initiator, so that monomer mixture is carried out polymerisation in water, the monomer mixture contain monomer D,
Monomer E and monomer F, the monomer D are the monomer with structure shown in formula (4), and the monomer E is with structure shown in formula (5)
Monomer, the monomer F is the monomer with structure shown in formula (6), and with the total mole number of monomer in the monomer mixture
On the basis of, the content of the monomer D is 60-75 moles of %, and the content of the monomer E is 10-20 moles of %, the monomer F's
Content is 5-30 moles of %；The condition of the polymerisation so that the viscosity average molecular weigh of gained copolymer after polymerisation is 300
Ten thousand to 15,000,000；
Wherein, R1-R3And m and M is as defined in above-mentioned claims 1 or 2.
4. a kind of shale gas pressure break drag reducer, wherein in the drag reducer containing Acrylamide terpolymer, stabilizer,
Inorganic salts and water, the Acrylamide terpolymer be Acrylamide terpolymer as claimed in claim 1 or 2 or
Person is the Acrylamide terpolymer being prepared by the method for claim 3.
5. drag reducer according to claim 4, wherein on the basis of the total weight of the drag reducer, the acrylamide
The content for being terpolymer is 10-30 weight %, and the content of the stabilizer is 0.5-2 weight % and the inorganic salts
Content is 15-30 weight %.
6. drag reducer according to claim 4, wherein the stabilizer is to contain the structural unit A and the structure
The bipolymer of unit G, wherein the structural unit A is the structural unit with structure shown in formula (1), the structure list
First G is the structural unit with structure shown in formula (7), and on the basis of the total weight of the stabilizer, the structural unit A's
Content is that the content of 0.1-10 weight %, the structural unit G are 90-99.9 weight %, the viscosity average molecular weigh of the stabilizer
It is 300,000 to 800,000,
Wherein, in formula (1), R1For H, methyl, ethyl, n-propyl or isopropyl；And/or
In formula (7), R5And R6It is each independently the alkyl of H or C1-C4, R4For H, methyl, ethyl, n-propyl or isopropyl,
N is the integer of 1-4, M Li, Na, K, Rb or Cs.
7. drag reducer according to claim 6, wherein in formula (1), R1For H；And/or in formula (7), R4、R5And R6
It is methyl, n 1, M Na.
8. drag reducer according to claim 6, wherein the inorganic salts include Na2SO4、NaH2PO4、K2CO3、(NH4)2HPO4, NaCl and (NH4)2SO4At least one of.
9. a kind of preparation method of shale gas pressure break drag reducer, this method include：This method includes：In the polymerisation in solution of alkene
Under reaction condition, in the presence of initiator, monomer D, the monomer mixture of monomer E and monomer F, stabilizer, inorganic salts will be contained
Hybrid reaction is carried out with water, wherein the monomer D is the monomer with structure shown in formula (4), and the monomer E is with formula (5)
The monomer of shown structure, the monomer F are the monomer with structure shown in formula (6),
Wherein, R1-R3And m and M is as defined in above-mentioned claims 1 or 2.
10. according to the method described in claim 9, wherein, with the total weight of the monomer mixture, the use of the monomer D
It is the dosage of 5-30 weight %, the monomer F is 5-50 weight % that amount, which is the dosage of 40-75 weight %, the monomer E,.
11. according to the method described in claim 9, wherein, the total weight with the shale gas pressure break drag reducer being prepared is
The dosage of benchmark, the monomer mixture is 10-35 weight %；The dosage of the inorganic salts is 10-35 weight %；The stabilization
The dosage of agent is 0.01-5 weight %.
12. according to the method for claim 11, wherein the total weight with the shale gas pressure break drag reducer being prepared is
The dosage of benchmark, the monomer mixture is 15-25 weight %；The dosage of the inorganic salts is 18-25 weight %；The stabilization
The dosage of agent is 0.5-1 weight %.
13. according to the method described in claim 9, wherein, the condition of the hybrid reaction includes：Reaction temperature is 30-50 DEG C,
Reaction time is 2-8h.
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