CN104974737A - Resistance reducing agent for fracture and preparation method thereof - Google Patents
Resistance reducing agent for fracture and preparation method thereof Download PDFInfo
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- CN104974737A CN104974737A CN201410141765.7A CN201410141765A CN104974737A CN 104974737 A CN104974737 A CN 104974737A CN 201410141765 A CN201410141765 A CN 201410141765A CN 104974737 A CN104974737 A CN 104974737A
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Abstract
The invention relates to a preparation method of a resistance reducing agent for fracture. The preparation method includes the steps of: (1) mixing an acrylamide-series monomer, an anionic monomer containing a double bond, a cationic polymer template, a chelating agent and a molecular weight regulating agent with water with pH value being regulated to obtain a water solution of which the pH value is 6-9; (2) contacting an organic solvent with an emulsification agent to obtain an oil solution; (3) contacting the water solution with the oil solution to obtain a water-in-oil emulsion; and (4) under an inert atmosphere, contacting the water-in-oil emulsion with an initiator in batches, performing a polymerization reaction to obtain a mixture, and contacting the mixture with a phase conversion agent. The emulsification agent is 4-6 in hydrophilic-lipophilic balance value, the molecular weight of the anionic polymer template is less than 1000000, and the structure formula of the anionic polymer template is represented as the formula (I). The invention also relates to the resistance reducing agent for fracture prepared through the method. The resistance reducing agent for fracture is high in resistance reducing rate, is high in inhibition on clay expansion, is good in water solubility and is low in formation damage property.
Description
Technical field
The present invention relates to a kind of pressure break friction reducer, and a kind of preparation method of pressure break friction reducer.
Background technology
The reservoir of shale gas has the feature of low porosity and low permeability, exploitation difficulty is large, main employing slippery water fracturing technology exploitation at present, fracturing liquid is by after the supercharging of high-pressure pump injection device, pump into stratum at a high speed by tubing string, under high-voltage high-speed condition, fluid turbulent phenomenon in Bottomhole pressure process is serious, has larger friction resistance between fracturing liquid and tube wall, the friction resistance of fluid limits fluid flowing in the duct, causes pipeline throughput rate to reduce and energy waste increase.Therefore, need to adopt the method for adding friction reducer in a fluid to reduce the impact of friction resistance, improve operating efficiency.
Friction reducer adds a small amount of high molecular polymer or tensio-active agent in a liquid, makes liquid significantly reduce resistance, also referred to as Toms effect when turbulent flows by affecting turbulence structure.High molecular polymer resistance-reducing yield is high, low price, polymer friction reducer conventional in slippery water fracturing liquid is mainly guanidine glue and polyacrylamide polymer, and the insolubles of guanidine glue is generally about 8%, after broken glue, residue is more simultaneously, and the injury in formation and crack is larger.The insolubles of polyacrylamide polymer hydrolysis is relatively less, has certain resistance-reducing performance and resistant to shearing ability.
Patent application CN103045226A discloses a kind of friction reducer and preparation method thereof and slippery water fracturing liquid using this friction reducer and preparation method thereof, this friction reducer is using polyoxyethylene as mainly falling resistance composition, there is good resistance-reducing performance, but organic solvent account for friction reducer quality product 40% ~ 85%, nonionogenic tenside account for 0 ~ 10% of friction reducer quality product, there is serious environmental problem, polyoxyethylene resistant to shearing ability is poor in addition, can degrade rapidly in the slippery water pressing crack construction of high-shear, cause resistance-reducing performance to decline.
Patent application CN102977877A discloses a kind of shale gas pressure break flow improver and preparation method thereof, it is acrylamide triggered by free radical under the protection of dispersion agent in salt brine solution, 2-acrylamide-2-methylpro panesulfonic acid sodium and sodium acrylate three kinds of monomers carry out random copolymerization and obtain emulsus, homodisperse friction reducer, there is good resistant to shearing performance, but the product prepared according to the method for this patent application lumps after placing and spending the night, viscosity is very high, flow difficulties, site operation requirement cannot be met, and under flow comparatively low condition, the resistance-reducing efficiency of the friction reducer of this invention synthesis is only 20%.
Therefore, be badly in need of now that a kind of dissolution rate is fast, resistance-reducing yield is high, package stability is high, clay swelling inhibition is high, anti-shear performance good and the friction reducer of the advantage such as formation damage is low and preparation method thereof.
Summary of the invention
The defects such as the dissolution rate that the object of the invention is to overcome friction reducer in above-mentioned prior art is slow, resistance-reducing yield is low, package stability is low, clay swelling inhibition is low, anti-shear performance is poor and formation damage is high, a kind of preparation method of pressure break friction reducer is provided, and pressure break friction reducer prepared by a kind of the method.
The present inventor finds under study for action, as long as be the aqueous solution of 6-9 by obtained for the mixing of acrylamide monomer, double bond containing anionic monomer, cationic polymers template, sequestrant, molecular weight regulator and water pH value; Then this aqueous solution is made water-in-oil emulsion, under an inert atmosphere, water-in-oil emulsion is carried out polyreaction, the mixture then polyreaction obtained contacts with phase inversion agent; Wherein, the hydrophile-lipophile balance value of described emulsifying agent is 4-6, the molecular weight of described cationic polymers template is less than 1,000,000, the structural formula of described cationic polymers template, as shown in formula (I) below, can obtain the friction reducer that dissolution rate is fast, resistance-reducing yield is high, clay swelling inhibition is high, anti-shear performance good and formation damage is low.
R
1hydrogen or methyl;
A is O or NH;
R
2c
1-C
6alkylidene group;
R
3, R
4, R
5c
1-C
6alkyl;
Z is chlorine, bromine or iodine.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of preparation method of pressure break friction reducer, the method comprises:
(1) by acrylamide monomer, double bond containing anionic monomer, cationic polymers template, sequestrant, molecular weight regulator and water mixing also adjust ph, the aqueous solution that pH value is 6-9 is obtained;
(2) organic solvent is contacted with emulsifying agent, obtain oil solution;
(3) oil solution that aqueous solution step (1) obtained and step (2) obtain contacts, and obtains water-in-oil emulsion;
(4) under an inert atmosphere, contacted with initiator by the water-in-oil emulsion that step (3) obtains in batches, and carry out polyreaction, the mixture then polyreaction obtained contacts with phase inversion agent;
Wherein, the hydrophile-lipophile balance value of described emulsifying agent is 4-6, and the molecular weight of described cationic polymers template is less than 1,000,000, the structural formula of described cationic polymers template as shown in the formula (I):
R
1hydrogen or methyl;
A is O or NH;
R
2c
1-C
6alkylidene group;
R
3, R
4, R
5c
1-C
6alkyl;
Z is chlorine, bromine or iodine.
On the other hand, present invention also offers the pressure break friction reducer prepared according to aforesaid method.
Compared with the polymerization process of conventional inverter emulsion, preparation method of the present invention adopts the method adding high polymer template in polymerization reaction system, interacted by the hydrogen bond between polymer template molecule and polymerization single polymerization monomer, Van der Waals, electrostatic attraction or covalent linkage interact, the sequence of change polymerization rate, molecular weight product and molecular weight distribution, product copolymerization units is arranged evenly, the sterie configuration of product; By adjusting the distribution of acrylamide unit and anionic units block, change the molecular configuration of friction reducer polymkeric substance, space structure, thus improve resistance-reducing performance and the anti-shear performance of product, due to the distribution of different polymerized unit block, friction reducer product hydrolysis product occurs without insolubles, and due to the Relatively centralized of anionic units, the hydration swelling of hydrolysate to clay has obvious restraining effect.
The friction reducer that the present invention obtains rapid solution in water, can not form flake, meets the requirement of the online mixture of slippery water pressure break; The maximum resistance-reducing yield of the aqueous solution of the friction reducer of mass concentration 1% is 71.8-80%; And friction reducer hydrolysate occurs without insolubles, formation nocuity is very low, and the core damage rate of the aqueous solution of mass concentration 1% friction reducer is 2.3-4.8%; The clay swelling inhibiting rate of the aqueous solution of the friction reducer of mass concentration 1% is 65.3-72%, has significant restraining effect to clay swelling, does not thus need in actual use to add new expansion-resisting agent again, significantly reduces the cost of slippery water.Therefore, the resistance-reducing yield of the pressure break friction reducer adopting method of the present invention to prepare is high, clay swelling inhibition is high, good water solubility, anti-shear performance are good and formation damage is low.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the resistance-reducing yield of pressure break friction reducer and the relation curve of flow.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of preparation method of pressure break friction reducer, the method comprises:
(1) by acrylamide monomer, double bond containing anionic monomer, cationic polymers template, sequestrant, molecular weight regulator and water mixing also adjust ph, the aqueous solution that pH value is 6-9 is obtained;
(2) organic solvent is contacted with emulsifying agent, obtain oil solution;
(3) oil solution that aqueous solution step (1) obtained and step (2) obtain contacts, and obtains water-in-oil emulsion;
(4) under an inert atmosphere, contacted with initiator by the water-in-oil emulsion that step (3) obtains in batches, and carry out polyreaction, the mixture then polyreaction obtained contacts with phase inversion agent;
Wherein, the hydrophile-lipophile balance value of described emulsifying agent is 4-6, and the molecular weight of described cationic polymers template is less than 1,000,000, the structural formula of described cationic polymers template as shown in the formula (I):
R
1hydrogen or methyl;
A is O or NH;
R
2c
1-C
6alkylidene group;
R
3, R
4, R
5c
1-C
6alkyl;
Z is chlorine, bromine or iodine.
According to method of the present invention, as long as by structural formula as shown in the formula (I) and the molecular weight described cationic polymers template that is less than 1,000,000, with acrylamide monomer, double bond containing anionic monomer, sequestrant, molecular weight regulator and water mixing, obtained pH value is the aqueous solution of 6-9, then oil solution obtained with the emulsifying agent by hydrophile-lipophile balance value being 4-6 for this aqueous solution is contacted, make water-in-oil emulsion, then polyreaction is carried out, contact with phase inversion agent again, dissolution rate can be obtained fast, resistance-reducing yield is high, clay swelling inhibition is high, the friction reducer that anti-shear performance is high and formation damage is low.But in order to make, the dissolution rate of the friction reducer obtained is faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, described cationic polymers template is preferably selected from polymethyl monomethacryloxypropyl trimethyl ammonium chloride, polymethyl acyloxyethyl trimethyl ammonium chloride, polyacrylamide oxy-ethyl-trimethyl salmiac and poly-N, N, at least one in N-trimethylammonium-3-[(1-oxo-2-propenyl) is amino] propyl ammonium chloride, is more preferably polymethyl acyloxyethyl trimethyl ammonium chloride.
Preferably, described cationic polymers template molecule amount is 1-100 ten thousand.
In the present invention, molecular weight all refers to viscosity-average molecular weight.
According to method of the present invention, acrylamide monomer, the consumption of double bond containing anionic monomer, cationic polymers template, sequestrant, molecular weight regulator, water can be the conventional amount used of this area, but in order to make, the dissolution rate of the friction reducer obtained is faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, relative to the described acrylamide monomer of 100 weight parts, the consumption of described double bond containing anionic monomer is preferably 10-100 weight part, is more preferably 20-50 weight part; The consumption of described cationic polymers template is preferably 1-15 weight part, is more preferably 1-5 weight part; The consumption of described sequestrant is preferably 0.001-5 weight part, is more preferably 0.02-0.2 weight part; The consumption of described molecular weight regulator is preferably 0.001-1 weight part, is more preferably 0.01-0.1 weight part; The consumption of described water is preferably 50-200 weight part, is more preferably 100-150 weight part.
According to method of the present invention, described acrylamide monomer can be the acrylamide monomer of this area for the preparation of the routine of polyacrylamide emulsion, but in order to make the dissolution rate of the friction reducer obtained faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, described acrylamide monomer is preferably selected from acrylamide, Methacrylamide, N, N-DMAA, N, N-acrylamide, NIPA, at least one in N hydroxymethyl acrylamide and N-hydroxyethyl acrylamide, be more preferably acrylamide.
According to method of the present invention, described double bond containing anionic monomer can be the double bond containing anionic monomer preparing polyacrylamide emulsion that can be used in well known in the art, in order to make the dissolution rate of the friction reducer obtained faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, described double bond containing anionic monomer is preferably selected from double bond containing unsaturated carboxylic acid and ammonium salt thereof, an alkali metal salt or alkaline earth salt, double bond containing unsaturated sulfonic acid and ammonium salt thereof, an alkali metal salt or alkaline earth salt, double bond containing unsaturated phosphonic acids and ammonium salt thereof, an alkali metal salt or alkaline earth salt, the acrylamide of double bond containing unsaturated sulfomethylation or phosphono oxidation and ammonium salt thereof, at least one in an alkali metal salt or alkaline earth salt, more preferably double bond containing unsaturated carboxylic acid and ammonium salt, an alkali metal salt or alkaline earth salt is selected from, at least one in double bond containing unsaturated sulfonic acid and ammonium salt, an alkali metal salt or alkaline earth salt, be more preferably at least one in vinylformic acid, sodium acrylate and 2-acrylamide-2-methylpro panesulfonic acid sodium, be more preferably sodium acrylate.
According to method of the present invention, described sequestrant can be any one sequestrant well known in the art, in order to make, the dissolution rate of the friction reducer obtained is faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, and described sequestrant is preferably selected from least one in disodium ethylene diamine tetraacetate, Triethylene Diamine pentaacetic acid, citric acid, Citrate trianion and poly-hydroxyl acrylic; Be more preferably disodium ethylene diamine tetraacetate and/or Citrate trianion, described Citrate trianion is preferably selected from least one in Tripotassium Citrate, Trisodium Citrate, citrate of lime and ammonium citrate.
According to method of the present invention, to described molecular weight regulator, there is no particular limitation, such as, can be selected from least one in sodium formiate, sodium acetate, glycerine and Virahol, is preferably sodium formiate.
According to method of the present invention, described water can be the experimental water of this area routine, such as, can be distilled water and/or deionized water.
According to method of the present invention, in step (1), the order of acrylamide monomer, double bond containing anionic monomer, cationic polymers template, sequestrant, molecular weight regulator and water mixing is not particularly limited, as long as acrylamide monomer, double bond containing anionic monomer, cationic polymers template, sequestrant, molecular weight regulator and water can be made to be present in reaction system simultaneously.
According to method of the present invention, in step (1), the condition of acrylamide monomer, double bond containing anionic monomer, cationic polymers template, sequestrant, molecular weight regulator and water mixing can at room temperature to stir, preferably, the condition of mixing comprises: temperature 15-25 DEG C, is stirred to and dissolves completely.
According to method of the present invention, in step (1), to the method for described adjust ph, there is no particular limitation, the method of the adjust ph that this area routine can be adopted to use, such as, can be regulated the pH value of the aqueous solution by the method adding alkali or acid in reaction mixture, to described alkali, there is no particular limitation, as long as can make the pH value of the described aqueous solution in the scope of 6-9 with sour kind.
According to method of the present invention, in step (2), to the consumption of described organic solvent, there is no particular limitation, in order to make, the dissolution rate of the friction reducer obtained is faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, relative to the described acrylamide monomer of 100 weight parts, the consumption of described organic solvent is preferably 50-200 weight part, is more preferably 90-150 weight part.
According to method of the present invention, described organic solvent can be any one organic solvent well known by persons skilled in the art, and described organic solvent can be selected from least one in toluene, dimethylbenzene, hexane, hexanaphthene, normal heptane, isoparaffin, gasoline, kerosene and white oil; In order to make, the dissolution rate of the friction reducer obtained is faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, is preferably at least one in toluene, dimethylbenzene, normal heptane, isoparaffin, gasoline, kerosene and white oil; Be more preferably isoparaffin and/or white oil; Be more preferably boiling point higher than 150 DEG C, the flash-point isoparaffin and/or the white oil that are greater than 60 DEG C.
According to method of the present invention, in step (2), to the consumption of described emulsifying agent, there is no particular limitation, but in order to make, the dissolution rate of the friction reducer obtained is faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, relative to the described acrylamide monomer of 100 weight parts, the consumption of described emulsifying agent is preferably 5-20 weight part, is more preferably 8-15 weight part.
According to method of the present invention, in order to water in oil emulsion can be obtained in step (3), as long as the hydrophile-lipophile balance value of described emulsifying agent is defined as 4-6, but, in order to make the dissolution rate of the friction reducer obtained faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, described emulsifying agent is preferably nonionic emulsifying agent, more preferably sorbitan oleate is selected from, sorbitan monooleate Soxylat A 25-7, alkylphenol polyoxyethylene, benzylphenol oxygen Soxylat A 25-7, at least one in styroyl phenol polyethenoxy ether and aliphatic amine polyoxyethylene ether.
According to method of the present invention, in step (3), the contact order of addition of the described aqueous solution and described oil solution does not limit, and can add in the described aqueous solution by described oil solution, also the described aqueous solution can be added in described oil solution, the present invention is not particularly limited.But in order to more be conducive to the stability improving the water-in-oil emulsion obtained, thus make that the dissolution rate of the friction reducer obtained is faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, preferably, the described aqueous solution is added in described oil solution carry out contact mixing.Contact hybrid mode the present invention of described oil solution and the described aqueous solution is also not particularly limited, as long as the two contact mixing can form stable water-in-oil emulsion, preferably, carry out, to form stable water-in-oil emulsion under the contact of described oil solution and the described aqueous solution is blended in high speed shear emulsifying effect.In the present invention, described stable water-in-oil emulsion refers to monomer solution (drop) under the effect of emulsifying agent to be disperseed in organic solvent with short grained form equably.
According to method of the present invention, in step (4), the consumption of described initiator can be conventional amount used, but in order to make, the dissolution rate of the friction reducer obtained is faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, relative to the described acrylamide monomer of 100 weight parts, the consumption of described initiator is preferably 0.001-2 weight part, is more preferably 0.01-0.2 weight part.
According to method of the present invention, described initiator can be the conventional initiator for polyreaction, can be water soluble, redox system initiator and/or azo-initiator, wherein, described water soluble, redox system contains Oxidizing and Reducing Agents, preferably, the mass ratio of described Oxidizing and Reducing Agents is 5:1-1:1, described oxygenant is selected from hydrogen peroxide, persulphate, potassium permanganate, bromate, benzoyl peroxide, tert-butyl peroxide, at least one in ditertiary butyl peroxide and dicumyl peroxide, described reductive agent is selected from hydrosulphite, sulphite, rongalite, Sulfothiorine, vat powder, at least one in triethylamine and Tetramethyl Ethylene Diamine, azo-initiator is selected from 2, 2 '-azo diisobutyl amidine hydrochloride and 2, at least one in 2 '-azo [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride].
According to method of the present invention, in step (4), the consumption of described phase inversion agent can be conventional amount used, but in order to make, the dissolution rate of the friction reducer obtained is faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, relative to the described acrylamide monomer of 100 weight parts, the consumption of described phase inversion agent is preferably 1-20 weight part, is more preferably 5-10 weight part.
According to method of the present invention, as long as described phase inversion agent can ensure friction reducer when keep higher resistance-reducing yield in water-soluble dissolution rate comparatively fast, in order to make the dissolution rate of the friction reducer obtained faster, resistance-reducing yield is higher, clay swelling inhibition is higher, shear resistant is higher and formation damage is lower, preferably, described phase inversion agent is selected from polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, Ben-zylphenol Polyoxyethyl Ether, styroyl phenol polyethenoxy ether, isomery ten polyoxyethylenated alcohol, isomery undecyl alcohol Soxylat A 25-7, at least one in isomerous tridecanol polyoxyethylene ether and aliphatic amine polyoxyethylene ether, more preferably at least one in polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, Ben-zylphenol Polyoxyethyl Ether, styroyl phenol polyethenoxy ether, isomery ten polyoxyethylenated alcohol, isomery undecyl alcohol Soxylat A 25-7 and isomerous tridecanol polyoxyethylene ether is selected from.
According to method of the present invention, in step (4), the mode providing inert atmosphere can be the various methods of this area routine, such as, can pass into nitrogen and/or argon gas in reaction system.
According to method of the present invention, in step (4), described water-in-oil emulsion contacts with described initiator, there is no particular limitation for the order of adding, can water-in-oil emulsion be joined in initiator, also can initiator be joined in water-in-oil emulsion, preferably, described initiator is joined in batches in described water-in-oil emulsion, in the present invention, add in batches and refer to and point to add for 3-5 time, for often criticizing the amount added, there is no particular limitation, as long as the total amount added within the scope of the invention.When initiator is water soluble, redox system initiator, first add reductive agent, then divide 3-5 time to add oxygenant, also first can add oxygenant, then divide 3-5 time to add reductive agent, preferably, first add oxygenant, then divide 3-5 time to add reductive agent.
According to method of the present invention, in step (4), to the temperature contacted of described water-in-oil emulsion and described initiator, there is no particular limitation, such as, can be 15-25 DEG C.
According to method of the present invention, in step (4), the mixture that polyreaction obtains contacts with phase inversion agent, there is no particular limitation for the order of adding, can phase inversion agent be joined in mixture, also mixture can be joined in phase inversion agent, preferably, described phase inversion agent be joined in mixture.
According to method of the present invention, in step (4), for the condition of polyreaction without particular requirement, can adopt the condition of this area routine, such as, the condition of polyreaction can comprise: temperature is 20-50 DEG C, and the reaction times is 4-8 hour.
According to method of the present invention, in step (4), the condition that the mixture that polyreaction obtains contacts with phase inversion agent can for stir at conventional temperatures, preferably, the condition of contact comprises: temperature is 20-30 DEG C, and stirring velocity is 50-200rpm, and churning time is 20-40min.
On the other hand, present invention also offers the pressure break friction reducer prepared according to method as above.
Embodiment
The reagent used in embodiment and comparative example is commercially available product, and identical rule of origin is identical,
In embodiment and comparative example, molecular weight all refers to viscosity-average molecular weight; The hydrophile-lipophile balance value (HLB) of Span-80 is the hydrophile-lipophile balance value (HLB) of 4.3, Tween-80 is 10, and the HLB of blending emulsifiers is according to formulae discovery below:
Massfraction × 4.3+Tween-80 massfraction × 10 of the HLB=Span-80 of blending emulsifiers
Embodiment 1
The present embodiment is for illustration of pressure break friction reducer of the present invention and preparation method thereof.
(1) under 15 DEG C of conditions, by 100g acrylamide, 35g vinylformic acid, 2g polymethyl acyloxyethyl trimethyl ammonium chloride (molecular weight is 200,000), 0.1g disodium ethylene diamine tetraacetate, 0.05g sodium formiate and 120g deionized water mix in 1000mL beaker, are stirred to and dissolve completely, then slowly add the aqueous sodium hydroxide solution adjust ph to 8 of 10 % by weight wherein, obtain the aqueous solution that pH value is 8;
(2) 10.5g Span-80 and 1.5g Tween-80 is mixed to get blending emulsifiers, the hydrophile-lipophile balance value calculating this blending emulsifiers is 5, then by blending emulsifiers and 120g white oil, (boiling point boiling range is 220-255 DEG C, flash-point is 80 DEG C) be mixed in 1500mL beaker and dissolve completely, obtain oil solution;
(3) aqueous solution that step (1) obtains is joined in the oil solution obtained with step (2), with high speed shear dispersion and emulsion device emulsification 1min, obtain stable water-in-oil emulsion;
(4) then the water-in-oil emulsion that step (3) obtains is joined and be furnished with prolong, thermometer, in the 1000mL polymerization reaction kettle of nitrogen inlet and agitator, be that the deoxygenation of 400mL/min nitrogen is after 30 minutes with flow, under 16 DEG C of conditions, 10 % by weight 2 point are added for 3 times in water-in-oil emulsion, 2 '-azo [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride] aqueous solution 1.0g, the amount at every turn added is respectively 0.3g, 0.3g and 0.4g, under 45 DEG C of conditions, react 8 hours, then at 20 DEG C, in mixture, polyoxyethylene sorbitan fatty acid ester (Tween-85) 5g is added, with 100rpm stirring velocity, stir 20min, namely pressure break friction reducer P1 is obtained with 80 order filter-cloth filterings.
Embodiment 2
The present embodiment is for illustration of pressure break friction reducer of the present invention and preparation method thereof.
(1) under 25 DEG C of conditions, by 100g acrylamide, 50g sodium acrylate, 5g polymethyl acyloxyethyl trimethyl ammonium chloride (molecular weight is 10,000), 0.2g disodium ethylene diamine tetraacetate, 0.1g sodium formiate and 150g deionized water mix in 1000mL beaker, are stirred to and dissolve completely, then slowly add the aqueous sodium hydroxide solution adjust ph to 9 of 10 % by weight wherein, obtain the aqueous solution that pH value is 9;
(2) 10.5g Span-80 and 4.5g Tween-80 is mixed to get blending emulsifiers, the hydrophile-lipophile balance value of this blending emulsifiers calculated is 6, then by blending emulsifiers and 150g white oil, (boiling point boiling range is 240-280 DEG C, flash-point is 100 DEG C) be mixed in 1500mL beaker and dissolve completely, obtain oil solution;
(3) aqueous solution that step (1) obtains is joined in the oil solution obtained with step (2), with high speed shear dispersion and emulsion device emulsification 1min, obtain stable water-in-oil emulsion;
(4) then the water-in-oil emulsion that step (3) obtains is joined and be furnished with prolong, thermometer, in the 1000mL polymerization reaction kettle of nitrogen inlet and agitator, be that the deoxygenation of 400mL/min nitrogen is after 30 minutes with flow, under 24 DEG C of conditions, 10 % by weight 2 point are added for 4 times in water-in-oil emulsion, 2 '-azo [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride] aqueous solution 1.0g, the amount at every turn added is 0.25g, under 45 DEG C of conditions, react 4 hours, then at 25 DEG C, in mixture, polyoxyethylene nonylphenol ether (NP-10) 7.5g is added, with 50rpm stirring velocity, stir 40min, then pressure break friction reducer P2 is namely obtained with 80 order filter-cloth filterings.
Embodiment 3
The present embodiment is for illustration of pressure break friction reducer of the present invention and preparation method thereof.
(1) under 20 DEG C of conditions, by 100g acrylamide, 20g sodium acrylate, 1g polymethyl acyloxyethyl trimethyl ammonium chloride (molecular weight is 1,000,000), 0.02g disodium ethylene diamine tetraacetate, 0.01g sodium formiate and 100g deionized water mix in 1000mL beaker, are stirred to and dissolve completely, then slowly add the aqueous sodium hydroxide solution adjust ph to 7 of 10 % by weight wherein, obtain the aqueous solution that pH value is 7;
(2) hydrophile-lipophile balance value of 8g Span-80, Span-80 is 4.3, then Span-80 and 90g white oil (boiling point boiling range is 200-250 DEG C, and flash-point is 80 DEG C) is mixed to and is dissolved completely in 1500mL beaker, obtain oil solution;
(3) aqueous solution that step (1) obtains is joined in the oil solution obtained with step (2), with high speed shear dispersion and emulsion device emulsification 1min, obtain stable water-in-oil emulsion;
(4) then the water-in-oil emulsion that step (3) obtains is joined and be furnished with prolong, thermometer, in the 1000mL polymerization reaction kettle of nitrogen inlet and agitator, be that the deoxygenation of 400mL/min nitrogen is after 30 minutes with flow, under 20 DEG C of conditions, 1 % by weight 2 point are added for 5 times in water-in-oil emulsion, 2 '-azo [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride] aqueous solution 1.0g, the amount at every turn added is 0.2g, under 45 DEG C of conditions, react 6 hours, then at 30 DEG C, in mixture, polyoxyethylene octylphenol ether (OP-10) 10g is added, with 80rpm stirring velocity, stir 30min, then pressure break friction reducer P3 is namely obtained with 80 order filter-cloth filterings.
Embodiment 4
The present embodiment is for illustration of pressure break friction reducer of the present invention and preparation method thereof.
(1) under 25 DEG C of conditions, by 100g acrylamide, 100g2-acrylamide-2-methylpro panesulfonic acid, 2g polyacrylamide oxy-ethyl-trimethyl salmiac (molecular weight is 100,000), 0.5 disodium ethylene diamine tetraacetate, 0.5g sodium formiate and 50g deionized water mix in 1000mL beaker, are stirred to and dissolve completely, then slowly add the aqueous sodium hydroxide solution adjust ph to 8 of 10 % by weight wherein, obtain the aqueous solution that pH value is 8;
(2) 10.5g Span-80 and 4.5g Tween-80 is mixed to get blending emulsifiers, the hydrophile-lipophile balance value calculating this blending emulsifiers is 6, then by blending emulsifiers and 200g white oil, (boiling point boiling range is 220-250 DEG C, flash-point is 80 DEG C) be mixed in 1500mL beaker and dissolve completely, obtain oil solution;
(3) aqueous solution that step (1) obtains is joined in the oil solution obtained with step (2), with high speed shear dispersion and emulsion device emulsification 1min, obtain stable water-in-oil emulsion;
(4) then the water-in-oil emulsion that step (3) obtains is joined and be furnished with prolong, thermometer, in the 1000mL polymerization reaction kettle of nitrogen inlet and agitator, be that the deoxygenation of 400mL/min nitrogen is after 30 minutes with flow, under 25 DEG C of conditions, the ammonium persulfate aqueous solution of 2,g10 % by weight is added in water-in-oil emulsion, and then divide the aqueous solution of sodium bisulfite adding 2,g10 % by weight for 4 times, the amount at every turn added is 0.5g, under 35 DEG C of conditions, react 6 hours, then at 30 DEG C, in mixture, polyoxyethylene sorbitan fatty acid ester (Tween-85) 15g is added, with 80rpm stirring velocity, stir 25min, then pressure break friction reducer P4 is namely obtained with 80 order filter-cloth filterings.
Embodiment 5
The present embodiment is for illustration of pressure break friction reducer of the present invention and preparation method thereof.
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, polymethyl acyloxyethyl trimethyl ammonium chloride is replaced with polymethyl monomethacryloxypropyl trimethyl ammonium chloride, obtained pressure break friction reducer P5.
Embodiment 6
The present embodiment is for illustration of pressure break friction reducer of the present invention and preparation method thereof.
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, by vinylformic acid, polymethyl acyloxyethyl trimethyl ammonium chloride, disodium ethylene diamine tetraacetate, sodium formiate, water, Span-80, Tween-80, white oil, 10 % by weight 2, the consumption of 2 '-azo [2-(2-tetrahydroglyoxaline-2-propane)-dihydrochloride] aqueous solution and polyoxyethylene sorbitan fatty acid ester replaces with 60g, 15g, 0.5g, 0.5g, 200g, 8g, 8g, 160g, 40g and 15g respectively, obtained pressure break friction reducer P6.
Comparative example 1
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, do not add polymethyl acyloxyethyl trimethyl ammonium chloride, obtained pressure break friction reducer N1.
Comparative example 2
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, replace polymethyl acyloxyethyl trimethyl ammonium chloride with polyacrylamide base benzyl ammonium chloride, obtained pressure break friction reducer N2.
Comparative example 3
Pressure break friction reducer is prepared according to the method for embodiment 1, unlike, replace polymethyl acyloxyethyl trimethyl ammonium chloride with Poly Dimethyl Diallyl Ammonium Chloride, obtained pressure break friction reducer N3.
Test case
Test case 1
This test case is used for the resistance-reducing performance of mini-frac friction reducer.
The resistance-reducing performance test of friction-reducing agent of fracturing fluid P1-P6 and N1-N3 is measured by friction-reducing agent of fracturing fluid determinator (model is that friction test instrument falls in Hai'an oil scientific research Instrument Ltd. fracturing liquid), condition is as follows: under normal temperature, friction-reducing agent of fracturing fluid is dissolved in clear water the aqueous solution being made into 1 % by weight and joins in dissolving vessel, solution is flowed out by pump delivery, enters test section through spinner-type flowmeter.Use spinner-type flowmeter metered flow, uninterrupted, by Frequency Converter Control, measures the pressure drop of solution by test section.Test pipe diameter is 0.635 centimetre, and testing tube segment length is 3 meters, and resistance-reducing yield (DR, %) is calculated as follows:
In formula, △ P
0for the pressure drop produced when clear water under certain flow flows through test pipeline section, unit is Pa; △ P be under certain flow friction reducer solution stream after tested pipeline section time the pressure drop that produces, unit is Pa.
Get the friction reducer prepared in 40g embodiment 1-6 and comparative example 1-3 respectively, join under agitation and fill in the stainless steel dissolving vessel of 40L water, stir after 1 minute and the 1 % by weight friction reducer aqueous solution prepared is flowed out by pump delivery, enter test section through spinner-type flowmeter, measure the resistance-reducing yield of the friction reducer aqueous solution under different flow.Experiment is selected 10 millimeters to test pipeline sections and is tested, and the water solution flow recording clear water and the 1 % by weight friction reducer respectively pressure drop that produces of pipeline section after tested, calculate resistance-reducing yield, experimental result is shown in Fig. 1.
Embodiment 1-6 and comparative example 1-3 is compared and can be found out, the resistance-reducing yield of the friction reducer that the resistance-reducing yield of the friction reducer that the present invention obtains all obtains than comparative example is high.The reason that comparative example resistance-reducing yield is low is: the friction reducer N1 of comparative example 1 cannot appropriate design control due to the distribution of polymerized unit block, molecular configuration, space structure, and maximum resistance-reducing yield is only 56.8%; The template polyacrylamide base benzyl ammonium chloride added in the friction reducer N2 of comparative example 2 is due to the larger steric effect of phenyl ring in template, hamper template effect, maximum resistance-reducing yield is only 57.1%, the product resistance-reducing performance prepared does not have considerable change, the template Poly Dimethyl Diallyl Ammonium Chloride added in the friction reducer N3 of comparative example 3, because Poly Dimethyl Diallyl Ammonium Chloride master is a kind of five-membered ring structure, there is larger steric effect, hamper the product resistance-reducing performance that template effect prepares and do not have considerable change, maximum resistance-reducing yield is only 57%.
Embodiment 1 is compared can find out with embodiment 5, when cationic polymers template is polymethyl acyloxyethyl trimethyl ammonium chloride, the resistance-reducing yield of obtained friction reducer can be improved further.
Embodiment 1 is compared can be found out with embodiment 6, and relative to the described acrylamide monomer of 100 weight parts, the consumption of described double bond containing anionic monomer is 20-50 weight part; The consumption of described cationic polymers template is 1-5 weight part; The consumption of described sequestrant is 0.02-0.2 weight part; The consumption of described molecular weight regulator is 0.01-0.1 weight part; The consumption of described water is 100-150 weight part; The consumption of described organic solvent is 90-150 weight part; The consumption of described emulsifying agent is 8-15 weight part; The consumption of described initiator is 0.01-0.2 weight part; When the consumption of described phase inversion agent is 5-10 weight part, the resistance-reducing yield of obtained friction reducer can be improved further.
Test case 2
This test case is used for the core damage of mini-frac friction reducer.
Get the friction reducer prepared in 1.0g embodiment 1-6 and comparative example 1-3 respectively, join in the glass beaker filling 1L water under agitation, stir and add 0.2g ammonium persulphate after 1 minute, test for core damage after stirring half an hour, core damage test measures according to SY/T5107-2005 aqueous fracturing fluid method of evaluating performance, and measurement result is in table 1.
Embodiment 1-6 and comparative example 1-3 is compared and can be found out, the core damage rate of the friction reducer that the core damage rate of the friction reducer that the present invention obtains all obtains than comparative example is low.The reason that comparative example core damage rate is high is: the friction reducer N1 of comparative example is due to the distribution of polymerized unit block, molecular configuration, space structure cannot design by conservative control, the core damage rate of the aqueous solution of the friction reducer N1 of 1 % by weight is up to 14.2%, the template polyacrylamide base benzyl ammonium chloride added in the friction reducer N2 of comparative example is due to the larger steric effect of phenyl ring in template, hamper template effect, the nocuity of the product prepared to rock core does not have considerable change, the core damage rate of the aqueous solution of the friction reducer N2 of 1 % by weight is up to 14.1%, the template Poly Dimethyl Diallyl Ammonium Chloride added in the friction reducer N3 of comparative example, because Poly Dimethyl Diallyl Ammonium Chloride master is a kind of five-membered ring structure, there is larger steric effect, hamper template effect, the nocuity of the product prepared to rock core does not have considerable change, the core damage rate of the aqueous solution of the friction reducer N3 of 1 % by weight is up to 13.9%.
Embodiment 1 is compared can find out with embodiment 5, when cationic polymers template is polymethyl acyloxyethyl trimethyl ammonium chloride, the core damage rate of obtained friction reducer can be reduced further.
Embodiment 1 is compared can be found out with embodiment 6, and relative to the described acrylamide monomer of 100 weight parts, the consumption of described double bond containing anionic monomer is 20-50 weight part; The consumption of described cationic polymers template is 1-5 weight part; The consumption of described sequestrant is 0.02-0.2 weight part; The consumption of described molecular weight regulator is 0.01-0.1 weight part; The consumption of described water is 100-150 weight part; The consumption of described organic solvent is 90-150 weight part; The consumption of described emulsifying agent is 8-15 weight part; The consumption of described initiator is 0.01-0.2 weight part; When the consumption of described phase inversion agent is 5-10 weight part, the core damage rate of obtained friction reducer can be reduced further.
Table 1
| Sample | Basis rate of permeation K(md) | Friction reducer injury rate of permeation K1(md) | Injury rate (%) |
| P1 | 1.72 | 1.68 | 2.3 |
| P2 | 1.70 | 1.64 | 3.5 |
| P3 | 1.62 | 1.57 | 3.1 |
| P4 | 1.65 | 1.57 | 4.8 |
| P5 | 1.66 | 1.59 | 4.2 |
| P6 | 1.70 | 1.63 | 4.1 |
| N1 | 1.69 | 1.45 | 14.2 |
| N2 | 1.70 | 1.46 | 14.1 |
| N3 | 1.72 | 1.48 | 13.9 |
Test case 3
This test case is used for the clay swelling inhibition of mini-frac friction reducer.
Get friction reducer P1-P6 and N1-N3 prepared in 1.0g embodiment 1-6 and comparative example 1-3 respectively, join respectively under agitation in the glass beaker filling 1L water, stir 1 minute, P1-P6 and the N1-N3 friction reducer aqueous solution of obtained 1 % by weight, then measure the clay swelling inhibiting rate of the above-mentioned friction reducer aqueous solution according to SY-T5971-1994 water filling clay stabilizer method of evaluating performance, experimental result is in table 2.
Embodiment 1-6 and comparative example 1-3 is compared and can be found out, the clay swelling inhibiting rate of the friction reducer that the clay swelling inhibiting rate of the friction reducer that the present invention obtains all obtains than comparative example is high.The reason that comparative example clay swelling inhibiting rate is low is: the friction reducer N1 of comparative example is due to the distribution of polymerized unit block, molecular configuration, space structure cannot design by conservative control, the clay swelling inhibiting rate of the aqueous solution of the friction reducer N1 of 1 % by weight is only 21.5%, the template polyacrylamide base benzyl ammonium chloride added in the friction reducer N2 of comparative example is due to the larger steric effect of phenyl ring in template, hamper template effect, the expansion inhibition of the product prepared to clay does not have considerable change, the clay swelling inhibiting rate of the aqueous solution of the friction reducer N2 of 1 % by weight is only 21.8%, the template Poly Dimethyl Diallyl Ammonium Chloride added in the friction reducer N3 of comparative example, because Poly Dimethyl Diallyl Ammonium Chloride master is a kind of five-membered ring structure, there is larger steric effect, hamper template effect, the expansion inhibition of the product prepared to clay does not have considerable change, the clay swelling inhibiting rate of the aqueous solution of the friction reducer N3 of 1 % by weight is only 21.6%.
Embodiment 1 is compared can find out with embodiment 5, when cationic polymers template is polymethyl acyloxyethyl trimethyl ammonium chloride, the clay swelling inhibiting rate of obtained friction reducer can be improved further.
Embodiment 1 is compared can be found out with embodiment 6, and relative to the described acrylamide monomer of 100 weight parts, the consumption of described double bond containing anionic monomer is 20-50 weight part; The consumption of described cationic polymers template is 1-5 weight part; The consumption of described sequestrant is 0.02-0.2 weight part; The consumption of described molecular weight regulator is 0.01-0.1 weight part; The consumption of described water is 100-150 weight part; The consumption of described organic solvent is 90-150 weight part; The consumption of described emulsifying agent is 8-15 weight part; The consumption of described initiator is 0.01-0.2 weight part; When the consumption of described phase inversion agent is 5-10 weight part, the clay swelling inhibiting rate of obtained friction reducer can be improved further.
Table 2
| Sample | Expansion inhibiting rate (%) |
| P1 | 72.0 |
| P2 | 71.6 |
| P3 | 71.2 |
| P4 | 65.8 |
| P5 | 65.5 |
| P6 | 65.3 |
| N1 | 21.5 |
| N2 | 21.8 |
| N3 | 21.6 |
The friction reducer that the present invention obtains rapid solution in water, can not form flake, meets the requirement of the online mixture of slippery water pressure break; The maximum resistance-reducing yield of the aqueous solution of the friction reducer of mass concentration 1% is 71.8-80%; And friction reducer hydrolysate occurs without insolubles, formation nocuity is very low, and the core damage rate of the aqueous solution of mass concentration 1% friction reducer is 2.3-4.8%; The clay swelling inhibiting rate of the aqueous solution of the friction reducer of mass concentration 1% is 65.3-72%, has significant restraining effect to clay swelling, does not thus need in actual use to add new expansion-resisting agent again, significantly reduces the cost of slippery water.
Therefore, pressure break friction reducer prepared by the present invention is by adding the method for template polymer, have adjusted the distribution of polymerized unit block, molecular configuration, space structure, thus significantly improve the resistance-reducing yield of product, and with the friction reducer that preparation method of the present invention synthesizes have that formation damage is low, the advantage of clay swelling inhibition and good water solubility.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a preparation method for pressure break friction reducer, is characterized in that, the method comprises:
(1) by acrylamide monomer, double bond containing anionic monomer, cationic polymers template, sequestrant, molecular weight regulator and water mixing also adjust ph, the aqueous solution that pH value is 6-9 is obtained;
(2) organic solvent is contacted with emulsifying agent, obtain oil solution;
(3) oil solution that aqueous solution step (1) obtained and step (2) obtain contacts, and obtains water-in-oil emulsion;
(4) under an inert atmosphere, contacted with initiator by the water-in-oil emulsion that step (3) obtains in batches, and carry out polyreaction, the mixture then polyreaction obtained contacts with phase inversion agent;
Wherein, the hydrophile-lipophile balance value of described emulsifying agent is 4-6, and the molecular weight of described cationic polymers template is less than 1,000,000, the structural formula of described cationic polymers template as shown in the formula (I):
R
1hydrogen or methyl;
A is O or NH;
R
2c
1-C
6alkylidene group;
R
3, R
4, R
5c
1-C
6alkyl;
Z is chlorine, bromine or iodine.
2. method according to claim 1, wherein, described cationic polymers template is selected from polymethyl monomethacryloxypropyl trimethyl ammonium chloride, polymethyl acyloxyethyl trimethyl ammonium chloride, polyacrylamide oxy-ethyl-trimethyl salmiac and poly-N, N, at least one in N-trimethylammonium-3-[(1-oxo-2-propenyl) is amino] propyl ammonium chloride, is preferably polymethyl acyloxyethyl trimethyl ammonium chloride.
3. method according to claim 1, wherein, relative to the described acrylamide monomer of 100 weight parts, the consumption of described double bond containing anionic monomer is 10-100 weight part, is preferably 20-50 weight part; The consumption of described cationic polymers template is 1-15 weight part, is preferably 1-5 weight part; The consumption of described sequestrant is 0.001-5 weight part, is preferably 0.02-0.2 weight part; The consumption of described molecular weight regulator is 0.001-1 weight part, is preferably 0.01-0.1 weight part; The consumption of described water is 50-200 weight part, is preferably 100-150 weight part; The consumption of described organic solvent is 50-200 weight part, is preferably 90-150 weight part; The consumption of described emulsifying agent is 5-20 weight part, is preferably 8-15 weight part; The consumption of described initiator is 0.001-2 weight part, is preferably 0.01-0.2 weight part; The consumption of described phase inversion agent is 1-20 weight part, is preferably 5-10 weight part.
4. according to the method in claim 1-3 described in any one, wherein, described acrylamide monomer is selected from acrylamide, Methacrylamide, N, N-DMAA, N, at least one in N-acrylamide, NIPA, N hydroxymethyl acrylamide and N-hydroxyethyl acrylamide, is preferably acrylamide.
5. according to the method in claim 1-3 described in any one, wherein, described double bond containing anionic monomer is selected from double bond containing unsaturated carboxylic acid and ammonium salt, an alkali metal salt or alkaline earth salt, double bond containing unsaturated sulfonic acid and ammonium salt, an alkali metal salt or alkaline earth salt, double bond containing unsaturated phosphonic acids and ammonium salt, an alkali metal salt or alkaline earth salt, double bond containing unsaturated sulfomethylation or phosphono oxidation acrylamide and ammonium salt, an alkali metal salt or alkaline earth salt at least one; Be preferably selected from double bond containing unsaturated carboxylic acid and ammonium salt, an alkali metal salt or alkaline earth salt, at least one in double bond containing unsaturated sulfonic acid and ammonium salt, an alkali metal salt or alkaline earth salt; Be more preferably at least one in vinylformic acid, sodium acrylate and 2-acrylamide-2-methylpro panesulfonic acid sodium, be more preferably sodium acrylate.
6. according to the method in claim 1-3 described in any one, wherein, described sequestrant is selected from least one in disodium ethylene diamine tetraacetate, Triethylene Diamine pentaacetic acid, citric acid, Citrate trianion and poly-hydroxyl acrylic; Be preferably disodium ethylene diamine tetraacetate and/or Citrate trianion, described Citrate trianion is preferably selected from least one in Tripotassium Citrate, Trisodium Citrate, citrate of lime and ammonium citrate.
7. according to the method in claim 1-3 described in any one, wherein, described molecular weight regulator is selected from least one in sodium formiate, sodium acetate, glycerine and Virahol, is preferably sodium formiate.
8. according to the method in claim 1-3 described in any one, wherein, described emulsifying agent is nonionic emulsifying agent, is preferably at least one in sorbitan oleate, sorbitan monooleate Soxylat A 25-7, alkylphenol polyoxyethylene, benzylphenol oxygen Soxylat A 25-7, styroyl phenol polyethenoxy ether and aliphatic amine polyoxyethylene ether.
9. according to the method in claim 1-3 described in any one, wherein, described organic solvent is selected from least one in toluene, dimethylbenzene, hexane, hexanaphthene, normal heptane, isoparaffin, gasoline, kerosene and white oil; Be preferably selected from least one in toluene, dimethylbenzene, normal heptane, isoparaffin, gasoline, kerosene and white oil; Be more preferably isoparaffin and/or white oil; Be more preferably boiling point higher than 150 DEG C, the flash-point isoparaffin and/or the white oil that are greater than 60 DEG C.
10. according to the method in claim 1-3 described in any one, wherein, described initiator is water soluble, redox system initiator and/or azo-initiator, described water soluble, redox system contains Oxidizing and Reducing Agents, preferably, the mass ratio of described Oxidizing and Reducing Agents is 5:1-1:1.
11. according to the method in claim 1-3 described in any one, wherein, described phase inversion agent is selected from least one in polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, Ben-zylphenol Polyoxyethyl Ether, styroyl phenol polyethenoxy ether, isomery ten polyoxyethylenated alcohol, isomery undecyl alcohol Soxylat A 25-7, isomerous tridecanol polyoxyethylene ether and aliphatic amine polyoxyethylene ether; Be preferably selected from least one in polyoxyethylene sorbitan fatty acid ester, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, Ben-zylphenol Polyoxyethyl Ether, styroyl phenol polyethenoxy ether, isomery ten polyoxyethylenated alcohol, isomery undecyl alcohol Soxylat A 25-7 and isomerous tridecanol polyoxyethylene ether.
The 12. pressure break friction reducers prepared according to the method in claim 1-11 described in any one.
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