CN105885816A - Novel drag reducer for fracturing - Google Patents

Novel drag reducer for fracturing Download PDF

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Publication number
CN105885816A
CN105885816A CN201610268079.5A CN201610268079A CN105885816A CN 105885816 A CN105885816 A CN 105885816A CN 201610268079 A CN201610268079 A CN 201610268079A CN 105885816 A CN105885816 A CN 105885816A
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azo
drag reducer
initiator
vinyl
peroxide
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CN201610268079.5A
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CN105885816B (en
Inventor
李瑞清
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HEILONGJIANG YONGFENG CHEMICAL ADDITIVE Co Ltd
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HEILONGJIANG YONGFENG CHEMICAL ADDITIVE Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/28—Friction or drag reducing additives

Abstract

The invention provides a novel drag reducer for fracturing and particularly relates to a drag reducer for fracturing fluid in petroleum fracturing construction. Adding a small quantity of novel drag reducer for fracturing in the fluid can reduce flow resistance in the turbulence state. A drag reduction rate can be up to 79.5% and can still keep at 79.4% after 5 hours' high-strength shearing. The novel drag reducer for fracturing is suitable for long-distance transportation.

Description

Novel pressure break drag reducer
Technical field
The present invention relates to a kind of novel pressure break drag reducer, the fracturing fluid used in constructing particularly to a kind of oil fracturing Drag reducer.
Background technology
Adding a small amount of high molecular polymer in a fluid, can decline low flow resistance at turbulence state, this phenomenon is referred to as High polymer drag reduction, is added thereto and is referred to as drag reducer for the chemical addition agent reducing fluid flow resistance.Drag reducer is a kind of point The flexible macromolecule polymer of the son amount linear structure more than more than million, adds a small amount of such polymer in a fluid, Throughput rate will be made to increase, drag reduction.Using the method adding drag reducer to carry out fluid drag-reduction is numerous drag reduction technology kind apoplexy due to endogenous wind Apply most methods.
The turbulent flow drag reduction of high polymer is to have showing of Technological Economy and scientific meaning in all abnormal phenomenas of non-newtonian flow One of as.Research to high polymer drag reduction has the highest economic worth, and national economy and national defense construction are had important effect. In the tubing that industrial department is widely applied, reduce frictional resistance, it is possible to be substantially reduced the consumption running power.At pipe The original application with product oil of road conveying, it is possible to reduce the intermediate pump station of long conveyance conduit, shorten the emptying time of harbour, improve Work efficiency.So far, the research of drag reduction phenomenon has become one and has related to hydrodynamics, rheology, polymer chemistry and high score The new cross discipline of sub-solution, drag reduction phenomenon application in engineering also forms a unique comprehensive engineering science.
Along with the development of petroleum industry, super high molecular weight polymer is as original conveying drag reducer petroleum pipeline at home and abroad In obtain increasingly extensive application.Therefore about the concern of every research the most extremely people of super high molecular weight drag reducer.
But existing drag reducer also exists fatal weakness, through the local location such as bend pipe or pumping plant, and pipeline effect The shear stress produced makes the molecular chain rupture of drag reducer degrade.Increase rigid radical no matter is used still to be formed huge Side base improve the shear resistant of drag reducer, all can not reach to completely inhibit the degree of shearing.Because major key is made in high shear Rupturing with lower federation, post-rift little molecule presents original drag-reduction effect never again.
Summary of the invention
Relate to the subjects such as the physical chemistry of rheology, hydrodynamics, polymer due to drag reduction, drag reduction mechanism is more multiple Miscellaneous, understanding and the research focus of this phenomenon are also not quite similar by the many scholars of blood and research worker, the research work carried out Have nothing in common with each other in direction.Although through research, obtaining hypothesis and the theory much about drag reduction, and these hypothesis and theory all may be used Some or some drag reduction phenomenons are reasonably explained on the research angle and direction of oneself, but each hypothesis and reason Opinion all there is also unaccountable drag reduction phenomenon, or is obtained and actual phase when explaining other drag reduction phenomenons by these hypothesis The conclusion of contradiction.Up to the present, go back neither one complete convictive theory and drag reduction phenomenon is made perfect explanation.
High polymer drag reducer can reach the highest drag-reduction effect in the case of consumption is the least, but, at turbulent fluid High shear forces under, its molecular weight easily reduces because of molecule chain break, even loses anti-drag function, occurs to shear fall Solve.This degraded is permanent, irreversible, and it is indubitable that its drag-reduction effect declines.In long-distance conveying, valve with And pump is all high shear parts, drag-reduction effect all can be greatly reduced.
In order to solve prior art problem, the present invention provides a kind of novel pressure break drag reducer, and in parts by weight, it is prepared Raw material at least includes:
Acrylamides 100 parts；
Vinyl benzo-crown ether 4-6 part；
Inorganic salt 120-130 part；
Stabilizer 2-3 part；
Initiator 0.005-0.05 part；
Water 200-300 part.
As currently preferred a kind of embodiment, it is prepared raw material and also includes vinyl fluorobenzene 0.5-2 part.
Described acrylamides is selected from acrylamide, Methacrylamide, N methacrylamide, N-isopropyl Methacrylamide and N, at least one in N-DMAA.
As currently preferred a kind of embodiment, described vinyl benzo-crown ether is preced with selected from 4-vinyl benzo-18- One in ether-6,4-vinyl benzo-heptaoxacycloheneicosane-7-7,4-vinyl benzo-octaoxacyclotetracosane-8-8.
As currently preferred a kind of embodiment, described inorganic salt is selected from least in sodium salt, ammonium salt, magnesium salt Kind.
As currently preferred a kind of embodiment, described stabilizer is selected from 2-acrylamide-2-methylpro panesulfonic acid In salt, styrene sulfonate, vinyl sulfonate, Sodium allyl sulphonate, acrylates, methacrylate, hydroxyethylacrylate At least one.
As currently preferred a kind of embodiment, described vinyl fluorobenzene selected from 4-fluorobenzene ethylene, 2,6-difluorobenzene One in ethylene, 2,3,4,5,6-pentafluorostyrene.
As currently preferred a kind of embodiment, described initiator draws selected from azo-initiator and oxidation-reduction Sending out the combination of agent, the weight ratio of described azo-initiator and oxidation-reduction initiator is (0.8-1.2): 2.
As currently preferred a kind of embodiment, described azo-initiator is selected from azodiisobutyronitrile, azo two The double methylpent hydrochlorate of different heptonitrile, azo, 2,2 '-azo diisobutyl amidine hydrochlorate, azo two isobutyl imidazoline hydrochloride, 2, At least one in 2 '-azo two [2-(2-imidazoline-2-propane)-dihydrochloride].
As currently preferred a kind of embodiment, the oxidant in described oxidation-reduction initiator is selected from persulfuric acid At least one in ammonium, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide；Reducing agent in described oxidation-reduction initiator is selected from Asia At least one in sodium bisulfate, sodium sulfite, sodium thiosulfate, ferrous sulfate and sodium dithionite；Described oxidant and The weight ratio of reducing agent is (3-2): 1.
The novel pressure break drag reducer that the present invention provides has good environmental-protecting performance, and resistance to antibacterial corrodes, during use Without adding of germicide, and good stability, do not fire, the most quick-fried, store transportation safety, there is higher drag reducing efficiency.Reusability or length When way uses, through high intensity shear action repeatedly, product property remains in that stable.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum of 4-vinyl benzo-hexaoxacyclooctadecane-6-6；
Fig. 2 is the nucleus magnetic hydrogen spectrum of 4-vinyl benzo-heptaoxacycloheneicosane-7-7；
Fig. 3 is the nucleus magnetic hydrogen spectrum of 4-vinyl benzo-octaoxacyclotetracosane-8-8.
Detailed description of the invention
Unless otherwise defined, all technology used herein and scientific terminology have skill common with art of the present invention The identical implication that art personnel are generally understood that.When there is contradiction, it is as the criterion with the definition in this specification.
" quality, concentration, temperature, time or other value or parameter are preferred with scope, preferred scope or a series of upper limit During the Range Representation that value and lower preferable values limit, this is appreciated that and specifically discloses by any range limit or preferred value All scopes that arbitrary pairing with any range lower limit or preferred value is formed, regardless of whether whether this scope separately discloses. Such as, the scope of 1-50 be understood to include selected from 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18, 19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、 44, any numeral, number combinatorics on words or the subrange and all between above-mentioned integer of 45,46,47,48,49 or 50 Fractional value, such as, 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8 and 1.9.About subrange, specifically consider from scope Interior any end points starts " the nested subrange " extended.Such as, the nested subrange of exemplary range 1-50 can include 1-10,1-20,1-30 and 1-40 on one direction, or 50-40,50-30,50-20 and the 50-10 on other direction.”
Novel pressure break drag reducer, in parts by weight, it is prepared raw material and at least includes:
Acrylamides 100 parts；
Vinyl benzo-crown ether 4-6 part；
Inorganic salt 120-130 part；
Stabilizer 2-3 part；
Initiator 0.005-0.05 part；
Water 200-300 part.
Acrylamides
The bulk composition of pressure break drag reducer is polyacrylamide, and monomer whose is mainly acrylamide monomer, described acryloyl Any one acrylamide monomer that amine system monomer can be known in the art, but so that the fall of the friction reducer prepared Resistance rate is higher, bin stability more preferable, clay swell inhibition is higher and formation damage is lower, described acrylic amide chemical combination Thing is selected from acrylamide, Methacrylamide, N methacrylamide, N-isopropyl acrylamide and N, N-dimethyl propylene At least one in acrylamide.
The polyacrylamide that the present invention is previously mentioned is acrylamide monomer homopolymerization or copolymerization gained under initiator effect The general designation of polymer, for other high polymer drag reducers, polyacrylamide is widely used in oil exploitation, Shui Chu In the industries such as reason, weaving, papermaking, ore dressing, medicine, agricultural, there is the title of " all trades auxiliary agent ".Polyacrylamide odorless, soluble in water And good water solubility, also can be completely dissolved in cold water, be practically insoluble in organic solvent.Its drag-reduction effect is obvious, adds a small amount of poly- Acrylamide dissolves in water, i.e. can get great drag-reduction effect.Polyacrylamide drag reducer, in certain temperature, can protect Hold relatively low degradation rate, but if temperature is more than 120 DEG C, then its degradation speed is substantially accelerated easily to decompose.Meanwhile, it is compared His high polymer drag reducer, has stronger anti-shear ability.
Vinyl benzo-crown ether
As currently preferred a kind of embodiment, described vinyl benzo-crown ether selected from 4-vinyl benzo-hexaoxacyclooctadecane-6- 6, the one in 4-vinyl benzo-heptaoxacycloheneicosane-7-7,4-vinyl benzo-octaoxacyclotetracosane-8-8.Preferably, described vinyl benzo Crown ether is selected from 4-vinyl benzo-heptaoxacycloheneicosane-7-7 or 4-vinyl benzo-octaoxacyclotetracosane-8-8.It is furthermore preferred that described vinyl benzene And crown ether is 4-vinyl benzo-octaoxacyclotetracosane-8-8.
As currently preferred a kind of embodiment, described vinyl benzo-crown ether by comprising 4-vinyl-1,2-benzene The raw material of diphenol and chloro glycols compound prepares.
The preparation method of described vinyl benzo-crown ether is as follows:
(1) load weighted glycols compound is placed in 250 mL equipped with in the double-neck flask of reflux condensing tube, adds excess Thionyl chloride and 2-3 drip DMF.It is heated to reflux 12-18 h, is cooled to room temperature after completion of the reaction, with Rotary Evaporators, dichloro is sub- Sulfone is drained, and obtains chloro glycols compound.
(2) load weighted 4-vinyl-1,2-Benzodiazepines and chloro glycols compound are placed in 250 mL round-bottomed flasks In, add sodium hydroxide and Lithium hydrate, using butanol as solvent, be heated to reflux 1-3 h.It is cooled to room after completion of the reaction Temperature, extracts thick product with chloroform.Mixing as flowing phase using petroleum ether and ethyl acetate volume ratio 7:1, silica gel is as fixing Carry out column separating purification mutually, obtain vinyl benzo-crown ether.
Described glycols compound one in hexaethylene glycol, seven glycol, eight glycol.
4-vinyl-1,2-Benzodiazepines is commercially available from Shanghai Shu Ya Pharmaceutical Technology Co., Ltd；Hexaethylene glycol is commercially available from upper Sea riel advanced in years chemical technology company limited；Seven glycol are commercially available from Jiaxing Bo Mei Bioisystech Co., Ltd；Eight glycol are commercially available From Jiaxing Bo Mei Bioisystech Co., Ltd.
Inorganic salt
As currently preferred a kind of embodiment, at least one in sodium salt, ammonium salt, magnesium salt of described inorganic salt.Excellent Choosing, at least one in ammonium sulfate, sodium sulfate, magnesium sulfate of described inorganic salt.It is furthermore preferred that described inorganic salt is sulphuric acid Ammonium.
Stabilizer
As currently preferred a kind of embodiment, described stabilizer is selected from 2-acrylamide-2-methylpro panesulfonic acid salt, benzene In vinyl sulfonate, vinyl sulfonate, Sodium allyl sulphonate, acrylates, methacrylate, hydroxyethylacrylate at least A kind of.Preferably, described stabilizer is selected from 2-acrylamide-2-methylpro panesulfonic acid sodium or sodium acrylate.It is furthermore preferred that it is described Stabilizer is 2-acrylamide-2-methylpro panesulfonic acid sodium.
Stabilizer can adsorb the surface at high molecular polymer, it is provided that spatial obstacle effect and electrostatic repulsion, is formed Layer protective layer, makes granule disperse, and prevents bonding, thus even suspension is dispersed in water, and forms white emulsion.Stabilizer makes base Fluid viscosity uniformly occurs without lamination.
Initiator
Initiator, also known as radical initiator, refers to that an easy decomposes of class becomes the compound of free radical (i.e. primary group of free radicals), Can be used for causing alkenes, the radical polymerization of double vinyl monomer and copolymerization it can also be used to the crosslinking of unsaturated polyester (UP) is solid Change and high molecular crosslink reacts.
Initiator includes organic peroxide evocating agent, inorganic peroxide initiator, azo-initiator, oxidoreduction Initiator.
Organic peroxide evocating agent can be acyl class peroxide, such as: the double lauroyl of peroxidating, peroxidating two (2, 4-dichloro-benzoyl), two (2-methylvaleryl) peroxide, two (3-toluyl) peroxide, two (the fluoro-4,4-of 4- Dinitro bytyry) peroxide, two (hexanoyl) peroxide, dibutyryl peroxide, acetylcyclohexane sulfonyl mistake Oxide, stearyl peroxide, acetyl group-Zhong Gengji sulfonyl-peroxide, two isobutyryl peroxide, double (3,5, 5-trimethyl acetyl) peroxide, phthalyl peroxide, acetyl group benzoyl peroxide, two decanol peroxide, two pungent Acyl peroxide, 3,3'-dichloro formoxyl peroxide, two (4-toluyl) peroxide, peroxidating are to chlorobenzene Formyl, dibenzoyl peroxide.
Organic peroxide evocating agent can be hydroperoxides, such as: hydrogen peroxide, hydrogen peroxide benzoyl, spy penta Base hydrogen peroxide, cyclohexyl hydroperoxide compound, tert-butyl hydroperoxide, 3,5-DIBHP, hydrogen peroxide are different Propyl benzene, 8-hydrogen peroxide eicosatetraenoic acid, 12-hydroperoxy-5,8,11,14,17-eicosapentaenoic acid, 15-hydroperoxy pine Fragrant acid, 1-(3-pyridine radicals) ethyl hydroperoxide, heptyl hydroperoxides, butyl hydroperoxides, propyl hydroperoxide, Cholesterol hydroperoxides, cuminyl hydroperoxides, trityl hydroperoxides, Herba Verbenae base hydroperoxides, 8-pair Menthyl hydroperoxides, 3-cyclohexenyl group hydroperoxides, 2-phenylethyl hydroperoxides, 2-Herba Verbenae base hydroperoxidation Thing, 4-methyl-benzyl hydroperoxides, 1-ethyl propyl hydroperoxides, diphenylethane hydroperoxides, methyl linoleate Hydroperoxides, diisopropyl benzene hydroperoxides, (1-methyl amyl) hydroperoxides, 2-cyclohexene-1-base hydroperoxidation Thing, 1-phenylcyclohexyl hydroperoxides, methyl linolenate hydroperoxides, 1,4-dioxanes-2-base hydroperoxides, 3- Methyl-3-pentyl hydroperoxides, docosahexenoic acid hydroperoxides, m-diisopropyl benzene dihydro-peroxidase, 1, 2,3,4-tetrahydrochysene-1-naphthyl hydroperoxides, 3-phenyl-2-propine-1-base hydroperoxides, 5-phenyl amyl-4-thiazolinyl-1-hydrogen Peroxide, 2,5-dimethylhexane-2,5-dihydro-peroxidase, dimethyl ethenyl acetenyl hydroperoxides, 4-isopropyl Base-1-methylcyclohexyl hydroperoxides, 2-isopropyl-5-methylcyclohexyl hydroperoxides, 2-isopropyl-5-methyl cyclohexane Base hydroperoxides, 1-isopropyl-4-methyl cyclohexyl hydroperoxide, 1-vinyl-3-cyclohexene-1-base hydroperoxidation Thing, 3-isopropyl-2-cyclohexene-1-base hydroperoxides, 1-methoxyl group-3-methylcyclohexyl hydroperoxides, 3-pyridine radicals Imido acute pyogenic infection of nails acyl hydroperoxides, 7-oxabicyclo [4.1.0] hept-2-base hydroperoxides, two epoxides two (1-methyl-prop Asias Base) hydroperoxides, 2-methyl isophthalic acid, 1-hexamethylene diyl dihydro-peroxidase, 1-methyl isophthalic acid-[4-(1-Methylethyl) phenyl] Ethyl hydroperoxide, 4-isopropyl-1-methyl-2,5-cyclohexadiene-1-base hydroperoxides, 4-[(1,1-dimethyl second Base) peroxide]-1,1,4-tri-methyl-amyl hydroperoxides, 3-ethyl-2-(ethylamino)-2-oxo-1,3,2-oxygen azepine phosphorus Azacyclohexane-4-base hydroperoxides.
Organic peroxide evocating agent can be dialkyl peroxide, such as: di-tert-butyl peroxide, two tertiary pentyls Peroxide, (1-methyl-prop subunit) two [tert-butyl] peroxide, two (1-Hydroxyheptyl) peroxide, diisopropyl mistake Oxide, dicyclohexyl peroxide, double dodecyl peroxide, 1,1-cyclohexane di-tert-butyl peroxide, (different sub-third Base) two (1-methyl isophthalic acid-phenylethyl) peroxide, (isopropylidene) two [tert-butyl] peroxide, 1,1-dimethyl-1- Methyl isophthalic acid-[(4-Methylethyl) phenyl] ethyl peroxide, two (tert-butyl) peroxide, diethyl peroxide, two (3-methylcyclohexyl) peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethyl-cyclohexane, (1-[3,5-bis-(1-first Base ethyl) phenyl]-1-Methylethyl) (1,1-dimethyl ethyl) peroxide, dimethyl peroxide, peroxidating diisopropyl Benzene.
Organic peroxide evocating agent can be esters peroxide, such as: peroxidating tert-butyl isobutyrate, tert-butyl group mistake Oxidation-3,5,5 Trimethylhexanoic acid ester, cumyl peroxyneodecanoate, peroxidating (2 ethyl hexanoic acid) tert-butyl ester, peroxidating T-butyl perbenzoate, peroxidating tertiary pentyl-2-ethylhexanoate, tert-Butyl peroxypivalate, 4,4-bis-(t-butyl peroxy Change) n-butyl pentanoate, 2-ethyl hexyl acyl group 2-ethyl peroxy caproic acid ester, tert-butyl peroxy acetate, acetyl group peracetic acid ester, benzene The tertiary hexyl ester of peroxyformic acid, 2-phenyl-propane-2-base 4,4-dimethyl pentane are percarboxylate, 1,1,4,4-tetramethyl four methylene Base pernoanoic acid ester, 1,1,4,4-4-methyl-butane-1,4-diyl two (2-ethyl peroxy caproic acid ester), 1,1,4,4-tetramethyl four Methylene peroxide pivalate, tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester, 2-(3-oxo-5-benzofurane-2-base) Peracetic acid methyl ester, 2-[5-(4-aminomethyl phenyl)-3-oxo furan-2-base] peracetic acid methyl ester, di-tert-butyl diperoxy Azelate, di-tert-butyl peroxy oxalate, two (tert-butyl) methyl diperoxy succinate, 3-phenyl acrylate-2-alkene peroxide Carboxylic acid tert-butyl ester, benzene-1,2-diperoxy carboxylic acid di tert butyl carbonate, peroxide p-phthalic acid di tert butyl carbonate, 2,2,4-trimethyl two mistake Oxygen adipic acid di tert butyl carbonate, 2,4,4-trimethyl diperoxy adipic acid di tert butyl carbonate, 1,1,3,3-tetramethyl butyl 2,2-diformazan Base propane is percarboxylate, 2-methyl benzoyl hydroperoxide tert-butyl ester, diperoxy decanedioic acid di tert butyl carbonate, peroxide heneicosanedioic acid Di tert butyl carbonate, the nonane peroxycarboxylic acid tert-butyl ester, cumyl peroxide pivalate, 4,4-bis-(tert-butyl peroxide) butyl valerate, mistake The oxygen butenoic acid tert-butyl ester, the 2-ethylbutane peroxycarboxylic acid tert-butyl ester, peroxide methyl oleate, the new heptanoic acid tert-butyl ester of peroxide, peroxide are new The capric acid tert-butyl ester, cumyl peroxyneodecanoate, the isononane peroxycarboxylic acid tert-butyl ester, 1,1,4,4-4-methyl-butane-1,4- Diyl two (isononane is percarboxylate), peroxidating (2 ethyl hexanoic acid) tert-butyl ester, (2-chlorobenzene formacyl) 2-chlorobenzene peroxide carboxylic Acid esters, (2-toluyl) 2-methylbenzene is percarboxylate, 2-methyl-2-propyl 2-ethyl peroxy caproic acid ester, propionyl propane Percarboxylate, two (2-methyl-2-propyl) 1,3-benzene diperoxy carboxylate, di-tert-butyl peroxy hexahydro p-phthalic acid Ester, the 2,2-dimethyl Perbutyric Acid tert-butyl ester, hexamethylene peroxycarboxylic acid 1,1,3,3-tetramethyl butyl ester, the 3,3-bis-(tert-butyl group Peroxide) ethyl n-butyrate., phenoxy group tert-butyl peroxy acetate, 1,1,3,3-tetramethyl butyl phenoxy group peracetic acid ester, 2-pyridine The peroxyformic acid tert-butyl ester, peroxide neodecanoic acid tert-hexyl ester, peroxide-2 ethyl hexanoic acid tert-butyl ester, the tertiary fourth of peroxide Pyromellitic Acid four Ester, t-amyl peroxy neodecanoic acid ester, 2-methybutane-2-base 3,5,5-trimethyl peroxy caproic acid ester, 2-methyl-2-butyne base Peracetic acid ester, butyl 3,3-bis-[(2-methyl-2-propyl) peroxide] valerate, 2-ethyl peroxy caproic acid butyl ester, 2-hydroxyl ring Amyl peroxy acetas, diperoxy dodecanedioic acid di tert butyl carbonate, 2,2-dimethyl Perbutyric Acid tert-pentyl ester, 1,1-dimethyl propylene Phenoxyl peracetic acid ester, 3-hydroxyl-1,1-dimethylbutyl peroxide (2-ethylhexanoate).
Organic peroxide evocating agent can be ketone peroxide, such as: acetone peroxide, cyclohexanone peroxide, 2,6-di-tert-butyl-4-methyl-4-tert-butyl peroxide-2,5-cyclohexadienone, methylethyl ketone peroxide, 2,4-pentane diketone mistake Oxide, 4-methyl-4-[(2-methyl-2-propyl) peroxide]-2 pentanone, hexone peroxide, 4-hydroxyl-4- Methyl-2 pentanone peroxide.
Organic peroxide evocating agent can be two carbonic ester peroxide, such as: di-isopropyl peroxydicarbonate, two Ethyl peroxydicarbonate, double (4-tert-butylcyclohexyl) peroxy dicarbonate, dicyclohexyl peroxydicarbonate, two-(2- Ethylhexyl) peroxydicarbonate, dibutyl peroxydicarbonate, peroxidating two (cetyl) two carbonic ester, didecyl mistake Oxygen two carbonic ester, two (3,5,5-trimethyl) peroxydicarbonate, two (2-Phenoxyethyl) peroxydicarbonate, two (3-methoxybutyl) peroxydicarbonate, distearyl peroxydicarbonate, two-2-ethoxyethyl group peroxydicarbonate, Double tridecyl peroxydicarbonate, peroxy dicarbonate double myristyl ester, peroxide two carbonic acid two isotridecyl ester.
Inorganic peroxide initiator can be persulfate, such as: sodium peroxydisulfate, potassium peroxydisulfate, peroxidating sulfate mono Potassium salt, peroxidation sulfuric acid ammonium.
Azo initiator refers to the radical initiator in molecule structure containing nitrogen nitrogen double bond.General formula is R N =N R, wherein R N key is weak bond, is easily broken off forming free radical, and decomposition temperature is relevant with alkyl structure.If two ends are symmetrical Polarized substituted radical (such as-CN ,-COOH ,-COOR etc.) in alkyl structure or alkyl, then decomposition temperature declines.
The azo initiator that the present invention uses can list such as: 1,1'-azo dinaphthyl, azodiisobutyronitrile, azo Diformamide, 2,2'-Azobis(2,4-dimethylvaleronitrile), 4,4'-azoic diphenylamine, 2,2'-azo oxalic acid, 3,3'-azo dibenzoic acid, azo Dicarboxylate, azo acid dimethyl ester, azoformic acid dibenzyl ester, azodicarbonyldipiperidine, azoformic acid two The tert-butyl ester, diisopropyl azodiformate, 1,1'-azo two (cyclohexanecarbonitrile), 2,2'-azo two (2-amidine propane), four different Propyl group azodicarbonamide, 4,4'-(azo dicarbapentaborane) dimorpholine, 1,1'-azo two (cyclohexane carbonitrile), 4', 4'''-azo Biphenyl-4-carboxylic acid, 4,4'-azo dibenzoic acid disodium salt, 4,4'-azo two-benzoic acid diethylester, double (4-chlorobenzyls) are occasionally Nitrogen dicarboxylic acid esters, 2,4'-dimethyl-2,2'-azo two valeronitrile, 4,4'-azo two [4-cyanopentanoic acid] disodium, 2,2'-azo Diisobutyl amidine dihydrochloride, 2,2'-azo two-2-amidine propane hydrochlorate, two-2-methoxy ethyl azodicarboxylates, N, N, N', N'-tetramethyl-4,4'-azoic diphenylamine, two (2,2,2-trichloroethyl) azodicarboxylate, N, N'-(azo two- 4,1-phenylene) diacetayl amide, 1,1'-azo two (1-Methylethyl) diacetate esters, 1,1'-azo two (1-Methylethyl) two Propionic ester, 1,1'-azo two (1-methyl-propyl) diacetate esters, 4,4'-azo two [N-(1-naphthalenyhnethylene) aniline], 6'- Butoxy-2,6-diaminourea-3,3'-azobispyridine, 2,2'-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2'- Azo two (1,3-dimethylbutyl) diacetate esters, azo-bis-iso-dimethyl, AMBN, (azo two is right for 2,2'- Phenylene) two (6-methylbenzothiazoles), 2,2'-azo two (2-(imidazoline-2-base) propane) dihydrochloride, 3,3''-azo [(4,1-phenylene is even for azo two for two (2,2', 4,4', 6,6'-hexanitro [1,1'-biphenyl]), azodicarbonamide, 4,4'- Nitrogen)] two [N-methyl isophthalic acid-naphthylamines], 4,4'-[azo two (4,1-phenylene azo)] two [N-ethyl-naphthalidines], 2,2'-(1, 2-azo diyl double (2,1-Asia benzene nitrogen methine)) biphenol, 4,4'-azo two [N-[[4-(dimethylamino) phenyl] methylene Base] aniline], 4,4'-[azo two (to phenylene azo)] two (N, N-dimethyl-1-naphthylamines), 3,3'-azo two [6-[2- (4-nitro-2-sulfo group phenyl) vinyl] benzenesulfonic acid], 4,4'-[azo two (4,1-phenylene azo)] two [N, N, 3,5-tetra- Monomethylaniline .], 4,4'-[azo two (4,1-phenylene azo)] two [N, N-diethyl-3-monomethylaniline .], azo diimidazole quinoline Base propane, azo two isobutyl imidazoline hydrochloride.
Peroxide initiator and azo-initiator decomposition temperature higher (50-100 DEG C), limit in low temperature polymerization anti- The application answered.Redox initiation system is that the free radical utilizing the electron transfer between Oxidizing and Reducing Agents to be generated causes Polyreaction.Therefore redox initiator have than thermal decomposition initiating can cause under lower temperature (0-50 DEG C) poly- Closing reaction, its advantage can improve reaction rate, reduces energy consumption.May make up redox system has benzoyl peroxide/sugarcane Sugar, tert-butyl hydroperoxide/sodium bisulphite formaldehyde, tert-butyl hydroperoxide/sodium pyrosulfite, benzoyl peroxide/N, N- Dimethylaniline, Ammonium persulfate ./sodium sulfite, potassium peroxydisulfate/sodium sulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/ Sodium bisulphite formaldehyde, Ammonium persulfate ./ferrous sulfate, hydrogen peroxide/sulfuric acid are ferrous, benzoyl peroxide //N, N-diethylbenzene Amine, benzoyl peroxide/ferrous pyrophosphate, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, isopropyl benzene hydroperoxide/chlorination Ferrous iron, potassium peroxydisulfate/ferrous chloride, hydrogen peroxide/ferrous chloride, isopropyl benzene hydroperoxide/tetra-aziridine etc..
As currently preferred a kind of embodiment, described initiator draws selected from azo-initiator and oxidation-reduction Sending out the combination of agent, the weight ratio of described azo-initiator and oxidation-reduction initiator is (0.8-1.2): 2.
As currently preferred a kind of embodiment, described azo-initiator is selected from azodiisobutyronitrile, azo two The double methylpent hydrochlorate of different heptonitrile, azo, 2,2 '-azo diisobutyl amidine hydrochlorate, azo two isobutyl imidazoline hydrochloride, 2, At least one in 2 '-azo two [2-(2-imidazoline-2-propane)-dihydrochloride].
As currently preferred a kind of embodiment, the oxidant in described oxidation-reduction initiator is selected from persulfuric acid At least one in ammonium, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide；Reducing agent in described oxidation-reduction initiator is selected from Asia At least one in sodium bisulfate, sodium sulfite, sodium thiosulfate, ferrous sulfate and sodium dithionite；Described oxidant and The weight ratio of reducing agent is (3-2): 1.
Vinyl fluorobenzene
As currently preferred a kind of embodiment, it is prepared raw material and also includes vinyl fluorobenzene 0.5-2 part.
The example of vinyl fluorobenzene specifically can list such as: 2-fluorobenzene ethylene, 3-fluorobenzene ethylene, 4-fluorobenzene ethylene, 2,3-difluorobenzene ethylene, 2,4 difluorobenzene ethylene, 2,5-difluorobenzene ethylene, 2,6-difluorobenzene ethylene, 3,4-difluorobenzene ethylene, 3, 5-difluorobenzene ethylene, 2,3,4-trifluorostyrene, 2,3,5-trifluorostyrene, 2,3,6-trifluorostyrene, 3,4,5-trifluoro-benzene Ethylene, 2,4,5-trifluorostyrene, 2,4,6-trifluorostyrene, 2,3,4,5-phenyl tetrafluoride ethylene, 2,3,4,6-phenyl tetrafluoride ethylene, 2,3,5,6-phenyl tetrafluoride ethylene, 2,3,4,5,6-pentafluorostyrene.
As currently preferred a kind of embodiment, described vinyl fluorobenzene selected from 4-fluorobenzene ethylene, 2,6-difluorobenzene One in ethylene, 2,3,4,5,6-pentafluorostyrene.
As a kind of preparation method of the novel pressure break drag reducer that the present invention provides, the steps include: to fill four-neck flask Upper condensing tube, mechanical agitator, temperature controller, constant pressure funnel, wherein condensing tube upper end connecting tee, threeway one end connects nitrogen Gas entrance, one end connects oil sealing and leads to air.Acrylamide, vinyl benzo-crown ether, inorganic salt, stabilizer, azo are drawn Send out agent, oxidant, water stir in four-neck flask.Logical nitrogen 30 min, arranges the air in reaction unit.By perseverance Pressure Dropping funnel is added dropwise over reducing agent in reaction system, and controlling reaction temperature is 40 DEG C, increases the temperature to after reacting 8 hours 45 DEG C, it is further continued for reacting 2 hours.Reaction is cooled to room temperature after terminating, and to obtain final product.
As a kind of preparation method of the novel pressure break drag reducer that the present invention provides, the steps include: to fill four-neck flask Upper condensing tube, mechanical agitator, temperature controller, constant pressure funnel, wherein condensing tube upper end connecting tee, threeway one end connects nitrogen Gas entrance, one end connects oil sealing and leads to air.Acrylamide, vinyl benzo-crown ether, inorganic salt, stabilizer, azo are drawn Send out agent, oxidant, water, vinyl fluorobenzene stir in four-neck flask.Logical nitrogen 30 min, by reaction unit Air is arranged.Being added dropwise over reducing agent in reaction system with constant pressure funnel, controlling reaction temperature is 40 DEG C, reacts 8 hours After increase the temperature to 45 DEG C, be further continued for reacting 2 hours.Reaction is cooled to room temperature after terminating, and to obtain final product.
The novel pressure break drag reducer that the present invention provides, has good environmental-protecting performance, and resistance to antibacterial corrodes, during use Without adding of germicide, and good stability, do not fire, the most quick-fried, store transportation safety.After vinyl benzo-crown ether participates in copolymerization, it is possible to Significantly improve the drag reducing efficiency of drag reducer.According to the principle of fluids within pipes mechanics, viscous fluid along a fixed boundary flow through time, no Opinion is interior stream or outflow, and its borderline flow velocity is 0, border exists normal direction current gradient, therefore between fluid and border There is shearing force.The result of this shearing force acting is to consume the part energy in fluid, and finally with form of heat to Around dissipate.In order to offset the energy that this part is scattered and disappeared, to maintain the motion of fluid, it is necessary to external energy.According to Reynolds number Size two distinct types of flowing, i.e. turbulent flow and laminar flow can occur.In laminar flow, fluid resistance is only by adjacent in fluid Momentum-exchange between each fluid layer is determined.In turbulent flow, VELOCITY DISTRIBUTION tends to equalization, and fluid resistance depends primarily on turbulent flow The momentum transmission between momentum transmission and various sizes of whirlpool between whirlpool and tube wall.In turbulent flow, the fortune of fluid particle Dynamic speed change at random, forms each whirlpool.Maelstrom absorbs energy from fluid and deforms, crushes, and converts to little whirlpool. Little whirlpool weakens under viscous force effect, evaluates and analyses.Its energetic portions is converted into heat energy and is dissipated.In the boundary region near tube wall In, due to wall shear stress and viscous force effect, this conversion is the most serious.Therefore, join when vinyl benzo-crown ether After pipeline, it is by the viscoelasticity of itself, and molecule long-chain following current directly affects the fortune of fluid infinitesimal to natural drawing, molecule infinitesimal Dynamic.Radial forces from fluid infinitesimal acts on the molecule infinitesimal of vinyl benzo-crown ether so that it is be distorted, and rotates Deformation.Vinyl benzo-crown ether contains the phenyl ring of rigid structure and the crown ether of flexible structure, the molecular force between its molecule Counteracting force can be produced by convection cell infinitesimal, and then change the fluid infinitesimal size and Orientation to molecular force, make a part The active force of radial direction be changed into following current to the active force of axial direction, thus reduce the consumption of idle work, from macroscopically See, it is simply that play reducing friction resistance and reduce the effect of energy dissipation.In the long-distance transport or Reusability of fluid, curved The positions such as pipe or pumping plant all can produce powerful shearing force, and its shear action always reduces the drag reducing efficiency of drag reducer.The application sends out A person of good sense is found surprisingly that, drag reducer can be greatly improved after vinyl fluorobenzene and acrylamide, vinyl benzo-crown ether copolymerization Anti-shearing effect, even at relatively high temperatures, experience is transported for long-distance or repeatedly remains in that higher after high intensity is sheared Drag reducing efficiency, thus it is speculated that its possible reason is, the vinyl fluorobenzene chemical combination that vinyl fluoride benzene compound particularly symmetry is higher Thing, can produce sedimentation between its aromatic rings, in the fluorophenyl compound that symmetry is higher, the performance of this character becomes apparent from, Do not only exist face, the face sedimentation that between aromatic rings plane, full weight is folded, there is also half overlapping face, face heap between aromatic rings plane Long-pending effect.Additionally, there is also a face sedimentation between fluorine atom and aromatic rings center.It can make drag reducer under jointly acting on Under experience high intensity shear action repeatedly, can guarantee that molecule is still long-chain, and then keep outstanding drag reducing efficiency.The present invention is also This mechanism can be not limited to explain.
It is described in further detail the present invention below in conjunction with specific embodiment.
A is acrylamides, and B is vinyl benzo-crown ether, and C is inorganic salt, and D is stabilizer, and E is that azo draws Sending out agent, F is oxidant, and G is reducing agent, and H is vinyl fluorobenzene.
A1 N-methyl (methyl) acrylamide
A2 Methacrylamide
A3 acrylamide
B1 4-vinyl benzo-hexaoxacyclooctadecane-6-6
B2 4-vinyl benzo-heptaoxacycloheneicosane-7-7
B3 4-vinyl benzo-octaoxacyclotetracosane-8-8
C1 ammonium sulfate
C2 sodium sulfate
D1 2-acrylamide-2-methylpro panesulfonic acid sodium
D2 sodium acrylate
E azo two isobutyl imidazoline hydrochloride
F Ammonium persulfate.
G sodium sulfite
H1 4-fluorobenzene ethylene
H2 2,6-difluorobenzene ethylene
H3 2,3,4,5,6-pentafluorostyrene
The synthetic method of 4-vinyl benzo-hexaoxacyclooctadecane-6-6 is:
(1) weigh 10 mL hexaethylene glycols and be placed in 250 mL equipped with in the double-neck flask of reflux condensing tube, add 50 mL thionyl chlorides With 2 DMF.It is heated to reflux 15 h, is cooled to room temperature after completion of the reaction, with Rotary Evaporators, thionyl chloride is drained, obtain two Chlorine hexaethylene glycol.
(2) 0.01 mol 4-vinyl-1,2-Benzodiazepines and 0.012 mol dichloro hexaethylene glycol are placed in 250 mL round bottoms In flask, add 0.01 mol sodium hydroxide and 0.005 mol Lithium hydrate, using 100 mL butanol as solvent, heat back Flow 2 h.It is cooled to room temperature after completion of the reaction, extracts thick product with chloroform.Mix with petroleum ether and ethyl acetate volume ratio 7:1 As flowing phase, silica gel carries out column separating purification mutually as fixing, obtains 4-vinyl benzo-hexaoxacyclooctadecane-6-6.With deuterated DMSO For solvent,1H NMR characterizes, chemical shift δ (ppm): 6.52-6.65 (m, 4H), 5.51-5.59 (m, 2H), 4.15 (t, 4H), 3.74 (t, 4H) ,3.51 (t, 12H)。
The synthetic method of 4-vinyl benzo-heptaoxacycloheneicosane-7-7 is:
(1) weigh 10 mL seven glycol and be placed in 250 mL equipped with in the double-neck flask of reflux condensing tube, add 50 mL thionyl chlorides With 2 DMF.It is heated to reflux 15 h, is cooled to room temperature after completion of the reaction, with Rotary Evaporators, thionyl chloride is drained, obtain two Chlorine seven glycol.
(2) 0.01 mol 4-vinyl-1,2-Benzodiazepines and 0.012 mol dichloro seven glycol are placed in 250 mL round bottoms In flask, add 0.01 mol sodium hydroxide and 0.005 mol Lithium hydrate, using 100 mL butanol as solvent, heat back Flow 2 h.It is cooled to room temperature after completion of the reaction, extracts thick product with chloroform.Mix with petroleum ether and ethyl acetate volume ratio 8:1 As flowing phase, silica gel carries out column separating purification mutually as fixing, obtains 4-vinyl benzo-heptaoxacycloheneicosane-7-7.With deuterated DMSO For solvent,1H NMR characterizes, chemical shift δ (ppm): 6.47-6.57 (m, 4H), 5.3-5.5 (m, 2H), 4.08 (t, 4H), 3.85 (t, 4H) ,3.61 (t, 16H)。
The synthetic method of 4-vinyl benzo-octaoxacyclotetracosane-8-8 is:
(1) weigh 10 mL eight glycol and be placed in 250 mL equipped with in the double-neck flask of reflux condensing tube, add 50 mL thionyl chlorides With 2 DMF.It is heated to reflux 15 h, is cooled to room temperature after completion of the reaction, with Rotary Evaporators, thionyl chloride is drained, obtain two Chlorine eight glycol.
(2) 0.01 mol 4-vinyl-1,2-Benzodiazepines and 0.012 mol dichloro eight glycol are placed in 250 mL round bottoms In flask, add 0.01 mol sodium hydroxide and 0.005 mol Lithium hydrate, using 100 mL butanol as solvent, heat back Flow 2 h.It is cooled to room temperature after completion of the reaction, extracts thick product with chloroform.Mix with petroleum ether and ethyl acetate volume ratio 10:1 Cooperation is flowing phase, and silica gel carries out column separating purification mutually as fixing, obtains 4-vinyl benzo-octaoxacyclotetracosane-8-8.With deuterated DMSO is solvent,1H NMR characterizes, chemical shift δ (ppm): 6.44-6.58 (m, 4H), 5.4-5.5 (m, 2H), and 4.32 (t, 4H), 4.14 (t, 4H) ,3.48 (t, 20H)。
Table 1 embodiment 1-9, composition is by weight
The preparation method of embodiment 1-9 is: four-neck flask is loaded onto condensing tube, mechanical agitator, temperature controller, constant pressure addition leakage Bucket, wherein condensing tube upper end connecting tee, threeway one end connects nitrogen inlet, and one end connects oil sealing and leads to air.By acryloyl Amine, vinyl benzo-crown ether, inorganic salt, stabilizer, azo-initiator, oxidant, water weigh according to the parts by weight of table 1, Four-neck flask stirs.Logical nitrogen 30 min, arranges the air in reaction unit.With constant pressure funnel to instead Answering and be added dropwise over reducing agent in system, controlling reaction temperature is 40 DEG C, increases the temperature to 45 DEG C after reacting 8 hours, is further continued for anti- Answer 2 hours.Reaction is cooled to room temperature after terminating, and to obtain final product.
Table 2 embodiment 10-12 and comparative example 1-2, composition is by weight
The preparation method of embodiment 10-12 is: four-neck flask is loaded onto condensing tube, mechanical agitator, temperature controller, constant pressure addition leakage Bucket, wherein condensing tube upper end connecting tee, threeway one end connects nitrogen inlet, and one end connects oil sealing and leads to air.By acryloyl Amine, vinyl benzo-crown ether, inorganic salt, stabilizer, azo-initiator, oxidant, water, vinyl fluorobenzene are according to the weight of table 2 Amount number weighs, and stirs in four-neck flask.Logical nitrogen 30 min, arranges the air in reaction unit.Use constant voltage Dropping funnel is added dropwise over reducing agent in reaction system, and controlling reaction temperature is 40 DEG C, increases the temperature to 45 after reacting 8 hours DEG C, it is further continued for reacting 2 hours.Reaction is cooled to room temperature after terminating, and to obtain final product.
Comparative example 1 is same as in Example 1, and difference is without vinyl benzo-crown ether.
Comparative example 2 is same as in Example 1, and difference is without stabilizer.
Comparative example 3 is commercially available polyacrylamide, and molecular weight is 15,000,000.
Evaluation methodology
1. the inspection of outward appearance
Take 100 mL samples with the graduated cylinder of dried and clean, load in 20 mL color comparison tubes, estimate under non-direct projection available light.
2. the mensuration of pH value
At 25 DEG C, the aqueous solution of preparation sample 1 mass %, drips testing sample on accurate pH test paper with dropper, with standard Color board contrasts, and determines pH value.
3. the mensuration of density
Perform according to the regulation of the 4.3.3 in GB/T 4472-2011, unit g/cm3。
4. the mensuration of apparent viscosity
Use ZNN-D6 six speed rotating cylinder viscometer or like product, measure and mix after constant temperature 30 min in the water bath with thermostatic control of 25 DEG C The apparent viscosity of uniform sample, units MPa s.
5. the mensuration of clear water drag reducing efficiency
A. assay method
The configuration of 0.5% guar gum solution: add 2 g melon collagen powder, high-speed stirred 5 min, swelling 4 h at 500 mL clear water.
The preparation of testing liquid: add 2 g embodiment or comparative examples in 500 mL clear water, uses low-speed agitator stirring 1 h, makes embodiment or comparative example be completely dissolved, and adds 2 g melon collagen powder, high-speed stirred 5 min, swelling 4 h.
The 0.5% guar gum solution prepared above and testing liquid are separately added into filter pressing in ZNS-3 type commit a breach of etiquette, at 0.7 MPa Under carry out leak-off test.After the complete leak-off of liquid is complete, open filter cylinder, obtain filter cake.
The slide block method of testing using ZN-3A type tester for viscosity factor measures that step obtains respectively filter cake viscous system Number.
B. the calculating of clear water drag reducing efficiency
Clear water drag reducing efficiency A formula as described below calculates:
In formula:
A: clear water drag reducing efficiency, %；
V1: the coefficient of viscosity of 0.5% guar gum solution；
V2: the coefficient of viscosity of testing liquid.
6. anti-shear performance
The test condition of anti-shear performance is as follows: measured by fracturing fluid drag reduction determinator, is 70 DEG C keeping temperature, by sample Adding storage tank, solution is by 0.75kW, and rotating speed is that the centrifugal pump conveying of 3000rpm is flowed out, and enters test section through spinner flowmeter. Using spinner flowmeter metered flow, uninterrupted, by Frequency Converter Control, measures the solution pressure drop by test section.Test pipe is straight Footpath 0.7 cm, testing tube segment length is 3.5 m, and sample mass concentration in water is 0.2 %, and rate of flow of fluid is 10 m/s.Subtract Resistance rate B formula as described below calculates:
In formula:
B: anti-shearing drag reducing efficiency, %；
ΔP1: clear water pressure drop, Pa；
ΔP2: testing liquid's pressure drop under Reynolds constant identical with clear water, Pa.
B1 and B2 that record water pump circulation shear 30 min and 5h obtains.
Result of the test
The above, only presently preferred embodiments of the present invention, it is not intended to limit protection scope of the present invention.Every basis Equalization change and the modification that present invention is done, is encompassed by the scope of the claims of the present invention.

Claims (10)

  1. The most novel pressure break drag reducer, in parts by weight, it is prepared raw material and at least includes:
    Acrylamides 100 parts；
    Vinyl benzo-crown ether 4-6 part；
    Inorganic salt 120-130 part；
    Stabilizer 2-3 part；
    Initiator 0.005-0.05 part；
    Water 200-300 part.
  2. Novel pressure break drag reducer the most as claimed in claim 1, it is prepared raw material and also includes vinyl fluorobenzene 0.5-2 part.
  3. Novel pressure break drag reducer the most as claimed in claim 1, it is characterised in that described acrylamides is selected from third In acrylamide, Methacrylamide, N methacrylamide, N-isopropyl acrylamide and N, N-DMAA At least one.
  4. Novel pressure break drag reducer the most as claimed in claim 1, it is characterised in that described vinyl benzo-crown ether is selected from 4-second One in thiazolinyl benzo-hexaoxacyclooctadecane-6-6,4-vinyl benzo-heptaoxacycloheneicosane-7-7,4-vinyl benzo-octaoxacyclotetracosane-8-8.
  5. Novel pressure break drag reducer the most as claimed in claim 1, it is characterised in that described inorganic salt is selected from sodium salt, ammonium salt, magnesium At least one in salt.
  6. Novel pressure break drag reducer the most as claimed in claim 1, it is characterised in that described stabilizer is selected from 2-acrylamide Base-2-methyl propane sulfonic acid salt, styrene sulfonate, vinyl sulfonate, Sodium allyl sulphonate, acrylates, methacrylate, hydroxyl At least one in ethyl acrylate.
  7. Novel pressure break drag reducer the most as claimed in claim 2, it is characterised in that described vinyl fluorobenzene is selected from 4-fluorophenethyl One in alkene, 2,6-difluorobenzene ethylene, 2,3,4,5,6-pentafluorostyrene.
  8. Novel pressure break drag reducer the most as claimed in claim 1, it is characterised in that described initiator is selected from azo-initiator With the combination of oxidation-reduction initiator, the weight ratio of described azo-initiator and oxidation-reduction initiator is (0.8-1.2): 2。
  9. Novel pressure break drag reducer the most as claimed in claim 8, it is characterised in that described azo-initiator is selected from azo two Isopropyl cyanide, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo double methylpent hydrochlorate, 2,2 '-azo diisobutyl amidine hydrochlorate, azo two isobutyl imidazoles At least one in quinoline hydrochlorate, 2,2 '-azo two [2-(2-imidazoline-2-propane)-dihydrochloride].
  10. Novel pressure break drag reducer the most as claimed in claim 8, it is characterised in that the oxygen in described oxidation-reduction initiator At least one in Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide of agent；In described oxidation-reduction initiator Reducing agent in sodium sulfite, sodium sulfite, sodium thiosulfate, ferrous sulfate and sodium dithionite at least one Kind；The weight ratio of described Oxidizing and Reducing Agents is (3-2): 1.
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CN115340454A (en) * 2022-05-10 2022-11-15 中国石油大学(华东) Oligomerization type drag reducer for natural gas pipeline and preparation method thereof

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