CN104592968A - Water-based cleaning sand-carrying fluid thickener for well fracturing and preparation method thereof - Google Patents
Water-based cleaning sand-carrying fluid thickener for well fracturing and preparation method thereof Download PDFInfo
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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
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- 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
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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
- C09K8/84—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
Abstract
The invention relates to a water-based cleaning sand-carrying fluid thickener for well fracturing and a preparation method thereof. The thickener is a copolymer of a monomer containing a long-chain n-alkyl-amine end group and N,N-dimethacrylamide, a jelly which is relatively great in strength can be formed in water, and the formed jelly can be broken when encountering the oil gas in an oil layer, so that the purposes of cleaning, sand carrying and fracturing are realized.
Description
Technical field
The invention belongs to oilfield chemical auxiliary field, particularly relate to a kind of wellfracturing water-based clean sand-carrying agent thickening material and preparation method thereof.
Background technology
The Main Yield-increasing measure of Low permeable oil and gas reservoirs is wellfracturing, and to affect one of successful key factor of wellfracturing technique be pressure break sand-carrying agent.There are problems as the fracturing liquid of thickening material at present conventional linear polysaccharide and artificial polymer, as broken glue not thoroughly, the row of returning is difficult etc.As the breakthrough of traditional polymer-gel breaking method, the expert of Ani-Agip and Schlumberger has developed jointly out the pressure break sand-carrying agent that tensio-active agent forms, and is called for short VES.After this, this pressure break is taken sand body system and is obtained constantly abundant and development.But the type pressure break sand-carrying agent is with high costs, configuration is too accurate, limits the widespread use in its oil field at home to a certain extent.
A kind of wellfracturing water-based clean sand-carrying agent thickening material that the present invention develops, hydrophobic grouping wherein in amphiphile, amphiphilic molecule has certain being inclined to from dimerization, its nonpolar moiety and water segregation can be come, forming structure is coccoid or long bar-shaped molecular network structure, this network structure has certain distortion resistance, thus gives the higher viscosity of solution and elasticity.When organic substance diffuses into this network structure core, structural damage can be caused again: change original network structure into ball-like structure and soltion viscosity is reduced.Utilize this principle, when pressure liquid runs into oil in stratum or gas, its viscosity can reduce greatly.In addition, such fracturing fluid system has again washing oil ability, crude oil can be peeled away from rock surface, and reduce viscosity of crude, has distinctive feature to the pressure break of highly viscous crude oil reservoir.
Summary of the invention
Object of the present invention is just to provide a kind of wellfracturing water-based clean sand-carrying agent thickening material and preparation method thereof.
First the present invention prepares a kind of monomer containing long chain primary amines end group, and then with N,N-DMAA copolymerization, the multipolymer prepared can form the larger frozen glue of intensity in water, and the frozen glue formed can be met oil gas and break glue in oil reservoir, arrive the clean object taking sand pressure break.
The present invention is further illustrated below by specific examples.
Embodiment
Embodiment 1
(1) the sodium bicarbonate ethanolic soln being 2% by 0.05mol 1,6-hexanediamine and 30ml mass percent joins in the reaction vessel with whipping appts, in stirred at ambient temperature 1 ~ 2h; 0.06mol tert-Butyl dicarbonate is added in 150ml dioxane, mixing; Then slowly dropped in made 1,6-hexanediamine mixed solution by made tert-Butyl dicarbonate solution, temperature controls below 10 DEG C, drip and finish, stirred at ambient temperature 24h, termination reaction, pH to 3 is adjusted with dilute hydrochloric acid, rotary evaporation, except desolventizing, dissolves residuum with methylene dichloride, filtering sodium-chlor, solution is instilled in cold diethyl ether, separate out light yellow solid, washed with diethylether 3 times, 25 DEG C of vacuum-dryings;
(2) be dissolved in 60ml ethanol by gained light yellow solid in (1), slowly instillation 0.05mol acrylate chloride, temperature controls at 0 ~ 5 DEG C, drips and finishes, in 0 ~ 5 DEG C of stirring reaction 3h, there is clear crystal to separate out, filter, washed with diethylether 3 times, obtains clear crystal, 25 DEG C of vacuum-dryings;
(3) 20ml trifluoroacetic acid is dissolved in 50ml ethylene dichloride, add gained clear crystal in (2), stirring and dissolving, room temperature reaction 2h, rotary evaporation removes desolventizing, residuum dissolve with ethanol, pH to 9 is adjusted with aqueous sodium carbonate, underpressure distillation, except desolventizing, obtains clear crystal, 25 DEG C of vacuum-dryings;
(4) by (3) gained clear crystal and 0.3molN, N-DMAA is dissolved in deionized water, add 0.001g disodium EDTA, being warming up to 40 DEG C makes disodium EDTA dissolve completely, add 0.005g ammonium persulphate and 0.002g sodium bisulfite again, stir, be warming up to 60 DEG C of polymerizations, insulation 3 ~ 4h, generates elastic gel, colloid is cut into tiny blob of viscose, be placed in pallet, be dried to water ratio less than 10% in about 50 DEG C, be cooled to room temperature, be ground into particle.Gel chromatography records product weight-average molecular weight and is about 9032.
Embodiment 2
(1) the sodium bicarbonate ethanolic soln being 2% by 0.05mol 1,10-certain herbaceous plants with big flowers diamines and 30ml mass percent adds in the reaction vessel with whipping appts, stirred at ambient temperature 1 ~ 2h; 0.06mol tert-Butyl dicarbonate is added in 150ml dioxane, mixing; Then made tert-Butyl dicarbonate solution slowly drops in made 1,10-certain herbaceous plants with big flowers diamines mixing solutions, and temperature controls below 10 DEG C, drip and finish, in stirring at room temperature 24h, termination reaction, pH to 3 is adjusted with dilute hydrochloric acid, rotary evaporation, except desolventizing, dissolves residuum with methylene dichloride, filtering sodium-chlor, solution is instilled in cold diethyl ether, separate out light yellow solid, washed with diethylether 3 times, 25 DEG C of vacuum-dryings;
(2) be dissolved in 60ml ethanol by (1) gained light yellow solid, slowly instillation 0.05mol acrylate chloride, temperature controls at 0 ~ 5 DEG C, drips and finishes, in 0 ~ 5 DEG C of stirring reaction 3h, there is clear crystal to separate out, filter, washed with diethylether 3 times, obtains clear crystal, 25 DEG C of vacuum-dryings;
(3) 20ml trifluoroacetic acid is dissolved in 50ml ethylene dichloride, add (2) gained clear crystal, stirring and dissolving, in room temperature reaction 2h, rotary evaporation removes desolventizing, residuum dissolve with ethanol, pH to 9 is adjusted to aqueous sodium carbonate, underpressure distillation, except desolventizing, obtains clear crystal, 25 DEG C of vacuum-dryings;
(4) by (3) gained clear crystal and 0.4molN, N-DMAA is dissolved in deionized water, add 0.001g disodium EDTA, being warming up to 40 DEG C makes disodium EDTA dissolve completely, add 0.005g ammonium persulphate and 0.002g sodium bisulfite, stir, be warming up to 60 DEG C of polymerizations, insulation 3 ~ 4h, generates elastic gel, colloid is cut into tiny blob of viscose, be placed in pallet, be dried to water ratio less than 10% in about 50 DEG C, be cooled to room temperature, be ground into particle.Gel chromatography records product weight-average molecular weight and is about 12250.
Embodiment 3
(1) the sodium bicarbonate ethanolic soln being 2% by 0.05mol 1,12-bay diamines and 30ml mass percent adds in the reaction vessel with whipping appts, stirred at ambient temperature 1 ~ 2h; 0.06mol tert-Butyl dicarbonate is added in 150ml dioxane, mixing; Made tert-Butyl dicarbonate solution is slowly dropped in made 1,12-bay two amine aqueous solution, drip and finish, stirred at ambient temperature 24h, termination reaction, adjusts pH to 3 with dilute hydrochloric acid, and rotary evaporation is except desolventizing, residuum is dissolved with methylene dichloride, filtering sodium-chlor, instills solution in cold diethyl ether, separates out light yellow solid, washed with diethylether 3 times, 25 DEG C of vacuum-dryings;
(2) be dissolved in 60ml ethanol by (1) gained yellow solid, slowly instillation 0.05mol acrylate chloride, temperature controls, at 0 ~ 5 DEG C, have clear crystal to separate out, drip and finish, in 0 ~ 5 DEG C of stirring reaction 3h, filter, washed with diethylether 3 times, obtains clear crystal, 25 DEG C of vacuum-dryings;
(3) 20ml trifluoroacetic acid is dissolved in 50ml ethylene dichloride, then (2) gained clear crystal is added, after stirring and dissolving, at room temperature reaction 2h, rotary evaporation removes desolventizing, residuum dissolve with ethanol, pH to 9 is adjusted with aqueous sodium carbonate, underpressure distillation, except desolventizing, obtains clear crystal, 25 DEG C of vacuum-dryings;
(4) by (3) gained clear crystal and 0.5molN, N-DMAA is dissolved in deionized water, add 0.001g disodium EDTA, being warming up to 40 DEG C makes disodium EDTA dissolve completely, add 0.005g ammonium persulphate and 0.002g sodium bisulfite again, stir evenly, be warming up to 60 DEG C of polymerizations, insulation 3 ~ 4h, generates elastic gel, colloid is cut into tiny blob of viscose, be placed in pallet, be dried to water ratio less than 10% in about 50 DEG C, be cooled to room temperature, be ground into particle.Gel chromatography records product weight-average molecular weight and is about 14550.
Embodiment 4
(1) the sodium bicarbonate ethanolic soln being 2% by 0.05mol 1,6-hexanediamine and 30ml mass percent adds in the reaction vessel with whipping appts, stirred at ambient temperature 1 ~ 2h; 0.06mol tert-Butyl dicarbonate is added in 150ml dioxane, mixing; Made tert-Butyl dicarbonate solution is slowly dropped to made 1,6-hexanediamine mixing solutions, and temperature controls below 10 DEG C, drip and finish, stirred at ambient temperature 24h, termination reaction, pH to 3 is adjusted with dilute hydrochloric acid, rotary evaporation, except desolventizing, dissolves residuum with methylene dichloride, filtering sodium-chlor, solution is instilled in cold diethyl ether, separate out light yellow solid, washed with diethylether 3 times, 25 DEG C of vacuum-dryings;
(2) be dissolved in 60ml ethanol by (1) gained yellow solid, slowly instillation 0.05mol acrylate chloride, temperature controls at 0 ~ 5 DEG C, drips and finishes, in 0 ~ 5 DEG C of stirring reaction 3h, there is clear crystal to separate out, filter, washed with diethylether 3 times, obtains clear crystal, 25 DEG C of vacuum-dryings;
(3) 20ml trifluoroacetic acid is dissolved in 50ml ethylene dichloride, add (2) gained clear crystal, stirring and dissolving, react 2h under room temperature, rotary evaporation removes desolventizing, residuum dissolve with ethanol, pH to 9 is adjusted with aqueous sodium carbonate, underpressure distillation, except desolventizing, obtains clear crystal, 25 DEG C of vacuum-dryings;
(4) by (3) gained clear crystal and 0.6molN, N-DMAA is dissolved in deionized water, add 0.00lg disodium EDTA, being warming up to 40 DEG C makes disodium EDTA dissolve completely, add 0.005g ammonium persulphate and 0.002g sodium bisulfite again, stir, be warming up to 60 DEG C of polymerizations, insulation 3 ~ 4h, generates elastic gel, colloid is cut into tiny blob of viscose, be placed in pallet, be dried to water ratio less than 10% in about 50 DEG C, be cooled to room temperature, be ground into particle.Gel chromatography records product weight-average molecular weight and is about 12680.
Embodiment 5
(1) the sodium bicarbonate ethanolic soln being 2% by 0.05mol 1,10-certain herbaceous plants with big flowers diamines and 30ml mass percent adds in the reaction vessel with whipping appts, stirred at ambient temperature 1 ~ 2h; 0.06mol tert-Butyl dicarbonate is added in 150ml dioxane, mixing; Made tert-Butyl dicarbonate solution is slowly dropped in made 1,10-certain herbaceous plants with big flowers diamines mixing solutions, drip and finish, stirred at ambient temperature 24h, termination reaction, adjusts pH to 3 with dilute hydrochloric acid, and rotary evaporation is except desolventizing, residuum is dissolved with methylene dichloride, filtering sodium-chlor, instills solution in cold diethyl ether, separates out light yellow solid, washed with diethylether 3 times, 25 DEG C of vacuum-dryings;
(2) be dissolved in 60ml ethanol by above-mentioned light yellow solid, slowly instillation 0.05mol acrylate chloride, temperature controls at 0 ~ 5 DEG C, drips and finishes, in 0 ~ 5 DEG C of stirring reaction 3h, there is clear crystal to separate out, filter, washed with diethylether 3 times, obtains clear crystal, 25 DEG C of vacuum-dryings;
(3) 20ml trifluoroacetic acid is dissolved in 50ml ethylene dichloride, add (2) gained clear crystal, stirring and dissolving, room temperature reaction 2h, rotary evaporation removes desolventizing, residuum dissolve with ethanol, pH to 9 is adjusted with aqueous sodium carbonate, underpressure distillation, except desolventizing, obtains clear crystal, 25 DEG C of vacuum-dryings;
(4) by (3) gained clear crystal and 0.5molN, N-DMAA is dissolved in deionized water, add 0.001g disodium EDTA, being warming up to 40 DEG C makes disodium EDTA dissolve completely, add 0.005g ammonium persulphate and 0.002g sodium bisulfite again, stir, be warming up to 60 DEG C of polymerizations, insulation 3-4h, generates elastic gel, colloid is cut into tiny blob of viscose, be placed in pallet, be dried to water ratio less than 10% in about 50 DEG C, be cooled to room temperature, be ground into particle.Gel chromatography records product weight-average molecular weight and is about 13590.
Embodiment 6
By the sample clear water dissolved dilution of preparation in embodiment 1 ~ 5, make the aqueous solution that mass percent is 0.5%, under normal temperature, measure viscosity, the results are shown in Table 1.Data show: molecular weight is larger, and its solution viscosity is larger, and wherein the viscosity of embodiment 3 products therefrom 0.5% aqueous solution is more than 50mPa.s; Embodiment 1,2, the viscosity of 4 products therefrom 0.5% aqueous solution is lower than 40mPa.s; The viscosity of embodiment 5 products therefrom 0.5% aqueous solution is 45mPa.s.
0.5% solution viscosity (25 DEG C, mPa.s) of table 1 each sample
| Embodiment | M value | N value | Weight-average molecular weight | Viscosity, mPa.s |
| 1 | 80 | 6 | 9032 | 15 |
| 2 | 100 | 10 | 12250 | 28 |
| 3 | 120 | 10 | 14550 | 58 |
| 4 | 110 | 10 | 12680 | 30 |
| 5 | 110 | 11 | 13590 | 45 |
Embodiment 7
Wellfracturing water-based clean sand-carrying agent can not be too high in uncrosslinked front base fluid viscosity, so that pumping.Below investigated embodiment 5 products therefrom sample dissolve in water after viscosity, determine its viscosity-temperature dependency.In table 2: the soltion viscosity under each concentration reduces along with the rising of temperature, wherein the solution of 0.7% viscosity at 25 DEG C of temperature is maximum, is 48mPa.s; Meet site pumping requirement.
Viscosity (mPa.s) under table 2 differing temps
| Embodiment 5 base fluid concentration | 25℃ | 60℃ | 90℃ | 120℃ |
| 0.05％ | 18 | 11 | 5 | 4 |
| 0.1％ | 22 | 15 | 8 | 5 |
| 0.3％ | 30 | 22 | 14 | 12 |
| 0.5％ | 45 | 30 | 23 | 18 |
| 0.7％ | 48 | 40 | 31 | 22 |
Embodiment 8
Get the different concns aqueous solution (base fluid) of 100g embodiment 5 products therefrom, the glutaraldehyde water solution (mass percent is 5%) adding 5% of different amount respectively, as linking agent, investigates the viscosity of crosslinked rear system under normal temperature, different crosslinking ratio.In table 3: when under various base fluid concentration, crosslinking ratio reaches 100: 0.5, cross-linking system viscosity reaches peak value.
Viscosity (linking agent: the glutaraldehyde of 5%, 25 DEG C under the different crosslinking ratio of table 3; Shearing rate: 7.34s
-1)
| Crosslinking ratio/100:x | 0.00 | 0.03 | 0.05 | 0.1 | 0.3 | 0.5 | 0.7 | 1.0 |
| 0.3％ | 30 | 606 | 623 | 645 | 850 | 1270 | 1270 | 1269 |
| 0.5％ | 45 | 718 | 750 | 835 | 972 | 1380 | 1382 | 1380 |
| 0.7％ | 48 | 890 | 1075 | 1350 | 1540 | 1705 | 1702 | 1704 |
Embodiment 9
The different concns base fluid 100g of Example 5 products therefrom, the linking agent (mass percent is the glutaraldehyde water solution of 5%) adding different amount stirs, and carries out crosslinking reaction and timing.Until base fluid be cross-linked to can hang time timing again.Calculate the rate of crosslinking under the different crosslinking ratio of different base fluid concentration.In table 4: base fluid concentration is 0.3 ~ 0.7%, and crosslinking ratio scope is 100/0.03 ~ 0.5, and crosslinking time scope is 1 ~ 6 second.
Rate of crosslinking (min, 25 DEG C) under the different crosslinking ratio of table 4
| Crosslinking ratio/100:x | 0.03 | 0.05 | 0.1 | 0.3 | 0.5 |
| 0.3％ | 6 | 4 | 3 | 2 | 2 |
| 0.5％ | 5 | 3 | 2.5 | 2 | 2 |
| 0.7％ | 4 | 3 | 2 | 1.5 | 1 |
Embodiment 10
The pressing crack construction time, period required that pressure break sand-carrying agent can have certain viscosity in case anti-avulsion sand usually within 2h.Therefore, high strength shears 2h at a certain temperature, and fracturing fluid system can not break glue.Be respectively at 60 ~ 180 DEG C, the sand-carrying agent system (embodiment 5 products therefrom, crosslinking ratio is 100: 0.5) base fluid concentration being respectively to 0.3%, 0.5% and 0.7% is sheared, and shearing rate is 7.34s
-1, shear the viscosity after 120min, in table 5.
Viscosity after table 5 differing temps down cut
(crosslinking ratio: 100/0.5, shearing rate: 7.34s
-1, shear time: 120min)
Embodiment 11
Aqueous fracturing fluid belongs to aquogel system, and in fracturing process, under High Temperature High Pressure effect, water molecules can be fled from gelling system and enter oil reservoir, thus causes swelling clay mineral, oil reservoir percolation ability is weakened, affects fracturing effect.Therefore, fracturing fluid system is required to reduce as much as possible and the moisture leak-off that slows down.Table 6 is moisture leak-off situations that base fluid concentration is respectively 0.3% and 0.5%, crosslinking ratio is the fracturing liquid gelling system (embodiment 5 products therefrom) of 100/0.5.
The leak-off situation (crosslinking ratio: 100/0.5,25 DEG C) of table 6 fracturing liquid gelling system
| Base fluid concentration | 0.5％ | 0.7％ |
| Experimental period, min | 36 | 36 |
| Leak-off area, cm 2 | 5.06 | 5.06 |
| Slope | 1.03 | 1.10 |
| Intercept, cm 3 | 1.12 | 0 |
| Spurt loss volume, × 10 -3m 3/m 2 | 2.21 | 0 |
| Filtration rate, × 10 -6m/min | 1.7 | 1.1 |
| Leakoff coefficent, × 10 -5m/min 0.5 | 1.08 | 1.02 |
Embodiment 12
The major function of pressure break sand-carrying agent has be the gap that oil reservoir shale pressed off certain length and width at two: one, and two is carried by ceramsite sand to enter pressed off gap so that support.Therefore, require ceramsite sand at operating tool string and enter in the process of gap and can not precipitate.Table 7 is pressure break sand-carrying agent (embodiment 5 products therefrom) prop-carrying capacities to different-grain diameter ceramsite sand that base fluid concentration is respectively 0.3%, 0.5% and 0.7%, crosslinking ratio is 100/0.5.
The settling velocity (cm/h) (crosslinking ratio: 100/0.5,25 DEG C) of table 7 different-grain diameter ceramsite sand
Embodiment 13
Pressure break sand-carrying agent presses off oil reservoir and is carried by ceramsite sand and enters after in pressed off gap, in order to not cause or not reduce the infringement to oil reservoir, will return discharge oil reservoir as much as possible; And gelling system is difficult to return row by reservoir pressure, therefore, need to carry out brokenly glue to it, viscosity is reduced greatly, so that the row of returning.With the microcapsule of oxygenant ammonium persulphate for gel breaker, dosage is 0.05% (mass percent) of gelling system, at different temperatures for the gelling system that generate at 100: 0.5, glue is carried out brokenly to different base fluid (embodiment 5 products therefrom) viscosity, crosslinking ratio, break the glue time (after broken glue, system viscosity is less than 10mPa.s) in table 8.
Table 8 breaks the glue time
Embodiment 14
Still having good oil-in-water emulsified ability to heavy crude after system breaks glue, is the characteristic of this pressure break sand-carrying agent system.Select different base fluid concentration respectively, crosslinking ratio is 100: 0.5, broken glue ratio is 100: 0.05, after broken glue, at a certain temperature reducing viscosity by emulsifying test is carried out, in table 9 to the crude oil of different viscosity.
The viscosity break ratio (water oil ratio 7: 3) of table 9 pair different viscosity crude oil
| The crude oil of different viscosity scope, mpa.S | Base fluid concentration, % | Emulsifying temperature, DEG C | Emulsion viscosity, mPa.S | Viscosity break ratio, % |
| 5000～20000 | 0.1～0.3 | 50 | ≤300 | ≥90 |
| 20000～50000 | 0.3～0.5 | 60 | ≤300 | ≥90 |
| 50000～100000 | 0.5～0.7 | 70 | ≤300 | ≥90 |
| ≥100000 | 0.7～1.0 | 80 | ≤500 | ≥90 |
Claims (2)
1. a wellfracturing water-based clean sand-carrying agent thickening material, is characterized in that its structure can represent with following general formula:
In formula, R is C
6or C
10or C
12alkyl, m is the integer of 100 ~ 120, and n is the integer of 10 ~ 12.
2. the preparation method of a kind of wellfracturing water-based clean sand-carrying agent thickening material according to claim 1, is characterized in that implementing as follows:
(1) the sodium bicarbonate ethanolic soln being 2% by 0.05mol alkyl diamines and 30ml mass percent joins in the reaction vessel with whipping appts, stirred at ambient temperature 1 ~ 2h; 0.06mol tert-Butyl dicarbonate is added in 150ml dioxane, mixing; Slowly dropped in made alkyl diamines mixing solutions by made tert-Butyl dicarbonate solution, temperature controls below 10 DEG C, drips and finishes, stirred at ambient temperature reaction 24h, termination reaction, adjusts pH to 3 with dilute hydrochloric acid, and rotary evaporation is except desolventizing, residuum is dissolved with methylene dichloride, filtering sodium-chlor, instills solution in cold diethyl ether, separates out light yellow solid, finally use washed with diethylether 3 times, 25 DEG C of vacuum-dryings; Alkyl diamines described above is 1,6-hexanediamine, or 1,10-certain herbaceous plants with big flowers diamines, or 1,12-bay diamines;
(2) be dissolved in 60ml ethanol by (1) gained light yellow solid, slowly instillation 0.05mol acrylate chloride, temperature controls at 0 ~ 5 DEG C, drips and finishes, in 0 ~ 5 DEG C of stirring reaction 3h, there is clear crystal to separate out, filter, washed with ether 3 times, obtains clear crystal, 25 DEG C of vacuum-dryings;
(3) 20ml trifluoroacetic acid is dissolved in 50ml ethylene dichloride, then (2) gained clear crystal is added, stirring and dissolving, react 2h under room temperature, rotary evaporation removes desolventizing, residuum dissolve with ethanol, pH to 9 is adjusted with aqueous sodium carbonate, underpressure distillation, except desolventizing, obtains clear crystal, 25 DEG C of vacuum-dryings;
(4) by (3) gained clear crystal and 0.3 ~ 0.6molN, N-DMAA is dissolved in deionized water, add 0.001g disodium EDTA, being warming up to 40 DEG C makes disodium EDTA dissolve completely, add 0.005g ammonium persulphate and 0.002g sodium bisulfite again, stir, be warming up to 60 DEG C and carry out polyreaction, insulation 3 ~ 4h, generates elastic gel, colloid is cut into tiny blob of viscose, be placed in pallet, be dried to water ratio less than 10% in 50 DEG C, be cooled to room temperature, be ground into particle, obtain the finished product.
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| CN106634933A (en) * | 2016-10-18 | 2017-05-10 | 佛山慧创正元新材料科技有限公司 | High-temperature-resistant clean fracturing fluid thickener and preparation method of same |
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| CN106634933A (en) * | 2016-10-18 | 2017-05-10 | 佛山慧创正元新材料科技有限公司 | High-temperature-resistant clean fracturing fluid thickener and preparation method of same |
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