CN115701437B - Microgel temperature-sensitive foam stabilizer and preparation method thereof - Google Patents
Microgel temperature-sensitive foam stabilizer and preparation method thereof Download PDFInfo
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- CN115701437B CN115701437B CN202110881876.1A CN202110881876A CN115701437B CN 115701437 B CN115701437 B CN 115701437B CN 202110881876 A CN202110881876 A CN 202110881876A CN 115701437 B CN115701437 B CN 115701437B
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- 239000006260 foam Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000003381 stabilizer Substances 0.000 title abstract description 5
- 229920005604 random copolymer Polymers 0.000 claims abstract description 29
- ATTMPECCODOGBK-UHFFFAOYSA-N prop-2-enamide;prop-2-enoic acid;n-[(prop-2-enoylamino)methyl]prop-2-enamide Chemical compound NC(=O)C=C.OC(=O)C=C.C=CC(=O)NCNC(=O)C=C ATTMPECCODOGBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008346 aqueous phase Substances 0.000 claims description 57
- 239000012074 organic phase Substances 0.000 claims description 53
- 239000007795 chemical reaction product Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 29
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 25
- 238000000502 dialysis Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 11
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 10
- 229940094933 n-dodecane Drugs 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 230000006641 stabilisation Effects 0.000 claims description 7
- 238000011105 stabilization Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000003999 initiator Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000004872 foam stabilizing agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 241001620634 Roger Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a microgel temperature-sensitive foam stabilizer and a preparation method thereof. The gel is poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer, and the number average molecular weight of the gel is 2000 ten thousand to 6000 ten thousand.
Description
Technical Field
The invention relates to the technical field of foam stabilization, and particularly provides a polymer with foam stabilization performance at high temperature.
Background
At high temperatures, the aqueous phase in the foam begins to accelerate evaporation and even boiling, resulting in a sudden drop in the stability of the foam at high temperatures. In this case, the increase in viscosity of the liquid phase is insufficient to keep the foam stable. Therefore, in order to prevent evaporation of the liquid at high temperatures, it is necessary to add a foam stabilizer. However, since many foam stabilizers in the prior art are low-temperature foam stabilizers, development of foam stabilizers that exert a foam stabilizing effect at high temperatures is highly demanded.
Disclosure of Invention
One of the present invention provides a poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer having a number average molecular weight of 2000 to 6000 tens of thousands.
In a specific embodiment, the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer is a microgel particle having a particle size of 50 to 150nm.
The second invention provides a preparation method for preparing the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer, which comprises the following steps:
1) Mixing n-dodecane with Span80 to form an organic phase;
2) Dissolving acrylamide, acrylic acid and N, N-methylene bisacrylamide in water to form a water phase;
3) After deoxidizing the organic phase and the aqueous phase respectively, uniformly adding the aqueous phase into the organic phase to obtain a mixed system;
4) Heating and stirring the mixed system, adding an initiator, and continuously reacting to obtain a reaction product;
5) Removing the organic phase from the reaction product to obtain an aqueous phase reaction product;
6) Washing, precipitating and centrifuging the aqueous phase reaction product by ethanol to obtain a precipitated product, wherein the washing, precipitating and centrifuging are repeated for M times, and M is an integer which is more than or equal to 1 and less than or equal to 5;
7) Dissolving the precipitate in water, and dialyzing to obtain a dialyzed product;
8) And freeze-drying the dialysis product to obtain the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer.
In one embodiment, in step 1), the volume ratio of n-dodecane to Span80 is 3 (2-12).
In a specific embodiment, in step 2), the amount of acrylamide is from 0.1% to 1%, the amount of acrylic acid is from 0.2% to 0.8% and the amount of N, N-methylenebisacrylamide is from 0.3% to 0.9% by mass of water.
In a specific embodiment, in step 3), the aqueous phase is added to the organic phase at a rate of 1 to 2mL/min at average speed; and/or the volume ratio of the organic phase to the aqueous phase in the mixed system is (1.3-2): 1.
In a specific embodiment, in step 4), the initiator is added to the mixed system in an amount of 0.1% to 0.3% by mass of the mixed system of 100%.
In a specific embodiment, in step 4), the heating temperature is 50 to 80 ℃, the stirring speed is 300 to 1000rpm, and the duration of the reaction is 3 to 6 hours.
In a specific embodiment, in step 5), the organic phase is removed by spin-evaporation.
In a specific embodiment, in step 6), the speed of centrifugation is 1000 to 3000rpm and the time of centrifugation is 30 to 60 minutes.
In a specific embodiment, in step 7), the dialysis is performed using a dialysis bag having a molecular weight cut-off of 1000 to 6000 tens of thousands, and the dialysis is performed for 7 to 14 days.
The third invention provides an application of the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer according to one of the invention or the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer prepared by the second preparation method according to the invention in foam stabilization; preferably in high temperature foam stabilization; more preferably, it is an application in foam stabilization at temperatures of 40 to 80 ℃.
The invention has the beneficial effects that:
the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles prepared by the invention can play a role in stabilizing foam at high temperature (for example, at the temperature of 40-80 ℃) and defoaming at low temperature (for example, at the temperature of less than 40 ℃) when being used as a foam stabilizer.
Detailed Description
The invention is further illustrated below with reference to the examples, which are merely illustrative of the invention and do not constitute a limitation of the invention in any way.
Example 1
(1) The organic phase is prepared: n-dodecane was mixed with Span80 in a 1:4 volume ratio to form an organic phase.
(2) Preparing an aqueous phase: 100% of acrylamide, 0.8% of acrylic acid and 0.3% of N, N-methylenebisacrylamide were dissolved in pure water to form an aqueous phase.
(3) Copolymerization and crosslinking: after 30min of deoxygenation of the organic phase and the aqueous phase with nitrogen, the organic phase was added to a 500mL three-necked flask, and then the aqueous phase was added to the organic phase at a constant rate of 2.0mL/min to control the droplet volume and to make the final volume ratio of the organic phase and the aqueous phase 1.3:1, to obtain a mixed system. Then, the mixed system was heated to 50℃and stirred at a speed of 300rpm, 0.1% ammonium persulfate (100% by mass of the mixed system) was added thereto as an initiator, and the reaction was continued under stirring in a nitrogen atmosphere for 3 hours, keeping the stirring rate unchanged from the nitrogen atmosphere, and cooled to room temperature to obtain a reaction product.
(4) And (3) reaction product treatment: the reaction product was subjected to rotary evaporation to remove the organic phase, to obtain an aqueous phase reaction product, and then the aqueous phase reaction product was washed 2 times with ethanol, specifically, to add absolute ethanol to the aqueous phase reaction product, to precipitate, and to centrifuge at a centrifugation speed of 1000rpm for 60 minutes, to obtain a precipitated product. Dissolving the precipitate in deionized water, and dialyzing with a dialysis bag with a cutoff number average molecular weight of 2000 ten thousand for 2 weeks to obtain a dialysis product. Freezing the dialysis product overnight and then freeze-drying to obtain the target product, namely the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the microgel particles have a size of 50 to 90nm.
The number average molecular weight of the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer was 2000 ten thousand as determined by gel chromatography.
Example 2
(1) The organic phase is prepared: n-dodecane was mixed with Span80 in a 3:7 volume ratio to form an organic phase.
(2) Preparing an aqueous phase: 100% by mass of water was dissolved in pure water with 0.3% of acrylamide, 0.6% of acrylic acid and 0.5% of N, N-methylenebisacrylamide to form an aqueous phase.
(3) Copolymerization and crosslinking: after deoxygenation of the organic phase and the aqueous phase with nitrogen for 40min, the organic phase was added to a 500mL three-necked flask, respectively, and then the aqueous phase was added to the organic phase at a constant rate of 1.7mL/min to control the droplet volume and to make the final volume ratio of the organic phase and the aqueous phase 1.5:1, to obtain a mixed system. Then, the mixed system was heated to 60℃and stirred at 500rpm, 0.15% ammonium persulfate (100% by mass of the mixed system) was added thereto as an initiator, and the reaction was continued under stirring in a nitrogen atmosphere for 4 hours, keeping the stirring rate unchanged from the nitrogen atmosphere, and cooled to room temperature to obtain a reaction product.
(4) And (3) reaction product treatment: and (3) performing rotary evaporation on the reaction product to remove an organic phase, obtaining an aqueous phase reaction product, washing the aqueous phase reaction product for 2 times by using ethanol, specifically adding absolute ethanol into the aqueous phase reaction product, precipitating, and centrifuging for 50min at a centrifugation speed of 1500rpm to obtain a precipitated product. Dissolving the precipitate in deionized water, and dialyzing with a dialysis bag with a cutoff number average molecular weight of 3000 ten thousand for 12 days to obtain a dialysis product. Freezing the dialysis product overnight and then freeze-drying to obtain the target product, namely the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the microgel particles have a size of 60 to 110nm.
The number average molecular weight of the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer was 3000 ten thousand as determined by gel chromatography.
Example 3
(1) The organic phase is prepared: n-dodecane was mixed with Span80 in a volume ratio of 2:3 to form an organic phase.
(2) Preparing an aqueous phase: 100% by mass of water was dissolved in pure water with 0.5% of acrylamide, 0.45% of acrylic acid and 0.6% of N, N-methylenebisacrylamide to form an aqueous phase.
(3) Copolymerization and crosslinking: after deoxygenation of the organic phase and the aqueous phase with nitrogen for 40min, the organic phase was added to a 500mL three-necked flask, respectively, and then the aqueous phase was added to the organic phase at a constant rate of 1.5mL/min to control the droplet volume and to make the final volume ratio of the organic phase and the aqueous phase 1.6:1, to obtain a mixed system. Then, the mixed system was heated to 65℃and stirred at 700rpm, 0.2% ammonium persulfate (100% by mass of the mixed system) was added thereto as an initiator, and the reaction was continued under stirring in a nitrogen atmosphere for 4.5 hours, keeping the stirring rate unchanged from the nitrogen atmosphere, and cooled to room temperature to obtain a reaction product.
(4) And (3) reaction product treatment: the reaction product was subjected to rotary evaporation to remove the organic phase, to obtain an aqueous phase reaction product, and then the aqueous phase reaction product was washed 2 times with ethanol, specifically, to add absolute ethanol to the aqueous phase reaction product, to precipitate, and to centrifuge at a centrifugation speed of 2000rpm for 45 minutes, to obtain a precipitated product. Dissolving the precipitate in deionized water, and dialyzing with 4000 ten thousand dialysis bags to obtain the dialysis product. Freezing the dialysis product overnight and then freeze-drying to obtain the target product, namely the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the microgel particles have a size of 70 to 120nm.
The number average molecular weight of the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer was 4000 tens of thousands as determined by gel chromatography.
Example 4
(1) The organic phase is prepared: n-dodecane was mixed with Span80 in a 1:1 volume ratio to form an organic phase.
(2) Preparing an aqueous phase: 100% by mass of water was dissolved in pure water with 0.7% of acrylamide, 0.3% of acrylic acid and 0.75% of N, N-methylenebisacrylamide to form an aqueous phase.
(3) Copolymerization and crosslinking: after the organic phase and the aqueous phase were deoxygenated with nitrogen for 50min, respectively, the organic phase was added to a 500mL three-necked flask, and then the aqueous phase was added to the organic phase at a constant rate of 1.2mL/min to control the droplet volume and to make the final volume ratio of the organic phase and the aqueous phase 1.8:1, to obtain a mixed system. Then, the mixed system was heated to 70℃and stirred at 850rpm, 0.25% ammonium persulfate (100% by mass of the mixed system) was added thereto as an initiator, and the stirring reaction was continued in a nitrogen atmosphere for 5 hours, keeping the stirring rate unchanged from the nitrogen atmosphere, and cooled to room temperature to obtain a reaction product.
(4) And (3) reaction product treatment: the reaction product was subjected to rotary evaporation to remove the organic phase to obtain an aqueous phase reaction product, and then the aqueous phase reaction product was washed 2 times with ethanol, specifically, to add absolute ethanol to the aqueous phase reaction product, precipitate, and centrifuge at a centrifugation speed of 2500rpm for 40min to obtain a precipitated product. Dissolving the precipitate in deionized water, and dialyzing with a dialysis bag with a cut-off number average molecular weight of 5000 ten thousand for 8 days to obtain a dialysis product. Freezing the dialysis product overnight and then freeze-drying to obtain the target product, namely the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the microgel particles have a size of 80 to 130nm.
The number average molecular weight of the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer was 5000 ten thousand as determined by gel chromatography.
Example 5
(1) The organic phase is prepared: n-dodecane was mixed with Span80 in a 3:2 volume ratio to form an organic phase.
(2) Preparing an aqueous phase: 100% by mass of water was dissolved in pure water with 1.0% of acrylamide, 0.2% of acrylic acid and 0.9% of N, N-methylenebisacrylamide to form an aqueous phase.
(3) Copolymerization and crosslinking: after the organic phase and the aqueous phase are deoxygenated by nitrogen for 60min respectively, the organic phase is added into a 500mL three-necked flask, then the aqueous phase is added into the organic phase at a constant rate of 1.0mL/min to control the volume of the liquid drops, and the final volume ratio of the organic phase to the aqueous phase is 2:1, so as to obtain a mixed system. Then, the mixed system was heated to 80℃and stirred at 1000rpm, 0.3% ammonium persulfate (100% by mass of the mixed system) was added thereto as an initiator, and the reaction was continued under stirring in a nitrogen atmosphere for 6 hours, keeping the stirring rate unchanged from the nitrogen atmosphere, and cooled to room temperature to obtain a reaction product.
(4) And (3) reaction product treatment: the reaction product was subjected to rotary evaporation to remove the organic phase to obtain an aqueous phase reaction product, and then the aqueous phase reaction product was washed 2 times with ethanol, specifically, to add absolute ethanol to the aqueous phase reaction product, precipitate, and centrifuge at a centrifuge speed of 3000rpm for 30min to obtain a precipitated product. Dissolving the precipitate in deionized water, and dialyzing with a dialysis bag with a cutoff number average molecular weight of 6000 ten thousand for 1 week to obtain a dialysis product. Freezing the dialysis product overnight and then freeze-drying to obtain the target product, namely the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the microgel particles have a size of 90 to 150nm.
The number average molecular weight of the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer was 6000 ten thousand as determined by gel chromatography.
The poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer microgel prepared in each of the above examples was added in an amount of 0.3% by mass (100% based on the mass of the foaming agent) to a foaming agent prepared from 2% by weight of sodium dodecyl sulfate, 15% by weight of dodecyl betaine and 83% by weight of water having a mineralization degree of 200000ppm, respectively, to obtain a solution n# (where N is the same as the number of the added example for preparing the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer microgel) to be tested for foam stability and temperature-sensitive responsiveness by measuring the foam stability and foam stability of the solution to be tested by a roger foam meter.
Foaming agents that do not polyaddite (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer microgels were used as a blank.
The specific method comprises the following steps:
(1) Opening a thermostat, and when the temperature reaches the test temperature, opening a water bath preheating jacket pipe to enable the water bath preheating jacket pipe to be stable at the test temperature;
(2) Washing the inner wall of the scale tube with distilled water, and then washing the tube wall with the solution N# to be tested, wherein the washing must be complete;
(3) Closing a piston of the scale tube, injecting 50ml of solution N# to be tested into the scale tube by using a liquid dropping tube, and preheating the solution N# to be tested to a test temperature;
(4) Filling 200ml of solution N# to be tested into a drip tube, and preheating the solution N# to be tested in the drip tube to a test temperature;
(5) The drip tube is arranged on the tube rack and the section of the scale tube is vertical, and the outlet of the drip tube is arranged on a scale mark of 900mm in a pressing way, so that the solution N# to be tested flows to the center of the scale tube;
(6) The piston of the drip tube is opened to allow the solution N# to be tested to flow down. When the solution N# to be tested in the dropping tube flows out, a stopwatch is started immediately, the foam height is measured by a well, and then the foam height of 200mL of the test solution N# just flowing out and the foam height after 5min are recorded, so that the foaming capacity and the foam stabilizing capacity of the solution to be tested are respectively evaluated;
(7) The above test was repeated three times and finally an average value was taken. Wherein the walls must be cleaned before each test to avoid affecting the accuracy of the data.
The results are shown in Table 1.
As can be seen from the experimental data in Table 1, the monodisperse random copolymer microgel particles prepared according to the present invention have a foam having a stable initial foam height H with increasing temperature 0 And foam height H after 5min 5 Will show a gradual increase in the initial foam height H as the temperature decreases again 0 And foam height H after 5min 5 Gradually decreasing again and having an initial foam height H at a temperature above 40 DEG C 0 And foam height H after 5min 5 The foaming property and the foam stability of the blank control are not obviously changed along with the change of temperature.
In conclusion, the monodisperse random copolymer microgel particles prepared by the invention have better foam stability and temperature-sensitive responsiveness.
Table 1: foam properties of temperature sensitive foaming agent at different temperatures (foaming agent concentration 0.3%, mineralization 200000 ppm)
Although the invention has been described with reference to specific embodiments, those skilled in the art will appreciate that various modifications might be made without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of materials, and method to the essential scope, spirit, and scope of the present invention. All such modifications are intended to be included within the scope of this invention as defined in the following claims.
Claims (11)
1. A poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer having a number average molecular weight of 2000 to 6000 tens of thousands;
which are microgel particles having a particle size of 50 to 150 nm;
the preparation method comprises the following steps:
1) Mixing n-dodecane with Span80 to form an organic phase;
2) Dissolving acrylamide, acrylic acid and N, N-methylene bisacrylamide in water to form a water phase; wherein the amount of the acrylamide is 0.1 to 1%, the amount of the acrylic acid is 0.2 to 0.8%, and the amount of the N, N-methylenebisacrylamide is 0.3 to 0.9% based on 100% by mass of water;
3) After deoxidizing the organic phase and the aqueous phase respectively, uniformly adding the aqueous phase into the organic phase to obtain a mixed system;
4) Heating the mixed system, stirring, adding ammonium persulfate, and continuously reacting for 3 to 6 hours at a heating temperature of 50 to 80 ℃ to obtain a reaction product;
5) Removing the organic phase from the reaction product to obtain an aqueous phase reaction product;
6) Washing, precipitating and centrifuging the aqueous phase reaction product by ethanol to obtain a precipitated product, wherein the washing, precipitating and centrifuging are repeated for M times, and M is an integer which is more than or equal to 1 and less than or equal to 5;
7) Dissolving the precipitate in water, and dialyzing to obtain a dialyzed product;
8) And freeze-drying the dialysis product to obtain the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer.
2. A method of preparing the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer of claim 1, comprising the steps of:
1) Mixing n-dodecane with Span80 to form an organic phase;
2) Dissolving acrylamide, acrylic acid and N, N-methylene bisacrylamide in water to form a water phase; wherein the amount of the acrylamide is 0.1 to 1%, the amount of the acrylic acid is 0.2 to 0.8%, and the amount of the N, N-methylenebisacrylamide is 0.3 to 0.9% based on 100% by mass of water;
3) After deoxidizing the organic phase and the aqueous phase respectively, uniformly adding the aqueous phase into the organic phase to obtain a mixed system;
4) Heating the mixed system, stirring, adding ammonium persulfate, and continuously reacting for 3 to 6 hours at a heating temperature of 50 to 80 ℃ to obtain a reaction product;
5) Removing the organic phase from the reaction product to obtain an aqueous phase reaction product;
6) Washing, precipitating and centrifuging the aqueous phase reaction product by ethanol to obtain a precipitated product, wherein the washing, precipitating and centrifuging are repeated for M times, and M is an integer which is more than or equal to 1 and less than or equal to 5;
7) Dissolving the precipitate in water, and dialyzing to obtain a dialyzed product;
8) And freeze-drying the dialysis product to obtain the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer.
3. The method according to claim 2, wherein in step 1), the volume ratio of n-dodecane to Span80 is 3 (2-12).
4. The process according to claim 2, characterized in that in step 3) the aqueous phase is added to the organic phase at a speed of 1 to 2mL/min at average speed; and/or the volume ratio of the organic phase to the aqueous phase in the mixed system is (1.3-2): 1.
5. The production method according to claim 2, wherein in step 4), the ammonium persulfate is added to the mixed system in an amount of 0.1% to 0.3% by mass of the mixed system as 100%.
6. The method of claim 2, wherein in step 4), the stirring speed is 300 to 1000 rpm.
7. The process according to claim 2, characterized in that in step 5) the organic phase is removed by rotary evaporation.
8. The method of claim 2, wherein in step 6), the centrifugation is performed at a speed of 1000 to 3000rpm for a period of 30 to 60 minutes.
9. The method according to claim 2, wherein in step 7), dialysis is performed using a dialysis bag having a molecular weight cut-off of 1000 to 6000 tens of thousands, and the dialysis is performed for 7 to 14 days.
10. Use of the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer according to claim 1 or the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer prepared according to any one of claims 2 to 9 in foam stabilization.
11. The use according to claim 10, characterized by the fact that it is in high temperature foam stabilization; is an application in stabilizing foam at a temperature of 40 to 80 ℃.
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| CN202110881876.1A CN115701437B (en) | 2021-08-02 | 2021-08-02 | Microgel temperature-sensitive foam stabilizer and preparation method thereof |
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| CN202110881876.1A CN115701437B (en) | 2021-08-02 | 2021-08-02 | Microgel temperature-sensitive foam stabilizer and preparation method thereof |
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| CA1111595A (en) * | 1977-11-21 | 1981-10-27 | Maurice L. Zweigle | Cross-linked, water-swellable polymer microgels |
| CN106928957A (en) * | 2015-12-31 | 2017-07-07 | 北京爱普聚合科技有限公司 | A kind of foam fracturing structural type polymer foam stabilizer and preparation method thereof |
| WO2020169478A1 (en) * | 2019-02-22 | 2020-08-27 | Rhodia Operations | Foaming formulations for enhanced oil recovery |
| CN111961451A (en) * | 2020-08-27 | 2020-11-20 | 西安奥德石油工程技术有限责任公司 | Oil-gas well slow-release foaming agent and preparation method thereof |
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| CA1111595A (en) * | 1977-11-21 | 1981-10-27 | Maurice L. Zweigle | Cross-linked, water-swellable polymer microgels |
| CN106928957A (en) * | 2015-12-31 | 2017-07-07 | 北京爱普聚合科技有限公司 | A kind of foam fracturing structural type polymer foam stabilizer and preparation method thereof |
| WO2020169478A1 (en) * | 2019-02-22 | 2020-08-27 | Rhodia Operations | Foaming formulations for enhanced oil recovery |
| CN111961451A (en) * | 2020-08-27 | 2020-11-20 | 西安奥德石油工程技术有限责任公司 | Oil-gas well slow-release foaming agent and preparation method thereof |
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