CN115701437A - 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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- acrylamide
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- 239000006260 foam Substances 0.000 title claims abstract description 33
- 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 16
- 239000008346 aqueous phase Substances 0.000 claims description 48
- 239000012074 organic phase Substances 0.000 claims description 44
- 239000007795 chemical reaction product Substances 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 238000000502 dialysis Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 9
- 229940094933 n-dodecane Drugs 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 230000006641 stabilisation Effects 0.000 claims description 9
- 238000011105 stabilization Methods 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 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
- 238000005187 foaming Methods 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
- 238000010926 purge Methods 0.000 description 5
- 239000004872 foam stabilizing agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material 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
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
Abstract
The invention provides a microgel temperature-sensitive foam stabilizer and a preparation method thereof. The gel is a poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer, and the number average molecular weight of the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer is 2000-6000 million.
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 evaporate or even boil more rapidly, 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 not sufficient to keep the foam stable. Therefore, in order to prevent evaporation of the liquid at high temperature, a foam stabilizer needs to be added. However, many of the conventional foam stabilizers are low-temperature foam stabilizers, and therefore, it is desired to develop a foam stabilizer which exhibits a foam stabilizing effect at a high temperature.
Disclosure of Invention
One aspect 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 million.
In one embodiment, the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer is microgel particles having a particle size of 50 to 150nm.
The second invention provides a method for preparing the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer according to the first invention, 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 the organic phase and the aqueous phase are respectively deoxidized, the aqueous phase is added into the organic phase at a uniform speed 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 water-phase reaction product by using ethanol to obtain a precipitation 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 (3) freeze-drying the dialyzed 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 0.1% to 1%, the amount of acrylic acid is 0.2% to 0.8%, and the amount of N, N-methylenebisacrylamide is 0.3% to 0.9%, based on 100% by mass of water.
In one embodiment, in step 3), the aqueous phase is added to the organic phase at a rate of 1 to 2 mL/min; and/or the volume ratio of the organic phase to the aqueous phase in the mixed system is (1.3-2): 1.
In one embodiment, in step 4), the initiator is added to the mixed system in an amount of 0.1% to 0.3% based on 100% by mass of the mixed system.
In one embodiment, in step 4), the heating temperature is 50 to 80 ℃, the stirring speed is 300 to 1000rpm, and the reaction time is 3 to 6 hours.
In one embodiment, in step 5), the organic phase is removed by rotary evaporation.
In one embodiment, in step 6), the speed of centrifugation is 1000 to 3000rpm and the time of centrifugation is 30 to 60min.
In a specific embodiment, in step 7), a dialysis bag with a molecular weight cut-off of 1000 to 6000 ten thousand is used for dialysis, and the dialysis time is 7 to 14 days.
The third invention provides the application of the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer prepared according to the first invention or the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer prepared according to the second preparation method in foam stabilization; preferably, in high temperature bubble stabilization; more preferably, it is used in the foam stabilization at a temperature of 40 to 80 ℃.
The invention has the beneficial effects that:
when the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles prepared by the invention are used as foam stabilizers, the effects of foam stabilization at high temperature (such as the temperature of 40-80 ℃) and foam removal at low temperature (such as the temperature of lower than 40 ℃) can be achieved.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the invention in any way.
Example 1
(1) Preparing an organic phase: n-dodecane was mixed with Span80 in a volume ratio of 1.
(2) Preparing a water phase: 0.1% acrylamide, 0.8% acrylic acid and 0.3% N, N-methylenebisacrylamide, based on 100% by mass of water, were dissolved in pure water to form an aqueous phase.
(3) Copolymerization and crosslinking: after purging the organic phase and the aqueous phase with nitrogen for 30min, 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 2.0mL/min to control the droplet volume and make the volume ratio of the final organic phase and aqueous phase 1.3. And then heating the mixed system to 50 ℃, stirring at the speed of 300rpm, adding 0.1% of ammonium persulfate (taking the mass of the mixed system as 100%) serving as an initiator, continuously stirring and reacting for 3 hours in a nitrogen atmosphere, keeping the stirring speed unchanged with the nitrogen atmosphere, and cooling to room temperature to obtain a reaction product.
(4) Treatment of reaction products: and (3) carrying out rotary evaporation on the reaction product to remove an organic phase to obtain an aqueous phase reaction product, then 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 at the centrifugal speed of 1000rpm for 60min to obtain a precipitated product. Dissolving the precipitated product in deionized water, and dialyzing for 2 weeks by using a dialysis bag with the interception number average molecular weight of 2000 ten thousand to obtain a dialysis product. Freezing the dialyzed product overnight, and freeze-drying to obtain a target product which is poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the size of the microgel particles is 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) Preparing an organic phase: n-dodecane was mixed with Span80 at a volume ratio of 3.
(2) Preparing a water phase: 0.3% acrylamide, 0.6% acrylic acid and 0.5% N, N-methylenebisacrylamide, based on 100% by mass of water, were dissolved in pure water to form an aqueous phase.
(3) Copolymerization and crosslinking: after purging the organic phase and the aqueous phase with nitrogen for 40min, 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 1.7mL/min to control the droplet volume and make the volume ratio of the final organic phase and aqueous phase 1.5. And then heating the mixed system to 60 ℃, stirring at the speed of 500rpm, adding 0.15 percent of ammonium persulfate (taking the mass of the mixed system as 100 percent) as an initiator, continuously stirring and reacting for 4 hours in a nitrogen atmosphere, keeping the stirring speed unchanged with the nitrogen atmosphere, and cooling to room temperature to obtain a reaction product.
(4) And (3) treating a reaction product: and (3) carrying out rotary evaporation on the reaction product to remove an organic phase to obtain an aqueous phase reaction product, then 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 centrifugal speed of 1500rpm to obtain a precipitated product. Dissolving the precipitation product in deionized water, and dialyzing for 12 days by using a dialysis bag with the interception number average molecular weight of 3000 ten thousand to obtain a dialysis product. Freezing the dialyzed product overnight, and freeze-drying to obtain a target product which is poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the size of the microgel particles is 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) Preparing an organic phase: n-dodecane was mixed with Span80 at a volume ratio of 2.
(2) Preparing an aqueous phase: 0.5% acrylamide, 0.45% acrylic acid and 0.6% N, N-methylenebisacrylamide were dissolved in pure water with the mass of water taken as 100% to form an aqueous phase.
(3) Copolymerization and crosslinking: after purging the organic phase and the aqueous phase with nitrogen and removing oxygen for 40min, 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 1.5mL/min to control the droplet volume and make the volume ratio of the final organic phase and aqueous phase 1.6. And then heating the mixed system to 65 ℃, stirring at the speed of 700rpm, adding 0.2 percent of ammonium persulfate (taking the mass of the mixed system as 100 percent) as an initiator, continuously stirring and reacting for 4.5 hours in a nitrogen atmosphere, keeping the stirring speed constant with the nitrogen atmosphere, and cooling to room temperature to obtain a reaction product.
(4) And (3) treating a reaction product: and (3) carrying out rotary evaporation on the reaction product to remove an organic phase to obtain an aqueous phase reaction product, then 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 45min at a centrifugal speed of 2000rpm to obtain a precipitated product. Dissolving the precipitation product in deionized water, and dialyzing for 10 days by using a dialysis bag with the interception number average molecular weight of 4000 ten thousand to obtain a dialysis product. Freezing the dialyzed product overnight, and freeze-drying to obtain a target product which is poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the size of the microgel particles is 70 to 120nm.
The number average molecular weight of the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer was 4000 ten thousand as determined by gel chromatography.
Example 4
(1) Preparing an organic phase: n-dodecane was mixed with Span80 at a volume ratio of 1.
(2) Preparing an aqueous phase: 0.7% acrylamide, 0.3% acrylic acid and 0.75% N, N-methylenebisacrylamide, based on 100% by mass of water, were dissolved in pure water to form an aqueous phase.
(3) Copolymerization and crosslinking: after purging the organic phase and the aqueous phase with nitrogen and removing oxygen 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 make the volume ratio of the final organic phase and aqueous phase 1.8. And then heating the mixed system to 70 ℃, stirring at 850rpm, adding 0.25% of ammonium persulfate (taking the mass of the mixed system as 100%) serving as an initiator into the mixed system, continuously stirring and reacting for 5 hours in a nitrogen atmosphere, keeping the stirring rate unchanged with the nitrogen atmosphere, and cooling to room temperature to obtain a reaction product.
(4) And (3) treating a reaction product: and (3) carrying out rotary evaporation on the reaction product to remove an organic phase to obtain an aqueous phase reaction product, then 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 40min at the centrifugal speed of 2500rpm to obtain a precipitated product. Dissolving the precipitation product in deionized water, and dialyzing for 8 days by using a dialysis bag with the interception number average molecular weight of 5000 ten thousand to obtain a dialysis product. Freezing the dialyzed product overnight, and freeze-drying to obtain a target product which is poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the size of the microgel particles is 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) Preparing an organic phase: n-dodecane was mixed with Span80 at a volume ratio of 3.
(2) Preparing a water phase: 1.0% acrylamide, 0.2% acrylic acid and 0.9% N, N-methylenebisacrylamide, based on 100% by mass of water, were dissolved in pure water to form an aqueous phase.
(3) Copolymerization and crosslinking: after purging the organic phase and the aqueous phase with nitrogen for 60min, 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 1.0mL/min to control the droplet volume and make the volume ratio of the final organic phase and aqueous phase 2. And then heating the mixed system to 80 ℃, stirring at the speed of 1000rpm, adding 0.3% of ammonium persulfate (taking the mass of the mixed system as 100%) serving as an initiator, continuously stirring and reacting for 6 hours in a nitrogen atmosphere, keeping the stirring speed unchanged with the nitrogen atmosphere, and cooling to room temperature to obtain a reaction product.
(4) And (3) treating a reaction product: and (3) carrying out rotary evaporation on the reaction product to remove an organic phase to obtain an aqueous phase reaction product, then 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 30min at a centrifugal speed of 3000rpm to obtain a precipitated product. Dissolving the precipitation product in deionized water, and dialyzing for 1 week by using a dialysis bag with the interception number average molecular weight of 6000 ten thousand to obtain a dialysis product. Freezing the dialyzed product overnight, and freeze-drying to obtain a target product which is poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel particles. Wherein the size of the microgel particles is 90 to 150nm.
The number average molecular weight of the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer was 6000 ten thousand as determined by gel chromatography.
The poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel prepared in each example is added into a foaming agent prepared from 2wt% of sodium dodecyl sulfate, 15wt% of dodecyl betaine and 83% of water with the mineralization degree of 200000ppm in an amount of 0.3% (by mass of the foaming agent, taken as 100%) to obtain a solution to be tested N # (wherein N is the same as the serial number of the added example for preparing the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer microgel), and the foaming capacity and the temperature-sensitive foam stability of the solution to be tested are measured by a Roche foam tester to test the foam stability and the temperature-sensitive response.
A foaming agent without addition polymerization (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer microgel was used as a blank.
The specific method comprises the following steps:
(1) Opening a thermostat, and opening a water bath preheating jacket pipe when the test temperature is reached so as to stabilize the temperature at the test temperature;
(2) Washing the inner wall of the scale tube by using distilled water, and then washing the tube wall by using a solution N # to be tested, wherein the washing must be complete;
(3) Closing the graduated tube piston, injecting 50ml of solution N # to be tested by using a dropping liquid tube, and preheating the solution N # to be tested to the testing temperature;
(4) Filling 200ml of solution N # to be tested into the dropping liquid pipe, and preheating the solution N # to be tested in the dropping liquid pipe to the testing temperature;
(5) The dropping liquid pipe is arranged on the pipe frame and the section of the graduated pipe is vertical, the outlet of the dropping liquid pipe is arranged on the graduated line of 900mm, so that the solution N # to be tested flows to the center of the graduated pipe;
(6) The piston of the dropping tube is opened and the solution to be tested N # is allowed to flow down. When the solution N # to be tested in the dropping liquid pipe finishes flowing, a stopwatch is started immediately, the foam height is measured by a well, and then the foam height of the 200mL test solution N # just after flowing and the foam height after 5min are recorded so as to respectively evaluate the foaming capacity and the foam stabilizing capacity of the solution to be tested;
(7) The above experiment was repeated three times and finally averaged. Where the vessel walls must be cleaned prior to each test to avoid compromising data accuracy.
The results are shown in Table 1.
As can be seen from the experimental data in Table 1, the stable foam of the microgel particles of the monodisperse random copolymer prepared by the present invention has an initial foaming height H with the temperature rise 0 And a foam height H after 5min 5 Will exhibit a tendency to increase gradually as the temperature decreases again, with an initial height H of the foam 0 And a foam height H after 5min 5 And gradually decreases and has an initial height H of foam at a temperature above 40 DEG C 0 And a foam height H after 5min 5 The foaming property and the foam stability of the blank control do not change obviously 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: foaming performance of temperature-sensitive foaming agent at different temperatures (foaming agent concentration 0.3%, mineralization degree 200000 ppm)
While the invention has been described with reference to specific embodiments, those skilled in the art will appreciate that various changes can 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 matter, and method to the essential scope and spirit of the present invention. All such modifications are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (12)
1. A poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer having a number average molecular weight of 2000 to 6000 million.
2. The poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer according to claim 1, which is a microgel particle having a particle size of 50 to 150nm.
3. A method for preparing the poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer of claim 1 or 2, 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;
3) After the organic phase and the aqueous phase are respectively deoxygenated, the aqueous phase is added into the organic phase at a uniform speed 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 water-phase reaction product by using ethanol to obtain a precipitation 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 (3) freeze-drying the dialyzed product to obtain the poly (acrylamide-acrylic acid-N, N-methylene bisacrylamide) monodisperse random copolymer.
4. The method according to claim 3, wherein in the step 1), the volume ratio of n-dodecane to Span80 is 3 (2-12).
5. The production method according to claim 3, wherein in step 2), 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.
6. The method according to claim 3, wherein in step 3), the aqueous phase is added to the organic phase at a rate of 1 to 2 mL/min; and/or the volume ratio of the organic phase to the aqueous phase in the mixed system is (1.3-2): 1.
7. The production method according to claim 3, wherein in step 4), the amount of the initiator added to the mixed system is 0.1% to 0.3% based on 100% by mass of the mixed system.
8. The method of claim 3, wherein in the step 4), the heating temperature is 50 to 80 ℃, the stirring speed is 300 to 1000rpm, and the reaction time is 3 to 6 hours.
9. The process according to claim 3, wherein in step 5) the organic phase is removed by rotary evaporation.
10. The method according to claim 3, wherein in step 6), the speed of centrifugation is 1000 to 3000rpm and the time of centrifugation is 30 to 60min.
11. The preparation method according to claim 3, wherein in step 7), a dialysis bag having a molecular weight cut-off of 1000 to 6000 ten thousand is used for dialysis for 7 to 14 days.
12. Use of a poly (acrylamide-acrylic acid-N, N-methylenebisacrylamide) monodisperse random copolymer according to claim 1 or 2 or prepared according to the preparation method of any one of claims 3 to 11 for foam stabilization; preferably, in high temperature foam stabilization; more preferably, it is used in foam stabilization at a temperature of 40 to 80 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2021
- 2021-08-02 CN CN202110881876.1A patent/CN115701437B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 申迎华等: "反相微乳液聚合法制备聚(丙烯酰胺-co-丙烯酸)pH敏感微凝胶及其性能", 《高分子学报》, no. 9, pages 917 - 921 * |
| 程启华: "钻井液用高效起泡剂ＺＱＰ的评价", 《 石油与天然气化工》, vol. 35, no. 1, pages 79 - 80 * |
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