CN115926772A - Temperature-controllable trigger type rosin resin capsule gel breaker and preparation method thereof - Google Patents
Temperature-controllable trigger type rosin resin capsule gel breaker and preparation method thereof Download PDFInfo
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 80
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 67
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000011347 resin Substances 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000002775 capsule Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229940117986 sulfobetaine Drugs 0.000 claims abstract description 21
- -1 methacryloyl ethyl sulfobetaine Chemical compound 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 14
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000013067 intermediate product Substances 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims description 13
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 claims description 6
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 claims description 6
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 claims description 6
- 229940118781 dehydroabietic acid Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000007142 ring opening reaction Methods 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 abstract description 2
- 239000003209 petroleum derivative Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010276 construction Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000011557 critical solution Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
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- 239000007789 gas Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
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- 238000000053 physical method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 238000002479 acid--base titration Methods 0.000 description 1
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- 229920002401 polyacrylamide Polymers 0.000 description 1
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- 230000001960 triggered effect Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Developing Agents For Electrophotography (AREA)
Abstract
The invention discloses a temperature-controllable trigger type rosin resin capsule gel breaker and a preparation method thereof, and belongs to the technical field of petroleum and natural gas exploration and development. The method comprises the following steps: rosin acid is used as a raw material, the rosin acid and glycidyl methacrylate are subjected to ring-opening esterification reaction, then, the rosin acid and methacryloyl ethyl sulfobetaine are subjected to double-bond polymerization reaction to obtain the temperature-controllable triggering type rosin resin, and finally, the temperature-controllable triggering type rosin resin capsule gel breaker is obtained by physically blending the rosin acid and the gel breaker. The method has low cost and improves the stability of the gel breaker.
Description
Technical Field
The invention belongs to the technical field of petroleum and natural gas exploration and development, and particularly relates to a controllable temperature trigger type rosin resin capsule gel breaker and a preparation method thereof.
Background
Water-based or emulsified fracturing fluids have special requirements for the maintenance and gel breaking viscosity of the fracturing fluid prior to entry or return to the formation fractures. But the conventional ammonium persulfate and potassium persulfate breakers can hardly meet the requirements of both the conventional ammonium persulfate and the conventional potassium persulfate breakers at the same time. In order to realize complete gel breaking of the fracturing fluid, a commonly adopted means is to increase the usage amount of the gel breaker or prolong the gel breaking action time. However, in conventional fracturing construction, if the dosage of the gel breaker is increased, the conditions of rapid reduction of the viscosity of the fracturing fluid and gel breaking in advance are easy to occur, so that the fracture viscosity is influenced, the construction failure is caused, and the fluid loss is influenced. If the gel breaking time is prolonged, a large amount of filtration loss is also caused by the fact that residual liquid stays in the stratum for a long time, and damage to the stratum is increased.
In order to avoid the harm, the requirements of keeping higher viscosity in the construction process and thoroughly breaking the gel after construction are met as much as possible, and a delayed release type capsule gel breaker can be adopted. There is great potential for current breakers that trigger release under downhole conditions, with temperature being one of the more common conditions. The polysulfonylbetaine is a commonly used polymer having a high critical solution temperature (UCST) which means that the polymer changes from insoluble to soluble when heated to a certain temperature, and a temperature-sensitive effect can be imparted to the polymer by the monomer. However, the existing capsule gel breaker still has the problems of high cost, low stability, poor delayed release effect and the like.
Therefore, there is a need to develop a resin capsule breaker that is low in cost, stable, effective in delaying release, and capable of triggering release of the breaker at downhole temperatures.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a temperature-controllable trigger type rosin resin capsule gel breaker and a preparation method thereof, so as to solve the problems of high cost, low stability and poor delayed release effect of the existing capsule gel breaker.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention provides a preparation method of a temperature-controllable trigger type rosin resin capsule gel breaker, which comprises the following steps:
s1: uniformly stirring abietic acid, glycidyl methacrylate and absolute ethyl alcohol, adding a catalyst and a polymerization inhibitor, introducing protective gas, performing esterification reaction, and performing rotary evaporation to obtain an intermediate product I;
s2: uniformly stirring the intermediate product I, methacryloyl ethyl sulfobetaine and dimethyl sulfoxide, adding an initiator, carrying out double bond polymerization reaction, then precipitating in chloroform, dialyzing by using distilled water, and carrying out freeze drying to obtain the temperature-controllable trigger type rosin resin;
s3: heating the temperature-controllable trigger type rosin resin oil bath to a set temperature, adding the gel breaker, stirring for a set time to obtain a mixture, cooling and curing the mixture, and crushing the mixture by using a ball mill to obtain the temperature-controllable trigger type rosin resin capsule gel breaker.
Further, in the S1, the abietic acid is any one of dehydroabietic acid and abietic acid; the catalyst is one of potassium hydroxide or sodium hydroxide; the polymerization inhibitor is p-hydroxyanisole.
In the step S1, the mass ratio of the abietic acid, the glycidyl methacrylate, the absolute ethyl alcohol, the catalyst and the polymerization inhibitor is 1: (0.5-1): (5-7): (0.005-0.01): (0.003-0.005).
Further, in the S1, the temperature of the esterification reaction is 70-80 ℃, and the time of the esterification reaction is 7-8 h.
In the step S2, the initiator is one of azobisisobutyronitrile or azobisisoheptonitrile; the mass ratio of the intermediate product I, the methacryloyl ethyl sulfobetaine and the initiator is 1: (10-15): (0.3-0.5).
In the present invention, in S2, the mass of the dimethyl sulfoxide is 10 to 12 times that of methacryloyl ethyl sulfobetaine.
In the S2, the temperature of the double bond polymerization reaction is 75-85 ℃, and the time of the double bond polymerization reaction is 48-72 hours.
Further, in the step S3, the gel breaker is one or more of potassium persulfate and ammonium persulfate; the mass ratio of the gel breaker to the temperature-controllable trigger rosin resin is 1: (7 to 9).
In the step S3, the set temperature is 120-150 ℃, and the set time is 1-2 hours.
The temperature-controllable trigger type rosin resin capsule gel breaker is prepared by adopting any one preparation method of the temperature-controllable trigger type rosin resin capsule gel breaker.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a controllable temperature trigger type rosin resin capsule gel breaker, which comprises the steps of taking rosin acid as a raw material, firstly carrying out ring-opening esterification reaction on the rosin acid and glycidyl methacrylate, then further carrying out double bond polymerization reaction on the rosin acid and methacryloyl ethyl sulfobetaine to obtain controllable temperature trigger type rosin resin, and finally physically blending the rosin acid and the gel breaker to obtain the controllable temperature trigger type rosin resin capsule gel breaker. The resin capsule is endowed with temperature sensitivity by utilizing methacryloylethyl sulfobetaine, the release temperature can be adjusted by the proportion of rosin and methacryloylethyl sulfobetaine, the high critical solution temperature of the sulfobetaine can be improved by the rigid structure of the rosin, the polymer is dissolved from insoluble to soluble when the temperature is higher than the high critical solution temperature, the gel breaker is released, the effect of releasing the gel breaker by triggering at 60-90 ℃ in the pit can be realized, the efficient implementation of oil and gas exploitation and other projects is ensured, and different construction requirements can be met.
The temperature-controllable trigger type rosin resin capsule gel breaker prepared by the preparation method disclosed by the invention is synthesized by combining a chemical method of ring-opening esterification and double bond polymerization and a physical method of heating melting and freezing solidification, can delay the release of the gel breaker, and can achieve the effect of releasing at a specific temperature by adjusting a molecular structure. The effective content of the gel breaker is high, and when the temperature is higher than the high critical dissolution temperature, the temperature-controllable trigger type rosin resin capsule gel breaker is released from insolubility to dissolution, and the release rate is increased along with the increase of the temperature.
Drawings
FIG. 1 is a reaction scheme for the preparation of example 1 according to the present invention;
FIG. 2 is a graph of the release rate of the capsule breaker of the present invention at 25 ℃ and 80 ℃ as a function of time.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without being limited by any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," "including," "having," or similar terms, shall mean "consisting of 8230; \8230, composition" and "consisting essentially of 8230; \8230, composition" such as "A comprises a" shall mean "A comprises a and the other" and "A comprises a only".
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, as long as there is no contradiction between combinations of these technical features, any combinations of the technical features in the respective embodiments or examples may be made, and all possible combinations should be considered as the scope of the present specification.
The invention provides a temperature-controllable trigger type rosin resin capsule gel breaker and a preparation method thereof.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
The following examples use instrumentation conventional in the art. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
The invention discloses a preparation method of a temperature-controllable trigger type rosin resin capsule gel breaker, which comprises the following steps: rosin acid is used as a raw material, the rosin acid and glycidyl methacrylate are subjected to ring-opening esterification reaction, then, the rosin acid and methacryloyl ethyl sulfobetaine are subjected to double-bond polymerization reaction to obtain the temperature-controllable triggering type rosin resin, and finally, the temperature-controllable triggering type rosin resin capsule gel breaker is obtained by physically blending the rosin acid and the gel breaker.
The preparation method comprises the following specific steps:
the method comprises the following steps: mixing the components in a mass ratio of 1: (0.5-1): (5-7) adding abietic acid, glycidyl methacrylate and absolute ethyl alcohol into a three-neck flask, uniformly stirring, and adding the mixture according to the mass ratio of 1: (0.005-0.01): (0.003-0.005) introducing protective gas such as nitrogen or argon into potassium hydroxide or sodium hydroxide serving as a catalyst and p-hydroxyanisole serving as a polymerization inhibitor for 15-30 min, performing esterification reaction at the temperature of 70-80 ℃ for 7-8 h, and performing rotary evaporation to obtain an intermediate product I; the abietic acid is dehydroabietic acid or abietic acid;
step two: mixing the components in a mass ratio of 1: (10-15): (10-12) adding the intermediate product I, methacryloyl ethyl sulfobetaine and dimethyl sulfoxide into a three-neck flask, uniformly stirring, adding an initiator azobisisobutyronitrile or azobisisoheptonitrile, ultrasonically oscillating for 1-2 h, introducing nitrogen or argon for 15-30 min, carrying out double bond polymerization reaction for 48-72 h at the temperature of 75-85 ℃, then precipitating in chloroform, dialyzing with distilled water, and freeze-drying to obtain the temperature-controllable trigger type rosin resin;
step three: adding the temperature-controllable trigger rosin resin into a three-neck flask, heating the three-neck flask to 120-150 ℃ in an oil bath, and adding the rosin resin in a mass ratio of 1: (7-9) stirring the gel breaker for 1-2 h. And (3) solidifying the mixture after cooling, and crushing the mixture by using a ball mill to obtain the temperature-controllable trigger type rosin resin capsule gel breaker.
The gel breaker is one or more of potassium persulfate and ammonium persulfate.
The method is low in cost and improves the stability of the gel breaker. The methyl acryloyl ethyl sulfobetaine can endow the resin capsule with temperature sensitivity, the proportion of rosin and methyl acryloyl ethyl sulfobetaine can realize the adjustment of release temperature, the rigid structure of the rosin can improve the high critical solution temperature of the sulfobetaine, the temperature triggering is that the polymer is dissolved from insoluble to soluble when the temperature is higher than the high critical solution temperature, the gel breaker is released, the effect of releasing the gel breaker by triggering at 60-90 ℃ in the pit can be realized, the high-efficiency proceeding of oil and gas exploitation and other projects is ensured, and different construction requirements can be met.
Example 1
S1: adding 1g of dehydroabietic acid, 0.5g of glycidyl methacrylate and 5mL of absolute ethyl alcohol into a three-neck flask, uniformly stirring, adding 0.05g of potassium hydroxide and 0.003g of p-hydroxyanisole, introducing nitrogen for 15min, reacting for 7h at 70 ℃, and performing rotary evaporation to obtain an intermediate product I;
s2: adding 1g of intermediate product I, 10g of methacryloyl ethyl sulfobetaine and 100mL of dimethyl sulfoxide into a three-neck flask, uniformly stirring, adding 0.3g of azobisisobutyronitrile, ultrasonically oscillating for 1h, introducing nitrogen for 15min, reacting for 48h at 75 ℃, then precipitating in chloroform, dialyzing with distilled water, and freeze-drying to obtain the temperature-controllable trigger type rosin resin;
s3: 10g of temperature-controllable trigger type rosin resin is added into a three-neck flask, the three-neck flask is heated to 120 ℃ in an oil bath, 8g of potassium persulfate is added, and the mixture is stirred for 1 hour. And (3) solidifying the mixture after cooling, and crushing the mixture by using a ball mill to obtain the temperature-controllable trigger type rosin resin capsule gel breaker.
Example 2
S1: adding 1g of dehydroabietic acid, 0.6g of glycidyl methacrylate and 5mL of absolute ethyl alcohol into a three-neck flask, uniformly stirring, adding 0.06g of potassium hydroxide and 0.003g of p-hydroxyanisole, introducing nitrogen for 20min, reacting for 7h at 70 ℃, and performing rotary evaporation to obtain an intermediate product I;
s2: adding 1g of intermediate product I, 11g of methacryloyl ethyl sulfobetaine and 110mL of dimethyl sulfoxide into a three-neck flask, uniformly stirring, adding 0.3g of azobisisobutyronitrile, ultrasonically oscillating for 1h, introducing nitrogen for 20min, reacting for 48h at 75 ℃, then precipitating in chloroform, dialyzing with distilled water, and freeze-drying to obtain the temperature-controllable trigger type rosin resin;
s3: 10g of temperature-controllable trigger type rosin resin is added into a three-neck flask, the three-neck flask is heated to 130 ℃ in an oil bath, 7g of potassium persulfate is added, and the mixture is stirred for 1 hour. And (3) solidifying the mixture after cooling, and crushing the mixture by using a ball mill to obtain the temperature-controllable trigger type rosin resin capsule gel breaker.
Example 3
S1: adding 1g of dehydroabietic acid, 0.7g of glycidyl methacrylate and 6mL of absolute ethyl alcohol into a three-neck flask, uniformly stirring, adding 0.07g of potassium hydroxide and 0.004g of p-hydroxyanisole, introducing nitrogen for 30min, reacting for 7.5h at 75 ℃, and performing rotary evaporation to obtain an intermediate product I;
s2: adding 1g of intermediate product I, 12g of methacryloyl ethyl sulfobetaine and 120mL of dimethyl sulfoxide into a three-neck flask, uniformly stirring, adding 0.4g of azobisisobutyronitrile, ultrasonically oscillating for 1.5h, introducing nitrogen for 30min, reacting for 60h at 80 ℃, then precipitating in chloroform, dialyzing with distilled water, and freeze-drying to obtain the temperature-controllable trigger type rosin resin;
s3: 10g of temperature-controllable trigger type rosin resin is added into a three-neck flask, the three-neck flask is heated to 130 ℃ in an oil bath, 8g of potassium persulfate is added, and the mixture is stirred for 1 hour. And (3) solidifying the mixture after cooling, and crushing the mixture by using a ball mill to obtain the temperature-controllable trigger type rosin resin capsule gel breaker.
Example 4
S1: adding 1g of abietic acid, 0.8g of glycidyl methacrylate and 6mL of absolute ethyl alcohol into a three-neck flask, uniformly stirring, adding 0.08g of sodium hydroxide and 0.004g of p-hydroxyanisole, introducing argon for 15min, reacting for 7.5h at 75 ℃, and then carrying out rotary evaporation to obtain an intermediate product I;
s2: adding 1g of intermediate product I, 13g of methacryloyl ethyl sulfobetaine and 130mL of dimethyl sulfoxide into a three-neck flask, uniformly stirring, adding 0.4g of azobisisoheptonitrile, ultrasonically oscillating for 1.5h, introducing argon for 15min, reacting for 60h at 80 ℃, then precipitating in chloroform, dialyzing by distilled water, and freeze-drying to obtain the temperature-controllable trigger type rosin resin;
s3: 10g of temperature-controllable trigger type rosin resin is added into a three-neck flask, the three-neck flask is heated to 140 ℃ in an oil bath, 9g of ammonium persulfate is added, and the mixture is stirred for 2 hours. And (3) solidifying the mixture after cooling, and crushing the mixture by using a ball mill to obtain the temperature-controllable trigger type rosin resin capsule gel breaker.
Example 5
S1: adding 1g of abietic acid, 0.9g of glycidyl methacrylate and 7mL of absolute ethyl alcohol into a three-neck flask, uniformly stirring, adding 0.09g of sodium hydroxide and 0.005g of p-hydroxyanisole, introducing argon for 20min, reacting for 8h at 80 ℃, and performing rotary evaporation to obtain an intermediate product I;
s2: adding 1g of intermediate product I, 14g of methacryloyl ethyl sulfobetaine and 140mL of dimethyl sulfoxide into a three-neck flask, uniformly stirring, adding 0.5g of azobisisoheptonitrile, ultrasonically oscillating for 2h, introducing argon for 20min, reacting for 72h at 85 ℃, then precipitating in chloroform, dialyzing by distilled water, and freeze-drying to obtain the temperature-controllable trigger type rosin resin;
s3: 10g of temperature-controllable trigger type rosin resin is added into a three-neck flask, the three-neck flask is heated to 140 ℃ in an oil bath, 8g of ammonium persulfate is added, and the three-neck flask is stirred for 2 hours. And (3) solidifying the mixture after cooling, and crushing the mixture by using a ball mill to obtain the temperature-controllable trigger type rosin resin capsule gel breaker.
Example 6
S1: adding 1g of abietic acid, 1g of glycidyl methacrylate and 7mL of absolute ethyl alcohol into a three-neck flask, uniformly stirring, adding 0.01g of sodium hydroxide and 0.005g of p-hydroxyanisole, introducing argon for 30min, reacting for 8h at 80 ℃, and performing rotary evaporation to obtain an intermediate product I;
s2: adding 1g of intermediate product I, 15g of methacryloyl ethyl sulfobetaine and 150mL of dimethyl sulfoxide into a three-neck flask, uniformly stirring, adding 0.5g of azobisisoheptonitrile, ultrasonically oscillating for 2h, introducing argon for 30min, reacting for 72h at 85 ℃, then precipitating in chloroform, dialyzing by distilled water, and freeze-drying to obtain the temperature-controllable trigger type rosin resin;
s3: adding 10g of temperature-controllable trigger type rosin resin into a three-neck flask, heating the three-neck flask to 140 ℃ in an oil bath, adding 7g of ammonium persulfate, and stirring the mixture for 2 hours. And (3) solidifying the mixture after cooling, and crushing the mixture by using a ball mill to obtain the temperature-controllable trigger type rosin resin capsule gel breaker.
The application effect is as follows:
1. active content test
According to 7.2.1-7.2.4 in the national standard SY/T6380-2008, na is configured in the testing process 2 S 2 O 3 Standard solution, starch indicator, potassium iodide powder as auxiliary reagent and 36% acetic acid solution, and Na is consumed by titration 2 S 2 O 3 The volume of the standard solution is converted into effective content.
Preparing a starch indicator: 1g of starch is put into a 50mL beaker and is dissolved into paste by cold water drops, 180mL of boiling water is added, the beaker is cleaned by the rest water, all the water is merged and is boiled for 3min, and the water consumption is 200mL in total. Na (Na) 2 S 2 O 3 Preparation of a standard solution: 125g of Na 2 S 2 O 3 Slowly adding the powder into 500mL of boiling water to completely dissolve the powder, and fixing the volume to 0.1mol/L of Na 2 S 2 O 3 And (4) standard solution. The above reagents are all prepared at room temperature, and the potassium iodide powder is preserved in a dark place.
The samples of the examples were tested by acid-base titration at 30 ℃ at room temperature for Na consumption 2 S 2 O 3 The volume of the standard solution and the converted effective content are shown in Table 1. The data in Table 1 show that the effective content of the controlled temperature trigger type rosin resin capsule breaker in example 1 is 91.27%.
2. Release Rate testing
In combination with the effective content obtained by the test, the release rate at 25 ℃ and 80 ℃ was tested as a function of time, and the release rate at different temperatures of the microcapsule gel breaker as a function of time was tested, and the results are shown in fig. 2. From the data in FIG. 2, it can be seen that the core release of example 1 can reach 92.24% at a temperature of 80 ℃ for 105 min. At 80 ℃, the release rate is rapidly increased because the controllable temperature triggered rosin resin capsule gel breaker is released from dissolution to dissolution when the temperature is higher than the high critical dissolution temperature, so that the release rate is correspondingly increased.
3. Gel breaking performance test
The polyacrylamide nano composite fracturing system gel without the gel breaker, 0.1000g of microcapsule gel breaker in different embodiments and pure potassium persulfate gel breaker with corresponding effective content are added, the gel is placed in a constant temperature water bath kettle at 80 ℃, and the viscosity of the gel breaker is measured by a rotational viscometer, and the results are shown in table 1. As can be seen from Table 1, the capsule breaker meets the breaking requirements.
TABLE 1 test data for the samples of the examples
The temperature-controllable triggering rosin resin capsule gel breaker disclosed by the invention is synthesized by combining a chemical method of ring-opening esterification and double bond polymerization and a physical method of heating melting and freezing solidification, can delay the release of the gel breaker, and can achieve the effect of releasing at a specific temperature by adjusting a molecular structure.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the temperature-controllable trigger type rosin resin capsule gel breaker is characterized by comprising the following steps:
s1: uniformly stirring abietic acid, glycidyl methacrylate and absolute ethyl alcohol, adding a catalyst and a polymerization inhibitor, introducing protective gas, performing esterification reaction, and performing rotary evaporation to obtain an intermediate product I;
s2: uniformly stirring the intermediate product I, methacryloyl ethyl sulphobetaine and dimethyl sulfoxide, adding an initiator, carrying out double bond polymerization reaction, then precipitating in chloroform, dialyzing with distilled water, and carrying out freeze drying to obtain the temperature-controllable trigger type rosin resin;
s3: heating the temperature-controllable trigger type rosin resin oil bath to a set temperature, adding the gel breaker, stirring for a set time to obtain a mixture, cooling and curing the mixture, and crushing the mixture by using a ball mill to obtain the temperature-controllable trigger type rosin resin capsule gel breaker.
2. The method for preparing the controllable temperature trigger rosin resin capsule breaker according to claim 1, wherein in S1, the rosin acid is either dehydroabietic acid or abietic acid; the catalyst is one of potassium hydroxide or sodium hydroxide; the polymerization inhibitor is p-hydroxyanisole.
3. The method for preparing the controllable temperature trigger type rosin resin capsule breaker according to claim 1, wherein in the step S1, the mass ratio of the abietic acid, the glycidyl methacrylate, the absolute ethyl alcohol, the catalyst and the polymerization inhibitor is 1: (0.5-1): (5-7): (0.005-0.01): (0.003-0.005).
4. The method for preparing the controllable temperature trigger type rosin resin capsule breaker according to claim 1, wherein in S1, the temperature of the esterification reaction is 70-80 ℃ and the time of the esterification reaction is 7-8 h.
5. The method for preparing the controllable temperature triggering type rosin resin capsule breaker according to claim 1, wherein in S2, the initiator is one of azobisisobutyronitrile or azobisisoheptonitrile; the mass ratio of the intermediate product I, the methacryloyl ethyl sulfobetaine and the initiator is 1: (10-15): (0.3-0.5).
6. The method for preparing the controllable temperature trigger type rosin resin capsule breaker according to claim 1, wherein the mass of the dimethyl sulfoxide in the S2 is 10-12 times of that of the methacryloyl ethyl sulfobetaine.
7. The method for preparing the controllable temperature trigger type rosin resin capsule breaker according to claim 1, wherein in S2, the temperature of the double bond polymerization reaction is 75-85 ℃, and the time of the double bond polymerization reaction is 48-72 h.
8. The method for preparing the controllable temperature trigger type rosin resin capsule breaker according to claim 1, wherein in S3, the breaker is one or more of potassium persulfate and ammonium persulfate; the mass ratio of the gel breaker to the temperature-controllable trigger rosin resin is 1: (7 to 9).
9. The method for preparing the controllable temperature triggering type rosin resin capsule breaker according to claim 1, wherein in the step S3, the set temperature is 120-150 ℃, and the set time is 1-2 h.
10. The controlled temperature trigger rosin resin capsule breaker prepared by the method for preparing the controlled temperature trigger rosin resin capsule breaker according to any one of claims 1 to 9.
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Citations (2)
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|---|---|---|---|---|
| CN105647389A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing esters with rosin acrylic acid and GMA (glycidyl methacrylate) |
| CN115260046A (en) * | 2022-08-22 | 2022-11-01 | 贵州大学 | Abietate compound and preparation method and application thereof |
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|---|---|---|---|---|
| CN105647389A (en) * | 2016-03-13 | 2016-06-08 | 桂林理工大学 | Method for preparing esters with rosin acrylic acid and GMA (glycidyl methacrylate) |
| CN115260046A (en) * | 2022-08-22 | 2022-11-01 | 贵州大学 | Abietate compound and preparation method and application thereof |
Non-Patent Citations (2)
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| 王丹;于钢;刘文波;宋湛谦;商士斌;: "松香改性新型微胶囊壁材的制备研究", 林产化学与工业, no. 1, pages 51 - 54 * |
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