CN114426505B - Polyphenyl hydrophobic crosslinking monomer, thickener containing same and application thereof - Google Patents
Polyphenyl hydrophobic crosslinking monomer, thickener containing same and application thereof Download PDFInfo
- Publication number
- CN114426505B CN114426505B CN202011097692.8A CN202011097692A CN114426505B CN 114426505 B CN114426505 B CN 114426505B CN 202011097692 A CN202011097692 A CN 202011097692A CN 114426505 B CN114426505 B CN 114426505B
- Authority
- CN
- China
- Prior art keywords
- thickener
- formula
- polyphenyl
- crosslinking monomer
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/58—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the field of functional polymers, and relates to a polyphenyl hydrophobic crosslinking monomer, a thickener containing the same and application thereof. The preparation method of the monomer comprises the following steps: 3-acrylamidophenol is dissolved in an organic solvent and heated, and then a catalyst and terephthalyl diisocyanate are added under the protection of inert gas to react to obtain the polyphenyl hydrophobic crosslinking monomer. The preparation method of the thickener comprises the following steps: dissolving alkenyl amide, alkenyl carboxylate, ionic liquid and a polyphenyl hydrophobic crosslinking monomer in an organic solvent, stirring until the alkenyl amide, the alkenyl carboxylate, the ionic liquid and the polyphenyl hydrophobic crosslinking monomer are dissolved to obtain a liquid-phase reactant, and introducing inert gas to remove dissolved oxygen; adding an initiator into the liquid phase reactant, heating to 30-90 ℃ in an inert gas atmosphere, and reacting for 16-36h under stirring to obtain a crude product; and precipitating, filtering, washing and drying the crude product to obtain the thickening agent. The synthesis method of the thickener is simple, the reaction condition is mild, the equipment requirement is low, and the thickener is easy to implement.
Description
Technical Field
The invention belongs to the field of functional polymers, and relates to a polyphenyl hydrophobic crosslinking monomer, a thickener containing the same and application thereof.
Background
At present, the thickener for acidizing and fracturing at home and abroad is mainly divided into natural vegetable gum and derivatives thereof, cellulose and derivatives thereof, synthetic polymers and the like. Compared with the former two, the synthetic polymer has the advantages of strong thickening capability, good gel breaking performance, low residue content and good temperature resistance effect, but also has certain disadvantages, such as high friction resistance of gel pumping formed by chemical crosslinking, poor shearing resistance, weak salt resistance and the like. In recent years, the molecular chain of the thickener is modified by utilizing a hydrophobic monomer, so that the performance defects can be overcome to a great extent. Hydrophobic association polymers dissolved in water, wherein hydrophobic side chains in the molecules are aggregated with each other in the form of surfactant-like hydrophobic groups to form micelles, i.e., hydrophobic domains, resulting in intramolecular and intermolecular associations. Intramolecular association can increase the rigidity of the molecule, while intermolecular association can form a reversible three-dimensional network. When the three-dimensional network structure is subjected to high shear, the three-dimensional network structure is disassembled, the viscosity is reduced, and under the low shear or static state, the three-dimensional network structure can be reconstructed, the viscosity is increased, namely, the three-dimensional network structure shows a certain reversible thixotropic property and shearing resistance, and the three-dimensional network structure has positive effects of reducing pumping friction and improving sand carrying capacity. The technical means for improving the salt resistance of the thickener is mainly focused on introducing functional monomers containing sulfonic acid or quaternary ammonium groups into molecules so as to reduce the sensitivity of the thickener molecules to salt.
It has been found that enhancing the shear resistance of hydrophobically associative polymeric thickeners can be accomplished in 2 ways, one being increasing the proportion of hydrophobic groups in the polymer or enhancing the hydrophobicity of the hydrophobic groups, but rather increasing the molecular rigidity of the polymer, particularly the rigidity of the crosslinking groups. The first approach realizes the shearing resistance of the thickener, but has the defects of long dissolution time and easy precipitation; the second approach is limited by the fact that currently conventional crosslinking monomers (e.g., N-methylenebisacrylamide, ethylene glycol dimethacrylate, etc.) generally do not contain rigid groups and are difficult to achieve.
Disclosure of Invention
The present invention addresses the deficiencies of the prior art by providing a polyphenyl hydrophobic crosslinking monomer, a thickener comprising the monomer, and uses thereof. The synthesis method of the thickener is simple, the reaction condition is mild, the equipment requirement is low, and the thickener is easy to implement.
According to a first aspect of the present invention, there is provided a process for the preparation of a polyphenyl hydrophobic cross-linking monomer, said process comprising:
3-acrylamidophenol is dissolved in an organic solvent and heated, and then a catalyst and terephthalyl diisocyanate are added under the protection of inert gas to react to obtain the polyphenyl hydrophobic crosslinking monomer.
The molar ratio of the 3-acrylamidophenol to the terephthalyl diisocyanate is (2.10-2.25): 1, preferably (2.12-2.20): 1.
the catalyst is dibutyl tin dilaurate, and the dosage is 0.05-0.10% of the molar quantity of the p-phenylene diisocyanate, and preferably 0.06-0.08%.
The chemical reaction formula of the reaction of the polyphenyl hydrophobic crosslinking monomer is as follows:
according to a second aspect of the present invention, there is provided a monomer prepared by the above preparation method, wherein the structural formula of the monomer is shown in formula (1):
according to a third aspect of the present invention, there is provided a process for preparing a thickener comprising the monomer described above, the process comprising:
(1) Dissolving alkenyl amide, alkenyl carboxylate, ionic liquid and a polyphenyl hydrophobic crosslinking monomer in an organic solvent, stirring until the alkenyl amide, the alkenyl carboxylate, the ionic liquid and the polyphenyl hydrophobic crosslinking monomer are dissolved to obtain a liquid-phase reactant, and introducing inert gas to remove dissolved oxygen;
(2) Adding an initiator into the liquid phase reactant, heating to 30-90 ℃ in an inert gas atmosphere, and reacting for 16-36h under stirring to obtain a crude product;
(3) And precipitating, filtering, washing and drying the crude product to obtain the thickening agent.
The structural formula of the alkenylamide is shown as formula (2):
wherein R is 0 is-H or C 1 ～C 6 Is a hydrocarbon group.
R 1 Is an amide group.
The structural formula of the alkenyl carboxylate is shown as the formula (3):
wherein R is 2 Selected from-H or C 1 ～C 6 Is selected from H, na, K, rb or Cs.
The structural formula of the ionic liquid is shown as formula (4):
wherein m is a natural number of 0 or 6 or less, R 3 is-H or C 1 ～C 6 Alkyl of R 4 is-H or C 1 ～C 6 Alkyl of X - For BF 4 - 、PF 6 - 、 One of them.
According to a fourth aspect of the present invention, there is provided a thickener prepared by the above preparation method, wherein the thickener has a structural formula shown in formula (5):
wherein a: b: c: d= (10-30): (20-60): (1-2): (1-4), d=e;
R 0 is-H or C 1 ～C 6 Alkyl of R 1 Is an amide group;
R 2 selected from-H or C 1 ～C 6 Alkyl of (a);
a is selected from H, na, K, rb or Cs;
m is a natural number of 0 or less than or equal to 6;
R 3 is-H or C 1 ～C 6 Alkyl of (a);
R 4 is-H or C 1 ～C 6 Alkyl of (a);
X - for BF 4 - 、PF 6 - 、 One of them.
According to a fifth aspect of the invention, the invention provides the use of the thickener as described above in acidizing fracturing fluids of oil fields.
The thickening agent for the fracturing fluid is prepared by adopting the polyphenyl hydrophobic crosslinking monomer. Compared with the existing thickener, the thickener provided by the invention is a stable three-dimensional network structure formed by the crosslinking points formed by covalent bond action, and meanwhile, hydrophobic association micro-areas can be formed by utilizing the association effect between hydrophobic groups, so that the thickener can serve as physical crosslinking points in the three-dimensional network structure. Under the condition of low shear rate, chemical crosslinking and intermolecular association stable structure are formed between molecules, so that the thickening agent is stopped from being pumped into the initial stage of stratum fracture, and a larger hydrodynamic volume can be obtained. In addition, the aromatic ring is introduced into the crosslinking monomer of the molecule, so that not only is the hydrophobic group, but also the rigid group, and the shearing and dilution resistance effect of the thickener is further enhanced. The introduction of the ionic monomer can effectively improve the salt resistance of the thickener.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the examples of the present invention, the thickener aqueous solution having a mass percentage concentration of 0.7% was 170s -1 The viscosity retention rate after 128 hours of stirring is still maintained above 60%, namely the thickener molecules have the effect of better shearing resistance and dilution resistance;
(2) In an embodiment of the invention, the thickener with a mass percentage concentration of 0.7% is in a 4.0% saline solution for 170s -1 The viscosity retention rate after stirring for 8 hours is still maintained above 70%, namely the thickener molecules have better salt resistance effect;
(3) In the development of deep oil gas resources in a high-temperature and high-salt environment, the treating agent can effectively improve the viscosity of the acidizing fracturing fluid;
(4) The synthesis method of the thickener is simple, mild in reaction condition, low in equipment requirement and easy to implement.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of the polyphenyl hydrophobic crosslinking monomer obtained in example 1;
fig. 2 shows an infrared spectrum of the thickener obtained in example 4.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a process for the preparation of a polyphenyl hydrophobic cross-linking monomer, said process comprising:
3-acrylamidophenol is dissolved in an organic solvent and heated, and then a catalyst and terephthalyl diisocyanate are added under the protection of inert gas to react to obtain the polyphenyl hydrophobic crosslinking monomer.
The molar ratio of the 3-acrylamidophenol to the terephthalyl diisocyanate is (2.10-2.25): 1, preferably (2.12-2.20): 1.
the catalyst is dibutyl tin dilaurate, and the dosage is 0.05-0.10% of the molar quantity of the p-phenylene diisocyanate, and preferably 0.06-0.08%.
In an embodiment of the present invention, the organic solvent is one of acetone, benzene, toluene, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide, and preferably toluene or acetone.
In the embodiment of the invention, the reaction condition is that the heating temperature is 50-90 ℃ and the reaction time is 8-16h.
In an embodiment of the present invention, the inert gas is one of nitrogen, helium, neon, argon, krypton, xenon, radon, and preferably is nitrogen or helium.
In one embodiment of the present invention, the method for preparing the monomer comprises: dissolving 3-acrylamide phenol in an organic solvent, heating in a water bath to 50-90 ℃, vacuumizing for 2-6 hours while heating, then adding a catalyst under the protection of inert gas, then adding terephthalyl diisocyanate, reacting for 8-16 hours, distilling under reduced pressure to remove the organic solvent to obtain a crude product, and washing and drying to obtain the polyphenyl hydrophobic crosslinking monomer.
In a more specific embodiment of the present invention, the method for preparing the monomer includes: adding an organic solvent and 3-acrylamide phenol into a dry three-neck flask with a stirrer, a condenser and a dropping funnel, and starting stirring until the 3-acrylamide phenol in the flask is fully dissolved; heating in water bath to 50-90 deg.c, vacuum pumping for 2-6 hr to eliminate air from the flask, adding catalyst under the protection of inert gas, adding p-benzene diisocyanate into the three-neck flask, reaction for 8-16 hr, and vacuum distillation to eliminate organic solvent to obtain coarse product. And (3) pouring the crude product with chloroform for 2-3 times, and then placing the crude product in an oven for drying to constant weight to obtain the polyphenyl hydrophobic crosslinking monomer.
The chemical reaction formula of the reaction of the polyphenyl hydrophobic crosslinking monomer is as follows:
according to a second aspect of the present invention, there is provided a monomer prepared by the above preparation method, wherein the structural formula of the monomer is shown in formula (1):
according to a third aspect of the present invention, there is provided a process for preparing a thickener comprising the monomer described above, the process comprising:
(1) Dissolving alkenyl amide, alkenyl carboxylate, ionic liquid and a polyphenyl hydrophobic crosslinking monomer in an organic solvent, stirring until the alkenyl amide, the alkenyl carboxylate, the ionic liquid and the polyphenyl hydrophobic crosslinking monomer are dissolved to obtain a liquid-phase reactant, and introducing inert gas to remove dissolved oxygen;
(2) Adding an initiator into the liquid phase reactant, heating to 30-90 ℃ in an inert gas atmosphere, and reacting for 16-36h under stirring to obtain a crude product;
(3) And precipitating, filtering, washing and drying the crude product to obtain the thickening agent.
The structural formula of the alkenylamide is shown as formula (2):
wherein R is 0 is-H or C 1 ～C 6 Alkyl groups of (C), preferably-H, -CH 3 or-C 2 H 5 More preferably-H or-CH 3 。
R 1 Is an amide group, and has a structural formula shown as a formula (2-1) or a formula (2-2):
wherein R is a And R is b Each independently selected from-H, C 1 ～C 6 Alkyl, C of (2) 1 ～C 6 Alkyl alcohol, C 1 ～C 8 Alkyl ketones of (C) are preferably selected from the group consisting of-H, -CH 3 、—CH 2 CH 3 、—CH(CH 3 ) 2 、—CH 2 OH、—CH 2 CH 2 OH or formula (2-1-1);
R c selected from-H or C 1 ～C 6 Preferably selected from the group consisting of-H, -CH 3 、—C 2 H 5 or-CH (CH) 3 ) 2 ；R d Selected from C 1 ～C 6 Is preferably selected from the group consisting of-CH 3 、—C 2 H 5 or-CH (CH) 3 ) 2 。
The structural formula of the alkenyl carboxylate is shown as the formula (3):
wherein R is 2 Selected from-H or C 1 ～C 6 Is preferably selected from-H or-CH 3 ；
A is selected from H, na, K, rb or Cs, preferably from H, na or K, more preferably Na.
The structural formula of the ionic liquid is shown as formula (4):
wherein m is a natural number of 0 or 6 or less, preferably a natural number of 0 or 3 or less, more preferably 0 or 1;
R 3 is-H or C 1 ～C 6 Alkyl groups of (C), preferably-H, -CH 3 、—CH 2 CH 3 or-CH 2 CH 2 CH 3 More preferably-H or-CH 3 ；
R 4 is-H or C 1 ～C 6 Alkyl groups of (C), preferably-H, -CH 3 、—CH 2 CH 3 or-CH 2 CH 2 CH 3 。
X - For BF 4 - 、PF 6 - 、 One of them.
In an embodiment of the invention, the molar ratio of the alkenyl amide, alkenyl carboxylate, ionic liquid, and polyphenyl hydrophobic crosslinking monomer is (10-30): (20-60): (1-2): (1-4); the total mass percentage concentration of the four monomers in the organic solvent is 2.0-20.0%, preferably 5.0-10.0%.
In an embodiment of the present invention, the organic solvent is selected from one of 1, 4-dioxane, acetonitrile, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
In an embodiment of the present invention, the initiator is selected from one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobis Ding Qingji formamide, dibenzoyl peroxide and lauroyl peroxide.
In embodiments of the present invention, the initiator is used in an amount of 0.2% to 1.0%, preferably 0.3% to 0.8%, of the total mass of the alkenyl amide, alkenyl carboxylate, ionic liquid, and the polyphenyl hydrophobic crosslinking monomer.
In one embodiment of the present invention, the thickener is prepared by the following steps:
(1) Sequentially adding an organic solvent, alkenyl amide, sodium alkenyl carboxylate, ionic liquid and a polyphenyl hydrophobic crosslinking monomer into a reactor, stirring until the organic solvent, the alkenyl amide, the sodium alkenyl carboxylate, the ionic liquid and the polyphenyl hydrophobic crosslinking monomer are completely dissolved to obtain a liquid-phase reactant, and introducing inert gas for 30-60min at room temperature to remove dissolved oxygen.
(2) And adding an initiator into the liquid phase reactant, heating to a reaction temperature of 30-90 ℃ in an inert gas atmosphere, and reacting for 16-36h under stirring to obtain a pale yellow gelatinous crude product.
(3) And (3) sequentially placing the crude product into water and methanol for precipitation, filtering, washing the obtained solid product with acetone, extracting with glacial acetic acid-ethylene glycol mixed solvent, and drying in vacuum to obtain the thickener.
According to a fourth aspect of the present invention, there is provided a thickener prepared by the above preparation method, wherein the thickener has a structural formula shown in formula (5):
wherein a: b: c: d= (10-30): (20-60): (1-2): (1-4), d=e;
R 0 、R 1 r in the formula (2) 0 、R 1 Identical, R 2 A and R in formula (3) 2 A is the same, m, R 3 、R 4 、X - And m and R in formula (4) 3 、R 4 、X - The same applies.
According to a fifth aspect of the invention, the invention provides the use of the thickener as described above in acidizing fracturing fluids of oil fields. There is no particular requirement for the specific application, and the application may be a conventional application manner in the field, and will not be described in detail herein.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
The invention will be further illustrated with reference to specific examples.
In the present invention, the devices or apparatus used are all conventional devices or apparatus known in the art, and are commercially available.
In the following examples and comparative examples, each reagent used was a chemically pure reagent from commercial sources, unless otherwise specified.
Example 1 preparation of a polyphenyl hydrophobic crosslinking monomer
Into a dry three-necked flask equipped with a stirrer, a condenser and a dropping funnel, 500mL of toluene and 35.246g (0.216 mol) of 3-acrylamidophenol were charged, and stirring was started until the 3-acrylamidophenol in the flask was sufficiently dissolved. The water bath was heated to 85℃and vacuum was applied for 5 hours while heating to remove air from the flask. Then adding under nitrogen protection0.0442g of dibutyltin dilaurate, 16.0132g (0.1 mol) of terephthalyl diisocyanate were then added to a three-necked flask and reacted for 15 hours, and toluene was removed by distillation under reduced pressure to obtain a crude product. The crude product is showered with chloroform for 3 times, and then is dried in an oven until the weight is constant, thus obtaining a monomer A 1 。
Nuclear magnetic characterization of the product obtained in example 1 [ (CD) 3 ) 2 SO，25℃]The results are shown in Table 1.
TABLE 1 example 1 1 H NMR analysis
/>
Nuclear magnetic resonance spectrum [ ] 1 H NMR) is shown in fig. 1.
The results of the full elemental analysis performed for example 1 are shown in table 2.
TABLE 2 elemental analysis measurements of example 1
| Element(s) | C(％) | H(％) | N(％) | O(％) |
| Theoretical value | 64.19 | 4.56 | 11.52 | 19.73 |
| Measurement value | 64.17 | 4.60 | 11.51 | 19.72 |
| Deviation of | 0.02 | 0.04 | 0.01 | 0.01 |
According to 1 The results of the H NMR and elemental analysis test revealed that example 1 was the target monomer.
Example 2 preparation of a polyphenyl hydrophobic crosslinking monomer
Into a dry three-necked flask equipped with a stirrer, a condenser and a dropping funnel, 500mL of toluene and 34.6g (0.212 mol) of 3-acrylamidophenol were charged, and stirring was started until the 3-acrylamidophenol in the flask was sufficiently dissolved. The water bath was heated to 55℃and vacuum was applied for 5 hours while heating to remove air from the flask. Then 0.048g of dibutyl tin dilaurate was added under the protection of argon, 16.0132g (0.1 mol) of terephthalyl diisocyanate was added into a three-necked flask, and the mixture was reacted for 16 hours, and then acetone was removed by distillation under reduced pressure, thus obtaining a crude product. The crude product is showered with chloroform for 3 times, and then is dried in an oven until the weight is constant, thus obtaining a monomer A 2 。
Example 3 preparation of a polyphenyl hydrophobic crosslinking monomer
Into a dry three-necked flask equipped with a stirrer, a condenser and a dropping funnel, 500mL of toluene and 35.5724g (0.218 mol) of 3-acrylamidophenol were charged, and stirring was started until the 3-acrylamidophenol in the flask was sufficiently obtainedDissolving. The water bath was heated to 90℃and a vacuum was applied for 5 hours while heating to remove air from the flask. Then 0.05g of dibutyl tin dilaurate was added under the protection of argon, then 16.0132g (0.1 mol) of terephthalyl diisocyanate was added into a three-necked flask, the reaction was carried out for 10 hours, and toluene was removed by distillation under reduced pressure, thus obtaining a crude product. The crude product is showered with chloroform for 3 times, and then is dried in an oven until the weight is constant, thus obtaining a monomer A 3 。
EXAMPLE 4 preparation of thickener
1180g of acetonitrile, 11.316g (0.1 mol) of N-isopropylacrylamide, 56.424g (0.6 mol) of sodium acrylate, 2.7224g (0.01 mol) of 1-vinyl-3-ethylimidazole triflate and 4.8648g (0.01 mol) of the polyphenyl hydrophobic crosslinking monomer A prepared in example 1 were sequentially charged into a reactor 1 Stirring until the monomers are completely dissolved, and introducing nitrogen for 60min to remove dissolved oxygen. 0.339g of azo-iso Ding Qingji formamide is added, the temperature is raised to the preset reaction temperature of 74 ℃, and the reaction is stirred under nitrogen atmosphere for 32h to obtain a pale yellow gelatinous crude product.
The crude product was precipitated by sequentially adding 1000mL of water and 500mL of methanol, and filtered to give a solid phase product. Washing 3 times by using acetone, extracting a product by using a Soxhlet extractor for 24 hours by using a glacial acetic acid-glycol mixed solvent with the volume ratio of 3:2 as an extracting agent, and vacuum drying to constant weight at 25 ℃ to obtain the thickening agent, wherein the molecular structure is as follows:
wherein a: b: c: d=10: 60:1:1, d=e.
The thickener obtained in example 4 was subjected to infrared spectroscopic test, the spectrum is shown in fig. 2, and the spectrum analysis is shown in table 3.
TABLE 3 analysis of the IR spectrum of example 4
EXAMPLE 5 preparation of a thickener
Into a reactor were successively charged 800g of 1, 4-dioxane, 17.0212g (0.2 mol) of methacrylamide, 37.616g (0.4 mol) of sodium acrylate, 8.0663g (0.02 mol) of 1-allyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and 4.8648g (0.01 mol) of the polyphenyl hydrophobic crosslinking monomer A prepared in example 2 2 Stirring until the monomers are completely dissolved, and introducing argon for 60min to remove dissolved oxygen. 0.5405g of lauroyl peroxide was added, the temperature was raised to a predetermined reaction temperature of 60℃and the reaction was stirred under nitrogen atmosphere for 36 hours to give a pale yellow gummy crude product.
The crude product was precipitated by sequentially adding 1000mL of water and 500mL of methanol, and filtered to give a solid phase product. Washing 3 times by using acetone, extracting a product by using a Soxhlet extractor for 24 hours by using a glacial acetic acid-glycol mixed solvent with the volume ratio of 3:2 as an extracting agent, and vacuum drying to constant weight at 25 ℃ to obtain the thickening agent, wherein the molecular structure is as follows:
wherein a: b: c: d=20: 40:2:1, d=e.
EXAMPLE 6 preparation of thickener
1000g of tetrahydrofuran, 29.7399g (0.3 mol) of N-vinyl-N-methylacetamide, 18.808g (0.2 mol) of sodium acrylate, 6.0497g (0.015 mol) of 1-vinyl-3-ethylimidazole tetrafluoroborate and 9.7297g (0.02 mol) of the polyphenyl hydrophobic crosslinking monomer A prepared in example 3 were successively charged into a reactor 3 Stirring until the monomers are completely dissolved, and introducing nitrogen for 60min to remove dissolved oxygen. 0.386g of azobisisoheptonitrile was added thereto, the temperature was raised to a predetermined reaction temperature of 50℃and the reaction was stirred under nitrogen atmosphere for 28 hours to give a pale yellow gummy crude product.
The crude product was precipitated by sequentially adding 1000mL of water and 500mL of methanol, and filtered to give a solid phase product. Washing 3 times by using acetone, extracting a product by using a Soxhlet extractor for 24 hours by using a glacial acetic acid-glycol mixed solvent with the volume ratio of 3:2 as an extracting agent, and vacuum drying to constant weight at 25 ℃ to obtain the thickening agent, wherein the molecular structure is as follows:
wherein a: b: c: d=30: 20:1.5:2, d=e.
EXAMPLE 7 preparation of thickener
Into a reactor were successively charged 1820.8856g of N, N-dimethylformamide, 24.7833g (0.25 mol) of N, N-dimethylacrylamide, 48.6315g (0.45 mol) of sodium methacrylate, 2.962g (0.01 mol) of 1-vinyl-3-butylimidazole hexafluorophosphate and 19.4594g (0.04 mol) of the polyphenyl hydrophobic crosslinking monomer A prepared in example 1 1 Stirring until the monomers are completely dissolved, and introducing nitrogen for 60min to remove dissolved oxygen. 0.2875g of azo-iso Ding Qingji formamide is added, the temperature is raised to the preset reaction temperature of 90 ℃, and the reaction is stirred for 16h under nitrogen atmosphere to obtain a pale yellow gelatinous crude product.
The crude product was precipitated by sequentially adding 1000mL of water and 500mL of methanol, and filtered to give a solid phase product. Washing 3 times by using acetone, extracting a product by using a Soxhlet extractor for 24 hours by using a glacial acetic acid-glycol mixed solvent with the volume ratio of 3:2 as an extracting agent, and vacuum drying to constant weight at 25 ℃ to obtain the thickening agent, wherein the molecular structure is as follows:
wherein a: b: c: d=25: 45:1:4, d=e.
Example 8 preparation of thickener
1300g of dimethyl sulfoxide, 50.7672g (0.3 mol) of diacetone acrylamide, 37.616g (0.4 mol) of sodium acrylate, 4.9265g (0.02 mol) of 1-propenyl-3-propylimidazole methanesulfonate and 4.8648g (0.01) of the polyphenyl hydrophobic crosslinking monomer A prepared in example 2 are sequentially charged into a reactor 2 Stirring toThe monomers were completely dissolved and the dissolved oxygen was removed by introducing nitrogen for 60 min. 0.5g of dimethyl azodiisobutyrate was added, the temperature was raised to 66℃as the predetermined reaction temperature, and the reaction was stirred under nitrogen atmosphere for 32 hours to give a pale yellow gummy crude product.
The crude product was precipitated by sequentially adding 1000mL of water and 500mL of methanol, and filtered to give a solid phase product. Washing 3 times by using acetone, extracting a product by using a Soxhlet extractor for 24 hours by using a glacial acetic acid-glycol mixed solvent with the volume ratio of 3:2 as an extracting agent, and vacuum drying to constant weight at 25 ℃ to obtain the thickening agent, wherein the molecular structure is as follows:
wherein a: b: c: d=30: 40:2:1, d=e.
EXAMPLE 9 preparation of thickener
Into a reactor were successively charged 802.4326g of N, N-dimethylacetamide, 1.1079g (0.1 mol) of acrylamide, 56.424g (0.6 mol) of sodium acrylate, 6.1679g (0.02 mol) of 1-propenyl-2, 3-dimethylimidazole p-toluenesulfonate and 19.4594g (0.04 mol) of the polyphenyl hydrophobic crosslinking monomer A prepared in example 3 3 Stirring until the monomers are completely dissolved, and introducing nitrogen for 60min to remove dissolved oxygen. 0.4458g of dibenzoyl peroxide was added, the temperature was raised to 75℃as a predetermined reaction temperature, and the reaction was stirred under nitrogen atmosphere for 24 hours to give a pale yellow gummy crude product.
The crude product was precipitated by sequentially adding 1000mL of water and 500mL of methanol, and filtered to give a solid phase product. Washing 3 times by using acetone, extracting a product by using a Soxhlet extractor for 24 hours by using a glacial acetic acid-glycol mixed solvent with the volume ratio of 3:2 as an extracting agent, and vacuum drying to constant weight at 25 ℃ to obtain the thickening agent, wherein the molecular structure is as follows:
wherein a: b: c: d=10: 60:2:4, d=e.
EXAMPLE 10 preparation of thickener
1000g of dimethyl sulfoxide, 34.6424g (0.2 mol) of N, N-bis (2-hydroxyethyl) methacrylamide, 47.02g (0.5 mol) of sodium acrylate, 4.6863g (0.018 mol) of 1-vinyl-2, 3-dimethylimidazole ethanesulfonate and 12.1621g (0.025 mol) of the polyphenyl hydrophobic crosslinking monomer A prepared in example 1 are introduced into a reactor in this order 1 Stirring until the monomers are completely dissolved, and introducing nitrogen for 60min to remove dissolved oxygen. 0.788g of azobisisobutyronitrile was added, the temperature was raised to a predetermined reaction temperature of 55℃and the reaction was stirred under nitrogen atmosphere for 28 hours to give a pale yellow gummy crude product.
The crude product was precipitated by sequentially adding 1000mL of water and 500mL of methanol, and filtered to give a solid phase product. Washing 3 times by using acetone, extracting a product by using a Soxhlet extractor for 24 hours by using a glacial acetic acid-glycol mixed solvent with the volume ratio of 3:2 as an extracting agent, and vacuum drying to constant weight at 25 ℃ to obtain the thickening agent, wherein the molecular structure is as follows:
wherein a: b: c: d=20: 50:1.8:2.5, d=e.
Comparative examples 1-7 preparation of thickeners
Comparative examples 1-7 the procedure of examples 4-10 was repeated, respectively, except that N, N-methylenebisacrylamide was used as the crosslinking monomer in the added starting material in place of the polyphenyl hydrophobic crosslinking monomer prepared in example 1.
Preparation of comparative examples 1'-7' thickeners
Comparative examples 1'-7' the procedure was repeated for examples 4-10, respectively, except that no alkenylimidazole monomer was added to the starting material.
Experimental example 1 evaluation of shear resistance of thickener
Distilled water was added to the thickener prepared in examples 4 to 10 and comparative examples 1 to 7, respectively, to prepare solutions having a mass percentage concentration of 0.7%. At a shear rate of 170s -1 After shearing for a certain period of time, the Apparent Viscosity (AV) was measured, and the test was concludedThe results are shown in Table 4:
TABLE 4 determination of the test pulps at AV (mPas) during different shearing times
As can be seen from Table 4, the solutions formulated with the different thickeners do not differ much in AV when not sheared. Compared with the AV of the thickener solution without shearing action, the shearing action causes the AV of the thickener solution to be reduced to different degrees, and the longer the shearing action is, the smaller the AV is. The AV of the example solutions was significantly higher than that of the comparative thickener solutions for the same shear time, and the AV of the example solutions was significantly less than that of the comparative thickener solutions with increasing shear time. Experimental results show that compared with the thickener synthesized by taking N, N-methylene bisacrylamide as the crosslinking monomer, the thickener synthesized by the polyphenyl hydrophobic crosslinking monomer has a stronger shearing resistance effect.
Experimental example 2 evaluation of salt resistance of thickener
The thickener prepared in examples 4 to 10 and comparative examples 1'-7' were each prepared by adding NaCl solutions of different concentrations to prepare a solution having a mass percent concentration of 0.7%. At a shear rate of 170s -1 After 8 hours of shearing, the Apparent Viscosity (AV) was measured, and the experimental results are shown in table 5:
TABLE 5 determination of the test pulps at AV (mPas) during different shearing times
As can be seen from table 5, the AV of solutions formulated with different thickeners showed a significant decrease with increasing NaCl concentration. Obviously, the AV of the thickener solution obtained from the examples is significantly smaller than that of the thickener solution obtained from the comparative examples at the same NaCl concentration. Experimental results show that compared with the thickener synthesized by using the reaction monomer without adding the alkenyl imidazole monomer in the synthesis raw material, the thickener synthesized by using the alkenyl imidazole monomer as the reaction monomer has stronger salt resistance.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (17)
1. The preparation method of the polyphenyl hydrophobic crosslinking monomer is characterized by comprising the following steps:
dissolving 3-acrylamide phenol in an organic solvent, heating, and then adding a catalyst under the protection of inert gas to react with terephthalyl diisocyanate to obtain a polyphenyl hydrophobic crosslinking monomer; the molar ratio of the 3-acrylamidophenol to the terephthalyl diisocyanate is (2.10-2.25): 1, a step of;
the structural formula of the polyphenyl hydrophobic crosslinking monomer is shown as formula (1):
2. the method according to claim 1, wherein the molar ratio of 3-acrylamidophenol to terephthalisocyanate is (2.12-2.20): 1.
3. the preparation method according to claim 1, wherein the catalyst is dibutyl tin dilaurate, and the dosage is 0.05% -0.10% of the molar quantity of the terephthalyl diisocyanate.
4. The process of claim 3, wherein the catalyst is used in an amount of 0.06% to 0.08% by mole of terephthal-diisocyanate.
5. The preparation method according to claim 1, wherein the reaction condition is a heating temperature of 50-90 ℃ and a reaction time of 8-16h.
6. The method according to claim 1, wherein the organic solvent is one of acetone, benzene, toluene, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
7. The hydrophobic cross-linking monomer of polyphenyl prepared by the preparation method according to any one of claims 1 to 6, wherein the structural formula of the monomer is shown as a formula (1):
8. a process for preparing a thickener comprising the monomer of claim 7, wherein said thickener comprises:
(1) Dissolving alkenyl amide, alkenyl carboxylate, ionic liquid and a polyphenyl hydrophobic crosslinking monomer in an organic solvent, stirring until the alkenyl amide, the alkenyl carboxylate, the ionic liquid and the polyphenyl hydrophobic crosslinking monomer are dissolved to obtain a liquid-phase reactant, and introducing inert gas to remove dissolved oxygen;
(2) Adding an initiator into the liquid phase reactant, heating to 30-90 ℃ in an inert gas atmosphere, and reacting for 16-36h under stirring to obtain a crude product;
(3) Precipitating, filtering, washing and drying the crude product to obtain a thickening agent;
the structural formula of the alkenylamide is shown as formula (2):
wherein R is 0 is-H or C 1 ～C 6 Alkyl of (a);
R 1 is an amide group;
the structural formula of the alkenyl carboxylate is shown as the formula (3):
wherein R is 2 Selected from-H or C 1 ～C 6 Is selected from H, na, K, rb or Cs;
the structural formula of the ionic liquid is shown as formula (4):
wherein m is a natural number of 0 or 6 or less, R 3 is-H or C 1 ～C 6 Alkyl of R 4 is-H or C 1 ～C 6 Alkyl of X - For BF 4 - 、PF 6 - 、 One of the following;
the structural formula of the thickener is shown as formula (5):
wherein a: b: c: d= (10-30): (20-60): (1-2): (1-4), d=e;
R 0 、R 1 r in the formula (2) 0 、R 1 The same;
R 2 a and R in formula (3) 2 A and A are the same;
m、R 3 、R 4 、X - and m and R in formula (4) 3 、R 4 、X - The same applies.
9. The method for preparing a thickener according to claim 8, wherein the amide group has a structural formula represented by formula (2-1) or formula (2-2):
wherein:
R a and R is b Each independently selected from-H, C 1 ～C 6 Alkyl, C of (2) 1 ～C 6 Hydroxyalkyl of C 1 ～C 8 A carbonylalkyl group of (a); r is R c Selected from-H or C 1 ～C 6 Alkyl of (a); r is R d Selected from C 1 ～C 6 Is a hydrocarbon group.
10. The method of preparing a thickener according to claim 9, wherein said R is a And R is b Each independently selected from the group consisting of-H, -CH 3 、—CH 2 CH 3 、—CH(CH 3 ) 2 、—CH 2 OH、—CH 2 CH 2 OH or formula (2-1-1),
R c selected from the group consisting of-H, -CH 3 、—C 2 H 5 or-CH (CH) 3 ) 2 ；
R d Selected from-CH 3 、—C 2 H 5 or-CH (CH) 3 ) 2 。
11. The method of preparing a thickener according to claim 8, wherein the molar ratio of said alkenylamide, alkenylcarboxylate, ionic liquid and polyphenyl hydrophobic cross-linking monomer is (10-30): (20-60): (1-2): (1-4); the total mass percentage concentration of the four monomers in the organic solvent is 2.0-20.0%.
12. The method for preparing a thickener according to claim 8, wherein the organic solvent is one of 1, 4-dioxane, acetonitrile, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
13. The method for preparing a thickener according to claim 8, wherein the initiator is one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobis Ding Qingji formamide, dibenzoyl peroxide and lauroyl peroxide.
14. The method for preparing a thickener according to claim 8 or 13, wherein the amount of the initiator is 0.2% -1.0% of the total mass of the alkenyl amide, the alkenyl carboxylate, the ionic liquid and the polyphenyl hydrophobic crosslinking monomer.
15. The method of claim 8, wherein the inert gas is one of nitrogen, helium, neon, argon, krypton, xenon, and radon.
16. The thickener prepared by the thickener preparation method according to any of claims 8 to 15, wherein the thickener has a structural formula shown in formula (5):
wherein a: b: c: d= (10-30): (20-60): (1-2): (1-4), d=e;
R 0 、R 1 r in the formula (2) 0 、R 1 The same;
R 2 a and R in formula (3) 2 A and A are the same;
m、R 3 、R 4 、X - and m and R in formula (4) 3 、R 4 、X - The same applies.
17. Use of a thickener according to claim 16 in oilfield acidizing fracturing fluids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011097692.8A CN114426505B (en) | 2020-10-14 | 2020-10-14 | Polyphenyl hydrophobic crosslinking monomer, thickener containing same and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011097692.8A CN114426505B (en) | 2020-10-14 | 2020-10-14 | Polyphenyl hydrophobic crosslinking monomer, thickener containing same and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114426505A CN114426505A (en) | 2022-05-03 |
| CN114426505B true CN114426505B (en) | 2023-08-04 |
Family
ID=81309842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011097692.8A Active CN114426505B (en) | 2020-10-14 | 2020-10-14 | Polyphenyl hydrophobic crosslinking monomer, thickener containing same and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114426505B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005008034A1 (en) * | 2005-02-22 | 2006-08-31 | Lanxess Deutschland Gmbh | Acid group-containing condensation products |
| CN106349114B (en) * | 2015-07-16 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of hydrophobic monomer and the clay-free drilling fluid tackifier based on the monomer |
| CN106349111B (en) * | 2015-07-16 | 2017-11-21 | 中国石油化工股份有限公司 | A kind of cross-linking monomer containing phenyl hydrophobic and the hydrogel based on the monomer |
| CN109971438B (en) * | 2017-12-28 | 2021-05-18 | 中国石油化工股份有限公司 | Modified starch coated anti-sloughing agent for drilling fluid and preparation method thereof |
-
2020
- 2020-10-14 CN CN202011097692.8A patent/CN114426505B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114426505A (en) | 2022-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Koschella et al. | A “click-chemistry” approach to cellulose-based hydrogels | |
| CN104762077B (en) | The polymer oil-displacing agent of high temperature resistant salt resistance | |
| CN108948231B (en) | Water-soluble polyrotaxane crosslinking agent and preparation method thereof | |
| CN103214629B (en) | Antistatic agent for dacron textile and preparation method of antistatic agent | |
| Tang et al. | Metallo-supramolecular hydrogels based on amphiphilic polymers bearing a hydrophobic Schiff base ligand with rapid self-healing and multi-stimuli responsive properties | |
| CN103980440A (en) | Semi-interpenetrating intelligent hydrogel and preparation method and application thereof | |
| CN102603903B (en) | Method for preparing double-crosslinking amphoteric tapioca starch | |
| CN105733159A (en) | Preparation method of semi-interpenetrating water-absorbent resin particles | |
| Li et al. | Lanthanide-based hydrogels with adjustable luminescent properties synthesized by thiol-Michael addition | |
| CN107880280B (en) | Preparation method of rosin-based multi-active-site acrylamide composite hydrogel | |
| CN110655612A (en) | Hydrophobic association polymer, preparation method thereof and application of hydrophobic association polymer in high-temperature-resistant fracturing fluid | |
| Miao et al. | Alkynyl-functionalization of hydroxypropyl cellulose and thermoresponsive hydrogel thereof prepared with P (NIPAAm-co-HEMAPCL) | |
| CN114426505B (en) | Polyphenyl hydrophobic crosslinking monomer, thickener containing same and application thereof | |
| Liubimtsev et al. | Redox-sensitive ferrocene functionalised double cross-linked supramolecular hydrogels | |
| CN114230714A (en) | Hydrophobic association double-network oil displacement polymer and preparation method thereof | |
| CN110330667B (en) | Simple preparation method of water-soluble polyrotaxane crosslinking agent and product thereof | |
| CN107434851B (en) | Preparation method of photosensitive hydrogel | |
| CN111500010A (en) | Degradable polypropylene antibacterial mask material and preparation method thereof | |
| Wan et al. | Synthesis and solution properties of hydrophobically associative polyacrylamides by microemulsion polymerization | |
| CN109134769A (en) | A kind of producing high-molecular method of imide fluorescent dye | |
| CN105461865B (en) | A kind of tree-like polyacrylamide and preparation method thereof and the application as thickener | |
| You et al. | Supramolecular linear polymer formed by host–guest interactions of β-cyclodextrin dimers and polyacrylamide end-capped with adamantane | |
| CN107090086A (en) | A kind of cyclic backbones azobenzene polymer self-healing gel and its preparation method and application | |
| CN107383377B (en) | Cyclic polycaprolactone-polyethylene glycol amphiphilic block copolymer, and preparation and application thereof | |
| CN113651927B (en) | Salt thickening polymer containing double-tail inner salt structure, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |