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Supramolecular star polymer taking beta-CD (beta-cyclodextrin) as core and preparation method of supramolecular star polymer

A molecular star and polymer technology, applied in drilling compositions, chemical instruments and methods, etc., can solve the problems of poor hydrolysis resistance, prone to breakage or entanglement, unstable molecular chain structure, etc. synergistic effect, improving hydrophobic association effect, reducing the effect of hydrolysis risk

Active Publication Date: 2022-03-01
SOUTHWEST PETROLEUM UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Styrenic hydrophobic monomer (Zhong Chuanrong et al., Characterization and heat resistance of AM-STD-NaAMPS ternary hydrophobic association copolymer. Polymer Materials Science and Engineering, 2003,19(6):126-130), although it has The rigid benzene ring can effectively improve the temperature resistance and hydrolysis resistance of the polymer, but the benzene ring is too close to the main chain of the molecule, which is not conducive to the copolymerization of hydrophobic monomers and acrylamide, and is not conducive to improving the viscosity of the polymer solution. Effect
Allyl-type hydrophobic monomer (Rosan et al., Synthesis and solution properties of a hydrophobic association polymer with imidazoline structure. Chemical Research and Application, 2015,27(8):1151-1156), due to containing allyl, It is not easy to realize the copolymerization with the main monomer acrylamide, the molecular weight of the prepared hydrophobic association polymer is not high, and the viscosity increasing effect is not obvious
Acrylamide-type hydrophobic monomer (Geng Tongmou. Hydrophobic association water-soluble polymer P(AM / NaAA / DiAC 16 ) viscosity behavior of aqueous solution. Fine Chemical Industry, 2007,24(9):914-918), its structure is similar to that of acrylamide, which is beneficial to the polymerization reaction, but there is a certain disadvantage of poor hydrolysis resistance
[0004] At present, hydrophobic association polymers are mainly linear chain structures, and the main disadvantages are: under high-speed shearing, the molecular chain structure is unstable, prone to breakage or entanglement, and the viscosity drops sharply

Method used

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  • Supramolecular star polymer taking beta-CD (beta-cyclodextrin) as core and preparation method of supramolecular star polymer
  • Supramolecular star polymer taking beta-CD (beta-cyclodextrin) as core and preparation method of supramolecular star polymer
  • Supramolecular star polymer taking beta-CD (beta-cyclodextrin) as core and preparation method of supramolecular star polymer

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Embodiment 1

[0034] A kind of preparation method of supramolecular star polymer with β-CD as core, it comprises the following steps:

[0035] Step S1: Prepare β-cyclodextrin modified branched monomer F-β-CD, the specific operation is as follows:

[0036] S11: Add freshly dried β-CD (14.0 g, 12.3 mmol) into a three-neck flask, add 100 mL of dry pyridine at room temperature, stir magnetically, and dissolve evenly. After it was completely dissolved, a pyridine solution of p-toluenesulfonyl chloride (16.9 g, 88.6 mmol) was added under ice-water bath conditions. After the dropwise addition, the reaction system was raised to room temperature and reacted for 24 hours. The solvent pyridine was recovered by rotary evaporation, the crude product was poured into a large amount of cold water, and the white precipitate was obtained by suction filtration, which was washed with 100 mL of water and ether respectively; at 62-65 ° C, the crude product was stirred in methanol for 30 min, and suction filtere...

Embodiment 2

[0043] A kind of preparation method of supramolecular star polymer with β-CD as core, it comprises the following steps:

[0044] Step S1: prepare β-cyclodextrin modified branched monomer F-β-CD, the specific method is the same as Step S1 of Example 1.

[0045] Step S2: Prepare supramolecular star polymer with β-CD as the core, the specific operation is as follows:

[0046] S21: Add 9.6g of acrylamide, 2.5g of acrylic acid and 0.3g of surface-active macromonomer allyl polyoxyethylene ether into distilled water, adjust the pH to about 7 with 10% NaOH solution, and then add 0.1 of the hydrophobic monomer N -Phenylethyl-N-tetradecyl methacrylamide and 0.25g surfactant sodium lauryl sulfate, stir until the solution is clear and transparent, then add β-cyclodextrin modified branched monomer F-β -CD (0.3‰ of the total monomer mass fraction), add a certain amount of distilled water to make the total monomer concentration 25%, and pass nitrogen gas for more than 15 minutes to remove d...

Embodiment 3

[0049] A kind of preparation method of supramolecular star polymer with β-CD as core, it comprises the following steps:

[0050] Step S1: prepare β-cyclodextrin modified branched monomer F-β-CD, the specific method is the same as Step S1 of Example 1.

[0051] Step S2: Prepare supramolecular star polymer with β-CD as the core, the specific operation is as follows:

[0052] S21: Add 9.6g of acrylamide, 2.5g of acrylic acid and 0.2g of surface-active macromonomer polyoxyethylene cetyl methacrylate to distilled water, adjust the pH to about 7 with 10% NaOH solution, and then add 0.1 Hydrophobic monomer N-benzyl-N-tetradecyl methacrylamide and 0.4g surfactant sodium lauryl sulfate, stir until the solution is clear and transparent, then add β-cyclodextrin modified branched monomer F-β-CD (0.5‰ of the total mass fraction of the monomer), add a certain amount of distilled water to make the total monomer concentration 25%, pass nitrogen for more than 15 minutes, and remove the dissol...

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Abstract

The invention relates to a supramolecular star polymer taking beta-CD as a core and a preparation method of the supramolecular star polymer. The supramolecular star polymer takes a beta-cyclodextrin modified branched monomer F-beta-CD as an inner core and is grafted with acrylamide, acrylic acid, a hydrophobic monomer and a surface active macromonomer; the hydrophobic monomer is one or more of N-benzyl-N alkyl (methyl) acrylamide and N-phenethyl-N alkyl (methyl) acrylamide; the surface active macromonomer is one or more of allyl polyoxyethylene ether, alkylphenol polyoxyethylene ether (methyl) acrylate, alkylphenol polyoxyethylene ether allyl ether, alkyl alcohol polyoxyethylene ether (methyl) acrylate and alkyl alcohol polyoxyethylene ether allyl ether. The preparation method has the advantages of cheap and easily available raw materials, easily controllable synthesis conditions and high yield. The tackifying agent has excellent tackifying performance, temperature resistance, salt resistance and hydrolysis resistance, and shows good application prospects in the aspects of oil field recovery efficiency improvement and hydraulic fracturing.

Description

technical field [0001] The invention relates to a supramolecular star-shaped polymer used for oilfield enhanced recovery and hydraulic fracturing and a preparation method thereof. Background technique [0002] Hydrophobic-associated polymers refer to water-soluble polymers that introduce a small amount of hydrophobic groups (usually <2 mol%) on the macromolecular chain of hydrophilic polymers, so they are also called water-soluble hydrophobic-associated polymers. Owing to the interaction between hydrophobic groups, HAP exhibits unique properties different from conventional polymers in solution. In aqueous solution, due to the hydrophobic interaction, the hydrophobic groups aggregate with each other, making the polymer macromolecular chains produce intramolecular and intermolecular associations. When the polymer concentration is higher than the critical association concentration (CAC), the polymer macromolecular chains aggregate through hydrophobic associations to form a ...

Claims

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Application Information

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IPC IPC(8): C08F251/00C08F220/56C08F220/06C08F220/54C08F2/48C09K8/588C09K8/68C09K8/88
CPCC08F251/00C08F2/48C09K8/588C09K8/68C09K8/885C08F220/56C08F220/06C08F220/54C09K8/88C08F220/285C08F216/085
Inventor 李勇明吴建发付永强任强曾波常程
Owner SOUTHWEST PETROLEUM UNIV
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