CN115028771B - Method for preparing dendritic amphiphilic acrylamide copolymer by suspension polymerization method and application thereof - Google Patents

Method for preparing dendritic amphiphilic acrylamide copolymer by suspension polymerization method and application thereof Download PDF

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CN115028771B
CN115028771B CN202210725645.6A CN202210725645A CN115028771B CN 115028771 B CN115028771 B CN 115028771B CN 202210725645 A CN202210725645 A CN 202210725645A CN 115028771 B CN115028771 B CN 115028771B
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acrylamide copolymer
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dendritic
acrylamide
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CN115028771A (en
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汪艳
刘彭城
张传银
陈建波
张弓
李�杰
周迟俊
于冬梅
胡盛伟
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Anhui Tianrun Chemicals Co ltd
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    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
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    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants

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Abstract

The invention discloses a method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method and application thereof, comprising the following steps: s1: preparing materials; s2: adding 2,4, 5-triaminopyridine and AA into deionized water, stirring and dissolving, adding tungsten sulfate, and stirring at 80-90 ℃ for 1.5-2h; s3: adding AM and AMPS, stirring and dissolving, regulating pH to 6-8, adding dispersant, stirring and dispersing at 150-300r/min, adding metal chelating agent and chain branching agent, and stirring to form suspension; s4: introducing nitrogen, removing oxygen, adding hexadecyl dimethyl allyl ammonium chloride, heating to 30-35 ℃, adding an oxidant and a reducing agent, initiating polymerization reaction, reacting for 5-6h, cooling to 25 ℃, filtering, washing and drying to obtain the product. The dendritic amphiphilic acrylamide copolymer prepared by the invention has high solubility, high molecular weight, high temperature resistance, high mineralization resistance and excellent shearing resistance, meets the use requirement of oil reservoir cracks under extreme conditions, and has wide application prospect.

Description

Method for preparing dendritic amphiphilic acrylamide copolymer by suspension polymerization method and application thereof
Technical Field
The invention belongs to the field of dendritic polymer synthesis, and also relates to the technical field of profile control and oil displacement, in particular to a method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method and application thereof.
Background
Currently, in recent years, acrylamide polymers have been widely used in the industries of oil fields, water treatment, papermaking, and the like. In particular, the method is widely applied to industries such as petroleum, natural gas and the like. However, some severe application environments, such as high temperature and high pressure during exploitation of underground oil gas, and some salt substances in common environments, because the existing acrylamide polymer is generally linear and linear, is easy to curl and wind, and is unstable in molecular chain structure, the viscosity, expansion performance and viscoelasticity of the linear polyacrylamide are rapidly reduced under extreme conditions such as high temperature, high salt and the like, and the shearing resistance is poor, so that the product cannot meet the application requirements.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method and application thereof.
The technical scheme of the invention is summarized as follows:
a method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method comprises the following steps:
s1: the preparation method comprises the following steps of: 3-6 parts of 2,4, 5-triaminopyridine, 9-18 parts of acrylic acid, 0.05-0.1 part of tungsten sulfate, 30-50 parts of acrylamide, 10-22.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.5-1.5 parts of dispersing agent, 0.1-0.5 part of metal chelating agent, 0.5-3 parts of chain branching agent, 1.5-7.5 parts of cetyl dimethyl allyl ammonium chloride, 0.05-0.1 part of oxidant, 0.05-0.1 part of reducing agent and 120-150 parts of deionized water;
s2: adding 2,4, 5-triaminopyridine and acrylic acid into deionized water, stirring and dissolving, adding tungsten sulfate, and stirring at 80-90 ℃ for 1.5-2h to obtain an initial reaction solution;
s3: adding acrylamide and 2-acrylamide-2-methylpropanesulfonic acid into the initial reaction solution obtained in the step S2, stirring and dissolving, regulating the pH value to 6-8, adding a dispersing agent, stirring and dispersing at the rotating speed of 150-300r/min, continuously adding a metal chelating agent and a chain branching agent, and uniformly stirring to form a suspension system;
s4: introducing nitrogen into the suspension system obtained in the step S3 to remove oxygen, adding hexadecyl dimethyl allyl ammonium chloride when the oxygen content in the system is less than or equal to 0.25%, heating to 30-35 ℃, adding an oxidant and a reducing agent to initiate polymerization reaction, reacting for 5-6h, cooling to room temperature of 25 ℃, filtering, washing and drying to obtain the dendritic amphiphilic acrylamide copolymer.
Preferably, the dispersing agent is acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer with a molecular weight of 10-65 ten thousand.
Preferably, the metal chelating agent is one or more of disodium ethylenediamine tetraacetate, disodium ethylenediamine tetraacetate dihydrate and ferric ethylenediamine tetraacetate sodium salt.
Preferably, the chain branching agent is one or more of pentaerythritol diacrylate, glycerol diacrylate, trimethylolpropane diacrylate, dipropylene glycol diacrylate and triallylamine.
Preferably, the oxidant is one or more of ammonium persulfate, potassium persulfate, permanganate and hydrogen peroxide.
Preferably, the reducing agent is one or more of sodium sulfite, mercaptosuccinic acid, cobalt dichloride, hydroxylamine and dimethylamine.
Preferably, in S3, the pH is adjusted to 7.0-7.9.
Preferably, the particle size of the dendritic amphiphilic acrylamide copolymer prepared by the method is 35-400 mu m, and the molecular weight is 3500-4500 ten thousand.
The dendritic amphiphilic acrylamide copolymer prepared by the method is applied to deep profile control of a high-temperature high-salt oil reservoir.
Preferably, the expansion multiple of the dendritic amphiphilic acrylamide copolymer is up to 22.7 under the conditions of the mineralization degree of 60000ppm and the temperature of 130 ℃, and the viscosity retention rate is up to 78.4%.
The invention has the beneficial effects that:
1. according to the invention, 2,4, 5-triaminopyridine is taken as a branched inner core, amidation reaction is carried out with acrylic acid in advance to form 3 divergent vinyl end group-containing skeleton arms, then acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, a dispersing agent, a chain branching agent and hexadecyl dimethyl allyl ammonium chloride are sequentially divergently connected from inside to outside through a suspension polymerization method, and as the chain branching agent is provided with 2-3 vinyl groups, the chain branching agent is taken as a diverging point on a branched chain to diffuse outwards for the second time, finally a dendritic amphiphilic acrylamide copolymer with a plurality of branches is synthesized, the copolymer product has a dendritic structure with a compact periphery and a larger internal cavity, is similar to a three-dimensional highly ordered ball type, compared with a linear acrylamide copolymer, the curling and entanglement between molecules are avoided, the radius of gyration is small, the dynamic mechanical size is smaller, the fluidity and the stability are better, the copolymer product is not easy to fracture and deform, and meanwhile, the 2,4, 5-triaminopyridine is a rigid structure of aromatic heterocycle, the copolymer product has a certain rigidity, the structural stability and the mechanical strength are further improved, the copolymer is not damaged in a deep part, and is not influenced by a deep-driving part, and is not influenced by a carboxyl group, and is taken as an ideal high-ion complexing agent, and has a high-ion-resistant stratum ion-complexing agent.
2. The dendritic amphiphilic acrylamide copolymer prepared by the invention has high solubility, high molecular weight, high temperature resistance, high mineralization resistance and excellent shearing resistance, has expansion times as high as 22.7 and viscosity retention rate as high as 78.4 percent under the conditions of mineralization of 60000ppm and temperature of 130 ℃, meets the use requirements of oil reservoir cracks under extreme conditions, and has wide application prospect.
3. The invention adopts suspension polymerization to prepare the dendritic amphiphilic acrylamide copolymer, the reaction temperature is easy to control, the molecular weight and the particle size range are narrower, and the product is spherical particles, easy to separate and uniformly dispersed.
4. According to the invention, an anionic surfactant monomer 2-acrylamide-2-methylpropanesulfonic acid and a cationic hydrophobic association monomer cetyl dimethyl allyl ammonium chloride are simultaneously introduced into the acrylamide copolymer, so that the copolymer product is characterized by both hydrophilic and lipophilic amphiphilic properties, and the interfacial tension of crude oil is cooperatively reduced.
Drawings
FIG. 1 is a flow chart of a method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method of the invention;
FIG. 2 is a view showing the appearance of the dendrimeric amphiphilic acrylamide copolymer prepared in example 1;
FIG. 3 is a graph showing the particle diameter distribution of the dendritic amphiphilic acrylamide copolymer prepared in example 1;
FIG. 4 is an SEM image of a dendritic amphiphilic acrylamide-based copolymer prepared in example 7.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
The invention provides a method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method, which comprises the following steps of:
s1: the preparation method comprises the following steps of: 3-6 parts of 2,4, 5-triaminopyridine, 9-18 parts of acrylic acid, 0.05-0.1 part of tungsten sulfate, 30-50 parts of acrylamide, 10-22.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.5-1.5 parts of dispersing agent, 0.1-0.5 part of metal chelating agent, 0.5-3 parts of chain branching agent, 1.5-7.5 parts of cetyl dimethyl allyl ammonium chloride, 0.05-0.1 part of oxidant, 0.05-0.1 part of reducing agent and 120-150 parts of deionized water;
the dispersing agent is acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer with the molecular weight of 10-65 ten thousand; the metal chelating agent is one or more of disodium ethylenediamine tetraacetate, disodium ethylenediamine tetraacetate dihydrate and ferric ethylenediamine tetraacetate sodium salt; the chain branching agent is one or more of pentaerythritol diacrylate, glycerol diacrylate, trimethylolpropane diacrylate, dipropylene glycol diacrylate and triallylamine; the oxidant is one or more of ammonium persulfate, potassium persulfate, permanganate and hydrogen peroxide; the reducing agent is one or more of sodium sulfite, mercaptosuccinic acid, cobalt dichloride, hydroxylamine and dimethylamine;
s2: adding 2,4, 5-triaminopyridine and acrylic acid into deionized water, stirring and dissolving, adding tungsten sulfate, and stirring at 80-90 ℃ for 1.5-2h to obtain an initial reaction solution;
s3: adding acrylamide and 2-acrylamide-2-methylpropanesulfonic acid into the initial reaction solution obtained in the step S2, stirring and dissolving, regulating the pH value to 7.0-7.9, adding a dispersing agent, stirring and dispersing at the rotating speed of 150-300r/min, continuously adding a metal chelating agent and a chain branching agent, and uniformly stirring to form a suspension system;
s4: introducing nitrogen into the suspension system obtained in the step S3 to remove oxygen, adding hexadecyl dimethyl allyl ammonium chloride when the oxygen content in the system is less than or equal to 0.25%, heating to 30-35 ℃, adding an oxidant and a reducing agent to initiate polymerization reaction, reacting for 5-6h, cooling to room temperature of 25 ℃, filtering, washing and drying to obtain the dendritic amphiphilic acrylamide copolymer.
The particle size of the dendritic amphiphilic acrylamide copolymer prepared by the method is 35-400 mu m, and the molecular weight is 3500-4500 ten thousand; the method is applied to deep profile control and flooding of high-temperature and high-salt oil reservoirs.
According to the embodiment, 2,4, 5-triaminopyridine is taken as a branched inner core, amidation reaction is carried out on the branched inner core and acrylic acid in advance to form 3 divergent vinyl end group-containing skeleton arms, then acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, a dispersing agent, a chain branching agent and hexadecyl dimethyl allyl ammonium chloride are sequentially divergently connected from inside to outside through a suspension polymerization method, and as the chain branching agent is provided with 2-3 vinyl groups, the branched chain branching agent is taken as a diverging point on a branched chain to be diffused outwards for the second time, a dendritic amphiphilic acrylamide copolymer with a plurality of branches is finally synthesized, and the copolymer product is provided with a dendritic structure with a relatively compact periphery and a relatively large internal cavity, is similar to a three-dimensional highly ordered ball type, and has smaller dynamic mechanical dimension and better fluidity and stability compared with a linear acrylamide copolymer, so that curling and entanglement between molecules are avoided, the radius of gyration is small, and meanwhile, the 2,4, 5-triaminopyridine is a rigid structure of aromatic heterocycle, so that the copolymer product has certain rigidity, further structural stability and mechanical strength, deep driving part of the product is not destroyed, and is not subjected to the deep driving part, and is not subjected to metal chelating agent and has high-ion complexing property and high-ion formation resistance to the high-phase ion complexing agent.
The dendritic amphiphilic acrylamide copolymer prepared by the embodiment has high solubility, high molecular weight, high temperature resistance, high mineralization resistance and excellent shearing resistance, has expansion times as high as 22.7 and viscosity retention rate as high as 78.4 percent under the conditions of mineralization of 60000ppm and temperature of 130 ℃, meets the use requirements of oil reservoir cracks under extreme conditions, and has wide application prospect.
In the embodiment, the dendritic amphiphilic acrylamide copolymer is prepared by adopting a suspension polymerization method, the reaction temperature is easy to control, the molecular weight and the particle size range are narrow, the product is spherical particles, the separation is easy, and the dispersion is uniform.
According to the embodiment, an anionic surfactant monomer 2-acrylamide-2-methylpropanesulfonic acid and a cationic hydrophobic association monomer cetyl dimethyl allyl ammonium chloride are simultaneously introduced into an acrylamide copolymer, so that the copolymer product is made to have hydrophilic and lipophilic amphiphilic properties, and the interfacial tension of crude oil is reduced synergistically.
Example 1
A method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method comprises the following steps:
s1: the preparation method comprises the following steps of: 3 parts of 2,4, 5-triaminopyridine, 9 parts of acrylic acid, 0.05 part of tungsten sulfate, 30 parts of acrylamide, 10 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.5 part of acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer with the molecular weight of 12 ten thousand, 0.1 part of ferric sodium ethylenediamine tetraacetate, 0.5 part of pentaerythritol diacrylate, 1.5 parts of cetyl dimethyl allyl ammonium chloride, 0.05 part of ammonium persulfate, 0.05 part of sodium sulfite and 120 parts of deionized water;
s2: adding 2,4, 5-triaminopyridine and acrylic acid into deionized water, stirring and dissolving, adding tungsten sulfate, and stirring at 80 ℃ for 1.5h to obtain an initial reaction solution;
s3: adding acrylamide and 2-acrylamido-2-methylpropanesulfonic acid into the initial reaction solution obtained in the step S2, stirring and dissolving, regulating the pH to 7.0, adding an acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer (MW: 12 ten thousand), stirring and dispersing at a rotating speed of 150r/min, continuously adding ethylenediamine tetraacetic acid iron sodium salt and pentaerythritol diacrylate, and uniformly stirring to form a suspension system;
s4: introducing nitrogen into the suspension system obtained in the step S3 to remove oxygen, adding hexadecyl dimethyl allyl ammonium chloride when the oxygen content in the system is less than or equal to 0.25%, heating to 30 ℃, adding ammonium persulfate and sodium sulfite to initiate polymerization, cooling to room temperature of 25 ℃ after 5 hours of reaction, filtering, washing and drying to obtain the dendritic amphiphilic acrylamide copolymer.
Example 2
A method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method comprises the following steps:
s1: the preparation method comprises the following steps of: 3.5 parts of 2,4, 5-triaminopyridine, 10.5 parts of acrylic acid, 0.05 part of tungsten sulfate, 35 parts of acrylamide, 15 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.8 part of acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer with the molecular weight of 15 ten thousand, 0.2 part of ethylene diamine tetraacetic acid disodium salt, 1 part of glycerol diacrylate, 2.5 parts of hexadecyl dimethyl allyl ammonium chloride, 0.07 part of ammonium persulfate, 0.07 part of mercaptosuccinic acid and 130 parts of deionized water;
s2: adding 2,4, 5-triaminopyridine and acrylic acid into deionized water, stirring and dissolving, adding tungsten sulfate, and stirring at 85 ℃ for 1.5 hours to obtain an initial reaction solution;
s3: adding acrylamide and 2-acrylamido-2-methylpropanesulfonic acid into the initial reaction solution obtained in the step S2, stirring and dissolving, regulating the pH to 7.2, adding an acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer (MW: 15 ten thousand), stirring and dispersing at the rotating speed of 250r/min, continuously adding ethylene diamine tetraacetic acid disodium salt and glycerol diacrylate, and uniformly stirring to form a suspension system;
s4: introducing nitrogen into the suspension system obtained in the step S3 to remove oxygen, adding hexadecyl dimethyl allyl ammonium chloride when the oxygen content in the system is less than or equal to 0.25%, heating to 30 ℃, adding ammonium persulfate and mercaptosuccinic acid to initiate polymerization reaction, cooling to room temperature of 25 ℃ after 5.5 hours of reaction, filtering, washing and drying to obtain the dendritic amphiphilic acrylamide copolymer.
Example 3
A method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method comprises the following steps:
s1: the preparation method comprises the following steps of: 4 parts of 2,4, 5-triaminopyridine, 12 parts of acrylic acid, 0.075 part of tungsten sulfate, 38 parts of acrylamide, 12 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1 part of acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer with a molecular weight of 30 ten thousand, 0.3 part of disodium ethylenediamine tetraacetate dihydrate, 1.5 parts of trimethylolpropane diacrylate, 3 parts of cetyl dimethylallyl ammonium chloride, 0.08 part of permanganate, 0.08 part of cobalt dichloride and 125 parts of deionized water;
s2: adding 2,4, 5-triaminopyridine and acrylic acid into deionized water, stirring and dissolving, adding tungsten sulfate, and stirring at 85 ℃ for 2 hours to obtain an initial reaction solution;
s3: adding acrylamide and 2-acrylamido-2-methylpropanesulfonic acid into the initial reaction solution obtained in the step S2, stirring and dissolving, regulating the pH to 7.2, adding an acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer (MW: 30 ten thousand), stirring and dispersing at a rotating speed of 260r/min, continuously adding disodium ethylenediamine tetraacetate dihydrate and trimethylolpropane diacrylate, and uniformly stirring to form a suspension system;
s4: introducing nitrogen into the suspension system obtained in the step S3 to remove oxygen, adding hexadecyl dimethyl allyl ammonium chloride until the oxygen content in the system is less than or equal to 0.25%, heating to 35 ℃, adding permanganate and cobalt dichloride to initiate polymerization reaction, reacting for 6 hours, cooling to room temperature of 25 ℃, filtering, washing and drying to obtain the dendritic amphiphilic acrylamide copolymer.
Example 4
A method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method comprises the following steps:
s1: the preparation method comprises the following steps of: 5 parts of 2,4, 5-triaminopyridine, 15 parts of acrylic acid, 0.1 part of tungsten sulfate, 40 parts of acrylamide, 18 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1.2 parts of acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer with the molecular weight of 47 ten thousand, 0.5 part of ferric sodium ethylenediamine tetraacetate, 2.5 parts of dipropylene glycol diacrylate, 6 parts of cetyl dimethyl allyl ammonium chloride, 0.1 part of potassium persulfate, 0.1 part of hydroxylamine and 130 parts of deionized water;
s2: adding 2,4, 5-triaminopyridine and acrylic acid into deionized water, stirring and dissolving, adding tungsten sulfate, and stirring at 80-90 ℃ for 1.5-2h to obtain an initial reaction solution;
s3: adding acrylamide and 2-acrylamido-2-methylpropanesulfonic acid into the initial reaction solution obtained in the step S2, stirring and dissolving, regulating the pH to 7.4, adding an acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer (MW: 47 ten thousand), stirring and dispersing at a rotating speed of 270r/min, continuing adding ethylene diamine tetraacetic acid iron sodium salt and dipropylene glycol diacrylate, and uniformly stirring to form a suspension system;
s4: introducing nitrogen into the suspension system obtained in the step S3 to remove oxygen, adding hexadecyl dimethyl allyl ammonium chloride until the oxygen content in the system is less than or equal to 0.25%, heating to 32 ℃, adding potassium persulfate and hydroxylamine to initiate polymerization reaction, reacting for 5.2h, cooling to room temperature of 25 ℃, filtering, washing and drying to obtain the dendritic amphiphilic acrylamide copolymer.
Example 5
A method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method comprises the following steps:
s1: the preparation method comprises the following steps of: 6 parts of 2,4, 5-triaminopyridine, 18 parts of acrylic acid, 0.1 part of tungsten sulfate, 50 parts of acrylamide, 22.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 1.5 parts of acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer with the molecular weight of 65 ten thousand, 0.5 part of disodium ethylenediamine tetraacetate dihydrate, 3 parts of triallylamine, 7.5 parts of cetyl dimethylallyl ammonium chloride, 0.1 part of ammonium persulfate, 0.1 part of dimethylamine and 150 parts of deionized water;
s2: adding 2,4, 5-triaminopyridine and acrylic acid into deionized water, stirring and dissolving, adding tungsten sulfate, and stirring at 90 ℃ for 2 hours to obtain an initial reaction solution;
s3: adding acrylamide and 2-acrylamido-2-methylpropanesulfonic acid into the initial reaction solution obtained in the step S2, stirring and dissolving, regulating the pH to 7.9, adding an acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer (MW: 65 ten thousand), stirring and dispersing at a rotating speed of 300r/min, continuously adding disodium ethylenediamine tetraacetate dihydrate and triallylamine, and uniformly stirring to form a suspension system;
s4: introducing nitrogen into the suspension system obtained in the step S3 to remove oxygen, adding hexadecyl dimethyl allyl ammonium chloride until the oxygen content in the system is less than or equal to 0.25%, heating to 35 ℃, adding ammonium persulfate and dimethylamine to initiate polymerization, cooling to room temperature of 25 ℃ after reaction for 6 hours, filtering, washing and drying to obtain the dendritic amphiphilic acrylamide copolymer.
The comparative example is identical to example 1, except that: in the preparation process, 2,4, 5-triaminopyridine and tungsten sulfate are not added, and the preparation method specifically comprises the following steps:
s1: the preparation method comprises the following steps of: 9 parts of acrylic acid, 30 parts of acrylamide, 10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 0.5 part of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer with a molecular weight of 12 ten thousand, 0.1 part of ethylenediamine tetraacetic acid iron sodium salt, 0.5 part of pentaerythritol diacrylate, 1.5 parts of hexadecyl dimethyl allyl ammonium chloride, 0.05 part of ammonium persulfate, 0.05 part of sodium sulfite and 120 parts of deionized water;
s2: adding acrylic acid, acrylamide and 2-acrylamido-2-methylpropanesulfonic acid into deionized water, stirring and dissolving, regulating the pH to 7.0, adding an acrylic acid-2-acrylamido-2-methylpropanesulfonic acid copolymer (MW: 12 ten thousand), stirring and dispersing at a rotating speed of 150r/min, continuing adding ethylenediamine tetraacetic acid iron sodium salt and pentaerythritol diacrylate, and stirring uniformly to form a suspension system;
s4: introducing nitrogen into the suspension system obtained in the step S2 to remove oxygen, adding hexadecyl dimethyl allyl ammonium chloride when the oxygen content in the system is less than or equal to 0.25%, heating to 30 ℃, adding ammonium persulfate and sodium sulfite to initiate polymerization, reacting for 5 hours, cooling to room temperature of 25 ℃, filtering, washing and drying to obtain the amphiphilic acrylamide copolymer.
The expansion times of the amphiphilic acrylamide-based copolymer prepared in examples 1 to 5 and comparative example were tested: 0.5g of the amphiphilic acrylamide copolymer prepared in examples 1 to 5 and comparative example was weighed and designated as m 0 Filling into 80 mesh nylon screen filter bag, immersing into 500mL of saline water (NaCl solution) with mineralization of 60000ppm and temperature of 130deg.C, maintaining for 48 hr, taking out the filter bag, wiping off excessive water on microsphere surface with filter paper, weighing, recording as mt, and determining according to formula m t -m 0 /m t The expansion times of the amphiphilic acrylamide-based copolymers prepared in examples 1 to 5 and comparative example were calculated.
Viscosity retention measurement was performed on the amphiphilic acrylamide-based copolymer prepared in examples 1 to 5 and comparative example: 0.5g of the amphiphilic acrylamide copolymer prepared in examples 1 to 5 and comparative example was weighed, dissolved in 500mL of deionized water, and its apparent viscosity m was measured at 25℃using a cloth viscometer 1 Then 30g NaCl (high salt environment with simulated mineralization of 60000 ppm) is added into the solution under the water bath condition of 130 ℃, after stirring and dissolving, the solution is kept warm and kept stand for 3h, and the apparent viscosity m is measured 2 According to 100%. Times.m 2 /m 1 And calculating the viscosity retention rate under the high-temperature and high-salt conditions.
The test results are shown in the following table:
from the above table, the highly branched dendritic amphiphilic acrylamide copolymer prepared by taking 2,4, 5-triaminopyridine as a branched core in examples 1-5 has remarkable high temperature resistance and salt resistance, and the particle size of the product is adjustable, so that the use requirements of different oil reservoir cracks under extreme conditions are met.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.

Claims (9)

1. A method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method, which is characterized by comprising the following steps:
s1: the preparation method comprises the following steps of: 3-6 parts of 2,4, 5-triaminopyridine, 9-18 parts of acrylic acid, 0.05-0.1 part of tungsten sulfate, 30-50 parts of acrylamide, 10-22.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 0.5-1.5 parts of dispersing agent, 0.1-0.5 part of metal chelating agent, 0.5-3 parts of chain branching agent, 1.5-7.5 parts of cetyl dimethyl allyl ammonium chloride, 0.05-0.1 part of oxidant, 0.05-0.1 part of reducing agent and 120-150 parts of deionized water;
s2: adding 2,4, 5-triaminopyridine and acrylic acid into deionized water, stirring and dissolving, adding tungsten sulfate, and stirring at 80-90 ℃ for 1.5-2h to obtain an initial reaction solution;
s3: adding acrylamide and 2-acrylamide-2-methylpropanesulfonic acid into the initial reaction solution obtained in the step S2, stirring and dissolving, regulating the pH value to 6-8, adding a dispersing agent, stirring and dispersing at the rotating speed of 150-300r/min, continuously adding a metal chelating agent and a chain branching agent, and uniformly stirring to form a suspension system;
s4: introducing nitrogen into the suspension system obtained in the step S3 to remove oxygen, adding hexadecyl dimethyl allyl ammonium chloride when the oxygen content in the system is less than or equal to 0.25%, heating to 30-35 ℃, adding an oxidant and a reducing agent to initiate polymerization reaction, cooling to room temperature of 25 ℃ after 5-6 hours of reaction, filtering, washing and drying to obtain the dendritic amphiphilic acrylamide copolymer;
the chain branching agent is one or more of pentaerythritol diacrylate, glycerol diacrylate, trimethylolpropane diacrylate, dipropylene glycol diacrylate and triallylamine.
2. The method for preparing a dendritic amphiphilic acrylamide copolymer by a suspension polymerization method according to claim 1, wherein the dispersing agent is an acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer and has a molecular weight of 10-65 ten thousand.
3. The method for preparing a dendritic amphiphilic acrylamide copolymer according to claim 1, wherein the metal chelating agent is one or more of disodium ethylenediamine tetraacetate, disodium ethylenediamine tetraacetate dihydrate and ferric ethylenediamine tetraacetate sodium salt.
4. The method for preparing a dendritic amphiphilic acrylamide copolymer according to claim 1, wherein the oxidant is one or more of ammonium persulfate, potassium persulfate, permanganate and hydrogen peroxide.
5. The method for preparing the dendritic amphiphilic acrylamide copolymer by using the suspension polymerization method according to claim 1, wherein the reducing agent is one or more of sodium sulfite, mercaptosuccinic acid, cobalt dichloride, hydroxylamine and dimethylamine.
6. The method for preparing a dendritic amphiphilic acrylamide copolymer according to claim 1, wherein in S3, the pH is adjusted to 7.0 to 7.9.
7. The method for preparing the dendritic amphiphilic acrylamide copolymer by using the suspension polymerization method according to any one of claims 1 to 6, wherein the particle size of the dendritic amphiphilic acrylamide copolymer prepared by the method is 35-400 μm, and the molecular weight is 3500-4500 ten thousand.
8. An application of the dendritic amphiphilic acrylamide copolymer prepared by the method according to any one of claims 1-6 in deep profile control of a high-temperature high-salt oil reservoir.
9. The use according to claim 8, wherein the dendritic amphiphilic acrylamide copolymer has an expansion ratio of up to 22.7 and a viscosity retention ratio of up to 78.4% at a mineralization of 60000ppm and a temperature of 130 ℃.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07109352A (en) * 1993-10-15 1995-04-25 Toyota Central Res & Dev Lab Inc Crosslinked star-shaped nylon and production of molding thereof
US6124396A (en) * 1995-07-07 2000-09-26 Nalco Chemical Company Branched water-soluble acrylamide copolymers of high molecular weight and process for manufacturing them
CN110105494A (en) * 2019-05-28 2019-08-09 安徽天润化学工业股份有限公司 A kind of preparation method of hyperbranched amphoteric ionic polyacrylamide and its application in oilfield exploitation
CN111592616A (en) * 2020-06-28 2020-08-28 安徽天润化学工业股份有限公司 Preparation method of nanoscale hyperbranched hydrophobically associating polyacrylamide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07109352A (en) * 1993-10-15 1995-04-25 Toyota Central Res & Dev Lab Inc Crosslinked star-shaped nylon and production of molding thereof
US6124396A (en) * 1995-07-07 2000-09-26 Nalco Chemical Company Branched water-soluble acrylamide copolymers of high molecular weight and process for manufacturing them
CN110105494A (en) * 2019-05-28 2019-08-09 安徽天润化学工业股份有限公司 A kind of preparation method of hyperbranched amphoteric ionic polyacrylamide and its application in oilfield exploitation
CN111592616A (en) * 2020-06-28 2020-08-28 安徽天润化学工业股份有限公司 Preparation method of nanoscale hyperbranched hydrophobically associating polyacrylamide

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