CN111073198B - Copolymerization nanocomposite and preparation method and application thereof - Google Patents

Copolymerization nanocomposite and preparation method and application thereof Download PDF

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CN111073198B
CN111073198B CN201911365985.7A CN201911365985A CN111073198B CN 111073198 B CN111073198 B CN 111073198B CN 201911365985 A CN201911365985 A CN 201911365985A CN 111073198 B CN111073198 B CN 111073198B
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柯扬船
王东银
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China University of Petroleum Beijing
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    • 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
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    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
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Abstract

The invention discloses a copolymerization nano composite material and a preparation method and application thereof. The preparation method of the copolymerization nano composite material comprises the following steps: 1) mixing an amide monomer, a benzenesulfonate monomer and a solvent, adding a cross-linking agent, and stirring to obtain a comonomer reaction system; 2) adjusting the pH value of the comonomer reaction system obtained in the step 1), adding an inorganic nano phase, and stirring to obtain a reactant mixed system; 3) mixing and stirring the reactant mixed system obtained in the step 2), an oxidant and a reducing agent for a certain time under an anaerobic condition, and then heating for copolymerization reaction to obtain the copolymerization nano composite material. The invention also provides a copolymerization nano composite material and application thereof. The copolymerization nano composite material prepared by the method is more beneficial to redispersion of the nano particles in the polymer in the actual industrial application process, so that the copolymerization nano composite material and the preparation method thereof can realize industrial application.

Description

Copolymerization nanocomposite and preparation method and application thereof
Technical Field
The invention relates to the technical field of oilfield chemical treatment agents of oil and gas engineering. More particularly, it relates to a copolymerized nano composite material and its preparation method and application.
Background
In the well drilling and well completion and fracturing engineering of oil and gas engineering, viscous fluid for dissolving various treating agents is required to meet the requirements of engineering quality and high efficiency. In the drilling and development of oil and gas wells, the viscosity of the drilling fluid and completion fluid is utilized to carry cuttings, protect the well wall from being stable and balance the pressure characteristics of stratum and pore space, so that an oil and gas production well with high quality integrity is built, and the oil and gas production operation, the oil and gas reservoir transformation project or the recovery efficiency improvement measure are implemented through the built oil and gas well, so that the aims of greatly increasing the oil and gas yield and the yield are fulfilled.
In the existing oil and gas well engineering such as well drilling and completion engineering, water is adopted to dissolve various treating agents to prepare water-based well drilling and completion fluid for the oil and gas engineering, the problems of shaft shrinkage, collapse and incompleteness thereof caused by the oil and gas engineering are long-term worldwide problems, and the problems of instability and functionality of the well drilling and completion fluid in the prior art always influence the production and yield stability of the oil and gas well. It is clear that the completion fluids of existing oil and gas wells are key working fluid fluids for stable production of the completed wells, and the main properties of the working fluid fluids depend on the treatment agents used in oil and gas engineering to regulate or maintain the viscosity and functionality of the working fluid fluids, such as completion fluids.
The treating agent of the existing oil and gas engineering technology is mainly an organic and inorganic material or a composite material system thereof, is a soluble linear organic micromolecule or a high molecular compound, is used for improving the viscosity of a working fluid and the efficiency of carrying rock debris, generates the effect of protecting the well wall and the reservoir permeability, and greatly reduces the viscosity of a drilling and completion fluid under the environment of underground high-concentration electrolyte, high temperature and high pressure, wherein the chain or functional group of the linear organic micromolecule or the high molecular is easy to break; under the environment of high-temperature and high-pressure activation and catalytic activity of underground high-concentration salts and salts, unsaturated bonds of linear organic small molecules or polymer functional groups or molecular chains are subjected to physical erosion or double layer compression action of the salts (Liu Z, et al, Nitrogen-treated word-like functionalized Carbon dioxide for enhancing the area-catalyzed capacitance of electric double layer reactors, Carbon,117(2017):163-173), and the reaction of the molecular groups or molecular chains is initiated, which all cause the performance of the treating agent to be reduced, cannot be effectively changed for a long time or uncontrollable performance, and obviously and directly influences the performance of the drilling completion fluid and the functional intelligence of the drilling completion fluid.
It can be seen that the linear structure treating agents used in the prior art for a long time have significant problems of uncontrollable structural variation and structural destruction in the complex environment in the well, and related technical reports (Hu X, et al, "Synthesis and characterization of a β -cyclic modified polyacrylic amide and materials and biological properties by hybridization with silicon nanoparticles A: physical and Engineering applications, 548(2018):10-18) can be seen. Therefore, in the prior art, an inorganic nano phase is added into the linear organic molecule or the polymer chain to improve the high temperature resistance of the linear organic molecule or the polymer chain, and the high temperature degradation resistance and stability of the organic molecule or the polymer chain are improved through the adsorption and high temperature degradation blocking effects of the inorganic nano dispersed phase and the organic molecule or the polymer chain, so that the high temperature resistance and salt resistance of the drilling and completion fluid are improved. For example, the invention patent [ publication No. CN104109525A ] discloses a preparation method of polyacrylamide nano composite fracturing fluid, which adopts an organic long-chain intercalating agent to carry out intercalation reaction with layered silicate, and the intercalation reaction is mixed with nitrate to form an inorganic nano phase, and then the inorganic nano phase and polyacrylamide monomer are subjected to in-situ polymerization composite reaction to prepare a composite material treating agent, and the composite material treating agent has the characteristics of high temperature resistance, shear resistance and the like. However, the problems of controllable dispersibility of the inorganic nano-phase in the organic molecule or the polymer chain or controllable dispersion and long-term stability of the inorganic nano-phase in the application of the organic molecule or the polymer chain in a complex oil and gas well can reduce the oil and gas channel conductivity of the oil and gas well constructed in the complex oil and gas reservoir and reduce the oil and gas drilling efficiency.
The prior art designs a large number of random, block and graft copolymerization macromolecular chain structures and a method for preparing a copolymerization nano composite treating agent, so as to improve the high-temperature resistance and salt resistance of the treating agent, and because of the difference of reactivity ratios of comonomers, difficulty in controlling the distribution of molecular weight and agglomeration of inorganic nano phases in the copolymer, the obtained copolymer or the nano composite treating agent thereof often has the problems of long-term stability and long-term durability of salt resistance although the copolymer or the nano composite treating agent thereof has certain high temperature resistance, and furthermore, in the prior art, sulfonic acid groups and phenyl units are introduced into a macromolecular main chain to form the copolyamide and the nano composite material thereof, and the obtained treating agent has the problems of easy degradation, instability and poor salt resistance of a molecular chain for a long.
Obviously, the problems of poor high-temperature resistance and salt resistance and poor molecular chain degradation and long-acting stability of the existing treating agent technology exist for a long time, and the fundamental reason is that the creative problem of the chain structure design is not solved.
Accordingly, the present invention provides a copolymerized nanocomposite material, a method for preparing the same, and applications thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide a copolymerization nano composite material, a preparation method and application thereof, and aims to solve the problems of molecular structure and long-acting property of a treating agent and drilling and completion of oil and gas engineering caused by the treatment agent in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a copolymerization nano composite material comprises the following steps:
1) mixing an amide monomer, a benzenesulfonate monomer and a solvent, adding a cross-linking agent, and stirring to obtain a comonomer reaction system;
2) adjusting the pH value of the comonomer reaction system obtained in the step 1), adding an inorganic nano phase, and stirring to obtain a reactant mixed system;
3) mixing and stirring the reactant mixed system obtained in the step 2), an oxidant and a reducing agent for a certain time under an anaerobic condition, and then heating for copolymerization reaction to obtain the copolymerization nano composite material.
According to the preparation method provided by the invention, a mixed composition reaction system consisting of an amide monomer, a benzenesulfonate monomer and an inorganic nano-phase is adopted, in-situ copolymerization and crosslinking reaction are carried out to form a copolymerization nano-composite material treating agent, and the problems of high temperature resistance, long-acting stability and multifunction of the treating agent are solved by designing a high-molecular block main chain structure and chain crosslinking and in-situ nano-uniform dispersibility of the high-molecular block main chain structure, wherein the prepared copolymerization nano-composite material is a polyacrylamide copolymerization nano-composite material. In addition, a large number of experiments prove that when other reaction conditions are the same and benzene sulfonate monomers are not used, the obtained nano composite material has poor apparent viscosity, temperature resistance and salt resistance.
Preferably, the amide monomers in step 1) are acrylamide monomers; further, the acrylamide monomer may be a crystalline monomer.
Preferably, the benzenesulfonate monomers in step 1) are p-benzenesulfonate monomers, o-benzenesulfonate monomers or m-benzenesulfonate monomers; more preferably, the benzenesulfonate monomers in step 1) are sodium p-benzenesulfonate monomers, sodium o-benzenesulfonate monomers or sodium m-benzenesulfonate monomers; further, the sodium p-toluenesulfonate monomer is a sodium p-toluenesulfonate monomer.
Preferably, the mass ratio of the amide monomer, the benzenesulfonate monomer and the solvent in step 1) is 1: 0.1-0.5: 3.0 to 13.
Preferably, the solvent in step 1) is pure water.
Preferably, the crosslinking agent in step 1) is a reaction product of isocyanate methacrylate and beta-cyclodextrin. The novel water-soluble cyclodextrin cross-linking agent used in the invention has novel structure, strong temperature resistance, good salt resistance and environmental friendliness; in addition, the experiments of the invention prove that when the cross-linking agent N, N-Methylene Bisacrylamide (MBA) is used for replacing the reaction product of isocyanate methacrylate and beta-cyclodextrin, the apparent viscosity, the temperature resistance and the salt resistance of the obtained nano composite material are all reduced.
Preferably, the method for preparing the reaction product of isocyanate methacrylate and beta-cyclodextrin comprises the following steps:
i) dissolving the pretreated beta-cyclodextrin in the pretreated N, N-dimethylacetamide in a nitrogen atmosphere to obtain a mixed solution A;
ii) adding isocyanate methacrylate into the mixed solution A in a nitrogen atmosphere, and stirring for 10-50 min to obtain a mixed solution B;
iii) adding stannous isooctanoate into the mixed solution B in nitrogen atmosphere, stirring and reacting for 0.5-3.0 h at room temperature, heating to 30-70 ℃, and keeping the temperature to react for 3-9 h to obtain reaction liquid;
iv) treating the reaction liquid by a rotary evaporator to remove most of N, N-dimethylacetamide, adding acetone at the temperature of 0-15 ℃ for crystallization and precipitation, and performing suction filtration to obtain a product A;
v) dissolving the product A in water, adding diethyl ether or acetone at the temperature of 0-15 ℃ for recrystallization, and performing suction filtration to obtain a product B; and drying the product B to obtain a reaction product of the isocyanate methacrylate and the beta-cyclodextrin.
Compared with the prior art, in the preparation method of the reaction product of the cross-linking agent isocyanate methacrylate and the beta-cyclodextrin, N-dimethylacetamide is used as a solvent instead of N, N-dimethylformamide, in addition, after the reaction liquid is obtained, the residual N, N-dimethylacetamide in the reaction liquid is removed, then the acetone is cooled and precipitated, and the yield of the reaction product of the isocyanate methacrylate and the beta-cyclodextrin is over 81.3%.
Preferably, the pretreatment process of the pretreated beta-cyclodextrin in the step i) comprises three times of recrystallization purification of the beta-cyclodextrin and vacuum drying at 35-60 ℃ for 30-72 h.
Preferably, the pretreatment process of the pretreated N, N-dimethylacetamide in the step i) includes subjecting N, N-dimethylacetamide to an anhydrous drying treatment.
Preferably, the mass-to-volume ratio of the pretreated beta-cyclodextrin to the pretreated N, N-dimethylacetamide in step i) is 1g: 2-15 mL.
Preferably, the mass ratio of the isocyanate methacrylate to the pretreated beta-cyclodextrin in the step ii) is 1: 20-80.
Preferably, the volume ratio of the stannous isooctanoate to the mixed solution B in the step iii) is 1: 300-900.
Preferably, the drying condition of the product B in the step v) is vacuum drying for 30 to 72 hours at the temperature of between 35 and 60 ℃.
Preferably, the mass of the cross-linking agent in the step 1) is 0.5-1.0 wt% of the sum of the mass of the acrylamide monomer and the mass of the sodium p-styrene sulfonate monomer.
Preferably, the stirring conditions in step 1) are: stirring at 400-450 rpm/min for 30-240 min at room temperature.
Preferably, the pH value in the step 2) is 8-9.
Preferably, the mass of the inorganic nano-phase in the step 2) is 0.5wt% -5.0 wt% of the sum of the mass of the acrylamide monomer and the mass of the sodium p-styrene sulfonate monomer.
Preferably, the preparation method of the inorganic nanophase in the step 2) includes the steps of:
mixing the layered silicate and water according to the mass ratio of 1: 10-20, and stirring for 30-40 min at the conditions of 400-450 rpm/min and room temperature to form a layered silicate suspension swelling system;
mixing the layered silicate swelling system with an intercalation agent with the same mass as layered silicate at the temperature of 50-55 ℃, and stirring and reacting for 8-10 h at the rotating speed of 400-450 rpm/min to form a layered silicate intercalation reaction system;
and carrying out suction filtration, washing, drying, grinding and crushing on the phyllosilicate intercalation reaction system to obtain the inorganic nano phase.
Preferably, the layered silicate may be a silicate mineral having a layered crystal structure and a sheet crystal form, and in a specific embodiment, the layered silicate may be montmorillonite, clay, or the like, or a mixed system thereof.
Preferably, the intercalating agent is a cationic surfactant; further, the cationic surfactant is butyl methacrylate hexadecylammonium bromide (DMB).
Preferably, the interlayer spacing of the phyllosilicate in the phyllosilicate intercalation reaction system is 1.9 nm-4.0 nm; in particular, the larger the interlayer distance of the layered silicate is, the smaller the force between the layers is, and the layered silicate can be dispersed again by the weak force of the organic molecules or the high molecules of the polymer.
Preferably, the mixing and stirring time in the step 3) is 10min to 50 min.
Preferably, the conditions of the copolymerization reaction in step 3) are: the temperature of the copolymerization reaction is 75-85 ℃, and when the reaction temperature is not increased any more, the reaction temperature is kept for 6-8 h.
Preferably, the oxidant in step 3) is ammonium persulfate or potassium persulfate.
Preferably, the reducing agent in step 3) is sodium bisulfite or sodium bisulfite.
Preferably, said step 3) is carried outThe oxygen environment is realized by the following steps: introducing inert gas into the polymerization kettle to form an oxygen-free environment, wherein nitrogen is mostly used in practical operation, for example, the nitrogen is kept introduced for 30-45 min to remove air in the polymerization kettle, and in a specific embodiment, the purity of the used nitrogen is 98.99-99.999%, the pressure is 0.50-0.55 MPa, and the flow is 40m3/h～50m3/h。
Preferably, after the copolymerization reaction in step 3) is completed, the process further comprises the steps of drying, granulating and crushing.
Before testing the performance of the copolymerization nano composite material, the copolymerization nano composite material can be processed by adopting the following steps: the copolymerization reaction product is pressed into blocks, the copolymerization nano composite material particles with the particle size of 4 mm-6 mm are obtained through coarse granulation and fine granulation, then the copolymerization nano composite material particles are dried, crushed and put in a warehouse for testing, in a specific embodiment, the copolymerization nano composite material particles are crushed, then are packaged and put in the warehouse through a 200-mesh sieve, the drying temperature is controlled to be 70-75 ℃, and the fluctuation of +/-2 ℃ can be realized.
The invention also provides a copolymerization nano composite material prepared by the preparation method.
The invention also provides application of the copolymerization nano composite material prepared by the preparation method in preparing a treating agent in the fields of sewage treatment, papermaking or petroleum drilling and production and the like.
Preferably, the copolymeric nanocomposite is used in the preparation of oil and gas production fracturing fluids.
The copolymerization nano composite material provided by the invention can be used in industrial processes, particularly oil and gas engineering or well drilling and completion engineering processes, the generated copolymer phase is uniform in nano dispersion, high in molecular weight, good in water solubility and tackifying effect, the copolymerization nano composite material treating agent has comprehensive characteristics of high temperature resistance, salt resistance, shear resistance and pollution resistance, and is used as a well drilling and completion fluid treating agent for oil and gas engineering well drilling and completion engineering, particularly a well drilling and completion fluid with the high temperature resistance of 100-200 ℃.
In addition, unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.
The invention has the following beneficial effects:
(1) in the preparation method provided by the invention, a composite system of inorganic nano-phase and copolymer monomer and cross-linking agent is subjected to in-situ initiated copolymerization, intercalation reaction and cross-linking reaction of the cross-linking agent under the initiation reaction of an initiator and free radicals to prepare a copolymerized nano-composite material; the in-situ initiated copolymerization reaction generates nanometer uniform dispersion, high temperature resistance, salt resistance or high-efficiency nanometer effect by controlling the suspension stability, reaction rate and uniform heat release characteristic of a copolymer monomer and inorganic nanometer phase reaction system;
(2) the copolymerization nano composite material prepared by the method is more beneficial to redispersion of the nano particles in the polymer in the actual industrial application process, so that the copolymerization nano composite material and the preparation method thereof can realize industrial application.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows the beta-CD-AOI obtained in example 1 of the present invention2FTIR chart of (1).
FIG. 2 shows the beta-CD-AOI obtained in example 1 of the present invention2Is/are as follows1H-NMR chart.
FIG. 3 shows the apparent viscosity test curves of the copolymerized nanocomposites of different concentrations in inventive test examples 1-6 and comparative test examples 1-6.
FIG. 4 is a graph showing the variation trend of the temperature resistance test curves of the copolymerized nanocomposites with different concentrations in test examples 7-27 of the present invention and comparative test examples 7-13.
FIG. 5 is a graph showing the trend of the salt resistance test curve of the copolymerized nanocomposites with different concentrations in test examples 28 to 37 of the present invention and comparative test examples 14 to 18.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the invention, the preparation method is a conventional method if no special description is provided; the starting materials used are commercially available from published sources unless otherwise specified.
Example 1
The embodiment provides a preparation method of a cross-linking agent, which comprises the following steps:
i) putting 10g (namely 7.6mmol) of industrial-grade beta-cyclodextrin powder which is subjected to three-time recrystallization purification and vacuum drying at 45 ℃ for 48 hours into a 100mL three-neck flask, then adding 50mL of N, N-Dimethylacetamide (DMAC) purified liquid subjected to water removal treatment, and stirring at room temperature under the protection of nitrogen until the solid is completely dissolved to form a mixed solution A;
ii) 2.14g (i.e. 15.2mmol) of 2-isocyanoethyl Acrylate (AOI) are added dropwise to the beta-cyclodextrin solution system obtained in step i) using a constant pressure dropping funnel2) Continuously stirring for 30min under the nitrogen atmosphere to obtain a mixed solution B;
iii) under the protection of nitrogen, adding 80 mu L of stannous isooctanoate purified liquid by using a microsyringe, keeping the temperature and continuously stirring for reaction for 1.5h, then slowly heating the reaction to 50 ℃, and keeping the temperature for reaction for 8h to form reaction liquid;
iv) removing most DMAC (dimethylacetamide) in the reaction solution prepared in the step iii) by using a rotary evaporator, adding 400mL of acetone with the temperature of 0 ℃ for precipitation, and performing suction filtration to obtain a product A;
v) placing the product A prepared in the step iv) into a 250mL beaker, adding 10mL of deionized water to dissolve the product A, adding 200mL of acetone with the temperature of 0 ℃ after the product A is completely dissolved to perform recrystallization, and repeating the recrystallization for three times so as to wash away residual DMAC and AOI2Residual liquid is obtained to obtain a product B; drying the product B in a vacuum drying oven at 45 ℃ for 48h to prepare a reaction product (beta-CD-AOI) of isocyanate methacrylate and beta-cyclodextrin2) The yield was 81.3%. By using existing devices1H-NMR and FTIR instruments characterize the product molecular structure (test junction)See fig. 1 and 2). 1705cm in FIG. 1-1And 1595cm-1Represents the characteristic peak of isocyanate methacrylate, which indicates that the novel crosslinking agent has been synthesized. The chemical shifts of 1, CD:2-6,7-8, in FIG. 2 further confirm the accurate synthesis of the novel cross-linking agents.
Example 2
The embodiment provides a preparation method of a cationic surfactant butyl methylbutenoate hexadecylammonium bromide (DMB), which comprises the following steps:
a) dissolving 10.38g (66 mmol) of 2- (dimethylamino) ethyl methacrylate in 100mL of absolute ethyl alcohol, and continuously stirring for 15min at the temperature of 50 ℃ to form a reaction system;
b) dropwise adding 20.15g (66 mmol) of bromohexadecane into the reaction system prepared in the step a) by using a constant-pressure dropping funnel to form a mixed reaction system, and stirring for 24 hours at the temperature of 50 ℃ to obtain a reaction solution;
c) decompressing and concentrating the reaction liquid prepared in the step b) by using a rotary evaporator, and then carrying out acetone recrystallization, suction filtration, washing and vacuum drying treatment to obtain a snow white powdery solid product, namely DMB.
Example 3
The embodiment provides a preparation method of an inorganic nano phase, which comprises the following steps:
adding 3.33g of industrial-grade montmorillonite into a 250mL three-neck flask containing 100mL of deionized water, ultrasonically dispersing for 30min, and fully stirring at room temperature to uniformly disperse the montmorillonite to form montmorillonite suspension;
dissolving 3.33g DMB prepared in example 2 in 50mL deionized water, dropwise adding the DMB into the montmorillonite suspension by using a constant-pressure dropping funnel, uniformly mixing, heating to 50 ℃, continuously stirring for 24 hours, and carrying out intercalation reaction to form an intercalation reaction system;
and (2) carrying out suction filtration on the intercalation reaction system, alternately washing the intercalation reaction system with ethanol and water for three times, drying the intercalation reaction system in a vacuum drying oven at 50 ℃ for 24 hours, crushing, grinding and sieving to obtain an inorganic nano-phase powder product, testing a sample diffraction curve by using X-rays (lambda is 0.1540nm), and calculating the interlayer spacing and the biodegradability of the layered compound, wherein the table 1 shows. The inorganic nanophase prepared in this example showed two peaks in an X-ray diffraction (XRD) test, and the interlayer spacing was calculated according to the diffraction angle and the bragg equation.
TABLE 1 physical Properties of inorganic nanophase
Figure BDA0002338433160000091
Example 4
The embodiment provides a preparation method of a copolymerization nano composite material, which comprises the following steps:
1) 26.3307g of acrylamide, 6.6666g of sodium p-styrenesulfonate, 0.3333g of the reaction product of isocyanate methacrylate prepared in example 1 and beta-cyclodextrin (beta-CD-AOI)2) And relative to the acrylamide monomer and the sodium p-styrenesulfonate monomer with the total mass of 1.0wt%, the inorganic nano-phase prepared in the embodiment 3 is sequentially added into a 250mL three-neck flask containing 100mL of deionized water and fully stirred for 1h at the rotating speed of 400rpm/min, so as to obtain a comonomer reaction system;
2) adjusting the pH value of the comonomer reaction system obtained in the step 1) to be 8-9 by adopting 1mol/L sodium hydroxide solution, and adding an initiator (namely 68.46mg of ammonium persulfate and 31.22mg of sodium bisulfite are mixed) which is 0.3 wt% of the total mass ratio of the acrylamide monomer and the sodium p-styrene sulfonate monomer to form a reactant mixed system;
3) introducing nitrogen gas, stirring for 30min, heating the reactant mixed system to 50 ℃, reacting for 8h to obtain a product, washing the product by using a mixed solution of ethanol and water in a mass ratio of 9:1 for three times, and performing vacuum drying, crushing and sieving on the treated product to obtain the copolymer nano composite material powder.
Example 5
This example provides a method for preparing a copolymerized nanocomposite, which is similar to example 4, except that: the mass of the inorganic nanophase in the step 1) is 0.5wt% relative to the total mass of the acrylamide monomer and the sodium p-styrenesulfonate monomer.
Example 6
This example provides a method for preparing a copolymerized nanocomposite, which is similar to example 4, except that: the mass of the inorganic nanophase in the step 1) is 2.0 wt% relative to the total mass of the acrylamide monomer and the sodium p-styrenesulfonate monomer.
Example 7
This example provides a method for preparing a copolymerized nanocomposite, which is similar to example 4, except that: 0.3333g of the reaction product of isocyanate methacrylate and beta-cyclodextrin prepared in example 1 (. beta. -CD-AOI) in step 1)2) The reaction was changed to 0.3333g N, N-Methylenebisacrylamide (MBA).
Comparative example 1
This comparative example provides a method of preparing a neat copolymer treatment, the procedure being the same as example 4, except that: the mass of the inorganic nano-phase in the step 1) is 0wt% relative to the total mass of the acrylamide monomer and the sodium p-styrenesulfonate monomer.
Comparative example 2
This comparative example provides a method of preparing a neat copolymer treatment, the procedure being the same as example 4, except that: 0.3333g of the reaction product of isocyanate methacrylate and beta-cyclodextrin prepared in example 1 (. beta. -CD-AOI) in step 1)2) The mass of the inorganic nanophase was 0wt% relative to the total mass of acrylamide monomer and sodium p-styrenesulfonate monomer, instead of 0.3333g N, N-Methylenebisacrylamide (MBA).
Test examples 1 to 6
Test examples 1-6 provide a method for preparing a tackifying solution of a copolymer nanocomposite treating agent and testing the apparent viscosity thereof, comprising the following steps:
100mg, 300mg, 500mg, 700mg, 900mg and 1100mg of the copolymerized nanocomposite material containing 1wt% of the inorganic nanophase prepared in example 4 were placed in 500mL beakers containing 100mL of deionized water, respectively, to form a mixed suspension system;
stirring the mixed suspension system at room temperature for 24 hours, stopping stirring after the copolymerization nano composite material is completely dissolved, standing at room temperature for 5 hours to obtain a tackifying solution of the treatment agent of the copolymerization nano composite material, and testing the performance of the tackifying solution;
the apparent viscosity was measured with a DV-79+ PRO digital viscometer under the conditions of a constant temperature water bath of 35 + -1 deg.C, B spindle, 70rpm, and the results are shown in Table 2 and FIG. 3. As can be seen from Table 2 and FIG. 3, as the concentration of the viscosifying solution of the copolymeric nanocomposite treating agent increases, the apparent viscosity thereof increases in sequence; wherein ASD in fig. 3 represents the neat polymer and ASD/x wt% O-Mt (x ═ 1.0) represents the addition of a copolymeric nanocomposite containing a certain amount of inorganic nanophase.
TABLE 2 apparent viscosity of the Copolymer nanocomposite treating agent viscosifying solution
Figure BDA0002338433160000111
Test examples 7 to 27
Test examples 7-27 provide a method for testing and characterizing the temperature resistance of a copolymerized nanocomposite solution, comprising the steps of:
firstly, 500mg of the copolymerized nanocomposite material containing 0.5wt% of the inorganic nanophase obtained in example 5, 500mg of the copolymerized nanocomposite material containing 1.0wt% of the inorganic nanophase obtained in example 4, and 500mg of the copolymerized nanocomposite material containing 2 wt% of the inorganic nanophase obtained in example 6 were respectively added into a 500mL beaker containing 100mL of deionized water and mixed and dissolved to obtain a mixed and dissolved system;
secondly, stirring the mixed dissolution system at room temperature for 24 hours respectively, stopping stirring after the copolymerization nanocomposite is completely dissolved, standing at room temperature for 5 hours, and testing the viscosity of the copolymerization nanocomposite;
finally, the apparent viscosity was measured by DV-79+ PRO digital viscometer in a water bath at constant temperature (temperature set to 35. + -.1 ℃, 45. + -.1 ℃, 55. + -.1 ℃, 65. + -.1 ℃, 75. + -.1 ℃, 85. + -.1 ℃, 95. + -.1 ℃ respectively), rotor B, 70rpm, and the results are shown in Table 3 and FIG. 4. As can be seen from Table 3 and FIG. 4, the temperature resistance of the copolymerized nanocomposite solution was the best when the inorganic nanophase content was 1.0 wt%; wherein ASD in fig. 4 represents the neat polymer and ASD/x wt% O-Mt (x ═ 0.5, 1.0, 2.0) represents the addition of a copolymeric nanocomposite containing a certain amount of inorganic nanophase.
TABLE 3 temperature resistance test results of the copolymerized nanocomposite solution
Figure BDA0002338433160000121
Figure BDA0002338433160000131
Test examples 28 to 37
Test example 28 to test example 37 provide a method for testing the salt resistance of a solution characterizing a copolymerized nanocomposite, comprising the steps of:
first, 500mg of the co-polymer nanocomposite containing 1.0wt% of the inorganic nanophase obtained in example 4 and 500mg of the co-polymer nanocomposite containing 2 wt% of the inorganic nanophase obtained in example 6 were added to 500mL series of beakers containing 100mL of the sodium chloride salt solution to form mixed solutions, the concentrations of the sodium chloride salt solution in the series of beakers being 200mg/100mL, 400mg/100mL, 600mg/100mL, 800mg/100mL, and 1000mg/100mL, respectively;
then, stirring the mixed solution system at room temperature for 24 hours to completely dissolve the copolymerization nano composite material, stopping stirring, and standing at room temperature for 5 hours;
finally, the apparent viscosity and water loss of the mixed solution were measured using a DV-79+ PRO digital viscometer under conditions of constant temperature water bath 35. + -. 1 ℃ with a B spindle at 70rpm, and the results are shown in Table 4 and FIG. 5. As can be seen from Table 4 and FIG. 5, when the content of the inorganic nano-phase is 1.0wt%, the salt resistance of the copolymerized nanocomposite solution is the best; wherein ASD in fig. 5 represents the neat polymer and ASD/x wt% O-Mt (x ═ 1.0, 2.0) represents the addition of a copolymeric nanocomposite containing a certain amount of inorganic nanophase.
TABLE 4 salt resistance test results of the copolymerized nanocomposite solution
Figure BDA0002338433160000132
Figure BDA0002338433160000141
Test example 38
The test example provides a high-temperature roller heating furnace test characterization method of a copolymerization nano composite material, which comprises the following steps:
firstly, 1g of the copolymerized nanocomposite containing 1wt% of the inorganic nanophase prepared in example 4 was placed in a 500mL beaker containing 400mL of deionized water to form a mixed suspension system;
then stirring the mixed suspension system at room temperature for 24 hours, stopping stirring after the copolymerized nano composite material is completely dissolved, injecting the uniformly mixed suspension system into an aging kettle, and hot rolling for 24 hours at 120 ℃ by using a GW300 type variable frequency high temperature roller heating furnace of Qingdao Tongchun petroleum instruments Limited company;
finally, the apparent viscosity of the suspension was measured with a DV-79+ PRO digital viscometer in a constant temperature water bath at 35. + -. 1 ℃ with a rotor B at 70rpm, and the results are shown in Table 5. The test result shows that the nano composite material is suitable for being used as an electrochemical treatment agent for oil and gas well engineering oil.
TABLE 5 high temperature roller oven test results for co-polymeric nanocomposites
Comparative test example 19 Test example 38
Sample concentration (mg/100mL) 250.0 250.0
Initial apparent viscosity (mPa.s) 15.5 35.0
Hot Rolling temperature (. degree.C.) 120.0 120.0
Hot rolling time (h) 24.0 24.0
Viscosity after Hot Rolling (mPa.s) 3.6 5.4
Comparative test example 1 to comparative test example 6
Comparative test examples 1-6 provide a method for preparing a neat copolymer treatment viscosifying solution and testing its apparent viscosity, comprising the steps of:
100mg, 300mg, 500mg, 700mg, 900mg, 1100mg of the pure copolymer treatment agent containing 0wt% of the inorganic nanophase prepared in comparative example 1 was placed in a 500mL beaker containing 100mL of deionized water to form a mixed suspension system;
stirring the mixed suspension system at room temperature for 24 hours, stopping stirring after full dissolution, standing at room temperature for 5 hours to obtain a pure copolymer treating agent tackifying solution, and testing the performance of the pure copolymer treating agent tackifying solution;
the apparent viscosity of the neat copolymer treatment viscosified solution was measured using a DV-79+ PRO digital viscometer in a constant temperature water bath at 35 + -1 deg.C, B spindle, 70rpm, and the results are compared to the copolymer nanocomposite treatment containing 1wt% inorganic nanophase in Table 2 and FIG. 3.
Comparative test example 7 to comparative test example 13
Comparative test examples 7-13 provide a method for preparing a temperature resistant pure copolymer treatment agent solution and testing the apparent viscosity thereof, comprising the steps of:
adding 500mg of the pure copolymer treating agent containing 0wt% of the inorganic nano-phase prepared in the comparative example 1 into a 500mL beaker filled with 100mL of deionized water for dissolving, stirring at room temperature for 24 hours, stopping stirring after complete dissolution, standing at room temperature for 5 hours to obtain a temperature-resistant pure copolymer treating agent solution, and testing the viscosity of the temperature-resistant pure copolymer treating agent solution;
the apparent viscosity of the temperature-resistant pure copolymer treating agent solution was measured in a constant temperature water bath with a DV-79+ PRO digital viscometer under conditions of rotor B and 70rpm at 35 + -1 deg.C, 45 + -1 deg.C, 55 + -1 deg.C, 65 + -1 deg.C, 75 + -1 deg.C, 85 + -1 deg.C, 95 + -1 deg.C, and the results were compared with the treatment agents for copolymerized nanocomposites containing 0.5wt%, 1.0wt%, and 2.0 wt% of inorganic nanophase, respectively, as shown in Table 3 and FIG. 4.
Comparative test example 14 to comparative test example 18
Comparative test examples 14-18 provide a method of preparing a salt-resistant neat copolymer treatment solution and testing its apparent viscosity, comprising the steps of:
firstly, 500mg of the pure copolymer treating agent containing 0wt% of the inorganic nanophase prepared in comparative example 1 was added to 500mL series of beakers containing 100mL of the sodium chloride solution to form sodium chloride solutions at concentrations of 200mg/100mL, 400mg/100mL, 600mg/100mL, 800mg/100mL and 1000mg/100mL, respectively;
then, stirring the salt solution system at room temperature for 24 hours, stopping stirring after complete dissolution, and standing at room temperature for 5 hours to obtain a salt-resistant pure copolymer treating agent solution;
finally, the apparent viscosity of the salt-resistant pure copolymer treatment agent solution was measured using a DV-79+ PRO digital viscometer in a constant temperature water bath at 35 + -1 deg.C, B spindle, 70rpm, and the results are compared to the copolymerization nanocomposite treatment agent containing 1.0wt% and 2.0 wt% inorganic nanophase, respectively, as shown in Table 4 and FIG. 5.
Comparative test example 19
This comparative test example provides a high temperature roller oven test characterization method for a pure copolymer treatment agent, comprising the steps of:
firstly, 1g of the pure copolymer treating agent containing 0wt% of the inorganic nanophase prepared in comparative example 1 was placed in a 500mL beaker containing 400mL of deionized water to form a mixed suspension system;
then stirring the mixed suspension system at room temperature for 24 hours, stopping stirring after the copolymerized nano composite material is completely dissolved, injecting the uniformly mixed suspension system into an aging kettle, and hot rolling for 24 hours at 120 ℃ by using a GW300 type variable frequency high temperature roller heating furnace of Qingdao Tongchun petroleum instruments Limited company;
finally, the apparent viscosity of the suspension was measured by DV-79+ PRO digital viscometer under the conditions of constant temperature water bath 35 + -1 deg.C, B rotor, 70rpm, and the results are shown in Table 5 in comparison with the treatment agents for the copolymerized nanocomposites, each containing 1.0wt% of the inorganic nanophase.
Test example 39
The test example provides a method for preparing a copolymer nano composite material treating agent solution and testing the apparent viscosity of the copolymer nano composite material treating agent solution, and the method comprises the following steps of:
500mg of the copolymeric nanocomposite containing 1wt% of the inorganic nanophase prepared in example 7 was placed in a 500mL beaker containing 100mL of deionized water to form a mixed suspension system;
stirring the mixed suspension system at room temperature for 24 hours, stopping stirring after the copolymerization nano composite material is completely dissolved, standing at room temperature for 5 hours to obtain a copolymerization nano composite material treating agent solution, and testing the performance of the copolymerization nano composite material treating agent solution;
the apparent viscosity of the suspension was measured by using a DV-79+ PRO digital viscometer under conditions of a water bath at constant temperature (temperature set to 35. + -. 1 ℃ C., 95. + -. 1 ℃ C., respectively), a rotor B, and 70rpm, and the results are shown in Table 6.
Comparative test example 20
This comparative test example provides a method for preparing a pure copolymer treatment solution and testing its apparent viscosity, comprising the steps of:
500mg of the pure copolymer containing 0wt% of the inorganic nanophase prepared in comparative example 2 was placed in a 500mL beaker containing 100mL of deionized water to form a mixed suspension system;
stirring the mixed suspension system at room temperature for 24 hours, stopping stirring after the copolymerization nano composite material is completely dissolved, standing at room temperature for 5 hours to obtain a pure copolymer treating agent solution, and testing the performance of the pure copolymer treating agent solution;
the apparent viscosity was measured by a DV-79+ PRO digital viscometer under conditions of a water bath at constant temperature (temperature set to 35. + -. 1 ℃ C., 95. + -. 1 ℃ C., respectively), a rotor B, and 70rpm, and the results are shown in Table 6.
Test example 40
The test example provides a method for testing and characterizing the salt resistance of a copolymerization nano composite material solution, which comprises the following steps:
firstly, 500mg of the copolymerization nanocomposite containing 1.0wt% of the inorganic nanophase prepared in example 7 was added to a 500mL beaker containing 100mL of a sodium chloride salt solution to form a mixed solution, the concentration of the sodium chloride salt solution in the beaker being 200mg/100 mL;
then, stirring the mixed solution system at room temperature for 24 hours to completely dissolve the copolymerization nano composite material, stopping stirring, and standing at room temperature for 5 hours; the apparent viscosity was measured by a DV-79+ PRO digital viscometer under conditions of a water bath at constant temperature (temperature set to 35. + -. 1 ℃ C., 95. + -. 1 ℃ C., respectively), a rotor B, and 70rpm, and the results are shown in Table 6.
Comparative test example 21
This comparative test example provides a method for testing the salt resistance of a solution of a neat copolymer characterized by the steps of:
firstly, 500mg of the pure copolymer containing 0.0 wt% of the inorganic nanophase prepared in comparative example 2 was added to a 500mL beaker containing 100mL of a sodium chloride salt solution to form a mixed solution, the concentration of the sodium chloride salt solution in the beaker being 200mg/100 mL;
then, stirring the mixed solution system at room temperature for 24 hours to completely dissolve the pure copolymer, stopping stirring, and standing at room temperature for 5 hours; the apparent viscosity was measured by a DV-79+ PRO digital viscometer under conditions of a water bath at constant temperature (temperature set to 35. + -. 1 ℃ C., 95. + -. 1 ℃ C., respectively), a rotor B, and 70rpm, and the results are shown in Table 6.
TABLE 6 comparative parameters for pure and copolymeric nanocomposites synthesized using different classes of crosslinking agents
Figure BDA0002338433160000181
From Table 6, it can be seen that when the cross-linking agent N, N-Methylenebisacrylamide (MBA) is used instead of the reaction product of isocyanate methacrylate and beta-cyclodextrin, the apparent viscosity, temperature resistance and salt resistance of the resulting nanocomposite are all reduced.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (22)

1. A preparation method of a copolymerization nano composite material is characterized by comprising the following steps:
1) mixing an amide monomer, a benzenesulfonate monomer and a solvent, adding a cross-linking agent, and stirring to obtain a comonomer reaction system;
2) adjusting the pH value of the comonomer reaction system obtained in the step 1), adding an inorganic nano phase, and stirring to obtain a reactant mixed system; the mass of the inorganic nano phase is 1wt% of the sum of the mass of the amide monomers and the mass of the benzene sulfonate monomers;
3) mixing and stirring the reactant mixed system obtained in the step 2), an oxidant and a reducing agent for a certain time under an anaerobic condition, and then heating for copolymerization reaction to obtain a copolymerization nano composite material;
the cross-linking agent in the step 1) is a reaction product of isocyanate methacrylate and beta-cyclodextrin;
the preparation method of the reaction product of the isocyanate methacrylate and the beta-cyclodextrin comprises the following steps:
i) dissolving the pretreated beta-cyclodextrin in the pretreated N, N-dimethylacetamide in a nitrogen atmosphere to obtain a mixed solution A;
ii) adding isocyanate methacrylate into the mixed solution A in a nitrogen atmosphere, and stirring for 10-50 min to obtain a mixed solution B;
iii) adding stannous isooctanoate into the mixed solution B in a nitrogen atmosphere, stirring and reacting for 0.5-3.0 h at room temperature, heating to 30-70 ℃, and keeping the temperature to react for 3-9 h to obtain a reaction solution;
iv) treating the reaction liquid by a rotary evaporator, adding acetone at the temperature of 0-15 ℃ for crystallization and precipitation, and performing suction filtration to obtain a product A;
v) dissolving the product A in water, adding diethyl ether or acetone at the temperature of 0-15 ℃ for recrystallization, and performing suction filtration to obtain a product B; drying the product B to obtain a reaction product of the isocyanate methacrylate and the beta-cyclodextrin;
in the step 1), the amide monomer is an acrylamide monomer;
the benzenesulfonate monomers in the step 1) are p-benzenesulfonate monomers, o-benzenesulfonate monomers or m-benzenesulfonate monomers.
2. The method of claim 1, wherein the p-benzenesulfonate monomer is sodium p-styrenesulfonate monomer.
3. The method for preparing the copolymerized nanocomposite material of claim 1, wherein the pretreatment of the pretreated β -cyclodextrin in step i) includes purifying the β -cyclodextrin by three-time recrystallization and vacuum drying at 35-60 ℃ for 30-72 hours.
4. The method of claim 1, wherein the pretreatment of the pretreated N, N-dimethylacetamide in step i) comprises drying the pretreated N, N-dimethylacetamide in an anhydrous state.
5. The method of claim 1, wherein the mass-to-volume ratio of the pretreated beta-cyclodextrin to the pretreated N, N-dimethylacetamide in step i) is 1g: 2-15 mL.
6. The method for preparing the copolymerized nanocomposite material of claim 1, wherein the mass ratio of the isocyanate methacrylate to the pretreated β -cyclodextrin in step ii) is 1:20 to 80.
7. The method for preparing the copolymerized nanocomposite material of claim 1, wherein the volume ratio of the stannous isooctanoate to the mixed solution B in step iii) is 1: 300-900.
8. The preparation method of the copolymerization nanocomposite material as claimed in claim 1, wherein the drying condition of the product B in the step v) is vacuum drying at 35-60 ℃ for 30-72 h.
9. The method for preparing the copolymerized nanocomposite material of claim 1, wherein the mass ratio of the amide monomer, the benzenesulfonate monomer and the solvent in step 1) is 1: 0.1-0.5: 3.0 to 13.
10. The preparation method of the copolymerization nanocomposite material as claimed in claim 1, wherein the mass of the crosslinking agent in the step 1) is 0.5wt% to 1.0wt% of the sum of the mass of the amide monomer and the mass of the benzenesulfonate monomer.
11. The method for preparing a copolymerized nanocomposite material according to claim 1, wherein the stirring conditions in step 1) are: stirring at 400-450 rpm for 30-240 min at room temperature.
12. The method for preparing a copolymerized nanocomposite material according to claim 1, wherein the pH in step 2) is 8 to 9.
13. The method for preparing a copolymerized nanocomposite material according to claim 1, wherein the method for preparing the inorganic nanophase in step 2) comprises the steps of:
mixing the layered silicate and water according to the mass ratio of 1: 10-20, and stirring for 30-40 min at the conditions of 400-450 rpm and room temperature to form a layered silicate suspension swelling system;
mixing the layered silicate swelling system with an intercalation agent with the same mass as layered silicate at the temperature of 50-55 ℃, and stirring and reacting for 8-10 h at the rotating speed of 400-450 rpm to form a layered silicate intercalation reaction system;
and carrying out suction filtration, washing, drying, grinding and crushing on the phyllosilicate intercalation reaction system to obtain the inorganic nano phase.
14. The method of claim 13, wherein the layered silicate is montmorillonite and/or clay.
15. The method of claim 13, wherein the intercalant is a cationic surfactant.
16. The method of claim 15, wherein the cationic surfactant is butyl methylbutenoate hexadecylammonium bromide.
17. The method for preparing a copolymerized nanocomposite material according to claim 1, wherein the mixing and stirring time in step 3) is 10 to 50 min.
18. The method for preparing a copolymerized nanocomposite material according to claim 1, wherein the conditions of the copolymerization reaction in step 3) are: the temperature of the copolymerization reaction is 75-85 ℃, and when the reaction temperature is not increased any more, the reaction temperature is kept for 6-8 hours.
19. The method of preparing a copolymerized nanocomposite according to claim 1, wherein the oxidizing agent in step 3) is ammonium persulfate or potassium persulfate.
20. The method for preparing a copolymerized nanocomposite material according to claim 1, wherein the reducing agent in step 3) is sodium bisulfite.
21. A copolymerized nanocomposite obtained by the method of producing a copolymerized nanocomposite as claimed in any one of claims 1 to 20.
22. An application of the copolymerization nano composite material prepared by the preparation method of the copolymerization nano composite material as defined in any one of claims 1 to 20 in the preparation of a treating agent in the sewage treatment field, the papermaking field or the oil drilling and production field.
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