CN110776606B - Modified chitosan/nitrogen-oxygen branched monomer functional polymer and preparation method and application thereof - Google Patents
Modified chitosan/nitrogen-oxygen branched monomer functional polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer and a preparation method and application thereof, belonging to the field of polymer flooding. A preparation method of a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer comprises the following steps: s1, preparing a nitrogen-oxygen branching functional monomer; s2, preparing modified chitosan; s3, preparing a modified chitosan/nitrogen-oxygen branching functional monomer graft; s4, preparing the modified chitosan/nitrogen-oxygen branched monomer functional polymer. The modified chitosan/nitrogen-oxygen branched monomer functionalized polymer provided by the invention has the advantages of multiple branches, low viscosity loss, good shear resistance and good biodegradability; meanwhile, the flocculant is used as a sewage flocculant and has good flocculation effect.
Description
Technical Field
The invention belongs to the field of polymer flooding, and particularly relates to a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer, and a preparation method and application thereof.
Background
At present, petroleum is still an indispensable main energy source in human daily life. After most oil and gas fields are driven by water injection or gas injection means of primary and secondary oil recovery, about 50 percent of oil remained in the oil fields is not recovered. Through continuous research and study of researchers, people find that the polymer flooding technology can reduce the water-oil flow rate ratio in a macroscopic view, improve the sweep efficiency, lead the flooding front edge to be smooth and stable, and improve the oil washing efficiency in a microscopic view due to viscoelasticity. The polymer flooding obviously improves the recovery ratio, and is exclusively used for chelating in the tertiary oil flooding technology. It is known that polymer flooding is a simple, mature and stable technology for increasing recovery efficiency. The following polymers are commonly used, Polyacrylamide (PAM), partially Hydrolyzed Polyacrylamide (HPAM), crosslinked polymers, modified polymers, all of which are essentially linear polymers based on a linear structure.
However, in actual flooding applications, linear polymers are easily subjected to a series of shearing actions during the processes of configuration, transportation, injection and the like, and the most obvious and intuitive influence is that the viscosity loss of the polymers reaches 50-70%. The less branched chains the linear structure of the polymer leads to, the more the shear degradation problem is affected and even the less the oil recovery efficiency is affected. Meanwhile, the poor biodegradability of the polymer is a problem which troubles people for a long time, and most of the polymers have poor biodegradability, are not easy to degrade and are difficult to flocculate in subsequent treatment. Similar treatment results can be achieved with other chemicals, but at higher cost and with less ease.
Therefore, the invention designs and synthesizes the polymer with more branch structures, better anti-shearing performance, lower viscosity loss and better biodegradability based on the outstanding problems of poorer anti-shearing performance, higher viscosity loss, weaker biodegradability and the like of the linear polymer.
Disclosure of Invention
Aiming at the problems, the invention provides a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer which has the characteristics of multiple branches, low viscosity loss, good shear resistance and good biodegradation performance.
The invention also aims to provide a preparation method of the modified chitosan/nitrogen-oxygen branched monomer functionalized polymer.
It is a further object of the present invention to provide uses of the polymers.
The technical scheme adopted by the invention is as follows:
a preparation method of a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer comprises the following steps:
s1, nitrogen-oxygen branching functional monomer: slowly dripping the nitrogen-oxygen branched monomer solution into the continuously stirred maleic anhydride solution by using a constant-pressure funnel under the nitrogen atmosphere, after finishing dripping, heating to 70-80 ℃, performing reflux reaction for 6-9 h, and repeatedly precipitating and filtering by using trichloromethane to obtain a nitrogen-oxygen branched functional monomer;
s2, preparing modified chitosan: adding protonated chitosan into methanol under the nitrogen atmosphere, stirring for 1-2 h, and then slowly adding the methanol dissolved with methyl acrylate into the methanol by using a constant-pressure funnel; under stirring, placing the system in a water bath at 25 ℃ for reaction for 3 days, dialyzing for 7 days, and freeze-drying to obtain modified chitosan;
s3, preparing a modified chitosan/nitrogen-oxygen branching functional monomer graft: placing the nitrogen-oxygen branching functional monomer solution obtained in the step S1 in a constant-pressure funnel under the nitrogen atmosphere, then dropping the nitrogen-oxygen branching functional monomer solution into a maleic anhydride solution, stirring and dropping the modified chitosan obtained in the step S2, carrying out water bath reaction at 70-80 ℃ for 8-10 hours, and repeatedly precipitating and filtering by using trichloromethane to obtain a modified chitosan/nitrogen-oxygen branching functional monomer graft;
s4, preparing a modified chitosan/nitrogen-oxygen branched monomer functional polymer: dissolving the modified chitosan/nitrogen-oxygen branched functional monomer graft in an acrylic acid aqueous solution, adding acrylamide into the acrylic acid aqueous solution after the modified chitosan/nitrogen-oxygen branched functional monomer graft is completely dissolved, shaking up, adjusting the pH to be neutral by using sodium hydroxide, then sequentially adding a reduction initiator and an oxidation initiator while stirring, stopping stirring after the system becomes viscous, reacting in a water bath for 6 hours, cooling to room temperature, washing for three times by using absolute ethyl alcohol, and drying to obtain the polymer.
Specifically, the preparation method of the nitrogen-oxygen branched monomer comprises the following steps:
first step MA0.5The synthesis of (2): under the ice bath condition, dissolving ethylenediamine in methanol, adding methyl acrylate into the methanol at a rate of 1-2 drops per second in the nitrogen atmosphere, performing reflux reaction at 20-25 ℃ for 24 hours to obtain a composition, filling the composition into a chromatographic column by a wet method, adding a proper amount of quartz sand into the chromatographic column after washing a small amount of eluent (a solution with a molar ratio of ethyl acetate to petroleum ether of 1: 5), eluting the eluent, opening a piston, connecting an effluent with a small glass bottle, performing rotary evaporation on the effluent to remove excessive methyl acrylate and methanol to obtain MA (methyl acrylate and methanol)0.5And (3) obtaining a crude product. The molar ratio of the ethylenediamine to the methyl acrylate is 1: 8.
Second step MA1.0The synthesis of (2): ethylenediamine was dissolved in methanol under ice bath conditions and subsequently added under nitrogen atmosphere 1 to 2 drops per second to MA0.5Carrying out reflux reaction in a methanol solution at 20-25 ℃ for 40-45 h to obtain a product, carrying out reduced pressure distillation on the product at 70-80 ℃ for 2-3 h, washing the product with methanol for three times during the reduced pressure distillation, and removing redundant ethylenediamine and methanol to obtain MA1.0And (3) obtaining a crude product. The MA is0.5The molar ratio to ethylenediamine was 1: 24.
Third step MA1.5The synthesis of (2): methyl acrylate was dissolved in methanol under ice bath conditions and subsequently added to MA in 1 to 2 drops per second under nitrogen atmosphere1.0Carrying out reflux reaction at 20-25 ℃ for 55h in a methanol solution to obtain a product, carrying out reduced pressure distillation on the product at 70-80 ℃ for 2-3 h, adding methanol for 3 times of repeated rotary evaporation and purification, and carrying out MA (maleic anhydride)1.5Packing the crude product into column by wet method, developing with ethyl acetate methanol solution at ratio of 5:1, eluting with ethyl acetate methanol solution at ratio of 10:1, and performing the same operation as MA0.5Purification followed by rotary evaporation to obtain pure MA1.5. The MA is1.0The molar ratio to methyl acrylate was 1: 16.
The fourth step of nitroxide branching Monomer (MA)2.0) The synthesis of (2): ethylenediamine was dissolved in methanol under ice bath conditions and subsequently added under nitrogen atmosphere 1 to 2 drops per second to MA1.5And (2) carrying out reflux reaction for 40-45 h at 20-25 ℃ in a methanol solution to obtain a product, carrying out reduced pressure distillation on the product for 2-3 h at 70-80 ℃, washing the product with methanol for three times during the period to remove redundant ethylenediamine and methanol to obtain a light yellow colloid nitrogen-oxygen branched monomer, wherein the molar ratio of MA1.5 to ethylenediamine is 1: 48.
Further, in step S1, the molar ratio of the nitroxide branched monomer to maleic anhydride is 1: 10.
Further, in the step S2, the mole ratio of the protonated chitosan to the methyl acrylate is 1 (13-20).
Further, in step S4, the modified chitosan/nitroxide branched functional monomer graft is added in an amount of 0.1 to 1.0 wt.%, and the mass ratio of acrylamide to acrylic acid is 5 to 8: 2-5, and the total concentration of the system is 20-32%.
Specifically, the total mass concentration of the system refers to the total mass concentration of acrylic acid, acrylamide and modified chitosan/nitrogen-oxygen branched functional monomer graft. The nitrogen-oxygen branched monomer solution is obtained by dissolving a nitrogen-oxygen branched monomer in a DMF solvent, and the addition amount of DMF is used for dispersing and dissolving the nitrogen-oxygen branched monomer; the nitrogen-oxygen branching functional monomer solution is obtained by dissolving a nitrogen-oxygen branching functional monomer in a DMF solvent, and the addition amount of DMF is used for dispersing and dissolving the nitrogen-oxygen branching functional monomer; the maleic anhydride solution is obtained by dissolving maleic anhydride in a DMF solvent, and the addition amount of DMF ensures that the maleic anhydride is dispersed and dissolved; the maleic anhydride solution is prepared by dissolving maleic anhydride in DMF solvent, and dispersing and dissolving the maleic anhydride by adding DMF.
Further, in the step S4, the water bath temperature is 36-45 ℃.
Further, in step S4, the total mass concentration of the reduction initiator and the oxidation initiator is 0.1 to 1.0%, and the addition mass ratio is 1: 2.
The invention also provides a modified chitosan/nitrogen-oxygen branched monomer functional polymer, which is prepared by the preparation method of the modified chitosan/nitrogen-oxygen branched monomer functional polymer.
The invention also provides application of the modified chitosan/nitrogen-oxygen branched monomer functionalized polymer in the aspects of oil displacement agents for oil exploitation and sewage flocculants.
The invention has the beneficial effects that: the modified chitosan/nitrogen-oxygen branched monomer functionalized polymer provided by the invention has the advantages of multiple branches, low viscosity loss, good shear resistance and good biodegradability; meanwhile, the flocculant is used as a sewage flocculant and has good flocculation effect.
Drawings
FIG. 1 a polymer microstructure diagram;
FIG. 2 is a graph of biodegradability evaluation of HPAM and polymer;
FIG. 3 HPAM and Polymer flocculation Effect graph;
FIG. 4 is a plot of apparent viscosity for HPAM and polymer concentration;
FIG. 5 apparent viscosity relationship of HPAM and polymer concentration at the same shear rate;
FIG. 6 Effect of different shear rates on HPAM and polymer apparent viscosity.
Detailed Description
The embodiments of the present invention can be obtained by different substitutions in specific ranges on the basis of the above technical solutions, and the adopted technical solutions are as follows:
a preparation method of a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer comprises the following steps:
s1, nitrogen-oxygen branching functional monomer: slowly dripping the nitrogen-oxygen branched monomer solution into the continuously stirred maleic anhydride solution by using a constant-pressure funnel under the nitrogen atmosphere, after finishing dripping, heating to 70-80 ℃, performing reflux reaction for 6-9 h, and repeatedly precipitating and filtering by using trichloromethane to obtain a nitrogen-oxygen branched functional monomer;
s2, preparing modified chitosan: adding protonated chitosan into methanol under the nitrogen atmosphere, stirring for 1-2 h, and then slowly adding the methanol dissolved with methyl acrylate into the methanol by using a constant-pressure funnel; under stirring, placing the system in a water bath at 25 ℃ for reaction for 3 days, dialyzing for 7 days, and freeze-drying to obtain modified chitosan; the molar ratio of the protonated chitosan to the methyl acrylate is 1: 13-20;
s3, preparing a modified chitosan/nitrogen-oxygen branching functional monomer graft: placing the nitrogen-oxygen branching functional monomer solution obtained in the step S1 in a constant-pressure funnel under the nitrogen atmosphere, then dropping the nitrogen-oxygen branching functional monomer solution into a maleic anhydride solution, stirring and dropping the modified chitosan obtained in the step S3, carrying out water bath reaction at 70-80 ℃ for 8-10 hours, and repeatedly precipitating and filtering by using trichloromethane to obtain a modified chitosan/nitrogen-oxygen branching functional monomer graft;
s4, preparing a modified chitosan/nitrogen-oxygen branched monomer functional polymer: dissolving the modified chitosan/nitrogen-oxygen branched functional monomer graft in an acrylic acid aqueous solution, adding acrylamide into the acrylic acid aqueous solution after the modified chitosan/nitrogen-oxygen branched functional monomer graft is completely dissolved, shaking up, adjusting the pH to be neutral by using sodium hydroxide, then sequentially adding a reduction initiator and an oxidation initiator while stirring, stopping stirring after the system becomes viscous, carrying out water bath reaction on the reaction system at 36-45 ℃ for 6 hours, cooling to room temperature, washing with absolute ethyl alcohol for three times, and drying to obtain a polymer;
in step S4, the modified chitosan/nitroxide branched functional monomer graft is added in an amount of 0.1 to 1.0 wt.%, and the mass ratio of acrylamide to acrylic acid is 5 to 8: 2-5, and the total mass concentration of the system is 20-32%. Specifically, the total mass concentration of the system refers to the total mass concentration of acrylic acid, acrylamide and modified chitosan/nitrogen-oxygen branched functional monomer graft.
In step S4, the total mass concentration of the reduction initiator and the oxidation initiator is 0.1-1.0%, and the addition mass ratio is 1: 2.
A modified chitosan/nitrogen-oxygen branched monomer functionalized polymer is prepared by the preparation method of any one of claims 1 to 6.
An application of a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer in the aspects of oil displacement agents for oil exploitation and sewage flocculants.
Examples 1 to 8
A preparation method of a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer comprises the following steps:
s1, nitrogen-oxygen branching functional monomer: under the nitrogen atmosphere, slowly dripping a DMF solution of a nitrogen-oxygen branched monomer into a continuously stirred DMF solution dissolved with maleic anhydride by using a constant-pressure funnel, after finishing dripping, heating to 70 ℃, performing reflux reaction for 6 hours, and repeatedly precipitating and filtering by using trichloromethane to obtain a nitrogen-oxygen branched functional monomer; the molar ratio of the nitrogen-oxygen branched monomer to the maleic anhydride is 1: 10.
S2, preparing modified chitosan: adding protonated chitosan into methanol under nitrogen atmosphere, stirring for 1h, and then slowly adding methanol dissolved with methyl acrylate into the mixture by using a constant-pressure funnel; under stirring, placing the system in a water bath at 25 ℃ for reaction for 3 days, dialyzing for 7 days, and freeze-drying to obtain modified chitosan; the molar ratio of the protonated chitosan to the methyl acrylate is 1: 13.
S3, preparing a modified chitosan/nitrogen-oxygen branching functional monomer graft: under the nitrogen atmosphere, placing DMF dissolved with a nitrogen-oxygen branching functional monomer into a constant pressure funnel, then dripping DMF dissolved with maleic anhydride into the constant pressure funnel, stirring and dripping modified chitosan into the constant pressure funnel, performing water bath reaction at 70 ℃ for 8 hours, and repeatedly precipitating and filtering by using trichloromethane to obtain a modified chitosan/nitrogen-oxygen branching functional monomer graft;
s4, preparing a modified chitosan/nitrogen-oxygen branched monomer functional polymer: dissolving the modified chitosan/nitrogen-oxygen branched functional monomer graft in an acrylic acid aqueous solution, adding acrylamide into the acrylic acid aqueous solution after the modified chitosan/nitrogen-oxygen branched functional monomer graft is completely dissolved, shaking up, adjusting the pH to be neutral by using sodium hydroxide, then sequentially adding a reduction initiator and an oxidation initiator while stirring, stopping stirring after the system becomes viscous, carrying out water bath reaction on the reaction system at a certain temperature for 6 hours, cooling to room temperature, washing for three times by using absolute ethyl alcohol, and drying to obtain the polymer.
The experimental conditions of S5 of examples 1 to 8 are shown in table 1 below, wherein the mass ratio of the oxidation initiator to the reduction initiator is 2: 1.
Example 9
A preparation method of a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer comprises the following steps:
s1, nitrogen-oxygen branching functional monomer: under the nitrogen atmosphere, slowly dripping a DMF solution of a nitrogen-oxygen branched monomer into a continuously stirred DMF solution dissolved with maleic anhydride by using a constant-pressure funnel, after finishing dripping, heating to 75 ℃, performing reflux reaction for 7.5 hours, and repeatedly precipitating and filtering by using trichloromethane to obtain a nitrogen-oxygen branched functional monomer; the molar ratio of the nitrogen-oxygen branched monomer to the maleic anhydride is 1: 10;
s2, preparing modified chitosan: adding protonated chitosan into methanol under nitrogen atmosphere, stirring for 1.5h, and then slowly adding methanol dissolved with methyl acrylate into the methanol by using a constant-pressure funnel; under stirring, placing the system in a water bath at 25 ℃ for reaction for 3 days, dialyzing for 7 days, and freeze-drying to obtain modified chitosan; the molar ratio of the protonated chitosan to the methyl acrylate is 1: 16;
s3, preparing a modified chitosan/nitrogen-oxygen branching functional monomer graft: under the nitrogen atmosphere, placing DMF dissolved with a nitrogen-oxygen branching functional monomer into a constant pressure funnel, then dripping DMF dissolved with maleic anhydride into the constant pressure funnel, stirring and dripping modified chitosan into the constant pressure funnel, carrying out water bath reaction at 75 ℃ for 9 hours, and repeatedly precipitating and filtering by using trichloromethane to obtain a modified chitosan/nitrogen-oxygen branching functional monomer graft;
s4, preparing a modified chitosan/nitrogen-oxygen branched monomer functional polymer: dissolving the modified chitosan/nitrogen-oxygen branched functional monomer graft in an acrylic acid aqueous solution, adding acrylamide into the acrylic acid aqueous solution after the modified chitosan/nitrogen-oxygen branched functional monomer graft is completely dissolved, shaking up, adjusting the pH to be neutral by using sodium hydroxide, then sequentially adding a reduction initiator and an oxidation initiator while stirring, stopping stirring after the system becomes viscous, carrying out water bath reaction on the reaction system at 40 ℃ for 6 hours, cooling to room temperature, washing for three times by using absolute ethyl alcohol, and drying to obtain the polymer. The addition amount of the modified chitosan/nitrogen-oxygen branched functional monomer graft is 0.26 wt.%, and the mass ratio of acrylamide to acrylic acid is 7.0: 3.0, the total mass concentration of the system is 20 percent; the total mass concentration of the reduction initiator and the oxidation initiator is 0.5%, wherein the mass ratio of the oxidation initiator to the reduction initiator is 2: 1.
Example 10
A preparation method of a modified chitosan/nitrogen-oxygen branched monomer functionalized polymer comprises the following steps:
s1, nitrogen-oxygen branching functional monomer: under the nitrogen atmosphere, slowly dripping a DMF solution of a nitrogen-oxygen branching monomer into a continuously stirred DMF solution dissolved with maleic anhydride by using a constant-pressure funnel, after finishing dripping, heating to 80 ℃, performing reflux reaction for 9 hours, and repeatedly precipitating and filtering by using trichloromethane to obtain a nitrogen-oxygen branching functional monomer; the molar ratio of the nitrogen-oxygen branched monomer to the maleic anhydride is 1: 10;
s2, preparing modified chitosan: adding protonated chitosan into methanol under nitrogen atmosphere, stirring for 2h, and then slowly adding methanol dissolved with methyl acrylate into the mixture by using a constant-pressure funnel; under stirring, placing the system in a water bath at 25 ℃ for reaction for 3 days, dialyzing for 7 days, and freeze-drying to obtain modified chitosan; the mole ratio of the protonated chitosan to the methyl acrylate in the S3 is 1: 20;
s3, preparing a modified chitosan/nitrogen-oxygen branching functional monomer graft: under the nitrogen atmosphere, placing DMF dissolved with a nitrogen-oxygen branching functional monomer into a constant pressure funnel, then dripping DMF dissolved with maleic anhydride into the constant pressure funnel, stirring and dripping modified chitosan into the constant pressure funnel, performing water bath reaction at 80 ℃ for 10 hours, and repeatedly precipitating and filtering by using trichloromethane to obtain a modified chitosan/nitrogen-oxygen branching functional monomer graft;
s4, preparing a modified chitosan/nitrogen-oxygen branched monomer functional polymer: dissolving the modified chitosan/nitrogen-oxygen branched functional monomer graft in an acrylic acid aqueous solution, adding acrylamide into the acrylic acid aqueous solution after the modified chitosan/nitrogen-oxygen branched functional monomer graft is completely dissolved, shaking up, adjusting the pH to be neutral by using sodium hydroxide, then sequentially adding a reduction initiator and an oxidation initiator while stirring, stopping stirring after the system becomes viscous, carrying out water bath reaction on the reaction system at 45 ℃ for 6 hours, cooling to room temperature, washing with absolute ethyl alcohol for three times, and drying to obtain a polymer; the addition amount of the modified chitosan/nitrogen-oxygen branched functional monomer graft is 0.26 wt.%, and the mass ratio of acrylamide to acrylic acid is 7.1: 3.2, the total mass concentration of the system is 20 percent; the total mass concentration of the reduction initiator and the oxidation initiator is 0.5%, wherein the mass ratio of the oxidation initiator to the reduction initiator is 2: 1.
For the examples, the mole ratio of the nitroxide branching monomer to maleic anhydride in S1 is 1: 10; the nitrogen-oxygen branched monomer solution is a DMF solution of 20 mass percent nitrogen-oxygen branched monomer; the maleic anhydride solution is a DMF solution of maleic anhydride with the mass concentration of 20%. The mass ratio of the methyl acrylate to the methanol is 1: 5; the mass ratio of the protonated chitosan to the methanol was 1: 5. The maleic anhydride solution is a DMF solution of maleic anhydride with the mass concentration of 10%. The mass concentration of the acrylic acid aqueous solution was 10%.
The related performance tests were performed on some of the above examples, and the results are shown in table 2 below. Apparent viscosity measurements were performed using a Brookfield DV-III viscometer. FIG. 1 is a view of a polymer microstructure.
TABLE 1 Experimental conditions
Table 2 results of apparent viscosity test of the polymers obtained in examples 1 to 10.
| Examples | Concentration of aqueous Polymer solution | Apparent viscosity |
| Example 1 | 1500ppm | 109.8 |
| Example 2 | 1500ppm | 220.1 |
| Example 3 | 1500ppm | 288.8 |
| Example 4 | 1500ppm | 212.2 |
| Example 5 | 1500ppm | 292 |
| Example 6 | 1500ppm | 205.8 |
| Example 7 | 1500ppm | 159.5 |
| Example 8 | 1500ppm | 129.2 |
| Example 9 | 1500ppm | 179.5 |
| Example 10 | 1500ppm | 190.5 |
Biodegradability of the polymer was evaluated by comparison with example 3 using HPAM as a comparison substance, at a concentration of 200 ppm. The specific synthesis conditions for HPAM were: weighing 2.51g of acrylic acid into a 125mL wide-mouth bottle, adding 40mL of water, adjusting the pH of the system to be neutral by using NaOH, cooling, sequentially adding 5.75g of acrylamide and 0.35g of initiator (ammonium persulfate: sodium bisulfite ═ 1:1) under the stirring condition to prepare an aqueous solution with the total mass percentage concentration of the monomers being 20%, and placing the aqueous solution into a constant-temperature water bath kettle at 39 ℃ for 6 hours to obtain the acrylic acid/acrylic acid copolymer. Selecting Biochemical Oxygen Demand (BOD) as a test index, and evaluating the biodegradability of the polymer by using a microbial degradation respirator. The results are shown in FIG. 2.
As can be seen from FIG. 2, the polymer is easily biodegradable, and can start to be degraded by microorganisms within a short time; meanwhile, compared with HPAM, the polymer is found to have a degradation time starting point earlier than that of HPAM, and applicable microorganisms are more.
The flocculation performance of the polymer was evaluated by simulating the change in light transmittance of the wastewater with kaolin, using the polymer as the flocculant and also using HPAM as the comparative flocculant sample. The method comprises the following steps: kaolin simulated water samples were prepared at a concentration of 1g/L and the polymer solution of example 3 was prepared at a concentration of 100 ppm. Pouring a kaolin water sample into 5 beakers on average, adding 1mL, 2mL, 3mL, 4mL and 5mL of flocculating agents into the beakers in sequence, then mechanically stirring the kaolin simulated water sample for 30 seconds at a high speed (the rotating speed is 200r/min), then continuously stirring the mixture at a low speed for 5 minutes, standing and settling the mixture for 30 minutes after the stirring is finished, taking supernatant liquid, and detecting the transmittance of the solution in a 752N ultraviolet visible spectrophotometer (the detection wavelength is 550nm), wherein the result is shown in figure 3.
As can be seen from FIG. 3, the light transmittance of the polymer is significantly better than that of HPAM when the same amount of flocculant is added, which shows that the polymer of the present invention has a good flocculation effect.
The apparent viscosities of different concentrations of the polymer obtained in example 3 were compared with HPAM as a comparative material, and the viscosity measurements were carried out using a Brookfield DV-III viscometer, the results of which are shown in FIG. 4.
From fig. 4, it can be seen that the polymer thickening properties are consistently stable and increase relatively rapidly within the experimental test range.
The results of preparing a polymer solution and a HPAM solution each having a concentration of 1500mg/L using HPAM as a comparative material, shearing the polymer solution at 3000, 7000 and 10500rpm for 20 seconds while changing the rotational speed of the Wu-Yin stirrer, and measuring the apparent viscosities after standing for 0, 12 and 24 hours using a Brookfield DV-III viscometer are shown in FIGS. 5 and 6.
As can be seen from FIG. 5, the apparent viscosity of the polymer solution decreases with the increase of the shear time, which indicates that the branched chains in the polymer structure reduce the influence of the shear effect, and the polymer can maintain a good apparent viscosity after being placed for a long time under shear, indicating that the polymer has a good shear resistance.
As can be seen from FIG. 6, the viscosity of the polymer solution is continuously decreased with the increase of the shear rate, and when the shear rate is greater than 7000rpm, the polymer solution is sheared, the decrease range of the apparent viscosity is obviously increased after the polymer solution is placed for 12 hours, and the apparent viscosity is extremely low after the polymer solution is placed for about 24 hours, which indicates that the polymer has good shear resistance within a certain range of applicable conditions.
The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (8)
1. A preparation method of a modified chitosan/nitrogen-oxygen branched monomer functional polymer is characterized by comprising the following steps:
s1 preparation of nitrogen-oxygen branching functional monomer: slowly dripping the nitrogen-oxygen branched monomer solution into the continuously stirred maleic anhydride solution by using a constant-pressure funnel under the nitrogen atmosphere, after finishing dripping, heating to 70-80 ℃, performing reflux reaction for 6-9 h, and repeatedly precipitating and filtering by using trichloromethane to obtain a nitrogen-oxygen branched functional monomer; the preparation steps of the nitrogen-oxygen branched monomer are the first step of MA0.5 synthesis: under the ice bath condition, dissolving ethylenediamine in methanol, adding methyl acrylate into the methanol at a rate of 1-2 drops per second in the nitrogen atmosphere, performing reflux reaction at 20-25 ℃ for 24 hours to obtain a composition, filling the composition into a column by a wet method, adding the composition into a chromatographic column, adding a proper amount of quartz sand after a small amount of eluent is washed, eluting the eluent, opening a piston, connecting an effluent with a small glass bottle, performing rotary evaporation on the effluent, and removing redundant methyl acrylate and methanol to obtain a MA0.5 crude product, wherein the molar ratio of ethylenediamine to methyl acrylate is 1:8, and the eluent is a solution prepared from ethyl acetate and petroleum ether according to the molar ratio of 1: 5;
second step MA1.0 Synthesis: under the ice bath condition, dissolving ethylenediamine in methanol, then adding the methanol solution into MA0.5 dropwise at the rate of 1-2 drops per second under the nitrogen atmosphere, then carrying out reflux reaction at the temperature of 20-25 ℃ for 40-45 hours to obtain a product, carrying out reduced pressure distillation on the product at the temperature of 70-80 ℃ for 2-3 hours, washing the product with methanol for three times during the reflux reaction, and removing redundant ethylenediamine and methanol to obtain a MA1.0 crude product, wherein the molar ratio of MA0.5 to ethylenediamine is 1: 24; step three, synthesis of MA 1.5: under the ice bath condition, dissolving methyl acrylate in methanol, then dropwise adding the methyl acrylate into MA1.0 methanol solution at the temperature of 1-2/s under the nitrogen atmosphere, then carrying out reflux reaction at the temperature of 20-25 ℃ for 55h to obtain a product, carrying out reduced pressure distillation on the product at the temperature of 70-80 ℃ for 2-3 h, then adding methanol for 3 times of repeated rotary evaporation and purification, then carrying out wet column packing on a MA1.5 crude product, wherein a developing agent is ethyl acetate methanol solution with the ratio of 5:1, an eluent is ethyl acetate methanol solution with the ratio of 10:1, the operation is the same as the purification of MA0.5, and then carrying out rotary evaporation to obtain pure MA1.5, wherein the molar ratio of MA1.0 to methyl acrylate is 1: 16; fourth step Synthesis of Nitrogen oxygen branched monomer (MA 2.0): under the ice bath condition, dissolving ethylenediamine in methanol, then adding the methanol solution into MA1.5 dropwise at the rate of 1-2 drops per second under the nitrogen atmosphere, then carrying out reflux reaction at the temperature of 20-25 ℃ for 40-45 hours to obtain a product, carrying out reduced pressure distillation on the product at the temperature of 70-80 ℃ for 2-3 hours, washing the product with methanol for three times during the reflux reaction to remove redundant ethylenediamine and methanol to obtain a light yellow colloid nitrogen-oxygen branched monomer, wherein the molar ratio of MA1.5 to ethylenediamine is 1: 48;
s2, preparing modified chitosan: adding protonated chitosan into methanol under the nitrogen atmosphere, stirring for 1-2 h, and then slowly adding the methanol dissolved with methyl acrylate into the methanol by using a constant-pressure funnel; under stirring, placing the system in a water bath at 25 ℃ for reaction for 3 days, dialyzing for 7 days, and freeze-drying to obtain modified chitosan;
s3 preparation of modified chitosan/nitrogen-oxygen branching functional monomer graft: placing the nitrogen-oxygen branching functional monomer solution obtained in the step S1 in a constant-pressure funnel under the nitrogen atmosphere, then dropping the nitrogen-oxygen branching functional monomer solution into a maleic anhydride solution, stirring and dropping the modified chitosan obtained in the step S2, carrying out water bath reaction at 70-80 ℃ for 8-10 hours, and repeatedly precipitating and filtering by using trichloromethane to obtain a modified chitosan/nitrogen-oxygen branching functional monomer graft;
s4 preparation of modified chitosan/nitrogen-oxygen branched monomer functionalized polymer: dissolving the modified chitosan/nitrogen-oxygen branched functional monomer graft in an acrylic acid aqueous solution, adding acrylamide into the acrylic acid aqueous solution after the modified chitosan/nitrogen-oxygen branched functional monomer graft is completely dissolved, shaking up, adjusting the pH to be neutral by using sodium hydroxide, then sequentially adding a reduction initiator and an oxidation initiator while stirring, stopping stirring after the system becomes viscous, reacting in a water bath for 6 hours, cooling to room temperature, washing for three times by using absolute ethyl alcohol, and drying to obtain the polymer.
2. The method of claim 1, wherein the mole ratio of the nitroxide branching monomer to maleic anhydride in step S1 is 1: 10.
3. The method of claim 1, wherein in step S2, the mole ratio of the protonated chitosan to the methyl acrylate is 1 (13-20).
4. The method of claim 1, wherein in step S4, the modified chitosan/nitroxide branched functional monomer graft is added in an amount of 0.1 to 1.0 wt%, and the mass ratio of acrylamide to acrylic acid is 5 to 8: 2-5, and the total mass concentration of the system is 20-32%.
5. The method for preparing the modified chitosan/nitrogen-oxygen branched monomer functionalized polymer according to claim 1, wherein in the step S4, the water bath temperature is 36-45 ℃.
6. The method of claim 1, wherein in step S4, the total mass concentration of the reduction initiator and the oxidation initiator is 0.1-1.0%, and the mass ratio of the reduction initiator to the oxidation initiator is 1: 2.
7. A modified chitosan/nitrogen-oxygen branched monomer functionalized polymer is characterized by being prepared by the preparation method of any one of claims 1-6.
8. The application of the modified chitosan/nitrogen-oxygen branched monomer functional polymer obtained by the preparation method of any one of claims 1-6 in the aspects of oil displacement agents for oil exploitation and sewage flocculants.
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