Polymer microspheres capable of intelligent absorption and release of fuel under pH control and a preparation method thereof

Abstract

The application discloses a kind of polymer microspheres and preparation method of intelligent oil adsorption and release under pH regulation, wherein the polymer microspheres are composed of the following components: 75-95 parts by weight of amino acrylate monomer, 5-25 parts by weight of alkyl acrylate monomer, 16-22 parts by weight of dispersant, 0.1-2 parts by weight of crosslinking agent and 1-3 parts by weight of initiator. The polymer microspheres of the application can not only adsorb organic solvents, but also adsorb fuel oil, and can realize oil desorption under acidic conditions.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oil absorption materials. Specifically, it is a kind of polymer microspheres for intelligent absorption and release of fuel oil under pH control and a preparation method thereof. BACKGROUND

[0002] Fuel leakage and the discharge of sewage containing dyes, organic solvents and the like cause serious environmental pollution and resource waste, and the use of oil absorption materials is one of the main measures to solve the above problems. Acrylate oil absorption resin has high oil absorption ratio and fast oil absorption rate, and has good application prospect in oil spill absorption field, but its excellent oil retention performance also poses a challenge to the recovery of oil spill and the reuse of absorption materials.

[0003] By using a nucleophile as a polymer monomer, the polymer product can be converted from hydrophobic to hydrophilic under pH stimulation, thereby completing the absorption and desorption of oil. Because the alkyl group directly connected to the nitrogen atom in the amino compound has an electron-donating effect, the electron cloud density on the nitrogen atom is increased, which is conducive to the combination of H + Therefore, the amino compound can participate in the polymerization reaction as a nucleophilic monomer, thereby making the polymer have pH response function.

[0004] Based on the above theory, the pH-responsive oil absorption materials reported so far have shown good results in the absorption and desorption of organic solvents and acid dyes, but have not been involved in the absorption and desorption of fuel oil. Therefore, the design and preparation of a kind of polymer material that can intelligently absorb and release fuel oil under pH control is of great significance for environmental protection and non-renewable energy recycling. SUMMARY

[0005] To this end, the technical problem to be solved by the present application is to provide a kind of polymer microspheres for intelligent absorption and release of fuel oil under pH control and a preparation method thereof, wherein the polymer microspheres can absorb organic solvents and also absorb fuel oil, and can realize the desorption of oil under acidic conditions.

[0006] To solve the above technical problems, the present application provides the following technical solutions:

[0007] A kind of polymer microspheres for intelligent absorption and release of fuel oil under pH control, characterized by consisting of: 75-95 parts by weight of amino acrylate monomer, 5-25 parts by weight of alkyl acrylate monomer, 16-22 parts by weight of dispersant, 0.1-2 parts by weight of crosslinking agent and 1-3 parts by weight of initiator.

[0008] The polymer microspheres for intelligent absorption and release of fuel under pH control, the amino acrylate monomer is one or more of 2-methyl-2-propenoic acid 2-(diethylamino) ethyl ester, 2-(diisopropylamino) methacrylic acid ethyl ester and 2-methyl-2-propenoic acid-2-[(1,1, dimethyl ethyl) amino] ethyl ester.

[0009] The polymer microspheres for intelligent absorption and release of fuel under pH control, the acrylic alkyl ester monomer is one or more of butyl acrylate, methacrylic acid octadecyl ester, methacrylic acid hexadecyl ester, methacrylic acid dodecyl ester, methyl methacrylate, isobornyl methacrylate.

[0010] The polymer microspheres for intelligent absorption and release of fuel under pH control, the dispersant is one or more of polyvinyl alcohol, polyethylene glycol, sodium dodecyl benzene sulfonate.

[0011] The polymer microspheres for intelligent absorption and release of fuel under pH control, the crosslinking agent is divinyl benzene or 2-methyl-2-propenoic acid (1,4-butanediol) ester.

[0012] The polymer microspheres for intelligent absorption and release of fuel under pH control, the initiator is azobis isobutyronitrile or benzoyl peroxide.

[0013] The preparation method of the polymer microspheres for intelligent absorption and release of fuel under pH control, comprising the following steps:

[0014] Step 1), a polyvinyl alcohol aqueous solution with a mass fraction of 5wt% is added to a reaction container for mechanical stirring and heating to 35-45℃;

[0015] Step 2), the amino acrylate monomer, the acrylic alkyl ester monomer, the initiator and the crosslinking agent are uniformly mixed to obtain a mixed solution;

[0016] Step 3), the mixed solution prepared in step 2) is slowly added to the reaction container in step 1), and deionized water is added;

[0017] Step 4), the oil bath is heated to 65-80℃, the reaction is stopped after 6-8h, and the reaction system is cooled to room temperature to obtain a crude product;

[0018] Step 5), the crude product prepared in step 4) is soaked and washed with deionized water for 2-4 times, and then is filtered and vacuum dried to obtain the polymer microspheres.

[0019] The technical scheme of the present application has the following beneficial technical effects:

[0020] 1. The preparation process is stable and easy to operate, and can realize industrialized production.

[0021] 2、The polymer microspheres prepared by the application have a fast adsorption rate, and can reach a saturated adsorption state within 5 minutes.

[0022] 3、The polymer microspheres prepared by the application can adsorb organic solvents and fuel oil, and can realize desorption of the fuel oil under acidic conditions. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 It is an electron micrograph of the polymer microspheres in the application;

[0024] Figure 2 It is a graph of the relationship between the oil absorption amount and time of the polymer microspheres with different particle sizes in the application. DETAILED DESCRIPTION

[0025] Example 1

[0026] A kind of polymer microspheres for intelligent absorption and release of fuel oil under pH control, the preparation steps are as follows:

[0027] Step 1), weigh 20 parts of polyvinyl alcohol in a four-necked flask, mechanically stir and heat to 40 DEG C;

[0028] Step 2), weigh 80 parts of 2-methyl-2-propenoic acid 2-(diethylamino) ethyl ester, 15 parts of butyl acrylate, 1 part of 2-methyl-2-propenoic acid (1,4-butanediol) ester in a 100 mL beaker, dissolve 2 parts of azobisisobutyronitrile in 15 mL of ethanol solution and add to the beaker, magnetically stir until the mixture is uniform to obtain a mixed solution;

[0029] Step 3), slowly add the mixed solution in step 2) to the four-necked flask, and then add 400 mL of deionized water;

[0030] Step 4), heat to 70 DEG C in an oil bath, start the reaction, stop heating after 7 hours of reaction, and cool the reaction system to room temperature to obtain a crude product;

[0031] Step 5), soak and wash the crude product prepared in step 4) with deionized water for 2 times, suction filter and vacuum dry to obtain polymer microspheres, and the shape structure of the polymer microspheres is shown in Figure 1 .

[0032] Example 2

[0033] A kind of polymer microspheres for intelligent absorption and release of fuel oil under pH control, the preparation steps are as follows:

[0034] Step 1), weigh 20 parts of polyvinyl alcohol in a four-necked flask, mechanically stir and heat to 40 DEG C;

[0035] Step 2), 75 parts of 2-methyl-2-propenoic acid 2-[(1,1-dimethylethyl)amino]ethyl ester, 15 parts of butyl acrylate, 5 parts of dodecyl methacrylate, and 0.5 parts of 2-methyl-2-propenoic acid (1,4-butanediol) ester are weighed in a 100 mL beaker, 1 part of azobisisobutyronitrile is dissolved in 10 mL of ethanol solution and added to the beaker, and magnetic stirring is performed until the mixture is uniform to obtain a mixed solution;

[0036] Step 3), the mixed solution in step 2) is slowly added to a four-necked flask, and 400 mL of deionized water is further added;

[0037] Step 4), the oil bath is heated to 70°C, the reaction is started, and after 7 hours of reaction, the heating is stopped, and the reaction system is cooled to room temperature to obtain a crude product;

[0038] Step 5), the crude product obtained in step 4) is soaked and washed with deionized water for 4 times, and then filtered and vacuum dried to obtain polymer microspheres.

[0039] Example 3

[0040] A kind of polymer microspheres for intelligent absorption and release of fuel under pH regulation, the preparation steps are as follows:

[0041] Step 1), 20 parts of polyvinyl alcohol are weighed in a four-necked flask, mechanically stirred and heated to 40°C;

[0042] Step 2), 75 parts of 2-methyl-2-propenoic acid 2-[(1,1-dimethylethyl)amino]ethyl ester, 15 parts of butyl acrylate, 5 parts of dodecyl methacrylate, and 0.5 parts of 2-methyl-2-propenoic acid (1,4-butanediol) ester are weighed in a 100 mL beaker, 1 part of azobisisobutyronitrile is dissolved in 10 mL of ethanol solution and added to the beaker, and magnetic stirring is performed until the mixture is uniform to obtain a mixed solution;

[0043] Step 3), the mixed solution in step 2) is slowly added to a four-necked flask, and 400 mL of deionized water is further added;

[0044] Step 4), the oil bath is heated to 70°C, the reaction is started, and after 7 hours of reaction, the heating is stopped, and the reaction system is cooled to room temperature to obtain a crude product;

[0045] Step 5), the crude product obtained in step 4) is soaked and washed with deionized water for 4 times, and then filtered and vacuum dried to obtain polymer microspheres.

[0046] Example 4

[0047] A kind of polymer microspheres for intelligent absorption and release of fuel under pH regulation, the preparation steps are as follows:

[0048] Step 1), 20 parts of polyvinyl alcohol are weighed in a four-necked flask, mechanically stirred and heated to 40°C;

[0049] Step 2), 80 parts of 2-methyl-2-propenoic acid-2-[(1,1-dimethylethyl)amino]ethyl ester, 20 parts of butyl acrylate, 5 parts of methacrylic acid dodecyl ester, and 0.5 parts of 2-methyl-2-propenoic acid (1,4-butanediol) ester were weighed in a 100 mL beaker, 1 part of azobisisobutyronitrile was dissolved in 10 mL of ethanol solution and added to the beaker, and magnetic stirring was performed until the mixture was uniform to obtain a mixed solution;

[0050] Step 3), the mixed solution in step 2) was slowly added to a four-necked flask, and 400 mL of deionized water was further added;

[0051] Step 4), the oil bath was heated to 70°C, the reaction was started, and after 7 h of reaction, the heating was stopped, and the reaction system was cooled to room temperature to obtain a crude product;

[0052] Step 5), the crude product obtained in step 4) was soaked and washed with deionized water for 3 times, and then was filtered and vacuum dried to obtain polymer microspheres.

[0053] Example 5

[0054] A kind of polymer microspheres for intelligent absorption and release of fuel under pH regulation, the preparation steps are as follows:

[0055] Step 1), 20 parts of polyvinyl alcohol were weighed in a four-necked flask, and mechanical stirring was performed while the temperature was raised to 40°C;

[0056] Step 2), 75 parts of 2-methyl-2-propenoic acid 2-(diethylamino)ethyl ester, 5 parts of 2-(diisopropylamino)ethyl methacrylate, 15 parts of butyl acrylate, and 0.5 parts of 2-methyl-2-propenoic acid (1,4-butanediol) ester were weighed in a 100 mL beaker, 1 part of azobisisobutyronitrile was dissolved in 10 mL of ethanol solution and added to the beaker, and magnetic stirring was performed until the mixture was uniform to obtain a mixed solution;

[0057] Step 3), the mixed solution in step 2) was slowly added to a four-necked flask, and 400 mL of deionized water was further added;

[0058] Step 4), the oil bath was heated to 70°C, the reaction was started, and after 7 h of reaction, the heating was stopped, and the reaction system was cooled to room temperature to obtain a crude product;

[0059] Step 5), the crude product obtained in step 4) was soaked and washed with deionized water for 4 times, and then was filtered and vacuum dried to obtain polymer microspheres.

[0060] When the polymer microspheres prepared in Examples 1 to 5 are used to remove fuel oil from contaminated water, the polymer microspheres are put into the contaminated water and stirred for 1 minute, then left to stand for 5 minutes, the polymer microspheres after absorbing oil are filtered out and put into an empty container, hydrochloric acid is added, stirred, and then the oil absorbed by the polymer microspheres is desorbed from the polymer microspheres. Taking gasoline as an example, the polymer microspheres can absorb 9 to 12 times of their own weight, and the oil release efficiency can reach about 85% in 20 seconds. The polymer microspheres can absorb 10 to 15 times of their own weight of organic solvents, and the specific case depends on the density of the organic solvent.

[0061] After the oil is released, the pH value of the polymer microspheres is adjusted to greater than or equal to 7 by using an alkaline solution or other reagent solution to deprotonate the polymer microspheres after oil release, so that the polymer microspheres become hydrophobic microspheres, and then dried, so that the polymer microspheres can be used to absorb oil again.

[0062] In the preparation method described in Example 1, the mixed solution described in step 2) is prepared by changing the stirring speed, and polymer microspheres with different particle sizes are prepared, such as 18 to 35 mesh, 35 to 65 mesh and 100 to 200 mesh, and the three kinds of polymer microspheres are tested for oil absorption, and the results are shown in Table 1. Figure 2 When the three kinds of polymer microspheres with equal weight in the above particle size range are tested for desorption, the 18 to 35 mesh polymer microspheres take 3 to 5 minutes to completely desorb, the 35 to 65 mesh polymer microspheres take 4 to 7 minutes to completely desorb, and the 100 to 200 mesh polymer microspheres take 11 to 15 minutes to completely desorb. The three kinds of polymer microspheres in the above particle size range are mixed in a weight ratio of W1:W2:W3=(1 to 1.8):(1.2 to 2.3):(2.7 to 3.2) to form a polymer microsphere mixture with a certain grading, and the time taken for the polymer microsphere mixture to absorb oil to about 95% of the saturated state is comparable to that of the 100 to 200 mesh polymer microspheres, and the time taken for the former to completely desorb is only about 75% of that of the latter, wherein W1 is the weight of the 18 to 35 mesh polymer microspheres, W2 is the weight of the 35 to 65 mesh polymer microspheres, and W3 is the weight of the 100 to 200 mesh polymer microspheres.

[0063] Obviously, the above examples are only examples for the purpose of clarity, and are not limitations on the embodiments. Based on the above description, other different forms of changes or variations can also be made by those of ordinary skill in the art. It is not necessary or possible to exhaust all embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the claims of the present patent application.

Claims

1. A polymer microsphere for intelligent fuel adsorption and desorption under pH control, characterized in that, It is composed of the following components: 75-95 parts by weight of aminoacrylate monomers, 5-25 parts by weight of alkyl acrylate monomers, 16-22 parts by weight of dispersant, 0.1-2 parts by weight of crosslinking agent, and 1-3 parts by weight of initiator; wherein, the aminoacrylate monomers are one or more of 2-methyl-2-acrylate 2-(diethylamino)ethyl ester, 2-(diisopropylamino)methacrylate ethyl ester, and 2-methyl-2-acrylate-2-[(1,1,dimethylethyl)amino]ethyl ester, the alkyl acrylate monomers are one or more of butyl acrylate, octadecyl methacrylate, hexadecyl methacrylate, dodecyl methacrylate, methyl methacrylate, and isobornyl methacrylate, and the crosslinking agent is divinylbenzene or 2-methyl-2-acrylate (1,4-butanediol) ester.

2. The polymer microspheres for intelligent fuel adsorption and desorption under pH control according to claim 1, characterized in that, The dispersant is one or more of polyvinyl alcohol, polyethylene glycol, and sodium dodecylbenzenesulfonate.

3. The polymer microspheres for intelligent fuel adsorption and desorption under pH control according to claim 1, characterized in that, The initiator is azobisisobutyronitrile or benzoyl peroxide.

4. The polymer microspheres for intelligent fuel adsorption and desorption under pH control according to claim 1, characterized in that, It is composed of the following components: 75-80 parts by weight of amino acrylate monomers, 15.5-25 parts by weight of alkyl acrylate monomers, 16-22 parts by weight of dispersant, 0.5-1 parts by weight of crosslinking agent and 1-2 parts by weight of initiator.

5. The polymer microspheres for intelligent fuel adsorption and desorption under pH control according to claim 1, characterized in that, It consists of the following components: 75-80 parts by weight of amino acrylate monomers, 20-25 parts by weight of alkyl acrylate monomers, 20 parts by weight of dispersant, 0.5-1 parts by weight of crosslinking agent and 1-2 parts by weight of initiator.

6. The method for preparing polymer microspheres for intelligent fuel adsorption and desorption under pH control as described in claim 1, characterized in that, Includes the following steps: Step 1): Add a 5 wt% polyvinyl alcohol aqueous solution to the reaction vessel, stir mechanically, and heat to 35–45°C. Step 2), mix amino acrylate monomers, alkyl acrylate monomers, initiators and crosslinking agents evenly to obtain a mixed solution; Step 3): Slowly add the mixed solution obtained in Step 2) to the reaction vessel in Step 1), and add deionized water; Step 4), heat in an oil bath to 65-80°C, react for 6-8 hours, then stop heating and allow the reaction system to cool to room temperature to obtain the crude product; Step 5): Soak the crude product obtained in step 4) in deionized water and wash it. Repeat this process 2 to 4 times. Filter the product and dry it under vacuum to obtain polymer microspheres.

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