CN112851869B - Method for preparing morphology-adjustable polyion liquid-based anisotropic composite particles based on seed polymerization method - Google Patents
Method for preparing morphology-adjustable polyion liquid-based anisotropic composite particles based on seed polymerization method Download PDFInfo
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Abstract
The invention discloses a method for preparing morphology-adjustable polyion liquid-based anisotropic composite particles based on a seed polymerization method. Preparing PMMA polymer seed balls by using purified MMA as a polymerization monomer through a polymerization method in a reaction solvent in the presence of an initiator and an emulsifier; dropping an ionic liquid monomer into the PMMA polymer seed ball dispersion liquid, after the ionic liquid monomer fully swells into the seed ball, dropping an initiator potassium persulfate aqueous solution, uniformly stirring, and heating to 70 ℃ for reaction for 24 hours. According to the invention, the shape of the PMMA-PIL anisotropic composite particle is conveniently regulated and controlled by a simple and convenient method, and the prepared particles with different shapes can be applied differently according to conditions. And because the PIL is a functional polymer, the PIL can be simply modified by methods such as anion exchange and the like, and the PIL also has a very positive effect on expanding the application range of the particle.
Description
Technical Field
The invention relates to a preparation method of appearance-adjustable polyion liquid-based anisotropic composite particles, in particular to a novel method for adjusting and controlling the appearance of polymer composite particles.
Background
The anisotropic composite particles are particles with multiple different properties, are special functional particles, and have great research interest due to the great application prospects in various aspects such as particle emulsifiers, biological carriers, interface catalysis, self-assembly systems, electronic displays and the like. With the continuous progress of scientific research techniques, researchers have developed a variety of methods for preparing anisotropic composite particles. However, among the various preparation methods, the seed polymerization method is undoubtedly the most basic method for synthesizing anisotropic composite particles due to the advantages of simple operation, controllability, large-scale preparation and the like.
Ionic Liquids (IL) are considered "green solvents" and, in addition to being non-volatile and non-flammable, have a high CO content2Solubility, ionic conductivity, and the like, and therefore, attention has been drawn to the field of functional materials. Many studies have focused on the preparation of solid ionic liquids, such as ionic liquid gels, polyionic liquids (PILs), and the like. In addition to retaining the properties of IL, these polymers also have very good mechanical strength. In particular the particles of the PIL, are,it can be surface modified by simple solution mixing, and its solubility in water can be adjusted by anion exchange. In recent years, researchers have also introduced PIL into the preparation of composite particles to impart more functionality to the particles. Minami et al successfully prepared micron-sized P ([ MTMA ] in 70 deg.C methanol solution using PVP as stabilizer by dispersion polymerization ][TFSA]) The quaternary ammonium salt type polyionic liquid can prepare monodisperse PIL with different sizes by adjusting the mass ratio of ethanol to methanol in the solvent, and the water solubility of the particles is changed by anion exchange. Subsequently, they also conceived that PS or PMMA was used as a seed and IL was used as a monomer to prepare polymer/polyion liquid composite particles by a seed dispersion polymerization method. During the experiment, it is found that only the PS/PIL with the core-shell shape can be obtained in the ethanol environment regardless of the change of the polymerization speed and the temperature. Further theoretical calculation results show that the relation of diffusion coefficients S of the three phases PS, PIL and ethanol tends to form a core-shell structure because the surface tension gamma is determined by the dispersion force gammadAnd a polar force gammapTwo parts, albeit gammaPSAnd gammaPILThe values are close to but
Ratio of
Much larger, this results in a large interfacial tension between the PS and the PIL. While
And
the phase difference is small, so in the system taking PMMA as the seed, the calculated diffusion coefficient of the three phases shows that the formation of the composite particles is possible, and the same as the experimental result. The recent Minami group synthesized PMMA/PIL Janus particles based on the first two tasks. Firstly, PMMA/PIL core-shell structure is prepared through seed dispersion polymerization, and the core-shell structure is further converted into Janus structure by using SARM phase separation method. The place of The composite particles with obvious partition of two-phase interface can be successfully obtained because excessive Li [ TFSA ] is added in the SARM process]The addition of this electrolyte prevents ion exchange between the PIL and the anions in the water. Because ion pairs are formed between anions and cations on the outer surface of the PIL particles, the PIL particles do not show electric property, and the surface of the PIL particles is hydrophobic. However, after anion exchange, the anions successfully exchanged to the surface of the PIL will dissociate in water, thereby increasing the hydrophilicity of the particle surface, which results in
And with
(where l represents the reaction medium, i.e., water) are increasingly different, which, according to the conclusion made by Kim et al, does not allow the phase separation of the second phase. While adding Li [ TFSA ]]The post anion exchange is prevented, thus providing a suitable environment for successful phase separation. However, the conventional method for synthesizing the composite particles containing the polyion liquid cannot realize convenient regulation and control of the particle morphology, so that the application range of the particles is limited.
However, the above methods for preparing polyion liquid-based composite particles still have certain defects, for example, the method cannot realize convenient regulation and control of particle morphology, so that the potential application range of the particles is severely limited. Therefore, if the seed polymerization method is used for preparing the anisotropic composite particles containing the polyion liquid, the complexity of the existing method is abandoned, the convenient regulation and control of the particle morphology can be realized, and the method has a very positive significance on the batch production and large-scale application of the particles.
Disclosure of Invention
The invention utilizes a seed polymerization method to prepare anisotropic composite particles containing functional polyion liquid, and simultaneously realizes convenient regulation and control of particle morphology through changes of seed sphere size and interfacial tension.
The technical scheme adopted by the invention is as follows: a method for preparing morphology-adjustable polyion liquid-based anisotropic composite particles based on a seed polymerization method comprises the following steps:
1) preparation of ionic liquid monomer: stirring a methacryloyloxyethyl trimethyl ammonium chloride ([ MTMA ] Cl) aqueous solution and lithium bis (trifluoromethanesulfonyl) imide (Li [ TFSA ]) at room temperature for 12 hours to perform an ion exchange reaction to obtain an ionic liquid monomer ([ MTMA ] [ TFSA ]);
2) preparation of PMMA polymer seed spheres: preparing PMMA polymer seed spheres by a polymerization method in a reaction solvent in the presence of an initiator and an emulsifier by taking purified Methyl Methacrylate (MMA) as a polymerization monomer;
3) dispersing the PMMA polymer subspheres prepared in the step 2) in a composite solvent composed of deionized water and a nonionic surfactant, carrying out ultrasonic treatment for 10min, and stirring for 2h at room temperature to uniformly disperse the PMMA polymer subspheres to obtain PMMA polymer subsphere dispersion liquid;
4) Dropwise adding the ionic liquid monomer ([ MTMA ] [ TFSA ]) obtained in the step 1) into the PMMA polymer seed ball dispersion liquid, fully swelling the ionic liquid monomer ([ MTMA ] [ TFSA ]) into the seed ball, dropwise adding an initiator potassium persulfate (KPS) aqueous solution, uniformly stirring, and heating to 70 ℃ for reaction for 24 hours.
Preferably, in the above method, step 2), the method for purifying Methyl Methacrylate (MMA) is: passing Methyl Methacrylate (MMA) monomer slowly through the Al-charged cell2O3And colorless transparent MMA monomer of the polymerization inhibitor is filtered off at an outlet at the lower end of the filter column and collected by a brown sample bottle.
Preferably, in the method, step 2), the emulsifier is polyvinylpyrrolidone (PVP), and the addition amount of the emulsifier is 1.0-10.0% of the MMA monomer by mass.
Preferably, in the above method, step 2), the initiator is Azobisisobutyronitrile (AIBN) or potassium persulfate (KPS), and the amount of the initiator is 1.0% to 2.0% of the MMA monomer by mass.
Preferably, in the method, in the step 2), the reaction solvent is deionized water or a mixture of methanol and deionized water according to a volume ratio of 1: 1-2.5: 1.
Preferably, in the above method, step 3), the nonionic surfactant is nonylphenol polyoxyethylene ether (NP-40).
Preferably, in the method, step 3), the mass ratio of the PMMA polymer seed spheres to the deionized water in the PMMA polymer seed sphere dispersion liquid is 0.2: 10.
Preferably, in the above method, step 4), the ratio by mass of the ionic liquid monomer to the PMMA polymeric species daughter spheres is 1: 1.
The invention has the beneficial effects that: according to the invention, the shape of the PMMA-PIL anisotropic composite particle is conveniently regulated and controlled by a simple and convenient method, and the prepared particles with different shapes can be applied differently according to conditions. And because the PIL is a functional polymer, the PIL can be simply modified through anion exchange and the like, and the PIL also has a very positive effect on expanding the application range of the particle.
Description of the drawings:
FIG. 1 shows the IR absorption spectra of PMMA (1), ionic liquid monomer [ MTMA ] [ TFSA ] (2) and PMMA-PIL composite particles (3).
FIG. 2 is a Differential Scanning Calorimetry (DSC) spectrum of ionic liquid monomer [ MTMA ] [ TFSA ].
FIG. 3 shows the effect of different PMMA seed sphere sizes on the morphology of PMMA-PIL composite particles;
wherein, the PMMA seed balls have the diameter of a1)200nm；b1)500nm；c1)800nm；d1)1100nm。
FIG. 4 shows the effect of different NP-40 addition amounts on the appearance of PMMA-PIL composite particles;
wherein, the addition amount of NP-40 is a)0 g; b)0.5 g; c)1.0 g; d)1.5 g; e)2.0 g.
Detailed Description
In order that the invention may be better understood, the invention is further illustrated by the following examples, which are intended to better illustrate the invention and are not to be construed as limiting the scope of the invention in any way.
EXAMPLE 1 preparation of Ionic liquid monomer
The reaction formula for synthesizing the ionic liquid monomer is as follows:
the preparation method comprises the following steps: 2.0g of 75% concentration MTMA Cl aqueous solution and 2.3g of Li TFSA are uniformly mixed, stirred for 12 hours at room temperature to carry out anion exchange reaction, the obtained reaction liquid is divided into an upper layer and a lower layer, the lower layer ionic liquid phase is taken, a small amount of deionized water is added into the ionic liquid phase to be continuously stirred and washed, the reaction is repeated for five times and then placed into a vacuum drying oven, and after drying is carried out for 24 hours at 50 ℃, colorless viscous ionic liquid monomer ([ MTMA ] [ TFSA ]) is prepared.
As shown in FIG. 1, 2 in FIG. 1 is an ionic liquid monomer ([ MTMA ]][TFSA]) Infrared absorption spectrum of (2). From the infrared absorption spectrum of the synthesized ionic liquid monomer, 1728cm-1The peak is the stretching vibration peak of C ═ O in the ester group, 1353cm-1Where is S (═ O)21190 + 1100cm-1Is of-CF3The structural integrity of the ionic liquid monomer can be qualitatively obtained through the stretching vibration peak. And the DSC curve shown in figure 2 shows that a very low glass transition temperature exists at-52 ℃, which is also agreed in the literature, further proving that the ionic liquid monomer has been successfully synthesized.
EXAMPLE 2 preparation of PMMA Polymer seed spheres
The method comprises the following steps:
purification of MMA: passing Methyl Methacrylate (MMA) monomer slowly through the Al-charged bed2O3And a colorless transparent MMA monomer obtained by filtering off the polymerization inhibitor is collected by a brown sample bottle for standby at an outlet at the lower end of the filter column.
Weighing 0.1g of PVP, dispersing the PVP in 60mL of deionized water, adding 5.0g of purified MMA monomer, carrying out ultrasonic emulsification completely, transferring the system to an oil bath pan, and starting to heat. In the heating process, 10mL KPS aqueous solution (1 wt%) is added at 50 deg.C and 85 deg.C respectively for two times, and is finally stabilized at 100 deg.C for 2h to complete the polymerization process. And after the reaction is finished, centrifuging to take a lower-layer product, adding 20mL of water into the lower-layer product, performing ultrasonic dispersion uniformly, centrifuging, pouring out the upper-layer solvent, washing for 5 times in the way, and freeze-drying the obtained product to obtain the PMMA polymer seed ball.
As shown in fig. 1, 1 in fig. 1 is an infrared absorption spectrum of PMMA polymer species subsphere. As can be seen from 1 in FIG. 1, 1728cm is seen in the IR absorption spectrum of the synthesized PMMA-1The peak is the stretching vibration peak of C ═ O in the ester group, 1272cm-1Asymmetric stretching vibration peak at-C-O-C-, 1148cm -1The symmetric stretching vibration peak of-C-O-C-is positioned, so that the structural integrity of the PMMA can be qualitatively obtained.
From fig. 3 a1The scanning electron microscope image of the PMMA seed sphere synthesized in the embodiment can be seen to have the particle size of about 200nm and good dispersibility and uniformity.
EXAMPLE 3 preparation of PMMA Polymer seed spheres
The method comprises the following steps:
purification of MMA: passing Methyl Methacrylate (MMA) monomer slowly through the Al-charged2O3And a colorless transparent MMA monomer obtained by filtering off the polymerization inhibitor is collected by a brown sample bottle for standby at an outlet at the lower end of the filter column.
0.3g of PVP is weighed out and added to 60mL of reaction solvent composed of methanol and deionized water respectively, wherein the volume ratio of methanol to deionized water is 1:1 (methanol/deionized water 30.0mL/30.0mL), 5:3 (methanol/deionized water 37.5mL/22.5mL) and 7:3 (methanol/deionized water 42.0mL/18.0mL), and the PVP is completely dispersed by ultrasonic wave. 3.0g of purified MMA monomer, 30.0mg of AIBN was added thereto. The whole system is subjected to vacuum pumping-nitrogen gas introduction three times of circulation and then reacts for 11 hours at the temperature of 70 ℃. And after the reaction is finished, centrifuging to take a lower-layer product, adding 20mL of water into the lower-layer product, performing ultrasonic dispersion uniformly, centrifuging, pouring out the upper-layer solvent, washing for 5 times in the way, and freeze-drying the obtained product to obtain the PMMA polymer seed ball.
B in FIG. 31、c1And d1Scanning electron micrographs of PMMA polymer seed spheres obtained with methanol/deionized water of 30.0mL/30.0mL, 37.5mL/22.5mL, and 42.0mL/18.0mL, respectively, as can be seen in FIG. 3, synthesized in this exampleThe particle size of PMMA polymer seed spheres is 500nm (b)1)、800nm(c1) And 1100nm (d)1) And the product has good dispersibility and uniformity.
Example 4 polyion liquid based Anisotropic composite particles (PMMA-PIL)
The preparation method comprises the following steps: 0.2g of PMMA polymer seed ball powder prepared in the example 2 and the example 3 is respectively added into a single-mouth bottle containing 1.0g of NP-40 and 10g of deionized water, after ultrasonic treatment is carried out for 10min, stirring is carried out for 2h at room temperature, so that the seed balls are uniformly dispersed, and PMMA polymer seed dispersion liquid is respectively prepared.
0.2g of the ionic liquid monomer synthesized in the example 1 is respectively dripped into PMMA polymer seed dispersion liquid, the mixture is stirred for 11 hours at room temperature to enable the ionic liquid to be fully swelled into seed spheres, 0.2g of KPS aqueous solution (1 wt%) is dripped, the mixture is continuously stirred for 1 hour, and the temperature is raised to 70 ℃ to react for 24 hours, so that polyion liquid-based anisotropic composite particles (PMMA-PIL) are obtained.
FIG. 1 shows an infrared absorption spectrum 3 of PMMA-PIL. 1728cm, as can be seen in FIG. 1 at 3-1、2980cm-1The peak positions are respectively the stretching vibration peak of C ═ O in the ester group and C-H in the alkyl group on PMMA, 1353cm -1、1190-1100cm-1Where are respectively S (═ O) on PIL2and-CF3Thereby demonstrating the successful combination of the two polymers into PMMA-PIL composite particles. While a in FIG. 32Is deionized water; b2Is methanol/deionized water 30.0mL/30.0mL, c2Is methanol/deionized water 37.5mL/22.5mL, d2Scanning electron microscope images of PMMA-PIL obtained by using methanol/deionized water of 42.0mL/18.0mL as a composite solvent. As can be seen from fig. 3, the PMMA-PIL composite particles synthesized in the present embodiment have different sizes, but exhibit Patchy morphology with distinct structural partitions, and have good dispersibility and uniformity. The morphology of the PMMA-PIL composite particles is changed in this example by changing the size of the modified seed spheres.
Example 5 polyion liquid based Anisotropic composite particles (PMMA-PIL)
The preparation method comprises the following steps: 0.2g of PMMA polymer seed ball powder prepared in example 2 was respectively added into a single-neck flask containing NP-40 and 10g of deionized water, wherein the addition amount of NP-40 was 0g, 0.5g, 1.0g, 1.5g and 2.0g, and after 10 minutes of ultrasonic treatment, the mixture was stirred at room temperature for 2 hours to uniformly disperse the seed balls, and PMMA polymer seed dispersion solutions were respectively prepared.
0.2g of the ionic liquid monomer synthesized in the example 1 is respectively dripped into PMMA polymer seed dispersion liquid, the mixture is stirred for 11 hours at room temperature to enable the ionic liquid to be fully swelled into seed spheres, 0.2g of KPS aqueous solution (1 wt%) is dripped, the mixture is continuously stirred for 1 hour, and the temperature is raised to 70 ℃ to react for 24 hours, so that polyion liquid-based anisotropic composite particles (PMMA-PIL) are obtained.
As shown in the scanning electron microscope image of PMMA-PIL prepared by adding NP-40 in the amounts of a (0g), b (0.5g), c (1.0g), d (1.5g) and e (2.0g) in FIG. 4, in the present example, when the amount of NP-40 is 0g, the PMMA-PIL composite particles are in a core-shell shape; when the addition amount of NP-40 is 0.5g respectively, the PMMA-PIL composite particles are of a Patch structure with two patches; when the addition amount of NP-40 is 1.0g, the PMMA-PIL composite particles have a Patchy structure with three patches, and the composite particles have obvious phase partition in both cases from the aspect of EDS characterization. However, when the addition amount of NP-40 is increased to 1.5g, the PMMA-PIL composite particle still has a Patchy structure with three patches, but in EDS characterization, a layer of PIL is covered on the surface of the seed sphere to indicate that the anisotropic structure of the PMMA-PIL composite particle is changed, and when the addition amount of NP-40 is continuously increased to 2.0g, IL has good affinity with a solvent phase, so that the amount of IL entering the interior of the seed sphere is small, most of the IL enters the exterior of the seed sphere and is adhered to the exterior of the seed sphere to form a random shape which is adhered together. Therefore, in the present example, the morphology of the PMMA-PIL composite particles was changed by changing the addition amount of NP-40.
The results of the examples show that: the PMMA-PIL anisotropic composite particle prepared by the invention has a complete structure and a simple synthesis process, and the shape of the composite particle can be regulated and controlled by simply changing the size of the seed ball and the addition amount of the non-ionic surfactant NP-40. In addition, the anisotropic composite particles prepared by the method also have good emulsifying property, can be used as a particle emulsifier, combines the functionality of the PIL, and has promising application prospect in the fields of interface catalysis and the like.
Claims (7)
1. A method for preparing morphology-adjustable polyion liquid-based anisotropic composite particles based on a seed polymerization method is characterized by comprising the following steps:
1) preparation of ionic liquid monomer: stirring a methacryloyloxyethyl trimethyl ammonium chloride [ MTMA ] Cl aqueous solution and bis (trifluoromethanesulfonyl) imide lithium Li [ TFSA ] for 12 hours at room temperature to obtain an ionic liquid monomer [ MTMA ] [ TFSA ];
2) preparation of PMMA polymer seed spheres: preparing PMMA polymer seed balls by using purified methyl methacrylate MMA as a polymerization monomer through a free radical polymerization method in a reaction solvent in the presence of an initiator and an emulsifier; the reaction solvent is deionized water or a mixture of methanol and deionized water according to a volume ratio of 1: 1-2.5: 1;
3) Dispersing the PMMA polymer subspheres prepared in the step 2) in a composite solvent composed of deionized water and a nonionic surfactant, carrying out ultrasonic treatment for 10min, and stirring for 2h at room temperature to uniformly disperse the PMMA polymer subspheres to obtain PMMA polymer subsphere dispersion liquid;
4) dropwise adding the ionic liquid monomer [ MTMA ] [ TFSA ] obtained in the step 1) into PMMA polymer seed ball dispersion liquid, after the ionic liquid monomer [ MTMA ] [ TFSA ] is fully swelled into the seed ball, dropwise adding an initiator potassium persulfate KPS aqueous solution, uniformly stirring, and heating to 70 ℃ for reaction for 24 h.
2. The method as claimed in claim 1, wherein in step 2), the method for purifying methyl methacrylate MMA comprises: the MMA monomer methyl methacrylate is slowly passed through the catalyst containing Al2O3The effluent liquid is collected by the filter column.
3. The method according to claim 1, wherein in the step 2), the emulsifier is polyvinylpyrrolidone PVP, and the addition amount of the emulsifier is 1.0-10.0% of the MMA monomer mass.
4. The method as claimed in claim 1, wherein in step 2), the initiator is Azobisisobutyronitrile (AIBN) or potassium persulfate (KPS), and the amount of the initiator is 1.0-2.0% of the mass of MMA monomer.
5. The method as claimed in claim 1, wherein in step 3), the nonionic surfactant is nonylphenol polyoxyethylene ether NP-40.
6. The method of claim 1, wherein in step 3), the mass ratio of the PMMA polymer seed spheres to the deionized water in the PMMA polymer seed sphere dispersion liquid is 0.2: 10.
7. The method according to claim 1, wherein in step 4), the ionic liquid monomer to PMMA polymer species subspheres =1:1 by mass ratio.
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