CN111454468B - A shape-controllable smart responsive microsphere and its preparation method - Google Patents

A shape-controllable smart responsive microsphere and its preparation method Download PDF

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CN111454468B
CN111454468B CN202010231520.9A CN202010231520A CN111454468B CN 111454468 B CN111454468 B CN 111454468B CN 202010231520 A CN202010231520 A CN 202010231520A CN 111454468 B CN111454468 B CN 111454468B
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白永康
张纪雯
陈鑫
陈莉
田然
田雨
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Xian Jiaotong University
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Abstract

一种形状可控的智能响应微球及其制备方法，将醋酸纤维素溶解于N,N二甲基甲酰胺中，然后加入二氯甲烷，得到油相；将十二烷基硫酸钠溶于水中，得到水相；在搅拌下，将油相滴入水相中，得到分散液，冷冻干燥，然后分散于聚乙烯醇溶液中，再浇筑于聚四氟乙烯模具中，固化，得到薄膜；将薄膜在加热下沿不同方向拉伸，溶解于水中，搅拌至薄膜溶剂溶解，离心水洗，冷冻干燥，得到形状可控的智能响应微球。本发明基于醋酸纤维素中的氢键交联作用，可以通过加热的方式实现微球的微观形状记忆性能。本发明不仅可以调控微球的大小，并且可以在二维甚至三维空间上调控微球的形状。这种能够响应外部刺激从而控制形状转换的微球具有广阔的应用前景。

Figure 202010231520

A shape-controllable intelligent response microsphere and a preparation method thereof. Cellulose acetate is dissolved in N,N dimethylformamide, and then dichloromethane is added to obtain an oil phase; sodium lauryl sulfate is dissolved in water to obtain an aqueous phase; under stirring, drop the oil phase into the aqueous phase to obtain a dispersion, freeze-dry, then disperse in a polyvinyl alcohol solution, and then pour it into a polytetrafluoroethylene mold, and solidify to obtain a film; The film is stretched in different directions under heating, dissolved in water, stirred until the film solvent is dissolved, centrifugally washed with water, and freeze-dried to obtain shape-controllable smart responsive microspheres. Based on the hydrogen bond cross-linking in cellulose acetate, the invention can realize the microscopic shape memory performance of the microspheres by heating. The invention can not only control the size of the microsphere, but also control the shape of the microsphere in two-dimensional or even three-dimensional space. Such microspheres, which can control shape transformation in response to external stimuli, have broad application prospects.

Figure 202010231520

Description

Shape-controllable intelligent response microsphere and preparation method thereof
Technical Field
The invention relates to the field of intelligent microsphere preparation, in particular to an intelligent response microsphere with a controllable shape and a preparation method thereof.
Background
It is well known that in nature, a large number of microscopic particles, such as viruses, bacteria, cells, etc., exist, and the ultimate distribution, delivery, and biological activity of these particles in a living body is largely dependent on the size, morphology, and surface characteristics of the particles. The characteristics are regulated and controlled on a micro-nano scale and can be switched at any time according to requirements, so that the actual application prospect of the material can be remarkably expanded, and particularly the material can be applied to the fields of drug delivery, micro sensors, micro motors and the like. Many methods (seed dispersion polymerization, emulsion polymerization, electrospray, microfluidic generation, etc.) have been used to prepare microparticles of various shapes, such as raspberry, acorn, cylinder, bowl, etc. However, these particles can only be applied to a single microenvironment, and the micro morphology of the particles cannot be controlled according to various changes of the microenvironment, so as to meet the requirements of various practical applications.
Shape memory polymers (Shape memory polymers) are smart materials that undergo a Shape transition under an external stimulus and retain the temporary Shape under certain conditions, but return to their original Shape autonomously when the stimulus is reapplied. The shape transformation characteristic has been widely studied on a macroscopic scale and has been primarily applied to the fields of aerospace, biomedical science, intelligent drivers and the like.
Disclosure of Invention
The invention aims to provide an intelligent response microsphere with a controllable shape and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing shape-controllable intelligent response microspheres comprises the following steps:
1) preparing an oil phase: dissolving cellulose acetate in a solvent, then adding dichloromethane, and performing ultrasonic dispersion uniformly to obtain an oil phase;
preparing an aqueous phase: dissolving sodium dodecyl sulfate in water to obtain a water phase;
2) dropwise adding the oil phase into the water phase under stirring, uniformly stirring to obtain a dispersion liquid, washing the dispersion liquid with hot water, and freeze-drying to obtain the shape memory microspheres;
3) dispersing shape memory microspheres in a polyvinyl alcohol solution by ultrasound, pouring the polyvinyl alcohol solution into a mold, and curing to obtain a PVA film loaded with microspheres;
4) and (3) stretching the PVA film loaded with the microspheres in different directions under heating, cooling, dissolving in water, stirring until the film is dissolved, centrifugally washing, and freeze-drying to obtain the shape-controllable intelligent response microspheres.
The invention has the further improvement that in the step 1), the hydroxyl content in the cellulose acetate is 8.7 percent, 4.0 percent or 3.5 percent by mass; the mass of the cellulose acetate is 5-8% of the mass of the solvent; the solvent is N, N dimethylformamide, dimethyl sulfoxide or tetrahydrofuran.
The invention is further improved in that in the step 1), the addition amount of the dichloromethane solution is 4-6 times of the volume of the solvent; the ultrasonic power is 400W, and the time is 2-5 min.
The invention further improves that in the step 1), the mass concentration of the sodium dodecyl sulfate solution in the water phase is 0.5-1 wt%, and the using amount of water is 20-25 times of the volume of the solvent.
The invention further improves that in the step 1), a photo-thermal filling material is also added into the water.
The further improvement of the invention is that in the step 1), the photo-thermal filling material is multi-walled carbon nano-tube, graphene oxide or polydopamine; the dosage of the photo-thermal filling material is 20-40% of the mass of the cellulose acetate.
The further improvement of the invention is that in the step 2), the rotating speed of the stirrer is 500 rpm-2000 rpm, and the stirring time is 12-18h after the dripping is finished.
The further improvement of the invention is that in the step 3), the ultrasonic power is 400W, and the time is 3-5 h; the mass concentration of polyvinyl alcohol in the polyvinyl alcohol solution is 1-3%; the polyvinyl alcohol model is 1788; the mass of the shape memory microsphere is 0.1-0.2% of that of the polyvinyl alcohol 1788; the curing temperature is 60-70 ℃ and the curing time is 12-18 h.
The further improvement of the invention is that in the step 4), the heating temperature is 70-80 ℃, and the stirring time is 6-8 h.
The intelligent response microsphere with the controllable shape is prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses natural high molecular material Cellulose Acetate (CA) as a substrate, firstly, the particle size of the microsphere is regulated and controlled by regulating the rotating speed by an emulsion solvent volatilization method; then, microspheres with different shapes can be easily obtained by a film stretching method; based on the hydrogen bond crosslinking action in the cellulose acetate, the microscopic shape memory performance of the microsphere can be realized in a heating mode. The process involved in the invention can regulate the size of the microsphere and regulate the shape of the microsphere in two-dimensional or even three-dimensional space. The microsphere capable of responding to external stimulus to control shape conversion has wide application prospect, and the multifunctional property of the microsphere can be suitable for various complex practical applications.
Furthermore, the photo-thermal filling material is doped in the oil phase, so that the shape memory composite microsphere with photo-responsiveness can be prepared, and therefore, infrared light can be used as a stimulus source to control the change of the microsphere shape in practical application. Combined with the light responsiveness, the material has wide application prospect in micro-drivers and biomedical applications.
Furthermore, the polyvinyl alcohol 1788 and the microspheres can be stretched at 60-70 ℃, and the polyvinyl alcohol 1788 has certain water solubility at normal temperature, so the polyvinyl alcohol 1788 is selected.
Drawings
FIG. 1 shows a polymer microsphere CA provided in example 1 of the present invention1000The original shape of (a); wherein (a) is CA1000(b) is CA1000Optical microscopy of (a).
FIG. 2 is a schematic representation of a polymeric microsphere CA according to example 1 of the present invention1000An optical microscope image of the shape recovery process with increasing temperature after 100% axial deformation; wherein (a) is 25 ℃, (b) is 65 ℃, (c) is 70 ℃, (d) is 80 ℃.
FIG. 3 is a schematic representation of a polymeric microsphere CA provided in example 1 of the present invention1000Scanning electron micrographs after 100% axial deformation and recovery; wherein (a) is an original shape, (b) is a temporary shape, and (c) is a restored original shape.
FIG. 4 is a schematic representation of a polymeric microsphere CA provided in example 2 of the present invention1000(a-b) optical microscopy images and (c-d) scanning electron microscopy images of 200% axial deformation and recovery from the original shape at 80 ℃; wherein, (a) is an optical microscopic image of the temporary shape, (c) is a scanning microscopic image of the temporary shape, (b) is an optical microscopic image of the restored original shape, and (d) is a scanning microscopic image of the restored original shape.
FIG. 5 shows a polymer microsphere CA provided in example 3 of the present invention1000(a-b) optical microscopy images and (c-d) scanning electron microscopy images of 300% axial deformation and recovery of the original shape at 80 ℃; wherein (a) and (c) are temporary shapes, and (b) and (d) are restored original shapes.
FIG. 6 shows example 4 of the present inventionProvided polymer microspheres CA1000A scanning electron microscope image of the disc-shaped microspheres obtained by biaxial stretching and shape recovery; wherein (a) is an original shape, (b) is a temporary shape, and (c) is a restored original shape.
FIG. 7 is a scanning electron micrograph of the original shapes of the polymer microspheres provided in example 5, example 6 and example 7 of the present invention; wherein (a) is CA500(ii) a (b) Is CA1500(ii) a (c) Is CA2000。
FIG. 8 is a statistic of the particle size distribution of the polymeric microspheres provided in examples 1, 5, 6 and 7 of the present invention; wherein (a) is CA500(ii) a (b) Is CA1000(ii) a (c) Is CA1500(ii) a (d) Is CA2000。
FIG. 9 is the original shape of the composite microsphere CA/MWCNT provided in example 8 of the present invention; wherein (a) is a polarization microscope image of CA/MWCNT, (b) is a scanning electron microscope image of CA/MWCNT, and (c) is an enlarged surface image of CA/MWCNT.
FIG. 10 is the particle size statistics of the composite microsphere CA/MWCNT provided in example 8 of the present invention.
FIG. 11 is a photo-thermal conversion graph of the composite microsphere CA/MWCNT provided in example 8 of the present invention.
Fig. 12 is a photothermographic image at the arrows in fig. 11.
FIG. 13 shows the axial deformation of the composite microsphere CA/MWCNT provided in example 8 of the present invention at 1.55W cm-2An optical micrograph of the shape recovery process was illuminated with infrared light.
Detailed Description
The invention prepares an intelligent response deformation microsphere. The present invention will be described in further detail with reference to the accompanying drawings and examples. The specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.
The preparation method of the shape-controllable intelligent response microsphere comprises the following steps:
1) preparing an oil phase: dissolving CA (cellulose acetate) in a container filled with solvent, and stirring at 60-80 deg.C for 3-5 h; cooling the reacted solution to room temperature, adding dichloromethane into the solution, and performing ultrasonic dispersion uniformly to obtain a water phase;
wherein the cellulose acetate as the substrate may be selected from cellulose acetate having a hydroxyl group content of 8.7%, 4.0% or 3.5% by mass.
The mass of the cellulose acetate is 5-8% of the mass of the solvent.
The amount of dichloromethane solution added is 4-6 times the volume of the solvent.
The solvent is N, N dimethylformamide, dimethyl sulfoxide or tetrahydrofuran.
The ultrasonic power is 400W, and the time is 2-5 min.
2) Preparing an aqueous phase: dissolving a certain amount of Sodium Dodecyl Sulfate (SDS) in water to prepare an SDS aqueous solution, and uniformly mixing to obtain a water phase;
wherein the mass concentration of the sodium dodecyl sulfate solution (SDS) is 0.5-1% wt, and the dosage of the sodium dodecyl sulfate solution is 20-25 times of the volume of the solvent.
3) And under the condition of magnetic stirring, dropwise adding the oil phase into the water phase, continuously stirring for 12-18h, washing the obtained dispersion with hot water, and freeze-drying to obtain the shape memory microspheres.
The rotation speed of the magnetic stirrer is 500rpm to 2000rpm, preferably 500rpm, 1000rpm, 1500rpm or 2000 rpm.
4) Dispersing the freeze-dried particles in polyvinyl alcohol (PVA) by ultrasonic dispersion1788) Pouring the solution into a polytetrafluoroethylene mold, and curing at 60-70 ℃ for 12-18h to obtain the PVA film loaded with the microspheres.
Wherein, the mass concentration of the polyvinyl alcohol 1788 solution is 1-3 wt%, and the mass of the shape memory microsphere is 0.1-0.2% of the mass of the polyvinyl alcohol 1788 solution.
The ultrasonic power is 400W, and the time is 3-5 h.
5) Stretching the solidified PVA film at 70-80 ℃ in different directions in different proportions, cooling, dissolving the PVA film in cold water, stirring for 6-8h, centrifugally washing, and freeze-drying to obtain deformed microspheres with different particle sizes and shapes.
The second aspect of the invention provides a preparation method of a photoresponse shape memory microsphere, which comprises the following steps:
1) preparing an oil phase: dissolving CA in a container filled with solvent, and stirring at 60-80 deg.C for 3-5 h; cooling the reacted solution to room temperature, adding dichloromethane into the solution, and performing ultrasonic dispersion uniformly to obtain a water phase;
2) preparing an aqueous phase: mixing a certain amount of photo-thermal filling material and lauryl sodium sulfate in water and performing ultrasonic treatment to uniformly disperse the photo-thermal filling material and the lauryl sodium sulfate to obtain a water phase;
the photo-thermal filling material is a multi-wall carbon nano tube, graphene oxide or polydopamine. The dosage of the photo-thermal filling material is 20-40% of the mass of the CA. The ultrasonic power is 400W, and the time is 10-30 min.
3) Dropwise adding the oil phase into the water phase stirred by a magnetic stirrer, stirring for 12-18h, washing the obtained dispersion with hot water, and freeze-drying to obtain the photoresponse shape memory microspheres.
The rest steps 4) and 5) are the same as the preparation method of the intelligent response microsphere with the controllable shape.
When the photoresponse shape memory microspheres are prepared, the steps are the same as those of preparing the shape-controllable intelligent response microspheres except that photo-thermal filling materials are added into a water phase, and ultrasonic waves (the ultrasonic power is 400W and the time is 10-30min) are adopted for uniformly mixing.
The following are specific examples.
Example 1
Preparing an oil phase: 1.00g of cellulose acetate (mass fraction of hydroxyl group: 8.7%, CA)8.7％) Dissolving in 20mL of N, N-dimethylformamide, and stirring at 80 ℃ for 3 h; and (3) cooling the reacted solution to room temperature, adding 80mL of dichloromethane solution, and performing 400w ultrasonic dispersion for 2min to uniformly disperse the dichloromethane solution to obtain an oil phase.
Preparing an aqueous phase: 2.00g of sodium lauryl sulfate was dissolved in 400mL of water to obtain an aqueous phase.
Dropwise adding the oil phase into the water phase under stirring with a magnetic stirrer at 1000rpm, stirring for 12 hr, centrifuging, washing with hot water for 5 times, and freeze drying to obtain shape memory microsphere CA1000。
0.05g of freeze-dried particles CA1000Dissolving in 40.00g of a polyvinyl alcohol solution with the mass fraction of 1%, ultrasonically dispersing for 3h at 400w, pouring the solution into a polytetrafluoroethylene mold, and curing at 70 ℃ for 12h to obtain the microsphere-loaded CA1000The PVA film of (1).
Loading the solidified microspheres with CA1000The PVA film is stretched by 100 percent along the axial direction at the temperature of 80 ℃, after being cooled, the PVA film is dissolved in cold water, stirred for 6 hours, centrifugally washed for 3 times, and then freeze-dried to obtain the microsphere CA after being stretched by 100 percent along the axial direction and deformed1000。
Referring to FIG. 1, the polymer microspheres CA obtained at 1000rpm provided in example 1 of the present invention1000Scanning electron microscopy and optical microscopy images of the original shape of (a). As can be seen from FIG. 1, the spherical microspheres can be obtained by the preparation method, and the particle size of the microspheres obtained at 1000rpm is relatively uniform.
Referring to FIG. 8 (b), the polymer microsphere CA provided in example 1 of the present invention1000Statistics of the particle size distribution of (2). Indicating the CA1000Has an average particle diameter of about 9.95. + -. 2.17. mu.m.
Referring to FIG. 2, the microspheres CA obtained at 1000rpm provided in example 1 of the present invention1000An optical microscope picture of gradual shape recovery in the process of heating from 25 ℃ to 80 ℃ after axial deformation of 100% proves that the microsphere has good shape memory performance.
Referring to FIG. 3, the microspheres CA obtained at 1000rpm provided in example 1 of the present invention1000The scanning electron microscope image of the microsphere after the axial deformation of 100 percent and the recovery of the original shape at 80 ℃ proves that the microsphere has good shape memory performance.
Example 2
Preparation of microsphere-loaded CA according to example 11000The PVA film of (1).
Steps 1) to 4) are the same as in example 1.
5) Stretching the solidified PVA film by 200% along the axial direction at 80 ℃, cooling, dissolving the PVA film in cold water, stirring for 6h, centrifugally washing for 3 times, and freeze-drying to obtain the PVA filmMicrosphere CA after axial elongation of 200% deformation1000。
Referring to FIG. 4, the microspheres CA obtained at 1000rpm provided in example 2 of the present invention1000The microsphere microscopic picture and the optical microscopic picture after the axial deformation is 200 percent and the original shape is recovered at 80 ℃ prove that the microsphere has good shape memory performance.
Example 3
Preparation of microsphere-loaded CA according to example 11000The PVA film of (1).
Steps 1) to 4) are the same as in example 1.
5) Stretching the solidified PVA film by 300 percent along the axial direction at the temperature of 80 ℃, dissolving the PVA film in cold water after cooling, stirring for 6h, centrifugally washing for 3 times, and then freeze-drying to obtain the microsphere CA after the PVA film is stretched by 300 percent along the axial direction and deformed1000。
Referring to FIG. 5, the microspheres CA provided in example 3 of the present invention were obtained at 1000rpm1000The optical microscope picture and the scanning electron microscope picture of the microsphere after the axial deformation is 300 percent and the original shape is recovered at 80 ℃ prove that the microsphere has good shape memory performance.
Example 4
Preparation of microsphere-loaded CA according to example 11000The PVA film of (1).
Steps 1) to 4) are the same as in example 1.
5) Respectively stretching the solidified PVA film along two axial directions at 80 ℃, cooling, dissolving the PVA film in cold water, stirring for 6h, centrifugally washing for 3 times, and freeze-drying to obtain the biaxially stretched and deformed disc-shaped microsphere CA1000。
Referring to FIG. 6, the microspheres CA provided in example 4 of the present invention were obtained at 1000rpm1000The scanning electron microscope picture that the shape of the disk shape after the biaxial stretching is gradually recovered in the process of heating from 25 ℃ to 80 ℃ proves that the microsphere has good shape memory performance.
Example 5
Steps 1) to 2) are the same as in example 1.
3) Dropwise adding the oil phase into a 500rpm magnetic stirrer for stirringStirring the aqueous phase for 12h, washing the obtained dispersion with hot water for 5 times, and freeze drying to obtain shape memory microsphere CA500。
Steps 4) to 5) were the same as in example 1, and microspheres CA deformed by 100% of elongation in the axial direction were prepared500。
Referring to FIG. 7 (a), the polymer microspheres CA obtained at 500rpm according to example 5 of the present invention500Scanning electron microscope picture of the original shape.
Referring to FIG. 8 (a), the polymer microsphere CA provided in example 5 of the present invention500Statistics of the particle size distribution of (2). Indicating the CA500Has an average particle diameter of about 15.5. + -. 5.0. mu.m.
Example 6
Steps 1) to 2) the aqueous phase and the oil phase were prepared as in example 1.
3) Dropwise adding the oil phase into the water phase stirred by a 1500rpm magnetic stirrer, stirring for 12h, washing the obtained dispersion with hot water for 5 times, and freeze-drying to obtain shape memory microsphere CA1500。
Steps 4) to 5) were the same as in example 1, and microspheres CA deformed by 100% of elongation in the axial direction were prepared1500。
Referring to FIG. 7 (b), the polymer microspheres CA obtained at 1500rpm according to example 6 of the present invention1500Scanning electron microscope picture of the original shape.
Referring to FIG. 8 (c), the polymer microsphere CA provided in example 6 of the present invention1500Statistics of the particle size distribution of (2). Indicating the CA1500Has an average particle diameter of about 5.75. + -. 1.6. mu.m.
Example 7
Steps 1) to 2) the aqueous phase and the oil phase were prepared as in example 1.
3) Dropwise adding the oil phase into the water phase stirred by a magnetic stirrer at 2000rpm, stirring for 12h, washing the obtained dispersion with hot water for 5 times, and freeze-drying to obtain shape memory microsphere CA2000。
Steps 4) to 5) were the same as in example 1, and microspheres deformed at 100% elongation in the axial direction were preparedCA2000。
Referring to FIG. 7 (c), the polymer microspheres CA obtained at 2000rpm according to example 7 of the present invention2000Scanning electron microscope picture of the original shape.
Referring to FIG. 8 (d), the polymer microsphere CA provided in example 7 of the present invention2000Statistics of the particle size distribution of (2). Indicating the CA2000Has an average particle diameter of about 3.2. + -. 0.6. mu.m. Meanwhile, the polymer microspheres CA obtained at the rotating speed of 2000rpm can be seen2000The particle size distribution of (a) is more uniform.
Example 8
1) Preparing an oil phase: 1.00g of CA8.7％Dissolving in 20mLN, N-dimethylformamide, and stirring at 80 ℃ for 3 h; the reacted solution was cooled to room temperature, and 80mL of a dichloromethane solution was added thereto, and dispersed uniformly by 400w ultrasonic dispersion for 3 min.
2) Preparing an aqueous phase: 0.20g of multi-walled carbon nanotubes (MWCNTs) and 2.00g of sodium dodecyl sulfate were mixed in 40mL of water, and 400w of ultrasound was applied for 10min to disperse the MWCNTs uniformly.
3) And dropwise adding the oil phase into the water phase stirred by a magnetic stirrer at 1000rpm, stirring for 12h, washing the obtained dispersion with hot water for 5 times, and freeze-drying to obtain the photo-responsive shape memory composite microsphere CA/MWCNT.
4) Dissolving 0.05g of freeze-dried particles CA/MWCNT in 40.00g of 1% polyvinyl alcohol solution by mass concentration, ultrasonically dispersing for 5h by 400w, pouring the solution in a polytetrafluoroethylene mold, and curing for 12h at 70 ℃ to obtain the PVA film loaded with the composite microspheres CA/MWCNT.
5) And stretching the solidified PVA film by 100 percent along the axial direction at the temperature of 80 ℃, cooling, dissolving the PVA film in cold water, stirring for 6h, centrifugally washing for 3 times, and freeze-drying to obtain the composite microsphere CA/MWCNT after being deformed by 100 percent along the axial extension.
Referring to fig. 9, a polarization microscope image, a scanning electron microscope image and a surface magnified image of the composite microsphere CA/MWCNT provided in this example 8. Indicating that the incorporation of MWCNTs roughens the surface of the microspheres.
Referring to fig. 10, the particle size statistics of the composite microsphere CA/MWCNT provided in this example 8. The composite microspheres are shown to have an average diameter of 6.4 + -1.5 μm.
Referring to fig. 11 and 12, the photo-thermal conversion ratio of the composite microsphere CA/MWCNT provided in this example 8 is shown. The composite microsphere is proved to have higher photo-thermal conversion efficiency.
Referring to fig. 13, this example 8 provides a shape recovery process of the composite microsphere CA/MWCNT after being deformed by 100% along the axial elongation under infrared light irradiation. The composite microsphere is proved to have good shape memory effect.
Example 9
1) The oil phase was prepared as in example 8.
2) Preparing an aqueous phase: 0.20g of Graphene Oxide (GO) and 2.00g of sodium dodecyl sulfate are mixed in 40mL of water, and 400w of ultrasonic waves are carried out for 30min to uniformly disperse GO.
3) The photo-responsive shape memory composite microspheres CA/GO and the composite microspheres CA/GO after being deformed by 100% of the axial elongation are prepared according to example 8.
Example 10
1) The oil phase was prepared as in example 8.
2) Preparing an aqueous phase: 0.40g Polydopamine (PDA) and 2.00g sodium dodecyl sulfate were mixed in 40mL water and dispersed evenly with 400w ultrasound for 20 min.
3) The photo-responsive shape memory composite microsphere CA/PDA and the composite microsphere CA/PDA after being elongated 100% along the axial direction were prepared as in example 8.
Example 11
Preparing an oil phase: dissolving 1.60g of cellulose acetate (the mass fraction of hydroxyl groups is 4%) in 20mL of N, N-dimethylformamide, and stirring at 60 ℃ for 5 hours; and (3) cooling the reacted solution to room temperature, adding 120mL of dichloromethane solution, and performing 400w ultrasonic dispersion for 4min to uniformly disperse the dichloromethane solution to obtain an oil phase.
Preparing an aqueous phase: 3.00g of sodium lauryl sulfate was dissolved in 300mL of water to obtain an aqueous phase.
Dropwise adding the oil phase into the water phase under stirring of a magnetic stirrer at 1200rpm, stirring for 15h, centrifuging, washing with hot water for 5 times, and freeze-drying to obtain shape memory microsphere particles.
Dissolving 0.04g of freeze-dried particles in 40.00g of a polyvinyl alcohol solution with the mass fraction of 1%, ultrasonically dispersing for 4h at 400w, pouring the solution in a polytetrafluoroethylene mold, and curing for 18h at 60 ℃ to obtain the PVA film loaded with microspheres.
And stretching the solidified PVA film loaded with the microspheres by 100 percent at 70 ℃ along the axial direction, dissolving the solidified PVA film in cold water after cooling, stirring for 7 hours, centrifugally washing for 3 times, and then freeze-drying to obtain the microspheres which are deformed by 100 percent along the axial extension.
Example 12
Preparing an oil phase: dissolving 1.20g of cellulose acetate (the mass fraction of hydroxyl groups is 3.5%) in 20mL of dimethyl sulfoxide, and stirring at 70 ℃ for 4 hours; and (3) cooling the reacted solution to room temperature, adding 100mL of dichloromethane solution, and performing 400w ultrasonic dispersion for 5min to uniformly disperse the dichloromethane solution to obtain an oil phase.
Preparing an aqueous phase: 0.24g of multi-walled carbon nanotubes and 4.00g of sodium dodecyl sulfate were dissolved in 400mL of water to obtain an aqueous phase.
Dropwise adding the oil phase into the water phase under stirring of a magnetic stirrer at 2000rpm, stirring for 18h, centrifuging, washing with hot water for 5 times, and freeze-drying to obtain shape memory microsphere particles.
Dissolving 0.08g of freeze-dried particles in 40.00g of a polyvinyl alcohol solution with the mass fraction of 2%, ultrasonically dispersing for 5h at 400w, pouring the solution in a polytetrafluoroethylene mold, and curing for 15h at 65 ℃ to obtain the PVA film loaded with microspheres.
And stretching the solidified PVA film loaded with the microspheres by 100 percent at 65 ℃ along the axial direction, dissolving the solidified PVA film in cold water after cooling, stirring for 8 hours, centrifugally washing for 3 times, and then freeze-drying to obtain the microspheres which are deformed by 100 percent along the axial extension.
Example 13
Preparing an oil phase: dissolving 1.50g of cellulose acetate (the mass fraction of hydroxyl groups is 4%) in 20mL of tetrahydrofuran, and stirring at 80 ℃ for 3 h; and (3) cooling the reacted solution to room temperature, adding 110mL of dichloromethane solution, and performing 400w ultrasonic dispersion for 2min to uniformly disperse the dichloromethane solution to obtain an oil phase.
Preparing an aqueous phase: 0.24g of polydopamine 2.00g of sodium dodecyl sulfate was dissolved in 200mL of water to obtain an aqueous phase.
Dropwise adding the oil phase into the water phase under stirring of a magnetic stirrer at 1000rpm, stirring for 16h, centrifuging, washing with hot water for 5 times, and freeze-drying to obtain shape memory microsphere particles.
Dissolving 0.06g of the freeze-dried particles in 40.00g of a polyvinyl alcohol solution with the mass fraction of 3%, ultrasonically dispersing for 3h at 400w, pouring the solution in a polytetrafluoroethylene mold, and curing for 12h at 70 ℃ to obtain the PVA film loaded with microspheres.
And stretching the solidified PVA film loaded with the microspheres by 100 percent at 80 ℃ along the axial direction, dissolving the solidified PVA film in cold water after cooling, stirring for 6h, centrifugally washing for 3 times, and then freeze-drying to obtain the microspheres which are deformed by 100 percent along the axial extension.
The microsphere in the invention takes cellulose acetate as a substrate, shape memory microspheres with different particle sizes are prepared by an emulsion solvent volatilization method and by adjusting the stirring rotating speed, and microspheres with different shapes are further prepared by a film stretching technology.

Claims (9)

1. A preparation method of intelligent response microspheres with controllable shapes is characterized by comprising the following steps:
1) preparing an oil phase: dissolving cellulose acetate in a solvent, then adding dichloromethane, and performing ultrasonic dispersion uniformly to obtain an oil phase; wherein, the mass content of hydroxyl in the cellulose acetate is 8.7 percent, 4.0 percent or 3.5 percent;
preparing an aqueous phase: dissolving sodium dodecyl sulfate in water to obtain a water phase;
2) dropwise adding the oil phase into the water phase under stirring, uniformly stirring to obtain a dispersion liquid, and freeze-drying the dispersion liquid to obtain the shape memory microspheres; wherein the stirring speed is 500-2000 rpm, and the stirring time is 12-18h after dripping is finished;
3) dispersing shape memory microspheres in a polyvinyl alcohol solution by ultrasound, pouring the polyvinyl alcohol solution into a mold, and curing to obtain a PVA film loaded with microspheres;
4) and (3) stretching the PVA film loaded with the microspheres in different directions under heating, cooling, dissolving in water, stirring until the film is dissolved, centrifugally washing, and freeze-drying to obtain the shape-controllable intelligent response microspheres.
2. The method for preparing the intelligent response microspheres with controllable shapes according to claim 1, wherein in the step 1), the mass of the cellulose acetate is 5% -8% of the mass of the solvent; the solvent is N, N dimethylformamide, dimethyl sulfoxide or tetrahydrofuran.
3. The method for preparing intelligent response microspheres with controllable shapes according to claim 1, wherein in step 1), the amount of dichloromethane solution added is 4-6 times of the volume of the solvent; the ultrasonic power is 400W, and the time is 2-5 min.
4. The method for preparing intelligent response microspheres with controllable shapes according to claim 1, wherein in step 1), the mass concentration of the sodium dodecyl sulfate solution in the water phase is 0.5-1 wt%, and the amount of water is 20-25 times of the volume of the solvent.
5. The method for preparing shape-controllable intelligent response microspheres according to claim 1, wherein in the step 1), photo-thermal filling materials are further added into water.
6. The method for preparing intelligent response microspheres with controllable shapes according to claim 5, wherein in the step 1), the photo-thermal filling material is multi-walled carbon nanotubes, graphene oxide or polydopamine; the dosage of the photo-thermal filling material is 20-40% of the mass of the cellulose acetate.
7. The method for preparing intelligent response microspheres with controllable shapes according to claim 1, wherein in the step 3), the ultrasonic power is 400W, and the time is 3-5 h; the mass concentration of polyvinyl alcohol in the polyvinyl alcohol solution is 1-3%; the polyvinyl alcohol model is 1788; the mass of the shape memory microsphere is 0.1-0.2% of that of the polyvinyl alcohol 1788; the curing temperature is 60-70 ℃ and the curing time is 12-18 h.
8. The method for preparing intelligent response microspheres with controllable shapes according to claim 1, wherein in the step 4), the heating temperature is 70-80 ℃ and the stirring time is 6-8 h.
9. Shape-controllable smart-responsive microspheres prepared according to the method of any one of claims 1 to 8.
CN202010231520.9A 2020-03-27 2020-03-27 A shape-controllable smart responsive microsphere and its preparation method Expired - Fee Related CN111454468B (en)

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