CN101406820B - Method for preparing nucleocapsid type microgel composite microsphere using polymerisable surfactant - Google Patents
Method for preparing nucleocapsid type microgel composite microsphere using polymerisable surfactant Download PDFInfo
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- CN101406820B CN101406820B CN2008101684046A CN200810168404A CN101406820B CN 101406820 B CN101406820 B CN 101406820B CN 2008101684046 A CN2008101684046 A CN 2008101684046A CN 200810168404 A CN200810168404 A CN 200810168404A CN 101406820 B CN101406820 B CN 101406820B
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Abstract
The invention discloses a method for preparing a nucleocapsid type microgel compound microsphere through a polymeric surfactant, which comprises the following process steps: preparing an oil phase, preparing an evenly-dispersed oil phase, preparing a water phase, preparing microgel, preparing swollen microgel, preparing porous microgel, preparing the porous microgel containing the polymeric surfactant of acrylamide propyl dodecyl dimethyl ammonium bromide, and preparing the microgel compound microsphere. The method has the advantages of reasonable design, feasible process, simple operation, reaction at room temperature, and the like. The microgel compound microsphere has the characteristics of nucleocapsid structure, has larger size, easy separation, a large specific surface, reversible swelling and shrinking, and phosphotungstic acid contained in the surface. The material can be popularized and applied in the fields of structural type catalyst preparation, quick enrichment and separation, and the like.
Description
Technical field
The invention belongs to the material technology field, be specifically related to the manufacture method of the microcapsules or the microballoon of colloid chemistry.
Background technology
Microgel is that a class has three-dimensional net structure, size at spherical latex particle little, nanometer scale.The kinds of the size of microgel, internal structure and contained functional group etc. can be controlled by changing monomer, crosslinking agent type and preparation condition.Therefore, the preparation template of, nanometer materials little as sphere, microgel have natural template incomparable advantage.It is many to be engaged in spherical micro-nano composite organic-inorganic material research work at present both at home and abroad.People such as Pich utilize emulsifier-free emulsion polymerization to make acetoacetoxyethyl methacrylate (AAEM) and N-vinylcaprolactam (VCL) copolymerization microgel, synthesize magnetic iron ore in water-soluble bloated microgel inside afterwards, so just obtained a kind of microballoon that is embedded in magnetic nanoparticle in the microgel network of novelty.This microballoon has the stability of temperature sensitive property, magnetic and micella concurrently, and further research shows that also this microballoon shows swelling-the go invertibity of swelling in the aqueous solution.People such as Antonietti have prepared the polystyrene microgel by microemulsion polymerization method, handle through sulfonation, this microgel is soaked in the solution of slaine, by the crosslink density of control microgel and the reduction mode of slaine, preparation is except having the ball shaped nano metal of different-grain diameter and structure.Room analogy group is equipped with PAM and P (NAPAM-AA) microgel with the inverse suspension polymerization legal system, with this microgel swelling in the metal salt solution, feeds hydrogen sulfide gas again, and promptly micro-gel surface forms sulfide.Concentration and the feeding mode of hydrogen sulfide and the sulfide organic/inorganic complex microsphere that speed has been synthesized a series of patterned surfaces by the control slaine.This method can make the different composite micro-sphere material by changing microgel template and sedimental thing composition, also can change the complex microsphere surface topography by the conditioned reaction condition.This complex microsphere has typical hud typed design feature, and these characteristics make this class material have special application.
Acrylamide propyl dodecyl dimethyl ammonium bromide is a kind of polymerisable surfactant, and its particularity is not only to have the effect of surfactant, and has polymerizable groups.This material can with monomer generation copolyreaction, be implemented in the polymer to introduce and have surface-active group.Although be that various objectives is more with polymer or the research in the composite materials that polymerisable surfactant is incorporated into the different structure characteristics, to be template be incorporated into micro-gel surface with this type of material forms the research with hud typed structure composite microsphere material and do not report but with the macromolecule microgel, created condition because this material has the core water-swellable for storing water-soluble substances, positively charged shell is that the electronegative functional species of ion-exchange introducing have been created condition.Therefore, this class material has potential using value.The invention provides the method that a kind of preparation has the microgel composite microsphere of These characteristics.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of reasonable in design, feasible process, easy and simple to handle, the reaction time short, reaction is carried out at normal temperatures prepares the method for nucleocapsid type microgel composite microsphere with polymerisable surfactant.
Solving the problems of the technologies described above the technical scheme that is adopted comprises the steps:
1, preparation oil phase
Surfactant Si Ban-80 is joined in the beaker that fills cyclohexane, and surfactant Si Ban-80 is hybridly prepared into oil phase by mass ratio with 1: 100～115 with cyclohexane.
2, preparation evenly disperses oil phase
The oil phase of step 1 preparation is packed in the there-necked flask, stir with mixer, mixing speed is 380 rev/mins, feeds N with 2～3mL/ minute flow velocity
2, stirred 30～60 minutes at 18～30 ℃, make it even, make even dispersion oil phase.
3, preparation water
Acrylamide is dissolved in the secondary water, adds N again, N '-methylene-bisacrylamide, ammonium persulfate; Secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate are 1: 0.24: 0.008～0.012: 0.016, stir, and filter, and till importing nitrogen to oxygen has been arranged, are prepared into water.
4, preparation microgel
The water of step 3 preparation is joined in the even dispersion oil phase of step 2 fast, the mixing speed of adjusting mixer is 380 rev/mins, adding volumetric concentration after 15～30 minutes is the tetramethylethylenediamine of 50mg/mL, water is 1: 79.9: 0.00066 with evenly disperseing the mass ratio of oil phase, tetramethylethylenediamine, reacted 2～4 hours, inclining reactant liquor, isolates sediment, replace washing precipitate 5～6 times with acetone and secondary water, make polyacrylamide microgel.
5, the microgel of preparation swelling
The microgel of step 4 preparation is put into beaker, add water to till the submergence, standing over night makes its abundant swelling.
6, preparation porous microgel
The swelling microgel of step 5 preparation inhaled with filter paper go after the free water, to-70～-50 ℃, put into freeze-dryer, be prepared into the porous microgel-55～-50 ℃ of dryings 12～24 hours through cooled with liquid nitrogen.
7, preparation includes the porous microgel of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide
It is 3.3%～40.7% methanol solution that polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is mixed with mass concentration, with the made porous microgel of prepared methanol solution impregnation steps 6, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide.
8, preparation microgel composite microsphere
With the polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide porous microgel mass concentration that includes of step 7 preparation is 50% phosphotungstic acid aqueous solution swelling, the mol ratio of phosphotungstic acid and acrylamide propyl dodecyl dimethyl ammonium bromide is 10～30: 1,35～40 ℃ of jolting device joltings 2～7 days.The natural subsidence sediment adds secondary water in sediment, be the supersonic wave cleaning machine of 80W with power, in frequency is to wash 3 times under the ultrasonic wave condition of 50Hz.Sediment after the washing is alternately washed 6～7 times with secondary water and acetone, dry naturally, be prepared into microgel composite microsphere.
In preparation oil phase processing step 1 of the present invention, surfactant Si Ban-80 is joined in the beaker that fills cyclohexane, surfactant and preferred mass ratio by cyclohexane are 1: 100～110 to be hybridly prepared into oil phase.Evenly disperse in the oil phase processing step 2 in preparation of the present invention, preferably made even dispersion oil phase in 40～60 minutes 18～25 ℃ of dispersed with stirring.In preparation aqueous process step 3 of the present invention, with acrylamide, N, N '-methylene-bisacrylamide, ammonium persulfate are dissolved in the secondary water, secondary water and acrylamide, N, the preferred mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.008～0.010: 0.016, stir, till importing nitrogen to oxygen has been arranged, make water.In preparation porous microgel processing step 6 of the present invention, the swelling microgel inhaled with filter paper go after the free water, preferably be cooled to-60～-50 ℃, put into freeze-dryer and be prepared into the porous microgel in 15～24 hours through liquid nitrogen-55～-50 ℃ of dryings.Include in the porous microgel processing step 7 of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide in the present invention's preparation, it is 3.3%～21.7% methanol solution that polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is mixed with preferred mass concentration, the porous microgel is immersed in the methanol solution, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide.Prepare in the microgel composite microsphere step 8 in the present invention, the porous microgel mass concentration that will include polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 50% phosphotungstic acid aqueous solution swelling, the preferred molar ratio of phosphotungstic acid and acrylamide propyl dodecyl dimethyl ammonium bromide is that 15～25: 1,36～40 ℃ of jolting devices shake and were prepared into microgel composite microsphere in 4～7 days.
In preparation oil phase processing step 1 of the present invention, surfactant Si Ban-80 is joined in the beaker that fills cyclohexane, surfactant be to be hybridly prepared into oil phase at 1: 103 by the cyclohexane optimum quality ratio.Evenly disperse in the oil phase processing step 2 in preparation of the present invention, the best was made even oil phase in 50 minutes 20 ℃ of dispersed with stirring.Prepare in the aqueous process step 3 in the present invention, with acrylamide, N, N '-methylene-bisacrylamide, ammonium persulfate are dissolved in the secondary water, secondary water and acrylamide, N, the optimum quality ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.010: 0.016, mix, till importing nitrogen to oxygen has been arranged, make water.In preparation porous microgel processing step 6 of the present invention, the swelling microgel after swelling institute water is removed in suction, is cooled to-55 ℃, puts into freeze-dryer through liquid nitrogen the best ,-55 ℃ of dryings 24 hours, be prepared into the porous microgel.Include in the porous microgel processing step 7 of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide in preparation of the present invention, it is 3.3% methanol solution that polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is mixed with best in quality concentration, the porous microgel is immersed in the methanol solution, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide.In preparation microgel composite microsphere step 8 of the present invention, the porous microgel mass concentration that will include polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 50% phosphotungstic acid aqueous solution swelling, the optimum mole ratio of phosphotungstic acid and polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 20: 1,40 ℃ of jolting devices shook 7 days, were prepared into microgel composite microsphere.
The present invention adopts the swelling microgel to inhale with filter paper and goes after the free water, use cooled with liquid nitrogen,-55～-50 ℃ of freeze dryings, be prepared into the porous microgel, with polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution dipping porous microgel, contain the porous microgel of polymerisable surfactant with the phosphotungstic acid aqueous solution swelling, be prepared into microgel composite microsphere.That the present invention has is reasonable in design, feasible process, simple to operate, advantage such as reaction is carried out at normal temperatures; Adopt the microgel composite microsphere of the present invention's preparation, have hud typed design feature; Whole microballoon has large-size and is easy to separate; The microballoon of surface coverage has bigger specific surface, has advantage on catalysis and adsorbing separation; Made complex microsphere has good swelling and goes the reversible characteristics of swelling; Phosphotungstic acid is contained on the surface makes composite microsphere material have correspondingly functional.These characteristics makes this material at structural type Preparation of Catalyst, fast enriching with the field such as separate and have using value.
Description of drawings
Fig. 1 is the electron scanning micrograph that adopts the microgel composite microsphere of the embodiment of the invention 1 preparation.
Fig. 2 is the electron scanning micrograph that Fig. 1 surface local amplifies.
Fig. 3 is that crosslinking agent is a 0.05g porous microgel, and mass concentration is to flood the prepared electron scanning micrograph that obtains complex microsphere in the 6.6% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution.
Fig. 4 is the electron scanning micrograph that Fig. 3 surface local amplifies.
Fig. 5 is that crosslinking agent is a 0.05g porous microgel, and mass concentration is to flood the prepared electron scanning micrograph that obtains complex microsphere in the 13.6% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution.
Fig. 6 is the electron scanning micrograph that Fig. 5 surface local amplifies.
Fig. 7 is that crosslinking agent is a 0.05g porous microgel, and mass concentration is to flood the prepared electron scanning micrograph that obtains complex microsphere in the 21.3% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution.
Fig. 8 is the electron scanning micrograph that Fig. 7 surface local amplifies.
Fig. 9 is the electron scanning micrograph of embodiment 4.
Figure 10 is the electron scanning micrograph that Fig. 9 surface local amplifies.
Figure 11 is the electron scanning micrograph of embodiment 5.
Figure 12 is the electron scanning micrograph that Figure 11 surface local amplifies.
Figure 13 is the electron scanning micrograph of embodiment 6.
Figure 14 is the electron scanning micrograph that Figure 13 surface local amplifies.
Figure 15 is that crosslinking agent is a 0.04g porous microgel, and mass concentration is to flood the prepared electron scanning micrograph that obtains complex microsphere in the 6.6% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution.
Figure 16 is the electron scanning micrograph that Figure 15 surface local amplifies.
Figure 17 is that crosslinking agent is a 0.04g porous microgel, and mass concentration is to flood the prepared electron scanning micrograph that obtains complex microsphere in the 13.6% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution.
Figure 18 is the electron scanning micrograph that Figure 17 surface local amplifies.
Figure 19 is the electron scanning micrograph that adopts the microgel composite microsphere of the embodiment of the invention 2 preparations.
Figure 20 is the electron scanning micrograph that Figure 19 surface local amplifies.
Figure 21 is that crosslinking agent is a 0.04g porous microgel, and mass concentration is to flood the prepared electron scanning micrograph that obtains complex microsphere in the 31.3% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution.
Figure 22 is the electron scanning micrograph that Figure 21 surface local amplifies.
Figure 23 is that crosslinking agent is a 0.04g porous microgel, and mass concentration is to flood the prepared electron scanning micrograph that obtains complex microsphere in the 40.7% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution.
Figure 24 is the electron scanning micrograph that Figure 23 surface local amplifies.
Figure 25 is that crosslinking agent is the porous microgel of 0.05g, is to flood the electron scanning micrograph of 2 days resultant complex microspheres of jolting in Salkowski's solution in the 20% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution in mass concentration.
Figure 26 is the electron scanning micrograph of embodiment 7.
Figure 27 is that crosslinking agent is the porous microgel of 0.05g, is to flood the electron scanning micrograph of 4 days resultant complex microspheres of jolting in Salkowski's solution in the 20% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution in mass concentration.
Figure 28 is that crosslinking agent is the porous microgel of 0.05g, is to flood the electron scanning micrograph of 5 days resultant complex microspheres of jolting in Salkowski's solution in the 20% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution in mass concentration.
Figure 29 is that crosslinking agent is the porous microgel of 0.05g, in mass concentration is to flood in the 20% acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution, jolting is 7 days in Salkowski's solution, the electron scanning micrograph of resultant complex microsphere after the supersound washing.
Figure 30 is the FFIR figure that adopts the nucleocapsid type microgel composite microsphere of the embodiment of the invention 1 preparation.
Figure 31 adopts the thermogravimetric analysis curve map of the nucleocapsid type microgel composite microsphere of the embodiment of the invention 1 preparation.
The specific embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
0.026g is that other used raw material of example and preparation method thereof is as follows with the raw materials used polymerisable surfactant acrylamide propyl of preparation microgel composite microsphere dodecyl dimethyl ammonium bromide:
1, preparation oil phase
0.52g surfactant Si Ban-80 is joined in the beaker that fills the 70mL cyclohexane, surfactant be to be hybridly prepared into oil phase at 1: 103 by the cyclohexane weight ratio.
2, preparation evenly disperses oil phase
The oil phase of step 1 preparation is packed in the there-necked flask, stir with mixer, mixing speed is 380 rev/mins, feeds N with 2～3mL/ minute flow velocity
2,, be prepared into even dispersion oil phase 20 ℃ of dispersed with stirring 50 minutes.
3, preparation water
With 1.2g acrylamide, N, N '-methylene-bisacrylamide 0.05g, ammonium persulfate 80mg are dissolved in the secondary water of 5.5mL, secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.010: 0.016, mix, till importing nitrogen to oxygen has been arranged, make water.
4, preparation microgel
The water of step 3 preparation is joined in the even dispersion oil phase of step 2 fast, the mixing speed of adjusting mixer is 380 rev/mins, adding volumetric concentration after 30 minutes is the tetramethylethylenediamine 0.5mL of 50mg/mL, water is 1: 79.9: 0.00066 with evenly disperseing the mass ratio of oil phase, tetramethylethylenediamine, reacted 4 hours, inclining reactant liquor, isolates sediment, replace washing precipitate 5～6 times with acetone and secondary water, make polyacrylamide microgel.
5, the microgel of preparation swelling
The microgel of step 4 preparation is put into beaker, add water to till the submergence, standing over night makes its abundant swelling.
6, preparation porous microgel
The swelling microgel of step 5 preparation inhaled with filter paper go after the free water, to-60 ℃, put into freeze-dryer, be prepared into the porous microgel-55 ℃ of dryings 24 hours through cooled with liquid nitrogen.
7, preparation includes the porous microgel of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide
It is 3.3% methanol solution that polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide 0.026g is mixed with mass concentration, flood 0.5g by the made porous microgel of step 6 with prepared 1mL methanol solution, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide.
8, preparation microgel composite microsphere
It with the porous microgel 0.5g mass concentration that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide of step 7 preparation 50% phosphotungstic acid aqueous solution 7.4g swelling, the mol ratio of phosphotungstic acid and polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 20: 1,40 ℃ of jolting devices jolting 7 days, with power is the supersonic wave cleaning machine of 80W, it in frequency washing 3 times under the ultrasonic wave condition of 50Hz, sediment after the washing is alternately washed 6～7 times with secondary water and acetone, naturally dry, be prepared into microgel composite microsphere.The electron scanning micrograph of prepared microgel composite microsphere is seen Fig. 1,2, and by Fig. 1,2 as seen, the fold that makes the complex microsphere surface is to form by the nanoscale microballoon is tightly packed.
Embodiment 2
0.21g is that other used raw material of example and preparation method thereof is as follows with the raw materials used polymerisable surfactant acrylamide propyl of preparation microgel composite microsphere dodecyl dimethyl ammonium bromide:
In preparation oil phase processing step 1,0.52g surfactant Si Ban-80 is joined in the beaker that fills the 67mL cyclohexane, surfactant be to be hybridly prepared into oil phase at 1: 100 by the cyclohexane weight ratio.Evenly disperse in the oil phase processing step 2 in preparation, 18 ℃ of dispersed with stirring 60 minutes, other step in this processing step was identical with embodiment 1, makes even dispersion oil phase.In preparation aqueous process step 3, with the 1.2g acrylamide, N, N '-methylene-bisacrylamide 0.04g, ammonium persulfate 80mg are dissolved in the secondary water of 5.5mL, secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate are 1: 0.24: 0.008: 0.016, mix, till importing nitrogen to oxygen has been arranged, make water.In preparation porous microgel processing step 6, the swelling microgel of step 5 preparation inhaled with filter paper go, to put into freeze-dryer and be prepared into the porous microgel in 12 hours to-70 ℃ through cooled with liquid nitrogen after the free water-50 ℃ of dryings.Include in the porous microgel processing step 7 of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide in preparation, it is 21.3% methanol solution that polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide 0.21g is mixed with mass concentration, 0.5g porous microgel is immersed in the 1mL methanol solution, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide.In preparation microgel composite microsphere 8, the porous microgel 0.5g mass concentration that will include polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 50% phosphotungstic acid aqueous solution 29.8g swelling, the mol ratio of phosphotungstic acid and polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 10: 1,38 ℃ of jolting devices jolting 2 days, other step in this processing step is identical with embodiment 1, is prepared into microgel composite microsphere.Identical in other processing step with embodiment 1.The electron scanning micrograph of prepared microgel composite microsphere is seen Figure 19,20, and by Figure 19,20 as seen, the fold that makes the complex microsphere surface is to form by the nanoscale microballoon is tightly packed.
Embodiment 3
0.5g is that other used raw material of example and preparation method thereof is as follows with the raw materials used polymerisable surfactant acrylamide propyl of preparation microgel composite microsphere dodecyl dimethyl ammonium bromide:
In preparation oil phase processing step 1,0.52g surfactant Si Ban-80 is joined in the beaker that fills the 76.8mL cyclohexane, surfactant be to be hybridly prepared into oil phase at 1: 115 by the cyclohexane weight ratio.Evenly disperse in the oil phase processing step 2 in preparation, 30 ℃ of dispersed with stirring 30 minutes, other step in this processing step was identical with embodiment 1, makes even dispersion oil phase.In preparation aqueous process step 3, with 1.2g acrylamide, N, N '-methylene-bisacrylamide 0.06g, ammonium persulfate 80mg are dissolved in the secondary water of 5.5mL, secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.012: 0.016, mix, till importing nitrogen to oxygen has been arranged, make water.In preparation porous microgel processing step 6, the swelling microgel of step 5 preparation inhaled with filter paper go, to put into freeze-dryer and be prepared into the porous microgel in 18 hours to-50 ℃ through cooled with liquid nitrogen after the free water-55 ℃ of dryings.Include in the porous microgel processing step 7 of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide in preparation, it is 40.7% methanol solution that polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide 0.5g is mixed with mass concentration, 0.5g porous microgel is immersed in the 1mL methanol solution, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide.In preparation microgel composite microsphere 8, the porous microgel 0.5g mass concentration that will include polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 50% phosphotungstic acid aqueous solution 106.8g swelling, the mol ratio of phosphotungstic acid and polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 30: 1,35 ℃ of jolting devices jolting 5 days, other step in this processing step is identical with embodiment 1, is prepared into microgel composite microsphere.Identical in other processing step with embodiment 1.
Embodiment 4
0.33g is that other used raw material of example and preparation method thereof is as follows with the raw materials used polymerisable surfactant acrylamide propyl of preparation microgel composite microsphere dodecyl dimethyl ammonium bromide:
Preparation at embodiment 1 includes in the porous microgel processing step 7 of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide, it is 31.3% methanol solution that polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide 0.33g is mixed with mass concentration, 0.5g porous microgel is immersed in the 1mL methanol solution, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide.In preparation microgel composite microsphere 8, the porous microgel 0.5g mass concentration that will include polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 50% phosphotungstic acid aqueous solution 85.4g swelling, the mol ratio of phosphotungstic acid and polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 30: 1, other step in this processing step is identical with embodiment 1, is prepared into microgel composite microsphere.Other processing step is identical with embodiment 1.The electron scanning micrograph of prepared microgel composite microsphere is seen Fig. 9,10, and by Fig. 9,10 as seen, the fold that makes the complex microsphere surface is to form by the nanoscale microballoon is tightly packed.
Embodiment 5
0.5g is that other used raw material of example and preparation method thereof is as follows with the raw materials used polymerisable surfactant acrylamide propyl of preparation microgel composite microsphere dodecyl dimethyl ammonium bromide:
In the preparation aqueous process step 3 of embodiment 3, with 1.2g acrylamide, N, N '-methylene-bisacrylamide 0.05g, ammonium persulfate 80mg are dissolved in the secondary water of 5.5mL, secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.010: 0.016, mix, till importing nitrogen to oxygen has been arranged, make water.Other processing step is identical with embodiment 3.The electron scanning micrograph of prepared microgel composite microsphere is seen Figure 11,12, and by Figure 11,12 as seen, the fold that makes the complex microsphere surface is to form by the nanoscale microballoon is tightly packed.
0.026g is that other used raw material of example and preparation method thereof is as follows with the raw materials used polymerisable surfactant acrylamide propyl of preparation microgel composite microsphere dodecyl dimethyl ammonium bromide:
In the preparation aqueous process step 3 of embodiment 1, with 1.2g acrylamide, N, N '-methylene-bisacrylamide 0.04g, ammonium persulfate 80mg are dissolved in the secondary water of 5.5mL, secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.008: 0.016, mix, till importing nitrogen to oxygen has been arranged, make water.Other processing step is identical with embodiment 1.The electron scanning micrograph of prepared microgel composite microsphere is seen Figure 13,14, and by Figure 13,14 as seen, the fold on obtained complex microsphere surface is to form by the nanoscale microballoon is tightly packed.
Embodiment 7
0.20g is that other used raw material of example and preparation method thereof is as follows with the raw materials used polymerisable surfactant acrylamide propyl of preparation microgel composite microsphere dodecyl dimethyl ammonium bromide:
Preparation at embodiment 1 includes in the porous microgel processing step 7 of acrylamide propyl dodecyl dimethyl ammonium bromide, it is 20% methanol solution that acrylamide propyl dodecyl dimethyl ammonium bromide 0.20g is mixed with mass concentration, 0.5g porous microgel is immersed in the 1mL methanol solution, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide.In preparation microgel composite microsphere 8, the porous microgel 0.5g mass concentration that will include polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 50% phosphotungstic acid aqueous solution 87.0g swelling, the mol ratio of phosphotungstic acid and polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 30: 1,40 ℃ of jolting devices shook 3 days, other step in this processing step is identical with embodiment 1, is prepared into microgel composite microsphere.Other processing step is identical with embodiment 1.The electron scanning micrograph of prepared microgel composite microsphere is seen Figure 26, and as seen from Figure 26, the fold that makes the complex microsphere surface is to form by the nanoscale microballoon is tightly packed.
In order to determine optimum material proportion of the present invention and processing step, the inventor has carried out a large amount of laboratory research tests, and various test situation are as follows:
1, dosage of crosslinking agent is to the influence of complex microsphere pattern
0.52g surfactant Si Ban-80 is joined in the beaker that fills the 70mL cyclohexane, surfactant be to be hybridly prepared into oil phase at 1: 103 by the cyclohexane weight ratio.Put it in the there-necked flask, stir with mixer, mixing speed is 380 rev/mins, feeds N with 2～3mL/ minute flow velocity
2,, make even dispersion oil phase 20 ℃ of dispersed with stirring 50 minutes.With the 1.2g acrylamide, N, N '-methylene-bisacrylamide 0.05g, ammonium persulfate 80mg are dissolved in the secondary water of 5.5mL, secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.010: 0.016, mix, make water.Till importing nitrogen to oxygen has been arranged, make the water that cumulative volume is 5.5mL.The water of preparation joins in the oil phase fast, the mixing speed of adjusting mixer is 380 rev/mins, the 50mg/mL tetramethylethylenediamine that adds 0.5mL after 30 minutes, reacted 4 hours, incline and reactant liquor, separating solids and liquid alternately wash solid 5～6 times with acetone and secondary water, make polyacrylamide microgel.With microgel water swelling, left standstill 24 hours, fully after the swelling, inhale with filter paper and to go to-60 ℃, to put into freeze drier dry 24 hours with cooled with liquid nitrogen after the free water, make the porous microgel.It is among 3.3% the polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution 1mL that 0.5g porous microgel is immersed in mass concentration, places after 4 hours, with vavuum pump solvent is removed.Use methanol wash again 3～4 times.Being 50% phosphotungstic acid aqueous solution swelling at last with the 7.4g mass fraction, being positioned in the jolting device, is under 40 ℃ the condition at bath temperature, jolting 7 days.Wash for several times in ultrasonic mode with secondary water, alternately wash 3～4 times with secondary water and acetone again, wash 3～4 times again with acetone at last and removed fully, dry naturally up to the adsorbed water of high molecular composite microsphere, make white complex microsphere, stereoscan photograph is seen Fig. 1,2.
In preparation aqueous process step 3, get 1.2g acrylamide, N, N '-methylene-bisacrylamide 0.04g, ammonium persulfate 80mg are dissolved in the secondary water of 5.5mL, secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.008: 0.016, other step is identical with above-mentioned experimental procedure, and prepared microgel composite microsphere stereoscan photograph is seen Figure 13,14.From the stereoscan photograph as can be seen crosslinking agent that to be the template of the 0.05g fold that makes the complex microsphere surface be than crosslinking agent that 0.04g makes the fold on complex microsphere surface is intensive.The local complex microsphere surface of amplifying forms by the nanoscale microballoon is tightly packed.
Result of the test shows: under identical reaction condition, when selecting for use the different microgel of cross-linked dosage to be template, make the complex microsphere of different-shape.The present invention selects secondary water and acrylamide, N, and the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.008～0.012: 0.016.
2, the concentration of methanol solution of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is to the influence of complex microsphere pattern
In preparation complex microsphere processing step 7 of the present invention, upward the step makes the porous microgel to get 0.5g, be each 1mL dipping of 3.3%, 6.6%, 13.6%, 21.3%, 31.3%, 40.7% polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide methanol solution with mass concentration respectively, raw materials used consumption and other steps are with to test 1 identical.Prepared microgel composite microsphere stereoscan photograph mass concentration be 3.3% see Fig. 1,2,13,14, mass concentration be 6.6% see Fig. 3,4,15,16, mass concentration be 13.6% see Fig. 5,6,17,18, mass concentration be 21.3% see Fig. 7,8,19,20, mass concentration be 31.3% see Fig. 9,10,21,22, mass concentration be 40.7% see Figure 11,12,23,24, from above figure as can be seen, the surface is to form the microgel composite microsphere that has fold by the nanoscale microballoon, the thickness difference of fold under different condition.
Result of the test shows: under identical reaction condition, select the methanol solution of the acrylamide propyl dodecyl dimethyl ammonium bromide of variable concentrations for use, generate the complex microsphere of different-shape.The acrylamide propyl dodecyl dimethyl ammonium bromide methanol concentration that the present invention selects is respectively 3.3%～40.7%.
3, in the Salkowski's solution jolting time to the influence of complex microsphere pattern
Investigated the influence of time when adopting experiment 1 method to prepare complex microsphere to it, jolting is taken out after 2 days, 3 days, 4 days, 5 days, 7 days in the isothermal vibration device, it is alternately washed 3～4 times with secondary water and acetone, naturally dry Figure 28 that sees that sees Figure 27, jolting 5 days that sees Figure 26, jolting 4 days that sees Figure 25, jolting 3 days of prepared microgel composite microsphere stereoscan photograph jolting 2 days.Wherein 7 days microballoon after supersound washing, alternately washs 3～4 times with secondary water and acetone earlier again, dries naturally, and prepared microgel composite microsphere stereoscan photograph is seen Figure 29.
Result of the test shows: elected when being used in the phosphotungstic acid jolting asynchronism(-nization) under identical reaction condition, generate the complex microsphere of different-shape.The jolting time that the present invention selects is 2～7 days.
In order to verify beneficial effect of the present invention, the inventor adopts the hud typed structure microgel composite microsphere of the embodiment of the invention 1 preparation, use SEM, Fourier transformation infrared spectrometer, thermogravimetric analyzer to carry out observation experiment, various test situation are as follows:
Observe article: nucleocapsid type microgel composite microsphere.
Laboratory apparatus: SEM, model are XL-20, are produced by Britain Philips company; Fourier transformation infrared spectrometer, model are that AVTAR360 is produced by Nicolet company; Thermogravimetric analyzer, model are PEVKIN-ELMER, are produced by U.S. TA company.
1, observes
Method of testing by SEM is observed nucleocapsid type microgel composite microsphere.
2, test
Method of testing by Fourier transformation infrared spectrometer, thermogravimetric analyzer is tested nucleocapsid type microgel composite microsphere.
3, observed result
With sem observation to picture on surface see accompanying drawing 1,2, test with Fourier transformation infrared spectrometer, the infrared curve of being drawn is seen Figure 30, tests with thermogravimetric analyzer, the thermogravimetric analysis curve of being drawn is seen Figure 31.
From Fig. 1,2 as seen, complex microsphere is spherical in shape, structural integrity, and diameter 300 μ m, the complex microsphere surface is by many uniform acrylamide propyl dodecyl dimethyl ammonium phosphotungstates bunch tightly packed formation of integrated 300～600nm ball.The infrared spectrum curve of complex microsphere is seen Figure 30, in Figure 30, at 658cm
-1(υ C=O), 2944cm
-1(υ CH
2), 3500-3300cm
-1(υ NH) occurs is absorbed as the polyacrylamide microgel template; 1403,1066,982,897,813cm
-1The strong absorption occur and be respectively NH4
+Ion, (P-O), (W-O), (W-O-W) and, the vibration peak of (W-O-W); Simultaneously, 596,524cm
-1The weak absworption peak of Keggin structure appears.The infrared spectrum curve table understands that the composition of complex microsphere is the Keggin structure that polyacrylamide and the last acrylamide propyl dodecyl dimethyl ammonium phosphotungstate of acrylamide propyl dodecyl dimethyl ammonium phosphotungstate and surface still keep phosphotungstic acid, can be used as effective catalyst.From Figure 31 as seen, curve a, b, c are respectively the thermogravimetric curve of phosphotungstic acid, complex microsphere, polyacrylamide microgel among the figure, the curve of complex microsphere has the common trait of phosphotungstic acid and polyacrylamide microgel, and 620 ℃ of left and right sides constant weights, its residual solid is WO
3And PO
x, residual volume is 21.4%.
Claims (3)
1. one kind prepares the method for nucleocapsid type microgel composite microsphere with polymerisable surfactant, it is characterized in that this preparation method comprises the steps:
(1) preparation oil phase
Surfactant Si Ban-80 is joined in the beaker that fills cyclohexane, and surfactant and cyclohexane are 1: 100～115 to be hybridly prepared into oil phase by mass ratio;
(2) preparation evenly disperses oil phase
The oil phase of step 1 preparation is packed in the there-necked flask, stir with mixer, mixing speed is 380 rev/mins, feeds N with 2～3mL/ minute flow velocity
2, evenly disperseed 30～60 minutes at 18～30 ℃, make even dispersion oil phase;
(3) preparation water
Acrylamide is dissolved in the secondary water, add N again, N '-methylene-bisacrylamide, ammonium persulfate, secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is stirring in 1: 0.24: 0.008～0.012: 0.016, filter, till importing nitrogen to oxygen has been arranged, be prepared into water;
(4) preparation microgel
The water of step (3) preparation is joined in the even dispersion oil phase fast, the mixing speed of adjusting mixer is 380 rev/mins, adding volumetric concentration after 15～30 minutes is the tetramethylethylenediamine of 50mg/mL, water is 1: 79.9: 0.00066 with evenly disperseing the mass ratio of oil phase, tetramethylethylenediamine, reacted 2～4 hours, inclining reactant liquor, separating solids, alternately wash solid 5～6 times with acetone and secondary water, make polyacrylamide microgel;
(5) microgel of preparation swelling
The microgel of step 4 preparation is put into beaker, add water to till the submergence, standing over night makes its abundant swelling;
(6) preparation porous microgel
The swelling microgel of step 5 preparation inhaled with filter paper go, to put into freeze-dryer and be prepared into the porous microgel in 12～24 hours to-70～-50 ℃ through cooled with liquid nitrogen after the free water-55～-50 ℃ of dryings;
(7) preparation includes the porous microgel of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide
It is 3.3%～40.7% methanol solution that polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is mixed with mass concentration, with prepared methanol solution dipping porous microgel, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide;
(8) preparation microgel composite microsphere
It with the porous microgel mass concentration that includes acrylamide propyl dodecyl dimethyl ammonium bromide of step 7 preparation 50% phosphotungstic acid aqueous solution swelling, the mol ratio of phosphotungstic acid and acrylamide propyl dodecyl dimethyl ammonium bromide is 10～30: 1,35～40 ℃ of jolting devices jolting 2～7 days, natural subsidence, with power is that the supersonic wave cleaning machine frequency of 80W is the ultrasonic washing sediment 3 times of 50Hz, alternately wash 6～7 times with secondary water and acetone again, naturally dry, be prepared into microgel composite microsphere.
2. according to the described method for preparing nucleocapsid type microgel composite microsphere with polymerisable surfactant of claim 1, it is characterized in that: in preparation oil phase processing step (1), surfactant Si Ban-80 is joined in the beaker that fills cyclohexane, wherein surfactant be 1: 100～110 to be hybridly prepared into oil phase by the mass ratio of cyclohexane; Evenly disperse wherein to make even dispersion oil phase in 40～60 minutes in the oil phase processing step (2) in preparation 18～25 ℃ of dispersed with stirring; In preparation aqueous process step (3), with acrylamide, N, N '-methylene-bisacrylamide, ammonium persulfate are dissolved in the secondary water, wherein secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is stirring in 1: 0.24: 0.009～0.012: 0.016, till importing nitrogen to oxygen has been arranged, makes water; In preparation porous microgel processing step (6), the swelling microgel inhaled with filter paper go after the free water, wherein be cooled to-60～-50 ℃, put into freeze-dryer and be prepared into the porous microgel in 15～24 hours through liquid nitrogen-55～-50 ℃ of dryings; Include in the porous microgel processing step (7) of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide in preparation, wherein polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is mixed with mass concentration and is 3.3%～21.7% methanol solution, the porous microgel is immersed in the methanol solution, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide; In preparation microgel composite microsphere processing step (8), the porous microgel mass concentration that will include polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 50% phosphotungstic acid aqueous solution swelling, wherein the mol ratio of phosphotungstic acid and polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is that 15～25: 1,36～40 ℃ of jolting device joltings were prepared into microgel composite microsphere in 4～7 days.
3. according to the described method for preparing nucleocapsid type microgel composite microsphere with polymerisable surfactant of claim 1, it is characterized in that: in preparation oil phase processing step (1), surfactant Si Ban-80 is joined in the beaker that fills cyclohexane, surfactant with by cyclohexane wherein mass ratio be to be hybridly prepared into oil phase at 1: 103; In the even oil phase processing step of preparation (2), wherein stir and made even dispersion oil phase in 50 minutes at 20 ℃; In preparation aqueous process step (3), with acrylamide, N, N '-methylene-bisacrylamide, ammonium persulfate are dissolved in the secondary water, wherein secondary water and acrylamide, N, the mass ratio of N '-methylene-bisacrylamide, ammonium persulfate is 1: 0.24: 0.010: 0.016, mix, till importing nitrogen to oxygen has been arranged, make water; In preparation porous microgel processing step (6), the swelling microgel inhaled with filter paper go after the free water, wherein be cooled to-55 ℃, put into freeze-dryer and be prepared into the porous microgel in 24 hours through liquid nitrogen-55 ℃ of dryings; Include in the porous microgel processing step (7) of polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide in preparation, wherein polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is mixed with mass concentration and is 3.3% methanol solution, the porous microgel is immersed in the methanol solution, the mass ratio of methanol solution and porous microgel is 1: 0.62, after 4 hours, with vavuum pump methyl alcohol is taken out to doing, use methanol wash again 3～4 times, be prepared into the porous microgel that includes polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide; In preparation microgel composite microsphere processing step (8), the porous microgel mass concentration that will include polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 50% phosphotungstic acid aqueous solution swelling, wherein the mol ratio of phosphotungstic acid and polymerisable surfactant acrylamide propyl dodecyl dimethyl ammonium bromide is 20: 1,40 ℃ of jolting devices jolting 7 days is prepared into nucleocapsid type microgel composite microsphere.
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