CN100393408C - Method for preparing surface patterned SiO2 high molecular composite microsphere - Google Patents
Method for preparing surface patterned SiO2 high molecular composite microsphere Download PDFInfo
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- CN100393408C CN100393408C CNB2006100426584A CN200610042658A CN100393408C CN 100393408 C CN100393408 C CN 100393408C CN B2006100426584 A CNB2006100426584 A CN B2006100426584A CN 200610042658 A CN200610042658 A CN 200610042658A CN 100393408 C CN100393408 C CN 100393408C
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Abstract
The present invention relates to a preparation method of silicon oxide macromolecular compound microspheres with patternized surfaces, which comprises the following steps: mixed surfactant preparation, synthetic template oil phase preparation, emulsion preparation, water phase preparation, copolymerization microgel preparation, swollen copolymerization microgel preparation, preparation of mixed liquor of tetraethoxy normal silicane and normal heptane, and preparation of silicon oxide macromolecular compound microspheres with patternized surfaces. Compared with the existing preparation methods of silicon dioxide macromolecular compound microspheres, the present invention has the advantages of reasonable design, feasible technology, simple operation, reaction at normal temperature, short reaction time, etc. The macromolecular compound microspheres synthesized by the method have the advantages of rigidity and stability of inorganic materials, flexibility of organic materials, etc., and SiO2 macromolecular compound microspheres with patternized surfaces have large specific surface area and relatively small mass, and can be popularized and applied in the fields of biomedicine, wave and shock absorption, catalyst supporting, quick enrichment and separation, sensing technology, environmental protection, oceanic mining, etc.
Description
Technical field
The invention belongs to chemistry or physical method technical field, be specifically related to the manufacturing of the microcapsules or the microballoon of colloid chemistry.
Background technology
Silicon dioxide composite material makes it become a big class material that is widely used in colloid and the material science owing to have the special nature that is different from bulk material.A lot of both at home and abroad, but mainly contain following three kinds about the preparation method of silicon dioxide composite material, i.e. sol-gel process, layer assembly method, silicon dioxide gel and high polymer monomer mixing copolymerization process.
The preparation method's of above-mentioned three kinds of silicon dioxide composite materials weak point is: adopt the synthetic composite microsphere material of sol-gel process to be difficult for forming the single type particle, and dispersed bad; Layer assembly method preparation process complexity, the material structure of preparation is loose, and stability is not high; Silicon dioxide gel and high polymer monomer mixing copolymerization process, organic principle and inorganic constituents are difficult to form the structural type composite.
Because the structural type composite, as the structural characteristics of core/shell type SiO 2 composite microsphere material itself, scientists has produced very big interest to this type of investigation of materials.For example, Hotta etc. are template with the polystyrene, by TEOS hydrolysis under acid condition, make the polystyrene/SiO of ordered big hole structure
2Complex microsphere.SiO
2Shell can be regulated and control by changing the reaction time, and its aperture can be regulated controlled by pH.Zhang etc. have synthesized the polystyrene microsphere that is embedded with quantum dot CdSe, be surfactant then with the softex kw, by the hydrolysis in HCl of the positive silane of tetraethoxy, in the process of hydrolysis, add a spot of rhodamine B, and obtained structural type SiO
2/ polystyrene and quantum dot composite fluorescent microballoon.The design feature of this type of material is that shell is SiO
2, examine polystyrene microsphere into the quantum dot disperse.Caruso etc. utilize the surface of different-grain diameter has negative electrical charge after the modification polystyrene microsphere as template, will have different electrical polyelectrolyte in the self assembly layer by layer of its surface, then with the TiO of different size size
2, SiO
2Repeatedly be deposited on the template respectively with Laponite clay nano particle, and obtained the composite microsphere material of pattern and controllable size.Wu etc. are monomer with the methymethacrylate, and 2-methacryl ethyl-trimethyl salmiac is made auxiliary monomer, and polymerization in the presence of silicon dioxide gel prepares the silica hybrid microspheres material of strawberry type.
The comprehensive literature report finds not that also the complex microsphere of preparation not only has structural type but also present the patterned surface that nano silicon forms, and makes the application of this complex microsphere be subjected to certain restriction.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned SiO 2 composite microsphere material preparation method, provide a kind of reasonable in design, feasible process, easy and simple to handle, the reaction time short, the preparation method of reacted surface patterned silicon dioxide high molecular composite microsphere at normal temperatures.
Solving the problems of the technologies described above the technical scheme that is adopted is that this preparation method comprises the steps:
1, preparation mixed surfactant
With Si Ban-80 and Tween-80 is to be hybridly prepared into mixed surfactant at 5: 1 by weight.
2, the synthetic template oil phase of preparation
The mixed surfactant of step 1 preparation is joined in the there-necked flask that fills normal heptane, and mixed surfactant and normal heptane are 1: 115～130 to be hybridly prepared into and to synthesize the template oil phase by weight.
3, preparation emulsion
The synthetic template oil phase of step 2 preparation is put into there-necked flask, stir with mixer, mixing speed is 360～400 rev/mins, feeds N with 2～3mL/ minute flow velocity
2,, make emulsion 18～30 ℃ of scope internal emulsifications 40～60 minutes.
4, preparation water
With N, N '-methylene-bisacrylamide, ammonium persulfate, N-N-isopropylacrylamide are mixing in 1: 1.17: 28.3 in molar ratio, stir, and make solution A.Acrylic acid and NaOH are that 1: 0.3～1 to be mixed with concentration be that 23% acrylic acid aqueous solution is a solution B in molar ratio.With solution A and solution B is to mix at 6: 1 by volume, imports till nitrogen to oxygen arranged, and makes water.
5, preparation copolymerization microgel
With the emulsion of the water of step 4 preparation and step 3 preparation is to make mixed liquor at 1: 10 by volume, and with the mixer stirring, mixing speed is 360～400 rev/mins, stirs 15 minutes.The 4.76% tetramethylethylenediamine aqueous solution of mixeding liquid volume 1/154 is joined in the mixed solution, reacted 3～4 hours, generate the copolymerization microgel, incline and remaining reactant liquor, the copolymerization microgel is alternately washed 5～6 times with acetone and secondary water, wash 3～4 times again with acetone at last and removed fully, dry naturally, make sand-like P (NIPAM-co-20%AA) the copolymerization microgel of white up to the adsorbed water of copolymerization microgel.
6, the copolymerization microgel of preparation swelling
Be 1: 11～13 to be that 9%～28% ammoniacal liquor evenly mixes by weight, placed 12 hours, make its abundant swelling, make P (NIPAM-co-20%AA) the copolymerization microgel of swelling copolymerization microgel and concentration.
7, the mixed liquor of preparation positive silane of tetraethoxy and normal heptane
With the positive silane of tetraethoxy and normal heptane is to be mixed and made into the mixed liquor of positive silane of tetraethoxy and normal heptane at 1: 4 by volume.
8, preparation surface patterned SiO 2 high molecular composite microsphere
The swelling copolymerization microgel of step 6 preparation is joined in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is Si Ban-80 with normal heptane is to be mixed and made at 1: 160 by weight, being 10～34 ℃ in temperature stirs with mixer, mixing speed is 600 rev/mins, drip positive silane of tetraethoxy and the normal heptane mixed liquors that step 7 prepares with constant pressure funnel with 7～8 droplets/minute, reacted 6 hours, generate SiO 2 high molecular composite microsphere, remaining reactant liquor inclines, alternately wash SiO 2 high molecular composite microsphere 6～7 times with secondary water and acetone, washing 3～4 times again with acetone is at last removed fully up to the adsorbed water of SiO 2 high molecular composite microsphere, naturally dry, make P (the NIPAM-co-20%AA)/SiO of white
2Complex microsphere.
The present invention is in the synthetic template oil phase processing step 2 of preparation, and mixed surfactant and normal heptane preferably are 1: 120～125 to be hybridly prepared into and to synthesize the template oil phase by weight.In the processing step 3 of preparation emulsion, the preferred temperature of emulsification is 20～25 ℃.In preparation aqueous process step 4, acrylic acid and NaOH are that 1: 0.6～0.8 to be mixed with concentration be 23% acrylic acid aqueous solution by preferred molar ratio.In the copolymerization microgel processing step 6 of preparation swelling, microgel is 14%～28% with the preferred concentration of ammoniacal liquor swelling.In preparation surface patterned SiO 2 high molecular composite microsphere processing step 8, preferable reaction temperature is 20～30 ℃.
The present invention is in the synthetic template oil phase processing step 2 of preparation, and mixed surfactant and normal heptane the best are to be hybridly prepared at 1: 122 to synthesize the template oil phase by weight.In preparation emulsion processing step 3, the optimum temperature of emulsification is 25 ℃.In preparation aqueous process step 4, the optimum mole ratio of acrylic acid and NaOH is that to be mixed with concentration at 1: 0.6 be 23% acrylic acid aqueous solution.In the copolymerization microgel processing step 6 of preparation swelling, microgel is 28% with the optium concentration of ammoniacal liquor swelling.In preparation surface patterned SiO 2 high molecular composite microsphere processing step 8, the optimum temperature of reaction is 20 ℃.
The present invention utilizes the hydrophilic interaction of copolymerization microgel inside and to temperature and pH stimulating responsive, the ammonia spirit swelling with 28%, and the positive silane of tetraethoxy is at copolymerization micro-gel surface base catalysis in-situ hydrolysis.The SiO that the copolymerization micro-gel surface generates
2Possess hydrophilic property, hydrolysis and polycondensation reaction further take place in the ammonia molecule that helps positive silane of tetraethoxy and copolymerization microgel diffusion inside, make the hydrolysis of the positive silane of tetraethoxy and polycondensation to the microgel internal migration.Copolymerization microgel network structure can be limited the size of silica presoma, stops the gathering of particulate, has improved the stability of silica.Three-dimensional net structure that microgel had and spherical morphology apply confinement and guide effect to inorganic crystal or the deposition reaction of carrying out therein, the growth of control silica, arrangement etc. form the closelypacked patterned surface complex microsphere of nano silicon bead.
The present invention compares with existing SiO 2 high molecular composite microsphere preparation method, has reasonable in design, feasible process, simple to operate, advantages such as reaction is carried out at normal temperatures, the reaction time is short, and its design feature is that shell is nanoscale SiO
2Bead is examined to having the macromolecule microgel of water-swellable.This design feature and properties of materials have potential specific use, can effectively control SiO by adjusting reaction time
2The thickness of microballoon shell.Adopt the synthetic high molecular composite microsphere of this method, have the advantages such as pliability of rigidity, stability and the organic material of inorganic material, patterned surface SiO
2Great specific surface that high molecular composite microsphere also has and relative little quality, can biomedical, inhale ripple damping, catalyst loading, fast enriching and separate, fields such as sensing technology, environmental protection, marine mining obtain to use widely.
Description of drawings
Fig. 1 is patterned surface P (the NIPAM-co-20%AA)/SiO that adopts the embodiment of the invention 1 preparation
2The electron scanning micrograph of complex microsphere.
Fig. 2 is the electron scanning micrograph that Fig. 1 surface local amplifies.
Fig. 3 selects P (NIPAM-co-20%AA) microgel for use, in the time of 34 ℃, will contain disposable the joining in the deposition oil phase of mixed liquor of positive silane of 1.0mL tetraethoxy and normal heptane, reacts the P of generation (NIPAM-co-20%AA)/SiO 6 hours
2The electron scanning micrograph of complex microsphere.
Fig. 4 is the electron scanning micrograph that Fig. 3 surface local amplifies.
Fig. 5 selects P (NIPAM-co-20%AA) microgel for use, in the time of 34 ℃, the mixed liquor that will contain positive silane of 1.0mL tetraethoxy and normal heptane is added drop-wise in the deposition oil phase with 7～8 droplets/minute speed through constant pressure funnel, reacted the P of generation (NIPAM-co-20%AA)/SiO 6 hours
2The electron scanning micrograph of complex microsphere.
Fig. 6 is the electron scanning micrograph that Fig. 5 surface local amplifies.
Fig. 7 selects the polyacrylic acid microgel for use, in the time of 20 ℃, will contain the mixed liquor of positive silane of 1.0mL tetraethoxy and normal heptane, is added drop-wise in the deposition oil phase with 7～8 droplets/minute speed, reacts the PAA/SiO of generation 6 hours
2The complex microsphere electron scanning micrograph.
Fig. 8 is the electron scanning micrograph that Fig. 7 surface local amplifies.
Fig. 9 is patterned surface P (the NIPAM-co-20%AA)/SiO that adopts the embodiment of the invention 1 preparation
2The FFIR figure of complex microsphere.
Figure 10 adopts patterned surface P (the NIPAM-co-20%AA)/SiO of the embodiment of the invention 1 preparation
2The thermogravimetric analysis curve map of complex microsphere.
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.
Embodiment 1
1, preparation mixed surfactant
With Si Ban-80 and Tween-80 is to be hybridly prepared into mixed surfactant at 5: 1 by weight.
2, the synthetic template oil phase of preparation
The mixed surfactant of step 1 preparation is joined in the there-necked flask that fills normal heptane, and mixed surfactant and normal heptane are to be hybridly prepared at 1: 122 to synthesize the template oil phase by weight.
3, preparation emulsion
The synthetic template oil phase of step 2 preparation is put into there-necked flask, stir with mixer, mixing speed is 360～400 rev/mins, feeds N with 2～3mL/ minute flow velocity
2,, make emulsion 25 ℃ of scope internal emulsifications 40～60 minutes.
4, preparation water
With N, N '-methylene-bisacrylamide, ammonium persulfate, N-N-isopropylacrylamide are mixing in 1: 1.17: 28.3 in molar ratio, stir, and are mixed with solution A.Acrylic acid and NaOH are that to be mixed with concentration at 1: 0.6 be that 23% acrylic acid aqueous solution is a solution B in molar ratio.With solution A and solution B is to mix at 6: 1 by volume, imports till nitrogen to oxygen arranged, and makes the water that cumulative volume is 7mL.
5, preparation copolymerization microgel
The water of step 4 preparation is joined in the emulsion of 70mL, stir with mixer, mixing speed is 360～400 rev/mins, add 4.76% tetramethylethylenediamine aqueous solution 0.5mL after 15 minutes, reacted 3～4 hours, generate the copolymerization microgel, incline and remaining reactant liquor, the copolymerization microgel is alternately washed 5～6 times with acetone and secondary water, washing 3～4 times again with acetone is at last removed fully up to the adsorbed water of copolymerization microgel, naturally dry, make sand-like P (NIPAM-co-20%AA) the copolymerization microgel of white.
6, the copolymerization microgel of preparation swelling
Adding concentration is 28% 2.3g ammonia spirit in the copolymerization microgel 0.2g of step 5 preparation, places 12 hours, makes its abundant swelling, makes P (NIPAM-co-20%AA) the copolymerization microgel of swelling.
7, the mixed liquor of preparation positive silane of tetraethoxy and normal heptane
The positive silane of the tetraethoxy of 1.0mL and normal heptane are mixed and made into the positive silane of tetraethoxy that total amount is 5.0mL and the mixed liquor of normal heptane.
8, preparation surface patterned SiO 2 high molecular composite microsphere
The swelling copolymerization microgel of step 6 preparation is joined in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is Si Ban-80 with normal heptane is to be mixed and made at 1: 160 by weight, being 20 ℃ in temperature stirs with mixer, mixing speed is 600 rev/mins, drip positive silane of tetraethoxy and the normal heptane mixed liquors that step 7 prepares with constant pressure funnel with 7～8 droplets/minute, reacted 6 hours, generate SiO 2 high molecular composite microsphere, remaining reactant liquor inclines, alternately wash SiO 2 high molecular composite microsphere 6～7 times with secondary water and acetone, washing 3～4 times again with acetone is at last removed fully up to the adsorbed water of SiO 2 high molecular composite microsphere, naturally dry, make P (the NIPAM-co-20%AA)/SiO of white
2Complex microsphere.
Embodiment 2
In the present embodiment, in the synthetic template oil phase processing step 2 of preparation, mixed surfactant and normal heptane are to be hybridly prepared at 1: 115 to synthesize the template oil phase by weight.In the processing step 3 of preparation emulsion, emulsifying temperature is 18 ℃.In preparation aqueous process step 4, acrylic acid and NaOH are that to be mixed with concentration at 1: 0.3 be 23% acrylic acid aqueous solution in molar ratio.In the copolymerization microgel processing step 6 of preparation swelling, microgel concentration is 9% ammoniacal liquor swelling.In preparation surface patterned SiO 2 high molecular composite microsphere processing step 8, reaction temperature is 18 ℃.Other processing step is identical with embodiment 1.
Embodiment 3
In the present embodiment, in the synthetic template oil phase processing step 2 of preparation, mixed surfactant and normal heptane are to be hybridly prepared at 1: 130 to synthesize the template oil phase by weight.In the processing step 3 of preparation emulsion, emulsifying temperature is 30 ℃.In preparation aqueous process step 4, acrylic acid and NaOH are that to be mixed with concentration at 1: 1 be 23% acrylic acid aqueous solution in molar ratio.In the copolymerization microgel processing step 6 of preparation swelling, microgel concentration is 28% ammoniacal liquor swelling.In preparation surface patterned SiO 2 high molecular composite microsphere processing step 8, reaction temperature is 34 ℃.Other processing step is identical with embodiment 1.
In order to determine the processing step of the best of the present invention, the inventor has carried out a large amount of laboratory research tests, and various test situation are as follows:
1, feeding mode is to the influence of complex microsphere pattern
Prepared P (NIPAM-co-20%AA) microgel with 28% the abundant swelling of ammonia spirit 2.5mL after, in joined emulsification 40 minutes the deposition oil phase, the deposition oil phase is Si Ban-80 with normal heptane is to be mixed and made into the positive silane of tetraethoxy that total amount is 5.0mL and the mixed liquor of normal heptane at 1: 160 by weight, with 600 rev/mins of mixing speeds, in reaction temperature is 34 ℃, to contain the positive silane of tetraethoxy of 1.0mL and the mixed liquor 5.0mL of normal heptane and be respectively disposable adding, secondary adds and drips with the speed of constant pressure funnel with 7～8 droplets/minute, after adding, the identical reaction down of other conditionally complete 6 hours, make surface patterned SiO 2 high molecular composite microsphere.Positive silane of tetraethoxy and normal heptane mixed liquor are added drop-wise in the deposition oil phase through the speed of constant pressure funnel with 7～8 droplets/minute, the electron scanning micrograph of the composite of preparation is shown as sphere, see Fig. 1, Fig. 2 is seen by tightly packed formation of the little silica of nanometer in the local complex microsphere surface of amplifying.Positive silane of tetraethoxy and normal heptane mixed liquor are disposable to join in the deposition oil phase, the electron scanning micrograph of the composite of preparation is shown as sphere, see Fig. 3, the local complex microsphere surface of amplifying presents tiny particle and many big sheet deposits, sees Fig. 4.Positive silane of tetraethoxy and normal heptane mixed liquor join deposition at twice and make complex microsphere in the oil phase and observe under light microscope that complex microsphere is spherical to keep better, and sphere is smooth.
Result of the test shows: under identical reaction condition, when selecting different feeding modes for use, generate the complex microsphere of different-shape, wherein, the complex microsphere made from the feeding mode of 7～8 droplets/minute speed with constant pressure funnel has patterned surface.The present invention selects mixed liquor that positive silane of 1.0mL tetraethoxy and normal heptane be mixed and made into positive silane of tetraethoxy that total amount is 5.0mL and normal heptane respectively with disposable adding, and secondary adds and with the speed dropping of constant pressure funnel with 7～8 droplets/minute.
2, reaction temperature is to the influence of complex microsphere surface topography
It with concentration 28% the abundant swelling copolymerization of ammoniacal liquor 2.5mL microgel, join in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is Si Ban-80 with normal heptane is to be mixed and made at 1: 160 by weight, with 600 rev/mins, be respectively 34 ℃, 20 ℃, 10 ℃ in reaction temperature and drip the mixed liquor 5.0mL that contains positive silane of 1.0mL tetraethoxy and normal heptane with constant pressure funnel with 7～8 droplets/minute down, after dripping, the identical reaction down of other conditionally complete 6 hours.Reaction temperature is 34 ℃, generate SiO 2 high molecular composite microsphere, adopt sem observation, the electron scanning micrograph of the composite of preparation is shown as sphere, see Fig. 5, the sem observation surface of the local complex microsphere that amplifies presents the granule deposit, sees Fig. 6.Reaction temperature is 20 ℃, and the SiO 2 high molecular composite microsphere of generation to homodisperse spherical morphology, is seen Fig. 1 through sem observation, and the local complex microsphere performance nanometer grade silica bead that amplifies is tightly packed, sees Fig. 2.Reaction temperature is 10 ℃, and the SiO 2 high molecular composite microsphere of generation adopts sem observation, complex microsphere with when reacting for 20 ℃, present identical surface topography.
Result of the test shows: under identical reaction condition, along with the rising of reaction temperature, the electron scanning micrograph of the SiO 2 high molecular composite microsphere of making is observed lip-deep particle and is become inhomogeneous gradually.The present invention prepares that reaction temperature is 10～34 ℃ in the surface patterned SiO 2 high molecular composite microsphere processing step.
3, ammonia concn is to the influence of complex microsphere surface topography
With concentration is 9%, 14%, 28% ammonia spirit swelling copolymerization microgel, join in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is Si Ban-80 with normal heptane is to be mixed and made at 1: 160 by weight, with 600 rev/mins of mixing speeds, in reaction temperature is to contain positive silane of 1.0mL tetraethoxy and normal heptane mixed liquor 5.0mL with 7～8 droplets/minute speed droppings under 20 ℃, the identical reaction down of other conditionally complete 6 hours, generate SiO 2 high molecular composite microsphere.With concentration is 9% ammonia spirit swelling microgel, and the SiO 2 high molecular composite microsphere of preparation is observed under light microscope, and the SiO 2 high molecular composite microsphere monodispersity is bad.With concentration is 14% ammonia spirit swelling, and the SiO 2 high molecular composite microsphere of preparation is observed under light microscope, and the edge is rough, and is jagged on the limit.It with concentration 28% ammonia spirit swelling microgel, the SiO 2 high molecular composite microsphere of preparation, adopt SEM to observe, the microballoon monodispersity is good, and the surface shows as patterning, see Fig. 1, Fig. 2 is seen by tightly packed formation of the little silica spheres of nanometer in the local complex microsphere surface of amplifying.
Result of the test shows: under identical reaction condition, along with the increase of the used ammonia spirit concentration of swelling, the SiO 2 high molecular composite microsphere of generation is uniformly dispersed, and surface topography becomes even gradually.The present invention prepares that the used ammonia spirit concentration of swelling is 9～28% in the SiO 2 high molecular composite microsphere processing step.
4, microgel is to the influence of complex microsphere pattern
After P (NIPAM-co-20%AA), polyacrylic acid and poly-N-isopropyl acrylamide microgel are used 28% the abundant swelling of ammonia spirit respectively, join in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is Si Ban-80 with normal heptane is to be mixed and made at 1: 160 by weight, with 600 rev/mins of mixing speeds, in reaction temperature is 20 ℃, contain positive silane of 1.0mL tetraethoxy and normal heptane mixed liquor 5.0mL with 7～8 droplets/minute droppings, the identical reaction down of other conditionally complete 6 hours, obtain SiO 2 high molecular composite microsphere.When selecting polyacrylic acid copolymerized microgel for use, the SiO 2 high molecular composite microsphere of preparation arrives with sem observation, and the complex microsphere adhesion phenomenon is serious, sees Fig. 7, and the local ball surface of amplifying presents a small amount of granule deposit, sees Fig. 8.When adopting poly-N-isopropyl acrylamide microgel, the complex microsphere of preparation is observed the spherical maintenance of deposition under light microscope bad.Adopt the complex microsphere of P (NIPAM-co-20%AA) preparation to observe under SEM, the monodispersity of complex microsphere is good especially, sees Fig. 1, the local complex microsphere surface of amplifying, and complex microsphere is to form by bead is tightly packed, sees Fig. 2.
Result of the test shows: under identical reaction condition, when selecting different microgels for use, generate the complex microsphere of different-shape.Select for use P (NIPAM-co-20%AA) to make the patterning complex microsphere.The present invention prepares in the SiO 2 high molecular composite microsphere processing step and selects polyacrylic acid, poly-N-isopropyl acrylamide and P (NIPAM-co-20%AA) microgel.
In order to verify beneficial effect of the present invention, the inventor adopts the surface patterned SiO 2 high molecular 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: P (NIPAM-co-20%AA)/SiO
2The patterned surface complex microsphere.
Laboratory apparatus: SEM, model are XL-20, are produced by Britain Philips company; Fourier transformation infrared spectrometer, model are EQUINX55, are produced by German Brucher company; Thermogravimetric analyzer, model are PEVKIN-ELMER, are produced by U.S. TA company.
1, observes
Method of testing by SEM is observed SiO 2 high molecular composite microsphere.
2, test
Method of testing by Fourier transformation infrared spectrometer, thermogravimetric analyzer is tested SiO 2 high molecular composite microsphere.
3, observed result
With sem observation to picture on surface see Fig. 1, test with Fourier transformation infrared spectrometer, the infrared curve of being drawn is seen Fig. 9, tests with thermogravimetric analyzer, the thermogravimetric analysis curve of being drawn is seen Figure 10.
From Fig. 1 as seen, P (NIPAM-co-20%AA)/SiO
2Complex microsphere is spherical in shape, structural integrity, and monodispersity is good, and about diameter 30 μ m, the complex microsphere surface is by tightly packed formation of many uniform little nano silicon balls.From Fig. 9 as seen, the infrared spectrum curve is at 3446cm
-1More weak hydroxyl stretching vibration peak appears, at 1627cm
-1The C=O characteristic absorption peak that carboxylic acid occurs is at 1092cm
-1And 805cm
-1Feature asymmetric stretching vibration peak and stretching vibration peak that very strong Si-O-Si occurs, simultaneously, at 950cm
-1And 560cm
-1The characteristic absorption peak of more weak Si-OH appears in the place.From Figure 10 as seen, 100 ℃ were lost 7.61% weight in the past, had lost 47.20% weight between 100 ℃ to 300 ℃, when temperature is higher than 300 ℃, the zero gravity loss, the content of silica is 45.09% in the last remaining weight presentation of results SiO 2 high molecular composite microsphere.
Claims (3)
1. the preparation method of a surface patterned SiO 2 high molecular composite microsphere is characterized in that this preparation method comprises the steps:
(1) preparation mixed surfactant
With Si Ban-80 and Tween-80 is to be hybridly prepared into mixed surfactant at 5: 1 by weight;
(2) the synthetic template oil phase of preparation
The mixed surfactant of step (1) preparation is joined in the there-necked flask that fills normal heptane, and mixed surfactant and normal heptane are 1: 115～130 to be hybridly prepared into and to synthesize the template oil phase by weight;
(3) preparation emulsion
The synthetic template oil phase of step (2) preparation is put into there-necked flask, stir with mixer, mixing speed is 360～400 rev/mins, feeds N with 2～3mL/ minute flow velocity
2,, make emulsion 18～30 ℃ of scope internal emulsifications 40～60 minutes;
(4) preparation water
With N, N '-methylene-bisacrylamide, ammonium persulfate, N-N-isopropylacrylamide are mixing in 1: 1.17: 28.3 in molar ratio, stir, and make solution A; Acrylic acid and NaOH are that 1: 0.3～1 to be mixed with concentration be that 23% acrylic acid aqueous solution is a solution B in molar ratio; With solution A and solution B is to mix at 6: 1 by volume, imports till nitrogen to oxygen arranged, and makes water;
(5) preparation copolymerization microgel
With the emulsion of the water of step (4) preparation and step (3) preparation is to make mixed liquor at 1: 10 by volume, and with the mixer stirring, mixing speed is 360～400 rev/mins, stirs 15 minutes; The 4.76% tetramethylethylenediamine aqueous solution of mixeding liquid volume 1/154 is joined in the mixed solution, reacted 3～4 hours, generate the copolymerization microgel, incline and remaining reactant liquor, the copolymerization microgel is alternately washed 5～6 times with acetone and secondary water, wash 3～4 times again with acetone at last and removed fully, dry naturally, make sand-like P (NIPAM-co-20%AA) the copolymerization microgel of white up to the adsorbed water of copolymerization microgel;
(6) the copolymerization microgel of preparation swelling
Be 1: 11～13 to be that 9%～28% ammoniacal liquor evenly mixes by weight, placed 12 hours, make its abundant swelling, make P (NIPAM-co-20%AA) the copolymerization microgel of swelling copolymerization microgel and concentration;
(7) mixed liquor of preparation positive silane of tetraethoxy and normal heptane
With the positive silane of tetraethoxy and normal heptane is to be mixed and made into the mixed liquor of positive silane of tetraethoxy and normal heptane at 1: 4 by volume;
(8) preparation surface patterned SiO 2 high molecular composite microsphere
The swelling copolymerization microgel of step (6) preparation is joined in 40 minutes the deposition oil phase of emulsification, the deposition oil phase is Si Ban-80 with normal heptane is to be mixed and made at 1: 160 by weight, being 10～34 ℃ in temperature stirs with mixer, mixing speed is 600 rev/mins, drip positive silane of tetraethoxy and the normal heptane mixed liquors that step 7 prepares with constant pressure funnel with 7～8 droplets/minute, reacted 6 hours, generate SiO 2 high molecular composite microsphere, remaining reactant liquor inclines, alternately wash SiO 2 high molecular composite microsphere 6～7 times with secondary water and acetone, washing 3～4 times again with acetone is at last removed fully up to the adsorbed water of SiO 2 high molecular composite microsphere, naturally dry, make P (the NIPAM-co-20%AA)/SiO of white
2Complex microsphere.
2. according to the preparation method of the described surface patterned SiO 2 high molecular composite microsphere of claim 1, it is characterized in that: in the synthetic template oil phase processing step (2) of preparation, mixed surfactant and normal heptane are 1: 120～125 to be hybridly prepared into and to synthesize the template oil phase by weight; In the processing step (3) of preparation emulsion, the temperature of emulsification is 20～25 ℃; In preparation aqueous process step (4), acrylic acid and NaOH are that 1: 0.6～0.8 to be mixed with concentration be 23% acrylic acid aqueous solution in molar ratio; In the copolymerization microgel processing step (6) of preparation swelling, microgel is 14%～28% with the concentration of ammoniacal liquor swelling; In preparation surface patterned SiO 2 high molecular composite microsphere processing step (8), reaction temperature is 20～30 ℃.
3. according to the preparation method of the described surface patterned SiO 2 high molecular composite microsphere of claim 1, it is characterized in that: in the synthetic template oil phase processing step (2) of preparation, mixed surfactant and normal heptane are to be hybridly prepared at 1: 122 to synthesize the template oil phase by weight; In preparation emulsion processing step (3), the temperature of emulsification is 25 ℃; In preparation aqueous process step (4), the mol ratio of acrylic acid and NaOH is that to be mixed with concentration at 1: 0.6 be 23% acrylic acid aqueous solution; In the copolymerization microgel processing step (6) of preparation swelling, microgel is 28% with the concentration of ammoniacal liquor swelling; In preparation surface patterned SiO 2 high molecular composite microsphere processing step (8), the temperature of reaction is 20 ℃.
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| US20050192381A1 (en) * | 2003-07-18 | 2005-09-01 | Bringley Joseph F. | Amine polymer-modified nanoparticulate carriers |
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| US20050192381A1 (en) * | 2003-07-18 | 2005-09-01 | Bringley Joseph F. | Amine polymer-modified nanoparticulate carriers |
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