CN103933911A - Preparation method for polymer-based hierarchical porous structure interlocking microcapsule - Google Patents
Preparation method for polymer-based hierarchical porous structure interlocking microcapsule Download PDFInfo
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Abstract
The invention discloses a preparation method for a polymer-based hierarchical porous structure interlocking microcapsule. The method comprises the steps of modifying a silicon dioxide colloid crystal template, controllably grafting a polymer by a surface triggering atom transferring free radical polymerization method and a double-bond free radical polymerization method, crosslinking a linear polymer chain section by an Friedel-Crafts crosslinking method for an external crosslinking agent, removing the silicon dioxide colloid crystal template to prepare the polymer-based hierarchical porous structure interlocking microcapsule. Due to the controllably grafted polymer layer, a certain slit is reserved between every two adjacent microcapsules, so that the mass is reduced, and more mass transfer ways are formed; by the adoption of the Friedel-Crafts crosslinking method for the external crosslinking agent, micropores and mesoporous are formed by crosslinking capsule walls made of polymer materials; the apertures of the formed holes and the crosslinking degree are adjusted according to the type of the crosslinking agent; a foundation is laid for the application; communicating windows formed among the micropores, the mesoporous and the interlocking microcapsules in the capsule walls and the slits between the microcapsules adopt classified hole interlocking structures in the mass.
Description
Technical field
Technical scheme of the present invention relates to polymeric material field, is specifically related to a kind of preparation method of Polymers hierarchical porous structure interlocking micro-capsule.
Background technology
Micro-capsule (Microcapsule) refers to have hollow structure, the miniature vessel taking macromolecular material, inorganic material or hybrid inorganic-organic materials as shell.Micro-capsule has the intracardiac core material of protection capsule, changes the function of substance weight, volume, state and surface property, isolation active component, can also control the slow release of core material etc.(the Narty J J such as late 1970s Narty, Oppenheim R C, Speiser P.Nanoparticles a new colloidal drug delivering system.Pharmaceutica Acta Helvetiae, 1978,53:17-23.) propose the concept of capsule of nano (Nanocapsules), microcapsules have been extended to the new material in order to have nano-scale.Micro-capsule development is in recent years rapid, at present at response material (Alireza Abbaspourrad, Sujit S.Datta, David A.Weitz.Controlling Release From pH-Responsive Microcapsules, Langmuir, 2013,29:12697-12702., Koichiro Hayashi, Michihiro Nakamura, Kazunori Ishimura.In situ synthesis and photoresponsive rupture of organosilica nanocapsules.Chemical Communications, 2011, 47:1518-1520.), controllable release (Alireza Abbaspourrad, Nick J.Carroll, Shin-Hyun Kim, David A.Weitz.Polymer Microcapsules with Programmable Active Release.Journal of the American Chemical Society, 2013, 135:7744-7750), processing of farm products (shines recklessly, Jiang Rongqing, Yu Hansong, Zheng Wei, Liu Junmei. spray drying process is produced the technical study of walnut protein peptide microcapsules. agricultural machinery, 2011, 20:155-158.) and catalytic field (Xiao Nan, Zhou Ying, Ling Zheng, Zhao Zongbin, Qiu Jieshan.Carbon foams made of in situ produced carbon nanocapsules and the use as a catalyst for oxidative dehydrogenation of ethylbenzene.Carbon, 2013, 60:514-522.) etc. aspect all has a wide range of applications.
The preparation of micro-capsule mainly comprises: template (Bogdan V.Parakhonskiy, Alexey M.Yashchenok, Manfred Konradd, Andre G.Skirtach.Colloidal micro-and nano-particles as templates for polyelectrolyte multilayer capsules.2014, DOI:10.1016/j.cis.2014.01.022., Hu Yang, YangYu, NingYin, WangChaoyang, Tong Zhen.Facile preparation of artemisia argyi oil-loaded antibacterial microcapsules by hydroxyapatite-stabilized Pickering emulsion templating.Colloids and Surfaces B:Biointerfaces, 2013, 112:96-102), self-assembly method (Jae Won Shim, Shin-Hyun Kim, Seog-Jin Jeon, Seung-Man Yang, Gi-Ra Yi.Microcapsules with Tailored Nanostructures by Microphase Separation of Block Copolymers.Chemistry of Materials, 2010, 22:5593-5600), emulsion polymerization (Cao Zhihai, Shan Guorong.Synthesis of Polymeric Nanocapsules with a Crosslinked Shell through Interfacial Miniemulsion Polymerization.Journal of Polymer Science:Part A:Polymer Chemistry, 2009, 47:1522-1534.) etc., wherein template because of its method simple, product repetitive rate is high and foresight good, product form and steady performance are the most conventional.This patent adopts colloid crystal template legal system for micro-capsule, forms polymer at the silica colloidal crystal template surface of regular arrangement, remove form after template be interconnected, the interlocking micro-capsule aggregation of regular arrangement.This structure, by micro-capsule interlocking is assembled, forms multidirectional mass transfer on the one hand, greatly promotes mass transfer rate; On the other hand, this micro-capsule macroscopic view is solid-state, is conducive to liquid-solid separation, promotes the repetition regenerability of micro-capsule, reduces loaded down with trivial details last handling process.
Aspect the selection of micro-capsule cyst wall material, polymerizable material density is much smaller than mineral-type materials, when having alleviated micro-capsule quality, improve specific area, in addition cross-linked polymer has good mechanical performance and solvent resistance, biocompatibility preferably, and more easily carrying out functionalization, is the good material of preparing micro-capsule.In the application of micro-capsule, wall thickness is the key factor that mass transfer diffusion process be can not ignore.Surface Atom Transfer Radical Polymerization (SI-ATRP) (Matyjaszewski K., Tsarevsky N.V.Nanostructured functional materials prepared by atom transfer radical polymerization.Nature Chemistry, 2009,1:276-288.) extensive, the polymerization process adjusting easy to control of applicable monomer, be the better method of controllable adjustment Polymers wall thickness, traditional two key radical polymerizations also can be controlled wall thickness by controlling polymerizing condition in addition.The method of this patent employing SI-ATRP and two key radical polymerizations, at silica colloidal crystal template surface graft polymers segment, reach the controlled of wall thickness.
Hierarchical porous structure (Hierarchically Porous Structure) is by micropore, the structure that mesoporous, each single-stage hole of macropore is incorporated into one, this class formation has made up the defect to a certain degree that single-stage hole exists, the multi-stage porous gap structure of its huge specific area of this external cause, prosperity, make it be better than other single pore passage structure at aspects such as diffusion, mass transfers, be more conducive to its application at aspects such as absorption, catalysis, sensing and biologies.At present synthetic hierarchical porous structure adopts two template, emulsion method, and only limits to phenolic resins, melamine class material for Polymers material.Its limitation is: in (1) two template, template will obvious interfacial interaction occur or form stronger interaction force (as hydrogen bond) with skeleton material, in skeleton material, complete self assembly, after removing template, can form duct, the macromolecular compounds with special structure that adopt at present two template more, this family macromolecule requires high for segmented structure unit composition and molecular weight, prepare loaded down with trivial details and expensive, skeleton material is selected only for melamine etc. can form compared with the polymer of strong hydrogen bonding effect simultaneously, these have limited two template greatly in the application of preparing Polymers multilevel hole material, (2) for emulsion polymerization, suitable surfactant and proportioning are the keys that determines duct size, and are prone to collapse hole, shrinkage cavity phenomenon taking drop as the synthetic pore volume of template, and pore structure is unstable.Along with the research expansion that deepens continuously of hole forming technology, Fu Ke is cross-linked hole forming technology (Vadim A.Davankov, Maria P.Tsyurupa.Hypercrosslinked Polymeric Networks and Adsorbing Materials.Comprehensive Analytical Chemistry, 2011, 56:195-295.) prepare micropore, the discovery of mesoporous material, can well solve Polymers hierarchical porous structure and prepare limitation, and the pore structure of preparation is stable, reaction method is simple and direct, easy to operate, usually be used to prepare polymer class micropore, mesoporous material, and about Fu Ke crosslinking technological (the Fernando Maya that adopts additional crosslink agent, Frantisek Svec.A new approach to the preparation of large surface area poly (styrene-co-divinylbenzene) monoliths via knitting of loose chains using external crosslinkers and application of these monolithic columns for separation of small molecules.Polymer, 2014, 55:340-346.) aperture in the hole of the formation prepared, the degree of cross linking after crosslinked, can control according to the kind of crosslinking agent, it is one of method usually adopting in the crosslinked pore of Fu Ke.
A kind of Polymers hierarchical porous structure interlocking microcapsule preparation method of being combined with Fu Ke cross-linking method about surperficial Atom Transfer Radical Polymerization, two key radical polymerization at present has no relevant report.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method of Polymers hierarchical porous structure interlocking micro-capsule, the method flow process as shown in Figure 1, by silica colloidal crystal template is carried out to modification, adopt the controlled graft polymers segment of method of surperficial Atom Transfer Radical Polymerization and two key radical polymerizations, Fu Ke cross-linking method by additional crosslink agent is cross-linked linear polymer segment, remove after silica colloidal crystal template, prepare a kind of Polymers hierarchical porous structure interlocking micro-capsule.The present invention is different from the method for the tradition filling of preparing ordered 3 D structure employing, controlled graft polymer layer makes originally to fill sufficient region and also has certain gap space, alleviate quality and form more mass transfer approach simultaneously, the cyst wall of polymerizable material is cross-linked to form micropore by the crosslinked hole forming technology of Fu Ke, mesoporous, self-crosslinking technology relatively, the aperture in the hole that the Fu Ke of additional crosslink agent is cross-linked to form, the degree of cross linking after crosslinked, can control according to the kind of crosslinking agent, micropore in this cyst wall, the blister cavities of mesoporous and macropore rank, gap between connection window and the micro-capsule forming between interlocking micro-capsule presents hierarchical porous structure on the whole.This special construction can greatly improve mass-transfer efficiency, has higher specific area simultaneously, and more avtive spot is provided, and therefore demonstrates huge superiority in adsorbing separation, supported catalyst field.
Technical scheme of the present invention is:
A preparation method for Polymers hierarchical porous structure interlocking micro-capsule, the method comprises the following steps:
(1) preparation of silica colloidal crystal template
According to the difference of particle size range, take one of following methods:
Method one: average particle size range is in the preparation of the silica colloidal crystal template of 80nm-600nm
Utilize
synthetic method, in room temperature downhill reaction device, add successively absolute ethyl alcohol, ammoniacal liquor, distilled water, stir, add rapidly ethyl orthosilicate, after reaction 8h, gained suspension is transferred in beaker, treat that solvent volatilizees completely naturally, obtain the silica colloidal crystal template of average grain diameter within the scope of 80nm-600nm, the most at last template in Muffle furnace at 200-800 DEG C sintering 2-8h, slowly be down to room temperature, obtain the silica colloidal crystal template that average particle size range bonds mutually at the silicon dioxide microsphere of 80nm-600nm;
Wherein material proportion is that mass ratio is ammoniacal liquor: absolute ethyl alcohol: distilled water: ethyl orthosilicate=1:0.5-60:1-5:0.2-10;
Or method two: average particle size range is in the preparation of the silica colloidal crystal template of 600nm-1200nm
In the reaction system of the silica colloidal crystal template in preparation average grain diameter within the scope of 80nm-600nm, after ethyl orthosilicate reaction 8h to be added, add the ammoniacal liquor of the equivalent of identical proportioning, absolute ethyl alcohol, distilled water and ethyl orthosilicate, reaction 8h, repeat to add, reaction 8h process 1-4 time, suspension is transferred in beaker, treat that solvent volatilizees completely naturally, obtain the silica colloidal crystal template of average particle size range at 600nm-1200nm, the most at last template in Muffle furnace at 200-800 DEG C sintering 2-8h, slowly be down to room temperature, obtain average particle size range in the inter-adhesive silica colloidal crystal template of the silicon dioxide microsphere of 600nm-1200nm,
(2) surface modification of silica colloidal crystal template is one of following two kinds of methods:
Method one: silane coupler [3-(2-bromo isobutyryl) amine propyl group]-triethoxysilane (BITS) improved silica colloid
Crystal template
Silica colloidal crystal template after the sintering obtaining in dry step (1) is placed in reactor, add absolute ethyl alcohol, ammoniacal liquor, distilled water, 60 DEG C of mechanical agitation, add 60 DEG C of condensing reflux reaction 24-48h of [3-(2-bromo isobutyryl) aminopropyl]-triethoxysilane (BITS).Reaction stops after finishing stirring, and discards liquid, cleans displacement with absolute ethyl alcohol, and final 50 DEG C of vacuum drying 12-24h obtain the silica colloidal crystal template of BITS modification;
Wherein material proportion is that volume ratio is absolute ethyl alcohol: distilled water: ammoniacal liquor=20-200:0.1-2:0.1-1.5; In every 20-200mL ethanol, be dissolved with 0.1-1g BITS, and add the silica colloidal crystal template of 0.4g;
Or, method two: gamma-methyl allyl acyloxypropyl trimethoxysilane (MPS) improved silica colloid crystal template
In the silica colloidal crystal template after the sintering obtaining in the step (1) of reactor inner drying, add successively absolute ethyl alcohol, distilled water and ammoniacal liquor, stirring at room temperature, add condensing reflux reaction 24-48h under gamma-methyl allyl acyloxypropyl trimethoxysilane (MPS) room temperature condition, after finishing, reaction stops stirring, discard liquid, clean displacement with absolute ethyl alcohol, last 25 DEG C of vacuum drying 12-24h, obtain the silica colloidal crystal template of MPS modification;
Wherein material proportion is that volume ratio is absolute ethyl alcohol: distilled water: ammoniacal liquor=10-200:0.1-2:0.1-5; In every 10-200mL absolute ethyl alcohol, be dissolved with 0.1-10mL MPS, and add the silica colloidal crystal template of 0.6g;
(3) the controlled graft polymers segment of silica colloidal crystal template is one of following two kinds of methods:
Method one: the controlled graft polymers segment of silica colloidal crystal template surface Atom Transfer Radical Polymerization
In reactor, add the silica colloidal crystal template of the BITS modification that in step (2), method one obtains, 100 DEG C vacuumize 2h, under inert gas shielding, catalyst, solvent, part and grafted monomers are mixed, inject at 100 DEG C of the silica colloidal crystal templates of BITS modification and react 5-48h, reaction finishes rear with reaction solvent clean extracting 12h used, use again absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12-24h, obtain the silica colloidal crystal template of graft polymers, i.e. silica/polymer composite;
Material proportion is silica colloidal crystal template: catalyst=1:0.3-3 after mass ratio BITS modification, mol ratio grafted monomers, catalyst, part=10-100:1:1; Volume ratio monomer: solvent=1:0.2-3;
Catalyst in described step (3) is cuprous bromide (CuBr), stannous chloride (CuCl), stannous chloride (CuCl)/copper bromide (CuBr
2) or cuprous bromide (CuBr)/copper bromide (CuBr
2);
Inert gas in described step (3) is nitrogen or argon gas;
Part in described step (3) is N, N ', N ', N ", N " pentamethyl-diethylenetriamine (PMDETA) or three-(N, N-dimethylaminoethyl) amine (Me
6tREN);
Grafted monomers in described step (3) is styrene or substituted phenylethylene;
Solvent in described step (3) is DMF (DMF), cyclohexanone or methyl alcohol;
Or, method two: the two key radical polymerization graft polymers segments of silica colloidal crystal template surface
The silica colloidal crystal template that adds the MPS modification that in step (2), method two obtains in reactor, adds distilled water, polyvinylpyrrolidone (PVP), stirring at room temperature 12-24h subsequently; Under argon shield, be warming up to 60 DEG C, in 0.5h, drip potassium persulfate solution, drip subsequently the emulsion by dodecyl sodium sulfate (SDS), distilled water, potassium hydroxide and monomer composition, again be warming up to the potassium persulfate solution of adding same ratio equivalent after 70 DEG C, after 0.5h dropwises, keep thermotonus 2-12h, reaction finishes to clean with absolute ethyl alcohol afterwards, use again absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12-24h, obtain the silica colloidal crystal template of graft polymers, i.e. silica/polymer composite;
The material proportion adding in method two in described step (3) is the silica colloidal crystal template of mass ratio MPS modification: polyvinylpyrrolidone: distilled water: potassium peroxydisulfate: monomer=0.03:0.1-0.5:0.01-0.3:0.01-0.05:0.5-5 in emulsion; (distilled water in proportioning is the distilled water while adding polyvinylpyrrolidone, and the amount of potassium peroxydisulfate is the amount of potassium peroxydisulfate in the potassium persulfate solution dripping for the first time);
In described step (3), in method two, potassium persulfate solution consists of: 0.02g potassium peroxydisulfate is dissolved in 1-5mL distilled water;
In described step (3), in method two, the composition and ratio of emulsion is that quality is than dodecyl sodium sulfate: potassium hydroxide=0.01:0.01-0.05, volume ratio monomer: distilled water=2:0.01-0.05, every 0.01g dodecyl sodium sulfate is dissolved in 1-5mL monomer;
Grafted monomers in described step (3) is styrene or substituted phenylethylene;
(4) the crosslinked pore process of the Fu Ke of polymer segment
Dried silica/polymer composite is put into reactor, add solvent and additional crosslink agent swelling, until swelling completely after, under argon shield, the mixed liquor of catalysts and solvents composition is injected to silica/polymer composite, 60-120 DEG C of reaction 2-24h, reaction finishes rear with absolute ethyl alcohol, the cleaning of acidic alcohol mixed liquor, absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12-24h, obtain the Fu Ke of the additional crosslink agent silica/polymer composite after crosslinked;
Described step (4) method two material proportion is quality than silica/polymer composite: catalyst: additional crosslink agent=0.1:0.01-0.3:0.01-0.5g, wherein 0.1g silica/polymer composite adopts 1-30mL solvent swell, and 0.01g catalyst is dissolved in 1-30mL solvent;
Additional crosslinking agent in described step (4) method two is Cyanuric Chloride, 4,4 ,-dimethyl diphenyl or to xylylene dichlorides;
Catalyst in described step (4) method two is anhydrous ferric trichloride (FeCl
3), aluminum trichloride (anhydrous) (AlCl
3), anhydrous stannic chloride (SnCl
4) or anhydrous zinc dichloride (ZnCl
2);
Solvent in described step (4) method two is anhydrous 1,2-dichloroethanes, anhydrous nitrobenzene, anhydrous nitromethane or carbon tetrachloride;
(5) remove silica in silica/polymer composite
It is that in 40% hydrofluoric acid, silica colloidal crystal template is removed in ultrasonic cleaning that silica/polymer composite after the Fu Ke of the additional crosslink agent that step (4) is obtained is crosslinked is immersed in mass fraction, is washed to dryly after neutral to obtain a kind of Polymers hierarchical porous structure interlocking micro-capsule;
The preparation method of silane coupler [3-(2-bromo isobutyryl) the aminopropyl]-triethoxysilane in described step (2), comprises the following steps:
In reactor, add toluene, (3-aminopropyl) triethoxysilane (APTS), triethylamine (TEA), being placed in ice-water bath stirs, drip the mixed liquor of toluene and 2-bromine isobutyl acylbromide to reaction system, in 1h, dropwise, ice-water bath continues to stir 3h, then under room temperature, stir 10h and obtain solidliquid mixture, mixture is filtered, filtrate is removed unreacted triethylamine and solvent toluene by the method for decompression distillation, can obtain [3-(2-bromo isobutyryl) aminopropyl]-triethoxysilane that modification is used;
Wherein material proportion is volume ratio toluene: (3-aminopropyl) triethoxysilane (APTS): triethylamine (TEA): 2-bromine isobutyryl toluene bromide solution=20-40:8-16:4.73-9.46:20-60, wherein, in proportioning, the amount of toluene does not comprise toluene in 2-bromine isobutyryl toluene bromide mixed solution;
In 2-bromine isobutyryl toluene bromide mixed solution, every 20-60mL toluene that consists of of its mixed liquor of toluene adds 4.21-8.42mL2-bromine isobutyl acylbromide.
The invention has the beneficial effects as follows:
(1) a kind of Polymers hierarchical porous structure interlocking micro-capsule that prepared by the present invention is cross-linked polymer material, there is excellent physical and chemical performance, increase the specific area of micro-capsule simultaneously, promoted the application performance of micro-capsule in the field such as adsorbing separation, catalysis;
(2) the present invention is by surface atom transition free radical aggregation method and two key free radical polymerisation process graft polymers segment, make wall thickness there is controllability, then adopt micropore that the crosslinked method of Fu Ke forms, mesoporous, pore structure is stable, specific area increases substantially simultaneously, can reach 600m
2g
-1left and right, far above three-dimensional ordered macroporous material (30-90m
2g
-1), more avtive spot is provided, demonstrate huge advantage in supported catalyst, adsorbing separation field, Friedel-Crafts reaction method is simple and direct, easy to operate in addition, and the Fu Ke of additional crosslink agent is cross-linked and can regulates aperture and the degree of cross linking after being cross-linked according to crosslinking agent kind and consumption; (note: the final specific area of material often depends on micropore, mesoporous contributed, macropore contribution is little, so specific area says much larger than the material of macropore rank)
(3) a kind of Polymers hierarchical porous structure interlocking micro-capsule that prepared by the present invention, can find out by the electromicroscopic photograph in accompanying drawing 3 that micro-capsule ordered arrangement is interconnected and present interlocking structure.In addition cyst wall contains micropore, mesoporous, blister cavities is of a size of macropore rank, the gap that what this formed between micro-capsule with interlocking be communicated with between window and micro-capsule presents grading-hole and distributes, this just integrally combines hierarchical porous structure and interlocking structure, being conducive to material enters from all directions, form multidirectional mass transfer, greatly promote mass transfer rate.Can be seen by the photo in kind in accompanying drawing 4, such micro-capsule is solid granulates/powder, is conducive to liquid-solid separation, has greatly improved micro-capsule usability, reduces loaded down with trivial details post processing flow process in application, thereby lays the foundation for further improving its application performance.
Brief description of the drawings
Fig. 1: Polymers hierarchical porous structure interlocking micro-capsule preparation flow figure;
Fig. 2: embodiment mono-mesoporous is the electromicroscopic photograph of 600nm silica colloidal crystal template grafted polystyrene segment;
The electromicroscopic photograph of Polymers hierarchical porous structure interlocking micro-capsule in Fig. 3: embodiment mono-;
The photo in kind of Polymers hierarchical porous structure interlocking micro-capsule in Fig. 4: embodiment mono-;
Fig. 5: embodiment bis-mesoporous are the electromicroscopic photograph of 600nm silica colloidal crystal template grafted polystyrene segment;
The electromicroscopic photograph of Polymers hierarchical porous structure interlocking micro-capsule in Fig. 6: embodiment bis-
Detailed description of the invention
Embodiment mono-:
(1) preparation of 600nm silica colloidal crystal template
Under room temperature, add successively to being furnished with in churned mechanically 500mL there-necked flask ammoniacal liquor, the 35.0g deionized water that 145g absolute ethyl alcohol, 34.1g mass fraction are 25%, after stirring, then add rapidly 15.4g ethyl orthosilicate, room temperature reaction 8h in there-necked flask.The suspension of gained is transferred in beaker, treat that solvent volatilizees completely naturally, obtaining average grain diameter is 600nm silicon dioxide colloid template, template sintering 3h at 500 DEG C in Muffle furnace the most at last, slowly be down to room temperature, obtaining average grain diameter is the inter-adhesive silica colloidal crystal template of silicon dioxide microsphere of 600nm;
(2) surface modification of silica colloidal crystal template
Silane coupler [3-(2-bromo isobutyryl) aminopropyl]-triethoxysilane (BITS) improved silica template: by the silica colloidal crystal template after sintering dried 1.25g, put into and get 250mL there-necked flask, add ethanol 101mL, ammoniacal liquor 2.5mL, distilled water 3.8mL, 60 DEG C of mechanical agitation, add BITS3.125g condensing reflux reaction 24h.After finishing, reaction stops stirring, discard liquid, clean and replace three times with 100mL absolute ethyl alcohol, (pressure is lower than atmospheric pressure 0.1MPa to last 50 DEG C of vacuum drying 12h, following steps and case study on implementation vacuum drying pressure are same), the average grain diameter surface that is 600nm is connected to the silica colloidal crystal template after the modification of SI-ATRP initator, the silica colloidal crystal template after the BITS modification that average grain diameter is 600nm;
(3) the controlled graft polymers segment of silica colloidal crystal template
The silica colloidal crystal template 0.1713g taking after BITS modification obtained above is placed in two-mouth bottle, and 100 DEG C vacuumize 2h (pressure is lower than atmospheric pressure 0.1MPa, and it is same that following steps and case study on implementation vacuumize processing pressure).Under argon shield, 0.0610g CuCl (0.616mmol), 6.8mL DMF (0.088mol), 12.86 μ L PMDETA (0.616mmol), 3.4mL styrene (0.0296mol) are stirred.Mixed liquor is injected in the silica colloidal crystal template of BITS modification, 100 DEG C of isothermal reaction 24h, reaction finishes rear with DMF cleaning extracting 12h, absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12h, obtain the silica colloidal crystal template of graft polymers, obtain silica/polystyrene complex;
Fig. 2 model is that FEI Nano SEM450 electron scanning electron-microscope scanning silica/polystyrene complex obtains, between the ball of the silica/polystyrene complex after grafting and ball, present as seen from the figure orderly connected structure, single microsphere surface can be seen the not formation polymer part of ordered arrangement, and this is for micro-capsule interlocking is afterwards connected, the connection window of formation provides the foundation.
(4) the crosslinked pore process of the Fu Ke of polymer segment
Subsequently dried 0.0859g silica/polystyrene complex is put into catalyst bottle, adds the anhydrous nitrobenzene of 5mL and 0.1606g Cyanuric Chloride to mix swelling spending the night, swelling completely after, by anhydrous 0.1289g FeCl
3mix with the anhydrous nitrobenzene of 15ml, under argon shield, mixed solution is injected to silica/polystyrene complex, stirring at normal temperature 2h, after being slowly warming up to 100 DEG C, react 5h, reaction finishes that rear (wherein to account for mixed liquor mass fraction be 1% to hydrochloric acid with absolute ethyl alcohol, acidic alcohol mixed liquor, the mass percentage concentration of hydrochloric acid used itself is 37.5%) clean, absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12h, obtain the Fu Ke of the additional crosslink agent silica/polymer composite after crosslinked;
(5) remove silica in silica/polystyrene complex
By silica/polystyrene composite colloid crystalline substance be immersed in mass fraction be in 40% hydrofluoric acid to remove silica template, frequency is 40Hz ultrasonic cleaning 5h, is washed till neutrality with distilled water, is drying to obtain Polymers hierarchical porous structure interlocking micro-capsule.
Accompanying drawing 3 is to be the electromicroscopic photograph of Polymers grading-hole interlocking micro-capsule after the removal silica colloidal crystal template of FEI Nano SEM450 electron scanning electron-microscope scanning by model, found out by photo, be interconnected and present interlocking structure through the crosslinked micro-capsule of additional crosslink agent Fu Ke.
Accompanying drawing 4 is photos in kind of Polymers hierarchical porous structure interlocking micro-capsule after removal silica, and because interlocking structure is assembled each single micro-capsule to be interconnected together, difficult drop-off or loss, can see that such micro-capsule is 1-10mm solid granulates in macroscopic view.
Example one resulting materials records surface area with the full-automatic specific surface area analysis instrument of model Micromeritics ASAP2020M+C can reach 600m
2g
-1.
Illustrate: in step in the present invention (2), the preparation method of silane coupler [3-(2-bromo isobutyryl) aminopropyl]-triethoxysilane is as follows: (other embodiment are same)
In there-necked flask, add 40.0mL toluene, 16.0mL (3-aminopropyl) triethoxysilane (APTS), 9.40mL triethylamine (TEA), being placed in ice bath stirs, 8.40mL2-bromine isobutyl acylbromide is dissolved in to 40mL toluene, mixed liquor is added drop-wise in there-necked flask, 1h drips off, in ice bath, stir 3h, then under room temperature, stir 10h, obtain solidliquid mixture, mixture is filtered, filtrate is removed wherein unreacted TEA and solvent toluene by the method for decompression distillation, can obtain surface modifier BITS, synthetic this silane coupler can directly be used for silica surface to carry out modification, and then introducing SI-ATRP initator,
Embodiment bis-:
(1) preparation of 600nm silica colloidal crystal template is with embodiment mono-step (1);
(2) surface modification of silica colloidal crystal template
Gamma-methyl allyl acyloxypropyl trimethoxysilane (MPS) improved silica colloid crystal template, by the silica colloidal crystal template after sintering dried 0.3g, put into 250mL there-necked flask, add ethanol 100ml, distilled water 2.5mL, ammoniacal liquor 0.25mL, 25 DEG C of mechanical agitation, add condensing reflux reaction 24h under gamma-methyl allyl acyloxypropyl trimethoxysilane (MPS) 1.5mL room temperature.Reaction stops after finishing stirring, and discards liquid, cleans displacement three times with absolute ethyl alcohol, and last 25 DEG C of vacuum drying 12h obtain average grain diameter and be the silica colloidal crystal template after the MPS modification of 600nm;
(3) the controlled graft polymers segment of silica colloidal crystal template
In reactor, add the silica colloidal crystal template 0.03g of MPS modification, add subsequently 0.1g distilled water, 0.2g polyvinylpyrrolidone (PVP) stirring at room temperature 12h.Under argon shield, be warming up to 60 DEG C, in 0.5h, drip the mixed solution being formed by 0.02g potassium peroxydisulfate and 1mL distilled water, drip subsequently by 0.01g dodecyl sodium sulfate (SDS), 0.01mL distilled water, the emulsion of 0.015g potassium hydroxide and 2mL styrene (1.812g) composition, again be warming up to the equivalent potassium persulfate solution of adding same ratio after 70 DEG C, after 0.5h dropwises, keep thermotonus 5h, reaction finishes to clean with absolute ethyl alcohol afterwards, use again absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12h, obtain the silica colloidal crystal template of graft polymers, obtain silica/polystyrene complex.
Fig. 5 model is that FEI Nano SEM450 electron scanning electron-microscope scanning silica/polystyrene complex obtains, between the ball of the silica/polystyrene complex after grafting and ball, present as seen from the figure orderly connected structure, single microsphere surface can be seen the not formation polymer part of ordered arrangement, and this is for micro-capsule interlocking is afterwards connected, formation is communicated with window and provides the foundation.
(4) crosslinked pore implementation Process example one step (4) of the Fu Ke of polymer segment;
(5) remove in silica/polystyrene complex silica with embodiment mono-step (5);
Accompanying drawing 6 is to be the electromicroscopic photograph of Polymers grading-hole interlocking micro-capsule after the removal silica colloidal crystal template of FEI Nano SEM450 electron scanning electron-microscope scanning by model, found out by photo, be interconnected and present interlocking structure through the crosslinked micro-capsule of additional crosslink agent Fu Ke.
Embodiment tri-:
(1) preparation of 600nm silica colloidal crystal template is with embodiment mono-step (1);
(2) surface modification of silica colloidal crystal template is with embodiment mono-step (2);
(3) the controlled graft polymers segment of silica colloidal crystal template
The silica colloidal crystal template 0.1423g taking after BITS modification obtained above is placed in two-mouth bottle, and 100 DEG C vacuumize 2h.Under argon shield, 0.0509g CuCl (0.514mmol), 5.6mL DMF (0.072mol), 10.73 μ LPMDETA (0.514mmol), 2.8mL styrene (0.0244mol) are stirred.Mixed liquor is injected in silica colloidal crystal template, 100 DEG C of reaction 12h, reaction finishes rear with DMF cleaning extracting 12h, absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12h, obtain the silica colloidal crystal template of graft polymers, obtain silica/polystyrene complex;
(4) the crosslinked pore process of the Fu Ke of polymer segment;
Subsequently dried 0.0886g silica/polystyrene complex thing is put into reactor, add 5mL nitrobenzene and 0.1660g Cyanuric Chloride to mix swelling spending the night, swelling completely after, anhydrous 0.1330g FeCl3 and the anhydrous nitrobenzene of 15mL are mixed, under argon shield, mixed solution is injected to silica/polystyrene complex, stirring at normal temperature 2h, after being slowly warming up to 100 DEG C, react 5h, reaction finishes rear with absolute ethyl alcohol, (wherein to account for mixed liquor mass fraction be 1% to hydrochloric acid to acidic alcohol mixed liquor, the mass percentage concentration of hydrochloric acid used itself is 37.5%) clean, absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12h, obtain the Fu Ke of the additional crosslink agent silica/polymer composite after crosslinked,
(5) remove in silica/polystyrene complex silica with embodiment mono-step (5);
Embodiment tetra-:
(1) preparation of 600nm silica colloidal crystal template is with embodiment mono-step (1);
(2) surface modification embodiment bis-steps (2) of silica colloidal crystal template
(3) the controlled graft polymers segment of silica colloidal crystal template
In reactor, add the silica colloidal crystal template 0.03g of MPS modification, add subsequently 0.1g distilled water, 0.2g polyvinylpyrrolidone (PVP) stirring at room temperature 12h.Under argon shield, be warming up to 60 DEG C, in 0.5h, drip the mixed solution being formed by 0.02g potassium peroxydisulfate and 1mL distilled water, drip subsequently by 0.01g dodecyl sodium sulfate (SDS), 0.01mL distilled water, the emulsion of 0.015g potassium hydroxide and 2mL styrene (1.812g) composition, again be warming up to the equivalent potassium persulfate solution of adding same ratio after 70 DEG C, after 0.5h dropwises, keep thermotonus 2h, reaction finishes to clean with absolute ethyl alcohol afterwards, use again absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12h, obtain the silica colloidal crystal template of graft polymers.
(4) crosslinked pore implementation Process example one step (4) of the Fu Ke of polymer segment;
(5) remove in silica/polystyrene complex silica with embodiment mono-step (5);
Embodiment five:
(1) preparation of 600nm silica colloidal crystal template is with embodiment mono-step (1);
(2) surface modification of silica colloidal crystal template is with embodiment mono-step (2);
(3) the controlled graft polymers segment of silica colloidal crystal template is with embodiment mono-step (3);
(4) the crosslinked pore process of the Fu Ke of polymer segment
Subsequently dried 0.0639g silica/polystyrene complex is put into reactor, add 5mL1, 2 dichloroethanes and 0.0499g4, 4,-dimethyl diphenyl mixes swelling, swelling completely after, anhydrous 0.0096g FeCl3 and the anhydrous dichloroethanes of 10mL are mixed, under argon shield, mixed solution is injected to silica/polystyrene complex, stirring at normal temperature 2h, after being slowly warming up to 80 DEG C, react 5h, reaction finishes rear with absolute ethyl alcohol, (wherein to account for mixed liquor mass fraction be 1% to hydrochloric acid to acidic alcohol mixed liquor, the mass percentage concentration of hydrochloric acid used itself is 37.5%) clean, absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12h, obtain the Fu Ke of the additional crosslink agent silica/polymer composite after crosslinked,
(5) remove in silica/polystyrene complex silica with embodiment mono-step (5).
Embodiment six:
(1) preparation of 600nm silica colloidal crystal template is with embodiment mono-step (1);
(2) surface modification of silica colloidal crystal template is with embodiment bis-steps (2);
(3) the controlled graft polymers segment of silica colloidal crystal template is with embodiment bis-steps (3);
(4) the crosslinked pore process of the Fu Ke of polymer segment
Subsequently dried 0.05g silica/polystyrene complex is put into reactor, adds 5mL1,2 dichloroethanes and 0.0385g4,4 ,-dimethyl diphenyl mixes swelling, swelling completely after, by anhydrous 0.0078g FeCl
3mix with the anhydrous dichloroethanes of 10mL; under argon shield, mixed solution is injected to silica/polystyrene complex; stirring at normal temperature 2h; after being slowly warming up to 80 DEG C, react 5h; reaction finishes that rear (wherein to account for mixed liquor mass fraction be 1% to hydrochloric acid with absolute ethyl alcohol, acidic alcohol mixed liquor; the mass percentage concentration of hydrochloric acid used itself is 37.5%) clean; absolute ethyl alcohol extracting 12h; 60 DEG C of vacuum drying 12h, obtain the Fu Ke of the additional crosslink agent silica/polymer composite after crosslinked.
(5) remove in silica/polystyrene complex silica with embodiment mono-step (5)
Embodiment seven:
(1) preparation of 800nm silica colloidal crystal template;
Under room temperature, in churned mechanically 500mL there-necked flask, add successively to being furnished with ammoniacal liquor, the 16.1g distilled water that 167.5g absolute ethyl alcohol, 8.5g mass fraction are 25%, after stirring, in there-necked flask, add rapidly 15.3g ethyl orthosilicate again, then at interval of 8h, add ammoniacal liquor, absolute ethyl alcohol, distilled water and the ethyl orthosilicate of the equivalent of equal in quality proportioning, add three times.The suspension of gained is transferred in beaker, treat that solvent volatilizees completely naturally, obtaining average grain diameter is the silica colloidal crystal template of 800nm, template sintering 3h at 500 DEG C in Muffle furnace the most at last, slowly be down to room temperature, obtaining average grain diameter is the inter-adhesive silica colloidal crystal template of silicon dioxide microsphere of 800nm;
(2) surface modification of silica colloidal crystal template is with embodiment mono-step (3);
(3) the controlled graft polymers segment of silica colloidal crystal template
The silica colloidal crystal template 0.1772g taking after BITS modification obtained above is placed in two-mouth bottle, and 100 DEG C vacuumize 2h.Under argon shield, 0.0633g CuCl (0.639mmol), 7.0mL DMF (0.091mol), 13.34 μ LPMDETA (0.639mmol), 3.5mL styrene (0.0304mol) are stirred.Mixed liquor is injected in silica colloidal crystal template, 100 DEG C of reaction 18h, reaction finishes rear with DMF cleaning, absolute ethyl alcohol extracting 12h, and 60 DEG C of vacuum drying 12h, obtain silica/polystyrene complex.
(4) crosslinked pore implementation Process example one step (4) of the Fu Ke of polymer segment;
(5) remove in silica/polystyrene complex silica with embodiment mono-step (5);
Embodiment eight:
(1) preparation of 800nm silica colloidal crystal template is with embodiment seven steps (1);
(2) surface modification of silica colloidal crystal template is with embodiment bis-steps (2);
(3) the controlled graft polymers segment of silica colloidal crystal template
In reactor, add the silica colloidal crystal template 0.05g of MPS modification, add subsequently 0.17g distilled water, 0.33g polyvinylpyrrolidone (PVP) stirring at room temperature 12h.Under argon shield, be warming up to 60 DEG C, in 0.5h, drip the mixed solution being formed by 0.04g potassium peroxydisulfate and 2mL distilled water, drip subsequently by 0.017g dodecyl sodium sulfate (SDS), 0.017mL distilled water, the emulsion of 0.0255g potassium hydroxide and 3.4mL styrene (3.084g) composition, again be warming up to the equivalent potassium persulfate solution of adding same ratio after 70 DEG C, after 0.5h dropwises, keep thermotonus 5h, reaction finishes to clean with absolute ethyl alcohol afterwards, use again absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12h, obtain the silica colloidal crystal template of graft polymers.
(4) crosslinked pore implementation Process example one step (4) of the Fu Ke of polymer segment;
(5) remove in silica/polystyrene complex silica with embodiment mono-step (5);
Unaccomplished matter of the present invention is known technology.
Claims (5)
1. a preparation method for Polymers hierarchical porous structure interlocking micro-capsule, is characterized by the method and comprises the following steps:
(1) preparation of silica colloidal crystal template
According to the difference of particle size range, take one of following methods:
Method one: average particle size range is in the preparation of the silica colloidal crystal template of 80nm-600nm
Utilize
synthetic method, in room temperature downhill reaction device, add successively absolute ethyl alcohol, ammoniacal liquor, distilled water, stir, add rapidly ethyl orthosilicate, after reaction 8h, gained suspension is transferred in beaker, treat that solvent volatilizees completely naturally, obtain the silica colloidal crystal template of average grain diameter within the scope of 80nm-600nm, the most at last template in Muffle furnace at 200-800 DEG C sintering 2-8h, slowly be down to room temperature, obtain the silica colloidal crystal template that average particle size range bonds mutually at the silicon dioxide microsphere of 80nm-600nm;
Wherein material proportion is that mass ratio is ammoniacal liquor: absolute ethyl alcohol: distilled water: ethyl orthosilicate=1:0.5-60:1-5:0.2-10;
Or method two: average particle size range is in the preparation of the silica colloidal crystal template of 600nm-1200nm
In the reaction system of the silica colloidal crystal template in preparation average grain diameter within the scope of 80nm-600nm, after ethyl orthosilicate reaction 8h to be added, add the ammoniacal liquor of the equivalent of identical proportioning, absolute ethyl alcohol, distilled water and ethyl orthosilicate, reaction 8h, repeat to add, reaction 8h process 1-4 time, suspension is transferred in beaker, treat that solvent volatilizees completely naturally, obtain the silica colloidal crystal template of average particle size range at 600nm-1200nm, the most at last template in Muffle furnace at 200-800 DEG C sintering 2-8h, slowly be down to room temperature, obtain average particle size range in the inter-adhesive silica colloidal crystal template of the silicon dioxide microsphere of 600nm-1200nm,
(2) surface modification of silica colloidal crystal template is one of following two kinds of methods:
Method one: silane coupler [3-(2-bromo isobutyryl) amine propyl group]-triethoxysilane (BITS) improved silica colloid
Crystal template
Silica colloidal crystal template after the sintering obtaining in dry step (1) is placed in reactor, add absolute ethyl alcohol, ammoniacal liquor, distilled water, 60 DEG C of mechanical agitation, add 60 DEG C of condensing reflux reaction 24-48h of [3-(2-bromo isobutyryl) aminopropyl]-triethoxysilane (BITS).Reaction stops after finishing stirring, and discards liquid, cleans displacement with absolute ethyl alcohol, and final 50 DEG C of vacuum drying 12-24h obtain the silica colloidal crystal template of BITS modification;
Wherein material proportion is that volume ratio is absolute ethyl alcohol: distilled water: ammoniacal liquor=20-200:0.1-2:0.1-1.5; In every 20-200mL ethanol, be dissolved with 0.1-1g BITS, and add the silica colloidal crystal template of 0.4g;
Or, method two: gamma-methyl allyl acyloxypropyl trimethoxysilane (MPS) improved silica colloid crystal template
In the silica colloidal crystal template after the sintering obtaining in the step (1) of reactor inner drying, add successively absolute ethyl alcohol, distilled water and ammoniacal liquor, stirring at room temperature, add condensing reflux reaction 24-48h under gamma-methyl allyl acyloxypropyl trimethoxysilane (MPS) room temperature condition, after finishing, reaction stops stirring, discard liquid, clean displacement with absolute ethyl alcohol, last 25 DEG C of vacuum drying 12-24h, obtain the silica colloidal crystal template of MPS modification;
Wherein material proportion is that volume ratio is absolute ethyl alcohol: distilled water: ammoniacal liquor=10-200:0.1-2:0.1-5; In every 20-200mL absolute ethyl alcohol, be dissolved with 0.1-10mL MPS, and add the silica colloidal crystal template of 0.6g;
(3) the controlled graft polymers segment of silica colloidal crystal template is one of following two kinds of methods:
Method one: the controlled graft polymers segment of silica colloidal crystal template surface Atom Transfer Radical Polymerization
In reactor, add the silica colloidal crystal template of the BITS modification that in step (2), method one obtains, 100 DEG C vacuumize 2h, under inert gas shielding, catalyst, solvent, part and grafted monomers are mixed, inject at 100 DEG C of the silica colloidal crystal templates of BITS modification and react 5-48h, reaction finishes rear with reaction solvent clean extracting 12h used, use again absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12-24h, obtain the silica colloidal crystal template of graft polymers, i.e. silica/polymer composite;
Material proportion is silica colloidal crystal template: catalyst=1:0.3-3 after mass ratio BITS modification, mol ratio grafted monomers, catalyst, part=10-100:1:1; Volume ratio monomer: solvent=1:0.2-3;
Catalyst in described step (3) is cuprous bromide (CuBr), stannous chloride (CuCl), stannous chloride (CuCl)/copper bromide (CuBr
2) or cuprous bromide (CuBr)/copper bromide (CuBr
2);
Inert gas in described step (3) is nitrogen or argon gas;
Part in described step (3) is N, N ', N ', N ", N " pentamethyl-diethylenetriamine (PMDETA) or three-(N, N-dimethylaminoethyl) amine (Me
6tREN);
Grafted monomers in described step (3) is styrene or substituted phenylethylene;
Solvent in described step (3) is DMF (DMF), cyclohexanone or methyl alcohol;
Or, method two: the two key radical polymerization graft polymers segments of silica colloidal crystal template surface
The silica colloidal crystal template that adds the MPS modification that in step (2), method two obtains in reactor, adds distilled water, polyvinylpyrrolidone (PVP), stirring at room temperature 12-24h subsequently; Under argon shield, be warming up to 60 DEG C, in 0.5h, drip potassium persulfate solution, drip subsequently the emulsion by dodecyl sodium sulfate (SDS), distilled water, potassium hydroxide and monomer composition, again be warming up to the potassium persulfate solution of adding same ratio equivalent after 70 DEG C, after 0.5h dropwises, keep thermotonus 2-12h, reaction finishes to clean with absolute ethyl alcohol afterwards, use again absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12-24h, obtain the silica colloidal crystal template of graft polymers, i.e. silica/polymer composite;
The material proportion adding in method two in described step (3) is the silica colloidal crystal template of mass ratio MPS modification: polyvinylpyrrolidone: distilled water: potassium peroxydisulfate: monomer=0.03:0.1-0.5:0.01-0.3:0.01-0.05:0.5-5 in emulsion; (distilled water in proportioning is the distilled water while adding polyvinylpyrrolidone, and the amount of potassium peroxydisulfate is the amount of potassium peroxydisulfate in the potassium persulfate solution dripping for the first time);
In described step (3), in method two, potassium persulfate solution consists of: 0.02g potassium peroxydisulfate is dissolved in 1-5mL distilled water;
In described step (3), in method two, the composition and ratio of emulsion is that quality is than dodecyl sodium sulfate: potassium hydroxide=0.01:0.01-0.05, volume ratio monomer: distilled water=2:0.01-0.05, every 0.01g dodecyl sodium sulfate is dissolved in 1-5mL monomer;
Grafted monomers in described step (3) is styrene or substituted phenylethylene;
(4) the crosslinked pore process of the Fu Ke of polymer segment
Dried silica/polymer composite is put into reactor, add solvent and additional crosslink agent swelling, until swelling completely after, under argon shield, the mixed liquor of catalysts and solvents composition is injected to silica/polymer composite, 60-120 DEG C of reaction 2-24h, reaction finishes rear with absolute ethyl alcohol, the cleaning of acidic alcohol mixed liquor, absolute ethyl alcohol extracting 12h, 60 DEG C of vacuum drying 12-24h, obtain the Fu Ke of the additional crosslink agent silica/polymer composite after crosslinked;
Described step (4) method two material proportion is quality than silica/polymer composite: catalyst: additional crosslink agent=0.1:0.01-0.3:0.01-0.5g, wherein 0.1g silica/polymer composite adopts 1-30mL solvent swell, and 0.01g catalyst is dissolved in 1-30mL solvent;
Additional crosslinking agent in described step (4) method two is Cyanuric Chloride, 4,4 ,-dimethyl diphenyl or to xylylene dichlorides;
Catalyst in described step (4) method two is anhydrous ferric trichloride (FeCl
3), aluminum trichloride (anhydrous) (AlCl
3), anhydrous stannic chloride (SnCl
4) or anhydrous zinc dichloride (ZnCl
2);
Solvent in described step (4) method two is anhydrous 1,2-dichloroethanes, anhydrous nitrobenzene, anhydrous nitromethane or carbon tetrachloride;
(5) remove silica in silica/polymer composite
It is that in 40% hydrofluoric acid, silica colloidal crystal template is removed in ultrasonic cleaning that silica/polymer composite after the Fu Ke of the additional crosslink agent that step (4) is obtained is crosslinked is immersed in mass fraction, is washed to dryly after neutral to obtain a kind of Polymers hierarchical porous structure interlocking micro-capsule.
2. the preparation method of Polymers hierarchical porous structure as claimed in claim 1 interlocking micro-capsule, the additional crosslinking agent it is characterized by step (4) method two described in the method is Cyanuric Chloride, 4,4 ,-dimethyl diphenyl or to xylylene dichlorides.
3. the preparation method of Polymers hierarchical porous structure interlocking micro-capsule as claimed in claim 1, the catalyst it is characterized by described step (4) method two is anhydrous ferric trichloride (FeCl
3), aluminum trichloride (anhydrous) (AlCl
3), anhydrous stannic chloride (SnCl
4) or anhydrous zinc dichloride (ZnCl
2).
4. the preparation method of Polymers hierarchical porous structure as claimed in claim 1 interlocking micro-capsule, it is characterized by solvent in described step (4) method two and be anhydrous 1,2-dichloroethanes, anhydrous nitrobenzene, anhydrous nitromethane or carbon tetrachloride.
5. the preparation method of Polymers hierarchical porous structure interlocking micro-capsule as claimed in claim 1, the preparation method who it is characterized by silane coupler [3-(2-bromo isobutyryl) the aminopropyl]-triethoxysilane in described step (2), comprises the following steps:
In reactor, add toluene, (3-aminopropyl) triethoxysilane (APTS), triethylamine (TEA), being placed in ice-water bath stirs, drip the mixed liquor of toluene and 2-bromine isobutyl acylbromide to reaction system, in 1h, dropwise, ice-water bath continues to stir 3h, then under room temperature, stir 10h and obtain solidliquid mixture, mixture is filtered, filtrate is removed unreacted triethylamine and solvent toluene by the method for decompression distillation, can obtain [3-(2-bromo isobutyryl) aminopropyl]-triethoxysilane that modification is used;
Wherein material proportion is volume ratio toluene: (3-aminopropyl) triethoxysilane (APTS): triethylamine (TEA): 2-bromine isobutyryl toluene bromide solution=20-40:8-16:4.73-9.46:20-40, and in proportioning, the amount of toluene does not comprise toluene in 2-bromine isobutyryl toluene bromide mixed solution;
In 2-bromine isobutyryl toluene bromide mixed solution, every 20-60mL toluene that consists of of its mixed liquor of toluene adds 4.21-8.42mL2-bromine isobutyl acylbromide.
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