CN102120855B - pH-responsive three-dimensional ordered macroporous controlled-release material - Google Patents
pH-responsive three-dimensional ordered macroporous controlled-release material Download PDFInfo
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- CN102120855B CN102120855B CN2010105990207A CN201010599020A CN102120855B CN 102120855 B CN102120855 B CN 102120855B CN 2010105990207 A CN2010105990207 A CN 2010105990207A CN 201010599020 A CN201010599020 A CN 201010599020A CN 102120855 B CN102120855 B CN 102120855B
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Abstract
The invention relates to a pH-responsive three-dimensional ordered macroporous controlled-release material. The sizes of macropores and communicating windows of the pH-responsive three-dimensional ordered macroporous controlled-release material are uniform, the sizes of the macropores are 100-1000nm, the sizes of the communicating windows are 40-120nm, and the pore volume is 1.3-2.8 cm<3>/g; the substrate is monodisperse three-dimensional ordered macroporous crosslinked polystyrene with windows which are mutually communicated, and a pH-responsive polymer chain section is introduced into the substrate by an atom transfer free-radical activity-controllable graft polymerization method; and the uncurling-curling action of the pH-responsive polymer chain section under different pH values is utilized to control the opening and closing of the communicating windows among the macropores: as the pH value increases, macromolecule chains gradually uncurl, and the pore windows are gradually closed, thereby realizing the controllable release of the contained filler. The pH-responsive three-dimensional ordered macroporous controlled-release material has wide application values in the controlled-release fields of biomedicine, medicine controlled-release systems, organized enzymes, slow release-embedding of catalysts, and the like.
Description
Technical field
Scheme of the present invention relates to macromolecular material, specifically relates to the three-dimensional ordered macroporous sustained release material of a kind of pH value response.
Technical background
Controlled release is meant that the active ingredient in the system can be discharged in the surrounding environment by predefined speed and goes; Thereby in certain period; In specific zone; The concentration of active ingredient can remain on (Reineccius G A.Carbonhydrates for Flavor Encapulation.Food Technology, 1991,45 (3): 144-149) in certain scope of setting in advance.Obtain the ideal release behavior, require to have suitable physical and chemical performance, can produce certain response, have biocompatibility etc. environment as the material of carrier.At present; Utilize carrier or the medium of organic high molecular polymer as active ingredient, processing sustained release dosage is a research focus in the polymer science field, realizes the controlled release of active ingredient; Extensive studies and application (Yang Q have been obtained in fields such as medicine, agricultural chemicals, biotechnology; Wang S C, Fan P W, et al.pH-Responsive Carrier System Based on Carboxylic Acid Modified Mesoporous Silica and Polyelectrolyte for Drug Delivery.Chem.Mater.; 2005,17:5999-6003).
(Yoshio O such as Yoshio; Hiroshi N; Takahiro S.Functional Capsule Membranes Permeability Control of Polymer-Grafted Capsule Membranes Responding to Ambient pH Changes.Macromolecules; 1987; 20:15-21) prepared the porous capsule (is the wall film with nylon) that surface grafting has pH value response polymer segment, in the porous capsule film, wrap water miscible naphthalene molecule, controlled the external rate of diffusion of filling core in the capsule through the graftomer conformational change that molecular chain is curled, stretched under different pH value environment through the method for dialysis.People such as Ma (Ma R J; Wang B L; Liu X J.Pyranine-Induced Micellization of Poly (ethyleneglycol)-block-poly (4-vinylpyridine) and pH-Triggered Release of Pyranine from the Complex Micelles.Langmuir 2007; 23:7498-7504) synthesized controlled and double-hydrophilic block copolymer polyoxyethylene glycol-b-narrow distribution of molecular weight and gathered (4-vinylpridine) (PEG-b-P4VP) through (ATRP) method; Utilize fluorescent yellow to induce PEG-b-P4VP self-assembly in the aqueous solution of pH2, having obtained with the P4VP/Pyranine mixture is that nuclear, PEG chain are single composite micelle that disperses of shell.Studied the influence of preparation method through scattering of light (LS), proton nmr spectra (1H NMR) and transmission electron microscope means such as (TEM), and adopted ultraviolet spectrophotometer (UV) that composite micelle release behavior to fluorescent yellow under different pH value conditions is characterized the micellar morphological structure.People such as Qu (Qu F Y; Lin H M, Wu X, et al.Bio-templated synthesis of highly ordered macro-mesoporous silica material for sustained drug delivery.Solid State Sciences; 2010; 12:851-856) (Qu Fengyu, Cui Lingfei, Huang Shiying. the mesopore molecular sieve pore passage structure is to the influence of medicine captopril release performance. SCI; 2007; 28:1440-1442) use polyamines silane that mesopore molecular sieve is modified, introduce the new avtive spot of the conduct of silicon hydroxyl and organic guest molecule reaction therein, be dispersed in the duct of mesoporous molecule thereby the model drug ibuprofen is combined on the avtive spot silicon hydroxyl.This assembly is placed manual simulation's intestinal juice, its release is monitored by ultraviolet spectrophotometer.Under the simulated intestinal fluid alkaline condition, to compare with the hydrogen bond action between the silicon hydroxyl in drug molecule and the mesopore molecular sieve, the hydrogen bond action between dissolution medium and drug molecule is stronger, thereby makes drug molecule be able to slow release.(Park Y S such as Park; Ito Y; Imanishi Y.pH-Controlled Gating of a Porous Glass Filter by Surface Grafting of Polyelectrolyte Brushes.Chemical Materail, 1997,9:2755-2758.) grafted polyacrylic acid molecular brush on the thin slice of porous silane; Through regulating curling and stretching, extension of pH value control ROHM molecular chain, realized adjusting control to the thin slice permeability rate.
Three-dimensional ordered macroporous material (3DOM material; Three-dimensionally Ordered Macroporous Materials) pore structure is at the three-dimensional space ordered arrangement; Each ball hole and 12 holes on every side are interconnected through the hole window; Have uniform macropore duct and aperture more than 50nm (maximum can reach several microns); Have higher pore volume, can be used for macromolecular catalysis, filtration and separate, remedied small structure molecular sieve and mesoporous material and be difficult to let macromole get into the shortcoming of cavity.Through the discovery and the enforcement of controlled/living polymerisation process, make the synthetic various multipolymers novel, that have stimulating responsive of design become one of focus of Polymer Synthesizing area research.Method through ATRP reaction back functionalization is at 3DOM material surface grafting functional property polymer segment; " graft-from " method (Balachandra A M; Baker GL, Bruening M L.Journal of Membrane Science, 2003; 227:1) in the preparation polymer process; Monomer small molecules in the solution is being fixed on initiated polymerization under the action of evocating of material surface, and the grafting layer that adopts this grafting method to obtain has higher grafting density, and the advantage of the easy control of grafted chain length.
Yet; Thereby also be not utilized in the research report that the preparation of ordered big hole material hole wall grafting responsive polymer segment has responsiveness sustained release material at present in the document; Therefore; The present invention provides a kind of novel pH of having value response sustained release material through combining the advantage of three-dimensional ordered macroporous polymer materials.
Summary of the invention
Technical problem to be solved by this invention is: the mesoporous material pore volume responsive to current pH is lower; The deficiency of the burst effect that the responsive capsule existence of pH is difficult for overcoming etc.; The present invention provide a kind of brand-new pH value to respond the sustained release material based on three-dimensional ordered macroporous material, have the characteristics of pore capacities height, slowly-releasing.
The present invention solves this technical problem the technical scheme that is adopted:
The three-dimensional ordered macroporous sustained release material of a kind of pH value response, the macropore of this material and connection window aperture homogeneous, macropore diameter is 100～1000nm, and the connection window size is 40～120nm, and pore volume is 1.3～2.8cm
3/ g; Its matrix is the monodisperse three dimensional ordered macroporous cross-linked polystyrene with the window that is interconnected; On matrix, introduce polymer segment with pH value response through active " controlled " graft polymerization procedure of atom transferred free radical; The polymer segment that utilizes the pH value response is communicated with the on-off control of window between the stretching, extension under the different pH values-curling action is realized macropore: during as pH=2, molecular chain is taked the conformation of curling, and the hole window is opened; Along with the increase of pH value, macromolecular chain extends gradually, and the hole window is closed gradually; When pH=6 or pH=12, the macromolecular chain full extension comes, and hole window and macropore wall thickness increase 20～60nm; The hole window is closed fully, and then reaches filling the effect of the controlled release that contains material.
The three-dimensional ordered macroporous sustained release preparation methods of described pH value response may further comprise the steps:
(1). the preparation of colloid crystal template
Under the room temperature, in there-necked flask, add mass percent concentration successively and be 25% ammoniacal liquor, absolute ethyl alcohol, zero(ppm) water and tetraethoxy; Mass ratio is that percentage concentration is 25% ammoniacal liquor: absolute ethyl alcohol: zero(ppm) water: tetraethoxy=11: 70: 6.2: 3; Be stirred to mixed solution and be homogeneous, stablize the shape suspension liquid, add ammoniacal liquor, absolute ethyl alcohol, zero(ppm) water and the tetraethoxy of the equivalent of equal in quality proportioning, repeat 1～4 time; The gained suspension liquid is poured in the beaker; The static solvent that makes volatilizees fully naturally under the room temperature, then prepared silicon dioxide colloid crystal template is placed Gan Guozhong, in muffle furnace in 400 ℃ of following sintering after 5 hours; Slowly be cooled to room temperature, promptly obtaining median size is the inter-adhesive colloid crystal template of silicon dioxide microsphere of 130～1300nm;
(2). the preparation of three-dimensional ordered macroporous crosslinked polystyrene material:
Under the anhydrous and oxygen-free condition; In two-mouth bottle, add the prepared silicon dioxide colloid crystal template of step (1), adding styrene monomer, divinyl benzene crosslinked agent, initiator make it the submergence template under argon shield, and volume ratio is a Vinylstyrene: vinylbenzene=1: 1～8; Initiator is 0.1～15% of vinylbenzene and a Vinylstyrene quality sum; After stirring, soaked 0.5～2 hour 80 ℃ of following polymerizations 20～32 hours; The PS on lift-off stencil surface promptly obtains three-dimensional ordered macroporous crosslinked polystyrene/silica composite; It is 40% hydrofluoric acid that mixture is placed mass percent concentration; Behind the ultra-sonic dispersion 10～60 minutes; Soaked 6～15 hours; Then repeated water washing is to neutral, 80 ℃ of following vacuum-drying 20～28 hours, and promptly obtaining pore diameter range is the three-dimensional ordered macroporous crosslinked polystyrene material (3DOM CLPS) of 100～1000nm.
(3). have the grafting of pH value response polymer segment:
Chlorine atom initiator is anchored on three-dimensional ordered macroporous crosslinked polystyrene material hole wall surface: under the anhydrous and oxygen-free condition, be zinc chloride with the quality proportioning: the mixed solution of chloromethyl ether=1: 20～60 joins in the reactor drum that three-dimensional ordered macroporous crosslinked polystyrene material is housed under the negative pressure state; To the submergence material; Stirring reaction is after 22～30 hours under 35 ℃ of conditions; Carry out extracting 6～15 hours with absolute ethyl alcohol, obtain the three-dimensional ordered macroporous crosslinked polystyrene material (chloromethylation 3DOM CLPS) of chloromethylation after the oven dry;
The chloromethylation 3DOM CLPS hole wall grafting that makes in the above then has pH value response polymer segment, adopts one of following two kinds of methods:
Method 1; Adopt the three-dimensional ordered macroporous crosslinked polystyrene material hole wall grafting pH value response polymer chain of ATRP (ATRP) method: under the anhydrous and oxygen-free condition at the chloromethylation of preparation; In two-mouth bottle, add cuprous chloride, function monomer, pimelinketone and pentamethyl-diethylenetriamine successively; After being stirred to abundant dissolving; Mixed solution is extracted out, injected the two-mouth bottle of the three-dimensional ordered macroporous crosslinked polystyrene material that fills chloromethylation under the negative pressure state rapidly, its quality proportioning is chloromethylation 3DOM CLPS: cuprous chloride: function monomer: pimelinketone: pentamethyl-diethylenetriamine=1: 1～6: 20～60: 1～5: 1～5; Reacted 16～32 hours down at 65～90 ℃; To get product and after 28～32 hours,, make the three-dimensional ordered macroporous crosslinked polystyrene material of hole wall surface grafting functional polymer chain again 60 ℃ of following vacuum-dryings 20～28 hours with the THF extracting;
The three-dimensional ordered macroporous crosslinked polystyrene material of the hole wall surface grafting functional polymer chain that makes put into vacuumize after two-mouth bottle adds magneton; Under negative pressure state, inject 1; 4-dioxane to submergence material; Soaked 1～5 hour, normal pressure adds concentrated hydrochloric acid, oil bath reflux 6～10 hours down then.Hydrolysis finishes 80 ℃ of following vacuum-dryings of after product 20～28 hours, finally makes the hole wall surface grafting and has the three-dimensional ordered macroporous crosslinked polystyrene material of pH value response ROHM segmental (3DOM CLPS-g-PAA or 3DOM CLPS-g-PMAA);
Or method 2; Adopt the three-dimensional ordered macroporous crosslinked polystyrene material hole wall grafting pH value response polymer chain of ATRP (ATRP) method: under the anhydrous and oxygen-free condition at the chloromethylation of preparation; In two-mouth bottle, add cuprous chloride, function monomer, pimelinketone and pentamethyl-diethylenetriamine successively; After being stirred to abundant dissolving; Mixed solution is extracted out; Inject the two-mouth bottle that fills the three-dimensional ordered macroporous crosslinked polystyrene material of chloromethylation under the vacuum state rapidly, wherein the quality proportioning is chloromethylation 3DOM CLPS: cuprous chloride: function monomer: pimelinketone: pentamethyl-diethylenetriamine=1: 1～6: 20～60: 1～5: 1～5, function monomer are 4-vinylpridine; Reacted 16～32 hours down at 65～90 ℃; To get product and after 28～32 hours,, finally make the three-dimensional ordered macroporous crosslinked polystyrene material (3DOM CLPS-g-P4VP) of hole wall surface grafting pH value response polymer chain again 60 ℃ of following vacuum-dryings 20～28 hours with the THF extracting.
Initiator in the described step (2) is the special butyl ester of Diisopropyl azodicarboxylate, ABVN, BPO, dilauroyl peroxide, di-isopropyl peroxydicarbonate or peroxo-phenylformic acid.
Function monomer is tert-butyl acrylate or n-BMA in the method 1 in the described step (3);
The invention has the beneficial effects as follows: a kind of new pH value response controlled release material proposed by the invention is based on being communicated with the on-off control of window between the three-dimensional ordered macroporous crosslinked polystyrene macropore; Therefore they characteristics that possess ordered big hole material itself apply it to the controlled release field; For example pore volume is big, can reach 1.3～2.8cm
3/ g can store more releasable material; Secondly, utilize three-dimensional ordered macroporous polymkeric substance can introduce more atom transferred free radical graft polymerization initiator activity point at its hole wall, can obtain higher grafting density like this, better content is carried out controlled release as matrix; In addition, because ordered big hole itself has the macropore and connection window of size homogeneous, in conjunction with active " controlled " graft polymerization procedure of atom transferred free radical, on the one hand, may command grafting segmental length, the size of trip switch; On the other hand; Make the polymer segment with switching effect of introducing reach on-off control to being close to all connection windows; Polymer segment is curling under different pH condition, extension degree is different; Therefore finally realize control through control pH value, thereby played the effect of good threshold stream hole " on-off ".When pH=2, molecular chain is taked the conformation of curling, and the hole window is opened; Along with the increase of pH value, macromolecular chain extends gradually, and the hole window is closed gradually, and when pH=6 or pH=12, the macromolecular chain full extension comes, and hole window and macropore wall thickness increase 20～60nm, and the hole window is closed fully.Therefore this kind material can be with a wide range of applications in the controlled release fields such as slowly-releasing-embedding of biomedicine, medicine controlled releasing system, organized enzyme and catalyzer.
Description of drawings
Fig. 1 for mean pore size among the embodiment 1 be obtain after the 3DOM CLPS material graft polypropylene tert-butyl acrylate segment hydrolysis of 800nm have the stereoscan photograph of pH responsiveness 3DOM CLPS-g-PAA material under different pH values.(a)pH＝6，(b)pH＝4，(c)pH＝2。
Fig. 2 for mean pore size among the embodiment 2 be obtain after the 3DOM CLPS material grafting Vinalac 5920 segment hydrolysis of 800nm have the stereoscan photograph of pH responsiveness 3DOM CLPS-g-PMAA material under different pH values.(a)pH＝6，(b)pH＝4，(c)pH＝2。
Fig. 3 for mean pore size among the embodiment 3 be the 3DOM CLPS material grafting of 500nm gather that (4-vinylpridine) segment obtains have the stereoscan photograph of pH responsiveness 3DOM CLPS-g-P4VP material under different pH values.(a)pH＝12，(b)pH＝4，(c)pH＝2
Fig. 4 is the 3DOM CLPS material with pH responsiveness 3DOM CLPS-g-PAA and sulfonation reaction hydrophilic treatment that obtains after the 3DOM CLPS material graft polypropylene tert-butyl acrylate segment hydrolysis of the 800nm cumulative release curve to fluorescent yellow in different pH value for mean pore size among the embodiment 1.
Embodiment
Embodiment 1
Mean pore size is the preparation with responsiveness 3DOM CLPS-g-PAA material that obtains after the 3DOM CLPS material graft polypropylene tert-butyl acrylate segment hydrolysis of 800nm.
(1) median size is the preparation of the colloid crystal template of 1100nm
Under the room temperature, in there-necked flask, add the 11g mass percent concentration successively and be 25% ammoniacal liquor, 70g absolute ethyl alcohol, 6.2g zero(ppm) water, 3g tetraethoxy.Be stirred to mixed solution and be homogeneous, stablize the shape suspension liquid, add ammoniacal liquor, absolute ethyl alcohol, zero(ppm) water and the tetraethoxy of the equivalent of equal in quality proportioning, repeat 3 times; The gained suspension liquid is poured in the beaker, and the static solvent that makes volatilizees fully naturally under the room temperature, obtains the silicon dioxide colloid crystal template; Be placed on Gan Guozhong; In muffle furnace, after 5 hours, slowly be cooled to room temperature in 400 ℃ of following sintering, promptly obtaining median size is the inter-adhesive colloid crystal template of silicon dioxide microsphere of 1100nm;
(2) mean pore size is the preparation of the three-dimensional ordered macroporous crosslinked polystyrene material of 800nm:
Under the anhydrous and oxygen-free condition; In two-mouth bottle, adding the prepared median size of step (1) is the inter-adhesive colloid crystal template of silicon dioxide microsphere of 1100nm, and under argon shield, adding volume is 5ml (4.5g) styrene monomer, the agent of 1ml (0.9g) divinyl benzene crosslinked, 0.06g Diisopropyl azodicarboxylate initiator, after stirring; Soaked 2 hours; 80 ℃ of following polyase 13s 0 hour, the PS on lift-off stencil surface promptly obtains three-dimensional ordered macroporous crosslinked polystyrene/silica composite; It is 40% hydrofluoric acid that mixture is placed mass percent concentration; Behind the ultra-sonic dispersion 50 minutes, soaked 9 hours, then repeated water washing is to neutral; 80 ℃ of following vacuum-drying 20 hours, promptly obtaining mean pore size is the three-dimensional ordered macroporous crosslinked polystyrene material of 800nm (3DOM CLPS);
(3) has the grafting of pH value response polymer segment
At first utilize chloromethylation; Chlorine atom initiator is anchored on three-dimensional ordered macroporous crosslinked polystyrene material hole wall surface: (vacuum of the present invention, negative pressure state are: vacuum tightness is-0.1Mpa being equipped with under the vacuum state that mean pore size is the three-dimensional ordered macroporous crosslinked polystyrene material of 800nm under the anhydrous and oxygen-free condition; Other embodiment with) reactor drum in add 1g zinc chloride, 40g chloromethyl ether successively; Make it the submergence material; Stirring reaction carried out extracting 15 hours with absolute ethyl alcohol after 28 hours under 35 ℃ of conditions, obtained the three-dimensional ordered macroporous crosslinked polystyrene material (chloromethylation 3DOM CLPS) of chloromethylation after the oven dry.
Then; Adopt the three-dimensional ordered macroporous crosslinked polystyrene material hole wall graft acrylic acid tert-butyl ester (tBA) polymer chain of ATRP (ATRP) method: under the anhydrous and oxygen-free condition at chloromethylation; In two-mouth bottle, add 1g cuprous chloride, 50g tert-butyl acrylate monomer, 4g pimelinketone, 2g pentamethyl-diethylenetriamine successively; After being stirred to abundant dissolving; Mixed solution is extracted out, injected the two-mouth bottle of the three-dimensional ordered macroporous crosslinked polystyrene material that fills the 1g chloromethylation under the vacuum state rapidly.Reacted 16 hours down at 65 ℃, will get product and after 28 hours,, get hole wall surface graft acrylic acid uncle in the three-dimensional ordered macroporous crosslinked polystyrene material of ester polymer chain again 60 ℃ of following vacuum-dryings 26 hours with the THF extracting.
The three-dimensional ordered macroporous crosslinked polystyrene material of 0.5g hole wall surface grafted propylene tert-butyl acrylate polymer chain put into vacuumize after two-mouth bottle adds magneton; Under vacuum state, inject 1; 4-dioxane to submergence material; Soaked 5 hours, normal pressure adds concentrated hydrochloric acid, oil bath reflux 10 hours down then.Hydrolysis finishes 80 ℃ of following vacuum-dryings of after product 20 hours, finally makes the hole wall surface grafting and has the three-dimensional ordered macroporous crosslinked polystyrene material of pH value response ROHM segmental (3DOM CLPS-g-PAA).
With make to have a responsiveness 3DOM CLPS-g-PAA material dry under different pH values; See accompanying drawing 1; Can find out among Fig. 1, resulting mean pore size be 800nm have responsiveness 3DOM CLPS-g-PAA material macropore and hole window diameter has considerable change, with reducing of pH value; Macropore and hole window diameter increase gradually, have realized that it is by " pass " process to " opening ".When pH=2, the carboxylase gene in the polymkeric substance is protonated to be existed with-COOH form, and stronger hydrogen bond association is arranged between the polymer macromolecule chain, becomes contraction schedule, and molecular chain is taked the conformation of curling, and the hole window is opened; Along with the increase of pH value, carboxyl ionization ,-COOH is dissociated into-COO gradually
-, because the Coulomb repulsion effect, macromolecular chain extends gradually between this moment molecule, and the hole window is closed gradually, and when pH=6, the macromolecular chain full extension comes, and hole window and macropore wall thickness increase 50nm, and the hole window is closed fully.
Embodiment 2
Mean pore size is the preparation with pH responsiveness 3DOM CLPS-g-PMAA material that obtains after the 3DOM CLPS material grafting Vinalac 5920 segment hydrolysis of 800nm
(1) median size is the preparation of the colloid crystal template of 1100nm
Median size is that preparing method's step of colloid crystal template of 1100nm is with embodiment 1 (1).
(2) mean pore size is the preparation of the three-dimensional ordered macroporous crosslinked polystyrene material of 800nm:
Mean pore size is that three-dimensional ordered macroporous other step of crosslinked polystyrene preparation methods of 800nm is with embodiment 1 (2); What adjust is 6ml (5.5g) styrene monomer, the agent of 1ml (0.9g) divinyl benzene crosslinked, 0.03g Diisopropyl azodicarboxylate initiator for adding volume; Soaked 1.5 hours; 80 ℃ of following polymerization times are 32 hours, and the PS on lift-off stencil surface promptly obtains three-dimensional ordered macroporous crosslinked polystyrene/silica composite; It is 40% hydrofluoric acid that mixture is placed mass percent concentration; Behind the ultra-sonic dispersion 60 minutes, soaked 12 hours, then repeated water washing is to neutral; 80 ℃ of following vacuum-drying 22 hours, promptly obtaining mean pore size is the three-dimensional ordered macroporous crosslinked polystyrene material (3DOM CLPS) of 800nm.
(3) has the grafting of pH value response polymer segment
Utilize chloromethylation; Chlorine atom initiator is anchored on three-dimensional ordered macroporous other step of crosslinked polystyrene material hole wall surface with embodiment 1 (3); That adjusts is respectively 1g zinc chloride, 50g chloromethyl ether for adding quality; Stirring reaction carried out extracting 8 hours with absolute ethyl alcohol after 23 hours under 35 ℃ of conditions, obtained the three-dimensional ordered macroporous crosslinked polystyrene material (chloromethylation 3DOM CLPS) of chloromethylation after the oven dry.
Adopt the three-dimensional ordered macroporous crosslinked polystyrene material hole wall grafting n-BMA polymer chain of ATRP (ATRP) method at chloromethylation.Under the anhydrous and oxygen-free condition; In two-mouth bottle, add 1g cuprous chloride, 40g n-BMA monomer, 3g pimelinketone, 1.5g pentamethyl-diethylenetriamine successively; After being stirred to abundant dissolving; Mixed solution is extracted out, injected the two-mouth bottle of the three-dimensional ordered macroporous crosslinked polystyrene material that fills the 1g chloromethylation under the vacuum state rapidly.Reacted 26 hours down at 75 ℃, will get product and after 30 hours,, get the three-dimensional ordered macroporous crosslinked polystyrene material of hole wall surface grafting n-BMA polymer chain again 60 ℃ of following vacuum-dryings 25 hours with the THF extracting.
The three-dimensional ordered macroporous crosslinked polystyrene material of 0.5g hole wall surface grafting n-BMA polymer chain put into vacuumize after two-mouth bottle adds magneton; Under negative pressure state, inject 1; 4-dioxane to submergence material; Soaked 4.5 hours, normal pressure adds concentrated hydrochloric acid, oil bath reflux 9 hours down then.Hydrolysis finishes 80 ℃ of following vacuum-dryings of after product 25 hours, finally makes the hole wall surface grafting and has the three-dimensional ordered macroporous crosslinked polystyrene material of pH value response polymethyl acrylic acid segmental (3DOM CLPS-g-PMAA).
With make to have a responsiveness 3DOM CLPS-g-PMAA material dry under different pH values; See accompanying drawing 2; Can find out among Fig. 2, resulting mean pore size be 800nm have responsiveness 3DOM CLPS-g-PMAA material macropore and hole window diameter has considerable change, with reducing of pH value; Macropore and hole window diameter increase gradually, have realized that it is by " pass " process to " opening ".When pH=2, the carboxylase gene in the polymkeric substance is protonated to be existed with-COOH form, and stronger hydrogen bond association is arranged between the polymer macromolecule chain, becomes contraction schedule, and molecular chain is taked the conformation of curling, and the hole window is opened; Along with the increase of pH value, carboxyl ionization ,-COOH is dissociated into-COO gradually
-, because the Coulomb repulsion effect, macromolecular chain extends gradually between this moment molecule, and the hole window is closed gradually, and when pH=6, the macromolecular chain full extension comes, and hole window and macropore wall thickness increase 50nm, and the hole window is closed fully.
Embodiment 3
Mean pore size is that the 3DOM CLPS material grafting of 500nm gathers the preparation with pH responsiveness 3DOM CLPS-g-P4VP material that (4-vinylpridine) segment obtains.
(1) median size is the preparation of the colloid crystal template of 660nm
Median size is that other step of preparation method of colloid crystal template of 660nm is with embodiment 1 (1); Adjustment to be respectively the 14.3g mass percent concentration be 25% ammoniacal liquor, 91g absolute ethyl alcohol, 8.06g zero(ppm) water, 3.9g tetraethoxy in order to add quality; Repeat 2 times, obtaining average particle size is the colloid crystal template of 660nm.
(2) mean pore size is the preparation of the three-dimensional ordered macroporous crosslinked polystyrene material of 500nm:
Mean pore size is that three-dimensional ordered macroporous other step of crosslinked polystyrene preparation methods of 500nm is with embodiment 1 (2); What adjust is 5ml (4.5g) styrene monomer, the agent of 1ml (0.9g) divinyl benzene crosslinked, 0.06g Diisopropyl azodicarboxylate initiator for adding volume; Soaked 1 hour; 80 ℃ of following polymerization times are 22 hours, and the PS on lift-off stencil surface promptly obtains three-dimensional ordered macroporous crosslinked polystyrene/silica composite; It is 40% hydrofluoric acid that mixture is placed mass percent concentration; Behind the ultra-sonic dispersion 30 minutes, soaked 8 hours, then repeated water washing is to neutral; 80 ℃ of following vacuum-drying 26 hours, promptly obtaining mean pore size is the three-dimensional ordered macroporous crosslinked polystyrene material (3DOM CLPS) of 500nm.
(3) has the grafting of pH value response polymer segment
Utilize chloromethylation; Chlorine atom initiator is anchored on three-dimensional ordered macroporous other step of crosslinked polystyrene material hole wall surface with embodiment 1 (3); That adjusts is respectively 1g zinc chloride, 30g chloromethyl ether for adding quality; Stirring reaction carried out extracting 12 hours with absolute ethyl alcohol after 30 hours under 35 ℃ of conditions, obtained the three-dimensional ordered macroporous crosslinked polystyrene material (chloromethylation 3DOM CLPS) of chloromethylation after the oven dry.
Adopt the three-dimensional ordered macroporous crosslinked polystyrene material hole wall graft copolymerized 4-vinyl pyridine polymer chain of ATRP (ATRP) method at chloromethylation.Under the anhydrous and oxygen-free condition; In two-mouth bottle, add 1g cuprous chloride, 40g 4-vinylpridine monomer, 3g pimelinketone, 2g pentamethyl-diethylenetriamine successively; After being stirred to abundant dissolving; Mixed solution is extracted out, injected the two-mouth bottle of the three-dimensional ordered macroporous crosslinked polystyrene material that fills the 1g chloromethylation under the vacuum state rapidly.Reacted 26 hours down at 75 ℃; To get product with the THF extracting after 30 hours; 60 ℃ of following vacuum-dryings 25 hours, finally make the three-dimensional ordered macroporous crosslinked polystyrene material (3DOM CLPS-g-P4VP) of hole wall surface graft copolymerized 4-vinyl pyridine polymer chain again.
With make to have a responsiveness 3DOM CLPS-g-P4VP material dry under different pH values; See accompanying drawing 3; Can find out among Fig. 3, resulting mean pore size be 500nm have responsiveness 3DOM CLPS-g-P4VP material macropore and hole window diameter has considerable change, with reducing of pH value; Macropore and hole window diameter increase gradually, have realized that it is by " pass " process to " opening ".When pH=2, poly 4 vinyl pyridine becomes contraction schedule because of between the protonated polymer macromolecule chain stronger hydrogen bond association being arranged, and molecular chain is taked the conformation of curling, and the hole window is opened; Along with the increase of pH value, when pH value to alkalescence, poly 4 vinyl pyridine then extends owing to the deprotonation macromolecular chain gradually; The hole window is closed gradually, and when pH=12, the macromolecular chain full extension comes; Hole window and macropore wall thickness increase 30nm, and the hole window is closed fully.
Embodiment 4
Mean pore size is that the 3DOM CLPS material grafting of 700nm gathers the preparation with pH responsiveness 3DOM CLPS-g-P4VP material that (4-vinylpridine) segment obtains.
(1) median size is the preparation of the colloid crystal template of 930nm
Median size is that preparing method's step of colloid crystal template of 930nm is with embodiment 1 (1).
(2) mean pore size is the preparation of the three-dimensional ordered macroporous crosslinked polystyrene material of 700nm:
Mean pore size is that the three-dimensional ordered macroporous crosslinked polystyrene preparation methods of 700nm step is with embodiment 1 (2).
(3) has the grafting of pH value response polymer segment
Utilize chloromethylation; Other step of preparation method that chlorine atom initiator is anchored on three-dimensional ordered macroporous crosslinked polystyrene material hole wall surface is with embodiment 1 (3); That adjusts is respectively 1g zinc chloride, 35g chloromethyl ether for adding quality; Stirring reaction carried out extracting 11 hours with absolute ethyl alcohol after 29 hours under 35 ℃ of conditions, obtained the three-dimensional ordered macroporous crosslinked polystyrene material of chloromethylation after the oven dry.
Adopt the three-dimensional ordered macroporous crosslinked polystyrene material hole wall graft copolymerized 4-vinyl pyridine polymer chain of ATRP (ATRP) method at chloromethylation.Under the anhydrous and oxygen-free condition; In two-mouth bottle, add 1g cuprous chloride, 45g 4-vinylpridine monomer, 3.2g pimelinketone, 2.3g pentamethyl-diethylenetriamine successively; After being stirred to abundant dissolving; Mixed solution is extracted out, injected the two-mouth bottle of the three-dimensional ordered macroporous crosslinked polystyrene material that fills the 1g chloromethylation under the vacuum state rapidly.Reacted 28 hours down at 85 ℃; To get product with the THF extracting after 28 hours; 60 ℃ of following vacuum-dryings 26 hours, finally make the three-dimensional ordered macroporous crosslinked polystyrene material (3DOM CLPS-g-P4VP) of hole wall surface graft copolymerized 4-vinyl pyridine polymer chain again.
Embodiment 5
Mean pore size is the preparation with pH responsiveness 3DOM CLPS-g-PAA material that obtains after the 3DOM CLPS material graft polypropylene tert-butyl acrylate segment hydrolysis of 500nm.
(1) median size is the preparation of the colloid crystal template of 660nm
Median size is that preparing method's step of colloid crystal template of 660nm is with embodiment 3 (1).
(2) mean pore size is the preparation of the three-dimensional ordered macroporous crosslinked polystyrene material of 500nm:
Mean pore size is that the three-dimensional ordered macroporous crosslinked polystyrene preparation methods of 500nm step is with embodiment 3 (2).
(3) has the grafting of pH value response polymer segment
Utilize chloromethylation; Chlorine atom initiator is anchored on three-dimensional ordered macroporous crosslinked polystyrene material hole wall surface, adopt ATRP (ATRP) method in the three-dimensional ordered macroporous crosslinked polystyrene material hole wall graft acrylic acid tert-butyl ester polymer chain step of chloromethylation with embodiment 1 (3).Finally make the hole wall surface grafting and have the three-dimensional ordered macroporous crosslinked polystyrene material of pH value response ROHM segmental (3DOM CLPS-g-PAA).
Embodiment 6
Mean pore size is the preparation with pH responsiveness 3DOM CLPS-g-PMAA material that obtains after the 3DOM CLPS material grafting Vinalac 5920 segment hydrolysis of 500nm.
(1) median size is the preparation of the colloid crystal template of 660nm
Median size is that preparing method's step of colloid crystal template of 660nm is with embodiment 3 (1).
(2) mean pore size is the preparation of the three-dimensional ordered macroporous crosslinked polystyrene material of 500nm:
Mean pore size is that the three-dimensional ordered macroporous crosslinked polystyrene preparation methods of 500nm step is with embodiment 3 (2).
(3) has the grafting of pH value response polymer segment
Utilize chloromethylation; Chlorine atom initiator is anchored on three-dimensional ordered macroporous crosslinked polystyrene material hole wall surface, adopt ATRP (ATRP) method in the three-dimensional ordered macroporous crosslinked polystyrene material hole wall grafting n-BMA polymer chain step of chloromethylation with embodiment 2 (3).Finally make the hole wall surface grafting and have the three-dimensional ordered macroporous crosslinked polystyrene material of pH value response polymethyl acrylic acid segmental (3DOM CLPS-g-PMAA).
Embodiment 7
Mean pore size is the preparation with pH responsiveness 3DOM CLPS-g-PAA material that obtains after the 3DOM CLPS material graft polypropylene tert-butyl acrylate segment hydrolysis of 500nm.
(1) median size is the preparation of the colloid crystal template of 660nm
Median size is that preparing method's step of colloid crystal template of 660nm is with embodiment 3 (1).
(2) mean pore size is the preparation of the three-dimensional ordered macroporous crosslinked polystyrene material of 500nm:
Mean pore size be three-dimensional ordered macroporous other step of crosslinked polystyrene preparation methods of 500nm with embodiment 3 (2), adjustment use BPO instead for initiator.
(3) has the grafting of pH value response polymer segment
Utilize chloromethylation; Chlorine atom initiator is anchored on three-dimensional ordered macroporous crosslinked polystyrene material hole wall surface, adopt ATRP (ATRP) method in the three-dimensional ordered macroporous crosslinked polystyrene material hole wall graft acrylic acid tert-butyl ester polymer chain step of chloromethylation with embodiment 1 (3).Finally make the hole wall surface grafting and have the three-dimensional ordered macroporous crosslinked polystyrene material of pH value response ROHM segmental (3DOM CLPS-g-PAA).
Embodiment 8
Mean pore size is that the 3DOM CLPS material grafting of 800nm gathers the preparation with pH responsiveness 3DOM CLPS-g-P4VP material that (4-vinylpridine) segment obtains.
(1) median size is the preparation of the colloid crystal template of 1100nm
Median size is that preparing method's step of colloid crystal template of 1100nm is with embodiment 1 (1).
(2) mean pore size is the preparation of the three-dimensional ordered macroporous crosslinked polystyrene material of 800nm:
Mean pore size be three-dimensional ordered macroporous other step of crosslinked polystyrene preparation methods of 800nm with embodiment 1 (2), adjustment use the special butyl ester of peroxo-phenylformic acid instead for initiator.
(3) has the grafting of pH value response polymer segment
Utilize chloromethylation; Chlorine atom initiator is anchored on three-dimensional ordered macroporous crosslinked polystyrene material hole wall surface, adopt ATRP (ATRP) method in the three-dimensional ordered macroporous crosslinked polystyrene material hole wall graft copolymerized 4-vinyl pyridine polymer chain step of chloromethylation with embodiment 3 (3).Finally make the hole wall surface grafting and have the three-dimensional ordered macroporous crosslinked polystyrene material of pH value response ROHM segmental (3DOM CLPS-g-P4VP).
Fig. 4 is the prepared 3DOM CLPS material with pH responsiveness 3DOM CLPS-g-PAA material and sulfonation reaction hydrophilic treatment of embodiment 1 cumulative release curve to fluorescent yellow in different pH value.Can be found out by Fig. 4: the rate of change of absorbancy was greater than the rate of change of absorbancy in pH=6 solution when pH responsiveness material was simulated controlled release in pH=2 solution, and curve tends towards stability after the 2h.PAA is one type of polyanion electrolyte in the aqueous solution, and its solvability can receive the influence of pH value of solution value.In the solution of pH=2, the carboxylase gene in the polymkeric substance is protonated to be existed with-COOH form, and stronger hydrogen bond association is arranged between the polymer macromolecule chain; Become contraction schedule; Molecular chain is taked the conformation of curling, and the hole window is opened, the indicator snap-out release of filling in the material of hole; Along with the increase of pH value, carboxyl ionization ,-COOH is dissociated into-COO gradually
-, because the Coulomb repulsion effect, macromolecular chain extends gradually between this moment molecule, and when pH=6, the macromolecular chain full extension comes, and hole window and macropore wall thickness increase 50nm, and the hole window is closed fully, and the indicator release rate of filling in the material of hole is relatively slow.PH responsiveness 3DOM material releasing degree and release rate to filler under different pH value conditions is different.The releasing degree of material and release rate are all bigger when pH=2.Effect for contrast responsiveness material; We with 3DOM CLPS material sulfonation reaction hydrophilic treatment after; Under identical filling process condition, in different pH value, simulate controlled release, by seeing among Fig. 4 that the indicator releasing degree and the release rate of filling in the material that portals are basic identical.Explanation thus, the three-dimensional ordered macroporous material of grafting pH responsiveness functional group polymer segment has the characteristic of pH controlled release to weighting material.Therefore this kind material can be with a wide range of applications in the controlled release fields such as slowly-releasing-embedding of biomedicine, medicine controlled releasing system, organized enzyme and catalyzer.
From above embodiment, can find out; Utilize monodisperse three dimensional ordered large pore material aperture and be communicated with window size homogeneous characteristics; Chlorine atom initiator is anchored on three-dimensional ordered macroporous crosslinked polystyrene material hole wall surface; Adopt active " controlled " graft polymerization (ATRP) method of atom transferred free radical to have gathering weak acid or gathering the weak base polymer segment of pH responsiveness then in the grafting of 3DOM CLPS hole wall; Through the achieve a butt joint control of a chain length of the control to the grafting reaction times, finally make the hole wall surface grafting and have the three-dimensional ordered macroporous crosslinked polystyrene material of pH responsive polymer segmental.Utilize its stretching, extension under different pH condition-curling action to be communicated with the on-off control of window between realizing macropore, and then reach filling the effect of the controlled release that contains material.
Claims (2)
1. the three-dimensional ordered macroporous sustained release material of pH value response is characterized by the macropore of this material and is communicated with the window aperture homogeneous, and macropore diameter is 100～1000nm, and the connection window size is 40～120nm, and pore volume is 1.3～2.8cm
3/ g; Its matrix is the monodisperse three dimensional ordered macroporous cross-linked polystyrene with the window that is interconnected; On matrix, introduce polymer segment with pH value response through active " controlled " graft polymerization procedure of atom transferred free radical; The polymer segment that utilizes the pH value response is communicated with the on-off control of window between the stretching, extension under the different pH values-curling action is realized macropore: during as pH=2, molecular chain is taked the conformation of curling, and the hole window is opened; Along with the increase of pH value, macromolecular chain extends gradually, and the hole window is closed gradually; When pH=6 or pH=12, the macromolecular chain full extension comes, and hole window and macropore wall thickness increase 20～60nm; The hole window is closed fully, and then reaches filling the effect of the controlled release that contains material;
This preparation methods may further comprise the steps:
(1). the preparation of colloid crystal template
Under the room temperature, in there-necked flask, add mass percent concentration successively and be 25% ammoniacal liquor, absolute ethyl alcohol, zero(ppm) water and tetraethoxy; Mass ratio is that percentage concentration is 25% ammoniacal liquor: absolute ethyl alcohol: zero(ppm) water: tetraethoxy=11: 70: 6.2: 3; Be stirred to mixed solution and be homogeneous, stablize the shape suspension liquid, add ammoniacal liquor, absolute ethyl alcohol, zero(ppm) water and the tetraethoxy of the equivalent of equal in quality proportioning, repeat 1～4 time; The gained suspension liquid is poured in the beaker; The static solvent that makes volatilizees fully naturally under the room temperature, then prepared silicon dioxide colloid crystal template is placed Gan Guozhong, in muffle furnace in 400 ℃ of following sintering after 5 hours; Slowly be cooled to room temperature, promptly obtaining median size is the inter-adhesive colloid crystal template of silicon dioxide microsphere of 130～1300nm;
(2). the preparation of three-dimensional ordered macroporous crosslinked polystyrene material:
Under the anhydrous and oxygen-free condition; In two-mouth bottle, add the prepared silicon dioxide colloid crystal template of step (1), adding styrene monomer, divinyl benzene crosslinked agent, initiator make it the submergence template under argon shield, and volume ratio is a Vinylstyrene: vinylbenzene=1: 1～8; Initiator is 0.1～15% of vinylbenzene and a Vinylstyrene quality sum; After stirring, soaked 0.5～2 hour 80 ℃ of following polymerizations 20～32 hours; The PS on lift-off stencil surface promptly obtains three-dimensional ordered macroporous crosslinked polystyrene/silica composite; It is 40% hydrofluoric acid that mixture is placed mass percent concentration; Behind the ultra-sonic dispersion 10～60 minutes; Soaked 6～15 hours; Then repeated water washing is to neutral, 80 ℃ of following vacuum-drying 20～28 hours, and promptly obtaining pore diameter range is the three-dimensional ordered macroporous crosslinked polystyrene material (3DOM CLPS) of 100～1000nm;
(3). have the grafting of pH value response polymer segment:
Chlorine atom initiator is anchored on three-dimensional ordered macroporous crosslinked polystyrene material hole wall surface: under the anhydrous and oxygen-free condition, be zinc chloride with the quality proportioning: the mixed solution of chloromethyl ether=1: 20～60 joins in the reactor drum that three-dimensional ordered macroporous crosslinked polystyrene material is housed under the negative pressure state; To the submergence material; Stirring reaction is after 22～30 hours under 35 ℃ of conditions; Carry out extracting 6～15 hours with absolute ethyl alcohol, obtain the three-dimensional ordered macroporous crosslinked polystyrene material (chloromethylation 3DOMCLPS) of chloromethylation after the oven dry;
The chloromethylation 3DOM CLPS hole wall grafting that makes in the above then has pH value response polymer segment, adopts one of following two kinds of methods:
Method 1; Adopt the three-dimensional ordered macroporous crosslinked polystyrene material hole wall grafting pH value response polymer chain of ATRP (ATRP) method: under the anhydrous and oxygen-free condition at the chloromethylation of preparation; In two-mouth bottle, add cuprous chloride, function monomer, pimelinketone and pentamethyl-diethylenetriamine successively; After being stirred to abundant dissolving; Mixed solution is extracted out, injected the two-mouth bottle of the three-dimensional ordered macroporous crosslinked polystyrene material that fills chloromethylation under the negative pressure state rapidly, its quality proportioning is chloromethylation 3DOM CLPS: cuprous chloride: function monomer: pimelinketone: pentamethyl-diethylenetriamine=1: 1～6: 20～60: 1～5: 1～5; Reacted 16～32 hours down at 65～90 ℃; To get product and after 28～32 hours,, make the three-dimensional ordered macroporous crosslinked polystyrene material of hole wall surface grafting functional polymer chain again 60 ℃ of following vacuum-dryings 20～28 hours with the THF extracting;
The three-dimensional ordered macroporous crosslinked polystyrene material of the hole wall surface grafting functional polymer chain that makes put into vacuumize after two-mouth bottle adds magneton; Under negative pressure state, inject 1; 4-dioxane to submergence material; Soaked 1～5 hour, normal pressure adds concentrated hydrochloric acid, oil bath reflux 6～10 hours down then; Hydrolysis finishes 80 ℃ of following vacuum-dryings of after product 20～28 hours, finally makes the hole wall surface grafting and has the three-dimensional ordered macroporous crosslinked polystyrene material of pH value response ROHM segmental;
Or method 2; Adopt the three-dimensional ordered macroporous crosslinked polystyrene material hole wall grafting pH value response polymer chain of ATRP (ATRP) method: under the anhydrous and oxygen-free condition at the chloromethylation of preparation; In two-mouth bottle, add cuprous chloride, function monomer, pimelinketone and pentamethyl-diethylenetriamine successively; After being stirred to abundant dissolving, mixed solution is extracted out, injected the two-mouth bottle of the three-dimensional ordered macroporous crosslinked polystyrene material that fills chloromethylation under the vacuum state rapidly; Wherein the quality proportioning is chloromethylation 3DOM CLPS: cuprous chloride: function monomer: pimelinketone: pentamethyl-diethylenetriamine=1: 1～6: 20～60: 1～5: 1～5; Function monomer is a 4-vinylpridine, 65～90 ℃ of down reactions 16～32 hours, will get product with the THF extracting after 28～32 hours; 60 ℃ of following vacuum-dryings 20～28 hours, finally make the three-dimensional ordered macroporous crosslinked polystyrene material of hole wall surface grafting pH value response polymer chain again;
Function monomer is tert-butyl acrylate or n-BMA in the method 1 in the described step (3).
2. the three-dimensional ordered macroporous sustained release material of pH value response as claimed in claim 1, the initiator that it is characterized by in the described step (2) is the special butyl ester of Diisopropyl azodicarboxylate, ABVN, BPO, dilauroyl peroxide, di-isopropyl peroxydicarbonate or peroxo-phenylformic acid.
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| Xu Zhang et al.Graft polymerization from pore wall or three-dimensionally ordered macroporous cross-linked polystyrene via atom transfer radical polymerization.《European Polymer Journal》.2009,第45卷(第5期),第1359－1366页. * |
| 张旭等.三维有序大孔交联聚苯乙烯孔壁接枝聚丙烯酸叔丁酯的制备与表征.《2009年全国高分子学术论文报告会论文摘要集(上册)》.2009,第340页. * |
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