CN1176961C - Sensitive ordered porous polymer gel and its preparing process - Google Patents
Sensitive ordered porous polymer gel and its preparing processInfo
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- CN1176961C CN1176961C CNB011183179A CN01118317A CN1176961C CN 1176961 C CN1176961 C CN 1176961C CN B011183179 A CNB011183179 A CN B011183179A CN 01118317 A CN01118317 A CN 01118317A CN 1176961 C CN1176961 C CN 1176961C
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Abstract
The present invention discloses ordered porous polymer gel having sensitivity. Pores have uniform size, and are regularly arranged in space. The size of the pores can be adjusted within the range of 10<0> nanometers to 10<1> microns, and the connectivity between the pores can be controlled. Basic frameworks of pore walls in the gel are sensitivity polymer gel resin which has response characteristics to external fields, and at the same time, various functional substances can be compounded in the pores and on the pore walls. The present invention has the advantages of simple needed equipment and operation and convenient template preparation, and is suitable for detecting micro substances. Mesoscopic functional substances can be selectively assembled, and controllable release can be realized. The present invention has important effects on the fields of heterogeneity compounding of ordered pores, chemical industry, medical treatment, biology, information, etc.
Description
The present invention relates to a kind of polymer porous material, particularly a kind of ordered porous polymer gel with susceptibility.
In the nineties later stage, the preparation of ordered porous materials becomes the research focus.This material have to arrange in order in the hole and the hole between the characteristics that can regulate and control to the hundreds of nanometer range in several nanometers of connectedness and aperture, thereby significant in fields such as absorption, sepn process, catalyzed reaction.It has sequence characteristics in sub-micrometer range, give its special optical characteristics again, might play a significant role at aspects such as information communications.
Ordered porous materials generally all adopts the preparation of template synthetic technology.1998, people such as Stein and Pine is that to have prepared the aperture be the orderly inorganic hole material (B.T.Holland of inorganics of hundreds of nanometer to template with the polystyrene colloid crystalline substance respectively, C.F.Blanford, A.Stein, " Synthesis ofMacroporous Minerals with Highly Ordered Three-Dimensional Arrays ofSpherical Voids ", Science, 1998,281,538; G.Subramanian, V.N.Manoharan, J.D.Thorne, D.J.Pine, " Ordered Macroporous Materialsby Colloidal Assembly:A Possible Route to Photonic BandgapMaterials ", Adv.Mater., 1999,11,1261).These ordered porous materials skeletons are inorganics, though have functional performances such as some photoelectromagnetism, it is carried out further functional modification still a lot of difficulties.
Polymer ordered hole material also successfully is synthesized simultaneously.It is that to have prepared the aperture be the polyurethane film (S.H.Park of 200-3000 nanometer to template that Xia etc. have reported with the polystyrene colloid crystalline substance, Y.Xia, " Fabrication of Three-Dimensional Macroporous Membranes withAssemblies of Microspheres as Templates ", Chem.Mater., 1998,10.1745).They inject the template hole with polyurethane precursor, use uv-light polymerization, form urethane.Go polystyrene is molten with toluene again, promptly obtain the ordered porous material of urethane.This polyurethane film has the three-dimensional order cavernous structure, and is interconnected between the hole, and the research at aspects such as adsorbing, separate, concentrate has the potential using value.People such as Mallouk utilize particle diameter be the silicon dioxide colloid crystalline substance of 35 nanometers for template has prepared order mesoporous polydivinylbenezene and polydimethyl vinylformic acid glyceryl ester or both multipolymers (S.A.Johnson, P.J.Ollivier, T.E.Mallouk, " OrderedMesoporous Polymers of Tunable Pore Size from Colloidal SilicaTemplates ", Science, 1999,283,963), this several ordered polymers hole has the three-dimensional order pore structure equally, and owing to the contraction of polymkeric substance in the template removal processes causes the aperture in the multipolymer to regulate continuously between the 15-35 nanometer with two kinds of monomeric proportioning differences.But Bao Dao organic polymer ordered porous materials so far, all be can not deformation hard hole, lack response characteristic to the outfield, do not mention the functionalization problem of ordered porous materials yet.
Recently, Yang Zhenzhong, Wang Lijun etc. prepare a kind of orderly hydrogel of sulfonated polystyrene (Chinese invention patent application number: 01100391.x) that contains.By single step reaction the polymeric colloid crystalline substance is carried out functionalization, finishes simultaneously the crosslinked of polymkeric substance and affinity modification, the gel resin that obtains can be in water or other polar solvent swelling and form orderly hydrogel.But the ordered structure of this hydrogel is made of spheroidal particle, and the hole between particulate is less, is unfavorable for the assembling of the transmission of material and functional mass and compound.In addition, this gel is also very weak to the susceptibility of temperature and potential of hydrogen.People such as Asher adopt has the hydrogel of response characteristic that the ordered structure that the polystyrene spherical particle alignment forms is fixed up to the outfield, has prepared sensitive polymer colloid crystalline substance.(J.H.Holtz, J.S.W.Holtz, C.H.Munro, S.A.Asher " Intelligent Polymerized Crystalline Colloidal Arrays:Novel Chemical Sensor Materials ", Anal.Chem., 1998,70 780-791), has effect at aspects such as intelligence sensors.But wherein do not possess big pore structure, be unfavorable for mass transfer, responsive response speed is slow, also is unfavorable for simultaneously the assembling of other functional mass and compound.Yang Zhenzhong, Rong Jianhua etc. have prepared gelatinous material by chemical modification based on the orderly hole of orderly polystyrene first, and (the Chinese invention patent application number: 01100390.1), wherein all arrange at spacial ordering in the lump in the aperture, and hole dimension is in sub-micrometer scale.In addition, the aperture can change with the character such as the soda acid difference of solvent, is keeping the homogeneity and the order in hole simultaneously.Under acidic conditions, gel size diminishes; Under alkaline condition, it is big that gel size becomes, and tentatively realized the sensitivity response characteristic.But its responsive response is also not fairly obvious.Obtain through chemical postmodification because this gel resin is a macromole, be unfavorable for that extraneous functional substance assembling with compound, has also limited its application.
The object of the present invention is to provide a kind of setting out to carry out the polymeric ordered porous polymer gel by monomer.
The invention provides a kind of being set out by monomer and carry out the preparation method of polymeric ordered porous polymer gel, the responsive response of prepared ordered porous polymer gel obviously is easy to extraneous functional substance assembling simultaneously with compound.
The sensitive ordered porous gel resin that the present invention is prepared, the size homogeneous in hole, and regularly arranged in the space, hole dimension is 10
0Nanometer-10
1The micron dimension scope is adjustable; Connective controlled between the hole; The basic framework of hole wall is the sensitive polymer gel resin in the gel, and the outfield is had response characteristic; Simultaneously can be in the hole and on the hole wall compound various functional substance.
Described sensitive polymer gel resin is monomer or adopts conventional mass polymerization or solution polymerization process polymerization to obtain polymer gel with comonomer;
Described monomer comprises following monomer or its mixture:
1. can form the monomer and the salt derivative thereof of polymkeric substance: the monomer such as vinylformic acid, the methacrylic acid etc. that contain carboxyl with electrical charge rejection effect; Contain sulfonic monomer such as vinylbenzenesulfonic acid; The monomer that contains phosphate; The vinyl monomer that contains positive charge such as quaternary ammonium salt; Or two kinds of simultaneous monomers of electric charge; Wherein preferred vinylformic acid, methacrylic acid and its esters, vinylbenzenesulfonic acid and its esters, dimethylaminoethyl methacrylate.
2. can form monomer: vinyl alcohol and derivative thereof such as methoxy-ethylene ether with hydrogen bond force effect polymkeric substance; The acrylamide of hydroxyl and derivative thereof; Acrylamide and derivative thereof such as N, the N N-isopropylacrylamide; Vinyl monomer such as acrylate and derivative such as Hydroxyethyl acrylate; The ethylene oxide/propylene oxide class; The compound such as Mierocrystalline cellulose and the derivative thereof that contain many carboxyls or hydroxyl; Other natural compounds such as chitosan derivatives; Heterobicyclic compounds is as dicyclo oxalactone etc.Wherein preferred acrylamide, N, the N N-isopropylacrylamide, the acrylamide of hydroxyl and derivative thereof, Hydroxyethyl acrylate and derivative thereof can form the ethylene oxide/propylene oxide class mix monomer of segmented copolymer.
3. functional monomer: have the monomer of sensitive polymer to comprise azo monomer to optical signal, contain the monomer of two alkynes structures etc.; Can form the monomer of electric conductive polymer, the thiophene phenols, imidazoles, the alkynes class, arsenic is coughed up, aniline etc.
Described comonomer is vinyl monomer and salt derivatives thereof such as vinylbenzene, acrylate, vinyl acetate, vinyl cyanide, dienes such as divinyl and isoprene monomer and salt derivative thereof, or their mixture, as vinylbenzene and methacrylic ester, vinyl acetate and acrylate etc.Wherein preferred: acrylic amide, vinylformic acid and salt derivative thereof, acrylic ester monomer.
Orderly hole of the present invention gel prepares by template, and the arrangement mode of its mesopore is by the orderly packed structures decision of template.Composition classification from template can be inorganics, organic polymer or its hybrid; From the classification of the geometry of template, template can be the ordered structure that is formed by mono-dispersion microballoon, or the ordered structure that is formed by the hole that is interconnected; Anisotropy dimension classification from template can be one dimension, two dimension, or three-dimensional.
Skeleton contains a kind of susceptibility gel resin at least, also can be the multimeshed network of multiple susceptibility gel.The physico-chemical property of gel such as volume, optical property, hydrophilic and oleophilic character, microtextures etc. can be because of outfield such as pH value, temperature, electric field or magnetic field, light field, additional substances etc. and changing present sensitive natur, and this mainly is relevant with the electrical charge rejection power and the change of hydrogen bond force effect in the system.
The connectedness in hole can be regulated by the control template structure.As for arrange the template forms by microballoon, regulate by the contact fusion degree between the control microballoon: for inorganic template, the fusion degree that can regulate microballoon by the temperature and time of adjustment pyroprocessing; For organic formwork, can regulate the fusion degree of microballoon by pyroprocessing, also can especially increase the fraction of subcritical molecular weight by regulating the molecular weight and the distribution thereof of microballoon, so just can be lower than the fusion degree of regulating microballoon under the second-order transition temperature; Also can be by adding the fusion degree of softening agent or solvent adjustment microballoon.For orderly casement plate, the connectedness of regulating orderly hole gel by the connection degree of regulating form cage.
The preparation method of ordered porous gel of the present invention, carry out in the following order:
One. prepare orderly template
1a: the orderly accumulation of mono-dispersion microballoon:
With St ber method (W.St ber, A.Fink, E.Bohn,, Journal of Colloid ﹠amp; Interface Science 1968 26:62-69) prepares silicon-dioxide list disperse particles dispersion system, or prepares polymkeric substance list disperse particles system (Wang Lijun, Beijing Normal University, Master's thesis, 2000) by method of emulsion polymerization.The orderly accumulation of single disperse particles can be by monodisperse system is centrifugal or sedimentation, seasoning or slow means such as the drying colloid crystalline substance that obtains having different packed structures.
1b: orderly casement plate
With the polymeric colloid crystalline substance, tensio-active agent or segmented copolymer are template, and the sol/gel process by inorganics obtains orderly inorganic casement plate (as silicon-dioxide) (Qi Kai, chemistry institute of the Chinese Academy of Sciences, Master's thesis, 2000), is interconnected aperture 10 between the hole in order
1Nanometer-10
0The micron dimension range regulation.
With inorganic silicon dioxide colloid list disperse particles ordered structure be template preparation polymer ordered hole material (Rong Jianhua etc., Science Bulletin, 2000,45,1627-1630), the aperture is 10
1Nanometer-10
0Micrometer range is regulated.
2. template is handled
Template can be carried out following processing in order:
2a: the connective processing.
For inorganic template, as the silicon dioxide colloid crystalline substance, by regulating between microballoon in 1 hour to 24 hours 400-800 ℃ of pyroprocessing or the fusion degree of hole on framework; For the organic polymer template, processing mode can be a little less than handling under the second-order transition temperature 1-4 hour, or adjusting molecular weight and distribution thereof, especially increase the fraction of subcritical molecular weight, so just, can also can add softening agent or solvent adjustment template connectedness being lower than adjusting fusion degree under the second-order transition temperature.Concrete grammar is seen document: Hernan Miguez, Francisco Meseguer, et al.Control of potonic crystalproperiteds of fcc-packed submicrometer SiO2 spheres by sintering, Adv.Mater.1998,10,480-483 and Wang Lijun, the self-assembly of monodisperse polymer particulate and functionalization thereof, Beijing Normal University, 1999.
2b: anisotropy is handled.
For organic formwork, a little more than under the second-order transition temperature,, template stretches or force of compression by being applied, cool off fixed sturcture then fast, realize the anisotropy processing.The dimension that applies power can be a unidimensional, two dimension, three-dimensional; Can carry out synchronously, also can proceed step by step.Concrete grammar is seen document Peng Jiang, Jane F.Bertone, Vicki LiColvin, Alost-wax approach tomonodisperse colloids and their crystals, Science, 2001,291,453-457.
Two. the preparation of template/polymer gel mixture
Immerse in the ordered module plate hole crack with monomer or with the monomeric mixture of copolymerization, adopt conventional mass polymerization or solution polymerization process polymerization to obtain template/polymer gel mixture; The monomeric ratio of described monomer and copolymerization is 1～10: 1 (weight percent).
Described monomer comprises following monomer or its mixture:
1. can form the monomer and the salt derivative thereof of polymkeric substance: the monomer such as vinylformic acid, the methacrylic acid etc. that contain carboxyl with electrical charge rejection effect; Contain sulfonic monomer such as vinylbenzenesulfonic acid; The monomer that contains phosphate; The vinyl monomer that contains positive charge such as quaternary ammonium salt; Or two kinds of simultaneous monomers of electric charge; Wherein preferred vinylformic acid, methacrylic acid and its esters, vinylbenzenesulfonic acid and its esters, dimethylaminoethyl methacrylate.
2. can form monomer: vinyl alcohol and derivative thereof such as methoxy-ethylene ether with hydrogen bond force effect polymkeric substance; The acrylamide of hydroxyl and derivative thereof; Acrylamide and derivative thereof such as N, the N N-isopropylacrylamide; Vinyl monomer such as acrylate and derivative such as Hydroxyethyl acrylate; The ethylene oxide/propylene oxide class; The compound such as Mierocrystalline cellulose and the derivative thereof that contain many carboxyls or hydroxyl; Other natural compounds such as chitosan derivatives; Heterobicyclic compounds is as dicyclo oxalactone etc.Wherein preferred acrylamide, N, the N N-isopropylacrylamide, the acrylamide of hydroxyl and derivative thereof, Hydroxyethyl acrylate and derivative thereof can form the ethylene oxide/propylene oxide class mix monomer of segmented copolymer.
3. functional monomer: have the monomer of sensitive polymer to comprise azo monomer to optical signal, contain the monomer of two alkynes structures etc.; Can form the monomer of electric conductive polymer, the thiophene phenols, imidazoles, the alkynes class, arsenic is coughed up, aniline etc.
Described comonomer is vinyl monomer and salt derivatives thereof such as vinylbenzene, acrylate, vinyl acetate, vinyl cyanide, dienes such as divinyl and isoprene monomer and salt derivative thereof, or their mixture, as vinylbenzene and methacrylic ester, vinyl acetate and acrylate etc.Wherein preferred: acrylic amide, vinylformic acid and salt derivative thereof, acrylic ester monomer.
The present invention adopts conventional mass polymerization or solution polymerization, and initiator, linking agent and solution polymerization solvent for use are had no special requirements, and can use following raw material and consumption particularly:
The 0%-5% initiator, 0.1-20% linking agent etc.,
Linking agent is:
Can form the system of crosslinking structure by Raolical polymerizable: many vinyl compounds, as divinylbenzene, dicthenone, dimethylene acrylamide, contain the acrylic ester compound of a plurality of pairs of keys etc.Or:
Can form the system of crosslinking structure by condensation reaction: unsaturated list or polycarboxylic acid, the polyester that polyvalent alcohol or polynary epoxide form, the unsaturated polyester that unsaturated poly carboxylic acid and polyvalent alcohol form, diisocyanate compound, N hydroxymethyl acrylamide, glyceral methacrylate, glycidyl acrylate, polyvalent alcohol, polyamine, polyaldehyde, polyprotonic acid etc.
Wherein preferably by the radical crosslinking system: divinylbenzene, systems such as dimethylene acrylamide.
Initiator: radical initiator, light trigger, radiation initiators etc., or do not add initiator, directly adopt thermal-initiated polymerization.Wherein preferred free radical initiator system and light initiation system.
Can introduce ergasia simultaneously in the above-mentioned system, as magnetic substance such as Fe
3O
4Nano particle, optical active substance as azo compound, contains the compound of two alkynes structures, and chemical awareness material or group are as enzyme, crown ether or cyclodextrin.
Three. remove template
With this template/polymer gel mixture removal template soaked in solvent, washing, drying obtain ordered big hole polymer gel resin then.For the inorganics silica template, solvent for use is a hydrofluoric acid; For polymer template, solvent for use is organic solvents such as trichloromethane or toluene.
Gel resin immerses back swelling in water or other solvent, forms orderly gel, is reduced to gel resin behind gel dehydration or other solvent, and this process is reversible.Its swelling degree can change with certain trace ingredients and different solvents in temperature, pH value, electromagnetic field, light field, the solution.
The sensitive ordered hole gel that the present invention relates to has the dual nature of above ordered porous materials and two kinds of materials of responsive gel resin.Gel is set out by monomer and carries out polymerization and obtain, rather than polymkeric substance is carried out chemical modification.Therefore, easier to be compound in the gel of the present invention with other functional mass.The pore structure of hole gel and size can realize regulating by changing envrionment conditions (as containing certain micro substance etc. in temperature, pH value, ionic strength, light, electromagnetic field, the solution) in order, can realize the modulation process to light simultaneously, are suitable for detecting micro substance; Can assemble selectively is situated between sees functional mass and realizes controllable release, has vital role in the fields such as hole Heterogeneous Composite, chemical industry, medical treatment, biology, information in order.
Preparation method of the present invention and products characteristics are as follows:
● experiment required equipment, simple to operate: template prepares easy, and monomer polymerization adopts the general polymerization method;
● can regulate the aperture of gel by the particle diameter of control template, the aperture is 10
0-10
4Controlled in the nanometer range;
● the swelling of ordered gel resin and color can be regulated and control by external environment, and process is reversible;
● the present invention has universality; Can be used to the polymer gel of synthetic all similar types;
● the ordered gel resin among the present invention can be further used as other functional ordered structure of template for preparing.
Below in conjunction with embodiment the present invention is done further detailed description.
Embodiment 1. radical polymerizations prepare acrylic amide ordered big hole hydrogel
Be equipped with monodisperse silica particulate aqueous based dispersions with St ber legal system, mean particle dia is controlled in the 50-900 nanometer range.The above-mentioned dispersion system of drying at room temperature obtains orderly silica template.Orderly template (wherein diameter of particle is 300 nanometers) is soaked in the deionized water solution that contains 20% acrylamide, 0.2% methylene-bisacrylamide and 0.1% ammonium persulphate, be the colourful transparent shape to template, the ratio of template and monomer mixed solution is in very large range adjustable, and being immersed in fully in the solution with template is benchmark.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, obtains template/gel composite in 1 hour 50 ℃ of polymerizations.This mixture is dipped in ultrasonic 40 minutes removal templates in 10% hydrofluoric acid, and washing, drying at room temperature obtain ordered big hole polymer gel resin then.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly.Bright-colored shows in the large pore gel aperture homogeneous and arranges in order that this is the Bragg scattering result that the ordered arrangement structure produces visible light.Elevated temperature, sample size diminishes, and the color basket moves, and shows that it has sensitive natur to temperature.
Embodiment 2: light initiation polymerization prepares acrylic amide ordered big hole hydrogel
Silica template among the embodiment 1 was obtained merging between spherolite more orderly template in 2 hours 800 ℃ of following sintering processes.This template is soaked in the deionized water solution that contains 20% acrylamide, 0.2% methylene-bisacrylamide and 0.05% diethoxy acetophenone ultraviolet initiator, is transparence to template.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, obtains template/gel composite in polymerization under the UV-irradiation of 365 nanometers after 40 minutes.This mixture is dipped in ultrasonic 40 minutes removal templates in 10% hydrofluoric acid, washing then, drying at room temperature obtains the ordered big hole polymer gel.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly.Bright-colored shows in the large pore gel aperture homogeneous and arranges in order that this is the Bragg scattering result that the ordered arrangement structure produces visible light.Its sensitivity characteristic is with embodiment 1.
Embodiment 3. radical polymerizations prepare the orderly hydrogel of vinyl cyanide derivative
Silica template among the embodiment 1 was obtained the big orderly template of fusion degree between spherolite in 8 hours 800 ℃ of following sintering processes.It is in 60% the salpeter solution that 30% vinyl cyanide is dissolved in concentration, adding 2% (with respect to vinyl cyanide) concentration is 10% ammonium persulfate solution, after mixing, orderly template is immersed wherein, be transparence to template, the ratio of template and monomer mixed solution is in very large range adjustable, and being immersed in fully in the mixed solution with template is benchmark.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, 3 weeks obtains template/gel composite 15 ℃ of maintenances then.This mixture is dipped in ultrasonic 40 minutes removal templates in 40% hydrofluoric acid, and it is neutral then gel being made the pH value with the cleaning of 2% sodium bicarbonate aqueous solution, promptly obtains the ordered big hole polymer gel.This gel resin is the water white transparency shape in dry state, and suction is risen and presented transparent bright-colored after big, shows in the large pore gel aperture homogeneous and arranges in order, and this is the Bragg scattering result that ordered arrangement produces.This gelling system increases with the pH value and rises greatly, has bright-colored simultaneously, though maintenance order when showing also changes Datong District, aperture.
The preparation of the orderly hydrogel of embodiment 4. natural compoundss
Template used with embodiment 2.With 10% chitosan, 6% ethylene oxide and 84% concentration are that 13% sodium hydroxide solution mixes, and are heated to 60 ℃ of reactions and obtain deacetylated glycol-chitosan in 15 hours.With the 10% deacetylated glycol-chitosan and the methyl alcohol uniform mixing of 5% deionized water and 85%.Orderly template immersed in the mixing solutions to template be transparence.Add 5% 0.01N hydrochloric acid again, react and obtained template/crosslinked glycol-chitosan in 10 hours.Behind the methyl alcohol thorough washing, this mixture is dipped in ultrasonic 40 minutes removal templates in 10% hydrofluoric acid, washing, drying at room temperature obtain ordered big hole polymer gel resin then.This gel resin is the water white transparency shape in dry state, and suction is risen and presented transparent bright-colored after big, shows in the large pore gel aperture homogeneous and arranges in order, and this is the Bragg scattering result that ordered arrangement produces.This system has the temperature sensitive characteristic, with embodiment 1.
The preparation of the sensitive ordered hydrogel of embodiment 5.pH
Template used with embodiment 2.Prepare 5% sodium acrylate, the deionized water solution of the ammonium persulphate of 15% acrylamide, 0.2% methylene-bisacrylamide and 0.03% (with respect to monomer).Orderly template immersed wherein to template be transparence, the ratio of template and monomer mixed solution is in very large range adjustable, and being immersed in fully in the mixed solution with template is benchmark.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, obtains template/gel composite in 1 hour 50 ℃ of polymerizations then.This mixture is dipped in ultrasonic 40 minutes removal templates in 10% hydrofluoric acid, and washing, drying at room temperature obtain ordered big hole polymer gel resin then.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly.Bright-colored shows in the large pore gel aperture homogeneous and arranges in order that this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel changes with the ionic strength variation of pH value and solution.The pH value of increase system, the volume of gel increases, and the visible transmission spectrum of different pH value time hydrogel, and the ordering size that all shows this hydrogel increases with the increase of pH value.
The preparation of the orderly hydrogel of embodiment 6. temperature sensitivities
Template used with embodiment 3.Preparation 15%N, N-N-isopropylacrylamide, the deionized water solution of 1% acrylamide, 0.1% methylene-bisacrylamide and 0.02% (with respect to monomer) diethoxy acetophenone light trigger.Orderly template immersed in the mixing solutions to template be transparence, the ratio of template and monomer mixed solution is in very large range adjustable, and being immersed in fully in the mixed solution with template is benchmark.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, cooling and shine with 365 nano-ultraviolet lights and to obtain template/gel composite in 20 minutes in ice-water bath.This mixture is dipped in ultrasonic 40 minutes removal templates in 10% hydrofluoric acid, and washing, drying at room temperature obtain the ordered big hole polymer gel then.This gel resin is the water white transparency shape in dry state, and suction is risen and presented transparent bright-colored after big, shows in the large pore gel aperture homogeneous and arranges in order, and this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel raises with temperature and reduces.The visible transmission spectrum of hydrogel under the differing temps, the ordering size that shows this hydrogel reduces with the increase of temperature.
The preparation of the sensitive ordered hydrogel of embodiment 7. chemical substances
Template used with embodiment 2.Prepare 10% acrylamide, 0.15% methylene-bisacrylamide, the basic acrylamide of 5%N-phendioxin 8-crown ether-6 (acryloylamidobenzo-18-crown-6, AAB18C6) and the deionized water solution of 0.02% diethoxy acetophenone light trigger.Orderly template immersed in the mixing solutions to template be transparence.Remove wherein oxygen 20 minutes with nitrogen under the normal temperature, cooling and shine with 365 nano-ultraviolet lights and to obtain template/gel composite in 5 minutes in ice-water bath.This mixture is dipped in ultrasonic 40 minutes removal templates in 10% hydrofluoric acid, and washing, drying at room temperature obtain the ordered big hole polymer gel then.This gel presents transparent bright-colored in solution, shows in the large pore gel aperture homogeneous and arranges in order, and this is the Bragg scattering result that ordered arrangement produces.Gel is to Pb
2+, Ba
2+And K
+The plasma sensitivity.The Pb that in solution, contains 20ppb-4000ppm
2+The time, thereby can be caused that gel volume increases by the crown ether perception, promptly the ordering size of hole gel becomes big in order.The visible transmission spectrum of hydrogel under the different ions concentration, the ordering size that shows this hydrogel increases with the increase of ionic concn.
The preparation of the sensitive ordered hydrogel of embodiment 8. chemical substances
Template used with embodiment 3.The 10%N-N-isopropylacrylamide, the deionized water solution of 0.5% acrylamide, 0.15% methylene-bisacrylamide and 0.02% (with respect to monomer) diethoxy acetophenone light trigger and 0.2% glucose oxidase.Orderly template immersed in the mixing solutions to template be transparence.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, cooling and shine with 365 nano-ultraviolet lights and to obtain template/gel composite in 50 minutes in ice-water bath.Glucose oxidase is embedded in the gel.This mixture is dipped in 40 minutes removal templates in 10% hydrofluoric acid, and washing, drying at room temperature obtain the ordered big hole polymer gel then.This gel presents transparent bright-colored, shows in the large pore gel aperture homogeneous and arranges in order, and this is the Bragg scattering result that ordered arrangement produces.When containing 20-80ppm glucose in the solution, thereby can be caused that gel volume increases by the enzyme perception, promptly the ordering size of hole gel becomes big in order.The visible transmission spectrum of hydrogel shows that the ordering size of this hydrogel increases with the increase of concentration under the different glucose concn.
Embodiment 9. temperature sensitivities have the preparation of ordered magnetism hydrogel
Adopt template among the embodiment 3.With the 15%N-N-isopropylacrylamide, 1.2% acrylamide, 0.15% methylene-bis acryloyl ammonium, 0.02% ammonium persulphate is in nanometer Fe
2O
3(median size 20nm, solid content 1%) dissolving mixes in the water dispersion solution.Orderly template immersed in the mixing solutions to template be transparence.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, is warming up to 60 ℃ of polymerizations 1 hour, obtains template/gel composite.This mixture is removed polystyrene with the tetrahydrofuran (THF) extracting, with the cleaning of second alcohol and water, drying at room temperature, obtain ordered polymer magnetic gel resin then.This gel resin is light yellow transparence in dry state, and suction presents transparent bright-colored after rising greatly, shows to have ordered structure in the gel, and this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel changes with the ionic strength variation of pH value and solution.The visible transmission spectrum of different pH values time hydrogels shows that the size of the ordered structure (microballoon size and gap) of this hydrogel increases with the increase of pH value.In addition, this ordered gel network has magnetic, can regulate anisotropy with the variation in magnetic field.
The preparation of the sensitive ordered photolytic activity hydrogel of embodiment 10.pH value
Adopt template among the embodiment 2.(about 8 nanometers of CdS particle diameter, the solid content 5%) dissolving in the nano-tube/CdS aqueous dispersions of 20% sodium acrylate, 1.5% acrylamide, 0.2% methylene-bisacrylamide, 0.02% ammonium persulphate mixes.Orderly template immersed wherein to template be transparence.Logical nitrogen deoxygenation is 40 minutes under the normal temperature, is warming up to 60 ℃ of polymerizations 1 hour, obtains template/gel composite.This mixture is dipped in ultrasonic 40 minutes removal templates in 5% hydrofluoric acid, washing then, drying at room temperature obtains the ordered big hole polymer gel.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly, shows to have ordered structure in the gel, and this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel changes with the ionic strength variation of pH value and solution.The visible transmission spectrum of different pH values time hydrogels shows that the size of the ordered structure (microballoon size and gap) of this hydrogel increases with the increase of pH value.
The preparation of the sensitive ordered photolytic activity hydrogel of embodiment 11.pH value
The template that adopts is with embodiment 2.To prepare 5% sodium acrylate, the deionized water solution of the ammonium persulphate of 15% acrylamide, 0.2% methylene-bisacrylamide and 0.03% (with respect to monomer).Orderly template immersed in the mixing solutions to template be transparence.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, is warming up to 60 ℃ of polymerizations 1 hour, obtains template/gel composite.This mixture is dipped in ultrasonic 40 minutes removal templates in 40% hydrofluoric acid, washing then, drying at room temperature obtains the ordered big hole polymer gel.The xerogel resin is dipped in the 2M chromium nitrate solution, makes Cd through ion-exchange
2+Enter in the gel net, feed H again
2It is CdS nano particle about 20 nanometers that S gas obtains particle diameter by sulfuration.This gel resin is the yellow transparent shape in dry state, and suction presents transparent bright-colored after rising greatly, shows to have ordered structure in the gel, and this is the Bragg scattering result that ordered arrangement produces.The visible transmission spectrum of different pH values time hydrogels shows that the size of the ordered structure (microballoon size and gap) of this hydrogel increases with the increase of pH value.
The preparation of the sensitive ordered photolytic activity hydrogel of embodiment 12.pH value
The template that adopts is with embodiment 2.Preparation 6% sodium acrylate, 20% acrylamide, 0.3% methylene-bisacrylamide, the deionized water solution of 0.15% ammonium persulphate and 5% acrylamido nitrogen benzide.Orderly casement plate immersed wherein to template be transparence.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, obtains template/gel composite in 1 hour 50 ℃ of polymerizations then.This mixture is dipped in ultrasonic 20 minutes removal templates in 10% hydrofluoric acid, and washing, drying at room temperature obtain ordered gel resin then.This gel resin is the water white transparency shape in dry state, and after suction was risen greatly, the hole was in open state in order, and the size in hole changes with the ionic strength variation of pH value and solution.
Embodiment 12. prepares the sensitive ordered macropore hydrogel of pH value with polymer template
Adopt seed emulsion polymerization to prepare the monodisperse polystyrene corpuscle emulsion, mean particle dia is controlled in the 50-800 nanometer.Drying at room temperature above-mentioned emulsion (250 nanometer) obtains orderly polystyrene moulding.The sodium acrylate aqueous solution of preparation 10%, 20% acrylamide, 0.3% methylene-bisacrylamide, the aqueous solution of 0.15% ammonium persulphate.Orderly template immersed wherein to template be transparence, the ratio of template and monomer mixed solution is in very large range adjustable, and being immersed in fully in the mixed solution with template is benchmark.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, obtains template/gel composite in 1 hour 50 ℃ of polymerizations.This mixture is dipped in ultrasonic 60 minutes removal templates in the trichloromethane, uses ethanol, water washing, drying at room temperature then, obtain the ordered big hole polymer gel.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly.Bright-colored shows in the large pore gel aperture homogeneous and arranges in order that this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel changes with the ionic strength variation of pH value and solution.
Embodiment 13. is that template prepares the sensitive ordered macropore hydrogel of pH value with hud typed colloid crystalline substance
Prepare hud typed monodisperse polystyrene emulsion (intended diameter 300 nanometers are examined and are that polystyrene, shell are the multipolymer of vinylbenzene and ethyl propenoate, and the two mass ratio is 1: 3 in the design shell, thick 20 nanometers of design shell) with the seeded emulsion polymerization method.This emulsion of drying at room temperature obtains orderly template.The sodium acrylate aqueous solution of preparation 10%, 20% acrylamide, 0.3% methylene-bisacrylamide, the aqueous solution of 0.15% ammonium persulphate.Orderly template immersed wherein to template be transparence, the ratio of template and monomer mixed solution is in very large range adjustable, and being immersed in fully in the mixed solution with template is benchmark.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, obtains template/gel composite in 1 hour 50 ℃ of polymerizations.This mixture is dipped in ultrasonic 60 minutes removal templates in the toluene, uses ethanol, water washing, drying at room temperature then, obtain the ordered big hole polymer gel.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly.Bright-colored shows in the large pore gel aperture homogeneous and arranges in order that this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel changes with the ionic strength variation of pH value and solution.The ordering size that the visible transmission spectrum of different pH values time hydrogels shows this hydrogel increases with the increase of pH value.Macropore in this gel is isolated each other, is not interconnected, and big hole pitch is from the gauge control by the diameter and the shell of nucleocapsid structure.
The preparation of the sensitive ordered hydrogel of embodiment 14. soda acids
The way of employing document (Qi Kai etc., Science Bulletin, 2000,45,267-269) prepared the orderly casement plate of orderly silicon-dioxide, its hole dimension is 250 nanometers.Prepare 5% sodium acrylate, 10% acrylamide, 0.15% methylene-bisacrylamide, the aqueous solution of 0.01% ammonium persulphate.Orderly casement plate immersed wherein to template be transparence.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, obtains template/gel composite in 1 hour 50 ℃ of polymerizations then.This mixture is dipped in ultrasonic 20 minutes removal templates in 10% hydrofluoric acid, and washing, drying at room temperature obtain ordered gel resin then.This resin is made up of gel micro-ball, and microballoon is crosslinked by chemical bond in the contact position, has hole between microballoon.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly, shows to have ordered structure in the gel, and this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel changes with the ionic strength variation of pH value and solution.The visible transmission spectrum of different pH values time hydrogels shows that the size of the ordered structure (microballoon size and gap) of this hydrogel increases with the increase of pH value.
The preparation of the orderly hydrogel of embodiment 15. temperature sensitivities
The way of employing document (Rong Jianhua etc., Science Bulletin, 2000,45,1627-1630) prepared the orderly casement plate of orderly polystyrene, its hole dimension is about 200 nanometers.With the 10%N-N-isopropylacrylamide, 3% acrylamide, 1% methylene-bis acryloyl ammonium, 10% ethanol, the aqueous solution of 0.02% diethoxy acetophenone.Orderly template immersed in the mixing solutions to template be transparence.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, is warming up to 60 ℃ of polymerizations 1 hour, obtains template/gel composite.This mixture is removed polystyrene with the tetrahydrofuran (THF) extracting, with the cleaning of second alcohol and water, drying at room temperature, obtain the ordered polymer gel resin then.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly, shows to have ordered structure in the gel, and this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel raises to send out with temperature and reduces.The visible transmission spectrum of differing temps hydrogel shows that the size of the ordered structure (microballoon size and gap) of this hydrogel reduces with the temperature rising.
The preparation of the orderly hydrogel of embodiment 16. anisotropy temperature sensitivities
The way of employing document (Rong Jianhua etc., Science Bulletin, 2000,45,1627-1630) prepared the orderly casement plate of orderly polystyrene, its hole dimension is about 200 nanometers.In the hole, inject mineral oil, 105 ℃ along X-axis unilateral stretching sample, keeping cooling fast under the stretched state, the state of deformation is fixed up, removes mineral oil with ethanol then, just obtain axiolitic hole, the ratio of major and minor axis can reach 5, and its value can be controlled by tensile deformation.The major-minor axis ratio of used deformation pattern hole is 2.5 in this example.Repeat in the embodiment preparation gelation process in 15, obtain the ordered polymer gel resin.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly, shows to have ordered structure in the gel, and this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel changes with the ionic strength variation of pH value and solution.The visible transmission spectrum of different pH values time hydrogels shows that the size of the ordered structure (microballoon size and gap) of this hydrogel increases with the increase of pH value.At XY, XZ, the spectral results on the YZ plane is inconsistent, illustrates that it has anisotropy.
The anisotropy ordered big hole hydrogel of embodiment 17.pH value susceptibility
Set out with the orderly template of the polystyrene among the embodiment 12, inject mineral oil by the way that vacuumizes therein, be warming up to 105 ℃ then, along Z-direction compression 50%, the quick state that cools off deformation is fixed up under the compressed state keeping, remove mineral oil with ethanol then, just obtain the anisotropy template, anisotropy is controlled by compression degree.Repeat the preparation gelation process among the embodiment 13, obtain the ordered polymer gel resin.This gel resin is the water white transparency shape in dry state, and suction presents transparent bright-colored after rising greatly, shows to have ordered structure in the gel, and this is the Bragg scattering result that ordered arrangement produces.The swelling degree of this gel changes with the ionic strength variation of pH value and solution.The visible transmission spectrum of different pH values time hydrogels shows that the size of the ordered structure (microballoon size and gap) of this hydrogel increases with the increase of pH value.At XY, XZ, the spectral results on the YZ plane is inconsistent, illustrates that it has anisotropy.
The preparation of the sensitive ordered mesoporous hydrogel of embodiment 18.pH value
Adopt way (Brinker, the C.J. of document; Lu Y.; Sellinger, A.; Fan, H., " Evaporation-induced self-assembly:nanostructures made easy ", Adv.Mater., 1999,11,579-85) prepared ordered nano silicon-dioxide hole, the size in hole is regulated in the 2-30 nanometer range, the arrangement mode in hole can be in column, six sides, cube, sheet is crystalline, regulates between the structures such as co-continuous.The sodium acrylate of preparation 5%, 10% acrylamide, 0.15% methylene-bisacrylamide, the aqueous solution of 0.01% ammonium persulphate.Column, hole are of a size of 20 nano ordered casement plates to be immersed wherein to template and is transparence.Logical nitrogen deoxygenation is 20 minutes under the normal temperature, obtains template/gel composite in 1 hour 50 ℃ of polymerizations then.This mixture is dipped in ultrasonic 20 minutes removal templates in 10% hydrofluoric acid, and washing, drying at room temperature obtain ordered gel resin then.This gel resin is the water white transparency shape in dry state, and after suction was risen greatly, the hole was in open state in order, and the size in hole changes with the ionic strength variation of pH value and solution.
Embodiment 19. is that template prepares the sensitive ordered macropore hydrogel of pH value with hud typed colloid crystalline substance
(intended diameter 300 nanometers are examined and are that polystyrene, shell are vinylbenzene, ethyl propenoate and DAAM[CH to prepare hud typed monodisperse polystyrene emulsion with the seeded emulsion polymerization method
2=CH-NH-CH (CH
2)
2-CH
2COCH
3] multipolymer, the two mass ratio is 1: 3: 0.1 in the design shell, design shell thick 30 nanometers), in this emulsion, add ADDH[(NH
2-NH-CO)
2(CH
2)
3], making the ADDH/DAAM mol ratio is 1: 1.This emulsion of drying at room temperature obtains orderly nucleocapsid crosslinking structure.In the aqueous sodium hydroxide solution with ordered structure immersion 20%, be warming up to 50 ℃ of hydrolysis ester groups, obtain gel composite.This mixture is dipped in ultrasonic 40 minutes removal polystyrene core in the toluene, obtains the ordered big hole polymer gel.This gel resin is the water white transparency shape in dry state, and suction is risen and presented transparent bright-colored after big, shows in the large pore gel aperture homogeneous and arranges in order, and this is the Bragg scattering result that ordered arrangement produces.Further the result shows that macropore is isolated mutually.The swelling degree of this gel changes with the ionic strength variation of pH value and solution.The ordering size that the visible transmission spectrum of different pH values time hydrogels shows this hydrogel increases with the increase of pH value.
Claims (4)
1. sensitive ordered porous gel, the size homogeneous in hole, and regularly arranged in the space, hole dimension is 10
0Nanometer-10
1The micron dimension scope is adjustable; Connective controlled between the hole; The basic framework of hole wall is the sensitive polymer gel resin in the gel; Described sensitive polymer gel resin is monomer or adopts conventional mass polymerization or solution polymerization process polymerization to obtain polymer gel with comonomer; The monomeric ratio of described monomer and copolymerization is 1～10: 1 weight percent;
Described monomer comprises following monomer or its mixture:
1. can form the monomer and the salt derivative thereof of polymkeric substance with electrical charge rejection effect: contain carboxyl monomer, contain sulfonic monomer, contain the monomer of phosphate, the vinyl monomer that contains positive charge or two kinds of simultaneous monomers of electric charge;
2. can form monomer: the acrylamide of vinyl alcohol and derivative thereof, hydroxyl and derivative thereof, acrylamide and derivative thereof, acrylate and derivative thereof, ethylene oxide/propylene oxide class, the compound that contains many carboxyls or hydroxyl and derivative thereof, chitosan derivatives, Heterobicyclic compounds with hydrogen bond force effect polymkeric substance;
3. functional monomer: azo monomer, the monomer, the monomer that can form electric conductive polymer, thiophene phenols, imidazoles, alkynes class, the arsenic that contain two alkynes structures are coughed up, aniline;
Described comonomer is vinyl monomer and salt derivative, dienes monomer and salt derivative thereof or their mixture.
2. according to a kind of sensitive ordered porous gel of claim 1, it is characterized in that the described monomer that can form the polymkeric substance with electrical charge rejection effect is vinylformic acid, methacrylic acid and its esters, vinylbenzenesulfonic acid and its esters, dimethylaminoethyl methacrylate.
3. according to a kind of sensitive ordered porous gel of claim 1, it is characterized in that it is acrylamide, N that described energy forms the monomer with hydrogen bond force effect polymkeric substance, the acrylamide of N N-isopropylacrylamide, hydroxyl and derivative thereof, Hydroxyethyl acrylate and derivative thereof, ethylene oxide/propylene oxide class mix monomer.
4. according to a kind of sensitive ordered porous gel of claim 1, it is characterized in that described comonomer is acrylic amide, vinylformic acid and salt derivative thereof, acrylic ester monomer.
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| CN101654495B (en) * | 2009-07-06 | 2012-10-17 | 陕西科技大学 | Preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel |
| CN102558601B (en) * | 2012-01-04 | 2013-09-25 | 上海理工大学 | Preparation method of high-strength porous chitosan microcarrier |
| CN109467628B (en) * | 2018-10-26 | 2020-06-12 | 上海交通大学 | Preparation method of polymer composite nanoparticles |
| CN110229271B (en) * | 2019-06-19 | 2021-06-29 | 哈尔滨工业大学（深圳） | Preparation and application of micro magnetic rod-shaped gel for measuring viscosity of trace liquid |
| CN110404514B (en) * | 2019-06-28 | 2021-12-21 | 江苏大学 | Method for preparing high-density crown ether site porous adsorbent by surface photo-initiation |
| CN110818833B (en) * | 2019-11-12 | 2021-08-31 | 东华大学 | Construction method of oriented ordered pore canal in elastic hydrogel |
| CN113637180B (en) * | 2020-05-11 | 2023-12-05 | 清华-伯克利深圳学院筹备办公室 | Optically anisotropic hydrogel, preparation method, production system thereof and optical device |
| CN112791511B (en) * | 2020-12-21 | 2023-04-04 | 扬州大学 | Oriented porous structure material for filtration and preparation method thereof |
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