CN1362439A - Prepn of ordered porous polymer gel - Google Patents
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- CN1362439A CN1362439A CN 01100390 CN01100390A CN1362439A CN 1362439 A CN1362439 A CN 1362439A CN 01100390 CN01100390 CN 01100390 CN 01100390 A CN01100390 A CN 01100390A CN 1362439 A CN1362439 A CN 1362439A
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Abstract
The preparation method of polymer ordered porous gel includes the following steps: preparing silicon dioxide monodisperse microparticle dispersion system; soaking (wt%) 0.01%-5% of initiating agent, 1-30% of cross-linking agent and 98.99-65% of monomer and polymer in which polymer is 1-30% of monomer weight into silicon dioxide template pore, initiating and polymerizing to obtain ordered inorganic/organic compound; extracting non-crosslinking polymer being in the copound, if in the uses monomer the benzene ring is contained, mixing the compound and concentrated sulfuric acid according to the mass ratio of 10:1-1:100 and making sulfonation treatment at 20-150 deg.C and soaking said compound in fluohydric acid to remove silicon dioxide template so as to obtain the ordered gel resin.
Description
The present invention relates to a kind of preparation method of polymer porous material.
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 controllable aperture built in the characteristics of several nanometers to the hundreds of nanometer, its order can promote the process of material transfer effectively, thereby it is significant in some practical application (such as absorption, sepn process, catalyzed reaction etc.), and its submicron is given its special optical characteristics with interior size characteristic, might play a significant role in information industry as photonic bandgap material.Another kind of material---gel resin has extensive use because of its superpower affinity and high porosity in all many-sides, as ion exchange resin, water-absorbing material, soil moisturizing agent, sealant, sanitary care article etc.
Ordered porous materials generally adopts the template preparation.People such as A.Stein in 1998 and D.J.Pine are that to have prepared the aperture be the TiO of hundreds of nanometer to template with the polystyrene colloid crystalline substance respectively
2, ZrO
2, Al
2O
3XH
2Ordered porous materials (the Brian T.Holland that O and silicon-dioxide etc. are inorganic, ChristopherF.Blanford, Andreas Stein, " Synthesis of Macroporous Minerals with HighlyOrdered Three-Dimensional Arrays of Spherical Voids ", Science1998,281,538; G.Subramanian, Vinothan N.Manoharan, James D.Thorne, andDavid J.Pine, " Ordered Macroporous Materials by Colloidal Assembly:APossible Route to Photonic Bandgap Materials ", Adv.Mater.1999,11,1261).These ordered porous materials skeletons are inorganics, though have some photoelectric characteristic, it is carried out functional modification still a lot of difficulties.
S.H.Park, it is that to have prepared the aperture be the orderly hole of the urethane film (S.H.Park of 200-3000nm to template that Y.Xia has reported with the polystyrene colloid crystalline substance, Y.Xia, " Fabrication of Three-Dimensional Macroporous Membranes with Assemblies of Microspheres asTemplates ", Chem.Mater.1998,10,1745).They inject the template hole with the Polyurethane precursor, use uv-light polymerization, form Polyurethane.Go polystyrene is molten with toluene again, promptly obtain the ordered porous material of Polyurethane.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 Thomas E.Mallouk utilize inorganic template, be that to be that the silicon dioxide colloid of 35nm is brilliant prepared order mesoporous polydivinylbenezene and polydimethyl vinylformic acid glyceryl ester or both multipolymers (Stacy A.Johnson for template to particle diameter, Patricia J.Ollivier, Thomas E.Mallouk, " OrderedMesoporous Polymers of Tunable Pore Size from Cooooedal Silica Templates ", Science 1999,283,963), these several orderly pore polymers have 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 be continuous variation with two kinds of monomeric proportioning differences between 15-35nm.
The above polymer ordered porous materials of Jie Shaoing, all be can not deformation hard hole, lack functional groups on the surface in hole, also lack response characteristic simultaneously to the outfield, limited its range of application greatly.
The orderly hole gel resin that the present invention relates to also adopts silicon dioxide colloid crystal template method preparation, and its space geometry structure and above-mentioned materials have similarity, all is made up of regularly arranged honeycomb hole.But its difference is that the hole wall of this ordered porous materials has passed through functionalization, has functional groups, thereby has the solvent affinity.Can expand the formation gel behind this ordered porous materials lyosorption, and still can guarantee the ordered arrangement structure of macropore.Gel is in drying process, and macropore can dwindle distortion gradually until closure, and material becomes water white transparency.This expansion and contraction process are reversible.
About orderly hydrogel material, people such as Osada once reported hydrogel (the Atsushi Matsuda that contains the aggregate ordered structure, Jun ' ichi Sato, Hidekazu Yasunage, and Yoshihito Osada, " Order-Disorder Transition of a Hydrogel Containing an n-Alkyl Acrylate ", Macromolecules 1994,27,7695-7698; Y.Tanaka, Y.Kagami, A.Matsuda, andY.Osada, " Thermoreversible Transition of the Tensile Modulus of a Hydrogelwith Ordered Aggregates ", Macromolecules 1995,28,2574-2576), and study the temperature sensitive reversible transition characteristic of its mechanical strength, provided the structural models of this gel simultaneously.The result shows that the ordered structure in this gel derives from the self-assembly of hydrophilic and oleophilic aggregate, and the ordered structure characteristic dimension is in nanometer scale.People such as Asher have also reported a kind of ordered gel mixture.(Jesse?M.Weissman，Hari?B.Sunkara，Albert?S.Tse，Sanford?A.Asher，“ThermallySwitchable?Periodicities?and?Diffraction?from?Mesoscopically?OrderedMaterials”，Sciences?1996，274，959-960)。Single dispersed latex microparticulate is in water miscible monomer, and in drying process, particulate is piled up and is formed into ordered structure (being referred to as the colloid crystalline substance).Then, cause water-soluble monomer and carry out polymerization crosslinking, thereby above-mentioned ordered structure is fixed up, just made the ordered gel mixture.The preparation of this ordered structure is wayward, and does not have larger-size hole in the structure.Recently, Yang Zhenzhong etc. prepare a kind of polymer ordered hydrogel (patent in the application, 2000).The colloid crystalline substance that forms after to single dispersed latex particulate drying by a step chemical reaction carries out functionalization, finish 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 ordered gel.But the ordered structure of this gel is made of spheroidal particle.
Basic framework all is made of the polymer beads of ordered arrangement in the above mentioned ordered gel, voidage and hole dimension are all less relatively, be unfavorable for the transmission of material and the recombination process between material, as with compound assemblings such as other functional substance especially larger-size nanoparticle.
Basic framework in the ordered gel among the present invention then is made of the polymkeric substance thin-walled, hole between skeleton is ordered arrangement, and size is bigger, by changing ambient conditions, realize easily the regulation process of the connectedness between orderly pore morphology, size and hole, these characteristics all help the transmission of material and further with the compound assembling of other material.Its structure as shown in Figure 1, the ordered gel resin of this structure is not seen report as yet.
The orderly hole gel resin that the present invention relates to is a kind of macropore Ordered Materials, and hole wall is formed by containing sulfonated polystyrene superpolymer gel, and gel resin can swelling be an ordered gel in polar solvent.
Gel resin hole dimension homogeneous, adjustable in the 50-1000nm scope;
Hole wall is made up of superpolymer, wherein contains sulfonated polystyrene, and polystyrene is crosslinked by sulfuryl;
Polar solvent can be a water, alcohols, and carboxylic-acid, nitrile, amidess etc. are preferably water, ethanol, vinylformic acid, acetonitrile, N, N dimethyl formamide; Preferential water, ethanol, N, the N dimethyl formamide selected.
Polymer ordered hole of the present invention gel has the dual nature of ordered porous materials and gel resin.Gel aperture homogeneous and arrangement are orderly, and this reduces resistance to flow significantly with the utmost point, increase the process of material transfer, and be significant for practical application (such as absorption, catalyzed reaction).And pore structure can realize by the variation that is deployed into closure state with the variation of environment.This characteristic shows that this material has the solvent irritability, and promptly available solvent (water or other solvent) comes the on off state of control punch.In addition, there is double-pore structure in the gel of hole in order, except orderly macropore, also has small structure on the polymkeric substance hole wall, aperture form and size can be regulated by kind and the concentration of selecting additive, and these characteristics are significant as microreactor for it.
The present invention relates to adopt the silicon dioxide colloid with ordered structure brilliant is template, by infiltration, polymerization, go template, sulfonation (or infiltration, polymerization, sulfonation, go template) process to prepare polymer ordered large pore gel resin, gel resin can form ordered gel in solvent (as water, ethanol etc.).The present invention is characterised in that and adds monomer and linking agent simultaneously in the template hole, form crosslinked polymkeric substance, and it is carried out functionalization, thereby make and have affinity groups on the matrix hole wall and have the solvent affinity, have crosslinked group simultaneously, make that the product after the modification can form gel in solvent.This affinity groups can be sulfonic group, amino, carboxylic acid group etc., plays the effect that combines or react with solvent, molecule, ion or other material.Crosslinked group can be sulfuryl
The ordered porous gel resin that the present invention relates to has ordered porous materials and two kinds of properties of materials of gel resin.
The preparation method of polymer ordered hole of the present invention gel carries out (as shown in drawings) in the following order:
1. with St ber method (W.St ber, A.Fink, E.Bohn, " Controlled Growth ofMonodisperse Silica Spheres in the Micron Size Range ", Journal of Colloid ﹠amp; Interface Science 1968,26:62-69) preparation silicon-dioxide list disperse particles dispersion system, the orderly accumulation of monodisperse polymer particulate can obtain by monodisperse system is centrifugal or methods such as sedimentation, seasoning, and its structure is seen in the accompanying drawing shown in the i.
2. monomer, 0.01%-5% initiator, 1-30% linking agent and 1-30% polymkeric substance (with respect to amount of monomer) are immersed in the silica template hole, initiated polymerization obtains inorganic/organic composite under certain condition, and its structure is seen in the accompanying drawing shown in the ii.This process is the 1st step in the accompanying drawing.But the monomer of initiated polymerization comprises vinylbenzene, Vinylstyrene, vinyl cyanide, acrylate, acrylic amide etc. or its mixture.Initiator can be radical initiator (AIBN, BPO etc.), light trigger, radiation initiators, active ion initiator system etc.Polymkeric substance is for dissolving in monomeric homopolymer, multipolymer (as PS, ABS, SBS, SEABS, PEO-PS-PEO etc.), and the adding of this polymkeric substance can impel the formation of aperture in the polymeric matrix, to help the removal of template;
3. the no cross-linked polymer in the mixture of the first step preparation is extracted under certain condition with appropriate solvent, so that in polymeric matrix, form aperture;
4. the mixture and the vitriol oil (or oleum) are pressed mass ratio 10: 1-1: mix between 100, carrying out sulfonation under 20-150 ℃ (being preferably 20-99 ℃) handles, mixture swellable after the sulfonation, its structure see in the accompanying drawing shown in the iii that this process is the 2a step in the accompanying drawing.Generate sulfonic group and sulfuryl on the polystyrene molecular chain, make polymkeric substance have the solvent affinity and solvent insoluble; Sulfonation is handled and also can be carried out under microwave heating condition.
5. the mixture that affinity is handled immerses in the hydrofluoric acid and removes silica template, obtains orderly gel resin, and its structure is shown in v in the accompanying drawing, and this process is the 3a step in the accompanying drawing.
(or, be that 2b step and 3b go on foot among the figure, promptly remove template earlier and again polymer network is carried out functionalization that the porous polymer network structure of going to obtain after the template is seen in the accompanying drawing vi) with 2a and 3a step exchange
6. gel resin is immersed back swelling in water or other solvent, form ordered gel, be reduced to gel resin behind gel dehydration or other solvent, this process is reversible.
Preparation method of the present invention and products characteristics are as follows:
● experiment required equipment, simple to operate: template can prepare at normal temperatures, and monomer polymerization adopts the general polymerization condition.
● it is big to be used for the scope that the polymeric monomer can select altogether, comprises styrenic, vinyl cyanide, esters of acrylic acid, acrylic amide etc.
● can regulate the aperture of gel simply by the particle diameter of control template, the aperture is 10
1-10
4Controlled in the nm scope;
● ordered gel resin suction or other polar solvent after form ordered gel.Be reduced to gel resin behind this gel dehydration or other solvent, this process is reversible;
● the ordered gel among the present invention has double-pore structure, except that orderly macropore, can form aperture on the polymeric matrix.When replacing homopolymer to immerse in the template hole with monomer and initiator etc. with segmented copolymer, finally can form orderly aperture on the polymeric matrix, the interaction according between relative concentration and polymkeric substance and monomer can be structures such as column, stratiform, vermiform.Also can adopt whipping agent commonly used such as ammonia, carbonic acid gas, sodium bicarbonate, volatile salt in addition, bicarbonate of ammonia, urea etc. form aperture on the polymer backbone matrix.
● the present invention has universality, can be used to the polymkeric substance of synthetic and other type of functionalization, as synthetic polyacrylonitrile.The functionalization such as carboxylation of orderly hole and amidation thereof, carboxylation modification, polymethylmethacrylate.
● the ordered gel resin among the present invention can be further used as other functional three-dimensional order complex construction of template for preparing.
Material that the present invention relates to and preparation method thereof can be used as sorbing material, support of the catalyst, microreactor, and can be used for synthetic other functional material, matrix material, as orderly electro-conductive material, orderly magneticsubstance, optical material etc.
Brief Description Of Drawings
Fig. 1 shows orderly large pore gel preparation process (i: silica template; Ii: orderly silica/polymer composite; Iii: sulfonation mixture; Vi: orderly pore polymer network; V: the ordered big hole hydrogel)
The preparation of EXAMPLE Example 1. ordered big hole hydrogels
Be equipped with monodisperse silica particulate aqueous based dispersions with St ber legal system, mean particle dia is 280nm.The above-mentioned dispersion system of drying at room temperature obtains orderly silica template.Orderly template is soaked in monomer styrene, 0.5% (to monomer) initiator A IBN, 5% (to monomer) linking agent Vinylstyrene homogeneous mixture solotion, to the template shape that is translucent.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.Obtained inorganic/organic composite in 12 hours 60 ℃ of polymerizations then.This mixture is dipped in 12 hours removal templates in 40% hydrofluoric acid, and washing, drying at room temperature obtain the ordered big hole polymer network then.Scanning electron microscope result shows that the sample of this moment has orderly pore structure, and the aperture is about 180nm, less than the particle diameter of silicon-dioxide bead in the template.Again with its with the 95-98% vitriol oil 80 ℃, handled 2 hours under stirring, washing, drying at room temperature obtain ordered big hole gel resin (as the b synthetic route in the accompanying drawing).This gel resin is the yellow transparent shape in dry state, and suction presents transparent bright-colored after rising greatly, and water regain is 3 times of original weight.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.Electronic Speculum result shows that the aperture of hydrogel is about 280nm.In synthetic route b process, because the orderly pore polymer network before the sulfonation is a short texture, intensity is less, thus in sulfonation process, easily cracked under stirring action, can only obtain the fritter product.The preparation of embodiment 2. ordered big hole hydrogels
Template used and polymerization obtains the method for organic/inorganic composite with embodiment 1.Then with this mixture with concentration 95-98% sulfuric acid 80 ℃, handled 2 hours under stirring, with a large amount of deionized water rinsings up to neutrality, and drying at room temperature.Again it is dipped in 40% hydrofluoric acid 12 hours and removes silica template, after washing, drying at room temperature obtain ordered big hole gel resin (as a route in the accompanying drawing).This gel resin is the yellow transparent 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 water regain is 4 times of original weight.Scanning electron microscope result shows the hole arrangement in order, and hole dimension is 280nm.In synthetic route a, it is higher to remove template composite strength before, is difficult for fragmentation during sulfonation in whipping process, thereby can accesses relatively large product.The preparation of embodiment 3. ordered big hole hydrogels
Be equipped with monodisperse silica particulate aqueous based dispersions with St ber legal system, mean particle dia is 80nm.This dispersion system of vacuum filtration in funnel makes the silicon-dioxide spherolite be deposited on the aperture less than on the polycarbonate membrane of 50nm and form orderly template.This template is soaked in monomer styrene, 0.5% (to monomer) initiator A IBN, 5% (to monomer) linking agent Vinylstyrene homogeneous mixture solotion, to the template shape that is translucent.Obtained inorganic/organic composite in 10 hours 70 ℃ of polymerizations.Then with this mixture with 80% sulfuric acid 90 ℃, handled 2 hours under stirring, with a large amount of deionized water rinsings up to neutrality, and drying at room temperature.Again it is dipped in 40% hydrofluoric acid 10 hours and removes silica template, after washing, drying at room temperature obtain the ordered big hole gel resin.This gel resin is the yellow transparent 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 water regain is about 3.5 times of original weight.Scanning electron microscope result shows the arrangement of hydrogel mesopore in order, and hole dimension is about 70nm.The preparation of embodiment 4. ordered big hole hydrogels
Template used and polymerization obtains the method for organic/inorganic composite with embodiment 1.(SO dissociates with cigarette sulfuric acid with this mixture then
3Content is 20-25%) 60 ℃, handled 2 hours under stirring, with a large amount of deionized water rinsings up to neutrality, and drying at room temperature.Again it is dipped in 40% hydrofluoric acid 12 hours and removes silica template, after washing, drying at room temperature obtain ordered big hole gel resin (as a route in the accompanying drawing).This gel resin is the yellow transparent 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 water regain is 4 times of original weight.Scanning electron microscope result shows the hole arrangement in order, and hole dimension is 280nm.In synthetic route a, it is higher to remove template composite strength before, is difficult for fragmentation during sulfonation in whipping process, thereby can accesses relatively large product.The preparation of embodiment 5. ordered big hole hydrogels
Template used and polymerization obtains the method for organic/inorganic composite with embodiment 1.(SO dissociates with cigarette sulfuric acid with this mixture then
3Content is 50-60%) 40 ℃, handled 2 hours under stirring, with a large amount of deionized water rinsings up to neutrality, and drying at room temperature.Again it is dipped in 40% hydrofluoric acid 12 hours and removes silica template, after washing, drying at room temperature obtain ordered big hole gel resin (as a route in the accompanying drawing).This gel resin is the yellow transparent 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 water regain is about 4 times of original weight.Scanning electron microscope result shows the hole arrangement in order, and hole dimension is 280nm.In synthetic route a, it is higher to remove template composite strength before, is difficult for fragmentation during sulfonation in whipping process, thereby can accesses relatively large product.The preparation of embodiment 6. diplopore hydrogels
Template is with embodiment 1, with its be dipped in monomer styrene, 0.5% (to monomer) initiator A IBN, 5% (to monomer) linking agent Vinylstyrene and 10% (to monomer) polystyrene (Mn=58000, in homogeneous mixture solotion BASF) to the template shape that is translucent.Obtained inorganic/organic composite in 12 hours 60 ℃ of polymerizations then.In apparatus,Soxhlet's with added polystyrene before uncrosslinked in the chloroform extraction mixture and the polymerization 60 hours.The processing of carrying out functionalization and removing template by mixture after 1 pair of extraction of embodiment obtains the diplopore gel resin then.This gel resin is the yellow transparent 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 water regain is 6 times of original weight, and scanning electron microscope result also shows the macropore ordered arrangement, and hole dimension is 280nm.Transmission electron microscope results shows and has unordered aperture on the polymeric matrix that the aperture is less than 10nm.The characteristics of this process are that the polystyrene that adds before the polymerization can impel the more aperture of formation in the polymer network, makes the easier removal of template shorten preparation cycle, and product to be a double-pore structure.The preparation of embodiment 7. diplopore hydrogels
Template is with embodiment 1, with its be dipped in monomer styrene, 0.5% (to monomer) initiator A IBN, 5% (to monomer) linking agent Vinylstyrene and 10% (to monomer) polystyrene (Mn=58000, in homogeneous mixture solotion BASF) to the template shape that is translucent.Obtained inorganic/organic composite in 12 hours 60 ℃ of polymerizations then.In apparatus,Soxhlet's with added polystyrene before uncrosslinked in the chloroform extraction mixture and the polymerization 60 hours.The processing of carrying out functionalization and removing template by mixture after 2 pairs of extractions of embodiment obtains the diplopore gel resin then.This gel resin is the yellow transparent shape in dry state, presents transparent bright-colored after the suction, shows in the large pore gel aperture homogeneous and arranges in order, and water regain is 6.6 times of original weight, and scanning electron microscope result also shows the macropore ordered arrangement, and hole dimension is 280nm.Compare with embodiment 5, the products obtained therefrom piece is big and water regain is high.The preparation of embodiment 8. ordered dual-pore hydrogels
Orderly template among the embodiment 1 is soaked in the homogeneous mixture solotion of monomer styrene, 0.5% (to monomer) initiator A IBN, 5% (to monomer) linking agent Vinylstyrene and 15% (to monomer) styrene-butadiene block copolymer SB (molecular weight 10000, wherein butadiene content is 30%) to the template shape that is translucent.Carry out polymerization, extraction, functionalization and removing template reaction by embodiment 6 then and obtain the ordered dual-pore gel resin.This gel resin is the yellow transparent shape in dry state, presents transparent bright-colored after the suction, shows in the large pore gel aperture homogeneous and arranges in order, and water regain is 6.5 times of original weight.Scanning electron microscope result shows the hole ordered arrangement, and hole dimension is 280nm.Transmission electron microscope results shows that existence is the aperture that hexangle type is arranged on the polymeric matrix, and the aperture is about 20nm.The preparation of embodiment 9. ordered dual-pore hydrogels
Orderly template among the embodiment 1 is soaked in monomer styrene, 1.0% (to monomer) initiator B PO, 10% (to monomer) linking agent Vinylstyrene and 15% (to monomer) vinylbenzene-ethylene oxide ammonium salt segmented copolymer SE1030A (vinylbenzene segment molecule amount 1000, ethylene oxide segment molecule amount is 3000, ethylene oxide part ammonium salt-containing end group, Goldschmidt A.G. company produces) homogeneous mixture solotion in to the template shape that is translucent.80 ℃ of polymerizations 10 hours.Then by embodiment 6 extract, process such as functionalization and removing template obtains the ordered dual-pore gel resin.This gel resin is the yellow transparent 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 water regain is 6 times of original weight.Scanning electron microscope result shows the hole ordered arrangement, and hole dimension is 270nm.Transmission electron microscope results shows on the polymeric matrix to exist and is the aperture that hexangle type is arranged, and the aperture is about 21nm, the columnar structure of the six sides accumulation of corresponding segmented copolymer.The preparation of embodiment 10. ordered dual-pore hydrogels
Orderly template among the embodiment 1 is soaked in monomer styrene, 1.0% (to monomer) initiator B PO, 10% (to monomer) linking agent Vinylstyrene and 25% (to monomer) vinylbenzene-ethylene oxide ammonium salt segmented copolymer SE1030A (vinylbenzene segment molecule amount 1000, ethylene oxide segment molecule amount is 3000, ethylene oxide part ammonium salt-containing end group, Goldschmidt A.G. company produces) homogeneous mixture solotion in to the template shape that is translucent.The ratio of template and monomer mixture is in very large range adjustable, and being immersed in fully in the mixture with template is benchmark.Carry out polymerization by embodiment 9 then, extract, functionalization and removing template reaction obtain ordered dual-pore and obtain the ordered big hole gel resin.This gel resin is the yellow transparent 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 water regain is 6 times of original weight.Scanning electron microscope result shows the hole ordered arrangement, and hole dimension is 270nm.Transmission electron microscope results shows on the polymeric matrix and to have the small duct that is layered arrangement, and interlamellar spacing is about 20nm, corresponding the lamellar structure structure of segmented copolymer.The preparation of embodiment 11. ordered dual-pore hydrogels
Orderly template among the embodiment 1 is soaked in monomer styrene, 1.0% (to monomer) initiator B PO, 10% (to monomer) linking agent Vinylstyrene and 40% (to monomer) vinylbenzene-ethylene oxide ammonium salt segmented copolymer SE1030A (vinylbenzene segment molecule amount 1000, ethylene oxide segment molecule amount is 3000, ethylene oxide part ammonium salt-containing end group, Goldschmidt A.G. company produces) homogeneous mixture solotion in to the template shape that is translucent.Carry out polymerization by embodiment 9 then, extract, functionalization and removing template reaction obtain the ordered dual-pore gel resin.This gel resin is the yellow transparent 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 water regain is 6.5 times of original weight.Scanning electron microscope result shows the hole ordered arrangement, and hole dimension is 280nm.Transmission electron microscope results shows on the polymeric matrix to exist and is vermiform aperture, and the aperture is about 21nm, corresponding the co-continuous phase structure of segmented copolymer.The preparation of embodiment 12. ordered big hole hydrogels
Template used and polymerization obtains the method for organic/inorganic composite with embodiment 1.This mixture with concentration 95-98% sulfuric acid immersion treatment 2 hours, was handled 2 minutes with lowest power on MG-5529ST type LG temperature control spirit microwave oven then, with a large amount of deionized water rinsings up to neutrality, and drying at room temperature.Again it is dipped in 40% hydrofluoric acid 12 hours and removes silica template, after washing, drying at room temperature obtain ordered big hole gel resin (as a route in the accompanying drawing).This gel resin is the yellow transparent 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 water regain is 5 times of original weight.Scanning electron microscope result shows the hole arrangement in order, and hole dimension is 280nm.In synthetic route a, it is higher to remove template composite strength before, is difficult for fragmentation during sulfonation in whipping process, thereby can accesses relatively large product.The preparation of embodiment 13. polycomponent ordered big hole hydrogels
Orderly template among the embodiment 1 is soaked in styrene/acrylonitrile in the monomer mixture (60/40 weight ratio), 0.5% (to monomer) initiator A IBN, 5% (to monomer) linking agent Vinylstyrene homogeneous mixture solotion, to the template shape that is translucent.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.Obtained inorganic/organic composite in 12 hours 60 ℃ of polymerizations then.This mixture is dipped in 12 hours removal templates in 40% hydrofluoric acid, and washing, drying at room temperature obtain the ordered big hole polymer network then.Scanning electron microscope result shows that the sample of this moment has orderly pore structure, and the aperture is about 180nm, less than the particle diameter of silicon-dioxide bead in the template.The result shows that further hole wall presents Gradient distribution, near a sidewall enrichment polyacrylonitrile of silica spheres surface, and at hole wall internal layer enrichment polystyrene.With its with the 95-98% vitriol oil 80 ℃, handled 2 hours under stirring, washing, drying at room temperature obtain ordered big hole gel resin (as the b synthetic route in the accompanying drawing).This gel resin is the yellow transparent shape in dry state, and suction presents transparent bright-colored after rising greatly, and water regain is 7 times of original weight.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.Electronic Speculum result shows that the aperture of hydrogel is about 280nm.Spectroscopic analysis is the result show, contains sulfonic group in the sample, sulfuryl, and the carboxylic acid group, amide group, the former two comes from the phenyl ring sulfonation, and the latter two come from the result of itrile group in vitriol oil effect.The preparation of embodiment 14. polycomponent ordered big hole hydrogels
The orderly template of using among the embodiment 13 is handled through phenyl triethoxysilane, makes template ball surface be hydrophobicity.Repeat polymerization and last handling process among the embodiment 13, obtain the ordered big hole polymer network.Scanning electron microscope result shows that the sample of this moment has orderly pore structure, and the aperture is about 180nm, less than the particle diameter of silicon-dioxide bead in the template.The result shows that further hole wall presents Gradient distribution, near a sidewall enrichment polystyrene of silica spheres surface, and at hole wall internal layer enrichment polyacrylonitrile.With its with the 95-98% vitriol oil 80 ℃, handled 2 hours under stirring, washing, drying at room temperature obtain ordered big hole gel resin (as the b synthetic route in the accompanying drawing).This gel resin is the yellow transparent shape in dry state, and suction presents transparent bright-colored after rising greatly, and water regain is 7 times of original weight.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.Electronic Speculum result shows that the aperture of hydrogel is about 280nm.Spectroscopic analysis is the result show, contains sulfonic group in the sample, sulfuryl, and the carboxylic acid group, amide group, the former two comes from the phenyl ring sulfonation, and the latter two come from the result of itrile group in vitriol oil effect.The preparation of embodiment 15. polycomponent ordered big hole hydrogels
Orderly template among the embodiment 1 is soaked in styrene/acrylic ethyl ester in the monomer mixture (60/40 weight ratio), 0.5% (to monomer) initiator A IBN, 3% (to monomer) linking agent N, in the N methylene-bisacrylamide homogeneous mixture solotion, to the template shape that is translucent.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.Obtained inorganic/organic composite in 12 hours 60 ℃ of polymerizations then.This mixture is dipped in 12 hours removal templates in 40% hydrofluoric acid, and washing, drying at room temperature obtain the ordered big hole polymer network then.Scanning electron microscope result shows that the sample of this moment has orderly pore structure, and the aperture is about 180nm, less than the particle diameter of silicon-dioxide bead in the template.The result shows that further hole wall presents Gradient distribution, near a sidewall enrichment polyethyl acrylate of silica spheres surface, and at hole wall internal layer enrichment polystyrene.With its with the 95-98% vitriol oil 80 ℃, handled 2 hours under stirring, washing, drying at room temperature obtain ordered big hole gel resin (as the b synthetic route in the accompanying drawing).This gel resin is the yellow transparent shape in dry state, and suction presents transparent bright-colored after rising greatly, and water regain is 7 times of original weight.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.Electronic Speculum result shows that the aperture of hydrogel is about 280nm.Spectroscopic analysis is the result show, contains sulfonic group in the sample, sulfuryl, and carboxylic acid group, the former two come from the phenyl ring sulfonation, and the latter two come from the hydrolytic process of ethyl propenoate in vitriol oil effect.
Claims (5)
1. the preparation method of an ordered porous polymer gel may further comprise the steps:
(1) preparation silicon-dioxide list disperse particles dispersion system;
(2) with 0.01%-5% (weight) initiator, 1-30% (weight) linking agent, and monomer and the polymkeric substance of 98.99-65% (weight), wherein polymkeric substance is the 1-30% (weight) of monomer weight, immerse in the silica template hole, initiated polymerization obtains inorganic/organic composite, wherein, described monomer is selected from vinylbenzene, vinyl cyanide, acrylate, acrylic amide and their mixture, linking agent is selected from Vinylstyrene, methylene diacrylamine, the vinylformic acid glycol ester, the vinylformic acid propylene glycol ester, initiator is a radical initiator, light trigger, radiation initiators, or the active ion initiator system, polymkeric substance is for being dissolved in monomeric homopolymer, and/or multipolymer;
(3) no cross-linked polymer in the mixture of preparation in (2) step of extraction;
(4) if contain phenyl ring in the employed monomer, the mixture and the vitriol oil are pressed mass ratio 10: 1-1: mix between 100, under 20-150 ℃, carry out sulfonation and handle;
(5) remove silica template with immersing in the hydrofluoric acid through the mixture that sulfonation is handled in the mixture that obtains in the step (3) or the step (4), obtain orderly gel resin;
(6) gel resin is immersed back swelling in water or other solvent, form orderly gel, be reduced to gel resin after the gel dehydration.
2. the preparation method of an ordered porous polymer gel may further comprise the steps:
(1) preparation silicon-dioxide list disperse particles dispersion system;
(2) with 0.01%-5% (weight) initiator, 1-30% (weight) linking agent, and monomer and the polymkeric substance of 98.99-65% (weight), wherein polymkeric substance is the 1-30% (weight) of monomer weight, immerse in the silica template hole, initiated polymerization obtains inorganic/organic composite, wherein, described monomer is selected from vinylbenzene, vinyl cyanide, acrylate, acrylic amide and their mixture, linking agent is selected from Vinylstyrene, methylene diacrylamine, the vinylformic acid glycol ester, the vinylformic acid propylene glycol ester, initiator is a radical initiator, light trigger, radiation initiators, or the active ion initiator system, polymkeric substance is for being dissolved in monomeric homopolymer, and/or multipolymer;
(3) no cross-linked polymer in the mixture of preparation in (2) step of extraction;
(4) mixture is immersed remove silica template in the hydrofluoric acid;
(5) if contain phenyl ring in the employed monomer, the resin and the vitriol oil of removing template mixed, under 20-150 ℃, carry out sulfonation and handle;
(6) swelling after the gel resin through sulfonation is handled that obtains in gel resin that step (4) is obtained or the step (5) immerses in water or other solvent forms orderly gel, is reduced to gel resin behind gel dehydration or other solvent.
3. according to claim 1 or 2 described methods, wherein, described radical initiator is AIBN or BPO.
4. according to claim 1 or 2 described methods, wherein, described polymkeric substance is PS, ABS, SBS, SEBS and/or PEO-PS-PEO.
5. according to claim 1 or 2 described methods, wherein, sulfonation temperature is 20-99 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374488C (en) * | 2006-04-14 | 2008-03-12 | 清华大学 | Method for preparing two-dimensional regular polymer nano-micron pore array template |
| CN103013016A (en) * | 2011-09-28 | 2013-04-03 | 国家纳米科学中心 | Medical carrier and medical composition and preparation method thereof |
| CN105800703A (en) * | 2016-03-31 | 2016-07-27 | 任晓明 | Silicon dioxide modified nitrite removal material and preparation and regeneration method thereof |
| CN114075431A (en) * | 2020-08-17 | 2022-02-22 | 中石化石油工程技术服务有限公司 | Weak cross-linked polymer for oil-based drilling fluid plugging and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335531C (en) * | 2005-12-29 | 2007-09-05 | 清华大学 | Method for preparing nano micron pore array template of two-dimensional regular polymer |
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2001
- 2001-01-04 CN CN 01100390 patent/CN1209398C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374488C (en) * | 2006-04-14 | 2008-03-12 | 清华大学 | Method for preparing two-dimensional regular polymer nano-micron pore array template |
| CN103013016A (en) * | 2011-09-28 | 2013-04-03 | 国家纳米科学中心 | Medical carrier and medical composition and preparation method thereof |
| CN103013016B (en) * | 2011-09-28 | 2014-11-26 | 国家纳米科学中心 | Medical carrier and medical composition and preparation method thereof |
| CN105800703A (en) * | 2016-03-31 | 2016-07-27 | 任晓明 | Silicon dioxide modified nitrite removal material and preparation and regeneration method thereof |
| CN105800703B (en) * | 2016-03-31 | 2018-12-21 | 任晓明 | A kind of silica modified nitrite removal material and its preparation regeneration method |
| CN114075431A (en) * | 2020-08-17 | 2022-02-22 | 中石化石油工程技术服务有限公司 | Weak cross-linked polymer for oil-based drilling fluid plugging and preparation method thereof |
| CN114075431B (en) * | 2020-08-17 | 2023-10-13 | 中石化石油工程技术服务有限公司 | Weak cross-linked polymer for plugging oil-based drilling fluid and preparation method thereof |
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| CN1209398C (en) | 2005-07-06 |
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