CN104437437A - Hyperbranched polymer functionalized mesoporous material and application thereof - Google Patents
Hyperbranched polymer functionalized mesoporous material and application thereof Download PDFInfo
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Abstract
The invention discloses a hyperbranched polymer functionalized mesoporous material and application thereof. The preparation method comprises the following steps: carboxylating cyano-modified mesoporous silicon synthesized by copolycondensation, thereby obtaining carboxyl functionalized mesoporous silicon; and grafting an amino-terminated hyperbranched polymer on the carboxyl functionalized mesoporous silicon by adopting a 'grafting to' strategy, thereby obtaining a carboxylated mesoporous silicon/amino-terminated hyperbranched polymer hybrid material. The macroscopical shape of functionalized mesoporous material provided by the invention is low-density powder, the microstructure is regular and ordered, the functionalized mesoporous material is generally a two-dimensional hexagonal p6mm porous structure and is large in specific surface area, the pore surface is coated with hyperbranched organic functional components, and the functionalized mesoporous material is enriched in active adsorption sites, has good capacity of adsorbing heavy metal ions and organic dye pollutants and can be applied to the field of wastewater treatment or functional carriers.
Description
Technical field
The present invention relates to a kind of dissaving polymer functional mesoporous material and application thereof, be specially the functional mesoporous silicon hybridization material of a kind of Hyperbranched Polymer with Terminal Amido and application, belong to functional material technical field.
Background technology
Mesoporous material is the porous material of a kind of aperture between 2nm and 50nm, general porous material of comparing, and the distribution of its pore passage structure is homogeneous, specific area is larger.Wherein, mesoporous silicon material is with low cost, and raw material sources are extensive.SBA-15 type mesoporous silicon oxide a kind ofly has larger aperture, the mesoporous silicon material of thicker hole wall and good hydrothermal stability, and its duct is two-dimentional hexagonal structure, distributes in height rule.These characteristics make SBA-15 as good carrier matrix, can demonstrate huge application potential in fields such as absorption, catalysis, sensing, separation.
But, simple mesopore silicon oxide inorganic material due to its structure single, lack surface-active, functional deficiency, applies limited, carries out function modified significant to it.Usually the method for modifying taked is organo silane coupling agent method, and the silanol key generated after the alkoxy grp hydrolysis of organo silane coupling agent and inorganic silicon surface silanol group form chemical bonding, thus organofunctional moieties is grafted on inorganic skeleton.Organo silane coupling agent modifies approach rear grafting and copolycondensation method.The modification mesoporous silicon material synthesis step that after adopting, grafting is obtained is complicated, functional modification component poor stability, and organic group may be caused to block duct.Template is removed in high-temperature calcination then can make pore passage structure thermal contraction be out of shape.Copolycondensation method also known as one kettle way (one-pot), grafting after comparing, the formation of mesoporous framework is participated in organosilicon source directly, modifying process can affect pore passage structure to a certain extent, but modified technique is simple and quick, functionalized modification uniform component distribution controllable, is more suitable for industrial production in enormous quantities.
Dissaving polymer is that one is rich in various functional end-group, has the macromolecular structure polymer of the spherical 3-D solid structure of similar network.To compare linear polymer, its strand of highly branched structure polymer not easy entanglement, solubility is high, and viscosity is low, and molecular structure is spherical in shape, and there is a large amount of cavity inside, and active reaction sites is many, and its functioning efficiency is improved greatly; And dissaving polymer is compared, dendritic polymer synthesis technique is simple, only one-step method just can by monomer synthesize, without the need to purifying, be easy to industrial production, and the existence of a large amount of active function groups can make it prepare the polymer of heterogeneity and application function by modifying and decorating, be widely used in multiple fields such as catalytic chemistry, rheology modifier, nanometer technology, coatings industry, membrane material, bio-medical material, supramolecular chemistries, be also desirable multi-functional dressing agent simultaneously.As carrier matrix, mesopore silicon oxide has homogeneous adjustable mesoporous pore size and larger specific area and pore volume, because hole wall surface exists a large amount of free silicone hydroxyl and double bond silicone hydroxyl, is easy to introduce functional group, hole wall composition and character equally also controllable, plasticity and adaptability stronger.In view of both advantages, if a kind of method can be had dissaving polymer and inorganic mesoporous silicon materials to be organically combined, be applied to absorption or functional vector, have a extensive future.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, provide a kind of compound with regular structure and stablize, there is the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido and the application thereof of high absorption property.
To achieve the above object of the invention, technical scheme provided by the invention is for providing a kind of dissaving polymer functional mesoporous material, and its preparation method comprises the steps:
1, the PEO-PPOX-PEO be denoted as P123 is dissolved in deionized water, obtains the P123 solution that concentration is 5 ~ 50 g/L; Add the HCL solution that concentration is 2mol/L again, the mass volume ratio of P123 and HCL solution is 1:5 ~ 100 g/mL, stirs, and obtains P123 acid solution;
2, joined by organo silane coupling agent in P123 acid solution, the mass ratio of organo silane coupling agent and P123 is 1:5 ~ 1:30, temperature be 30 ~ 90 DEG C, under rotating speed is the condition of 300 ~ 700r/min, stir process 30 ~ 120 min; Dropwise add positive esters of silicon acis again, the mass ratio of positive esters of silicon acis and P123 is 1:2 ~ 5:1, temperature be 30 ~ 90 DEG C, under rotating speed is the condition of 300 ~ 700r/min, stir process 6 ~ 24h, obtains Ludox presoma;
3, Ludox presoma is placed in the reactor of tetrafluoroethene liner, be Crystallizing treatment 6 ~ 48h under the condition of 50 ~ 150 DEG C in temperature, the white precipitate of gained is filtered, through vacuum drying, the obtained functional mesoporous silicon of white powder cyano group, is denoted as CN-SBA-15;
4, CN-SBA-15 is joined the H that concentration is 48 ~ 98wt%
2sO
4in solution, compound concentration is the CN-SBA-15 sulfuric acid solution of 0.5 ~ 10g/L, temperature be 70 ~ 120 DEG C, under rotating speed is the condition of 400 ~ 800r/min, stir process 6 ~ 24h, the product obtained after filtering, spends deionized water to neutral, vacuum drying, obtained carboxylated SBA-15, is denoted as CA-SBA-15;
5, Hyperbranched Polymer with Terminal Amido is dissolved in organic solvent, obtain the Hyperbranched Polymer with Terminal Amido solution that concentration is 2 ~ 30g/L, the CA-SBA-15 that step 4 is obtained is scattered in Hyperbranched Polymer with Terminal Amido solution, the concentration of CA-SBA-15 is 0.05 ~ 0.85wt%, obtains mesoporous material dispersion liquid;
6, under nitrogen or controlled atmosphere, temperature are the condition of 40 ~ 120 DEG C, by mesoporous material dispersion liquid stirring and refluxing 8 ~ 36h, be under the condition of 3000 ~ 8000 r/min after centrifugal treating at rotating speed, with organic solvent washing;
7, the product obtained is scattered in Hyperbranched Polymer with Terminal Amido solution again, after repeating step 6 about 3 ~ 10 times, then through vacuum drying, obtains a kind of dissaving polymer functional mesoporous material.
Organo silane coupling agent of the present invention is the one in 2-cyanoethyl triethoxysilane, 3-cyanoethyl triethoxysilane, isocyanatopropyl triethoxysilane, or multiple.Described positive esters of silicon acis is the one in methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, or multiple.Described organic solvent is the one in methyl alcohol, ethanol, acetone, toluene, cyclohexane, isopropyl alcohol, or multiple.
Technical solution of the present invention also comprises the heavy metal ion, organic dyestuff or other organic matters that are applied in absorption waste water of dissaving polymer functional mesoporous material.
Hyperbranched Polymer with Terminal Amido described in the present invention is by the one also contained containing double bond in the monomer of carboxyl or fat base, is obtained by reacting with acid anhydrides and polyamines base monomer synthesize.The synthetic method of Hyperbranched Polymer with Terminal Amido is see document Zhang Feng, Chen Yuyue, Lin Hong, et al. Synthesis of an amino-terminated hyperbranched polymer and its application in reactive dyeing on cotton as a salt-free dyeing auxiliary [J]. Coloration technology, 2007,123 (6): 351-357.Described acid anhydrides is succinic anhydride, phthalic anhydride, ring butyric anhydride; Monomer containing double bond and containing carboxyl or fat base is methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic or methacrylic acid; Described many amine-containing monomers are ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine or five vinyl hexamines.
The approach of usual dissaving polymer modification has three kinds: " grafting-on-grafting ", and " grafting from " and " grafting to ", is summarised as Stepwise synthesis, surface in situ method of formation and direct Graft Method." grafting to " compares other two kinds, and to have preparation method simple, fast, and product such as easily to obtain at the advantage.The present invention adopts a kind of Hyperbranched Polymer with Terminal Amido to modify mesoporous silicon SBA-15, its principle is: high-ratio surface matrix dissaving polymer chemical graft being fixed to modification mesoporous silicon, based on the dimensional network structure of dissaving polymer inside uniqueness, Small molecular fully can be adsorbed in the specified end group functional group of its surface enrichment, chelating ion, improves the absorption property of material monolithic.Through the inorganic mesoporous silicon materials of modification, " grafting to " method grafting dissaving polymer can be passed through, obtain the hybrid material of particular functionality, its macroscopic form is low-density powder, and microstructure is in order regular, substantially in two-dimentional six side p6mm loose structures, specific area is high, and channel surfaces is covered with hyperbranched organic functions component, is rich in activated adoption site, heavy metal ion and organic dye pollutant have good adsorption capacity, can be applicable to wastewater treatment or functional vector field.
Compared with prior art, the invention has the advantages that:
1, using mesoporous SBA-15 as host material, utilize the regular texture of its high-ratio surface, large pore volume and hydrothermally stable, grafting has the dissaving polymer of near-spherical three-dimensional structure cavity and a large amount of active function groups again, can maximize active sites and count, realize efficient adsorption.
2, " one kettle way (one-pot) " copolycondensation is first adopted to synthesize cyanomodified SBA-15, carboxyl-functional mesoporous silicon is obtained again through carboxylation, adopt " grafting to " strategy grafting Hyperbranched Polymer with Terminal Amido on carboxyl-functional mesoporous silicon, final acquisition carboxylation SBA-15/ Hyperbranched Polymer with Terminal Amido hybrid material, building-up process is simple, and the cycle is short, and efficiency is higher, with low cost, be easy to realize suitability for industrialized production.
3, the primary amino radical that is rich in of Hyperbranched Polymer with Terminal Amido and imino group, amido link or hydrogen bond is formed with the part carboxyl on mesoporous silicon based, have benefited from dissaving polymer stereochemical structure cavity, the three-dimensional adsorption space of polymer at mesoporous silicon based surface construction containing a large amount of avtive spot, carboxyl wherein and amino not only can absorbing dye Small molecular, all right sequester heavy metal ions, makes its advantage function group be fully used.
4, the present invention's mesoporous silicon material used and dissaving polymer safety non-toxic, environmental protection, mesoporous silicon material abundance, with low cost, plasticity is strong, and application prospect is extensive.
Accompanying drawing explanation
Fig. 1 is the structural representation of dissaving polymer functional mesoporous material prepared by the embodiment of the present invention 1;
Fig. 2 is the functional mesoporous silicon materials of the embodiment of the present invention 1 preparation and the infrared spectrum comparison diagram of SBA-15;
Fig. 3 is the functional mesoporous silicon materials of the embodiment of the present invention 1 preparation and the transmission electron microscope comparison diagram of SBA-15;
Fig. 4 is the Static Adsorption kinetic curve figure of functional mesoporous silicon materials absorbing dye prepared by the embodiment of the present invention 1;
Fig. 5 is the Static Adsorption kinetic curve figure of functional mesoporous silicon materials Adsorption of Heavy Metal Ions prepared by the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with drawings and the specific embodiments, technical solution of the present invention is further elaborated.
Embodiment 1:
Take that quantitative PEO-PPOX-PEO (P123) adds in deionized water, stirring and dissolving at 30 DEG C, the concentration of control P123 is 14.50 g/L; Add 2mol/L HCL solution, the mass volume ratio (g/mL) of control P123 and HCL solution is 1:35, is stirred to evenly, obtains P123 acid solution.
Add 2-cyano group triethoxysilane (CTES) in P123 acid solution, the mass ratio of control CTES and P123 is 1:11.76,40 min are stirred with the speed of 400r/min at 30 DEG C, dropwise add ethyl orthosilicate (TEOS), the mass ratio of control TEOS and P123 is 2.15:1, stir 24h with the speed of 400r/min at 40 DEG C, obtain Ludox presoma.
Ludox presoma is moved to reactor crystallization 24h at 90 DEG C with tetrafluoroethene liner, gained white precipitate is filtered, and in 80 DEG C of vacuum drying, obtained white powder is that the functional mesoporous silicon SBA-15(of cyano group is denoted as CN-SBA-15).
Take quantitative CN-SBA-15 and add the H that concentration is 48wt%
2sO
4in solution, configuration concentration is the CN-SBA-15 sulfuric acid solution of 6.64g/L, at 95 DEG C with 400r/min agitating heating 20h, product is filtered, with a large amount of deionized water washing to neutral, and in 60 DEG C of vacuum drying, obtained carboxylated SBA-15(is denoted as CA-SBA-15).
Getting quantitative Hyperbranched Polymer with Terminal Amido (HBP) is dissolved in absolute ethyl alcohol, configuration concentration is the HBP solution of 4g/L, then getting quantitative CA-SBA-15 is scattered in the ethanol solution of Hyperbranched Polymer with Terminal Amido, and the concentration of control CA-SBA-15 is 0.15wt%, obtains mesoporous material dispersion liquid.The preparation of HBP is see document Synthesis of an amino-terminated hyperbranched polymer and its application in reactive dyeing on cotton as a salt-free dyeing auxiliary (Zhang Feng, Chen Yuyue, Lin Hong, et al. [J]. Coloration technology, 2007,123 (6): 351-357).
Mesoporous material dispersion liquid is placed in N
2protect lower 80 DEG C with after 400r/min stirring and refluxing 24h, by whole liquid through 3000 r/min centrifugal treating 5min, with absolute ethanol washing; again dispersion again, centrifugal, filtration; 4 times repeatedly, last 80 DEG C of vacuum drying, obtain the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido.See accompanying drawing 1, be the structural representation of dissaving polymer functional mesoporous material prepared by the present embodiment, bottom annular represents the mesoporous silicon based end.
See accompanying drawing 2, it is the infrared spectrum comparison diagram of the functional mesoporous silicon materials that provide of the present embodiment and SBA-15, and curve a, b, c are respectively the infrared spectrum curve map of the functional mesoporous silicon hybridization material of mesoporous SBA-15, carboxyl-functional mesoporous silicon CA-SBA-15 and Hyperbranched Polymer with Terminal Amido.In Fig. 2, curve is at 3436 cm
-1, 1630cm
-1, 1085cm
-1and 960cm
-1the absworption peak at place is respectively silanol key Si-OH stretching vibration peak, Si-OH flexural vibrations peak, Si-O-Si asymmetric stretching vibration peak and Si-OH symmetrical stretching vibration peak, and the pore passage structure skeleton that the mesoporous silicon after functionalized modification still keeps complete is described.And with the mesoporous silicon of unmodified (curve a) compared with, (curve b, above-mentioned corresponding absorption peak strength c) present weakening in various degree, illustrate that modifying process has certain influence to mesopore orbit structure for mesoporous silicon after modifying.Curve b is at 1718cm
-1the absworption peak at place is C=O feature stretching vibration peak, shows that carboxyl functional group is successfully grafted to SBA-15 surface.In curve c, 1562cm
-1belong to-NH
2scissoring vibration peak, and 1718cm
-1the absworption peak at place is very faint, and illustrate that the carboxyl functional group in CA-SBA-15 reacts with the amino of Hyperbranched Polymer with Terminal Amido and is consumed, namely Hyperbranched Polymer with Terminal Amido is successfully grafted to mesoporous silicon surface.
See accompanying drawing 3, it is the transmission electron microscope comparison diagram of the functional mesoporous silicon materials prepared of the present embodiment and SBA-15, and a figure, b figure are respectively the transmission electron microscope picture of mesoporous silicon SBA-15 and the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido.What a figure showed is the two-dimentional hexagonal hole road structure of SBA-15 high-sequential, as can be seen from b figure, through the mesoporous silicon of functional modification while being grafted with dissaving polymer, maintains pore passage structure regular in order.
See accompanying drawing 4, it is the functional mesoporous hybrid material prepared of the present embodiment to the Static Adsorption kinetic curve figure of cation and anionic dye.The initial concentration of cation and anionic dye solution is 500mg/L, dye of positive ion pH value of solution=5.85, anionic dye solution pH=9.53, and adsorption temp is 30 DEG C.As shown in Figure 4, saturated adsorption time is all at about 2h, the saturated extent of adsorption of the dye of positive ion is 399.5mg/g, and the saturated extent of adsorption of anionic dye is 609.7mg/g, illustrates that the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido has the high efficiency of additive capability to zwitterion dyestuff.
See accompanying drawing 5, the functional mesoporous hybrid material heavy metal ion Fe that it is prepared for the present embodiment
3+and Cu
2+static Adsorption kinetic curve figure.Fe
3+and Cu
2+the initial concentration of solution is 500mg/L, Fe
3+and Cu
2+solution all keeps original pH, and adsorption temp is 30 DEG C.If shown in, hybrid material is to Fe
3+and Cu
2+absorption reach balance in 4h and 3h respectively, saturated extent of adsorption is respectively up to 208mg/g and 146mg/g, adsorption effect is excellent, illustrate that Hyperbranched Polymer with Terminal Amido functional mesoporous silicon hybridization material has superelevation specific surface and a large amount of activated adoption group, the Adsorption of organic molecule and heavy metal ion can be widely used in, or as function carrier materials application in other field.
Embodiment 2:
Take that quantitative PEO-PPOX-PEO (P123) adds in deionized water, stirring and dissolving at 30 DEG C, the concentration of control P123 is 25.86 g/L.Then add 2mol/L HCL solution, the mass volume ratio (g/mL) of control P123 and HCL solution is 1:60, is stirred to evenly, obtains P123 acid solution.
Add 3-cyano group triethoxysilane (CETES) in P123 acid solution, the mass ratio of control CETES and P123 is 1:6.49,30 min are stirred with the speed of 600r/min at 45 DEG C, dropwise add methyl silicate (TMOS), the mass ratio of control TMOS and P123 is 1.54:1, stir 12h with the speed of 600r/min at 50 DEG C, obtain Ludox presoma.
Ludox presoma is moved to reactor crystallization 36h at 80 DEG C with tetrafluoroethene liner, gained white precipitate is filtered, and in 80 DEG C of vacuum drying, obtained white powder is the functional mesoporous silicon SBA-15(CN-SBA-15 of cyano group).
Take quantitative CN-SBA-15 and add the H that concentration is 98wt%
2sO
4in solution, configuration concentration is the CN-SBA-15 sulfuric acid solution of 8.12g/L, at 90 DEG C with 600r/min agitating heating 24h, is filtered by product, with a large amount of deionized water washing to neutral, and in 60 DEG C of vacuum drying, and obtained carboxylated SBA-15(CA-SBA-15).
Getting quantitative Hyperbranched Polymer with Terminal Amido (HBP) is dissolved in toluene, configuration concentration is the HBP solution of 10g/L, then getting quantitative CA-SBA-15 is scattered in the toluene solution of Hyperbranched Polymer with Terminal Amido, and the concentration of control CA-SBA-15 is 0.08wt%, obtains mesoporous material dispersion liquid.
Mesoporous material dispersion liquid is placed in N
2protect lower 78 DEG C with after 600r/min stirring and refluxing 20h, by whole liquid through 4500 r/min centrifugal treating 5min, with toluene and absolute ethanol washing; again dispersion again, centrifugal, filtration; 8 times repeatedly, last 80 DEG C of vacuum drying, obtain the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido.
Embodiment 3:
Take that quantitative PEO-PPOX-PEO (P123) adds in deionized water, stirring and dissolving at 30 DEG C, the concentration of control P123 is 7.86 g/L.Then add 2mol/L HCL solution, the mass volume ratio (g/mL) of control P123 and HCL solution is 1:40, is stirred to evenly, obtains P123 acid solution.
Add 2-cyano group triethoxysilane (CTES) in P123 acid solution, the mass ratio of control CTES and P123 is 1:7.70,30 min are stirred with the speed of 400r/min at 60 DEG C, dropwise add ethyl orthosilicate (TEOS), the mass ratio of control TEOS and P123 is 2.65:1, stir 8h with the speed of 500r/min at 60 DEG C, obtain Ludox presoma.
Ludox presoma is moved to reactor crystallization 12h at 110 DEG C with tetrafluoroethene liner, gained white precipitate is filtered, and in 80 DEG C of vacuum drying, obtained white powder is the functional mesoporous silicon SBA-15(CN-SBA-15 of cyano group).
Take quantitative CN-SBA-15 and add the H that concentration is 68wt%
2sO
4in solution, configuration concentration is the CN-SBA-15 sulfuric acid solution of 5.72g/L, at 110 DEG C with 500r/min agitating heating 20h, is filtered by product, with a large amount of deionized water washing to neutral, and in 60 DEG C of vacuum drying, and obtained carboxylated SBA-15(CA-SBA-15).
Getting quantitative Hyperbranched Polymer with Terminal Amido (HBP) is dissolved in methyl alcohol, configuration concentration is the HBP solution of 20g/L, then getting quantitative CA-SBA-15 is scattered in the methanol solution of Hyperbranched Polymer with Terminal Amido, and the concentration of control CA-SBA-15 is 0.22wt%, obtains mesoporous material dispersion liquid.
Mesoporous material dispersion liquid is placed in N
2protect lower 98 DEG C with after 500r/min stirring and refluxing 15h; by whole liquid through 4000 r/min centrifugal treating 10min; with methyl alcohol and absolute ethanol washing; again dispersion again, centrifugal, filtration; 5 times repeatedly; last 80 DEG C of vacuum drying, obtain the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido.
Claims (5)
1. a dissaving polymer functional mesoporous material, is characterized in that preparation method comprises the steps:
(1) PEO-PPOX-PEO be denoted as P123 is dissolved in deionized water, obtains the P123 solution that concentration is 5 ~ 50 g/L; Add the HCL solution that concentration is 2mol/L again, the mass volume ratio of P123 and HCL solution is 1:5 ~ 100 g/mL, stirs, and obtains P123 acid solution;
(2) joined by organo silane coupling agent in P123 acid solution, the mass ratio of organo silane coupling agent and P123 is 1:5 ~ 1:30, temperature be 30 ~ 90 DEG C, under rotating speed is the condition of 300 ~ 700r/min, stir process 30 ~ 120 min; Dropwise add positive esters of silicon acis again, the mass ratio of positive esters of silicon acis and P123 is 1:2 ~ 5:1, temperature be 30 ~ 90 DEG C, under rotating speed is the condition of 300 ~ 700r/min, stir process 6 ~ 24h, obtains Ludox presoma;
(3) Ludox presoma is placed in the reactor of tetrafluoroethene liner, be Crystallizing treatment 6 ~ 48h under the condition of 50 ~ 150 DEG C in temperature, the white precipitate of gained is filtered, through vacuum drying, the obtained functional mesoporous silicon of white powder cyano group, is denoted as CN-SBA-15;
(4) CN-SBA-15 is joined the H that concentration is 48 ~ 98wt%
2sO
4in solution, compound concentration is the CN-SBA-15 sulfuric acid solution of 0.5 ~ 10g/L, temperature be 70 ~ 120 DEG C, under rotating speed is the condition of 400 ~ 800r/min, stir process 6 ~ 24h, the product obtained after filtering, spends deionized water to neutral, vacuum drying, obtained carboxylated SBA-15, is denoted as CA-SBA-15;
(5) Hyperbranched Polymer with Terminal Amido is dissolved in organic solvent, obtain the Hyperbranched Polymer with Terminal Amido solution that concentration is 2 ~ 30g/L, the CA-SBA-15 that step (4) is obtained is scattered in Hyperbranched Polymer with Terminal Amido solution, the concentration of CA-SBA-15 is 0.05 ~ 0.85wt%, obtains mesoporous material dispersion liquid;
(6) under nitrogen or controlled atmosphere, temperature are the condition of 40 ~ 120 DEG C, by mesoporous material dispersion liquid stirring and refluxing 8 ~ 36h, be under the condition of 3000 ~ 8000 r/min after centrifugal treating at rotating speed, with organic solvent washing;
(7) product obtained is scattered in Hyperbranched Polymer with Terminal Amido solution again, after repeating step (6) 3 ~ 10 times, then through vacuum drying, obtains a kind of dissaving polymer functional mesoporous material.
2. dissaving polymer functional mesoporous material according to claim 1, is characterized in that: described organo silane coupling agent is one or more in 2-cyanoethyl triethoxysilane, 3-cyanoethyl triethoxysilane, isocyanatopropyl triethoxysilane.
3. dissaving polymer functional mesoporous material according to claim 1, is characterized in that: described positive esters of silicon acis is one or more in methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate.
4. dissaving polymer functional mesoporous material according to claim 1, is characterized in that: described organic solvent is one or more in methyl alcohol, ethanol, acetone, toluene, cyclohexane, isopropyl alcohol.
5. the application of dissaving polymer functional mesoporous material as claimed in claim 1, is characterized in that: use it for heavy metal ion, organic dyestuff or other organic matters in absorption waste water.
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| CN201410762915.6A CN104437437B (en) | 2014-12-14 | 2014-12-14 | Hyperbranched polymer functionalized mesoporous material and application thereof |
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| CN104437437B CN104437437B (en) | 2017-04-12 |
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| CN110438117A (en) * | 2019-07-29 | 2019-11-12 | 江西理工大学 | The method that polycyclic aromatic hydrocarbon substrate adsorbs liner and screens degrading polycyclic aromatic hydrocarbons mutant bacteria |
| CN111495324A (en) * | 2020-05-25 | 2020-08-07 | 海泰纺织（苏州）有限公司 | Preparation method of porous aerogel composite material and porous aerogel composite material |
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| CN114272889A (en) * | 2021-12-30 | 2022-04-05 | 洛阳双罗铼材料科技有限公司 | Topological silicon dioxide for rhenium adsorption and preparation method and application thereof |
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| CN104923186A (en) * | 2015-06-02 | 2015-09-23 | 中山大学 | Amine-terminated hyperbranched polymer solid amine adsorption material as well as preparation method and application thereof |
| CN109706535A (en) * | 2018-12-13 | 2019-05-03 | 东华大学 | Polyacrylonitrile fibre and preparation method thereof containing dissaving polymer |
| CN109763188A (en) * | 2018-12-13 | 2019-05-17 | 东华大学 | The fiber and preparation method thereof of the hybridization porous material containing hyperbranched type |
| CN109763188B (en) * | 2018-12-13 | 2020-06-12 | 东华大学 | Fiber containing hyperbranched hybrid porous material and preparation method thereof |
| CN110438117A (en) * | 2019-07-29 | 2019-11-12 | 江西理工大学 | The method that polycyclic aromatic hydrocarbon substrate adsorbs liner and screens degrading polycyclic aromatic hydrocarbons mutant bacteria |
| CN110438117B (en) * | 2019-07-29 | 2021-04-23 | 江西理工大学 | Polycyclic aromatic hydrocarbon substrate adsorption lining and method for screening polycyclic aromatic hydrocarbon degradation mutant bacteria |
| CN111495324A (en) * | 2020-05-25 | 2020-08-07 | 海泰纺织（苏州）有限公司 | Preparation method of porous aerogel composite material and porous aerogel composite material |
| CN111495324B (en) * | 2020-05-25 | 2024-05-21 | 海泰纺织（苏州）有限公司 | Preparation method of porous aerogel composite material and porous aerogel composite material |
| CN114573823A (en) * | 2020-12-02 | 2022-06-03 | 中国科学院大连化学物理研究所 | Tree-shaped molecule functionalized mesoporous material and preparation method and application thereof |
| CN113019343A (en) * | 2021-03-15 | 2021-06-25 | 苏州纳微科技股份有限公司 | Organic-inorganic hybrid microsphere with ordered pore structure and preparation method and application thereof |
| CN113019343B (en) * | 2021-03-15 | 2023-06-16 | 苏州纳微科技股份有限公司 | Organic-inorganic hybrid microsphere with ordered pore canal structure and preparation method and application thereof |
| CN114272889A (en) * | 2021-12-30 | 2022-04-05 | 洛阳双罗铼材料科技有限公司 | Topological silicon dioxide for rhenium adsorption and preparation method and application thereof |
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