CN104437437B - 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 its application, specially a kind of amine-terminated hyperbranced
The functional mesoporous silicon hybridization material of fluidized polymer and application, belong to functional material technical field.
Background technology
Mesoporous material is a kind of porous material of aperture between 2nm and 50nm, compares more general porous material, its hole
Road structure distribution is homogeneous, specific surface area is larger.Wherein, mesoporous silicon material is with low cost, and raw material sources are extensive.SBA-15 types are mesoporous
Silicon dioxide is a kind of mesoporous silicon material with larger aperture, thicker hole wall and good hydrothermal stability, its duct
For two-dimentional hexagonal structure, it is distributed in height rule.These characteristics allow SBA-15 as good carrier matrix, absorption,
The fields such as catalysis, sensing, separation show huge application potential.
However, simple mesopore silicon oxide inorganic material is single due to its structure, lack surface activity, feature is not enough,
Using limited, which is carried out function modified significant.The method of modifying being usually taken is organo silane coupling agent method, organosilicon
The silanol key generated after the alkoxy grp hydrolysis of alkane coupling agent forms chemical bonding with inorganic silicon surface silanol group, so that having
Machine functional moieties are grafted on inorganic skeleton.Organo silane coupling agent modification approach has rear grafting and copolycondensation method.Using
Being modified obtained in grafting afterwards, mesoporous silicon material synthesis step is complicated, and functional modification component stability is poor, may cause organic
Group blocks duct.And high-temperature calcination goes template agent removing that pore passage structure thermal contraction can then deformed.Copolycondensation method is also known as one kettle way
（one-pot）, relatively rear grafting is compared, organic silicon source directly participates in the composition of mesoporous framework, and modifying process is to a certain extent
Pore passage structure can be affected, but modified technique is simple and quick, functionalized modification uniform component distribution controllable is more suitable for high-volume industry
Production.
Dissaving polymer is that one kind is rich in various functional end-groups, with the spherical 3-D solid structure of similar network
Macromolecular structure polymer.Compare linear polymer, highly branched structure polymer its strand not easy entanglement, dissolubility
Height, viscosity are low, and molecular structure is spherical in shape, and there are a large amount of cavitys inside, and active reaction sites are more so as to which functioning efficiency is greatly improved；
And dissaving polymer compares dendritic polymer synthesis technique simply, only one-step method just can be synthesized by monomer, without the need for purification,
It is easy to commercial production, and the presence of a large amount of active function groups can be passed to modifying and decorating and prepare heterogeneity and application function
Polymer, in catalytic chemistry, rheology modifier, nanotechnology, coatings industry, membrane material, bio-medical material, supermolecule
The multiple fields such as chemistry are widely used, while and preferable multifunctionality dressing agent.As carrier matrix, mesopore silicon oxide
With homogeneous adjustable mesoporous pore size and larger specific surface area and pore volume, due to hole wall surface exist a large amount of free silicone hydroxyls with
Double bond silicone hydroxyl, it is easy to introduce functional group, hole wall composition and property equally also controllable, plasticity and adaptability it is stronger.Mirror
In both advantages, if there can be a kind of method to organically combine dissaving polymer and inorganic mesoporous silicon materials, absorption is applied to
Or functional vector, have a extensive future.
The content of the invention
The present invention is in view of the shortcomings of the prior art, there is provided a kind of compound with regular structure is stable, with high absorption property
The functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido and its application.
To achieve the above object of the invention, the technical scheme that the present invention is provided is a kind of dissaving polymer functionalization of offer
Mesoporous material, its preparation method comprise the steps：
1st, the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) being denoted as P123 is dissolved in deionized water, is obtained
Concentration is the P123 solution of 5～50 g/L；Add the quality volume of the HCL solution that concentration is 2mol/L, P123 and HCL solution
Than for 1:5～100 g/mL, stir, and obtain P123 acid solutions；
2nd, organo silane coupling agent is added in P123 acid solutions, organo silane coupling agent with the mass ratio of P123 is
1:5～1:30, temperature be 30～90 DEG C, rotating speed be 300～700r/min under conditions of, 30～120 min of stir process；Again
Positive esters of silicon acis is added dropwise over, positive esters of silicon acis is 1 with the mass ratio of P123:2～5:1, temperature be 30～90 DEG C, rotating speed be 300
Under conditions of～700r/min, 6～24h of stir process obtains Ludox presoma；
3rd, Ludox presoma is placed in the reactor of tetrafluoroethene liner, under conditions of temperature is 50～150 DEG C
6～48h of Crystallizing treatment, the white precipitate of gained is filtered, vacuum dried, white powder cyano group is obtained functional mesoporous
Silicon, is denoted as CN-SBA-15；
4th, CN-SBA-15 is added to into the H that concentration is 48～98wt%2SO4In solution, compound concentration is 0.5～10g/L
CN-SBA-15 sulfuric acid solutions, temperature be 70～120 DEG C, rotating speed be 400～800r/min under conditions of, stir process 6
～24h, the product for obtaining after filtering, are washed with deionized to neutrality, vacuum drying, carboxylated SBA-15 are obtained, are denoted as
CA-SBA-15；
5th, Hyperbranched Polymer with Terminal Amido is dissolved in organic solvent, obtains amine-terminated hyperbrancedization that concentration is 2～30g/L
Polymer solution, CA-SBA-15 obtained in step 4 is scattered in Hyperbranched Polymer with Terminal Amido solution, and CA-SBA-15's is dense
Spend for 0.05～0.85wt%, obtain mesoporous material dispersion liquid；
6th, under conditions of nitrogen or controlled atmosphere, temperature are 40～120 DEG C, mesoporous material dispersion liquid is stirred at reflux
8～36h, under conditions of rotating speed is 3000～8000 r/min after centrifugal treating, uses organic solvent washing；
7th, the product for obtaining is scattered in Hyperbranched Polymer with Terminal Amido solution again, repeat step 6 about 3～10 times
Afterwards, it is then vacuum dried, obtain a kind of dissaving polymer functional mesoporous material.
Organo silane coupling agent of the present invention is 2- cyanoethyl triethoxysilanes, 3- cyanoethyl triethoxysilicanes
One kind in alkane, isocyanatopropyl triethoxysilane, or it is various.Described positive esters of silicon acis is methyl silicate, positive silicic acid second
One kind in ester, positive silicic acid propyl ester, butyl silicate, or it is various.Described organic solvent be methanol, ethanol, acetone, toluene,
One kind in hexamethylene, isopropanol, or it is various.
Technical solution of the present invention also includes being applied to dissaving polymer functional mesoporous material in absorption waste water
Heavy metal ion, organic dyestuff or other Organic substances.
Heretofore described Hyperbranched Polymer with Terminal Amido is by containing double bond and in the monomer containing carboxyl or aliphatic radical
One kind, is obtained with anhydride and many amine-containing monomers synthetic reactions.The synthetic method of Hyperbranched Polymer with Terminal Amido is referring to 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 anhydride is succinic anhydride, phthalic anhydride, ring butyryl oxide.；Containing double bond and the monomer containing carboxyl or aliphatic radical be third
E pioic acid methyl ester, ethyl acrylate, methyl methacrylate, acrylic or methacrylic acid；Described many amine-containing monomers are second two
Amine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine or five vinyl hexamines.
The generally modified approach of dissaving polymer has three kinds：“grafting-on-grafting”,“grafting
From " and " grafting to ", are summarised as Stepwise synthesis, surface in situ method of formation and direct Graft Method.“grafting
To " compares other two kinds and has preparation method simple, quick, and product is the advantages of easily obtain.The present invention adopts a kind of end
Amino dissaving polymer modifies mesoporous silicon SBA-15, and its principle is：Dissaving polymer chemical graft is fixed to into modified Jie
The high-ratio surface substrate of hole silicon, based on dimensional network structure unique inside dissaving polymer, the particular end of its surface enrichment
Small molecule can fully be adsorbed in base functional group, and chelating ion improves the overall absorption property of material.It is inorganic mesoporous through what is be modified
Silicon materials, can be grafted dissaving polymer by " grafting to " method, obtain the hybrid material of particular functionality, and which is grand
Sight form is low-density powder, and microstructure is regular in order, and substantially in two-dimentional six sides p6mm loose structures, specific surface area is high, hole
Road surface is covered with hyperbranched organic functionses component, rich in activated adoption site, heavy metal ion and organic dye pollutant tool
There is good absorbability, can be applicable to wastewater treatment or functional vector field.
Compared with prior art, it is an advantage of the current invention that：
1st, using mesoporous SBA-15 as host material, using the rule of its high-ratio surface, big pore volume and hydrothermally stable
Then structure, then grafting has the dissaving polymer of near-spherical three dimensional structure cavity and a large amount of active function groups, can maximize work
Property number of sites, realizes efficient absorption.
2nd, initially with " one kettle way（one-pot）" copolycondensation obtains carboxyl into cyanomodified SBA-15, then Jing carboxylations
Functional mesoporous silicon, using " grafting to " strategy grafting Hyperbranched Polymer with Terminal Amido on carboxyl-functional mesoporous silicon,
Final to obtain carboxylation SBA-15/ Hyperbranched Polymer with Terminal Amido hybrid material, building-up process is simple, and cycle is short, efficiency are higher, into
This is cheap, it is easy to accomplish industrialized production.
3rd, the part carboxyl on the primary amino radical and imino group, with mesoporous silicon substrate that Hyperbranched Polymer with Terminal Amido is rich in forms acyl
Amine key or hydrogen bond, have benefited from dissaving polymer stereochemical structure cavity, and polymer is constructed containing a large amount of in mesoporous silicon substrate surface
The three-dimensional adsorption space of avtive spot, carboxyl therein and amino not only can absorbing dye small molecule, can also chelate a huge sum of money
Category ion so as to which advantage function group is fully used.
4th, mesoporous silicon material used by the present invention and dissaving polymer safety non-toxic, environmental protection, mesoporous silicon material come
Source is enriched, with low cost, and plasticity is strong, and application prospect is extensive.
Description of the drawings
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 infrared spectrum comparison diagram of functional mesoporous silicon materials prepared by the embodiment of the present invention 1 and SBA-15；
Fig. 3 is the transmission electron microscope comparison diagram of functional mesoporous silicon materials prepared by the embodiment of the present invention 1 and SBA-15；
Fig. 4 is the static adsorption kinetic curve of functional mesoporous silicon materials absorbing dye prepared by the embodiment of the present invention 1
Figure；
Fig. 5 is the static adsorption power of functional mesoporous silicon materials Adsorption of Heavy Metal Ions prepared by the embodiment of the present invention 1
Learn curve chart.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment is further elaborated to technical solution of the present invention.
Embodiment 1：
Weigh quantitative poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)（P123）In adding deionized water, at 30 DEG C
Stirring and dissolving, the concentration for controlling P123 are 14.50 g/L；2mol/L HCL solution is added, the quality of P123 and HCL solution is controlled
Volume ratio（g/mL）For 1:35, it is stirred until homogeneous, obtains P123 acid solutions.
Add 2- cyano group triethoxysilanes（CTES）Into P123 acid solutions, the mass ratio for controlling CTES and P123 is
1:11.76,40 min are stirred with the speed of 400r/min at 30 DEG C, tetraethyl orthosilicate is added dropwise over（TEOS）, control TEOS
Mass ratio with P123 is 2.15:With the speed stirring 24h of 400r/min at 0 DEG C of Isosorbide-5-Nitrae, Ludox presoma is obtained.
Ludox presoma is moved to into crystallization 24h at 90 DEG C of the reactor with tetrafluoroethene liner, by gained white
Precipitation is filtered, and is vacuum dried in 80 DEG C, and it is the functional mesoporous silicon SBA-15 of cyano group that white powder is obtained（It is denoted as CN-SBA-
15）.
Weigh the H that quantitative CN-SBA-15 adds concentration for 48wt%2SO4In solution, CN- of the configuration concentration for 6.64g/L
SBA-15 sulfuric acid solutions, at 95 DEG C with 400r/min agitating heating 20h, product are filtered, with a large amount of deionized water wash into
Property, and be vacuum dried in 60 DEG C, carboxylated SBA-15 is obtained（It is denoted as CA-SBA-15）.
Take quantitative Hyperbranched Polymer with Terminal Amido（HBP）It is dissolved in dehydrated alcohol, HBP solution of the configuration concentration for 4g/L,
Then take quantitative CA-SBA-15 to be scattered in the ethanol solution of Hyperbranched Polymer with Terminal Amido, control CA-SBA-15's
Concentration is 0.15wt%, obtains mesoporous material dispersion liquid.The preparation of HBP is referring to 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 into N2Lower 80 DEG C are protected to be stirred at reflux after 24h with 400r/min, by whole liquid Jing 3000
R/min centrifugal treating 5min, with absolute ethanol washing, then again dispersion, centrifugation, filter, 4 times repeatedly, last 80 DEG C of vacuum are done
It is dry, obtain the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido.Referring to accompanying drawing 1, it is over-expense manufactured in the present embodiment
The structural representation of fluidized polymer functional mesoporous material, bottom annular represent mesoporous silicon base.
Referring to accompanying drawing 2, it is the infrared spectrum comparison diagram of the functional mesoporous silicon materials that the present embodiment is provided and SBA-15,
Curve a, b, c are respectively mesoporous SBA-15, carboxyl-functional mesoporous silicon CA-SBA-15 and Hyperbranched Polymer with Terminal Amido
The infrared spectrum curve figure of functional mesoporous silicon hybridization material.In Fig. 2, curve is in 3436 cm-1、1630cm-1、1085cm-1With
960cm-1The absworption peak at place is respectively silanol key Si-OH stretching vibration peaks, Si-OH flexural vibrations peaks, Si-O-Si asymmetric stretches
Vibration peak and Si-OH symmetrical stretching vibrations peak, illustrate that the mesoporous silicon Jing after functionalized modification remains in that complete pore passage structure
Skeleton.And with unmodified mesoporous silicon（Curve a）Compare, the mesoporous silicon after modification（Curve b, c）It is above-mentioned correspondence absorb
Peak intensity is presented different degrees of decrease, illustrates that modifying process has certain impact to mesopore orbit structure.Curve b is in 1718cm-1
The absworption peak at place is C=O feature stretching vibration peaks, shows that carboxyl functional group has successfully been grafted to SBA-15 surfaces.In curve c,
1562cm-1Belong to-NH2Scissoring vibration peak, and 1718cm-1The absworption peak at place is very faint, illustrates the carboxylic in CA-SBA-15
Base functional group is reacted with the amino of Hyperbranched Polymer with Terminal Amido and is consumed, i.e. Hyperbranched Polymer with Terminal Amido success
It is grafted to mesoporous silicon face.
Referring to accompanying drawing 3, it is the transmission electron microscope comparison diagram of functional mesoporous silicon materials manufactured in the present embodiment and SBA-15,
A figures, b figures are respectively the transmission electron microscope of mesoporous silicon SBA-15 and the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido
Figure.The two-dimentional hexagonal hole road structure for SBA-15 high-sequentials that a figures show, from b figures as can be seen that through functional modification
Mesoporous silicon maintains pore passage structure regular in order while dissaving polymer is grafted with.
Referring to accompanying drawing 4, it is functional mesoporous hybrid material manufactured in the present embodiment to cation and anionic dye
Static adsorption dynamic curve diagram.Cation is 500mg/L with the initial concentration of anionic dye solution, and the dye of positive ion is molten
Liquid pH=5.85, anionic dye solution pH=9.53, adsorption temp are 30 DEG C.As shown in figure 4, saturated adsorption time is left in 2h
The right side, 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 end
The functional mesoporous silicon hybridization material of amino dissaving polymer is with the high efficiency of additive capability to zwitterion dyestuff.
Referring to accompanying drawing 5, it is functional mesoporous hybrid material heavy metal ion Fe manufactured in the present embodiment3+And Cu2+'s
Static adsorption dynamic curve diagram.Fe3+And Cu2+The initial concentration of solution is 500mg/L, Fe3+And Cu2+Solution keeps former
Beginning pH, adsorption temp are 30 DEG C.If shown, hybrid material is to Fe3+And Cu2+Absorption reach balance in 4h and 3h respectively, satisfy
208mg/g and 146mg/g is up to respectively with adsorbance, adsorption effect is excellent, illustrate that Hyperbranched Polymer with Terminal Amido functionalization is situated between
Hole silicon hybridization material has superelevation specific surface and a large amount of activated adoption groups, can be widely used for organic molecule and heavy metal ion
Adsorption, or as function carrier materials application in other field.
Embodiment 2：
Weigh quantitative poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)（P123）In adding deionized water, at 30 DEG C
Stirring and dissolving, the concentration for controlling P123 are 25.86 g/L.2mol/L HCL solution is subsequently adding, and P123 is controlled with HCL solution
Mass volume ratio（g/mL）For 1:60, it is stirred until homogeneous, obtains P123 acid solutions.
Add 3- cyano group triethoxysilanes（CETES）Into P123 acid solutions, the mass ratio of CETES and P123 is controlled
For 1:6.49,30 min are stirred with the speed of 600r/min at 45 DEG C, methyl silicate is added dropwise over（TMOS）, control TMOS
Mass ratio with P123 is 1.54:With the speed stirring 12h of 600r/min at 1,50 DEG C, Ludox presoma is obtained.
Ludox presoma is moved to into crystallization 36h at 80 DEG C of the reactor with tetrafluoroethene liner, by gained white
Precipitation is filtered, and is vacuum dried in 80 DEG C, and it is the functional mesoporous silicon SBA-15 of cyano group that white powder is obtained（CN-SBA-15）.
Weigh the H that quantitative CN-SBA-15 adds concentration for 98wt%2SO4In solution, CN- of the configuration concentration for 8.12g/L
SBA-15 sulfuric acid solutions, at 90 DEG C with 600r/min agitating heating 24h, product are filtered, with a large amount of deionized water wash into
Property, and be vacuum dried in 60 DEG C, carboxylated SBA-15 is obtained（CA-SBA-15）.
Take quantitative Hyperbranched Polymer with Terminal Amido（HBP）It is dissolved in toluene, HBP solution of the configuration concentration for 10g/L, then
Take quantitative CA-SBA-15 to be scattered in the toluene solution of Hyperbranched Polymer with Terminal Amido, the concentration for controlling CA-SBA-15 is
0.08wt%, obtains mesoporous material dispersion liquid.
Mesoporous material dispersion liquid is placed in into N2Lower 78 DEG C are protected to be stirred at reflux after 20h with 600r/min, by whole liquid Jing 4500
R/min centrifugal treating 5min, with toluene and absolute ethanol washing, then again dispersion, centrifugation, filter, 8 times repeatedly, last 80 DEG C
Vacuum drying, obtains the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido.
Embodiment 3：
Weigh quantitative poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)（P123）In adding deionized water, at 30 DEG C
Stirring and dissolving, the concentration for controlling P123 are 7.86 g/L.2mol/L HCL solution is subsequently adding, and P123 is controlled with HCL solution
Mass volume ratio（g/mL）For 1:40, it is stirred until homogeneous, obtains P123 acid solutions.
Add 2- cyano group triethoxysilanes（CTES）Into P123 acid solutions, the mass ratio for controlling CTES and P123 is
1:7.70,30 min are stirred with the speed of 400r/min at 60 DEG C, tetraethyl orthosilicate is added dropwise over（TEOS）, control TEOS with
The mass ratio of P123 is 2.65:With the speed stirring 8h of 500r/min at 1,60 DEG C, Ludox presoma is obtained.
Ludox presoma is moved to into crystallization 12h at 110 DEG C of the reactor with tetrafluoroethene liner, by gained white
Precipitation is filtered, and is vacuum dried in 80 DEG C, and it is the functional mesoporous silicon SBA-15 of cyano group that white powder is obtained（CN-SBA-15）.
Weigh the H that quantitative CN-SBA-15 adds concentration for 68wt%2SO4In solution, CN- of the configuration concentration for 5.72g/L
SBA-15 sulfuric acid solutions, at 110 DEG C with 500r/min agitating heating 20h, product are filtered, with a large amount of deionized water wash extremely
Neutrality, and be vacuum dried in 60 DEG C, carboxylated SBA-15 is obtained（CA-SBA-15）.
Take quantitative Hyperbranched Polymer with Terminal Amido（HBP）It is dissolved in methanol, HBP solution of the configuration concentration for 20g/L, then
Take quantitative CA-SBA-15 to be scattered in the methanol solution of Hyperbranched Polymer with Terminal Amido, the concentration for controlling CA-SBA-15 is
0.22wt%, obtains mesoporous material dispersion liquid.
Mesoporous material dispersion liquid is placed in into N2Lower 98 DEG C are protected to be stirred at reflux after 15h with 500r/min, by whole liquid Jing 4000
R/min centrifugal treating 10min, with methanol and absolute ethanol washing, then again dispersion, centrifugation, filter, 5 times repeatedly, last 80 DEG C
Vacuum drying, obtains the functional mesoporous silicon hybridization material of Hyperbranched Polymer with Terminal Amido.
Claims (4)
1. a kind of dissaving polymer functional mesoporous material, it is characterised in that preparation method comprises the steps：
（1）Poly(ethylene oxide)-poly(propylene oxide)-the poly(ethylene oxide) being denoted as P123 is dissolved in deionized water, obtains dense
Spend the P123 solution for 5～50 g/L；Add the mass volume ratio of the HCL solution that concentration is 2mol/L, P123 and HCL solution
For 1:5～100 g/mL, stir, and obtain P123 acid solutions；
（2）Organo silane coupling agent is added in P123 acid solutions, organo silane coupling agent is 1 with the mass ratio of P123:5
～1:30, temperature be 30～90 DEG C, rotating speed be 300～700r/min under conditions of, 30～120 min of stir process；Again by
Positive esters of silicon acis is added dropwise to, positive esters of silicon acis is 1 with the mass ratio of P123:2～5:1, temperature be 30～90 DEG C, rotating speed be 300～
Under conditions of 700r/min, 6～24h of stir process obtains Ludox presoma；Described organo silane coupling agent is 2- cyanogen second
One or more in ethyl triethoxy silicane alkane, 3- cyanoethyl triethoxysilanes, isocyanatopropyl triethoxysilane；
（3）Ludox presoma is placed in the reactor of tetrafluoroethene liner, the crystallization under conditions of temperature is for 50～150 DEG C
6～48h is processed, the white precipitate of gained is filtered, it is vacuum dried, the functional mesoporous silicon of white powder cyano group, note is obtained
Make CN-SBA-15；
（4）CN-SBA-15 is added to into the H that concentration is 48～98wt%2SO4In solution, compound concentration is 0.5～10g/L's
CN-SBA-15 sulfuric acid solutions, temperature be 70～120 DEG C, under conditions of rotating speed is 400～800r/min, stir process 6～
24h, the product for obtaining after filtering, are washed with deionized to neutrality, vacuum drying, carboxylated SBA-15 are obtained, CA- is denoted as
SBA-15；
（5）Hyperbranched Polymer with Terminal Amido is dissolved in organic solvent, amine-terminated hyperbrancedization that concentration is 2～30g/L is obtained and is gathered
Polymer solution, by step（4）Obtained CA-SBA-15 is scattered in Hyperbranched Polymer with Terminal Amido solution, and CA-SBA-15's is dense
Spend for 0.05～0.85wt%, obtain mesoporous material dispersion liquid；
（6）Under conditions of nitrogen or controlled atmosphere, temperature are 40～120 DEG C, mesoporous material dispersion liquid is stirred at reflux into 8～
36h, under conditions of rotating speed is 3000～8000 r/min after centrifugal treating, uses organic solvent washing；
（7）The product for obtaining is scattered in Hyperbranched Polymer with Terminal Amido solution again, after repeat step (6) 3～10 times, then
It is vacuum dried, obtain a kind of dissaving polymer functional mesoporous material.
2. dissaving polymer functional mesoporous material according to claim 1, it is characterised in that：Described positive esters of silicon acis
For one or more in methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester, butyl silicate.
3. dissaving polymer functional mesoporous material according to claim 1, it is characterised in that：Described organic solvent
For one or more in methanol, ethanol, acetone, toluene, hexamethylene, isopropanol.
4. the application of dissaving polymer functional mesoporous material as claimed in claim 1, it is characterised in that：Use it for inhaling
Heavy metal ion, organic dyestuff or other Organic substances in attached waste water.
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| CN104923186B (en) * | 2015-06-02 | 2017-06-20 | 中山大学 | A kind of Hyperbranched Polymer with Terminal Amido solid amine absorption material and its preparation method and application |
| CN109763188B (en) * | 2018-12-13 | 2020-06-12 | 东华大学 | Fiber containing hyperbranched hybrid porous material and preparation method thereof |
| CN109706535B (en) * | 2018-12-13 | 2020-08-14 | 东华大学 | Polyacrylonitrile fiber containing hyperbranched polymer and preparation method thereof |
| 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 |
| 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 |
| CN114573823B (en) * | 2020-12-02 | 2023-03-31 | 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 |
| 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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