CN110452388A - A kind of preparation method of the hybridization porous polymer based on cage modle and trapezoidal-structure silsesquioxane - Google Patents
A kind of preparation method of the hybridization porous polymer based on cage modle and trapezoidal-structure silsesquioxane Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
The present invention provides a kind of preparation method of hybridization porous polymer based on cage modle and trapezoidal-structure silsesquioxane, comprising steps of replacing tricyclic trapezoidal half siloxane (PLS) to be dissolved in organic solvent eight vinyl silsesquioxanes (OVS), ten diphenyl of cagelike structure, catalyst is added, after mixing evenly, heating reaction is carried out；After reaction, it is cooled to room temperature, is filtered, washed to obtain solid I；Obtained solid I carry out soxhlet extraction, then it is vacuum dried to obtain the final product.Preparation step of the present invention is simple, and preparation process condition is easily controllable, raw materials used to be easily obtained；The hybridization porous polymer of gained has high specific surface area and big pore volume and good chemical stability and thermal stability, and being applied to absorption dyestuff and heavy metal ion has preferable adsorption capacity.
Description
Technical field
The present invention relates to a kind of preparation method of hybridization porous polymer based on cage modle and trapezoidal-structure silsesquioxane,
Belong to field of polymer material preparing technology.
Background technique
In recent years, key areas of the porous material as material science is concerned, extensively due to its excellent performance
It is general to be applied to the fields such as catalysis, absorption, separation, gas storage.Based on the various actual requirements in different application field, it is special to have
Chemistry, mechanically or physically the design and synthesis of the novel porous materials of performance become more and more important.In numerous porous materials of synthesis
In the raw material of material, silsesquioxane is considered as hybridization porous material due to the special other hybrid inorganic-organic structure of molecular level
The ideal construction unit of material.Silsesquioxane group becomes [RSiO1.5]n(R is organic group, the most typical as n=8), with
Inorganic Si-O-Si structure is kernel, and connection modified organic group in periphery has excellent hot property and mechanical performance for preparation
Novel hybride materials provide excellent platform, become the ideal construction unit for constructing hybridization porous polymer；Especially
While being that organic moiety makes it have good dissolubility, new synergisticing performance can also be generated, this is in practical applications
It is very important.In numerous different structure silesquioxane compounds, the silsesquioxane (Cage of cagelike structure
Silsesquioxane, abbreviation POSS) and its material be widely studied, correlated performance and potential application are also by examen.
And for the silsesquioxane molecule of trapezoidal-structure (Ladder-Type Silsesquioxanes, LTSs), certainly
After nineteen sixty is reported by Brown et al. for the first time, special structure and property are attracted extensive attention.LTSs is unique miscellaneous by its
Change structure (double inorganic siloxanes chain backbones and organic side group), LTSs shows excellent heat resistance and radiation resistance, low dielectric
Constant, good dissolubility and film forming ability more better than commonly single-stranded siloxanes；Meanwhile the side by changing LTSs main chain
Base can further realize the functionalization of LTSs, to meet the fields such as liquid crystal display, photoelectronics, device for non-linear optical
Various actual requirements.For example, as crucial construction unit, LTSs, which is usually used in building, has the various of special space configuration and function
Polysiloxanes, such as mesomorphic or liquid crystal scalariform polysiloxanes, Tubular polysiloxane and false sieve plate polysiloxanes etc..By LTSs this
A little unrivaled overall merits show greatly research and application value in advanced Material Field based on the material of LTSs.
However, the research of the porous material based on LTSs is still insufficient, and there has been no the reports of pertinent literature；By cage modle and
Ladder type silsesquioxane combines resulting hybrid material to be expected to show some more superior performances, thus this research seems
It is very necessary.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provide it is a kind of miscellaneous based on cage modle and trapezoidal-structure silsesquioxane
Change poromeric preparation method.The present invention is anti-by Friedel-Crafts by raw material of the silsesquioxane of different structure
Novel hybride porous material should be prepared, there is good chemical stability and thermal stability, substantially increase silsesquioxane
The specific surface area and pore volume of the hybridization porous material of alkyl, and keep it big to the adsorption capacity of Wastewater Dyes and heavy metal ion
It is big to improve, there is huge potential using value in adsorbing domain.
Technical scheme is as follows:
A kind of preparation method of the hybridization porous polymer based on cage modle and trapezoidal-structure silsesquioxane, comprising steps of
(1) eight vinyl silsesquioxanes (OVS), ten diphenyl of cagelike structure are replaced into tricyclic trapezoidal half siloxane
(PLS) it is dissolved in organic solvent, catalyst is added and carries out heating reaction after mixing evenly；After reaction, it is cooled to
Room temperature is filtered, washed to obtain solid I；
(2) the solid I obtained step (1) carries out soxhlet extraction, obtained solid it is vacuum dried up to based on cage modle and
The hybridization porous polymer of trapezoidal-structure silsesquioxane.
, according to the invention it is preferred to, eight vinyl silsesquioxanes (OVS) of cagelike structure described in step (1) and
Ten diphenyl replace the molar ratio of tricyclic trapezoidal half siloxane (PLS) to be (2~8): 1；Further preferably (4~6): 1.
, according to the invention it is preferred to, organic solvent described in step (1) is 1,2- dichloroethanes or o-dichlorohenzene；It is excellent
It is selected as 1,2- dichloroethanes.
, according to the invention it is preferred to, eight vinyl silsesquioxanes (OVS) of cagelike structure described in step (1)
Quality and the volume ratio of organic solvent are 1:(35~45) g/mL.
, according to the invention it is preferred to, catalyst described in step (1) is anhydrous AlCl3Or anhydrous FeCl3；Preferably without
Water AlCl3；The molar ratio of eight vinyl silsesquioxanes (OVS) of the catalyst and cagelike structure is (1~2): 1.
, according to the invention it is preferred to, when organic solvent described in step (1) is 1,2- dichloroethanes, heating reaction temperature
Degree is 80~90 DEG C；When the organic solvent is o-dichlorohenzene, heating reaction temperature is 190~200 DEG C.The heating is anti-
It is 12~48h between seasonable；It is preferred that for 24 hours.
, according to the invention it is preferred to, washing step described in step (1) are as follows: obtained solid after filtering is successively used into first
Alcohol, tetrahydrofuran, chloroform and each washing of acetone difference 3 times.
The eight vinyl silsesquioxanes (OVS), ten diphenyl of cagelike structure replace the trapezoidal sesquialter silicon of tricyclic in the present invention
The structural formula of oxygen alkane (PLS) is as follows:
Eight vinyl silsesquioxanes (OVS) of heretofore described cagelike structure can refer to document
J.Am.Chem.Soc., 1964,86,1120-1125 is prepared；Ten diphenyl replace tricyclic trapezoidal half siloxane (PLS)
It can refer to document Organometallics, 2014,3,4148-4151 is prepared.
, according to the invention it is preferred to, Soxhlet extraction step described in step (2) are as follows: the solid I for obtaining step (1)
Soxhlet extraction is for 24 hours in methanol and methylene chloride respectively.The effect of Soxhlet extraction of the present invention is the impurity removed in solid I, main
If remaining monomer and catalyst.
, according to the invention it is preferred to, vacuum drying temperature described in step (2) be 60~100 DEG C, preferably 70~80
℃；The drying time is 12~48h, preferably 20~for 24 hours.
Reaction route of the invention is as follows:
It technical characterstic of the invention and has the beneficial effect that:
1, the preparation step of the hybridization porous polymer of the present invention is simple, and preparation process condition is easily controllable, raw materials used easy
In acquisition.The present invention uses specific raw material, i.e. the ten of the eight vinyl silsesquioxanes (OVS) and trapezium structure of cagelike structure
Diphenyl replaces tricyclic trapezoidal half siloxane (PLS) to be used as construction unit, is reacted by Friedel-Crafts, in OVS
Vinyl reacts with the hydrogen on phenyl in PLS, and the connection bridged bond of certain degree of cross linking and the degree of polymerization is prepared with Si-CH2-
CH2Novel hybride porous material based on-Ph.
2, the resulting polymer of the present invention is a kind of porous material of organic inorganic hybridization, due to the spy of construction unit structure
Different property and complicated interaction and spatial relationship between construction unit are formed after polymer, makes gained porous material tool
There are high specific surface area and big pore volume and good chemical stability and thermal stability, specific surface area is up to 1273m2g-1, pore volume is up to 0.950cm3g-1.The tricyclic trapezoidal half siloxane that ten diphenyl of the invention replaces contains 12 phenyl ring and replaces
Base, each phenyl theoretically at most can provide 5 Friedel-Crafts reaction sites, therefore the monomer can provide 60 reactions
Site；The vinyl on the eight each vertex of vinyl silsesquioxane provides 8 reaction sites simultaneously；Although due to steric hindrance
Etc. reasons, reaction site cannot react completely, but numerous reaction sites advantageously forms highly cross-linked mesh structural porous knot
Structure；Additionally due to the class planar structure and OVS rigidity stereoscopic three-dimensional structure of monomer PLS special trapezoidal distortion, so that gained
Porous material have biggish specific surface area.
3, present invention gained porous hybrid material is applied to the absorption to Wastewater Dyes molecule and heavy metal ion, due to
The biggish specific surface area of gained porous material and pore volume, therefore there is excellent adsorption capacity；Meanwhile silsesquioxane
Si-O-Si core is rich in O atom, is electronegativity unit, and mesoporous accounting is larger, therefore present invention gained porous material is more prone to
In absorption large scale cationic substance.Therefore present invention gained porous hybrid material has huge potential application in adsorbing domain
Value.
Detailed description of the invention
Fig. 1 is eight vinyl silsesquioxanes (OVS) used in embodiment 1, the ten diphenyl substitution trapezoidal silsesquioxane of tricyclic
The infrared spectrogram of alkane (PLS) and prepared hybridization porous polymer (LCHPP).
Fig. 2 is eight vinyl silsesquioxanes (OVS) and prepared hybridization porous polymer used in embodiment 1
(LCHPP) solid carbon spectrogram.
Fig. 3 is eight vinyl silsesquioxanes (OVS) and prepared hybridization porous polymer used in embodiment 1
(LCHPP) solid silicon spectrogram.
Fig. 4 is eight vinyl silsesquioxanes (OVS) and prepared hybridization porous polymer used in embodiment 1
(LCHPP) X-ray diffraction spectra figure.
Fig. 5 is eight vinyl silsesquioxanes (OVS) used in embodiment 1, the ten diphenyl substitution trapezoidal silsesquioxane of tricyclic
The thermal gravimetric analysis curve figure of alkane (PLS) and prepared hybridization porous polymer (LCHPP).
Fig. 6 is the N of hybridization porous polymer (LCHPP) prepared by embodiment 12Adsorption-desorption curve graph, wherein bottom right
Angle figure is its graph of pore diameter distribution.
Fig. 7 is scanning electron microscope of the hybridization porous polymer (LCHPP) under different amplification prepared by embodiment 1
Figure.
Fig. 8 is 1 hybridization porous polymer (LCHPP) (CR) water Congo red to various concentration of gained of embodiment in test example 1
The adsorbance curve graph of solution and methylene blue (MB) aqueous solution.
Fig. 9 be in test example 2 the hybridization porous polymer (LCHPP) of the gained of embodiment 1 to various concentration Pb2+Aqueous solution and
Hg2+The adsorbance curve graph of aqueous solution.
Specific embodiment
Below by specific embodiment and in conjunction with attached drawing, the present invention is further described, but protection scope of the present invention is not
It is limited to this.In embodiment it is raw materials used unless otherwise specified, commercially obtain；Method therefor is unless otherwise specified
It is conventional method, device therefor is conventional equipment unless otherwise specified.
Eight vinyl silsesquioxanes (OVS) of cagelike structure used can refer to document in embodiment
J.Am.Chem.Soc., 1964,86,1120-1125 are prepared, and specific preparation process is as follows:
(1) 300mL acetone, 60mL vinyltrimethoxysilane, 60mL water, stirring are added in 500mL single-necked flask
After uniformly, it is slowly added to the hydrochloric acid that 80mL mass concentration is 36%~38% at 0 DEG C, after being added dropwise, stirs 2~3min, to
It is warmed to room temperature, is stirred at room temperature 5 days after stable system.
(2) after the reaction was completed, filter, obtained solid is washed till no yellow substance with acetone, be dried in vacuo white powder is solid
Body.Synthetic route is as follows:
Ten diphenyl replace tricyclic ladder type silsesquioxane (PLS) to can refer to document Organometallics, and 2014,3,
4148-4151 is prepared, and specific preparation process is as follows:
(1) in the case where 0 DEG C of argon gas is protected, by 1,3- bis- chloro- 1,1,3,3- tetraphenyl disiloxane (2.9g, 6.4mmol)
THF (10mL) solution be added to all-cis formula -1,3,5,7- tetrahydroxy -1,3,5,7- tetraphenyl cyclotetrasiloxane (1.7g,
3.1mmol) and in THF (10mL) solution of triethylamine (1.2g, 12mmol), it will flow back 1 day at 80 DEG C of mixture.
(2) after reaction, it is added chloroform into reaction mixture, organic phase saturated aqueous ammonium chloride and full
It is washed with sodium-chloride water solution, it is then dry with anhydrous sodium sulfate, it filtered, rotated except solvent, obtain crude product.With methanol, second
Alcohol washs crude product, then recrystallizes in acetone, and production is further purified finally by settling in chloroform and n-hexane
Object obtains white solid PLS (0.37g, yield 9%).
Synthetic route is as follows:
Embodiment 1
A kind of preparation method of the hybridization porous polymer (LCHPP) based on cage modle and trapezoidal-structure silsesquioxane, packet
Include step:
(1) to drying, with magnetic agitation, the 50mL of condenser pipe there-necked flask in, 0.632g cagelike structure is added
Eight vinyl silsesquioxanes (OVS), ten diphenyl of 0.291g replace tricyclic ladder type silsesquioxane (PLS), 25mL 1,2- bis-
Chloroethanes stirs 15 minutes, and 0.200g aluminum trichloride (anhydrous) is added, and stirs 30 minutes at room temperature, is then heated to 85 DEG C, reaction
24h；After reaction, it by reaction system cooled to room temperature, filters, obtained solid is successively used to methanol, tetrahydrofuran, three
Each washing of chloromethanes, acetone difference 3 times, obtains solid I；
(2) obtained solid I is used into methanol and methylene chloride Soxhlet extraction for 24 hours respectively, obtained solid vacuum at 80 DEG C
Drying is for 24 hours to get LCHPP.
The specific surface area of the present embodiment products therefrom is 1273m2g-1, pore volume 0.950cm3g-1。
Eight vinyl silsesquioxanes (OVS) used in the present embodiment, ten diphenyl replace tricyclic ladder type silsesquioxane
(PLS) and the infrared spectrogram of prepared hybridization porous polymer (LCHPP) is as shown in Figure 1, Si-O-Si feature in LCHPP
Peak (1109cm-1) and vinyl reaction after the saturation c h bond (2941cm that produces-1) characteristic peak show Fridel-Crafts
The successful generation of reaction.
Eight vinyl silsesquioxanes (OVS) used in the present embodiment and hybridization porous polymer (LCHPP) of preparation consolidate
Body carbon spectrogram is as shown in Fig. 2, the formant of 120~140ppm belongs to the phenyl ring of PLS unit and lacking from OVS in LCHPP
Unreacted vinyl is measured, the appearance of the characteristic peak of saturated alkyl carbon (δ=28.6 and 13.7ppm) confirms the shape of C -- C single bond
At showing the successful preparation of LCHPP.
Eight vinyl silsesquioxanes (OVS) and prepared hybridization porous polymer (LCHPP) used in the present embodiment
Solid silicon spectrogram is as shown in figure 3, it can be seen from the figure that T in LCHPP3(Tn: CSi (OSi)n(OH)3-n], δ=- 66.7 and-
80.4ppm) the presence of characteristic peak illustrates that during the preparation process the cagelike structure of eight vinyl silsesquioxanes keeps complete, does not have
There is collapsing phenomenon.- 66.7 are respectively belonging to be formed after Friedel-Crafts reaction with the two main signal peaks -80.4ppm
Si-CH2-CH2The silicon of-Ar and unreacted Si-CH2=CH2The silicon atom of unit.
The X of eight vinyl silsesquioxanes (OVS) and prepared hybridization porous polymer (LCHPP) used in the present embodiment
Ray diffraction spectrum is as shown in figure 4, it can be seen from the figure that LCHPP is disordered structure.
Eight vinyl silsesquioxanes (OVS) used in the present embodiment, ten diphenyl replace tricyclic ladder type silsesquioxane
(PLS) and the thermal gravimetric analysis curve figure of prepared hybridization porous polymer (LCHPP) as shown in figure 5, it can be seen from the figure that
LCHPP weightlessness 5% shows that LCHPP has good heat resistance at 500 DEG C or more.
The N of hybridization porous polymer (LCHPP) prepared by the present embodiment2Adsorption-desorption curve graph as shown in fig. 6, from
As can be seen that LCHPP is that one kind is mesoporous and micropore coexists, the porous material with bimodal distribution in figure；The average diameter of micropore
For 1.41nm or so, the average diameter of mesoporous is 3.79nm or so.
Scanning electron microscope (SEM) photograph of the hybridization porous polymer (LCHPP) under different amplification prepared by the present embodiment is as schemed
Shown in 7, the pattern of the hybridization porous polymer (LCHPP) of gained is made of the particle reunited as seen from the figure, and structure shows phase
The irregular shape to connect has the wide size distribution from 100 nanometers to tens micron, and aperture is relatively uniform, but does not grow
Phase orderly structure.
Embodiment 2
A kind of preparation method of the hybridization porous polymer (LCHPP) based on cage modle and trapezoidal-structure silsesquioxane, packet
Include step:
(1) to drying, with magnetic agitation, the 50mL of condenser pipe there-necked flask in, 0.632g cagelike structure is added
Eight vinyl silsesquioxanes (OVS), ten diphenyl of 0.437g replace tricyclic ladder type silsesquioxane (PLS), 25ml 1,2- bis-
Chloroethanes stirs 15 minutes, and 0.200g aluminum trichloride (anhydrous) is added, and stirs 30 minutes at room temperature, is then heated to 85 DEG C, reaction
24h；After reaction, it by reaction system cooled to room temperature, filters, obtained solid is successively used to methanol, tetrahydrofuran, three
Each washing of chloromethanes, acetone difference 3 times, obtains solid I；
(2) obtained solid I is used into methanol and methylene chloride Soxhlet extraction for 24 hours respectively, obtained solid vacuum at 80 DEG C
Drying is for 24 hours to get LCHPP.
The specific surface area of the present embodiment products therefrom is 834m2g-1, pore volume 0.510cm3g-1。
Embodiment 3
A kind of preparation method of the hybridization porous polymer (LCHPP) based on cage modle and trapezoidal-structure silsesquioxane, packet
Include step:
(1) to drying, with magnetic agitation, the 50mL of condenser pipe there-necked flask in, 0.632g cagelike structure is added
Eight vinyl silsesquioxanes (OVS), ten diphenyl of 0.218g replace tricyclic ladder type silsesquioxane (PLS), 25mL 1,2- bis-
Chloroethanes stirs 15 minutes, and 0.200g aluminum trichloride (anhydrous) is added, and stirs 30 minutes at room temperature, is then heated to 85 DEG C, reaction
24h；After reaction, it by reaction system cooled to room temperature, filters, obtained solid is successively used to methanol, tetrahydrofuran, three
Each washing of chloromethanes, acetone difference 3 times, obtains solid I；
(2) obtained solid I is used into methanol and methylene chloride Soxhlet extraction for 24 hours respectively, obtained solid vacuum at 80 DEG C
Drying is for 24 hours to get LCHPP.
The specific surface area of the present embodiment products therefrom is 1028m2g-1, pore volume 0.786cm3g-1。
Embodiment 4
A kind of preparation method of the hybridization porous polymer (LCHPP) based on cage modle and trapezoidal-structure silsesquioxane, packet
Include step:
(1) to drying, with magnetic agitation, the 50mL of condenser pipe there-necked flask in, 0.632g cagelike structure is added
Eight vinyl silsesquioxanes (OVS), ten diphenyl of 0.175g replace tricyclic ladder type silsesquioxane (PLS), 25mL 1,2- bis-
Chloroethanes stirs 15 minutes, and 0.200g aluminum trichloride (anhydrous) is added, and stirs 30 minutes at room temperature, is then heated to 85 DEG C, reaction
24h；After reaction, it by reaction system cooled to room temperature, filters, obtained solid is successively used to methanol, tetrahydrofuran, three
Each washing of chloromethanes, acetone difference 3 times, obtains solid I；
(3) obtained solid I is used into methanol and methylene chloride Soxhlet extraction for 24 hours respectively, obtained solid vacuum at 80 DEG C
Drying is for 24 hours to get LCHPP.
The specific surface area of the present embodiment products therefrom is 984m2g-1, pore volume 0.646cm3g-1。
Embodiment 5
A kind of preparation method of the hybridization porous polymer (LCHPP) based on cage modle and trapezoidal-structure silsesquioxane, packet
Include step:
(1) to drying, with magnetic agitation, the 50mL of condenser pipe there-necked flask in, eight vinyl of 0.632g times is added
Half siloxanes (OVS), ten diphenyl of 0.291g replace tricyclic ladder type silsesquioxane (PLS), and 25mL 1,2- dichloroethanes stirs
It mixes 15 minutes, 0.133g aluminum trichloride (anhydrous) is added, stir 30 minutes at room temperature, be then heated to 85 DEG C, reaction is for 24 hours；Reaction
After, reaction system cooled to room temperature filters, obtained solid is successively used methanol, tetrahydrofuran, chloroform,
Each washing of acetone difference 3 times, obtains solid I；
(2) obtained solid I is used into methanol and methylene chloride Soxhlet extraction for 24 hours respectively, obtained solid vacuum at 80 DEG C
Drying is for 24 hours to get the hybridization porous polymer of silsesquioxane (LCHPP) based on cage modle and trapezoidal-structure.
The specific surface area of the present embodiment products therefrom is 1167m2g-1, pore volume 0.806cm3g-1。
Test example 1
Dye Adsorption test:
The 1 hybridization porous polymer (LCHPP) of gained of embodiment is carried out to the dyestuff of Congo red (CR) and methylene blue (MB)
Absorption is probed into.
Test specimen: the 1 hybridization porous polymer (LCHPP) of gained of embodiment.
The preparation of dye solution: compound concentration is 50,100,200,300,400,500,550,600,650 and respectively
700mg L-1Congo red (CR) aqueous solution and concentration be 10,20,40,60,80,100,120,140,160 and 180mg L-1's
Methylene blue (MB) aqueous solution.
Test method: test specimen 3mg is added into 50mL sample bottle, prepared dye solution 30mL, room temperature is added
Stirring 16 hours.The concentration that front and back dye solution is adsorbed using measurement of ultraviolet-visible spectrophotometer, can be calculated institute of the present invention
Hybridization porous polymer (LCHPP) is obtained to the adsorbance of dyestuff.
Fig. 8 is the 1 hybridization porous polymer (LCHPP) of gained of embodiment (CR) aqueous solution Congo red to various concentration and methylene
The adsorbance curve of base indigo plant (MB) aqueous solution.The hybridization porous polymer (LCHPP) of gained of the invention is to Congo red and methylene blue
Adsorbance respectively up to 1873 and 667mg g-1。
Analysis: since the electronegativity and mesoporous accounting of the Si-O-Si of hybridization porous polymer obtained by the present invention are larger, more
Tend to adsorb large-sized cationic dyes, and according to literature survey, in adsorption process, dyestuff size is to influence absorption
Leading factor.Thus while Congo red is anionic dyes, methylene blue is cationic dyes, but Congo red size
Larger, material is shown to Congo red superior adsorption capacity.
Test example 2
Heavy metal ion adsorbed test:
The absorption that the 1 hybridization porous polymer (LCHPP) of gained of embodiment carries out heavy metal ion is probed into.
Test specimen: the 1 hybridization porous polymer (LCHPP) of gained of embodiment.
The preparation of heavy metal ion solution: Pb is prepared respectively2+Concentration is 8,24,56,96,112,128 and 140mgL-1's
Pb2+Aqueous solution (anion NO3 -) and Hg2+Concentration is 8,24,40,64 and 160mg L-1Hg2+(anion is aqueous solution
Cl-)。
Test method: test specimen 3mg is added into 50mL sample bottle, prepared heavy metal ion solution is added
30mL is stirred at room temperature 16 hours.The concentration that absorption front and back metal ion solution is measured using flame atomic absorption spectrophotometer, is calculated
The hybridization porous polymer of gained of the present invention can be obtained to the adsorbance of metal ion.
Fig. 9 is the 1 hybridization porous polymer (LCHPP) of gained of embodiment to various concentration Pb2+Aqueous solution and Hg2+Aqueous solution
Adsorbance curve.The hybridization porous polymer (LCHPP) of gained of the invention is to Pb2+And Hg2+Adsorbance respectively up to 300.7
With 138.9mg g-1。
Analysis: since the hybridization porous polymer of the present invention is rich in O atom, electronegativity is presented, therefore have to metal ion
Biggish adsorbance.Due to factors such as level-density parameter and metal ion sizes, to Pb2+Adsorbance it is bigger.
Claims (10)
1. a kind of preparation method of the hybridization porous polymer based on cage modle and trapezoidal-structure silsesquioxane, comprising steps of
(1) eight vinyl silsesquioxanes (OVS), ten diphenyl of cagelike structure are replaced into tricyclic trapezoidal half siloxane
(PLS) it is dissolved in organic solvent, catalyst is added and carries out heating reaction after mixing evenly；After reaction, it is cooled to
Room temperature is filtered, washed to obtain solid I；
(2) the solid I for obtaining step (1) carries out soxhlet extraction, and obtained solid is vacuum dried up to based on cage modle and ladder type
The hybridization porous polymer of structure silsesquioxane.
2. the preparation side of the hybridization porous polymer according to claim 1 based on cage modle and trapezoidal-structure silsesquioxane
Method, which is characterized in that eight vinyl silsesquioxanes (OVS) of cagelike structure described in step (1) and ten diphenyl replace
The molar ratio of tricyclic trapezoidal half siloxane (PLS) is (2~8): 1；Further preferably (4~6): 1.
3. the preparation side of the hybridization porous polymer according to claim 1 based on cage modle and trapezoidal-structure silsesquioxane
Method, which is characterized in that organic solvent described in step (1) is 1,2- dichloroethanes or o-dichlorohenzene；Preferably 1,2- dichloro
Ethane.
4. the preparation side of the hybridization porous polymer according to claim 1 based on cage modle and trapezoidal-structure silsesquioxane
Method, which is characterized in that the quality of eight vinyl silsesquioxanes (OVS) of cagelike structure described in step (1) with it is organic molten
The volume ratio of agent is 1:(35~45) g/mL.
5. the preparation side of the hybridization porous polymer according to claim 1 based on cage modle and trapezoidal-structure silsesquioxane
Method, which is characterized in that catalyst described in step (1) is anhydrous AlCl3Or anhydrous FeCl3；Preferably anhydrous AlCl3；It is described
Catalyst and cagelike structure eight vinyl silsesquioxanes (OVS) molar ratio be (1~2): 1.
6. the preparation side of the hybridization porous polymer according to claim 1 based on cage modle and trapezoidal-structure silsesquioxane
Method, which is characterized in that when organic solvent described in step (1) is 1,2- dichloroethanes, heating reaction temperature is 80~90 DEG C；
When the organic solvent is o-dichlorohenzene, heating reaction temperature is 190~200 DEG C.
7. the preparation side of the hybridization porous polymer according to claim 1 based on cage modle and trapezoidal-structure silsesquioxane
Method, which is characterized in that the heating reaction time described in step (1) is 12~48h；It is preferred that for 24 hours.
8. the preparation side of the hybridization porous polymer according to claim 1 based on cage modle and trapezoidal-structure silsesquioxane
Method, which is characterized in that washing step described in step (1) are as follows: by obtained solid after filtering successively use methanol, tetrahydrofuran,
Chloroform and acetone distinguish each washing 3 times.
9. the preparation side of the hybridization porous polymer according to claim 1 based on cage modle and trapezoidal-structure silsesquioxane
Method, which is characterized in that Soxhlet extraction step described in step (2) are as follows: the solid I for obtaining step (1) respectively in methanol and
Soxhlet extraction is for 24 hours in methylene chloride.
10. the preparation side of the hybridization porous polymer according to claim 1 based on cage modle and trapezoidal-structure silsesquioxane
Method, which is characterized in that vacuum drying temperature described in step (2) is 60~100 DEG C；The drying time be 12~
48h。
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| CN112657469A (en) * | 2020-12-03 | 2021-04-16 | 山东大学 | Preparation method of amino-functionalized silsesquioxane-based heavy metal ion adsorbent |
| CN115058011A (en) * | 2022-06-21 | 2022-09-16 | 北京理工大学 | Porous polyphenyl silsesquioxane, and preparation method and application thereof |
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| US20140128495A1 (en) * | 2012-11-08 | 2014-05-08 | New Sitech Llc | Organic-inorganic hybrid material compositions and polymer composites |
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| US20140128495A1 (en) * | 2012-11-08 | 2014-05-08 | New Sitech Llc | Organic-inorganic hybrid material compositions and polymer composites |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112657469A (en) * | 2020-12-03 | 2021-04-16 | 山东大学 | Preparation method of amino-functionalized silsesquioxane-based heavy metal ion adsorbent |
| CN115058011A (en) * | 2022-06-21 | 2022-09-16 | 北京理工大学 | Porous polyphenyl silsesquioxane, and preparation method and application thereof |
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