CN105312035A - Polyimide/silicon dioxide nano heavy metal adsorbing material as well as preparation and regeneration methods - Google Patents
Polyimide/silicon dioxide nano heavy metal adsorbing material as well as preparation and regeneration methods Download PDFInfo
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Abstract
The invention discloses a polyimide/silicon dioxide nano heavy metal adsorbing material which is prepared through uniformly mixing a benzimidazole unit-containing polyamide acid with silicon dioxide precursor sol, and carrying out co-heat precipitation reaction at the temperature of 150-250 DEG C. The adsorbing material is nano-composite powder, wherein the mass fraction of silicon dioxide is 5-50%; the mole fraction of benzimidazole unit is 25-50%; the first adsorbing capacity is 20-80 mg/g; the adsorbing capacity retention rate is larger than or equal to 98% after 100 times of the adsorption-regeneration cycle. The polyimide/silicon dioxide nano heavy metal adsorbing material provided by the invention is good in heat resistance, and can be used for a long time at the temperature of 250 DEG C or below, and the adsorbing capacity for heavy metal ions is high; when the material is matched with an easy and reliable regeneration method provided by the invention, the heavy metal adsorbing capacity retention rate of the material can keep 98% or above after the material is recycled for 100 times, the service life is long, the cost is low, the material is economic and environment-friendly, and the gap of macromolecular high temperature-resistant adsorbing materials is filled.
Description
Technical field
The invention belongs to heavy-metal adsorption material and Formation and regeneration technical field thereof, be specifically related to a kind of polyimide/silicon dioxide nanometer heavy-metal adsorption material and Formation and regeneration method thereof.
Background technology
Heavy metal be a class have savings property the material to environment permanent deleterious, as long as there is micro-content can produce poisonous effect in natural water body, and not by chemistry or biological prosthetic process transition be innocuous substance, its proportion is greater than 5g/cm
3, approximately have 45 kinds at occurring in nature, but people pay close attention to the larger heavy metal of several toxicity such as Hg, Cd, Pb, Cr, Cu, Co, Ni usually in environmental science.Biology absorbs heavy metal from environment can through the biological magnification of food chain, thousands of times ground enrichment is become in higher organisms body, then enter human body by food, in some organ of human body, savings gets up to cause slow poisoning, is detrimental to health.Therefore, how scientificlly and effectively to process heavy metal wastewater thereby and become one of focus of domestic and international researcher research.The processing method of current heavy metal waste water mainly contains: chemical precipitation method, oxidation-reduction method, absorption method, electrolysis, electroosmose process, concentration method, bioanalysis etc.Wherein, absorption method is cheaply easy to get because of its material, and cost is low, and removal effect is good, is subject to the favor of people always.
Classify according to adsorption mechanism, absorption method is mainly divided into physical absorption and chemisorbed.Common physical absorption adopts inorganic or carbon class sorbing material, as active carbon, natural zeolite, molecular sieve, nano material etc.They utilize higher specific area or the surface gap structure containing a large amount of micropore, cavity, the prosperity of passage equal altitudes to carry out efficient adsorption.But such sorbing material both Adsorption of Heavy Metals also adsorbs other compounds, thus its absorption is not selective.High score subclass sorbing material is due to special chemical functional group, chelating can be carried out with the heavy metal ion in waste water, form the compound with netted cage structure, or ionic bond, the incompatible object reaching Adsorption of Heavy Metal Ions of covalently bonded can be formed with heavy metal ion, thus, this kind of sorbing material heavy metal ion be have stronger selective.The high score subclass sorbing material of current employing mainly contains polyacrylamide, the shitosan of modification and the cellulose etc. of modification, although these polymer adsorbing material heavy metal ions all have stronger selective, but because the molecular backbone from them all belongs to the macromolecular material of aliphatic category, thus general heat resistance is poor, easily degrade as polyacrylamide polymer adsorbing material Long-Time Service more than 80 DEG C as the most frequently used, recycle rate variance (Kong Bailing, Luo Jiuming. hydrolysis of polyacrylamide repercussion study [J] under high-temperature oil reservoir condition. Petroleum finance, 1998, 25 (6): 67-69.).And though aromatic polyimide is the extraordinary high-molecular organic material of a class heat resistance, but because not having the group of Absorptive complex wave effect in general polyimide structures containing heavy metal ion, and it does not have hydrophily, therefore aromatic polyimide heavy metal ion does not almost have suction-operated, can not be used as sorbing material.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, first a kind of preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material is provided.
Another object of the present invention is to provide a kind of polyimide/silicon dioxide nanometer heavy-metal adsorption material prepared by said method.
Another object of the present invention is to provide a kind of renovation process of above-mentioned polyimide/silicon dioxide nanometer heavy-metal adsorption material.
The preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention, processing step and the condition of the method are as follows:
(1) diamine monomer, dianhydride monomer and polar non-solute are obtained by existing typical polymerization methods polymerization the polyamic acid solution that solid content is 5 ~ 20%, and the benzimidazole unit containing molar fraction 25 ~ 50% in this polyamic acid;
(2) acid solution of ethyl orthosilicate, pH=1 ~ 3 and polar non-solute sol-gel process are conveniently prepared silica precursor colloidal sol;
(3) proportioning that the silica precursor colloidal sol that polyamic acid solution step (1) obtained and step (2) obtain is 5 ~ 50% by the mass fraction of silica in gained polyimide/silicon dioxide nanometer powder mixes, and then carries out heat sinkly altogether analysing reaction 2 ~ 4 hours at 150 ~ 250 DEG C.
Typical polymerization methods in above method described in step (1) is specifically see the preparation method of the polyamic acid solution of the low apparent viscosity disclosed in CN103788651A.
The sol-gel process of the routine in above method described in step (2) is specifically see ZhangP, ChenY, LiG, etal.Enhancementofpropertiesofpolyimide/silicahybridnano compositesbybenzimidazoleformedhydrogenbond [J] .PolymersforAdvancedTechnologies, 2012, method disclosed in 23 (10): 1362-1368..
Diamine monomer described in above method or be that 2-(4-aminophenyl)-5-aminobenzimidazole is or/and 2-(3-aminophenyl)-5-aminobenzimidazole, or be that 2-(4-aminophenyl)-5-aminobenzimidazole is or/and 2-(3-aminophenyl)-5-aminobenzimidazole and 4,4 '-diphenyldiamine, p-phenylenediamine (PPD), 2-(4-aminophenyl)-5-An base benzoxazole, benzidine, m-phenylene diamine (MPD) and 4,4 ', the mixture that at least one in-diaminobenzene anilid is formed.The structural formula of each diamine monomer is as follows:
Dianhydride monomer described in above method is at least one in pyromellitic acid dianhydride, BPDA, oxydiphthalic, benzophenone tetracarboxylic dianhydride, terphenyl tetracarboxylic dianhydride and bis trifluoromethyl tetracarboxylic dianhydride.The structural formula of each dianhydride monomer is as follows:
Acid solution described in above method is the solution of at least one preparation in hydrochloric acid, oxalic acid, nitric acid, sulfuric acid, acetic acid.
Polar non-solute described in above method is 1-METHYLPYRROLIDONE, N, N '-dimethyl acetamide, N, any one in N '-dimethyl formamide or dimethyl sulfoxide (DMSO).
The preferably reaction 2 ~ 4 hours at 170 ~ 200 DEG C of the common heat sink operating condition analysed described in above method step (3).
Polyimide/silicon dioxide nanometer heavy-metal adsorption material prepared by said method provided by the invention, this sorbing material is polyimide/silicon dioxide nano composite powder, wherein silica containing mass fraction is 5 ~ 50%, the molar fraction of contained benzimidazole unit is 25 ~ 50%, first time, adsorbance was 20 ~ 80mg/g, adsorbance conservation rate >=98% after adsorption-desorption-regeneration cycle 100 times.
The renovation process of above-mentioned polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention, processing step and the condition of the method are as follows:
(1) hydrochloric acid solution polyimide/silicon dioxide nano composite powder having adsorbed heavy metal ion being placed in pH=1 ~ 3 processes at least 10 minutes, then filters;
(2) gained powder will be filtered in 320 ~ 350 DEG C of heat treatments at least 10 minutes.
In above renovation process, the process of step (1) is ultrasonic oscillation process or mechanical agitation process.
Fig. 4 is shown in by " adsorption-desorption-regeneration " circulation schematic diagram of above-mentioned polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention.
The present invention compared with prior art, has the following advantages:
1, due in polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention, polyimides and silica bi-material all can be high temperature resistant, thus the glass transition temperature of material can be made up to 423 DEG C, good heat resistance, can use for a long time in environment below 250 DEG C, and cover the environment temperature that most sorbing material may use, overcome the shortcoming of existing polymer adsorbing material poor heat resistance.
2, because the inventive method introduces the benzimidazole unit of Sq in the polyimides contained by the polyimide/silicon dioxide nano composite powder provided, and benzimidazole can form the very strong complex compound of chemical chelation with heavy metal ion, thus not give only the new function of polyimides---suction-operated, expand its purposes, also fill up the blank of high temperature resistant sorbing material for high score subclass sorbing material field.
3, because the inventive method not only introduces the benzimidazole unit of energy Adsorption of Heavy Metal Ions in the polyimide/silicon dioxide nano composite powder provided in polyimides main chain, and the silica simultaneously introduced containing hydrophilic hydroxy group, thus the polyimide/silicon dioxide nano composite powder of gained is made to have good hydrophily and dispersiveness, not only solve the problem of polyimide powder bad dispersibility in water, also better catch heavy metal ion for benzimidazole, the adsorbance increasing heavy metal ion provides strong support.
The physical aspect of the polyimide/silicon dioxide heavy-metal adsorption material 4, prepared due to the present invention is nanometer powder, thus has larger specific area, can increase the contact area with heavy metal ion, thus further increase its adsorbance.
5, because preparation method provided by the invention is not only skillfully constructed, and simply ripe, thus more easily apply.
6, because renovation process provided by the invention can not only realize desorption to the polyimide/silicon dioxide nanometer powder after Adsorption of Heavy Metal Ions, and method is simple and reliable, thus can realize the regeneration of sorbing material easily and recycle, reduce the use cost of material.
7, because polyimide/silicon dioxide heavy-metal adsorption material provided by the invention can repeatedly recycle, and the conservation rate of the Adsorption of Heavy Metals ability after " adsorption-desorption-regeneration " recycles 100 times is more than 98%, thus long service life, economic environmental protection.
Accompanying drawing explanation
Fig. 1 is the photo that the polyimide/silicon dioxide nano composite powder of the embodiment of the present invention 1 preparation and the pure polyimide powder of comparative example 1 preparation disperse in water, wherein PI-10 is polyimide/silicon dioxide nano composite powder prepared by embodiment 1, and PI-0 is pure polyimide powder prepared by comparative example 1.From photo comparison, polyimide/silicon dioxide nano composite powder prepared by embodiment 1 is dispersed in water, show that hydrophily is better, and pure polyimide powder prepared by comparative example 1 is deposited in bottom, show that hydrophily is bad, not can be uniformly dispersed in water.
Fig. 2 is ESEM (SEM) photo of polyimide/silicon dioxide nano composite powder prepared by the embodiment of the present invention 1.From photo, this composite powder is nanoscale.
Fig. 3 is dynamic mechanical analysis (DMA) resolution chart (the tester model: TAQ800 of polyimide/silicon dioxide nanometer heavy-metal adsorption material prepared by the embodiment of the present invention 1, programming rate 10 DEG C/min, amplitude 25um, frequency: 1Hz).As we know from the figure, the glass transition temperature of this sorbing material, up to 423 DEG C, illustrates good heat resistance.
Fig. 4 is " adsorption-desorption-regeneration " circulation schematic diagram of polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention.
Detailed description of the invention
Provide embodiment below to be specifically described the present invention; but what be necessary to herein means out is that following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that the person skilled in the art in this field makes the present invention according to content of the present invention and adjustment still belong to protection scope of the present invention.
In addition, what deserves to be explained is:
(1) following examples and comparative example prepare the adsorption effect of material is the adsorption test adopting copper ion to carry out, and concrete operation method is: get the Cu that 1g powder puts into 0.1mol/L
2+in solution, slight concussion is by sorbing material powder filter after 10 minutes, and the sorbing material powder after filtration spends deionized water 3 times, dries, and weighing and obtaining quality is m
1sorbing material powder.
Adsorbance W
1be expressed as the adsorbable copper ion quality of polyimide/silicon dioxide nano composite powder of unit mass, its computing formula is:
W
1＝(m
1-1)
(2) adsorbance conservation rate % " adsorption-desorption-regeneration " the circulation experiment step after the circulation of polyimide/silicon dioxide nano adsorption material for preparing of following examples 100 times is: what the method for (1) obtained has adsorbed Cu
2+polyimide/silicon dioxide nano composite powder put into the hydrochloric acid solution ultrasonic vibration of pH=1 ~ 3 or mechanical agitation at least 10 minutes, filter, namely complete Cu
2+desorption; The Cu by desorption
2+powder (because wherein having adsorbed HCl) heat treatment at least 10 minutes at 320 ~ 350 DEG C, namely complete the desorption of HCl, and reclaim HCl gas.After circulation like this 100th time, the adsorbance of powder is for being designated as W
100, adsorbance conservation rate is W
100/ W
1%.
Embodiment 1
In a nitrogen atmosphere, take mol ratio as PABZ and BPDA of 1:1 be raw material, first diamine monomer PABZ is joined in 1-METHYLPYRROLIDONE, at room temperature be stirred to after it is uniformly dispersed and add dianhydride monomer BPDA, continue stirring reaction and within 10 hours, obtain the BPDA/PABZ polyamic acid solution that solid content is 10%, wherein the molar content of benzimidazole unit is 50%; Stir until obtain silica precursor vitreosol at the oxalic acid solution of ethyl orthosilicate, pH=2 and 1-METHYLPYRROLIDONE are mixed in 40 DEG C according to mol ratio 1:4:1; Be 10% to be uniformly mixed the vitreosol of BPDA/PABZ polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution carried out heat sinkly altogether analysing reaction 4 hours 180 DEG C of stirrings, filter, dry.
The present invention has done following test to the present embodiment gained sorbing material and has investigated:
1) the dispersion situation in water, the results are shown in Figure the PI-10 in 1, and has done contrast with the deployment conditions of polyimide powder in water prepared by comparative example 1, sees the PI-0 in Fig. 1.
2) its pattern is observed, the results are shown in Figure 2.
3) dynamic mechanical analysis (DMA) test has been carried out to it, the results are shown in Figure 3.
4) it has been carried out to the test of adsorbance and adsorbance conservation rate, wherein adsorbance conservation rate is the hydrochloric acid solution mechanical agitation process 10 minutes polyimide/silicon dioxide nano composite powder having adsorbed heavy metal ion being placed in pH=1, then filters; Namely filtration gained powder is completed desorption and regeneration in 10 minutes in 320 DEG C of heat treatments, and the test carried out after totally 100 times of iterative cycles with this understanding.
Embodiment 2
In a nitrogen atmosphere, take mol ratio as PDA, PABZ and BPDA of 5:5:10 be raw material, first diamine monomer PDA and PABZ is joined N, in N '-dimethyl acetamide, at room temperature be stirred to it dissolve and after being uniformly dispersed, add dianhydride monomer BPDA, continue stirring reaction and within 8 hours, obtain the BPDA/PDA/PABZ polyamic acid solution that solid content is 12%, wherein the molar content of benzimidazole unit is 25%; By the oxalic acid solution of ethyl orthosilicate, pH=2 and N, stir until obtain silica precursor vitreosol at N '-dimethyl acetamide is mixed in 50 DEG C according to mol ratio 1:4:1.5; Be 50% to be uniformly mixed the vitreosol of BPDA/PDA/PABZ polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution is carried out heat sinkly altogether analysing reaction 3 hours 250 DEG C of stirrings, filter, dry.
It has been carried out to the test of adsorbance and adsorbance conservation rate, wherein adsorbance conservation rate is the hydrochloric acid solution ultrasonic oscillation process 10 minutes polyimide/silicon dioxide nano composite powder having adsorbed heavy metal ion being placed in pH=2, then filters; Namely filtration gained powder is completed desorption and regeneration in 10 minutes in 340 DEG C of heat treatments, and the test carried out after totally 100 times of iterative cycles with this understanding.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Embodiment 3
In a nitrogen atmosphere, take mol ratio as ODA, PABZ and BPDA of 3:7:10 be raw material, first diamine monomer ODA and PABZ is joined N, in N '-dimethyl formamide, at room temperature be stirred to it dissolve and after being uniformly dispersed, add dianhydride monomer BPDA, continue stirring reaction and within 5 hours, obtain the BPDA/ODA/PABZ polyamic acid solution that solid content is 15%, wherein the molar content of benzimidazole unit is 35%; By the salpeter solution of ethyl orthosilicate, pH=2 and N, stir until obtain silica precursor vitreosol at N '-dimethyl formamide is mixed in 45 DEG C according to mol ratio 1:4:1.2; Be 30% to be uniformly mixed the vitreosol of BPDA/ODA/PABZ polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution is carried out heat sinkly altogether analysing reaction 3 hours 170 DEG C of stirrings, filter, dry.
It has been carried out to the test of adsorbance and adsorbance conservation rate, wherein adsorbance conservation rate is the hydrochloric acid solution mechanical agitation process 20 minutes polyimide/silicon dioxide nano composite powder having adsorbed heavy metal ion being placed in pH=3, then filters; Namely filtration gained powder is completed desorption and regeneration in 10 minutes in 350 DEG C of heat treatments, and the test carried out after totally 100 times of iterative cycles with this understanding.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Embodiment 4
In a nitrogen atmosphere, take mol ratio as MABZ, PMDA and BPDA of 10:5:5 be raw material, first diamine monomer MABZ is joined N, in N '-dimethyl acetamide, at room temperature be stirred to after it is uniformly dissolved and add dianhydride monomer BPDA and PMDA, continue stirring reaction and within 8 hours, obtain the BPDA/PMDA/PABZ polyamic acid solution that solid content is 8%, wherein the molar content of benzimidazole unit is 50%; By the sulfuric acid solution of ethyl orthosilicate, pH=2 and N, stir until obtain silica precursor vitreosol at N '-dimethyl acetamide is mixed in 40 DEG C according to mol ratio 1:4.1:1; Be 15% to be uniformly mixed the vitreosol of BPDA/PABZ polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution carried out heat sinkly altogether analysing reaction 4 hours 190 DEG C of stirrings, filter, dry.
According to the condition of embodiment 3, it is carried out to the test of adsorbance and adsorbance conservation rate.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Embodiment 5
In a nitrogen atmosphere, take mol ratio as PABZ, MABZ and PMDA of 5:5:10 be raw material, first diamine monomer PABZ and MABZ is joined in dimethyl sulfoxide (DMSO), at room temperature be stirred to it dissolve and after being uniformly dispersed, add dianhydride monomer PMDA, continue stirring reaction and within 10 hours, obtain the PMDA/PABZ/MABZ polyamic acid solution that solid content is 5%, wherein the molar content of benzimidazole unit is 50%; Stir until obtain silica precursor vitreosol at the acetic acid solution of ethyl orthosilicate, pH=2 and dimethyl sulfoxide (DMSO) are mixed in 40 DEG C according to mol ratio 1:4:1; Be 20% to be uniformly mixed the vitreosol of PMDA/PABZ/MABZ polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution is carried out heat sinkly altogether analysing reaction 2 hours 200 DEG C of stirrings, filter, dry.
It has been carried out to the test of adsorbance and adsorbance conservation rate, wherein adsorbance conservation rate is the hydrochloric acid solution ultrasonic oscillation process 15 minutes polyimide/silicon dioxide nano composite powder having adsorbed heavy metal ion being placed in pH=1, then filters; Namely filtration gained powder is completed desorption and regeneration in 15 minutes in 330 DEG C of heat treatments, and the test carried out after totally 100 times of iterative cycles with this understanding.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Embodiment 6
In a nitrogen atmosphere, take mol ratio as MDA, MABZ and ODPA of 1:9:10 be raw material, first diamine monomer MDA and PABZ is joined in dimethyl sulfoxide (DMSO), at room temperature be stirred to it dissolve and after being uniformly dispersed, add dianhydride monomer ODPA, continue stirring reaction and within 7 hours, obtain the ODPA/MABZ/MDA polyamic acid solution that solid content is 20%, wherein the molar content of benzimidazole unit is 45%; Stir until obtain silica precursor vitreosol at the oxalic acid solution of ethyl orthosilicate, pH=1 and dimethyl sulfoxide (DMSO) are mixed in 40 DEG C according to mol ratio 1:4:1; Be 25% to be uniformly mixed the vitreosol of ODPA/MABZ/MDA polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution is carried out heat sinkly altogether analysing reaction 2.5 hours 160 DEG C of stirrings, filter, dry.
According to the condition of embodiment 5, it is carried out to the test of adsorbance and adsorbance conservation rate.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Embodiment 7
In a nitrogen atmosphere, take mol ratio as DABA, PABZ and 6FDA of 2:8:10 be raw material, first diamine monomer DABA and PABZ is joined N, in N '-dimethyl formamide, at room temperature be stirred to after it is uniformly dispersed and add dianhydride monomer 6FDA, continue stirring reaction and within 10 hours, obtain the 6FDA/PABZ/DABA polyamic acid solution that solid content is 15%, wherein the molar content of benzimidazole unit is 40%; By the hydrochloric acid solution of ethyl orthosilicate, pH=3 and N, stir until obtain silica precursor vitreosol at N '-dimethyl formamide is mixed in 40 DEG C according to mol ratio 1:4:1; Be 8% to be uniformly mixed the vitreosol of 6FDA/PABZ/DABA polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution is carried out heat sinkly altogether analysing reaction 4 hours 170 DEG C of stirrings, filter, dry.
According to the method for embodiment 1, it is carried out to the test of adsorbance and adsorbance conservation rate.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Embodiment 8
In a nitrogen atmosphere, take mol ratio as the BOA of 2:8:10, PABZ and TPDA is raw material, first diamine monomer BOA and PABZ is joined N, in N '-dimethyl formamide, at room temperature be stirred to it dissolve and add dianhydride monomer TPDA after being uniformly dispersed, continue stirring reaction and within 10 hours, obtain the TPDA/BOA/PABZ polyamic acid solution that solid content is 12%, wherein the molar content of benzimidazole unit is 40%; By the oxalic acid of ethyl orthosilicate, pH=3 and hydrochloric acid mixed solution and N, stir until obtain silica precursor vitreosol at N '-dimethyl formamide is mixed in 40 DEG C according to mol ratio 1:4:1; Be 10% to be uniformly mixed the vitreosol of TPDA/BOA/PABZ polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution is carried out heat sinkly altogether analysing reaction 4 hours 200 DEG C of stirrings, filter, dry.
According to the method for embodiment 1, it is carried out to the test of adsorbance and adsorbance conservation rate.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Embodiment 9
In a nitrogen atmosphere, take mol ratio as the HPA of 4:6:10, MABZ and BTDA is raw material, first diamine monomer HPA and MABZ is joined in 1-METHYLPYRROLIDONE, at room temperature be stirred to after it is uniformly dissolved and add dianhydride monomer BTDA, continue stirring reaction and within 5 hours, obtain the BTDA/HPA/MABZ polyamic acid solution that solid content is 18%, wherein the molar content of benzimidazole unit is 30%; Stir until obtain silica precursor vitreosol at the oxalic acid of ethyl orthosilicate, pH=2 and nitric acid mixed solution and 1-METHYLPYRROLIDONE are mixed in 40 DEG C according to mol ratio 1:4:1; Be 5% to be uniformly mixed the vitreosol of BTDA/HPA/MABZ polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution is carried out heat sinkly altogether analysing reaction 3 hours 150 DEG C of stirrings, filter, dry.
According to the method for embodiment 1, it is carried out to the test of adsorbance and adsorbance conservation rate.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Embodiment 10
In a nitrogen atmosphere, take mol ratio as ODA, MABZ, PABZ and BTDA of 1:4:5:10 be raw material, first diamine monomer ODA, MABZ and PABZ are joined in 1-METHYLPYRROLIDONE, at room temperature be stirred to it dissolve and after being uniformly dispersed, add dianhydride monomer BTDA, continue stirring reaction and within 9 hours, obtain the BTDA/ODA/MABZ/PABZ polyamic acid solution that solid content is 12%, wherein the molar content of benzimidazole unit is 45%; Stir until obtain silica precursor vitreosol at the salpeter solution of ethyl orthosilicate, pH=2 and 1-METHYLPYRROLIDONE are mixed in 40 DEG C according to mol ratio 1:4:1; Be 18% to be uniformly mixed the vitreosol of BTDA/ODA/MABZ/PABZ polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution is carried out heat sinkly altogether analysing reaction 2 hours 210 DEG C of stirrings, filter, dry.
According to the method for embodiment 1, it is carried out to the test of adsorbance and adsorbance conservation rate.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Embodiment 11
In a nitrogen atmosphere, take mol ratio as ODA, MDA, MABZ, PABZ and PMDA of 1:2:4:3:10 be raw material, first diamine monomer ODA, MDA, MABZ and PABZ are joined in 1-METHYLPYRROLIDONE, at room temperature be stirred to it dissolve and after being uniformly dispersed, add dianhydride monomer PMDA, continue stirring reaction and within 8 hours, obtain the PMDA/ODA/MDA/MABZ/PABZ polyamic acid solution that solid content is 16%, wherein the molar content of benzimidazole unit is 35%; Stir until obtain silica precursor vitreosol at the oxalic acid solution of ethyl orthosilicate, pH=2 and 1-METHYLPYRROLIDONE are mixed in 40 DEG C according to mol ratio 1:4:1; Be 12% to be uniformly mixed the vitreosol of PMDA/ODA/MDA/MABZ/PABZ polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution is carried out heat sinkly altogether analysing reaction 3 hours 200 DEG C of stirrings, filter, dry.
According to the method for embodiment 1, it is carried out to the test of adsorbance and adsorbance conservation rate.
Adsorbance and the adsorbance conservation rate of gained sorbing material see attached list.
Comparative example 1
In a nitrogen atmosphere, take mol ratio as PABZ and BPDA of 1:1 be raw material, first diamine monomer PABZ is joined in 1-METHYLPYRROLIDONE, at room temperature be stirred to after it is uniformly dispersed and add dianhydride monomer BPDA, continue stirring reaction and within 10 hours, obtain the BPDA/PABZ polyamic acid solution that solid content is 10%, wherein the molar content of benzimidazole unit is 50%; Again BPDA/PABZ polyamic acid solution carried out heat sinkly altogether analysing reaction 4 hours 180 DEG C of stirrings, filter, dry and can obtain polyimide powder.
According to the method for embodiment 1, the test of adsorbance is carried out to it.
The adsorbance of gained sorbing material sees attached list.
Comparative example 2
In a nitrogen atmosphere, take mol ratio as ODA and BPDA of 1:1 be raw material, first diamine monomer ODA is joined in 1-METHYLPYRROLIDONE, at room temperature be stirred to after it dissolves and add dianhydride monomer BPDA, continue stirring reaction and within 10 hours, obtain the BPDA/ODA polyamic acid solution that solid content is 10%, wherein the molar content of benzimidazole unit is 0%; Stir until obtain silica precursor vitreosol at the oxalic acid solution of ethyl orthosilicate, pH=2 and 1-METHYLPYRROLIDONE are mixed in 40 DEG C according to mol ratio 1:4:1; Be 10% to be uniformly mixed the vitreosol of BPDA/ODA polyamic acid solution and silica precursor by the mass fraction of wherein silica, then this mixed solution carried out heat sinkly altogether analysing reaction 4 hours 180 DEG C of stirrings, filter, dry.
According to the method for embodiment 1, the test of adsorbance is carried out to it.
The adsorbance of gained sorbing material sees attached list.
Subordinate list
From subordinate list, the polyimide/silicon dioxide nanometer heavy-metal adsorption material that the present invention obtains is 20 ~ 80mg/g to the adsorbance of copper ion, recycles the adsorbance conservation rate > 98% after 100 times.Only using polyimides as sorbing material, almost there is no suction-operated, and if there is no benzimidazole unit in polyimides, there is no suction-operated yet.Polyimides and silica because having benzimidazole unit in visible polyimide/silicon dioxide nanometer heavy-metal adsorption material of the present invention interact, and reach good adsorption effect, and good heat resistance, can be recycled.
Claims (9)
1. a preparation method for polyimide/silicon dioxide nanometer heavy-metal adsorption material, it is characterized in that the processing step of the method and condition as follows:
(1) diamine monomer, dianhydride monomer and polar non-solute are obtained by existing typical polymerization methods polymerization the polyamic acid solution that solid content is 5 ~ 20%, and the benzimidazole unit containing molar fraction 25 ~ 50% in this polyamic acid;
(2) acid solution of ethyl orthosilicate, PH=1 ~ 3 and polar non-solute sol-gel process are conveniently prepared silica precursor colloidal sol;
(3) proportioning that the silica precursor colloidal sol that polyamic acid solution step (1) obtained and step (2) obtain is 5 ~ 50% by the mass fraction of silica in gained polyimide/silicon dioxide nanometer powder mixes, and then carries out heat sinkly altogether analysing reaction 2 ~ 4 hours at 150 ~ 250 DEG C.
2. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 1, it is characterized in that the diamine monomer described in the method or for 2-(4-aminophenyl)-5-aminobenzimidazole or/and 2-(3-aminophenyl)-5-aminobenzimidazole, or be that 2-(4-aminophenyl)-5-aminobenzimidazole is or/and 2-(3-aminophenyl)-5-aminobenzimidazole and 4, 4 '-diphenyldiamine, p-phenylenediamine (PPD), 2-(4-aminophenyl)-5-An base benzoxazole, benzidine, m-phenylene diamine (MPD) and 4, 4 ', the mixture that at least one in-diaminobenzene anilid is formed.
3. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 1 and 2, is characterized in that the dianhydride monomer described in the method is at least one in pyromellitic acid dianhydride, BPDA, oxydiphthalic, benzophenone tetracarboxylic dianhydride, terphenyl tetracarboxylic dianhydride and bis trifluoromethyl tetracarboxylic dianhydride.
4. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 1 or 2, is characterized in that described acid solution is the solution of at least one preparation in hydrochloric acid, oxalic acid, nitric acid, sulfuric acid and acetic acid.
5. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 3, is characterized in that described acid solution is the solution of at least one preparation in hydrochloric acid, oxalic acid, nitric acid, sulfuric acid and acetic acid.
6. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 1 or 2, it is characterized in that described polar non-solute is 1-METHYLPYRROLIDONE, N, N '-dimethyl acetamide, N, any one in N '-dimethyl formamide or dimethyl sulfoxide (DMSO).
7. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 5, it is characterized in that described polar non-solute is 1-METHYLPYRROLIDONE, N, N '-dimethyl acetamide, N, any one in N '-dimethyl formamide or dimethyl sulfoxide (DMSO).
8. the polyimide/silicon dioxide nanometer heavy-metal adsorption material prepared of method described in a claim 1, this sorbing material is polyimide/silicon dioxide nano composite powder, wherein silica containing mass fraction is 5 ~ 50%, the molar fraction of contained benzimidazole unit is 25 ~ 50%, first time, adsorbance was 20 ~ 80mg/g, adsorbance conservation rate >=98% after adsorption-regeneration cycles 100 times.
9. be suitable for a renovation process for polyimide/silicon dioxide nanometer heavy-metal adsorption material described in claim 8, processing step and the condition of the method are as follows:
(1) hydrochloric acid solution polyimide/silicon dioxide nano composite powder having adsorbed heavy metal ion being placed in PH=1 ~ 3 processes at least 10 minutes, then filters;
(2) gained powder will be filtered in 320 ~ 350 DEG C of heat treatments at least 10 minutes.
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