CN105312035B - Polyimide/silicon dioxide nanometer heavy-metal adsorption material and its preparation and renovation process - Google Patents
Polyimide/silicon dioxide nanometer heavy-metal adsorption material and its preparation and renovation process Download PDFInfo
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Abstract
Polyimide/silicon dioxide nanometer heavy-metal adsorption material disclosed by the invention be with the polyamic acid solution containing benzimidazole unit and silica precursor colloidal sol by evenly mixing, and heat sink analysis reaction altogether is carried out at 150~250 DEG C and is prepared, the sorbing material is nano composite powder, the mass fraction of silica contained therein is 5~50%, the molar fraction of contained benzimidazole unit is 25~50%, first time adsorbance is 20~80mg/g, absorption regeneration circulate 100 times after adsorbance conservation rate >=98%.Polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention is not only heat-resist, it can be used for a long time in the environment below 250 DEG C, and the adsorbance of heavy metal ion is big, simultaneously can be under the matching of simple and reliable renovation process provided by the invention, it adsorbs the conservation rate of heavy metal ability and is positively retained at more than 98% after recycling 100 times, and service life is grown, and cost is low, more economical environmental protection, the blank of high score subclass high temperature resistant sorbing material is also filled up.
Description
Technical field
The invention belongs to heavy-metal adsorption material and its preparation and technical field of regeneration, and in particular to and a kind of polyimides/
Silica nanometer heavy-metal adsorption material and its preparation and renovation process.
Background technology
Heavy metal is a kind of material to environment permanent deleterious with savings property, as long as there is micro contain in natural water body
Amount can produce poisonous effect, and can not be changed into innocuous substance by chemical or biological prosthetic process, and its proportion is more than 5g/
cm3, about have 45 kinds in nature, but to be generally concerned with Hg, Cd, Pb, Cr, Cu, Co, Ni etc. several by people in environmental science
The larger heavy metal of kind toxicity.Biology absorbs heavy metal from environment can pass through the biological magnification of food chain, higher
It is enriched with level organism into thousands of times, human body is then entered by food, savings gets up in some organs of human body
Slow poisoning is caused, is detrimental to health.Therefore, how scientificlly and effectively to handle heavy metal wastewater thereby and have become domestic and international scientific research
One of focus of worker's research.The processing method of heavy metal waste water mainly has at present：Chemical precipitation method, oxidation-reduction method,
Absorption method, electrolysis, electroosmose process, concentration method, bioanalysis etc..Wherein, absorption method because its material it is cheap and easily-available, cost is low, goes
Except effect is good, the favor of people is constantly subjected to.
Classified according to adsorption mechanism, absorption method is broadly divided into physical absorption and chemisorbed.Common physical absorption
It is to use inorganic or carbons sorbing material, such as activated carbon, natural zeolite, molecular sieve, nano material.They are using higher
The highly developed gap structure such as a large amount of micropores, cavity, passage is contained to carry out efficient absorption in specific surface area or surface.But should
Class sorbing material had both adsorbed heavy metal or had adsorbed other compounds, thus its absorption is without selectivity.High score subclass sorbing material
Due to that with special chemical functional group, can be chelated with the heavy metal ion in waste water, formation has netted cage type knot
The compound of structure, or the purpose of absorption heavy metal ion can be reached with heavy metal ion formation ionic bond, Covalent bonding together,
Thus, this kind of sorbing material heavy metal ion is that have stronger selectivity.The high score subclass sorbing material master used at present
Have cellulose of polyacrylamide, the chitosan of modification and modification etc., although these polymer adsorbing material heavy metals from
Son all has stronger selectivity, but due to belonging to the high polymer material of aliphatic category from the point of view of their molecular backbone, because
It is such as the most frequently used as long-term use of easy more than 80 DEG C such as polyacrylamide polymer adsorbing material and generally heat resistance is poor
Degraded, recycling rate poor (Kong Bailing, hydrolysis of polyacrylamide repercussion study [J] oil under the conditions of the bright high-temperature oil reservoirs of sieve nine
Exploration and development, 1998,25 (6):67-69.).And though aromatic polyimide is the extraordinary organic high score of a kind of heat resistance
Sub- material, but the group that because not containing heavy metal ion in general polyimide structures there is Absorptive complex wave to act on, and it is not
With hydrophily, therefore aromatic polyimide heavy metal ion does not almost have suction-operated, it is impossible to as sorbing material.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, to provide a kind of polyimide/silicon dioxide nanometer weight first
The preparation method of metal-adsorbing material.
It is a further object to provide a kind of polyimide/silicon dioxide nanometer huge sum of money prepared by the above method
Belong to sorbing material.
Another object of the present invention is to provide a kind of above-mentioned polyimide/silicon dioxide nanometer heavy-metal adsorption material again
Generation method.
The preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention, the work of this method
Skill step and condition are as follows：
(1) diamine monomer, dianhydride monomer and polar non-solute are polymerize by existing typical polymerization methods and consolidated
Content is 5~20% polyamic acid solution, and the benzimidazole unit containing molar fraction 25~50% in the polyamic acid；
(2) sol-gel by tetraethyl orthosilicate, the acid solution of pH=1~3 and polar non-solute according to routine
Method prepares silica precursor colloidal sol；
(3) the silica precursor colloidal sol that the polyamic acid solution for obtaining step (1) obtains with step (2) is by gained
The proportioning that the mass fraction of silica is 5~50% in polyimide/silicon dioxide nanometer powder is well mixed, Ran Hou
Heat sink analysis reaction 2~4 hours altogether are carried out at 150~250 DEG C.
Typical polymerization methods in above method described in step (1) are referring specifically to low apparent disclosed in CN103788651A
The preparation method of the polyamic acid solution of viscosity.
Conventional sol-gel process in above method described in step (2) is referring specifically to Zhang P, Chen Y, Li
G,et al.Enhancement of properties of polyimide/silica hybrid nanocomposites
by benzimidazole formed hydrogen bond[J].Polymers for Advanced Technologies,
2012,23(10):Method disclosed in 1362-1368..
Diamine monomer described in above method is 2- (4- aminophenyls) -5- aminobenzimidazoles or/and 2- (3- ammonia
Base phenyl) -5- aminobenzimidazoles, or for 2- (4- aminophenyls) -5- aminobenzimidazoles or/and 2- (3- aminophenyls) -
5- aminobenzimidazoles and 4,4 '-diphenyldiamine, p-phenylenediamine, 2- (4- aminophenyls) -5- An bases benzoxazole, biphenyl two
The mixture that at least one of amine, m-phenylene diamine (MPD) and 4,4 ' ,-diaminobenzene anilid are formed.The knot of each diamine monomer
Structure formula is as follows：
Dianhydride monomer described in above method is pyromellitic acid dianhydride, BPDA, oxydiphthalic, two
At least one of benzophenone tetracarboxylic dianhydride, terphenyl tetracarboxylic dianhydride and bis trifluoromethyl tetracarboxylic dianhydride.The structure of each dianhydride monomer
Formula is as follows：
Acid solution described in above method is what at least one of hydrochloric acid, oxalic acid, nitric acid, sulfuric acid, acetic acid were prepared
Solution.
Polar non-solute described in above method is 1-METHYLPYRROLIDONE, N, N '-dimethyl acetamide, N,
Any of N '-dimethyl formamide or dimethyl sulfoxide (DMSO).
Reaction 2~4 is small at preferably 170~200 DEG C of the operating condition of common heat sink analysis described in above method step (3)
When.
Polyimide/silicon dioxide nanometer heavy-metal adsorption material prepared by the above method provided by the invention, the absorption
Material is polyimide/silicon dioxide nano composite powder, and the mass fraction of silica contained therein is 5~50%, contained
The molar fraction of benzimidazole unit is 25~50%, and first time adsorbance is 20~80mg/g, adsorption-desorption-regeneration cycle
Adsorbance conservation rate >=98% after 100 times.
The renovation process of above-mentioned polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention, this method
Processing step and condition it is as follows：
(1) the polyimide/silicon dioxide nano composite powder for having adsorbed heavy metal ion is placed in the salt of pH=1~3
Handle in acid solution at least 10 minutes, then filter；
(2) filtering gained powder is heat-treated at least 10 minutes in 320~350 DEG C.
The processing of step (1) is that ultrasonic oscillation is handled or mechanical agitation is handled in above renovation process.
" adsorption-desorption-regeneration " of above-mentioned polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention
Circulation schematic diagram is shown in Fig. 4.
The present invention compared with prior art, has advantages below：
1st, due in polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention, polyimides and two
Two kinds of materials of silica can be with high temperature resistant, thus the glass transition temperature of material can be made to be up to 423 DEG C, heat-resist, energy
Used for a long time in enough environment below 250 DEG C, and cover the environment temperature that most sorbing materials may use, overcome
The shortcomings that existing polymer adsorbing material poor heat resistance.
2nd, due in the polyimides contained by polyimide/silicon dioxide nano composite powder of the inventive method in offer
Introduce the benzimidazole unit of Sq, and chemical chelation can be formed with heavy metal ion very strong for benzimidazole
Complex compound, thus the new function of polyimides is not give only --- suction-operated, its purposes is expanded, also inhaled for high score subclass
The blank of high temperature resistant sorbing material has been filled up in enclosure material field.
3rd, due to the inventive method in the polyimide/silicon dioxide nano composite powder of offer not only in polyimides
The benzimidazole unit of heavy metal ion can be adsorbed by being introduced in main chain, and introduce the dioxy containing hydrophilic hydroxy group simultaneously
SiClx, thus make the polyimide/silicon dioxide nano composite powder of gained that there is good hydrophily and dispersiveness, not only solve
Polyimide powder of having determined the problem of bad dispersibility, also preferably catches heavy metal ion, increase pair in water for benzimidazole
The adsorbance of heavy metal ion provides strong support.
4th, the physical aspect of the polyimide/silicon dioxide heavy-metal adsorption material prepared due to the present invention is nano powder
End, thus there is larger specific surface area, the contact area with heavy metal ion can be increased, so as to further increase its absorption
Amount.
5th, because preparation method provided by the invention is not only skillfully constructed, and it is simple ripe, thus easily popularization and application.
6th, because renovation process provided by the invention can not only be to polyimides/titanium dioxide after absorption heavy metal ion
Silicon nanopowder realizes desorption, and method is simple and reliable, thus can easily realize the regeneration and recycling of sorbing material,
Reduce the use cost of material.
7th, because polyimide/silicon dioxide heavy-metal adsorption material provided by the invention can be recycled for multiple times, and
The conservation rate of absorption heavy metal ability after " adsorption-desorption-regeneration " recycles 100 times uses more than 98%
Long lifespan, it is economic and environment-friendly.
Brief description of the drawings
Fig. 1 is prepared by polyimide/silicon dioxide nano composite powder prepared by the embodiment of the present invention 1 and comparative example 1
The photo that pure polyimide powder disperses in water, wherein PI-10 are polyimide/silicon dioxide nanometer prepared by embodiment 1
Composite powder, PI-0 are pure polyimide powder prepared by comparative example 1.It is sub- from photo comparison, polyamides prepared by embodiment 1
Amine/silicon dioxide nano composite powder end is dispersed in water, shows that hydrophily is preferable, and pure polyamides prepared by comparative example 1 is sub-
Amine powder is to be deposited in bottom, shows that hydrophily is bad, it is impossible to be dispersed in water.
Fig. 2 is the ESEM (SEM) of polyimide/silicon dioxide nano composite powder prepared by the embodiment of the present invention 1
Photo.From photo, the composite powder is nanoscale.
Fig. 3 is the dynamic mechanically of polyimide/silicon dioxide nanometer heavy-metal adsorption material prepared by the embodiment of the present invention 1
Analyze (DMA) test chart (tester model：TA Q800,10 DEG C/min, amplitude 25um of programming rate, frequency：1Hz).From
Understood in figure, the glass transition temperature of the sorbing material is up to 423 DEG C, illustrates heat-resist.
Fig. 4 is the " adsorption-desorption-again of polyimide/silicon dioxide nanometer heavy-metal adsorption material provided by the invention
It is raw " circulation schematic diagram.
Embodiment
Embodiment is given below so that the present invention to be specifically described, but it is necessarily pointed out that following examples
It is only used for that the present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the technology in the field is ripe
Practice some nonessential modifications and adaptations that personnel make according to present invention to the present invention and still belong to protection scope of the present invention.
In addition, what deserves to be explained is：
(1) adsorption effect that following examples and comparative example prepare material is the adsorption test carried out using copper ion, is had
Body operating method is：1g powder is taken to be put into 0.1mol/L Cu2+In solution, by sorbing material powder mistake after slightly shaking 10 minutes
Filter, the sorbing material powder after filtering are washed with deionized 3 times, dry, and it is m that weighing, which obtains quality,1Sorbing material powder.
Adsorbance W1It is expressed as the adsorbable copper ion matter of the polyimide/silicon dioxide nano composite powder of unit mass
Amount, its calculation formula are：
W1=(m1-1)
(2) suction after the circulation for the polyimide/silicon dioxide nano adsorption material that following examples are prepared 100 times
Attached amount conservation rate % " adsorption-desorption-regeneration " circulation experiment step is：Cu has been adsorbed by what the method for (1) obtained2+Polyamides it is sub-
Amine/silicon dioxide nano composite powder end is put into the hydrochloric acid solution of pH=1~3 ultrasonic vibration or mechanical agitation at least 10 minutes,
Filtering, that is, complete Cu2+Desorption；Cu will be desorbed2+Powder (because wherein having adsorbed HCl) be heat-treated at 320~350 DEG C
It is few 10 minutes, that is, HCl desorption is completed, and reclaim HCl gases.The adsorbance of powder is to be designated as after so circulating the 100th time
W100, adsorbance conservation rate is W100/W1%.
Embodiment 1
In a nitrogen atmosphere, using mol ratio as 1：1 PABZ and BPDA is raw material, and diamine monomer PABZ first is added into N-
In methyl pyrrolidone, it is stirred at room temperature to it after being uniformly dispersed and adds dianhydride monomer BPDA, continue stirring reaction 10 hours
The BPDA/PABZ polyamic acid solutions that solid content is 10% are obtained, the wherein molar content of benzimidazole unit is 50%；Will just
Silester, pH=2 oxalic acid solution and 1-METHYLPYRROLIDONE are according to mol ratio 1：4：1 is mixed in stirring at 40 DEG C until obtaining
To silica precursor vitreosol；The vitreosol of BPDA/PABZ polyamic acid solutions and silica precursor is pressed
Wherein the mass fraction of silica is uniformly mixed for 10%, and the mixed solution then is carried out into common heat in 180 DEG C of stirrings
Precipitating is reacted 4 hours, filtering, drying.
The present invention has made following test to sorbing material obtained by the present embodiment and investigated：
1) the scattered situation in water, the PI-10 as a result seen in Fig. 1, and the polyimide powder prepared with comparative example 1 exists
Deployment conditions in water contrast, the PI-0 seen in Fig. 1.
2) its pattern is observed, as a result sees Fig. 2.
3) dynamic mechanical analysis (DMA) test has been carried out to it, has as a result seen Fig. 3.
4) test of adsorbance and adsorbance conservation rate has been carried out to it, wherein adsorbance conservation rate is will to have adsorbed a huge sum of money
The polyimide/silicon dioxide nano composite powder of category ion is placed in mechanical agitation in pH=1 hydrochloric acid solution and handled 10 minutes,
Then filter；Filtering gained powder is completed into desorption and regeneration, and iterative cycles on this condition for 10 minutes in 320 DEG C of heat treatments
The test carried out after totally 100 times.
Embodiment 2
In a nitrogen atmosphere, using mol ratio as 5：5：10 PDA, PABZ and BPDA is raw material, first by diamine monomer PDA and
PABZ is added to N, in N '-dimethyl acetamide, is stirred at room temperature to its dissolving and adds dianhydride monomer after being uniformly dispersed
BPDA, continue stirring reaction and obtain within 8 hours the BPDA/PDA/PABZ polyamic acid solutions that solid content is 12%, wherein benzo miaow
The molar content of azoles unit is 25%；By tetraethyl orthosilicate, pH=2 oxalic acid solution and N, N '-dimethyl acetamide is according to rubbing
That ratio 1：4：1.5 are mixed at 50 DEG C stirring until obtaining silica precursor vitreosol；By BPDA/PDA/PABZ polyamides
The vitreosol of amino acid solution and silica precursor is uniformly mixed by the mass fraction of wherein silica for 50%,
Then the mixed solution is subjected to heat sink analysis reaction 3 hours altogether, filtering, drying in 250 DEG C of stirrings.
The test of adsorbance and adsorbance conservation rate is carried out to it, wherein adsorbance conservation rate is will to have adsorbed heavy metal
The polyimide/silicon dioxide nano composite powder of ion is placed in ultrasonic oscillation in pH=2 hydrochloric acid solution and handled 10 minutes,
Then filter；Filtering gained powder is completed into desorption and regeneration, and iterative cycles on this condition for 10 minutes in 340 DEG C of heat treatments
The test carried out after totally 100 times.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Embodiment 3
In a nitrogen atmosphere, using mol ratio as 3：7：10 ODA, PABZ and BPDA is raw material, first by diamine monomer ODA with
PABZ is added to N, in N '-dimethyl formamide, is stirred at room temperature to its dissolving and adds dianhydride monomer after being uniformly dispersed
BPDA, continue stirring reaction and obtain within 5 hours the BPDA/ODA/PABZ polyamic acid solutions that solid content is 15%, wherein benzo miaow
The molar content of azoles unit is 35%；By tetraethyl orthosilicate, pH=2 salpeter solution and N, N '-dimethyl formamide is according to rubbing
That ratio 1：4：1.2 are mixed at 45 DEG C stirring until obtaining silica precursor vitreosol；By BPDA/ODA/PABZ polyamides
The vitreosol of amino acid solution and silica precursor is uniformly mixed by the mass fraction of wherein silica for 30%,
Then the mixed solution is subjected to heat sink analysis reaction 3 hours altogether, filtering, drying in 170 DEG C of stirrings.
The test of adsorbance and adsorbance conservation rate is carried out to it, wherein adsorbance conservation rate is will to have adsorbed heavy metal
The polyimide/silicon dioxide nano composite powder of ion is placed in mechanical agitation processing 20 minutes in pH=3 hydrochloric acid solution, so
After filter；Filtering gained powder is completed into desorption and regeneration in 10 minutes in 350 DEG C of heat treatments, and iterative cycles are total on this condition
The test carried out after 100 times.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Embodiment 4
In a nitrogen atmosphere, using mol ratio as 10:5:5 MABZ, PMDA and BPDA is raw material, first by diamine monomer MABZ
It is added to N, in N '-dimethyl acetamide, is stirred at room temperature to it after being uniformly dissolved and adds dianhydride monomer BPDA and PMDA, after
Continuous stirring reaction obtains the BPDA/PMDA/PABZ polyamic acid solutions that solid content is 8% for 8 hours, wherein benzimidazole unit
Molar content is 50%；By tetraethyl orthosilicate, pH=2 sulfuric acid solution and N, N '-dimethyl acetamide is according to mol ratio 1：
4.1：1 is mixed at 40 DEG C stirring until obtaining silica precursor vitreosol；By BPDA/PABZ polyamic acid solutions with
The vitreosol of silica precursor is uniformly mixed by the mass fraction of wherein silica for 15%, then mixes this
Close solution and carry out heat sink analysis reaction 4 hours altogether, filtering, drying in 190 DEG C of stirrings.
The test of adsorbance and adsorbance conservation rate has been carried out to it according to the condition of embodiment 3.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Embodiment 5
In a nitrogen atmosphere, using mol ratio as 5:5:10 PABZ, MABZ and PMDA is raw material, first by diamine monomer PABZ
It is added to MABZ in dimethyl sulfoxide (DMSO), is stirred at room temperature to its dissolving and adds dianhydride monomer PMDA after being uniformly dispersed, after
Continuous stirring reaction obtains the PMDA/PABZ/MABZ polyamic acid solutions that solid content is 5%, wherein benzimidazole unit for 10 hours
Molar content be 50%；By tetraethyl orthosilicate, pH=2 acetic acid solution and dimethyl sulfoxide (DMSO) according to mol ratio 1：4：1 mixing
Stirring is until obtain silica precursor vitreosol at 40 DEG C；By PMDA/PABZ/MABZ polyamic acid solutions and dioxy
The vitreosol of SiClx presoma is uniformly mixed by the mass fraction of wherein silica for 20%, then that the mixing is molten
Liquid carries out heat sink analysis reaction 2 hours altogether, filtering, drying in 200 DEG C of stirrings.
The test of adsorbance and adsorbance conservation rate is carried out to it, wherein adsorbance conservation rate is will to have adsorbed heavy metal
The polyimide/silicon dioxide nano composite powder of ion is placed in ultrasonic oscillation in pH=1 hydrochloric acid solution and handled 15 minutes,
Then filter；Filtering gained powder is completed into desorption and regeneration, and iterative cycles on this condition for 15 minutes in 330 DEG C of heat treatments
The test carried out after totally 100 times.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Embodiment 6
In a nitrogen atmosphere, using mol ratio as 1:9:10 MDA, MABZ and ODPA is raw material, first by diamine monomer MDA with
PABZ is added in dimethyl sulfoxide (DMSO), is stirred at room temperature to its dissolving and is added dianhydride monomer ODPA after being uniformly dispersed, continues
Stirring reaction obtains the ODPA/MABZ/MDA polyamic acid solutions that solid content is 20% for 7 hours, and wherein benzimidazole unit is rubbed
Your content is 45%；By tetraethyl orthosilicate, pH=1 oxalic acid solution and dimethyl sulfoxide (DMSO) according to mol ratio 1：4：1 is mixed in 40
Stirring is until obtain silica precursor vitreosol at DEG C；By ODPA/MABZ/MDA polyamic acid solutions and silica
The vitreosol of presoma is uniformly mixed by the mass fraction of wherein silica for 25%, and then the mixed solution exists
160 DEG C of stirrings carry out heat sink analysis reaction 2.5 hours altogether, filtering, drying.
The test of adsorbance and adsorbance conservation rate has been carried out to it according to the condition of embodiment 5.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Embodiment 7
In a nitrogen atmosphere, using mol ratio as 2:8:10 DABA, PABZ and 6FDA is raw material, first by diamine monomer DABA
N is added to PABZ, in N '-dimethyl formamide, is stirred at room temperature to it after being uniformly dispersed and is added dianhydride monomer 6FDA, after
Continuous stirring reaction obtains the 6FDA/PABZ/DABA polyamic acid solutions that solid content is 15%, wherein benzimidazole unit for 10 hours
Molar content be 40%；By tetraethyl orthosilicate, pH=3 hydrochloric acid solution and N, N '-dimethyl formamide is according to mol ratio 1：
4：1 is mixed at 40 DEG C stirring until obtaining silica precursor vitreosol；6FDA/PABZ/DABA polyamic acids is molten
The vitreosol of liquid and silica precursor is uniformly mixed by the mass fraction of wherein silica for 8%, then will
The mixed solution carries out heat sink analysis reaction 4 hours altogether, filtering, drying in 170 DEG C of stirrings.
The test of adsorbance and adsorbance conservation rate has been carried out to it according to the method for embodiment 1.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Embodiment 8
In a nitrogen atmosphere, using mol ratio as 2:8:10 BOA, PABZ and TPDA is raw material, first by diamine monomer BOA with
PABZ is added to N, in N '-dimethyl formamide, is stirred at room temperature to its dissolving and adds dianhydride monomer after being uniformly dispersed
TPDA, continue stirring reaction and obtain within 10 hours the TPDA/BOA/PABZ polyamic acid solutions that solid content is 12%, wherein benzo miaow
The molar content of azoles unit is 40%；By tetraethyl orthosilicate, pH=3 oxalic acid and hydrochloric acid mixed solution and N, N '-dimethyl first
Acid amides is according to mol ratio 1：4：1 is mixed at 40 DEG C stirring until obtaining silica precursor vitreosol；By TPDA/BOA/
The vitreosol of PABZ polyamic acid solutions and silica precursor is 10% stirring by the mass fraction of wherein silica
It is well mixed, the mixed solution is then subjected to heat sink analysis reaction 4 hours altogether, filtering, drying in 200 DEG C of stirrings.
The test of adsorbance and adsorbance conservation rate has been carried out to it according to the method for embodiment 1.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Embodiment 9
In a nitrogen atmosphere, using mol ratio as 4:6:10 HPA, MABZ and BTDA is raw material, first by diamine monomer HPA and
MABZ is added in 1-METHYLPYRROLIDONE, is stirred at room temperature to it after being uniformly dissolved and is added dianhydride monomer BTDA, continues to stir
Mix mole that reaction obtains BTDA/HPA/MABZ polyamic acid solutions, wherein benzimidazole unit that solid content is 18% for 5 hours
Content is 30%；By tetraethyl orthosilicate, pH=2 oxalic acid and nitric acid mixed solution and 1-METHYLPYRROLIDONE according to mol ratio 1：
4：1 is mixed at 40 DEG C stirring until obtaining silica precursor vitreosol；By BTDA/HPA/MABZ polyamic acid solutions
It is uniformly mixed for 5% by the mass fraction of wherein silica with the vitreosol of silica precursor, then should
Mixed solution carries out heat sink analysis reaction 3 hours altogether, filtering, drying in 150 DEG C of stirrings.
The test of adsorbance and adsorbance conservation rate has been carried out to it according to the method for embodiment 1.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Embodiment 10
In a nitrogen atmosphere, using mol ratio as 1:4:5:10 ODA, MABZ, PABZ and BTDA is raw material, first by diamines list
Body ODA, MABZ and PABZ are added in 1-METHYLPYRROLIDONE, are stirred at room temperature to its dissolving and are added two after being uniformly dispersed
Anhydride monomer BTDA, continue stirring reaction and obtain within 9 hours the BTDA/ODA/MABZ/PABZ polyamic acid solutions that solid content is 12%,
Wherein the molar content of benzimidazole unit is 45%；By tetraethyl orthosilicate, pH=2 salpeter solution and 1-METHYLPYRROLIDONE
According to mol ratio 1：4：1 is mixed at 40 DEG C stirring until obtaining silica precursor vitreosol；By BTDA/ODA/
The vitreosol of MABZ/PABZ polyamic acid solutions and silica precursor is 18% by the mass fraction of wherein silica
It is uniformly mixed, the mixed solution is then subjected to heat sink analysis reaction 2 hours altogether, filtering, drying in 210 DEG C of stirrings.
The test of adsorbance and adsorbance conservation rate has been carried out to it according to the method for embodiment 1.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Embodiment 11
In a nitrogen atmosphere, using mol ratio as 1:2:4:3:10 ODA, MDA, MABZ, PABZ and PMDA is raw material, first will
Diamine monomer ODA, MDA, MABZ and PABZ are added in 1-METHYLPYRROLIDONE, are stirred at room temperature to its dissolving and are disperseed equal
Dianhydride monomer PMDA is added after even, continues stirring reaction and obtains within 8 hours the PMDA/ODA/MDA/MABZ/ that solid content is 16%
The molar content of PABZ polyamic acid solutions, wherein benzimidazole unit is 35%；Tetraethyl orthosilicate, pH=2 oxalic acid is molten
Liquid and 1-METHYLPYRROLIDONE are according to mol ratio 1：4：1 is mixed at 40 DEG C stirring until to obtain silica precursor transparent molten
Glue；By the vitreosol of PMDA/ODA/MDA/MABZ/PABZ polyamic acid solutions and silica precursor by wherein titanium dioxide
The mass fraction of silicon is uniformly mixed for 12%, and it is small that the mixed solution then is carried out into heat sink analysis reaction 3 altogether in 200 DEG C of stirrings
When, filtering, drying.
The test of adsorbance and adsorbance conservation rate has been carried out to it according to the method for embodiment 1.
The adsorbance and adsorbance conservation rate of gained sorbing material are seen attached list.
Comparative example 1
In a nitrogen atmosphere, using mol ratio as 1：1 PABZ and BPDA is raw material, and diamine monomer PABZ first is added into N-
In methyl pyrrolidone, it is stirred at room temperature to it after being uniformly dispersed and adds dianhydride monomer BPDA, continue stirring reaction 10 hours
The BPDA/PABZ polyamic acid solutions that solid content is 10% are obtained, the wherein molar content of benzimidazole unit is 50%；Again will
BPDA/PABZ polyamic acid solutions carry out heat sink analysis reaction 4 hours altogether in 180 DEG C of stirrings, and filtering, drying can obtain polyamides Asia
Amine powder.
The test of adsorbance has been carried out to it according to the method for embodiment 1.
The adsorbance of gained sorbing material is seen attached list.
Comparative example 2
In a nitrogen atmosphere, using mol ratio as 1：1 ODA and BPDA is raw material, and diamine monomer ODA first is added into N- first
In base pyrrolidones, dianhydride monomer BPDA is added after being stirred at room temperature to its dissolving, continues stirring reaction and is consolidated for 10 hours
Content is 10% BPDA/ODA polyamic acid solutions, and wherein the molar content of benzimidazole unit is 0%；By positive silicic acid second
Ester, pH=2 oxalic acid solution and 1-METHYLPYRROLIDONE are according to mol ratio 1：4：1 is mixed at 40 DEG C stirring until obtaining dioxy
SiClx presoma vitreosol；By the vitreosol of BPDA/ODA polyamic acid solutions and silica precursor by wherein dioxy
The mass fraction of SiClx is uniformly mixed for 10%, and the mixed solution then is carried out into heat sink analysis reaction 4 altogether in 180 DEG C of stirrings
Hour, filtering, drying.
The test of adsorbance has been carried out to it according to the method for embodiment 1.
The adsorbance of gained sorbing material is seen attached list.
Subordinate list
It was found from subordinate list, polyimide/silicon dioxide nanometer heavy-metal adsorption material produced by the present invention is to copper ion
Adsorbance is 20~80mg/g, the adsorbance conservation rate ＞ 98% after recycling 100 times.Absorption is only used as using polyimides
Material, almost without suction-operated, and if there is no benzimidazole unit in polyimides, also without suction-operated.It can be seen that
Invent in the polyimide/silicon dioxide nanometer heavy-metal adsorption material because of the polyimides and two with benzimidazole unit
Silica interacts, and reaches good adsorption effect, and heat-resist, can be recycled.
Claims (10)
- A kind of 1. preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material, it is characterised in that the work of this method Skill step and condition are as follows：(1) diamine monomer, dianhydride monomer and polar non-solute are polymerize to obtain solid content by existing typical polymerization methods For 5~20% polyamic acid solution, and the benzimidazole unit containing molar fraction 25~50% in the polyamic acid；(2) sol-gel process by tetraethyl orthosilicate, the acid solution of pH=1~3 and polar non-solute according to routine Prepare silica precursor colloidal sol；(3) the silica precursor colloidal sol that the polyamic acid solution for obtaining step (1) obtains with step (2) is by gained polyamides The proportioning that the mass fraction of silica is 5~50% in imines/silica nano-powders is well mixed, then 150~ Heat sink analysis reaction 2~4 hours altogether are carried out at 250 DEG C.
- 2. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 1, its feature It is 2- (4- aminophenyls) -5- aminobenzimidazoles, 2- (3- aminophenyls) -5- ammonia to be the diamine monomer described in this method At least one of base benzimidazole.
- 3. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 1, its feature It is diamine monomer described in this method for 2- (4- aminophenyls) -5- aminobenzimidazoles, 2- (3- aminophenyls) -5- amino At least one of benzimidazole and 4,4 '-diphenyldiamine, p-phenylenediamine, 2- (4- aminophenyls) -5- An bases benzoxazole, The mixture that at least one of benzidine, m-phenylene diamine (MPD) and 4,4 ' ,-diaminobenzene anilid are formed.
- 4. the polyimide/silicon dioxide nanometer heavy-metal adsorption material according to any claim in claims 1 to 3 Preparation method, it is characterised in that the dianhydride monomer described in this method is pyromellitic acid dianhydride, BPDA, diphenyl ether four At least one of acid dianhydride, benzophenone tetracarboxylic dianhydride, terphenyl tetracarboxylic dianhydride and bis trifluoromethyl tetracarboxylic dianhydride.
- 5. the polyimide/silicon dioxide nanometer heavy-metal adsorption material according to any claim in claims 1 to 3 Preparation method, it is characterised in that described acid solution is that at least one of hydrochloric acid, oxalic acid, nitric acid, sulfuric acid and acetic acid are prepared Solution.
- 6. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 4, its feature exists In the solution that described acid solution is the preparation of at least one of hydrochloric acid, oxalic acid, nitric acid, sulfuric acid and acetic acid.
- 7. the polyimide/silicon dioxide nanometer heavy-metal adsorption material according to any claim in claims 1 to 3 Preparation method, it is characterised in that described polar non-solute is 1-METHYLPYRROLIDONE, N, N '-dimethyl acetamide, N, Any of N '-dimethyl formamide or dimethyl sulfoxide (DMSO).
- 8. the preparation method of polyimide/silicon dioxide nanometer heavy-metal adsorption material according to claim 6, its feature exists In described polar non-solute be 1-METHYLPYRROLIDONE, N, N '-dimethyl acetamide, N, N '-dimethyl formamide or Any of dimethyl sulfoxide (DMSO).
- 9. polyimide/silicon dioxide nanometer heavy-metal adsorption material prepared by a kind of claim 1 methods described, the adsorption material Expect for polyimide/silicon dioxide nano composite powder, the mass fraction of silica contained therein is 5~50%, contained benzene And the molar fraction of imidazole unit is 25~50%, first time adsorbance is 20~80mg/g, after adsorption-regeneration cycles 100 times Adsorbance conservation rate >=98%.
- 10. a kind of renovation process for being suitable for polyimide/silicon dioxide nanometer heavy-metal adsorption material described in claim 9, The processing step and condition of this method are as follows：(1) hydrochloric acid that the polyimide/silicon dioxide nano composite powder for having adsorbed heavy metal ion is placed in p H=1~3 is molten Handle in liquid at least 10 minutes, then filter；(2) filtering gained powder is heat-treated at least 10 minutes in 320~350 DEG C.
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| TWI665281B (en) * | 2018-03-23 | 2019-07-11 | 台虹科技股份有限公司 | Composition and solution for temporary bonding |
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