CN102766272B - Porous material and its preparation method - Google Patents
Porous material and its preparation method Download PDFInfo
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- CN102766272B CN102766272B CN201110116544.0A CN201110116544A CN102766272B CN 102766272 B CN102766272 B CN 102766272B CN 201110116544 A CN201110116544 A CN 201110116544A CN 102766272 B CN102766272 B CN 102766272B
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Abstract
The invention discloses a porous material and its preparation method. The method comprises the following steps of: uniformly mixing a base material and polyaldehyde or polyketones in a solvent, then adding polyamine for a reaction, forming a film after the reaction, and immersing and washing in an acid to obtain the porous material. The method can be used to prepare different porous materials, and simultaneously pore size distribution from nanometer to micron order is controllable. The preparation method provided by the invention has advantages of simple method and process, high preparation efficiency and good universality, is green and environmentally friendly, and is beneficial to large-scale production. In addition, raw materials can be recovered and repeatedly used.
Description
Technical field
The invention belongs to material technology field, particularly a kind of porous material and preparation method thereof.
Background technology
Porous material refers to have a large amount of certain size pore textures and the material of high specific surface area.Porous material generally has that relative density is low, specific surface area is high, lightweight, sound insulation, heat insulation, good penetrability and the excellent features such as absorption property, thereby be widely applied to aerospace, telecommunications, communications and transportation, nuclear power, medical science, environmental protection, metallurgy, machinery, building, electrochemistry and field of petrochemical industry, relate to all many-sided purposes such as absorption, separation, filtration, noise reduction, heat insulation, electromagnetic shielding, energy storage, drug loading, catalyzed reaction and biotechnology, in science and technology and the development of the national economy, play an important role.
The preparation method of porous material can be divided into sintering process, stretching method, track etch method, phase inversion process and template.Sintering process requires material will have good chemical stability, thermotolerance and mechanical stability, and the porosity of porous material of preparation is generally lower; Stretching method is applicable to partially crystalline polymer material, and thickness and the pore size distribution of film are wayward; Pore structure prepared by track etch method is cylindric parallel hole, does not connect each other; Phase inversion process be with specific control mode, polymkeric substance is precipitated from homogeneous phase liquid state change into solid-state, but the size in hole, distribute wayward.Template is that material and pore-creating agent is compound, then removes pore-creating agent, forms vesicular structure, by changing the conditions such as component ratio, pore-creating agent kind, controls pore size distribution.Conventional pore-creating agent has inorganic pore-creating agent (as sodium bicarbonate (NaHCO
3), ammonium hydrogencarbonate (NH
4hCO
3), sodium carbonate (Na
2cO
3), calcium carbonate (CaCO
3) and silicon-dioxide (SiO
2) etc.), small organic molecule (glycerine, glycol ether, ethanol, toluene, octane-iso, aviation spirit, normal heptane, silicone oil and whiteruss etc.), polymer pore-creating agent (polyoxyethylene glycol, hydroxypropylcellulose, polyvinylpyrrolidone etc.).But no matter these conventional pore-creating agents, be inorganic pore-creating agent or small organic molecule, poor with the consistency of polymers soln, and polymer pore-creating agent is also only good with specific one or more polymer phase capacitives, does not have universality.
Summary of the invention
The object of this invention is to provide a kind of porous material and preparation method thereof.
The method of preparing porous material provided by the invention, comprises the steps: body material and polyaldehyde or polyketones to mix in solvent, then adds polyamine to react, film forming after completion of the reaction, then in acid washing by soaking, obtain described porous material.
In the method, described body material is selected from the polyethersulfone that limiting viscosity is 0.24-0.36, number-average molecular weight is the polyimide prepolymer of 1000-5000, weight-average molecular weight is 50,000-200,000 polystyrene, viscosity-average molecular weight is 50,000-100,000 poly(lactic acid), weight-average molecular weight is 400,000-600,000 polyvinylidene difluoride (PVDF), weight-average molecular weight is 350,000-400,000 polymethylmethacrylate, number-average molecular weight is the epoxy resin prepolymer of 300-1000, number-average molecular weight is at least one in the resol performed polymer of 1000-5000 and urea resin prepolymer that number-average molecular weight is 500-1000, preferred characteristics viscosity is 0.24 polyethersulfone, molecular weight is 5000 polyimide prepolymer, weight-average molecular weight is 200,000 polystyrene, viscosity-average molecular weight is at least one in 100,000 poly(lactic acid) and the weight-average molecular weight polyvinylidene difluoride (PVDF) that is 400,000,
Described polyaldehyde be selected from oxalic dialdehyde, at least one in glutaraldehyde, terephthalaldehyde, m-terephthal aldehyde and 2,4-dimethyl-2-methoxymethyl glutaraldehyde, preferably at least one in glutaraldehyde, terephthalaldehyde and m-terephthal aldehyde; Due to glutaraldehyde highly volatile, therefore in actually operating, can select the glutaraldehyde water solution that the mass percentage concentration that is purchased is 50%;
Described polyketones are selected from dimethyl diketone, 3, at least one in 4-hexanedione and 4,5-acetyl caproyl, preferred dimethyl diketone, 3, at least one in 4-hexanedione and 4,5-acetyl caproyl;
Described polyamine is selected from polymine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, Ursol D, mphenylenediamine, 4,4 '-diaminodiphenylsulfone(DDS), 3, at least one in 4 '-diaminodiphenyl oxide and trimeric cyanamide, at least one in preferably polyethylene imines, triethylene tetramine, tetraethylene pentamine, Ursol D, mphenylenediamine, 4,4′ diaminodiphenyl sulfone and trimeric cyanamide; The weight-average molecular weight of described polymine is 1000-10000;
Described solvent is selected from N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N, at least one in 2-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), m-cresol, tetrahydrofuran (THF), ethanol, methyl alcohol, methylene dichloride and trichloromethane, preferred N, at least one in N-N,N-DIMETHYLACETAMIDE, DMF and methylene dichloride;
Described acid is selected from least one in hydrochloric acid, acetic acid, nitric acid and sulfuric acid, preferably at least one in hydrochloric acid, acetic acid and nitric acid.
The mass ratio of described body material, described polyaldehyde or polyketones and described polyamine is 0.5-4: 0.5-2: 0.5-2, preferably 2: 1: 1;
The volumetric molar concentration of described acid is 0.001-4mol/L, preferably 2mol/L.
In described reactions steps, temperature is 5-80 ℃, and preferably 25 ℃, the time is 0.5-4 hour, preferably 0.5 hour;
In described film forming step, temperature is 50-100 ℃, specifically can be 60 ℃-90 ℃, 60-80 ℃, 80-90 ℃, preferably 80 ℃, and the time is 0.5-4 hour, specifically can be 1-4 hour, 3-4 hour, 0.5-3 hour, 0.5-2 hour, 2-4 hour or 2-3 hour, preferably 2 hours;
In described soaking step, the time is 0.5-8 hour, preferably 1 hour;
In described washing step, number of times is 1-5 time, preferably 3 times, cleaning solvent is selected from the hydrochloric acid that concentration is 0.001-4mol/L, concentration is the acetic acid of 0.001-4mol/L, concentration is the nitric acid of 0.001-4mol/L, concentration is at least one in the sulfuric acid of 0.001-4mol/L and phosphoric acid that concentration is 0.001-4mol/L, preferred concentration is the hydrochloric acid of 0.5-4mol/L, concentration is the sulfuric acid of 0.5-4mol/L, concentration is at least one in the nitric acid of 0.5-4mol/L and acetic acid that concentration is 0.5-4mol/L, more preferably at least one in the acetic acid that the hydrochloric acid that concentration is 2mol/L and concentration are 2mol/L.
Described body material is selected from least one the method for preparing porous material in polyimide prepolymer, epoxy resin prepolymer and the resol performed polymer that number-average molecular weight is 1000-5000, in order to make the further curing cross-linked of film, improve the thermostability of film, after described film forming step, institute is set forth in acid before washing by soaking step, also the system after film forming is cured, or, in be set forth in acid, after washing by soaking step, gained porous material is cured;
In described curing schedule, temperature is 80-300 ℃, and preferably 300 ℃, the time is 0.5-6 hour, preferably 2 hours.This solidification value and time can be selected different curing modes according to the difference of matrix used material, keep certain hour to be cured, or adopt the mode of ladder-elevating temperature to be cured as can be in single temperature.While being resol performed polymer as matrix used material, this curing schedule can carry out in the following manner: at 150 ℃, be incubated 2h; While being polyimide prepolymer as matrix used material, this curing schedule can carry out in the following manner: successively at 80 ℃ of insulation 1h, and 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h.
The porous material of preparing according to the method described above and obtaining, also belongs to protection scope of the present invention.The aperture of this porous material can be 9 nanometers to 20 micron, and BET specific surface area can be 179-190m
2/ g, pore volume can be 0.59-0.63cm
3/ g.
In preparation method provided by the invention, polyaldehyde or polyketones react with polyamine and pore-creating agent compound there is Schiff's base (Schiff base) structure, Schiff's base is that nitrogen-atoms and carbon atom link with two keys the compounds forming, and by aldehydes or ketones and ammonia or amine condensation, is formed.Its reaction mechanism is: by aldehyde, ketone compounds and primary amine compounds containing carbonyl, carry out nucleophilic addition, nucleophilic reagent is aminated compounds, in its compound structure with on the nitrogen-atoms attack carbonyl group of lone electron pair with the carbon atom of positive charge, complete nucleophilic addition, form intermediate Alpha-hydroxy aminated compounds, then further dehydration forms Schiff's base.Polyaldehyde and polyamine are under alkaline condition, and easily reaction generates Schiff's base, forms gel network structure; Because Schiff's base is not rock steady structure, under acidic conditions, can again be decomposed into amine and aldehyde.Therefore the present invention is applied in this characteristic of Schiff's base in body material, first the co-continuous gel network structure that two-phase runs through under alkaline condition, then under acidic conditions, be decomposed into micromolecular amine and aldehyde, easily unreacted polyaldehyde, polyketones or polyamine removed from body material.By select different structure, from the Schiff's base of the different consistencies of body material, make itself and body material compound, the pore size of compound rear porous material can be controlled, by controlling polyaldehyde or polyketones in the amount ratio of polyamine and body material, the porosity of compound rear porous material can be controlled.Thereby, the method of preparing porous material provided by the invention, can prepare pore size distribution controlled porous material from nanometer to micron level, and the method preparation process is simple, and preparation efficiency is high, environmental protection, raw material can reclaim Reusability, be conducive to scale operation, universality is good, has important using value.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of polyimide prepolymer of the present invention and Schiff's base pore-creating agent composite membrane.
Fig. 2 is the electron scanning micrograph of the embodiment of the present invention 1 polyimide porous membrane.
Fig. 3 is the electron scanning micrograph of the embodiment of the present invention 2 polyimide porous membranes.
Fig. 4 is the electron scanning micrograph of the embodiment of the present invention 3 polyimide porous membranes.
Fig. 5 is the electron scanning micrograph of the embodiment of the present invention 4 polyethersulfone porous-films.
Fig. 6 is the electron scanning micrograph of the embodiment of the present invention 5 polyvinylidene fluoride porous films.
Fig. 7 is the electron scanning micrograph of the embodiment of the present invention 6 polystyrene porous membranes.
Fig. 8 is the electron scanning micrograph of the embodiment of the present invention 7 porous polylactic acid films.
Fig. 9 is the electron scanning micrograph of the embodiment of the present invention 8 resol porous-films.
Figure 10 is nitrogen adsorption-desorption curve of the embodiment of the present invention 1 polyimide porous membrane.
Figure 11 is the pore size distribution curve of the embodiment of the present invention 1 polyimide porous membrane.
Figure 12 is nitrogen adsorption-desorption curve of the embodiment of the present invention 4 polyethersulfone porous-films.
Figure 13 is the pore size distribution curve of the embodiment of the present invention 4 polyethersulfone porous-films.
Figure 14 is the infrared spectrum of the embodiment of the present invention 4 polyethersulfones and Schiff's base composite membrane, polyethersulfone porous-film and Schiff's base.
Figure 15 forms the electron scanning micrograph of Schiff's base porous-film after the embodiment of the present invention 4 polyethersulfones and Schiff's base composite membrane removal polyethersulfone.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.Described concentration if no special instructions, is mass percentage concentration.
In following embodiment nitrogen adsorption-desorption curve of gained porous-film, aperture respectively curve all measure as follows and obtain: porous-film vacuumize degassing at 100 ℃ is processed after 10h, with BET specific surface area, pore volume and the pore size distribution of ASAP 2020M specific surface area and micropore/mesoporous analysis-e/or determining sample.
Embodiment 1
The polyimide prepolymer that is 1000 by 0.1g number-average molecular weight is dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, add 0.048g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.052g triethylene tetramine to react after 0.5 hour in 25 ℃, in 80 ℃ of dry 2 hours volatilization film forming, in 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and triethylene tetramine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: successively at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The stereoscan photograph of this porous-film as shown in Figure 2.As shown in Figure 2, film is vesicular structure, and aperture is 10nm to 1 μ m.As shown in figure 10, as seen from the figure, BET specific surface area is 179m to nitrogen adsorption-desorption curve
2/ g.As shown in figure 11, as seen from the figure, the aperture of this porous-film is 10.6nm to pore size distribution curve, and pore volume is 0.59cm
3/ g.
Embodiment 2
The polyimide prepolymer that is 5000 by 0.1g number-average molecular weight is dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, add again 0.041g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.059g tetraethylene pentamine to react after 0.5 hour in 25 ℃, 80 ℃ of dry 2 hours volatilization film forming, with 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and tetraethylene pentamine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, obtain polyimide porous membrane provided by the invention.The stereoscan photograph of this porous-film as shown in Figure 3.As shown in Figure 3, film is vesicular structure, and aperture is 10nm to 200nm.
The polyimide prepolymer that is 3000 by 0.1g number-average molecular weight is dissolved in 5g solvent N, in N-N,N-DIMETHYLACETAMIDE (DMAc), ultrasonic being uniformly dispersed, add 0.055g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.045g Ursol D to react after 0.5 hour in 25 ℃, after 80 ℃ of dry 2 hours volatilization film forming, with 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and Ursol D again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyimide prepolymer porous-film.
In order to improve the thermostability of this polyimide prepolymer porous-film, this performed polymer porous-film is cured in accordance with the following steps: at 80 ℃ of insulation 1h, 120 ℃ of insulation 1h, 160 ℃ of insulation 1h, 200 ℃ of insulation 1h, 250 ℃ of insulation 1h, 300 ℃ of insulation 1h, form polyimide porous membrane.The stereoscan photograph of this porous-film as shown in Figure 4.As shown in Figure 4, film is vesicular structure, and aperture is 10nm to 50nm.
Embodiment 4
The polyethersulfone that is 0.24 by 0.05g limiting viscosity is dissolved in 5g solvent N, in dinethylformamide (DMF), ultrasonic being uniformly dispersed, add 0.025g terephthalaldehyde, dissolving is uniformly dispersed, adding 0.025g weight-average molecular weight is that 10000 polymine (PEI) is in 25 ℃ of reactions after 0.5 hour again, 80 ℃ obtain polyethersulfone and Schiff's base composite membrane after volatilization film forming in dry 2 hours, with 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and polymine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyethersulfone porous-film provided by the invention.In addition, polyethersulfone and Schiff's base composite membrane soak 1 hour with DMF, wash 3 times, obtain Schiff's base porous-film.
As shown in figure 12, as shown in Figure 12, BET specific surface area is 190m to nitrogen adsorption-desorption curve of this porous-film
2/ g.As shown in figure 13, as shown in Figure 13, the aperture of this porous-film is 9.2nm to pore size distribution curve, and pore volume is 0.63cm
3/ g.Figure 14 is the infrared spectrum of polyethersulfone and Schiff's base composite membrane, polyethersulfone porous-film and Schiff's base in this embodiment.As shown in Figure 14,1670cm
-1be the vibration peak of the carbon-to-nitrogen double bon of Schiff's base, the generation of Schiff's base is described.Fig. 5 and 15 is the electron scanning micrograph of polyethersulfone porous-film and Schiff's base porous-film, and known polyethersulfone and Schiff's base composite membrane are bicontinuous structure, remove respectively Schiff's base and polyethersulfone, obtains polyethersulfone porous-film and Schiff's base porous-film.
Embodiment 5
The polyvinylidene difluoride (PVDF) that is 600,000 by 0.2g weight-average molecular weight is dissolved in 5g solvent N, in dinethylformamide (DMF), ultrasonic being uniformly dispersed, add 0.082g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.118g tetraethylene pentamine to react after 4 hours in 5 ℃, 80 ℃ of dry 2 hours volatilization film forming, with 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and tetraethylene pentamine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyvinylidene fluoride porous film provided by the invention.The stereoscan photograph of this porous-film as shown in Figure 6.As shown in Figure 6, film is vesicular structure, and aperture is 1 μ m to 20 μ m.
Embodiment 6
In the polystyrene 5g solvents tetrahydrofurane (THF) that is 50,000 by 0.1g weight-average molecular weight, ultrasonic being uniformly dispersed, add 0.048g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.052g triethylene tetramine to react after 0.5 hour in 25 ℃, 50 ℃ of dry 0.5 hour volatilization film forming, with 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into terephthalaldehyde and triethylene tetramine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polystyrene porous membrane provided by the invention.The stereoscan photograph of this porous-film as shown in Figure 7.As shown in Figure 7, film is vesicular structure, and aperture is 1 μ m.
Embodiment 7
The poly(lactic acid) 5g methylene chloride (CH that is 50,000 by 0.1g viscosity-average molecular weight
2cl
2) in, ultrasonic being uniformly dispersed, add 0.05g terephthalaldehyde, dissolving is uniformly dispersed, then adds 0.05g polymine to react after 0.5 hour in 25 ℃, 50 ℃ of dry 4 hours volatilization film forming, with 2M hydrochloric acid soln, soak 1 hour, under acidic conditions, Schiff's base resolves into terephthalaldehyde and polymine again again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain porous polylactic acid film provided by the invention.The stereoscan photograph of this porous-film as shown in Figure 8.As shown in Figure 8, film is vesicular structure, and aperture is 10nm to 100nm.
Embodiment 8
The resol performed polymer that is 1000 by 0.1g number-average molecular weight is dissolved in 5g etoh solvent, ultrasonic being uniformly dispersed, add 0.055g terephthalaldehyde, dissolving is uniformly dispersed, add again 0.045g Ursol D to react after 0.5 hour in 25 ℃, 60 ℃ of dry 1 hour volatilization film forming, obtain resol performed polymer and Schiff's base composite membrane, in order further to improve the thermostability of film, this composite membrane is solidified at 150 ℃ to 2h, form after resol and Schiff's base composite membrane, again this composite membrane is soaked 1 hour with 2M hydrochloric acid soln, under acidic conditions, Schiff's base resolves into terephthalaldehyde and Ursol D again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain resol porous-film provided by the invention.The stereoscan photograph of this porous-film as shown in Figure 9.As shown in Figure 9, film is vesicular structure, and aperture is 10nm to 50nm.
Embodiment 9
The polyethersulfone that is 0.36 by 0.05g limiting viscosity is dissolved in 5g solvent N, in dinethylformamide (DMF), ultrasonic being uniformly dispersed, adding 0.05g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, adding 0.025g weight-average molecular weight is that 1000 polymines (PEI) react after 0.5 hour in 80 ℃ again, 90 ℃ of dry 4 hours volatilization film forming, with 2M hydrochloric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into glutaraldehyde and polymine again, with 2M hydrochloric acid soln washing 3 times, remove Schiff's base, obtain polyethersulfone porous-film provided by the invention.
The polyvinylidene difluoride (PVDF) that is 400,000 by 0.2g weight-average molecular weight is dissolved in 5g solvent N, in dinethylformamide (DMF), ultrasonic being uniformly dispersed, adding 0.164g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, add again 0.118g tetraethylene pentamine to react after 1 hour in 50 ℃, 100 ℃ of dry 3 hours volatilization film forming, with 2M sulphuric acid soln, soak 1 hour again, under acidic conditions, Schiff's base resolves into again to glutaraldehyde and tetraethylene pentamine, with 2M sulphuric acid soln washing 3 times, remove Schiff's base, obtain polyvinylidene fluoride porous film provided by the invention.
Embodiment 11
In the polystyrene 5g solvents tetrahydrofurane (THF) that is 200,000 by 0.1g weight-average molecular weight, ultrasonic being uniformly dispersed, adding 0.096g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, add again 0.052g triethylene tetramine to react after 0.5 hour in 25 ℃, 50 ℃ of dry 3 hours volatilization film forming, with 2M salpeter solution, soak 1 hour again, under acidic conditions, Schiff's base resolves into glutaraldehyde and triethylene tetramine again, with 2M salpeter solution washing 3 times, remove Schiff's base, obtain polystyrene porous membrane provided by the invention.
Embodiment 12
The poly(lactic acid) 5g methylene chloride (CH that is 100,000 by 0.1g viscosity-average molecular weight
2cl
2) in, ultrasonic being uniformly dispersed, adding 0.1g concentration is 50wt% glutaraldehyde water solution, and dissolving is uniformly dispersed, then adds 0.05g polymine to react after 0.5 hour in 25 ℃, 50 ℃ of dry 0.5 hour volatilization film forming, with 0.5M acetum, soak 0.5 hour, under acidic conditions, Schiff's base resolves into glutaraldehyde and polymine again again, with 0.5M acetum washing 5 times, remove Schiff's base, obtain porous polylactic acid film provided by the invention.
Embodiment 13
The resol performed polymer that is 5000 by 0.1g number-average molecular weight is dissolved in 5g etoh solvent, ultrasonic being uniformly dispersed, adding 0.11g concentration is 50wt% glutaraldehyde water solution, dissolving is uniformly dispersed, add again 0.045g Ursol D to react after 0.5 hour in 25 ℃, 60 ℃ of dry 1 hour volatilization film forming, form resol and Schiff's base composite membrane, in order further to improve the thermostability of film, this resol and Schiff's base composite membrane are solidified to 2h at 150 ℃, form resol and Schiff's base composite membrane, with 4M hydrochloric acid soln, soak 8 hours again, under acidic conditions, Schiff's base resolves into glutaraldehyde and Ursol D again, with 4M hydrochloric acid soln washing 1 time, remove Schiff's base, obtain resol porous-film provided by the invention.
Claims (9)
1. a method of preparing porous material, comprises the steps: body material and polyaldehyde or polyketones to mix in solvent, then adds polyamine to react, film forming after completion of the reaction, then in acid washing by soaking, obtain described porous material;
Described body material is selected from the polyethersulfone that limiting viscosity is 0.24-0.36, number-average molecular weight is the polyimide prepolymer of 1000-5000, weight-average molecular weight is 50,000-200,000 polystyrene, viscosity-average molecular weight is 50,000-100,000 poly(lactic acid), weight-average molecular weight is 400,000-600,000 polyvinylidene difluoride (PVDF), weight-average molecular weight is 350,000-400,000 polymethylmethacrylate, number-average molecular weight is the epoxy resin prepolymer of 300-1000, number-average molecular weight is at least one in the resol performed polymer of 1000-5000 and urea resin prepolymer that number-average molecular weight is 500-1000,
Described polyaldehyde be selected from oxalic dialdehyde, at least one in glutaraldehyde, terephthalaldehyde, m-terephthal aldehyde and 2,4-dimethyl-2-methoxymethyl glutaraldehyde;
Described polyketones are selected from dimethyl diketone, 3, at least one in 4-hexanedione and 4,5-acetyl caproyl;
Described polyamine is selected from polymine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, Ursol D, mphenylenediamine, 4,4'-diaminodiphenylsulfone(DDS), 3, at least one in 4'-diaminodiphenyl oxide and trimeric cyanamide; The weight-average molecular weight of described polymine is 1000-10000;
Described solvent is selected from least one in N,N-dimethylacetamide, DMF, dimethyl sulfoxide (DMSO), m-cresol, tetrahydrofuran (THF), ethanol, methyl alcohol, methylene dichloride and trichloromethane;
Described acid is selected from least one in hydrochloric acid, acetic acid, nitric acid and sulfuric acid;
The mass ratio of described body material, described polyaldehyde or polyketones and described polyamine is 0.5-4:0.5-2:0.5-2;
The volumetric molar concentration of described acid is 0.001-4mol/L.
2. method according to claim 1, is characterized in that: described body material is selected from least one in the polyvinylidene difluoride (PVDF) that limiting viscosity is 0.24 polyethersulfone, molecular weight is 5000 polyimide prepolymer, polystyrene that weight-average molecular weight is 200,000, poly(lactic acid) that viscosity-average molecular weight is 100,000 and weight-average molecular weight are 400,000;
Described polyaldehyde is selected from least one in glutaraldehyde, terephthalaldehyde and m-terephthal aldehyde;
Described polyketones are selected from dimethyl diketone, 3, at least one in 4-hexanedione and 4,5-acetyl caproyl;
Described polyamine is selected from polymine, triethylene tetramine, tetraethylene pentamine, Ursol D, mphenylenediamine, 4, at least one in 4'-diaminodiphenylsulfone(DDS) and trimeric cyanamide;
Described solvent is selected from least one in N,N-dimethylacetamide, DMF and methylene dichloride;
Described acid is selected from least one in hydrochloric acid, acetic acid and nitric acid.
3. method according to claim 1, is characterized in that: the mass ratio of described body material, described polyaldehyde or polyketones and described polyamine is 2:1:1;
The volumetric molar concentration of described acid is 2mol/L.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: in described reactions steps, temperature is 5-80 ℃, and the time is 0.5-4 hour;
In described film forming step, temperature is 50-100 ℃, and the time is 0.5-4 hour;
In described soaking step, the time is 0.5-8 hour;
In described washing step, number of times is 1-5 time, and cleaning solvent is selected from least one in the phosphoric acid that hydrochloric acid that concentration is 0.001-4mol/L, acetic acid that concentration is 0.001-4mol/L, nitric acid that concentration is 0.001-4mol/L, sulfuric acid that concentration is 0.001-4mol/L and concentration are 0.001-4mol/L.
5. method according to claim 4, is characterized in that: in described reactions steps, temperature is 25 ℃, and the time is 0.5 hour;
In described film forming step, temperature is 80 ℃, and the time is 2 hours;
In described soaking step, the time is 1 hour;
In described washing step, number of times is 3 times, and cleaning solvent is selected from least one in the acetic acid that hydrochloric acid that concentration is 0.5-4mol/L, sulfuric acid that concentration is 0.5-4mol/L, nitric acid that concentration is 0.5-4mol/L and concentration are 0.5-4mol/L.
6. according to the method described in claim 1 or 3, it is characterized in that: described body material is selected from least one the method for preparing porous material in the resol performed polymer that polyimide prepolymer that number-average molecular weight is 1000-5000, epoxy resin prepolymer that number-average molecular weight is 300-1000 and number-average molecular weight are 1000-5000, after described film forming step, institute is set forth in acid before washing by soaking step, also the system after film forming is cured, or, in be set forth in acid, after washing by soaking step, gained porous material is cured;
In described curing schedule, temperature is 80-300 ℃, and the time is 0.5-6 hour.
7. method according to claim 6, is characterized in that: in described curing schedule, temperature is 300 ℃, and the time is 2 hours.
The arbitrary described method preparation of claim 1-7 and porous material.
9. porous material according to claim 8, is characterized in that: the aperture of described porous material is 9 nanometers to 20 micron, and BET specific surface area is 179-190m
2/ g, pore volume is 0.59-0.63cm
3/ g.
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| CN102875835B (en) * | 2011-07-12 | 2014-07-02 | 中国科学院化学研究所 | Polyimide porous film and preparation method thereof |
| CN104559067B (en) * | 2014-12-24 | 2017-06-06 | 中科院广州化学有限公司 | A kind of self-emulsifying epoxy base heat conduction water-proof composite material and its preparation method and application |
| CN104448713B (en) * | 2014-12-24 | 2016-10-05 | 中科院广州化学有限公司 | A kind of open cell type heat conductivity epoxy radicals composite porous material and preparation method thereof and application |
| CN105037759A (en) * | 2015-07-01 | 2015-11-11 | 南京工业大学 | Polyimide composite film with electromagnetic shielding function and preparation method thereof |
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| CN105566629B (en) * | 2016-03-18 | 2018-05-15 | 中国科学院化学研究所 | A kind of porous o-phthalonitrile resin and its preparation method and application |
| CN105837771B (en) * | 2016-04-27 | 2018-04-24 | 四川理工学院 | The preparation process of coralliform porous adsorption resin |
| CN106967205B (en) * | 2017-03-17 | 2019-03-22 | 暨南大学 | Preparation method and applications with excellent photocatalysis hydrogen production performance conjugation Schiff base polymer |
| CN108864438B (en) * | 2018-06-20 | 2021-08-03 | 上海师范大学 | Preparation method and application of polymer microsphere with core-shell and hierarchical pore structure |
| CN110880573A (en) * | 2018-09-05 | 2020-03-13 | 张家港祥成医用材料科技有限公司 | Preparation method of polyether ketone battery diaphragm |
| US10889678B2 (en) | 2019-01-28 | 2021-01-12 | King Fahd University Of Petroleum And Minerals | Amine-based porous polymer for selective carbon dioxide capture |
| CN111659357B (en) * | 2019-03-06 | 2021-08-24 | 中南大学 | Polymeric Schiff base type adsorption material, preparation and application thereof in heavy metal adsorption |
| CN111070668B (en) * | 2019-12-18 | 2022-04-01 | 华中科技大学鄂州工业技术研究院 | Method for preparing pore-diameter-controllable nano porous structure workpiece by fused deposition molding technology |
| CN112250863A (en) * | 2020-10-12 | 2021-01-22 | 江南大学 | Recoverable and recyclable thermosetting polyimide material, preparation method and application |
| CN114196063A (en) * | 2021-12-08 | 2022-03-18 | 安徽国风塑业股份有限公司 | Low-dielectric polyimide film and preparation method thereof |
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