CN105148875B - A kind of easy preparation method for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled - Google Patents
A kind of easy preparation method for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled Download PDFInfo
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Abstract
The invention discloses a kind of easy preparation method for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled, using the polyurethane sponge of commercialization as carrier, carrier is dipped in first ultrasonically treated in the mixed solution of CNT and water, obtain the polyurethane sponge of carbon nano-tube modification, the in-situ polymerization by aniline monomer on polyurethane sponge skeleton, has obtained Polyaniline-Supported polyurethane sponge composite again.The present invention is using polyurethane sponge as carrier, by in-situ polymerization of the aniline monomer on the polyurethane sponge skeleton of carbon nano-tube modification, and single step reaction has obtained Polyaniline-Supported polyurethane sponge, and preparation method is easy, and cost is low.Polyaniline-Supported polyurethane sponge prepared by the present invention has three-dimensional cavernous structure, specific surface area is big, have the segregative characteristic of elasticity, lightweight of carrier concurrently simultaneously, there is good adsorption effect to organic dyestuff, can realize that adsorbate is sufficiently separated with adsorbent and material is recycled by way of external force extrded material.
Description
Technical field
The present invention relates to a kind of preparation method of Polyaniline-Supported polyurethane sponge sorbing material.
Background technology
In recent years, absorption method is as a kind of physico-chemical process simple to operate, easy to use, wide adaptation range, useless
Water treatment field has obtained extensive research and application.Traditional industrial high-efficient adsorbent has that price is high, be not easily recycled
The problems such as, limit its extensive use.Polyurethane sponge has three-dimensional cavernous structure, and the carrier as sorbing material can be carried effectively
The specific surface area of high material, lightening material density played an important role in sorbing material field.
The content of the invention
In order to solve the problem of existing sorbing material is not easily recycled, cost is high, it can be followed the invention provides a kind of easily reclaim
The preparation method for the Polyaniline-Supported polyurethane sponge sorbing material that ring is used, using environment-friendly synthesis mode, without three
The severe corrosive such as chromium oxide, concentrated sulfuric acid reagent pre-processes sponge, and reaction condition is gentle, and method is easy, at organic dyestuff
Reason field.
The purpose of the present invention is achieved through the following technical solutions：
A kind of easy preparation method for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled, with commercialization
Polyurethane sponge be carrier, carrier is dipped in first it is ultrasonically treated in the mixed solution of CNT and water, obtain carbon nanometer
The polyurethane sponge that pipe is modified, then the in-situ polymerization by aniline monomer on polyurethane sponge skeleton, have obtained polyaniline and have born
Carry polyurethane sponge composite.Comprise the following steps that：
First, polyurethane sponge is cut into fritter, is respectively placed in ultrasonically treated 1 ~ 2h in distilled water and alcohol solvent, then
Dried under the conditions of 40 ~ 60 DEG C and be cut into the regular cuboid that quality is 0.1 ~ 0.2g；Wherein, ultrasonic power is 180W.
2nd, 0.2 ~ 0.4g of CNT is scattered in 1000mL distilled water, 3 ~ 5h is disperseed under ultrasound condition, carbon is obtained
The mixture that nanotube is dispersed in water；Wherein, CNT is functionalized multi-wall carbonnanotubes, a diameter of 10-20nm.
3rd, the polyurethane sponge that step one is obtained is immersed in the mixture of the CNT of step 2 and water, passed through
The mode of extruding, the mixture of CNT and water is drawn into sponge, 1.5 ~ 3h is then sonicated；Then carbon will have been adsorbed
The polyurethane sponge of nanotube is taken out with tweezers, is placed in 60 ~ 80 DEG C of baking ovens and is dried 8 ~ 16h, obtains the poly- of carbon nano-tube modification
Urethane sponge；Wherein, the volume of the mixture of CNT and water is 500mL.
4th, by 0.9 ~ 6mL of aniline and water：328.5mL amount ratio prepares the aqueous solution of aniline, and the pH value of regulation solution is
1~3；By ammonium persulfate and 2.1 ~ 14g of water:300mL amount ratio prepares ammonium persulfate aqueous solution, the pH value of regulation solution for 1 ~
3；Wherein, the solution for adjusting pH is hydrochloric acid or sulfuric acid.
5th, the aniline-water solution that step 4 is obtained is placed in there-necked flask, the mechanical agitation under 0 ~ 10 DEG C of condition of ice bath
Uniformly, 1 ~ 15min is persistently stirred after the ammonium persulfate aqueous solution described in step 4, completion of dropping is added dropwise；Wherein, aniline water
The volume of solution is 36 ~ 65mL, and the volume of ammonium persulfate aqueous solution is 36 ~ 65mL, the material of aniline monomer and ammonium persulfate
Amount is than being 1:0.8~1.5.
What the 6th, the polyurethane sponge composite for the carbon nano-tube modification for obtaining step 3 was immersed in that step 5 obtains is mixed
Close in solution, sponge is absorbed mixed solution by extruding, mixture is then stirred into 3 ~ 8h under conditions of 0 ~ 10 DEG C；Its
In, the polyurethane sponge of carbon nano-tube modification and the mass ratio of aniline monomer are 1 ~ 24:1.
7th, the solid formation in step 6 is taken out, unnecessary liquid is squeezed out and is washed with distilled water and ethanol alternate immersion
To filtrate clarification, 8 ~ 20h of forced air drying under the conditions of 40 ~ 60 DEG C obtains Polyaniline-Supported polyurethane sponge sorbing material.
The invention has the advantages that：
1st, the present invention use polyurethane sponge for carrier, by aniline monomer carbon nano-tube modification polyurethane sponge bone
In-situ polymerization on frame, single step reaction has obtained Polyaniline-Supported polyurethane sponge, and preparation method is easy, and cost is low.
2nd, Polyaniline-Supported polyurethane sponge prepared by the present invention has three-dimensional cavernous structure, and specific surface area is big, to organic
Dyestuff has good adsorption effect.
3rd, Polyaniline-Supported polyurethane sponge prepared by the present invention has absorption property of the polyaniline to organic dyestuff, simultaneously
Have the segregative characteristic of elasticity, lightweight of carrier concurrently, can realize that adsorbate fills with adsorbent by way of external force extrded material
Point separation and material recycle.
Brief description of the drawings
The photograph in kind for the Polyaniline-Supported polyurethane sponge sorbing material that Fig. 1 obtains for step 7 in embodiment one
Piece；
The photograph in kind for the Polyaniline-Supported polyurethane sponge sorbing material that Fig. 2 obtains for step 7 in embodiment two
Piece.
Embodiment
Technical scheme is further described below in conjunction with the accompanying drawings, but is not limited thereto, it is every to this
Inventive technique scheme is modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, all should be covered
In protection scope of the present invention.
Embodiment one：The preparation method for the Polyaniline-Supported polyurethane sponge sorbing material that present embodiment is provided
Carry out according to the following steps：
First, polyurethane sponge is cut into fritter, is respectively placed in ultrasonically treated 1h, Ran Hou in distilled water and alcohol solvent
Dried under the conditions of 60 DEG C and be cut into the regular cuboid that quality is 0.1g.
2nd, a diameter of 10 ~ 20nm functionalized multi-wall carbonnanotubes 0.25g is scattered in 1000mL distilled water, surpassed
Disperse 3h under the conditions of sound, obtain the mixture that CNT is dispersed in water.
3rd, the polyurethane sponge that step one is obtained is immersed in the mixture of CNT water of step 2, by squeezing
The mode of pressure, the mixture of CNT and water is drawn into sponge, 2h is then sonicated.Then CNT will have been adsorbed
Polyurethane sponge taken out with tweezers, be placed in 60 DEG C of baking ovens dry 8h, obtain the polyurethane sponge of carbon nano-tube modification.Its
In, CNT aqueous mixtures volume is 500mL.
4th, by aniline and water 6mL：328.5mL amount ratio prepares the aqueous solution of aniline, and the pH value of regulation solution is 1.5.
By ammonium persulfate and water 14g:300mL amount ratio prepares ammonium persulfate aqueous solution, and the pH value of regulation solution is 1.5.Wherein, use
In regulation pH solution be hydrochloric acid.
5th, the aniline-water solution that step 4 is obtained is placed in there-necked flask, mechanical agitation is equal under 4 ~ 6 DEG C of condition of ice bath
It is even, persistently stir 1min after the ammonium persulfate aqueous solution described in step 4, completion of dropping is added dropwise；Wherein, aniline-water solution
Volume be 65mL, the volume of ammonium persulfate aqueous solution is 65mL.
What the 6th, the polyurethane sponge composite for the carbon nano-tube modification for obtaining step 3 was immersed in that step 5 obtains is mixed
Close in solution, sponge is absorbed mixed solution by extruding, mixture is then stirred into 6h under conditions of 4 ~ 6 DEG C；Wherein,
The polyurethane sponge of carbon nano-tube modification and the mass ratio of aniline monomer are 24:1.
7th, the solid formation in step 6 is taken out, unnecessary liquid is squeezed out and is washed with distilled water and ethanol alternate immersion
To filtrate clarification, the forced air drying 15h under the conditions of 60 DEG C obtains Polyaniline-Supported polyurethane sponge sorbing material（Fig. 1）.
The preparation method of the Polyaniline-Supported polyurethane sponge sorbing material of present embodiment, with the polyurethane sea of commercialization
Silk floss is carrier, by in-situ polymerization of the aniline monomer on the polyurethane sponge skeleton of carbon nano-tube modification, has obtained polyaniline
Load polyurethane sponge sorbing material.The Polyaniline-Supported polyurethane sponge of present embodiment uses environment-friendly synthesis side
Formula, without the pretreatment of the severe corrosive such as chromium trioxide, concentrated sulfuric acid reagent, reaction condition is gentle, and single step reaction can be prepared by polyphenyl
Amine loads polyurethane sponge sorbing material.The Polyaniline-Supported polyurethane sponge of present embodiment have high-specific surface area, elasticity,
Lightweight, the characteristic for easily reclaiming separation.
The Polyaniline-Supported polyurethane sponge sorbing material for taking present embodiment to prepare is used for adsorption test, and adsorbent is poly-
Aniline loads polyurethane sponge sorbing material, and adsorbate is the methyl blue solution that concentration is 10mg/L.By 30mL adsorbent solutions
Adsorbed in three times, the amount ratio of adsorbate and adsorbent is 10mg in each adsorption process:10mL, under conditions of 25 DEG C
Concussion absorption 1h, by the solution in Polyaniline-Supported polyurethane sponge sorbing material by way of external force is extruded after the completion of absorption
Discharge, and carry out absorption next time.Test result shows, under the adsorption conditionses, and polyaniline prepared by present embodiment is born
Carry polyurethane sponge adsorption effect substantially, adsorption rate is up to 80%.
Embodiment two：The preparation method for the Polyaniline-Supported polyurethane sponge sorbing material that present embodiment is provided
Carry out according to the following steps：
First, polyurethane sponge is cut into fritter, is respectively placed in ultrasonically treated 1h, Ran Hou in distilled water and alcohol solvent
Dried under the conditions of 40 DEG C and be cut into the cuboid that quality is 0.1g；Wherein, ultrasonic power is 180W.
2nd, a diameter of 10 ~ 20nm functionalized multi-wall carbonnanotubes 0.25g is scattered in 1000mL distilled water, surpassed
Disperse 3h under the conditions of sound, obtain the mixture that CNT is dispersed in water.
3rd, the polyurethane sponge that step one is obtained is immersed in the mixture of CNT water of step 2.By squeezing
The mode of pressure, the mixture of CNT and water is drawn into sponge, 2h is then sonicated.Then CNT will have been adsorbed
Polyurethane sponge taken out with tweezers, be placed in 80 DEG C of baking ovens dry 10h, obtain the polyurethane sponge of carbon nano-tube modification.Its
In, CNT aqueous mixtures volume is 500mL.
4th, by aniline and water 0.9mL：328.5mL amount ratio prepares the aqueous solution of aniline, and the pH value of regulation solution is
1.5.By ammonium persulfate and water 2.1g:300mL amount ratio prepares ammonium persulfate aqueous solution, and the pH value of regulation solution is 1.5.Its
In, the solution for adjusting pH is hydrochloric acid；
5th, the aniline-water solution that step 4 is obtained is placed in there-necked flask, mechanical agitation is equal under 2 ~ 8 DEG C of condition of ice bath
It is even, persistently stir 15min after the ammonium persulfate aqueous solution described in step 4, completion of dropping is added dropwise；Wherein, aniline-water solution
Volume be 36mL, the volume of ammonium persulfate aqueous solution is 36mL.
What the 6th, the polyurethane sponge composite for the carbon nano-tube modification for obtaining step 3 was immersed in that step 5 obtains is mixed
Close in solution, sponge is absorbed mixed solution by extruding, mixture is then stirred into 6h under conditions of 2 ~ 8 DEG C；Wherein,
The polyurethane sponge of carbon nano-tube modification and the mass ratio of aniline monomer are 1:1.
7th, the solid formation in step 6 is taken out, unnecessary liquid is squeezed out and is washed with distilled water and ethanol alternate immersion
To filtrate clarification, the forced air drying 20h under the conditions of 40 DEG C obtains Polyaniline-Supported polyurethane sponge sorbing material（Fig. 2）.
Claims (8)
1. a kind of easy preparation method for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled, it is characterised in that
The preparation method is as follows：
First, polyurethane sponge is cut into fritter, ultrasonically treated 1 ~ 2h in distilled water and alcohol solvent is respectively placed in, then 40
Dried under the conditions of ~ 60 DEG C and be cut into the regular cuboid that quality is 0.1 ~ 0.2g；
2nd, 0.2 ~ 0.4g of CNT is scattered in 1000mL distilled water, 3 ~ 5h is disperseed under ultrasound condition, obtain carbon nanometer
The mixture that pipe is dispersed in water；
3rd, the polyurethane sponge that step one is obtained is immersed in the mixture of the CNT of step 2 and water, passes through extruding
Mode, the mixture of CNT and water is drawn into sponge, 1.5 ~ 3h is then sonicated；Then carbon nanometer will have been adsorbed
The polyurethane sponge of pipe is taken out with tweezers, is placed in 60 ~ 80 DEG C of baking ovens and is dried 8 ~ 16h, obtains the polyurethane of carbon nano-tube modification
Sponge；
4th, by 0.9 ~ 6mL of aniline and water：328.5mL amount ratio prepares the aqueous solution of aniline, and the pH value of regulation solution is 1 ~ 3；
By ammonium persulfate and 2.1 ~ 14g of water:300mL amount ratio prepares ammonium persulfate aqueous solution, and the pH value of regulation solution is 1 ~ 3；
5th, the aniline-water solution that step 4 is obtained is placed in there-necked flask, mechanical agitation is uniform under 0 ~ 10 DEG C of condition of ice bath,
1 ~ 15min is persistently stirred after the ammonium persulfate aqueous solution described in step 4, completion of dropping is added dropwise；
6th, to be immersed in the mixing that step 5 obtains molten for the polyurethane sponge composite for the carbon nano-tube modification for obtaining step 3
In liquid, sponge is absorbed mixed solution by extruding, mixture is then stirred into 3 ~ 8h under conditions of 0 ~ 10 DEG C；
7th, the solid formation in step 6 is taken out, unnecessary liquid is squeezed out and is washed with distilled water and ethanol alternate immersion to filter
Liquid is clarified, and 8 ~ 20h of forced air drying under the conditions of 40 ~ 60 DEG C obtains Polyaniline-Supported polyurethane sponge sorbing material.
2. the easy preparation for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled according to claim 1
Method, it is characterised in that in the step one, ultrasonic power is 180W.
3. the easy preparation for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled according to claim 1
Method, it is characterised in that in the step 2, CNT is functionalized multi-wall carbonnanotubes.
4. the Polyaniline-Supported polyurethane sponge sorbing material that the easy recovery according to claim 1 or 3 can be recycled
Preparation method, it is characterised in that a diameter of 10-20nm of the CNT.
5. the easy preparation for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled according to claim 1
Method, it is characterised in that in the step 3, the volume of the mixture of CNT and water is 500mL.
6. the easy preparation for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled according to claim 1
Method, it is characterised in that in the step 4, the solution for adjusting pH is hydrochloric acid or sulfuric acid.
7. the easy preparation for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled according to claim 1
Method, it is characterised in that in the step 5, the amount ratio of the material of aniline monomer and ammonium persulfate is 1:0.8~1.5.
8. the easy preparation for reclaiming the Polyaniline-Supported polyurethane sponge sorbing material that can be recycled according to claim 1
Method, it is characterised in that in the step 6, the polyurethane sponge of carbon nano-tube modification and the mass ratio of aniline monomer are 1 ~ 24:
1。
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| CN111569843B (en) * | 2020-04-22 | 2023-01-03 | 湖南大学 | Material for treating diclofenac wastewater and preparation method and application thereof |
| CN114984903B (en) * | 2022-05-23 | 2023-04-28 | 中南大学 | Calcium magnesium aluminum ternary fluoride loaded polyurethane sponge and preparation method and application thereof |
| CN115304121B (en) * | 2022-06-27 | 2023-11-17 | 河海大学 | Preparation method and application of polyaniline-wood double-layer evaporation material |
| CN115554999B (en) * | 2022-09-27 | 2024-03-19 | 南京大学 | Synthesis method and application of aminated polyurethane sponge adsorbent |
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