CN117482927B - Preparation method and application of polyurethane sponge adsorption material - Google Patents
Preparation method and application of polyurethane sponge adsorption material Download PDFInfo
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 93
- 239000004814 polyurethane Substances 0.000 title claims abstract description 93
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 37
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 31
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 25
- 239000012153 distilled water Substances 0.000 claims description 21
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004088 foaming agent Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000005187 foaming Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- HPDIRFBJYSOVKW-UHFFFAOYSA-N 2-pyrrol-1-ylethanamine Chemical compound NCCN1C=CC=C1 HPDIRFBJYSOVKW-UHFFFAOYSA-N 0.000 claims description 7
- 239000006184 cosolvent Substances 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- KTOIESNTVCLSFG-UHFFFAOYSA-N 1-chloropropan-2-ol;sodium Chemical compound [Na].CC(O)CCl KTOIESNTVCLSFG-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 2
- -1 stirred for reaction Chemical compound 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 229920000128 polypyrrole Polymers 0.000 abstract description 16
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 19
- 238000010521 absorption reaction Methods 0.000 description 17
- 238000010559 graft polymerization reaction Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920003243 conjugated conducting polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of polyurethane sponge and discloses a preparation method and application of a polyurethane sponge adsorption material. The polyurethane sponge adsorption material contains carboxyl and polypyrrole containing sulfonic acid groups, can form coordination and electrostatic adsorption with Pb 2+, and remarkably improves the Pb 2+ removal rate of the polyurethane sponge adsorption material. The adsorption material has small dosage, and the adsorption balance of Pb 2+ in a short time, has high removal rate, and can be well applied to the treatment of metal wastewater containing lead and the like.
Description
Technical Field
The invention relates to the technical field of polyurethane sponge, in particular to a preparation method and application of a polyurethane sponge adsorption material.
Background
The metal ions such as lead, copper and the like and the compounds thereof widely exist in the wastewater discharged by industries such as mining industry, smelting industry and the like, the metal is extremely toxic, cannot be degraded in ecological environment, and is extremely harmful to the health and safety of aquatic animals, plants and human bodies, so that the metal wastewater such as lead needs to be effectively treated. The traditional methods mainly comprise a membrane exchange method, a chemical precipitation method, an adsorption method and the like. The adsorption method has the advantages of low cost, simple and convenient operation, difficult secondary pollution and the like.
The polyurethane sponge has a large number of pore canal structures, the water absorption rate is very high, the application in the field of wastewater treatment is very wide, and the patent CN111167421B discloses that the polydopamine modified polyurethane sponge is immersed in polyethylene glycol di-ethylene oxide methyl ether modified graphene oxide and ethylenediamine modified graphene oxide solution for assembly, and the graphene-loaded polyurethane sponge adsorption material has wide application prospect in the field of water pollution treatment.
Polypyrrole and its copolymer are one kind of heterocyclic conjugated conducting polymer with functional groups, such as chemical imino, and have excellent complexing effect on metal ion and wide application foreground in waste water treatment. Therefore, polypyrrole and copolymer thereof are loaded into polyurethane sponge to obtain high-performance adsorption material, and the adsorption material is applied to the treatment of metal wastewater such as lead.
Disclosure of Invention
The technical problems to be solved are as follows: the polyurethane sponge adsorbing material with high adsorbing performance to pollutants such as metal ions is prepared.
The technical scheme is as follows:
The preparation method of the polyurethane sponge adsorption material comprises the following steps: according to the parts by weight, 100 parts of pyrrole hydrophilic polyurethane sponge are soaked in distilled water, 15-100 parts of pyrrole and 3-50 parts of 3-pyrrole-2-hydroxy sodium propane sulfonate are added, the mixture is stirred uniformly, then hydrochloric acid solution is added under ice water bath, the mixture is stirred uniformly, water solution containing 13-80 parts of ferric trichloride is added dropwise, the mixture is stirred at 0-5 ℃ for 3-6 hours, the sponge is taken out, washed by water and ethanol in sequence, and dried, thus obtaining the polyurethane sponge adsorption material.
Further, the mass fraction of the hydrochloric acid solution is 20-37%.
Further, the preparation method of the pyrrole-based hydrophilic polyurethane sponge comprises the following steps:
s1, adding 100 parts of maleic anhydride grafted polyvinyl alcohol into distilled water, heating, refluxing, stirring, dissolving, cooling to 40-55 ℃, adding 12-30 parts of sodium hydroxide, 30-80 parts of 2- (1H-pyrrol-1-yl) ethylamine and a cosolvent, stirring, reacting for 6-12 hours, cooling, pouring the solution into methanol to precipitate, filtering, and washing with ethanol to obtain the pyrrolyl polyvinyl alcohol. The reaction mechanism is as follows:
s2, uniformly mixing the dried and dehydrated polyethylene glycol and toluene diisocyanate according to the ratio of n (OH): N (NCO) =1 (2-2.4), and reacting for 2-3 hours at 60-70 ℃ in nitrogen atmosphere to obtain a polyurethane prepolymer;
S3, adding 0.4-0.6 part of stannous octoate and 1.2-2 parts of organosilicon foam stabilizer into distilled water, and uniformly mixing to obtain a foaming agent solution; then adding the foaming agent solution, 100 parts of polyurethane prepolymer and 2-5 parts of pyrrole-based polyvinyl alcohol into a mold, uniformly mixing, foaming and curing to obtain the pyrrole-based hydrophilic polyurethane sponge.
Further, the cosolvent in S1 is ethanol, acetone or tetrahydrofuran.
Further, the curing temperature is 20-40 ℃ and the curing time is 24-48h.
Further, the preparation method of the 3-pyrrole-2-hydroxy propane sodium sulfonate comprises the following steps: 100 parts of pyrrole, 420-660 parts of 3-chloro-2-hydroxy propane sodium sulfonate and 60-90 parts of sodium hydroxide are added into tetrahydrofuran, stirred and reacted for 4-10 hours at 50-75 ℃, hydrochloric acid is added until the volume pH is 6, the mixture is concentrated under reduced pressure, saturated sodium bicarbonate solution is used for washing the product, and then the product is placed into ethanol aqueous solution for recrystallization, so that 3-pyrrole-2-hydroxy propane sodium sulfonate is obtained. Preparing a reaction formula:
The invention has the technical effects that: the invention utilizes 2- (1H-pyrrole-1-yl) ethylamine and maleic anhydride grafted polyvinyl alcohol to carry out Michael addition reaction to obtain pyrrole-based polyvinyl alcohol, then carries out chain extension and foaming with polyurethane prepolymer, and introduces pyrrole groups and hydrophilic carboxyl groups into polyurethane sponge to obtain pyrrole-based hydrophilic polyurethane sponge.
According to the invention, pyrrole groups in pyrrole-based hydrophilic polyurethane sponge are used as polymerization sites, so that pyrrole and 3-pyrrole-2-hydroxy sodium propane sulfonate are subjected to in-situ graft polymerization on the surface of pyrrole-based hydrophilic polyurethane sponge, the chemical bonding of polypyrrole sulfonate in the polyurethane sponge is realized, the polypyrrole sulfonate cannot fall off from the polyurethane sponge after washing and water soaking, and finally hydrophilic carboxyl groups and polypyrrole containing hydrophilic sulfonic acid groups are grafted on the surface of a polyurethane sponge adsorption material. The hydrophilicity and the water absorption rate of the polyurethane sponge adsorption material are improved.
The polyurethane sponge adsorption material contains carboxyl and polypyrrole containing sulfonic acid groups, can form coordination and electrostatic adsorption with Pb 2+, and remarkably improves the Pb 2+ removal rate of the polyurethane sponge adsorption material. The adsorption material has small dosage, and the adsorption balance of Pb 2+ in a short time, has high removal rate, and can be well applied to the treatment of metal wastewater containing lead and the like.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
The preparation method of the maleic anhydride grafted polyvinyl alcohol comprises the following steps: 10g of polyvinyl alcohol was added to 90mL of distilled water, and the mixture was dissolved by stirring under reflux, 6.7g of maleic anhydride and 0.1g of polyphosphoric acid were added, and the mixture was reacted at 90℃for 4 hours. Cooling, precipitating with ethanol, filtering, washing with ethanol to obtain maleic anhydride grafted polyvinyl alcohol with structural formula
Example 1
(1) Adding 5g of maleic anhydride grafted polyvinyl alcohol into 300mL of distilled water, heating, refluxing, stirring and dissolving, cooling to 40 ℃, adding 0.6g of sodium hydroxide, 1.5g of 2- (1H-pyrrol-1-yl) ethylamine and 20mL of acetone cosolvent, stirring and reacting for 6H, cooling, pouring the solution into methanol to precipitate, filtering, and washing with ethanol to obtain the pyrrolyl polyvinyl alcohol.
(2) Uniformly mixing the dried and dehydrated polyethylene glycol and toluene diisocyanate according to the ratio of n (OH): N (NCO) =1:2, and reacting for 3 hours at 60 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer;
(3) Adding 0.04g of stannous octoate and 0.12g of organosilicon foam stabilizer AK-8805 into 4mL of distilled water, and uniformly mixing to obtain a foaming agent solution; then adding the foaming agent solution, 10g of polyurethane prepolymer and 0.2g of pyrrole-based polyvinyl alcohol into a mold, uniformly mixing and foaming, and then standing and curing for 48 hours at 30 ℃ to obtain the pyrrole-based hydrophilic polyurethane sponge.
(4) To 30mL of tetrahydrofuran, 0.5g of pyrrole, 3.3g of 3-chloro-2-hydroxy propane sodium sulfonate and 0.45g of sodium hydroxide were added, the mixture was stirred and reacted for 10 hours at 65 ℃, hydrochloric acid was added to adjust the pH to 6, the mixture was concentrated under reduced pressure, and the product was washed with saturated sodium bicarbonate solution, and then recrystallized in ethanol aqueous solution to obtain 3-pyrrole-2-hydroxy propane sodium sulfonate.
(5) 10G of pyrrole-based hydrophilic polyurethane sponge is soaked in 3L of distilled water, 1.5g of pyrrole and 0.3g of 3-pyrrole-2-hydroxy sodium propane sulfonate are added, the mixture is stirred uniformly, then a 37% hydrochloric acid solution with the mass fraction of 20mL is added under ice water bath, the mixture is stirred uniformly, 50mL of an aqueous solution containing 1.3g of ferric trichloride is added dropwise, the mixture is stirred at 5 ℃ for 3h, the sponge is taken out, and the sponge is washed with water and ethanol sequentially and dried, so that the polyurethane sponge adsorbing material is obtained.
Example 2
(1) Adding 5g of maleic anhydride grafted polyvinyl alcohol into 400mL of distilled water, heating, refluxing, stirring and dissolving, cooling to 40 ℃, adding 0.9g of sodium hydroxide, 2.5g of 2- (1H-pyrrol-1-yl) ethylamine and 30mL of ethanol cosolvent, stirring and reacting for 12H, cooling, pouring the solution into methanol to precipitate, filtering, and washing with ethanol to obtain the pyrrolyl polyvinyl alcohol.
(2) Uniformly mixing the dried and dehydrated polyethylene glycol and toluene diisocyanate according to the ratio of n (OH): N (NCO) =1:2.4, and reacting for 2 hours at 70 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer;
(3) Adding 0.05g stannous octoate and 0.16g organosilicon foam stabilizer AK-8805 into 5mL distilled water, and uniformly mixing to obtain a foaming agent solution; then adding the foaming agent solution, 10g of polyurethane prepolymer and 0.35g of pyrrole-based polyvinyl alcohol into a mold, mixing uniformly, foaming, and then standing and curing for 24 hours at 40 ℃ to obtain the pyrrole-based hydrophilic polyurethane sponge.
(4) To 15mL of tetrahydrofuran, 0.5g of pyrrole, 2.1g of 3-chloro-2-hydroxy propane sodium sulfonate and 0.3g of sodium hydroxide were added, the mixture was stirred and reacted for 4 hours at 75 ℃, hydrochloric acid was added to adjust the pH to 6, the mixture was concentrated under reduced pressure, and the product was washed with saturated sodium bicarbonate solution, and then recrystallized in ethanol aqueous solution to obtain 3-pyrrole-2-hydroxy propane sodium sulfonate.
(5) 10G of pyrrole-based hydrophilic polyurethane sponge is soaked in 4L of distilled water, 6.2 g of pyrrole and 2.5g of 3-pyrrole-2-hydroxy sodium propane sulfonate are added, the mixture is stirred uniformly, then 25% hydrochloric acid solution with the mass fraction of 30mL is added under ice water bath, the mixture is stirred uniformly, 50mL of aqueous solution containing 0.52g of ferric trichloride is added dropwise, the mixture is stirred at the temperature of 0 ℃ for 6h for reaction, the sponge is taken out, washed with water and ethanol in sequence, and the polyurethane sponge adsorbing material is obtained after drying.
Example 3
(1) Adding 5g of maleic anhydride grafted polyvinyl alcohol into 400mL of distilled water, heating, refluxing, stirring and dissolving, cooling to 55 ℃, adding 1.5g of sodium hydroxide, 4g of 2- (1H-pyrrol-1-yl) ethylamine and 30mL of tetrahydrofuran cosolvent, stirring and reacting for 10H, cooling, pouring the solution into methanol to precipitate, filtering, and washing with ethanol to obtain the pyrrolyl polyvinyl alcohol.
(2) Uniformly mixing the dried and dehydrated polyethylene glycol and toluene diisocyanate according to the ratio of n (OH): N (NCO) =1:2.4, and reacting for 2 hours at 65 ℃ in a nitrogen atmosphere to obtain a polyurethane prepolymer;
(3) Adding 0.06g of stannous octoate and 0.2g of organosilicon foam stabilizer AK-8805 into 6mL of distilled water, and uniformly mixing to obtain a foaming agent solution; then adding the foaming agent solution, 10g of polyurethane prepolymer and 0.5g of pyrrole-based polyvinyl alcohol into a mold, uniformly mixing and foaming, and then standing and curing for 48 hours at 20 ℃ to obtain the pyrrole-based hydrophilic polyurethane sponge.
(4) To 20mL of tetrahydrofuran, 0.5g of pyrrole, 2.5g of 3-chloro-2-hydroxy propane sodium sulfonate and 0.38g of sodium hydroxide were added, the mixture was stirred and reacted for 10 hours at 50 ℃, hydrochloric acid was added to adjust the pH to 6, the mixture was concentrated under reduced pressure, and the product was washed with saturated sodium bicarbonate solution, and then recrystallized in ethanol aqueous solution to obtain 3-pyrrole-2-hydroxy propane sodium sulfonate.
(5) Soaking 10g of pyrrole-based hydrophilic polyurethane sponge into 4L of distilled water, adding 10g of pyrrole and 5g of 3-pyrrole-2-hydroxy propane sodium sulfonate, stirring uniformly, then adding a 20% hydrochloric acid solution with the mass fraction of 40mL under ice water bath, stirring uniformly, dropwise adding 50mL of an aqueous solution containing 8g of ferric trichloride, stirring at 0 ℃ for reaction for 6 hours, taking out the sponge, washing with water and ethanol sequentially, and drying to obtain the polyurethane sponge adsorption material.
Comparative example 1
The difference between this comparative example and example 1 is that: in the step (3), pyrrole-based polyvinyl alcohol is not added, and the polyvinyl alcohol is added; and (4) and (5) are not needed.
Adding 0.04g of stannous octoate and 0.12g of organosilicon foam stabilizer AK-8805 into 4mL of distilled water, and uniformly mixing to obtain a foaming agent solution; then adding the foaming agent solution, 10g of polyurethane prepolymer and 0.2g of polyvinyl alcohol into a mold, mixing uniformly, foaming, and then standing and curing for 48 hours at 30 ℃ to obtain the polyurethane sponge.
Comparative example 2
Pyrrole-based hydrophilic polyurethane sponge was prepared in the same manner as in example 1.
Comparative example 3
The difference between this comparative example and example 1 is that: in the step (3), pyrrole-based polyvinyl alcohol is not added, and maleic anhydride grafted polyvinyl alcohol is added.
Adding 0.04g of stannous octoate and 0.12g of organosilicon foam stabilizer AK-8805 into 4mL of distilled water, and uniformly mixing to obtain a foaming agent solution; then adding the foaming agent solution, 10g of polyurethane prepolymer and 0.2g of maleic anhydride grafted polyvinyl alcohol into a mold, mixing uniformly, foaming, and then standing and curing for 48 hours at 30 ℃ to obtain the polyurethane sponge.
10G of polyurethane sponge is soaked in 3L of distilled water, 1.5g of pyrrole and 0.3g of 3-pyrrole-2-hydroxy propane sodium sulfonate are added, the mixture is stirred uniformly, then a 37% hydrochloric acid solution with the mass fraction of 20mL is added under ice water bath, the mixture is stirred uniformly, 50mL of an aqueous solution containing 1.3g of ferric trichloride is added dropwise, the mixture is stirred at 5 ℃ for 3h, the sponge is taken out, washed with water and ethanol in sequence, and the polyurethane sponge adsorbing material is obtained after drying.
Comparative example 4
This comparative example 1 differs from example 1 in that: and (3) adding no sodium 3-pyrrole-2-hydroxy propane sulfonate in the step (5).
Pyrrole-based hydrophilic polyurethane sponge was prepared in the same manner as in example 1.
10G of pyrrole-based hydrophilic polyurethane sponge is soaked in 3L of distilled water, 5g of pyrrole is added, stirring is carried out uniformly, then 37% hydrochloric acid solution with the mass fraction of 20mL is added under ice water bath, stirring is carried out uniformly, 50mL of water solution containing 4g of ferric trichloride is dropwise added, stirring reaction is carried out for 3h at 5 ℃, the sponge is taken out, washing with water and ethanol are carried out sequentially, and the polyurethane sponge adsorbing material is obtained.
And (3) weighing polyurethane sponge adsorption material with certain mass, soaking in distilled water for 12 hours, taking out the sponge until no obvious water drops drop, weighing, and carrying out water absorption.
M 0 is the mass of the sponge before water absorption, and m is the mass of the sponge after water absorption.
Example 1-3 preparation a Michael addition reaction is carried out on an amino group of 2- (1H-pyrrol-1-yl) ethylamine and an alkenyl group of maleic anhydride grafted polyvinyl alcohol, a pyrrole structure is introduced into the polyvinyl alcohol, and further chain extension and foaming are carried out on the polyvinyl alcohol and a polyurethane prepolymer, so as to obtain a pyrrole hydrophilic polyurethane sponge; and finally, taking pyrrole groups on the surface of the polyurethane sponge as polymerization sites, enabling pyrrole, 3-pyrrole-2-hydroxy sodium propane sulfonate to undergo in-situ graft polymerization on the surface of the polyurethane, and enabling sulfonic acid polypyrrole to be chemically bonded in the polyurethane sponge, so that the surface of the polyurethane sponge adsorption material is grafted with hydrophilic carboxyl groups and polypyrrole containing hydrophilic sulfonic acid groups. The hydrophilicity of the polyurethane sponge is obviously improved, and the water absorption rate is favorably improved to be 1362.1-1965.4%.
Comparative example 1 polyurethane sponge was obtained by chain extension and foaming by adding only polyvinyl alcohol and polyurethane prepolymer. Finally, in-situ polymerization is not carried out on the polyurethane sponge with pyrrole and 3-pyrrole-2-hydroxy propane sodium sulfonate, the polyurethane sponge does not contain carboxyl, sulfonic acid and other groups, the hydrophilicity is worst, and the water absorption rate is only 832.0%.
The pyrrole-based hydrophilic polyurethane sponge prepared in comparative example 2 contains hydrophilic carboxyl, but does not carry out in-situ polymerization with pyrrole and 3-pyrrole-2-hydroxy propane sodium sulfonate, and hydrophilic sulfonic acid groups are not grafted on the surface of the polyurethane sponge adsorption material, so that the water absorption rate is only 990.7%.
In comparative example 3, the polyurethane sponge obtained by grafting polyvinyl alcohol with maleic anhydride and chemically expanding and foaming the polyurethane prepolymer does not contain pyrrole structure, the polyurethane sponge cannot undergo in-situ graft polymerization reaction with pyrrole and 3-pyrrole-2-hydroxy sodium propane sulfonate, and the two cannot undergo chemical bonding, and although polypyrrole containing hydrophilic sulfonic acid groups is generated in the polyurethane sponge by reaction, the sulfonic acid polypyrrole is easy to fall off from the polyurethane sponge after washing and soaking, so that the water absorption rate of the polyurethane sponge adsorbing material is poor and is only 1129.9%.
In comparative example 4, pyrrole-based hydrophilic polyurethane sponge and pyrrole are subjected to graft polymerization, sodium 3-pyrrole-2-hydroxy propane sulfonate is not added, hydrophilic sulfonic acid groups are not introduced into the surface of the polyurethane sponge adsorption material, and the water absorption rate is only 945.2%.
Lead nitrate is added into 1L of water to prepare a standard solution with Pb 2+ concentration of 200mg/L, 2g of polyurethane sponge adsorption material (polyurethane sponge in comparative example 1 and pyrrole-based hydrophilic polyurethane sponge in comparative example 2) is added, and vibration adsorption is carried out at 25 ℃ with the vibration frequency of 200r/min. And (3) transferring the upper layer solution at different adsorption time, measuring the absorbance and the concentration of Pb 2+ by using an atomic absorption spectrophotometer, and calculating the removal rate Q. Q= (C 0-C)/C0×100％,C0 is Pb 2+ initial concentration, C is post-adsorption concentration.
The polyurethane sponge adsorption material prepared in the examples 1-3 has good hydrophilicity and high water absorption, and simultaneously contains carboxyl and polypyrrole containing sulfonic acid groups, which can form coordination and electrostatic adsorption with Pb 2+, so that the removal rate of Pb 2+ by the polyurethane sponge adsorption material is remarkably improved. The removal rate of Pb 2+ is basically balanced when the adsorption time is 3h.
The polyurethane sponge of comparative example 1 has no carboxyl group, polypyrrole sulfonate, low water absorption and lowest Pb 2+ removing rate.
The polyurethane sponge of comparative example 2 does not have polypyrrole sulfonate, has low water absorption, and has poor removal rate of Pb 2+.
The polyurethane sponge of comparative example 3 does not contain pyrrole groups, can not undergo in-situ graft polymerization reaction with pyrrole and 3-pyrrole-2-hydroxy sodium propane sulfonate, and does not undergo chemical bonding, and although polypyrrole containing hydrophilic sulfonic acid groups is generated by reaction in the polyurethane sponge, the sulfonic acid polypyrrole is easy to fall off from the polyurethane sponge after washing and soaking, so that the water absorption rate of the polyurethane sponge adsorbing material is low, and the adsorption performance of Pb 2+ is poor.
In comparative example 4, pyrrole-based hydrophilic polyurethane sponge and pyrrole were subjected to graft polymerization, sodium 3-pyrrole-2-hydroxy propane sulfonate was not added, hydrophilic sulfonic acid groups were not introduced into the surface of the polyurethane sponge adsorption material, the water absorption rate was low, and the adsorption performance to Pb 2+ was poor.
Lead nitrate is added into 1L of water to prepare a standard solution with Pb 2+ concentration of 200mg/L, polyurethane sponge adsorption materials with different masses (polyurethane sponge in comparative example 1 and pyrrole-based hydrophilic polyurethane sponge in comparative example 2) are added, and vibration adsorption is carried out for 3h at 25 ℃, and the vibration frequency is 200r/min. And measuring the absorbance and the concentration of Pb 2+ by using an atomic absorption spectrophotometer, and calculating the removal rate Q. Q= (C 0-C)/C0×100％,C0 is Pb 2+ initial concentration, C is post-adsorption concentration.
When the mass of the polyurethane sponge adsorbing material is 3g, the removal rate of Pb 2+ by the polyurethane sponge adsorbing materials prepared in the examples 2 and 3 reaches 99.1-99.8%.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. The preparation method of the polyurethane sponge adsorption material is characterized by comprising the following steps of: according to the parts by weight, 100 parts of pyrrole hydrophilic polyurethane sponge are soaked in distilled water, 15-100 parts of pyrrole and 3-50 parts of 3-pyrrole-2-hydroxy sodium propane sulfonate are added, the mixture is stirred uniformly, then hydrochloric acid solution is added under ice water bath, the mixture is stirred uniformly, 13-80 parts of ferric trichloride aqueous solution is added dropwise, the mixture is stirred for reaction, the sponge is taken out, washed by water and ethanol in sequence, and dried, thus obtaining polyurethane sponge adsorption material;
the preparation method of the pyrrole-based hydrophilic polyurethane sponge comprises the following steps:
S1, adding 100 parts of maleic anhydride grafted polyvinyl alcohol into distilled water, heating, refluxing, stirring and dissolving, cooling to 40-55 ℃, adding 12-30 parts of sodium hydroxide, 30-80 parts of 2- (1H-pyrrol-1-yl) ethylamine and a cosolvent, stirring and reacting for 6-12 hours, cooling, pouring the solution into methanol to precipitate, filtering, and washing with ethanol to obtain pyrrolyl polyvinyl alcohol;
s2, uniformly mixing the dried and dehydrated polyethylene glycol and toluene diisocyanate according to the ratio of n (OH): N (NCO) =1 (2-2.4), and reacting for 2-3 hours at 60-70 ℃ in nitrogen atmosphere to obtain a polyurethane prepolymer;
S3, adding 0.4-0.6 part of stannous octoate and 1.2-2 parts of organosilicon foam stabilizer into distilled water, and uniformly mixing to obtain a foaming agent solution; then adding the foaming agent solution, 100 parts of polyurethane prepolymer and 2-5 parts of pyrrole-based polyvinyl alcohol into a mold, uniformly mixing, foaming and curing to obtain the pyrrole-based hydrophilic polyurethane sponge.
2. The method for preparing a polyurethane sponge adsorption material as claimed in claim 1, wherein the mass fraction of the hydrochloric acid solution is 20-37%.
3. The method for preparing a polyurethane sponge adsorption material as claimed in claim 1, wherein the reaction temperature is 0-5 ℃ and the reaction time is 3-6h.
4. The method for preparing a polyurethane sponge adsorption material according to claim 1, wherein the cosolvent in S1 is ethanol, acetone or tetrahydrofuran.
5. The method for preparing a polyurethane sponge adsorption material as claimed in claim 1, wherein the curing temperature is 20-40 ℃ and the time is 24-48 hours.
6. The method for preparing the polyurethane sponge adsorption material according to claim 1, wherein the preparation method of the 3-pyrrole-2-hydroxy propane sodium sulfonate is as follows: 100 parts of pyrrole, 420-660 parts of 3-chloro-2-hydroxy propane sodium sulfonate and 60-90 parts of sodium hydroxide are added into tetrahydrofuran, stirred for reaction, hydrochloric acid is added to adjust the pH to 6, the mixture is concentrated under reduced pressure, saturated sodium bicarbonate solution is used for washing the product, and then the product is placed into ethanol aqueous solution for recrystallization, so that 3-pyrrole-2-hydroxy propane sodium sulfonate is obtained.
7. The method for preparing a polyurethane sponge adsorption material as claimed in claim 6, wherein the reaction temperature is 50-75 ℃ and the reaction time is 4-10h.
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