CN109942768B - Spherical porous melamine-formaldehyde-thiourea polymer resin and preparation method thereof - Google Patents
Spherical porous melamine-formaldehyde-thiourea polymer resin and preparation method thereof Download PDFInfo
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- CN109942768B CN109942768B CN201910240737.3A CN201910240737A CN109942768B CN 109942768 B CN109942768 B CN 109942768B CN 201910240737 A CN201910240737 A CN 201910240737A CN 109942768 B CN109942768 B CN 109942768B
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- 239000002952 polymeric resin Substances 0.000 title claims abstract description 36
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 36
- SKHRWYIOPCHLGQ-UHFFFAOYSA-N formaldehyde thiourea 1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC(N)=S.NC1=NC(N)=NC(N)=N1 SKHRWYIOPCHLGQ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 47
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
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- 230000007935 neutral effect Effects 0.000 claims abstract description 11
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
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- 238000003756 stirring Methods 0.000 claims description 47
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 24
- 239000012074 organic phase Substances 0.000 abstract description 17
- 150000002500 ions Chemical class 0.000 abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 3
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- 239000011324 bead Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
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- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 8
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 239000004312 hexamethylene tetramine Substances 0.000 description 5
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- 239000000463 material Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 3
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- 238000012856 packing Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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Abstract
The invention discloses a spherical porous melamine-formaldehyde-thiourea polymer resin and a preparation method thereof. The preparation method comprises the steps of carrying out prepolymerization on aqueous solutions of melamine, thiourea and formaldehyde under a neutral or weakly alkaline condition, then mixing the obtained prepolymer with a pore-forming agent, adjusting the prepolymer to be neutral or weakly acidic, and dispersing the prepolymer into an organic phase containing a surfactant for polymerization to obtain the spherical porous melamine-formaldehyde-thiourea polymer resin. The spherical porous melamine-formaldehyde-thiourea polymer resin obtained by the invention can be used for adsorbing Au3+Ag + and Pd2+The noble metal ions have the advantages of smooth surface, uniform particle size, convenient filling, good heat resistance, stable volume, high specific surface area, high adsorption efficiency and the like.
Description
Technical Field
The invention relates to the field of porous resin materials, in particular to spherical porous melamine-formaldehyde-thiourea polymer resin and a preparation method thereof.
Background
The polymer porous resin material is also called macroporous resin, and is widely used in the fields of adsorption separation, catalysis, enzyme immobilization and the like, such as ion exchange resin, adsorption resin, chelating resin, a catalyst or a catalyst carrier, an enzyme immobilization carrier and the like. Among porous resin materials, spherical resins have many advantages over irregular granular resins, such as high mechanical strength, good hydrodynamic properties when used as a fixed bed packing, and the like. The most commonly used polymeric porous resins are spherical porous styrene-divinylbenzene copolymer resins, the spherical porous resins generally have a particle size in the range of 0.1 to 1.5mm, the most commonly used resin particle size in the range of 0.3 to 1.2mm, and resins having a particle size within this size range are most convenient in either fixed bed applications or reaction vessel type applications, where the pressure drop of the fluid flowing through the fixed bed is small in the application as a fixed bed packing, and where the resin can be separated from the liquid of the reaction system by simple filtration in the reaction vessel type application. The porous styrene-divinylbenzene copolymer resin can be directly used as an adsorption resin, or can be used for preparing resin materials with various functions through functionalization, such as introducing sulfonic groups into cation exchange resin, introducing amine groups (including primary, secondary, tertiary and quaternary amine groups) into anion exchange resin, introducing chelating groups into chelating resin, introducing groups capable of forming hydrogen bonds into the adsorption resin through hydrogen bond action, and the like.
The chelating groups in the chelating resin often contain atoms such as nitrogen, oxygen, phosphorus, sulfur and the like, the groups have high complexing ability with heavy metal ions, and 2 or more than 2 complexing groups form a chelating ring with the heavy metal ions, so that the chelating resin has good adsorption performance on the heavy metal ions. By selecting different complexing groups, the chelating resin has higher chelating performance on one or a certain class of heavy metal ions and has smaller chelating performance on other heavy metal ions, so that the or the class of heavy metal ions are selectively adsorbed, the adsorption effect on other heavy metal ions is smaller, and the aim of separating the heavy metal ions is fulfilled. Such as melamine-formaldehyde-thiourea copolymer resin, has amino group, oxygen atom and sulfur atom3 +、Ag+And Pd2+The noble metal ions have high adsorption effect but can adsorb Cu2+And Zn2+Etc. have little adsorption of common heavy metal ions, and thus are useful for removing Cu from the metal2+And Zn2+Selectively adsorbing Au in solution of plasma3+、Ag+And Pd2+And the like noble metal ions.
However, the melamine-formaldehyde-thiourea copolymer resins prepared in these documents were in the form of blocks, and then were pulverized into irregular particles to conduct adsorption experiments. The irregular particle adsorbent is much inferior to the spherical bead adsorbent, and particularly, when the spherical bead adsorbent is used as a filler for column adsorption, the spherical bead adsorbent is more excellent. Chinese patent (application No. 2011102028258) prepares micron-sized spherical melamine-formaldehyde-thiourea chelating resin through ultrasonic-initiated emulsion polymerization, and the particle size of the obtained chelating resin is submicron (0.5 mm). The use of such chelate resins having a particle size of the order of micrometers or submicron as a preparative adsorbent is difficult to achieve because such small particle size resins are difficult to separate from the adsorbed solution by filtration after adsorption and cannot be used as a packing for preparative column adsorption.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a spherical porous melamine-formaldehyde-thiourea polymer resin which has the advantages of smooth surface, uniform particle size, convenience in filling, good heat resistance, stable volume, high specific surface area, high adsorption efficiency and the like.
Another object of the present invention is to provide a method for preparing the above spherical porous melamine-formaldehyde-thiourea polymer resin.
The invention is realized by the following technical scheme:
the spherical porous melamine-formaldehyde-thiourea polymer resin has skeleton of melamine-formaldehyde-thiourea polymer, spherical shape and porous resin.
The particle size of the resin is 0.1-1.5mm, preferably 0.3-1.2 mm.
The invention provides a preparation method of the spherical porous melamine-formaldehyde-thiourea polymer resin, which comprises the following preparation steps of 2:
1) carrying out prepolymerization on aqueous solutions of melamine, thiourea and formaldehyde under neutral or weakly alkaline conditions to obtain a prepolymer solution;
2) adding a pore-foaming agent into the prepolymer solution, adjusting the pH value to be neutral or weakly acidic, suspending the prepolymer solution in an organic solvent containing a surfactant, and heating and polymerizing under stirring to obtain the spherical porous melamine-formaldehyde-thiourea polymer resin.
In step 1), the molar ratio of melamine, thiourea and formaldehyde is 1:0.2:1.5-1:10:4, and the pH range under neutral or weakly alkaline conditions is 7-10. The bases used to adjust the pH of the prepolymerization solution include: inorganic bases such as sodium hydroxide, sodium carbonate, etc.; organic bases such as hexamethylenetetramine, ethanolamine, etc. The temperature of the prepolymerization is 40-100 ℃, the end point of the prepolymerization is controlled when the prepolymerization system becomes clear or basically clear, and then the temperature of the prepolymerization system is reduced to be below 30 ℃.
Adding pore-forming agent into the cooled prepolymer solution, wherein the amount of the pore-forming agent (including water contained in the prepolymer) is 0.25-3 times of the total mass of melamine, thiourea and formaldehyde in the prepolymer system. The porogenic agent comprises: water (including water already contained in the prepolymer and additional water) and an organic compound. The organic compound comprises alcohol compounds such as ethylene glycol, glycerol, etc., and/or mixture of monosaccharide or oligosaccharide such as glucose, fructose, sucrose, cyclodextrin, etc. Water (including water contained in the prepolymer and additional water) can be used as a pore-forming agent independently, or a mixed pore-forming agent of water and an organic compound can be used, wherein the mass ratio of the water to the organic compound in the mixed pore-forming agent is 1:0-1: 3. The organic compound in the mixed porogen may be any one of the organic compounds described above, or any two or more of the organic compounds described above, and if two or more organic compound porogens are used, the ratio of the different organic compounds may be any ratio. The pore structure of the final product is adjusted by adjusting the type and the proportion of the pore-forming agent. And adjusting the pH value of the prepolymer solution and the mixed solution after adding the pore-foaming agent to 4-7, and immediately using the mixture for the next suspension polymerization.
The oil phase used for suspension polymerization is an organic solvent which contains a surfactant and is immiscible with water, and comprises halogenated hydrocarbon such as dichloroethane and the like, alkane such as n-heptane and the like, aromatic hydrocarbon such as toluene and the like, and the organic solvent can be used alone or a mixture of any two organic solvents, wherein the ratio of the two organic solvents is 0:100-100: 0. The surfactant comprises span such as span-80, carboxymethyl cellulose, cellulose acetate and polyethylene glycol, the proportion of the surfactant in the organic phase is 0.5-3%, any one of the surfactants or the combination of any two or more surfactants can be adopted in the organic phase, and the proportion of different surfactants in the combined surfactant can be any proportion.
Adding the water phase with the pH value adjusted to be slightly acidic into the oil phase, adjusting the stirring speed to disperse the water phase into droplets with proper size in the oil phase, and heating for polymerization to obtain the spherical porous melamine-formaldehyde-thiourea polymer resin, wherein the polymerization temperature range is 40-100 ℃ and the polymerization time is 2-12 hours. After hydrothermal treatment, the obtained resin balls are respectively washed by ethanol and water, dried in vacuum and sieved to obtain 20-100 meshes.
Compared with the prior art, the invention has the following beneficial effects:
the spherical porous resin obtained by polymerization of melamine, formaldehyde and thiourea in the presence of the pore-forming agent has the advantages of smooth surface, uniform particle size, convenience in filling, good heat resistance, stable volume, high specific surface area, high adsorption efficiency and the like, and can be used for adsorbing Au3+、Ag+And Pd2+And the like noble metal ions.
Drawings
FIG. 1 is a microphotograph of a spherical porous melamine-formaldehyde-thiourea polymer resin prepared in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials used in the examples and comparative examples of the present invention were all commercially available.
Example 1
Adjusting the pH value of 12.9mL (14g) of formaldehyde aqueous solution (the concentration is 37%) to 8.5 by using ethanolamine, starting stirring, adding 5.3g of melamine and 1.5g of thiourea while stirring, slowly heating to 80 ℃ for reaction, stopping heating when the system becomes clear, and cooling to below 30 ℃ by using water bath to obtain a prepolymer solution.
8.9g of sucrose and 9.2g of water were added to the prepolymer solution, stirred to dissolve it, concentrated hydrochloric acid was added dropwise with stirring to adjust the pH to 5, and then added to a previously prepared organic phase (150 mL) of 1, 2-dichloroethane containing 1% span-80 and 1% polyethylene glycol (average molecular weight 6000). Stirring is started to disperse the water phase into small liquid beads, the stirring speed is adjusted to adjust the size of the liquid beads, the temperature is slowly increased to 75 ℃, and the reaction is carried out for 4 hours. Stopping heating, cooling the temperature of the system to room temperature, filtering, washing with ethanol for several times after hydrothermal treatment, fully washing the resin with hot water, drying in vacuum, and screening to obtain the porous spherical melamine-formaldehyde-thiourea polymer resin with 30-60 meshes.
As can be seen from the photomicrograph of FIG. 1, the prepared spherical porous melamine-formaldehyde-thiourea polymer resin has a spherical shape, a porous resin and a uniform particle size, and has a specific surface area of 173m measured by a low-temperature nitrogen adsorption method2In g, the mean pore diameter is 18 nm.
Example 2
0.025g of hexamethylenetetramine was added to 9.2mL (10g) of an aqueous formaldehyde solution (37% concentration), and the solid was dissolved by stirring. Adding 7.7g of melamine and 1.2g of thiourea under stirring, adjusting the pH value to 8 by using 10mol/L NaOH, slowly heating to 80 ℃ for reaction, stopping heating when the system becomes clear, and cooling to below 30 ℃ by using water bath to obtain a prepolymer solution.
3g of ethylene glycol and 1.5g of water are added to the prepolymer solution, concentrated hydrochloric acid is added dropwise under stirring to adjust the pH value to 5.5, and then the mixture is added to a prepared organic phase (150 mL), wherein the organic phase is 1, 2-dichloroethane containing 1% span-80, 1% polyethylene glycol (average molecular weight 6000) and 1% cellulose diacetate. Stirring is started to disperse the water phase into small liquid beads, the stirring speed is adjusted to adjust the size of the liquid beads, the temperature is slowly increased to 75 ℃, and the reaction is carried out for 4 hours. Stopping heating, and regulating the temperature of the systemCooling to room temperature, filtering, washing the obtained resin with ethanol for several times after hydrothermal treatment, fully washing the resin with hot water, vacuum drying, and screening to obtain the porous spherical melamine-formaldehyde polymer resin with 40-100 meshes. The specific surface area is 108m determined by a low-temperature nitrogen adsorption method2In g, the mean pore diameter is 15 nm.
Example 3
Adding 3.4g of melamine and 3.4g of thiourea into 9.2mL (10g) of formaldehyde aqueous solution (the concentration is 37%), adding the mixture under stirring, slowly heating the mixture to 60 ℃ for reaction when the pH value of ethanolamine is 9, stopping heating when the system becomes clear, and cooling the mixture to below 30 ℃ by using a water bath to obtain a prepolymer solution.
5g of glucose and 5g of water were added to the prepolymer solution, concentrated hydrochloric acid was added dropwise with stirring to adjust the pH to 6, and then the solution was added to a previously prepared organic phase (120 mL) which was toluene containing 1% span-80 and 1% polyethylene glycol (average molecular weight 6000). Stirring is started to disperse the water phase into small liquid beads, the stirring speed is adjusted to adjust the size of the liquid beads, the temperature is slowly increased to 60 ℃, and the reaction is carried out for 8 hours. Stopping heating, cooling the temperature of the system to room temperature, filtering, washing the obtained resin with ethanol for several times, fully washing the resin with hot water, drying in vacuum, and sieving to obtain the porous spherical melamine-formaldehyde polymer resin with 40-100 meshes. The specific surface area is 62m determined by a low-temperature nitrogen adsorption method2In terms of/g, the mean pore diameter is 11 nm.
Example 4
0.025g of hexamethylenetetramine was added to 9.2mL (10g) of an aqueous formaldehyde solution (37% concentration), and the solid was dissolved by stirring. Adding 5.3g of melamine and 0.5g of thiourea under stirring, adjusting the pH value to 8.5 by using ethanolamine, slowly heating to 70 ℃ for reaction, stopping heating when the system becomes clear, and cooling to below 30 ℃ by using water bath to obtain a prepolymer solution.
Adding 6g g-cyclodextrin and 6g water into the prepolymer solution, adding concentrated hydrochloric acid dropwise under stirring to adjust pH to 6, heating to 50 deg.C to dissolve the solid, and adding into a prepared organic phase (150 mL) containing 1% span-80, 1% cellulose acetate and 1% polyethylene glycol (PEGylate)Average molecular weight of 6000) of 1, 2-dichloroethane. Stirring is started to disperse the water phase into small liquid beads, the stirring speed is adjusted to adjust the size of the liquid beads, the temperature is slowly increased to 75 ℃, and the reaction is carried out for 8 hours. Stopping heating, cooling the temperature of the system to room temperature, filtering, washing the obtained resin with ethanol for several times after hydrothermal treatment, fully washing the resin with hot water, drying in vacuum, and screening to obtain the porous spherical melamine-formaldehyde polymer resin with 30-60 meshes. The specific surface area is 98m determined by a low-temperature nitrogen adsorption method2(ii)/g, average pore diameter 13 nm.
Example 5
11mL (12 g) of formaldehyde aqueous solution (the concentration is 37%) is added with 5.3g of melamine and 2.6g of thiourea under stirring, the pH value is adjusted to 8.5 by using ethanolamine, the mixture is slowly heated to 50 ℃ for reaction, when the system becomes clear, the heating is stopped, and the mixture is cooled to below 30 ℃ by using water bath to obtain a prepolymer solution.
4g of glycerol and 6g of water are added to the prepolymer solution, concentrated hydrochloric acid is added dropwise under stirring to adjust the pH value to 6, and then the solution is added into a prepared organic phase (135 mL), wherein the organic phase is toluene containing 1.5% of span-80. Stirring is started to disperse the water phase into small liquid beads, the stirring speed is adjusted to adjust the size of the liquid beads, the temperature is slowly increased to 75 ℃, and the reaction is carried out for 4 hours. Stopping heating, cooling the temperature of the system to room temperature, filtering, washing the obtained resin with ethanol for several times, fully washing the resin with hot water, drying in vacuum, and screening to obtain the porous spherical melamine-formaldehyde polymer resin with 20-60 meshes. The specific surface area is 73m determined by a low-temperature nitrogen adsorption method2In g, the mean pore diameter is 9 nm.
Example 6
0.025g of hexamethylenetetramine was added to 15.6mL (17g) of an aqueous formaldehyde solution (37% strength), and the solid was dissolved by stirring. 2.3g of melamine and 5.26g of thiourea are added under stirring, the pH value is adjusted to 8.5 by using ethanolamine, the mixture is slowly heated to 65 ℃ for reaction, heating is stopped when the system becomes clear, and the mixture is cooled to below 30 ℃ by using water bath to obtain a prepolymer solution.
Adding 2g of gamma-cyclodextrin, 2g of sucrose and 4g of water into the prepolymer solution, dropwise adding concentrated hydrochloric acid while stirring to adjust the pH value to 6,the solid was dissolved by heating to 50 ℃ and then added to a pre-formulated organic phase (150 mL) of 1, 2-dichloroethane containing 2% span-80, 1.5% carboxymethylcellulose and 1% polyethylene glycol (average molecular weight 6000). Stirring is started to disperse the water phase into small liquid beads, the stirring speed is adjusted to adjust the size of the liquid beads, the temperature is slowly increased to 65 ℃, and the reaction is carried out for 8 hours. Stopping heating, cooling the temperature of the system to room temperature, filtering, washing the obtained resin with ethanol for several times after hydrothermal treatment, fully washing the resin with hot water, drying in vacuum, and screening to obtain the porous spherical melamine-formaldehyde polymer resin with 30-60 meshes. The specific surface area is 158m determined by a low-temperature nitrogen adsorption method2In g, the mean pore diameter is 17 nm.
Example 7
To 14.2mL (15.4g) of an aqueous formaldehyde solution (37% concentration) was added, and the solid was dissolved by stirring. Adding 5.3g of thiourea and 1.7g of melamine under stirring, adjusting the pH value to 8.5 by using 10mol/L of sodium hydroxide, slowly heating to 60 ℃ for reaction, stopping heating when the system becomes clear, and cooling to below 30 ℃ by using water bath to obtain a prepolymer solution.
1g of ethylene glycol, 5g of glycerol and 5g of water are added into the prepolymer solution, concentrated hydrochloric acid is added dropwise under stirring to adjust the pH value to 6, and then the solution is added into a prepared organic phase (150 mL), wherein the organic phase is 1, 2-dichloroethane containing 2% span-80 and 1% cellulose acetate. Stirring is started to disperse the water phase into small liquid beads, the stirring speed is adjusted to adjust the size of the liquid beads, the temperature is slowly increased to 65 ℃, and the reaction is carried out for 8 hours. Stopping heating, cooling the temperature of the system to room temperature, filtering, washing the obtained resin with ethanol for several times, fully washing the resin with hot water, drying in vacuum, and sieving to obtain the porous spherical melamine-formaldehyde polymer resin with 40-60 meshes. The specific surface area is 63m determined by a low-temperature nitrogen adsorption method2In g, the mean pore diameter is 15 nm.
Example 8
0.025g of hexamethylenetetramine was added to 9.2mL (10g) of an aqueous formaldehyde solution (37% concentration), and the solid was dissolved by stirring. Adding 3.3g of melamine and 1.3g of thiourea under stirring, adjusting the pH value to 8.5 by using ethanolamine, slowly heating to 50 ℃ for reaction, stopping heating when the system becomes clear, and cooling to below 30 ℃ by using water bath to obtain a prepolymer solution.
Adding 2g of sucrose, 5g of fructose and 7g of water into the prepolymer solution, dropwise adding concentrated hydrochloric acid while stirring to adjust the pH value to 6, and then adding the solution into a prepared organic phase (100 mL), wherein the organic phase is n-heptane containing 1% of span-80. Stirring is started to disperse the water phase into small liquid beads, the stirring speed is adjusted to adjust the size of the liquid beads, the temperature is slowly increased to 75 ℃, and the reaction is carried out for 6 hours. Stopping heating, cooling the temperature of the system to room temperature, filtering, washing the obtained resin with ethanol for several times after hydrothermal treatment, fully washing the resin with hot water, drying in vacuum, and screening to obtain the porous spherical melamine-formaldehyde polymer resin with 30-60 meshes. The specific surface area is 107m determined by a low-temperature nitrogen adsorption method2In terms of/g, the mean pore diameter is 21 nm.
Example 9
15mL (16.3g) of formaldehyde aqueous solution (with the concentration of 37%) is adjusted to pH value of 10 by 10mol/L sodium hydroxide, stirring is started, 5.3g of melamine and 3.7g of thiourea are added under stirring, the mixture is slowly heated to 70 ℃ for reaction, heating is stopped when the system becomes clear, and the mixture is cooled to below 30 ℃ by water bath to obtain a prepolymer solution.
1.5g of glucose, 1.8g of fructose, 2g of gamma-cyclodextrin and 8g of water are added to the prepolymer solution, concentrated hydrochloric acid is added dropwise under stirring to adjust the pH value to 4, the solution is heated to 50 ℃ to dissolve the solid, and then the solid is added to a prepared organic phase (150 mL), wherein the organic phase is 1, 2-dichloroethane containing 3% span-801.5% cellulose acetate and 1.5% polyethylene glycol (average molecular weight 6000). Stirring is started to disperse the water phase into small liquid beads, the stirring speed is adjusted to adjust the size of the liquid beads, the temperature is slowly increased to 75 ℃, and the reaction is carried out for 4 hours. Stopping heating, cooling the temperature of the system to room temperature, filtering, washing the obtained resin with ethanol for several times after hydrothermal treatment, fully washing the resin with hot water, drying in vacuum, and screening to obtain the porous spherical melamine-formaldehyde polymer resin with 40-60 meshes. The specific surface area is 124m determined by a low-temperature nitrogen adsorption method2In g, the mean pore diameter is 15 nm.
Claims (10)
1. The spherical porous melamine-formaldehyde-thiourea polymer resin is characterized in that a framework of the resin is a melamine-formaldehyde-thiourea polymer, the shape of the resin is spherical, the resin has porosity, and the particle size of the resin is 0.1-1.5 mm;
the preparation method of the spherical porous melamine-formaldehyde-thiourea polymer resin comprises the following preparation steps of 2:
1) pre-polymerizing aqueous solution of melamine, thiourea and formaldehyde under neutral or alkalescent conditions to obtain prepolymer solution;
2) adding a pore-foaming agent into the prepolymer solution, adjusting the pH value to be neutral or weakly acidic, suspending the prepolymer solution in an organic solvent containing a surfactant, and heating and polymerizing under stirring to obtain spherical porous melamine-formaldehyde-thiourea polymer resin;
in the step 1), the molar ratio of melamine, thiourea and formaldehyde is 1:0.2:1.5-1:10: 4;
in step 2), the pore-forming agent comprises one or more of water, ethylene glycol, glycerol, glucose, fructose, sucrose or cyclodextrin.
2. The spherical porous melamine-formaldehyde-thiourea polymer resin of claim 1, wherein the particle size of the resin is 0.3-1.2 mm.
3. A method for preparing a spherical porous melamine-formaldehyde-thiourea polymer resin according to claim 1 or 2, characterized in that the preparation steps are divided into 2 steps:
1) pre-polymerizing aqueous solution of melamine, thiourea and formaldehyde under neutral or alkalescent conditions to obtain prepolymer solution;
2) adding a pore-foaming agent into the prepolymer solution, adjusting the pH value to be neutral or weakly acidic, suspending the prepolymer solution in an organic solvent containing a surfactant, and heating and polymerizing under stirring to obtain the spherical porous melamine-formaldehyde-thiourea polymer resin.
4. The method for preparing spherical porous melamine-formaldehyde-thiourea polymer resin according to claim 3, wherein in step 1), the molar ratio of melamine, thiourea and formaldehyde is 1:0.2:1.5-1:10: 4.
5. The method for preparing spherical porous melamine-formaldehyde-thiourea polymer resin of claim 3, wherein in step 1), the pH value of neutral or weakly alkaline conditions is in the range of pH 7-10.
6. The method for preparing spherical porous melamine-formaldehyde-thiourea polymer resin according to claim 3, wherein in the step 1), the prepolymerization temperature is 40 ℃ to 100 ℃.
7. The method for preparing spherical porous melamine-formaldehyde-thiourea polymer resin according to claim 3, wherein in step 2), the pore-forming agent comprises one or more of water, ethylene glycol, glycerol, glucose, fructose, sucrose or cyclodextrin.
8. The method for preparing a spherical porous melamine-formaldehyde-thiourea polymer resin according to claim 3, wherein in the step 2), the mass ratio of the sum of the amount of water contained in the prepolymer solution and the amount of the pore-forming agent added to the total amount of melamine, formaldehyde and thiourea added in preparing the prepolymer is 3:1 to 0.25: 1.
9. The method for preparing spherical porous melamine-formaldehyde-thiourea polymer resin according to claim 3, wherein in the step 2), the pH is adjusted to a neutral or weakly acidic pH range of 4 to 7; the polymerization temperature is 40-100 ℃; the polymerization time is 2 to 12 hours.
10. The method for preparing spherical porous melamine-formaldehyde-thiourea polymer resin according to claim 3, wherein in step 2), the surfactant comprises one or more of span-80, carboxymethyl cellulose, cellulose acetate or polyethylene glycol; the organic solvent is one or more of dichloroethane, n-heptane or toluene; the mass percentage of the surfactant in the organic solvent is 0.5-3%.
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| CN105254830A (en) * | 2015-11-20 | 2016-01-20 | 天津大学 | Method for preparing water-soluble thiourea aldehyde heavy metal capturing agent with low formaldehyde content |
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| CN105254830A (en) * | 2015-11-20 | 2016-01-20 | 天津大学 | Method for preparing water-soluble thiourea aldehyde heavy metal capturing agent with low formaldehyde content |
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| Separation and recovery of gold(III) from base metal ions using melamine–formaldehyde–thiourea chelating resin;Abdülhakim Aydin et al;《Applied Polymer scinece》;20071009;第107卷(第2期);第1201-1206页 * |
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