CN109942768A - Spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin and preparation method thereof - Google Patents
Spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin and preparation method thereof Download PDFInfo
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- CN109942768A CN109942768A CN201910240737.3A CN201910240737A CN109942768A CN 109942768 A CN109942768 A CN 109942768A CN 201910240737 A CN201910240737 A CN 201910240737A CN 109942768 A CN109942768 A CN 109942768A
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- CN
- China
- Prior art keywords
- thiocarbamide
- formaldehyde
- melamine
- fluoropolymer resin
- spherical porous
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- 229920005989 resin Polymers 0.000 title claims abstract description 75
- 239000011347 resin Substances 0.000 title claims abstract description 75
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 30
- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 42
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 26
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 229920002301 cellulose acetate Polymers 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 229920000858 Cyclodextrin Polymers 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 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 2
- 239000002904 solvent Substances 0.000 claims description 2
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 claims 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000012074 organic phase Substances 0.000 abstract description 20
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 150000002894 organic compounds Chemical class 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229920001429 chelating resin Polymers 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 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 7
- 238000010335 hydrothermal treatment Methods 0.000 description 7
- 229940031098 ethanolamine Drugs 0.000 description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 5
- 239000004312 hexamethylene tetramine Substances 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- -1 alcohol compound Chemical class 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000001914 filtration Methods 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
- 230000001788 irregular Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001291 vacuum drying 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
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- KFUSEUYYWQURPO-UHFFFAOYSA-N 1,2-dichloroethene Chemical compound ClC=CCl KFUSEUYYWQURPO-UHFFFAOYSA-N 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical group [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a kind of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin and preparation method thereof, the skeleton of the resin is melamine-formaldehyde-thiocarbamide polymer, and shape is spherical shape, and resin has porosity.Preparation method is that the aqueous solution of melamine, thiocarbamide and formaldehyde is carried out prepolymerization under neutral or weak basic condition, then obtained performed polymer is mixed with pore-foaming agent, and it adjusts to neutral or faintly acid, it is distributed in the organic phase containing surfactant and is polymerize, obtain spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin.Spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin that the present invention obtains can be used for adsorbing Au3+, Ag+ and Pd2+Equal precious metal ions have many advantages, such as smooth surface, uniform particle diameter, are convenient for filling, heat-resist, volume stability, specific surface area height, adsorption efficiency high.
Description
Technical field
The present invention relates to porous resin Material Fields, and in particular to a kind of spherical porous melamine-formaldehyde-thiocarbamide polymerization
Resin and preparation method thereof.
Background technique
Polyalcohol stephanoporate resin material is also referred to as macroreticular resin, is widely used in the fields such as adsorbing separation, catalysis and enzyme immobilization,
Such as ion exchange resin, absorption resin, chelating resin, catalyst or catalyst carrier, enzyme immobilization carrier.In porous resin
In material, spherical resin has many advantages than irregular granular resin, such as high mechanical strength, as fixed bed fillers when stream
Mechanics performance is good etc..Most common polyalcohol stephanoporate resin is spherical porous styrene-divinylbenzene copolymer resin, spherical
The particle size range of porous resin is generally 0.1-1.5mm, and most common particle size range is 0.3-1.2mm, and partial size is in this size model
Resin in enclosing either in fixed bed applications or reacts most convenient in autoclave application, in the application as fixed bed fillers,
The pressure drop very little for flowing through the fluid of fixed bed, reaction autoclave in use, by simply filtering can by resin with react
The liquid of system separates.Porous styrene-divinylbenzene copolymer resin can be directly used as absorption resin, or pass through function
Baseization preparation have various functions resin material, such as introduce sulfonic group become cation exchange resin, introduce amido (including
Primary, secondary, tertiary and quaternary amido) become anion exchange resin, introducing chelation group becomes chelating resin, and introducing can form hydrogen bond
Group can be used for the absorption resin etc. by hydrogen bond action.
Chelation group in chelating resin often contains the atoms such as nitrogen, oxygen, p and s, these groups and heavy metal ion have
There is higher complexing power, and chelate ring is formed by 2 or 2 or more complexing groups and heavy metal ion, therefore chelate tree
Rouge has good absorption property to heavy metal ion.By selecting different complexing groups, chelating resin can be made to a certain
Kind or certain a kind of heavy metal ion chelating ability with higher, and it is smaller to the chelating ability of other heavy metal ion, thus
This or this kind of heavy metal ion is selectively adsorbed, and it is smaller to the suction-operated of other heavy metal ion, reach separation weight
The purpose of metal ion.As melamine-formaldehyde-thiocarbamide copolymer resin because containing amino, oxygen atom and due to sulphur atom to Au3 +、Ag+And Pd2+Equal precious metal ions have very high suction-operated, but for Cu2+And Zn2+Etc. the absorption of common heavy metal ion
Very little is acted on, for from containing Cu2+And Zn2+Au is selectively adsorbed in the solution of plasma3+、Ag+And Pd2+Etc. your gold
Belong to ion.
But melamine-formaldehyde-thiocarbamide copolymer resin of these documents preparation is bulk, is then comminuted into irregular
Adsorption experiment is carried out after granular.The performance of irregular particle shape adsorbent is more far short of what is expected than the adsorbent of spherical beaded, especially
Be as column method absorption filler when, using spherical beaded adsorbent when performance it is more preferable.Chinese patent (application number
2011102028258) emulsion polymerization is caused by ultrasound and is prepared for micron level spherical melamine-formaldehyde-thiocarbamide chelating
Resin, the partial size of gained chelating resin are submicron order (~ 0.5mm).This partial size is the chelating resin of micron or submicron order
The application of adsorbent as preparative is difficult to realize, because of that the resin of small particle is difficult to pass through filtering after absorption
It is separated with the solution being adsorbed, it is also not possible to be used to prepare the filler of the column absorption of type.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of spherical porous melamine-formaldehyde-thiocarbamides
Fluoropolymer resin, the resin have surface is smooth, uniform particle diameter, convenient for filling, heat-resist, volume stability, specific surface area height,
The advantages that adsorption efficiency is high.
Another object of the present invention is to provide the systems of above-mentioned spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin
Preparation Method.
The present invention is achieved by the following technical solutions:
The skeleton of a kind of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin, resin is poly- for melamine-formaldehyde-thiocarbamide
Object is closed, shape is spherical shape, and resin has porosity.
The partial size of the resin is 0.1-1.5mm, preferably 0.3-1.2mm.
The present invention provides above-mentioned spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin preparation method, preparations
2 steps of step point:
1) it is molten to obtain prepolymer for the progress prepolymerization under neutral or weak basic condition of the aqueous solution of melamine, thiocarbamide and formaldehyde
Liquid；
2) pore-foaming agent is added in pre-polymer solution, adjusts pH value to neutral or faintly acid, is suspended in containing surfactant
In organic solvent, heating polymerization, obtains spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin under stiring.
In step 1), the molar ratio of melamine, thiocarbamide and formaldehyde is 1:0.2:1.5-1:10:4, neutral or alkalescent
The pH range of condition is 7-10.Adjusting alkali used in the pH value of pre-gathering solutions includes: inorganic base such as sodium hydroxide, sodium carbonate etc.；Have
Machine alkali such as hexamethylenetetramine, ethanol amine etc..Prepolymerization temperature range is 40-100 °C, when prepolymerization system change clarification or substantially
Control is prepolymerization terminal after clarification, and the temperature of prepolymerization system is then dropped to 30 °C or less.
Pore-foaming agent, amount (including moisture contained in performed polymer) phase of pore-foaming agent are added into the prepolymer solution to have cooled down
When 0.25-3 times of quality of the gross mass of melamine, thiocarbamide and formaldehyde in prepolymerization system.Pore-foaming agent used includes: water
(including moisture already contg in performed polymer and separately plus water) and organic compound.Organic compound includes alcohol compound such as second
The mixture of glycol, glycerol etc. and (or) monosaccharide or oligosaccharide such as glucose, fructose, sucrose and cyclodextrin etc..It can individually use
Water (including moisture already contg in performed polymer and separately plus water) is used as pore-foaming agent, can also use the mixing of water and organic compound
Pore-foaming agent, the mass ratio for mixing water and organic compound in pore-foaming agent is 1:0-1:3.Mix the organic compound in pore-foaming agent
Can be any one above-mentioned organic compound, be also possible in above-mentioned organic compound it is any two or more, such as
When fruit uses two or more organic compound pore-foaming agents, the ratio of different organic compounds can be arbitrary proportion.Pass through tune
Type and its ratio of pore-foaming agent are saved to adjust the pore structure of final products.By the mixing after prepolymer solution and addition pore-foaming agent
Solution adjusts pH value to 4-7, is used for next step suspension polymerisation at once.
Oil used in suspension polymerisation is mutually for containing surfactant, with water immiscible organic solvent, including halogenated hydrocarbons is such as
Dichloroethanes etc., alkane such as normal heptane etc., aromatic hydrocarbons such as toluene etc., organic solvent can be used alone or it is any two kinds it is organic
The mixture of solvent, the ratio of two kinds of organic solvents are 0:100-100:0.Surfactant includes Span such as Span-80, carboxylic first
Base cellulose, cellulose acetate and polyethylene glycol, the ratio of surfactant is 0.5-3% in organic phase, can be adopted in organic phase
With any one above-mentioned surfactant, or the combination of two or more any surfactants, combined surfactant
The ratio of middle different surfaces activating agent can be arbitrary proportion.
The water phase of adjusted pH value to subacidity is added in oily phase, mixing speed is adjusted, makes water phase in oily Xiang Zhongfen
The drop of suitable size is dissipated into, spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin, polymerization temperature are obtained after heating polymerization
Spending range is 40-100 °C, and polymerization time is 2-12 hours.After gained resin balls hydrothermal treatment, ethyl alcohol and washing are used respectively
It washs, is dried in vacuo, screening takes 20-100 mesh.
Compared with prior art, the invention has the following beneficial effects:
In the presence of pore-foaming agent, the spherical porous resin obtained by the polymerization of melamine, formaldehyde and thiocarbamide has the present invention
Surface is smooth, uniform particle diameter, convenient for filling, heat-resist, volume stability, specific surface area height, adsorption efficiency is high the advantages that, can use
In absorption Au3+、Ag+And Pd2+Equal precious metal ions.
Detailed description of the invention
Fig. 1 is that spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin microscope that embodiment 1 is prepared shines
Piece.
Specific embodiment
Further illustrate that the present invention, following embodiment are the preferable embodiment party of the present invention below by specific embodiment
Formula, but embodiments of the present invention are not limited by following embodiments.
Raw material used by the embodiment of the present invention and comparative example derives from commercially available.
Embodiment 1
12.9mL (14g) formalin (concentration 37%) ethanol amine is adjusted into pH value to 8.5, stirring is started, is stirring
Lower addition 5.3g melamine, 1.5g thiocarbamide, are slowly heated to 80 °C and are reacted, and stop heating after system, which becomes, to be clarified, use
Water-bath cooling is to 30 °C hereinafter, obtaining prepolymer solution.
8.9g sucrose and 9.2g water are added into prepolymer solution, stirs to dissolve, concentrated hydrochloric acid tune is added dropwise under stiring
PH value is saved to 5, is then added in the organic phase (150mL) prepared in advance, organic phase is to contain 1% Span-80 and 1% poly- second two
The 1,2- dichloroethanes of alcohol (average molecular weight 6000).Starting stirring makes Aqueous dispersions at small liquid pearl, adjusts mixing speed to adjust
The size for saving liquid pearl is to slowly warm up to 75 °C, reacts 4 hours.Stop heating, the greenhouse cooling of system to room temperature filter,
After hydrothermal treatment, for several times with ethanol washing, resin is sufficiently washed with hot water, be dried in vacuo, screening takes 30-60 mesh, obtains more
Hole spherical shape melamine-formaldehyde-thiocarbamide fluoropolymer resin.
By Fig. 1 microscope photo it is found that the spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin being prepared
Shape is spherical shape, and resin has porosity, and uniform particle diameter is 173m with low temperature nitrogen determination of adsorption method specific surface area2/ g, it is average
Aperture is 18nm.
Embodiment 2
0.025g hexamethylenetetramine is added in 9.2mL (10g) formalin (concentration 37%), stirring is started, makes
Solid dissolution.7.7g melamine, 1.2g thiocarbamide are added under stiring, adjusts pH value to 8 with 10mol/L NaOH, is slowly heated
It is reacted to 80 °C, stops heating after system, which becomes, to be clarified, with water-bath cooling to 30 °C hereinafter, obtaining prepolymer solution.
3g ethylene glycol and 1.5g water are added into prepolymer solution, concentrated hydrochloric acid is added dropwise under stiring and adjusts pH value to 5.5, so
It is added in the organic phase (150mL) prepared in advance afterwards, organic phase is to contain 1% Span-80,1% polyethylene glycol (average molecular weight
And the 1,2- dichloroethanes of 1% cellulose diacetate 6000).Starting stirring makes Aqueous dispersions at small liquid pearl, adjusts mixing speed and comes
The size for adjusting liquid pearl is to slowly warm up to 75 °C, reacts 4 hours.Stop heating, by the greenhouse cooling of system to room temperature, mistake
It filters, after obtained resin hydrothermal treatment, for several times with ethanol washing, sufficiently washs resin with hot water, be dried in vacuo, screening takes
40-100 mesh obtains porous spherical melamine-formaldehyde fluoropolymer resin.It is with low temperature nitrogen determination of adsorption method specific surface area
108m2/ g, average pore size 15nm.
Embodiment 3
3.4g melamine, 3.4g thiocarbamide are added in 9.2mL (10g) formalin (concentration 37%), under stiring
It is added, with ethanol amine pH value to 9, is slowly heated to 60 °C and is reacted, stop heating after system, which becomes, to be clarified, use water-bath cooling
To 30 °C hereinafter, obtaining prepolymer solution.
5g glucose and 5g water are added into prepolymer solution, concentrated hydrochloric acid is added dropwise under stiring and adjusts pH value to 6, then plus
Enter into the organic phase (120mL) prepared in advance, organic phase is to contain 1% Span-80 and 1% polyethylene glycol (average molecular weight
6000) toluene.Starting stirring makes Aqueous dispersions at small liquid pearl, adjusts mixing speed to adjust the size of liquid pearl, slowly heats up
To 60 °C, react 8 hours.Stop heating, by the greenhouse cooling of system to room temperature, filtering, obtained resin ethanol washing number
It is secondary, resin is sufficiently washed with hot water, is dried in vacuo, screening takes 40-100 mesh, obtains porous spherical melamine-formaldehyde polymer
Resin.It is 62m with low temperature nitrogen determination of adsorption method specific surface area2/ g, average pore size 11nm.
Embodiment 4
0.025g hexamethylenetetramine is added in 9.2mL (10g) formalin (concentration 37%), stirring is started, makes
Solid dissolution.5.3g melamine, 0.5g thiocarbamide are added under stiring, adjusts pH value to 8.5 with ethanol amine, is slowly heated to
70 °C are reacted, and stop heating after system, which becomes, to be clarified, with water-bath cooling to 30 °C hereinafter, obtaining prepolymer solution.
6g g- cyclodextrin and 6g water are added into prepolymer solution, concentrated hydrochloric acid is added dropwise under stiring and adjusts pH value to 6, adds
Heat dissolves solid to 50 °C, is then added in the organic phase (150mL) prepared in advance, organic phase be containing 1% Span-80,
The 1,2- dichloroethanes of 1% cellulose acetate and 1% polyethylene glycol (average molecular weight 6000).Starting stirring makes Aqueous dispersions at small
Liquid pearl adjusts mixing speed to adjust the size of liquid pearl, is to slowly warm up to 75 °C, reacts 8 hours.Stop heating, by system
Greenhouse cooling is filtered to room temperature, after obtained resin hydrothermal treatment for several times with ethanol washing, sufficiently washs resin with hot water,
Vacuum drying, screening take 30-60 mesh, obtain porous spherical melamine-formaldehyde fluoropolymer resin.It is surveyed with low temperature nitrogen absorption method
Determining specific surface area is 98m2/ g, average pore size 13nm.
Embodiment 5
5.3g melamine, 2.6g thiocarbamide is added in 11mL(12g) formalin (concentration 37%) under stiring, uses ethyl alcohol
Amine adjusts pH value to 8.5, is slowly heated to 50 DEG C and is reacted, and stops heating after system, which becomes, to be clarified, with water-bath cooling to 30
DEG C hereinafter, obtaining prepolymer solution.
4g glycerol and 6g water are added into prepolymer solution, concentrated hydrochloric acid is added dropwise under stiring and adjusts pH value to 6, is then added
Into the organic phase (135mL) prepared in advance, organic phase is the toluene containing 1.5% Span-80.Starting stirring makes Aqueous dispersions
At small liquid pearl, mixing speed is adjusted to adjust the size of liquid pearl, is to slowly warm up to 75 DEG C, is reacted 4 hours.Stop heating, by body
The greenhouse cooling of system is filtered to room temperature, and obtained resin for several times, sufficiently washs resin with hot water with ethanol washing, is dried in vacuo,
Screening takes 20-60 mesh, obtains porous spherical melamine-formaldehyde fluoropolymer resin.With low temperature nitrogen determination of adsorption method specific surface
Product is 73m2/ g, average pore size 9nm.
Embodiment 6
0.025g hexamethylenetetramine is added in 15.6mL (17g) formalin (concentration 37%), stirring is started, makes
Solid dissolution.2.3g melamine, 5.26g thiocarbamide are added under stiring, adjusts pH value to 8.5 with ethanol amine, is slowly heated to
65 DEG C are reacted, and stop heating after system, which becomes, to be clarified, with water-bath cooling to 30 DEG C hereinafter, obtaining prepolymer solution.
2g gamma-cyclodextrin, 2g sucrose and 4g water are added into prepolymer solution, concentrated hydrochloric acid is added dropwise under stiring and adjusts pH value
To 6, being heated to 50 DEG C dissolves solid, is then added in the organic phase (150mL) prepared in advance, and organic phase is containing 2% department
The 1,2- dichloroethanes of class -80,1.5% carboxymethyl cellulose and 1% polyethylene glycol (average molecular weight 6000).Starting stirring makes water
It is mutually dispersed into small liquid pearl, mixing speed is adjusted to adjust the size of liquid pearl, is to slowly warm up to 65 DEG C, react 8 hours.Stop adding
Heat filters the greenhouse cooling of system to room temperature, after obtained resin hydrothermal treatment for several times with ethanol washing, is filled with hot water
Divide washing resin, vacuum drying, screening takes 30-60 mesh, obtains porous spherical melamine-formaldehyde fluoropolymer resin.Use low temperature
Nitrogen adsorption methods measurement the specific area is 158m2/ g, average pore size 17nm.
Embodiment 7
By in 14.2mL (15.4g) formalin (concentration 37%), stirring is started, solid is dissolved.It is added under stiring
5.3g thiocarbamide, 1.7g melamine adjust pH value to 8.5 with 10mol/L sodium hydroxide, are slowly heated to 60 DEG C and are reacted,
Stop heating after system, which becomes, to be clarified, with water-bath cooling to 30 DEG C hereinafter, obtaining prepolymer solution.
1g ethylene glycol, 5g glycerol and 5g water are added into prepolymer solution, concentrated hydrochloric acid adjusting pH value is added dropwise under stiring and arrives
6, it is then added in the organic phase (150mL) prepared in advance, organic phase is 1 containing 2% Span-80 and 1% cellulose acetate,
2- dichloroethanes.Starting stirring makes Aqueous dispersions at small liquid pearl, adjusts mixing speed to adjust the size of liquid pearl, is to slowly warm up to
It 65 DEG C, reacts 8 hours.Stop heating, the greenhouse cooling of system to room temperature filter, obtained resin with ethanol washing for several times,
Resin is sufficiently washed with hot water, is dried in vacuo, screening takes 40-60 mesh, obtains porous spherical melamine-formaldehyde polymer tree
Rouge.It is 63m with low temperature nitrogen determination of adsorption method specific surface area2/ g, average pore size 15nm.
Embodiment 8
0.025g hexamethylenetetramine is added in 9.2mL (10g) formalin (concentration 37%), stirring is started, makes
Solid dissolution.3.3g melamine, 1.3g thiocarbamide are added under stiring, adjusts pH value to 8.5 with ethanol amine, is slowly heated to 50
It DEG C is reacted, stops heating after system, which becomes, to be clarified, with water-bath cooling to 30 DEG C hereinafter, obtaining prepolymer solution.
2 sucrose, 5g fructose and 7g water are added into prepolymer solution, concentrated hydrochloric acid is added dropwise under stiring and adjusts pH value to 6, so
It is added in the organic phase (100mL) prepared in advance afterwards, organic phase is the normal heptane containing 1% Span-80.Starting stirring makes water
It is mutually dispersed into small liquid pearl, mixing speed is adjusted to adjust the size of liquid pearl, is to slowly warm up to 75 DEG C, react 6 hours.Stop adding
Heat filters the greenhouse cooling of system to room temperature, after obtained resin hydrothermal treatment for several times with ethanol washing, is filled with hot water
Divide washing resin, vacuum drying, screening takes 30-60 mesh, obtains porous spherical melamine-formaldehyde fluoropolymer resin.Use low temperature
Nitrogen adsorption methods measurement the specific area is 107m2/ g, average pore size 21nm.
Embodiment 9
By 15mL (16.3g) formalin (concentration 37%), pH value is adjusted to 10 with 10mol/L sodium hydroxide, starts and stirs
It mixes, 5.3g melamine, 3.7g thiocarbamide is added under stiring, is slowly heated to 70 DEG C and is reacted, stop after system becomes clarification
It only heats, with water-bath cooling to 30 DEG C hereinafter, obtaining prepolymer solution.
1.5g glucose, 1.8g fructose, 2g gamma-cyclodextrin and 8g water are added into prepolymer solution, is added dropwise under stiring
Concentrated hydrochloric acid adjusts pH value to 4, and being heated to 50 DEG C dissolves solid, is then added in the organic phase (150mL) prepared in advance, has
Machine is mutually bis- chloroethene of 1,2- containing 3% Span-80,1.5% cellulose acetate and 1.5% polyethylene glycol (average molecular weight 6000)
Alkane.Starting stirring makes Aqueous dispersions at small liquid pearl, adjusts mixing speed to adjust the size of liquid pearl, is to slowly warm up to 75 DEG C, instead
It answers 4 hours.Stop heating, the greenhouse cooling of system to room temperature filters, uses ethanol washing after obtained resin hydrothermal treatment
For several times, resin is sufficiently washed with hot water, be dried in vacuo, screening takes 40-60 mesh, obtains the polymerization of porous spherical melamine-formaldehyde
Resin.It is 124m with low temperature nitrogen determination of adsorption method specific surface area2/ g, average pore size 15nm.
Claims (10)
1. a kind of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin, which is characterized in that the skeleton of resin is melamine
Amine-for-aldehyde-thiocarbamide polymer, shape are spherical shape, and resin has porosity.
2. spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin according to claim 1, which is characterized in that described
The partial size of resin is 0.1-1.5mm, preferably 0.3-1.2mm.
3. a kind of preparation method of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin of any of claims 1 or 2,
It is characterized in that, 2 steps of preparation step point:
1) aqueous solution of melamine, thiocarbamide and formaldehyde is carried out to prepolymerization under neutral or weak basic condition, and to obtain prepolymer molten
Liquid；
2) pore-foaming agent is added in pre-polymer solution, adjusts pH value to neutral or faintly acid, is suspended in containing surfactant
In organic solvent, heating polymerization, obtains spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin under stiring.
4. the preparation method of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin according to claim 3, special
Sign is, in step 1), the molar ratio of melamine, thiocarbamide and formaldehyde is 1:0.2:1.5-1:10:4.
5. the preparation method of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin according to claim 3, special
Sign is, in step 1), neutral or weak basic condition pH value range is pH 7-10.
6. the preparation method of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin according to claim 3, special
Sign is, in step 1), prepolymerization temperature is 40 °C -100 °C.
7. the preparation method of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin according to claim 3, special
Sign is, in step 2, pore-foaming agent include one of water, ethylene glycol, glycerol, glucose, fructose, sucrose or cyclodextrin or
It is a variety of.
8. the preparation method of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin according to claim 3, special
Sign is, in step 2, the amount summation of the pore-foaming agent of the amount and addition of water contained in prepolymer solution and prepares performed polymer
When the mass ratio of the total amount of melamine, formaldehyde and thiocarbamide that is added be 3:1-0.25:1.
9. the preparation method of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin according to claim 3, special
Sign is, in step 2, adjusting pH value to neutral or weakly acidic pH range is 4-7；Polymerization temperature is 40 °C -100 °C；It is poly-
Closing the time is 2-12 hours.
10. the preparation method of spherical porous melamine-formaldehyde-thiocarbamide fluoropolymer resin according to claim 3, special
Sign is, in step 2, the surfactant includes Span-80, carboxymethyl cellulose, cellulose acetate or polyethylene glycol
One or more of mixing；The organic solvent is one or more of dichloroethanes, normal heptane or toluene；It is described to have
The quality accounting of surfactant is 0.5-3% in solvent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110841608A (en) * | 2019-11-28 | 2020-02-28 | 朱润栋 | Preparation method of penicillin fermentation liquor refined adsorbent |
| CN113651764A (en) * | 2021-08-20 | 2021-11-16 | 浙江工业大学 | Synthesis method and application of heavy metal stabilizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352006A (en) * | 2011-07-20 | 2012-02-15 | 合肥工业大学 | Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin |
| 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 |
-
2019
- 2019-03-28 CN CN201910240737.3A patent/CN109942768B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352006A (en) * | 2011-07-20 | 2012-02-15 | 合肥工业大学 | Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| ABDÜLHAKIM AYDIN ET AL: "Separation and recovery of gold(III) from base metal ions using melamine–formaldehyde–thiourea chelating resin", 《APPLIED POLYMER SCINECE》 * |
| 吴珂等: "螯合树脂/SBA-15复合材料的制备及其对重金属的吸附研究", 《湖南师范大学自然科学学报》 * |
| 孟胜男等: "《药剂学 在线学习版》", 31 January 2016, 中国医药科技出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110841608A (en) * | 2019-11-28 | 2020-02-28 | 朱润栋 | Preparation method of penicillin fermentation liquor refined adsorbent |
| CN113651764A (en) * | 2021-08-20 | 2021-11-16 | 浙江工业大学 | Synthesis method and application of heavy metal stabilizer |
| CN113651764B (en) * | 2021-08-20 | 2024-07-23 | 浙江工业大学 | Synthesis method and application of heavy metal stabilizer |
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