CN102352006B - Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin - Google Patents
Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin Download PDFInfo
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- CN102352006B CN102352006B CN201110202825A CN201110202825A CN102352006B CN 102352006 B CN102352006 B CN 102352006B CN 201110202825 A CN201110202825 A CN 201110202825A CN 201110202825 A CN201110202825 A CN 201110202825A CN 102352006 B CN102352006 B CN 102352006B
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Abstract
The invention discloses an ultrasonic preparation method of a micron spherical melamine-formaldehyde-thiourea chelating resin. Polymerization monomers of melamine, formaldehyde and thiourea are treated with an emulsion polymerization initiated by ultrasonic in a nitrogen atmosphere with existence of dispersant, colloid protective agent, pore forming agent, chain end terminator and pH conditioning agent, so as to obtain the micron spherical melamine-formaldehyde-thiourea chelating resin. Compared with a prior liquid phase synthesis method, the preparation method of the invention requires no initiator and has a 60% shortened reaction time, small energy consumption and simple and reliable process. The melamine-formaldehyde-thiourea chelating resin prepared by the invention is in micron-nano level sphere, has large specific surface area, excellent adsorption performance on silver ion and can be directly used as a carrier for nano silver material preparation.
Description
One, technical field
The present invention relates to a kind of preparation method of ternary resin, specifically the supersonically preparation method of micron level spherical carbamide-sulfourea chelate resin.
Two, background technology
Thiocarbamide is the good complexing agent of precious metal ion, and the resin that contains thiourea group has good absorption property (A.W.Trochimczuk, B.N.Kolarz to precious metal ions such as gold and silver, platinum, palladiums; European Polymer Journal; 2000,36,2359; Qu Rongjun: doctorate paper, 2002,13; He Qi, application number: 200910058178.0; Li Peng's journey etc., application number: 200910020084.4; Zhang Youming etc., application number: 200910117550.0; Ni Caihua etc., application number: 200710021212.8).Trimeric cyanamide not only has complexing action (X.G.Li, M.R.Huang, S.X.Li, Acta Materialia to metals ion; 2004,52,363), also can be used as the good material (W.B.Gurnule of synthetic resins; H.D.Juneja, L.J.Paliwal, Reactive &Functional Polymers; 2002,50,95; Fu abyss, application number: 200610052043.X; Du Guanben, Lei Hong, application number: 200810058522.1).
In order to improve the performance of resin; Investigators; As: Okada etc., ElGhaffar etc., Yirikoglu etc.; Aydin etc.; Birinci etc.,
etc. prepared carbamide-thiocarbamide ternary resin (Okada, etal.United States Patent:4562116 through different liquid phase synthesizing methods respectively; M.A.A.Ghaffar, Z.H.A.Wahab, K.Z.Elwakeel, Hydrometallurgy, 2009,96,27; H.Yirikoglu, M.G ü lfen, Separation Science and Technology, 2008,43,376; A.Aydin; M.
et al.Journal of Applied Polymer Science; 2008; 107,1201; E.Birinci, M.Gulfen, et al.Hydrometallurgy, 2009,95,15; S.
M.Gulfen; Et al.2009; Separation Science and Technology; 44,1869).Research shows that this type of resin all has the good adsorption performance to metals ions such as gold and silver, copper, palladium, zinc, and wherein the adsorptive capacity to silver ions can reach 0.95mmoL/g (M.A.A.Ghaffar; Z.H.A.Wahab, K.Z.Elwakeel, Hydrometallurgy; 2009,96,27).
Literature survey shows: up till now for this reason, the synthetic of above-mentioned various resins all implemented through liquid phase synthesizing method.During actually operating, need through more synthesis step, generated time surpasses 8 hours usually, and needs controlled temperature and stirring.
On the other hand, ultrasonic synthesis method has the following advantages with respect to common liquid phase synthesizing method: speed of response is fast, can carry out at normal temperatures, and the synthetic product particle is little, specific surface area big (K.S.Suslick.Science, 1990,247,1439).Based on above advantage, ultrasonic method has been used in synthesizing of polymkeric substance.For example: Chou etc. carry out letex polymerization with sodium lauryl sulphate as emulsifying agent under the ultrasonic irradiation condition, have made polymethylmethacrylate (H.C.Joe Chou; J.O.Stoffer, Journal ofApplied Polymer Science, 1999; 72,797); Bahattab discovers: when not having emulsifying agent and initiator to exist; Only depend on action of ultrasonic waves just can cause polyreaction (M.A.Bahattab, Journal ofApplied Polymer Science, 2005 of vinyl acetate in emulsion; 98,812).But, up till now for this reason, utilize ultrasonic method to prepare carbamide-sulfourea chelate resin, do not appear in the newspapers as yet.
Three, summary of the invention
The present invention aims to provide a kind of supersonically preparation method of micron level spherical carbamide-sulfourea chelate resin, and this preparation method need not add initiator, and the reaction times shortens 60%, the little and simple and reliable process of energy consumption.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of the supersonically preparation method of micron level spherical carbamide-sulfourea chelate resin of the present invention are: with trimeric cyanamide, formaldehyde and thiocarbamide is polymerization single polymerization monomer; In the presence of dispersion agent, colloid protective agent, pore-creating agent, end of the chain terminator and pH value regulator, in nitrogen atmosphere, obtain micron level spherical carbamide-sulfourea chelate resin through ultrasonic initiation emulsion polymerization;
The mol ratio of said trimeric cyanamide, formaldehyde and thiocarbamide is 1: 5: 2-1: 10: 5;
Said dispersion agent is a sodium lauryl sulphate, and addition is the 0.15-2% of monomer total mass;
Said colloid protective agent is a Z 150PH, and addition is the 0.05-0.2% of monomer total mass;
Said pore-creating agent is one or both in acetone, phenol, the polyoxyethylene glycol, and addition is the 0.02-0.2% of monomer total mass, and when pore-creating agent was two kinds, ratio between the two was any;
Said end of the chain terminator is tolyl acid or trolamine, and addition is the 0.01-0.2% of monomer total mass;
Said pH value regulator is NaOH.
The characteristics of the supersonically preparation method of micron level spherical carbamide-sulfourea chelate resin of the present invention are to operate according to the following steps:
A, trimeric cyanamide, formaldehyde and thiocarbamide mixed obtain monomer mixed solution, in monomer mixed solution, add dispersion agent, colloid protective agent and pore-creating agent, and with pH value regulator transfer to solid reactant dissolve reaction solution;
B, under nitrogen protection with step a gained reaction solution in the ultrasonic 30-90 of normal temperature minute, add terminator, continue ultrasonic reaction finished in 1-10 minute to react polymerized emulsion;
C, the gained polymerized emulsion is left standstill 2-10 hour breakdown of emulsion in 4-15 ℃, subsequently in 80-110 ℃ of following vacuum-drying 3-10 hour, and water, acetone and washing with alcohol after drying successively, obtain micron level spherical carbamide-sulfourea chelate resin.
The structural formula of the carbamide-sulfourea chelate resin of the present invention's preparation is following, and wherein functional group A is the trimeric cyanamide group, and functional group B is a thiourea group.
Functional group A functional group B
Get the resin that a certain amount of the present invention prepares, transfer to turbid solution with acetone, toluene or formic acid, spinning goes out solid, is placed on Silver Nitrate (AgNO with the second distillation water wash
3) in the aqueous solution, AgNO wherein
3With the mass ratio of resin be 1: 10-20, regulator solution pH are 4.5-5.5, at temperature 10-50 ℃ of following lucifuge absorption 30-120min; Spinning goes out to be adsorbed with the carbamide-sulfourea chelate resin of silver ions; Place redistilled water, add glucose, xitix or boric acid as reductive agent, the addition of reductive agent is 1-3 a times of Silver Nitrate molar weight; Behind the ultrasonic synthetic 5-15min, obtain the carbamide-sulfourea chelate resin matrix material of silver-loaded.
Concrete reactions step is following:
(a) take by weighing sodium lauryl sulphate and wiring solution-forming, the quality of sodium lauryl sulphate is the 0.15-2% of monomer mass; Formaldehyde and the trimeric cyanamide of thiocarbamide, 37wt% (mass percentage concentration, down together) are made into monomer mixed solution, and wherein the mol ratio of thiocarbamide, formaldehyde and trimeric cyanamide is 1: 5: 2-1: 10: 5, monomer mixed solution is mixed with sodium dodecyl sulfate solution.
(b) in above-mentioned solution, add colloid protective agent and pore-creating agent, and transfer to the solid reactant dissolving with 0.1mol/L NaOH solution, the addition of colloid protective agent is the 0.05-0.2% of monomer mass, and the addition of pore-creating agent is the 0.02-0.2% of monomer mass.
(c) ultrasonic at normal temperatures 30-90 minute, ultrasonic power was 40-60W, added end of the chain terminator, continue ultrasonic 1-10min finish to react polymerized emulsion, the addition of end of the chain terminator is the 0.01-0.2% of monomer mass.
(d) with the gained polymerized emulsion under 4-15 ℃, place breakdown of emulsion after 2-10 hour.
(e) with the breakdown of emulsion emulsion at 80-110 ℃ of following vacuum-drying 3-10 hour, obtain the dried glue of thick resin; The dried glue of thick resin is used redistilled water, acetone, washing with alcohol after drying successively, obtain carbamide-sulfourea chelate resin.
(f) get 0.5-1g carbamide-sulfourea chelate resin, transfer to turbid solution with acetone, toluene or formic acid, high speed centrifugation is isolated solid, and the second distillation water wash is to neutral, with being placed on 25-50mL, 0.01mol/LAgNO
3In the solution, regulator solution pH is 4.5-5.5, under temperature 10-50 ℃, and lucifuge whip attachment 30-120min.
(g) spinning goes out to be adsorbed with the resin of silver ions; Place 50mL, 0.01mol/L reductant solution; Ultrasonic 5-15min promptly accomplishes reduction reaction, through spinning and washing, can get the carbamide-sulfourea chelate resin matrix material of silver-loaded.
Compared with present technology, beneficial effect of the present invention is embodied in:
1, the compound method that the present invention adopted is compared with existing liquid phase synthesizing method, need not add initiator, and the reaction times shortens 60%, the little and simple and reliable process of energy consumption.
2, institute of the present invention synthetic carbamide-sulfourea chelate resin is that micro-nano is spherical, and specific surface area is bigger, and silver ions is had good absorption property, can be directly as the carrier for preparing the nanometer silver material.
Four, description of drawings
Fig. 1 is the FT-IR spectrogram of carbamide-sulfourea chelate resin of preparing of the present invention.The functional group of said resin is by FT-IR (KBr) spectroscopic identification, and the ownership of having carried out each spectrum peak reaches the comparative analysis with raw material.Wherein curve a is the FT-IR spectrum of carbamide-sulfourea chelate resin, and curve b, c, d be the FT-IR spectrum of corresponding trimeric cyanamide, formaldehyde, thiocarbamide respectively.As shown in Figure 1,3338cm
-1For connecting the stretching vibration peak of methylenimine N-H bridge joint, 1553cm
-1Stretching vibration peak for the N-H group in imines knee; Demonstrate place's characteristic peak of fluoropolymer resin among the curve a, promptly be positioned at 1156cm
-1-the stretching vibration absorption peak (M.A.A.Ghaffar, Z.H.A.Wahab, K.Z.Elwakeel, Hydrometallurgy, 2009,96,27) of N-C=S-group.Through the FT-IR spectrogram, show that carbamide-sulfourea chelate resin is synthesized.
Fig. 2 is the TG-DTA figure of carbamide-sulfourea chelate resin of preparing of the present invention.Can find out that by Fig. 2 resin quality before being warming up to 80 ℃ is kept constant basically, shows resin good thermal stability in this TR, does not have weightlessness, does not promptly have signs of degradation to take place; Between 80-182 ℃, loss 14.5%, for the decomposition course resin in this temperature, deviate from the monomer that residual water-content and unreacted finish; The resin weightlessness is obvious between 182-345 ℃, is decomposition course, possibly be the decomposition of trimeric cyanamide group, thiourea group etc.
Fig. 3 is the field emission scanning electron microscope figure of the carbamide-sulfourea chelate resin of the silver-loaded for preparing of the present invention.Visible by Fig. 3: carbamide-sulfourea chelate resin is spherical, and particle diameter is at 400 ± 200nm, and nanometer silver is evenly distributed on this resin, and particle diameter is at 30 ± 20nm.
Fig. 4 is the X-crystallogram of the carbamide-sulfourea chelate resin of the silver-loaded for preparing of the present invention.Reining in the median size that equation can calculate Ag by seat is 25nm, conforms to result among Fig. 3.
Five, embodiment
Embodiment 1:
Take by weighing 0.03g sodium lauryl sulphate solid; Be mixed with the 50mL aqueous solution; In sodium dodecyl sulfate solution, add 0.6g thiocarbamide, 37wt% formaldehyde 5mL, 0.7g trimeric cyanamide, 0.002g Z 150PH and 0.002g phenol, transfer to the solid reactant dissolving with 0.1mol/LNaOH solution; Logical nitrogen deoxygenation, ultrasonic at normal temperatures 30 minutes (power is 60W); Add 0.002g tolyl acid terminator, continue ultrasonic 5min and finish reaction; The gained polymerized emulsion under 4 ℃, is placed breakdown of emulsion after 2 hours, 80 ℃ of following vacuum-dryings 3 hours, obtain the dried glue of thick resin then; With the dried glue of thick resin water successively, acetone, washing with alcohol after drying, obtain carbamide-sulfourea chelate resin.
Get the above-mentioned resin of 0.5g, transfer to turbid solution with toluene, high speed centrifugation is isolated solid, and the second distillation water wash is to neutral; The resin of gained places 25mL 0.01mol/L AgNO
3Solution, lucifuge whip attachment 60min; Spinning goes out to be adsorbed with the trimeric cyanamide sulfourea chelate resin of silver ions; Be placed in 50mL, the 0.01mol/L aqueous ascorbic acid; Ultrasonic 2min promptly accomplishes reduction reaction, through spinning and cleaning, can get the carbamide-sulfourea chelate resin matrix material of silver-loaded.
Embodiment 2:
Take by weighing 0.04g sodium lauryl sulphate solid; Be mixed with the 50mL aqueous solution; In sodium dodecyl sulfate solution, add 2.4g thiocarbamide, 37wt% formaldehyde 8mL, 1.0g trimeric cyanamide, 0.005g Z 150PH and 0.006g acetone, transfer to the solid reactant dissolving with 0.1mol/LNaOH solution; Logical nitrogen deoxygenation, ultrasonic at normal temperatures 50 minutes (power is 60W); Add 0.003g trolamine terminator, continue ultrasonic 5min and finish reaction; The gained polymerized emulsion under 10 ℃, is placed breakdown of emulsion after 5 hours, 100 ℃ of following vacuum-dryings 3 hours, obtain the dried glue of thick resin then; With the dried glue of thick resin water successively, acetone, washing with alcohol after drying, obtain carbamide-sulfourea chelate resin.
Get the above-mentioned resin of 0.5g, transfer to turbid solution with acetone, high speed centrifugation is isolated solid, and the second distillation water wash is to neutral; The resin of gained places 25mL 0.01mol/L AgNO
3Solution, lucifuge whip attachment 70min; Spinning goes out to be adsorbed with the trimeric cyanamide sulfourea chelate resin of silver ions; Be placed in 50mL, the 0.01mol/L boric acid aqueous solution; Ultrasonic 5min promptly accomplishes reduction reaction, through spinning and cleaning, can get the carbamide-sulfourea chelate resin matrix material of silver-loaded.
Embodiment 3:
Take by weighing 0.07g sodium lauryl sulphate solid; Be mixed with the 100mL aqueous solution; In sodium dodecyl sulfate solution, add 2.0g thiocarbamide, 37wt% formaldehyde 15mL, 2.0g trimeric cyanamide, 0.008g Z 150PH and 0.01g polyoxyethylene glycol, transfer to the solid reactant dissolving with 0.1mol/L NaOH solution; Logical nitrogen deoxygenation, ultrasonic at normal temperatures 60 minutes (power is 60W); Add 0.006g trolamine terminator, continue ultrasonic 15min and finish reaction; The gained emulsion under 15 ℃, is placed breakdown of emulsion after 3 hours, 90 ℃ of following vacuum-dryings 2 hours, obtain the dried glue of thick resin then; With the dried glue of thick resin water successively, acetone, washing with alcohol after drying, obtain carbamide-sulfourea chelate resin.
Get the above-mentioned resin of 0.5g, transfer to turbid solution with formic acid, high speed centrifugation is isolated solid, the second distillation water wash; The resin of gained places 25mL 0.01mol/L AgNO
3Solution, lucifuge whip attachment 90min; Spinning goes out to be adsorbed with the trimeric cyanamide sulfourea chelate resin of silver ions; Be placed in 50mL, the 0.01mol/L D/W; Ultrasonic 10min promptly accomplishes reduction reaction, through spinning and cleaning, can get the carbamide-sulfourea chelate resin matrix material of silver-loaded.
The ultimate analysis of table 1 synthetic resins, to the concentration effect of silver
Functional group A
*: trimeric cyanamide; Functional group B
*: thiocarbamide.
Visible by table 1, adopt the carbamide-sulfourea chelate resin of the inventive method preparation to contain functional group trimeric cyanamide proportion at 32-37%, the proportion of functional group thiocarbamide is at 21-27%, is 0.95-1.09mmol/g to the enriching quantity of silver ions.
Claims (2)
1. the supersonically preparation method of micron level spherical carbamide-sulfourea chelate resin; It is characterized in that: with trimeric cyanamide, formaldehyde and thiocarbamide is polymerization single polymerization monomer; In the presence of dispersion agent, colloid protective agent, pore-creating agent, end of the chain terminator and pH value regulator, in nitrogen atmosphere, obtain micron level spherical carbamide-sulfourea chelate resin through ultrasonic initiation emulsion polymerization;
The mol ratio of said trimeric cyanamide, formaldehyde and thiocarbamide is 1:5:2-1:10:5;
Said dispersion agent is a sodium lauryl sulphate, and addition is the 0.15-2% of monomer total mass;
Said colloid protective agent is a Z 150PH, and addition is the 0.05-0.2% of monomer total mass;
Said pore-creating agent is one or both in acetone, phenol, the polyoxyethylene glycol, and addition is the 0.02-0.2% of monomer total mass;
Said end of the chain terminator is tolyl acid or trolamine, and addition is the 0.01-0.2% of monomer total mass;
Said pH value regulator is NaOH;
Ultrasonic power during said ultrasonic initiation emulsion polymerization is 40-60W.
2. preparation method according to claim 1 is characterized in that operating according to the following steps:
A, trimeric cyanamide, formaldehyde and thiocarbamide mixed obtain monomer mixed solution, in monomer mixed solution, add dispersion agent, colloid protective agent and pore-creating agent, and with pH value regulator transfer to solid reactant dissolve reaction solution;
B, under nitrogen protection with step a gained reaction solution in the ultrasonic 30-90 of normal temperature minute, add terminator, continue ultrasonic reaction finished in 1-10 minute to react polymerized emulsion;
C, the gained polymerized emulsion is left standstill 2-10 hour breakdown of emulsion in 4-15 ℃, subsequently in 80-110 ℃ of following vacuum-drying 3-10 hour, and water, acetone and washing with alcohol after drying successively, obtain micron level spherical carbamide-sulfourea chelate resin.
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| CN109942768B (en) * | 2019-03-28 | 2021-11-23 | 太尔胶粘剂(广东)有限公司 | Spherical porous melamine-formaldehyde-thiourea polymer resin and preparation method thereof |
| CN110252250A (en) * | 2019-05-27 | 2019-09-20 | 河南工业大学 | A kind of melamine/thiocarbamide/formaldehyde aerogels preparation method |
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