CN108250381A - The preparation method and applications of the phenolic resin microspheres containing selenium - Google Patents
The preparation method and applications of the phenolic resin microspheres containing selenium Download PDFInfo
- Publication number
- CN108250381A CN108250381A CN201810144682.1A CN201810144682A CN108250381A CN 108250381 A CN108250381 A CN 108250381A CN 201810144682 A CN201810144682 A CN 201810144682A CN 108250381 A CN108250381 A CN 108250381A
- Authority
- CN
- China
- Prior art keywords
- containing selenium
- phenolic resin
- preparation
- resin microspheres
- selenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to a kind of preparation methods of phenolic resin microspheres containing selenium, include the following steps：Hydroxyl carbon source containing selenium, phenolic compound are dissolved in the aqueous solution of alcohol, polycondensation reaction occurs with formaldehyde under the action of ammonium hydroxide, reacts and is carried out under 10 60 DEG C of ultrasound condition, forms the phenolic resin microspheres containing selenium.The present invention also provides a kind of application of phenolic resin microspheres containing selenium using prepared by above-mentioned preparation method in water phase is adsorbed in heavy metal ion.The present invention is caused polycondensation using ultrasound, is prepared the resin microsphere containing selenium that size is controllable, selenium content is controllable, position containing selenium is controllable using the difference of the nucleation rate of two kinds of carbon sources.
Description
Technical field
The present invention relates to field of macromolecule polymerization more particularly to a kind of phenolic resin microspheres containing selenium preparation method and its should
With.
Background technology
Condensation polymerization is a kind of polymerisation the most classical in polymer chemistry, is made in prepared by current Resin Industryization
With a kind of most reactions.In early 20th century, the artificial synthesized of phenolic resin is just had been realized in, at present the dosage of phenolic resin
Still account for the 60% of the total usage amount of resin.
Resorcinol is a kind of common carbon source for preparing phenolic resin, polycondensation, the phenol prepared can occur with formaldehyde
Urea formaldehyde is had excellent performance, and is widely used in the industries such as biochemistry, coating, adhesive.Resin microsphere is compared to other patterns
Resin material possesses the pattern of determining good spherical shape and controllable size, not only possesses the characteristic of all resin materials, it
Also possess higher fluid passability so that it has potential application value in purification, adsorption and de-adsorption field.At present, it sets
The main application of lipid microspheres has：Energy storage, drug loading and release, photocatalysis, sensor, auxiliary catalysis etc..
Although resin microsphere has a series of excellent characteristic, rarely have in the synthetic method of its various complexity
A kind of method that its size can be precisely harmonized, until Zhao east member in 2011 et al. reports derivativeMethod can be used for
Synthesis size determines and controllable novalac polymer microballoon.Method be it is a kind of nineteen sixty-eight byReport
It in alcohol solution, is hydrolyzed using ammonia-catalyzed tetraethyl orthosilicate and polycondensation, prepares that size is controllable and narrow ditribution, the smooth silicon in surface
A kind of method of ball.Zhao east member et al. done on this basis it is a series of the study found thatMethod is to be based on producing in hydrolytie polycondensation
Raw silicon sol-gel process by four coordination sites of tetraethyl orthosilicate, forms four sides in sol-gel process
Body coordination structure is simultaneously further formed three-dimensional net structure.Research finds that phenolic resin can equally form similar three simultaneously
Tie up network structure.Based on this, they report be based on for the first timeThe simple method for preparing phenolic resin microspheres of method, cost
Cheap and suitable large-scale production.Obtained Microsphere Size can subsequently be carbonized to obtain porous carbon ball micro-nano controllable,
Yield can reach 62wt%.But shortcoming is, the reaction time is usually longer (one day or more), and needs to use reaction under high pressure
Kettle.The selectivity of raw material is smaller, most currently used only two kinds of phenol and resorcinol.This causes modified control limited,
Using being also difficult to widen.
Invention content
In order to solve the above technical problems, the object of the present invention is to provide a kind of phenolic resin microspheres containing selenium preparation method and
It is applied, and using the difference of the nucleation rate of two kinds of carbon sources, causes polycondensation using ultrasound, preparation size is controllable, selenium content is controllable,
The controllable resin microsphere containing selenium in position containing selenium.
The present invention provides a kind of preparation methods of phenolic resin microspheres containing selenium, include the following steps：
Hydroxyl carbon source containing selenium, phenolic compound are dissolved in the aqueous solution of alcohol, polycondensation occurs with formaldehyde under the action of ammonium hydroxide
Reaction, reacts and is carried out under 10-60 DEG C of ultrasound condition, forms phenolic resin microspheres containing selenium.
Further, hydroxyl carbon source containing selenium is to hydroxy diphenyl list selenide, to hydroxy diphenyl diselenide, 2,4- dihydroxies
Base phenyl list selenide or 2,4- dihydroxy phenyl diselenides.Hydroxyl carbon source containing selenium is a kind of phenol derivative containing selenium, simultaneously
Containing phenolic hydroxyl group and selenium atom, polycondensation can occur with formaldehyde and form macromolecule, and the introducing of selenium atom imparts material more
Mostly special performance.
Preferably, hydroxyl carbon source containing selenium is to hydroxy diphenyl list selenide, and molecular formula is as follows：
The preparation method of hydroxy diphenyl list selenide is included the following steps：
Selenium chloride is prepared in organic solvent using sulfonic acid chloride and selenium, the organic solution of phenol is then added in, after reaction
It obtains to hydroxy diphenyl list selenide.
Further, phenolic compound is resorcinol, hydroquinone, catechol or phenol.Preferably, phenols chemical combination
Object is resorcinol.
Further, hydroxyl carbon source containing selenium and the molar ratio of phenolic compound are 0.33-3:1.
Further, alcohol is one or more of methanol, ethyl alcohol, isopropanol, ethylene glycol, diethylene glycol and glycerine.
Preferably, alcohol is ethyl alcohol.
Further, in the aqueous solution of alcohol, the volume ratio of alcohol and water is 0.2-1:1.
Further, a concentration of 0.05-0.20mol/L of ammonium hydroxide.Preferably, a concentration of 0.15mol/L of ammonium hydroxide.Whole
In a reaction system, the concentration of ammonium hydroxide is controlled, the pH value that may be such that reaction system is 5-7, under the conditions of this weak base, can be catalyzed
Polycondensation reaction, therefore ammonium hydroxide plays the role of pH adjusting agent and catalyst.
Further, a concentration of 0.08-0.20mol/L of formaldehyde.
Further, it is carried out in the case where power is the ultrasound condition of 2200-2600W.Traditional hydro-thermal reaction is changed to ultrasound
The original preparation process for taking one day or more can be substantially reduced in hundreds of seconds by reaction.
Further, reaction time 100-500s.Preferably, 300s is reacted under 25 DEG C of ultrasound condition.
Further, the grain size of the phenolic resin microspheres containing selenium is 150-650nm.
In above-mentioned preparation method, the order by merging packet of hydroxyl carbon source containing selenium, phenolic compound and formaldehyde in reaction system
Include three kinds of modes：
(1) hydroxyl carbon source containing selenium is reacted in advance with formaldehyde, and then adding in phenolic compound thereto, the reaction was continued, with to hydroxyl
For base diphenyl list selenide and resorcinol, reaction route schematic diagram is as shown in figure 15, and site containing selenium 1 is gathered in spherical contain
At the center of selenium phenolic resin microspheres 2.
(2) hydroxyl carbon source containing selenium and phenolic compound mix simultaneously with formaldehyde, are then reacted, with to hydroxy diphenyl
For single selenide and resorcinol, reaction route schematic diagram is as shown in figure 16, and site containing selenium 1 is uniformly distributed in spherical phenol containing selenium
On urea formaldehyde microballoon 2.
(3) phenolic compound reacts in advance with formaldehyde, and then adding in hydroxyl carbon source containing selenium thereto, the reaction was continued, with to hydroxyl
For base diphenyl list selenide and resorcinol, reaction route schematic diagram is as shown in figure 17, and site containing selenium 1 is distributed in spherical contain
The outer rim of selenium phenolic resin microspheres 2.
The present invention has used hydroxyl carbon source containing selenium in resin microsphere preparation, plays the role of nucleating agent and selenium source, with it
His phenols difference lies in：Hydroxyl carbon source containing selenium is class phenol derivative containing selenium, anti-compared to other phenol (such as resorcinol)
Should be active and relatively low into nuclearity, but its degree of functionality is still 3, polycondensation can occur with the formaldehyde that degree of functionality is 2 and form three dimension polymerization
Object material.Using the relatively low activity of hydroxyl carbon source containing selenium, and the characteristic of three-dimensional polycondensation can be carried out, use it as the second carbon
Source is used together with phenolic compound, adjusts their the when feeding sequence that feeds intake, it is possible to realize size, Se content, selenium point
The controllable adjustment of cloth.
The present invention also provides a kind of phenolic resin microspheres containing selenium using prepared by above-mentioned preparation method in absorption water phase
Application in middle heavy metal ion.
Coordination based on selenium element in phenolic resin microspheres containing selenium and heavy metal ion, prepared phenolic resin are micro-
Ball shows excellent heavy metal ion adsorbed effect in water phase.
Further, heavy metal ion is one or more of palladium ion, platinum ion and copper ion.
Further, during absorption, using static adsorptive method or dynamic adsorption method.
According to the above aspect of the present invention, the present invention has at least the following advantages：
The present invention under the action of ultrasound, is surpassed using the activity difference reacted between two kinds of carbon sources with formaldehyde for one kettle way
Quick size, Se content, the resin microsphere containing selenium of selenium distribution controllably of preparing provides a kind of effective method.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be implemented in accordance with the contents of the specification, below with presently preferred embodiments of the present invention and after attached drawing is coordinated to be described in detail such as.
Description of the drawings
Fig. 1 is in the embodiment of the present invention 1, and carbon source containing selenium characterizes the nucleus magnetic hydrogen spectrum of hydroxy diphenyl list selenide；
Fig. 2 is in the embodiment of the present invention 1, and carbon source containing selenium levies the nuclear-magnetism carbon stave of hydroxy diphenyl list selenide；
Fig. 3 is the scanning electron microscope image of the resin microsphere containing selenium prepared by 25wt%.B.f groups in the embodiment of the present invention 2；
Fig. 4 is the scanning electron microscope image of the resin microsphere containing selenium prepared by 50wt%.B.f groups in the embodiment of the present invention 2；
Fig. 5 is the scanning electron microscope image of the resin microsphere containing selenium prepared by 75wt%.B.f groups in the embodiment of the present invention 2；
Fig. 6 is the scanning electron microscope image of the resin microsphere containing selenium prepared by 25wt%.B.s groups in the embodiment of the present invention 3；
Fig. 7 is the scanning electron microscope image of the resin microsphere containing selenium prepared by 50wt%.B.s groups in the embodiment of the present invention 3；
Fig. 8 is the scanning electron microscope image of the resin microsphere containing selenium prepared by 75wt%.B.s groups in the embodiment of the present invention 3；
Fig. 9 is the scanning electron microscope image of the resin microsphere containing selenium prepared by 25wt%.B.l groups in the embodiment of the present invention 4；
Figure 10 is the scanning electron microscope image of the resin microsphere containing selenium prepared by 50wt%.B.l groups in the embodiment of the present invention 4；
Figure 11 is the scanning electron microscope image of the resin microsphere containing selenium prepared by 75wt%.B.l groups in the embodiment of the present invention 4；
In Figure 12 embodiment of the present invention 3, the Fourier of carbon source containing selenium and the resin microsphere containing selenium changes infrared spectrum；
In Figure 13 embodiment of the present invention 3, the x-ray photoelectron diffraction analysis of the resin microsphere containing selenium composes spectrogram entirely；
Figure 14 is the ICP testing results of palladium ion concentration in water phase during Static Adsorption；
Figure 15 is the reaction route schematic diagram that hydroxyl carbon source containing selenium reacts synthesis phenolic resin microspheres containing selenium with formaldehyde in advance；
Figure 16 is that hydroxyl carbon source containing selenium and phenolic compound react the anti-of synthesis phenolic resin microspheres containing selenium with formaldehyde simultaneously
Answer route schematic diagram；
Figure 17 is the reaction route schematic diagram that phenolic compound reacts synthesis phenolic resin microspheres containing selenium with formaldehyde in advance；
Reference sign：
1- sites containing selenium；2- phenolic resin microspheres containing selenium.
Specific embodiment
With reference to the accompanying drawings and examples, the specific embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but be not limited to the scope of the present invention.
In following embodiment, the test method used is as follows：
(1) nucleus magnetic hydrogen spectrum (1H NMR) it is by Bruker 300MHz nuclear magnetic resonance spectrometers, by sample to be tested with DMSO-d6It is molten
Agent, tetramethylsilane (TMS) is is tested after internal standard dissolving；
(2) nuclear-magnetism carbon spectrum (13H NMR) it is by Bruker 300MHz nuclear magnetic resonance spectrometers, by sample to be tested with DMSO-d6It is molten
Agent, tetramethylsilane (TMS) is is tested after internal standard dissolving
(3) it obtains sample to be uniformly applied to conducting resinl and be sticked on sample stage, metal spraying uses after 60 seconds under 30mA
SU8010HITICHI cold field emission scanning electron microscope, sample is observed under 5kV operating voltages.
(4) sample is sticked at into 5 × 5mm double faced adhesive tapes, sample stage is affixed on after tabletting, and sample surfaces element is characterized using XPS
Composition.
(5) using KBr pressed disc methods, sample chemical composition is analyzed on Bruker Tensor330FT-IR.
(6) using heavy metal ion content in icp analysis aqueous phase solution.
Synthesis of the embodiment 1 to hydroxy diphenyl list selenide
40 milliliters of chloroforms and 0.79g selenium powders is taken to add in 100 milliliters of round-bottomed flasks, is sufficiently stirred and adds in after ten minutes
1.35g sulfonic acid chlorides continue stirring until selenium powder and are completely dissolved, and add phenol solution (1.88g phenol is in 20 milliliters of anhydrous ethers).
It is stirred at room temperature three hours, completes reaction.Be slowly added in 4 milliliters of 25wt% aqueous sodium carbonates and system in sulfonic acid chloride, liquid separation,
Organic phase is taken, rotation removes excess of solvent, obtains target product.Reaction route is as follows：
Fig. 1, Fig. 2 are in the embodiment of the present invention 1, and carbon source containing selenium says the nuclear-magnetism characterization result of hydroxy diphenyl list selenide
Bright the present embodiment has successfully been obtained to hydroxy diphenyl list selenide.
The synthesis of 2 resin microsphere containing selenium of embodiment
Three groups of experiments are done, 50 ml deionized waters and 20 milliliters of absolute ethyl alcohols is taken to add in 100 milliliters of beakers, then respectively add respectively
Enter 0.7 milliliter of mass concentration be 37% ammonium hydroxide, using ultrasonic cell disrupte device ultrasound 10 seconds after be rapidly added to hydroxyl hexichol
The formalin of base list selenide (quality is respectively 0.125g, 0.25g, 0.375g) and 0.7 milliliter of 36-38% mass concentration.After
Continuous ultrasound adds resorcinol (quality is respectively 0.375g, 0.25g, 0.125g) after 150 seconds, ultrasonic under 2400W power
It obtains the dark brown lotion of milk within 300 seconds, solid will be obtained after centrifugation and is dispersed again in ethyl alcohol, is centrifuged again to remove residual ammonium hydroxide,
Obtain resin microsphere containing selenium.In 0.5g, accounting is controlled as (with to hydroxyl hexichol for the overall control of two kinds of carbon sources in system
Base list selenide meter, respectively 25wt%, 50wt%, 75wt%, be denoted as respectively 25wt%.B.f groups, 50wt%.B.f groups and
75wt%.B.f groups).Reaction route schematic diagram is as shown in figure 15.
Fig. 3-5 is the SEM figures of the resin microsphere containing selenium of above-mentioned three groups of preparations, is followed successively by 25wt%.B.f groups, 50wt%
.B.f group and 75wt%.B.f groups, it is seen that obtained phenolic resin microspheres containing selenium size in 200-300nm not
Deng, also, there are the adhesions between ball and ball in 25wt%.B.f groups, 50wt%.B.f groups.
The synthesis of 3 resin microsphere containing selenium of embodiment
Three groups of experiments are done, 50 ml deionized waters and 20 milliliters of absolute ethyl alcohols is taken to add in 100 milliliters of beakers, then respectively add respectively
Enter 0.7 milliliter of mass concentration be 37% ammonium hydroxide, using ultrasonic cell disrupte device ultrasound 10 seconds after be rapidly added to hydroxyl hexichol
Base list selenide (quality is respectively 0.125g, 0.25g, 0.375g), resorcinol (quality be respectively 0.375g, 0.25g,
0.125g) and the formalin of 0.7 milliliter of 36~38% mass concentration.It is dark brown to obtain milk for ultrasound under 2400W power after 300 seconds
Lotion will obtain solid and be dispersed again in ethyl alcohol after centrifugation, centrifuge to remove residual ammonium hydroxide again, it is micro- to obtain resin containing selenium
Ball.In 0.5g, accounting is controlled as (in terms of to hydroxy diphenyl list selenide, dividing for the overall control of two kinds of carbon sources in system
Not Wei 25wt%, 50wt%, 75wt%, be denoted as 25wt%.B.s groups, 50wt%.B.s groups and 75wt%.B.s groups respectively).Instead
Answer route schematic diagram as shown in figure 16.
Fig. 6-8 is the SEM figures of the resin microsphere containing selenium of above-mentioned three groups of preparations, is followed successively by 25wt%.B.s groups, 50wt%
.B.s group and 75wt%.B.s groups, it is seen that obtained phenolic resin microspheres containing selenium size in 200-330nm not
Deng the obtained surface of phenolic resin microspheres containing selenium is smooth, well dispersed.
Figure 12 is above-mentioned carbon source containing selenium and the infrared spectrogram of the resin microsphere containing selenium prepared, and wherein curve BHPS representatives contain
Selenium carbon source, it can be seen from the figure that the chemical composition of the resin microsphere containing selenium is similar with the carbon source containing selenium.
Figure 13 is the x-ray photoelectron diffraction analysis spectrogram entirely of the above-mentioned resin microsphere containing selenium, it can be seen from the figure that selenium
Element is present in resin microsphere and is connected in the form of covalent bond.
The synthesis of 4 resin microsphere containing selenium of embodiment
Three groups of experiments are done, 50 ml deionized waters and 20 milliliters of absolute ethyl alcohols is taken to add in 100 milliliters of beakers, then respectively add respectively
Enter 0.7 milliliter of mass concentration be 37% ammonium hydroxide, using ultrasonic cell disrupte device ultrasound 10 seconds after be rapidly added resorcinol (matter
Amount be respectively 0.375g, 0.25g, 0.125g) and 0.7 milliliter of 36-38% mass concentration formalin.Continue ultrasound 150 seconds
It is separately added into afterwards to hydroxy diphenyl list selenide (quality is respectively 0.125g, 0.25g, 0.375g), surpassed under 2400W power again
Sound obtains the dark brown lotion of milk in 300 seconds, and solid will be obtained after centrifugation and is dispersed again in ethyl alcohol, centrifuges to remove residual ammonia again
Water obtains resin microsphere containing selenium.The overall control of two kinds of carbon sources is controlled as in 0.5g, accounting (with to hydroxyl in system
Diphenyl list selenide meter, respectively 25wt%, 50wt%, 75wt%, be denoted as respectively 25wt%.B.l groups, 50wt%.B.l groups and
75wt%.B.l groups).Reaction route schematic diagram is as shown in figure 17.
Fig. 9-11 is the SEM figures of the resin microsphere containing selenium of above-mentioned three groups of preparations, is followed successively by 25wt%.B.l groups, 50wt%
.B.l group and 75wt%.B.l groups, it is seen that obtained phenolic resin microspheres containing selenium size in 150-650nm not
Deng, also, in 25wt%.B.l groups, 50wt%.B.l, there are the phenolic resin microspheres containing selenium of two kinds of Size Distributions, their rulers
Very little about 150-200nm and 600-650nm.
Embodiment 5
Resin microsphere containing selenium prepared by embodiment 2-4 is used for the absorption of palladium ion in water phase, using dynamic adsorption method or
Static adsorptive method.
During Dynamic Adsorption, selenium resin microsphere will be contained and inserted in Filter column, the amount of inserting is 0.04g/ roots；Simultaneously in mistake
The underfill absorbent cotton of filter column, for fixed absorbent, prevents it from being flowed out from Filter column.7mg/ is added in from Filter column upper end
L palladium chloride aqueous solutions collect bottom efflux, detect palladium ion concentration in water phase by ICP, palladium ion is dense in water phase after absorption
Degree is about 0.019-0.021mg/L.
During Static Adsorption, 0.01g resin microspheres containing selenium are taken in 20mL vials, add in 10mL166.5mg/L
Palladium chloride aqueous solution, 1000rpm stirs 12h at 25 DEG C.It is centrifuged after reaching adsorption-desorption balance, supernatant is taken to be examined by ICP
Survey water phase in palladium ion concentration, so as to calculate unit mass phenolic resin microspheres containing selenium adsorbable palladium bichloride quality.
During Figure 14 is Static Adsorption, the ICP testing results of palladium ion concentration in water phase, Se content are represented in figure
Selenium element mass percentage in resin microsphere containing selenium, madsorpRepresent every gram of adsorbable palladium bichloride of the institute of resin microsphere containing selenium
The biggest quality.It is seen that resin microsphere containing selenium can reach every gram of 0.15g to the adsorbance maximum of palladium bichloride.
Embodiment 6
50 ml deionized waters and 20 milliliters of absolute ethyl alcohols is taken to add in 100 milliliters of beakers, then respectively 0.7 milliliter of quality of addition is dense
Spend the ammonium hydroxide for 37%, using ultrasonic cell disrupte device ultrasound 10 seconds after be rapidly added to hydroxy diphenyl diselenide (molal quantity
0.33mol) and the formalin of 0.7 milliliter of 36-38% mass concentration.Continue ultrasound 150 seconds after add hydroquinone (mole
Number 1mol), ultrasound obtains lotion in 300 seconds under 2600W power, and solid will be obtained after centrifugation and is dispersed again in ethyl alcohol, again
Centrifugation obtains resin microsphere containing selenium to remove residual ammonium hydroxide.
Embodiment 7
50 ml deionized waters and 20 milliliters of absolute ethyl alcohols is taken to add in 100 milliliters of beakers, then respectively 0.7 milliliter of quality of addition is dense
The ammonium hydroxide for 37% is spent, is rapidly added and (rubs to 2,4- dihydroxy phenyl list selenides after 10 seconds using ultrasonic cell disrupte device ultrasound
Your number 3mol) and 0.7 milliliter of 36-38% mass concentration formalin.Continue ultrasound and add phenol (molal quantity after 150 seconds
3mol), under 2200W power ultrasound 250 seconds obtain lotion, solid will be obtained after centrifugation and is dispersed again in ethyl alcohol, again from
The heart obtains resin microsphere containing selenium to remove residual ammonium hydroxide.
Embodiment 8
50 ml deionized waters and 20 milliliters of absolute ethyl alcohols is taken to add in 100 milliliters of beakers, then respectively 0.7 milliliter of quality of addition is dense
Spend the ammonium hydroxide for 37%, using ultrasonic cell disrupte device ultrasound 10 seconds after be rapidly added to hydroxy diphenyl diselenide (molal quantity
1mol) and the formalin of 0.7 milliliter of 36-38% mass concentration.Continue ultrasound and add hydroquinone (molal quantity after 150 seconds
1mol), under 2600W power ultrasound 200 seconds obtain lotion, solid will be obtained after centrifugation and is dispersed again in ethyl alcohol, again from
The heart obtains resin microsphere containing selenium to remove residual ammonium hydroxide.The above is only the preferred embodiment of the present invention, is not used to limit
The system present invention, it is noted that for those skilled in the art, before the technology of the present invention principle is not departed from
It puts, several improvement and modification can also be made, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. the preparation method of a kind of phenolic resin microspheres containing selenium, which is characterized in that include the following steps：
Hydroxyl carbon source containing selenium, phenolic compound are dissolved in the aqueous solution of alcohol, polycondensation reaction occurs with formaldehyde under the action of ammonium hydroxide,
Reaction carries out under 10-60 DEG C of ultrasound condition, forms the phenolic resin microspheres containing selenium.
2. the preparation method of the phenolic resin microspheres according to claim 1 containing selenium, it is characterised in that：The hydroxyl carbon containing selenium
Source is to hydroxy diphenyl list selenide, to hydroxy diphenyl diselenide, 2,4- dihydroxy phenyl list selenides or 2,4- dihydroxy benzenes
Base diselenide.
3. the preparation method of the phenolic resin microspheres according to claim 1 containing selenium, it is characterised in that：The phenolic compound
For resorcinol, hydroquinone, catechol or phenol.
4. the preparation method of the phenolic resin microspheres according to claim 1 containing selenium, it is characterised in that：The hydroxyl carbon containing selenium
The molar ratio of source and phenolic compound is 0.33-3:1.
5. the preparation method of the phenolic resin microspheres according to claim 1 containing selenium, it is characterised in that：The alcohol for methanol,
One or more of ethyl alcohol, isopropanol, ethylene glycol, diethylene glycol and glycerine.
6. the preparation method of the phenolic resin microspheres according to claim 1 containing selenium, it is characterised in that：The concentration of the ammonium hydroxide
For 0.05-0.20mol/L.
7. the preparation method of the phenolic resin microspheres according to claim 1 containing selenium, it is characterised in that：The concentration of the formaldehyde
For 0.08-0.20mol/L.
8. the preparation method of the phenolic resin microspheres according to claim 1 containing selenium, it is characterised in that：It is 2200- in power
It is carried out under the ultrasound condition of 2600W.
9. the preparation method of the phenolic resin microspheres according to claim 1 containing selenium, it is characterised in that：Reaction time is 100-
500s。
10. the phenolic resin microspheres containing selenium prepared by preparation method described in any one of claim 1-9 are in absorption heavy metal
Application in ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810144682.1A CN108250381B (en) | 2018-02-12 | 2018-02-12 | Preparation method and application of selenium-containing phenolic resin microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810144682.1A CN108250381B (en) | 2018-02-12 | 2018-02-12 | Preparation method and application of selenium-containing phenolic resin microspheres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108250381A true CN108250381A (en) | 2018-07-06 |
| CN108250381B CN108250381B (en) | 2020-03-10 |
Family
ID=62744855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810144682.1A Active CN108250381B (en) | 2018-02-12 | 2018-02-12 | Preparation method and application of selenium-containing phenolic resin microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108250381B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575209A (en) * | 2018-12-20 | 2019-04-05 | 苏州大学 | The preparation method and application of the phenolic resin microspheres containing selenium |
| CN110813242A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | Flue gas CO2Trapping material and method for producing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4748214A (en) * | 1985-05-13 | 1988-05-31 | Unitika Ltd. | Microspherical cured phenolic resin particles and process for production thereof using emulsion stabilizers |
| CN104891468A (en) * | 2015-03-26 | 2015-09-09 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanospheres, and preparation and application thereof |
| CN107118316A (en) * | 2017-06-01 | 2017-09-01 | 河北大学 | A kind of phenolic resin microspheres and preparation method and application |
-
2018
- 2018-02-12 CN CN201810144682.1A patent/CN108250381B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4748214A (en) * | 1985-05-13 | 1988-05-31 | Unitika Ltd. | Microspherical cured phenolic resin particles and process for production thereof using emulsion stabilizers |
| CN104891468A (en) * | 2015-03-26 | 2015-09-09 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanospheres, and preparation and application thereof |
| CN107118316A (en) * | 2017-06-01 | 2017-09-01 | 河北大学 | A kind of phenolic resin microspheres and preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110813242A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | Flue gas CO2Trapping material and method for producing same |
| CN109575209A (en) * | 2018-12-20 | 2019-04-05 | 苏州大学 | The preparation method and application of the phenolic resin microspheres containing selenium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108250381B (en) | 2020-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Chiral metal–organic framework d-His-ZIF-8@ SiO2 core–shell microspheres used for HPLC enantioseparations | |
| Xu et al. | Chiral core-shell microspheres β-CD-COF@ SiO2 used for HPLC enantioseparation | |
| Shi et al. | Sustainable preparation of bio-based polybenzoxazine resins from amino acid and their application in CO2 adsorption | |
| Lu et al. | Structural elucidation and regioselective functionalization of an unexplored carbide cluster metallofullerene Sc2C2@ Cs (6)-C82 | |
| CN110302381B (en) | Mesoporous silica nanosphere with carborane modified on surface and preparation method thereof | |
| CN108250381A (en) | The preparation method and applications of the phenolic resin microspheres containing selenium | |
| CN102489275A (en) | Phenylalanine-substituted calix [4] arene bonded silica gel stationary phase, preparation method thereof, and application thereof | |
| CN111533919B (en) | Synthesis method and application of metal-organic framework material with chiral hollow structure | |
| Guo et al. | A facile and efficient one‐step strategy for the preparation of β‐cyclodextrin monoliths | |
| Bagheri et al. | Recent advances in the application of covalent organic frameworks in extraction: a review | |
| CN109456486A (en) | A kind of multi-functional high temperature resistant POSS nano molecular material and preparation method thereof | |
| CN109894082B (en) | Preparation method and application of nanoflowers covalent organic framework composite material | |
| CN110183338B (en) | Thiourea betaine eutectic crystal and preparation method and application thereof | |
| CN108586660A (en) | The preparation method of TNT magnetic molecularly imprinted polymer microballoons | |
| CN108409591B (en) | Star-shaped carboxylic acid group zwitterionic compound and preparation method and application thereof | |
| Tang et al. | Materials, workflows and applications of IMAC for phosphoproteome profiling in the recent decade: A review | |
| CN105964306A (en) | Poly(ionic liquid)-based magnetic nanoparticle and its preparation method and use in three-ingredient reaction | |
| Shen et al. | Green conversion of saponins to diosgenin in an alcoholysis system catalyzed by solid acid derived from phosphorus tailings | |
| Li et al. | Organic syntheses on an icosahedral borane surface: Closomer structures with twelvefold functionality | |
| CN107661780A (en) | A kind of hydrophobic solid base catalyst and its applied in alcohol ester 12 is prepared | |
| CN103949284B (en) | For the synthesis of catalysts system and the application of bridged polysilsesquioxane microballoon | |
| CN109590482B (en) | Modified graphene oxide, modified graphene oxide-loaded gold nanoparticles and preparation method thereof | |
| CN114671780B (en) | Covalent organic polymer based on column arene and application thereof | |
| CN103979613B (en) | A kind of method preparing ferriferrous oxide nano rod | |
| CN104248971B (en) | A kind of carried phospho-tungstic acid catalyst and its preparation method and application and the preparation method of cyclohexanone glycerol ketal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |