CN107652377A - The preparation method of the chelating resin of polyfunctional group modification - Google Patents
The preparation method of the chelating resin of polyfunctional group modification Download PDFInfo
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- CN107652377A CN107652377A CN201710968568.6A CN201710968568A CN107652377A CN 107652377 A CN107652377 A CN 107652377A CN 201710968568 A CN201710968568 A CN 201710968568A CN 107652377 A CN107652377 A CN 107652377A
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- chelating resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of preparation method of the chelating resin of polyfunctional group modification, the high molecular polymer microballoon of high-crosslinking-degree is prepared using styrene and talan as raw material, then in styrene styrene copolymer microsphere surface chloromethylation, iminodiacetic acid, thiocarbamide and amineothiot group are introduced on copolymerization microsphere surface by the bonding reaction of chloromethyl and amino under basic conditions again, so as to obtain the chelating resin of surface polyfunctional group modification.The preparation method of the present invention is simple, the resin property prepared using high-crosslinking-degree condition is more stable, rigidity is strong, avoid conventional resins and inconvenience caused by swelling contraction occurs in different pH environment, at the same it is multi-functional in the presence of so that chelating resin of the present invention is respectively provided with good selectivity to multiple elements such as lead, cadmium, iron, copper, nickel, cobalt, zinc, mercury, aluminium, manganese, silver, palladium, gold.
Description
Technical field
It is more particularly to a kind of for the multifunctional of Element detection sample pre-treatments the present invention relates to technical field of analytical chemistry
The preparation method of the chelating resin of group's modification.
Background technology
It is well known that sodium chloride content reaches 6%-20% in the high salt food such as salty sauce, soy sauce and salted vegetables.When using inductive
When plasma mass detects to trace metal element in this based food, one side high concentration sodium salt can be to testing result band
To disturb；Another aspect salinity easily blocks atomizer, and is deposited in torch pipe and sampling spiroid, substantially reduces these accessories
Service life, improve testing cost.
At present, the method for heavy metal element mainly has organic solvent extractionprocess, network in detection high salt food samples both at home and abroad
Mixture extraction method or Matrix phase etc., but these methods all have great limitation on icp mses
Property.Organic solvent extractionprocess not only has injury to human body, and is difficult to direct injected；Complexing agent extraction selectivity is stronger, nothing
Method plays the advantage that ICP-MS multielements detect simultaneously, and the life-span is shorter, it is difficult to reuses.
The content of the invention
The purpose of the present invention is：A kind of preparation method of the chelating resin of polyfunctional group modification is provided, utilizes the more of gained
The chelating resin of modified with functional group carries out sample pre-treatments, removes in sample substrate more than 99% alkali metal ion.
The technical solution adopted by the present invention is：The polyphosphazene polymer of high-crosslinking-degree is prepared using styrene and talan as raw material
Compound microballoon, then in styrene styrene copolymer microsphere surface chloromethylation, then under basic conditions by chloromethyl with
The bonding reaction of amino introduces iminodiacetic acid, thiocarbamide and amineothiot group on copolymerization microsphere surface, so as to obtain surface
The chelating resin of polyfunctional group modification.
Wherein, the preparation method includes step in detail below：
（1）Aqueous phase is added into 10L four-hole boiling flasks, is stirred overnight；Wherein aqueous phase is by hydroxypropyl methyl cellulose and deionized water
Composition；
（2）When being warming up to 45 DEG C, oil phase is put into four-hole boiling flask, rotating speed 300~500r/min stir, to particle diameter 40~
80 DEG C are warming up at 60 μm, continues isothermal reaction 10h；Wherein oil phase is by the isonitrile of azo two, styrene, talan, toluene group
Into；
（3）Reaction stop after, using core filtering flask filter, and with originally washing three times, again with methanol rinse three times, after drying
Sieved with 200-400 mesh standard sieves, obtain copolymerization microsphere；
（4）Prepared copolymerization microsphere 20g and 80mL chloromethyl ethers are successively added to 250mL four-hole boiling flasks, 20~25 DEG C of immersions
2h；Stirring, 30 DEG C are warming up to, add 6g zinc chloride, react half an hour；6g zinc chloride are added, are warming up to 40 DEG C, isothermal reaction
3~10h；After the completion of reaction, mother liquor is absorbed, is washed 4~5 times, dried with ethanol, obtain chloromethylation copolymerization microsphere；
（5）200g chloromethylations copolymerization microsphere is put into 2000mL there-necked flasks, adds 1200mLN, dinethylformamide is molten
Swollen 2h；Then iminodiacetic acid, thiocarbamide, mercaptoethanol and sodium hydroxide are added in there-necked flask, back flow reaction 48h；It is cold
But to room temperature, deionized water is washed till filtrate as neutrality, and ethanol washs 3 times；Again toward the mass concentration of addition 1400mL in there-necked flask
50% methanol aqueous solution, and 2~8h of back flow reaction；Room temperature is cooled to, is washed respectively three times with deionized water, methanol, vacuum is done
Dry 5~12 hours, much chelating resins of modified with functional group.
Wherein, in step 1, the mass ratio of hydroxypropyl methyl cellulose and deionized water is 25 in aqueous phase: 5000.
Wherein, in step 2, the isonitrile of azo two, styrene, talan, the mass ratio of toluene are 5 in oil phase:200:
700: 1000。
Wherein, the mass ratio of aqueous phase and oil phase is about 5:2.
Wherein, in step 3, the copolymerization microsphere：For particle diameter at 35~70 μm, average pore size is 4~8nm.
Wherein, in step 4, the chloromethyl load capacity of prepared chloromethylation copolymerization microsphere is in 1.1~1.4mmol/g.
Wherein, in step 5, iminodiacetic acid, thiocarbamide, the quality of mercaptoethanol and sodium hydroxide be respectively 200g,
80g, 40g and 22g.
Beneficial effects of the present invention are：Provide a kind of preparation method of the chelating resin of polyfunctional group modification, method
Simply, strong operability, cost are low；Prepared resin is respectively provided with good chelation, application to more than ten kind elements
Extensively；Prepared resins selective is good, and load capacity is high, practical；Prepared resin's crosslinkage is high, in acid system
Be not in swelling shrinkage phenomenon in neutral system exchange process, dress post it is convenient and simple, renewable reuse, substantially reduce
Cost.
Brief description of the drawings
Fig. 1 is the optical microscope photograph of the chelating resin of the present invention.
Fig. 2 is the elution curve that chelating resin of the present invention removes sodium chloride matrix process（By taking cadmium as an example）.
Embodiment
It is real with reference to application to promote those skilled in the art to become apparent from getting information about technical scheme
Example does more detailed description to the present invention, but is not to be construed as the limitation of technical scheme.
Embodiment 1：The copolymerization microsphere of chloromethylation is prepared according to following steps
（1）Aqueous phase is added into 10L four-hole boiling flasks, is stirred overnight；The matter of hydroxypropyl methyl cellulose and deionized water in aqueous phase
Amount ratio is 25:1000；
（2）When being warming up to 45 DEG C, oil phase is put into four-hole boiling flask, rotating speed stirs in 300r/min, to liter during 40 μm of particle diameter
Temperature continues isothermal reaction 10h to 80 DEG C；The isonitrile of azo two, styrene, talan, the mass ratio of toluene are 5 in oil phase:
200:700:1000；The mass ratio of aqueous phase and oil phase is about 5:2；
（3）Reaction stop after, using core filtering flask filter, and with originally washing three times, again with methanol rinse three times, after drying
Sieved with 200 mesh standard sieves, obtain copolymerization microsphere；The copolymerization microsphere：Particle diameter at 35~70 μm, average pore size is 4~
8nm；
（4）Prepared copolymerization microsphere 20g and 80mL chloromethyl ethers are successively added to 250mL four-hole boiling flasks, 20 DEG C of immersion 2h；Stir
Mix, be warming up to 30 DEG C, add 6g zinc chloride, react half an hour；6g zinc chloride are added, are warming up to 40 DEG C, isothermal reaction 3h；Instead
After the completion of answering, mother liquor is absorbed, is washed 4 times, dried with ethanol, obtain chloromethylation copolymerization microsphere；Prepared chloromethylation copolymerization
The chloromethyl load capacity of microballoon is in 1.2mmol/g.
Embodiment 2：The chelating resin of polyfunctional group modification is prepared according to following steps
200g chloromethylations copolymerization microsphere is put into 2000mL there-necked flasks, adds 1200mLN, dinethylformamide, swelling
2h；Then iminodiacetic acid, thiocarbamide, mercaptoethanol and sodium hydroxide 20g are added in there-necked flask, back flow reaction 48h；It is cold
But to room temperature, deionized water is washed till filtrate as neutrality, and ethanol washs 3 times；Again toward the mass concentration of addition 1400mL in there-necked flask
50% methanol aqueous solution, and back flow reaction 2h；Room temperature is cooled to, is washed respectively three times with deionized water, methanol, vacuum drying 5
Hour, much chelating resins of modified with functional group；Wherein, function dough raw material proportioning one is：Iminodiacetic acid：Thiocarbamide：Mercapto
Base ethanol=200:0:0；
Function dough raw material proportioning two is：Iminodiacetic acid：Thiocarbamide：Mercaptoethanol=200:80:0；Function dough raw material proportioning
Third,：Iminodiacetic acid：Thiocarbamide：Mercaptoethanol=200:80:40.
Embodiment 3：Influence of the different functional groups raw material proportioning condition to the adion category of chelating resin
Prepare solution：Deionized water using pH as 6-7 is prepared containing 1000 μ g lead, cadmium, iron, copper, nickel, cobalt, zinc, mercury（It is divided into nothing
Machine mercury and organic mercury）, aluminium, manganese, silver, palladium, the solution of the element such as gold, volume is 100 mL.
The chelating resin 1.0g prepared in Example 2, it is respectively placed in the solution containing different elements of foregoing preparation,
Each solution system is placed in shaking table concussion 24h, taken after each solution system is centrifuged remaining in supernatant ICP-MS measure solution
The content of metallic element.Experimental result can be seen that when using function dough raw material proportioning for the moment, chelating resin can to lead,
Cadmium, iron, copper, nickel, cobalt, zinc, inorganic mercury, aluminium, manganese etc. have sequestering power；When using function dough raw material proportioning two, chelating
Resin significantly increases the sequestering power to silver, palladium, gold etc.；When using function dough raw material proportioning three, chelating resin is obvious
The sequestering power to organic mercury is added, and the sequestering power of inorganic mercury has also been strengthened.
Embodiment 4：Chelating resin removes the capacity experimental that sodium chloride disturbs（By taking cadmium as an example）
Prepare solution：Contain in solution：The mg/L of sodium 100, μ g/L, the pH regulations of cadmium 20 are in 6-7.
The chelating resin prepared in Example 2 according to function dough raw material proportioning three, equip the solid Xiang Cui of easy glass
Post is taken, carrying out SPE to foregoing preparation solution conciliates adsorption experiment.In experimentation, to cadmium and sodium in every milliliter of efflux
Concentration monitored in real time, and draw elution curve, as shown in Figure 2.As seen from the figure：1-10mL is loading process, chela
Resin does not adsorb sodium ion, the sodium ion of high concentration is detected in efflux, but cadmium ion is extracted post absorption, efflux
Middle concentration of cadmium ions is zero；11-20mL is deionized water cleaning process, in washing process, is remained in solid-phase extraction column post
Sodium ion is washed out, and concentration is gradually reduced to zero, and concentration of cadmium ions is still zero；21-30mL is 5% nitric acid desorption process, this
During cadmium ion depart from from chelating resin, be kept completely separate so as to realize with high concentration NaCl.
Embodiment described above is merely to illustrate the technological thought and feature of the present invention, in the art its object is to make
Technical staff it will be appreciated that present disclosure and implement according to this, it is impossible to the scope of the present invention is only limited with the present embodiment,
The equal change or modification that i.e. all disclosed spirit is made, still fall within the scope of the present invention.
Claims (7)
1. the preparation method of the chelating resin of polyfunctional group modification, high-crosslinking-degree is prepared using styrene and talan as raw material
High molecular polymer microballoon, then in styrene styrene copolymer microsphere surface chloromethylation, then pass through under basic conditions
The bonding reaction of chloromethyl and amino introduces iminodiacetic acid, thiocarbamide and amineothiot group on copolymerization microsphere surface, so as to
Obtain the chelating resin of surface polyfunctional group modification；It is characterized in that its preparation method includes step in detail below：
（1）Aqueous phase is added into 10L four-hole boiling flasks, is stirred overnight；Wherein aqueous phase is by hydroxypropyl methyl cellulose and deionized water
Composition；
（2）When being warming up to 45 DEG C, oil phase is put into four-hole boiling flask, rotating speed 300~500r/min stir, to particle diameter 40~
80 DEG C are warming up at 60 μm, continues isothermal reaction 10h；Wherein oil phase is by the isonitrile of azo two, styrene, talan, toluene group
Into；
（3）Reaction stop after, using core filtering flask filter, and with originally washing three times, again with methanol rinse three times, after drying
Sieved with 200-400 mesh standard sieves, obtain copolymerization microsphere；
（4）Prepared copolymerization microsphere 20g and 80mL chloromethyl ethers are successively added to 250mL four-hole boiling flasks, 20~25 DEG C of immersions
2h；Stirring, 30 DEG C are warming up to, add 6g zinc chloride, react half an hour；6g zinc chloride are added, are warming up to 40 DEG C, isothermal reaction
3~10h；After the completion of reaction, mother liquor is absorbed, is washed 4~5 times, dried with ethanol, obtain chloromethylation copolymerization microsphere；
（5）200g chloromethylations copolymerization microsphere is put into 2000mL there-necked flasks, adds 1200mLN, dinethylformamide is molten
Swollen 2h；Then iminodiacetic acid, thiocarbamide, mercaptoethanol and sodium hydroxide are added in there-necked flask, back flow reaction 48h；It is cold
But to room temperature, deionized water is washed till filtrate as neutrality, and ethanol washs 3 times；Again toward the mass concentration of addition 1400mL in there-necked flask
50% methanol aqueous solution, and 2~8h of back flow reaction；Room temperature is cooled to, is washed respectively three times with deionized water, methanol, vacuum is done
Dry 5~12 hours, much chelating resins of modified with functional group.
2. the preparation method of the chelating resin of polyfunctional group modification according to claim 1, it is characterized in that：In step 1, water
The mass ratio of hydroxypropyl methyl cellulose and deionized water is 25 in phase: 5000.
3. the preparation method of the chelating resin of polyfunctional group modification according to claim 1, it is characterized in that：In step 2, oil
The isonitrile of azo two, styrene, talan, the mass ratio of toluene are 5 in phase:200:700: 1000.
4. the preparation method of the chelating resin of polyfunctional group modification according to claim 1, it is characterized in that：Aqueous phase and oil phase
Mass ratio be about 5：2.
5. the preparation method of the chelating resin of polyfunctional group modification according to claim 1, it is characterized in that：In step 3, institute
State copolymerization microsphere：For particle diameter at 35~70 μm, average pore size is 4~8nm.
6. the preparation method of the chelating resin of polyfunctional group modification according to claim 1, it is characterized in that：In step 4, institute
The chloromethyl load capacity of the chloromethylation copolymerization microsphere of preparation is in 1.1~1.4mmol/g.
7. the preparation method of the chelating resin of polyfunctional group modification according to claim 1, it is characterized in that：It is sub- in step 5
Aminodiacetic acid, thiocarbamide, the quality of mercaptoethanol and sodium hydroxide are respectively 200g, 80g, 40g and 22g.
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Cited By (5)
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| CN109777439A (en) * | 2019-03-07 | 2019-05-21 | 安徽省农业科学院土壤肥料研究所 | Soil heavy metal passivant and its application in reduction tomato Accumulation of heavy metals amount |
| CN110028610A (en) * | 2019-04-02 | 2019-07-19 | 天津南开和成科技有限公司 | A kind of solid macromolecule Grignard Reagent and preparation method thereof |
| CN111537498A (en) * | 2020-05-13 | 2020-08-14 | 深圳市深投环保科技有限公司 | Method for determining low-concentration heavy metal elements in high-chlorine high-salt wastewater |
| CN113499757A (en) * | 2021-06-16 | 2021-10-15 | 中南大学 | Preparation method of resin material for selectively adsorbing mercury and application of resin material in removing mercury in selenium-containing solution |
| CN113498790A (en) * | 2021-07-02 | 2021-10-15 | 上海鑫灵精细化工有限公司 | Functional group immobilized nano-silver material, and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777439A (en) * | 2019-03-07 | 2019-05-21 | 安徽省农业科学院土壤肥料研究所 | Soil heavy metal passivant and its application in reduction tomato Accumulation of heavy metals amount |
| CN110028610A (en) * | 2019-04-02 | 2019-07-19 | 天津南开和成科技有限公司 | A kind of solid macromolecule Grignard Reagent and preparation method thereof |
| CN111537498A (en) * | 2020-05-13 | 2020-08-14 | 深圳市深投环保科技有限公司 | Method for determining low-concentration heavy metal elements in high-chlorine high-salt wastewater |
| CN113499757A (en) * | 2021-06-16 | 2021-10-15 | 中南大学 | Preparation method of resin material for selectively adsorbing mercury and application of resin material in removing mercury in selenium-containing solution |
| CN113499757B (en) * | 2021-06-16 | 2022-05-20 | 中南大学 | Preparation method of resin material for selectively adsorbing mercury and application of resin material in removing mercury in selenium-containing solution |
| CN113498790A (en) * | 2021-07-02 | 2021-10-15 | 上海鑫灵精细化工有限公司 | Functional group immobilized nano-silver material, and preparation method and application thereof |
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