CN108976325A - A kind of amidoxime group pyridine chelating resin and preparation method thereof - Google Patents
A kind of amidoxime group pyridine chelating resin and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention discloses a kind of amidoxime group pyridine chelating resin and preparation method thereof, the structural unit of amidoxime group pyridine chelating resin is as follows:Amidoxime group pyridine chelating resin of the present invention prepares simple, low in cost, strong to the adaptive of different heavy metal water bodys；Oximido contains oxygen atom, can occur effectively to be bonded with soft metal ions, furthermore pyridine nitrogen atom is not susceptible to protonate, and can form backdonation with heavy metal ion, therefore still has biggish removal ability to heavy metal ion when acidity is higher；It can be applied in Complex water body fields, economic benefit and the obvious environment benefit such as separation and preenrichment of boundary heavy metal and soft metal in the removal and environmental analysis of heavy metal.
Description
Technical field
The present invention relates to a kind of amidoxime group pyridine chelating resins and preparation method thereof, belong to modified resin field.
Background technique
Heavy metal pollution has become the great environmental problem for threatening human development, and heavy metal wastewater thereby is to environment dirt
It contaminates most serious and maximum industrial wastewater is endangered to the mankind, heavy metal cannot be degraded by microorganisms as harmless object, it is therefore desirable to right
It is effectively removed.
Heavy metal ion in industrial wastewater usually coexists in acidic environment with inorganic salts, organic matter etc., alkali (soil) gold
Strong competitive effect can be generated to adsorption site and seriously undermine removal of heavy metal ions effect by belonging to ion and hydrionic presence
Rate, conventional ion exchange resin cannot effectively selective removal and separate and recover heavy metal in such Complex water body from
Son.
The problems such as being substantially reduced in peracid hypersaline environment there are adsorption capacity due to conventional nitrogen-type chelating resin, and pass through
Resin backbone structure is constructed, while modifying pyridyl group and oximido dual-functional group, design synthesis is with antiacid salt resistance characteristic together with amine
Oximido pyridine chelating resin has not been reported for heavy metal adsorption.
Summary of the invention
The problems such as adsorption capacity is substantially reduced in peracid hypersaline environment for chelating resin in the prior art, the present invention mentions
A kind of amidoxime group pyridine chelating resin and preparation method thereof is supplied, amidoxime group pyridine chelating resin can be used for selective absorption
Separation of heavy metal ions, removal and environment point suitable for heavy metal in the purification of mining and metallurgy production mother liquor, peracid complex system with high salt
Fields, economic benefit and the obvious environment benefit such as separation Yu preenrichment of heavy metal in analysis；Preparation method is low in cost, operation is simple
It is single.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows:
A kind of amidoxime group pyridine chelating resin, structural unit are as follows:
Applicant it has been investigated that, exist while two groups of oximido and pyridyl group in same chelating resin so that tree
Rouge significantly improves the adsorption capacity of heavy metal ion, and amidoxime group pyridine chelating resin produced by the present invention has heavy metal height
The characteristics such as the high resistance to soiling of selectivity, acid resistance, inorganic salts are a kind of multiple tooth dentate chelating resins of heterocyclic nitrogen atom, on the one hand
Due to the Draw electronic effect of pyridine ring, the nitrogen-atoms cloud density on pyridine ring is reduced, and is not easy to protonate, and and heavy metal from
Son can form backdonation, the enhancing of acid-resisting ability；On the other hand due to containing oxygen atom in oximido, so as to soft metal ions
The removal ability having had, and oxygen atom can cooperate with chelating contents of many kinds of heavy metal ion with pyridine ring nitrogen, be formed stable
Complex, and in complexation process not with alkali (soil) metal ion coexist be bonded, show excellent characterization of adsorption and highly selective
Separating capacity, therefore, chelating resin of the present invention are applicable to Selective Separation recycling heavy metal ion, in electronics finishing, wet process
The fields such as metallurgy are with a wide range of applications.
For the application resin in faint yellow, partial size is 0.20~0.90mm.
The functional group of the application amidoxime group pyridine chelating resin is pyridyl group, amino and oximido, functional group content
For 1.50~1.96mmol/g.
Applicant it has been investigated that, which adsorbs heavy metal ion by the chelation of nitrogen, oxygen atom, can be formed steady
Fixed cyclic chelate structures:
In formula, M is heavy metal ion.
The preparation method of above-mentioned amidoxime group pyridine chelating resin, including the following steps being connected in order:
1) polystyrene-divinylbenzene resin is prepared；
2) by the resulting polystyrene-divinylbenzene resin chloromethylation of step 1), chloromethylation low cross-linking macropore is obtained
Polystyrene-divinylbenzene resin；
3) step 2) resulting material is extracted 10-20 hours through Soxhlet extractor, is then added 50~70 times of weight resin
Toluene, 1~5 times of weight resin of 3- amino -6- cyanopyridine and 2~4 times of weight resin of sodium carbonate, at 55~95 DEG C
Reaction 8~20 hours, obtains yellow 3- amino -6- cyanopyridine chelating resin；
4) by after the resulting resin of step 3) (yellow 3- amino -6- cyanopyridine chelating resin) washing, hydrochloric acid hydroxyl is added
Amine, and with ethanol as solvent, it is reacted 5~30 hours at 50-90 DEG C, filters and wash drying, obtain faint yellow amidoxime group pyrrole
Pyridine chelating resin, wherein the quality dosage of hydroxylamine hydrochloride is 1~5 times of weight resin.
Cyano group is introduced into pyridine chelating resin by the present invention, and makes cyano become oxime by the way that oxammonium hydrochloride is added
Base.
In order to further ensure the adsorption effect of gained resin, it is preferable that step 1) is to do monomer, diethyl using styrene
Alkene benzene makees crosslinking agent, makees pore-foaming agent using the mixing of one or both of polyvinylpyrrolidone or polyethylene glycol, uses hydroxide
Dispersing agent is made in the mixing of one or more of magnesium, methylcellulose or hydroxypropyl methyl cellulose, is made with cumyl peroxide
Initiator prepares low crosslinking degree macropore styrene benzene copolymer using suspension polymerization, select petroleum ether (60-90 DEG C of boiling range),
Chloroform, ethanol as solvent extracting, remove remaining pore-foaming agent in resin duct, and it is poly- to obtain low cross-linking macropore using pneumatic conveying drying
Styrene-divinyl benzene resin, abbreviation Archon.
In order to further increase acidproof, the salt tolerance of gained resin, it is preferable that in step 1), the quality dosage of crosslinking agent is
The 5~10% of monomer and crosslinking agent quality total amount, the quality dosage of pore-foaming agent are the 50~90% of monomer mass, the matter of initiator
Amount dosage be monomer, crosslinking agent and pore-foaming agent quality total amount 2.5~4%, the quality dosage of dispersing agent be monomer mass 2~
8%, extraction solvent volume is 10~20 times of resin volume, low cross-linking macroporous polystyrene-divinylbenzene resins obtained
The degree of cross linking is 3~8%.
In order to further increase the adsorption effect of gained resin, step 1) includes the following steps:
1.1) monomer, crosslinking agent and pore-foaming agent are mixed；
1.2) dispersing agent is dissolved in water, and is mixed with step 1.1) resulting material, initiator, adjustment stirring speed is then added
Degree makes oil droplet 0.5~1mm of size, then successively proceeds as follows: being gradually warming up to 75 DEG C with the speed of 1 DEG C/5min, heat preservation
2h；80 DEG C are gradually warming up to the speed of 1 DEG C/5min, keeps the temperature 2h；90 DEG C are gradually warming up to the speed of 1 DEG C/5min, heat preservation
5h；95 DEG C are gradually warming up to the speed of 1 DEG C/5min, keeps the temperature 5h, end of reaction filters out resin, is first washed, dried with hot water,
It is reloaded into Soxhlet extractor, carries out solvent extraction, then pneumatic conveying drying, sieving obtains low cross-linking macroporous polystyrene-divinylbenzene
Resin.
In order to further ensure the adsorption effect of gained resin, it is preferable that step 2) is that Archon is soaked in its weight 8-20
In chloromethyl ether again, the anhydrous zinc chloride that the 2-15% of Archon weight is added makees catalyst, and chloromethane is carried out at a temperature of 30-50 DEG C
Glycosylation reaction filters out resin sphere, is washed in most resin and remained with water or ethyl alcohol until chlorinity reaches 12% or more stopping reaction
Chlorination mother solution, pneumatic conveying drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resins, abbreviation chlorine ball.
In order to further increase acidproof, the salt tolerance of gained resin, it is preferable that in step 2), the control reaction time is 8~25
Hour, obtain the chlorine ball that chlorinity is 15~21%.
Above-mentioned chlorine ball is as follows to amidoxime group pyridine chelating resin reaction process:
The unmentioned technology of the present invention is referring to the prior art.
Compared with the prior art, the invention has the benefit that
(1) present invention prepares the lower cost for material of resin, and preparation process is simple, and the function base modified has stable
Space structure, the oxygen atom on nitrogen-atoms and oximido in pyridyl group can play coordination chelating to hard metal or soft metal simultaneously
Effect；
(2) chelating resin provided by the invention can not only adsorb soft, hard metal ion, and have heavy metal high selection
The characteristics such as property, acid resistance, the high resistance to soiling of inorganic salts, can be selectively adsorbing and separating in peracid complex environment with high salt Cu (II),
The heavy metal ion such as Ni (II), Cd (II), the heavy metal in mining and metallurgy production mother liquor purification and production waste water treatment, complex system
The fields such as separation and enrichment are with a wide range of applications, economic benefit and obvious environment benefit；
(3) chelating resin preparation method provided by the invention is simple and convenient, and common pyridine chelating resin is to pass through resin
Matrix and pyridine single step reaction are completed, and resin provided by the invention is to first pass through grafting cyanopyridine, then modifying pyrrole
Cyano in piperidinyl group makes cyano be converted into oximido, and function base utilization rate is high, and modification amount is big, and is not easy to protonate, therefore counterweight
The adsorbance of metal obviously increases, additionally due to the presence of oximido, also has preferable effect to the absorption of soft metal.Thus together with amine
Oximido pyridine chelating resin in selective absorption heavy metal, can well solve adsorbance in engineering is small and the rate of adsorption is slow,
The technical problems such as amount of resin is big, the operating time is long are needed, while the absorption of preferable degree can be reached to soft metal.
Detailed description of the invention
Fig. 1 is the infrared spectrum of 1 reaction product of embodiment；
Fig. 2 is the photoelectron spectroscopy figure of 1 reaction product of example；
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
(a) suspension polymerisation
Styrene monomer is passed through the resin column equipped with strong basic anion-exchange resin to filter to remove polymerization inhibitor；
In 1000mL beaker, 210g styrene, 20g divinylbenzene, 140g polyvinylpyrrolidone (model is added
PVPK30K -90, brand: German BASF), it is spare after mixing evenly.
In 1000mL three-necked flask, 600mL distilled water is added and is warming up to 50 DEG C, adds 8g methylcellulose
(M15), stirring is to being completely dissolved, while being warming up to 60 DEG C, and 2mL methyl blue is added, stirs evenly, above-mentioned styrene, two is added
Initiator cumyl peroxide 12.0g is added in the mixed liquor of Ethenylbenzene and polypyrrole alkanone；Adjusting mixing speed appropriate makes
Oil droplet size be 0.5~1mm, be gradually warming up to 75 DEG C with the speed of 1 DEG C/5min, and keep the temperature 2h, with the speed of 1 DEG C/5min by
Step is warming up to 80 DEG C of heat preservation 2h, is gradually warming up to 90 DEG C of heat preservation 5h with the speed of 1 DEG C/5min, then with the speed of 1 DEG C/5min by
Step is warming up to 95 DEG C of heat preservation 5h, and end of reaction filters out resin, first washed with hot water, filter out resin, dries, and is packed into soxhlet type
Device, pneumatic conveying drying clean with chloroform, sieving obtain low cross-linking macroporous polystyrene-divinylbenzene resins, the degree of cross linking
It is 3%, i.e. Archon, takes the resin of 0.20~1.10mm of granularity spare.
(b) chloromethylation
In 2000mL three-necked flask, 50g Archon, 400g chloromethyl ether is added, 2h or more is impregnated at 30 DEG C, under stirring,
7.5g anhydrous zinc chloride is added, control temperature is not higher than 30 DEG C, after stirring 2h, is warming up to 40 DEG C, keeps the temperature 15h, controls chlorinity
It, can reaction was completed 12% or more.After reaction, resin sphere is filtered out, resin is extracted after washing, is washed with water into
Property, pneumatic conveying drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resins, hereinafter referred to as chlorine ball.
(c) nucleophilic substitution
In 250mL three-necked flask, chloromethyl resin 2g prepared by step (b) is added, is extracted through Soxhlet extractor
3- amino -6- cyanopyridine 5g is added with 120mL toluene swell 10h in 10h, and natrium carbonicum calcinatum 4g then heats to 60 DEG C, stirs
It mixes, reacts 8h, filter out resin, successively use ethyl alcohol, water, ethanol washing, drying can be prepared by intermediate yellow coloured resin.
(d) electrophilic addition reaction
In 100mL three-necked flask, resin 2g and 2g hydroxylamine hydrochloride prepared by ethyl alcohol 20ml, step (c) is added, is condensing
Under the conditions of in 80 DEG C of sufficiently reaction 30h, filter and successively through washing, ethanol washing and washing, obtain amidoxime group pyridine after dry
Chelating resin.
Infrared analysis result such as Fig. 1, as shown in Figure 1, chlorine ball reacted with 3- amino -6- cyanopyridine after 3- amino -6-
In cyanopyridine resin (APN), in 2222cm-1Locate appearance-C ≡ N absorption peak, illustrates that 3- amino -6- cyanopyridine successfully reacts
To chlorine ball surface.After electrophilic addition reaction occurs with hydroxylamine hydrochloride again, 2222cm-1Place's-C ≡ N absorption peak disappears, and occurs
949cm-1The N-O absorption peak at place, explanation-C ≡ N are completely reformed into amidoxime group, obtain amidoxime group pyridine chelating resin
(APO)。
XPS Analysis such as Fig. 2, as shown in Figure 2, there are three characteristic absorptions in 397eV, 400eV, 404eV for N element
Peak, the N atom (pyridine N, amino N, oximido N) corresponding to varying environment.
Amidoxime group pyridine chelating resin made from the present embodiment, partial size are 0.70~0.80mm, and functional group contains
Amount is shown in Table 1.Use resin 0.05g processing pH=2, sodium nitrate concentration for the cupric heavy metal wastewater thereby of 100mmol/L, adsorbance
Up to 1.63mmol/g, adsorption saturation time 120min.0.05g resin treatment pH=2, sodium nitrate concentration 100mmol/
The cupric of L, cadmium, nickel complicated heavy metal wastewater thereby, the adsorbance of copper reaches 1.03mmol/g, and the adsorbance of cadmium reaches
0.44mmol/g, the adsorbance of nickel are 0.20mmol/g.
Embodiment 2
It is substantially the same manner as Example 1, except that:
(a) suspension polymerisation
Make monomer using styrene, divinylbenzene makees crosslinking agent, makees pore-foaming agent using Macrogol 4000, with hydroxypropyl first
Base cellulose (daily use chemicals grade is purchased from Nai Tesi chemical industry) makees dispersing agent, makees initiator with cumyl peroxide, using suspension polymerisation
Method synthesizes low crosslinking degree macroporous polystyrene-divinylbenzene copolymer, and petroleum ether (60-90 DEG C of boiling range) is selected to make solvent extraction,
Remaining pore-foaming agent in resin duct is removed, obtains low cross-linking macroporous polystyrene-divinylbenzene resins using pneumatic conveying drying,
That is Archon；
Wherein, dosage of crosslinking agent is the 5% of monomer and crosslinking agent total amount, and pore-foaming agent dosage is the 50% of monomer weight, is drawn
Hair agent accounts for the 2.5% of monomer, crosslinking agent and pore-foaming agent total amount, and dispersing agent agent dosage is the 2% of monomer weight, the body of extraction solvent
Product is 10 times of resin volume, and the degree of cross linking of low cross-linking macroporous polystyrene is 3%, remaining is the same as embodiment 1.
(b) chloromethylation
Archon is soaked in the chloromethyl ether of 8 times of its weight, 2% anhydrous zinc chloride that Archon weight is added is catalyzed
Agent carries out chloromethylation in 30 DEG C of temperature, reacts 10h, until chlorinity reaches 12% or more stopping reaction, filters out tree
Rouge sphere, is washed with water chlorination mother solution remaining in most resin, and pneumatic conveying drying obtains chloromethylation low cross-linking macroporous polystyrene-two
Ethenylbenzene resin, i.e. chlorine ball.
(c) nucleophilic substitution
In 250mL three-necked flask, chloromethyl resin 2g prepared by step (b) is added, is extracted through Soxhlet extractor
20h is added 3- amino -6- cyano in pyridine 2g, natrium carbonicum calcinatum 5g and is then heated to 55 DEG C with 100mL toluene swell 10h,
Stirring reacts 16h, filters out resin, successively uses ethyl alcohol, water, ethanol washing, and drying can be prepared by intermediate yellow coloured resin..
(d) electrophilic addition reaction
In 100mL three-necked flask, resin 2g prepared by step (c) is added, 4g hydroxylamine hydrochloride is added, under condensing condition
70 DEG C of sufficiently reaction 20h, filter and successively through washing, ethanol washing and washing, obtain amidoxime group pyridine chelating resin after dry.
Amidoxime group pyridine chelating resin made from the present embodiment, partial size are 0.78~0.90mm, and functional group contains
Amount is shown in Table 1.Use resin 0.05g processing pH=2, sodium nitrate concentration for the cupric heavy metal wastewater thereby of 100mmol/L, adsorbance
Up to 1.50mmol/g, adsorption saturation time 120min.0.05g resin treatment pH=2, sodium nitrate concentration 100mmol/
The cupric of L, cadmium, nickel complicated heavy metal wastewater thereby, the adsorbance of copper reaches 0.95mmol/g, and the adsorbance of cadmium reaches
0.42mmol/g, the adsorbance of nickel are 0.21mmol/g.
The obtained infrared spectrum of the present embodiment and photoelectron spectroscopy figure, it is almost the same with embodiment 1, therefore do not repeat to mention
For.
Embodiment 3
It is substantially the same manner as Example 1, except that:
(a) suspension polymerisation
Make monomer using styrene, divinylbenzene makees crosslinking agent, using polyvinylpyrrolidone (model PVPK30K -90,
Brand: German BASF) make pore-foaming agent, make dispersing agent with magnesium hydroxide, makees initiator with cumyl peroxide, using suspension
Polymerization synthesizes low crosslinking degree macroporous polystyrene-divinylbenzene copolymer, selects ethanol as solvent extracting, removes resin hole
Remaining pore-foaming agent in road obtains low cross-linking macroporous polystyrene-divinylbenzene resins, i.e. Archon using pneumatic conveying drying；
Wherein dosage of crosslinking agent is the 5% of monomer and crosslinking agent total amount, and pore-foaming agent dosage is the 50% of monomer weight, is caused
Agent accounts for the 4% of monomer, crosslinking agent and pore-foaming agent total amount, and dispersing agent agent dosage is the 5% of monomer weight, and the volume of extraction solvent is
10 times of resin volume, the degree of cross linking of low cross-linking macroporous polystyrene are 3%, remaining is the same as embodiment 1.
(b) chloromethylation
Archon is soaked in the chloromethyl ether of 8 times of its weight, 2% anhydrous zinc chloride that Archon weight is added is catalyzed
Agent carries out chloromethylation in 40 DEG C of temperature, reacts until chlorinity reaches 12% or more stopping, filtering out resin sphere,
Chlorination mother solution remaining in most resin is washed with water, pneumatic conveying drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene
Resin, i.e. chlorine ball.
(c) nucleophilic substitution
In 250mL three-necked flask, chloromethyl resin 2g prepared by step (b) is added, is extracted through Soxhlet extractor
10h is swollen 10h with 130mLDMF, 3- amino -6- cyanopyridine 8g is added, and natrium carbonicum calcinatum 6g then heats to 85 DEG C, stirs
It mixes, reacts 20h, filter out resin, successively use ethyl alcohol, water, ethanol washing, drying can be prepared by intermediate yellow coloured resin.
(d) electrophilic addition reaction
In 100mL three-necked flask, resin 2g prepared by step (c) is added, 8g hydroxylamine hydrochloride is added, under condensing condition
In 90 DEG C of sufficiently reaction 30h, suction filtration and successively through washing, ethanol washing and washing, amidoxime group pyridine chelating tree is obtained after dry
Rouge.
Amidoxime group pyridine chelating resin made from the present embodiment, partial size are 0.75~0.86mm, and functional group contains
Amount is shown in Table 1.Use resin 0.05g processing pH=2, sodium nitrate concentration for the cupric heavy metal wastewater thereby of 100mmol/L, adsorbance
Up to 1.57mmol/g, adsorption saturation time 120min.0.05g resin treatment pH=2, sodium nitrate concentration 100mmol/
The cupric of L, cadmium, nickel complicated heavy metal wastewater thereby, the adsorbance of copper reaches 0.99mmol/g, and the adsorbance of cadmium reaches
0.40mmol/g, the adsorbance of nickel are 0.22mmol/g.
The obtained infrared spectrum of the present embodiment and photoelectron spectroscopy figure, it is almost the same with embodiment 1, therefore do not repeat to mention
For.
Embodiment 4
It is substantially the same manner as Example 1, except that:
(a) suspension polymerisation
Make monomer using styrene, divinylbenzene makees crosslinking agent, using polyvinylpyrrolidone (model PVPK30K -90,
Brand: German BASF) it is mixed with Macrogol 4000 1:1 in mass ratio and makees pore-foaming agent, with hypromellose (daily use chemicals
Grade is purchased from Nai Tesi chemical industry) make dispersing agent, make initiator with cumyl peroxide, using suspension polymerization, synthesizes low cross-linking
Macroporous polystyrene-divinylbenzene copolymer is spent, petroleum ether (60-90 DEG C of boiling range) is selected to make solvent extraction, removes resin duct
In remaining pore-foaming agent, obtain low cross-linking macroporous polystyrene-divinylbenzene resins, i.e. Archon using pneumatic conveying drying；
Wherein dosage of crosslinking agent is the 10% of monomer and crosslinking agent total amount, and pore-foaming agent dosage is the 60% of monomer weight, is drawn
Hair agent accounts for the 4% of monomer, crosslinking agent and pore-foaming agent total amount, and dispersant dosage is the 8% of monomer weight, and extraction solvent volume is tree
20 times of rouge volume, the degree of cross linking of low cross-linking macroporous polystyrene are 8%, remaining is the same as embodiment 1.
(b) chloromethylation
Archon is soaked in the chloromethyl ether of 20 times of its weight, 15% anhydrous zinc chloride that Archon weight is added is catalyzed
Agent carries out chloromethylation in 50 DEG C of temperature, and the control reaction time is 25h, filters out resin sphere, is washed with water in most resin
Remaining chlorination mother solution, pneumatic conveying drying obtain low cross-linking macroporous polystyrene-divinylbenzene resins, i.e. chlorine ball.
(c) nucleophilic substitution
In 250mL three-necked flask, chloromethyl resin 2 prepared by step (b) is added, extracts 20h through Soxhlet extractor,
With 130mL toluene swell 10h, 3- amino -6- cyano is added and then heats to 95 DEG C in pyridine 10g, natrium carbonicum calcinatum 8g, stirs
It mixes, reacts 16h, filter out resin, successively use ethyl alcohol, water, ethanol washing, drying can be prepared by intermediate yellow coloured resin..
(d) electrophilic addition reaction
In 100mL three-necked flask, resin 2g prepared by step (c) is added, 10g hydroxylamine hydrochloride is added, in condensing condition
Lower 90 DEG C are sufficiently reacted 20h, filter simultaneously successively by washing, ethanol washing and washing, amidoxime group pyridine chelating is obtained after dry
Resin.
Amidoxime group pyridine chelating resin made from the present embodiment, partial size are 0.20~0.31mm, and functional group contains
Amount is shown in Table 1.Use resin 0.05g processing pH=2, sodium nitrate concentration for the cupric heavy metal wastewater thereby of 100mmol/L, adsorbance
Up to 1.96mmol/g, adsorption saturation time 120min.0.05g resin treatment pH=2, sodium nitrate concentration 100mmol/
The cupric of L, cadmium, nickel complicated heavy metal wastewater thereby, the adsorbance of copper reaches 1.23mmol/g, and the adsorbance of cadmium reaches
0.55mmol/g, the adsorbance of nickel are 0.29mmol/g.
The obtained infrared spectrum of the present embodiment and photoelectron spectroscopy figure, it is almost the same with embodiment 1, therefore do not repeat to mention
For.
Embodiment 5
It is substantially the same manner as Example 1, except that:
(a) suspension polymerisation
Make monomer using styrene, divinylbenzene makees crosslinking agent, makees pore-foaming agent using Macrogol 4000, uses magnesium hydroxide
Make dispersing agent, make initiator with cumyl peroxide, using suspension polymerization, synthesizes low crosslinking degree macroporous polystyrene-two
Ethenylbenzene copolymer selects ethanol as solvent extracting, removes remaining pore-foaming agent in resin duct, obtain using pneumatic conveying drying
Low cross-linking macroporous polystyrene-divinylbenzene resins, i.e. Archon；
Wherein dosage of crosslinking agent is the 7.5% of monomer and crosslinking agent total amount, and pore-foaming agent dosage is the 50% of monomer weight, is drawn
Hair agent accounts for the 2.5% of monomer, crosslinking agent and pore-foaming agent total amount, and dispersant dosage is the 2% of monomer weight, and extraction solvent volume is
10 times of resin volume, the degree of cross linking of low cross-linking macroporous polystyrene are 5%, remaining is the same as embodiment 1.
(b) chloromethylation
Archon being soaked in the chloromethyl ether of 8 times of its weight, 2% zinc chloride that Archon weight is added makees catalyst,
Chloromethylation is carried out in 40 DEG C of temperature, reacts 8h, until chlorinity reaches 12% or more stopping reaction, filters out resin balls
Body, chlorination mother solution remaining in most resin is washed with ethyl alcohol, and pneumatic conveying drying obtains low cross-linking macroporous polystyrene-divinylbenzene tree
Rouge, i.e. chlorine ball.
(c) nucleophilic substitution
In 250mL three-necked flask, chloromethyl resin 2g prepared by step (b) is added, is extracted through Soxhlet extractor
20h is added 3- amino -6- cyano in pyridine 6g, Anhydrous potassium carbonate 4g and is then heated to 80 DEG C with 100mL toluene swell 10h,
Stirring reacts 16h, filters out resin, successively uses ethyl alcohol, water, ethanol washing, and drying can be prepared by intermediate yellow coloured resin..
(d) electrophilic addition reaction
In 100mL three-necked flask, resin 2g prepared by step (c) is added, 6g hydroxylamine hydrochloride is added, under condensing condition
85 DEG C of sufficiently reactions for 24 hours, filter and successively through washing, ethanol washing and washing, obtain amidoxime group pyridine chelating resin after dry.
Amidoxime group pyridine chelating resin made from the present embodiment, partial size are 0.35~0.48mm, and functional group contains
Amount is shown in Table 1.Use resin 0.05g processing pH=2, sodium nitrate concentration for the cupric heavy metal wastewater thereby of 100mmol/L, adsorbance
Up to 1.85mmol/g, adsorption saturation time 120min.0.05g resin treatment pH=2, sodium nitrate concentration 100mmol/
The cupric of L, cadmium, nickel complicated heavy metal wastewater thereby, the adsorbance of copper reaches 1.15mmol/g, and the adsorbance of cadmium reaches
0.50mmol/g, the adsorbance of nickel are 0.26mmol/g.
The obtained infrared spectrum of the present embodiment and photoelectron spectroscopy figure, it is almost the same with embodiment 1, therefore do not repeat to mention
For.
Embodiment 6
It is substantially the same manner as Example 1, except that:
(a) suspension polymerisation: making monomer using styrene, and divinylbenzene makees crosslinking agent, makees pore using polyethylene glycol 2000
Agent makees dispersing agent with methylcellulose (M15), makees initiator with cumyl peroxide, using suspension polymerization, synthesizes low friendship
Connection degree macroporous polystyrene-divinylbenzene copolymer selects chloroform to do solvent extraction, removes remaining pore in resin duct
Agent obtains low cross-linking macroporous polystyrene-divinylbenzene resins, i.e. Archon using pneumatic conveying drying；
Wherein dosage of crosslinking agent is the 7% of monomer and crosslinking agent total amount, and pore-foaming agent dosage is the 90% of monomer weight, is caused
Agent accounts for the 2.5% of monomer, crosslinking agent and pore-foaming agent total amount, and dispersant dosage is the 8% of monomer weight, and extraction solvent volume is tree
10 times of rouge volume, the degree of cross linking of low cross-linking macroporous polystyrene are 5%, remaining is the same as embodiment 1.
(b) chloromethylation: Archon being soaked in the chloromethyl ether of 15 times of its weight, and the anhydrous of the 8% of Archon weight is added
Zinc chloride makees catalyst, and chloromethylation is carried out in 30 DEG C of temperature, reacts 8h, it is anti-that chlorinity reaches 12% or more stopping
It answers, filters out resin sphere, chlorination mother solution remaining in most resin is washed with ethyl alcohol, pneumatic conveying drying obtains low cross-linking macropore polyphenyl second
Alkene-divinylbenzene resins, i.e. chlorine ball.
(c) nucleophilic substitution
In 250mL three-necked flask, chloromethyl resin 2g prepared by step (b) is added, is extracted through Soxhlet extractor
20h is added 3- amino -6- cyano in pyridine 5.6g, natrium carbonicum calcinatum 6g and is then heated to 75 with 120mL toluene swell 10h
DEG C, stirring reacts 12h, filters out resin, successively uses ethyl alcohol, water, ethanol washing, and drying can be prepared by intermediate yellow coloured resin.
(d) electrophilic addition reaction
In 100mL three-necked flask, resin 2g prepared by step (c) is added, 8g hydroxylamine hydrochloride is added, under condensing condition
80 DEG C of sufficiently reaction 30h, filter and successively through washing, ethanol washing and washing, obtain amidoxime group pyridine chelating resin after dry.
Amidoxime group pyridine chelating resin made from the present embodiment, partial size are 0.50~0.61mm, and functional group contains
Amount is shown in Table 1.Using resin 0.05g Treatment of Copper heavy metal wastewater thereby, adsorbance is up to 1.77mmol/g.
Use resin 0.05g processing pH=2, sodium nitrate concentration for the cupric heavy metal wastewater thereby of 100mmol/L, adsorbance
Up to 1.77mmol/g, adsorption saturation time 120min.0.05g resin treatment pH=2, sodium nitrate concentration 100mmol/
The cupric of L, cadmium, nickel complicated heavy metal wastewater thereby, the adsorbance of copper reaches 1.09mmol/g, and the adsorbance of cadmium reaches
0.46mmol/g, the adsorbance of nickel are 0.27mmol/g.
The obtained infrared spectrum of the present embodiment and photoelectron spectroscopy figure, it is almost the same with embodiment 1, therefore do not repeat to mention
For.
Embodiment 7
It is substantially the same manner as Example 1, except that:
(a) suspension polymerisation
Make monomer using styrene, divinylbenzene makees crosslinking agent, using polyvinylpyrrolidone (model PVPK30K -90,
Brand: German BASF) make pore-foaming agent, with magnesium hydroxide and hydroxypropyl methyl cellulose (daily use chemicals grade is purchased from Nai Tesi chemical industry)
Dispersing agent is made in the mixing of 1:2 in mass ratio, makees initiator with cumyl peroxide, using suspension polymerization, synthesizes low crosslinking degree
Macroporous polystyrene-divinylbenzene copolymer selects ethanol as solvent extracting, removes remaining pore-foaming agent in resin duct, then
Low cross-linking macroporous polystyrene-divinylbenzene resins, i.e. Archon are obtained by pneumatic conveying drying；
Wherein dosage of crosslinking agent is the 5% of monomer and crosslinking agent total amount, and pore-foaming agent dosage is the 50% of monomer weight, is caused
Agent accounts for the 2.5% of monomer, crosslinking agent and pore-foaming agent total amount, and dispersant dosage is the 2% of monomer weight, and extraction solvent volume is tree
10 times of rouge volume, the degree of cross linking of low cross-linking macroporous polystyrene are 3%, remaining is the same as embodiment 1.
(b) chloromethylation
Archon is soaked in the chloromethyl ether of 8 times of its weight, 2% anhydrous zinc chloride that Archon weight is added is catalyzed
Agent carries out chloromethylation in 30 DEG C of temperature, reacts 12h, until chlorinity reaches 12% or more stopping reaction, filters out tree
Rouge sphere, chlorination mother solution remaining in most resin is washed with ethyl alcohol, and pneumatic conveying drying obtains low cross-linking macroporous polystyrene-divinylbenzene
Resin, i.e. chlorine ball.
(c) nucleophilic substitution
In 250mL three-necked flask, chloromethyl resin 2g prepared by step (b) is added, is extracted through Soxhlet extractor
20h is added 3- amino -6- cyano in pyridine 4g, natrium carbonicum calcinatum 4g and is then heated to 70 DEG C with 140mL toluene swell 10h,
Stirring reacts 12h, filters out resin, successively uses ethyl alcohol, water, ethanol washing, and drying can be prepared by intermediate yellow coloured resin.
(d) electrophilic addition reaction
In 100mL three-necked flask, resin 2g prepared by step (c) is added, 4g hydroxylamine hydrochloride is added, under condensing condition
70 DEG C of sufficiently reactions for 24 hours, filter and successively through washing, ethanol washing and washing, obtain amidoxime group pyridine chelating resin after dry.
Amidoxime group pyridine chelating resin made from the present embodiment, partial size are 0.63~0.72mm, and functional group contains
Amount is shown in Table 1.Using resin 0.05g Treatment of Copper heavy metal wastewater thereby, adsorbance is up to 1.68mmol/g.At the 0.05g resin
Manage pH=2, the complicated heavy metal wastewater thereby of the cupric that sodium nitrate concentration is 100mmol/L, cadmium, nickel, the adsorbance of copper reaches
1.05mmol/g, the adsorbance of cadmium reach 0.47mmol/g, and the adsorbance of nickel is 0.20mmol/g.
The obtained infrared spectrum of the present embodiment and photoelectron spectroscopy figure, it is almost the same with embodiment 1, therefore do not repeat to mention
For.
The key technical indexes of above-described embodiment 1-7 such as following table 1:(Resin A, B, C, D, E, F, G respectively correspond embodiment 1,
Resin obtained by 2,3,4,5,6,7).
Table 1
Claims (10)
1. a kind of amidoxime group pyridine chelating resin, it is characterised in that: its structural unit is as follows:
2. amidoxime group pyridine chelating resin according to claim 1, it is characterised in that: functional group include pyridyl group,
Amino and oximido, functional group content are 1.50~1.96mmol/g.
3. amidoxime group pyridine chelating resin according to claim 1 or 2, it is characterised in that: its partial size be 0.20~
0.90mm。
4. the preparation method of amidoxime group pyridine chelating resin described in claim 1-3 any one, it is characterised in that: including
The following steps being connected in order:
1) polystyrene-divinylbenzene resin is prepared；
2) by the resulting polystyrene-divinylbenzene resin chloromethylation of step 1), chloromethylation low cross-linking macropore polyphenyl is obtained
Ethylene-divinylbenzene resins；
3) step 2) resulting material is extracted 10-20 hours through Soxhlet extractor, 50~70 times of weight resin of first is then added
Benzene, 1~5 times of weight resin of 3- amino -6- cyanopyridine and 2~4 times of weight resin of sodium carbonate, react at 55~95 DEG C
8~20 hours, obtain yellow 3- amino -6- cyanopyridine chelating resin；
4) hydroxylamine hydrochloride will be added, and with ethanol as solvent after step 3) resulting resin washing, react 5 at 50-90 DEG C~
30 hours, drying is filtered and washed, obtains faint yellow amidoxime group pyridine chelating resin, wherein the quality dosage of hydroxylamine hydrochloride is
1~5 times of weight resin.
5. the preparation method according to claim 4, it is characterised in that: step 1) is to do monomer, divinyl using styrene
Benzene makees crosslinking agent, and at least one of polyvinylpyrrolidone or polyethylene glycol make pore-foaming agent, magnesium hydroxide, methylcellulose or
At least one of hydroxypropyl methyl cellulose makees dispersing agent, and cumyl peroxide makees initiator, using suspension polymerization, system
Standby low crosslinking degree macropore styrene benzene copolymer, then solvent extraction, removes remaining pore-foaming agent in product resin duct, then pass through
It crosses pneumatic conveying drying and obtains low cross-linking macroporous polystyrene-divinylbenzene resins, abbreviation Archon.
6. preparation method according to claim 5, it is characterised in that: solvent extraction solvent for use is chloroform, ethyl alcohol or boiling
The petroleum ether that journey is 60-90 DEG C.
7. preparation method according to claim 5, it is characterised in that: in step 1), the quality dosage of crosslinking agent is monomer
With the 5~10% of crosslinking agent quality total amount；The quality dosage of pore-foaming agent is the 50~90% of monomer mass；The quality of initiator is used
Amount is the 2.5~4% of monomer, crosslinking agent and pore-foaming agent quality total amount；The quality dosage of dispersing agent is the 2~8% of monomer mass；
When solvent extraction, the volume of solvent is 10~20 times of reaction product volume, low cross-linking macroporous polystyrene-divinyl obtained
Benzene cross-linkage of resin is 3~8%.
8. preparation method according to claim 5, it is characterised in that: step 1) includes the following steps:
1.1) monomer, crosslinking agent and pore-foaming agent are mixed；
1.2) dispersing agent is dissolved in water, and is mixed with step 1.1) resulting material, initiator is then added, adjustment mixing speed makes
Oil droplet size is 0.5~1mm, then is successively proceeded as follows: being gradually warming up to 75 DEG C with the speed of 1 DEG C/5min, keeps the temperature 2h；
80 DEG C are gradually warming up to the speed of 1 DEG C/5min, keeps the temperature 2h；90 DEG C are gradually warming up to the speed of 1 DEG C/5min, keeps the temperature 5h；
95 DEG C are gradually warming up to the speed of 1 DEG C/5min, keeps the temperature 5h, end of reaction filters out resin, is first washed, dried with hot water, then
It is packed into Soxhlet extractor, carries out solvent extraction, then pneumatic conveying drying, sieving obtains low cross-linking macroporous polystyrene-divinylbenzene tree
Rouge.
9. preparation method according to claim 8, it is characterised in that: in step 2), the control reaction time is 8~25 small
When, obtain the chlorine ball that chlorinity is 15~21%.
10. preparation method according to claim 5, it is characterised in that: step 2) is that Archon is soaked in its weight 8-20
In chloromethyl ether again, the anhydrous zinc chloride that the 2-15% of Archon weight is added makees catalyst, and chloromethane is carried out at a temperature of 30-50 DEG C
Glycosylation reaction filters out resin sphere, is washed in most resin and remained with water or ethyl alcohol until chlorinity reaches 12% or more stopping reaction
Chlorination mother solution, pneumatic conveying drying obtains chloromethylation low cross-linking macroporous polystyrene-divinylbenzene resins, abbreviation chlorine ball.
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| CN113004456A (en) * | 2021-03-11 | 2021-06-22 | 深圳市先进高分子材料合成研发有限公司 | Styrene-based monomer-based hydrophilic heavy metal ion chelating copolymer resin and synthetic method thereof |
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