CN105859962A - Preparation method and application of cross-linked resin modified by imidazole - Google Patents
Preparation method and application of cross-linked resin modified by imidazole Download PDFInfo
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- CN105859962A CN105859962A CN201610402371.1A CN201610402371A CN105859962A CN 105859962 A CN105859962 A CN 105859962A CN 201610402371 A CN201610402371 A CN 201610402371A CN 105859962 A CN105859962 A CN 105859962A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- 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
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J2339/00—Characterised by the use of homopolymers or 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
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Abstract
The invention discloses a preparation method and application of cross-linked resin modified by imidazole. The preparation method of cross-linked modified by imidazole comprises the steps that a vinyl-containing imidazole monomer, a divinylbenzene cross-linking agent, an initiator, an o-xylene and/or benzyl alcohol pore-forming agent and a dispersing agent are subjected to suspension polymerization to obtain precursor resin; the precursor resin is subjected to a Friedel-Crafts reaction under the Lewis acid catalytic action, and the cross-linked resin modified by imidazole with the high specific surface area, large pore volume and the proper pore structure and polarity is obtained. The resin is particularly applicable to adsorbing small polar molecular aromatic organic compounds in water. In addition, the preparation method of the cross-linked resin modified by imidazole is simple, low in cost and capable of achieving industrial production.
Description
Technical field
The present invention relates to the preparation method and application of a kind of rear crosslinked resin, hand over after modifying particularly to a kind of imidazoles
The preparation method and application of connection resin, belongs to functional polymer synthesis technical field.
Background technology
Early 1970s, Davankov etc. is reacted line polystyrene or low by Friedel-Crafts
Crosslinked polystyrene cross-links and has synthesized a class formation uniqueness, the porous polymer of function admirable, and this kind of porous is gathered
The crosslinking degree of compound is higher, is also called rear crosslinked resin.It is big, flat that rear crosslinked resin is generally of specific surface area
All architectural features such as aperture is little, pore-size distribution is narrow, mechanical strength is good, at present poisonous organic wastewater improvement,
The fields such as separation that store of gas show wide application prospect.Crosslinking tree after tradition preparation Davankov type
Fat frequently with chloromethyl methyl ether as chloromethylation reagents, but chloromethyl methyl ether have intense stimulus, severe toxicity,
, in use there is the more serious potential safety hazard of ratio in the shortcoming such as volatile and carcinogenic, crosslinking tree after being unfavorable for
The actual industrial metaplasia of fat is produced and application.After the production in crosslinked resin, in order to avoid using chloromethyl methyl ether,
Ando etc. utilize Friedel-Crafts to react, by the suspended double bond of initial self remnants of poly-divinylbenzene in catalysis
Under the effect of agent, phenyl ring adjacent thereto crosslinks, thus realizes the self-crosslinking of polymer, is prepared as hanging
Hang crosslinked resin after double bond.Adsorbent resin prepared by this method has bigger specific surface area, fine and close hole knot
Structure and microcellular structure are considerable, therefore have good absorbability to aromatic.
Organic chemical waste water usually contains the organic pollution of great amount of soluble, such as aromatic carboxylic acids, LOMAR PWA EINECS 246-676-2, benzene
Sulfonic acid etc., rely solely on macroporous adsorbent resin and rear cross-linked adsorbing resin that hydrophobic interaction is primary attachment motive force
It is difficult to process.In order to increase the hydrophilic of resin, researcher proposes a series of Improving Measurements, is included in
Before Friedel-Crafts reaction or after reaction, resin is chemically modified, uses polar monomer directly to carry out copolymerization
Prepare presoma resin.Chinese patent (Authorization Notice No. ZL CN103910823A) discloses a kind of ester group
The preparation method of crosslinked resin after modification；Chinese patent (Authorization Notice No. ZL CN104910313A) is open
A kind of amido modify after the preparation method of cross-linking type adsorbent resin；Chinese patent (Authorization Notice No. ZL
CN104693336A) preparation method of crosslinked resin after a kind of sulfonic group is modified is disclosed.Tree is cross-linked after these
The a number of ester group of area load of fat, amido, sulfonic group etc., improve the absorption to polar contaminants.
Their absorption property result shows, this resinoid to low pole or polar substances (such as: phenol, resorcinol,
Bisphenol-A) there is certain absorbability, but adsorption effect is the most very good.
The porous of adsorbent resin, derives from the pore method in its building-up process.Porogen is that a class is not involved in
Polyreaction, but it is wrapped in the atent solvent in polymer or Linear Polymer polymerization after completion of the polymerization reaction
Thing, it during polymerization relative to the effect of template.After polyreaction completes, often through surname extraction
Porogen is removed by device extracting and the method such as solvent distillation, thus gives the abundant pore passage structure of polymer, higher
Specific surface area and bigger pore volume.According to the difference of porogen character, porogen is broadly divided into good solvent, non-
Good solvent and linear polymer and their mixed type porogen.Wherein, good solvent be can be polymerized monomer
Miscible, again can the organic solvent of swollen polymer polymers.Benzene, toluene, Nitrobenzol, o-Dimethylbenzene, two chloroethenes
Alkane is the good solvent of polystyrene.Poor solvent is can be miscible with the monomer being polymerized, but having insoluble in polymer
Machine solvent.Poor solvent conventional during production of resins has alkane, fatty alcohol, fatty acid, gasoline, liquid
Paraffin etc..It addition, the linear polymers such as polystyrene, polypropylene glycol, polyvinyl acetate and polyacrylate
Also can be used as the porogen of resin.In the building-up process of resin, different types of porogen and consumption thereof are to tree
The pore volume of fat and specific surface area have significant difference.
Summary of the invention
For the defect that existing rear crosslinked resin is undesirable to polar organic matter matter absorption property in water, the present invention's
Purpose is to be to provide one to prepare specific surface area is higher and pore volume is relatively big, and has suitable pore structure and polarity,
It is particularly well-suited to crosslinked resin after the novel imidazole modification of polar micromolecules armaticity organic compound in absorption water
Method, the method is simple to operate, low cost, can meet industrialized production.
Another object of the present invention be to provide described imidazoles to modify after crosslinked resin at selective absorption water
The application in terms of polar micromolecules armaticity organic compound in solution, particularly Pyrogentisinic Acid, resorcinol or
Bisphenol-As etc. are easy eluting after having selective absorbing effect, and absorption, and resin can be reused, and repeats
Using effect is good.
The invention provides the preparation method of crosslinked resin after a kind of imidazoles is modified, the method is by containing vinyl miaow
Azole monomer, divinylbenzene crosslink agent, initiator, o-Dimethylbenzene and/or benzyl alcohol porogen and dispersant lead to
Cross suspension polymerisation, obtain presoma resin；Described presoma resin, under Louis acid catalysis effect, is carried out
Friedel-Crafts reacts, and obtains crosslinked resin after imidazoles is modified.
The technical scheme is that the synthesis to existing rear crosslinked resin improves, rear friendship of the prior art
Although connection resin Pyrogentisinic Acid, resorcinol or bisphenol-A isopolarity little molecule armaticity organic compound have one
Fixed adsorption, but absorption property poor (equilibrium adsorption capacity is little, absorption reaches balance and requires time for long etc.)；
Main cause is: (1) resin crosslinks degree is too high, causes a crosslinked resin internal existence part the finest and close
Pore structure, can only hold the little gas molecule of molecular dimension (such as: N2, Ar etc.) diffuse into, and molecule
Relatively large sized material (such as polar micromolecules armaticity Organic substance) can not spread into, therefore causes surpassing
High-polystyrene class crosslinked resin absorption property organic to polar micromolecules armaticity is poor.(2) existing
Rear crosslinked resin only chlorine by residual replaces modification polar group, and the modification amount of polar group is little, polarity
Modification power is limited.Technical scheme passes through copolymerization process, will contain vinyl imidazole class monomer and introduce two
In vinyl benzene crosslinked resin, its outstanding feature having is: on the one hand, modifies pole in crosslinked resin structure
Property suitable imidazole group, the polarity that imidazole group has and phenol and diphenols compound isopolarity aryl chemical combination
Thing has preferable matching, shows preferable selective absorption and strengthens absorbability；On the other hand,
Vinyl containing vinyl imidazole class monomer participates in copolymerization, and imidazole group is modified on main polymer chain, reduces
The tight pore structure formed during resin crosslinks so that it is pore structure is improved, beneficially molecular weight is relative
Bigger polar micromolecules armaticity Organic substance diffuses into inside crosslinked resin, is conducive to improving crosslinked resin
Absorption property.Secondly, technical scheme have employed special porogen, the o-Dimethylbenzene of employing and benzene
Methanol pore creating material and phenol and diphenol compound etc. have closer space structure, and the hole pore size made more connects
It is bordering on phenol and diphenols compound equimolecular size, is more beneficial for diffusing into of phenol and diphenols compound etc.
Enter polymeric inner, on the other hand, the o-Dimethylbenzene of employing and benzyl alcohol pore creating material safety, environmental protection, take completely
For prior art uses the porogen such as the bigger benzene of toxicity, toluene.
The method of crosslinked resin after imidazoles is modified of preparing of the present invention also includes following preferred version:
Preferably scheme, the mass percent containing vinyl imidazole class monomer and divinylbenzene crosslink agent consists of
(5%～30%): (70%～95%).Preferably scheme, imidazole group can carry out appointing in the larger context
Meaning regulation, the polarity of crosslinked resin after can modifying with Effective Regulation imidazoles, and the hole knot of regulation and control crosslinked resin
Structure, considerably increases absorbability organic to polar micromolecules armaticity.
More preferably scheme, the class monomer containing vinyl imidazole be 1-vinyl imidazole, 2-methyl isophthalic acid-vinyl imidazole,
At least one in 2-ethyl-1-vinyl imidazole.
Preferably scheme, the quality of o-Dimethylbenzene and/or benzyl alcohol porogen be containing vinyl imidazole class monomer with
The 100%～300% of divinylbenzene crosslink agent gross mass.Porogen on the one hand as solvent, on the other hand conduct
Porogen.
Preferably scheme, lewis acid consumption is the class unit mole Han vinyl imidazole in presoma resin used
120～140%.
Preferably scheme, lewis acid is FeCl3、ZnCl2、AlCl3、TiCl4Or SnCl4In at least one
Kind.
Preferably scheme, the BET specific surface area of presoma resin is 500～700m2/ g, pore volume is 0.8～1.5
cm3/ g, average pore size is 5～10nm.
Preferably scheme, Friedel-Crafts reaction is to react 8～16h at a temperature of 80～85 DEG C.
More preferably scheme, after the imidazoles modification that Friedel-Crafts reaction generates, the BET of crosslinked resin compares table
Area is 700～1000m2/ g, pore volume is 1.2～2.2cm3/ g, average pore size is 6～9nm.
Present invention also offers the application of crosslinked resin after described imidazoles is modified, crosslinking tree after being modified by described imidazoles
The little molecular polarity armaticity organic compound that fat is applied in selective absorption water.
Preferably scheme, little molecular polarity armaticity organic compound is in phenol, resorcinol, bisphenol-A
At least one.
Preferably scheme, after having adsorbed the imidazoles modification of little molecular polarity armaticity organic compound, crosslinked resin is adopted
With sodium hydroxide/ethyl alcohol mixed solution (volume fraction of ethanol is 20%, and naoh concentration is 0.01mol/L)
It is desorbed as desorbing agent.
The preparation of crosslinked resin after the imidazoles modification of the present invention, including step in detail below:
1) preparation of presoma resin:
With containing vinyl imidazole class monomer for polymerization monomer, divinylbenzene as cross-linking agent, azo isobutyronitrile for cause
Agent, in aqueous phase, suspension polymerisation prepares presoma resin；Specifically comprise the following steps that aqueous phase (distilled water 180mL,
Mass fraction is polyvinyl alcohol 20mL, the methylene blue few drops of 1%) in, add oil phase (monomer, cross-linking agent,
Initiator and porogen), it is heated to 45 DEG C, regulates mixing speed, control oil droplet size, stirring also slowly rises
Temperature is to 68～75 DEG C, after reaction 2～5h, reacts 2～5h at 78～85 DEG C, then is warming up to 90～95 DEG C, enter
Single step reaction 2～5h；After having reacted, products therefrom is washed with hot water, cold water, then uses petroleum ether respectively
Apparatus,Soxhlet's extracts, is vacuum dried 24h, prepared presoma resin, prepared presoma tree
Fat (when polar monomer is 1-vinyl imidazole, is abbreviated as PDV-X-Y；Polar monomer is 2-methyl isophthalic acid-ethylene
During base imidazoles, it is abbreviated as PDMV-X-Y；When polar monomer is 2-ethyl-1-vinyl imidazole, it is abbreviated as
PDEV-X-Y；Wherein, X is the mass percent of cross-linking agent divinylbenzene；Y is benzyl alcohol in porogen
Mass percent) BET specific surface area be 500～700m2/ g, pore volume is 0.8～1.5cm3/ g, average hole
Footpath is 5～10nm；Sieve 20～40 mesh, standby；Wherein, containing vinyl imidazole class monomer and divinylbenzene
Mass percent is 5%:95%～30%:70%；The class monomer containing vinyl imidazole is 1-vinyl imidazole, 2-methyl
At least one in-1-vinyl imidazole, 2-ethyl-1-vinyl imidazole；
2) Friedel-Crafts reaction:
Presoma resin is joined 1, in 2-dichloroethanes, swelling overnight after, add at a temperature of 35 DEG C～45 DEG C
Enter lewis acid and make catalyst, stir to after being completely dissolved, be warming up to 80～85 DEG C, and carry out at this temperature
Friedel-Crafts reaction 8～16h, terminates reaction with dehydrated alcohol, pours out reaction mother liquor, with mass fraction be
Alternately washing 3～5 times of the aqueous hydrochloric acid solution of 1% and dehydrated alcohol, and extract 8～24h with dehydrated alcohol, obtain
Crosslinked resin (being abbreviated as PDV-X-Y-pc, PDV-X-Y-pc or PDV-X-Y-pc) after imidazoles modification；
Described lewis acid is FeCl3、ZnCl2、AlCl3、TiCl4Or SnCl4In at least one；Described
The amount that lewis acid consumption is presoma resin medium vinyl imidazoles material used 120～140%；
After described imidazoles modification, the BET specific surface area of crosslinked resin is 700～1000m2/ g, pore volume is
1.2～2.2cm3/ g, average pore size is 6～9nm.
Hinge structure, the Advantageous Effects that technical scheme is brought:
1) technical scheme of the present patent application is by introducing in modified resins in divinylbenzene class crosslinked resin
Containing vinyl imidazole class unit；On the one hand, crosslinked resin structure is modified the imidazole group that polarity is suitable, miaow
The polarity that oxazolyl group has has preferable matching with phenol and diphenols compound isopolarity aryl compound,
Show preferable selective absorption and strengthen absorbability；On the other hand, containing vinyl imidazole class monomer
Vinyl participates in copolymerization, and imidazole group is modified on main polymer chain, is formed during decreasing resin crosslinks
Tight pore structure so that it is pore structure is improved, polar micromolecules that beneficially molecular weight is relatively large fragrance
Property Organic substance diffuses into inside crosslinked resin, is conducive to improving the absorption property of crosslinked resin.Overcome existing
The rear crosslinked resin reported in technology exists polar contaminants (such as: phenol, resorcinol or bisphenol-A)
The defect that adsorption effect is undesirable.
2) technical scheme have employed porogen preferably, and o-Dimethylbenzene and the benzyl alcohol of employing are made
Hole agent and phenol and diphenol compound etc. have closer space structure, and the hole pore size made is closer to benzene
Phenol and diphenols compound equimolecular size, be more beneficial for phenol and diphenols compound etc. diffuses into polymerization
Inside thing, on the other hand, the o-Dimethylbenzene of employing and benzyl alcohol pore creating material safety, environmental protection, replace existing completely
Technology uses the porogen such as benzene, toluene that toxicity is bigger.
3) technical scheme imidazole group can the most arbitrarily regulate, Ke Yiyou
The polarity of crosslinked resin after effect regulation and control imidazoles modification, and the pore structure of regulation and control crosslinked resin, considerably increase
Absorbability organic to polar micromolecules armaticity.
4) vinyl imidazole monomer is obtained by the method for suspension polymerisation by technical scheme with divinylbenzene
To presoma resin, the outstanding feature of prepared presoma resin is: vinyl remaining in resin can enter
Row Friedel-Crafts post-crosslinking reaction, significantly improves the specific surface area of resin.
5) after the imidazoles of the present invention is modified, after crosslinked resin absorption, eluting is easy, reusable, reuses
Effective, can be widely applied to the fields such as chemical analysis, medical separation purification, environmental pollution improvement.
6) after the imidazoles modification that prepared by the present invention, the method for crosslinked resin is simple, cost is relatively low, can be with industrialization
Produce.
Accompanying drawing explanation
[Fig. 1] be in the embodiment of the present invention 1 imidazoles modify after crosslinked resin PDV-90%-0%-pc,
The infrared spectrogram of PDV-90%-75%-pc and PDV-80%-0%-pc.
[Fig. 2] is presoma resin PDV-90%-0% and corresponding rear crosslinked resin in the embodiment of the present invention 1
The graph of pore diameter distribution (a) of PDV-90%-0%-pc；Use rear crosslinked resin prepared by different porogen
The graph of pore diameter distribution (b) of PDV-90%-0%-pc, PDV-90%-25%-pc and PDV-90%-100%-pc.
[Fig. 3] is the impact of resin Pyrogentisinic Acid's equilibrium adsorption capacity of the different degrees of cross linking of preparation in the embodiment of the present invention 1
(a): [(A): PDV-95%-0%, PDV-95%-0%-pc；(B): PDV-90%-0%, PDV-90%-0%-pc；
(C): PDV-85%-0%, PDV-85%-0%-pc；: PDV-80%-0%, PDV-80%-0%-pc] and adopt (D)
The impact (b) of the resin Pyrogentisinic Acid's adsorbance prepared with different porogen [(A): PDV-90%-100%,
PDV-90%-100%-pc；(B): PDV-90%-75%, PDV-90%-75%-pc；(C): PDV-90%-50%,
PDV-90%-50%-pc；(D): PDV-90%-25%, PDV-90%-25%-pc；(E): PDV-90%-0%,
PDV-90%-0%-pc].
[Fig. 4] is crosslinked resin (a) after the imidazoles prepared in the embodiment of the present invention 1 is modified: [PDV-95%-0%-pc,
PDV-90%-0%-pc, PDV-85%-0%-pc, PDV-80%-0%-pc] and (b): [PDV-90%-0%-pc,
PDV-90%-25%-pc and PDV-90%-100%-pc] Pyrogentisinic Acid adsorption isotherm absorption figure.
[Fig. 5] is (a) of the embodiment of the present invention 1 preparation: [PDV-90%-0% and PDV-90%-0%-pc] and (b)
[PDV-85%-0% and PDV-85%-0%-pc] Pyrogentisinic Acid's adsorption dynamics adsorption kinetics.
[Fig. 6] is the dynamic adsorption-desorption figure of the PDV-90%-0%-pc Pyrogentisinic Acid of the embodiment of the present invention 1 preparation.
[Fig. 7] be the embodiment of the present invention 1 preparation PDV-90%-0%-pc Pyrogentisinic Acid absorption reuse result.
Detailed description of the invention
Following example are intended to further illustrate present invention rather than to the claims in the present invention protection domain
Restriction.
Embodiment 1
1) preparation of presoma resin:
On the water bath device equipped with mechanical agitator, condensing tube and thermometer, place tri-mouthfuls of round bottoms of 500mL
Flask, be initially charged aqueous phase (distilled water 180mL, mass fraction be 1% polyvinyl alcohol 20mL, methylene blue
5), rear addition 20g divinylbenzene (DVB) and the mixture of 1-vinyl imidazole (VIM), 40g
O-Dimethylbenzene and the mixed solvent of benzyl alcohol, azodiisobutyronitrile (AIBN) 0.2g.It is heated to 45 DEG C, adjusts
Joint stirs 30min to suitable mixing speed, is warming up to 75 DEG C of reaction 3h, is warming up to 85 DEG C of reaction 3h,
It is continuously heating to 95 DEG C of reaction 3h.After cooling, replace washing resin with dehydrated alcohol, hot water, cold water successively
Clarify to cleaning mixture, in apparatus,Soxhlet's, extract 12h with petroleum ether, be vacuum dried 24h, obtain presoma
Resin PDV-90%-0%, PDV-90%-25% and PDV-90%-100%.
2) Friedel-Crafts reaction:
Dry three neck round bottom flask is separately added into 15g presoma resin PDV-90%-0%,
PDV-90%-25% and PDV-90%-100% and 50mL 1,2-dichloroethanes, room temperature lower seal is swelling overnight.
Load onto reflux condensing tube and motor stirrer, add 3.0g FeCl3Make catalyst, moderate-speed mixer 30min.Rise
Warm to 85 DEG C, back flow reaction 10h.Stop heating, terminate reaction with 50mL dehydrated alcohol, filter resin,
Replace washing resin with the aqueous hydrochloric acid solution that dehydrated alcohol, mass fraction are 1% successively to clarify to cleaning mixture, put
Enter in apparatus,Soxhlet's and extract 12h with dehydrated alcohol.Vacuum drying 24h, obtains crosslinked resin after imidazoles is modified
PDV-90%-0%-pc, PDV-90%-25%-pc and PDV-90%-100%-pc, Infrared Characterization as it is shown in figure 1,
After Friedel-Crafts reaction, the stretching vibration absworption peak 1630cm that suspended double bond C=C key is corresponding-1Substantially subtract
Weak, this shows that suspended double bond significantly reduces after Friedel-Crafts alkylated reaction, and suspended double bond take part in
Friedel-Crafts alkylated reaction.
The BET specific surface area of the presoma resin PDV-90%-0% of preparation is 660m2/ g, pore volume is 0.98
cm3/ g, average pore size is 6.0nm.The BET of crosslinked resin PDV-90%-0%-pc after the imidazoles modification of preparation
Specific surface area is 936m2/ g, pore volume is 2.08cm3/ g, average pore size is 8.9nm.
The BET specific surface area of the presoma resin PDV-90%-25% of preparation is 582m2/ g, pore volume is 1.49
cm3/ g, average pore size is 10.2nm.Crosslinked resin PDV-90%-25%-pc after the imidazoles modification of preparation
BET specific surface area is 741m2/ g, pore volume is 1.68cm3/ g, average pore size is 9.0nm.
The BET specific surface area of the presoma resin PDV-90%-100% of preparation is 647m2/ g, pore volume is 0.95
cm3/ g, average pore size is 5.9nm.Crosslinked resin PDV-90%-100%-pc after the imidazoles modification of preparation
BET specific surface area is 712m2/ g, pore volume is 1.21cm3/ g, average pore size is 6.8nm.
After the imidazoles modification of embodiment 1 preparation in the isothermal adsorption of crosslinked resin Pyrogentisinic Acid,
The maximal absorptive capacity of PDV-90%-0%-pc, PDV-90%-25%-pc and PDV-90%-100%-pc Pyrogentisinic Acid
It is respectively 170,151,184mg/g, and absorption is quickly, absorption can be made in 30min to reach balance.
After the imidazoles of embodiment 1 preparation is modified, crosslinked resin Pyrogentisinic Acid's solution circulates for 5 times through adsorption-desorption,
PDV-90%-0%-pc resin still has the repeat usage of more than 77.8%.In actual applications, this resin is permissible
Reuse repeatedly.
Embodiment 2
1) preparation of presoma resin:
On the water bath device equipped with mechanical agitator, condensing tube and thermometer, place tri-mouthfuls of round bottoms of 500mL
Flask, be initially charged aqueous phase (distilled water 180mL, mass fraction be 1% polyvinyl alcohol 20mL, methylene blue
5), the rear mixing adding 20g divinylbenzene (DVB) and 2-methyl isophthalic acid-vinyl imidazole (MVIM)
Thing；, 60.0g o-Dimethylbenzene and the mixed solvent of benzyl alcohol, azodiisobutyronitrile (AIBN) 0.2g.Heating
To 45 DEG C, it is adjusted to suitable mixing speed stirring 30min, is warming up to 68 DEG C of reaction 5h, is warming up to 78 DEG C
Reaction 5h, is continuously heating to 90 DEG C of reaction 5h.After cooling, hand over dehydrated alcohol, hot water, cold water successively
Clarify for washing resin to cleaning mixture, in apparatus,Soxhlet's, extract 12h with petroleum ether, be vacuum dried 24h,
Obtain presoma resin PDMV-95%-20%, PDMV-85%-50% and PDMV-70%-80%.
2) Friedel-Crafts reaction:
Dry three neck round bottom flask is separately added into 15g presoma resin PDMV-95%-20%,
PDMV-85%-50% and PDMV-70%-80% and 80mL 1,2-dichloroethanes, the swelling mistake of room temperature lower seal
Night.Load onto reflux condensing tube and motor stirrer, be separately added into 1.2,3.6,10.8g AlCl3Make catalyst,
Moderate-speed mixer 30min.It is warming up to 83 DEG C, back flow reaction 16h.Stop heating, use 50mL dehydrated alcohol
Terminate reaction, filter resin, successively with the aqueous hydrochloric acid solution that dehydrated alcohol, mass fraction are 1% alternately washing
Resin is clarified to cleaning mixture, puts in apparatus,Soxhlet's and extracts 12h with dehydrated alcohol.Vacuum drying 24h,
To imidazoles modify after crosslinked resin PDMV-95%-20%-pc, PDMV-85%-50%-pc and
PDMV-70%-80%-pc.
The BET specific surface area of the presoma resin PDMV-95%-20% of preparation is 510m2/ g, pore volume is 0.80
cm3/ g, average pore size is 10.0nm.Crosslinked resin PDMV-95%-20%-pc after the imidazoles modification of preparation
BET specific surface area is 713m2/ g, pore volume is 1.68cm3/ g, average pore size is 7.9nm.
The BET specific surface area of the presoma resin PDMV-85%-50% of preparation is 536m2/ g, pore volume is 1.21
cm3/ g, average pore size is 9.2nm.Crosslinked resin PDMV-85%-50%-pc after the imidazoles modification of preparation
BET specific surface area is 841m2/ g, pore volume is 1.43cm3/ g, average pore size is 8.1nm.
The BET specific surface area of the presoma resin PDMV-70%-80% of preparation is 618m2/ g, pore volume is 0.85
cm3/ g, average pore size is 7.5nm.Crosslinked resin PDMV-70%-80%-pc after the imidazoles modification of preparation
BET specific surface area is 785m2/ g, pore volume is 1.41cm3/ g, average pore size is 7.8nm.
The imidazoles of embodiment 2 preparation modify after crosslinked resin in the isothermal adsorption of resorcinol,
PDMV-95%-20%-pc, PDMV-85%-50%-pc and PDMV-70%-80%-pc are to resorcinol
Big adsorbance is respectively 86,91,104mg/g, and absorption is quickly, and absorption can be made in 60min to reach flat
Weighing apparatus.
After the imidazoles modification of embodiment 2 preparation, crosslinked resin PDMV-70%-80%-pc is to resorcinol solution warp
Crossing 5 circulations of adsorption-desorption, the repeat usage of resin still has 87.2%.In actual applications, this resin
Can reuse repeatedly.
Embodiment 3
1) preparation of presoma resin:
On the water bath device equipped with mechanical agitator, condensing tube and thermometer, place tri-mouthfuls of round bottoms of 500mL
Flask, be initially charged aqueous phase (distilled water 180mL, mass fraction be 1% polyvinyl alcohol 20mL, methylene blue
5), the rear mixing adding 20g divinylbenzene (DVB) and 2-ethyl-1-vinyl imidazole (EVIM)
Thing, 20.0g o-Dimethylbenzene and the mixed solvent of benzyl alcohol, azodiisobutyronitrile (AIBN) 0.2g.Heating
To 45 DEG C, it is adjusted to suitable mixing speed stirring 30min, is warming up to 68 DEG C of reaction 5h, is warming up to 78 DEG C
Reaction 5h, is continuously heating to 90 DEG C of reaction 5h.After cooling, hand over dehydrated alcohol, hot water, cold water successively
Clarify for washing resin to cleaning mixture, in apparatus,Soxhlet's, extract 12h with petroleum ether, be vacuum dried 24h,
Obtain presoma resin PDEV-90%-90%, PDEV-80%-60% and PDEV-70%-30%.
2) Friedel-Crafts reaction:
Dry three neck round bottom flask is separately added into 15g presoma resin PDEV-90%-90%,
PDEV-80%-60% and PDEV-70%-30% and 60mL 1,2-dichloroethanes, room temperature lower seal is swelling overnight.
Load onto reflux condensing tube and motor stirrer, be separately added into 6.3,4.2,2.1g TiCl4Make catalyst, middling speed
Stirring 30min.It is warming up to 82 DEG C, back flow reaction 12h.Stop heating, terminate with 50mL dehydrated alcohol
Reaction, filters resin, replaces washing resin with the aqueous hydrochloric acid solution that dehydrated alcohol, mass fraction are 1% successively
Clarify to cleaning mixture, put in apparatus,Soxhlet's and extract 12h with dehydrated alcohol.Vacuum drying 24h, obtains miaow
Azoles modify after crosslinked resin PDEV-90%-90%-pc, PDEV-80%-60%-pc and
PDEV-70%-30%-pc.
The BET specific surface area of the presoma resin PDEV-90%-90% of preparation is 680m2/ g, pore volume is 0.96
cm3/ g, average pore size is 9.3nm.Crosslinked resin PDEV-90%-90%-pc after the imidazoles modification of preparation
BET specific surface area is 983m2/ g, pore volume is 1.88cm3/ g, average pore size is 8.8nm.
The BET specific surface area of the presoma resin PDEV-80%-60% of preparation is 613m2/ g, pore volume is 1.75
cm3/ g, average pore size is 10.4nm.Crosslinked resin PDEV-80%-60%-pc after the imidazoles modification of preparation
BET specific surface area is 926m2/ g, pore volume is 2.16cm3/ g, average pore size is 7.2nm.
The BET specific surface area of the presoma resin PDEV-70%-30% of preparation is 711m2/ g, pore volume is 1.43
cm3/ g, average pore size is 8.9nm.Crosslinked resin PDEV-70%-30%-pc after the imidazoles modification of preparation
BET specific surface area is 998m2/ g, pore volume is 2.19cm3/ g, average pore size is 6.4nm.
The imidazoles of embodiment 3 preparation modify after crosslinked resin in the isothermal adsorption of resorcinol,
PDEV-90%-90%-pc, PDEV-80%-60%-pc and PDEV-70%-30%-pc are to resorcinol
Big adsorbance is respectively 106,121,143mg/g, and absorption is quickly, and absorption can be made in 40min to reach
Balance.
After the imidazoles modification of embodiment 3 preparation, crosslinked resin PDEV-90%-90%-pc is to resorcinol solution warp
Crossing 5 circulations of adsorption-desorption, the repeat usage of resin is more than 93.2%.In actual applications, resin can
To reuse repeatedly.
Embodiment 4
1) preparation of presoma resin:
On the water bath device equipped with mechanical agitator, condensing tube and thermometer, place tri-mouthfuls of round bottoms of 500mL
Flask, be initially charged aqueous phase (distilled water 180mL, mass fraction be 1% polyvinyl alcohol 20mL, methylene blue
5), rear addition 20g divinylbenzene (DVB) and the mixture of 1-vinyl imidazole (VIM), 20g
O-Dimethylbenzene and the mixed solvent of benzyl alcohol, azodiisobutyronitrile (AIBN) 0.2g.It is heated to 45 DEG C, adjusts
Joint stirs 30min to suitable mixing speed, is warming up to 72 DEG C of reaction 3h, is warming up to 82 DEG C of reaction 3h,
It is continuously heating to 92 DEG C of reaction 3h.After cooling, replace washing resin with dehydrated alcohol, hot water, cold water successively
Clarify to cleaning mixture, in apparatus,Soxhlet's, extract 12h with petroleum ether, be vacuum dried 24h, obtain presoma
Resin PDV-75%-50%, PDV-85%-50% and PDV-95%-50%.
2) Friedel-Crafts reaction:
Dry three neck round bottom flask is separately added into 16g presoma resin PDV-75%-50%,
PDV-85%-50% and PDV-95%-50% and 70mL 1,2-dichloroethanes, room temperature lower seal is swelling overnight.
Load onto reflux condensing tube and motor stirrer, be separately added into 7.0,5.2,1.4g SnCl4Make catalyst, in
Speed stirring 30min.It is warming up to 83 DEG C, back flow reaction 15h.Stop heating, with 60mL dehydrated alcohol eventually
Only reaction, filters resin, alternately washs tree with the aqueous hydrochloric acid solution that dehydrated alcohol, mass fraction are 1% successively
Fat is clarified to cleaning mixture, puts in apparatus,Soxhlet's and extracts 12h with dehydrated alcohol.Vacuum drying 24h, obtains
Crosslinked resin PDV-75%-50%-pc, PDV-85%-50%-pc and PDV-95%-50%-pc after imidazoles modification.
The BET specific surface area of the presoma resin PDV-75%-50% of preparation is 563m2/ g, pore volume is 1.28
cm3/ g, average pore size is 9.1nm.The BET of crosslinked resin PDV-75%-50%-pc after the imidazoles modification of preparation
Specific surface area is 866m2/ g, pore volume is 1.54cm3/ g, average pore size is 8.3nm.
The BET specific surface area of the presoma resin PDV-85%-50% of preparation is 591m2/ g, pore volume is 1.36
cm3/ g, average pore size is 8.4nm.The BET of crosslinked resin PDV-85%-50%-pc after the imidazoles modification of preparation
Specific surface area is 786m2/ g, pore volume is 1.76cm3/ g, average pore size is 8.3nm.
The BET specific surface area of the presoma resin PDV-95%-50% of preparation is 643m2/ g, pore volume is 1.45
cm3/ g, average pore size is 9.7nm.The BET of crosslinked resin PDV-95%-50%-pc after the imidazoles modification of preparation
Specific surface area is 875m2/ g, pore volume is 1.46cm3/ g, average pore size is 7.9nm.
The imidazoles of embodiment 4 preparation modify after crosslinked resin in the isothermal adsorption of bisphenol-A,
PDV-75%-50%-pc, PDV-85%-50%-pc and PDV-95%-50%-pc maximum adsorption to bisphenol-A
Amount is respectively 118,139,155mg/g, and absorption is quickly, and absorption can be made in 50min to reach balance.
After the imidazoles of embodiment 4 preparation is modified, bisphenol-A solution is passed through by crosslinked resin PDV-75%-50%-pc
5 circulations of adsorption-desorption, still have more than 91.2% repeat usage.In actual applications, this resin is permissible
Reuse repeatedly.
Embodiment 5
1) preparation of presoma resin:
On the water bath device equipped with mechanical agitator, condensing tube and thermometer, place tri-mouthfuls of round bottoms of 500mL
Flask, be initially charged aqueous phase (distilled water 180mL, mass fraction be 1% polyvinyl alcohol 20mL, methylene blue
5), the rear mixing adding 20g divinylbenzene (DVB) and 2-methyl isophthalic acid-vinyl imidazole (MVIM)
Thing；, 60.0g o-Dimethylbenzene and the mixed solvent of benzyl alcohol, azodiisobutyronitrile (AIBN) 0.2g.Heating
To 45 DEG C, it is adjusted to suitable mixing speed stirring 30min, is warming up to 72 DEG C of reaction 3h, is warming up to 82 DEG C
Reaction 3h, is continuously heating to 92 DEG C of reaction 3h.After cooling, hand over dehydrated alcohol, hot water, cold water successively
Clarify for washing resin to cleaning mixture, in apparatus,Soxhlet's, extract 12h with petroleum ether, be vacuum dried 24h,
Obtain presoma resin PDMV-X-Y (wherein, the mass percent of X divinylbenzene；Y is benzene in porogen
The mass percent of methanol).
2) Friedel-Crafts reaction:
Dry three neck round bottom flask is separately added into 12g presoma resin PDMV-95%-20%,
PDMV-85%-50% and PDMV-70%-80% and 55mL 1,2-dichloroethanes, the swelling mistake of room temperature lower seal
Night.Load onto reflux condensing tube and motor stirrer, be separately added into 1.3,3.9,7.8g ZnCl2Make catalyst,
Moderate-speed mixer 30min.It is warming up to 85 DEG C, back flow reaction 16h.Stop heating, use 50mL dehydrated alcohol
Terminate reaction, filter resin, successively with the aqueous hydrochloric acid solution that dehydrated alcohol, mass fraction are 1% alternately washing
Resin is clarified to cleaning mixture, puts in apparatus,Soxhlet's and extracts 12h with dehydrated alcohol.Vacuum drying 24h,
To imidazoles modify after crosslinked resin PDMV-95%-20%-pc, PDMV-85%-50%-pc and
PDMV-70%-80%-pc.
The BET specific surface area of the presoma resin PDMV-70%-0% of preparation is 550m2/ g, pore volume is 0.93
cm3/ g, average pore size is 9.3nm.Crosslinked resin PDMV-95%-20%-pc after the imidazoles modification of preparation
BET specific surface area is 747m2/ g, pore volume is 1.25cm3/ g, average pore size is 8.5nm.
The BET specific surface area of the presoma resin PDMV-80%-50% of preparation is 585m2/ g, pore volume is 1.32
cm3/ g, average pore size is 9.5nm.Crosslinked resin PDMV-85%-50%-pc after the imidazoles modification of preparation
BET specific surface area is 793m2/ g, pore volume is 1.22cm3/ g, average pore size is 7.1nm.
The BET specific surface area of the presoma resin PDMV-90%-100% of preparation is 697m2/ g, pore volume is
1.05cm3/ g, average pore size is 8.5nm.Crosslinked resin PDMV-70%-80%-pc after the imidazoles modification of preparation
BET specific surface area be 936m2/ g, pore volume is 1.45cm3/ g, average pore size is 7.5nm.
The imidazoles of embodiment 5 preparation modify after crosslinked resin in the isothermal adsorption of bisphenol-A,
PDMV-95%-20%-pc, PDMV-85%-50%-pc and PDMV-70%-80%-pc are to bisphenol-A
Big adsorbance is respectively 148,156,133mg/g, and absorption is quickly, and absorption can be made in 50min to reach
Balance.
After the PDMV-70%-80%-pc imidazoles modification of embodiment 5 preparation, crosslinked resin is to bisphenol-A solution warp
Crossing 5 circulations of adsorption-desorption, the repeat usage of resin still has 94.6%.In actual applications, this resin
Can reuse repeatedly.
Embodiment 6
1) preparation of presoma resin:
On the water bath device equipped with mechanical agitator, condensing tube and thermometer, place tri-mouthfuls of round bottoms of 500mL
Flask, be initially charged aqueous phase (distilled water 180mL, mass fraction be 1% polyvinyl alcohol 20mL, methylene blue
5), the rear mixing adding 20g divinylbenzene (DVB) and 2-ethyl-1-vinyl imidazole (EVIM)
Thing, 50.0g o-Dimethylbenzene and the mixed solvent of benzyl alcohol, azodiisobutyronitrile (AIBN) 0.2g.Heating
To 45 DEG C, it is adjusted to suitable mixing speed stirring 30min, is warming up to 75 DEG C of reaction 3h, is warming up to 83 DEG C
Reaction 3h, is continuously heating to 95 DEG C of reaction 3h.After cooling, hand over dehydrated alcohol, hot water, cold water successively
Clarify for washing resin to cleaning mixture, in apparatus,Soxhlet's, extract 12h with petroleum ether, be vacuum dried 24h,
Obtain presoma resin PDEV-X-Y (wherein, the mass percent of X divinylbenzene；Y is benzene in porogen
The mass percent of methanol).
2) Friedel-Crafts reaction:
Dry three neck round bottom flask is separately added into 13g presoma resin PDEV-85%-50%,
PDEV-90%-50% and PDEV-95%-50% and 50mL 1,2-dichloroethanes, room temperature lower seal is swelling overnight.
Load onto reflux condensing tube and motor stirrer, be separately added into 6.6,4.4,2.2g FeCl3Make catalyst, middling speed
Stirring 30min.It is warming up to 84 DEG C, back flow reaction 12h.Stop heating, terminate with 50mL dehydrated alcohol
Reaction, filters resin, replaces washing resin with the aqueous hydrochloric acid solution that dehydrated alcohol, mass fraction are 1% successively
Clarify to cleaning mixture, put in apparatus,Soxhlet's and extract 12h with dehydrated alcohol.Vacuum drying 24h, obtains miaow
Azoles modify after crosslinked resin PDEV-85%-50%-pc, PDEV-90%-50%-pc and
PDEV-95%-50%-pc.
The BET specific surface area of the presoma resin PDEV-85%-50% of preparation is 541m2/ g, pore volume is 1.06
cm3/ g, average pore size is 9.8nm.Crosslinked resin PDEV-85%-50%-pc after the imidazoles modification of preparation
BET specific surface area is 871m2/ g, pore volume is 1.66cm3/ g, average pore size is 8.6nm.
The BET specific surface area of the presoma resin PDEV-90%-50% of preparation is 588m2/ g, pore volume is 1.24
cm3/ g, average pore size is 10.3nm.Crosslinked resin PDEV-90%-50%-pc after the imidazoles modification of preparation
BET specific surface area is 925m2/ g, pore volume is 1.81cm3/ g, average pore size is 9.2nm.
The BET specific surface area of the presoma resin PDEV-95%-50% of preparation is 629m2/ g, pore volume is 1.36
cm3/ g, average pore size is 9.9nm.Crosslinked resin PDEV-95%-50%-pc after the imidazoles modification of preparation
BET specific surface area is 969m2/ g, pore volume is 1.92cm3/ g, average pore size is 8.4nm.
After the imidazoles modification of embodiment 6 preparation in the isothermal adsorption of crosslinked resin Pyrogentisinic Acid,
The maximum suction of PDEV-85%-50%-pc, PDEV-90%-50%-pc and PDEV-95%-50%-pc Pyrogentisinic Acid
Attached amount is respectively 156,161,173mg/g, and absorption is quickly, and absorption can be made in 30min to reach balance.
After the imidazoles of embodiment 6 preparation is modified, crosslinked resin PDEV-95%-50%-pc Pyrogentisinic Acid's solution passes through suction
Attached-desorption 5 times circulation, the repeat usage of resin is more than 93.2%.In actual applications, resin can weigh
Multiple use is repeatedly.
Embodiment 7
The absorption property of crosslinked resin after the imidazoles modification of embodiment 1～6 preparation is tested.
(1) isothermal adsorption:
Choose phenol (or resorcinol, bisphenol-A) as adsorbate, compare after the imidazoles of preparation is modified and cross-link
Resin is to adsorbate absorption property in aqueous.The assay method of adsorption isotherm is as follows:
Take one group of tool plug conical flask, be separately added into about 0.05g resin and the suction of 50mL variable concentrations wherein
They are placed in water bath chader, at a certain temperature constant temperature oscillation 4h by attached matter aqueous solution, make absorption reach
To balance.With ultraviolet-uisible spectrophotometer suction of residual liquid after the maximum absorption wave strong point of adsorbate measures absorption
Shading value, and equilibrium concentration C of adsorbate it is converted into according to standard curvee, calculate adsorbance according to the following formula:
qe=(C0-Ce)V/W
In formula: qeFor adsorbance (mg/g), C0、CeIt is respectively before adsorbing and adsorbate in absorption rear solution
Concentration (mg/L), V is the volume (L) of adsorption liquid, and W is the quality (g) of resin.With equilibrium concentration
CeFor abscissa, adsorbance qeFor vertical coordinate, make this resin at a certain temperature to adsorbate in aqueous solution
Adsorption isotherm.
(2) adsorption dynamics adsorption kinetics:
Weigh about 0.5g resin in 500mL conical flask, add 250mL original concentration 500mg/L
Phenol solution (or resorcinol, bisphenol-A), puts into conical flask in constant temperature oscillator and shakes.Molten from adding
Liquid starts timing, pipettes 0.5mL adsorption liquid in the small beaker of 100mL in certain time, by ultraviolet-can
See that spectrogrph measures the absorbance of different time points adsorption liquid and the absorbance of original solution.By standard curve equation
Calculate solution concentration.Resin adsorbance q in t is calculated according still further to formula 2-2t:
qt=(C0-Ct)V/W
With t (min) as abscissa, qt (mg/g) is vertical coordinate, draws out resin Pyrogentisinic Acid (or resorcinol, double
Phenol A) curve of adsorption kinetics.
(3) dynamic adsorption-desorption:
Measure the resin of 7.20mL in beaker, add 30mL distilled water, put in ultrasonic cleaner super
Sound 10min, be more carefully encased in the glass column that internal diameter is 16mm.By 400mg/L phenol (or isophthalic
Diphenol, bisphenol-A) solution flows through glass column, and the piston of regulation glass column lower end makes automatic collector every 5min
Collect a pipe effluent.Measure its absorbance, until absorbance and the initial phenol of effluent (or resorcinol,
Bisphenol-A) absorbance of solution is identical.With BV as abscissa, C/C0For vertical coordinate, draw out resin dynamic
Adsorption curve.After adsorption equilibrium, use distilled water washing resin.By NaOH and the nothing of the 0.02mol/L of equivalent
Water-ethanol preparation eluent, is desorbed with this eluent.The piston of regulation glass column lower end makes automatic collector
A pipe desorption liquid is collected every 3min.Measure its absorbance, until the absorbance of desorption liquid is 0.With BV
For abscissa, C is vertical coordinate, draws out the dynamic desorption curve of resin.
(4) repeat performance:
Take 2 and be separately added into about 0.05g resin wherein with the 100mL conical flask being dried of grinding port plug,
It is separately added into phenol (or resorcinol, bisphenol-A) solution that 50mL mass fraction is 500mg/L.Close
After sealing, put in the water bath with thermostatic control agitator of 298K, constant temperature oscillation 4h.After adsorption equilibrium, calculate
The equilibrium adsorption capacity of resin.Resin filter is outwelled the most afterwards residual liquid, obtains adsorbing saturated resin, by resin
Drying in original conical flask, (volume fraction is 20% ethanol and 0.01 to sequentially add the desorbing agent of 50mL
Mol/L sodium hydroxide), under 298K, constant temperature oscillation 4h is to desorption equilibrium.Resin filter is outwelled the most afterwards
Residual liquid, and dry in original conical flask.More than it is primary sorption detachment assays.Again above-mentioned steps is repeated
Four times, after mensuration absorption, the absorbance of adsorbate in solution, calculates each equilibrium adsorption capacity.
Claims (10)
1. the preparation method of crosslinked resin after an imidazoles is modified, it is characterised in that: will contain vinyl imidazole class monomer,
Divinylbenzene crosslink agent, initiator, o-Dimethylbenzene and/or benzyl alcohol porogen and dispersant pass through suspension polymerisation,
Obtain presoma resin；Described presoma resin, under Louis acid catalysis effect, carries out Friedel-Crafts
Reaction, obtains crosslinked resin after imidazoles is modified.
The preparation method of crosslinked resin after imidazoles the most according to claim 1 modification, it is characterised in that: containing second
The mass percent of thiazolinyl imidazoles monomer and divinylbenzene crosslink agent consists of (5%～30%):
(70%～95%).
The preparation method of crosslinked resin after imidazoles the most according to claim 1 and 2 modification, it is characterised in that:
The described class monomer containing vinyl imidazole is 1-vinyl imidazole, 2-methyl isophthalic acid-vinyl imidazole, 2-ethyl-1-
At least one in vinyl imidazole.
The preparation method of crosslinked resin after imidazoles the most according to claim 1 modification, it is characterised in that: described
O-Dimethylbenzene and/or benzyl alcohol porogen quality be total containing vinyl imidazole class monomer and divinylbenzene crosslink agent
The 100%～300% of quality.
The preparation method of crosslinked resin after imidazoles the most according to claim 1 modification, it is characterised in that: described
Lewis acid consumption be in described presoma resin containing vinyl imidazole class unit mole 120～140%；
Described lewis acid is FeCl3、ZnCl2、AlCl3、TiCl4Or SnCl4In at least one.
6. the preparation method of crosslinked resin after modifying according to the imidazoles described in any one of claim 1,2,4,5, its
It is characterised by: the BET specific surface area of described presoma resin is 500～700m2/ g, pore volume is 0.8～1.5
cm3/ g, average pore size is 5～10nm.
7. the preparation method of crosslinked resin after modifying according to the imidazoles described in any one of claim 1,2,4,5, its
It is characterised by: described Friedel-Crafts reaction is to react 8～16h at a temperature of 80～85 DEG C.
The preparation method of crosslinked resin after imidazoles the most according to claim 7 modification, it is characterised in that: described
After imidazoles modification, the BET specific surface area of crosslinked resin is 700～1000m2/ g, pore volume is 1.2～2.2cm3/ g,
Average pore size is 6～9nm.
9. the application of crosslinked resin after the imidazoles modification that the preparation method described in any one of claim 1～8 prepares, its
It is characterised by: the little molecular polarity armaticity organic compound being applied in selective absorption water.
10. the application of crosslinked resin after modifying according to the imidazoles described in right 9, it is characterised in that described little point
Sub-polarity armaticity organic compound is at least one in phenol, resorcinol, bisphenol-A.
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| CN107118294A (en) * | 2017-06-26 | 2017-09-01 | 中南大学 | A kind of vinylpyridine modification suspended double bond post-crosslinking resin and its preparation method and application |
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| CN107118294B (en) * | 2017-06-26 | 2019-11-15 | 中南大学 | A kind of vinylpyridine modification suspended double bond post-crosslinking resin and its preparation method and application |
| CN111040226A (en) * | 2019-12-02 | 2020-04-21 | 中南大学 | Preparation method of hypercrosslinked polymer rich in hydrogen bond acceptor oxygen atoms and application of hypercrosslinked polymer |
| CN111266088A (en) * | 2020-01-13 | 2020-06-12 | 武汉工程大学 | Efficient porous adsorbent for treating phenolic wastewater and preparation method thereof |
| CN111266088B (en) * | 2020-01-13 | 2022-03-15 | 武汉工程大学 | Efficient porous adsorbent for treating phenolic wastewater and preparation method thereof |
| CN111333776A (en) * | 2020-03-20 | 2020-06-26 | 暨南大学 | Nitrogen heterocyclic organic polymer integral material, preparation and application |
| CN111333776B (en) * | 2020-03-20 | 2021-11-09 | 暨南大学 | Nitrogen heterocyclic organic polymer integral material, preparation and application |
| CN113912757A (en) * | 2021-11-04 | 2022-01-11 | 怀化学院 | Imidazole modified high-crosslinking resin and preparation method and application thereof |
| CN114367311A (en) * | 2022-01-14 | 2022-04-19 | 北京化工大学 | Method for preparing micron-sized monodisperse polymer microsphere supported heteropolyacid catalyst by suspension polymerization method and application |
| CN116328739A (en) * | 2023-02-22 | 2023-06-27 | 东洋和光净化材料(江苏)有限公司 | Hydrophobic VOC adsorbent and production method thereof |
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