CN106146715B - A kind of controllable method for preparing of Modified with Polar Monomer hypercrosslinked polymeric resin and application - Google Patents

A kind of controllable method for preparing of Modified with Polar Monomer hypercrosslinked polymeric resin and application Download PDF

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CN106146715B
CN106146715B CN201610513855.3A CN201610513855A CN106146715B CN 106146715 B CN106146715 B CN 106146715B CN 201610513855 A CN201610513855 A CN 201610513855A CN 106146715 B CN106146715 B CN 106146715B
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resin
modified
polymeric resin
polar monomer
hypercrosslinked polymeric
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CN106146715A (en
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黄健涵
张婷
刘又年
邵礼书
刘明强
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Central South University
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a kind of controllable method for preparing of Modified with Polar Monomer hypercrosslinked polymeric resin and applications.The preparation method of Modified with Polar Monomer hypercrosslinked polymeric resin is that 4 vinyl benzyl chloride monomers, vinyl imidazole class polar monomer, divinylbenzene crosslink agent etc. are obtained presoma resin by suspension copolymerization；Gained presoma resin carries out Friedel Crafts reactions, has obtained Modified with Polar Monomer hypercrosslinked polymeric resin under Louis acid catalysis effect.By changing the percentage composition of 4 vinyl benzyl chloride monomers, divinylbenzene crosslink agent, a series of hypercrosslinked polymeric resin of Different Pore Structures and opposed polarity can be prepared；The structural controllability of this resinoid imparts its adsorptive selectivity different with the armaticity organic matter of size to opposed polarity.In addition, the controllable synthesis method of this Modified with Polar Monomer hypercrosslinked polymeric resin is simple, and it is at low cost, it can industrialized production.

Description

A kind of controllable method for preparing of Modified with Polar Monomer hypercrosslinked polymeric resin and application
Technical field
The present invention relates to a kind of preparation method of hypercrosslinked polymeric resin, more particularly to a kind of Modified with Polar Monomer hypercrosslinked polymeric resin Controllable method for preparing and its application in adsorbing water in polar molecule phenolic compound, belong to functional polymer synthesis skill Art field.
Background technology
Line polystyrene or low cross-linking are gathered in the early 1970s, Davankov etc. is reacted by Friedel-Crafts Styrene is crosslinked the porous polymer for having synthesized a kind of unique structure, function admirable, this kind of poromeric crosslinking degree again It is higher, also known as hypercrosslinked polymeric resin.Hypercrosslinked polymeric resin usually have large specific surface area, average pore size is small, pore-size distribution is narrow, The structure features such as mechanical strength is good, at present the improvement of poisonous organic wastewater, gas storage detach etc. fields show it is wide Application prospect.The use of chloromethyl ether is the super of crosslinking agent preparation during preparing hypercrosslinked polymeric resin using Davankov methods The structure of highly cross-linked resin is opposite with performance more excellent.But chloromethyl ether is strong carcinogenic, strong volatile materials.In order to avoid using Chloromethyl ether has researcher to replace styrene using vinyl chloride, is directly hanged with vinyl chloride and divinylbenzene Floating polymerization prepares the precursor polymer with chloromethyl, then carries out Friedel-Crafts reactions, is prepared for hypercrosslinked polymeric resin, This method is known as improved Davankov methods.But the hypercrosslinked polymeric resin that improved Davankov methods are prepared is free of polarity official Can group, it is bad to the adsorption effect of polarity organic pollution, and vinyl benzyl chloride and divinylbenzene be in suspension polymerization, by It is different in reactivity ratio, so as to get cross-linked copolymer becomes difficult point.And patent of the present invention provides a kind of ternary suspension copolymerization Preparation method greatly enhances the polarity of hypercrosslinked polymeric resin, simplifies system by introducing vinyl imidazole class polar monomer Standby process.
Organic industrial sewage usually contains the organic pollution of great amount of soluble, such as aromatic carboxylic acids, naphthols, acid dyes Deng, rely solely on hydrophobic effect be primary attachment motive force macroporous absorbent resin and post-crosslinking adsorb resin be difficult processing.For Increase the hydrophily of resin, researcher proposes a series of Improving Measurements, be included in before Friedel-Crafts reactions or Resin is chemically modified after reaction, copolymerization is directly carried out using polar monomer and prepares presoma resin.Chinese patent is (open Number CN101190974) disclose a kind of pyrrolidone-base modified composite function absorption resin and preparation method thereof；Chinese patent (publication number CN 1858088A) discloses a kind of pyridyl modified composite function super high crosslinked resin and preparation method thereof.These The a certain number of pyrrolidone-bases of area load of post-crosslinking resin, pyridyl group etc..But preparation process is more complex, and has used play The chloromethyl ether of poison makees crosslinking agent, their absorption property the result shows that, substance of this resinoid to different sizes and opposed polarity (such as：Phenol, salicylic acid, benzoic acid, rhodamine B, betanaphthol etc.) there is certain adsorption capacity, but adsorptive selectivity is not Obviously.
Invention content
For the defect that its polarity of existing hypercrosslinked polymeric resin and pore structure are difficult to control etc., it is an object of the invention to It is to provide a kind of preparation method that the hypercrosslinked polymeric resin that polarity and pore structure arbitrarily regulate and control may be implemented, this method operation letter Just, at low cost, industrialized production can be met.
Another object of the present invention be to provide a kind of polarity by regulating and controlling Modified with Polar Monomer hypercrosslinked polymeric resin and Pore structure is in proper range, in selective absorption aqueous solution in terms of opposed polarity and different size armaticity organic compounds Application, especially para Toluic Acid, salicylic acid or rhodamine B etc. have selective absorbing effect, and adsorb after be easy elution, tree Fat may be reused, and it is good to reuse effect.
In order to achieve the above technical purposes, the present invention provides a kind of controllable preparation sides of Modified with Polar Monomer hypercrosslinked polymeric resin Method, this method is will be including the raw material including 4- vinyl benzyl chlorides monomer, vinyl imidazole class monomer and divinylbenzene crosslink agent By suspension copolymerization, presoma resin is obtained；The presoma resin carries out Friedel- under Louis acid catalysis effect Crafts reacts, and has obtained Modified with Polar Monomer hypercrosslinked polymeric resin；Wherein, 4- vinyl benzyl chlorides monomer, vinyl imidazole class monomer And the mass percent of divinylbenzene crosslink agent is (5%~80%):(3~30%):(10%~90%).
The technical scheme is that being improved to the preparation of existing hypercrosslinked polymeric resin, the superhigh cross-linking of the prior art Although resin Pyrogentisinic Acid, benzoic acid, salicylic acid, rhodamine B, betanaphthol etc. have certain adsorptivity, adsorption effect is poor (to be inhaled Attached amount is small, and the time for reaching adsorption equilibrium is long), and adsorptive selectivity is poor.Main cause is that (1) resin's crosslinkage is excessively high, hole Rate is fine and close, only allows small molecule (such as N2Deng) enter, and the relatively large polar molecule of molecular dimension is not easy to diffuse into duct, It is poor to the adsorption effect of polar molecule so as to cause polystyrene type hypercrosslinked polymeric resin；(2) existing hypercrosslinked polymeric resin master Polar monomer modified by aminating reaction, and only modify polar group by remaining chlorine, polar group modification amount is few, polarity Modification power is limited, and process is more complex.So existing hypercrosslinked polymeric resin, not only polarity improvement ability is limited, and hole is tied Structure is difficult to realize adjust, it is difficult to obtain the hypercrosslinked polymeric resin with high-selectivity adsorption effect.Technical scheme of the present invention will 4- vinyl benzyl chlorides, vinyl imidazole class monomer and divinyl obtain ternary precursor tree by the method for ternary suspension copolymerization Fat, further crosslinking obtain hypercrosslinked polymeric resin, and it is big which not only may be implemented polarity in a certain range Small and pore structure size regulation and control, and its polarity and pore structure can be adjusted in a certain range, make it to particular pole Property and specific molecular size armaticity organic compound have highly selective adsorption effect.What technical solution of the present invention obtained Presoma resin, the divinylbenzene and 4- vinyl benzyl chlorides on the one hand having in itself provide a large amount of chloro-methyl group and suspension is double Key can significantly change the specific surface area and pore structure of resin, pass through and adjust 4- vinyl after progress Friedel-Crafts reactions Benzyl chloride and the content of divinyl tie size and specific surface area size to adjust hypercrosslinked polymeric resin hole, can increase superhigh cross-linking Selection adsorption capacity of the resin to the armaticity organic compound of different molecular size；On the other hand, vinyl imidazole is introduced Class monomer has the modification of polar imidazole group in resin backbone, not only reduces the cause that resin is formed in cross-linking process Close pore structure makes hypercrosslinked polymeric resin pore structure be improved, and has changed the polarity of hypercrosslinked polymeric resin, to polarity armaticity The selective absorption of molecule significantly improves, can be by changing vinyl imidazole class content of monomer, to realize hypercrosslinked polymeric resin Polar regulation and control can increase the selection adsorption capacity to the phenolic compound of opposed polarity size.In addition pole of the invention It elutes and is easy after the absorption of sex modification hypercrosslinked polymeric resin, reusable, reuse effect is good, can be widely applied to chemistry point The fields such as analysis, medical separation purification, environmental pollution improvement.
The Modified with Polar Monomer hypercrosslinked polymeric resin controllable synthesis method of the present invention further includes following preferred embodiment：
Preferred scheme, the raw material further include ortho-xylene pore-foaming agent.
The quality of more preferably scheme, the ortho-xylene pore-foaming agent is 4- vinyl benzyl chlorides monomer, vinyl imidazole class 1~3 times of monomer and divinylbenzene crosslink agent gross mass.
Preferred scheme, lewis acid FeCl3、ZnCl2、AlCl3、TiCl4、SnCl4At least one of.
Preferred scheme, the lewis acidic dosage are that the presoma resin medium vinyl imidazoles monomeric unit rubs The 120%~140% of that amount.
More preferably scheme, vinyl imidazole class monomer are 1- vinyl imidazoles, 2- methyl-1s-vinyl imidazole, 2- second At least one of base -1- vinyl imidazoles.
More preferably scheme, the mass percentage content of chlorine is 2%~12.5% in presoma resin, BET specific surface area For 0~650m20~1.0cm of/g, Kong Rongwei3/ g, average pore size are 0~6.5nm.
Preferred scheme, the condition that Friedel-Crafts reacts are：8~12h is reacted at a temperature of 80~85 DEG C.
More preferably scheme, Friedel-Crafts react the mass percent of residual chlorine in the hypercrosslinked polymeric resin generated Content is 0.5%~5.0%, and BET specific surface area is 400~1400m20.4~2.5cm of/g, Kong Rongwei3/ g, average pore size 2 ~9nm.
The present invention also provides a kind of applications of Modified with Polar Monomer hypercrosslinked polymeric resin, and Modified with Polar Monomer hypercrosslinked polymeric resin is answered For the polar molecule armaticity organic compound in selective absorption water.
Preferred scheme, the polar molecule armaticity organic compound are benzoic acid, salicylic acid, phenol, rhodamine B, at least one of betanaphthol.
Preferred scheme, when 4- vinyl benzyl chlorides, vinyl imidazole monomer and divinylbenzene mass percent be (40%~ 80%):(3%~30%):When (10%~30%), it is 400~1400m that BET specific surface area, which can be obtained,2/ g, Kong Rongwei 0.4~ 1.5cm3/ g, the hypercrosslinked polymeric resin that average pore size is 2~5nm, the armaticity such as para Toluic Acid, salicylic acid, phenol, betanaphthol pole Property small molecule shows good adsorption effect.When 4- vinyl benzyl chlorides, vinyl imidazole monomer and divinylbenzene quality percentage Than for (5%~60%):(3%~20%):When (40%~90%), it is 1000~1100m that BET specific surface area, which can be obtained,2/g、 1.0~2.5cm of Kong Rongwei3/ g, the hypercrosslinked polymeric resin that average pore size is 3~9nm, show the rhodamine B of medium size Good adsorptivity.
Preferred scheme, the Modified with Polar Monomer hypercrosslinked polymeric resin for having adsorbed polar molecule armaticity organic compound use hydrogen Sodium oxide molybdena/alcohol mixed solution (volume fraction of ethanol 100%, naoh concentration 0.01mol/L) as desorbing agent into Row desorption.
The controllable synthesis method of the Modified with Polar Monomer hypercrosslinked polymeric resin of the present invention, including step in detail below：
1) preparation of ternary polymerization precursor resin：
Using 4- vinyl benzyl chlorides as monomer, class containing vinyl imidazole is polar monomer, and divinylbenzene is crosslinking agent, and azo is different Butyronitrile is initiator, the obtained precursor resin of suspension polymerisation in water phase.It is as follows：In water phase (distilled water 180mL, matter Measure the polyvinyl alcohol 20mL that score is 1%) in, oil phase (4- vinyl benzyl chlorides monomer, vinyl imidazole class monomer, diethyl is added Alkene benzene crosslinking agent, initiator and pore-foaming agent), 40 DEG C are heated to, mixing speed is adjusted, controls oil droplet size, stirs and slowly rises Temperature is to 68~75 DEG C, after reacting 2~5h, 2~5h is reacted at 78~85 DEG C, then is warming up to 90~95 DEG C, further react 2~ 5h；After the completion of reaction, products therefrom is used to hot water, cold water, absolute ethyl alcohol respectively, and alternately washing 3~4 times then uses oil to colourless Ether extracts in Soxhlet extractor, normal drying 12h, then is dried in vacuo for 24 hours, and precursor resin is made；Precursor tree obtained Fat BET specific surface area is 0~650m20~1.0cm of/g, Kong Rongwei3/ g, average pore size are 0~6.5nm, cross 40~60 mesh sieve, standby With；4- vinyl benzyl chlorides monomer wherein in ternary suspension polymerisation raw material, vinyl imidazole class monomer, divinylbenzene crosslink agent matter It is (5%~80%) to measure percentage:(3~30%):(10%~90%)；
2) Friedel-Crafts reacts：
Precursor resin is added in 1,2- dichloroethanes, after swelling overnight, Louis is added at a temperature of 40 DEG C~45 DEG C This acid as catalyst, 30min is to after being completely dissolved for stirring, is warming up to 80~85 DEG C, and carry out Friedel- at this temperature Crafts reacts 8~12h, is terminated and is reacted with 50% ethanol water, pours out reaction mother liquor, the hydrochloric acid for being 1% with mass fraction Alternately washing 3~5 times of aqueous solution and absolute ethyl alcohol are used in combination absolute ethyl alcohol extracting 8~for 24 hours, obtain opposed polarity and different holes knot The hypercrosslinked polymeric resin of structure；
The lewis acid is FeCl3、ZnCl2、AlCl3、TiCl4Or SnCl4At least one of；The Louis Sour dosage is the 120~140% of the amount of presoma resin medium vinyl imidazoles substance used；
The BET specific surface area of the Modified with Polar Monomer hypercrosslinked polymeric resin is 400~1400m2/ g, Kong Rongwei 0.4~ 2.5cm3/ g, average pore size are 2~9nm.
Compared with the prior art, the advantageous effects that technical scheme of the present invention is brought：
1) technical scheme of the present invention can be by adjusting divinylbenzene crosslink agent, 4- vinyl benzyl chlorides monomer and vinyl The content ratio of imidazoles monomer realizes the pore size of hypercrosslinked polymeric resin and the arbitrary regulation and control of polarity size.On the one hand two Ethenylbenzene and 4- vinyl benzyl chlorides provide a large amount of chloro-methyl group and suspended double bond, can after progress Friedel-Crafts reactions The specific surface area and pore structure for significantly changing resin are passed through by adjusting the content of 4- vinyl benzyl chlorides and divinylbenzene come adjustment hole Size and specific surface area size can increase the selection adsorption capacity to the armaticity organic compound of different molecular size；Separately On the one hand, vinyl imidazole class monomer is introduced, has the modification of polar imidazole group on main polymer chain, not only reduces The tight pore structure formed in resin cross-linking process makes its pore structure be improved, and changes the pole of hypercrosslinked polymeric resin Property, the selective absorption of polarity armaticity molecule is significantly improved, can be come real by changing vinyl imidazole class content of monomer The polar regulation and control of existing hypercrosslinked polymeric resin, can increase the selection adsorption capacity to the phenolic compound of opposed polarity size.
2) technical scheme of the present invention can regulate and control the polarity size and pore size of hypercrosslinked polymeric resin in appropriate model In enclosing, to be applicable in the selective absorption of the polar molecule armaticity organic compound of opposed polarity and molecular size, as superelevation is handed over Suitably increasing vinyl imidazole class monomer in connection resin preparation process can improve to polarity relatively large polar molecule fragrance The selective adsorption capacity of property organic compound, and the content for suitably increasing divinyl cross-linking agent can improve to molecular dimension The selective adsorption capacity of relatively large polar molecule armaticity organic compound.Overcome reported in the prior art it is super Existing for highly cross-linked resin (such as to polar contaminants：Phenol, benzoic acid, salicylic acid, betanaphthol or rhodamine B) adsorption effect and The undesirable defect of selectivity.
3) it elutes and is easy after Modified with Polar Monomer hypercrosslinked polymeric resin of the invention absorption, it is reusable, reuse effect It is good, it can be widely applied to the fields such as chemical analysis, medical separation purification, environmental pollution improvement.
4) method of Modified with Polar Monomer hypercrosslinked polymeric resin prepared by the present invention is simple, cost is relatively low, can be with industrialized production.
Description of the drawings
【Fig. 1】For in the embodiment of the present invention 1 different monomers ratio prepare ternary polymerization presoma resin P1, P2, P3 and The infrared spectrogram (a) of P4 and Modified with Polar Monomer hypercrosslinked polymeric resin HP1, HP2, HP3 and HP4；Ternary prepared by the different degrees of cross linking The infrared spectrogram (b) of presoma resin P2, P5 and P6 and Modified with Polar Monomer hypercrosslinked polymeric resin HP2, HP5 and HP6.
【Fig. 2】For 1 apertures Modified with Polar Monomer hypercrosslinked polymeric resin HP1, HP2, HP3, HP4, HP5 and HP6 of the embodiment of the present invention Distribution map.
【Fig. 3】Hypercrosslinked polymeric resin HP1, HP2, HP3 and the HP4 prepared for different monomers ratio in the embodiment of the present invention 1 To different adsorbates (in benzoic acid, rhodamine B, phenol, salicylic acid, betanaphthol any) selective absorption block diagram (a)；No Hypercrosslinked polymeric resin HP2, HP5 and HP6 with degree of cross linking preparation is to different adsorbates (benzoic acid, rhodamine B, phenol, bigcatkin willow It is any in acid, betanaphthol) selective absorption block diagram (b).
【Fig. 4】Hypercrosslinked polymeric resin HP1, HP2, HP3 and the HP4 prepared for different monomers ratio in the embodiment of the present invention 1 The dynamic curve diagram of Adsorption of Benzoic Acid.
【Fig. 5】Sieve is adsorbed for hypercrosslinked polymeric resin HP2, HP5 and HP6 that in the embodiment of the present invention 1 prepared by the different degrees of cross linking The dynamic curve diagram of red bright B.
【Fig. 6】Repetition for the Modified with Polar Monomer hypercrosslinked polymeric resin HP2 para Toluic Acids absorption prepared in inventive embodiments 1 makes Use performance map.
Specific implementation mode
Following embodiment is intended to further illustrate the content of present invention, rather than to the limit of the claims in the present invention protection domain It is fixed.
Embodiment 1：
1) prepared by ternary polymerization precursor resin：
On the water bath device equipped with mechanical agitator, condenser pipe and thermometer, 500mL three neck round bottom flask is placed, first It is added water phase (distilled water 180mL, the polyvinyl alcohol 20mL that mass fraction is 1%), the rear 4- second that six kinds of 20g not ratios are added Alkenyl benzyl chloride, N- vinyl imidazoles and divinylbenzene mixture, ortho-xylene 40g, azodiisobutyronitrile (AIBN) 0.2g.Heating It to 45 DEG C, adjusts to suitable mixing speed and stirs 30min, be warming up to 75 DEG C of reaction 3h, 85 DEG C of reaction 2h are warming up to, after of continuing rising Temperature to 95 DEG C reaction 3h.After cooling, absolute ethyl alcohol, hot water, cold water is used alternately to wash 3~4 times to cleaning solution clarification, in rope successively 12h is extracted with petroleum ether in family name's extractor, vacuum drying for 24 hours, obtains ternary polymerization precursor resin P1 (4- vinyl benzyl chlorides:N- Vinyl imidazole:Divinylbenzene mass percent is 75%:5%:20%), P2 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Two Ethenylbenzene mass percent is 67.5%:12.5%:20%), P3 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene matter It is 62.5% to measure percentage:17.5%:20%), P4 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent It is 50%:30%:20%), P5 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 42.2%: 7.8%:50%), P6 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 16.88%:3.12%: 80%), IR Characterization as shown in Figure 1, presoma tree resin P1, P2, P3, P4, P5, P6 in 1270cm-1There is strong absworption peak in place, The C-Cl stretching vibrations of corresponding benzyl chloride；And P6 is in 907cm-1And 988cm-1Also there is moderate strength absorption peak, corresponding suspension in place C-H stretching vibrations in double bond；In 1608cm-1And 1450cm-1Also the C=C and C=N for phenyl ring and imidazole ring occur flexible shake It is dynamic, thus illustrate 4- vinyl benzyl chlorides, N- vinyl imidazoles and divinylbenzene copolyreaction success.
2) Friedel-Crafts reacts：
Be separately added into dry three neck round bottom flask 15g ternary polymerization precursor resin P1, P2, P3, P4, P5, P6 and 120mL 1,2- dichloroethanes, sealing swelling is overnight under room temperature.Reflux condensing tube and electric mixer are loaded onto, is sequentially added The anhydrous FeCl of 1.55g, 3.9g, 5.5g, 9.3g, 2.4g, 1.0g3Make catalyst, moderate-speed mixer 30min.80 DEG C are warming up to, reflux React 8h.Stop heating, terminated and reacted with 80mL50% ethanol waters, filter resin, uses absolute ethyl alcohol, mass fraction successively 3~4 times are alternately washed to cleaning solution clarification for 1% aqueous hydrochloric acid solution, are put into Soxhlet extractor and are extracted with absolute ethyl alcohol 12h.Normal drying 12h, then be dried in vacuo for 24 hours, obtain hypercrosslinked polymeric resin HP1, HP2, HP3, HP4, HP5, HP6, infrared table Sign as shown in Figure 1, Friedel-Crafts reaction after, 1270cm-1The absorption peak at place obviously weakens, and HP6 is in 907cm-1With 988cm-1The absorption peak at place also obviously weakens, and illustrates that chloromethyl and suspended double bond content drastically reduce, methylene-crosslinked to arrive resin On, crosslinking degree sharply increases.
The mass percent of chlorine is 12.03% in the precursor resin P1 of preparation, BET specific surface area, Kong Rong and average pore size All it is 0.The mass percent of chlorine is 1.17% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP1 of preparation, and BET specific surface area is 1300m2/ g, Kong Rongwei 0.8943cm3/ g, average pore size 2.74nm.
The mass percent of chlorine is 11.52% in the precursor resin P2 of preparation, BET specific surface area, Kong Rong and average pore size All it is 0.The mass percent of chlorine is 1.46% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP2 of preparation, and BET specific surface area is 1002.1m2/ g, Kong Rongwei 1.08cm3/ g, average pore size 3.56nm.
The mass percent of chlorine is 9.56% in the precursor resin P3 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 1.96% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP3 of preparation, and BET specific surface area is 685.4m2/ g, Kong Rongwei 0.924cm3/ g, average pore size 3.54nm.
The mass percent of chlorine is 7.83% in the precursor resin P4 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 2.73% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP4 of preparation, and BET specific surface area is 474.4m2/ g, Kong Rongwei 0.4254cm3/ g, average pore size 4.64nm.
The mass percent of chlorine is 9.1% in the precursor resin P5 of preparation, BET specific surface area 102.3m2/ g, Kong Rongwei 0.12cm3/ g, average pore size 4.69nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP5 of preparation 1.99%, BET specific surface area 1070m2/ g, Kong Rongwei 1.61cm3/ g, average pore size 6.02nm
The mass percent of chlorine is 2.8% in the precursor resin P6 of preparation, BET specific surface area 606.6m2/ g, Kong Rongwei 0.943cm3/ g, average pore size 6.22nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP6 of preparation 0.53%, BET specific surface area 1011m2/ g, Kong Rongwei 2.05cm3/ g, average pore size 8.13nm.
In the isothermal adsorption of Modified with Polar Monomer superhigh cross-linking para Toluic Acid prepared by embodiment 1, the maximum adsorption of para Toluic Acid Amount is respectively 207.2mg/g, 230.9mg/g, 198.5mg/g, 136.9mg/g, 210.5mg/g, 178.4mg/g, and is adsorbed fast Speed reaches balance in 20min.
Modified with Polar Monomer hypercrosslinked polymeric resin para Toluic Acid's solution prepared by embodiment 1 is by 5 cycles of adsorption-desorption, HP2 Resin still has 90.9% or more reuse rate.In practical applications, which may be reused repeatedly.
Embodiment 2：
1) prepared by ternary polymerization precursor resin
On the water bath device equipped with mechanical agitator, condenser pipe and thermometer, 500mL three neck round bottom flask is placed, first Water phase (distilled water 180mL, the polyvinyl alcohol 20mL that mass fraction is 1%), the rear 4- ethylene that six kinds of ratios of 20g are added is added Base benzyl chloride, 2- methyl-1s-vinyl imidazole and divinylbenzene mixture, 20g ortho-xylenes, azodiisobutyronitrile (AIBN) 0.2g.40 DEG C are heated to, adjusts to suitable mixing speed and stirs 30min, 73 DEG C of reaction 3h is warming up to, is warming up to 83 DEG C of reactions 3h is continuously heating to 93 DEG C of reaction 3h.After cooling, absolute ethyl alcohol, hot water, cold water is used alternately to wash 3~4 times to cleaning solution successively Clarification, 12h is extracted in Soxhlet extractor with petroleum ether, and vacuum drying for 24 hours, obtains ternary polymerization precursor resin P1 (4- ethylene Base benzyl chloride:N- vinyl imidazoles:Divinylbenzene mass percent is 70%:10%:20%), P2 (4- vinyl benzyl chlorides:N- second Alkenyl imidazoles:Divinylbenzene mass percent is 72.5%:7.5%:20%), P3 (4- vinyl benzyl chlorides:N- vinyl imidazoles: Divinylbenzene mass percent is 40%:10%:50%), P4 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene quality Percentage is 30%:20%:50%), P5 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 20%:30%:50%), P6 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 15%:5%: 80%), IR Characterization as shown in Figure 1, presoma tree resin P1, P2, P3, P4, P5, P6 in 1270cm-1There is strong absworption peak in place, The C-Cl stretching vibrations of corresponding benzyl chloride；And P6 is in 907cm-1And 988cm-1Also there is moderate strength absorption peak, corresponding suspension in place C-H stretching vibrations in double bond；In 1608cm-1And 1450cm-1Also the C=C and C=N for phenyl ring and imidazole ring occur flexible shake It is dynamic, thus illustrate 4- vinyl benzyl chlorides, N- vinyl imidazoles and divinylbenzene copolyreaction success.
2) Friedel-Crafts reacts：
Be separately added into dry three neck round bottom flask 15g ternary polymerization precursor resin P1, P2, P3, P4, P5, P6 and 100mL 1,2- dichloroethanes, sealing swelling is overnight under room temperature.Load onto reflux condensing tube and electric mixer, be added 1.81g, The anhydrous AlCl of 4.53g, 6.33g, 10.8g, 2.8g, 1.5g3Make catalyst, moderate-speed mixer 30min.83 DEG C are warming up to, reflux is anti- Answer 12h.Stop heating, terminated and reacted with 60mL50% ethanol waters, filter resin, uses absolute ethyl alcohol, mass fraction successively 3~4 times are alternately washed to cleaning solution clarification for 1% aqueous hydrochloric acid solution, are put into Soxhlet extractor and are extracted with absolute ethyl alcohol 12h.Normal drying 12h, then be dried in vacuo for 24 hours, obtain hypercrosslinked polymeric resin HP1, HP2, HP3, HP4, HP5, HP6, infrared table Levy 1270cm as shown in Figure 1-1The absorption peak at place obviously weakens, and HP6 is in 907cm-1And 988cm-1The absorption peak at place also obviously subtracts It is weak, illustrate that chloromethyl and suspended double bond content drastically reduce, methylene-crosslinked on resin, crosslinking degree sharply increases.
The mass percent of chlorine is 12.5% in the precursor resin P1 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 0.87% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP1 of preparation, and BET specific surface area is 1395m2/ g, Kong Rongwei 1.043cm3/ g, average pore size 3.74nm.
The mass percent of chlorine is 11.42% in the precursor resin P2 of preparation, BET specific surface area, Kong Rong and average pore size All it is 0.The mass percent of chlorine is 1.73% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP2 of preparation, and BET specific surface area is 1012.1m2/ g, Kong Rongwei 1.58cm3/ g, average pore size 4.53nm.
The mass percent of chlorine is 10.56% in the precursor resin P3 of preparation, BET specific surface area, Kong Rong and average pore size All it is 0.The mass percent of chlorine is 3.03% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP3 of preparation, and BET specific surface area is 1085.4m2/ g, Kong Rongwei 1.324cm3/ g, average pore size 4.91nm.
The mass percent of chlorine is 7.93% in the precursor resin P4 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 4.73% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP4 of preparation, and BET specific surface area is 1074.4m2/ g, Kong Rongwei 1.5321cm3/ g, average pore size 5.08nm.
The mass percent of chlorine is 10.1% in the precursor resin P5 of preparation, BET specific surface area 152.3m2/ g, Kong Rong For 0.32cm3/ g, average pore size 5.69nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP5 of preparation 1.09%, BET specific surface area 1070m2/ g, Kong Rongwei 1.91cm3/ g, average pore size 6.92nm
The mass percent of chlorine is 2.2% in the precursor resin P6 of preparation, BET specific surface area 706.6m2/ g, Kong Rongwei 1.0cm3/ g, average pore size 6.5nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP6 of preparation 0.53%, BET specific surface area 1100m2/ g, Kong Rongwei 2.5cm3/ g, average pore size 9.0nm.
In the isothermal adsorption of Modified with Polar Monomer superhigh cross-linking Pyrogentisinic Acid prepared by embodiment 2, the maximal absorptive capacity point of Pyrogentisinic Acid Not Wei 119.2mg/g, 125.4mg/g, 98.40mg/g, 54.38mg/g, 117.2mg/g, 97.7mg/g, and adsorb it is quick, Reach balance in 10min.
Modified with Polar Monomer hypercrosslinked polymeric resin Pyrogentisinic Acid's solution prepared by embodiment 2 is by 5 cycles of adsorption-desorption, HP2 trees Fat still has 93.9% or more reuse rate.In practical applications, which may be reused repeatedly.
Embodiment 3：
1) prepared by ternary polymerization presoma resin：
On the water bath device equipped with mechanical agitator, condenser pipe and thermometer, 500mL three neck round bottom flask is placed, first It is added water phase (distilled water 180mL, the polyvinyl alcohol 20mL that mass fraction is 1%), the rear 4- second that six kinds of 20g not ratios are added Alkenyl benzyl chloride, 2- ethyl -1- vinyl imidazoles and divinylbenzene mixture, ortho-xylene 60g, azodiisobutyronitrile (AIBN) 0.2g.45 DEG C are heated to, adjusts to suitable mixing speed and stirs 30min, 75 DEG C of reaction 3h is warming up to, is warming up to 85 DEG C of reactions 2h is continuously heating to 95 DEG C of reaction 3h.After cooling, absolute ethyl alcohol, hot water, cold water is used alternately to wash 3~4 times to cleaning solution successively Clarification, 12h is extracted in Soxhlet extractor with petroleum ether, and vacuum drying for 24 hours, obtains ternary polymerization precursor resin P1 (4- ethylene Base benzyl chloride:N- vinyl imidazoles:Divinylbenzene mass percent is 65%:5%:30%), P2 (4- vinyl benzyl chlorides:N- ethylene Base imidazoles:Divinylbenzene mass percent is 57.5%:12.5%:30%), P3 (4- vinyl benzyl chlorides:N- vinyl imidazoles: Divinylbenzene mass percent is 50%:20%:30%), P4 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene quality Percentage is 45%:25%:30%), P5 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 20%:20%:60%), P6 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 17%:3%: 80%), IR Characterization as shown in Figure 1, presoma tree resin P1, P2, P3, P4, P5, P6 in 1270cm-1There is strong absworption peak in place, The C-Cl stretching vibrations of corresponding benzyl chloride；And P6 is in 907cm-1And 988cm-1Also there is moderate strength absorption peak, corresponding suspension in place C-H stretching vibrations in double bond；In 1608cm-1And 1450cm-1Also the C=C and C=N for phenyl ring and imidazole ring occur flexible shake It is dynamic, thus illustrate 4- vinyl benzyl chlorides, N- vinyl imidazoles and divinylbenzene copolyreaction success.
2) Friedel-Crafts reacts：
Be separately added into dry three neck round bottom flask 15g ternary polymerization precursor resin P1, P2, P3, P4, P5, P6 and 80mL 1,2- dichloroethanes, sealing swelling is overnight under room temperature.Reflux condensing tube and electric mixer are loaded onto, is sequentially added The anhydrous ZnCl of 1.65g, 4.23g, 6.54g, 10.3g, 3.41g, 1.43g2Make catalyst, moderate-speed mixer 30min.It is warming up to 80 DEG C, back flow reaction 8h.Stop heating, with 80mL50% ethanol waters terminate react, filter resin, successively use absolute ethyl alcohol, The aqueous hydrochloric acid solution that mass fraction is 1% alternately washs 3~4 times and is clarified to cleaning solution, is put into Soxhlet extractor with anhydrous second Alcohol extracts 12h.Normal drying 12h, then be dried in vacuo for 24 hours, hypercrosslinked polymeric resin HP1, HP2, HP3, HP4, HP5, HP6 are obtained, IR Characterization is as shown in Figure 1,1270cm-1The absorption peak at place obviously weakens, and HP6 is in 907cm-1And 988cm-1The absorption peak at place Also apparent to weaken, illustrate that chloromethyl and suspended double bond content drastically reduce, methylene-crosslinked on resin, crosslinking degree drastically increases Add.
The mass percent of chlorine is 10.03% in the precursor resin P1 of preparation, BET specific surface area, Kong Rong and average pore size All it is 0.The mass percent of chlorine is 1.07% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP1 of preparation, and BET specific surface area is 1266m2/ g, Kong Rongwei 0.7943cm3/ g, average pore size 2.34nm.
The mass percent of chlorine is 9.52% in the precursor resin P2 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 2.43% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP2 of preparation, and BET specific surface area is 902.1m2/ g, Kong Rongwei 1.18cm3/ g, average pore size 3.94nm.
The mass percent of chlorine is 8.56% in the precursor resin P3 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 3.83% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP3 of preparation, and BET specific surface area is 625.4m2/ g, Kong Rongwei 0.794cm3/ g, average pore size 4.89nm.
The mass percent of chlorine is 7.13% in the precursor resin P4 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 4.73% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP4 of preparation, and BET specific surface area is 474.4m2/ g, Kong Rongwei 0.6231cm3/ g, average pore size 4.97nm.
The mass percent of chlorine is 9.7% in the precursor resin P5 of preparation, BET specific surface area 62.3m2/ g, Kong Rongwei 0.12cm3/ g, average pore size 2.69nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP5 of preparation 2.12%, BET specific surface area 1070m2/ g, Kong Rongwei 1.41cm3/ g, average pore size 6.52nm.
The mass percent of chlorine is 2.4% in the precursor resin P6 of preparation, BET specific surface area 606.6m2/ g, Kong Rongwei 0.943cm3/ g, average pore size 6.22nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP6 of preparation 0.53%, BET specific surface area 1191m2/ g, Kong Rongwei 2.45cm3/ g, average pore size 8.93nm.
Modified with Polar Monomer superhigh cross-linking prepared by embodiment 3 is in the isothermal adsorption of rhodamine B, inhaling the maximum of rhodamine B Attached amount is respectively 186.1mg/g, 232.4mg/g, 363.7mg/g, 121.8mg/g, 293.4mg/g, 379.2mg/g, and is adsorbed Quickly.
Modified with Polar Monomer hypercrosslinked polymeric resin prepared by embodiment 3 recycles rhodamine B solution for 5 times by adsorption-desorption, HP6 resins still have 92.4% or more reuse rate.In practical applications, which may be reused repeatedly.
Embodiment 4：
1) prepared by ternary polymerization presoma resin：
On the water bath device equipped with mechanical agitator, condenser pipe and thermometer, 500mL three neck round bottom flask is placed, first It is added water phase (distilled water 180mL, the polyvinyl alcohol 20mL that mass fraction is 1%), the rear 4- second that six kinds of 20g not ratios are added Alkenyl chlorine, N- vinyl imidazoles and divinylbenzene mixture, ortho-xylene 30g, azodiisobutyronitrile (AIBN) 0.2g.It is heated to It 45 DEG C, adjusts to suitable mixing speed and stirs 30min, be warming up to 75 DEG C of reaction 3h, be warming up to 85 DEG C of reaction 2h, continue to heat up To 95 DEG C of reaction 3h.After cooling, absolute ethyl alcohol, hot water, cold water is used alternately to wash 3~4 times to cleaning solution clarification, in Soxhlet successively 12h is extracted with petroleum ether in extractor, vacuum drying for 24 hours, obtains ternary polymerization precursor resin P1 (4- vinyl benzyl chlorides:N- second Alkenyl imidazoles:Divinylbenzene mass percent is 80%:10%:10%), P2 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Two Ethenylbenzene mass percent is 65%:10%:25%), P3 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene quality hundred Divide than being 55%:20%:25%), P4 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 45%: 30%:25%), P5 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 20%:10%:70%), P6 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 5%:5%:90%), IR Characterization such as Fig. 1 Shown, presoma tree resin P1, P2, P3, P4, P5, P6 are in 1270cm-1There is strong absworption peak in place, and the C-Cl of corresponding benzyl chloride stretches Contracting vibration；And P6 is in 907cm-1And 988cm-1Also there is moderate strength absorption peak in place, corresponds to C-H stretching vibrations in suspended double bond； In 1608cm-1And 1450cm-1Also C=C the and C=N stretching vibrations for phenyl ring and imidazole ring occur, thus illustrate 4- vinyl Benzyl chloride, N- vinyl imidazoles and divinylbenzene copolyreaction success.
2) Friedel-Crafts reacts：
Be separately added into dry three neck round bottom flask 15g ternary polymerization precursor resin P1, P2, P3, P4, P5, P6 and 80mL 1,2- dichloroethanes, sealing swelling is overnight under room temperature.Reflux condensing tube and electric mixer are loaded onto, is sequentially added The anhydrous TiCl of 1.15g, 3.23g, 5.54g, 8.3g, 2.41g, 1.03g4Make catalyst, moderate-speed mixer 30min.80 DEG C are warming up to, Back flow reaction 8h.Stop heating, terminated and reacted with 80mL50% ethanol waters, filter resin, uses absolute ethyl alcohol, quality successively The aqueous hydrochloric acid solution that score is 1% alternately washs 3~4 times and is clarified to cleaning solution, is put into Soxhlet extractor and is taken out with absolute ethyl alcohol Carry 12h.Normal drying 12h, then be dried in vacuo for 24 hours obtains hypercrosslinked polymeric resin HP1, HP2, HP3, HP4, HP5, HP6, infrared Characterization is as shown in Figure 1,1270cm-1The absorption peak at place obviously weakens, and HP6 is in 907cm-1And 988cm-1The absorption peak at place is also bright It is aobvious to weaken, illustrate that chloromethyl and suspended double bond content drastically reduce, methylene-crosslinked on resin, crosslinking degree sharply increases.
The mass percent of chlorine is 10.73% in the precursor resin P1 of preparation, BET specific surface area, Kong Rong and average pore size All it is 0.The mass percent of chlorine is 1.17% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP1 of preparation, and BET specific surface area is 1246m2/ g, Kong Rongwei 0.7543cm3/ g, average pore size 2.54nm.
The mass percent of chlorine is 9.92% in the precursor resin P2 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 2.53% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP2 of preparation, and BET specific surface area is 1102.1m2/ g, Kong Rongwei 0.981cm3/ g, average pore size 4.14nm.
The mass percent of chlorine is 8.16% in the precursor resin P3 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 2.93% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP3 of preparation, and BET specific surface area is 702.4m2/ g, Kong Rongwei 0.799cm3/ g, average pore size 4.99nm.
The mass percent of chlorine is 6.93% in the precursor resin P4 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 3.93% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP4 of preparation, and BET specific surface area is 474.4m2/ g, Kong Rongwei 0.478cm3/ g, average pore size 4.94nm.
The mass percent of chlorine is 11.7% in the precursor resin P5 of preparation, BET specific surface area 150.3m2/ g, Kong Rong For 0.122cm3/ g, average pore size 2.89nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP5 of preparation 1.92%, BET specific surface area 1080m2/ g, Kong Rongwei 1.71cm3/ g, average pore size 6.62nm
The mass percent of chlorine is 2.14% in the precursor resin P6 of preparation, BET specific surface area 656.6m2/ g, Kong Rong For 0.986cm3/ g, average pore size 5.22nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP6 of preparation 0.73%, BET specific surface area 1091m2/ g, Kong Rongwei 2.31cm3/ g, average pore size 8.53nm.
Modified with Polar Monomer superhigh cross-linking prepared by embodiment 4 is attached to salicylic maximum in salicylic isothermal adsorption Amount is respectively 182.1mg/g, 233.5mg/g, 206.5mg/g, 194.9mg/g, 190.1mg/g, 153.6mg/g, and is adsorbed fast Speed reaches balance in 10min.
Modified with Polar Monomer hypercrosslinked polymeric resin prepared by embodiment 4 is to salicylic acid solution by 5 cycles of adsorption-desorption, HP2 Resin still has 92.4% or more reuse rate.In practical applications, which may be reused repeatedly.
Embodiment 5：
1) prepared by ternary polymerization presoma resin：
On the water bath device equipped with mechanical agitator, condenser pipe and thermometer, 500mL three neck round bottom flask is placed, first It is added water phase (distilled water 180mL, the polyvinyl alcohol 20mL that mass fraction is 1%), the rear 4- second that six kinds of 20g not ratios are added Alkenyl benzyl chloride, 2- methyl-1s-vinyl imidazole and divinylbenzene mixture, ortho-xylene 60g, azodiisobutyronitrile (AIBN) 0.2g.45 DEG C are heated to, adjusts to suitable mixing speed and stirs 30min, 75 DEG C of reaction 3h is warming up to, is warming up to 85 DEG C of reactions 2h is continuously heating to 95 DEG C of reaction 3h.After cooling, absolute ethyl alcohol, hot water, cold water is used alternately to wash 3~4 times to cleaning solution successively Clarification, 12h is extracted in Soxhlet extractor with petroleum ether, and vacuum drying for 24 hours, obtains ternary polymerization precursor resin P1 (4- ethylene Base benzyl chloride:N- vinyl imidazoles:Divinylbenzene mass percent is 80%:5%:15%), P2 (4- vinyl benzyl chlorides:N- ethylene Base imidazoles:Divinylbenzene mass percent is 75%:10%:15%), P3 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Diethyl Alkene benzene mass percent is 70%:15%:15%), P4 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene quality percentage Than being 60%:25%:15%), P5 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 5%: 15%:80%), P6 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 7%:3%:90%), red It is outer to characterize as shown in Figure 1, presoma tree resin P1, P2, P3, P4, P5, P6 are in 1270cm-1There is strong absworption peak, corresponding benzyl in place The C-Cl stretching vibrations of chlorine；And P6 is in 907cm-1And 988cm-1Also there is moderate strength absorption peak in place, corresponds to C- in suspended double bond H stretching vibrations；In 1608cm-1And 1450cm-1Also C=C the and C=N stretching vibrations for phenyl ring and imidazole ring occur, thus say Bright 4- vinyl benzyl chlorides, N- vinyl imidazoles and divinylbenzene copolyreaction success.
2) Friedel-Crafts reacts：
Be separately added into dry three neck round bottom flask 15g ternary polymerization precursor resin P1, P2, P3, P4, P5, P6 and 80mL 1,2- dichloroethanes, sealing swelling is overnight under room temperature.Reflux condensing tube and electric mixer are loaded onto, is sequentially added The anhydrous SnCl of 1.15g, 3.53g, 6.24g, 9.3g, 3.81g, 0.93g4Make catalyst, moderate-speed mixer 30min.80 DEG C are warming up to, Back flow reaction 10h.Stop heating, terminated and reacted with 80mL50% ethanol waters, filter resin, uses absolute ethyl alcohol, matter successively It measures the aqueous hydrochloric acid solution that score is 1% and alternately washs 3~4 times to cleaning solution clarification, be put into Soxhlet extractor and use absolute ethyl alcohol Extract 12h.Normal drying 12h, then be dried in vacuo for 24 hours obtains hypercrosslinked polymeric resin HP1, HP2, HP3, HP4, HP5, HP6, red Outer characterization is as shown in Figure 1,1270cm-1The absorption peak at place obviously weakens, and HP6 is in 907cm-1And 988cm-1The absorption peak at place It is apparent to weaken, illustrate that chloromethyl and suspended double bond content drastically reduce, methylene-crosslinked on resin, crosslinking degree drastically increases Add.
The mass percent of chlorine is 12.33% in the precursor resin P1 of preparation, BET specific surface area, Kong Rong and average pore size All it is 0.The mass percent of chlorine is 1.13% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP1 of preparation, and BET specific surface area is 1356m2/ g, Kong Rongwei 0.9543cm3/ g, average pore size 2.44nm.
The mass percent of chlorine is 10.92% in the precursor resin P2 of preparation, BET specific surface area, Kong Rong and average pore size All it is 0.The mass percent of chlorine is 2.51% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP2 of preparation, and BET specific surface area is 1002.1m2/ g, Kong Rongwei 1.181cm3/ g, average pore size 3.54nm.
The mass percent of chlorine is 9.16% in the precursor resin P3 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 3.53% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP3 of preparation, and BET specific surface area is 682.4m2/ g, Kong Rongwei 0.799cm3/ g, average pore size 4.19nm.
The mass percent of chlorine is 6.93% in the precursor resin P4 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 4.93% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP4 of preparation, and BET specific surface area is 474.4m2/ g, Kong Rongwei 0.572cm3/ g, average pore size 4.79nm.
The mass percent of chlorine is 10.87% in the precursor resin P5 of preparation, BET specific surface area 130.3m2/ g, Kong Rong For 0.152cm3/ g, average pore size 3.19nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP5 of preparation 1.52%, BET specific surface area 1090m2/ g, Kong Rongwei 1.91cm3/ g, average pore size 6.92nm.
The mass percent of chlorine is 1.83% in the precursor resin P6 of preparation, BET specific surface area 606.6m2/ g, Kong Rong For 1.086cm3/ g, average pore size 5.92nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP6 of preparation 0.93%, BET specific surface area 1100m2/ g, Kong Rongwei 2.49cm3/ g, average pore size 8.53nm.
Modified with Polar Monomer superhigh cross-linking prepared by embodiment 5 is attached to the maximum of betanaphthol in the isothermal adsorption of betanaphthol Amount is respectively 358.9mg/g, 379.1mg/g, 307.8mg/g, 212.6mg/g, 331.6mg/g, 398.5mg/g, and is adsorbed fast Speed reaches balance in 30min.
Modified with Polar Monomer hypercrosslinked polymeric resin prepared by embodiment 5 is to salicylic acid solution by 5 cycles of adsorption-desorption, HP2 Resin still has 92.4% or more reuse rate.In practical applications, which may be reused repeatedly.
Embodiment 6：
1) prepared by ternary polymerization presoma resin：
On the water bath device equipped with mechanical agitator, condenser pipe and thermometer, 500mL three neck round bottom flask is placed, first It is added water phase (distilled water 180mL, the polyvinyl alcohol 20mL that mass fraction is 1%), the rear 4- second that six kinds of 20g not ratios are added Alkenyl benzyl chloride, 2- ethyl -1- vinyl imidazoles and divinylbenzene mixture, ortho-xylene 40g, azodiisobutyronitrile (AIBN) 0.2g.45 DEG C are heated to, adjusts to suitable mixing speed and stirs 30min, 75 DEG C of reaction 3h is warming up to, is warming up to 85 DEG C of reactions 2h is continuously heating to 95 DEG C of reaction 3h.After cooling, absolute ethyl alcohol, hot water, cold water is used alternately to wash 3~4 times to cleaning solution successively Clarification, 8h is extracted in Soxhlet extractor with petroleum ether, and vacuum drying for 24 hours, obtains ternary polymerization precursor resin P1 (4- vinyl Benzyl chloride:N- vinyl imidazoles:Divinylbenzene mass percent is 80%:15%:5%), P2 (4- vinyl benzyl chlorides:N- vinyl Imidazoles:Divinylbenzene mass percent is 65%:30%:5%), P3 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene Mass percent is 77.5%:12.5%:10%), P4 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene quality percentage Than being 75%:15%:10%), P5 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 25%: 5%:70%), P6 (4- vinyl benzyl chlorides:N- vinyl imidazoles:Divinylbenzene mass percent is 10%:5%:85%), red It is outer to characterize as shown in Figure 1, presoma tree resin P1, P2, P3, P4, P5, P6 are in 1270cm-1There is strong absworption peak, corresponding benzyl in place The C-Cl stretching vibrations of chlorine；And P6 is in 907cm-1And 988cm-1Also there is moderate strength absorption peak in place, corresponds to C- in suspended double bond H stretching vibrations；In 1608cm-1And 1450cm-1Also C=C the and C=N stretching vibrations for phenyl ring and imidazole ring occur, thus say Bright 4- vinyl benzyl chlorides, N- vinyl imidazoles and divinylbenzene copolyreaction success.
2) Friedel-Crafts reacts：
Be separately added into dry three neck round bottom flask 15g ternary polymerization precursor resin P1, P2, P3, P4, P5, P6 and 80mL 1,2- dichloroethanes, sealing swelling is overnight under room temperature.Reflux condensing tube and electric mixer are loaded onto, is sequentially added The anhydrous FeCl of 1.71g, 4.52g, 5.34g, 10.2g, 2.42g, 1.52g3Make catalyst, moderate-speed mixer 30min.It is warming up to 80 DEG C, back flow reaction 8h.Stop heating, with 80mL50% ethanol waters terminate react, filter resin, successively use absolute ethyl alcohol, The aqueous hydrochloric acid solution that mass fraction is 1% alternately washs 3~4 times and is clarified to cleaning solution, is put into Soxhlet extractor with anhydrous second Alcohol extracts 12h.Normal drying 12h, then be dried in vacuo for 24 hours, hypercrosslinked polymeric resin HP1, HP2, HP3, HP4, HP5, HP6 are obtained, IR Characterization is as shown in Figure 1,1270cm-1The absorption peak at place obviously weakens, and HP6 is in 907cm-1And 988cm-1The absorption peak at place Also apparent to weaken, illustrate that chloromethyl and suspended double bond content drastically reduce, methylene-crosslinked on resin, crosslinking degree drastically increases Add.
The mass percent of chlorine is 11.93% in the precursor resin P1 of preparation, BET specific surface area, Kong Rong and average pore size All it is 0.The mass percent of chlorine is 0.63% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP1 of preparation, and BET specific surface area is 1326m2/ g, Kong Rongwei 0.9043cm3/ g, average pore size 2.14nm.
The mass percent of chlorine is 9.92% in the precursor resin P2 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 1.91% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP2 of preparation, and BET specific surface area is 1092.8m2/ g, Kong Rongwei 1.321cm3/ g, average pore size 2.94nm.
The mass percent of chlorine is 8.96% in the precursor resin P3 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 3.53% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP3 of preparation, and BET specific surface area is 702.4m2/ g, Kong Rongwei 0.819cm3/ g, average pore size 3.12nm.
The mass percent of chlorine is 7.12% in the precursor resin P4 of preparation, and BET specific surface area, Kong Rong and average pore size are all It is 0.The mass percent of chlorine is 3.93% in the Modified with Polar Monomer hypercrosslinked polymeric resin HP4 of preparation, and BET specific surface area is 474.4m2/ g, Kong Rongwei 0.602cm3/ g, average pore size 4.64nm.
The mass percent of chlorine is 9.37% in the precursor resin P5 of preparation, BET specific surface area 150.3m2/ g, Kong Rong For 0.162cm3/ g, average pore size 4.19nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP5 of preparation 1.02%, BET specific surface area 1090m2/ g, Kong Rongwei 2.31cm3/ g, average pore size 7.08nm
The mass percent of chlorine is 1.63% in the precursor resin P6 of preparation, BET specific surface area 596.6m2/ g, Kong Rong For 1.586cm3/ g, average pore size 6.42nm.The mass percent of chlorine is in the Modified with Polar Monomer hypercrosslinked polymeric resin HP6 of preparation 0.63%, BET specific surface area 1001m2/ g, Kong Rongwei 2.47cm3/g, average pore size 8.93nm.
Modified with Polar Monomer superhigh cross-linking prepared by embodiment 6 is attached to the maximum of betanaphthol in the isothermal adsorption of betanaphthol Amount is respectively 358.9mg/g, 379.1mg/g, 307.8mg/g, 212.6mg/g, 331.6mg/g, 398.5mg/g, and is adsorbed fast Speed reaches balance in 30min.
Modified with Polar Monomer hypercrosslinked polymeric resin prepared by embodiment 6 is to salicylic acid solution by 5 cycles of adsorption-desorption, HP2 Resin still has 92.4% or more reuse rate.In practical applications, which may be reused repeatedly.
Embodiment 7
The absorption property for modifying imidazoles prepared by Examples 1 to 6 post-crosslinking resin is tested.
(1) isothermal adsorption：
It chooses benzoic acid (or salicylic acid, phenol, rhodamine B, betanaphthol) and is used as adsorbate, compare the Modified with Polar Monomer of preparation Absorption property of the hypercrosslinked polymeric resin to adsorbate in aqueous solution.The assay method of adsorption isotherm is as follows：
One group of conical flask with cover is taken, the adsorbate for being separately added into about 0.05g resins and 50mL various concentrations wherein is water-soluble They are placed in water bath chader by liquid, at a certain temperature constant temperature oscillation 4h, and absorption is made to reach balance.With UV, visible light point The absorbance value of light photometer raffinate after the maximum absorption wave strong point of adsorbate measures absorption, and be converted into according to standard curve The equilibrium concentration C of adsorbatee, adsorbance is calculated according to the following formula：
qe=(C0-Ce)V/W
In formula：qeFor adsorbance (mg/g), C0、CeRespectively absorption is preceding and adsorbs the concentration of adsorbate in rear solution (mg/L), V is the volume (L) of adsorption liquid, and W is the quality (g) of resin.With equilibrium concentration CeFor abscissa, adsorbance qeIt is sat to be vertical Mark, makees the resin at a certain temperature to the adsorption isotherm of adsorbate in aqueous solution.
(2) adsorption dynamics adsorption kinetics：
About 0.5g resins are weighed in 500mL conical flasks, benzoic acid (or the bigcatkin willow of 250mL original concentrations 500mg/L is added Acid, phenol, rhodamine B, betanaphthol), conical flask is put into constant temperature oscillator and is shaken.The timing since being added solution, one It fixes time and pipettes 0.5mL adsorption liquids in the small beaker of 100mL, different time points adsorption liquid is measured with ultraviolet-visible spectrometer Absorbance and original solution absorbance.Solution concentration is calculated by calibration curve equation.Resin is calculated according still further to formula 2-2 In the adsorbance q of t momentt：
qt=(C0-Ct)V/W
With t (min) for abscissa, qt (mg/g) is ordinate, draws out resin para Toluic Acid (or salicylic acid, phenol, sieve Red bright B, betanaphthol) curve of adsorption kinetics.
(3) Dynamic Adsorption-desorption：
The resin of 7.0mL is measured in beaker, the wetting of 30mL50% ethanol waters is added, is put into ultrasonic cleaner Ultrasonic 10min, then be carefully encased in the glass column that internal diameter is 16mm.With 540mg/L benzoic acid (or salicylic acid, phenol, Luo Dan Bright B, betanaphthol) solution flows through glass column, and adjusting the piston of glass column lower end makes automatic collector collect a pipe stream every 5min Go out liquid.Its absorbance is measured, until absorbance and initial benzoic acid (or salicylic acid, phenol, rhodamine B, the β-naphthalene of efflux Phenol) solution absorbance it is identical.Using BV as abscissa, C/C0For ordinate, resin Dynamic Adsorption curve is drawn out.Adsorption equilibrium Afterwards, it is washed with distilled water resin.Prepare eluent with the NaOH and absolute ethyl alcohol of the 0.01mol/L of equivalent, with the eluent into Row desorption.Adjusting the piston of glass column lower end makes automatic collector collect a pipe desorption liquid every 3min.Its absorbance is measured, directly Absorbance to desorption liquid is 0.Using BV as abscissa, C is ordinate, draws out the dynamic desorption curve of resin.
(4) repeat performance：
The 100mL conical flasks for taking 8 dryings with grinding port plug, are separately added into about 0.05g resins, are separately added into thereto 50mL mass fractions are the benzoic acid (or salicylic acid, phenol, rhodamine B, betanaphthol) of 600mg/L.After being sealed, it is put into 298K Thermostatic control oscillator vibration in, constant temperature oscillation 4h.After adsorption equilibrium, the equilibrium adsorption capacity of resin is calculated.Resin is filtered out Filtrate is outwelled after coming, the resin of adsorption saturation is obtained, resin is dried in original conical flask, sequentially adds the desorption of 50mL Agent ((A) 20%EtOH (B) 50%EtOH (C) 80%EtOH (D) 100%EtOH (E) 20%EtOH+0.01mol/LNaOH (F) 50%EtOH+0.01mol/LNaOH (G) 80%EtOH+0.01mol/LNaOH (H) 100%EtOH+0.01mol/LNaOH), Constant temperature oscillation 4h is to desorption equilibrium under 298K.Filtrate is outwelled after resin is filtered out, and is dried in original conical flask.More than An as adsorption/desorption experiment.Above-mentioned steps are repeated four times again, measure the absorbance value of adsorbate in solution after adsorbing, meter Calculate each equilibrium adsorption capacity.

Claims (6)

1. a kind of controllable method for preparing of Modified with Polar Monomer hypercrosslinked polymeric resin, it is characterised in that：To include 4- vinyl benzyl chloride lists Raw material including body, vinyl imidazole class monomer and divinylbenzene crosslink agent obtains presoma resin by suspension copolymerization；It is described Presoma resin carries out Friedel-Crafts reactions, has obtained Modified with Polar Monomer superhigh cross-linking under Louis acid catalysis effect Resin；Wherein, the mass percent of 4- vinylbenzylchloride monomers, vinyl imidazole class monomer and divinylbenzene crosslink agent is (5%~80%):(3%~30%):(10%~90%)；
The raw material includes ortho-xylene pore-foaming agent；The quality of the ortho-xylene pore-foaming agent is 4- vinyl chloride lists 1~3 times of body, vinyl imidazole class monomer and divinylbenzene crosslink agent gross mass；
The lewis acid is FeCl3、ZnCl2、AlCl3、TiCl4、SnCl4At least one of；The lewis acidic use Amount is the 120%~140% of the presoma resin medium vinyl imidazoles monomeric unit mole.
2. the controllable method for preparing of Modified with Polar Monomer hypercrosslinked polymeric resin according to claim 1, it is characterised in that：Described Vinyl imidazole class monomer is 1- vinyl imidazoles, 2- methyl-1s-vinyl imidazole, in 2- ethyl -1- vinyl imidazoles extremely Few one kind.
3. the controllable method for preparing of Modified with Polar Monomer hypercrosslinked polymeric resin according to claim 1, it is characterised in that：Described The mass percentage content of chlorine is 2%~12.5% in presoma resin, and BET specific surface area is 0~650m2/ g, Kong Rongwei 0~ 1.0cm3/ g, average pore size are 0~6.5nm.
4. the controllable method for preparing of Modified with Polar Monomer hypercrosslinked polymeric resin according to claim 1, it is characterised in that：It is described Friedel-Crafts reaction condition be：8~12h is reacted at a temperature of 80~85 DEG C.
5. the controllable method for preparing of Modified with Polar Monomer hypercrosslinked polymeric resin according to claim 4, it is characterised in that：Described The mass percentage content of residual chlorine is 0.5%~5.0% in the hypercrosslinked polymeric resin that Friedel-Crafts reactions generate, BET specific surface area is 400~1400m20.4~2.5cm of/g, Kong Rongwei3/ g, average pore size are 2~9nm.
6. the application of Modified with Polar Monomer hypercrosslinked polymeric resin, feature made from Claims 1 to 5 any one of them preparation method It is：Applied to the polar molecule armaticity organic compound in selective absorption water；
The polar molecule armaticity organic compound be benzoic acid, salicylic acid, phenol, rhodamine B, in betanaphthol at least It is a kind of；
BET specific surface area is 400~1400m20.4~1.5cm of/g, Kong Rongwei3/ g, the Modified with Polar Monomer that average pore size is 2~5nm Hypercrosslinked polymeric resin is applied to benzoic acid, salicylic acid, phenol, at least one of betanaphthol in selective absorption water；
BET specific surface area is 1000~1100m21.0~2.5cm of/g, Kong Rongwei3/ g, the Modified with Polar Monomer that average pore size is 3~9nm Hypercrosslinked polymeric resin is applied to the rhodamine B in selective absorption water.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1073458A (en) * 1991-12-19 1993-06-23 陶氏化学公司 Inoculation porous copolymers and ion exchange resin prepared therefrom
CN103182324A (en) * 2011-12-28 2013-07-03 中国石油天然气股份有限公司 Preparation method of hydrophobic organic framework solid base catalyst
CN103910823A (en) * 2014-03-21 2014-07-09 中南大学 Preparation method and application of polar group-modified pendent double bond post-crosslinked polydivinylbenzene resin
CN104910313A (en) * 2015-06-24 2015-09-16 中南大学 Method for preparing polar modified ultrahighly-crosslinked resin and application of resin
US20150315042A1 (en) * 2012-10-04 2015-11-05 Evoqua Water Technologies Llc High-Performance Anion Exchange Membranes and Methods of Making Same
CN105037626A (en) * 2015-07-31 2015-11-11 北京石油化工学院 Method for preparing big hole large particle diameter polymer microspheres

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1073458A (en) * 1991-12-19 1993-06-23 陶氏化学公司 Inoculation porous copolymers and ion exchange resin prepared therefrom
CN103182324A (en) * 2011-12-28 2013-07-03 中国石油天然气股份有限公司 Preparation method of hydrophobic organic framework solid base catalyst
US20150315042A1 (en) * 2012-10-04 2015-11-05 Evoqua Water Technologies Llc High-Performance Anion Exchange Membranes and Methods of Making Same
CN103910823A (en) * 2014-03-21 2014-07-09 中南大学 Preparation method and application of polar group-modified pendent double bond post-crosslinked polydivinylbenzene resin
CN104910313A (en) * 2015-06-24 2015-09-16 中南大学 Method for preparing polar modified ultrahighly-crosslinked resin and application of resin
CN105037626A (en) * 2015-07-31 2015-11-11 北京石油化工学院 Method for preparing big hole large particle diameter polymer microspheres

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
N-乙烯基咪唑共聚交联微球的制备及其对二氯苯酚的吸附特性;王蕊欣等;《功能高分子学报》;20100930;第23卷(第3期);第275-280页 *

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