CN102977487B - Cross-linking agent modified XAD-4 resin and method for preparing same - Google Patents
Cross-linking agent modified XAD-4 resin and method for preparing same Download PDFInfo
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- CN102977487B CN102977487B CN201210476825.1A CN201210476825A CN102977487B CN 102977487 B CN102977487 B CN 102977487B CN 201210476825 A CN201210476825 A CN 201210476825A CN 102977487 B CN102977487 B CN 102977487B
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Abstract
The invention discloses a cross-linking agent modified XAD-4 resin, which is a mesoporous resin containing rich micropores and prepared from a cross-linking agent and an XAD-4 resin through Friedel-Crafts reaction, wherein the pore diameters of the mesoporous resin are distributed between 1 to 9.5 nm, the average pore diameter is 2.58-4 nm, the specific surface area is 721-1284 m<2>/g, and the pore volume is 0.67-1.1 cm<3>/g. The method for preparing the cross-linking agent modified XAD-4 resin comprises the following step of carrying out the Friedel-Crafts reaction between the cross-linking agent and the XAD-4 resin to prepare the modified XAD-4 resin, wherein the dosage of the cross-linking agent is 50-100% of the quantity of the XAD-4 resin material. The adsorbent has the characteristics of large specific surface area, narrow pore diameter distribution and easily controllable porous structure, and is obviously superior to the XAD-4 resin in the adsorption capability to nonpolar and weakly polar materials; and therefore, the adsorbent is wide in application prospect in fields of treating and recycling phenols wastewater and the like.
Description
Technical field
The present invention relates to a kind of linking agent and modify XAD-4 resin and preparation method thereof, belong to polymer adsorbing material field.
Background technology
XAD-4 resin is considered to the Typical Representative of s-generation polymeric adsorbent, is produced by Rhom and Hass's research and development.It has higher specific surface area, larger pore volume and the constitutional features such as physical strength preferably, these excellent constitutional featuress are given it to the nonpolar and good adsorptive power of low-pole material (benzene, phenol etc.), and therefore XAD-4 resin is having significant application value aspect the improvement of nonpolar and low-pole phenolic compound, tensio-active agent, medicine, phenols and sterilant and resource utilization at present.
But on the one hand because the skeleton of XAD-4 resin is the polystyrene of strong-hydrophobicity, its strong-hydrophobicity makes it need before use, with polar reagent (as: methyl alcohol) pre-treatment, to have increased the complicacy of operation on the one hand; Because XAD-4 resin is macroporous resin, pore size distribution is wider (with the test of BJH method, draws its pore size distribution 2 ~ 15nm on the other hand; With the test of DFT method, draw its pore size distribution 2 ~ 30nm), therefore it is to the adsorptive capacity of micromolecular compound (as: phenol) little.For improving the XAD-4 resin adsorptive power to micromolecular compound, improve the wetting ability of XAD-4 resin, improve the pore structure of XAD-4 resin, and develop thus the New Polymeric Adsorbent that a class has certain polarity and appropriate bore structure and seem particularly important.
Summary of the invention
The linking agent that the object of the present invention is to provide that a kind of specific surface area is large, pore size distribution is narrow, mean pore size is little, can obviously promote the adsorptive power to nonpolar and low-pole compound is modified XAD-4 resin.
Another object of the present invention is to provide a kind of linking agent simple to operate to modify the preparation method of XAD-4 resin.
The invention provides a kind of linking agent and modify XAD-4 resin, described modification XAD-4 resin is by linking agent and XAD-4 resin, Friedel-Crafts to occur to react the mesoporous resin that enriches micropore that contains making; Described mesoporous resin pore size distribution 1 ~ 9.5nm, mean pore size 2.58 ~ 4nm, specific surface area 721 ~ 1284m
2/ g, pore volume 0.67 ~ 1.1cm
3/ g.
50 ~ 100% of the amount that in foregoing invention, dosage of crosslinking agent is resinous substances.
Described linking agent comprises: to dibenzyl chlorine, to dichloromethyl biphenyl, to dichloromethyl-Isosorbide-5-Nitrae-diphenyl butane or vinyl benzyl chloride.
The present invention also provides a kind of preparation method of modification XAD-4 resin described above, and specifically linking agent with XAD-4 resin, Friedel-Crafts occurs and reacts preparation modification XAD-4 resin; Described dosage of crosslinking agent be XAD-4 resinous substances amount 50 ~ 100%.
Foregoing invention method is that linking agent is dissolved in after organic solvent and joins in XAD-4 resin and obtain mixed solution; After swelling at 0 ~ 5 DEG C the XAD-4 resin in obtained mixed solution, add catalyst reaction 1 ~ 3h; At 45 ~ 70 DEG C of reaction 6 ~ 10h, at 75 ~ 85 DEG C, continue, after reaction 3 ~ 5h, to obtain final product again.
Swelling described in foregoing invention method, the time is 12 ~ 24h.
Catalyzer described in foregoing invention method comprises: tin tetrachloride, iron trichloride or aluminum chloride.
In foregoing invention method, catalyst levels is 100 ~ 300% of linking agent amount of substance.
The solvent in foregoing invention method, linking agent being dissolved comprises: one or both mixed solvent in 1,2-ethylene dichloride or oil of mirbane, described solvent load is 10g XAD-4 resin/50 ~ 80mL.
Linking agent described in foregoing invention method comprises: to dibenzyl chlorine (DCX), to dichloromethyl biphenyl (BCMBP), to dichloromethyl-Isosorbide-5-Nitrae-diphenyl butane (DPB) or vinyl benzyl chloride (VBC).
Modification XAD-4 resin pore size distribution 1 ~ 9.5nm that foregoing invention method makes, mean pore size 2.58 ~ 4nm, specific surface area 721 ~ 1284m
2/ g, pore volume 0.67 ~ 1.1cm
3/ g.
The concrete preparation method of modification XAD-4 resin of the present invention:
Linking agent is dissolved in solvent, join in XAD-4 resin, obtain mixed solution, the mixed solution of acquisition is placed in after the swelling 12 ~ 24h of ice-water bath; Add catalyzer in ice-water bath, to continue reaction 1 ~ 3h.Be warming up to 45 ~ 70 DEG C of reaction 6 ~ 10h, then be warming up to after 75 ~ 85 DEG C of continuation reaction 3 ~ 5h; Incline and reaction mother liquor, the aqueous hydrochloric acid that is 0.5 ~ 1.5% with mass percent and dehydrated alcohol alternately wash after 2 ~ 5 times, with dehydrated alcohol extracting resin 8 ~ 12h, obtain modifying XAD-4 resin.
Modification of the present invention XAD-4 resin-phase is for be cross-linked line style styrene polymer or low cross-linking (degree of crosslinking is not more than 8%) styrene polymer generation small-bore sorbent material advantage and the technical difficulty on producing effect by chloromethyl ether in prior art.Modification XAD-4 resin of the present invention is (as: to dibenzyl chlorine by the special linking agent containing dual-functional group or multi-functional base, to dichloromethyl biphenyl, to dichloromethyl-1, 4-diphenyl butane or vinyl benzyl chloride etc.) to be filled into a kind of high crosslinked cancellated polystyrene resin of (degree of crosslinking ≈ 80%) tool by chamical binding be in the macropore of XAD-4 resin, improve the pore structure of XAD-4 resin with this, acquisition pore size distribution is narrow, mean pore size is little, and pore volume keeps larger, nonpolar in the aqueous solution and adsorptive power low-pole material are had to the modification XAD-4 resin of very big raising, and can be by regulating the consumption of linking agent to reach the Effective Regulation of this resin pore structure, this class linking agent is modified XAD-4 resin and preparation method thereof and is had no report.
Beneficial effect of the present invention:
1, linking agent of the present invention modify XAD-4 resin overcome that existing XAD-4 resin pore size distribution is wider, mean pore size large, to shortcoming nonpolar or that low-pole compound adsorptive capacity is little.
2, linking agent of the present invention modify XAD-4 resin pore size distribution at the existing XAD-4 resin of 1 ~ 9.5nm(at 2 ~ 15nm); And XAD-4 resin relatively, the larger hole of resin of modified is nearly all filled, and micropore increases greatly, and pore volume increases to 0.67 ~ 1.1cm
3/ g.
3, another feature of the present invention is, by regulating the consumption of weighting agent (linking agent), can regulate and control pore size distribution and the mean pore size of resin.Because the resin after modification has special pore structure, nonpolar and organic molecule adsorptive power low-pole are improved greatly, the relative XAD-4 resin of adsorptive capacity increases by 20 ~ 50%, and rate of adsorption soon, also easy wash-out, resin is reusable, has broad prospect of application in the field such as improvement and resource utilization of phenols wastewater.
Brief description of the drawings
The graph of pore diameter distribution (acquisition of BJH method) that [Fig. 1] is XAD-4 resin and the present invention modifies XAD-4 resin: 1 is XAD-4 resin; 2 is DCX modification XAD-4 resin; 3 is BCMBP modification XAD-4 resin.
The graph of pore diameter distribution (acquisition of DFT method) that [Fig. 2] is XAD-4 resin and the present invention modifies XAD-4 resin: 1 is XAD-4 resin; 2 is DCX modification XAD-4 resin; 3 is BCMBP modification XAD-4 resin.
The graph of pore diameter distribution (acquisition of DFT method) that [Fig. 3] is XAD-4 resin and the present invention modifies XAD-4 resin: 1 is XAD-4 resin; 2 modify XAD-4 resin (dosage of crosslinking agent be XAD-4 resin 50%) for DCX; 3 modify XAD-4 resin (dosage of crosslinking agent be XAD-4 resin 100%) for DCX.
[Fig. 4] modifies the adsorption isothermal line of XAD-4 resin to phenol in aqueous solution for XAD-4 resin and the present invention: 1 is XAD-4 resin; 2 is DCX modification XAD-4 resin; 3 is BCMBP modification XAD-4 resin.
[Fig. 5] modifies XAD-4 resin Pyrogentisinic Acid kinetic curve for XAD-4 resin and the present invention: 1 is XAD-4 resin; 2 is DCX modification XAD-4 resin; 3 is BCMBP modification XAD-4 resin.
[Fig. 6] modifies XAD-4 resin Pyrogentisinic Acid's dynamic adsorption curve for XAD-4 resin and the present invention: 1 for XAD-4 resin 2 be DCX modification XAD-4 resin; 3 is BCMBP modification XAD-4 resin.
Embodiment
Embodiment 1
In the 250mL there-necked flask that mechanical stirrer, reflux condensing tube and thermometer are housed, add 9.5g XAD-4 resin, anhydrous 1 with 50mL, 2-ethylene dichloride dissolves 7.9g DCX and also joins in there-necked flask, mixing solutions in 0 ~ 5 DEG C of ice-water bath swelling 12 hours.Middling speed adds 11mL anhydrous stannic chloride and keeps 2 hours under stirring in there-necked flask; Be warming up to 60 DEG C of reactions 8 hours, then be warming up to 80 DEG C of reactions 4 hours.Use dehydrated alcohol termination reaction, incline and solution, the aqueous hydrochloric acid that is 1% by mass percent and dehydrated alcohol alternately wash 3 times, shift resin to apparatus,Soxhlet's, use dehydrated alcohol extracting resin 8 hours, and vacuum-drying is for subsequent use.The specific surface area 841.7m of resin
2/ g, pore volume 0.7686cm
3/ g, pore size distribution 1 ~ 8.8nm, mean pore size 3.65nm.
Embodiment 2
With 120mL1,2-ethylene dichloride dissolves 18.10g BCMBP, joins in 250mL there-necked flask, then add 15.0g XAD-4 resin in there-necked flask, and 0 ~ 5 DEG C swelling 24 hours.Start mechanical stirring, in there-necked flask, add fast 18mL anhydrous stannic chloride, and keep 3 hours; Again mixing solutions is warming up to 60 DEG C of reactions 10 hours, then is warming up to 85 DEG C of reactions 4 hours.Use acetone termination reaction, incline and solution, the aqueous hydrochloric acid that is 1% by mass percent and dehydrated alcohol alternately wash 3 times, until solution clarification.Resin transfer, to apparatus,Soxhlet's, is used to dehydrated alcohol extracting resin 12 hours, and vacuum-drying is for subsequent use.The specific surface area 1228m of resin
2/ g, pore volume 1.068cm
3/ g, pore size distribution 1 ~ 8.6nm, mean pore size 3.43nm.
Embodiment 3
In the 250mL there-necked flask that mechanical stirrer, reflux condensing tube and thermometer are housed, add 10.0g XAD-4 resin, with 60mL1,2-ethylene dichloride dissolves 13.20g DPB and also joins in there-necked flask, mixing solutions in 0 ~ 5 DEG C of ice-water bath swelling 12 hours.Middling speed adds 10.8mL anhydrous stannic chloride and keeps 2 hours under stirring in ice-water bath in there-necked flask; Be warming up to 65 DEG C and keep 8 hours, then be warming up to 80 DEG C of maintenances 4 hours.Use dehydrated alcohol termination reaction, incline and solution, the aqueous hydrochloric acid that is 1% by mass percent and dehydrated alcohol alternately wash 3 times, shift resin to apparatus,Soxhlet's, use dehydrated alcohol extracting resin 8 hours, and vacuum-drying is for subsequent use.The specific surface area 721.1m of resin
2/ g, pore volume 0.6274cm
3/ g, pore size distribution 1 ~ 9.0nm, mean pore size 3.88nm.
Embodiment 4
In 250mL there-necked flask, add dry XAD-4 resin 10.0g, anhydrous 1 with 50mL, 2-ethylene dichloride dissolves 7.34gVBC and also joins in there-necked flask, mixing solutions in 0 ~ 5 DEG C of ice-water bath swelling 15 hours.Middling speed adds 11.5mL anhydrous stannic chloride and keeps 1 hour under stirring in ice-water bath in there-necked flask; Be warming up to 60 DEG C and keep 8 hours, then be warming up to 80 DEG C of maintenances 4 hours.Stopped reaction, cooling hypsokinesis goes out solution, and the aqueous hydrochloric acid that solid is 1% by mass percent and dehydrated alcohol alternately wash 3 times, shift resin to apparatus,Soxhlet's, use dehydrated alcohol extracting resin 10 hours, and vacuum-drying is for subsequent use.The specific surface area 822.1m of resin
2/ g, pore volume 0.7574cm
3/ g, pore size distribution 1 ~ 9.4nm, mean pore size 3.78nm.
Embodiment 5
In the 250mL there-necked flask that mechanical stirrer, reflux condensing tube and thermometer are housed, add 10.0g XAD-4 resin, dissolve 8.42g DCX joining in there-necked flask with 50mL oil of mirbane, mixing solutions in 0 ~ 5 DEG C of ice-water bath swelling 18 hours.In ice-water bath, add 15.5g FERRIC CHLORIDE ANHYDROUS fast in there-necked flask, middling speed stirs lower maintenance 3 hours; Be warming up to 70 DEG C and keep 8 hours, then be warming up to 80 DEG C of maintenances 4 hours.Use acetone termination reaction, incline and solution, the aqueous hydrochloric acid that is 1% by mass percent and dehydrated alcohol alternately wash 3 times, shift resin to apparatus,Soxhlet's, use dehydrated alcohol extracting resin 10 hours, and vacuum-drying is for subsequent use.The specific surface area 1160m of resin
2/ g, pore volume 1.008cm
3/ g, pore size distribution 1 ~ 8.8nm, mean pore size 3.52nm.
Embodiment 6
In the 250mL there-necked flask that mechanical stirrer, reflux condensing tube and thermometer are housed, add 9.0g XAD-4 resin, with 22mL anhydrous 1,2-ethylene dichloride and 23ml oil of mirbane dissolve 7.9g DCX and also join in there-necked flask, mixing solutions in 0 ~ 5 DEG C of ice-water bath swelling 15 hours.Middling speed adds 11.5g aluminum trichloride (anhydrous) and keeps 2 hours under stirring in ice-water bath in there-necked flask; Be warming up to 60 DEG C and keep 10 hours, then be warming up to 85 DEG C of maintenances 4 hours.Use acetone termination reaction, incline and solution, the aqueous hydrochloric acid that is 1% by mass percent and dehydrated alcohol alternately wash 3 times, shift resin to apparatus,Soxhlet's, use dehydrated alcohol extracting resin 8 hours, and vacuum-drying is for subsequent use.The specific surface area 894.2m of resin
2/ g, pore volume 0.6786cm
3/ g, pore size distribution 1 ~ 9.5nm, mean pore size 3.46nm.
Embodiment 7
In 250mL there-necked flask, add 10.0gXAD-4 resin, anhydrous 1 with 80mL, 2-ethylene dichloride dissolves 16.2gDCX and also joins in there-necked flask, and 0 ~ 5 DEG C swelling 24 hours.Under middling speed mechanical stirring, in there-necked flask, add 24.6mL anhydrous stannic chloride and keep 2 hours; Be warming up to 60 DEG C and keep 8 hours, then be warming up to 83 DEG C of maintenances 4 hours.Use acetone termination reaction, incline and solution, the aqueous hydrochloric acid that is 1% by mass percent and dehydrated alcohol alternately wash 5 times, shift resin to apparatus,Soxhlet's, use dehydrated alcohol extracting resin 8 hours, and vacuum-drying is for subsequent use.The specific surface area 1282.2m of resin
2/ g, pore volume 0.8986cm
3/ g, pore size distribution 1 ~ 6nm, mean pore size 2.58nm.
Claims (8)
1. linking agent is modified an XAD-4 resin, it is characterized in that, described modification XAD-4 resin is by linking agent and XAD-4 resin, Friedel-Crafts to occur to react the mesoporous resin that enriches micropore that contains making; Described mesoporous resin pore size distribution 1～9.5nm, mean pore size 2.58～4nm, specific surface area 721～1284m
2/ g, pore volume 0.67～1.1cm
3/ g; Described linking agent comprises: to dibenzyl chlorine, to dichloromethyl biphenyl, to dichloromethyl-Isosorbide-5-Nitrae-diphenyl butane or vinyl benzyl chloride.
2. linking agent as claimed in claim 1 is modified XAD-4 resin, it is characterized in that, dosage of crosslinking agent be XAD-4 resinous substances amount 50～100%.
3. linking agent is modified a preparation method for XAD-4 resin, it is characterized in that, linking agent and XAD-4 resin Friedel-Crafts reaction preparation occur and modify XAD-4 resin; The consumption of described linking agent be XAD-4 resinous substances amount 50～100%; Linking agent comprises: to dibenzyl chlorine, to dichloromethyl biphenyl, to dichloromethyl-Isosorbide-5-Nitrae-diphenyl butane or vinyl benzyl chloride.
4. preparation method as claimed in claim 3, is characterized in that, linking agent is dissolved in after organic solvent and joins in XAD-4 resin and obtain mixed solution; After swelling at 0～5 DEG C the XAD-4 resin in obtained mixed solution, add catalyst reaction 1～3h; At 45～70 DEG C of reaction 6～10h, at 75～85 DEG C, continue, after reaction 3～5h, to obtain final product again.
5. preparation method as claimed in claim 4, is characterized in that, swelling time is 12～24h.
6. preparation method as claimed in claim 4, is characterized in that, described catalyzer comprises: tin tetrachloride, iron trichloride or aluminum chloride; Catalyst levels is 100～300% of linking agent amount of substance.
7. preparation method as claimed in claim 4, is characterized in that, described organic solvent comprises: one or both mixed solvent in 1,2-ethylene dichloride or oil of mirbane; Described solvent load is 10g XAD-4 resin/50～80mL.
8. the preparation method as described in claim 3～7 any one, is characterized in that, prepared modification XAD-4 resin pore size distribution 1～9.5nm, mean pore size 2.58～4nm, specific surface area 721～1284m
2/ g, pore volume 0.67～1.1cm
3/ g.
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| CN105622812B (en) * | 2014-10-30 | 2018-05-04 | 南通醋酸纤维有限公司 | A kind of aminated high-specific surface area polystyrene resin and its preparation method and application |
| CN104370705B (en) * | 2014-11-18 | 2017-01-04 | 复旦大学 | A kind of separating-purifying phenol and method of 2-methoxyphenol from biomass by hydro-thermal liquefaction water-phase product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101143311A (en) * | 2007-07-10 | 2008-03-19 | 南京大学 | Environmental functional composite material based on nano granule inorganic functional agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101143311A (en) * | 2007-07-10 | 2008-03-19 | 南京大学 | Environmental functional composite material based on nano granule inorganic functional agent |
Non-Patent Citations (3)
| Title |
|---|
| JP昭57－18688A 1982.01.30 |
| Katheline O.V.Flores et al.Microwave assisted Friedel-Crafts acrylation reactions of Amberlite XAD-4TM resin.《Materials Letters》.2006,第1190－1196页. |
| Microwave assisted Friedel-Crafts acrylation reactions of Amberlite XAD-4TM resin;Katheline O.V.Flores et al;《Materials Letters》;20060718;第1190－1196页 * |
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