CN103908955B - The preparation method of the superhigh cross-linking type polymeric adsorbent that a kind of acetamido is modified and application thereof - Google Patents
The preparation method of the superhigh cross-linking type polymeric adsorbent that a kind of acetamido is modified and application thereof Download PDFInfo
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Abstract
The invention discloses preparation method and the application thereof of the superhigh cross-linking type polymeric adsorbent that a kind of acetamido is modified; Preparation method is that raw material is cross-linked by Friedel-Crafts reaction successively with chloromethylated polystyrene, Del é pine reactive grafting amino and acetylization reaction is adopted to carry out acetylated, obtained high-ratio surface sum pore volume, and the superhigh cross-linking type polymeric adsorbent that the acetamido of aperture and polarity suitable size is modified, the superhigh cross-linking type resin that obtained acetamido is modified can be applicable to the polar organic compound in adsorbed water, particularly the effect of Pyrogentisinic Acid and/or the selective absorption of salicylic acid, is with a wide range of applications; Preparation method's process of the superhigh cross-linking type resin that this acetamido is modified is simple, cost is low, can suitability for industrialized production.
Description
Technical field
The present invention relates to preparation method and the application thereof of the superhigh cross-linking type polymeric adsorbent that a kind of acetamido is modified, belong to macromolecule modified field.
Background technology
Early 1970s, linear polystyrene to be cross-linked by Friedel-Crafts reaction or to have synthesized that a class formation is unique, the porous polymer of function admirable by crosslinked again for low cross linked polystyrene by Davankov etc.According to its preparation method, this kind of reaction is called superhigh cross-linking reaction (being also called the reaction of Davankov superhigh cross-linking).The porous polymer being reacted preparation by superhigh cross-linking is called superhigh cross-linking type polymeric adsorbent.Superhigh cross-linking type polymeric adsorbent is considered to the third generation polymeric adsorbent after gel-type, macroporous type polymeric adsorbent.Super high cross-linked adsorbing resin has the architectural features such as specific area is large, average pore size is little, pore-size distribution is narrow, mechanical strength is good usually, and the field such as to be separated with the storage of antibiotic extraction, gas at the improvement of poisonous organic wastewater, Chinese herbal medicine at present shows wide application prospect.
But the skeleton structure of superhigh cross-linking type polymeric adsorbent is all hydrophobic polystyrene, its strong-hydrophobicity makes it need before use, with polar reagent (as: methyl alcohol) pretreatment, to add the complexity of operation on the one hand; Make on the other hand it little to the adsorbance of the large polar substances (as: phenol, salicylic acid, sulfanilic acid etc.) of solubility in the aqueous solution, poor selectivity.In order to improve the adsorbance of this resinoid to the large polar substances of solubility in aqueous, developing the novel super-high cross-linking type polymeric adsorbent that a class has appropriate bore structure and certain polarity and seeming particularly important.Patent (Authorization Notice No. ZL201110179667.9) discloses the preparation method of the superhigh cross-linking type polymeric adsorbent that a kind of N-methyl vinyl amido is modified.The absorption property result of the superhigh cross-linking type polymeric adsorbent that N-methyl vinyl amido is modified shows, this resinoid has certain adsorption capacity to low pole or polar substances (as: phenol, salicylic acid), but adsorption effect is not very good.
Summary of the invention
The defect undesirable to polar organic matter matter (as: salicylic acid that the phenol of low pole, polarity the are strong) adsorption effect in water is there is for modified crosslinking polystyrene of the prior art, make it apply to be limited to, the object of the invention is to be to provide that a kind of process is simple, low cost prepares that specific area is high and pore volume large, and the method for superhigh cross-linking type polymeric adsorbent that the acetamido with suitable aperture and polarity pore structure is modified.
Another object of the present invention is the application in the superhigh cross-linking type polymeric adsorbent that is to provide described acetamido the to modify polarity adsorbate in the selective absorption aqueous solution, particularly Pyrogentisinic Acid and/or salicylic acid have selective absorbing effect, and easy wash-out after absorption, resin can be reused, and reuses effective.
The invention provides the preparation method of the superhigh cross-linking type polymeric adsorbent that a kind of acetamido is modified, this preparation method is by after solvent swell by chloromethylated polystyrene, using lewis acid as catalyst, under the temperature conditions of 80 ~ 85 DEG C, carry out Friedel-Crafts and react 5 ~ 8h, after having reacted, obtain superhigh cross-linking type resin; By described superhigh cross-linking type resin swelling in the solvent being dissolved with hexamethylenetetramine and KI, under the temperature conditions of 95 ~ 105 DEG C, carry out Del é pine and react after 8 ~ 12h, Del é pine react, obtain the superhigh cross-linking type resin of amido modification; After the superhigh cross-linking type resin that gained amido is modified adopts benzene kind solvent swelling, then add acetylation reagent, backflow, carries out acetylization reaction 10 ~ 12h, namely obtains the superhigh cross-linking type polymeric adsorbent that acetamido is modified; Wherein, the mole dosage of hexamethylenetetramine is 2.0 ~ 3.0 times of residual chlorine mole in superhigh cross-linking type resin, KI and hexamethylenetetramine equimolar amounts.
The present invention also comprises following preferred scheme further:
The mass fraction of the superhigh cross-linking type resin residue chlorine that the amido that described Del é pine is obtained by reacting is modified is 1.25% ~ 2.25%, and weak base exchange capacity is 0.8 ~ 1.5mmol/g.
In the acetylation reagent added in described preparation method, the mole of active acetyl is 1.5 ~ 3.0 times of the weak base exchange capacity of the superhigh cross-linking type resin that amido is modified.
Described acetylation reagent is acetic anhydride, chloroacetic chloride or acetic acid.
In described superhigh cross-linking type resin, the mass percent of residual chlorine is 3.35 ~ 6.24%.
The solvent that in described preparation method, swelling chloromethylated polystyrene adopts is a kind of in dichloroethanes, paracide, dichloroethanes, or dichloroethanes and paracide is any than mixing.
The solvent that in described preparation method, swelling superhigh cross-linking type resin adopts is N, N '-dimethyl formamide;
The benzene kind solvent that the superhigh cross-linking type resin that in described preparation method, swelling amido is modified adopts is toluene, dimethylbenzene or benzene; Be preferably benzene.
Described lewis acid is FeCl
3, AlCl
3or SnCl
4; Lewis acidic consumption is 20 ~ 40% of chloromethylated polystyrene quality.
The superhigh cross-linking type polymeric adsorbent specific area that described acetamido is modified is 650 ~ 950m
2/ g, pore volume is 0.38 ~ 0.64cm
3/ g.
Described chloromethylated polystyrene, by after solvent swell, adds lewis acid catalyst at 45 ~ 55 DEG C, then is warmed up to 80 ~ 85 DEG C and carries out Friedel-Crafts reaction.
The chlorinity of described raw material chloromethylated polystyrene is 17.3wt%, and the degree of cross linking is 6%.
Present invention also offers the application of the superhigh cross-linking type polymeric adsorbent of the acetamido modification that a kind of described preparation method obtains, this application is that the polarity be applied in selective absorption water by the superhigh cross-linking type polymeric adsorbent that described acetamido is modified is organic.
Described polarity organic matter is phenol and/or salicylic acid.
In the superhigh cross-linking type polymeric adsorbent that described acetamido is modified, the acetamido of grafting is more, more be conducive to tending to the higher polarity organic matter (as: salicylic acid) of adsorb polar, grafting acetamido is fewer, is more conducive to tending to the lower organic matter (as: phenol) of adsorb polar.
The absorption principle of the superhigh cross-linking type polymeric adsorbent Pyrogentisinic Acid compounds that described acetamido is modified: the amide groups nitrogen-atoms of described resin has a hydrogen atom, the six-membered ring structure in following expression can be formed with the phenolic hydroxyl group of phenolic compound (as: phenol) by dual hydrogen bond action, resin can be increased to the adsorbance of phenolic compound and adsorption enthalpy.
The preparation method of the superhigh cross-linking type polymeric adsorbent that acetamido of the present invention is modified, the concrete preparation of its synthesis comprises the following steps:
1) the Friedel-Crafts reaction of chloromethylated polystyrene:
Chloromethylated polystyrene is joined in solvent (as: dichloroethanes, paracide or dichloroethanes are any than mixing with paracide) and soak until swelling, then be warming up to 45 ~ 55 DEG C, add lewis acid (as: FeCl
3, AlCl
3or SnCl
4) as catalyst (lewis acidic addition is 20 ~ 40% of chloromethylated polystyrene quality), is stirred to after dissolving completely, is slowly warming up to 80 ~ 85 DEG C, and carry out Friedel ~ Crafts reaction 5 ~ 8h at this temperature; Incline and reaction mother liquor, be aqueous hydrochloric acid solution and the absolute ethyl alcohol alternately washing of 1.0% with mass fraction, and with absolute ethyl alcohol extracting resin 8 ~ 16h, obtain superhigh cross-linking type resin;
2) aminating reaction
Step 1) the superhigh cross-linking type resin N being dissolved with hexamethylenetetramine (hexamethylenetetramine mole dosage is 2.0 ~ 3.0 times of residual chlorine mole in superhigh cross-linking type resin) and KI (consumption of KI and hexamethylenetetramine equimolar amounts) of gained, N '-dimethyl formamide carry out swelling after, 95 ~ 105 DEG C of reaction 8 ~ 12h are warming up in oil bath, incline and mother liquor, use 6mol/L hydrochloric acid successively, water, the NaOH of mass fraction 10%, water washs 3 times respectively, use ethanolic extraction resin 8 ~ 16h again, the superhigh cross-linking type resin that amido is modified is obtained after drying,
3) acetylization reaction
Step 2) gained amido modify superhigh cross-linking type resin benzene kind solvent swelling after, add acetylation reagent (the active acetyl mole in acetylation reagent is 1.5 ~ 3.0 times of the weak base exchange capacity of the superhigh cross-linking type resin that amido is modified), back flow reaction 10 ~ 12h; Incline and reaction mother liquor, rinse for several times with water, use ethanolic extraction 12h, after drying, obtain the superhigh cross-linking type polymeric adsorbent that acetamido is modified.
Beneficial effect of the present invention: first passage Friedel-Crafts reaction bonded Del é pine reaction of the present invention and amidation process obtain one and have high-ratio surface sum pore volume, and the superhigh cross-linking type polymeric adsorbent that the acetamido of aperture and polarity suitable size is modified, the polarity be applied in adsorption aqueous solution is organic, can carry out efficient selective adsorption effect by the polar organic compound (as: compared with the phenol of low pole and/or the salicylic acid of stronger polarity) larger to solubility in water.Chlorine mass percentage remaining in the present invention's time-controllable superhigh cross-linking type resin that first strict control Friedel-Crafts reacts is between 3.35 ~ 6.24%, pore structure can be adjusted to suitable size on the one hand, on the other hand for the amount of grafting amide groups can be controlled; Again further by control Del é pine reaction condition, the little amino of appropriate steric hindrance is introduced in grafting, can finely tune, convert resin to polarity simultaneously, and be conducive to next step amidation process the pore structure of resin (aperture and pore volume); The upper further acetyl amination in this basis again, not only accuracy controlling is carried out further to suitable size to pore structure (aperture and pore volume) and polarity, and secondary amino group in the amide groups generated and carbonyl can and the organic matter of hydroxyl form the hydrogen bond structure of metastable hexatomic ring, effective increase resin is to the adsorption enthalpy of hydroxyl organic matter, considerably increase the adsorbance to organic matter and adsorption capacity, special phenolic compound effect is obvious.Preparation method of the present invention is modified by amination and acetylation two step, can transfer on the carbonylic oxygen atom of amide groups by the adsorption site that resin polarity is adsorbed on the one hand, reduce adsorption space steric hindrance; On the other hand by the modification of acetamido, resin polarity is also strong, substantially increases the ability of resin to the large low pole of solubility in the aqueous solution or polar substances adsorption selection.Preparation method of the present invention is reacted by Friedel-Crafts, and obtain different crosslinking degree and grafting degree in conjunction with Del é pine reaction and amidation process, obtained resin pore structure and polarity size can be regulated and controled, the superhigh cross-linking type polymeric adsorbent that a series of acetamidos obtaining Different Pore Structures and opposed polarity are modified, when regulation and control acetamido content is more, the material larger to salicylic acid isopolarity has good absorption property, when regulation and control acetamido content is less, the more weak organic matter of Pyrogentisinic Acid's isopolarity has good absorption property.After the superhigh cross-linking type polymeric adsorbent absorption that the acetamido that preparation method of the present invention obtains is modified, wash-out is easy, reusable, reuse effective, and preparation method is simple to operate, cost is lower, can suitability for industrialized production.
Accompanying drawing explanation
The infrared spectrogram of the superhigh cross-linking type resin that [Fig. 1] is the embodiment of the present invention 1 Raw chloromethylated polystyrene, intermediate superhigh cross-linking type resin, amido are modified and the superhigh cross-linking type polymeric adsorbent that obtained acetamido is modified; ChloromethylatedPS is chloromethylated polystyrene, and HP99 is superhigh cross-linking type resin, and HP09 is the superhigh cross-linking type resin that amido is modified, and HP-Y09 is the superhigh cross-linking type polymeric adsorbent that acetamido is modified.
The graph of pore diameter distribution of the superhigh cross-linking type resin that [Fig. 2] is the intermediate superhigh cross-linking type resin in the embodiment of the present invention 1, amido is modified and the superhigh cross-linking type polymeric adsorbent that obtained acetamido is modified: (1) is superhigh cross-linking type resin, (2) be the superhigh cross-linking type resin that amido is modified, the superhigh cross-linking type polymeric adsorbent that (3) are modified for acetamido.
Specific area, the pore volume changing trend diagram of the superhigh cross-linking type resin that [Fig. 3] is the embodiment of the present invention 1 Raw chloromethylated polystyrene, intermediate superhigh cross-linking type resin, amido are modified and the superhigh cross-linking type polymeric adsorbent that obtained acetamido is modified: (1) is chloromethylated polystyrene, (2) be superhigh cross-linking type resin, (3) be the superhigh cross-linking type resin that amido is modified, the superhigh cross-linking type polymeric adsorbent that (4) are modified for acetamido.
The adsorbance comparison diagram of the superhigh cross-linking type resin that [Fig. 4] is the intermediate superhigh cross-linking type resin in the embodiment of the present invention 1, amido is modified and the superhigh cross-linking type polymeric adsorbent Pyrogentisinic Acid that obtained acetamido is modified: (1) is superhigh cross-linking type resin, (2) be the superhigh cross-linking type resin that amido is modified, the superhigh cross-linking type polymeric adsorbent that (3) are modified for acetamido.
[Fig. 5] is for different desorbing agent is to the static desorption result figure of the superhigh cross-linking type polymeric adsorbent that acetylamino prepared by the embodiment of the present invention 1 of having adsorbed phenol is modified.
Dynamic Adsorption-the desorption curve of the superhigh cross-linking type polymeric adsorbent Pyrogentisinic Acid that [Fig. 6] modifies for acetamido prepared by the embodiment of the present invention 1.
The repetition adsorption/desorption utilization rate result of the superhigh cross-linking type polymeric adsorbent Pyrogentisinic Acid that [Fig. 7] modifies for acetamido prepared by the embodiment of the present invention 1.
Detailed description of the invention
Following examples are intended to content of the present invention is described, instead of the further restriction to scope.Embodiment 1
Friedel-Crafts reacts: the chloromethylated polystyrene (chlorinty is 17.3%, and the degree of cross linking is 6%) adding 20.0g drying in 250mL there-necked flask, then adds that 120mL dichloroethanes sweller is swelling to spend the night; Be warming up to 50 DEG C, add 4.0gFeCl
3and stir until FeCl
3be warming up to 80 DEG C after dissolving completely, and react 8h at this temperature.After having reacted, incline and reaction mother liquor, with hydrochloric acid solution and the absolute ethyl alcohol alternately washing of mass fraction 1.0%, until eluate clarification, transfer in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after drying, obtain superhigh cross-linking type resin.The residual chlorine content of resin is 3.35%, and the specific area of resin is 1032.6m
2/ g, pore volume is 0.6729cm
3/ g.
Aminating reaction: with appropriate N in 250mL there-necked flask, dinethylformamide dissolves 5.3g hexamethylenetetramine and 6.3g KI, join swelling in 20.1g superhigh cross-linking type resin spending the night, in oil bath, be warming up to 95 DEG C of reaction 8h, after reaction terminates, incline and mother liquor, 3 times are washed respectively with the NaOH of 6mol/L hydrochloric acid, water, mass fraction 10%, water, use ethanolic extraction 12h, produce resin, vacuum drying obtains the superhigh cross-linking type resin that amido is modified.The residual chlorine content of resin is 1.25%, and the weak base exchange capacity of resin is 0.8mmol/g, and the specific area of resin is 921.3m
2/ g, pore volume is 0.5673cm
3/ g.
Acetylization reaction: spend the night with the superhigh cross-linking type resin that the swelling 20.2g amido of benzene is modified, add 25.5mL acetic anhydride back flow reaction 10h.Incline and reaction mother liquor, wash 3 times with water, finally use absolute ethyl alcohol extracting 12h, after vacuum drying, obtain the superhigh cross-linking type polymeric adsorbent that acetamido is modified.The specific area of resin is 650.8m
2/ g, pore volume is 0.3758cm
3/ g.
As can be seen from infared spectrum (as Fig. 1), after Friedel-Crafts reaction, the infrared spectrum of chloromethylated polystyrene is at 1265cm
~ 1the CH at place
2cl characteristic peak weakens greatly; After aminating reaction, at 3928 ~ 3246cm
~ 1there is wider N-H stretching vibration peak in place, may with NH
2or the N-H stretching vibration of NH-is relevant; At 1662cm
~ 1there is the carbonyl absorption of vibrations of amide groups in place.
As can be seen from graph of pore diameter distribution (as Fig. 2), mesoporous based on 2 ~ 5nm of the superhigh cross-linking type resin that obtains after the superhigh cross-linking type polymeric adsorbent that acetamido is modified and Friedel-Crafts reaction, also part macropore is had, and chloromethylated polystyrene is based on the mesopore of 2 ~ 18nm, the key factor that the change resin property of resin pore structure improves is described.
As can be seen from specific area, pore volume changing trend diagram (as Fig. 3): chloromethylated polystyrene is through step 1) reaction after, specific area is by original 18.02m
2/ g is increased to 800 ~ 1200m
2/ g, pore volume is almost 0 is increased to 0.5 ~ 0.8cm by original
3/ g, after through step 2) and 3) after reaction kinetic, specific surface and pore volume slightly reduce, and (the minimizing amplitude of specific area is at 100 ~ 200m
2/ g, the minimizing amplitude of pore volume is at 0.1 ~ 0.2cm
3/ g).
Embodiment 2
Friedel-Crafts reacts: the chloromethylated polystyrene (chlorinty is 17.3%, and the degree of cross linking is 6%) adding 20.3g drying in 250mL there-necked flask, then adds that 120mL paracide sweller is swelling to spend the night; Be warming up to 50 DEG C, add 8.0gAlCl
3and stir until AlCl
3progressively be warming up to 85 DEG C after dissolving completely, and react 5h at this temperature.After having reacted, incline and reaction mother liquor, with hydrochloric acid solution and the absolute ethyl alcohol alternately washing of mass fraction 1.0%, until eluate clarification, transfer in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after drying, obtain superhigh cross-linking type resin.The residual chlorine content of resin is 6.24%, and the specific area of resin is 1045.6m
2/ g, pore volume is 0.7929cm
3/ g.
Aminating reaction: add with appropriate N in 250mL there-necked flask, dinethylformamide dissolves 10.2g hexamethylenetetramine and 12.0g KI, join swelling in 20.5g superhigh cross-linking type resin spending the night, in oil bath, be warming up to 105 DEG C of reaction 12h, after reaction terminates, incline and mother liquor, 3 times are washed respectively with the NaOH of 6mol/L hydrochloric acid, water, mass fraction 10%, water, use ethanolic extraction 12h, produce resin, vacuum drying obtains the superhigh cross-linking type resin that amido is modified.The residual chlorine content of resin is 2.25%, and the weak base exchange capacity of resin is 1.5mmol/g, and the specific area of resin is 936.3m
2/ g, pore volume is 0.6873cm
3/ g.
Acetylization reaction: spend the night with the superhigh cross-linking type resin that the swelling 20.0g amido of benzene is modified, add 45.5mL acetic acid back flow reaction 10h.Incline and reaction mother liquor, wash 3 times with water, finally use absolute ethyl alcohol extracting 12h, after vacuum drying, obtain the superhigh cross-linking type polymeric adsorbent that acetamido is modified.The specific area of resin is 950.8m
2/ g, pore volume is 0.5769cm
3/ g.
Embodiment 3
Friedel-Crafts reacts: the chloromethylated polystyrene (chlorinty is 17.3%, and the degree of cross linking is 6%) adding 20.0g drying in 250mL there-necked flask, then adds that 120mL dichloroethanes sweller is swelling to spend the night; Be warming up to 50 DEG C, add 7.0gSnCl
4and stir until SnCl
4progressively be warming up to 80 DEG C after dissolving completely, and react 5h at this temperature.After having reacted, incline and reaction mother liquor, with hydrochloric acid solution and the absolute ethyl alcohol alternately washing of mass fraction 1.0%, until eluate clarification, transfer in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after drying, obtain superhigh cross-linking type resin.The residual chlorine content of resin is 4.75%, and the specific area of resin is 976.5m
2/ g, pore volume is 0.6485cm
3/ g.
Aminating reaction: with appropriate N in 250mL there-necked flask, dinethylformamide dissolves 10.5g hexamethylenetetramine and 11.8g KI, join swelling in 21.0g superhigh cross-linking type resin spending the night, in oil bath, be warming up to 100 DEG C of reaction 10h, after reaction terminates, incline and mother liquor, 3 times are washed respectively with the NaOH of 6mol/L hydrochloric acid, water, mass fraction 10%, water, use ethanolic extraction 12h, produce resin, vacuum drying obtains the superhigh cross-linking type resin that amido is modified.The residual chlorine content of resin is 2.75%, and the weak base exchange capacity of resin is 1.0mmol/g, and the specific area of resin is 876.3m
2/ g, pore volume is 0.5134cm
3/ g.
Acetylization reaction: spend the night with the superhigh cross-linking type resin that the swelling 20.0g amido of benzene is modified, add 30.5 chloroacetic chloride back flow reaction 10h.Incline and reaction mother liquor, wash 3 times with water, finally use absolute ethyl alcohol extracting 12h, after vacuum drying, obtain the superhigh cross-linking type polymeric adsorbent that acetamido is modified.The specific area of resin is 760.8m
2/ g, pore volume is 0.4138cm
3/ g.
Embodiment 4
Friedel-Crafts reacts: the chloromethylated polystyrene (chlorinty is 17.3%, and the degree of cross linking is 6%) adding 21.5g drying in 250mL there-necked flask, then adds that 129mL paracide sweller is swelling to spend the night; Be warming up to 50 DEG C, add 5.0gAlCl
3and stir until AlCl
3progressively be warming up to 80 DEG C after dissolving completely, and react 6h at this temperature.After having reacted, incline and reaction mother liquor, with hydrochloric acid solution and the absolute ethyl alcohol alternately washing of mass fraction 1.0%, until eluate clarification, transfer in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after drying, obtain superhigh cross-linking type resin.The residual chlorine content of resin is 6.15%, and the specific area of resin is 912.6m
2/ g, pore volume is 0.5624cm
3/ g.
Aminating reaction: N appropriate in 250mL there-necked flask, dinethylformamide dissolves 9.8g hexamethylenetetramine and 11.5g KI, join swelling in 19.9g superhigh cross-linking type resin spending the night, in oil bath, be warming up to 95 DEG C of reaction 8h, after reaction terminates, incline and mother liquor, 3 times are washed respectively with the NaOH of 6mol/L hydrochloric acid, water, mass fraction 10%, water, use ethanolic extraction 12h, produce resin, vacuum drying obtains the superhigh cross-linking type resin that amido is modified.The residual chlorine content of resin is 1.74%, and the weak base exchange capacity of resin is 1.2mmol/g, and the specific area of resin is 917.3m
2/ g, pore volume is 0.5553cm
3/ g.
Acetylization reaction: spend the night with the superhigh cross-linking type resin that the swelling 20.2g amido of benzene is modified, add 36.0mL acetic anhydride back flow reaction 10h.Incline and reaction mother liquor, wash 3 times with water, finally use absolute ethyl alcohol extracting 12h, after vacuum drying, obtain the superhigh cross-linking type polymeric adsorbent that acetamido is modified.The specific area of resin is 650.8m
2/ g, pore volume is 0.3758cm
3/ g.
Embodiment 5
Friedel-Crafts reacts: in 250mL there-necked flask, adding the chloromethylated polystyrene of 20.0g drying, (chlorinty is 17.3%, the degree of cross linking is 6%), mixed solution (volume ratio 1:1) the swollen solvent swell then adding 120mL dichloroethanes and paracide is spent the night; Be warming up to 50 DEG C, add 4.0gSnCl
4and stir until SnCl
4progressively be warming up to 80 DEG C after dissolving completely, and react 5h at this temperature.After having reacted, incline and reaction mother liquor, with hydrochloric acid solution and the absolute ethyl alcohol alternately washing of mass fraction 1.0%, until eluate clarification, transfer in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after drying, obtain superhigh cross-linking type resin.The residual chlorine content of resin is 5.35%, and the specific area of resin is 916.6m
2/ g, pore volume is 0.5749cm
3/ g.
Aminating reaction: N appropriate in 250mL there-necked flask, dinethylformamide dissolves 8.6g hexamethylenetetramine and 10.2g KI, join swelling in 20.3g superhigh cross-linking type resin spending the night, in oil bath, be warming up to 95 DEG C of reaction 8h, after reaction terminates, incline and mother liquor, 3 times are washed respectively with the NaOH of 6mol/L hydrochloric acid, water, mass fraction 10%, water, use ethanolic extraction 12h, produce resin, vacuum drying obtains the superhigh cross-linking type resin that amido is modified.The residual chlorine content of resin is 1.85%, and the weak base exchange capacity of resin is 1.4mmol/g, and the specific area of resin is 869.3m
2/ g, pore volume is 0.4693cm
3/ g.
Acetylization reaction: spend the night with the superhigh cross-linking type resin that the swelling 20.0g amido of benzene is modified, add 42.5mL acetic anhydride back flow reaction 11h.Incline and reaction mother liquor, wash 3 times with water, finally use absolute ethyl alcohol extracting 12h, after vacuum drying, obtain the superhigh cross-linking type polymeric adsorbent that acetamido is modified.The specific area of resin is 871.6m
2/ g, pore volume is 0.4377cm
3/ g.
Embodiment 6
Friedel-Crafts reacts: the chloromethylated polystyrene (chlorinty is 17.3%, and the degree of cross linking is 6%) adding 21.0g drying in 250mL there-necked flask, then adds that 126mL dichloroethanes sweller is swelling to spend the night; Be warming up to 50 DEG C, add 6.0gFeCl
3and stir until FeCl
3progressively be warming up to 82 DEG C after dissolving completely, and react 7h at this temperature.After having reacted, incline and reaction mother liquor, with hydrochloric acid solution and the absolute ethyl alcohol alternately washing of mass fraction 1.0%, until eluate clarification, transfer in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after drying, obtain superhigh cross-linking type resin.The residual chlorine content of resin is 4.55%, and the specific area of resin is 932.5m
2/ g, pore volume is 0.5879cm
3/ g.
Aminating reaction: add appropriate N in 250mL there-necked flask, dinethylformamide dissolves 7.2g hexamethylenetetramine and 8.5g KI, join swelling in 19.8g superhigh cross-linking type resin spending the night, in oil bath, be warming up to 95 DEG C of reaction 8h, after reaction terminates, incline and mother liquor, 3 times are washed respectively with the NaOH of 6mol/L hydrochloric acid, water, mass fraction 10%, water, use ethanolic extraction 12h, produce resin, vacuum drying obtains the superhigh cross-linking type resin that amido is modified.The residual chlorine content of resin is 1.75%, and the weak base exchange capacity of resin is 0.9mmol/g, and the specific area of resin is 908.3m
2/ g, pore volume is 0.4872cm
3/ g.
Acetylization reaction: spend the night with the superhigh cross-linking type resin that the swelling 20.5g amido of benzene is modified, add 50.5mL acetic anhydride back flow reaction 12h.Incline and reaction mother liquor, wash 3 times with water, finally use absolute ethyl alcohol extracting 12h, after vacuum drying, obtain the superhigh cross-linking type polymeric adsorbent that acetamido is modified.The specific area of resin is 721.8m
2/ g, pore volume is 0.4633cm
3/ g.
Embodiment 7
Static Adsorption detachment assays: get one group 6 tool plug conical flasks, adds the resin of 0.10g embodiment 1 preparation and the phenol solution of 50.00mL same concentrations wherein respectively.They are placed in rotary water bath oscillator, constant temperature oscillation 6h under 298K, makes absorption reach balance.With the absorbance of ultraviolet-visual spectrometer raffinate after the maximum absorption wave strong point of phenol measures absorption, be converted into the concentration of adsorbing the phenol after reaching balance, be balanced adsorbance.
Raffinate after absorption is outwelled, and adds the washing of 10mL distilled water, add the desorbing agent of different ethanol and NaOH composition after pulp-water evacuation, be placed in 298K constant temperature oscillator and vibrate 6h, make desorption reach balance.Measure the content of phenol in eluent, calculate the eluting rate of each eluent under 298K (%), obtain the static analysis diagram shown in Fig. 5.
Dynamic Adsorption-detachment assays: measure the resin that the embodiment 1 of 9.8mL drying is obtained, be placed in ethanol water and soak, spend the night.Measure the soaked resin transfer of 10mL afterwards in glass column, strike and tightly fill reality.Certain density phenol solution is flow through exchange column adsorb, control mouth of pipe flow velocity constant, collect efflux with auto partial sampler, measure its absorbance.After the concentration of phenol in efflux is identical with the concentration of stoste, stop absorption.With bed volume number for abscissa, efflux absorbance is abscissa with the ratio of stoste absorbance, draws Dynamic Adsorption curve.Saturated resin has been adsorbed, till almost reactive phenol detects in efflux with the eluant, eluent washing that static state resolves effect best.Same timing measures the absorbance of efflux, take bed volume as abscissa, outflow concentration draws dynamic desorption curve for ordinate.
Repeat the experiment of adsorption/desorption utilization rate: the resin and the certain density phenol solution of 50.00mL that add 0.10g embodiment 1 preparation at tool plug conical flask, repeat the experiment of five Static Adsorption desorptions, the adsorption and desorption ability of determination experiment phenol, obtains the repetition adsorption/desorption utilization rate figure shown in Fig. 7.
As can be seen from Figure 5, along with the increase of volume fraction of ethanol or the increase of NaOH concentration, the static desorption efficiency of superhigh cross-linking type polymeric adsorbent Pyrogentisinic Acid that acetylamino is modified increases.The mixed solution desorption effect of NaOH and ethanol is better than independent ethanol or NaOH.When NaOH concentration be 0.1mol/L, volume fraction of ethanol be 50% solution as desorbing agent time, desorption efficiency can reach 99.33%.
As can be seen from Figure 6: initial phenol concentration 1000mg/L, flow velocity 4.8BV/h, reveals at 90.2BV place, and at 122.0BV place, absorption is saturated, shows good absorption property.And the resin having adsorbed phenol can use the NaOH of 0.01mol/L, the ethanolic solution desorption of 50%, when 8.0BV, wash-out is substantially complete, and in the use procedure of dress post, resin mechanical strength is good, does not occur breakage, reusable.
This resin Pyrogentisinic Acid is after adsorption-desorption-adsorb again-de-adsorption cycle uses again, and resin presents good regeneration and repeat performance.
Claims (5)
1. the preparation method of the superhigh cross-linking type polymeric adsorbent of an acetamido modification, it is characterized in that, by chloromethylated polystyrene by after solvent swell, using lewis acid as catalyst, at 80 ~ 85 DEG C, carry out Friedel-Crafts react 5 ~ 8h, after having reacted, obtain superhigh cross-linking type resin; By described superhigh cross-linking type resin swelling in the solvent being dissolved with hexamethylenetetramine and KI, at 95 ~ 105 DEG C, carry out Del é pine react 8 ~ 12h, obtain the superhigh cross-linking type resin that amido is modified; The superhigh cross-linking type resin that gained amido is modified adds acetylation reagent after adopting benzene kind solvent swelling, and backflow, carries out acetylization reaction 10 ~ 12h, obtains the superhigh cross-linking type polymeric adsorbent that acetamido is modified; Wherein, the mole dosage of hexamethylenetetramine is 2.0 ~ 3.0 times of residual chlorine mole in superhigh cross-linking type resin, KI and hexamethylenetetramine equimolar amounts; In described superhigh cross-linking type resin, the mass percent of residual chlorine is 3.35 ~ 6.24%; The mass fraction of the superhigh cross-linking type resin residue chlorine that the amido that described Del é pine is obtained by reacting is modified is 1.25% ~ 2.25%, and weak base exchange capacity is 0.8 ~ 1.5mmol/g; In the acetylation reagent added, the mole of active acetyl is 1.5 ~ 3.0 times of the weak base exchange capacity of the superhigh cross-linking type resin that amido is modified.
2. preparation method as claimed in claim 1, it is characterized in that, described lewis acid is FeCl
3, AlCl
3or SnCl
4; Lewis acidic consumption is 20 ~ 40% of chloromethylated polystyrene quality.
3. preparation method as claimed in claim 1, it is characterized in that, described acetylation reagent is acetic anhydride, chloroacetic chloride or acetic acid.
4. preparation method as claimed in claim 1, is characterized in that, the solvent that swelling chloromethylated polystyrene adopts is a kind of in dichloroethanes, paracide, or dichloroethanes and paracide is any than mixing; The solvent that swelling superhigh cross-linking type resin adopts is N, N '-dimethyl formamide; The benzene kind solvent that the superhigh cross-linking type resin that swelling amido is modified adopts is toluene, dimethylbenzene or benzene.
5. an application for the superhigh cross-linking type polymeric adsorbent that the acetamido that the preparation method as described in any one of Claims 1 to 4 obtains is modified, is characterized in that, be applied to the phenol in selective absorption water and/or salicylic acid.
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| CN109999762A (en) * | 2019-03-14 | 2019-07-12 | 广东工业大学 | A kind of amide group modified polystyrene system's super high cross-linked adsorbing resin and its application |
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