CN103908955A - Method for preparing acetamido-modified ultra-high crosslinking type adsorption resin and application of resin - Google Patents
Method for preparing acetamido-modified ultra-high crosslinking type adsorption resin and application of resin Download PDFInfo
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Abstract
The invention discloses a method for preparing acetamido-modified ultra-high crosslinking type adsorption resin and application of the resin. The preparation method comprises the following steps: with chloromethylated polystyrene as a raw material, and performing Friedel-Crafts reaction sequentially for crosslinking; and performing Delepine reaction to graft amino and acetylation to carry out amino acetylation, so as to prepare the acetamido-modified ultra-high crosslinking type adsorption resin with high specific surface area and pore volume, and appropriate aperture and polarity. The prepared acetamido-modified ultra-high crosslinking type adsorption resin can be applied to adsorption of a polar organic compound in water, especially has a selective adsorption effect on phenol and/or salicylic acid, and has a broad application prospect. The preparation method of the acetamido-modified ultra-high crosslinking type adsorption resin is simple in process, and low in cost, and can be applied to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of superhigh cross-linking type polymeric adsorbent of acetamido modification, belong to macromolecule modified field.
Background technology
Early 1970s, Davankov etc. react crosslinked linear polystyrene or by the low cross-linking polystyrene crosslinked porous polymer that has synthesized a class formation uniqueness, function admirable again by Friedel-Crafts.According to its preparation method, this class reaction is called superhigh cross-linking reaction (being called again the reaction of Davankov superhigh cross-linking).Porous polymer by superhigh cross-linking reaction preparation 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 conventionally, at present the field such as separates with the storage of antibiotic extraction, gas at improvement, the Chinese herbal medicine of poisonous organic wastewater and has shown 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 have increased the complexity of operation on the one hand; Make on the other hand the adsorbance of its polar substances large to solubility in the aqueous solution (as: phenol, salicylic acid, sulfanilic acid etc.) little, poor selectivity.In order to improve the adsorbance of this resinoid to the large polar substances of solubility in the aqueous solution, develop the novel superhigh cross-linking type polymeric adsorbent that a class has appropriate bore structure and certain polarity and seem particularly important.Patent (Granted publication ZL201110179667.9) discloses a kind of preparation method of superhigh cross-linking type polymeric adsorbent of N-methylacetamide base modification.The absorption property result of superhigh cross-linking type polymeric adsorbent that N-methylacetamide base 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
Exist the polar organic matter matter in water (as: phenol of low pole, the salicylic acid that polarity is strong) the undesirable defect of adsorption effect for modified crosslinking polystyrene of the prior art, its application is 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 is large, and has the method for the superhigh cross-linking type polymeric adsorbent that the acetamido of suitable aperture and polarity pore structure modifies.
Another object of the present invention is the application that is to provide aspect superhigh cross-linking type polymeric adsorbent that described acetamido the modifies polarity adsorbate in the selective absorption aqueous solution, particularly Pyrogentisinic Acid and/or salicylic acid have selective assimilation effect, and easy wash-out after absorption, resin can be reused, and reuses effective.
The invention provides a kind of preparation method of superhigh cross-linking type polymeric adsorbent of acetamido modification, this preparation method is by after solvent swell by chloromethylated polystyrene, using lewis acid as catalyst, under the temperature conditions of 80～85 ℃, carry out Friedel-Crafts reaction 5～8h, after having reacted, obtain superhigh cross-linking type resin; Described superhigh cross-linking type resin swelling, being dissolved with in the solvent of hexamethylenetetramine and KI, under the temperature conditions of 95～105 ℃, is carried out to Del é pine reaction 8～12h, after Del é pine has reacted, obtain the superhigh cross-linking type resin that amido is modified; After the superhigh cross-linking type resin that gained amido is modified adopts benzene kind solvent swelling, then add acetylation reagent, reflux, carry out acetylization reaction 10～12h, obtain 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 further preferred scheme:
The mass fraction that described Del é pine reacts the superhigh cross-linking type resin residual chlorine of the amido modification obtaining is 1.25%～2.25%, and weak base exchange capacity is 0.8～1.5mmol/g.
In the acetylation reagent adding in described preparation method, the mole of active acetyl is 1.5～3.0 times of weak base exchange capacity of the superhigh cross-linking type resin modified of amido.
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 ℃, then is warmed up to 80～85 ℃ 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%.
The application of the superhigh cross-linking type polymeric adsorbent that the acetamido that the present invention also provides a kind of described preparation method to make is modified, this application is that the superhigh cross-linking type polymeric adsorbent that described acetamido is modified is applied to the polarity organic matter in selective absorption water.
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 the higher polarity organic matter (as: salicylic acid) of trend absorption polarity, grafting acetamido is fewer, is more conducive to the lower organic matter (as: phenol) of trend absorption polarity.
The absorption principle of the superhigh cross-linking type polymeric adsorbent Pyrogentisinic Acid compounds that described acetamido is modified: have a hydrogen atom on the amide groups nitrogen-atoms of described resin, can form the six-membered ring structure in following expression by dual hydrogen bond action with the phenolic hydroxyl group of phenolic compound (as: phenol), can increase adsorbance and the adsorption enthalpy of resin to phenolic compound.
The preparation method of the superhigh cross-linking type polymeric adsorbent that acetamido of the present invention is modified, its synthetic concrete preparation comprises the following steps:
1) Friedel-Crafts of chloromethylated polystyrene reaction:
Chloromethylated polystyrene is joined and soaked in solvent (as: dichloroethanes, paracide or dichloroethanes are any than mixing with paracide) until swelling, then be warming up to 45～55 ℃, add lewis acid (as: FeCl
3, AlCl
3or SnCl
4) as catalyst (lewis acidic addition be chloromethylated polystyrene quality 20～40%), after being stirred to and dissolving completely, be slowly warming up to 80～85 ℃, and at this temperature, carry out Friedel～Crafts and react 5～8h; Incline and reaction mother liquor, the aqueous hydrochloric acid solution that is 1.0% with mass fraction and absolute ethyl alcohol be washing alternately, and with absolute ethyl alcohol extracting resin 8～16h, obtains superhigh cross-linking type resin;
2) aminating reaction
Step 1) N that is 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) for superhigh cross-linking type resin of gained, N '-dimethyl formamide carry out swelling after, in oil bath, be warming up to 95～105 ℃ of reaction 8～12h, incline and mother liquor, use successively 6mol/L hydrochloric acid, water, the NaOH of mass fraction 10%, water washs respectively 3 times, use again ethanol extracting resin 8～16h, after dry, obtain the superhigh cross-linking type resin that amido is modified,
3) acetylization reaction
Step 2) gained amido modify superhigh cross-linking type resin with benzene kind solvent swelling after, add acetylation reagent (the active acetyl mole in acetylation reagent is 1.5～3.0 times of weak base exchange capacity of the superhigh cross-linking type resin modified of amido), back flow reaction 10～12h; Incline and reaction mother liquor, water rinses for several times, with ethanol extracting 12h, after being dried, obtains 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 make one and have high-specific surface area and pore volume, and the superhigh cross-linking type polymeric adsorbent that the acetamido of aperture and polarity suitable size is modified, be applied to the polarity organic matter in adsorption aqueous solution, polar organic compound (as: compared with the salicylic acid of the phenol of low pole and/or stronger polarity) that can be larger to solubility in water carries out efficient selective adsorption effect.Chlorine quality percentage composition remaining in the present invention's time-controllable superhigh cross-linking type resin that first the strict Friedel-Crafts of control reacts is between 3.35～6.24%, pore structure can be adjusted to suitable size on the one hand, on the other hand for controlling the amount of grafting amide groups; Further by controlling Del é pine reaction condition, the amino that appropriate steric hindrance is little is introduced in grafting, can finely tune the pore structure of resin (aperture and pore volume), converts resin to polarity simultaneously, and is conducive to next step amidation process again; The upper further acetyl amination in this basis again, not only pore structure (aperture and pore volume) and polarity are further carried out to accuracy controlling to suitable size, and secondary amino group in the amide groups generating and carbonyl can and the organic matter of hydroxyl form the hydrogen bond structure of metastable hexatomic ring, effectively increase the adsorption enthalpy of resin to hydroxyl organic matter, greatly increased organic adsorbance and adsorption capacity, special phenolic compound effect is obvious.Preparation method of the present invention modifies by amination and acetylation two steps, the adsorption site of resin polarity absorption can be transferred on the carbonylic oxygen atom of amide groups on the one hand, has reduced adsorption space steric hindrance; By the modification of acetamido, resin polarity is not strong yet on the other hand, has greatly improved resin the large low pole of solubility in the aqueous solution or polar substances are selected to the ability of adsorbing.Preparation method of the present invention reacts by Friedel-Crafts, and obtain different crosslinking degrees and grafting degree in conjunction with Del é pine reaction and amidation process, the resin pore structure that can regulate and control to make and polarity size, obtain the superhigh cross-linking type polymeric adsorbent of a series of acetamidos modifications of Different Pore Structures and opposed polarity, when regulation and control acetamido content is more, the larger material of salicylic acid isopolarity is had to good absorption property, when regulation and control acetamido content is less, the weak organic matter of Pyrogentisinic Acid's isopolarity has good absorption property.After the superhigh cross-linking type polymeric adsorbent absorption that acetamido that preparation method of the present invention makes is modified, wash-out is easy, reusable, reuses effectively, and preparation method is simple to operate, cost is lower, can suitability for industrialized production.
Accompanying drawing explanation
[Fig. 1] is the infrared spectrogram of the superhigh cross-linking type polymeric adsorbent modified of the superhigh cross-linking type resin modified of the embodiment of the present invention 1 Raw chloromethylated polystyrene, intermediate superhigh cross-linking type resin, amido and the acetamido that makes; Chloromethylated PS 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 polymeric adsorbent that 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 modification and the acetamido making are modified: (1) is superhigh cross-linking type resin, (2) the superhigh cross-linking type resin of modifying for amido, the superhigh cross-linking type polymeric adsorbent that (3) are modified for acetamido.
[Fig. 3] is specific area, the pore volume changing trend diagram of the superhigh cross-linking type polymeric adsorbent modified of the superhigh cross-linking type resin modified of the embodiment of the present invention 1 Raw chloromethylated polystyrene, intermediate superhigh cross-linking type resin, amido and the acetamido that makes: (1) is chloromethylated polystyrene, (2) be superhigh cross-linking type resin, (3) the superhigh cross-linking type resin of modifying for amido, the superhigh cross-linking type polymeric adsorbent that (4) are modified for acetamido.
The superhigh cross-linking type polymeric adsorbent Pyrogentisinic Acid's that 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 modification and the acetamido making are modified adsorbance comparison diagram: (1) is superhigh cross-linking type resin, (2) the superhigh cross-linking type resin of modifying for amido, the superhigh cross-linking type polymeric adsorbent that (3) are modified for acetamido.
The static desorption result figure of the superhigh cross-linking type polymeric adsorbent that [Fig. 5] modifies the acetylamino that has adsorbed the embodiment of the present invention 1 of phenol and prepare for different desorbing agents.
Dynamic Adsorption-desorption curve of the superhigh cross-linking type polymeric adsorbent Pyrogentisinic Acid that the acetamido that [Fig. 6] prepared for the embodiment of the present invention 1 is modified.
The superhigh cross-linking type polymeric adsorbent Pyrogentisinic Acid's that the acetamido that [Fig. 7] prepared for the embodiment of the present invention 1 is modified repetition adsorption/desorption utilization rate result.
The specific embodiment
Following examples are intended to illustrate content of the present invention, rather than further restriction to protection domain of the present invention.Embodiment 1
Friedel-Crafts reaction: add the chloromethylated polystyrene that 20.0g is dry (chlorinty is 17.3%, and the degree of cross linking is 6%) in 250mL there-necked flask, then add swelling the spending the night of 120mL dichloroethanes sweller; Be warming up to 50 ℃, add 4.0g FeCl
3and stirring is until FeCl
3after dissolving completely, be warming up to 80 ℃, and react 8h at this temperature.After having reacted, incline and reaction mother liquor, use hydrochloric acid solution and the alternately washing of absolute ethyl alcohol of mass fraction 1.0%, until eluate clarification transfers in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after being dried, 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: in 250mL there-necked flask with appropriate N, dinethylformamide dissolves 5.3g hexamethylenetetramine and 6.3g KI, join swelling spending the night in 20.1g superhigh cross-linking type resin, in oil bath, be warming up to 95 ℃ of reaction 8h, after reaction finishes, incline and mother liquor, wash respectively 3 times with NaOH, the water of 6mol/L hydrochloric acid, water, mass fraction 10%, with ethanol extracting 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 with water 3 times, 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.
Can find out 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.
From graph of pore diameter distribution (as Fig. 2), can find out, the superhigh cross-linking type resin obtaining after the superhigh cross-linking type polymeric adsorbent that acetamido is modified and Friedel-Crafts reaction is mesoporous as main take 2～5nm's, also there is part macropore, and chloromethylated polystyrene is take the mesopore of 2～18nm as main, the key factor that the variation resin property of resin pore structure improves is described.
From finding out 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 and is increased to 0.5～0.8cm by original
3/ g, afterwards through step 2) and 3) after reaction kinetic, specific surface and pore volume slightly reduce that (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 reaction: add the chloromethylated polystyrene that 20.3g is dry (chlorinty is 17.3%, and the degree of cross linking is 6%) in 250mL there-necked flask, then add swelling the spending the night of 120mL paracide sweller; Be warming up to 50 ℃, add 8.0g AlCl
3and stirring is until AlCl
3after dissolving completely, be progressively warming up to 85 ℃, and react 5h at this temperature.After having reacted, incline and reaction mother liquor, use hydrochloric acid solution and the alternately washing of absolute ethyl alcohol of mass fraction 1.0%, until eluate clarification transfers in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after being dried, 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 in 250mL there-necked flask with appropriate N, dinethylformamide dissolves 10.2g hexamethylenetetramine and 12.0g KI, join swelling spending the night in 20.5g superhigh cross-linking type resin, in oil bath, be warming up to 105 ℃ of reaction 12h, after reaction finishes, incline and mother liquor, wash respectively 3 times with NaOH, the water of 6mol/L hydrochloric acid, water, mass fraction 10%, with ethanol extracting 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 with water 3 times, 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 reaction: add the chloromethylated polystyrene that 20.0g is dry (chlorinty is 17.3%, and the degree of cross linking is 6%) in 250mL there-necked flask, then add swelling the spending the night of 120mL dichloroethanes sweller; Be warming up to 50 ℃, add 7.0g SnCl
4and stirring is until SnCl
4after dissolving completely, be progressively warming up to 80 ℃, and react 5h at this temperature.After having reacted, incline and reaction mother liquor, use hydrochloric acid solution and the alternately washing of absolute ethyl alcohol of mass fraction 1.0%, until eluate clarification transfers in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after being dried, 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: in 250mL there-necked flask with appropriate N, dinethylformamide dissolves 10.5g hexamethylenetetramine and 11.8g KI, join swelling spending the night in 21.0g superhigh cross-linking type resin, in oil bath, be warming up to 100 ℃ of reaction 10h, after reaction finishes, incline and mother liquor, wash respectively 3 times with NaOH, the water of 6mol/L hydrochloric acid, water, mass fraction 10%, with ethanol extracting 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 with water 3 times, 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 reaction: add the chloromethylated polystyrene that 21.5g is dry (chlorinty is 17.3%, and the degree of cross linking is 6%) in 250mL there-necked flask, then add swelling the spending the night of 129mL paracide sweller; Be warming up to 50 ℃, add 5.0g AlCl
3and stirring is until AlCl
3after dissolving completely, be progressively warming up to 80 ℃, and react 6h at this temperature.After having reacted, incline and reaction mother liquor, use hydrochloric acid solution and the alternately washing of absolute ethyl alcohol of mass fraction 1.0%, until eluate clarification transfers in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after being dried, 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: appropriate N in 250mL there-necked flask, dinethylformamide dissolves 9.8g hexamethylenetetramine and 11.5g KI, join swelling spending the night in 19.9g superhigh cross-linking type resin, in oil bath, be warming up to 95 ℃ of reaction 8h, after reaction finishes, incline and mother liquor, wash respectively 3 times with NaOH, the water of 6mol/L hydrochloric acid, water, mass fraction 10%, with ethanol extracting 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 with water 3 times, 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 reaction: (chlorinty is 17.3% to add the chloromethylated polystyrene that 20.0g is dry in 250mL there-necked flask, the degree of cross linking is 6%), then add the swollen solvent swell of mixed solution (volume ratio 1:1) of 120mL dichloroethanes and paracide to spend the night; Be warming up to 50 ℃, add 4.0g SnCl
4and stirring is until SnCl
4after dissolving completely, be progressively warming up to 80 ℃, and react 5h at this temperature.After having reacted, incline and reaction mother liquor, use hydrochloric acid solution and the alternately washing of absolute ethyl alcohol of mass fraction 1.0%, until eluate clarification transfers in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after being dried, 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: appropriate N in 250mL there-necked flask, dinethylformamide dissolves 8.6g hexamethylenetetramine and 10.2g KI, join swelling spending the night in 20.3g superhigh cross-linking type resin, in oil bath, be warming up to 95 ℃ of reaction 8h, after reaction finishes, incline and mother liquor, wash respectively 3 times with NaOH, the water of 6mol/L hydrochloric acid, water, mass fraction 10%, with ethanol extracting 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 with water 3 times, 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 reaction: add the chloromethylated polystyrene that 21.0g is dry (chlorinty is 17.3%, and the degree of cross linking is 6%) in 250mL there-necked flask, then add swelling the spending the night of 126mL dichloroethanes sweller; Be warming up to 50 ℃, add 6.0g FeCl
3and stirring is until FeCl
3after dissolving completely, be progressively warming up to 82 ℃, and react 7h at this temperature.After having reacted, incline and reaction mother liquor, use hydrochloric acid solution and the alternately washing of absolute ethyl alcohol of mass fraction 1.0%, until eluate clarification transfers in apparatus,Soxhlet's, with absolute ethyl alcohol extracting 12h, after being dried, 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 spending the night in 19.8g superhigh cross-linking type resin, in oil bath, be warming up to 95 ℃ of reaction 8h, after reaction finishes, incline and mother liquor, wash respectively 3 times with NaOH, the water of 6mol/L hydrochloric acid, water, mass fraction 10%, with ethanol extracting 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 with water 3 times, 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 desorption experiment: get one group 6 tool plug conical flasks, add respectively wherein resin prepared by 0.10g embodiment 1 and the phenol solution of 50.00mL same concentrations.They are placed in to rotary water bath oscillator, and 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 is measured absorption, be converted into and adsorb the concentration that reaches the phenol after balance, be balanced adsorbance.
Raffinate after absorption is outwelled, and added 10mL distilled water washing, after pulp-water evacuation, add the desorbing agent of different ethanol and NaOH composition, be placed in the 298K constant temperature oscillator 6h that vibrates, make desorption reach balance.The content of measuring phenol in eluent, calculates the eluting rate (%) of each eluent under 298K, obtains the static analysis diagram shown in Fig. 5.
Dynamic Adsorption-desorption experiment: measure the resin that embodiment 1 that 9.8mL is dry makes, be placed in ethanol water and soak, spend the night.Measure afterwards the soaked resin transfer of 10mL in glass column, strike tight dress real.Certain density phenol solution is flow through to exchange column and 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.Take bed volume number as abscissa, efflux absorbance is abscissa with the ratio of stoste absorbance, draws Dynamic Adsorption curve.Resolve the washing of the best eluant, eluent of effect by static state and adsorbed saturated resin, until in efflux almost reactive phenol detect.The absorbance of efflux is measured in same timing, take bed volume as abscissa, outflow concentration draws dynamic desorption curve as 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 to prepare 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 is 0.1mol/L, the volume fraction of ethanol solution that is 50% during as desorbing agent, desorption efficiency can reach 99.33%.
As can be seen from Figure 6: initial phenol concentration 1000mg/L, flow velocity 4.8BV/h, 90.2BV place reveal, 122.0BV place adsorb saturated, show good absorption property.And the resin that has adsorbed phenol can be with the NaOH of 0.01mol/L, 50% ethanolic solution desorption, in the time of 8.0BV, wash-out is substantially complete, and in the use procedure of dress post, resin mechanical strength is good, does not occur damaged, reusable.
This resin Pyrogentisinic Acid is after adsorption-desorption-adsorb again-desorption recycles again, and resin presents good regeneration and repeat performance.
Claims (9)
1. the preparation method of the superhigh cross-linking type polymeric adsorbent of an acetamido modification, it is characterized in that, chloromethylated polystyrene is passed through after solvent swell, using lewis acid as catalyst, at 80～85 ℃, carry out Friedel-Crafts reaction 5～8h, after having reacted, obtain superhigh cross-linking type resin; Described superhigh cross-linking type resin swelling, being dissolved with in the solvent of hexamethylenetetramine and KI, is carried out to Del é pine reaction 8～12h at 95～105 ℃, 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, refluxes, and 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.
2. preparation method as claimed in claim 1, 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, is characterized in that, in described superhigh cross-linking type resin, the mass percent of residual chlorine is 3.35～6.24%.
4. preparation method as claimed in claim 1, is characterized in that, the mass fraction that described Del é pine reacts the superhigh cross-linking type resin residual chlorine of the amido modification obtaining is 1.25%～2.25%, and weak base exchange capacity is 0.8～1.5mmol/g.
5. preparation method as claimed in claim 1, is characterized in that, in the acetylation reagent adding, the mole of active acetyl is 1.5～3.0 times of weak base exchange capacity of the superhigh cross-linking type resin modified of amido.
6. preparation method as claimed in claim 5, is characterized in that, described acetylation reagent is acetic anhydride, chloroacetic chloride or acetic acid.
7. 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.
8. an application for the superhigh cross-linking type polymeric adsorbent that the acetamido that the preparation method as described in claim 1～7 any one makes is modified, is characterized in that, is applied to the polarity organic matter in selective absorption water.
9. application as claimed in claim 8, is characterized in that, described polarity organic matter is phenol and/or salicylic acid.
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| CN104861094A (en) * | 2015-04-14 | 2015-08-26 | 湖南师范大学 | pH buffering functional group-containing hyper-cross-linked polymeric adsorbent and preparation method thereof |
| CN104910313A (en) * | 2015-06-24 | 2015-09-16 | 中南大学 | Method for preparing polar modified ultrahighly-crosslinked resin and application of resin |
| CN105749877A (en) * | 2015-11-26 | 2016-07-13 | 王金明 | Preparation method of adsorbent applied to hydrogen peroxide purification |
| CN109364890A (en) * | 2018-10-29 | 2019-02-22 | 凯瑞环保科技股份有限公司 | A kind of hydrogen peroxide decarburization absorption resin and the preparation method and application thereof |
| 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 |
| CN113716779A (en) * | 2021-09-01 | 2021-11-30 | 珠海市科立鑫金属材料有限公司 | Treatment process of high-salinity wastewater |
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| WO2007005044A1 (en) * | 2005-07-01 | 2007-01-11 | Purolite International, Ltd. | Method for separating electrolytes |
| CN102350316A (en) * | 2011-06-29 | 2012-02-15 | 中南大学 | Preparation method of ultra-high crosslinking type adsorptive resin modified by N-methyl acetamido |
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| WO2007005044A1 (en) * | 2005-07-01 | 2007-01-11 | Purolite International, Ltd. | Method for separating electrolytes |
| CN102350316A (en) * | 2011-06-29 | 2012-02-15 | 中南大学 | Preparation method of ultra-high crosslinking type adsorptive resin modified by N-methyl acetamido |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861094A (en) * | 2015-04-14 | 2015-08-26 | 湖南师范大学 | pH buffering functional group-containing hyper-cross-linked polymeric adsorbent and preparation method thereof |
| CN104910313A (en) * | 2015-06-24 | 2015-09-16 | 中南大学 | Method for preparing polar modified ultrahighly-crosslinked resin and application of resin |
| CN104910313B (en) * | 2015-06-24 | 2017-10-17 | 中南大学 | Prepare method and the application of Modified with Polar Monomer hypercrosslinked polymeric resin |
| CN105749877A (en) * | 2015-11-26 | 2016-07-13 | 王金明 | Preparation method of adsorbent applied to hydrogen peroxide purification |
| CN105749877B (en) * | 2015-11-26 | 2018-08-17 | 王金明 | A kind of preparation method applied to hydrogen peroxide purifying adsorbent |
| CN109364890A (en) * | 2018-10-29 | 2019-02-22 | 凯瑞环保科技股份有限公司 | A kind of hydrogen peroxide decarburization absorption resin and the preparation method and application thereof |
| 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 |
| CN113716779A (en) * | 2021-09-01 | 2021-11-30 | 珠海市科立鑫金属材料有限公司 | Treatment process of high-salinity wastewater |
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