CN104693336A - Sulfonyl modified strong cationic hypercrosslinked resin and preparation method thereof - Google Patents
Sulfonyl modified strong cationic hypercrosslinked resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sulfonyl modified strong cationic hypercrosslinked resin and a preparation method thereof. The performance of the resin serving as a solid-phase extraction filler is evaluated. The preparation method comprises the following steps: by taking chloromethyl styrene and divinyl benzene as reaction raw materials and taking azodiisobutyronitrile as an initiator, synthesizing a resin white ball by virtue of a non-aqueous precipitation polymerization reaction; by taking ferric trichloride as a catalyst, synthesizing a hypercrosslinked resin by virtue of a Fourier crosslinking reaction; and finally, sulfonating by using concentrated sulfuric acid, and synthesizing the sulfonyl-containing strong cationic hypercrosslinked resin. The strong cationic hypercrosslinked resin disclosed by the invention belongs to a new generation of porous polymer resins, has the complex functions of strong cationic exchange interaction and non-polar interaction and serves as a solid-phase extraction filler, the performance of the resin is obviously superior to that of a commercial Oasis MCX solid-phase extraction column, and the resin can be used for separation and enrichment of alkali compounds in complex samples and has good application prospects in the fields of biology and environments.
Description
[technical field]
The present invention relates to resin technology field, specifically, is the preparation method of the strong cation type hypercrosslinked polymeric resin that a kind of sulfonic group is modified.
[background technology]
In Sample Pretreatment Technique, solid phase extraction techniques because it is simple efficient, be easy to automatization, organic solvent consumption less with the advantage such as result is stable, instead of traditional liquid-liquid extraction method gradually, become the main flow pre-treating process that complex system is analyzed.The clastotype of Solid-Phase Extraction depends primarily on the wire feeding in its stationary phase.Existing commercial extraction agent many employings macroporous resin polymkeric substance is as filler, and its specific surface area is less, and loading capacity is not high.And the hypercrosslinked polymeric resin extraction agent risen recently has the feature of high-specific surface area, if modify specific ion group at resin surface, greatly can be improved it to the selective adsorption of ionic compound and concentration effect.This will become an important development direction of complex sample Solid-Phase Extraction analysis field.
The present invention modifies sulfonic group on the hypercrosslinked polymeric resin material of preparation, thus makes this filler have strong cation reactive force and non-polar action power simultaneously, substantially increases its selectivity to alkaline organic compound.Routine all adopts macropore or gel type resin containing sulfonic strong cation type exchange resin, therefore its specific surface area is low, and loading capacity is not high, and selective adsorption capacity is limited.And disclose a kind of synthetic method containing sulfonic group composite function super high crosslinked adsorptive resin patent in early stage (application number 200510095298.X, publication number CN1772774A), but this method synthesis step is comparatively loaded down with trivial details, needs further improvement badly.Literature search shows, there is not been reported for strong cation type hypercrosslinked polymeric resin involved in the present invention and preparation method thereof.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, the preparation method of the strong cation type hypercrosslinked polymeric resin providing a kind of simple sulfonic group efficiently to modify and application.
The object of the invention is to be achieved through the following technical solutions:
Sulfonic group modify a strong cation type hypercrosslinked polymeric resin, its skeleton is made up of Vinylstyrene, 4-1-chloro-4-methyl-benzene and sulfuric acid, its synthesis step and structure as follows:
A preparation method for the strong cation type hypercrosslinked polymeric resin that sulfonic group is modified, its concrete steps are:
(a) with 1-chloro-4-methyl-benzene, Vinylstyrene for reaction monomers, be initiator with Diisopropyl azodicarboxylate, acetonitrile is reaction solvent, by oxygen that is ultrasonic and that lead to continuously in nitrogen removing reaction system, slowly be warming up to 60 DEG C, react 46 hours, after reaction terminates, by centrifugal obtain solid use methyl alcohol, toluene and washing with acetone successively repeatedly, remove the linear structure produced in reaction raw materials residual in reaction system and building-up process, then obtain the 1-chloro-4-methyl-benzene-divinyl benzene copolymer of white low crosslinking degree through vacuum-drying;
Described 4-1-chloro-4-methyl-benzene and the mass ratio of Vinylstyrene are 3: 1;
The charging capacity of initiator Diisopropyl azodicarboxylate accounts for 2% of the molar fraction of all double bonds in two kinds of reaction monomers;
Normally carry out to make reaction and obtain the comparatively suitable low cross-linking polymkeric substance of particle diameter, temperature of reaction system slowly (should be greater than 2 hours) and rise to 60 DEG C, thus the reaction chain being conducive to polymerizable molecular increases, and forms high molecular polymer.Adjusting rotary speed is 200r/min, thus prepares even, the monodispersed Archon of size.
1-chloro-4-methyl-benzene-the divinyl benzene copolymer of b low crosslinking degree that above-mentioned steps (a) obtains by (), swell in dichloroethane solvent, by the oxygen in ultrasonic and continuous logical nitrogen removing system, adding iron trichloride is catalyzer, be rapidly heated to 80 DEG C, react 18 hours.After reaction terminates, centrifugal removing reaction mother liquor, methyl alcohol and aqueous nitric acid (pH=1) is used by the solid obtained repeatedly to wash successively, the iron trichloride that ethylene dichloride in removing resin and reaction system remain, by the resin after washing, take acetone as solvent, surname extraction refluxes 12 hours; After reaction terminates, reaction system is cooled to room temperature, the acetone in centrifugal removing reaction system, after using methyl alcohol and washed with diethylether repeatedly successively, vacuum-drying obtains yellow highly cross-linked resin particulate;
In order to solve the low problem of iron trichloride solubleness in ethylene dichloride, available 15 ~ 40ml Nitromethane 99Min. hydrotropy;
The amount of substance of described ferric chloride catalyst is 1: 1 with the ratio of the amount of chlorine elemental substance in the affine low cross-linking resin of covalency.
1-chloro-4-methyl-benzene-the divinyl benzene copolymer of c high-crosslinking-degree that above-mentioned steps (b) obtains by (), swell in dichloroethane solvent, by the oxygen in ultrasonic and continuous logical nitrogen removing system, 80 DEG C are rapidly heated after dripping sulfuric acid, sustained reaction distilled out ethylene dichloride after 4 hours at this temperature, again temperature is risen to 100 DEG C, continue reaction 2 hours; After reaction terminates, question response system is cooled to room temperature, is joined by product in icy salt solution, the sulfuric acid that centrifugal removing is unnecessary, uses the hydrochloric acid of 2mol/L and pure water successively repeatedly, and vacuum-drying obtains the strong cation type hypercrosslinked polymeric resin that brown sulfonic group is modified;
Sulfuric acid is massfraction 95.0% ~ 98.0% vitriol oil;
The strong cation type hypercrosslinked polymeric resin that obtained sulfonic group is modified contains abundant micropore distribution, and aperture is 2.1nm, and specific surface area reaches 801m
2/ g.
The strong cation type hypercrosslinked polymeric resin cation exchange capacity that obtained sulfonic group is modified is 2.2mmol/g.
Compared with prior art, positively effect of the present invention is:
(1) the invention provides strong cation type hypercrosslinked polymeric resin of a kind of simple sulfonic group efficiently modification and preparation method thereof, the parent of resin is the polymkeric substance of Vinylstyrene and styrene compound, resin has superhigh specific surface area and pore volume, better absorption property can be provided, resin is monodispersed bead, narrow diameter distribution is desirable solid phase extraction filler.
(2) in resins synthesis step, add sulfuric acid and carry out sulfonation, enhance the hydrophilicity of resin, there is very high ion exchange volume (being 2 times of conventional commercialization solid extracting agent of the same type), can active adsorption complex system neutral and alkali organic compound.
[accompanying drawing explanation]
Fig. 1 is the scanning electron microscope (SEM) photograph of the strong cation type hypercrosslinked polymeric resin of the sulfonic group modification that the present invention synthesizes;
Fig. 2 is Archon (PP), the 1-chloro-4-methyl-benzene-divinyl benzene copolymer (HXLPP) of high-crosslinking-degree and strong cation type hypercrosslinked polymeric resin (HXLPP-SCX) infrared spectrogram of sulfonic group modification that the present invention synthesizes;
[embodiment]
The present invention preparation method of strong cation type hypercrosslinked polymeric resin that a kind of sulfonic group is modified and the embodiment of application are below provided.
Embodiment 1
The preparation of the strong cation type hypercrosslinked polymeric resin that sulfonic group is modified, comprises the steps:
A (), in the 1000ml there-necked flask that reflux condensing tube, thermometer and nitrogen protection device are housed, adds 800ml acetonitrile, system ice bath is cooled to 0 DEG C.To in ice-water bath system, add Diisopropyl azodicarboxylate 0.46g successively, Vinylstyrene 4g, 4-1-chloro-4-methyl-benzene 12g, system temperature maintains 0 DEG C, and logical nitrogen 2 hours, to eliminate the oxygen in system.Then be transferred in oil bath by reaction, regulate magnetic stirring apparatus to 200r/min, system is slowly risen to 60 DEG C (temperature rise rates by 4min/ DEG C) by room temperature, maintains this temperature and continues reaction 46 hours.After reaction terminates, reaction system is cooled to room temperature, the reaction solution nylon filter membrane filtration of 0.2 μm, filter cake uses 40ml methyl alcohol, 40ml toluene, each supersound washing of 40ml acetone twice rear 40 DEG C of vacuum-drying to constant weight successively, obtains the matrix polymer particulate of white.
B () is in the 250ml there-necked flask that reflux condensing tube, thermometer and nitrogen protection device are housed; add white matrix polymer particulate and 40ml 1 that 4.5g above-mentioned steps (d) obtains successively; 2-ethylene dichloride, makes resin fully swelling 1.5 hours under nitrogen atmosphere.Take FERRIC CHLORIDE ANHYDROUS 3.6g, add Nitromethane 99Min. hydrotropy, then add 40ml anhydrous ethylene dichloride and iron trichloride is dissolved completely drop in flask.Regulate magnetic stirring apparatus to suitable rotating speed, be rapidly heated to 80 DEG C, and continue reaction 18 hours at such a temperature.After reaction terminates, reaction system is cooled to room temperature, reaction solution filtration under diminished pressure, discard filtrate, it is repeatedly colourless to filtrate that filter cake uses methyl alcohol, salpeter solution (pH=1) to wash successively, and obtaining yellow-brown solid, is that solvent apparatus,Soxhlet's extracts 12 hours continuously with acetone by solid.After extraction completes, gained solid uses methyl alcohol, washed with diethylether repeatedly more successively, and filter, 40 DEG C of vacuum-dryings, to constant weight, obtain yellow hypercrosslinked polymeric resin particulate.
C () takes the faint yellow hypercrosslinked polymeric resin particulate that 3g above-mentioned steps (b) obtains; join containing 10ml 1; 2-ethylene dichloride be equipped with in the there-necked flask of reflux condensing tube, thermometer and nitrogen protection device, make resin under nitrogen atmosphere fully swelling 1.5 hours.Drip the 20ml vitriol oil, regulate suitable stirring velocity, be rapidly heated to 80 DEG C, react at this temperature after 4 hours and distill out 1,2-ethylene dichloride, temperature is adjusted to 100 DEG C, continue reaction 2 hours.After reaction terminates, be cooled to room temperature, reaction solution is dropped to cryosel dilution with water, the sulfuric acid that centrifugal removing is unnecessary, the solia particle obtained is used successively the hydrochloric acid of 2mol/L and pure water repeatedly, filter, filter cake vacuum-drying 40 DEG C time, to constant weight, obtains the strong cation type hypercrosslinked polymeric resin particulate that brown sulfonic group is modified.
The strong cation type hypercrosslinked polymeric resin that c sulfonic group that () obtains is modified, surface sweeping Electronic Speculum figure as shown in Figure 1.The synthesized affine hypercrosslinked polymeric resin size distribution of covalency is 3-5 μm, specific surface area 801m
2/ g.Strong cation type hypercrosslinked polymeric resin (HXLPP-SCX) infrared spectrogram that the 1-chloro-4-methyl-benzene-divinyl benzene copolymer (HXLPP) of Archon (PP), high-crosslinking-degree and sulfonic group are modified as shown in Figure 2.The infrared spectra display of resin, Archon is at 1265cm
-1and 710cm
-1the absorption peak at place, is respectively CH
2the upper C-H flexural vibration of-Cl and C-Cl stretching vibration absorption peak.And the absorption peak of the 1-chloro-4-methyl-benzene-divinyl benzene copolymer of high-crosslinking-degree at this two place obviously reduces, illustrate that C-Cl key obviously reduces in superhigh cross-linking reaction process.At 1224cm
-1and 1038cm
-1the absorption peak at place is the feature stretching vibration of S=O key, illustrates that sulfonic group is successfully modified on resin.
Embodiment 2
The strong cation type hypercrosslinked polymeric resin that the sulfonic group of this example is modified is used as solid phase extraction filler, and the alkaline organic compound in the selective adsorption aqueous solution, the steps include:
(a) preparation storing solution: accurately take urobenzoic acid, uric acid, xanthoglobulin, each 10mg of xanthine, be settled to 10mL with after a small amount of 0.1mol/LNaOH solubilize with water respectively.Accurately take inosine 10mg, be settled to 10mL with 0.13% acetic acid solution (pH=3).
B () prepares liquid to be measured: each 100 μ L of five kinds of storing solutions of accurately preparation in removing step (a), are settled to 10mL with 0.13% acetic acid solution (pH=3).
The filling of (c) solid-phase extraction column: accurately take the strong cation type hypercrosslinked polymeric resin resin 60mg that sulfonic group is modified, disperse with 30ml anhydrous methanol, adopting wet method dress post resin to be loaded volume is in the Solid-Phase Extraction void column pipe of 3ml, the sieve plate compacting of resin two ends.
(d) Solid-Phase Extraction activation step: used by solid-phase extraction column 5ml methyl alcohol, 3ml0.13% acetic acid solution (pH=3) to activate successively, flow velocity is 0.5ml/min.
(e) Solid-Phase Extraction loading step: accurately pipette 1ml step (b) join in solution to the solid-phase extraction column that activate, flow velocity 0.5ml/min, collection effluent liquid is to be measured.
F () Solid-Phase Extraction rinsing step: accurately pipette 3mL water successively, 3mL methyl alcohol carries out drip washing, flow rate control, at 1ml/min, collects Solid-Phase Extraction effluent liquid to be measured.
G () SPE elution step: accurately pipette 3ml5% ammoniated methanol solution and carry out wash-out, flow velocity 0.5ml/min, collects Solid-Phase Extraction effluent liquid to be measured.
(f) commodity in use solid-phase extraction column Waters Oasis MCX (3cc, 60mg), repeating step (d) ~ (g).
Adopt high performance liquid chromatography to measure the sample that each step obtains, the chromatographic peak peak area of comparative sample and standard specimen, obtain five kinds of materials rate of recovery in each step, experimental result is as shown in table 1:
Table 1 urobenzoic acid, uric acid, xanthine, xanthoglobulin and the inosine rate of recovery in Solid-Phase Extraction respectively walks
Experimental result shows, under acid loading condition, the strong cation type hypercrosslinked polymeric resin that five kinds of materials are modified at sulfonic group due to non-polar action power all has good reservation.Because uric acid and urobenzoic acid and interlaminar resin only exist more weak non-polar action power, so these two kinds of acidic cpds are eluted completely (rate of recovery > 93.9%) in water and methyl alcohol rinsing step.And xanthoglobulin, xanthine and inosine and interlaminar resin not only exist non-polar action power, also there is stronger cationic exchange effect, therefore do not washed in rinsing step; And in elution step, because ionization power under alkaline environment is destroyed, only there is non-polar action power in these alkaline matters and interlaminar resin, thus is eluted completely (rate of recovery > 87.3%) by methyl alcohol.And under same condition, in loading process, uric acid and urobenzoic acid not completely adsorb by OasisMCX solid-phase extraction column.In rinsing step, except uric acid and urobenzoic acid, most of xanthine and inosine are also eluted simultaneously, only have the double reaction plus between xanthoglobulin and filler comparatively strong, are in the end just eluted completely in elution process.The above results illustrates the strong cation type hypercrosslinked polymeric resin that the sulfonic group synthesized by the present invention is modified, there is nonpolar and cationic exchange two class reactive force simultaneously, compared with commercialization resin Oasis MCX, there is better selective adsorption effect to alkaline organic compound, can realize effectively being separated and enrichment this compounds.
The strong cation type hypercrosslinked polymeric resin that the sulfonic group of this example is modified is used as solid phase extraction filler, surveys its saturated extent of adsorption to xanthoglobulin, xanthine and inosine, the steps include:
A () preparing standard solution: accurately take xanthoglobulin 70mg, xanthine 10mg, is settled to 100mL (salt acid for adjusting pH is 3) with after a small amount of 0.1mol/LNaOH solubilize with water respectively.Accurately take inosine 150mg, be settled to 100mL with 0.13% acetic acid solution (pH=3).
The filling of (b) solid-phase extraction column: accurately take the strong cation type hypercrosslinked polymeric resin resin 60mg that sulfonic group is modified, disperse with 30ml anhydrous methanol, adopting wet method dress post resin to be loaded volume is in the Solid-Phase Extraction void column pipe of 3ml, the sieve plate compacting of resin two ends.
(c) Solid-Phase Extraction activation step: used by solid-phase extraction column 5ml methyl alcohol, 3ml0.13% acetic acid solution (pH=3) to activate successively, flow velocity is 0.5ml/min.
(d) Solid-Phase Extraction loading step: with 1ml join by the accurate removing step (a) of loading unit in solution to the solid-phase extraction column that activate, flow velocity 0.5ml/min, collection effluent liquid is to be measured.
E () effluent liquid measures: adopt high performance liquid chromatography to measure effluent liquid, the chromatographic peak peak area of comparative sample and standard specimen, until peak area no longer raises, namely resin reaches capacity absorption.
(f) commodity in use solid-phase extraction column Waters Oasis MCX (3cc, 60mg), repeating step (c) ~ (e).
Strong cation type hypercrosslinked polymeric resin (HXLPP-SCX) and the saturated extent of adsorption result of Oasis MCX solid-phase extraction column to xanthoglobulin, xanthine and inosine of sulfonic group modification are as shown in table 2:
Table 2 HXLPP-SCX and Oasis MCX is to the saturated extent of adsorption of xanthoglobulin, xanthine and inosine
Saturated extent of adsorption result shows, the strong cation type hypercrosslinked polymeric resin that sulfonic group is modified is used as solid phase extraction filler, to the saturated extent of adsorption of xanthoglobulin, xanthine and inosine all apparently higher than commercialization OasisMCX solid-phase extraction column.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (9)
1. a strong cation type hypercrosslinked polymeric resin for sulfonic group modification, it is characterized in that, its skeleton is made up of Vinylstyrene, 4-1-chloro-4-methyl-benzene and sulfuric acid, and its structural formula is as follows:
2. a preparation method for the strong cation type hypercrosslinked polymeric resin of sulfonic group modification, it is characterized in that, its concrete steps are:
A () utilizes 1-chloro-4-methyl-benzene, Vinylstyrene for reaction monomers, be initiator with Diisopropyl azodicarboxylate, acetonitrile is reaction solvent, by oxygen that is ultrasonic and that lead to continuously in nitrogen removing reaction system, slowly be warming up to 60 DEG C, react 46 hours, after reaction terminates, by centrifugal obtain solid use methyl alcohol successively, toluene and washing with acetone are repeatedly, remove the linear structure produced in reaction raw materials residual in reaction system and building-up process, then obtain the 1-chloro-4-methyl-benzene-divinyl benzene copolymer of white low crosslinking degree through vacuum-drying, i.e. Archon;
1-chloro-4-methyl-benzene-the divinyl benzene copolymer of b low crosslinking degree that above-mentioned steps (a) obtains by (), swell in dichloroethane solvent, by the oxygen in ultrasonic and continuous logical nitrogen removing system, adding iron trichloride is catalyzer, be rapidly heated to 80 DEG C, react 18 hours; After reaction terminates, centrifugal removing reaction mother liquor, repeatedly washs with the salpeter solution that methyl alcohol and pH are 1 successively by the solid obtained, the iron trichloride that ethylene dichloride in removing resin and reaction system remain, by the resin after washing, take acetone as solvent, surname extraction refluxes 12 hours; After reaction terminates, reaction system is cooled to room temperature, and the acetone in centrifugal removing reaction system, uses methyl alcohol and washed with diethylether repeatedly successively, and vacuum-drying obtains yellow highly cross-linked resin particulate;
1-chloro-4-methyl-benzene-the divinyl benzene copolymer of c high-crosslinking-degree that above-mentioned steps (b) obtains by (), swell in dichloroethane solvent, by the oxygen in ultrasonic and continuous logical nitrogen removing system, add sulfuric acid and be rapidly heated 80 DEG C, sustained reaction distilled out ethylene dichloride after 4 hours at this temperature, again temperature is risen to 100 DEG C, continue reaction 2 hours; After reaction terminates, question response system is cooled to room temperature, is joined by product in icy salt solution, the sulfuric acid that centrifugal removing is unnecessary, uses the hydrochloric acid of 2mol/L and pure water successively repeatedly, and vacuum-drying obtains the strong cation type hypercrosslinked polymeric resin that brown sulfonic group is modified.
3. the preparation method of the strong cation type hypercrosslinked polymeric resin of a kind of sulfonic group modification as claimed in claim 2, it is characterized in that, in described step (a), described 4-1-chloro-4-methyl-benzene and the mass ratio of Vinylstyrene are 3: 1.
4. the preparation method of the strong cation type hypercrosslinked polymeric resin of a kind of sulfonic group modification as claimed in claim 2, it is characterized in that, in described step (a), the charging capacity of initiator Diisopropyl azodicarboxylate accounts for 2% of the molar fraction of all double bonds in two kinds of reaction monomers.
5. the preparation method of the strong cation type hypercrosslinked polymeric resin of a kind of sulfonic group modification as claimed in claim 2, it is characterized in that, in described step (b), the amount of substance of ferric chloride catalyst is 1: 1 with the ratio of the amount of chlorine elemental substance in low cross-linking resin.
6. the preparation method of the strong cation type hypercrosslinked polymeric resin of a kind of sulfonic group modification as claimed in claim 2, it is characterized in that, in described step (c), sulphonating agent sulfuric acid is massfraction 95.0% ~ 98.0% vitriol oil.
7. the preparation method of the strong cation type hypercrosslinked polymeric resin of a kind of sulfonic group modification as claimed in claim 2, it is characterized in that, in described step (c), the strong cation type hypercrosslinked polymeric resin that obtained sulfonic group is modified contains abundant micropore distribution, aperture is 2.1nm, and specific surface area reaches 801m
2/ g.
8. the preparation method of the strong cation type hypercrosslinked polymeric resin of a kind of sulfonic group modification as claimed in claim 2, it is characterized in that, in described step (c), the strong cation type hypercrosslinked polymeric resin cation exchange capacity that obtained sulfonic group is modified is 2.2mmol/g.
9. the preparation method of the strong cation type hypercrosslinked polymeric resin of a kind of sulfonic group modification as claimed in claim 2, is characterized in that the application in solid phase extraction filler.
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| CN108283938A (en) * | 2018-01-25 | 2018-07-17 | 丹东明珠特种树脂有限公司 | Strong acid type cationic resin catalyst and its overlapping application of light petrol C 5/C 6 olefin |
| CN112452308A (en) * | 2020-12-09 | 2021-03-09 | 昆明理工大学 | Synthetic method and application of pyridine amide-containing adsorption polymer |
| CN112755971A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of adsorbent for removing trace amine liquid in light naphtha |
| CN113600150A (en) * | 2021-08-23 | 2021-11-05 | 湖南科技大学 | Method for preparing magnetic super-crosslinked polymer from vacuum residue |
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| CN105218724A (en) * | 2015-09-21 | 2016-01-06 | 安徽皖东化工有限公司 | A kind of preparation method of strong-acid cation-exchange resin |
| CN106519288A (en) * | 2016-11-09 | 2017-03-22 | 绍兴文理学院 | Method for preparation of sulfonate radical-functionalized large-specific surface area macroporous resin |
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| CN112755971A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of adsorbent for removing trace amine liquid in light naphtha |
| CN112755971B (en) * | 2019-10-21 | 2024-04-02 | 中国石油化工股份有限公司 | Preparation method of adsorbent for removing trace amine liquid in light naphtha |
| CN112452308A (en) * | 2020-12-09 | 2021-03-09 | 昆明理工大学 | Synthetic method and application of pyridine amide-containing adsorption polymer |
| CN112452308B (en) * | 2020-12-09 | 2022-10-25 | 昆明理工大学 | Synthetic method and application of pyridine amide-containing adsorption polymer |
| CN113600150A (en) * | 2021-08-23 | 2021-11-05 | 湖南科技大学 | Method for preparing magnetic super-crosslinked polymer from vacuum residue |
| CN113600150B (en) * | 2021-08-23 | 2023-03-28 | 湖南科技大学 | Method for preparing magnetic super-crosslinked polymer from vacuum residue |
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