CN114736382B - Linear polyamine polystyrene adsorption resin and preparation method and application thereof - Google Patents
Linear polyamine polystyrene adsorption resin and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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Abstract
The invention discloses a linear polyamine polystyrene adsorption resin and a preparation method and application thereof, wherein the preparation method comprises the following steps: weighing primary amine type polystyrene resin, and soaking the primary amine type polystyrene resin in an organic solvent for 2-24 hours; adding a poly 2-oxazoline derivative, and stirring and reacting for 4-24 hours at 20-60 ℃ to obtain an intermediate; washing the intermediate, and then placing the intermediate in concentrated hydrochloric acid for full reflux; and cooling the reflux liquid, filtering out the solid, fully washing, and vacuum drying to obtain the linear polyamine type polystyrene adsorption resin. Compared with the common polystyrene adsorption resin, the resin has larger adsorption capacity for some substances, the adsorption capacity for hydrogen chloride can be more than 10mmol/g, the adsorption capacity for copper ions can be more than 4.1mmol/g, and the adsorption capacity for carbon dioxide can be 3.35 mmol/g.
Description
Technical Field
The invention relates to a linear polyamine polystyrene adsorption resin, a preparation method and application thereof, and belongs to the technical field of adsorption resin materials.
Background
Due to the action of the lone pair of electrons on the nitrogen atom, the organic amine can bind to acidic species and have the property of complexing with certain transition metal ions. Polyamine organic matters are often used as functional groups to be immobilized on the surfaces of various carriers to prepare adsorption materials with different structures, and the adsorption materials are used for adsorbing acidic substances or metal ions through physical or chemical actions. Many adsorption materials using polyamine as functional group have obvious effect on efficiently and selectively adsorbing acidic substances or transition metal ions.
For example, the wheat straw modified by polyethyleneimine is used for adsorbing copper ions in an aqueous solution, and the saturated adsorption capacity can reach 0.77mmol/g; the adsorption material prepared from the diethylenetriamine bonded silica gel has excellent effect on adsorbing trace copper ions in recovered water, and the recovery rate can reach more than 95%; chelating resin with bipyridylmethylamine functional group has adsorption capacity to Cu (II), zn (II), co (II), ni (II) and other transition metal ions; grafting tetraethylenepentamine onto chloracetyl polystyrene resin, wherein the saturated adsorption capacity of Cu (II) can reach 46.15mg/mL; the adsorption capacity of the various polyamine chelate resins prepared by using the styrene resin, the acrylic resin and the like as the base materials shows novel characteristics, the Cu (II) adsorption capacity of the acrylic polyamine resin PAMD reaches 2.24mmol/g, and the adsorption activity is obviously higher than that of Zn (II) and Ni (II).
In addition, the effect of the amine resin prepared by amination of the XDC-BE-based ultrahigh crosslinked adsorption resin on adsorbing resorcinol is remarkable, and the adsorption capacity reaches 185mg/g; the polyamine chelating resin CEAD has good p-nitrophenol adsorption performance, and the maximum adsorption capacity can reach 225mg/g; the resin obtained by grafting diethylenetriamine, triethylenetetramine and tetraethylenepentamine respectively after chloracetyl of XAD-4 resin respectively has the combined HCl capacity of 5.95mmol/g,5.63mmol/g and 8.16mmol/g in water phase; PS-TETA resin obtained by the reaction of triethylene tetramine and chloromethylated polystyrene has good adsorption effect on Hg, cd, pb and other ions.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a linear polyamine type polystyrene adsorption resin, a preparation method and application thereof, wherein linear polyamine functional groups are indirectly grafted on polystyrene to prepare the linear polyamine type polystyrene adsorption resin, and the resin has large adsorption capacity and obvious adsorption effect on various substances such as inorganic acid, organic acid, phenols, metal ions, acid gas and the like.
In order to solve the technical problems, the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a linear polyamine-type polystyrene adsorbent resin, wherein the structural formula of the linear polyamine-type polystyrene adsorbent resin is shown as formula I:
in the formula I, PS is polystyrene, L is a connecting arm, and L is selected from-CH 2 -、-CH 2 CH 2 -、-CH 2 NHCH 2 CH 2 -、-CH 2 N(CH 2 CH 2 ) 2 -、-CH 2 N + (CH 2 CH 2 ) 3 Within the dashed line is a linear polyamine functional group, R is methyl or ethyl, n=4 to 30.
In a second aspect, the present invention provides a method for preparing a linear polyamine polystyrene adsorbent resin, comprising the steps of:
weighing primary amine type polystyrene resin, and soaking the primary amine type polystyrene resin in an organic solvent for 2 to 24 hours;
adding a poly 2-oxazoline derivative, and stirring and reacting for 4-24 hours at 20-60 ℃ to prepare an intermediate;
washing the intermediate, and then placing the intermediate in concentrated hydrochloric acid for full reflux;
cooling the reflux liquid, filtering out solids, fully washing, and vacuum drying to obtain the linear polyamine polystyrene adsorption resin;
the amine-type polystyrene resin comprises the following structures shown by APS-1 to APS-5:
in some embodiments, the poly-2-oxazoline derivative includes the following structure represented by PROZ-1 through PROZ-4:
wherein n=4 to 30.
In some embodiments, the primary amine-type polystyrene resin (based on primary amino groups therein) is mixed with the poly-2-oxazoline derivative in a ratio of 1 (1-5) by mass.
In some embodiments, the primary amine-based polystyrene resin (based on primary amino groups therein) is mixed with the poly-2-oxazoline derivative in a ratio of 1 (2-4) by mass.
In some embodiments, the organic solvent comprises one or more of chloroform, dichloromethane, dichloroethane, acetonitrile, tetrahydrofuran.
In some embodiments, the primary amine-type polystyrene resin is mixed with an organic solvent in a mass ratio of 1 (3-15).
In some embodiments, after the intermediate is washed clean, it is placed in concentrated hydrochloric acid for sufficient reflux, which is 2 to 12 hours.
In some embodiments, the reflux is cooled, the solids are filtered off, and washed thoroughly, comprising the steps of: the filtered solid is washed by deionized water, ethanol, 0.5-1mol/L dilute hydrochloric acid and 0.5-1mol/L sodium hydroxide aqueous solution respectively, and finally deionized water is used for washing to neutrality.
In a third aspect, the invention provides an application of the linear polyamine polystyrene adsorbent resin, which is characterized in that a compound shown in a structural formula I is used as an adsorbent for adsorbing inorganic acid, organic acid, phenols, metal ions and acid gases.
Compared with the prior art, the invention has the beneficial effects that:
compared with the prior reported polyamine type polyethylene adsorption resin, the resin has more ordered polyamine functional group structure, and all N on the functional groups are secondary amines, thus showing better adsorption effect. The preparation method comprises the following steps: weighing primary amine type polystyrene resin, and soaking the primary amine type polystyrene resin in an organic solvent for 2 to 24 hours; adding a poly 2-oxazoline derivative, and stirring and reacting for 4-24 hours at 20-60 ℃ to prepare an intermediate; washing the intermediate, and then placing the intermediate in concentrated hydrochloric acid for full reflux; and cooling the reflux liquid, filtering out the solid, fully washing, and vacuum drying to obtain the linear polyamine type polystyrene adsorption resin.
Compared with the common polystyrene adsorption resin, the linear polyamine type polystyrene adsorption resin has larger adsorption capacity for some substances, for example, the adsorption capacity of the linear polyamine type polystyrene adsorption resin for hydrogen chloride can be more than 10mmol/g (1 mol/L aqueous solution of hydrogen chloride), the adsorption capacity of p-nitrophenol can be more than 4.5mmol/g (3.5 mmol/L aqueous solution of p-nitrophenol), the adsorption capacity of trifluoroacetic acid can be more than 7.4mmol/g (50 mmol/L aqueous solution of trifluoroacetic acid), the adsorption capacity of copper ions can be more than 4.1mmol/g (10 mmol/L aqueous solution of copper sulfate), and the adsorption capacity of carbon dioxide can be 3.35mmol/g (gaseous state, 1 atm).
Detailed Description
The invention is further described below. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
The test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are commercially available.
The invention provides a linear polyamine type polystyrene adsorption resin, which is characterized in that the structural formula of the linear polyamine type polystyrene adsorption resin is shown as formula I:
in the formula I, PS is polystyrene, L is a connecting arm, and L is selected from-CH 2 -、-CH 2 CH 2 -、-CH 2 NHCH 2 CH 2 -、-CH 2 N(CH 2 CH 2 ) 2 -、-CH 2 N + (CH 2 CH 2 ) 3 Within the dashed line is a linear polyamine functional group, R is methyl or ethyl, n=4 to 30.
The invention also provides a preparation method of the linear polyamine polystyrene adsorption resin, which comprises the following steps:
step one: weighing primary amine type polystyrene resin, and soaking the primary amine type polystyrene resin in an organic solvent for 2 to 24 hours;
the organic solvent comprises one or more of chloroform, dichloromethane, dichloroethane, acetonitrile and tetrahydrofuran; but are not limited thereto, and those skilled in the art may substitute for other organic solvents;
the primary amine type polystyrene resin (based on the primary amino group thereof) may be mixed with an organic solvent in a mass ratio of 1 (3 to 15) by a person skilled in the art.
In the invention, the primary amine type polystyrene resin comprises the following structures shown by APS-1 to APS-5:
step two: adding a poly 2-oxazoline derivative, and stirring and reacting for 4-24 hours at 20-60 ℃ to prepare an intermediate;
wherein the poly-2-oxazoline derivative comprises the following structures shown in PROZ-1-PROZ-4:
wherein n=4 to 30.
In some embodiments, one skilled in the art may mix the primary amine type polystyrene resin APS-4 with poly 2-oxazoline derivative in a ratio of the amounts of materials of 1 (1-5);
preferably, the primary amine type polystyrene resin APS-4 and the poly 2-oxazoline derivative are mixed according to the mass ratio of 1 (2-4);
step three: washing the intermediate, and then placing the intermediate in concentrated hydrochloric acid for full reflux; in some embodiments, the intermediate is washed clean and then placed in concentrated hydrochloric acid for full reflux, wherein the reflux is 2-12 hours;
step four: cooling the reflux liquid, filtering out solids, fully washing, and vacuum drying to obtain the linear polyamine polystyrene adsorption resin;
in some embodiments, the reflux is cooled, the solids are filtered off, and washed thoroughly, comprising the steps of: the filtered solid is washed by deionized water, ethanol, 0.5-1mol/L dilute hydrochloric acid and 0.5-1mol/L sodium hydroxide aqueous solution respectively, and finally deionized water is used for washing to neutrality.
The invention also applies the linear polyamine polystyrene adsorbent resin to the adsorption of inorganic acid, organic acid, phenols, metal ions and acid gases.
The following describes the technical scheme of the present invention in detail with reference to examples, but is not limited thereto.
Example 1
Step one: 10g of APS-1 is taken and placed in 30g of dichloroethane for soaking for 6 hours;
step two: 52.8mmol of PROZ-1 (n=6) was added and the reaction was stirred at 20 ℃ for 12 hours to prepare an intermediate;
step three: taking out the intermediate, washing with deionized water and ethanol, and placing in concentrated hydrochloric acid for full reflux for 6 hours.
Step four: cooling the reflux liquid, filtering out solid, fully washing with deionized water, ethanol, dilute hydrochloric acid (1 mol/L) and sodium hydroxide aqueous solution (1 mol/L), finally washing with deionized water to neutrality, and vacuum drying to obtain target resin No. 1, wherein the N content is 10.9%.
Example 2
Step one: soaking 10g of APS-2 in 150g of acetonitrile for 2 hours;
step two: 22.8mmol of PROZ-3 (n=30) was added and the reaction was stirred at 50℃for 24 hours to prepare an intermediate;
step three: taking out the intermediate, washing the intermediate with deionized water and ethanol, and placing the intermediate in concentrated hydrochloric acid for full reflux for 8 hours;
step four: cooling the reflux liquid, filtering out solid, fully washing with deionized water, ethanol, dilute hydrochloric acid (0.5 mol/L) and sodium hydroxide aqueous solution (0.5 mol/L), finally washing with deionized water to be neutral, and vacuum drying to obtain target resin No. 2, wherein the N content is 10.4%.
Example 3
Step one: soaking 10g of APS-3 in 50g of chloroform for 24 hours;
step two: 70.2mmol of PROZ-2 (n=10) was added and the reaction was stirred at 30 ℃ for 6 hours to prepare an intermediate;
step three: taking out the intermediate, washing with deionized water and ethanol, and placing in concentrated hydrochloric acid for full reflux for 6 hours;
step four: cooling the reflux liquid, filtering out solid, fully washing with deionized water, ethanol, dilute hydrochloric acid (0.5 mol/L) and sodium hydroxide aqueous solution (0.5 mol/L), finally washing with deionized water to be neutral, and vacuum drying to obtain target resin No. 3, wherein the N content is 13.0%.
Example 4
Step one: soaking 10g of APS-4 in 60g of chloroform for 12 hours;
step two: 174.3mmol (PROZ-1 (n=15) was added and the reaction was stirred at 40 ℃ for 12 hours to prepare an intermediate;
step three: taking out the intermediate, washing with deionized water and ethanol, and placing in concentrated hydrochloric acid for full reflux for 12 hours;
step four: cooling the reflux liquid, filtering out solid, fully washing with deionized water, ethanol, dilute hydrochloric acid (1 mol/L) and sodium hydroxide aqueous solution (0.5 mol/L), finally washing with deionized water to be neutral, and vacuum drying to obtain target resin No. 4, wherein the N content is 14.1%.
Example 5
Step one: 10g of APS-5 is taken and placed in 100g of tetrahydrofuran for soaking for 8 hours;
step two: 254.0mmol of PROZ-4 (n=4) was added and the reaction was stirred at 60 ℃ for 20 hours to prepare an intermediate;
step three: taking out the intermediate, washing with deionized water and ethanol, and placing in concentrated hydrochloric acid for full reflux for 2 hours.
Step four: cooling the reflux liquid, filtering out solid, fully washing with deionized water, ethanol, dilute hydrochloric acid (0.5 mol/L) and sodium hydroxide aqueous solution (1 mol/L), finally washing with deionized water to be neutral, and vacuum drying to obtain target resin No. 5, wherein the N content is 13.6%.
Application testing
In the present invention, the adsorption effect of the target resins on different substances was studied by performing the performance test on the target resins obtained in the above preparation examples 1 to 5, wherein the adsorption effect of the target resins obtained in the examples 1 to 5 and the comparative example on different substances is shown in table 1.
TABLE 1 adsorption Effect of the target resins obtained in preparation examples 1 to 5 on different substances
As can be seen from Table 1, the linear polyamine type polystyrene adsorbent resin prepared by the invention has remarkable adsorption effect on various substances such as inorganic acid (such as hydrochloric acid), organic acid (such as trifluoroacetic acid), phenols (such as p-nitrophenol), metal ions (such as copper ions) and other acid gases (such as carbon dioxide); compared with the common polystyrene adsorption resin, the resin has larger adsorption capacity for some substances, specifically, the linear polyamine type polystyrene adsorption resin has the adsorption capacity for hydrogen chloride of more than 10mmol/g (1 mol/L aqueous solution of hydrogen chloride), the adsorption capacity for p-nitrophenol of more than 4.5mmol/g (3.5 mmol/L aqueous solution of p-nitrophenol), the adsorption capacity for trifluoroacetic acid of more than 7.3mmol/g (50 mmol/L aqueous solution of trifluoroacetic acid), the adsorption capacity for copper ions of more than 4.1mmol/g (10 mmol/L aqueous solution of copper sulfate) and the adsorption capacity for carbon dioxide of 3.35mmol/g (gaseous state, 1 atm).
According to the invention, the linear polyamine functional group is grafted on the polystyrene PS through the connecting arm L, and the tail end N of the linear polyamine functional group is connected with a methyl or ethyl group, so that the obtained linear polyamine type polystyrene adsorption resin is more orderly in structure, and all N on the functional groups are secondary amines, so that a better adsorption effect can be embodied. The resin has remarkable adsorption effect on inorganic acid, organic acid, phenols, carbon dioxide and partial metal ions, and has higher adsorption capacity on HCl and Cu (II) in water phase than the adsorption materials with the same structure reported in the prior art.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (9)
1. The linear polyamine type polystyrene adsorbent resin is characterized in that the structural formula of the linear polyamine type polystyrene adsorbent resin is shown as formula I:
in the formula I, PS is polystyrene, L is a connecting arm, and L is selected from-CH 2 -、-CH 2 CH 2 -、-CH 2 NHCH 2 CH 2 Within the dashed line is a linear polyamine functional group, R is methyl or ethyl, n=4 to 30.
2. A method for preparing the linear polyamine type polystyrene adsorbent resin according to claim 1, which comprises the following steps:
weighing primary amine type polystyrene resin, and soaking the primary amine type polystyrene resin in an organic solvent for 2 to 24 hours;
adding a poly 2-oxazoline derivative, and stirring and reacting for 4-24 hours at 20-60 ℃ to prepare an intermediate;
washing the intermediate, and then placing the intermediate in concentrated hydrochloric acid for full reflux;
cooling the reflux liquid, filtering out solids, fully washing, and vacuum drying to obtain the linear polyamine polystyrene adsorption resin;
the primary amine type polystyrene resin comprises the following structures shown by APS-1 to APS-3:
the poly-2-oxazoline derivative comprises the following structures shown in PROZ-1-PROZ-4:
wherein n=4 to 30.
3. The method for producing a linear polyamine-type polystyrene adsorbent resin according to claim 2, wherein the primary amine-type polystyrene resin and the poly-2-oxazoline derivative are mixed in a mass ratio of 1 (1-5).
4. The method for producing a linear polyamine-type polystyrene adsorbent resin according to claim 3, wherein the primary amine-type polystyrene resin and the poly-2-oxazoline derivative are mixed in a mass ratio of 1 (2-4).
5. The method for preparing a linear polyamine type polystyrene adsorbent resin according to claim 2, wherein the organic solvent comprises one or more of chloroform, methylene chloride, dichloroethane, acetonitrile, and tetrahydrofuran.
6. The method for producing a linear polyamine-type polystyrene adsorbent resin according to claim 2, wherein the primary amine-type polystyrene adsorbent resin is mixed with an organic solvent in a mass ratio of 1 (3 to 15).
7. The method for preparing a linear polyamine type polystyrene adsorbent resin according to claim 2, wherein the intermediate is washed clean and then placed in concentrated hydrochloric acid for full reflux, wherein the reflux time is 2-12 hours.
8. The method for preparing a linear polyamine type polystyrene adsorbent resin according to claim 2, wherein the steps of cooling the reflux liquid, filtering out the solid, and washing the solid thoroughly, comprise the steps of: the filtered solid is washed by deionized water, ethanol, 0.5-1mol/L dilute hydrochloric acid and 0.5-1mol/L sodium hydroxide aqueous solution respectively, and finally deionized water is used for washing to neutrality.
9. The use of the linear polyamine polystyrene adsorbent resin according to claim 1 wherein the compound of structural formula i is used as an adsorbent for the adsorption of mineral acids, organic acids, phenols, metal ions and acid gases.
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| US4011160A (en) * | 1975-03-03 | 1977-03-08 | The Dow Chemical Company | Process of using oxazoline and/or oxazine-modified polymers |
| US4163718A (en) * | 1975-12-09 | 1979-08-07 | The Dow Chemical Company | Complexing agents for phenolics |
| US4297452A (en) * | 1980-01-04 | 1981-10-27 | The Dow Chemical Company | Process for the manufacture of oxazoline and/or oxazine-modified adsorbent polymer resins |
| DE3483266D1 (en) * | 1983-12-27 | 1990-10-25 | Dow Chemical Co | POLYMER MIXTURES CONTAINING A POLYMER WITH OUTSTANDING OXAZOLINE GROUPS. |
| CN1321736C (en) * | 2003-08-14 | 2007-06-20 | 江苏工业学院 | Resin adsorbent for desulfurizing hydrocarbon and its prepn |
| CN1254307C (en) * | 2003-08-14 | 2006-05-03 | 江苏工业学院 | Adsorbent for desulfurizing hydrocarbon and its prepn |
| CN101296742A (en) * | 2005-08-26 | 2008-10-29 | 最佳空气控股公司 | Method and device for separating a substance from a process gas |
| CN105903452B (en) * | 2016-05-26 | 2018-10-23 | 东南大学 | A kind of preparation method of aromatic sulphonic acid selective ion exchange resin |
| CN110102274A (en) * | 2019-04-18 | 2019-08-09 | 常州大学 | A kind of novel polyphenyl Vinyl Graft polyamines resin material and its preparation method and application |
| CN113402640A (en) * | 2021-06-10 | 2021-09-17 | 青海亚洲硅业半导体有限公司 | Adsorption resin for impurity removal of chlorosilane and preparation method thereof |
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