Carboxyl functionalized super-crosslinked polymer as well as preparation method and application thereof

Abstract

The invention discloses a preparation method of a carboxyl functionalized super-crosslinked polymer, which comprises the following steps: carrying out nucleophilic substitution reaction on chloromethylated polystyrene microspheres and aromatic carboxylic acid monomers in an alkaline environment to obtain carboxylated polystyrene microspheres; and carrying out Friedel-Crafts reaction on the carboxylated polystyrene microspheres and a cross-linking agent under the action of an acid catalyst to obtain the carboxyl functionalized super-crosslinked polymer. According to the method, the pore structure size of the super-crosslinked polymer can be regulated and controlled, a large number of micropores are formed, the super-crosslinked polymer is endowed with a unique pore structure, and the polarity of the super-crosslinked polymer can be effectively regulated, so that the super-crosslinked polymer has a high-selectivity adsorption effect on polar aromatic micromolecules in a water body, is easy to elute after adsorption and can be repeatedly used.

Description

technical field

[0001] The present invention relates to an adsorption material, in particular to a carboxyl functionalized hypercrosslinked polymer, and also to a preparation method of a carboxyl functionalized hypercrosslinked polymer and the polar aromatic properties of a carboxyl functionalized hypercrosslinked polymer in adsorption water. The invention relates to the application of organic small molecules, and belongs to the technical field of functional hypercrosslinked polymer synthesis. Background technique

[0002] The methods for treating organic wastewater mainly include solvent extraction, electrochemical method, biological treatment method, adsorption method and so on. Solvent extraction is generally suitable for the treatment of high-concentration organic wastewater, but it is not suitable for use when the content is low, and the extraction agent used is easy to lose, the loss is serious, and the treatment effect is poor; the electrochemical method has high ener...

Examples

Embodiment 1

[0040] 1) Preparation of carboxylated polymer (PS-BTCA):

[0041] Add 10 g of macroporous low-crosslinked chloromethylated polystyrene microspheres (CMPS) to 100 mL of N,N-dimethylformamide (DMF), and allow the CMPS to fully swell at room temperature for 12 h. Add 8.524g trimesic acid and 20mL organic base N,N-diisopropylethylamine (the mol ratio of the chlorine content of CMPS, organic base, trimesic acid is 3:3:1), and the mixed reaction system is heated up to The reaction was continued at 90°C for 24h. The nucleophilic substitution reaction product was named PS-BTCA, and was washed repeatedly with deionized water, absolute ethanol, and 1% hydrochloric acid to remove residual organic bases and other substances. When the pH of the last washing liquid is neutral, stop the suction filtration, put the product into the Soxhlet extractor for extraction for 24 hours (the extraction solution should be clear and transparent), put the extracted product in the fume hood for about 1 ho...

Embodiment 2

[0057] 1) Preparation of carboxylated polymer (PS-PA):

[0058] Add 10 g of macroporous low-crosslinked chloromethylated polystyrene microspheres (CMPS) to 100 mL of N,N-dimethylformamide (DMF), and allow the CMPS to fully swell at room temperature for 12 h. Install a reflux condenser and a mechanical stirrer, add 4.04g phthalic acid and 4.8g basic catalyst K at room temperature 2 CO 3 (The molar ratio of the chlorine content of CMPS, the basic catalyst, and phthalic acid is 2:2:1), after stirring for 30 minutes until it is completely dissolved, the temperature is raised to 90° C., and the reaction is carried out at this temperature for 24 hours. Wash with 1% hydrochloric acid aqueous solution, ionized water, and absolute ethanol alternately for 3 to 4 times until colorless, then extract in a Soxhlet extractor overnight with ethanol, methanol, and water at a volume ratio of 1:1:1, and dry it normally for 12 hours. Then vacuum-dried for 24 hours to obtain the carboxylated pol...

Embodiment 3

[0065] 1) Preparation of carboxylated polymer (PS-BA):

[0066] Add 10 g of macroporous low-crosslinked chloromethylated polystyrene microspheres (CMPS) to 100 mL of N,N-dimethylformamide (DMF), and allow the CMPS to fully swell at room temperature for 12 h. Install reflux condenser and mechanical stirrer, add 6.14g benzoic acid and 4.8g basic catalyst K at normal temperature 2 CO 3(The molar ratio of the chlorine content of CMPS, the basic catalyst, and trimesic acid is 1:1:1), after stirring for 30 minutes until completely dissolved, the temperature is raised to 90° C., and the reaction is carried out at this temperature for 24 hours. Wash with 1% aqueous hydrochloric acid, ionized water, and absolute ethanol alternately for 3 to 4 times until colorless, then extract in a Soxhlet extractor overnight with ethanol, methanol, and water at a volume ratio of 1:1:1, and dry for 12 hours , and then vacuum-dried for 24h to obtain carboxylated polymer PS-BA;

[0067] 2) Preparatio...

technical field

[0001] The present invention relates to an adsorption material, in particular to a carboxyl functionalized hypercrosslinked polymer, and also to a preparation method of a carboxyl functionalized hypercrosslinked polymer and the polar aromatic properties of a carboxyl functionalized hypercrosslinked polymer in adsorption water. The invention relates to the application of organic small molecules, and belongs to the technical field of functional hypercrosslinked polymer synthesis. Background technique

[0002] The methods for treating organic wastewater mainly include solvent extraction, electrochemical method, biological treatment method, adsorption method and so on. Solvent extraction is generally suitable for the treatment of high-concentration organic wastewater, but it is not suitable for use when the content is low, and the extraction agent used is easy to lose, the loss is serious, and the treatment effect is poor; the electrochemical method has high ener...

Examples

Embodiment 1

[0040] 1) Preparation of carboxylated polymer (PS-BTCA):

[0041] Add 10 g of macroporous low-crosslinked chloromethylated polystyrene microspheres (CMPS) to 100 mL of N,N-dimethylformamide (DMF), and allow the CMPS to fully swell at room temperature for 12 h. Add 8.524g trimesic acid and 20mL organic base N,N-diisopropylethylamine (the mol ratio of the chlorine content of CMPS, organic base, trimesic acid is 3:3:1), and the mixed reaction system is heated up to The reaction was continued at 90°C for 24h. The nucleophilic substitution reaction product was named PS-BTCA, and was washed repeatedly with deionized water, absolute ethanol, and 1% hydrochloric acid to remove residual organic bases and other substances. When the pH of the last washing liquid is neutral, stop the suction filtration, put the product into the Soxhlet extractor for extraction for 24 hours (the extraction solution should be clear and transparent), put the extracted product in the fume hood for about 1 ho...

Embodiment 2

[0057] 1) Preparation of carboxylated polymer (PS-PA):

[0058] Add 10 g of macroporous low-crosslinked chloromethylated polystyrene microspheres (CMPS) to 100 mL of N,N-dimethylformamide (DMF), and allow the CMPS to fully swell at room temperature for 12 h. Install a reflux condenser and a mechanical stirrer, add 4.04g phthalic acid and 4.8g basic catalyst K at room temperature 2 CO 3 (The molar ratio of the chlorine content of CMPS, the basic catalyst, and phthalic acid is 2:2:1), after stirring for 30 minutes until it is completely dissolved, the temperature is raised to 90° C., and the reaction is carried out at this temperature for 24 hours. Wash with 1% hydrochloric acid aqueous solution, ionized water, and absolute ethanol alternately for 3 to 4 times until colorless, then extract in a Soxhlet extractor overnight with ethanol, methanol, and water at a volume ratio of 1:1:1, and dry it normally for 12 hours. Then vacuum-dried for 24 hours to obtain the carboxylated pol...

Embodiment 3

[0065] 1) Preparation of carboxylated polymer (PS-BA):

[0066] Add 10 g of macroporous low-crosslinked chloromethylated polystyrene microspheres (CMPS) to 100 mL of N,N-dimethylformamide (DMF), and allow the CMPS to fully swell at room temperature for 12 h. Install reflux condenser and mechanical stirrer, add 6.14g benzoic acid and 4.8g basic catalyst K at normal temperature 2 CO 3(The molar ratio of the chlorine content of CMPS, the basic catalyst, and trimesic acid is 1:1:1), after stirring for 30 minutes until completely dissolved, the temperature is raised to 90° C., and the reaction is carried out at this temperature for 24 hours. Wash with 1% aqueous hydrochloric acid, ionized water, and absolute ethanol alternately for 3 to 4 times until colorless, then extract in a Soxhlet extractor overnight with ethanol, methanol, and water at a volume ratio of 1:1:1, and dry for 12 hours , and then vacuum-dried for 24h to obtain carboxylated polymer PS-BA;

[0067] 2) Preparatio...

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