New functionalised polymeric microspheres for multicomponent solid phase extraction of phenolic compounds

Abstract

Three new porous copolymers possessing basic character were prepared by chemical modification of polymeric adsorbent (copolymer of bis[4(2-hydroxy-3-methacryloyloxypropoxy)phenyl]sulfide and glycidyl methacrylate, BES.DM ? GMA). Modification was carried out by reactions of surface epoxide groups of the precursor with amines: butylenediamine, diethylenetriamine and triethylenetetramine. Next, two of the synthesized materials were chosen for further modification involving addition of HCO 3 -groups to amine species. The obtained polymer adsorbents were characterised by elemental analyses, FTIR, nitrogen adsorption and thermal analyses. The prepared copolymers were studied for use as adsorbent in solid phase extraction (SPE) of multicomponent mixture of phenolic compounds consisting of: phenol, 2-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol. The SPE experiments were carried out in off-line mode. The influence of the chemical modification on adsorption properties of the presented materials was observed. The prepared adsorbents possessed different sorption properties towards the phenols. In addition, a competition phenomenon of the testing compounds for active sites on the polymer surface was observed. The most effective in adsorption of phenol and its chlorinated derivatives were the polymers with both amine and bicarbonate groups. The best recovery results were obtained for 2,4-dichlorophenol.

Chemical Structure of Phenols and Its Consequence for Sorption Processes

“…-Introduction of polar groups (acetyl, hydroxymethyl, benzoil, o-carboxybenzoil, carboxylic, sulfonic, amino [24]) to the hydrophobic skeleton of already existing sorbent [27,42]. This method is applicable to preparation of chemically modified polymers, activated or grafted carbons [42].…”

“…-Synthesis of a new sorbent using compounds with polar moieties. In this way, silica-based materials: RP-cyano, RP-hydroxyl, RP-amine [43], polar polymers [2,21,[25][26][27][28] and chemically activated or porous carbons [21,[27][28][29]39] can be produced.…”

“…On the other hand, there are many works indicating lack of correlation between the value of specific surface area and ability to adsorb phenols [16,24,25,27,33,41]. However, specific surface area is still put into characteristic in order to define the morphology of the adsorbent and for comparative purposes.…”

Sorption Properties of Polydivinylbenzene Polymers Towards Phenolic Compounds and Pharmaceuticals

“…Next, the aqueous solution of ibuprofen (100 mg·L −1 ), salicylic acid (100 mg·L −1 ) and a standard methanolic mixture of phenols (phenol (P), 2-chlorophenol (ChP), 2,4-dichlorophenol (DChP), and 2,4,6-trichlorophenol (TChP)-100 mg·L −1 of each compound) were prepared. The procedures of the sorption experiments and HPLC analyses for phenolic compounds were the same as in our previous works [7,10]. The aqueous solution of the phenolic compounds (2 mg·L −1 ) was prepared by dilution (1:50 v/v) of the standard methanolic solution.…”

“…In order to make their porous structure more suitable to adsorb a specific group of compounds, methods like surface sensitization or imprinting are used [6]. Additionally, functionalization reactions can be carried out to modify the chemical nature of their surface [7,8]. Other methods allow for the design of surface properties of the polymer (e.g., polarity, acidity) while already at the stage of synthesis [9,10].…”