New Copolymers of Vinylphosphonic Acid with Hydrophilic Monomers and Their Eu3+ Complexes

Abstract

Free radical copolymerization is used for the synthesis of novel water-soluble copolymers of vinylphosphonic acid with 2-deoxy-2-methacrylamido-D-glucose or 4-acryloylmorpholine, with varied compositions and molecular masses, as well as for the synthesis of copolymers of vinylphosphonic acid with acrylamide. The obtained copolymers contain 6-97 mol.% of vinylphosphonic acid units, and their molecular masses vary from 5 × 10³ to 310 × 10³. The monomer reactivity ratios of vinylphosphonic acid and 2-deoxy-2-methacrylamido-D-glucose in copolymerization are determined for the first time, and their values are 0.04 and 9.02, correspondingly. It is demonstrated that the synthesized copolymers form luminescent mixed-ligand complexes with Eu³⁺, thenoyltrifluoroacetone, and phenanthroline. The influence of the comonomer's nature on the intensity of the luminescence of complex solutions is revealed.

Keywords: 2-deoxy-2-methacrylamido-D-glucose; 4-acryloylmorpholine; complexes of Eu3+; water-soluble copolymers of vinylphosphonic acid.

Figure 1

VPA (I), MAG (II), 4-AM (III), AA (IV) units.

Figure 2

FTIR spectra of VPA homopolymer (a), AA homopolymer (b,1), AA-VPA copolymer (Experiment 11, Table 1) (b,2).

Figure 3

FTIR spectra of poly(4-acryloylmorpholine) (1), 4-AM-VPA copolymer (Experiment 5, Table 1) (2), the difference spectrum (3).

Figure 4

FTIR spectra of MAG homopolymer (1), MAG-VPA copolymer (2) (Experiment 3, Table 1), the difference spectrum (3).

Figure 5

¹H NMR spectra of MAG-VPA copolymer (Experiment 3, Table 1) (a), PVPA (b) in D₂O.

Figure 6

¹H NMR spectrum of the mixture containing MAG–VPA copolymer (Experiment 3, Table 1) and MPC in D₂O.

Figure 7

³¹P NMR spectra of the mixture of MAG–VPA copolymer with MPC (a) and PVPA (b) in D₂O.

Figure 8

TTA and PHEN structures.

Figure 9

Normalized electronic absorption spectra of aqueous solutions: Eu³⁺/4-AM-VPA copolymer (Experiment 5, Table 1) (1), Eu³⁺/4-AM-VPA copolymer/TTA (2), Eu³⁺/4-AM-VPA copolymer/TTA/PHEN (3), TTA (4), and phenanthroline (5).

Figure 10

Excitation (1) and photoluminescence (2) spectra of solutions of Eu³⁺/TTA (a), Eu³⁺/4-AM-VPA/TTA (b), Eu³⁺/PHEN (c), Eu³⁺/4-AM-VPA/PHEN (d), and Eu³⁺/4-AM-VPA/TTA/PHEN (e).