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. 2022 Jan 31;14(3):590.
doi: 10.3390/polym14030590.

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

Olga Nazarova  1 , Elena Chesnokova  1 , Tatyana Nekrasova  1 , Yulia Zolotova  1 , Anatoliy Dobrodumov  1 , Elena Vlasova  1 , Andrei Fischer  1 , Marina Bezrukova  1 , Eugeniy Panarin  1
Affiliations

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

Olga Nazarova et al. Polymers (Basel). .

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.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
VPA (I), MAG (II), 4-AM (III), AA (IV) units.
Figure 2
Figure 2
FTIR spectra of VPA homopolymer (a), AA homopolymer (b,1), AA-VPA copolymer (Experiment 11, Table 1) (b,2).
Figure 3
Figure 3
FTIR spectra of poly(4-acryloylmorpholine) (1), 4-AM-VPA copolymer (Experiment 5, Table 1) (2), the difference spectrum (3).
Figure 4
Figure 4
FTIR spectra of MAG homopolymer (1), MAG-VPA copolymer (2) (Experiment 3, Table 1), the difference spectrum (3).
Figure 5
Figure 5
1H NMR spectra of MAG-VPA copolymer (Experiment 3, Table 1) (a), PVPA (b) in D2O.
Figure 6
Figure 6
1H NMR spectrum of the mixture containing MAG–VPA copolymer (Experiment 3, Table 1) and MPC in D2O.
Figure 7
Figure 7
31P NMR spectra of the mixture of MAG–VPA copolymer with MPC (a) and PVPA (b) in D2O.
Figure 8
Figure 8
TTA and PHEN structures.
Figure 9
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
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).
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