УДК 541.64:544.725 1А.Ю. Антонов, 1,2А.А. Машенцева, 1,2Е.Г

ɍȾɄ 541.64:544.725
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Ⱥ.ɘ. Ⱥɧɬɨɧɨɜ, 1,2Ⱥ.Ⱥ. Ɇɚɲɟɧɰɟɜɚ, 1,2ȿ.Ƚ. Ƚɨɪɢɧ
ȿɜɪɚɡɢɣɫɤɢɣ ɧɚɰɢɨɧɚɥɶɧɵɣ ɭɧɢɜɟɪɫɢɬɟɬ ɢɦ. Ʌ.ɇ.Ƚɭɦɢɥɟɜɚ, Ʉɚɡɚɯɫɬɚɧ, ɝ. Ⱥɫɬɚɧɚ
Ⱥɫɬɚɧɢɧɫɤɢɣ ɮɢɥɢɚɥ ɂɧɫɬɢɬɭɬɚ ɹɞɟɪɧɨɣ ɮɢɡɢɤɢ ɇəɐ ɊɄ, Ʉɚɡɚɯɫɬɚɧ, ɝ. Ⱥɫɬɚɧɚ
E-mail: 2mashentseva.a@gmail.com
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Ɉɫɨɛɟɧɧɨɫɬɢ ɩɟɪɜɢɱɧɨɣ ɮɭɧɤɰɢɨɧɚɥɢɡɚɰɢɢ ɢ ɚɧɚɥɢɡɚ ɩɨɜɟɪɯɧɨɫɬɢ ɉɗɌɎ ɧɚɧɨɩɨɪɢɫɬɵɯ
ɬɪɟɤɨɜɵɯ ɦɟɦɛɪɚɧ
ɇɚɩɪɚɜɥɟɧɧɚɹ ɦɨɞɢɮɢɤɚɰɢɹ ɩɨɥɢɦɟɪɧɵɯ ɬɪɟɤɨɜɵɯ ɦɟɦɛɪɚɧ ɨɬɤɪɵɜɚɟɬ ɨɛɲɢɪɧɵɟ ɜɨɡɦɨɠɧɨɫɬɢ ɞɥɹ
ɪɚɡɪɚɛɨɬɤɢ ɦɟɦɛɪɚɧɧɵɯ ɮɢɥɶɬɪɨɜ ɫ ɭɥɭɱɲɟɧɧɵɦɢ ɯɚɪɚɤɬɟɪɢɫɬɢɤɚɦɢ, ɫɬɢɦɭɥ-ɱɭɜɫɬɜɢɬɟɥɶɧɵɯ ɦɟɦɛɪɚɧ ɢ
ɷɥɟɦɟɧɬɨɜ ɧɚɧɨɫɟɧɫɨɪɢɤɢ ɧɚ ɢɯ ɨɫɧɨɜɟ. ɗɮɮɟɤɬɢɜɧɨɫɬɶ ɩɪɨɜɟɞɟɧɢɹ ɯɢɦɢɱɟɫɤɢɯ ɬɪɚɧɫɮɨɪɦɚɰɢɣ ɫ ɤɨɧɰɟɜɵɦɢ
ɮɭɧɤɰɢɨɧɚɥɶɧɵɦɢ ɝɪɭɩɩɚɦɢ ɧɚɩɪɹɦɭɸ ɡɚɜɢɫɢɬ ɨɬ ɩɨɥɧɨɬɵ ɫɬɚɞɢɢ ɩɟɪɜɢɱɧɨɣ ɮɭɧɤɰɢɨɧɚɥɢɡɚɰɢɢ ɉɗɌɎ. ȼ
ɪɚɛɨɬɟ ɩɪɨɜɟɞɟɧ ɤɪɢɬɢɱɟɫɤɢɣ ɚɧɚɥɢɡ ɭɫɥɨɜɢɣ ɨɤɢɫɥɟɧɢɹ ɢ ɦɟɬɨɞɨɜ ɚɧɚɥɢɡɚ ɩɨɜɟɪɯɧɨɫɬɢ ɩɨɥɢɷɬɢɥɟɧɬɟɪɮɬɚɥɚɬ
(ɉɗɌɎ) ɬɪɟɤɨɜɨɣ ɦɟɦɛɪɚɧɵ (ɌɆ) ɢ ɩɪɢɜɨɞɹɬɫɹ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɞɚɧɧɵɟ ɩɪɨɰɟɫɫɚ ɩɨɥɭɱɟɧɢɹ ɋɈɈɇɧɚɫɵɳɟɧɧɵɯ ɉɗɌɎ ɌɆ. Ɋɚɫɫɦɚɬɪɢɜɚɟɬɫɹ ɢɡɦɟɧɟɧɢɟ ɤɨɥɢɱɟɫɬɜɟɧɧɵɯ ɯɚɪɚɤɬɟɪɢɫɬɢɤ ɢɫɯɨɞɧɵɯ ɢ
ɦɨɞɢɮɢɰɢɪɨɜɚɧɧɵɯ ɦɟɦɛɪɚɧ.
Ʉɥɸɱɟɜɵɟ ɫɥɨɜɚ: ɬɪɟɤɨɜɵɟ ɦɟɦɛɪɚɧɵ, ɯɢɦɢɱɟɫɤɚɹ ɦɨɞɢɮɢɤɚɰɢɹ, ɢɧɞɟɤɫ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ, ɂɄ-, ɍɎɫɩɟɤɬɪɨɫɤɨɩɢɹ.
ȼɜɟɞɟɧɢɟ
ɉɨɥɢɷɬɢɥɟɧɬɟɪɮɬɚɥɚɬ (ɉɗɌɎ) – ɩɨɥɢɦɟɪɧɚɹ ɩɥɟɧɤɚ ɹɜɥɹɟɬɫɹ ɨɞɧɢɦ ɢɡ ɧɚɢɛɨɥɟɟ ɢɫɩɨɥɶɡɭɟɦɵɯ
ɢ ɜɨɫɬɪɟɛɨɜɚɧɧɵɯ ɦɚɬɟɪɢɚɥɨɜ ɜ ɩɪɨɢɡɜɨɞɫɬɜɟ ɹɞɟɪɧɵɯ ɬɪɟɤɨɜɵɯ ɦɟɦɛɪɚɧ (ɌɆ). Ɉɬɧɨɫɢɬɟɥɶɧɚɹ
ɞɟɲɟɜɢɡɧɚ ɥɚɜɫɚɧɚ ɜ ɫɨɱɟɬɚɧɢɢ ɫ ɮɢɡɢɤɨ-ɯɢɦɢɱɟɫɤɢɦɢ ɫɜɨɣɫɬɜɚɦɢ, ɨɛɟɫɩɟɱɢɥɢ ɬɪɟɤɨɜɵɦ ɦɟɦɛɪɚɧɚɦ
ɧɚ ɟɝɨ ɨɫɧɨɜɟ ɲɢɪɨɤɨɟ ɩɪɢɤɥɚɞɧɨɟ ɩɪɢɦɟɧɟɧɢɟ. Ʉ ɧɟɨɫɩɨɪɢɦɵɦ ɩɪɟɢɦɭɳɟɫɬɜɚɦ ɉɗɌɎ ɦɨɠɧɨ
ɨɬɧɟɫɬɢ ɦɟɯɚɧɢɱɟɫɤɭɸ ɩɪɨɱɧɨɫɬɶ, ɬɜɟɪɞɨɫɬɶ, ɭɫɬɚɥɨɫɬɧɭɸ ɩɪɨɱɧɨɫɬɶ ɩɪɢ ɩɨɜɵɲɟɧɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ,
ɜɵɫɨɤɭɸ ɬɟɦɩɟɪɚɬɭɪɭ ɫɬɟɤɥɨɜɚɧɢɹ. ɇɟɫɦɨɬɪɹ ɧɚ ɧɟɜɵɫɨɤɭɸ ɚɞɝɟɡɢɸ, ɩɥɨɯɭɸ ɫɦɚɱɢɜɚɟɦɨɫɬɶ ɢ
ɧɢɡɤɭɸ ɛɢɨɫɨɜɦɟɫɬɢɦɨɫɬɶ, ɞɚɧɧɵɣ ɩɨɥɢɦɟɪ ɹɜɥɹɟɬɫɹ ɢɞɟɚɥɶɧɵɦ ɫɬɚɪɬɨɜɵɦ ɦɚɬɟɪɢɚɥɨɦ ɞɥɹ
ɩɪɨɜɟɞɟɧɢɹ ɞɚɥɶɧɟɣɲɟɣ ɮɭɧɤɰɢɨɧɚɥɢɡɚɰɢɢ ɩɨɜɟɪɯɧɨɫɬɢ [1].
ɏɢɦɢɱɟɫɤɨɟ ɬɪɚɜɥɟɧɢɟ ɌɆ ɨɛɥɭɱɟɧɧɨɣ ɭɫɤɨɪɟɧɧɵɦɢ ɬɹɠɟɥɵɦɢ ɢɨɧɚɦɢ ɢɧɟɪɬɧɵɯ ɝɚɡɨɜ (Ar, Kr, Xe ɢ
ɬ.ɞ.) ɜ ɧɟɤɨɬɨɪɨɣ ɫɬɟɩɟɧɢ ɦɨɠɟɬ ɪɚɫɫɦɚɬɪɢɜɚɬɶɫɹ ɜ ɤɚɱɟɫɬɜɟ ɫɬɚɞɢɢ ɩɪɟ-ɮɭɧɤɰɢɨɧɚɥɢɡɚɰɢɢ
ɩɨɜɟɪɯɧɨɫɬɢ ɬɪɟɤɨɜɵɯ ɦɟɦɛɪɚɧ.
ɓɟɥɨɱɧɨɣ ɝɢɞɪɨɥɢɡ ɉɗɌɎ ɌɆ ɜ ɡɚɜɢɫɢɦɨɫɬɢ ɨɬ ɭɫɥɨɜɢɣ ɩɨɫɬɯɢɦɢɱɟɫɤɨɣ ɨɛɪɚɛɨɬɤɢ ɨɛɪɚɡɰɨɜ ɦɨɠɟɬ
ɪɟɚɥɢɡɨɜɚɬɶɫɹ ɜ ɞɜɭɯ ɧɚɩɪɚɜɥɟɧɢɹɯ [2]:
O
O
I
OH
OH
1. NaOH (2,2 M, 85°C) O
2. CH3COOH (10 min).
O
O
OH 3. H2O (15 min).
O
OH
O
II
O 1. NaOH (2,2 M, 85°C)
O
O
2. H2O (15 min)
O
O Na
OH
O Na
O
OH
Ɋɢɫɭɧɨɤ 1 – Ɉɛɪɚɡɨɜɚɧɢɹ ɋɈɈ-Na+ (I) ɢ ɋɈɈɇ (II) ɮɨɪɦ ɩɨɜɟɪɯɧɨɫɬɢ ɉɗɌɎ ɩɥɟɧɤɢ ɜ ɪɟɡɭɥɶɬɚɬɟ ɪɟɚɤɰɢɢ
ɳɟɥɨɱɧɨɝɨ ɝɢɞɪɨɥɢɡɚ
ɉɪɢ ɪɟɚɥɢɡɚɰɢɢ ɩɟɪɜɨɝɨ ɧɚɩɪɚɜɥɟɧɢɹ ɩɪɨɢɫɯɨɞɢɬ ɷɥɟɤɬɪɨɫɬɚɬɢɱɟɫɤɨɟ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ ɦɟɠɞɭ
ɤɚɬɢɨɧɚɦɢ ɳɟɥɨɱɧɵɯ ɚɝɟɧɬɨɜ ɢ ɋɈɈí ɤɚɪɛɨɤɫɢɥɚɬ-ɚɧɢɨɧɚɦɢ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ ɢ ɜ ɬɪɟɤɚɯ ɉɗɌɎ.
ɇɟɣɬɪɚɥɢɡɚɰɢɹ ɢɡɛɵɬɤɚ ɳɟɥɨɱɢ ɩɭɬɟɦ ɩɪɨɦɵɜɚɧɢɹ ɨɛɪɚɡɰɨɜ ɉɗɌɎ ɜ ɪɚɫɬɜɨɪɟ ɭɤɫɭɫɧɨɣ ɤɢɫɥɨɬɵ
ɨɛɟɫɩɟɱɢɜɚɟɬ ɩɪɨɬɨɧɢɪɨɜɚɧɢɟ ɤɚɪɛɨɤɫɢɥɚɬ-ɢɨɧɨɜ ɫ ɨɛɪɚɡɨɜɚɧɢɟɦ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɧɚ
ɩɨɜɟɪɯɧɨɫɬɢ ɢ ɜ ɬɪɟɤɚɯ ɩɨɥɢɦɟɪɚ (ɧɚɩɪɚɜɥɟɧɢɟ II).
Ɉɞɧɚɤɨ, ɧɟɨɛɯɨɞɢɦɨ ɭɱɢɬɵɜɚɬɶ ɬɨɬ ɮɚɤɬ, ɱɬɨ ɪɟɚɥɢɡɚɰɢɹ ɤɨɜɚɥɟɧɬɧɨɣ ɩɪɢɜɢɜɤɢ ɩɭɬɟɦ ɤɨɧɞɟɧɫɚɰɢɢ
ɜɨɡɦɨɠɧɨ ɜ ɫɥɭɱɚɟ ɧɚɥɢɱɢɹ ɤɚɤ ɤɚɪɛɨɤɫɢɥɶɧɵɯ, ɬɚɤ ɢ ɝɢɞɪɨɤɫɢɥɶɧɵɯ ɮɭɧɤɰɢɨɧɚɥɶɧɵɯ ɝɪɭɩɩ [3,4].
Ɍɨɝɞɚ ɩɟɪɟɞ ɢɫɫɥɟɞɨɜɚɬɟɥɟɦ ɜɫɬɚɟɬ ɜɨɩɪɨɫ: ɤɚɤɚɹ ɢɡ ɮɭɧɤɰɢɨɧɚɥɶɧɵɯ ɝɪɭɩɩ ɦɨɠɟɬ ɛɵɬɶ ɛɨɥɟɟ
ɷɮɮɟɤɬɢɜɧɚ ɞɥɹ ɩɨɫɥɟɞɭɸɳɢɯ ɬɪɚɧɫɮɨɪɦɚɰɢɣ?
130
Ʉɢɫɥɨɬɧɨ-ɮɭɧɤɰɢɨɧɚɥɢɡɢɪɨɜɚɧɧɚɹ ɩɨɜɟɪɯɧɨɫɬɶ ɉɗɌɎ ɦɨɠɟɬ ɛɵɬɶ ɞɨɫɬɚɬɨɱɧɨ ɥɟɝɤɨ ɩɨɥɭɱɟɧɚ ɩɭɬɟɦ
ɫɟɥɟɤɬɢɜɧɨɝɨ ɨɤɢɫɥɟɧɢɹ Ɉɇ-ɝɪɭɩɩɵ ɜ ɋɈɈɇ. Ƚɢɞɪɨɤɫɢ-ɧɚɫɵɳɟɧɧɚɹ ɩɨɜɟɪɯɧɨɫɬɶ ɉɗɌɎ ɦɨɠɟɬ ɛɵɬɶ
ɩɨɥɭɱɟɧɚ ɩɪɢ ɫɟɥɟɤɬɢɜɧɨɦ ɜɨɫɫɬɚɧɨɜɥɟɧɢɢ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɢɥɢ ɱɟɪɟɡ ɬɪɚɧɫɷɬɟɪɟɮɢɤɚɰɢɸ ɫ
ɞɜɭɚɬɨɦɧɵɦɢ ɫɩɢɪɬɚɦɢ, ɧɚɩɪɢɦɟɪ, ɫ ɷɬɢɥɟɧɝɥɢɤɨɥɟɦ [5]. Ɉɛɲɢɪɧɵɟ ɪɟɡɭɥɶɬɚɬɵ ɢɫɫɥɟɞɨɜɚɧɢɣ
ɪɟɚɤɰɢɢ ɨɤɢɫɥɟɧɢɹ ɉɗɌɎ ɌɆ ɩɪɟɞɫɬɚɜɥɟɧɵ ɜ ɪɚɛɨɬɟ [6]: ɩɪɢɜɨɞɹɬɫɹ ɞɚɧɧɵɟ ɨɛ ɢɫɩɨɥɶɡɨɜɚɧɢɢ
ɧɢɠɟɩɪɢɜɟɞɟɧɧɵɯ ɫɢɫɬɟɦ ɨɤɢɫɥɢɬɟɥɟɣ ɉɗɌɎ: ɨɤɢɫɶ ɯɪɨɦɚ (VI) ɜ ɥɟɞɹɧɨɣ ɭɤɫɭɫɧɨɣ ɤɢɫɥɨɬɟ,
ɪɚɡɛɚɜɥɟɧɧɚɹ ɫɟɪɧɚɹ
ɤɢɫɥɨɬɚ ɜ ɚɰɟɬɨɧɟ, ɩɢɪɢɞɢɧɭɦ ɞɢɯɪɨɦɚɬ ɜ ɫɪɟɞɟ ɞɢɦɟɬɢɥɮɨɪɦɚɦɢɞɚ,
ɩɟɪɦɚɧɝɚɧɚɬ ɤɚɥɢɹ ɜ ɪɚɡɛɚɜɥɟɧɧɨɦ ɪɚɫɬɜɨɪɟ ɫɟɪɧɨɣ ɤɢɫɥɨɬɵ, ɜɨɞɧɵɟ ɪɚɫɬɜɨɪɵ ɬɪɢɯɥɨɪɭɤɫɭɫɧɨɣ ɢ
ɬɪɢɮɬɨɪɭɤɫɭɫɧɨɣ ɤɢɫɥɨɬ. ɉɨɤɚɡɚɧɨ, ɱɬɨ ɦɚɤɫɢɦɚɥɶɧɚɹ ɤɨɧɜɟɪɬɚɰɢɹ ɈɇíĺɋɈɈɇ ɦɨɠɟɬ ɛɵɬɶ
ɞɨɫɬɢɝɧɭɬɚ ɩɪɢ ɢɫɩɨɥɶɡɨɜɚɧɢɢ 5% ɪɚɫɬɜɨɪɚ KMnO4 ɜ 1,25 N H2SO4. ɋɯɟɦɚɬɢɱɧɨ ɪɟɚɤɰɢɸ ɨɤɢɫɥɟɧɢɹ
ɉɗɌɎ ɦɨɠɧɨ ɩɪɟɞɫɬɚɜɢɬɶ ɫɥɟɞɭɸɳɢɦ ɨɛɪɚɡɨɦ (ɪɢɫɭɧɨɤ 2).
O C
O
C O
O n
O
I
O C
O
C
O
hidrolysis
C O
O n
OH
HO C
O
O C
O m
C O
O
II
C O
O
O C *
O m
oxidation KMnO4/H2SO4
O C
O
OH
C O
O n
O
PET-COOH
Ɋɢɫɭɧɨɤ 2 – Ɉɤɢɫɥɟɧɢɟ ɮɨɪɦ (I) ɢ (2) ɉɗɌɎ ɌɆ ɫ ɨɛɪɚɡɨɜɚɧɢɟɦ ɋɈɈɇ-ɧɚɫɵɳɟɧɧɨɣ ɩɨɜɟɪɯɧɨɫɬɢ
Ɉɛ ɷɮɮɟɤɬɢɜɧɨɫɬɢ (ɩɨɥɧɨɬɟ) ɩɪɨɬɟɤɚɧɢɹ ɩɪɨɰɟɫɫɚ ɨɤɢɫɥɟɧɢɹ ɫɭɞɹɬ ɩɨ ɢɡɦɟɧɟɧɢɸ ɤɨɧɰɟɧɬɪɚɰɢɢ
ɩɨɜɟɪɯɧɨɫɬɧɵɯ ɤɢɫɥɨɪɨɞɫɨɞɟɪɠɚɳɢɯ Ɉɇ/ɋɈɈɇ-ɝɪɭɩɩ. ɋɪɟɞɢ ɦɧɨɠɟɫɬɜɚ ɩɪɟɞɥɚɝɚɟɦɵɯ ɜ ɥɢɬɟɪɚɬɭɪɟ
ɤɨɥɢɱɟɫɬɜɟɧɧɵɯ ɦɟɬɨɞɢɤ ɯɨɬɟɥɨɫɶ ɛɵ ɜɵɞɟɥɢɬɶ ɨɛɳɢɯ ɝɪɭɩɩ: ɬɢɬɪɨɦɟɬɪɢɱɟɫɤɢɟ, ɫɩɟɤɬɪɚɥɶɧɵɟ
ɦɟɬɨɞɵ (ɂɄ-, ɍɎ-, əɆɊ-ɫɩɟɤɬɪɨɫɤɨɩɢɹ), ɦɟɬɨɞ ɪɟɧɬɝɟɧɨɜɫɤɨɣ ɮɨɬɨɷɥɟɤɬɪɨɧɧɨɣ ɦɢɤɪɨɫɤɨɩɢɢ.
ȼ ɨɫɧɨɜɟ ɮɨɬɨɦɟɬɪɢɱɟɫɤɢɯ ɦɟɬɨɞɨɜ ɨɩɪɟɞɟɥɟɧɢɟ ɤɨɧɰɟɜɵɯ ɝɢɞɪɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɜ ɫɨɫɬɚɜɟ
ɫɥɨɠɧɵɯ ɩɨɥɢɷɮɢɪɨɜ ɨɫɧɨɜɚɧɨ ɧɚ ɪɟɚɤɰɢɢ ɝɢɞɪɨɤɫɢɥɶɧɨɣ ɝɪɭɩɩɵ ɫ ɚɤɬɢɜɧɵɦ ɞɢɯɥɨɪɬɪɢɚɡɢɧɨɜɵɦ
ɤɪɚɫɢɬɟɥɟɦ ɜ ɳɟɥɨɱɧɨɣ ɫɪɟɞɟ ɫ ɩɨɫɥɟɞɭɸɳɢɦ ɢɡɦɟɧɟɧɢɟɦ ɢɧɬɟɧɫɢɜɧɨɫɬɢ ɩɨɝɥɨɳɟɧɢɹ ɢɡɛɵɬɨɱɧɨɝɨ
ɤɪɚɫɢɬɟɥɹ ɩɪɢ 596 ɧɦ [7]. Ʉɨɧɰɟɧɬɪɚɰɢɸ ɋɈɈɇ-ɝɪɭɩɩ ɨɩɪɟɞɟɥɹɸɬ ɩɪɢ ɩɨɦɨɳɢ ɤɪɚɫɢɬɟɥɹ
ɬɨɥɭɢɞɢɧɨɜɨɝɨ ɫɢɧɟɝɨ-Ɉ (ɌȼɈ), ɤɨɬɨɪɵɣ ɨɤɪɚɲɢɜɚɟɬ ɞɟɩɪɨɬɨɧɢɪɨɜɚɧɧɵɟ ɤɢɫɥɨɬɧɵɟ ɨɫɬɚɬɤɢ ɧɚ
ɩɨɜɟɪɯɧɨɫɬɢ ɡɚ ɫɱɟɬ ɢɨɧɧɨɝɨ ɜɡɚɢɦɨɞɟɣɫɬɜɢɹ [8]. Ʉɚɥɢɛɪɨɜɨɱɧɭɸ ɤɪɢɜɭɸ ɫɬɪɨɹɬ ɩɨ ɭɤɫɭɫɧɨɣ
ɤɢɫɥɨɬɟ ɩɪɢ 633 ɧɦ, ɋɈɈɇ-ɝɪɭɩɩɵ ɨɩɪɟɞɟɥɹɸɬ ɢɡ ɪɚɫɱɟɬɚ, ɱɬɨ 1 ɦɨɥɶ ɌȼɈ ɜɡɚɢɦɨɞɟɣɫɬɜɭɟɬ ɫ 1
ɦɨɥɟɦ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɩɨɜɟɪɯɧɨɫɬɢ ɩɥɟɧɤɢ. Ɇɟɬɢɥɟɧɨɜɵɣ ɫɢɧɢɣ ɜ ɛɭɮɟɪɧɨɦ ɪɚɫɬɜɨɪɟ
Ȼɪɢɬɬɨɧɚ-Ɋɨɛɢɧɫɨɧɚ (ɪɇ 7,1-7,4) ɨɛɪɚɡɭɟɬ ɨɤɪɚɲɟɧɧɨɟ ɫɨɟɞɢɧɟɧɢɟ ɫ ɤɚɪɛɨɤɫɢɥɶɧɵɦɢ ɝɪɭɩɩɚɦɢ ɧɚ
ɩɨɜɟɪɯɧɨɫɬɢ ɩɨɥɢɦɟɪɚ; ɮɨɬɨɦɟɬɪɢɱɟɫɤɢɣ ɚɧɚɥɢɡ ɜ ɪɚɛɨɬɟ [8] ɩɪɨɜɨɞɢɥɢ ɩɪɢ 650 ɧɦ.
ȼɟɫɶɦɚ ɢɧɮɨɪɦɚɬɢɜɧɵɦ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɦ ɦɟɬɨɞɨɦ ɹɜɥɹɟɬɫɹ ɪɟɧɬɝɟɧɨɜɫɤɚɹ ɮɨɬɨɷɥɟɤɬɪɨɧɧɚɹ
ɞɢɮɪɚɤɰɢɹ XPS (ɏ-ray photoelectron spectroscopy). ɏɢɦɢɱɟɫɤɢɣ ɫɨɫɬɚɜ ɩɨɜɟɪɯɧɨɫɬɢ ɉɗɌɎ ɌɆ ɦɨɠɟɬ
ɛɵɬɶ ɨɩɪɟɞɟɥɟɧ ɢɡ ɩɥɨɳɚɞɢ ɩɢɤɨɜ ɧɚ ɫɩɟɤɬɪɚɯ ɫ ɩɨɫɥɟɞɭɸɳɟɣ ɤɨɧɜɟɪɬɚɰɢɟɣ ɫɨɨɬɧɨɲɟɧɢɣ ɚɬɨɦɧɵɯ
ɤɨɧɰɟɧɬɪɚɰɢɣ [9], ɢɡ ɤɨɬɨɪɵɯ ɨɩɪɟɞɟɥɹɸɬ ɚɬɨɦɧɵɟ ɮɪɚɤɰɢɢ ɷɥɟɦɟɧɬɨɜ ɡɚ ɢɫɤɥɸɱɟɧɢɟɦ ɜɨɞɨɪɨɞɚ
ɦɨɧɨɦɟɪɧɨɣ ɟɞɢɧɢɰɵ ɉɗɌɎ.
Ɍɚɤɠɟ ɩɥɨɬɧɨɫɬɶ ɮɭɧɤɰɢɨɧɚɥɶɧɵɯ ɝɪɭɩɩ ɦɨɠɟɬ ɛɵɬɶ ɨɩɪɟɞɟɥɟɧɚ ɩɨ ɤɨɥɢɱɟɫɬɜɭ ɜɜɨɞɢɦɵɯ ɜ
ɤɨɧɰɟɜɵɟ Ɉɇí ɢ ɋɈɈɇ-ɝɪɭɩɩɵ ɡɚɦɟɫɬɢɬɟɥɟɣ. Ɋɚɫɩɪɨɫɬɪɚɧɟɧɚ ɦɟɬɨɞɢɤɚ ɢɫɩɨɥɶɡɨɜɚɧɢɹ ɫɟɥɟɤɬɢɜɧɵɯ
ɪɟɚɝɟɧɬɨɜ, ɫɨɞɟɪɠɚɳɢɯ ɷɥɟɦɟɧɬɵ-ɦɟɬɤɢ, ɤɨɬɨɪɵɯ ɧɟɬ ɜ ɫɬɪɭɤɬɭɪɟ ɢɫɫɥɟɞɭɟɦɨɝɨ ɩɨɥɢɦɟɪɚ ɢ
ɢɦɟɸɳɢɯ ɜɵɪɚɠɟɧɧɭɸ ɜɵɫɨɤɭɸ ɢɧɬɟɧɫɢɜɧɨɫɬɶ ɮɨɬɨɷɥɟɤɬɪɨɧɧɵɯ ɥɢɧɢɣ.
ȼ ɪɚɛɨɬɟ [10] ɩɪɟɞɥɨɠɟɧ ɨɪɢɝɢɧɚɥɶɧɵɣ ɦɟɬɨɞ ɞɜɨɣɧɨɣ ɦɟɬɤɢ: ɢɫɩɨɥɶɡɨɜɚɧɢɟ (L)-[4,5-3ɇ]-N(ɬɪɢɮɬɨɪɷɬɢɥ)ɥɢɡɢɧɚɦɢɞɚ ɩɨɡɜɨɥɹɟɬ ɢɫɫɥɟɞɨɜɚɬɶ ɩɨɜɟɪɯɧɨɫɬɶ ɉɗɌɎ ɩɥɟɧɤɢ ɦɢɤɪɨɩɨɪɢɫɬɵɯ
ɦɟɦɛɪɚɧ ɦɟɬɨɞɨɦ ɠɢɞɤɨɫɬɧɨɣ ɫɰɢɧɰɢɥɹɰɢɢ (LSC) ɢ ɮɨɬɨɷɥɟɤɬɪɨɧɧɨɣ ɞɢɮɪɚɤɰɢɢ (XPS), ɩɪɢɱɟɦ
ɞɚɧɧɚɹ ɤɨɦɩɥɟɤɫɧɚɹ ɬɟɯɧɢɤɚ ɚɧɚɥɢɡɚ ɩɨɡɜɨɥɹɟɬ ɫ ɜɵɫɨɤɨɣ ɫɬɟɩɟɧɶɸ ɞɨɫɬɨɜɟɪɧɨɫɬɢ ɤɚɱɟɫɬɜɟɧɧɨ ɢ
ɤɨɥɢɱɟɫɬɜɟɧɧɨ ɨɯɚɪɚɤɬɟɪɢɡɨɜɚɬɶ ɩɨɜɟɪɯɧɨɫɬɶ ɩɨɥɢɦɟɪɧɨɣ ɦɟɦɛɪɚɧɵ.
Ɂɧɚɱɟɧɢɟ ɢɧɞɟɤɫɚ ɤɨɧɰɟɜɵɯ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɦɨɠɟɬ ɛɵɬɶ ɨɩɪɟɞɟɥɟɧɨ ɩɪɢ ɩɨɦɨɳɢ ɂɄɎɭɪɶɟ ɫɩɟɤɬɪɨɫɤɨɩɢɢ ɤɚɤ ɫɨɨɬɧɨɲɟɧɢɟ ɩɢɤɚ ɧɚɢɛɨɥɶɲɟɣ Ɉ-ɇ ɫɜɹɡɢ ɜ ɋɈɈɇ-ɝɪɭɩɩɟ ɩɪɢ 3290 ɫɦ-1 ɤ
131
ɩɥɨɳɚɞɢ ɩɢɤɚ ɫɪɚɜɧɟɧɢɹ ɩɪɢ 2970 ɫɦ-1. ɉɪɢ ɷɬɨɦ ɧɟɨɛɯɨɞɢɦɨ ɭɱɢɬɵɜɚɬɶ, ɱɬɨ ɢɧɬɟɧɫɢɜɧɨɫɬɶ ɩɨɥɨɫɵ
ɩɨɝɥɨɳɟɧɢɹ ɡɚɜɢɫɢɬ ɨɬ ɩɥɨɳɚɞɢ ɨɛɪɚɡɰɚ, ɭɝɥɚ ɤɨɧɬɚɤɬɚ ɚɧɚɥɢɡɢɪɭɟɦɨɝɨ ɨɛɪɚɡɰɚ ɫ ɩɪɢɛɨɪɨɦ ɢ
ɷɮɮɟɤɬɢɜɧɨɣ ɬɨɥɳɢɧɵ ɩɪɨɧɢɤɧɨɜɟɧɢɹ ɂɄ-ɩɭɱɤɚ [11].
Ɉɛɪɚɡɨɜɚɧɢɟ ɮɥɭɨɪɟɫɰɟɧɬɧɨ-ɚɤɬɢɜɧɵɯ ɫɨɟɞɢɧɟɧɢɣ (Ȝɫɯ=594, Ȝɫɬ=620) ɨɤɢɫɥɟɧɧɨɣ ɉɗɌɎ ɫ
ɬɢɨɧɢɧ ɚɰɟɬɚɬɨɦ ɬɚɤɠɟ ɹɜɥɹɟɬɫɹ ɨɞɧɢɦ ɢɡ ɷɤɫɩɪɟɫɫ-ɦɟɬɨɞɨɜ ɤɨɥɢɱɟɫɬɜɟɧɧɨɣ ɨɰɟɧɤɢ ɫɬɟɩɟɧɢ
ɤɨɧɜɟɪɫɢɢ ɋɈɈɇ-ɝɪɭɩɩ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ ɩɨɥɢɦɟɪɧɨɣ ɩɥɟɧɤɢ [12].
ɉɪɨɜɟɞɟɧɧɵɣ ɚɧɚɥɢɡ ɥɢɬɟɪɚɬɭɪɧɵɯ ɞɚɧɧɵɯ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɨ ɜɵɫɨɤɨɦ ɢɧɬɟɪɟɫɟ ɤ ɤɚɱɟɫɬɜɟɧɧɵɦ ɢ
ɤɨɥɢɱɟɫɬɜɟɧɧɵɦ ɩɚɪɚɦɟɬɪɚɦ ɩɪɨɰɟɫɫɚ ɩɟɪɜɢɱɧɨɣ ɮɭɧɤɰɢɨɧɚɥɢɡɚɰɢɢ ɩɨɜɟɪɯɧɨɫɬɢ ɩɥɟɧɨɱɧɵɯ
ɦɚɬɟɪɢɚɥɨɜ ɧɚ ɨɫɧɨɜɟ ɉɗɌɎ, ɲɢɪɨɤɢɣ ɫɩɟɤɬɪ ɢɫɩɨɥɶɡɭɟɦɵɯ ɩɪɢɟɦɨɜ ɢ ɦɟɬɨɞɨɜ ɩɨɡɜɨɥɹɟɬ ɩɪɨɜɨɞɢɬɶ
ɢɯ ɚɞɚɩɬɚɰɢɸ ɤ ɢɦɟɸɳɢɦɫɹ ɜ ɪɟɡɟɪɜɟ ɢɫɫɥɟɞɨɜɚɬɟɥɶɫɤɨɣ ɥɚɛɨɪɚɬɨɪɢɢ ɭɫɥɨɜɢɹɦ.
ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɚɹ ɱɚɫɬɶ
ɇɚɦɢ ɩɪɨɜɟɞɟɧɵ ɢɫɫɥɟɞɨɜɚɧɢɹ ɨɫɨɛɟɧɧɨɫɬɟɣ ɩɪɨɰɟɫɫɚ ɨɤɢɫɥɟɧɢɹ ɉɗɌɎ ɌɆ (Hostaphan® RNK23,0). Ɉɛɪɚɡɰɵ ɉɗɌɎ ɩɥɟɧɨɤ ɨɛɥɭɱɚɥɢ ɢɨɧɚɦɢ 84Kr15+ (ɷɧɟɪɝɢɹ 1,75 Ɇɷȼ/ɧɭɤɥɨɧ) ɧɚ ɭɫɤɨɪɢɬɟɥɟ
ɬɹɠɟɥɵɯ ɢɨɧɨɜ Ⱦɐ-60 ȺɎ ɂəɎ ɇəɐ ɊɄ. Ɏɥɸɟɧɫ ɢɨɧɨɜ ɫɨɨɬɜɟɬɫɬɜɨɜɚɥ ɩɥɨɬɧɨɫɬɢ ɬɪɟɤɨɜ 1,0·106
ɩɨɪ/ɫɦ2. ɉɨɫɥɟ ɨɛɥɭɱɟɧɢɹ ɨɛɪɚɡɰɵ ɯɪɚɧɢɥɢɫɶ ɧɚ ɜɨɡɞɭɯɟ ɩɪɢ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ.
ɉɪɟɞɜɚɪɢɬɟɥɶɧɭɸ ɫɟɧɫɢɛɢɥɢɡɚɰɢɸ ɢ ɯɢɦɢɱɟɫɤɨɟ ɬɪɚɜɥɟɧɢɟ ɨɛɪɚɡɰɨɜ ɜɵɩɨɥɧɹɥɢ ɩɨ ɫɬɚɧɞɚɪɬɧɨɣ
ɦɟɬɨɞɢɤɟ, ɭɫɥɨɜɢɹ ɤɨɬɨɪɨɣ ɩɪɢɜɟɞɟɧɵ ɧɚ ɪɢɫɭɧɤɟ 1. Ⱦɢɚɦɟɬɪ ɩɨɪ ɩɨ ɞɚɧɧɵɦ ɷɤɫɬɪɭɡɢɨɧɧɨɣ
ɩɨɪɨɦɟɬɪɢɢ ɫɨɫɬɚɜɢɥ 389±14 ɧɦ.
Ⱦɥɹ ɨɤɢɫɥɟɧɢɹ ɨɛɪɚɡɰɨɜ ɌɆ ɜ ɢɧɬɟɪɜɚɥɟ 10-180 ɦɢɧɭɬ ɢɫɩɨɥɶɡɨɜɚɥɢ ɫɢɫɬɟɦɭ KMnO4/H2SO4 ɩɪɢ
ɭɫɥɨɜɢɹɯ, ɨɩɢɫɚɧɧɵɯ ɜ ɪɚɛɨɬɟ [12]. ɋɨɞɟɪɠɚɧɢɟ ɋɈɈɇ ɝɪɭɩɩ ɧɚ ɩɨɜɟɪɯɧɨɫɬɢ ɌɆ ɨɩɪɟɞɟɥɹɥɢ ɩɨ
ɪɟɚɤɰɢɢ ɫ ɦɟɬɢɥɟɧɨɜɵɦ ɫɢɧɢɦ [8] ɩɪɢ ɞɥɢɧɟ ɜɨɥɧɵ 662 ɧɦ, ɱɬɨ ɫɨɨɬɜɟɬɫɬɜɭɟɬ ɦɚɤɫɢɦɭɦɭ
ɩɨɝɥɨɳɟɧɢɹ ɭɤɚɡɚɧɧɨɝɨ ɤɪɚɫɢɬɟɥɹ. Ʉɚɥɢɛɪɨɜɨɱɧɭɸ ɤɪɢɜɭɸ ɫɬɪɨɢɥɢ ɜ ɞɢɚɩɚɡɨɧɟ ɤɨɧɰɟɧɬɪɚɰɢɣ 0,110,0 ɦɤɆɨɥɶ/ɥ, ɩɨ ɭɪɚɜɧɟɧɢɸ y=0,0537x - 0,0033 (R2= 0,9977) ɨɩɪɟɞɟɥɹɥɢ ɫɨɞɟɪɠɚɧɢɟ ɋɈɈɇ-ɝɪɭɩɩ
ɧɚ ɨɛɪɚɡɰɟ ɪɚɡɦɟɪɨɦ 1×1 ɫɦ. ɂɄ-ɫɩɟɤɬɪɵ ɪɟɝɢɫɬɪɢɪɨɜɚɥɢ Ɏɭɪɶɟ-ɫɩɟɤɬɪɨɦɟɬɪɨɦ Perkin-Elmer
Spectrum BX-II, ɨɛɪɚɛɨɬɤɭ ɩɨɥɭɱɟɧɧɵɯ ɞɚɧɧɵɯ ɜɵɩɨɥɧɹɥɢ ɜ ɩɪɨɝɪɚɦɦɟ Spekwin-32.
Ɋɟɡɭɥɶɬɚɬɵ ɢ ɢɯ ɨɛɫɭɠɞɟɧɢɟ
Ⱥɧɚɥɢɡ ɂɄ-Ɏɭɪɶɟ ɫɩɟɤɬɪɨɜ ɉɗɌɎ ɞɚɟɬ ɞɜɨɣɫɬɜɟɧɧɭɸ ɢɧɮɨɪɦɚɰɢɸ: ɜɨ-ɩɟɪɜɵɯ, ɤɚɠɞɨɟ ɩɨɥɨɠɟɧɢɟ
ɩɢɤɚ ɢɦɟɟɬ ɮɭɧɞɚɦɟɧɬɚɥɶɧɨɟ ɡɧɚɱɟɧɢɟ ɞɥɹ ɭɫɬɚɧɨɜɥɟɧɢɹ ɦɨɥɟɤɭɥɹɪɧɨɣ ɫɬɪɭɤɬɭɪɵ ɂɄ-ɚɤɬɢɜɧɨɝɨ
ɦɚɬɟɪɢɚɥɚ, ɥɸɛɨɟ ɢɡɦɟɧɟɧɢɟ ɜ ɩɨɥɨɠɟɧɢɟ ɩɢɤɚ ɜ ɫɩɟɤɬɪɟ ɧɟɩɨɫɪɟɞɫɬɜɟɧɧɨ ɨɬɧɨɫɢɬɫɹ ɤ ɢɡɦɟɧɟɧɢɸ
ɩɪɨɱɧɨɫɬɢ ɢɥɢ ɭɝɥɚ ɫɜɹɡɢ ɜ ɦɨɥɟɤɭɥɟ. ȼ ɫɥɨɠɧɨɣ ɩɨɥɢɦɟɪɧɨɣ ɫɬɪɭɤɬɭɪɟ ɉɗɌ ɨɫɨɛɟɧɧɨ
ɢɧɮɨɪɦɚɬɢɜɧɵɦ ɹɜɥɹɸɬɫɹ =ɋɈ,íCHO,íOH ɮɭɧɤɰɢɨɧɚɥɶɧɵɟ ɝɪɭɩɩɵ, ɢ ɬ.ɞ.) ɦɚɬɟɪɢɚɥɚ. ȼɨ-ɜɬɨɪɵɯ,
ɢɡɦɟɧɟɧɢɟ ɢɧɬɟɧɫɢɜɧɨɫɬɢ ɩɢɤɨɜ ɜ ɂɄ-ɫɩɟɤɬɪɟ ɤɨɪɪɟɥɢɪɭɟɬ ɫ ɞɨɥɟɣ ɞɚɧɧɨɣ ɮɭɧɤɰɢɨɧɚɥɶɧɵɟ ɝɪɭɩɩɵ
ɜ ɢɫɫɥɟɞɭɟɦɨɦ ɦɚɬɟɪɢɚɥɟ.
1410
absorbance
1712
1728
4,5
3
1506
1578
1958
2904
3556
0
3428
A
2970
1,5
B
3500
2500
1500
500
wavenumber,1/cm
Ɋɢɫɭɧɨɤ 3 – ɂɄ-ɫɩɟɤɬɪɵ ɢɫɫɥɟɞɭɟɦɵɯ ɉɗɌɎ ɌɆ: ɨɛɪɚɡɰɚ ɢɫɯɨɞɧɨɣ ɩɥɟɧɤɢ (Ⱥ) ɢ
ɩɨɫɥɟ ɜɨɡɞɟɣɫɬɜɢɹ ɨɤɢɫɥɢɬɟɥɟɣ (ȼ)
132
ɇɚ ɂɄ-ɫɩɟɤɬɪɟ ɢɫɯɨɞɧɨɣ ɉɗɌɎ (ɪɢɫɭɧɨɤ 3Ⱥ), ɢɦɟɸɬɫɹ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɯɚɪɚɤɬɟɪɧɵɟ ɞɥɹ
ɋ=Ɉ ɝɪɭɩɩɵ (1720 ɫɦ-1), ɛɟɧɡɨɥɶɧɵɯ ɰɢɤɥɨɜ (1578, 1506 ɫɦ-1) ɦɟɬɢɥɟɧɨɜɵɯ ɝɪɭɩɩ (2960, 2880, 1440
ɫɦ-1), ɜɚɥɟɧɬɧɨɟ ɤɨɥɟɛɚɧɢɟ –ɋ-Ɉ– ɫɜɹɡɢ ɫɥɨɠɧɨɷɮɢɪɧɵɯ ɝɪɭɩɩ (1263ɫɦ-1). ɂɦɟɸɬɫɹ ɩɨɥɨɫɵ
ɩɨɝɥɨɳɟɧɢɹ ɝɢɞɪɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ (3432 ɫɦ-1), ɦɟɬɢɥɟɧɨɜɵɯ ɝɪɭɩɩ (2970 ɫɦ-1), ɤɚɪɛɨɧɢɥɶɧɵɯ,
ɫɥɨɠɧɨɷɮɢɪɧɵɯ ɝɪɭɩɩ (1713, 1292 ɫɦ-1).
Ƚɥɚɜɧɨɟ ɨɬɥɢɱɢɟ ɦɟɠɞɭ ɫɩɟɤɬɪɚɦɢ ɨɤɢɫɥɟɧɧɨɣ ɢ ɢɫɯɨɞɧɨɣ ɌɆ ɫɜɹɡɚɧɨ ɫ ɨɬɧɨɲɟɧɢɟɦ ɩɨɥɨɫ
ɩɨɝɥɨɳɟɧɢɹ ɩɪɢ 1728 (ȣ C=O) ɢ 1410 (ȣ C–H,ɚɪɨɦɚɬ.) ɫɦ-1. ȼ ɫɨɨɬɜɟɬɫɬɜɢɢ ɫ [11] ɛɵɥɢ ɪɚɫɫɱɢɬɚɧɵ
ɢɧɞɟɤɫɵ ɮɭɧɤɰɢɨɧɚɥɶɧɵɯ ɝɪɭɩɩ ɋɈɈɇ ɢ Ɉɇ (Ɍɚɛɥɢɰɚ 1) ɞɥɹ ɨɤɢɫɥɟɧɧɵɯ ɨɛɪɚɡɨɜ ɉɗɌɎ ɌɆ. Ɍɚɤɠɟ
ɩɪɢɜɨɞɹɬɫɹ ɡɧɚɱɟɧɢɹ ɤɨɧɰɟɧɬɪɚɰɢɢ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ ɧɚ ɟɞɢɧɢɰɭ ɩɥɨɳɚɞɢ ɉɗɌɎ ɌɆ.
Ɍɚɛɥɢɰɚ 1 – ɂɡɦɟɧɟɧɢɟ ɫɨɞɟɪɠɚɧɢɹ ɤɨɧɰɟɜɵɯ ɤɢɫɥɨɪɨɞɫɨɞɟɪɠɚɳɢɯ ɝɪɭɩɩ ɉɗɌɎ ɌɆ
ɂɧɞɟɤɫ COOH
ɂɧɞɟɤɫ OH
(A3290/A2970)
(A3545/A3545+A3430)
(A1728/A1728+A1712)
P_TM1
í
0,144
0,489
0,339
TM2
0,356±0,08
0,402
0,492
0,453
30
1,442±0,049
0,404
0,487
0,427
90
1,422±0,03
0,393
0,491
0,429
120
1,536±0,1
0,410
0,494
0,432
150
1,525±0,04
0,409
0,485
0,433
180
1,459±0,05
0,402
0,477
0,430
ɉɪɢɦɟɱɚɧɢɟ: 1- Ɋɚɞɢɚɰɢɨɧɧɨ-ɦɨɞɢɮɢɰɢɪɨɜɚɧɧɵɣ ɨɛɪɚɡɟɰ ɉɗɌɎ ɞɨ ɯɢɦɢɱɟɫɤɨɝɨ ɬɪɚɜɥɟɧɢɹ; 2Ɉɛɪɚɡɟɰ ɉɗɌɎ ɌɆ ɩɨɫɥɟ ɯɢɦɢɱɟɫɤɨɝɨ ɬɪɚɜɥɟɧɢɹ.
Ɉɛɪɚɡɟɰ
[COOH], µɆ/ɫɦ2
Ʉɚɤ ɜɢɞɧɨ ɢɡ ɩɪɟɞɫɬɚɜɥɟɧɧɵɯ ɞɚɧɧɵɯ, ɡɧɚɱɢɬɟɥɶɧɨɟ ɭɜɟɥɢɱɟɧɢɟ ɱɢɫɥɚ ɤɚɪɛɨɤɫɢɥɶɧɵɯ ɝɪɭɩɩ
ɧɚɛɥɸɞɚɟɬɫɹ ɭɠɟ ɩɨɫɥɟ 30 ɦɢɧɭɬ ɨɤɢɫɥɟɧɢɹ, ɭɜɟɥɢɱɟɧɢɟ ɩɪɨɞɨɥɠɢɬɟɥɶɧɨɫɬɢ ɪɟɚɤɰɢɢ ɧɟ ɢɦɟɟɬ
ɫɭɳɟɫɬɜɟɧɧɨɝɨ ɜɥɢɹɧɢɹ ɧɚ ɷɮɮɟɤɬɢɜɧɨɫɬɶ ɨɤɢɫɥɟɧɢɹ, ɤɪɨɦɟ ɬɨɝɨ, ɩɨ ɪɟɡɭɥɶɬɚɬɚɦ ɫɤɚɧɢɪɨɜɚɧɢɹ
ɩɨɜɟɪɯɧɨɫɬɢ ɨɛɪɚɡɰɨɜ ɧɚ ɚɬɨɦɧɨ-ɫɢɥɨɜɨɦ ɦɢɤɪɨɫɤɨɩɟ ɜɢɞɧɨ, ɱɬɨ ɞɥɢɬɟɥɶɧɨɟ ɜɨɡɞɟɣɫɬɜɢɟ
ɚɝɪɟɫɫɢɜɧɵɯ ɫɪɟɞ ɢɦɟɟɬ ɧɟɝɚɬɢɜɧɨɟ ɜɥɢɹɧɢɟ ɧɚ ɦɨɪɮɨɥɨɝɢɸ ɩɨɜɟɪɯɧɨɫɬɢ ɩɥɟɧɤɢ (ɪɢɫɭɧɨɤ 4).
ɚ
ɛ
Ɋɢɫɭɧɨɤ 4 – Ɇɢɤɪɨɮɨɬɨɝɪɚɮɢɢ ɩɨɜɟɪɯɧɨɫɬɢ ɢɫɯɨɞɧɨɣ ɉɗɌɎ (ɚ) ɢ ɩɨɫɥɟ ɟɟ
ɨɛɪɚɛɨɬɤɢ ɨɤɢɫɥɢɬɟɥɟɦ ɜ ɬɟɱɟɧɢɟ 150 ɦɢɧɭɬ (ɛ)
ɂɫɫɥɟɞɨɜɚɧɢɹ ɜɵɩɨɥɧɟɧɵ ɜ ɪɚɦɤɚɯ ɩɨɞɩɪɨɟɤɬɚ «ɋɨɡɞɚɧɢɟ ɮɢɥɶɬɪɚɰɢɨɧɧɵɯ ɦɚɬɟɪɢɚɥɨɜ ɢ
ɦɟɬɚɥɥɢɱɟɫɤɢɯ ɧɚɧɨɫɬɪɭɤɬɭɪ ɧɚ ɨɫɧɨɜɟ ɬɪɟɤɨɜɵɯ ɦɟɦɛɪɚɧ», ɮɢɧɚɧɫɢɪɭɟɦɨɝɨ ɜ ɪɚɦɤɚɯ ɉɪɨɟɤɬɚ
Ʉɨɦɦɟɪɰɢɚɥɢɡɚɰɢɢ Ɍɟɯɧɨɥɨɝɢɣ, ɩɨɞɞɟɪɠɢɜɚɟɦɨɝɨ ȼɫɟɦɢɪɧɵɦ Ȼɚɧɤɨɦ ɢ ɉɪɚɜɢɬɟɥɶɫɬɜɨɦ
Ɋɟɫɩɭɛɥɢɤɢ Ʉɚɡɚɯɫɬɚɧ.
Ʌɢɬɟɪɚɬɭɪɚ
1 Chen W., McCarthy T.J. Chemical surface modification of PET // Macromolecules. í 1998. í Vol.31.í P. 3648í3655.
2 Roux S. Surface-Initiated polymerization from PET // J. of polymer science. í 2003. í Vol.41.í P. 1347í1359.
3 Dauginet L., Duwez A.-S., Legras R., DemoustieríChampagne S. Surface modification of polycarbonate and
poly(ethyleneterephthalate) films and membranes by polyelectrolyte deposition // Langmuir. í 2001. í Vol.17. í P.
3952í3957.
133
4 Mougenot P., MarchandíBrynaert J. Reactivity assays of surface hydroxyl chainíends of poly(ethylene
terephthalate) (PET) film and membrane using original 3Hí and fluorine labelled derivatization reagents //
Macromolecules. í 1996. í Vol.29. í P. 3552í3559.
5 Papra A., Hicke H.-G., Paul D. Syntesis of peptides onto the surface of PET particle track membranes // J. of
applied polymer science.í 1999.í Vol.74.í P. 1669í1674.
6 MarchandíBrynaert J., Deldime M., Dupont I., Dewez JíL., Schneider YíJ. Surface functionalization of PET film
and membrane by controlled wet chemistry: chemical characterization of carboxylated surfaces // J. of colloid and
interface science. í1995.í Vol.173.í P. 236í244.
7 Ʉɚɥɢɧɢɧɚ Ʌ.ɋ., Ɇɨɬɨɪɢɧɚ Ɇ.Ⱥ., ɇɢɤɢɬɢɧɚ ɇ.ɂ., ɏɚɱɚɩɭɪɢɞɡɟ ɇ.Ⱥ, Ⱥɧɚɥɢɡ ɤɨɧɞɟɧɫɢɪɨɜɚɧɧɵɯ ɩɨɥɢɦɟɪɨɜ. í
Ɇɨɫɤɜɚ: ɏɢɦɢɹ, 1984. í 296 ɫ.
8 Tiraferri A., Elimelech M. Direct quantification of negatively charged functional groups on membrane surface // J.
of membrane science.í 2012.íVol.389.í P. 499í508.
9 Mougenot P., Koch M., Dupont I. Surface functionalization of polyethylene terephtalate film and membranes by
controlled wet chemistry // Journal of colloid and interface science.í 1996. íVol.177.í P. 162í170.
10 Deldime M., Dewez J. Reactivity assay of surface carboxyl chain-ends of PET film and track-etched microporous
membranes using fluorine labelledí and/or 3Hílabelled derivatization reagents: tandem analysis by Xíray
photoelectron spectroscopy (XPS) and liquid scintillation counting (LSC) // Applied surface science.í 1995.í Vol.90.í
P. 1í14.
11 Prasad S.G., De A., De U. Structural and Optical Investigations of Radiation Damage in Transparent PET Polymer
Films. // International Journal of Spectroscopy. í 2011. í Article ID 810936.
12 Geismann C., Ulbricht M. Photoreactive functionalization of PET trackíetched pore surface with "smart" polymer
systems // Macromolecular chemistry and physics.í 2005. í Vol.206.í P. 268í281.
Ⱥ.ɘ. Ⱥɧɬɨɧɨɜ, Ⱥ.Ⱥ. Ɇɚɲɟɧɰɟɜɚ, ȿ.Ƚ. Ƚɨɪɢɧ
ɉɗɌɎ ɧɚɧɨԕɭɵɫɬɵ ɬɪɟɤɬɿ ɦɟɦɛɪɚɧɚɥɚɪɵɧɵԙ ɚɥԑɚɲԕɵ ɮɭɧɤɰɢɨɧɚɥɢɡɚɰɢɹɫɵɧɵԙ ɠԥɧɟ ɛɟɬɬɿ
ɬɚɥɞɚɭ ɟɪɟɤɲɟɥɿɤɬɟɪɿ
ɉɨɥɢɦɟɪɥɿ ɬɪɟɤɬɿ ɦɟɦɛɪɚɧɚɥɚɪɞɵԙ ɛɚԑɵɬɬɚɥԑɚɧ ɦɨɞɢɮɢɤɚɰɢɹɫɵ ԕɚɫɢɟɬɬɟɪɿ ɠɚԕɫɚɪɬɵɥԑɚɧ ɦɟɦɛɪɚɧɚɥɵԕ
ɮɢɥɶɬɪɥɟɪ, ɠɿɝɟɪ-ɫɟɡɝɿɡ ɦɟɦɛɪɚɧɚɥɚɪ ɠԥɧɟ ɨɥɚɪɞɵԙ ɧɟɝɿɡɿɧɞɟ ɧɚɧɨɫɟɧɫɨɪɢɤɚ ɷɥɟɦɟɧɬɬɟɪɿɧ ɠɚɫɚɭ ԛɲɿɧ ɠɚԙɚ
ɦԛɦɤɿɧɞɿɤɬɟɪ ɚɲɚɞɵ. ɏɢɦɢɹɥɵԕ ԧɡɝɟɬɪɭɥɟɪɞɿԙ ɫɨԙԑɵ ɮɭɧɤɰɢɨɧɚɥɞɵ ɬɨɩɬɚɪɦɟɧ ԧɬɤɿɡɭ ɠɟɬɿɫɬɿɝɿ ɉɗɌɎ
ɮɭɧɤɰɢɨɧɚɥɢɡɚɰɢɹɫɵɧɵԙ ɚɥԑɚɲԕɵ ɤɟɡɟԙɿɧɿԙ ɬɨɥɵԕɬɵԑɵɧɚ ɬɿɤɟɥɟɣ ɛɚɣɥɚɧɵɫɬɵ. ɀԝɦɵɫɬɚ ɬɨɬɵԑɭɞɵԙ
ɲɚɪɬɬɚɪɵɧɚ ɠԥɧɟ ɉɗɌɎ ɌɆ ɛɟɬɬɟɪɿɧ ɬɚɥɞɚɭ ԥɞɿɫɬɟɪɿɧɟ ɤɪɢɡɢɫɬiɤ ɬɚɥɞɚɭ ɠԛɪɝiɡɿɥɝɟɧ, ɫɨɧɵɦɟɧ ԕɚɬɚɪ ɋɈɈɇԕɚɧɵԕԕɚɧ ɉɗɌɎ ɌɆ ɚɥɭ ɩɪɨɰɟɫɿɧɿԙ ɷɤɫɩɟɪɢɦɟɧɬɚɥɞɵ ɞɟɪɟɤɬɟɪɿ ɤɟɥɬɿɪɿɥɝɟɧ. Ȼɚɫɬɚɩԕɵ ɠԥɧɟ
ɦɨɞɢɮɢɤɚɰɢɹɥɚɧԑɚɧ ɦɟɦɛɪɚɧɚɥɚɪɞɵԙ ɫɚɧɞɵԕ ɫɢɩɚɬɬɚɦɚɥɚɪɵɧɵԙ ԧɡɝɟɪiɫi ԕɚɪɚɥɚɞɵ.
Ʉɿɥɬɬɿɤ ɫΫɡɞɟɪ: ɬɪɟɤɬɿ ɦɟɦɛɪɚɧɚɥɚɪ, ɯɢɦɢɹɥɵΙ ɬΟɪɥɟɧɞɿɪɭ, ɤɚɪɛɨɤɫɢɥɞɿ ɬɨɩɬɚɪɞɵΝ ɢɧɞɟɤɫɿ, ɂΘ-, ɍɄɫɩɟɤɬɪɨɫɤɨɩɢɹ
A.You. Antonov, A.A. Mashentseva, E.G. Gorin
Features of the primary functionalization and surface analysis of nanoporous PET track-etched membranes
Targeted modification of polymer track membranes offers the great opportunities for the development of
membrane filters with improved characteristics, stimuli-responsible membranes and sensors. The effectiveness of
chemical transformations with terminal functional groups depends on the completeness of the primary step i.e.
oxidation of PET. In the paper, a review analysis of the oxidation reaction conditions and methods of surface PET TM
analysis as well as experimental data of this reaction are studied. The shifting properties of the parent and modified
membranes were demonstrated.
Keywords: track membrane, chemical functionalization, carboxyl group indexes, IR-, UV-spectroscopy.
134