СПЕКТРАЛЬНЫЕ ХАРАКТЕРИСТИКИ И РАСЧЕТНЫЕ ПАРАМЕТРЫ КРАТНЫХ СВЯЗЕЙ МОЛЕКУЛ МОНОМЕРОВ ДЛЯ РАДИКАЛЬНОЙ ПОЛИМЕРИЗАЦИИ
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| Title |
СПЕКТРАЛЬНЫЕ ХАРАКТЕРИСТИКИ И РАСЧЕТНЫЕ ПАРАМЕТРЫ КРАТНЫХ СВЯЗЕЙ МОЛЕКУЛ МОНОМЕРОВ ДЛЯ РАДИКАЛЬНОЙ ПОЛИМЕРИЗАЦИИ
SPECTRAL CHARACTERISTICS AND CALCULATED PARAMETERS OF THE MULTIPLE BOND OF THE MONOMERS FOR RADICAL POLYMERIZATION |
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| Creator |
Тюрина, Татьяна Григорьевна
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| Subject |
химический сдвиг
структурно-спектральная взаимосвязь длина порядок двойная связь заряд на атомах углерода частота валентных колебаний monomers for radical (co)polymerization length order of the double bond charge on the carbon atoms frequency of stretching vibrations chemical shift structural and spectral correlation |
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| Description |
Установлена зависимость длины и порядка связей С1=С2 и С=О или заряда на атомах углерода С1 и C2 с частотой полосы их валентных колебаний в ИК или величиной химического сдвига в 13C ЯМР спектрах разбавленных растворов виниловых, аллиловых и циклических кислородсодержащих мономеров для радикальной (со)полимеризации.
There was found a linear relationship (R = 0.986) between the C1=C2 bond order and bond length (method AM1) in molecules of vinyl (styrene, acrylonitrile, methyl methacrylate, N-vinylpyrrolidone) and allyl (diallyl phthalate, diethylene glycol bis-allylcarbonate) monomers of the formula С1Н2=С2R1R2, where R1 = H or CH3, R2 – substituent with different nature. Data combining of the C=C bond length and order for the considered vinyl and allyl monomers within a single equation suggest that bonds have the similar type, and its properties are affected by the nature of substituent at the C2 atom. Increasing polarity of R2 in the series СН2ОС(=О) < Ph ≈ C≡N < C(=O)OR < N(cycle) leads to greater delocalization or reducing of the order bond and its elongation. There is observed a separation of linear relations between the order and length of the C=O by type of the carbonyl group - ester, carbonate or conjugated through a heteroatom. Stretching vibration frequency νС=С in the IR spectra shiftes to lower wavelengths with increasing C=C bond length, and for the "ether" monomers - methyl methacrylate, N-vinylpyrrolidone and allyls there is a linear relationship between their values with R ~ 0.9. The value of the stretching vibration frequency νС=О for vinyl monomers and diallylphthalate is linearly dependent on the length of the C=O or its order (R = 0.994) and the charge on the oxygen atom (R = 0.998). The total correlation does not include data for the diethylene glycol bis-allylcarbonate, due to the lack of conjugation in the molecule. There was found that for oxygen-containing vinyl and allyl monomers a greater shielding (lower value δС1) is associated with a greater magnitude of the negative charge on C1, and the reason for changes in the activity of the monomer may be a change of the charge on the atoms of the vinyl group, whereas close type of the relationship between the charge and the shift atom C2 was revealed. These results allow us to interpret the concentration dependence of the chemical shift in the 13C NMR spectra of the studied compounds as a result of changes in the electron density distribution on them molecules at the binding in the self-associates. |
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| Date |
2013-04-10T16:24:59Z
2013-04-10T16:24:59Z 2013-04-10 |
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| Type |
Article
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| Identifier |
2074-6652
http://ea.donntu.edu.ua/handle/123456789/18373 |
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| Relation |
Наукові праці ДонНТУ;Серія: Хімія і хімічна технологія, 2013. - Вип.1(20). - С.48-55
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