Penultimate effects in methyl methacrylate-4-vinyl pyridine copolymers

Natansohn, Almeria; Maxim, Steliana; Feldman, D.

doi:10.1016/0014-3057(78)90049-6

Cited by 11 publications

(11 citation statements)

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“…The triplet appearance of the signal suggests that a is approximately 0.5, i.e., there is a random configurational distribution of the alternate sequences. A similar value was obtained for poly(MMAco4VP) by analysing the rnethoxy signal in the proton spectra (7). The results of the decoupling experiments show that indeed the triplet pattem is common for all the proton signals but the magnitude of the splittings induced by the carbonyl group is not the same for every signal.…”

Section: The Carbonyl Regionsupporting

confidence: 76%

“…This paper therefore presents the 13C nmr spectra of the poly(MMA-co-4VP), poly(MMA-co-2M5VP), and their quaternized derivatives in solution. To our knowledge, these spectra have not been reported in the literature, and only the proton spectra of poly(MMA-co-4VP) were reported earlier by one of us (7). This paper does not intend to elucidate the microstructural mechanism that governs the copolymerization of MMA with 4VP or with 2M5VP.…”

Section: Introductionmentioning

confidence: 91%

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Nuclear magnetic resonance studies of ionomers. 5. Spectra of poly (methyl methacrylate-co-4-vinyl pyridine), poly (methyl methacrylate-co-2-methyl-5-vinyl pyridine), and their quaternized derivatives

Natansohn¹,

Eisenberg²

1987

Can. J. Chem.

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ALMERIA NATANSOHN and ADI EISENBERG. Can. J. Chem. 65, 1873Chem. 65, (1987. Proton and carbon nuclear magnetic resonance spectra in solution of poly(methy1 methacrylate-co-4-vinyl pyridine), poly-(methyl methacrylate-co-2-methyl-5-vinyl pyridine), and of their derivatives obtained by quaternization with methyl iodide are presented. The vinyl pyridine structural units content of the samples is ca. 10%. In different solvents, the spectra provide information about the sequence distribution and configuration of the copolymers. A "coisotactic" alternating addition, defined as the probability of finding a methoxy group and a pyridine ring neighboring each other on the same side of the main chain, can be estimated as about 0.5 in both cases. This information arises from the splitting of the aromatic and of the methoxy signals (both in proton and carbon spectra). As expected, quaternization does not affect the copolymer configuration. Heteronuclearcorrelated two-dimensional spectra can help in assigning the spectra.ALMERIA NATANSOHN et ADI EISENBERG. Can. J. Chem. 65, 1873Chem. 65, (1987.On rapporte les spectres rmn du 'H et du 13c, mesurks en solution, du poly(m6thacrylate de mithyle-co-vinyl-4 pyridine), du poly(mCthacry1ate de methyle-co-methyl-2 vinyl-5 pyridine) et de leurs dkrivis obtenus par quaternisation avec I'iodure de methyle. Les unites structurales vinylpyridines foment environ 10% des kchantillons. Dans les diffkrents solvants, les spectres fournissent de l'information sur la distribution des sCquences ainsi que sur la configuration des copolym6res. Dans chacun des cas, on peut evaluer 5 0,5 la proportion d'addition cc coisotactique >> alternante, dkfinie comme la probabilite de trouver un groupement methoxy et un cycle pyridine cBte i cBte sur le m&me cote de la chaine principale. On peut dCduire cette information 5 partir du dkdoublement des signaux dus aux groupements aromatiques et mCthoxy (tant en rmn du 'H que du I3C). Comme on pouvait s'y attendre, la quaternisation n'affecte pas la configuration du copolymkre. Les spectres bidimensionnels htt6ronucltaires peuvent &tre utiles dans l'attribution des spectres.[Traduit par la revue]

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Section: The Carbonyl Regionsupporting

confidence: 76%

Section: Introductionmentioning

confidence: 91%

Nuclear magnetic resonance studies of ionomers. 5. Spectra of poly (methyl methacrylate-co-4-vinyl pyridine), poly (methyl methacrylate-co-2-methyl-5-vinyl pyridine), and their quaternized derivatives

Natansohn¹,

Eisenberg²

1987

Can. J. Chem.

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“…Natanshon 36 has attributed such shifts to the increase content of VVV triads, which resonate at higher fields and to the decrease content of VVM and MVM triads that resonate at lower fields, part I Figure 1 FTIR spectra between 500 and 4000 cm 21 for PMMA (a) and MMA-4VP copolymers; mol % of 4VP in feed is 24.1% (b); 48.78% (c).…”

Section: Aromatic Signalmentioning

confidence: 96%

“…Similar behavior was observed by Natanshon et al with copolymers of methyl acrylate (MA) or MMA with 2VP or 4VP. [34][35][36] Simultaneously, The signals belonging to aromatic, methoxy, and a-CH 3 groups are split with an increase in 4VP content in copolymers due to their compositional (monomer sequence distribution) as well as configurational sensitivity. In agreement with Natanshon et al studies, these signals are tentatively assigned in terms of triads and are depicted in Figure 4, where M and V indicate MMA and 4VP, respectively.…”

Section: Copolymer Stereochemistrymentioning

confidence: 98%

Copolymerization of methyl methacrylate with 4‐vinylpyridine initiated by a novel Ni(II)α‐Benzoinoxime complex

Harrar-Ferfera

2007

J of Applied Polymer Sci

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Copolymerizations of methyl methacrylate (MMA) with 4-vinylpyridine (4VP) were performed from different monomer feed ratios in 1,4-dioxan at 308C under free radical initiation experimental conditions, using Ni(II)a-Benzoinoxime complex as initiator. The obtained copolymers (PMMA4VP) were examined by FTIR and 1 H NMR spectroscopies. The composition of these copolymers was calculated, using 1 H NMR spectra and elemental analysis. Monomer reactivity ratios were estimated from Fineman-Ross (FR, r m 5 0.550, r v 5 1.165) and Kelen-Tudos (KT, r m 5 0.559, r v 5 1.286) linearization methods, as well as nonlinear error in variables model (EVM) method using the RREVM computer program (RREVM, r m 5 0.559, r v 5 1.264). These values suggest that MMA-4VP pair copolymerizes randomly. 1 H NMR spectra provide information about the stereochemistry of the copolymers in terms of sequence distributions and configurations. These results showed that the age of the Ni complex has an impact not only on its activity towards polymerization reactions but also on the features of the corresponding copolymers, whereas the chemical composition was insensitive to this prominent factor. The mechanism of MMA-4VP copolymerization is consistent with a radical process as supported by microstructure and molecular weight distribution studies. Thermal behaviours of these copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis.

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“…The number of the parameters can be reduced to two if one of the monomers is incapable of homopolymerization. All the above-mentioned versions of the penultimate model are widely used in practice [26][27][28][29][30][31][32][33][34][35].…”

Section: Terminal and Penultimate Modelsmentioning

confidence: 99%

Modern aspects of quantitative theory of free-radical copolymerization

Кучанов

Free Radical Copolimerization Dispersions Glassy State Relaxation

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Penultimate effects in methyl methacrylate-4-vinyl pyridine copolymers

Cited by 11 publications

References 9 publications

Nuclear magnetic resonance studies of ionomers. 5. Spectra of poly (methyl methacrylate-co-4-vinyl pyridine), poly (methyl methacrylate-co-2-methyl-5-vinyl pyridine), and their quaternized derivatives

Nuclear magnetic resonance studies of ionomers. 5. Spectra of poly (methyl methacrylate-co-4-vinyl pyridine), poly (methyl methacrylate-co-2-methyl-5-vinyl pyridine), and their quaternized derivatives

Copolymerization of methyl methacrylate with 4‐vinylpyridine initiated by a novel Ni(II)α‐Benzoinoxime complex

Modern aspects of quantitative theory of free-radical copolymerization

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