Diad, triad, and pentad sequence‐distribution analysis of acrylonitrile–vinylidene chloride model copolymers by <sup>13</sup>C‐NMR

Bailey, David B.; Henrichs, P. M.

doi:10.1002/pol.1978.170161213

Cited by 22 publications

(11 citation statements)

References 23 publications

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“…Bailey et al 8 and Yamazaki et al 10 have assigned the methylene carbon signals to dyad/tetrad compositional sequences. From the inverse-HETCOR spectrum, the methylene protons signals are divided into three regions: 6 1.9-2.5, 2.5-3.4, and 3.5-4.0 ppm which are assigned to AA, A V(VA), and VV dyads.…”

Section: Resultsmentioning

confidence: 99%

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Complete Spectral Assignment of Acrylonitrile/Vinylidene Chloride Copolymers by One and Two Dimensional NMR Spectroscopy

Brar

Dutta

Pandey

1999

Polym J

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KEY WORDS Assignment IAcrylonitrileiVinylidene Chloride Copolymers I 20 NMR Spectroscopy I Spectral Over the last decade both one and two dimensional NMR spectroscopy have become an important technique for investigations of the structure of polymers 1 -3 and copolymers. 4 -6 Acrylonitrilefvinylidene chloride (A/V) copolymers has been extensively studied as it is an industrially important polymer. It has potential industrial application because of its excellent fiber formability together with high non-flammability. Many workers have reported the microstructure 7 -10 and reactivity ratios 7 -15 of A/V copolymers. Ito et al. 7 were the first to evaluate the sequence distribution of A/V copolymers by NMR spectroscopy. Bailey et a/. 8 assigned the methylene and the quaternary carbon resonance signals to dyad, triad and pentad sequences. They were not able to assign the methine and the nitrile carbon resonance signals. These signals were assigned to pentad sequences by Konig et a/. 9 and Yamazaki et a/. 10 However, the broad and overlapping 1 H NMR spectra of A/V copolymers has not been assigned by any of these workers.In this paper we report the complete and unambiguous signal assignment of broad and overlapping 1 H NMR spectra of A/V copolymers. The methine and the methylene proton signals were assigned to triad, pentad, heptad and tetrad compositional sequences, respectively, with the help of 2D NMR techniques, like DQFCOSY, TOCSY, and inverse-HETCOR. The various configurational arrangement within the tetrad or pentad sequences were also assigned. EXPERIMENTAL A/V were distilled under reduced pressure and was stored below soc. The A/V chloride copolymers of different monomer composition were prepared by photo polymerization using uranyl nitrate as photo sensitizer in a sealed tube. The percent conversion was kept below 10% by precipitating the copolymers in methanol. The copolymers were purified by N,N-dimethylformamide (DMF)/methanol system. The copolymer composition was calculated from the percent nitrogen of the copolymers and quantitative 13 C NMR spectroscopy.NMR experiments were performed in dimethyl sulfoxide (DMSO)-d 6 on a Bruker 300 MHz spectrometer at frequencies of 300.13 MHz and 75.5 MHz for 1 H and 13 C{ 1 H} NMR spectra, respectively. The 13 C{ 1 H} NMR t To whom all correspondence should be addressed. 396experiments were recorded with 32 K data points for 6000 scans with 2 s relaxation delay. The quantitative 13 C{ 1 H} NMR experiments were carried out using the inversegated decoupling pulse program with 12 s as delay time. The 90° pulse for the 1 H and the 13 C nuclei used was 7.6 JlS and 5.5 JlS, respectively. Two dimensional proton detected 1 H-13 C heteronuclear chemical shift correlation spectra were obtained using the standard pulse sequence. A total of 32 scans were accumulated with a relaxation delay of 2s for each of the 512 t 1 experiments. The DQFCOSY spectrum was obtained with 32 scans for each t 1 value. A total of 512 spectra each containing the 1 K data points were accumulated. Tw...

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Section: Resultsmentioning

confidence: 99%

“…Bailey et a/. 8 assigned the methylene and the quaternary carbon resonance signals to dyad, triad and pentad sequences. They were not able to assign the methine and the nitrile carbon resonance signals.…”

mentioning

confidence: 99%

Complete Spectral Assignment of Acrylonitrile/Vinylidene Chloride Copolymers by One and Two Dimensional NMR Spectroscopy

Brar

Dutta

Pandey

1999

Polym J

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“…[17]/ M 1 1 2 = K + 2(3/2n) 312 <P 0 ( oo )BM 112 (5) The values of Kp and f3 are given in Table IV. with …”

Section: Methods 2e (Stockmayer-fixman Plot) 12mentioning

confidence: 99%

“…The monomer sequence distribution and stereoregularity of the polymer were evaluated according to the method of Bailey and Henrichs. 5 …”

Section: Light Scatteringmentioning

confidence: 99%

“…Up to now, only sequence distribution of model copolymer was analyzed, 5 but no systematic study has been made on its dilute solution properties in conection with its molecular characteristics. In this article an attempt is made to investigate the dilute solution properties of AN/VDC copolymer (with 58 weight percent in AN) in various solvents to compare the molecular characteristic of AN/VDC copolymer with those of PAN.…”

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Dilute Solution Properties of Acrylonitrile/Vinylidene Chloride Copolymer

Kamide¹,

Miyazaki²,

Yamazaki³

1986

Polym J

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ABSTRACT:A copolymer of acrylonitrile (AN) and vinylidene chloride (VDC) was prepared using azobisisobutylonitrile as an initiator and was separated into 20 fractions by successive solution fractionation, using dimethyl sulfoxide (DMSO) as the solvent and toluene as the precipitant. The fractions had essentially the same chemical composition: 59 weight percent in AN. Light scattering for a fraction in dimethylacetamide (DMAc), y-butyrolactone (y-BL) and dimethylformamide (DMF) gave the same weight-average molecular weight M w within an experimental error ± 2%, which was evaluated assuming homopolymer. Viscosity and light and A2 =5.77x 10-3 M;:, 0 · 13 '. The unperturbed chain dimension A was determined by Baumann, Stockmayer-Fixman and Kamide-Moore methods. The value of a copolymer of AN and VDC was by ca. 10% smaller than that of polyacrylonitrile.

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Microstructure of vinylidene chloride-ethyl acrylate copolymers by one- and two-dimensional NMR spectroscopy

Brar

Malhotra

1998

J. Appl. Polym. Sci.

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Vinylidene chloride / ethyl acrylate ( V / E ) copolymers were prepared by photopolymerization using uranyl ion as a photosensitizer at room temperature. Copolymers were characterized by chlorine estimation, gel permeation chromatography, 1 H-and 13 C-NMR, 2D heteronuclear single quantum correlation ( HSQC ) , and homonuclear 1H -2D double quantum filter correlation spectroscopy ( DQF-COSY ) . Reactivity ratios for the copolymerization of V with E were calculated using the Kelen -Tudos ( KT ) and the nonlinear error in variables ( EVM ) methods. The reactivity ratios obtained from the EVM methods are r V Å 0.80 { 0.15 and r E Å 0.87 { 0.04. The microstructure was calculated in terms of the distribution of V-and Ecentered triad sequences from 13 C { 1 H } -NMR spectra of the copolymers. 2D HSQC was used to analyze the complex 1 H-NMR spectrum and 2D COSY shows the various bond interactions, thus inferring the possible structure of the copolymers.

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Diad, triad, and pentad sequence‐distribution analysis of acrylonitrile–vinylidene chloride model copolymers by ¹³C‐NMR

Cited by 22 publications

References 23 publications

Complete Spectral Assignment of Acrylonitrile/Vinylidene Chloride Copolymers by One and Two Dimensional NMR Spectroscopy

Complete Spectral Assignment of Acrylonitrile/Vinylidene Chloride Copolymers by One and Two Dimensional NMR Spectroscopy

Dilute Solution Properties of Acrylonitrile/Vinylidene Chloride Copolymer

Microstructure of vinylidene chloride-ethyl acrylate copolymers by one- and two-dimensional NMR spectroscopy

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Diad, triad, and pentad sequence‐distribution analysis of acrylonitrile–vinylidene chloride model copolymers by 13C‐NMR

Cited by 22 publications

References 23 publications

Complete Spectral Assignment of Acrylonitrile/Vinylidene Chloride Copolymers by One and Two Dimensional NMR Spectroscopy

Complete Spectral Assignment of Acrylonitrile/Vinylidene Chloride Copolymers by One and Two Dimensional NMR Spectroscopy

Dilute Solution Properties of Acrylonitrile/Vinylidene Chloride Copolymer

Microstructure of vinylidene chloride-ethyl acrylate copolymers by one- and two-dimensional NMR spectroscopy

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Diad, triad, and pentad sequence‐distribution analysis of acrylonitrile–vinylidene chloride model copolymers by ¹³C‐NMR