Stereochemical Structure of Poly(cyclohexyl acrylate) Studied by One-Dimensional and Two-Dimensional 13C-1H Spectroscopy

Bulai, A. Kh.; Jimeno, M. Luísa; Román, Julio San

doi:10.1021/ma00126a013

Cited by 29 publications

(27 citation statements)

References 8 publications

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“…These have been assigned upto the pen tad level, the expanded region is shown in Figure 3. The triads are labeled as VVV (6 83.74-83.94), VVB (6 87.89-88.68) and BVB (6 90.5-92.1 ppm) which are based on the variation in the resonating intensities with respect to the variation in the composition and are also found to be in agreement with assignments reported in the literature. 1 7 The methine carbon of the B unit of the V-B copolymer which appears at 6 39.74-41.30ppm is shown in Figure 4.…”

Section: Resultssupporting

confidence: 85%

Comprehensive Assignments of 1H and 13C NMR Signals for the Vinylidene Chloride-Butyl Acrylate Copolymers Using 2D NMR Spectroscopy

Brar

Malhotra

1998

Polym J

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ABSTRACT:Vinylidene chloride-butyl acrylate copolymers were prepared by photopolymerization at room temperature. The molecular weight of these copolymers have been determined using Gel Permeation Chromatography and the copolymer composition estimated using Schoneger technique. 2D NMR techniques such as 1 H-13 C heteronuclear single quantum correlation (HSQC) was used for the compositional and configurational assignments of 1 H and 13 C{ 1 H} NMR spectra for various resonating signals. 2D 1 H homonuclcar double quantum filter-correlated spectroscopy (DQF-COSY) is used to get better insight for the copolymer structure.KEY WORDS Photopolymerization / Gel Permeation Chromatography / Composition / Heteronuclear Single Quantum Correlation / Correlated Spectroscopy / Vinylidene Chloride / Butyl Acetylate / Copolymer/ Two dimensional homonuclear and heteronuclear NMR spectroscopy have been used extensively for the structure elucidation of polymers. The microstructure of homopolymers 1 such as poly(methacrylonitrile), 2 poly-(vinyl chloride), 3 polyisobutylene,4 poly(tert-butyl acrylate)5 and poly(cyclohexyl acrylate) 6 have reports by 2D NMR spectroscopy. 2D NMR has also been used for the characterization of the copolymers. 7 ,sIn our earlier publications on vinylidene chloridemethyl acrylate copolymers,9 we have determined their microstructure and reported the detailed assignment of the 13 C{ 1 H} NMR signals. In this the methine and methylene signals were assigned upto triad and diad levels respectively on the 1 H NMR using heteronuclear single quantum correlation (HSQC) experiments. Further splittings on the HSQC for these resonating regions were attempted in the vinylidene chloride-ethyl acrylate10 where the methine and methylene signals were assigned upto pen tad and tetrad levels, respectively. But 2D-COSY spectrum was not discussed in detail. In the continuation of our work, we report the 2D studies of commercially important 11 vinylidene chloride-butyl acrylate (V-B) copolymer by using one dimensional (1H and 13 C) and two dimensional NMR spectroscopy. The 2D-COSY spectrum shows all the I, 2 bond geminal couplings feasible for the methylene protons along with the 1, 3 bond coupling of the methine with the methylene protons. EXPERIMENT ALVinylidene chloride (Fluka) and butyl acrylate were freed from inhibitor by distilling under reduced pressure prior to use. The copolymers are prepared by photopolymerization 12 • 13 using uranyl nitrate as photosensitizer. 14 The molecular weights of the copolymers were determined by gel permeation chromatography (GPC) using polystyrene as narrow standard (Waters, 410). Tetrahydrofuran was used as solvent.t To whom all correspondence should be addressed.The compos1t10n was determined using Schoneger technique. 15 · 16 The 1 D NMR spectra and the 2D HSQC spectra of the copolymers were recorded on a JEOL 300 MHz spectrometer, whereas 2D DQF-COSY spectra was recorded on the Bruker-DPX 300 MHz spectrometer. Experimental details are mentioned in our earlier publication. 9 RESULTS AND...

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Section: Resultssupporting

confidence: 85%

Comprehensive Assignments of 1H and 13C NMR Signals for the Vinylidene Chloride-Butyl Acrylate Copolymers Using 2D NMR Spectroscopy

Brar

Malhotra

1998

Polym J

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“…[1][2][3][4][5] The 2-D technique that couples single bond carbon-proton correlation spectroscopy (2-D HSQC-TOCSY) can help in unambiguous stereochemical and compositional assignments of the polymers. 6 -8 Although poly(vinyl acetate) has been studied extensively by many workers, 9 -15 a complete and unambiguous signal assignment of the 13 C{ 1 H} NMR spectrum has not been done.…”

Section: Introductionmentioning

confidence: 99%

Spectral assignment of poly(vinyl acetate) by one and two dimensional NMR spectroscopy: Revisited

Dutta

Mukherjee

Brar

1999

J. Polym. Sci. A Polym. Chem.

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“…The spatial coupling between the methylene dyads SS and MS with the phenylic protons was observed and it was assigned to SSrSS (7), SSrSM (8), and MSrSM (9) tetrads for the coupling with SS at ␦1.4/6.88, ␦1.45/7.1, and ␦1.58/7.15 ppm, respectively. The SMmSS (10), SMmSM (11), and MMmSM (12) tetrads for the spatial coupling of the MS dyad with styrene protons at ␦1.6/6.92, ␦1.85/7.2, and ␦1.9/6.8 ppm were assigned.…”

Section: D-nmr Studiesmentioning

confidence: 99%

Characterization of styrene/methacrylic acid copolymers by 2D‐NMR spectroscopy

Brar

Hekmatyar

2001

J of Applied Polymer Sci

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Styrene/methacrylic acid copolymers were prepared by free-radical photopolymerization using the uranyl nitrate ion as the initiator. The copolymer composition was determined from 1 H-NMR spectroscopy. The comonomer reactivity ratios determined using Kelen Tudos and nonlinear error in variable methods (EVM) are r m ϭ 0.61 Ϯ 0.05 and r s ϭ 0.14Ϯ 0.07. The broad and overlapping 1 H-NMR spectrum was assigned using the help of 2D TOCSY and NOESY experiments. These methods were used to ascertain the various geminal, vicinal, and spatial couplings between the protons. The methyl and methine protons also show configurational and compositional sensitivity.

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Stereochemical Structure of Poly(cyclohexyl acrylate) Studied by One-Dimensional and Two-Dimensional 13C-1H Spectroscopy

Cited by 29 publications

References 8 publications

Comprehensive Assignments of 1H and 13C NMR Signals for the Vinylidene Chloride-Butyl Acrylate Copolymers Using 2D NMR Spectroscopy

Comprehensive Assignments of 1H and 13C NMR Signals for the Vinylidene Chloride-Butyl Acrylate Copolymers Using 2D NMR Spectroscopy

Spectral assignment of poly(vinyl acetate) by one and two dimensional NMR spectroscopy: Revisited

Characterization of styrene/methacrylic acid copolymers by 2D‐NMR spectroscopy

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