Tacticity measurement of polymethacrylate by peak-eliminated fourier-transform NMR

Department of Chemistry, Osaka University, Suika, Ōsaka, Japan
Journal of Polymer Science Polymer Letters Edition 09/1976; 14(9):531-535. DOI: 10.1002/pol.1976.130140904

ABSTRACT A number of works have centered on the structural determinations of macromolecules by using Fourier-transform NMR. However, in the PMR study of large biological molecules there are a variety of problems owing to a large residual HDO peak. Recently, water-eliminated Fourier-transform (WEFT) NMR was developed to overcome these problems and was applied to the study of biological molecules. In the reported work, the principle of WEFT method was successfully applied to the analysis of the tacticity of poly(alkyl methacrylate). The spectra of syndiotactic PMMA were measured in toluene-d//8 at 110 degree C by a pulse sequence of (180 degree minus t minus 90 degree minus 10 sec)//4 at various values of t, and the triad tacticities were determined from the intensity measurements of the three alpha -methyl peaks. The results are tabulated. The tacticities of several poly(alkyl methacrylates) were successfully determined by the peak-elimination method, and the results are shown. Agreement between the observed and the calculated dyad tacticities also shows the accuracy of the measurements.

  • Macromolecules 03/1979; 12(2):234-239. DOI:10.1021/ma60068a012 · 5.93 Impact Factor
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    ABSTRACT: Polymerizations of ethyl methacrylate were carried out in toluene with butyllithium at various temperatures. The polymer obtained at −78°C could be fractionated into methanol-insoluble and methanol-soluble fractions. The former was rather syndiotactic. The latter was found by gel-permeation chromatography and 1H NMR spectroscopy to be composed of highly isotactic polymer and isotactic oligomer. These three fractions were formed simultaneously at the beginning of the polymerization and the amounts and molecular weights of the isotactic and syndiotactic fractions increased during the polymerization, while the amount of oligomeric fraction remained almost constant after the initial rapid increase. These results indicate the coexistence of three different active species for isotactic and syndiotactic polymers and isotactic oligomer, respectively, at the initial stage of the polymerization and two propagating species during the polymerization. The amounts of syndiotactic fraction and oligomeric fraction decreased with an increase in the polymerization temperature and only the isotactic polymer was obtained above −20°C. When the polymerization was initiated with 1,1-diphenylhexyllithium, only an isotactic polymer was produced. In the polymerization initiated with butyllithium, an appreciable amount of lithium ethoxide formed at the initial stage of the reaction, but no formation of the ethoxide was observed in the case of 1,1-diphenylhexyllithium. This indicates that the multiplicity of the active species in the polymerization with butyllithium is strongly related to the lithium ethoxide formed.
    Polymer Journal 12/1979; 11(12):989-994. DOI:10.1295/polymj.11.989 · 1.55 Impact Factor
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    ABSTRACT: Polymerizations of various methacrylates and α-(p-substituted phenyl)acrylates were studied in toluene and tetrahydrofuran by several anionic initiators. The polymerization with octylpotassium in tetrahydrofuran was found to be the most suitable for the formation of the heterotactic polymer, defined as the polymer containing more than 50% heterotactic triads. Methacrylic acid esters of the primary alcohol gave the heterotactic polymers, whose heterotactic contents increased with an increase in the bulkiness of the ester group. Methacrylic esters of secondary alcohol generally gave heterotactic polymers with octylpotassium in tetrahydrofuran. In the polymerizations of methacrylic acid esters of tertiary alcohol, the heterotactic contents decreased with an increase in the bulkiness of the ester group. A perfectly atactic polymer was obtained in the polymerization of methyl α-phenylacrylate with butyllithium in tetrahydrofuran, but it gave the heterotactic polymer when initiated with octylpotassium in tetrahydrofuran. Methyl α-p-chlorophenylacrylate produced the heterotactic polymer in tetrahydrofuran with butyllithium as well as with octylpotassium. In the case of methyl α-p-bromophenylacrylate, the heterotactic polymer was obtained even in the polymerization in toluene with butyllithium. These results indicate that the acrylic acid ester having the bulkier substituent tends to give the heterotactic polymer more easily by anionic initiator.
    Polymer Journal 01/1980; 12(1):55-62. DOI:10.1295/polymj.12.55 · 1.55 Impact Factor
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