Quantitative13C NMR Analysis of Sequence Distributions in Poly(ethylene-co-1-hexene)

Mark R. Seger; Gary E. Maciel

doi:10.1021/ac040104i

NMR Composition Analysis of Copolymers

Rubber Chemistry and Technology ◽

10.5254/1.3539131 ◽

1967 ◽

Vol 40 (4) ◽

pp. 1200-1211 ◽

Cited By ~ 32

Author(s):

Virgil D. Mochel

Keyword(s):

Double Resonance ◽

Oxidative Degradation ◽

Resonance Region ◽

Accurate Method ◽

Composition Analysis ◽

Nmr Analysis ◽

Structural Isomers ◽

High Resolution Nmr ◽

Sequence Distributions ◽

Butadiene Styrene

Abstract High resolution NMR spectroscopy has been shown to be a most useful tool for elucidation of compositions and structures of polymers. It is a rapid, accurate method of analysis and requires no external calibration. This technique of composition analysis can be applied to any copolymer, terpolymer, or homopolymer with various structural isomers, provided a suitable number of resonance peaks can be unambiguously assigned to at least one proton of each of the structures present. Accuracy depends upon the relative isolation of these selected peaks. The method was applied to butadiene styrene and butadiene isoprene copolymers. Equations developed previously for both systems were extended and modified to give better accuracy. In the former copolymer the NMR analysis for block styrene agreed very well with the chemical oxidative degradation method over the range 0-20 per cent. It is believed that sequence lengths smaller than five styrene units can be observed as block styrene by NMR. It was also shown that there is a sequence distribution effect in the 1,2 addition butadiene olefinic resonance region of the spectrum. This effect is also observed in polybutadienes and in the butadiene isoprene copolymers. Further study of this might be fruitful. Accuracy of the NMR method was demonstrated in the butadiene isoprene case by study of four high conversion, emulsion copolymers and six blends of butadiene and isoprene homopolymers. In all samples except one the total isoprene content found by either the detailed NMR analysis or the much more simplified NMR analysis agreed within 2 per cent of that known to be present. Accuracy is greatest for those copolymers or blends which have relatively low 1,2 addition butadiene contents, such as with butyllithium-catalyzed polymers. Accuracy is poor when the copolymer or blend has an isoprene content less than 10 per cent along with a high 1,2 addition butadiene content. Composition analysis of copolymers by NMR will become increasingly important since it often provides a direct, simple fingerprint of the various structures. However, NMR will probably make its most significant contributions in stereochemical studies of tacticities, sequence distributions, and orientation, such as head-to-head or tail-to-tail linkages. In these problems deuteration techniques, double resonance techniques, and higher field strengths play an indispensable role.

Sequence distributions and a phase diagram for copolymers made from poly(ethylene terephthalate) and p-acetoxybenzoic acid

Macromolecules ◽

10.1021/ma00169a018 ◽

1987 ◽

Vol 20 (3) ◽

pp. 573-578 ◽

Cited By ~ 49

Author(s):

V. A. Nicely ◽

J. T. Dougherty ◽

L. W. Renfro

Keyword(s):

Phase Diagram ◽

Ethylene Terephthalate ◽

Poly Ethylene Terephthalate ◽

Sequence Distributions ◽

Poly Ethylene

Cationic copolymers of isobutylene. 7. Reactivity ratio determination by sequence distributions obtained through NMR analysis

Macromolecules ◽

10.1021/ma00131a007 ◽

1984 ◽

Vol 17 (1) ◽

pp. 37-41 ◽

Cited By ~ 9

Author(s):

Carlo Corno ◽

Aldo Priola ◽

G. Spallanzani ◽

Sebastiano Cesca

Keyword(s):

Reactivity Ratio ◽

Nmr Analysis ◽

Ratio Determination ◽

Cationic Copolymers ◽

Sequence Distributions

NMR analysis of poly(ethylene naphthalate) + poly(butylene terephthalate) blends

Materials Research Innovations ◽

10.1007/s10019-003-0249-z ◽

2003 ◽

Vol 7 (5) ◽

pp. 269-274 ◽

Cited By ~ 2

Author(s):

Dylan Dae Bong Jung ◽

Allan J. Easteal ◽

Debes Bhattacharyya

Keyword(s):

Nmr Analysis ◽

Butylene Terephthalate ◽

Poly Ethylene

Sequence distributions versus catalyst site behavior of in situ blends of polypropylene and poly(ethylene-co-propylene)

Journal of Polymer Science Part A Polymer Chemistry ◽

10.1002/(sici)1099-0518(19980730)36:10<1527::aid-pola6>3.0.co;2-n ◽

1998 ◽

Vol 36 (10) ◽

pp. 1527-1542 ◽

Cited By ~ 26

Author(s):

J. C. Randall

Keyword(s):

Sequence Distributions ◽

Poly Ethylene

Infrared Determination of Composition of Ethylene-Propylene Copolymers

Rubber Chemistry and Technology ◽

10.5254/1.3547379 ◽

1971 ◽

Vol 44 (4) ◽

pp. 1015-1024 ◽

Cited By ~ 12

Author(s):

I. J. Gardner ◽

C. Cozewith ◽

G. Ver Strate

Keyword(s):

Isotope Effects ◽

Catalyst System ◽

Nmr Analysis ◽

Atactic Polypropylene ◽

Ethylene Propylene ◽

Carbon 14 ◽

Sample Composition ◽

System Solution ◽

Sequence Distributions

Abstract Carbon-14 labeled ethylene and propylene were used to synthesize a series of copolymers of known composition to serve as standards for copolymer analyses. Polymers with broad and narrow compositional distributions and differing sequence distributions were produced by varying the catalyst system. Solution and combustion counting techniques were used to determine sample composition and then infrared calibration curves were determined on pressed polymer films utilizing several different infrared peaks. 1. Within the ranges systematically varied neither compositional nor sequence distributions affect the peak ratios studied. 2. No isotope effects exist in the polymerizations. 3. NMR analysis yields the same results as 14C analysis. 4. Use of the 1378 cm−1 methyl band as calibrated with atactic polypropylene yields agreement with the 14C data if the average of polypropylene and copolymer results is used. 5. We amend the results previously published by our laboratory.

NMR analysis and triad sequence distributions of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

Polymer Testing ◽

10.1016/j.polymertesting.2020.106754 ◽

2020 ◽

Vol 90 ◽

pp. 106754

Author(s):

H.N. Cheng ◽

Atanu Biswas ◽

Karl Vermillion ◽

Beatriz Melendez-Rodriguez ◽

Jose Maria Lagaron

Keyword(s):

Nmr Analysis ◽

Sequence Distributions

Quantitative13C NMR Analysis of Lignins with Internal Standards

Journal of Agricultural and Food Chemistry ◽

10.1021/jf010333v ◽

2001 ◽

Vol 49 (8) ◽

pp. 3573-3578 ◽

Cited By ~ 68

Author(s):

Zhicheng Xia ◽

Leonid G. Akim ◽

Dimitris S. Argyropoulos

Keyword(s):

Nmr Analysis ◽

Internal Standards ◽

Quantitative13c Nmr

Quantitative13C NMR analysis of mixtures of 2,4-di-isocyanatotoluene and 2,6-di-isocyanatotoluene

Organic Magnetic Resonance ◽

10.1002/mrc.1270060709 ◽

1974 ◽

Vol 6 (7) ◽

pp. 398-399 ◽

Cited By ~ 13

Author(s):

I. K. O'Neill ◽

M. A. Pringuer

Keyword(s):

Nmr Analysis ◽

Quantitative13c Nmr

The Structure of Radiation Cross-Linked Poly (ethylene oxide) Gels

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100064438 ◽

1971 ◽

Vol 29 ◽

pp. 76-77

Author(s):

C. E. Cluthe ◽

G. G. Cocks

Keyword(s):

Molecular Weight ◽

Ethylene Oxide ◽

Parallel Plate ◽

Average Molecular Weight ◽

Radical Reaction ◽

Free Radical Reaction ◽

Nitrogen Gas ◽

Poly Ethylene Oxide ◽

Poly Ethylene ◽

Initial Viscosity

Aqueous solutions of a 1 weight-per cent poly (ethylene oxide) (PEO) were degassed under vacuum, transferred to a parallel plate viscometer under a nitrogen gas blanket, and exposed to Co60 gamma radiation. The Co60 source was rated at 4000 curies, and the dose ratewas 3.8x105 rads/hr. The poly (ethylene oxide) employed in the irradiations had an initial viscosity average molecular weight of 2.1 x 106.The solutions were gelled by a free radical reaction with dosages ranging from 5x104 rads to 4.8x106 rads.