Citation:
NI Shaoru, SHEN Lianfang, YU Fusheng, QIAN Baogong. CARBON-13 NMR STUDY OF MOLECULAR MOTION OF 1, 2-POLYBUTADIENES IN SOLUTION Ⅰ. STRUCTURE DEPENDENCE
OF MOLECULAR MOTIOM[J]. Chinese Journal of Polymer Science,
1986, 4(1): 8-16.
CARBON-13 NMR STUDY OF MOLECULAR MOTION OF 1, 2-POLYBUTADIENES IN SOLUTION Ⅰ. STRUCTURE DEPENDENCE OF MOLECULAR MOTIOM
摘要:
Proton decoupled, partially relaxed, Fourier-transform 50.3 MHz carbon-13 NMR in natural abundance
was used to determine spin-lattice times (T1) and nuclear Overhauser enhancement
fac-tors (NOE) of individual carbon of a serics of 1,2-polybutadienes with different structures in
solutionin CDCl2. The structure dependence of molecular metion and the internal motion
of vinyl group in 1,2-polybutadiene have been studied by nT1 and NOE values. The
nT1 values of the carbons in cis-1,4-units are the highest and those of
the carbons in 1,2-units are the lowest in three types of units in 1,2-polybutadiene.The
nT1 values of carbons in the same unit become greater when the adjacent 1,2-units
are replaced by 1,4-units,and nT1 values of the carbons in all units decrease
sharply with the increase of content of 1,2-units in the polymers.The fact that
nT1 values of —CH=are larger than those of =CH2 in vinyl group
implies that there are complex internal motions of vinyl group.It is shown by calculation that the
dominant factor causing the difference in nT1 of—CH=and=CH2 in vinyl
group is a swing of vinyl group in a plane perpendicular to the chain backbone.
English
CARBON-13 NMR STUDY OF MOLECULAR MOTION OF 1, 2-POLYBUTADIENES IN SOLUTION Ⅰ. STRUCTURE DEPENDENCE OF MOLECULAR MOTIOM
Abstract:
Proton decoupled, partially relaxed, Fourier-transform 50.3 MHz carbon-13 NMR in natural abundance
was used to determine spin-lattice times (T1) and nuclear Overhauser enhancement
fac-tors (NOE) of individual carbon of a serics of 1,2-polybutadienes with different structures in
solutionin CDCl2. The structure dependence of molecular metion and the internal motion
of vinyl group in 1,2-polybutadiene have been studied by nT1 and NOE values. The
nT1 values of the carbons in cis-1,4-units are the highest and those of
the carbons in 1,2-units are the lowest in three types of units in 1,2-polybutadiene.The
nT1 values of carbons in the same unit become greater when the adjacent 1,2-units
are replaced by 1,4-units,and nT1 values of the carbons in all units decrease
sharply with the increase of content of 1,2-units in the polymers.The fact that
nT1 values of —CH=are larger than those of =CH2 in vinyl group
implies that there are complex internal motions of vinyl group.It is shown by calculation that the
dominant factor causing the difference in nT1 of—CH=and=CH2 in vinyl
group is a swing of vinyl group in a plane perpendicular to the chain backbone.
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