The improved mean-square radius of gyration and dipole moment of polymers with dipole substitutes are deduced by the rotational-isomeric-state model and the generator matrix method

and used to investigate the configuration-conformation dependent property of poly(vinyl halides)

including the relation of them with the conformational energy

the chain tacticity and temperature. It is found that the differences of characteristic ratios

the temperature coefficients and conformational energy dependent property for stereo-regular poly(vinyl halides) polymers are obvious

especially for the isotactic and syndiotactic chains. The differentiates of the dipole ratios with respect to the first conformational energy E of the syndiotactic poly(vinyl halides) are in -0.62~0.05 (J/mol)-1 for instance. However

the unperturbed dimensions of stereo-irregular poly(vinyl halides) chains are rather close to each other. The dipole characteristic ratios of atactic poly(vinyl fluoride)

poly(vinyl chloride) and poly(vinyl bromide) are obtained to be 0.80

0.69 and 0.59

respectively

and their temperature coefficients are -0.0710-3~-0.5310-3K-1

which are in agreement with the experiment dada. The results show that the effect of monomer property and configuration on the flexibility and dipole properties of poly(vinyl halides) is remarkable.