Abstract: | Poly(vinyl chloride) pendant with polysulfide (PS–PVC) having various degrees of substitution, various S substituents, and various numbers of atoms in the sulfur chain has been synthesized by the reaction of poly(vinyl chloride) with a thiol, sulfur, and triethylamine in dimethylformamide at 30°C for 0.4–5 hr. The photocrosslinking reaction has been investigated under ultraviolet irradiation at 250–450 mμ. The photocrosslinking reaction of PS–PVC is influenced by the degree of substitution, the nature of the S substituent, and the number of atoms in the sulfur chain. The degree of photocrosslinking r increased in the order, n-C4H9? < n-C8H17? < C6H5CH2? < i-C3H7? < t-C4H9? . On the photocrosslinking of PS–PVC having two different S substituents, r increases in the similar order for aliphatic substituents and in the order NO2C6H4? < ClC6H4? < C6H5CH2? < CH3C6H4? < t-C4H9C6H4? < C6H5? for the aromatic substituents. Further, r increases markedly with the increase of sulfur chain number for all PS–PVC. The chemical structure of the crosslinks and the crosslinking mechanism are discussed on the basis of the results. |