Homogeneous polymerization of p-diethynylbenzene initiated by nickel acetylide Ni(C ≡ C C6H4 C ≡ CH)2(PPh3)2has been investigated in terms of different solvents
addition agents
atmosphere gases
catalyst concentrations
monomerconcentrations and polymerization temperatures. The yield and catalytic efficiency approach 88% and 11. 1 kg polymer/molNi
respectively
under the optimum conditions: [cat] = 0.01 mol/L
[M] = 1.0 mol/L
NEt3/cat (mol ratio) = 3~5
1
4-dioxane/toluene (volume ratio) = 1 and T =25℃ for 5 h.The polymerization rate equation can be expressed as Rp=kp[M][cat]2
where kp=0.47 L2·mol-2·S-1(25℃).The overall polymerization activation energy was found to be 203 KJ·mol-.Poly(p-diethynylbenzene)so obtained is soluble in THF
CHCl3 and toluene with weight-average molecular weights as high as 27
100 and a rich-trans extended π-conjugated polyene chain structure with pendent groups of p-C6H4C=CH.
Abstract
Homogeneous polymerization of p-diethynylbenzene initiated by nickel acetylide Ni(C ≡ C C6H4 C ≡ CH)2(PPh3)2has been investigated in terms of different solvents
addition agents
atmosphere gases
catalyst concentrations
monomerconcentrations and polymerization temperatures. The yield and catalytic efficiency approach 88% and 11. 1 kg polymer/molNi
respectively
under the optimum conditions: [cat] = 0.01 mol/L
[M] = 1.0 mol/L
NEt3/cat (mol ratio) = 3~5
1
4-dioxane/toluene (volume ratio) = 1 and T =25℃ for 5 h.The polymerization rate equation can be expressed as Rp=kp[M][cat]2
where kp=0.47 L2·mol-2·S-1(25℃).The overall polymerization activation energy was found to be 203 KJ·mol-.Poly(p-diethynylbenzene)so obtained is soluble in THF
CHCl3 and toluene with weight-average molecular weights as high as 27
100 and a rich-trans extended π-conjugated polyene chain structure with pendent groups of p-C6H4C=CH.
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