Gel formation in cationic polymerization of divinyl ethers. I. 1,4-Bis(2-vinyloxyethoxy)benzene

Copolymerization of Silyl Vinyl Ethers with Olefins by (α-diimine)PdR+

“…Very similar polymers are generated by the reaction of 1a with [Ph 3 C][B(C 6 F 5 ) 4 ] or [Li(Et 2 O) 2.8 ][B(C 6 F 5 ) 4 ]. These results are consistent with a cationic polymerization mechanism . Addition of 2,6- t Bu 2 -pyridine does not significantly affect the polymerization of 1a by (α-diimine)PdMe + , which suggests that (α-diimine)PdR + species may play a direct role in initiation.…”

Cationic Polymerization and Insertion Chemistry in the Reactions of Vinyl Ethers with (α-Diimine)PdMe+Species

“…These −[CH 2 CH(O t Bu)] n − polymers are atactic (mm/mr/rr = 1:3:1) and contain methyl (−CH(O t Bu)C H 3 ), aldehyde (−CH 2 C(O) H ), and acetal (−C H (O t Bu) 2 ) end groups and internal −CHCH− units (ca. 3 mol %) . These features are characteristic of a cationic polymerization process. ,,, Interestingly, rapid formation of Pd 0 was observed during the polymerization of 2a .…”

“…3 mol %) . These features are characteristic of a cationic polymerization process. ,,, Interestingly, rapid formation of Pd 0 was observed during the polymerization of 2a . The reaction of 1 [B(C 6 F 5 ) 4 ] with excess 2b at 20 °C is similar.…”

Gel formation in cationic polymerization of divinyl ethers. III. Effect of oligooxyethylene chain versus oligomethylene chain as central spacer units

“…In our previous works, we polymerized 1,4‐bis[2‐(vinyloxy)ethoxy]benzene (CH 2 CHOCH 2 CH 2 OC 6 H 4 OCH 2 CH 2 OCHCH 2 )5 and 2,2‐bis{4‐[2‐(vinyloxy)ethoxy]phenyl}propane (CH 2 CHOCH 2 CH 2 OC 6 H 4 C(CH 3 ) 2 C 6 H 4 OCH 2 CH 2 OCHCH 2 )6 in CH 2 Cl 2 at 0 °C with the (C 6 H 5 O) 2 P(O)OH/ZnCl 2 initiating system and observed the formation of soluble polymers that lack residual unreacted vinyl groups. Although the initiator used and polymerization temperature are different, the formation of the soluble poly(divinyl ether)s with almost no unreacted vinyl groups was also observed in the present study for the polymerizations of O‐3 , O‐4 , O‐5 , O‐6 , and O‐8 .…”