Synthesis by metallocene/MAO catalyst and functionalization of poly(ethene-co-4-vinylcyclohexene)

Polymerization with TMA-protected polar vinyl comonomers. I. Catalyzed by group 4 metal complexes with ?5-type ligands

“…For instance Mü lhaupt, Duschek, and Rieger, 12 Shiono et al, 13 Marathe and Sivaram, 14 and Kaminsky, Arrowsmith, and Winkelbach 15 obtained polymers with polar functional groups through derivatization of terminal vinylidene group of the homopolymers or pendant vinyl groups of copolymers, but these methods are not relevant to this work.…”

Copolymerization of ethylene and 4-vinylcyclohexene by various metallocenes in the presence of Al(iBu)3/[Ph3C][B(C6F5)4]

“…The lower initial rate results in a slower viscosity change of the polymerization medium so that the decay of R p after reaching its maximum is moderate. The VCH content incorporated in copolymer was determined by 13 C NMR spectroscopy according to the literature [2]. The results are summarized in Tab.…”

“…Recalling that the copolymer represents a blocky character when the product of the two reactivity ratios (r E x r VCH ) is larger than unity, poly(ethylene-co-VCH) copolymers obtained by CAT-2 would appear to be composed of ethylene blocks and VCH distributed randomly. The vinyl double bond in VCH takes part in the homopolymerization, as the endocyclic double bond has little ring strain and large steric hindrance [2,5]. Chien and coworkers [5] investigated the homopolymerization of VCH, vinylcyclohexane and cyclohexene in order to elucidate which unsaturated group is involved in the polymerization reaction, vinyl or endocyclic double bonds, and reported that the polymerization activity of VCH or vinylcyclohexane is 10 times greater than that of cyclohexene.…”

“…Ethylene and/or propylene have been copolymerized with dienes, such as 1,4-hexadiene [1], 4-vinylcyclohexene (VCH) [2], and 5-vinyl-2-norbornene [3]. These dienes are copolymerized with the olefin regioselectively in the presence of a metallocene compound, leaving an unsaturated double bond in the pendant group.…”

“…5-Vinyl-2-norbornene is copolymerized through the endocyclic double bond leaving the vinyl group unreacted, because of the higher ring strain of the endocyclic double bond [3,4]. In case of VCH, vinyl double bonds were reported to take part in the polymerization reaction, as the endocyclic double bond shows little ring strain and large steric hindrance [2,5]. However, no detailed reports have been published to investigate the effect of the metallocene structure on the copolymerization of ethylene and VCH.…”