The production of ethene/propene/5‐ethylidene‐2‐norbornene terpolymers using metallocene catalysts: Polymerization, characterization and properties of the metallocene EPDM

Abstract

Metallocene catalysts Et(Ind) 2 ZrCl 2 /MAO and Et(Ind) 2 H fCl 2 /MAO were used in ethene/propene copolymerization and in ethene/propene/5-ethylidene-2-norbornene (E/P/ENB) terpolymerization. The copolymerization activity of the Et(Ind) 2 ZrCl 2 / MAO system was 20 1 10 3 kg polym /mol Mt * h, the Et(Ind) 2 H fCl 2 /MAO yielding 5 1 10 3 kg polym /mol Mt * h. The polymerization activity decreased with diene addition, but this effect was significant only at very large diene feeds. The catalysts incorporated diene readily. Materials with an ethene content of 55 to 70 mol % and an ENB content of 2 to 16 mol % were produced. Et(Ind) 2 H fCl 2 produced a considerably higher molar mass material than the Et(Ind) 2 ZrCl 2 catalyst. The molar mass distributions were narrow. Copolymers and terpolymers with up to 3 mol % ENB content had some crystallinity. Copolymer T g s were between 059ЊC and 055ЊC. The terpolymer glass transition temperature rose 1.5ЊC per wt % of ENB in the polymer. Polymer characteristics reported include composition, molar mass distribution, melt flow rate, density, and thermal behavior. The dynamic mechanical and rheological properties of the materials in comparison with commercial E/ P/ENB terpolymers are discussed.

Efficient copolymerization of ethylene with norbornene or its derivatives using half-metallocene zirconium(iv) catalysts

“…1,2 The existence of ring strain in the structure of norbornene (NBE) and its derivatives makes them facile polymerizable, thus NBE has become one of the most active participants in ethylene/cyclo-olen copolymerization. 7,[9][10][11][12][13][14][15][16][17][18][19] Catalysts play a crucial role in the production of ethylene/ ENB or ethylene/VNB copolymers, and most of catalysts reported are ansa-metallocenes. As the simplest method of functionalization, copolymerization of olen with polar monomer using early transition metal catalysts is rarely reported because of the highly oxophilic nature of polar monomer.…”

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

“…Ethylene and propylene (E/P) feed ratios of 80/20, 67/33, 50/50, and 33/67 mL/mL, were used in copolymerization process. The activity of the catalyst is reduced with decreased E/P feed ratio, which is a common behavior in a similar polymerization process2, 16 (Table I). The rates of the reaction based on monomer consumptions are presented in Figure 1.…”

“…These catalysts have the ability to allow random distributions of monomers and to provide good control over molecular weight distribution 11–13. The homogeneous metallocene catalysts have been extensively investigated by many researchers 14–16. The studies show that metallocene catalyst exhibits higher activities and higher incorporation rates of termonomers in the polymer without any noticeable side reactions 8, 17–19.…”

Thermal studies on ethylene–vinylcyclohexane copolymers prepared with bis-indenyl type metallocene catalyst systems

“…Earlier studies (47,48) on this type of copolymers, at norbornene Figure 9. Recent work (46) on glass transitions of ethylene-norbornene copolymers demonstrated a small increase in T g with higher comonomer content, in spite of decreasing crystallinity, due to growing incorporation of rigid norbornene chain segments.…”