Monomer‐isomerization polymerization. XXIII.. Monomer‐isomerization polymerization of 5‐phenyl‐2‐pentene with ziegler–natta catalysts

Endo, Kiyoshi; Tsujikawa, Hajime; Otsu, Takayuki

doi:10.1002/pola.1986.080240721

Cited by 9 publications

(2 citation statements)

References 14 publications

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“…The purities determined by gas chromatography were 99,8,99,7 and 99,0070, respectively. Alkylaluminium compounds, hydrogen-activated titanium trichloride and nickel chloride (commercially available reagents) were used without further purification.…”

Section: Experimental Partmentioning

confidence: 97%

Monomer‐isomerization polymerization, 35. Kinetics of monomer‐isomerization polymerization of 2‐butene with Ziegler‐Natta catalyst

1992

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The kinetics of monomer-isomerization polymerizations of cis-2-butene with TiCI3/AI(C2H,), catalysts in the presence and absence of NiCI, was studied. Both the rate of isomerization and polymerization increased as a function of the concentrations of the monomer and catalyst. The apparent activation energies for the polymerization with TiCl,/AI(C,H,), and with TiC13/NiC12/AI(C,H,), were estimated to be 25,6 and 17,2 kJ/mol, respectively. This difference in the apparent activation energy for monomer-isomerization polymerization may be accounted for by the rates of isomerization to 1-butene. The reaction constants for the isomerization and polymerization were evaluated by simulation. The rate of polymerization with the TiCI,/AI(C,H,), catalyst was found to be about 40 times higher than that of isomerization, and in the presence of NiCI, both rates become similar. From product analysis produced with TiCI, and alkylaluminium compounds, it is concluded that the active sites for isomerization involve Ti2+ complexes and those for the polymerization involve Ti3+ complexes.

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Section: Experimental Partmentioning

confidence: 97%

Monomer‐isomerization polymerization, 35. Kinetics of monomer‐isomerization polymerization of 2‐butene with Ziegler‐Natta catalyst

1992

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“…However, this catalyst did not induce the isomerization of olefins. 11 Hence, it is clear that the active sites for isomerization involve Ti 2 + -H bonds produced by the intramolecular /J-hydrogen elimination of rr-alkyltitanium complexes, and polymerization sites are different from isomerization sites.…”

Section: Hydride Source For Formation Of Ti-h Bondmentioning

confidence: 99%

Monomer-Isomerization Polymerization XXXIV. Active Sites for Isomerization in Monomer-Isomerization Polymerization of 2-Butene with Ziegler-Natta Catalyst

Endo

Ueda

Otsu

1991

Polym J

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ABSTRACT:Monomer-isomerization polymerization of cis-2-butene (c2B) with Ziegler-Natta catalysts was investigated to clarify the isomerization mechanism. With the TiCl3-(C2H 5)sAI catalyst, the isomerization of c2B to I-butene (18) and trans-2-butene (t2B) was determined as 42.7 and 52.8 kJ mo!-1 , respectively; i.e., the activation energy for geometric isomerization was higher than that for the positional one. From the effects of alkylaluminums on the monomer-isomerization polymerization of c2B and analysis of gaseous materials produced from the catalyst components, isomerization was concluded via a o--alkylmetal complexes formed by the insertion of c2B into the Ti 2 + -H bond produced from the catalyst components.

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Monomer‐isomerization polymerization, 27. Monomer‐isomerization in competition with polymerization of α‐olefins with Ziegler‐Natta catalysts

Endo

Otsu

1991

Makromol. Chem.

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The monomer-isomerization was studied in the polymerization of a-olefins with the catalytic systems TiCl,/(C,H,),AI and Ti (OC,H,)4/(C2H,)3Al. The isomerization to the corresponding olefins with internal double bond was found to occur during the polymerization. With the system TiCI,/(C2H,),Al only a small amount of isomerized olefin was produced as result of the rapid polymerization of the a-olefins. Significant isomerization was observed to take place with a poor polymerization catalyst such as Ti (OC4H9)4/(C,H5)3Al. Isomerization and polymerization of a-olefins with Ziegler-Natta catalysts were found to depend on the oxidation state of titanium.

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Monomer‐isomerization polymerization. XXIII.. Monomer‐isomerization polymerization of 5‐phenyl‐2‐pentene with ziegler–natta catalysts

Cited by 9 publications

References 14 publications

Monomer‐isomerization polymerization, 35. Kinetics of monomer‐isomerization polymerization of 2‐butene with Ziegler‐Natta catalyst

Monomer‐isomerization polymerization, 35. Kinetics of monomer‐isomerization polymerization of 2‐butene with Ziegler‐Natta catalyst

Monomer-Isomerization Polymerization XXXIV. Active Sites for Isomerization in Monomer-Isomerization Polymerization of 2-Butene with Ziegler-Natta Catalyst

Monomer‐isomerization polymerization, 27. Monomer‐isomerization in competition with polymerization of α‐olefins with Ziegler‐Natta catalysts

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