Polymerization of 1,3-cyclohexadiene with nickel/MAO catalytic systems

Anionic Polymerization of Cyclohexa‐1,3‐diene in Cyclohexane with High Stereoregularity and the Formation of Crystalline Poly(cyclohexa‐1,3‐diene)

“…The DSC trace (Figure 2) of the insoluble PCHD with calculated number‐average molecular weight of 3 000 showed an endothermic peak at 178 °C (enthalpy = 15.45 J · g −1 ) and a glass transition temperature at 80 °C. The melting temperatures for highly crystalline PCHDs formed using transition metal catalysts were reported to be about 32029 and 315 °C,30 which are close to their decomposition temperature. The reason why the melting temperature (178 °C) of the anionically prepared PCHD is lower than those results might be because of the lower regularity (only 76% cis planomer) that would lead to lower crystallinity.…”

“…Crystalline PCHD has been made with nickel catalysts such as the π ‐allyl complex of nickel,28 Ni(acac) 2 ‐MAO (acac = acetylacetone, MAO = methylaluminoxane),29 Cp 2 Ni‐MAO (Cp = cyclopentadienyl),30 bis(allylnickel bromide/MAO),31 and bis[(allyl)trifluoroacetatonickel( II )]32 catalytic systems. The X‐ray powder diffraction profile of crystalline PCHD prepared from Cp 2 Ni‐MAO showed three crystalline peaks, positioned at 2 θ values of 16.6, 19.6 and 22.5°,30 which are very close to the results reported herein for the insoluble PCHD fraction.…”

Anionic Polymerization of Cyclohexa‐1,3‐diene in Cyclohexane with High Stereoregularity and the Formation of Crystalline Poly(cyclohexa‐1,3‐diene)

“…The DSC trace (Figure 2) of the insoluble PCHD with calculated number‐average molecular weight of 3 000 showed an endothermic peak at 178 °C (enthalpy = 15.45 J · g −1 ) and a glass transition temperature at 80 °C. The melting temperatures for highly crystalline PCHDs formed using transition metal catalysts were reported to be about 32029 and 315 °C,30 which are close to their decomposition temperature. The reason why the melting temperature (178 °C) of the anionically prepared PCHD is lower than those results might be because of the lower regularity (only 76% cis planomer) that would lead to lower crystallinity.…”

“…Crystalline PCHD has been made with nickel catalysts such as the π ‐allyl complex of nickel,28 Ni(acac) 2 ‐MAO (acac = acetylacetone, MAO = methylaluminoxane),29 Cp 2 Ni‐MAO (Cp = cyclopentadienyl),30 bis(allylnickel bromide/MAO),31 and bis[(allyl)trifluoroacetatonickel( II )]32 catalytic systems. The X‐ray powder diffraction profile of crystalline PCHD prepared from Cp 2 Ni‐MAO showed three crystalline peaks, positioned at 2 θ values of 16.6, 19.6 and 22.5°,30 which are very close to the results reported herein for the insoluble PCHD fraction.…”

Catalytic 1,3‐Cyclohexadiene Homopolymerization and Regioselective Copolymerization with Ethylene

“…[12,21] DMN (2) and DCN (3) show lower activities, which could result from their higher steric hindrance at the catalytically active center. In comparison to the Brookhart type catalyst 2 the camphor-derived diimine complex 3 was four to five times more active, despite a lower polymerization temperature.…”

How well can renewable resources mimic commodity monomers and polymers?

“…Anionic, free-radical, and transition metal catalyzed polymerizations are common methods for polymerizing 1,3-CHD. [90][91][92][93][94][95] Anionic polymerization methods result in microstructures with 1,2 and 1,4-linkages whereas certain metal-based catalysts can produce predominately 1,4-linkages. The presence of 1,4-sequences in the polymer can serve as a precursor to polyparaphenylene.…”

Anionic Polymerization of Cyclohexa‐1,3‐diene in Cyclohexane with High Stereoregularity and the Formation of Crystalline Poly(cyclohexa‐1,3‐diene)

“…The DSC trace (Figure 2) of the insoluble PCHD with calculated number‐average molecular weight of 3 000 showed an endothermic peak at 178 °C (enthalpy = 15.45 J · g −1 ) and a glass transition temperature at 80 °C. The melting temperatures for highly crystalline PCHDs formed using transition metal catalysts were reported to be about 32029 and 315 °C,30 which are close to their decomposition temperature. The reason why the melting temperature (178 °C) of the anionically prepared PCHD is lower than those results might be because of the lower regularity (only 76% cis planomer) that would lead to lower crystallinity.…”

“…Crystalline PCHD has been made with nickel catalysts such as the π ‐allyl complex of nickel,28 Ni(acac) 2 ‐MAO (acac = acetylacetone, MAO = methylaluminoxane),29 Cp 2 Ni‐MAO (Cp = cyclopentadienyl),30 bis(allylnickel bromide/MAO),31 and bis[(allyl)trifluoroacetatonickel( II )]32 catalytic systems. The X‐ray powder diffraction profile of crystalline PCHD prepared from Cp 2 Ni‐MAO showed three crystalline peaks, positioned at 2 θ values of 16.6, 19.6 and 22.5°,30 which are very close to the results reported herein for the insoluble PCHD fraction.…”

Catalytic 1,3‐Cyclohexadiene Homopolymerization and Regioselective Copolymerization with Ethylene

“…[12,21] DMN (2) and DCN (3) show lower activities, which could result from their higher steric hindrance at the catalytically active center. In comparison to the Brookhart type catalyst 2 the camphor-derived diimine complex 3 was four to five times more active, despite a lower polymerization temperature.…”

How well can renewable resources mimic commodity monomers and polymers?

“…Anionic, free-radical, and transition metal catalyzed polymerizations are common methods for polymerizing 1,3-CHD. [90][91][92][93][94][95] Anionic polymerization methods result in microstructures with 1,2 and 1,4-linkages whereas certain metal-based catalysts can produce predominately 1,4-linkages. The presence of 1,4-sequences in the polymer can serve as a precursor to polyparaphenylene.…”

Anionic Polymerization of Cyclohexa‐1,3‐diene in Cyclohexane with High Stereoregularity and the Formation of Crystalline Poly(cyclohexa‐1,3‐diene)

“…The DSC trace (Figure 2) of the insoluble PCHD with calculated number‐average molecular weight of 3 000 showed an endothermic peak at 178 °C (enthalpy = 15.45 J · g −1 ) and a glass transition temperature at 80 °C. The melting temperatures for highly crystalline PCHDs formed using transition metal catalysts were reported to be about 32029 and 315 °C,30 which are close to their decomposition temperature. The reason why the melting temperature (178 °C) of the anionically prepared PCHD is lower than those results might be because of the lower regularity (only 76% cis planomer) that would lead to lower crystallinity.…”

“…Crystalline PCHD has been made with nickel catalysts such as the π ‐allyl complex of nickel,28 Ni(acac) 2 ‐MAO (acac = acetylacetone, MAO = methylaluminoxane),29 Cp 2 Ni‐MAO (Cp = cyclopentadienyl),30 bis(allylnickel bromide/MAO),31 and bis[(allyl)trifluoroacetatonickel( II )]32 catalytic systems. The X‐ray powder diffraction profile of crystalline PCHD prepared from Cp 2 Ni‐MAO showed three crystalline peaks, positioned at 2 θ values of 16.6, 19.6 and 22.5°,30 which are very close to the results reported herein for the insoluble PCHD fraction.…”

Catalytic 1,3‐Cyclohexadiene Homopolymerization and Regioselective Copolymerization with Ethylene

“…[12,21] DMN (2) and DCN (3) show lower activities, which could result from their higher steric hindrance at the catalytically active center. In comparison to the Brookhart type catalyst 2 the camphor-derived diimine complex 3 was four to five times more active, despite a lower polymerization temperature.…”

How well can renewable resources mimic commodity monomers and polymers?

“…Anionic, free-radical, and transition metal catalyzed polymerizations are common methods for polymerizing 1,3-CHD. [90][91][92][93][94][95] Anionic polymerization methods result in microstructures with 1,2 and 1,4-linkages whereas certain metal-based catalysts can produce predominately 1,4-linkages. The presence of 1,4-sequences in the polymer can serve as a precursor to polyparaphenylene.…”