Catalyst behaviour for 1-pentene and 4-methyl-1-pentene polymerisation for C2-, Cs- and C1-symmetric zirconocenes

Descour, Camille; Duchateau, Robbert; Mosia, Mamoeletsi R.; Gruter, Gert Jan M.; Severn, John R.; Rastogi, Sanjay

doi:10.1039/c1py00257k

Cited by 9 publications

(19 citation statements)

References 96 publications

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“…The melting point strongly depends on the type of monomer. In general, polymers from linear higher α‐olefins possess much lower melting points than polypropylene . Polymers of branched α‐olefins possess higher melting points.…”

Section: Methodsmentioning

confidence: 99%

Syndiotactic Polymer of Allylcyclopentane by a Metallocene Catalyst

2016

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Syndiospecific (co)polymerization of some higher α‐olefins was performed by using a metallocene catalyst. Homopolymers of allylcyclopentane, 4‐methyl‐1‐pentene, and allylcyclohexane are highly syndiotactic. The results of the copolymerization of allylcyclopentane with 1‐hexene, 1‐octene, or 1‐decene showed that the incorporation of a linear higher α‐olefin interfered with the syndiospecificity of the catalyst, and the melting point of the resulting copolymer decreased with the incorporation of the comonomer. In contrast, the copolymer of allylcyclopentane with 4‐methyl‐1‐pentene or allylcyclohexane maintained the high syndiotacticity, and the melting point also remained almost unchanged no matter how much the comonomer was incorporated. It followed that the “shape” of the monomer had a significant influence on the structure of the copolymer. The monomers employed in copolymerization with a similar “shape” gave a copolymer with a similar microstructure.

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Section: Methodsmentioning

confidence: 99%

Syndiotactic Polymer of Allylcyclopentane by a Metallocene Catalyst

2016

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“…Five main peaks were observed in δ = 46.2, 42.7, 31.5, 26.0, 23.7 ppm, corresponding to the five carbon atoms of 4M1P [24]. 13 C-NMR spectrum of sample 4 was also shown in Figure 1.…”

Section: Thementioning

confidence: 99%

“…By using the similar calculation method, the incorporation of 4P1O of sample 8 was found as 1.2 mol%. The melting point (T m ) of the homopolymer of 4M1P produced at 25°C was determined as 222°C, and higher polymerization temperature gave a poly- [24]. T m s of the copolymer of 4M1P with 9D1O were lower than that of the homopolymer of 4M1P, and when the feeding amount of 9D1O increased, T m decreased (see Figure 2).…”

Section: Thementioning

confidence: 99%

“…On the other hand, incorporation of comonomers would interrupt the successive insertion of the crystallizable monomer unit, resulting in the decreased melting point and the inhomogeneity of the crystallizable segment. The multiple melting endotherm in the DSC curve could be attributed to the process of melting, recrystallization and remelting: metastable crystallites are recrystallized into a more perfect form following the initial melting [24,32]. While the T m s of the copolymers of 4M1P and 9D1O were lower than that of the homopolymer of 4M1P, and decreased with the increase of the 9D1O incorporation, it was surprisingly found that the T m of the copolymer of 4M1P with 4P1O was almost equal to or a little bit higher than that of the homopolymer of 4M1P.…”

Section: Thementioning

confidence: 99%

“…Studies on the polymerization of higher α-olefin have drawn considerable attention for long years. Polymerization of either linear or branched α-olefin has been fully explored by using various catalyst systems, including the traditional Ziegler-Natta catalyst [19,20], metallocene catalyst [21][22][23][24], non-metallocene single-site catalyst [25] and later transition metal catalyst [26,27]. Properties of poly(α-olefin) could be improved by incorporating the second monomer with a functional group, but the successful examples were limited so far [28,29].…”

Section: Introductionmentioning

confidence: 99%

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Copolymerization of 4-methyl-1-pentene with α,ω-alkenols

Wang¹,

Hou²,

Sheng³

et al. 2016

Express Polym. Lett.

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Abstract. Copolymerization of 4-methyl-1-pentene (4M1P) with 9-decen-1-ol (9D1O) or 4-penten-1-ol (4P1O) was conducted by using metallocene catalysts. The activity could be improved under the higher polymerization temperature. The dyad distribution of poly(4M1P-co-4P1O) was presented. The results showed that 4P1O was uniformly distributed in the copolymer chain. The melting temperature (T m ) of the copolymer was lower than that of poly(4M1P), and was decreased with the increase of the incorporation of comonomer. T m of poly(4M1P-co-4P1O) was determined as 185°C, even the incorporation of 4P1O was high as 15.0 mol%. WAXD (wide-angle X-ray diffraction) results showed that the poly(4M1P) was observed as crystalline form II, and turned to form I when the incorporation of α,ω-alkenols were high. Some new peaks, which were never observed in the previous researches, appeared in the X-ray diffraction profiles for poly(4M1P-co-4P1O). It is inferred that the similar chain length of 4P1O and 4M1P may be the key factor.

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Stereomodulation of Poly(4‐methyl‐1‐pentene): Adoption of a Neglected and Misunderstood Commercial Polyolefin

2022

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A toolbox of living coordination polymerization methods based on CPAM group 4 metal initiators has been applied for the stereomodulation of poly(4‐methyl‐1‐pentene) (PMP) tacticity to provide new fundamental forms in which thermal phase transitions, Tg and Tm, can be adjusted over a wide range. Also reported for the first time are the synthesis and properties of authenticated 1,2‐regioregular atactic PMP, which serves to correct past errors regarding this fundamental polyolefin.

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Catalyst behaviour for 1-pentene and 4-methyl-1-pentene polymerisation for C2-, Cs- and C1-symmetric zirconocenes

Cited by 9 publications

References 96 publications

Syndiotactic Polymer of Allylcyclopentane by a Metallocene Catalyst

Syndiotactic Polymer of Allylcyclopentane by a Metallocene Catalyst

Copolymerization of 4-methyl-1-pentene with α,ω-alkenols

Stereomodulation of Poly(4‐methyl‐1‐pentene): Adoption of a Neglected and Misunderstood Commercial Polyolefin

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