Syndiospecific oligomerization and polymerization of norbornene with titanium catalysts

Ricci, Giovanni; Leone, Giuseppe; Rapallo, Arnaldo; Biagini, Paolo; Guglielmetti, Gianfranco; Porri, L.

doi:10.1016/j.polymer.2011.10.029

Cited by 12 publications

(11 citation statements)

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“…The chemical shifts due to the aromatic ring carbons can be detected in the region from 123.5 to 127.5 ppm [10,23], while the resonance peaks from 45.0 to 53.0 ppm are due to the cyclic chain methine carbons. The peaks in the regions of 35.0-38.0 ppm and 33.0-35.0 ppm can be assigned to the secondary carbon resonances of the cyclic chain methylene carbons, while those in the region of 28.2-33.0 ppm can be assigned to the ethylene units [21,[23][24][25]. The chemical shifts in the range of 36.0-54.0 ppm overlap those of poly(Ind) and Ind-copolymer with slight differences and small shifts depending on the type of C-C bond.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of hydrocarbon polymers by cationic polymerization and their thermal properties

Brum

Laux

Forte

2012

Designed Monomers and Polymers

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Cationic homo-and co-polymerization of indene (Ind), styrene (St), limonene (Lim), and 5-ethylidene-2-norbornene (ENB) was performed with AlCl 3 in dichloroethane at À20°C under inert N 2 . The aim of this work is to investigate the effect of the reaction conditions on the molecular weight of polyindene (PInd) obtained by cationic polymerization with AlCl 3 without an electron donor, and also to determine the effect of the use of cyclic diolefin comonomers on the polymer properties. The polymers were synthesized at a monomer/catalyst molar ratio (MR) of 100; St and Lim showed the highest and lowest reactivity, respectively. The polymers were characterized by 13 C and 1 H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, size exclusion chromatography, differential scanning calorimetry, and thermogravimetric analysis. PInd with a number average molecular weight (M n ) of 45 Â 10 3 g/mol and a glass transition temperature (T g ) of 207°C was obtained, whereas only oligomeric polylimonenes were obtained. Cyclic diolefins depressed both the M n and T g values of the Ind-copolymers. There was a dramatic decrease in the M n of the polymers: those obtained at a MR of 1:1 in the feed presented M n values lower than 10 4 g/mol, with the exception of poly(Ind-co-ENB), which is cross-linked. Poly(Ind-co-Lim) with lateral double bonds, a comonomer content of 1 to 20 mol%, and T g values in the range of 140-200°C were obtained.

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Section: Resultsmentioning

confidence: 99%

Synthesis of hydrocarbon polymers by cationic polymerization and their thermal properties

Brum

Laux

Forte

2012

Designed Monomers and Polymers

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“…[37] Sen and co-workers studied the addition polymerization of functionally substituted NBs and they found that the endo isomers were polymerized more slowly with respect to the exo analogues because of the coordination of the donor atom to the transition metal ( Figure 2). [38,39] Inspired by the discovery of Porri and co-workers, [34][35][36] in this work we report on the oligomerization of DCPD (mixture of endo and exo isomers), of the partially saturated dihydrodicyclopentadiene (H-DCPD) and, separately, of the endo and exo isomer catalyzed by TiCl 4 /Et 2 AlCl. Oligomers consisting of 2,3-enchained units were obtained.…”

Section: Introductionmentioning

confidence: 94%

“…Inspired by the discovery of Porri and co‐workers, in this work we report on the oligomerization of DCPD (mixture of endo and exo isomers), of the partially saturated dihydrodicyclopentadiene (H‐DCPD) and, separately, of the endo and exo isomer catalyzed by TiCl 4 /Et 2 AlCl. Oligomers consisting of 2,3‐enchained units were obtained.…”

Section: Introductionmentioning

confidence: 99%

“…[2][3][4][5][6][7] In general, analogously to norbornene (NB), the polymerization of DCPD can follow three pathways: (i) ring opening metathesis (2 of 8) 1600602 decomposition temperatures, high plasma etch resistance, good transparency for short wavelength radiation, and small optical birefringence, making them of potential interest for flexible flat panel displays, microelectric and microfluidic devices. [31][32][33] Moreover, Porri and coworkers found that naked TiCl 4 complex (naked because the metal is only surrounded by the growing polymer chain, the new incoming monomer, the chlorine atom, and the weakly coordinating anion, with no ancillary ligands) in combination with an aluminum alkyl gave a crystalline heptamer from NB, [34,35] and a crystalline polymer having a 2,3-exo disyndiotactic structure with an unique helical conformation, forming an empty accessible tubular channel at the core, depending on the NB/Ti ratio. [36] This structural feature made the polymer also of particular interest for porous materials in sensing and recognition/separation technologies.…”

Section: Introductionmentioning

confidence: 99%

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Addition Oligomerization of Dicyclopentadiene: Reactivity of Endo and Exo Isomers and Postmodification

Zanchin

Leone

Pierro

et al. 2017

Macromol. Chem. Phys.

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The oligomerization of dicyclopentadiene (DCPD, mixture of endo and exo isomers), 9,10‐dihydrodicyclopentadiene (H‐DCPD), exo‐DCPD, and endo‐DCPD catalyzed by TiCl4/Et2AlCl is studied. Oligomers containing 2,3‐enchained units are obtained in good yields. The endo‐DCPD is less reactive than the exo isomer, exhibiting a reactivity comparable with that of the partially saturated H‐DCPD. While all the products obtained from the oligomerization of the exo isomer and H‐DCPD are amorphous, from the endo isomer, at low DCPD/Ti ratio, a crystalline, stereoregular tetramer having a 2,3‐exo‐disyndiotactic structure is obtained. The results show that the presence of the double bond in the cyclopentene ring, the spatial disposition of the cyclopentene, and the oligomerization conditions play a fundamental role to give a unique crystalline material. Hydrogenation and epoxidation of the obtained products are reported as well.

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“…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%

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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Syndiospecific oligomerization and polymerization of norbornene with titanium catalysts

Cited by 12 publications

References 50 publications

Synthesis of hydrocarbon polymers by cationic polymerization and their thermal properties

Synthesis of hydrocarbon polymers by cationic polymerization and their thermal properties

Addition Oligomerization of Dicyclopentadiene: Reactivity of Endo and Exo Isomers and Postmodification

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

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