Ethylene copolymers with Fischer-Tropsch olefins

Joubert, Dawie

doi:10.1002/1521-3900(200202)178:1<69::aid-masy69>3.0.co;2-s

Cited by 9 publications

(11 citation statements)

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“…EO copolymers show higher T m at similar densities as compared to EH copolymers. This observation was also made by Joubert and Tincul who came to the conclusion that the higher 1‐olefins are generally more effective at decreasing density. In the present study, this observation is only made at higher comonomer contents.…”

Section: Resultssupporting

confidence: 67%

“…1‐octene is the comonomer of choice in the manufacture of LLDPEs as it gives a mechanically better product as compared to other even‐numbered 1‐olefins. Considering the high demand of 1‐olefins for LLDPE production and the recently observed global shortage of 1‐octene, odd numbered Fischer‐Tropsch‐derived 1‐olefins such as 1‐pentene and 1‐heptene can be interesting alternatives to 1‐hexene and 1‐octene, respectively. Furthermore, the microstructures of LLDPEs made from the odd‐numbered 1‐olefins may be closely related to those made from even‐numbered 1‐olefins of comparable molar mass.…”

Section: Introductionmentioning

confidence: 99%

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Ethylene/1‐heptene copolymers as interesting alternatives to 1‐octene‐based LLDPE: Molecular structure and physical properties

Ndiripo

Joubert

Pasch

2015

J. Polym. Sci. Part A: Polym. Chem.

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Classical linear low density polyethylenes (LLDPEs) are copolymers of ethylene and 1-octene or 1-hexene, respectively. In the past, other 1-olefins have been tested as comonomers but the resulting LLDPEs were never commercialized as large scale products. The present study focuses on the use of 1-heptene as an interesting comonomer for the synthesis of LLDPE. For a comparison of the molecular structure and the physical properties of 1-heptene-and 1-octene-based LLDPEs, five Ziegler-Natta LLDPEs of varying comonomer contents based on 1-heptene and 1-octene, respectively, were acquired and analysed using advanced methods. The comonomer contents of the resins were between 0.35 and 6.4 mol %. Crystallization-based techniques revealed similar bimodal distributions that are due to the formation of copolymer and polyethylene homopolymer fractions. The compositional distribution of the copolymers was studied by high-temperature (HT) HPLC and HT-2D-LC. The analytical results indicate similar chemical heterogeneities and molar mass distributions of the two sets of LLDPE up to a comonomer content of 3 mol %. Similar to the molecular structure, the physical properties of the materials are quite similar. At comonomer contents of 3 mol % differences between the two sets of samples are seen that are attributed to differences in the abilities of 1-heptene and 1-octene in disrupting the crystal arrangements of the polymer chains in solid state. V C 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 962-975

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Section: Resultssupporting

confidence: 67%

Section: Introductionmentioning

confidence: 99%

Ethylene/1‐heptene copolymers as interesting alternatives to 1‐octene‐based LLDPE: Molecular structure and physical properties

Ndiripo

Joubert

Pasch

2015

J. Polym. Sci. Part A: Polym. Chem.

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“…( range of applications. [16][17][18][19][20][21][22][23][24] Furthermore, metallocene copolymerization of ethylene with nonlinear, bulkier R-olefins such as 3-methyl-1-butene, [25][26][27][28] 4-methyl-1-pentene, [29][30][31][32] vinylcyclohexene, [33][34][35][36] and norbornene 28 has created a new class of materials with better impact strength than that of traditional ethylene linear R-olefin copolymers. By its nature, copolymerization of ethylene with R-olefins via chain-propagation chemistry incorporates structural defects via head-to-head or tail-to-tail monomer coupling.…”

Section: Introductionmentioning

confidence: 99%

Precision Polyethylene: Changes in Morphology as a Function of Alkyl Branch Size

et al. 2009

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Metathesis polycondensation chemistry has been employed to control the crystalline morphology of a series of 11 precision-branched polyethylene structures, the branch being placed on each 21st carbon and ranging in size from a methyl group to an adamantyl group. The crystalline unit cell is shifted from orthorhombic to triclinic, depending upon the nature of the precision branch. Further, the branch can be positioned either in the crystalline phase or in the amorphous phase of polyethylene, a morphology change dictated by the size of the precision branch. This level of morphology control is accomplished using step polymerization chemistry to produce polyethylene rather than conventional chain polymerization techniques. Doing so requires the synthesis of a series of unique symmetrical diene monomers incorporating the branch in question, followed by ADMET polymerization and hydrogenation to yield the precision-branched polyethylene under study. Exhaustive structure characterization of all reaction intermediates as well as the precision polymers themselves is presented. A clear change in morphology was observed for such polymers, where small branches (methyl and ethyl) are included in the unit cell, while branches equal to or greater in mass than propyl are excluded from the crystal. When the branch is excluded from the unit cell, all such polyethylene polymers possess essentially the same melting temperature, regardless of the size of the branch, even for the adamantyl branch.

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“…There are several publications about 4-methyl-1-pentene as a comonomer, , but 3MB1 as a comonomer still is a little neglected. This sterically hindered monomer has been nearly exclusively polymerized via classical Ziegler−Natta catalysis with supported catalysts until present, while most series were made as homopolymerizations. , There are some publications dealing with the properties of the obtained poly(3-methyl-1-butenes). , Tincul's experiments concerning the ethylene/3MB1 copolymerization by heterogeneous catalysis have shown that the branched monomer works more strongly reducing concerning the density than the corresponding linear α-olefin 1-pentene. Tincul has achieved an incorporation of 10 mol % of the branched olefin by Ziegler−Natta catalysis.…”

Section: Introductionmentioning

confidence: 99%

“…7,8 There are some publications dealing with the properties of the obtained poly(3-methyl-1-butenes). 9,10 Tincul's experiments 11 concerning the ethylene/ 3MB1 copolymerization by heterogeneous catalysis have shown that the branched monomer works more strongly reducing concerning the density than the corresponding linear R-olefin 1-pentene. Tincul has achieved an incorporation of 10 mol % of the branched olefin by Ziegler-Natta catalysis.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of Ethylene and Propylene with the Sterically Hindered Monomer 3-Methyl-1-butene by Homogeneous Catalysis

Derlin

Kaminsky

2007

Macromolecules

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Homogeneous catalysts in addition with MAO were used to synthesize copolymers of 3-methyl-1-butene (3MB1) with ethylene and propylene. Three series of ethylene/3MB1 copolymerizations were catalyzed by the organometallic compounds [Me 2 Si(Me 4 Cp)(N t Bu)]TiCl 2 (1), [Ph 2 Si(OctHFlu)(Ind)]ZrCl 2 (2), and rac-[Me 2 C(Ind) 2 ]ZrCl 2 (3). For the copolymerization of 3MB1 with propylene, the metallocenes rac-[Me 2 C(Ind) 2 ]-ZrCl 2 (3) and [Me 2 C(Cp)(Flu)]ZrCl 2 (4) were used. For each metallocene, the influence of the molar fraction of 3MB1 in the feed as well as the influence of the polymerization temperature on the copolymerization behavior was investigated. In this regard copolymerization parameters were calculated. All copolymers were characterized by 13 C NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography techniques. Very small amounts of incorporated 3MB1 have a remarkable effect on the melting temperatures of the obtained polymers. Already by incorporation of 1 mol % of 3MB1 in the polymer, the melting temperature of the obtained LLDPE is lowered to 120 °C, whereas twice as much 1-butene is necessary to achieve the same effect, which should facilitate the processing.

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Ethylene copolymers with Fischer-Tropsch olefins

Cited by 9 publications

References 0 publications

Ethylene/1‐heptene copolymers as interesting alternatives to 1‐octene‐based LLDPE: Molecular structure and physical properties

Ethylene/1‐heptene copolymers as interesting alternatives to 1‐octene‐based LLDPE: Molecular structure and physical properties

Precision Polyethylene: Changes in Morphology as a Function of Alkyl Branch Size

Copolymerization of Ethylene and Propylene with the Sterically Hindered Monomer 3-Methyl-1-butene by Homogeneous Catalysis

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