EP(D)M-synthesis with highly active homogeneous and heterogeneous metallocene/MAO-catalysts

Arrowsmith, D. J.; Kaminsky, Werner; Schauwienold, Anne-Meike; Weingarten, Ulrich

doi:10.1016/s1381-1169(00)00236-3

Cited by 26 publications

(15 citation statements)

References 19 publications

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“…A well‐known distinct feature of the single‐site catalysts is in their ability to copolymerize ethylene with α‐olefins in a homogeneous fashion. The application of single site catalysts has been limited to ethylene/α‐olefin copolymers like LLDPE, plastomers, elastomers and EPDM 8–10. There is an advantage of metallocene compared to Zigler‐Natta catalyst in EPDM production, both by the desire to avoid the use of toxic vanadium and to exploit the well‐known high activities of the metallocene systems.…”

Section: Introductionmentioning

confidence: 99%

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

Mortazavi

Arabi

Ahmadjo

et al. 2011

J of Applied Polymer Sci

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Ind) 2 ZrCl 2 catalyst was synthesized and used for copolymerization of ethylene and propylene (EPR) and terpolymerization of ethylene propylene and 5-ethyldiene-2-norbornene (ENB). Methylaluminoxane (MAO) was used as cocatalyst. The activity of the catalyst was higher in copolymerization of ethylene and propylene (EPR) rather than in terpolymerization of ethylene, propylene and diene monomers. The effects of [Al] : [Zr] molar ratio, polymerization temperature, pressure ratio of ethylene/propylene and the ENB concentration on the terpolymerization behavior were studied. The highest productivity of the catalyst was obtained at 60 C, [Al] : [Zr] molar ratios of 750 : 1 and 500 : 1 for copolymerization and terpolymerization, respectively. Increasing the molar ratio of [Al] : [Zr] up to 500 : 1 increased the ethylene and ENB contents of the terpolymers, while beyond this ratio the productivity of the cata-lyst dropped, leading to lower ethylene and ENB contents. Terpolymerization was carried out batchwise at temperatures from 40 to 70 C. Rate time profiles of the polymerization were a decay type for both copolymerization and terpolymerization. Glass transition temperatures (T g ) of the obtained terpolymers were between À64 and À52 C. Glass transition temperatures of both copolymers and terpolymers were decreased with increased ethylene content of the polymers. Dynamic mechanical and rheological properties of the obtained polymers were studied. A compounded EPDM showed good thermal stability with time.

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Section: Introductionmentioning

confidence: 99%

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

Mortazavi

Arabi

Ahmadjo

et al. 2011

J of Applied Polymer Sci

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“…[21][22][23][24] In comparison with abundant researches of addition homopolymerization of parent NB and other important commercial product of 5-vinyl-2-norbornene, [25][26][27][28][29][30] the homopolymerization or copolymerization of ENB as main comonomer in vinyl addition polymerization pathway is rarely reported in the literature. 31 The polymer achieved in this way posseses the exocyclic C=C double bond functionalities on the polymer side chain, which will provide reactive site for the further functionalization by post-polymerizations, such as epoxidation, crosslinking reaction, and/or graft polymerization as demonstrated in EPDM, which will be beneficial for expanding its performances and applications.…”

Section: Introductionmentioning

confidence: 99%

Addition polymerization of 5-ethylidene-2-norbornene by cationic palladium cationic complex and subsequent derivatization

Wang

Yang

et al. 2011

Macromol. Res.

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Poly(5-ethylidene-2-norbornene) (PENB) was synthesized via a vinylic pathway using a cationic palladium-based catalyst, displaying high activity up to 1.06×10 6 g-PENB/mol Pd. The effects of the monomer to catalyst ratio, temperature, reaction time, and concentration on the polymerization were investigated systematically. The control tests and spectroscopic analyses of the PENB indicate that 5-ethylidene-2-norbornene is polymerized via an addition polymerization using endocyclic double bonds. The post-modification was also performed using a free radical graft polymerization. The resulting PENB copolymers were characterized by IR, 1 H NMR, and GPC analyses.

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“…The obtained polymers show a random incorporation of monomer in the polymer backbone and narrow MWD [6], especially when they are compared with conventional Ziegler–Natta catalysts [7]. The most common method of applying metallocenes to heterogeneous polymerizations is to support the complexes on an inorganic solid, in most cases, silica gel [8].…”

Section: Introductionmentioning

confidence: 99%

A fast and reliable procedure to determine the copolymer composition by GPC‐IR: Application to ethylene/propylene copolymers and comparison with ¹³C NMR

Suárez

Caballero

Coto

2010

Polymer Engineering & Sci

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Copolymer properties depend on several parameters and one of the most important is its composition. Typically, this composition is determined by 13C nuclear magnetic resonance (13C NMR) analysis, which requires a long acquisition time and a fine adjustment of parameters to obtain the desired resolution. In this article, a method to determine the comonomer content of polymers based on the analysis from gel permeation chromatography (GPC) with an infrared (IR) detector is described. This GPC‐IR method is faster than NMR and can be carried out routinely during the GPC analysis. Three sets of ethylene/propylene copolymers synthesized using metallocene and Ziegler–Natta catalyst over a wide composition range. Linear and second order polynomial equations were checked for the relation between the ethylene percent and the IR CH3/CH ratio. Average deviation between GPC‐IR and NMR composition values was about 1% and allow conclude that this technique can be considered to be a goodalternative. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers

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EP(D)M-synthesis with highly active homogeneous and heterogeneous metallocene/MAO-catalysts

Cited by 26 publications

References 19 publications

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

Addition polymerization of 5-ethylidene-2-norbornene by cationic palladium cationic complex and subsequent derivatization

A fast and reliable procedure to determine the copolymer composition by GPC‐IR: Application to ethylene/propylene copolymers and comparison with ¹³C NMR

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EP(D)M-synthesis with highly active homogeneous and heterogeneous metallocene/MAO-catalysts

Cited by 26 publications

References 19 publications

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

Addition polymerization of 5-ethylidene-2-norbornene by cationic palladium cationic complex and subsequent derivatization

A fast and reliable procedure to determine the copolymer composition by GPC‐IR: Application to ethylene/propylene copolymers and comparison with 13C NMR

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A fast and reliable procedure to determine the copolymer composition by GPC‐IR: Application to ethylene/propylene copolymers and comparison with ¹³C NMR