A New Hydrocarbon Elastomer. Copolymerization of Olefins and Nonconjugated Dienes

Gladding, E. K.; Fisher, B. S.; Collette, John W.

doi:10.1021/i360002a001

Cited by 41 publications

(9 citation statements)

References 2 publications

(3 reference statements)

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“…Molar ratio Polymerization AI/V temperaturejK VOCI 3 -AI(C 6 H 13 )3 -heterogeneous 3 VCI 4 -AI(C6H13)3 -heterogeneous 3 VCI 3 -AI(C 6 H 13 )3 -heterogeneous 3 VA3 a-AI(C z H 5 )zCl -colloidal 5 -homogeneous VCI 4 [226) [227) [218) [228) [224), [229), [230) [229) [231) monomers mostly utilized in practice are [220] 5-ethylidene-2-norbornene (ENB) [233], I,4-hexadiene (I,4-HD) [234] and dicyclopentadiene (DCPD) [223,235,236]. Other termonomers are reported in literature [220,224,237].…”

Section: Catalytic Systemmentioning

confidence: 99%

Catalytic Olefin Polymerization

Pasquon

Giannini²

1984

Advances in Comparative and Environmental Physiology

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Section: Catalytic Systemmentioning

confidence: 99%

Catalytic Olefin Polymerization

Pasquon

Giannini²

1984

Advances in Comparative and Environmental Physiology

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“…However, the density of such macromonomer‐induced branches is typically small. Nonconjugated dienes (small molecules, often short linear alkenes, with two terminal double bonds at each end) can be used to increase the amount of branching in polyolefin resins . Contrary to the single terminal double bond in a macromonomer, copolymerization with diene introduces pendant double bonds at each of the incorporated diene sites.…”

Section: Introductionmentioning

confidence: 99%

“…Nonconjugated dienes (small molecules, often short linear alkenes, with two terminal double bonds at each end) can be used to increase the amount of branching in polyolefin resins. [19,20] Contrary to the single terminal double bond in a macromonomer, copolymerization with diene introduces pendant double bonds at each of the incorporated diene sites. Thus copolymerization with diene provides a route to create much more branched resins than is possible in homopolymerization of olefins.…”

Section: Introductionmentioning

confidence: 99%

“…Because of its commercial relevance, ethylene-diene copolymerization (often considered along with another comonomer like hexene, octene, or propylene to control crystallinity by introducing short-chain branches [23] ) has been the focus of a number of patents [24][25][26][27][28] and publications. [20,[29][30][31] However, the theoretical modeling of this important class of polymerization [32][33][34][35] has been mostly limited to calculations based on the method of moments. In this methodology, the branch-formation step couples the equations relating different moments.…”

Section: Introductionmentioning

confidence: 99%

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Static and Dynamic Scaling Close to Gelation in Chain‐Polymerization: Effect of Reactor Type

Das

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Soulages

et al. 2017

Macro Theory & Simulations

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Because of the familiarity of gelation theories in polycondensation reaction of multifunctional groups, often the gel‐point is defined as the point of diverging weight averaged molar mass. The authors present an industrially relevant counter‐example to this common perception. Chain‐growth polymerization in realistic reactors introduces history dependent crosslinking probability. For copolymerization of a two functional monomer (ethylene) with a four functional comonomer (nonconjugated diene), the authors show from a Monte Carlo scheme that standard gelation scaling exponents remain valid for a semibatch reactor. However, for syntheses in a continuous stirred tank reactor (CSTR), all commonly measured molar mass moments (number, weight and “z”‐averaged moment) remain finite at the gel‐point; the first moment to diverge is the fourth moment. Hence, identification of the gel point from experimental observations is difficult, and cannot be achieved through monitoring of the weight averaged molar mass. The authors use a numerical scheme based on the tube model of polymer melts to predict the rheology of the generated molecules. Stress relaxation follows a power‐law decay, but due to dynamic dilution effects the CSTR resins exhibit much slower increase in the zero shear viscosity as the gel point is approached as compared to the semibatch reactor resins.

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“…Those commonly used in EPDM industry can be classified in two categories: cyclic dienes, such as 2-ethylidenebi-cycl0[2.2.1] hept-5-ene (ENB) a) or dicyclopentadiene (DCP,system. name: 3a,4,7,tetrahydro-4,7-methanoindene) 7) and linear ones including 1 ,Chexadiene (HD) '). A larger series of linear non-conjugated dienes, see Scheme 1, has recently been described and patented as alternative ter-monomers for the synthesis of EPDM with improved proper tie^^-'^); some of them have already been produced at pilot scale12).…”

Section: Introductionmentioning

confidence: 99%

Linear non‐conjugated dienes from biomass as termonomers in EPDM synthesis, 1. Study of their reactivity in homo‐, co‐ and terpolymerizations

Dolatkhani

Cramail

Deffieux

1995

Macro Chemistry & Physics

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This paper deals with the use of 3,7-dimethylocta-l,6-diene (3,7-DMO) and 5,7-dimethylocta-l,6-diene (5,7-DMO), issued from terpene feedstock, as termonomers for the synthesis of ethylene-propylene-diene terpolymers (EPDM). Their reactivity is first compared to 7-methylocta-l,6-diene (MOCD), an industrial linear diene, in homopolymerization and cross-copolymerization. 'Itvo catalytic systems are used: TiCl,, 1 /3A1Cl3, 14MgC1, associated with Al(C,H,),, and VOCl, or VCl, associated with Al(C,H5),Cl. The influence of the diene structure on the observed order of reactivity is discussed. In a second part, the copolymerization and the terpolymerization of the different dienes with ethylene and propene are implemented. A drastic influence of the diene structure and concentration on the productivity (and activity) is observed. Potentiometric titrations of the vanadium, performed both in the absence and in the presence of dienes (and of other substituted olefins), indicate that the productivity loss mainly results from a reduction process of the vanadium, involving the di-or trisubstituted olefins

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A New Hydrocarbon Elastomer. Copolymerization of Olefins and Nonconjugated Dienes

Cited by 41 publications

References 2 publications

Catalytic Olefin Polymerization

Catalytic Olefin Polymerization

Static and Dynamic Scaling Close to Gelation in Chain‐Polymerization: Effect of Reactor Type

Linear non‐conjugated dienes from biomass as termonomers in EPDM synthesis, 1. Study of their reactivity in homo‐, co‐ and terpolymerizations

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