Structure and Reactivity of “Living” Polypropylene

Doi, Yoshiharu; Suzuki, Shigeo; Nozawa, Fumie; Soga, Kazuo; Keii, Tominaga

doi:10.1016/s0167-2991(09)60331-1

Cited by 7 publications

(1 citation statement)

References 10 publications

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“…In principle, the ZN-catalyzed PP polymerization is composed of three steps: insertion, propagation, and termination. The PP insertion is the rate determining step (RDS) [4,37], as well as the stereocontrol step [38]. Thus, the insertion step for ZN-catalyzed PP polymerization with five salicylates as given in Table 1 was investigated.…”

Section: Sidmentioning

confidence: 99%

Roles of Salicylate Donors in Enhancement of Productivity and Isotacticity of Ziegler–Natta Catalyzed Propylene Polymerization

2020

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Roles of internal salicylate donors (SID) in enhancing activity and stereoselectivity of Ziegler–Natta catalyzed propylene (PP) polymerization were examined using DFT calculations. Five salicylate donors were studied. The chelate mode is the preferred adsorption mode. The linear relationship (R2 = 0.96) between calculated adsorption energies (Eads) of five SIDs and the experimental PP activities was observed. Thus, the SID with the strongest adsorption energy will provide the highest activity in agreement with our previous studies. Compared with diisobutyl phthalate (DIBP), which is the industrial electron donor, SID has stronger Eads. The insertion step, which involves the π-complex formation (∆Eπ) and the insertion activation or intrinsic activation energy (Ea) for PP polymerization was also examined. The relation between ln(activity) and apparent activation energy (Ea(app)), which is ∆Eπ + Ea for the primary(1,2)-re insertion with R2 = 0.99, was observed. The salicylate donor also has a lower Ea(app) than that of DIBP. This explains the better catalytic performance of SID. Our results also demonstrated that the size and the type of hydrocarbon substituents play a key role in controlling stereoselectivity and activity. In addition, we found a good relationship between Eads and both intrinsic (Ea) and apparent (Ea(app)) activation energies of five salicylate donors with R2 of 0.90 and 0.97, respectively.

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Section: Sidmentioning

confidence: 99%

Roles of Salicylate Donors in Enhancement of Productivity and Isotacticity of Ziegler–Natta Catalyzed Propylene Polymerization

2020

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Polymerization – Homogeneous

Vlád

2002

Encyclopedia of Catalysis

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Polymers are among the largest manufactured industrial products. Their extremely diversified properties render a widespread presence possible in everyday life. Polymers can be synthesized either by homogeneous or heterogeneous processes. This article focuses on the homogeneous procedures. The first part of the article summarizes the polymerization of monomers containing at least one carbon–carbon double bond or carbon–carbon triple bond. This is followed by a description of the environmentally accepted and biocompatible poly(lactic acid)s and epoxide–carbon dioxide alternating copolymers. The next two paragraphs focus on special procedures, living and enzymatic polymerization, by which polymers can be synthesized with exotic architectures. The article concludes is finished with the description of step‐growth polymerizations of aromatic systems.

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Oligomerization and Polymerization

2017

Hydrocarbon Chemistry, Two Volume Set

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Structure and Reactivity of “Living” Polypropylene

Cited by 7 publications

References 10 publications

Roles of Salicylate Donors in Enhancement of Productivity and Isotacticity of Ziegler–Natta Catalyzed Propylene Polymerization

Roles of Salicylate Donors in Enhancement of Productivity and Isotacticity of Ziegler–Natta Catalyzed Propylene Polymerization

Polymerization – Homogeneous

Oligomerization and Polymerization

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