Electron Donors in Diene Polymerization

Cooper, W.; Eaves, D. E.; Vaughan, G.; Degler, G.; Hank, R.

doi:10.1021/ba-1966-0052.ch005

Cited by 31 publications

(13 citation statements)

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“…A number of cobalt‐based catalyst systems, especially CoCl 2 –AlR 3 –ligand and CoCl 2 –AlR 2 Cl–Al X 3 systems ( X = Cl, Br, or I), have been reported for 1,3‐butadiene polymerization 24–27. The activity and stereospecificity of the polymer solely depend on the types of cocatalysts and ligands attached to the cobalt species.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of 1,3‐butadiene and isoprene with cobalt dichloride/methylaluminoxane in the presence of triphenylphosphine

Nath

Shiono

Ikeda

2002

J. Polym. Sci. A Polym. Chem.

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The homopolymerization and copolymerization of 1,3‐butadiene and isoprene were achieved at 0 °C with cobalt dichloride in combination with methylaluminoxane and triphenylphosphine (Ph3P). For 1,3‐butadiene, highly cis‐specific and 1,2‐syndiospecific polymerization proceeded in the absence or presence of Ph3P, respectively, although the activity with Ph3P was much higher than that without Ph3P. Only a trace of the polymer was, however, obtained in isoprene polymerization when Ph3P had been added. For copolymerization, the polymer yield in the presence of Ph3P was about three times higher than that in its absence. Copolymerization in the presence of Ph3P was, therefore, investigated in more detail. Unimodal gel permeation chromatography elution curves with narrower polydispersity (weight‐average molecular weight/number‐average molecular weight ≈ 1.5) indicated that the propagation reaction proceeded by single‐site active species. Both the yield and molecular weight of the copolymer decreased with an increasing amount of isoprene in the feed, and this was followed by an increase in the isoprene content in the copolymer. The monomer reactivity ratios, r1 (1,3‐butadiene) and r2 (isoprene), were estimated to be 2.8 and 0.15, respectively. Although the 1,3‐butadiene content in the copolymer was strongly dependent on the comonomer composition in the feed, the ratio of 1,2‐inserted units to 1,4‐inserted units of 1,3‐butadiene was constant. Concerning the isoprene unit, the percentage of 1,2‐ and 3,4‐inserted units was increased at the expense of 1,4‐inserted units with an increasing isoprene content in the feed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3086–3092, 2002

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Section: Introductionmentioning

confidence: 99%

Copolymerization of 1,3‐butadiene and isoprene with cobalt dichloride/methylaluminoxane in the presence of triphenylphosphine

Nath

Shiono

Ikeda

2002

J. Polym. Sci. A Polym. Chem.

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“…Similar behavior was observed for the polymerizations of St and Bd with Ni(acac) 2 -MAO catalyst. [9,12] Effect of additives on the copolymerization of Co(acac) 3 …”

Section: Effect Of Mao/co(acac) 3 Mole Ratios On the Copolymerizationmentioning

confidence: 99%

“…[5][6][7][8][9][10] Among them, CoBr 2 (PPh 3 ) 2 -MAO catalyst was reported to give poly(Bd) with a high content of 1,2-units. [7] In our previous paper, we reported that Co(acac) 3 -MAO catalyst can initiate the polymerization of Bd to give a high cis-1,4-polymer. [9] Moreover, the Co(acac) 3 -MAO catalyst was also reported to initiate the polymerization of styrene (St), although the polymerization rate was not high.…”

Section: Introductionmentioning

confidence: 98%

“…[7] In our previous paper, we reported that Co(acac) 3 -MAO catalyst can initiate the polymerization of Bd to give a high cis-1,4-polymer. [9] Moreover, the Co(acac) 3 -MAO catalyst was also reported to initiate the polymerization of styrene (St), although the polymerization rate was not high. [11,12] The copolymers of St and Bd are important materials as synthetic rubbers.…”

Section: Introductionmentioning

confidence: 98%

“…Moreover, the microstructures of poly(Bd) obtained with Co-based catalysts are known to be affected strongly by the ligand of the cobalt compounds and additives as the third components. The CoCl 2 N 2Py-AlEt 2 Cl catalyst gives highly cis-1,4-poly(Bd), [1,2] and highly trans-1,4-poly(Bd) was prepared with the CoCl 2 -Et 2 AlCl catalyst in the presence of NEt 3 [3] . Highly syndiotactic 1,2-poly(Bd) was synthesized with CoBr 2 (PPh 3 ) 2 -Et 3 Al catalyst by adding H 2 O.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Copolymerization of styrene and butadiene with Co(acac)3-methylaluminoxane catalyst

Endo¹,

Matsuda

2000

Macromol. Chem. Phys.

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Butadiene Polymers

Kerns¹,

Henning²,

Rachita³

2002

Encyclopedia of Polymer Science and Technology

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This article provides an overview of polybutadiene materials as a progression from the monomer 1,3‐butadiene to a useful polymer product with a wide range of applications. A brief history of polybutadiene, with its development as a high cis ‐polybutadiene material during World War I through its present day use as a high vinyl substitute for styrene–butadiene rubber is included. The structure and properties of the monomer are presented, along with monomer manufacture, typical specifications, and health and safety issues. Following a detailed discussion on both polymer microstructure and macrostructure, there is an in‐depth review of polymerization methods that are typically used to produce polybutadiene. The state‐of‐the‐art in free‐radical, Ziegler–Natta, anionic, and cationic polymerization techniques that produce polybutadiene are thoroughly discussed in terms of the influence of catalyst/initiator technology on microstructure and the resulting relationship between microstructure and applications. The most popular commercial polymerization processes are also reviewed including solution, emulsion, and an introduction to gas‐phase polybutadiene polymerization technology. Finally, the economic aspects of polybutadiene materials are presented, including major producers, capacities, and pricing.

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Electron Donors in Diene Polymerization

Cited by 31 publications

References 0 publications

Copolymerization of 1,3‐butadiene and isoprene with cobalt dichloride/methylaluminoxane in the presence of triphenylphosphine

Copolymerization of 1,3‐butadiene and isoprene with cobalt dichloride/methylaluminoxane in the presence of triphenylphosphine

Copolymerization of styrene and butadiene with Co(acac)3-methylaluminoxane catalyst

Butadiene Polymers

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