Polymerization of 1,3-Butadiene Initiated by Neodymium Versatate/Diisobutylaluminium Hydride/Ethylaluminium Sesquichloride: Kinetics and Conclusions About the Reaction Mechanism

Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner

doi:10.1002/1521-3935(20020501)203:8<1055::aid-macp1055>3.0.co;2-h

Cited by 103 publications

(143 citation statements)

References 15 publications

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“…( Table 2) Cp*'Nd(BH 4 It is generally admitted that trans-polymerization can be related to single coordination of the diene monomer to the metal, 27,34,35 when double coordination of the diene is required to afford cis-polydiene.…”

Section: (Figure 1)mentioning

confidence: 99%

Highly trans-Stereospecific Isoprene Polymerization by Neodymium Borohydrido Catalysts

et al. 2005

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Abstract.Highly stereospecific polymerization of isoprene was achieved using borohydrido neodymium complexes. In combination with stoichiometric amounts of dialkylmagnesium, Nd(BH 4 ) 3 (THF) 3 (1) and Cp*'Nd(BH 4 ) 2 (THF) 2 (2) (Cp*' = C 5 Me 4 nPr) afford very efficient catalysts. Activity reaches 37300 g polyisoprene/mol Nd/h. Half-lanthanidocene 2 gives rise to polyisoprene 98.5 % trans-regular, the highest content yet described for a homogeneous organometallic catalyst. NMR experiments argue for the formation of bimetallic Nd(-BH 4 )Mg active species.

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Section: (Figure 1)mentioning

confidence: 99%

Highly trans-Stereospecific Isoprene Polymerization by Neodymium Borohydrido Catalysts

et al. 2005

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“…[10] Recently, we were able to show that the polymerization of 1,3-butadiene (BD) initiated by NdV a /DIBAH/EASC (Scheme 1) shows the features of a controlled polymerization (''living polymerization with a rapid and reversible chain transfer''). [11] To build up an AB block copolymer comprising a BR building block with a high cis-1,4 content, it appeared reasonable to apply this type of polymerization. The experimental conditions under which the polymerization of BD occurs in a controlled manner were elaborated in our previous paper.…”

Section: Introductionmentioning

confidence: 99%

“…The experimental conditions under which the polymerization of BD occurs in a controlled manner were elaborated in our previous paper. [11] By the sequential addition of a polar monomer (e.g. CL) to the living high cis-1,4-BR block, amphiphilic AB block copolymers should be formed to some extent as shown in Scheme 2.…”

Section: Introductionmentioning

confidence: 99%

In Situ Preparation of a Compatibilized Poly(cis‐1,4‐butadiene)/Poly(ε‐caprolactone) Blend

Friebe

Nuyken

Windisch

et al. 2003

Macro Materials & Eng

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The ternary Ziegler‐Natta‐type catalyst system based on neodymium versatate (NdV), diisobutylaluminium hydride (DIBAH) and ethylaluminium sesquichloride (EASC) was used for the in situ preparation of a compatibilized blend consisting of poly(cis‐1,4‐butadiene) (BR = butadiene rubber) and poly(ε‐caprolactone) (PCL). Poly(cis‐1,4‐butadiene)‐block‐poly(ε‐caprolactone) which acts as compatibilizer for the two immiscible polymers BR and PCL was obtained by a two step sequential polymerization with the preparation of a living cis‐1,4‐BR building block in the first stage and the subsequent polymerization of CL during the second stage. This preparation method resulted in a polymer blend comprising the homopolymers BR and PCL as well as the block copolymer BR‐block‐PCL. For detailed characterization the block copolymer was separated from the respective homopolymers BR and PCL by means of fractionation with the binary solvent mixture dimethylformamide/methylcyclohexane (DMF/MCH) which mixes well at elevated temperature and exhibits phase separation at ambient temperature. 1H NMR, IR, SEC and TEM were used for characterization of the block copolymer.TEM of BR‐block‐PCL.magnified imageTEM of BR‐block‐PCL.

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“…Although a number of catalytic systems have been reported to conduct stereospecific polymerization of 1,3-butadiene for cis-1,4, [1][2][3][4][5][6][7][8][9][10][11] trans-1,4, [12,13] syndiotactic-1,2, [14][15][16] atactic-1,2, [17] and isotactic-1,2, [18] polymers, only limited examples are reported for both stereospecific and living polymerization in 1,3-butadiene. [1][2][3][4] In transition metalcatalyzed polymerization, the addition of a Lewis base is sometimes very effective in the control of the activity, the stereospecificity, and the livingness of the system.…”

Section: Introductionmentioning

confidence: 99%

Additive Effect of Triphenylphosphine on the Living Polymerization of 1,3‐Butadiene with a Cobalt Dichloride‐Methylaluminoxane Catalytic System

Nath

Shiono

Ikeda

2003

Macro Chemistry & Physics

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The additive effect of triphenylphosphine (Ph3P) was investigated in 1,3‐butadiene polymerization with cobalt dichloride (CoCl2) activated by methylaluminoxane (MAO); the catalytic system resulted in slowly‐initiated living polymerization with a high cis‐1,4 content (about 99%) at 0 °C. The polymerization behavior, such as the relationship of polymer yield and number‐average molecular weight ($\overline M _{\rm n}$) with polymerization time, was dependent on the amount of Ph3P added. In the presence of a small amount of Ph3P (Ph3P/Co = 0.025), the kinetic behavior qualitatively resembled that observed in the absence of Ph3P, which indicated that the catalytic system conducted slowly‐initiated living polymerization. An increase in the amount of Ph3P (Ph3P/Co > 0.025), however, caused chain transfer reaction. The 1H NMR analysis of the produced polymers showed that Ph3P changed the microtacticity from 99% of cis‐1,4 to 88% of 1,2‐unit, depending on the amount of Ph3P added. At the maximum amount of Ph3P (Ph3P/Co = 0.025) necessary for maintaining the livingness of the propagating species, 14% of the 1,2‐inserted unit was incorporated at the expense of the cis‐1,4‐inserted unit. The addition of Ph3P (Ph3P/Co = 0.025) during the polymerization did not affect the livingness and gave a regio‐block copolymer of 1,3‐butadiene.

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Polymerization of 1,3-Butadiene Initiated by Neodymium Versatate/Diisobutylaluminium Hydride/Ethylaluminium Sesquichloride: Kinetics and Conclusions About the Reaction Mechanism

Cited by 103 publications

References 15 publications

Highly trans-Stereospecific Isoprene Polymerization by Neodymium Borohydrido Catalysts

Highly trans-Stereospecific Isoprene Polymerization by Neodymium Borohydrido Catalysts

In Situ Preparation of a Compatibilized Poly(cis‐1,4‐butadiene)/Poly(ε‐caprolactone) Blend

Additive Effect of Triphenylphosphine on the Living Polymerization of 1,3‐Butadiene with a Cobalt Dichloride‐Methylaluminoxane Catalytic System

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