Polymerization of butadiene with the NiCl2-methylaluminoxane catalyst

Endo, Kiyoshi; Yamanaka, Yoshihiro

doi:10.1002/(sici)1521-3927(19990601)20:6<312::aid-marc312>3.0.co;2-6

Cited by 16 publications

(7 citation statements)

References 13 publications

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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%

“…Simultaneous control of microtacticity and molecular weight of the polymer chain is an interesting topic, but a difficult task in the polymerization of 1,3‐butadiene. Although a number of catalytic systems have been reported to conduct stereospecific polymerization of 1,3‐butadiene for cis ‐1,4,1–11 trans ‐1,4,12,13 syndiotactic‐1,2,14–16 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 1–4. In transition metal‐catalyzed 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%

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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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Section: Introductionmentioning

confidence: 99%

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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“…Metallocene catalysts activated by methylaluminoxane (MAO) give homogeneous systems, leading to extensive control of the M w / M n and steric structure of polymers in the polymerization of ethylene, α‐olefins, and styrene. Triggered by those remarkable results, a variety of catalysts composed of transition‐metal (e.g., Ti,8–14 V,12, 15–17 Cr,18, 19 Co,12, 20–22 Ni,23–28 Nd,7, 12, 29–34 and Sm35, 36) compounds and MAO were examined in 1,3‐diene polymerization. In the polymerization of 1,3‐butadiene, the use of MAO in place of AlR 3 as a cocatalyst generally affects both the catalytic activity and stereospecificity of the transition‐metal catalysts.…”

Section: Introductionmentioning

confidence: 99%

Novel neodymium (III) isopropoxide‐methylaluminoxane catalyst for isoprene polymerization

Dong

Masuda

2002

J. Polym. Sci. A Polym. Chem.

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A novel catalyst composed of neodymium (III) isopropoxide [Nd(OiPr) 3 ] and methylaluminoxane (MAO) was examined in isoprene polymerization. The Nd(OiPr) 3 -MAO catalyst proved to be highly effective in heptane even at low [Al]/[Nd] ratios (ca. 30) to give polyisoprene that possessed high cis-1,4 stereoregularity (Ͼ ca. 90%), a high number-average molecular weight (M n ϳ10 5 ), and relatively narrow molecular weight distributions (M w /M n ϭ 1.9 -2.8). The catalyst activity increased with an increasing [Al]/[Nd] ratio from 10 to 80 as well as temperature of aging and polymerization from 0 to 60°C. The polymerization proceeded in the first order with respect to the monomer concentration. Aliphatic solvents (heptane and cyclohexane) achieved a higher yield and M n of polymer than toluene as a solvent. The M w /M n ratio remained around 2.0, and the gel permeation chromatographic curve was always unimodal, indicating that this system is homogeneous and involves a single active site. The microstructure of polyisoprene was determined by IR, 1 H NMR, and 13 C NMR. The cis-1,4 contents of the final polymers stayed in the range of 90 -92%, regardless of reaction conditions, indicating the high stability of stereospecificity of the catalyst.

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“…The property of a polymer depends on the microstructure, which is a very important factor for industrial and commercial applications. A number of transition‐metal complexes have been reported by several authors to give cis ‐1,4‐polybutadiene,1–9 trans ‐1,4‐polybutadiene,10, 11 and 1,2‐syndiotactic polybutadiene 12, 13. Basically, the mode of monomer insertion strongly depends on the types of transition‐metal complexes.…”

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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Polymerization of butadiene with the NiCl2-methylaluminoxane catalyst

Cited by 16 publications

References 13 publications

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

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

Novel neodymium (III) isopropoxide‐methylaluminoxane catalyst for isoprene polymerization

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

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