Synthetic rubbers prepared by lanthanide coordination catalysts

Chen, Wenqi

doi:10.1007/s11426-009-0214-9

Cited by 15 publications

(20 citation statements)

References 22 publications

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“…Generally, the polymerization of 1,3‐butadiene (BD) using Ni‐based catalysts comprised of nickel naphthenate, boron trifluoride etherate (BF 3 · Et 2 O), and trialkylalumimium such as triethylaluminum (TEAL) is carried out in solution such as aliphatic and aromatic solvents . The disadvantage of this polymerization system is more release of butadiene dimer (vinyl cyclohexene), which is harmful to the environment than the polymerization process using lanthanide catalysts . Moreover, the fluorine‐containing co‐catalyst such as hydrogen fluoride (HF) or BF 3 · Et 2 O required for the Ni‐based catalyst system generates strong acid when it contacts water.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, BR containing 99% cis −1,4 microstructure with a very low amount of vinyl −1,2 units (<1%) has been produced by using lanthanide catalysts based on neodymium (Nd) coordinating with aluminum halides acting as co‐catalysts . The lanthanide catalysts have high solubility in saturated alkanes, which are safer and more environmental friendly than benzene and toluene used as the general solvents in conventional butadiene polymerization . Moreover, the lanthanide catalysts promote high monomer conversion to achieve 100% conversion without gel formation in the resulting product .…”

Section: Introductionmentioning

confidence: 99%

“…The lanthanide catalysts have high solubility in saturated alkanes, which are safer and more environmental friendly than benzene and toluene used as the general solvents in conventional butadiene polymerization . Moreover, the lanthanide catalysts promote high monomer conversion to achieve 100% conversion without gel formation in the resulting product . This catalyst type also produces less content of a butadiene dimer .…”

Section: Introductionmentioning

confidence: 99%

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The influence of Ni/Nd‐based Ziegler–Natta catalyst on microstructure configurations and properties of butadiene rubber

Chatarsa

Prasassarakich

Rempel

et al. 2015

J of Applied Polymer Sci

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Neodymium (Nd)-based Ziegler-Natta catalyst has been well known for preparing polybutadiene rubber (BR) containing high, about 98%, cis21,4 configuration with extremely low gel content providing superior resistance to low-temperature fatigue and abrasion. However, its cost is more expensive than a conventional nickel (Ni)-based catalyst. The Nd-BR has poor processability with high cold flow due to its high linearity and molecular weight. To compare with a traditional process, the BR produced by Ni-based catalyst has higher level of branching resulting in the better processability, but it contains medium amount of gel. To balance the catalyst cost and the BR properties, this article reported the influence of a solution containing Ni-and Nd-based Ziegler-Natta catalyst (Ni/Nd) using diethyl aluminum chloride and triethyl aluminum as co-catalysts on 1,3-butadiene (BD) conversion and physical properties of the elastomeric materials based on obtained rubber (Ni/Nd-BR). In the presence of toluene, the increase in the Ni/Nd molar ratio from 0.0/1.0 to 0.4/0.6 yielded Ni/Nd-BR containing cis21,4 units of 95%-96% with significantly decreasing both levels of vinyl21,2 and trans21,4 configurations from 0.26% to 0.13% and 4.44% to 3.07%, respectively. When cyclohexane was applied as the reaction media, 100% BD conversion was achieved and the Ni/Nd-BR had very low content of vinyl21,2 unit (0.07%). The mechanical properties in terms of tensile properties and abrasion resistance of the elastomer based on Ni/Nd-BR having high cis-1,4 and relatively higher trans21,4 configurations were superior to elastomers based on commercial BRs produced by using Niand Nd-based catalyst systems.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The influence of Ni/Nd‐based Ziegler–Natta catalyst on microstructure configurations and properties of butadiene rubber

Chatarsa

Prasassarakich

Rempel

et al. 2015

J of Applied Polymer Sci

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“…Among the variety of organometallic complexes used for this purpose, rare-earth metal based compounds are the most effective and attractive candidates [1][2][3]. For the past fifty years, many efforts have been made to develop rare-earth metal based catalyst systems for cis-1,4 stereoselective polymerization of conjugated dienes.…”

Section: Introductionmentioning

confidence: 99%

Highly stereospecific polymerization of isoprene with homogeneous binary Ziegler-Natta catalysts based on NCN-pincer neodymium precursor

2010

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The aryldiimine NCN-pincer stabilized neodymium dichloride combined with aluminum alkyls established a new type of homogeneous binary neutral Ziegler-Natta catalyst system. This system exhibited high activity and high cis-1,4 selectivity for the polymerization of isoprene (T p = 20 °C, 98.2%; T p = 20 °C, > 99%). Such catalytic performances remained under a broad range of polymerization temperatures and monomer-to-neodymium ratios (from 500 to 8000), reaching high number-average molecular weight (M n = 1582 kg/mol) and relatively narrow molecular weight distribution (PDI = 1.68), which was, however, influenced by the amount and bulkiness of aluminum alkyls. Dynamic investigation of the polymerization was performed, which showed the number-average molecular weight of the resultant polyisoprene had an almost linear correlation with the conversion, suggesting, in some degree, the polymerization with this catalytic system was controllable.neodymium, cis-1,4 selectivity, NCN-pincer complex, polyisoprene

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“…Recently, Wang et al have reviewed to summarize the progress in this field in the past half century[7].…”

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confidence: 99%

Focus on polymer chemistry papers in Science in China Series B: Chemistry of the year 2009

Ying

2010

Sci. China Chem.

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to a percentage increase of 236% and thereby a great historic breakthrough of the journal. These papers mainly focus on three fields: (1) polymer synthesis, (2) functional polymer materials and (3) biomedical polymers. Several research groups published a series of papers in Science in China Series B: Chemistry and detailedly introduced their works in the related fields.Yan et al. paid a great attention on synthesizing functional polymers [1-2], such as hyperbranched polymers, supramolecular self-assembly and dynamics of polymerization reactions. For example, in ref.[1], they successfully prepared nanohybrids by in situ atom transfer radical polymerization (ATRP) of styrene from titanate nanotubes (TNTs), and the grafted PS content was well controlled and increased with increasing the monomer/initiator ratio. Further copolymerization of tert-butyl acrylate (t-BA) from the surface of PS-g-TNTs was studied, illustrating the "living" characteristics of the surface-induced ATRP method used in this work. Yan et al. also prepared well-defined polystyrene/silica hybrid nanoparticles by the ATRP method.Shen's group research interests are mainly on exploitation and development of new catalysts especially rare earth catalysts and methodologies in polymer synthesis [3][4][5][6]. Discrete ion-pair complexes [Ln(EDBP) 2 (DME)Na(DME) 3 ] [Ln = Er (1), Yb (2), Sm (3)] have been synthesized by the reaction between sodium salt of 2,2′-ethylidene-bis(4,6-ditert-butylphenol)(EDBPH 2 ) and Ln(BH 4 ) 3 ·3THF (Ln = Er, Yb, Sm) followed by centrifugation and recrystalization [3]. The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes/triisobutyl aluminum (Ln(H 2 salen) 2 Cl 3 ·2C 2 H 7 OH/Al(i-Bu) 3 ) at room temperature was also developed [4]. A series of diblock copolymers of poly(methyl methacrylate and 2-perfluorooctylethyl methacrylate) (PMMA-b-PFMA) with various PFMA block lengths were prepared by the ATRP, and their surface structures and properties were investigated by different techniques [5]. Shen et al. at Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (CIAC) have found the catalytic activities of lanthanide compounds in stereospecific polymerization of conjugated dienes in the early 1968, then launched extensive research activities on lanthanide compounds as diene polymerization catalysts, rare earth cis-1,4-polybutatine rubber and cis-1,4-polyisoprene rubber have been industried. Recently, Wang et al. have reviewed to summarize the progress in this field in the past half century [7]. Tang et al. [8-10] synthesized several kinds of hyperbranched polymers such as 1 Ndiethylamino)methyl]phenyl}-3,4-diphenylsilole fluorogen, poly(1-phenyl-1-octyne)s containing different stereogenic and chromophoric pendants, and soluble poly(aroxycarbonylphenylene) etc. They also further investigated the functions and potential applications of those synthesized hyperbranched polymers.Huang et al. focused their researches on long wavelength blue emission materials and further explored thei...

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Synthetic rubbers prepared by lanthanide coordination catalysts

Cited by 15 publications

References 22 publications

The influence of Ni/Nd‐based Ziegler–Natta catalyst on microstructure configurations and properties of butadiene rubber

The influence of Ni/Nd‐based Ziegler–Natta catalyst on microstructure configurations and properties of butadiene rubber

Highly stereospecific polymerization of isoprene with homogeneous binary Ziegler-Natta catalysts based on NCN-pincer neodymium precursor

Focus on polymer chemistry papers in Science in China Series B: Chemistry of the year 2009

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