Synthesis and characterization of polyoctenamer with WCl6e−AlCH2Cl2 catalyst system via ring‐opening metathesis polymerization

Çetinkaya, Sevil; Karabulut, Solmaz; Düz, Bülent; İmamoǧlu, Yavuz

doi:10.1002/aoc.863

Cited by 15 publications

(9 citation statements)

References 17 publications

(10 reference statements)

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“…Linear PCO, synthesized using catalyst 1 according to the optimal conditions using THF and PPh 3 , contained 56% cis olefin and exhibited a T m of 10 °C, which is in good agreement with published experimental values 32,33. Hydrogenation of PCO (Entry 18) was conducted by treatment of the polymer with tosyl hydrazide and tripropyl amine in xylenes9,34–38 and yielded linear, narrowly dispersed HDPE.…”

Section: Synthesis Of Linear High Density Polyethylenesupporting

confidence: 84%

The Living ROMP oftrans-Cyclooctene

Walker¹,

Conrad²,

Grubbs³

2009

Macromolecules

118

114

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The living ring-opening metathesis polymerization (ROMP) of trans-cyclooctene (tCO) was investigated. ROMP of tCO in the presence of PPh 3 in THF leads to the formation of narrowly dispersed polycyclooctene (PCO). The presence of PPh 3 as an additive and the use of THF as a solvent were demonstrated to be necessary to suppress competing secondary metathesis processes in the ROMP of tCO. Under optimal conditions, narrowly dispersed PCO was achieved without high molecular weight contaminates. The PCO was then hydrogenated to form linear, narrowly dispersed polyethylene with a melting temperature of 139 °C. Protected, hydroxy-functionalized tCO was polymerized by this method to afford narrowly dispersed, hydroxylated PCO. Block copolymers containing polynorbornene and PCO or containing differentially functionalized PCO were also synthesized and hydrogenated to form block copolymers containing blocks of linear, narrowly dispersed polyethylene.Ring-opening metathesis polymerization (ROMP) has been employed in the synthesis of a wide range well-defined polymer architectures. 1,2 ROMP is a chain-growth polymerization in which a cyclic olefin is converted to polymer. This process is driven by the release of ring strain which provides the main driving force that is required to overcome the unfavorable entropy change in polymerization. 3 Typical cyclic olefins for ROMP include norbornene, cyclobutene, cyclooctene, and dicyclopentadiene. Also, many functionalized derivatives of these monomers can be polymerized using the functional-group tolerant, late transition metal Grubbs' catalysts 1-3 (Figure 1). 3 In recent years, living ROMP has emerged as a valuable tool for polymer chemists. 4 A living ROMP polymerization is generally characterized by a low polydispersity index (PDI) < 1.1 and a linear relationship between polymer molecular weight and monomer conversion. [3][4][5] Norbornene and its functionalized derivatives have become the monomers of choice for living ROMP due to widespread commercial availability, low cost, and general ease of synthesis. Low polydispersity polymers are achieved with living ROMP when the rate of polymer chain initiation (k i ) occurs faster than chain propagation (k p ) 6 and competing secondary metathesis reactions (k s ), including inter-and intramolecular chain transfer by reaction of the initiator with olefins in the polymer backbone, are eliminated. Norbornene exhibits the characteristic high ring strain such needed for irreversible (k p ≫.k s ) ROMP ( Figure 2) and consequently produces polymers with low PDIs and controllable molecular weights with fast-initiating (k i /k p ≥ 1) catalysts 1 and 3. NIH Public Access Author ManuscriptMacromolecules. Author manuscript; available in PMC 2010 April 7. Secondary metathesis is limited by the steric hindrance of the olefins in the backbone of substituted polynorbornenes. In contrast, the living ROMP of monocyclic, unhindered alkenes has seen limited use. Cyclobutene and its functionalized derivatives have been used in living ROMP but to...

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Section: Synthesis Of Linear High Density Polyethylenesupporting

confidence: 84%

The Living ROMP oftrans-Cyclooctene

Walker¹,

Conrad²,

Grubbs³

2009

Macromolecules

118

114

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“…The monomer COC has been homopolymerized previously by ROMP techniques, yielding a polyoctenamer. 15 (1) Table 1 summarizes the results obtained from the homopolymerization and copolymerization of CPE and COC under the same conditions. The glass transition temperatures T g of polypentenamer and poly(CPE-co-COC) are −20.8 • C and −18.7 • C respectively.…”

Section: Resultsmentioning

confidence: 99%

“…2,3 A detailed 13 C NMR study of the polyoctenamer was previously reported. 15 In copolymers of the two monomers, M 1 (CPE) and M 2 (COC), the compositional dyads may be M 1 M 1 , M 1 M 2 , M 2 M 1 or M 2 M 2 (Scheme 2). The structural evidence of copolymerization lies in a detailed NMR analysis of poly(CPE-co-COC), which is additive for the homopolymer.…”

Section: Methodsmentioning

confidence: 99%

“…11,12 A recent study reveals the crucial role of WCl + 5 as the only possible active species in the WCl 6 -e − -Al-CH 2 Cl 2 system to produce the initial carbene by a 1,2-hydride shift following the complexation with the olefin. 13 We previously reported the homopolymerization of cyclododecene 14 and cyclooctene 15 by a WCl 6 -e − -Al-CH 2 Cl 2 catalyst system. We subsequently focused our efforts on the formation of copolymers by this catalyst.…”

Section: Introductionmentioning

confidence: 99%

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Electrochemically reduced tungsten-based active species as catalysts for metathesis-related reactions: ring-opening metathesis copolymerization of cyclopentene with cyclooctene

Karabulut

Çetinkaya

İmamoǧlu

2005

Appl. Organometal. Chem.

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The ring-opened metathesis copolymerization of cyclopentene with cyclooctene by an electrochemically generated WCl 6 -based catalyst has been prepared and 13 C NMR spectroscopy used to analyse in detail the nature of the homo-and hetero-dyad units. This copolymer was characterized by gel-permeation chromatography (M n = 12 900, PDI= 2.2) and differential scanning calorimetry analysis. The glass-transition temperature T g of the copolymer was −18.7 • C. Homopolymerization of cyclopentene is also reported to compare with copolymers produced in this work.

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“…9 -11 A WCl 6 -Al-CH 2 Cl 2 catalyst system that has been electrochemically reduced brings about the metathesis of α-and β-olefins, as well as the cross-metathesis of non-functionalized olefins 12,13 and the ADMET polymerization of 1,9-decadiene 14,15 , with good activity and selectivity. The electrochemical generation apparently stabilizes the higher oxidation state of the active species responsible for the metathesis reaction, resulting in a high selectivity.…”

Section: Introductionmentioning

confidence: 99%

Electrochemically reduced tungsten‐based active species as catalysts for cross‐metathesis reactions: cross‐metathesis of erucic acid with 2‐octene

Çetinkaya

Düz

İmamoǧlu

2003

Applied Organom Chemis

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The cross-metathesis of erucic acid, (CH 3 (CH 2 ) 7 CH CH(CH 2 ) 11 COOH), with an excess of 2-octene in the presence of an electrochemically produced tungsten-based catalyst has been studied. Crossand self-hydrocarbon products, viz. 2-undecene (C 11 ), 6-dodecene (C 12 ) and 6-pentadecene (C 15 ), were detected. The influence of several parameters, such as the 2-octene/erucic acid and 2-octene/catalyst ratios and the reaction time, on the yield of the cross-metathesis product, 6-pentadecene, was studied. The cross-metathesis of functionalized olefins in the presence of an Al-e − -WCl 6 -CH 2 Cl 2 system has not been reported in the literature so far. The cross-metathesis products in the presence of this catalyst system can be obtained with high yield and high specificity.

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Synthesis and characterization of polyoctenamer with WCl₆e⁻AlCH₂Cl₂ catalyst system via ring‐opening metathesis polymerization

Cited by 15 publications

References 17 publications

The Living ROMP oftrans-Cyclooctene

The Living ROMP oftrans-Cyclooctene

Electrochemically reduced tungsten-based active species as catalysts for metathesis-related reactions: ring-opening metathesis copolymerization of cyclopentene with cyclooctene

Electrochemically reduced tungsten‐based active species as catalysts for cross‐metathesis reactions: cross‐metathesis of erucic acid with 2‐octene

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