Ring-opening metathesis polymerization of dicyclopentadiene by unicomponent catalysts derived from WCl6

Balcar, Hynek; Dosedlová, Alena; Petrusová, Lidmila

doi:10.1016/0304-5102(92)80208-x

Cited by 21 publications

(5 citation statements)

References 8 publications

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“…The spectra for the waxprotected WCl 6 are qualitatively different with a significant absorption band above 500 nm. Complexes of WCl 6 with phenols have been reported to have similar absorption spectra (Balcar et al 1992), so this suggests that the tungsten in the wax-protected catalyst exists as a complex with the nonylphenol that is added. The as-received WCl 6 retained some presumably active WOCl 4 after 24 h of exposure, while the recrystallized and wax-encapsulated forms retained no WCl 6 or WOCl 4 .…”

Section: Mechanical Assessment Of Healing Performancementioning

confidence: 90%

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A new self-healing epoxy with tungsten (VI) chloride catalyst

Kamphaus

Rule

Moore

et al. 2007

J. R. Soc. Interface.

132

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Using self-healing materials in commercial applications requires healing chemistry that is cost-effective, widely available and tolerant of moderate temperature excursions. We investigate the use of tungsten (VI ) chloride as a catalyst precursor for the ring-opening metathesis polymerization of exo-dicyclopentadiene (exo-DCPD) in self-healing applications as a means to achieve these goals. The environmental stability of WCl 6 using three different delivery methods was evaluated and the associated healing performance was assessed following fracture toughness recovery protocols. Both as-received and recrystallized forms of the WCl 6 resulted in nearly complete fracture recovery in self-activated tests, where healing agent is manually injected into the crack plane, at 12 wt% WCl 6 loading. In situ healing using 15 wt% microcapsules of the exo-DCPD produced healing efficiencies of approximately 20%.

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Section: Mechanical Assessment Of Healing Performancementioning

confidence: 90%

“…A probable initial oxidation product is WOCl 4 , which is also a ROMP-active catalyst (Balcar et al 1992). Furthermore, WOCl 4 has been claimed to be a necessary component (in addition to the WCl 6 ) for effective catalysis (Breslow 1990).…”

Section: Introductionmentioning

confidence: 99%

A new self-healing epoxy with tungsten (VI) chloride catalyst

Kamphaus

Rule

Moore

et al. 2007

J. R. Soc. Interface.

132

View full text Add to dashboard Cite

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“…Polydicyclopentadiene (poly-DCPD) is formed through ring-opening metathesis polymerization (ROMP) of its monomer and exhibits excellent impact resistance, chemical corrosion resistance and high heat deflection temperature . A variety of transition-metal-based metathesis catalysts have been used for ROMP of DCPD. − The resulting polymers showed differences in molecular structure ranging from linear to highly cross-linked; therefore, the physical and chemical properties of the material formed are ultimately determined by the catalyst systems.…”

Section: Introductionmentioning

confidence: 99%

Curing Kinetics and Mechanical Properties of endo-Dicyclopentadiene Synthesized Using Different Grubbs’ Catalysts

Yang

Lee

2014

Ind. Eng. Chem. Res.

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Isothermal curing of endo-dicyclopentadiene (endo-DCPD) using the first and second generation Grubbs’ catalysts as the polymerization initiators was studied by means of differential scanning calorimetry (DSC) according to model-free isoconversional and model-fitting approaches. It revealed that the two Grubbs’ catalysts exhibited apparent differences in ring-opening metathesis polymerization (ROMP) of endo-DCPD. The second generation catalyst was more efficient in catalytic activity for overall ROMP of endo-DCPD than the first generation catalyst, as evident from the reaction rate and fractional conversion (α). The model-free isoconversional method showed similar dependence of the activation energy (E α) on α for the two catalyst systems; however, the second generation catalyst system involved a higher E α, up to α ≈ 0.8, above which the E α value suddenly drops with increase of conversion. The model-fitting method of the ROMP was satisfactorily described by the decelerating reaction and the autocatalytic reaction mechanisms for the first and the second generation catalyst systems, respectively. The effect of diffusion-control was incorporated into the model-fitting method to describe the ROMP reaction throughout the entire conversion. For fully cured samples (poly-DCPD), the first generation catalyst system has higher cross-linking density and lower tensile toughness relative to the second generation. Dynamic mechanical behaviors were also different for poly-DCPD formed using the two catalysts.

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“…An estimation of the cis/trans ratio is possible from the relative absorbance values of the latter bands to the absorbance at 1450 cm -1 , which is assigned to deformation vibration of -CH 2groups of the polymeric chain. 108 From those values (Tables 17 and 18) it is clear that Ru catalysts favor formation of trans polymeric chains, while W-based catalytic systems show the opposite trend (although marginally in the case W/PA). The most extreme cases are Ru-I, for which bands related to cis configuration are almost invisible and the cis/trans ratio is very low, and {W 2 }/PA, for which bands related to trans C=C bonds are very weak and the cis/trans ratio is high.…”

Section: Vibrational Spectroscopymentioning

confidence: 95%

“…Therefore, we proceeded by using the {W 2 }/PA catalytic system to synthesize poly(dicyclopentadiene) (PDCPD) gels. Among other catalytic systems, ROMP of DCPD can be induced by WCl 6 (Scheme 9) alone, 106,107 in the presence of organometallic alkylating reagents, 34 oxygen-containing compounds, 108 or PA. 109 Also, Ru-based 1 st and 2 nd generation Grubbs' catalysts (Ru-I and Ru-II; Scheme 9) have been recently utilized for the synthesis of PDCPD aerogels. 77,110,111 In this Chapter, we describe the synthesis and characterization of PDCPD gels with catalytic systems {W 2 }/PA and WCl 6 /PA, and we compare them to PDCPD aerogels synthesized using Ru-I and Ru-II.…”

Section: Applications Of Polydicyclopentadiene Gels Obtained Using a Ditungsten-based Catalytic System 81 Generalmentioning

confidence: 99%

Catalytic polymerization of olefins and cycloolefins with transition metal complexes

Ραπτόπουλος¹

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Στην παρούσα διατριβή μελετάμε δύο είδη πολυμερισμού που προάγονται από μεταλλικά σύμπλοκα: τον ελεγχόμενο ριζικό πολυμερισμό (CRP) και το μεταθετικό πολυμερισμό με διάνοιξη δακτυλίου (ROMP).CRP. Μελετήσαμε την καταλυτική δραστικότητα μιας οικογένειας συμπλόκων των CoII καιMnII που φέρουν τριφαινυλαμιδο-αμινικούς υποκαταστάτες ως προς τη CRP του στυρενίου και του μεθακρυλικού μεθυλεστέρα. Τα σύμπλοκα του CoII είναι πιο δραστικά, με τη στερεοχημεία τους να παίζει κύριο ρόλο στη δραστικότητα και τον έλεγχο του πολυμερισμού. Σε πολλές περιπτώσεις τα λαμβανόμενα πολυμερή εμφανίζουν διμοριακές κατανομές μοριακών βαρών, υποδεικνύοντας τη δράση δύο παράλληλων μηχανισμών.ROMP. Χρησιμοποιήσαμε το διμεταλλικό σύμπλοκο Na[W2(μ-Cl)3Cl4(THF)2]·(THF)3 ({W2},{W 3 W} 6+, a΄2 e΄4) για τη σύνθεση νέων πολυμερικών υλικών. Το {W2} είναι ένας δραστικός ενεργοποιητής της ROMP του νορβορνενίου (NBE) και παραγώγων του. Συνθέσαμε στατιστικά συμπολυμερή NBE/NBD (NBD: νορβορναδιένιο), που συνδυάζουν ιδιότητες γραμμικών και δικτυωμένων πολυμερών. Η καταλυτική δραστικότητα του {W2} μπορεί να βελτιωθεί με προσθήκη μικρής ποσότητας φαινυλακετυλενίου (PA) ως συγκαταλύτη. Το{W2} και το {W2}/PA παρέχουν πολυμερή με υψηλή cis στερεοεκλεκτικότητα. Μελετήσαμε τη δραστικότητα του {W2}/PA και το χρησιμοποιήσαμε για τη σύνθεση μέσω ROMP πηκτωμάτων πολυ(δικυκλοπενταδιενίου) (PDCPD) με υψηλό βαθμό δικτύωσης. Η δομή και οι ιδιότητές τους συγκρίθηκαν με εκείνες πηκτωμάτων PDCPD που ελήφθησαν με χρήση του εμπορικά διαθέσιμου WCl6 και των καταλυτών Grubbs 1ης και 2ης γενιάς. Η διαμόρφωση της αλυσίδας παίζει σημαντικό ρόλο στη διόγκωση των πηκτωμάτων PDCPD σε οργανικούς διαλύτες, η οποία μελετήθηκε διεξοδικά και οδήγησε στην εκτίμηση των παραμέτρων διαλυτότητας Hansen (HSP) του PDCPD με υψηλό ποσοστό cis και της δυνατότητας διαχωρισμού χλωριωμένων διαλυτών από το νερό. Συμπερασματικά, το{W2}/PA διαθέτει μοναδικά πλεονεκτήματα ως προς τη στερεοχημεία, τις ιδιότητες και τις πιθανές εφαρμογές των πηκτωμάτων PDCPD σε σχέση με μονοπυρηνικά συστήματα βασισμένα σε W ή Ru.

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Ring-opening metathesis polymerization of dicyclopentadiene by unicomponent catalysts derived from WCl6

Cited by 21 publications

References 8 publications

A new self-healing epoxy with tungsten (VI) chloride catalyst

A new self-healing epoxy with tungsten (VI) chloride catalyst

Curing Kinetics and Mechanical Properties of endo-Dicyclopentadiene Synthesized Using Different Grubbs’ Catalysts

Catalytic polymerization of olefins and cycloolefins with transition metal complexes

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