Vanadium-based pro-catalysts bearing depleted 1,3-calix[4]arenes for ethylene or ε-caprolactone polymerization

Lucy Clowes; Carl Redshaw; David L. Hughes

doi:10.1021/ic2010198

Vanadium-based pro-catalysts bearing depleted 1,3-calix[4]arenes for ethylene or ε-caprolactone polymerization

Lucy Clowes, Carl Redshaw, David L. Hughes

Research output: Contribution to journal › Article › peer-review

32 Citations (Scopus)

Abstract

Reaction of [V(X)(OR)₃] (X = O, Np-tolyl, R = nPr, tBu) with 5,11,17,23-tBu-25,27-dihydroxycalix[4]arene (LH₂) led to the formation of [V(X)(OR)L]₂ X = O, R = nPr (1); X = Np-tolyl, R = nPr (2); X = Np-tolyl, R = tBu (3) as the major product. In the case of X = O, the minor hydrolysis product {[VO(OnPr)]₂(µ-O)L}₂ (4) has also been characterized. Complexes (1)–(4), in the presence of the co-catalyst dimethylaluminum chloride and the reactivator ethyltrichloroacetate, are highly active (=16,400 g/mmol h bar), thermally stable pro-catalysts for the polymerization of ethylene. The use of silica supports with (1) and (2) under slurry conditions yielded polymer with activities =30 g/mmol h. Complexes (1)–(3) have also been screened as pro-catalysts for the ring-opening polymerization of e-caprolactone; the conversion rate order (1) (94%) > (2) (46%) > (3) (20%) was observed at 80 °C over 72 h.

Original language	English
Pages (from-to)	7838–7845
Number of pages	8
Journal	Inorganic Chemistry
DOIs	https://doi.org/10.1021/ic2010198
Publication status	Published - 2011

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10.1021/ic2010198

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@article{9306bc72e51e4b03b05bd486619edc4a,

title = "Vanadium-based pro-catalysts bearing depleted 1,3-calix[4]arenes for ethylene or ε-caprolactone polymerization",

abstract = "Reaction of [V(X)(OR)3] (X = O, Np-tolyl, R = nPr, tBu) with 5,11,17,23-tBu-25,27-dihydroxycalix[4]arene (LH2) led to the formation of [V(X)(OR)L]2 X = O, R = nPr (1); X = Np-tolyl, R = nPr (2); X = Np-tolyl, R = tBu (3) as the major product. In the case of X = O, the minor hydrolysis product {[VO(OnPr)]2(µ-O)L}2 (4) has also been characterized. Complexes (1)–(4), in the presence of the co-catalyst dimethylaluminum chloride and the reactivator ethyltrichloroacetate, are highly active (=16,400 g/mmol h bar), thermally stable pro-catalysts for the polymerization of ethylene. The use of silica supports with (1) and (2) under slurry conditions yielded polymer with activities =30 g/mmol h. Complexes (1)–(3) have also been screened as pro-catalysts for the ring-opening polymerization of e-caprolactone; the conversion rate order (1) (94%) > (2) (46%) > (3) (20%) was observed at 80 °C over 72 h.",

author = "Lucy Clowes and Carl Redshaw and Hughes, {David L.}",

year = "2011",

doi = "10.1021/ic2010198",

language = "English",

pages = "7838–7845",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Vanadium-based pro-catalysts bearing depleted 1,3-calix[4]arenes for ethylene or ε-caprolactone polymerization

AU - Clowes, Lucy

AU - Redshaw, Carl

AU - Hughes, David L.

PY - 2011

Y1 - 2011

N2 - Reaction of [V(X)(OR)3] (X = O, Np-tolyl, R = nPr, tBu) with 5,11,17,23-tBu-25,27-dihydroxycalix[4]arene (LH2) led to the formation of [V(X)(OR)L]2 X = O, R = nPr (1); X = Np-tolyl, R = nPr (2); X = Np-tolyl, R = tBu (3) as the major product. In the case of X = O, the minor hydrolysis product {[VO(OnPr)]2(µ-O)L}2 (4) has also been characterized. Complexes (1)–(4), in the presence of the co-catalyst dimethylaluminum chloride and the reactivator ethyltrichloroacetate, are highly active (=16,400 g/mmol h bar), thermally stable pro-catalysts for the polymerization of ethylene. The use of silica supports with (1) and (2) under slurry conditions yielded polymer with activities =30 g/mmol h. Complexes (1)–(3) have also been screened as pro-catalysts for the ring-opening polymerization of e-caprolactone; the conversion rate order (1) (94%) > (2) (46%) > (3) (20%) was observed at 80 °C over 72 h.

AB - Reaction of [V(X)(OR)3] (X = O, Np-tolyl, R = nPr, tBu) with 5,11,17,23-tBu-25,27-dihydroxycalix[4]arene (LH2) led to the formation of [V(X)(OR)L]2 X = O, R = nPr (1); X = Np-tolyl, R = nPr (2); X = Np-tolyl, R = tBu (3) as the major product. In the case of X = O, the minor hydrolysis product {[VO(OnPr)]2(µ-O)L}2 (4) has also been characterized. Complexes (1)–(4), in the presence of the co-catalyst dimethylaluminum chloride and the reactivator ethyltrichloroacetate, are highly active (=16,400 g/mmol h bar), thermally stable pro-catalysts for the polymerization of ethylene. The use of silica supports with (1) and (2) under slurry conditions yielded polymer with activities =30 g/mmol h. Complexes (1)–(3) have also been screened as pro-catalysts for the ring-opening polymerization of e-caprolactone; the conversion rate order (1) (94%) > (2) (46%) > (3) (20%) was observed at 80 °C over 72 h.

U2 - 10.1021/ic2010198

DO - 10.1021/ic2010198

M3 - Article

SP - 7838

EP - 7845

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

ER -