TY - JOUR
T1 - Titanacalixarenes in homogeneous catalysis
T2 - Synthesis, conformation and catalytic activity in ethylene polymerisation
AU - Espinas, Jeff
AU - Darbost, Ulrich
AU - Pelletier, Jeremie
AU - Jeanneau, Erwan
AU - Duchamp, Christian
AU - Bayard, François
AU - Boyron, Olivier
AU - Broyer, Jean Pierre
AU - Thivolle-Cazat, Jean
AU - Basset, Jean Marie
AU - Taoufik, Mostafa
AU - Bonnamour, Isabelle
PY - 2010
Y1 - 2010
N2 - Variously substituted titanacalixarenes were synthesised and tested for their performance as catalysts in ethylene polymerisation: p-tert-butylcalix[4] arene was derivatised to afford distal diether p-tert-butylcalix[4]arenes L1-L4, distal dihydroxy-depleted L5, proximal dihydroxy-depleted L6, proximal diether p-tert-butylcalix[4]arene L7, proximal intra-bridged disiloxane L8 and proximal monoether L9. (Dichlorotitana)-p-tert-butylcalix[4]arenes 1-8 and (monochlorotitana)-p-tertbutylcalix[4]arene 9 have been successfully synthesised by reacting L1-L4 with TiCl4·2THF or L5-L9 with TiCl 4. The structural conformation of complexes 1-9 in solution were determined by 1H NMR, 13C NMR, NOESY and COSY spectroscopic studies. Compounds 2, 3 and 4 have been structurally characterised by single-crystal X-ray diffraction. Upon activation with methylaluminoxane, compounds 1-8 revealed low to moderate activities for the production of high-density polyethylene (HDPE) to ultra-high-molecular-weight polyethylene (UHMWPE). 6/MAO gave the best activity at 770 kgPE(molTi) -1h-1.
AB - Variously substituted titanacalixarenes were synthesised and tested for their performance as catalysts in ethylene polymerisation: p-tert-butylcalix[4] arene was derivatised to afford distal diether p-tert-butylcalix[4]arenes L1-L4, distal dihydroxy-depleted L5, proximal dihydroxy-depleted L6, proximal diether p-tert-butylcalix[4]arene L7, proximal intra-bridged disiloxane L8 and proximal monoether L9. (Dichlorotitana)-p-tert-butylcalix[4]arenes 1-8 and (monochlorotitana)-p-tertbutylcalix[4]arene 9 have been successfully synthesised by reacting L1-L4 with TiCl4·2THF or L5-L9 with TiCl 4. The structural conformation of complexes 1-9 in solution were determined by 1H NMR, 13C NMR, NOESY and COSY spectroscopic studies. Compounds 2, 3 and 4 have been structurally characterised by single-crystal X-ray diffraction. Upon activation with methylaluminoxane, compounds 1-8 revealed low to moderate activities for the production of high-density polyethylene (HDPE) to ultra-high-molecular-weight polyethylene (UHMWPE). 6/MAO gave the best activity at 770 kgPE(molTi) -1h-1.
KW - Calixarenes
KW - Ethylene
KW - Homogeneous catalysis
KW - Polymerization
KW - Titanium
UR - http://www.scopus.com/inward/record.url?scp=77949362111&partnerID=8YFLogxK
U2 - 10.1002/ejic.200901185
DO - 10.1002/ejic.200901185
M3 - Article
AN - SCOPUS:77949362111
SN - 1434-1948
SP - 1349
EP - 1359
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 9
ER -