Supported metallocene complex and process for its preparation

A process for the preparation of a metallocene complex of titanium, zirconium or hafnium, supported on an inorganic solid, comprising the following steps in succession:

• (a) putting in contact and reacting an inorganic solid having hydroxide groups on the surface, which are reactive with an alkoxysilane group, with at least one organic compound having the following formula (II):
• ##STR7## wherein:
• C.sub.p represents a cyclopentadienyl ring;
• each R.sup.4 can independently be hydrogen, halogen, a C.sub.1 -C.sub.8 alkyl group, a C.sub.3 -C.sub.12 alkylsilyl group, a C.sub.5 -C.sub.8 cycloalkyl group, a C.sub.6 -C.sub.14 aryl group, a C.sub.6 -C.sub.15 arylalkyl group, a C.sub.1 -C.sub.8 alkoxy group, a C.sub.1 -C.sub.8 alkylcarbonyloxy group, or two adjacent R.sup.4 groups can combine with each other to form an aliphatic or aromatic cyclic structure comprising in the cycle at least three non-metal atoms different from hydrogen and halogen;
• R.sup.5 and R.sup.6 can, independently of each other, be a C.sub.1 -C.sub.5 alkyl group, a C.sub.5 -C.sub.8 cycloalkyl group, a C.sub.6 -C.sub.12 aryl group, a C.sub.7 -C.sub.12 arylalkyl group or a C.sub.1 -C.sub.5 alkoxy group;
• R.sup.7, R.sup.8, R.sup.9 and R.sup.10 can, independently of each other, be hydrogen, a C.sub.1 -C.sub.5 alkyl group, a C.sub.5 -C.sub.8 cycloalkyl group, a C.sub.6 -C.sub.12 aryl group, a C.sub.7 -C.sub.12 arylalkyl group or a C.sub.1 -C.sub.5 alkoxy group;
• R.sup.11 and R.sup.12 can, independently of each other, be a C.sub.1 -C.sub.5 alkyl group, a C.sub.5 -C.sub.8 cycloalkyl group, a C.sub.6 -C.sub.12 aryl group, a C.sub.7 -C.sub.12 arylalkyl group or a C.sub.1 -C.sub.5 alkoxy group;
• R.sup.13 is a C.sub.1 -C.sub.5 alkyl group;
• Ar is a C.sub.3 -C.sub.16 divalent aromatic or heteroaromatic group;
• the indexes "m" and "n" can be 0, or can independently have all the integer values between 1 and 4,
• the indexes "x" and "y" can independently have the value of 0 or 1,
• to obtain an inorganic solid functionalized with cyclopentadienyl groups;
• (b) putting in contact and reacting, in an inert liquid medium, said functionalized inorganic compound with a compound of a metal M having the following formula (III):
• ##STR8## wherein:
• M represents a metal selected from titanium, zirconium or hafnium;
• R' and R" each independently represent a substituent group selected from a hydrogen or halogen atom, a C.sub.1 -C.sub.8 alkyl group, a C.sub.3 -C.sub.12 akylsilyl group, a C.sub.5 -C.sub.8 cycloalkyl group, a C.sub.6 -C.sub.10 aryl group, a C.sub.1 -C.sub.8 alkoxy group, a C.sub.2 -C.sub.10 dialkylamide group and a C.sub.4 -C.sub.20 alkylsilylamide group;
• R'" represents a substituent group of the same nature as the previous groups R' and R", selected independently of these, or an anion containing an .eta..sup.5 -cyclopentadienyl ring co-ordinated to the metal M;
• and
• B represents a C.sub.1 -C.sub.8 alkyl group, a C.sub.5 -C.sub.8 cycloalkyl group, a C.sub.6 -C.sub.10 aryl group or a C.sub.2 -C.sub.10 dialkylamide group;
• to form said supported metallocene complex.