Apparatuses and processes that produce multimodal polyolefins, and in particular, polyethylene resins, are disclosed herein. This is accomplished by using two reactors in series, where one of the reactors is a multi-zone circulating reactor that can circulate polyolefin particles through two polymerization zones optionally having two different flow regimes so that the final multimodal polyolefin has improved product properties and improved product homogeneity.

Apparatuses and processes that produce multimodal polyolefins, and in particular, polyethylene resins, are disclosed herein. This is accomplished by using two reactors in series, where one of the reactors is a multi-zone circulating reactor that can circulate polyolefin particles through two polymerization zones optionally having two different flow regimes so that the final multimodal polyolefin has improved product properties and improved product homogeneity.

The invention relates to a metallocene complex according to formula (I), (I) wherein R.sub.1 and R.sub.2 are independently selected from H, an alkyl or an aryl group, wherein R.sub.3 is a C1-C10 alkyl group, wherein R′ is selected from H, an alkyl group, an aryl group and wherein different R′ substituents can be connected to form a ring structure and wherein B is a 1,2 phenylene bridging moiety, which can be optionally substituted, wherein Mt is selected from Ti, Zr and Hf, X is an anionic ligand, z is the number of X groups and equals the valence of Mt minus 2. The invention also relates to a catalyst comprising the reaction product of the metallocene complex and a cocatalyst. Further the invention relates to a (co)polymerisation process of olefinic monomers. ##STR00001##

The invention relates to a metallocene complex according to formula (I), (I) wherein R.sub.1 and R.sub.2 are independently selected from H, an alkyl or an aryl group, wherein R.sub.3 is a C1-C10 alkyl group, wherein R′ is selected from H, an alkyl group, an aryl group and wherein different R′ substituents can be connected to form a ring structure and wherein B is a 1,2 phenylene bridging moiety, which can be optionally substituted, wherein Mt is selected from Ti, Zr and Hf, X is an anionic ligand, z is the number of X groups and equals the valence of Mt minus 2. The invention also relates to a catalyst comprising the reaction product of the metallocene complex and a cocatalyst. Further the invention relates to a (co)polymerisation process of olefinic monomers. ##STR00001##

Embodiments of the disclosure include processes of polymerizing olefins. The process includes contacting ethylene and a (C.sub.3-C.sub.40)alpha-olefin comonomer in the presences of a catalyst system. The catalyst system comprises a procatalyst and a bimetallic activator complex. The bimetallic activator complex comprises an anion and a countercation, and the anion has a structure according to formula (I).

The heterogeneous procatalyst of this disclosure includes a titanium species; a hydrocarbon soluble transition metal compound having a structure M(OR.sup.1).sub.z; a chlorinating agent having a structure A(Cl).sub.x(R.sup.2).sub.3-x, and a magnesium chloride component. M of M(OR.sup.1).sub.z is a non-reducing transition metal other than titanium, the non-reducing transition metal being in an oxidation state of +2 or +3. Each R.sup.1 is independently (C.sub.1-C.sub.30)hydrocarbyl or —C(O)R.sup.11, where R.sup.11 is (C.sub.1-C.sub.30)hydrocarbyl. Subscript z of M(OR.sup.1).sub.z is 2 or 3. Each R.sup.1 and R.sup.11 may be optionally substituted with one or more than one halogen atoms, or one or more than one —Si(R.sup.S).sub.3, where each R.sup.S is (C.sub.1-C.sub.30)hydrocarbyl. A of A(Cl).sub.x(R.sup.2).sub.3-x is aluminum or boron; R.sup.2 is (C.sub.1-C.sub.30)hydrocarbyl; and x is 1, 2, or 3; and a magnesium chloride component.

The heterogeneous procatalyst of this disclosure includes a titanium species; a hydrocarbon soluble transition metal compound having a structure M(OR.sup.1).sub.z; a chlorinating agent having a structure A(Cl).sub.x(R.sup.2).sub.3-x, and a magnesium chloride component. M of M(OR.sup.1).sub.z is a non-reducing transition metal other than titanium, the non-reducing transition metal being in an oxidation state of +2 or +3. Each R.sup.1 is independently (C.sub.1-C.sub.30)hydrocarbyl or —C(O)R.sup.11, where R.sup.11 is (C.sub.1-C.sub.30)hydrocarbyl. Subscript z of M(OR.sup.1).sub.z is 2 or 3. Each R.sup.1 and R.sup.11 may be optionally substituted with one or more than one halogen atoms, or one or more than one —Si(R.sup.S).sub.3, where each R.sup.S is (C.sub.1-C.sub.30)hydrocarbyl. A of A(Cl).sub.x(R.sup.2).sub.3-x is aluminum or boron; R.sup.2 is (C.sub.1-C.sub.30)hydrocarbyl; and x is 1, 2, or 3; and a magnesium chloride component.

The present disclosure provides a composition. In an embodiment, the composition is an ethylene-based polymer composition formed by high pressure (greater or equal to 100 MPa) free radical polymerization. The ethylene-based polymer composition includes ethylene monomer and a mixture of hydroxyl-terminated polybutadiene molecules (PB-OH). Each PB-OH molecule includes internal alkene groups and terminal alkene groups. Each PB-OH molecule has more internal alkene groups than terminal alkene groups.

A process for preparing a catalyst component made from or containing Mg, Ti, and at least an electron donor compound (ID), including the steps of: (a) reacting a Mg based compound with a Ti compound, having at least a Ti—Cl bond, in an amount such that the Ti/Mg molar ratio is greater than 3 and at a temperature ranging from 0 to 150° C., thereby yielding an intermediate solid catalyst component containing Mg and Ti; and (b) contacting the intermediate solid catalyst component with a gaseous stream containing the electron donor compound (ID) in a gaseous dispersing medium, thereby yielding a final solid catalyst component having an ID/Ti molar ratio ranging from 0.5:1 to 20:1.

A process for preparing a catalyst component made from or containing Mg, Ti, and at least an electron donor compound (ID), including the steps of: (a) reacting a Mg based compound with a Ti compound, having at least a Ti—Cl bond, in an amount such that the Ti/Mg molar ratio is greater than 3 and at a temperature ranging from 0 to 150° C., thereby yielding an intermediate solid catalyst component containing Mg and Ti; and (b) contacting the intermediate solid catalyst component with a gaseous stream containing the electron donor compound (ID) in a gaseous dispersing medium, thereby yielding a final solid catalyst component having an ID/Ti molar ratio ranging from 0.5:1 to 20:1.