Metallocene compound, and preparation method therefor and application thereof

A preparation method of a metallocene compound of formula (I):

• RIRIIZ(CpIII)n(E)2-nMLIVLV, formula (I)
• wherein in formula (I), RI and RII are the same or different, and both of RI and RII are selected from amino-substituted C1-C6 hydrocarbyl, amino-substituted C1-C6 halohydrocarbyl, amino-substituted C1-C6 alkoxy, amino-substituted C6-C8 phenolic group, metallocene group-substituted C1-C6 hydrocarbyl, metallocene group-substituted C1-C6 halohydrocarbyl, metallocene group-substituted C1-C6 alkoxy, and metallocene group-substituted C6-C8 phenolic group;
• or,
• one of RI and RII is selected from amino-substituted C1-C6 hydrocarbyl, amino-substituted C1-C6 halohydrocarbyl, amino-substituted C1-C6 alkoxy, and amino-substituted C6-C8 phenolic group, metallocene group-substituted C1-C6 hydrocarbyl, metallocene group-substituted C1-C6 halohydrocarbyl, metallocene group-substituted C1-C6 alkoxy, and metallocene group-substituted C6-C8 phenolic group, and the other is a C1-C6 hydrocarbyl;
• Z is selected from carbon, silicon, germanium, and tin;
• CpIII is cyclopentadienyl containing a substituent, indenyl containing a substituent, or fluorenyl containing a substituent, as shown in formula (II), wherein Ri, Rii, and Riii are substituents in the corresponding rings;
• Ri, Rii and Riii are the same or different, and each independently selected from hydrogen, and linear or branched, saturated or unsaturated C1-C20 hydrocarbyl with or without a heteroatom;
• and Ri, Rii and Riii are not hydrogen at the same time;
• E is NRiv or PRiv;
• Riv is selected from hydrogen and linear or branched, saturated or unsaturated C1-C20 hydrocarbyl with or without a heteroatom;
• M is selected from Ti, Zr, and Hf;
• LIV and LV are the same or different, and each independently selected from hydrogen, chlorine, dimethylamino, and linear or branched, saturated or unsaturated C1-C20 hydrocarbyl with or without a heteroatom;
• and
• n is 1 or 2;
• when n is 2, the preparation method comprises:
• S1. reacting a H2(CpIII) with an alkali metal-organic compound to form a corresponding [H(CpIII)]− alkali metal salt;
• S2. reacting the [H(CpIII)]− alkali metal salt with a RIRIIZX2 to form a RIRIIZ[H(CpIII)]2;
• S3. reacting the RIRIIZ[H(CpIII)]2 with an alkali metal-organic compound to form a corresponding RIRIIZ(CpIII)22- alkali metal salt;
• S4. reacting the RIRIIZ(CpIII)22- alkali metal salt with an X2MLIVLV for salt elimination reaction, to obtain a RIRIIZ(CpIII)2MLIVLV;
• and
• when n is 1, the preparation method comprises:
• S1. reacting a H2(CpIII) and a H2(E) with an alkali metal-organic compound respectively, to form a corresponding [H(CpIII)]− alkali metal salt and a corresponding [H(E)]− alkali metal salt;
• S2. reacting the [H(CpIII)]− alkali metal salt and the [H(E)]− alkali metal salt with a RIRIIZX2 to form a RIRIIZ[H(CpIII)][H(E)];
• S3. reacting the RIRIIZ[H(CpIII)][H(E)] with an alkali metal-organic compound to form a corresponding RIRIIZ(CpIII)(E)2- alkali metal salt;
• S4. reacting the RIRIIZ(CpIII)(E)2- alkali metal salt with an X2MLIVLV for salt elimination reaction, to obtain a RIRIIZCpIII EMLIVLV;
• wherein X is selected from Cl, Br and I;
• and
• wherein, in S4, the RIRIIZ(CpIII)22- alkali metal salt or RIRIIZ(CpIII)(E)2- alkali metal salt, without separation, directly reacts with the X2MLIVLV for salt elimination reaction.

A preparation method of a metallocene compound of formula (I)

• RIRIIZ(CpIII)n(E)2-nMLIVLV, formula (I)
• wherein in formula (I), RI and RII are the same or different, and both RI and RII are selected from amino-substituted C1-C6 hydrocarbyl, amino-substituted C1-C6 halohydrocarbyl, amino-substituted C1-C6 alkoxy, amino-substituted C6-C8 phenolic group, metallocene group-substituted C1-C6 hydrocarbyl, metallocene group-substituted C1-C6 halohydrocarbyl, metallocene group-substituted C1-C6 alkoxy, and metallocene group-substituted C6-C8 phenolic group;
• or
• one of RI and RII is selected from selected from amino-substituted C1-C6 hydrocarbyl, amino-substituted C1-C6 halohydrocarbyl, amino-substituted C1-C6 alkoxy, amino-substituted C6-C8 phenolic group, metallocene group-substituted C1-C6 hydrocarbyl, metallocene group-substituted C1-C6 halohydrocarbyl, metallocene group-substituted C1-C6 alkoxy, and metallocene group-substituted C6-C8 phenolic group, the other group is a C1-C6 hydrocarbyl;
• Z is selected from carbon, silicon, germanium, and tin;
• CpIII is cyclopentadienyl containing a substituent, indenyl containing a substituent, or fluorenyl containing a substituent, as shown in formula (II), wherein Ri, Rii, and Riii are substituents in the corresponding rings;
• Ri, Rii and Riii are the same or different, and each independently selected from hydrogen, and linear or branched, saturated or unsaturated C1-C20 hydrocarbyl with or without a heteroatom;
• and Ri, Rii and Riii are not hydrogen at the same time;
• E is NRiv or PRiv;
• Riv is selected from hydrogen and linear or branched, saturated or unsaturated C1-C20 hydrocarbyl with or without a heteroatom;
• M is selected from Ti, Zr, and Hf;
• LIV and LV are the same or different, and each independently selected from hydrogen, chlorine, dimethylamino, and linear or branched, saturated or unsaturated C1-C20 hydrocarbyl with or without a heteroatom;
• and
• n is 1 or 2;
• the preparation method comprises:
• preparing the metallocene compound by carrying out a Z hydrogenation reaction between a precursor RIHZ(CpIII)n(E)2-nMLIVLV and a precursor of the RII;
• wherein the precursor of the RII is a molecule containing a multiple bond, wherein the molecule containing a multiple bond is selected from organic multiple bond molecules, CO and CO2, wherein the multiple bond is one or more bonds of C═C, C≡C, C═N, C≡N, C═O, C≡P, N═N, C═S, C═C═C, C═C═N, C═C═O, and N═C═N.