Fulvene, metallocene catalysts and preparation method thereof, and preparation of polyolefines copolymer using the same

A preparation method of a fulvene compound represented by the following Chemical Formula 7, which comprises:

• a) a step of reacting a ketal (dioxolane group) derivative represented by the following Chemical Formula 13 with a metal salt, and reacting it with an electrophile represented by the following Chemical Formula 12, and hydrolyzing it to obtain a compound represented by the following Chemical Formula 11;
• b) a step of protecting the alcohol group of the compound represented by Chemical Formula 11 using a compound represented by the following Chemical Formula 10 or by reacting it with dihydropyran or isobutene to obtain a compound represented by the following Chemical Formula 9;
• and
• c) a step of nucleophilic reaction of the intermediate compound represented by Chemical Formula 9 with an organometallic compound represented by the following Chemical Formula 8a or Chemical Formula 8b to prepare fulvene compound represented by the following Chemical Formula 7:
• R1—M Chemical Formula 8a
• R1—MgX Chemical Formula 8b
• R5—Y Chemical Formula 10
• wherein
• each of R1, R2, R3, and R4 is individually or simultaneously a hydrogen;
• a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl;
• a C1 to C20 alkyl or aryl having an oxygen atom or a nitrogen atom;
• or a group 14 metalloid radical substituted by a hydrocarbyl, wherein at least one of R1 and R2 is not a hydrogen, and R3 and R4 are not linked by an alkylidine radical including an alkyl or aryl radical to form a ring;
• R5 is a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl;
• a C1 to C20 alkyl or aryl having an oxygen atom or a nitrogen atom;
• or a group 14 metalloid radical substituted by a hydrocarbyl;
• X is a halogen atom;
• Y is a leaving group of the nucleophilic substitution, which is a halogen or a sulfonate group including trifluoromethylsulfonate or p-toluenesulfonate;
• and
• M is an alkali metal.

A compound represented by the following Chemical Formula 5:

• wherein
• each of R1 and R2 is individually or simultaneously a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl, a C1 to C20 alkyl or aryl having an oxygen atom or a nitrogen atom, or a group 14 metalloid radical substituted by a hydrocarbyl;
• each of R3, and R4 is individually or simultaneously a hydrogen, a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl, a C1 to C20 alkyl or aryl having an oxygen atom or a nitrogen atom, or a group 14 metalloid radical substituted by a hydrocarbyl, and R3 and R4 are not linked by an alkylidine radical including an alkyl or aryl radical to form a ring;
• and
• A is fluorenyl or its derivative, indenyl or its derivative, a substituted or unsubstituted amido, or a substituted or unsubstituted phosphino.

A metallocene compound represented by the following Chemical Formula 1:

• wherein
• each of R1 and R2 is individually or simultaneously a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl, a C1 to C20 alkyl or aryl having an oxygen atom or a nitrogen atom, or a group 14 metalloid radical substituted by a hydrocarbyl;
• each of R3 and R4 is individually or simultaneously a hydrogen, a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl, a C1 to C20 alkyl or aryl having an oxygen atom or a nitrogen atom, or a group 14 metalloid radical substituted by a hydrocarbyl, and R3 and R4 are not linked by an alkylidine radical including an alkyl or aryl radical to form a ring;
• M1 is a group 4transition metal;
• A is fluorenyl or its derivative, indenyl or its derivative, a substituted or unsubstituted amido, or a substituted or unsubstituted phosphino;
• and
• each of Q1 and Q2 is individually or simultaneously a halogen;
• a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl;
• a C1 to C20 substituted or unsubstituted alkylidene;
• a substituted or unsubstituted amido;
• or a C1 to C20 alkylalkoxy or arylalkoxy, or Q1 and Q2 are linked by an alkylidine radical including an alkyl or aryl radical to form a ring.

A preparation method of the metallocene compound represented by the following Chemical Formula 1, which comprises a step of reacting a fulvene compound represented by the following Chemical Formula 7 with a cyclopentadiene derivative to obtain a compound represented by the following Chemical Formula 5:

• wherein
• each of R1, R2, R3, and R4 is individually or simultaneously a hydrogen;
• a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl;
• a C1 to C20 alkyl or aryl having an oxygen atom or a nitrogen atom;
• or a group 14 metalloid radical substituted by a hydrocarbyl, wherein at least one of R1 and R2 is not a hydrogen, and R3 and R4 are not linked by an alkylidine radical including an alkyl or aryl radical to form a ring;
• M1 is a group 4 transition metal;
• A is cyclopentadienyl or its derivative;
• fluorenyl or its derivative;
• indenyl or its derivative;
• a substituted or unsubstituted amido;
• or a substituted or unsubstituted phosphino;
• and
• each of Q1 and Q2 is individually or simultaneously a halogen;
• a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl;
• a C1 to C20 substituted or unsubstituted alkylidene;
• a substituted or unsubstituted amido;
• or a C1 to C20 alkylalkoxy or arylalkoxy, or Q1 and Q2 are linked by an alkylidine radical including an alkyl or aryl radical to form a ring.

A preparation method of an ethylenic polyolefin polymer, which comprises a step of polymerizing a monomer selected from a group consisting of ethylene, an α-olefin, a dienic monomer, a trienic monomer, and a styrene monomer in the presence of a metallocene catalyst represented by the following Chemical Formula 1 and a cocatalyst selected from a group consisting of a linear, cyclic, or clustered compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, and a compound represented by the following Chemical Formula 4a or Chemical Formula 4b:

• wherein
• each of R1 and R2 is individually or simultaneously a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl, a C1 to C20 alkyl or aryl having an oxygen atom or a nitrogen atom, or a group 14 metalloid radical substituted by a hydrocarbyl;
• each of R3 and R4 is individually or simultaneously a hydrogen, a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl, a C1 to C20 alkyl or aryl having an oxygen atom or a nitrogen atom, or a group 14 metalloid radical substituted by a hydrocarbyl, and R3 and R4 are not linked by an alkylidine radical including an alkyl or aryl radical to form a ring;
• M1 is a group 4transition metal;
• A is fluorenyl or its derivative, indenyl or its derivative, a substituted or unsubstituted amido, or a substituted or unsubstituted phosphino;
• and
• each of Q1 and Q2 is independently or simultaneously a halogen, a C1 to C20 alkyl, alkenyl, alkylaryl, arylalkyl, or aryl, a C1 to C20 substituted or unsubstituted alkylidene, a substituted or unsubstituted amido, or a C1 to C20 alkylalkoxy or arylalkoxy,
• —[Al(R6)—O]a— Chemical Formula 2
• wherein
• R6 is a halogen, a C1 to C20 hydrocarbyl radical, or a C1 to C20 hydrocarbyl radical substituted by a halogen;
• and
• a is an integer of 2 to 5000,
• N(R6)3 Chemical Formula 3
• wherein
• N is a group XIII element;
• and
• each of three R6's is independently or simultaneously a halogen, a C1 to C20 hydrocarbyl radical, or a C1 to C20 hydrocarbyl radical substituted by a halogen, and
• [L—H]+[NE4]− Chemical Formula 4a
• [L]+[NE4]− Chemical Formula 4b
• wherein
• L is a neutral or cationic Lewis acid;
• N is a group 13 element;
• and
• each of four E's is independently or simultaneously a C6 to C20 aryl radical substituted by one or more substituents selected from a group consisting of a halogen, a C1 to C20 hydrocarbyl, a C1 to C20 alkoxy, and a phenoxy radical.