Metallocene compound and preparation method therefor

Patent metadata

Field	Value
Publication number	US-2018201638-A1
Application number	US-201615743391-A
Country	US
Kind code	A1
Filing date	Feb 18, 2016
Priority date	Jul 15, 2015
Publication date	Jul 19, 2018
Grant date	—

Abstract

A preparation method for a metallocene compound is provided. The method includes: stirring at least one compound I among compounds expressed by the following chemical formula (I) and a hydrogenation reaction catalyst of 0.10 to 0.55 parts by weight based on 100 parts by weight of the compound I under a hydrogen atmosphere; and obtaining a metallocene compound containing at least one first compound among the compounds expressed by the following chemical formula (1). Chemical formula (I) and (1) are provided in the specification.

First claim

1 . A preparation method for a metallocene compound, the method comprising:
stirring at least one compound I among compounds expressed by the following chemical formula (I) and a hydrogenation reaction catalyst of 0.10 to 0.55 parts by weight based on 100 parts by weight of the compound I under a hydrogen atmosphere; and obtaining a metallocene compound containing at least one first compound among the compounds expressed by the following chemical formula (1)

in each of the chemical formula (I) and the chemical formula (1),
M is any one of titanium (Ti), zirconium (Zr) or hafnium (Hf);
Q is any one of carbon (C), silicon (Si), germanium (Ge), or tin (Sn);
X is independently any one of halogen, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 satisfy the following (i) or (ii), and each of R 13 and R 14 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 14 carbon atoms.
(i) each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms.
(ii) among R m (m is an integer of 1 to 12), two adjacent R n and R n+1 (n is an integer from 1 to 11) are connected to each other to form a monocyclic or polycyclic rings having 3 to 15 carbon atoms in which the alkyl group having 1 to 4 carbon atoms is substituted or not substituted, and at this time, the remaining R m except R n and R n+1 is independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms.

2 . The method of claim 1 , wherein the alkyl group having 1 to 20 carbon atoms is a hetero alkyl group which has at least one carbon (C) substituted with at least one of oxygen (O), nitrogen (N), and sulfur (S), and
the monocyclic ring or polycyclic rings having 3 to 15 carbon atoms are a monocyclic or polycyclic hetero rings having 3 to 15 carbon atoms in which at least one carbon (C) is substituted with at least one of oxygen (O), nitrogen (N), and sulfur (S).

3 . The method of claim 1 , wherein the hydrogenation reaction catalyst contains at least one metal among nickel (Ni), platinum (Pt), ruthenium (Ru), rhodium (Rh) and palladium (Pd).

4 . The method of claim 3 , wherein the hydrogenation reaction catalyst is a palladium-carried catalyst in which palladium (Pd) is carried on a carbon carrier.

5 . The method of claim 1 , wherein stirring of the compound I and the hydrogenation reaction catalyst is performed in an aromatic solvent which is not halogenated.

6 . The method of claim 5 , wherein the non-halogenated aromatic solvent is at least one of benzene, toluene, xylene, o-xylene, m-xylene, p-xylene, mesitylene, tetralin, anisole, cumene, 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 1-ethyl-2-methylbenzene, 1-ethyl-3-methylbenzene, and 1-ethyl-4-methylbenzene.

7 . The method of claim 1 , wherein the metallocene compound further comprises at least one second compound among the compounds expressed by the following chemical formula (2):

in the chemical formula (2),
M is any one of titanium (Ti), zirconium (Zr) or hafnium (Hf);
Q is any one of carbon (C), silicon (Si), germanium (Ge), or tin (Sn);
X is independently any one of halogen, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 satisfy the following (i) or (ii), and each of R 13 and R 14 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 14 carbon atoms.
(i) each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms.
(ii) among R m (m is an integer of 1 to 12), two adjacent R n and R n+1 (n is an integer from 1 to 11) are connected to each other to form a monocyclic or polycyclic rings having 3 to 15 carbon atoms in which the alkyl group having 1 to 4 carbon atoms is substituted or not substituted, and at this time, the remaining R m except R n and R n+1 is independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms.

8 . (canceled)

9 . The method of claim 1 , wherein the metallocene compound further comprises the compound I.

10 . A metallocene compound containing at least one first compound among compounds expressed by the following chemical formula (1):

in the chemical formula (1),
M is any one of titanium (Ti), zirconium (Zr) or hafnium (Hf);
Q is any one of carbon I, silicon (Si), germanium (Ge), or tin (Sn);
X is independently any one of halogen, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 satisfy the following (i) or (ii), and each of R 13 and R 14 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 14 carbon atoms.
(i) each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms.
(ii) among R m (m is an integer of 1 to 12), two adjacent R n and R n+1 (n is an integer from 1 to 11) are connected to each other to form a monocyclic or polycyclic rings having 3 to 15 carbon atoms in which the alkyl group having 1 to 4 carbon atoms is substituted or not substituted, and at this time, the remaining R m except R n and R n+1 is independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms.

11 . The metallocene compound of claim 10 , further comprising:
at least one second compound among the compounds expressed by the following formula (2):

in the chemical formula (2),
M is any one of titanium (Ti), zirconium (Zr) or hafnium (Hf);
Q is any one of carbon I, silicon (Si), germanium (Ge), or tin (Sn);
X is independently any one of halogen, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 satisfy the following (i) or (ii), and each of R 13 and R 14 is independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 14 carbon atoms.
(i) each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms,

Assignees

• Hanwha Chemical Corp

Inventors

• Piao Lan Hua
• Jun Sung Hae
• Lee Hyun Seung
• Jeong Dong Wook

Classifications

• C07F17/00 Primary

  Metallocenes · CPC title

• C08F2420/06

  Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2420/07

  Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom · CPC title