Process for producing olefin polymer

Patent metadata

Field	Value
Publication number	US-9340628-B2
Application number	US-201314396509-A
Country	US
Kind code	B2
Filing date	Apr 23, 2013
Priority date	Apr 26, 2012
Publication date	May 17, 2016
Grant date	May 17, 2016

Abstract

To provide a process for producing an olefin polymer, which makes it possible to use, as a solvent for use in the catalyst preparation and the like, an aliphatic hydrocarbon solvent instead of an aromatic hydrocarbon solvent causing large environmental burden, and which has good olefin polymerization activity. A process for producing an olefin polymer, characterized by having a step comprising feeding an olefin polymerization catalyst solution, which is obtained by mixing a metallocene compound, a compound that reacts with the metallocene compound to form an ion pair and at least one compound selected from an organoaluminum compound and an organoaluminum oxy compound with a saturated hydrocarbon solvent, to a polymerization reactor and solution-polymerizing an olefin in the polymerization reactor.

First claim

The invention claimed is:

1. A process for producing an olefin polymer, having a step comprising feeding an olefin polymerization catalyst solution, which is obtained by mixing
(A) a metallocene compound represented by the general formula [A1] and/or a metallocene compound represented by the general formula [A2],
(B) a compound which is a compound that reacts with the metallocene compound (A) to form an ion pair, and is represented by the general formula [B1], and
(C) an organoaluminum compound (C-1) and/or an organoaluminum oxy compound (C-2),
with (D) a saturated hydrocarbon solvent under the following conditions (i) to (iv),
to a polymerization reactor and solution-polymerizing an olefin in the polymerization reactor;
(i) the amount of the metallocene compound (A) added to 1 liter of the saturated hydrocarbon solvent (D) is 0.02 to 0.6 mmol,
(ii) the molar ratio ((C)/(A)) of an aluminum atom in the compound (C) added to the saturated hydrocarbon solvent (D) to the metallocene compound (A) is 33 to 5000,
(iii) the amount of an aluminum atom in the compound (C) added to 1 liter of the saturated hydrocarbon solvent (D) is 3 to 1000 mmol, and
(iv) the molar ratio ((B)/(A)) of the compound (B) added to the saturated hydrocarbon solvent (D) to the metallocene compound (A) is 1 to 15;

wherein, in the formulas [A1] and [A2], M is an atom of the periodic table Group 4 or Group 5, Q is a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene, an anionic ligand or a neutral ligand capable of being coordinated with a lone electron pair, j is an integer of 1 to 4, when j is an integer of 2 or greater, plural Q are the same as or different from each other, and Cp 1 and Cp 2 are the same as or different from each other and are each a cyclopentadienyl group or a substituted cyclopentadienyl group capable of forming a sandwich structure together with M; and
Y in the formula [A2] is a divalent hydrocarbon group of 1 to 30 carbon atoms, a divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, —O—, —CO—, —S—, —SO—, —SO 2 —, —Ge—, —Sn—, —NR a —, —P(R a )—, —P(O)(R a )—, —BR a — or —AlR a — wherein R a is a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a hydrogen atom, a halogen atom or a nitrogen compound residue in which one or two hydrocarbon groups of 1 to 20 carbon atoms are bonded to a nitrogen atom;

wherein, in the formula [B1], R e+ is carbenium cation, and R f to R i are each independently a hydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms.

2. The process for producing an olefin polymer as claimed in claim 1 , wherein the compound (C) is a compound represented by the general formula [C1]:
[Chem. 4]
AlR 3   [C1]

wherein, in the formula [C1], R is a straight-chain or branched alkyl group of 3 to 10 carbon atoms.

3. The process for producing an olefin polymer as claimed in claim 1 , wherein the metallocene compound (A) is a compound represented by the general formula [A3]:

wherein, in the formula [A3], R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R′ 2 are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, and neighboring two groups of R 1 to R 4 are optionally bonded to each other to form a ring;
R 6 and R 11 are the same atoms or the same groups selected from hydrogen atoms, hydrocarbon groups, silicon-containing groups and hetero atom-containing groups other than silicon-containing groups, R 7 and R 10 are the same atoms or the same groups selected from hydrogen atoms, hydrocarbon groups, silicon-containing groups and hetero atom-containing groups other than silicon-containing groups, R 6 and R 7 are optionally bonded to each other to form a ring, and R 10 and R 11 are optionally bonded to each other to form a ring, with the proviso that there is no case where all of R 6 , R 7 , R 10 and R 11 are hydrogen atoms;
R 13 and R 14 are each an alkyl group or an aryl group, and R 13 and R 14 are optionally bonded to each other to form a ring;
M is a titanium atom, a zirconium atom or a hafnium atom;
Y 1 is a carbon atom or a silicon atom; and
Q is a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene of 4 to 20 carbon atoms, an anionic ligand or a neutral ligand capable of being coordinated with a lone electron pair, j is an integer of 1 to 4, or when j is an integer of 2 or greater, plural Q are the same as or different from each other.

4. The process for producing an olefin polymer as claimed in claim 1 , wherein the saturated hydrocarbon solvent used in the solution polymerization is an aliphatic hydrocarbon solvent and/or an alicyclic hydrocarbon solvent.

5. The process for producing an olefin polymer as claimed in claim 1 , wherein R f to R i in the formula [B1] are each independently an aromatic hydrocarbon groups of 6 to 20 carbon atoms or a halogenated aromatic hydrocarbon groups of 6 to 20 carbon atoms.

Assignees

• Mitsui Chemicals Inc

Inventors

• Tohi Yasushi
• Hasada Yasuhiro
• Noguchi Hiroshi

Classifications

• C08F10/00

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F210/16

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

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C08F2/06

  Organic solvent · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title