Catalyst composition for hydrogenation and method for hydrogenation using the same

Patent metadata

Field	Value
Publication number	US-10016749-B2
Application number	US-201314428622-A
Country	US
Kind code	B2
Filing date	Sep 12, 2013
Priority date	Sep 21, 2012
Publication date	Jul 10, 2018
Grant date	Jul 10, 2018

Abstract

A catalyst composition for hydrogenation including (A) to (D), in which a mass ratio ((C)/(A)) is 0.1 to 4.0 and a mass ratio ((D)/(A)) is 0.01 to 1.00,
(A): a titanocene compound represented by formula (1),

(wherein R 5 and R 6 are any group selected from hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, an aryloxy group, an alkoxy group, a halogen group, and a carbonyl group. R 1 and R 2 are any group selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 12 carbon atoms, and R 1 and R 2 are not all hydrogen atoms or all a hydrocarbon group having 1 to 12 carbon atoms),

(B): a reductant formed from a compound containing an element selected from the elements Li, Na, K, Mg, Zn, Al, and Ca,
(C): an unsaturated compound having a molecular weight of 400 or less, and
(D): a polar compound.

First claim

The invention claimed is:

1. A catalyst composition, comprising compounds (A), (B), (C), and (D) shown below,
wherein a mass ratio of the compound (C) to the compound (A) (the compound (C)/the compound (A)) is in a range of 2.0 to 4.0,
a mass ratio of the compound (D) to the compound (A) (the compound (D)/the compound (A)) is in a range of 0.01 to 1.00,
the compound (A) comprises a titanocene compound represented by following general formula (1),

(wherein R 5 and R 6 represent a group selected from the group consisting of a hydrocarbon group having 1 to 8 carbon atoms, an aryloxy group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a halogen group, R 5 and R 6 may be the same or different; and R 1 represents a group selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 4 carbon atoms, R 2 represents a group selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 4 carbon atoms, and R 1 and R 2 may be the same or different),
the compound (B) is an organic compound comprising one or more elements selected from the group consisting of elements Li and Al,
the compound (C) comprises a compound selected from the group consisting of unsaturated compounds that have a hydrocarbon having 4 to 12 carbon atoms,
the compound (C) has a molecular weight of 400 or less, and
the compound (D) comprises a polar compound selected from the group consisting of ether compounds, carboxylate compounds, and amine compounds, wherein
the ether compounds are selected from the group consisting of dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-sec-butyl ether, diphenyl ether, methyl ethyl ether, ethyl butyl ether, butyl vinyl ether, anisole, ethyl phenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, furan, tetrahydrofuran, a-methoxy tetrahydrofuran, pyran, tetrahydropyran, and dioxane; tetrahydrofuran carboxylic acid;
the carboxylate compounds are selected from the group consisting of methyl or ethyl esters of formic acid, acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, cyclohexyl propionic acid, cyclohexyl caproic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, acrylic acid, methacrylic acid, oxalic acid, maleic acid, malonic acid, fumaric acid, succinic acid, adipic acid, pimelic acid, suberic acid, sebacic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, and diphenic acid; and methyl acetoacetate or ethyl acetoacetate; and
the amine compounds are selected from the group consisting of methylamine, ethylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-amylamine, sec-amylamine, tert-amylamine, n-hexylamine, n-heptylamine, aniline, benzylamine, o-anisidine, m-anisidine, p-anisidine, α-naphthylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-tert-butylamine, di-n-amylamine, diisoamylamine, dibenzylamine, N-methylamine, N-ethylamine, N-ethyl-o-toluidine, N-ethyl-m-toluidine, N-ethyl-p-toluidine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-amylamine, triisoamylamine, tri-n-hexylamine, tribenzylamine, triphenyl methylamine, N,N-dimethyl benzylamine, N,N-dimethylamine, N,N-diethylamine, N,N-diethyl-o-toluidine, N,N-diethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-a-naphthylamine, N,N,N′,N′-tetramethyl ethylene diamine, N,N,N′,N′-tetraethyl ethylene diamine, pyrrolidine, piperidine, N-methylpyrrolidine, N-methylpiperidine, pyridine, piperazine, 2-acetylpyridine, N-benzylpiperazine, quinoline, and morpholine.

2. The catalyst composition according to claim 1 , wherein the compound (C) has an unsaturated group content of 2 mol or more based on 1 mol of the compound (C).

3. The catalyst composition according to claim 1 , wherein the compound (B) is an organic lithium compound.

4. A method of hydrogenating a compound, comprising bringing an olefinic unsaturated double bond-containing compound into contact with hydrogen in an inert organic solvent, in the presence of the catalyst composition according to claim 1 .

5. The method according to claim 4 , wherein the olefinic unsaturated double bond-containing compound is a conjugated diene polymer or a copolymer formed of a conjugated diene and a vinyl aromatic hydrocarbon.

6. The catalyst composition according to claim 2 , wherein the compound (B) is an organic lithium compound.

7. The catalyst composition according to claim 1 , wherein the compound (A) is selected from the group consisting of bis(η(5)-methylcyclopentadienyl)titanium dichloride, bis(η(5)-n-butylcyclopentadienyl)titanium dichloride, bis(η(5)-methylcyclopentadienyl)titanium diphenyl, bis(η(5)-n-butylcyclopentadienyl)titanium diphenyl, bis(η(5)-methylcyclopentadienyl)titanium di(p-tolyl) and bis(η(5)-n-butylcyclopentadienyl)titanium di(p-tolyl).

8. The catalyst composition according to claim 1 , wherein the compound (A) is selected from the group consisting of bis(η(5)-cyclopentadienyl)titanium di(p-tolyl), bis(η(5)-cyclopentadienyl)titanium di(phenyl), bis(η(5)-cyclopentadienyl)titanium di(3,4-xylyl) and bis(η(5)-1,3-dimethylcyclopentadienyl)titanium dichloride.

9. The catalyst composition according to claim 1 , wherein the compound (B) is triethylaluminum or sec-butyllithium.

10. The catalyst composition according to claim 1 , wherein the compound (C) is selected from the group consisting of myrcene, isoprene, octene, 1,7-Octadiene and polyisoprene.

11. The catalyst composition according to claim 10 , wherein the compound (C) has an unsaturated group content of 2 mol or more and 5 mol or less based on 1 mol of the compound (C).

12. The catalyst composition according to claim 10 , wherein the compound (C) has an unsaturated group content of 2 mol or more and 4 mol or less based on 1 mol of the compound (C).

13. The catalyst composition according to claim 1 , wherein the compound (D) is an amine compound or an ether compound.

14. The catalyst composition according to claim 1 , wherein the compound (D) is tetrahydrofuran, ethyl acetate or N,N,N′,N′-Tetramethylethylenediamine.

15. The method according to claim 4 , wherein the olefinic unsaturated double bond-containing compound is styrene-butadiene-styrene block copolymer.

16. A method of hydrogenating a compound, comprising bringing an olefinic unsaturated double bond-containing compound into contact with hydrogen in an inert organic solvent, in the presence of the catalyst composition according to claim 2 .

17. The method according to claim 16 , wherein the olefinic unsaturated double bond-containing compound is a conjugated diene polymer or a copolymer formed of a conjugated diene and a vinyl aromatic hydrocarbon.

18. A method of hydrogenating a compound, comprising bringing an olefinic unsaturated double bond-containing compound into contact with hydrogen in an inert organic solvent, in the presence of the catalyst composition according to claim 3 .

19. The method according to claim 18 , wherein the olefinic unsaturated double bond-containing compound is a conjugated diene polymer or a copolymer formed of a conjugated diene and a vinyl aromatic hydrocarbo

Assignees

• Asahi Kasei Chemicals Corp

Inventors

• Araki Yoshifumi
• Sasaya Eiji
• Nitta Katsunori

Classifications

• B01J31/0237

  Amines · CPC title

• B01J31/122

  Metal aryl or alkyl compounds · CPC title

• B01J31/0209

  Esters of carboxylic or carbonic acids · CPC title

• C07F7/28

  Titanium compounds · CPC title

• C08C19/02

  Hydrogenation · CPC title