EP0339986A1
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EP
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Novel catalyst for hydrogenation of polymer and process for hydrogenating polymer with the catalyst
Assignee: JSR Corp
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Filing: 1989-04-26
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Granted: —
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Expires: 2009-04-26
Abstract
Abstract A hydrogenation catalyst consisting essentially of (A) at least one bis(cyclopentadienyl)titanium compound represented by the formula (1): wherein R¹ and R², which may be the same or different, represent halogen atoms, hydrocarbon groups, aryloxy groups, alkoxy groups or carbonyl groups, and (B) at least one lithium compound represented by the formula (2): R³O-Li (2) wherein R³ represents a hydrocarbon group, or a reaction mixture of an organolithium compound with an alcoholic or phenolic hydroxyl group-containing compound, the (A) component/the (B) component molar ratio being 1/0.5 to 1/20, and optionally (C) at least one reducing organometallic compound selected from the group consisting of aluminum compounds, zinc compounds and magnesium compounds, the (A) component/the (C) component molar ratio being 1/0.5 to 1/20. The above hydrogenation catalyst is effectively applied to the hydrogenation of a polymer having olefinic double bonds to produce a hydrogenated polymer having a high degree of hydrogenation at a high hydrogenation rate with a high reproducibility.
Inventors
- 👤 Toshio Teramoto
- 👤 Kunio Goshima
- 👤 Mikio Takeuchi
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-05 05:26
CPC Classifications
C; C08; C08C; C08C19/00; C08C19/02; B; B01; B01J; B01J31/00; B01J31/02; B01J31/0201; B01J31/0211; B01J31/12; B01J31/128; B01J31/14; B01J31/143; B01J31/16; B01J31/22; B01J31/2282; B01J31/2295; B01J2231/00; B01J2231/60; B01J2231/64; B01J2231/641; B01J2231/645; B01J2531/00; B01J2531/40; B01J2531/46
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
88 words
A hydrogenation catalyst consisting essentially of (A) at least one bis(cyclopentadienyl)titanium compound represented by the formula (1): wherein R¹ and R², which may be the same or different, represent halogen atoms, hydrocarbon groups, phenolic hydroxyl groups, alkoxy groups or carbonyl groups, and (B) at least one lithium compound represented by the formula (2): R³O-Li (2) wherein R³ represents a hydrocarbon group, or a reaction mixture of an organolithium compound with an alcoholic or phenolic hydroxyl group-containing compound, the (A) component/the (B) component molar ratio being 1/0.5 to 1/20.
Claim 2
Dependent Claim
88 words
A hydrogenation catalyst consisting essentially of (A) at least one bis(cyclopentadienyl)titanium compound represented by the formula (1): wherein R¹ and R², which may be the same or different, represent halogen atoms, hydrocarbon groups, phenolic hydroxyl groups, alkoxy groups or carbonyl groups, and (B) at least one lithium compound represented by the formula (2): R³O-Li (2) wherein R³ represents a hydrocarbon group, or a reaction mixture of an organolithium compound with an alcoholic or phenolic hydroxyl group-containing compound, the (A) component/the (B) component molar ratio being 1/0.5 to 1/20.
Claim 3
Dependent Claim
55 words
The hydrogenation catalyst according to Claim 1, wherein the (A) component is selected from the group consisting of bis(cyclopentadienyl)titaniumdimethyl, bis(cyclopentadienyl)titaniumdiethyl, bis(cyclopentadienyl)titaniumdi-n-butyl, bis(cyclopentadienyl)titaniumdi-sec-butyl, bis(cyclopentadienyl) titaniumdihexyl, bis(cyclopentadienyl)titaniumdioctyl, bis(cyclopentadienyl)titaniumdimethoxide, bis(cyclopentadienyl)titaniumdiethoxide, bis(cyclopentadienyl)titaniumdibutoxide, bis(cyclopentadienyl)titaniumdiphenyl, bis(cyclopentadienyl)titaniumdi-m-tolyl, bis(cyclopentadienyl)titaniumdi-p-tolyl, bis(cyclopentadienyl)titaniumdi-m,p-xylyl, bis(cyclopentadienyl)titaniumdi-4-ethylphenyl, bis(cyclopentadienyl)titaniumdi-4-butylphenyl, bis(cyclopentadienyl)titaniumdi-4-hexylphenyl, bis(cyclopentadienyl)titanium diphenoxide, bis(cyclopentadienyl)titanium difluoride, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titanium dibromide, bis(cyclopentadienyl)titanium diiodide, bis(cyclopentadienyl)titaniumdicarbonyl, bis(cyclopentadienyl)titaniumchloridemethyl, bis(cyclopentadienyl)titanium chloride ethoxide, bis(cyclopentadienyl)titanium chloride phenoxide and bis(cyclopentadienyl)titaniumdibenzyl.
Claim 4
Dependent Claim
27 words
The hydrogenation catalyst according to Claim 1, wherein the (A) component is selected from the group consisting of bis(cyclopentadienyl)titaniumdimethyl, bis(cyclopentadienyl)titaniumdi-n-butyl, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titaniumdiphenyl, bis(cyclopentadienyl)titaniumdi-p-tolyl, bis(cyclopentadienyl)titaniumdicarbonyl and bis(cyclopentadienyl)titaniumdibenzyl.
Claim 5
Dependent Claim
15 words
The hydrogenation catalyst according to Claim 1, wherein the (A) component is bis(cyclopentadienyl) titanium dichloride.
Claim 6
Dependent Claim
37 words
The hydrogenation catalyst according to Claim 1, wherein the (B) component is at least one lithium compound selected from the group consisting of methoxylithium, ethoxylithium, n-propoxylithium, i-propoxylithium, n-butoxylithium, sec-butoxylithium, t-butoxylithium, pentyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, 2,6-di-t-butyl-4-methylphenoxylithium and benzyloxylithium.
Claim 7
Dependent Claim
13 words
The hydrogenation catalyst according to Claim 5, wherein the lithium compound is 2,6-di-t-butyl-4-methylphenoxylithium.
Claim 8
Dependent Claim
44 words
The hydrogenation catalyst according to Claim 1, wherein the (B) component is a reaction mixture of an organolithium compound with an alcoholic or phenolic hydroxyl group-containing compound in a molar ratio of the alkyllithium/the alcoholic or phenolic hydroxyl group-containing compound of 5/1 to 1/2.
Claim 9
Dependent Claim
26 words
The hydrogenation catalyst according to Claim 7, wherein the organolithium compound is selected from the group consisting of methyllithium, ethyllithium, n-propyllithium, n-butyllithium, phenyllithium, p-tolyllithium and xylyllithium.
Claim 10
Dependent Claim
15 words
The hydrogenation catalyst according to Claim 7, wherein the organolithium compound is n-butyllithium or sec-butyllithium.
Claim 11
Dependent Claim
64 words
The hydrogenation catalyst according to Claim 7, wherein the alcoholic or phenolic hydroxyl group- containing compound is selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, lauryl alcohol, 1,3-dichloro-2-propanol, allyl alcohol, cyclohexanol, cyclopentanol, phenol, o-bromophenol, dichlorophenol, trichlorophenol, o-cresol, m-cresol, p-cresol, p-allylphenol, 2,6-di-t-butyl-p-cresol, xylenol, dihydroxyanthraquinone, dihydroxycoumarine, 1-hydroxyanthranquinone, m-hydroxybenzyl alcohol, resolcinol and leucaurine.
Claim 12
Dependent Claim
17 words
The hydrogenation catalyst according to Claim 7, wherein the alcoholic or phenolic hydroxyl group-containing compound is 2,6-di-t-butyl-p-cresol.
Claim 13
Dependent Claim
19 words
The hydrogenation catalyst according to Claim 7, wherein the reaction mixture is that of n-butyllithium or sec-butyllithium with 2,6-di-t-butyl-p-cresol.
Claim 14
Dependent Claim
24 words
The hydrogenation catalyst according to Claim 7, wherein the molar ratio of the alkyllithium/the alcoholic or phenolic hydroxyl group-containing compound is 3/1 to 1/1.5.
Claim 15
Dependent Claim
41 words
The hydrogenation catalyst according to Claim 1, which further comprises (C) at least one reducing organometallic compound selected from the group consisting of aluminum compounds, zinc compounds and magnesium compounds, the (A) component/the (C) component molar ratio being 1/0.5 to 1/20.
Claim 16
Dependent Claim
19 words
The hydrogenation catalyst according to Claim 14, wherein the (A) component/the (C) component molar ratio is 1/1 to 1/10.
Claim 17
Dependent Claim
59 words
The hydrogenated catalyst according to Claim 14, wherein the aluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, diethylaluminum hydride, diisobutylaluminum hydride, triphenylaluminum and tri(2-ethylhexyl)aluminum; the zinc compounds include diethylzinc, bis(cyclopentadienyl)zinc and dihexylzinc; and the magnesium compounds include dimethylmagnesium, diethylmagnesium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, phenylmagnesium bromide, phenylmagnesium chloride and dimethylmagnesium chloride.
Claim 18
Dependent Claim
25 words
The hydrogenation catalyst according to Claim 14, wherein the (C) component is selected from the group consisting of triethylaluminum, triisobutylaluminum, diethylaluminum chloride and ethylaluminum dichloride.
Claim 19
Dependent Claim
19 words
The hydrogenation catalyst according to Claim 14, wherein the (A) component/the (C) component molar ratio is 1/1 to 1/10.
Claim 20
Dependent Claim
34 words
A process for hydrogenating a polymer having olefinic double bonds which comprises contacting the polymer with hydrogen in an inert organic solvent in the presence of the hydrogenation catalyst of Claim 1 or 14.
Claim 21
Dependent Claim
42 words
The process according to Claim 19, wherein the polymer having olefinic double bonds is a conjugated diene homopolymer, a copolymer of conjugated dienes or a random, block or graft copolymer of a conjugated diene and at least one olefinic monomer copolymerizable therewith.
Claim 22
Dependent Claim
16 words
The process according to Claim 20, wherein the conjugated diene has 4 to 12 carbon atoms.
Claim 23
Dependent Claim
27 words
The process according to Claim 21, wherein the conjugated diene having 4 to 12 carbon atoms includes 1,3-budtadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and chloroprene.
Claim 24
Dependent Claim
20 words
The process according to Claim 21, wherein the conjugated diene is selected from the group consisting of 1,3-butadiene and isoprene.
Claim 25
Dependent Claim
20 words
The process according to Claim 19, wherein the polymer having olefinic double bonds is polybutadiene, polyisoprene or a butadiene/isoprene copolymer.
Claim 26
Dependent Claim
21 words
The process according to Claim 19, wherein the polymer having olefinic double bonds has a 1,2-vinyl content of 10% or more.
Claim 27
Dependent Claim
21 words
The process according to Claim 19, wherein the polymer having olefinic double bonds has a molecular weight of 1,000 to 1,000,000.
Claim 28
Dependent Claim
26 words
The process according to Claim 19, wherein the inert organic solvent is selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and ethers.
Claim 29
Dependent Claim
41 words
The process according to Claim 27, wherein the aliphatic hydrocarbons include n-pentane, n-hexane, nheptane and n-octane; the alicyclic hydrocarbons include cyclopentane, cyclohexane and cycloheptane; the aromatic hydrocarbons include benzene, toluene, xylene and ethylbenzene; and the ethers include diethyl ether and tetrahydrofuran.
Claim 30
Dependent Claim
53 words
The process according to Claim 19, wherein a solution of the polymer having olefinic double bonds in the inert organic solvent is kept at a desired temperature, the hydrogenation catalyst is added thereto with or without stirring and the hydrogen is subsequently introduced thereinto to reach a desired pressure to hydrogenate the polymer.
Claim 31
Dependent Claim
46 words
The process according to Claim 19, wherein the alkylaluminum is first added to the inert organic solvent, the alcoholic or phenolic hydroxyl group-containing compound is then added thereto, the (A) component is then added and thereafter the polymer having olefinic double bonds is hydrogenated with hydrogen.
Claim 32
Dependent Claim
28 words
The process according to Claim 19, wherein the amount of the hydrogenation catalyst is 0.01 to 20 millimoles per 100 g of the polymer having olefinic double bonds.
Claim 33
Dependent Claim
48 words
The process according to Claim 31, wherein hydrogen molecule is introduced in the form of a gas into a solution of the polymer having olefinic double bonds in the inert organic solvent with stirring in the presence of the hydrogenation catalyst at a temperature of 0° to 120°C.
Claim 34
Dependent Claim
15 words
The process according to Claim 32, wherein the hydrogen pressure is 1 to 100 kg/cm²G.
References Cited (Backward Citations)
FR2539745A1
Cited
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