JPS61171437A - Production of 3-methylbutene-1 - Google Patents

Abstract

PURPOSE:To produce the titled substance by the partial hydrogenation of isoprene using a catalyst consisting of a Co compound, an organic phosphine compound, an Al compound and optionally a boron halide compound and/or a protonic acid and having a specific Co:P molar ratio. CONSTITUTION:The titled substance is produced by the partial hydrogenation of isoprene using a catalyst consisting of a Co compound, an organic phosphine compound, an Al compound and optionally a boron halide compound and/or a protonic acid having a pKa of <=1 (e.g. p-toluenesulfonic acid) wherein the molar number of the P atom in the organic phosphine compound is >=20 based on 1mol of the Co atom in the Co compound. The amount of the Co compound added to the system is 0.1-0.0001mol (in terms of Co atom) per 1mol of the isoprene used as a raw material. The temperature and pressure of the reaction is -5-45 deg.C and atmospheric pressure - 50kg/cm<2>, respectively, and the reaction is carried out usually in the presence of a solvent such as toluene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing 3-methylbutene-1, which is a useful raw material for polymers.

[Conventional technology]

Conventionally, it has been known that 3-methylbutene-1 is produced by partial hydrogenation of isoprene, but when isoprene is catalytically hydrogenated, in many cases it is possible to produce paraffin (- monomethylbutane). Furthermore, even if partial hydrogenation in which only one double bond is hydrogenated is successful, the main components are /, 4t-adduct λ-methylbutene, and co-methyl hydrogenated double bond with less steric hindrance. Butene-1, the desired 3-methylbutene-
The production ratio of l is very small.

Examples of 3-methylbutene-l produced by partial hydrogenation of isoprene with relatively high selectivity include (a) Co(C
N) i-catalytic method (Tarama et al., Bull, Ch.
em, 8oc, Jpn, 'I! r, Co7 Co3 (19 CoBr), (B) CoBr (pph,)
, BFs”0Et2 catalyst method (Mizorogi et al.
Ch@nh L・tt,, rdak(tqqt, )), and (c) P d C1t (PP h 3 )@
8 n C12 catalyst method (Itaya et al., Ind, K
ng, Cbem, Prod, R6&Dev,
Ri, Ako.

lda 6 (19ri 2)) etc. are known.

[Problem that the invention seeks to solve]

However, among these methods, the selectivity of 3-methylbutene-1 is not sufficiently high in the above methods (a) and (c), and the reaction rate and catalytic activity are not sufficient in the above method (b), so it is not suitable for industrial use. It is insufficient for practical use.

On the other hand, there is a method of partially hydrogenating isoprene in the presence of a catalyst consisting of a cobalt compound, a phosphorus compound, and an organoaluminum compound (Tokuko Shoq Yoichikoni 3 Coco), but the production ratio of 3-methylbutene-7 is at most It is 15%.

Furthermore, even in a reaction system with a high selectivity for 3-methylbutene-1, when the conversion rate of imprene increases, the isomerization reaction of the produced 3-methylbutene-1 occurs rapidly, and as a result, the main component is It had the disadvantage of becoming methylptenuco.

[Means for solving problems]

The present inventors have succeeded in producing 3-methylbutene-1 with high selectivity and high reaction rate through the partial hydrogenation reaction of imprene, and even when the conversion rate of isoprene is high.
The present invention was arrived at as a result of intensive studies to find a catalyst system and reaction conditions that can maintain high selectivity for -methylbutene-1.

That is, the present invention provides a method for producing 3-methylbutene-1 by partially hydrogenating imprene in the presence of a catalyst consisting of (1) a cobalt compound, (2) an organic phosphine compound, and (3) an aluminum compound. The number of moles of phosphorus atoms in the organic phosphine compound relative to mol is 2
3-Methylbutene-, which is larger than 0
7, and a method for producing 3-methylbutene-7 by partially hydrogenating isoprene in the presence of a catalyst consisting of (1) a cobalt compound and (2) an organic phosphine compound. A method for producing 3-methylbutene-1, characterized in that the number of moles of phosphorus atoms in the organic phosphine compound is made larger than 20.

The present invention will be explained in more detail below.

In the process of the invention, a catalyst system consisting of a cobalt compound, an organophosphine compound and an aluminum compound is used.

Examples of the cobalt compound include cobalt chloride, cobalt sulfate, and cobalt sulfate. i [salts such as cobalt, cobalt carbonate, cobalt acetate, cobalt formate, cobalt naphthenate, cobalt oleate, cobalt octoate, cobalt cyanide, cobalt fluoride, cobalt bromide, cobalt iodide;
Chelate compounds such as bis(acetylacetonato) cobalt, tris(acetylacetonato) cobalt; chlorotris() IJ phenylphosphine) cobalt, bromotris() IJ phenylphosphine) cobalt, dichlorobis(triphenylphosphine) cobalt, sifromobis(triphenyl) Examples include organic phosphorus compound complexes such as cobalt (phosphine).

The organic phosphine compounds include triphenylphosphine, tris(p-methoxy, diphenyl)phosphine, tris(o-1 toxyphenyl)phosphine, tris(p-trimethylsilylphenyl)phosphine, tri-p-tolylphosphine, tri- ) I
Triarylphosphines such as J luphosphin;
- trialkylphosphines such as butylphosphine, tri-n-7'ropylphosphine, tri-1so-propylphosphine; trialkylphosphines such as tribenzylphosphine; diphenyl-n-propylphosphine, diphenyl-1ao-propylphosphine, l-diphenylphosphine Coatrimethersilylethane J
Mixed alkylaryl phosphines such as /l cocose(diphenylphosphino)ethane; polymeric phosphines such as crosslinked oligomers of triphenylphosphine; and the like.

Further, as the aluminum compound, trimethylaluminum, triethylaluminum, tri-1ao-
butylaluminum, tri-n-butylaluminum,
tri-n-propyl aluminum, tri-n-hexyl aluminum, diethylaluminium hydride, di-1
s.

-butylaluminum hydride, diethylaluminum chloride, di-1so-butylaluminum chloride,
Organic aluminum compounds such as diethylaluminum chloride, ethylaluminum dichloride, 1ao-butylaluminum dichloride, ethylaluminum dichloride, ethylaluminum sesquichloride, 15o-butylaluminum sesquichloride, ethylaluminum sesquipromide; inorganic aluminum chloride, aluminum bromide, etc. Examples include aluminum compounds.

As the aluminum compound, it is preferable to use a combination of the above-described organic aluminum compound and an inorganic aluminum compound, or a combination of a plurality of organic aluminum compounds. Further, it is more preferable to use a combination of an aluminum compound containing a halogen atom, that is, an organoaluminum compound or an inorganic aluminum compound containing a halogen atom, and an organoaluminum compound containing no halogen atom.

It is effective to use tonic acid.

As the boron halide compound, boron trifluoride,
Boron trichloride, boron tribromide, boron trifluoride etherate (BF, ・oEt, ), boron trifluoride/nimethanolate (BF, ・coca, oH), etc. acids, hydrochloric acid, hydrobromic acid, nitric acid , phosphoric acid, perchloric acid, tetrafluoroboric acid, thiocyanic acid, and other inorganic protonic acids; trifluoroacetic acid, trichloroacetic acid, trichloromethanesulfonic acid, trifluoromethanesulfone [, p-)luenesulfonic acid, and other organic protonic acids, etc. can be mentioned. Among the above, organic protonic acids are more preferably used.

Further, in the present invention, the number of moles of phosphorus atoms in the organic phosphite/compound is increased by 20 to the cobalt atom/mol in the cobalt compound.

The cobalt compound is usually l~o, ooooimol, preferably 0.00, as cobalt atoms, based on the raw material isoprene/mol. / to 0.000/mol. The organic phosphine compound contains co(in a range greater than 7 mol, preferably 20 mol) as a phosphorus atom with respect to cobalt atoms/mol in the cobalt compound.
It is added in a range of 1000 mol or less, preferably 00 mol or less. If it is less than -0 mol, the conversion rate of the raw material isoprene is increased. The selectivity of the target product, 3-methylbutene-1, tends to decrease.

In addition, the aluminum compound is usually in the range of / = / 00 mol as an aluminum atom with respect to the cobalt atom / mol in the above cobalt compound, preferably 3 to θ
It is added in a mol range.

Further, when using a halogenated boron compound, when using a protonic acid of cobalt atom/mol in the cobalt compound, cobalt atom/mol in the cobalt compound
It is usually used in the range of 1 to /00 mol, preferably / to /0 mol.

As the reaction temperature, a temperature below SO° C. is usually employed. At temperatures higher than SO DEG C., the production ratio of the above-mentioned isomers other than the target product 3-methylbutene-1 increases. The reaction temperature is preferably 0°C to SO°C, more preferably -jC-! ℃ range.

The reaction pressure is usually normal pressure to 5 okf/at.

The reaction is usually carried out in the presence of a solvent. As a solvent,
Any solvent may be used as long as it is inert to the reaction, and for example, toluene, chlorobenzene, bromobenzene, etc. can be used.

The reaction can be carried out in any batch, semi-continuous or continuous manner. The reaction products, i.e., the target 3-methylbutene, its isomers, and -1-methylbutane, can be separated using conventional separation methods such as distillation, extraction,
It can be separated by adsorption etc. In particular, when the catalyst is separated by distillation, the distillation residue can be recycled as a catalyst liquid.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

The abbreviations represent the following, and the reaction rate and production ratio were calculated using the following formulas.

Engineering P: Isoprene JMB/: J-Methylbutene-l CoMB/: Comethylbutene-l -MB-Nicomethylbutene-l MB: Comethylbutane (b) Reduction product: JMB/, CoMB/, Co MB Co and CoMl Comparative Example-1 In a 100-vol.
mot), and after fully purging the system with nitrogen, add 7:10 ml total addition t, fC to chlorine.
. T of triethylaluminum in a solution of chlorobenzene
q, s wt% toluene solution O, mite-<0. Gu&
mmol) was added dropwise while stirring on ice. Furthermore, /JL of ethylaluminum sesquichloride! Vt% toluene solution o, sco (θ, j Q mmol) was added dropwise, and finally 0.3 m of isoprene (3,0 m+n
ol) was added to replace the inside of the system with hydrogen, and then hydrogen was introduced at normal pressure while stirring vigorously under water cooling. After the introduction started, hydrogen absorption started and the hydrogenation reaction progressed. When the reaction solution was analyzed by gas chromatography when the amount of hydrogen absorbed was about 90% of the theoretical amount, it was found that the rp reaction rate was 90% and the 3M
B/production ratio g Yuchi.

The hydrogenation reaction was further continued, and when the absorption of hydrogen close to the theoretical amount was observed, the reaction solution was analyzed again. Although the IP reaction rate increased by 9 points, the production ratio of 3MB/ac was o, ac.
s has almost disappeared, and on the contrary, the generation ratio of KoMBko has increased,
I was disappointed.

Ta.

Example-l Use of triphenylphosphine
The reaction was carried out in exactly the same manner as in Comparative Example-1 except that the amount was increased to (mol).

When the reaction solution was analyzed by gas chromatography at the time when the IP reaction rate was 90%, the production ratio was 1.3 MB/production ratio -
As in 1, I was disappointed, but when I further increased the IP reaction rate and observed absorption of hydrogen close to the theoretical amount, I analyzed the reaction solution and found that the IP reaction rate was 99. JMBI in Hirochi
Production ratio “Example - cotriphenylphosphine co, t, sf (10 mmol
) of triethylaluminum as VC, toluene solution of triethylaluminum/0. Ovt% toluene treatment solution fO,/, Omt<0.4' ls mmol
) and ethylaluminum sesquichloride as toluene solution m/0. The reaction was carried out in the same manner as in Example 7 except that 0.94 ml (0.3 da mmol) of Ovt% toluene solution was used. The reaction was stopped when hydrogen absorption close to the theoretical amount was observed, and the reaction solution was analyzed by gas chromatography, and the following results were obtained.

IP reaction rate 9F, 1% JMB/production ratio? A', 4c%2MB/b, 9%-MBco
/ 5. /%-MB
0.1% Example-3 A toluene solution of triethylaluminum and 0.1% of triethylaluminum. Ovt% toluene solution 0. A
The reaction was carried out in the same manner as in Example 1, except that aluminum chloride S (0.39 mmol) was added to Oml (0.114 mmol) in place of the toluene solution of ethylaluminum sesquichloride. The reaction was stopped when absorption of hydrogen close to the theoretical amount was observed, and the reaction solution was analyzed by gas chromatography.
The following results were obtained.

IP reaction rate 96. t% jMB / production ratio r 3.1%-MB
/ 4(,
/ /, J Chi M B
O,/% Example - Using a 11 volume flask, the amount of acetylacetate water used was 1. Da71f (!
r, Ommol), the amount of triphenylphosphine used was 32.7j f (/koj mmol)
K. Close the chlorobenzene addition lid! of triethylaluminum as a toluene solution of triethylaluminum to 0 tnt. Ovt% toluene solution I&/ml
(/1.II mmol) Ic, /S, J vt% of ethylaluminum sesquichloride as a toluene solution of ethylaluminum sesquichloride?Toluene? ig liquid/! ;、! ; ml (E,!; !r m
mol ), and the amount of isoprene used / 0 O
The reaction was carried out in the same manner as in Example 1 except that mt (/, Omol) was used, and the reaction was stopped when absorption of hydrogen amount close to the theoretical amount was observed, and the reaction solution was analyzed by gas chromatography. However, we obtained the following results.

IP Reaction rate 99.9% 3MR/ Generation ratio 77, g% MB/
44.2%koMB2
/7.9%2 M B 0.
1. Comparative Example - Toluene solution of triethylaluminum and triethylaluminum/0. Ovt% toluene solution 0.
Except that after adding A Oml (77,4'A mmol), 55 μL of boron trifluoride etherate (0,III mmol) was added without using the toluene solution of ethylaluminum sesquichloride, and then adding isoprene. The reaction was carried out in the same manner as in Comparative Example-1. When the reaction solution was analyzed when the hydrogen absorption amount was approximately gs% of the theoretical amount, the IP reaction rate was t5chi1.
7MB/generation ratio g:! However, when the IP reaction rate was further increased and an amount of hydrogen close to the theoretical amount was observed to be absorbed, the reaction solution was analyzed, and the following results were obtained.

IP Reaction rate Yuchi JMB/ Generation ratio O, Schu M B/
A,, f%-MB-g9 Aoko MB,? , Flathead Example-5 The amount of triphenylphosphine used was 1. J/f(j;,
When the reaction was carried out in the same manner as in Comparative Example 1 except that the amount was increased to When the hydrogen absorption was observed to be close to the theoretical amount, the reaction solution was analyzed and the following results were obtained.

IP Reaction rate 1 Width 3M'BI Generation ratio Dasanchi 2MB1
4.11%+2MB 2
1 g Coupling 2 M B /, Section A Comparative Example 3 The reaction was carried out in the same manner as Comparative Example 1 except that 50 μm (0, J J mmol) of trifluoromethanesulfonic acid was used instead of boron trifluoride etherate. Ta. When the reaction solution was analyzed when the amount of hydrogen absorbed was about 90 inches of the theoretical amount, the IP reaction rate was 90%, the 3MBI production ratio was
However, when the IP reaction rate was further increased and an amount of hydrogen close to the theoretical amount was observed to be absorbed, the reaction solution was analyzed once, and the following results were obtained.

IP Reaction rate 99% 3MR/ Generation ratio O, da% MB/
f % JMB Cozag % 2 M B J, A% Example-6 The amount of triphenylphosphine used is /, 3 / 7% (
! Comparative example-3 except that the amount was increased to r, Ommol)
When the reaction was carried out in the same manner as above, the IP reaction rate was ? The 7MB/generation ratio at Q% is the same as Comparative Example-3 (f 9
．． 1%, but when the IP reaction rate was further increased and an amount of hydrogen close to the theoretical amount was observed to be absorbed, the reaction solution was analyzed and the following results were obtained.

IP Reaction rate Dede, -% JMB/ Generation ratio 56% -Ml/ // %2MB2
．． 7/%koMB
% [Effects of the Invention] According to the method of the present invention, J-methylbutene-7 can be produced selectively in a high yield and at a sufficiently high reaction rate compared to isoprene, which is an inexpensive raw material, and it is possible to produce J-methylbutene-7 with a high yield and a sufficiently high reaction rate. Since high selectivity for 3-methylbutene-1 can be maintained even in the reaction conversion rate, the method of the present invention has extremely high industrial value.

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Hase - 1 other person

Claims (2)

[Claims] (1) Isoprene is partially hydrogenated in the presence of a catalyst consisting of [1] a cobalt compound, [2] an organic phosphine compound, and [3] an aluminum compound to produce 3-methylbutene-1.
3-, characterized in that the number of moles of phosphorus atoms in the organic phosphine compound is greater than 20 per mol of cobalt atoms in the cobalt compound.
Method for producing methylbutene-1. (2) [1] cobalt compound, [2] organic phosphine compound, [3] aluminum compound, and [4] boron halide compound and/or protonic acid with pKa 1 or less,
Partial hydrogenation of isoprene in the presence of a catalyst consisting of 3
- A method for producing 3-methylbutene-1, characterized in that the number of moles of phosphorus atoms in the organic phosphine compound is made larger than 20 with respect to cobalt atoms/mol in the cobalt compound.