JPH10306045A - Production of branched polyene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound at a high yield while suppressing isomerization of generating branched polyene compounds to internal olefin compound by reacting ethylene with a conjugated diene compound in the presence of a transition metal catalyst and deactivating the catalyst by a specific method. SOLUTION: Ethylene is reacted with a conjugated diene compound of formula I [(f) us 1-5; R<1> and R<2> are each H or a 1-5C alkyl; R<3> is H or an alkenyl of formula II (n) is 1-5; R<4> to R<6> are each H or a 1-5C alkyl in excepting simultaneously H of the R<4> to R<6> }; in excepting simultaneously H of the R<1> to R<3> ] in the presence of a transition metal catalyst. After finishing the reaction, a reaction mixture containing the produced objective compound of formula III is treated with water and an oxidizer (preferably oxygen, etc.) to deactivate the catalyst, then the compound of the formula III is separated by distillation. Preferably, 7-methyl-3-methylene-1,6-octadiene, etc., is used as the compound of the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a branched polyene compound, and more particularly to a method for reacting ethylene and a conjugated diene compound in the presence of a transition metal catalyst.
By deactivating the transition metal catalyst in the obtained reaction mixture, while suppressing the undesired isomerization reaction of the obtained branched polyene compound to the internal olefin compound, distillation from the reaction mixture is carried out. To obtain a high yield of branched polyene compounds.

[0002]

2. Description of the Related Art In general, a polyene compound refers to a hydrocarbon compound having two or more carbon-carbon double bonds in one molecule, and many compounds have been known. Such polyene compounds include, for example, 1,3-butadiene,
1,3-pentadiene, 1,4-hexadiene, ethylidene-2-norbornene, dicyclopentadiene and the like are known.

[0003] By copolymerizing such a polyene compound and an α-olefin such as ethylene or propylene, a vulcanizable unsaturated copolymer can be obtained. Saturated copolymers are excellent in weather resistance, heat resistance, ozone resistance, etc., and are used for automobile industrial parts, industrial rubber products, electrical insulating materials,
It is widely used as rubber products such as civil engineering building materials and rubberized fabrics, and as a material for polymer blending with polypropylene and polystyrene.

Among such ethylenically unsaturated copolymers, ethylene-propylene / 5-ethylidene-2-
Norbornene copolymers are particularly widely used because they have a higher vulcanization rate than other ethylenically unsaturated copolymers.

[0005] However, even if the conventionally known ethylenically unsaturated copolymer is, for example, the above-mentioned ethylene / propylene / 5-ethylidene-2-norbornene copolymer, natural rubber, styrene / butadiene rubber, isoprene, etc. Compared with ordinary diene rubbers such as rubber, butadiene rubber, and nitrile rubber, the vulcanization rate is lower and the co-vulcanization with the diene rubber is inferior.

Further, since the conventional ethylenically unsaturated copolymer has a low vulcanization rate, the vulcanization time is shortened, or the vulcanization temperature is lowered, and the energy consumption during vulcanization is reduced.
It is difficult to produce vulcanized rubber with good productivity.

Therefore, the present inventors have already disclosed in Japanese Unexamined Patent Application Publication No.
As described in JP-A-325170, an ethylenically unsaturated copolymer obtained by copolymerizing a branched polyene compound represented by the general formula (III) with an α-olefin such as ethylene or propylene is used. It has been found that the vulcanization rate is higher than that of an ethylene / propylene / 5-ethylidene-2-norbornene copolymer. According to the above publication, the branched polyene compound represented by the general formula (III) is obtained by reacting ethylene with a conjugated diene compound in the presence of a transition metal catalyst obtained by reacting a transition metal compound with an organoaluminum compound. Can be obtained by reacting

However, according to such a method,
After completion of the reaction between ethylene and the conjugated diene, when the intended branched polyene compound is separated from the obtained reaction mixture by distillation, the transition metal catalyst used for the reaction remains in the reaction mixture. , By heating during distillation,
A part of the obtained branched polyene compound isomerizes to an internal olefin compound not involved in the polymerization, thereby lowering the yield of the product (branched polyene compound). Therefore, it is necessary to deactivate the transition metal catalyst in the reaction mixture before the desired branched polyene compound is separated from the reaction mixture by distillation. That is, since the non-polymerizable internal olefin compound has no copolymerizability with α-olefins such as ethylene and propylene, it is used as a raw material for producing a vulcanizable ethylenically unsaturated copolymer as described above. Can not do.

As a method for deactivating such a transition metal catalyst, various methods have hitherto been known, one of which is a method using water as a deactivator. In this method, after completion of the reaction, water is added to the obtained reaction mixture, and the transition metal catalyst is hydrolyzed to be deactivated by converting the transition metal catalyst into an inactive transition metal hydroxide. Things. However, according to this method, depending on the type of the transition metal compound used as a catalyst, it is difficult to undergo hydrolysis, and thus there is a problem that the transition metal catalyst cannot be sufficiently deactivated.

It is also known to use an alcohol, an amine or the like as a deactivator in addition to the above-mentioned water. According to this method, the transition metal catalyst can be relatively easily deactivated. However, since the deactivator such as alcohol or amine is dissolved in the reaction mixture, the deactivator is separated from the reaction mixture. There is a problem that special equipment is required for recovery.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and comprises reacting ethylene with a conjugated diene compound in the presence of a transition metal catalyst to obtain a compound represented by the general formula (III) In producing the branched polyene compound represented by the formula (1), after the reaction is completed, the transition metal catalyst in the obtained reaction mixture is deactivated, and the desired branched polyene compound is separated from the reaction mixture by distillation. The present invention provides a method for producing a branched polyene compound which can suppress the isomerization of the branched polyene compound to an internal olefin compound and can obtain a desired branched polyene compound in a high yield. The purpose is to do.

[0012]

According to the present invention, ethylene and a compound of the formula (I)

[0013]

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(Wherein f represents an integer of 1 to 5, R ¹ and
R ² each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or a general formula (II)

[0015]

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(Wherein n represents an integer of 1 to 5, and R ⁴ , R ⁵
And R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R ⁴ , R ⁵ and R ⁶ are not hydrogen atoms at the same time. ) Represents an alkenyl group. However, R ¹ , R ² and R ³ are not hydrogen atoms at the same time. ) With a conjugated diene compound represented by the formula (III)

[0017]

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(Wherein f, R ¹ , R ² and R ³ are the same as those described above). In the method for producing a branched polyene compound represented by the formula: Is treated with water and an oxidizing agent,
After the deactivation of the transition metal catalyst, a method for producing a branched polyene compound is provided, wherein the branched polyene compound is separated from the reaction mixture by distillation.

In particular, according to the present invention, the above-mentioned general formula (I)
In the conjugated diene compound represented by the formula, when R ³ is an alkenyl group represented by the general formula (II), ethylene and the general formula (I ′)

[0020]

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(Where f represents an integer of 1 to 5;
5 represents an integer, and R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R ⁴ , R ⁵ and R ⁶ are not hydrogen atoms at the same time. The conjugated diene compound represented by the general formula (III ′) is reacted in the presence of a transition metal catalyst.

[0022]

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(Wherein, f, n, R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are the same as those described above).

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The conjugated diene compound used in the method of the present invention has the general formula (I)

[0025]

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(Wherein f represents an integer of 1 to 5, R ¹ and
R ² each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or a general formula (II)

[0027]

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(Wherein, n represents an integer of 1 to 5, and R ⁴ , R ⁵
And R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R ⁴ , R ⁵ and R ⁶ are not hydrogen atoms at the same time. ) Represents an alkenyl group. However, R ¹ , R ² and R ³ are not hydrogen atoms at the same time. ).

In the above general formula (I), R ¹ , R ² or R ³
Is an alkyl group having 1 to 5 carbon atoms, examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and t. -Butyl group, n-pentyl group, isopentyl group and the like. In the present invention, when R ¹ , R ² or R ³ is an alkyl group, such an alkyl group is particularly preferably a group having 1 to 3 carbon atoms, particularly a methyl group or an ethyl group. Is preferred.

In particular, in the present invention, the above-mentioned general formula (I)
In in the conjugated diene compound represented when R ³ is an alkenyl group represented by the general formula (II), the conjugated diene compound is represented by the general formula ^{(I '), R 1,} R ² ,
When R ⁴ , R ⁵ or R ⁶ is an alkyl group having 1 to 5 carbon atoms,
Examples of such an alkyl group include the specific examples described above. Particularly, it is preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

Specific examples of such a conjugated diene compound represented by the general formula (I) include the following compounds.

[0032]

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[0033]

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[0034]

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[0035]

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Among these, in particular,

[0037]

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7-methyl-3-methylene-
1,6-octadiene (β-myrcene) or the following formula

[0039]

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7,11-dimethyl-3-methylene-1,6,10-dodecatriene (β-farnesene) and the like are preferably used in practical use. The reaction between ethylene and a conjugated diene compound according to the method of the present invention can be represented by the following formula.

[0041]

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According to the present invention, the reaction between ethylene and the conjugated diene compound is carried out in the presence of a transition metal catalyst comprising a transition metal compound and an organoaluminum compound. Specific examples of the transition metal compound include iron, iron group such as ruthenium, cobalt group such as cobalt, rhodium and iridium, nickel, chloride, bromide and iodide of transition metal selected from nickel group such as palladium. , Carbonate, sulfate, nitrate, phosphate, acetate, thiocyanate, acetylacetonate and the like. Among these, cobalt (II) chloride or nickel chloride (I
I) and the like are preferable, and particularly, cobalt (II) chloride is preferably used.

Such a transition metal compound can be used as it is for preparing a transition metal catalyst. However, according to the invention, for the preparation of the catalyst, the transition metal compound is advantageously used as a transition metal complex with which an organic ligand is coordinated. That is, together with the transition metal compound, an organic compound that can be a ligand of the transition metal, that is, a coordination compound is allowed to coexist in the reaction system, or a transition metal complex is prepared from the transition metal compound and the coordination compound in advance. Thus, it is preferable to use it for preparing a catalyst.

Compounds that can be such ligands include oxygen-containing organic compounds such as dimethyl ether, diethyl ether, dipropyl ether, tetrahydrofuran and acetylacetone, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, cyclohexylamine , Dicyclohexylamine, aniline, diphenylamine, pyridine, picoline, 2,2′-bipyridine, 1,10-phenanthroline and other nitrogen-containing organic compounds, triethylphosphine, tripropylphosphine, tributylphosphine, triphenylphosphine, bis (diphenylphosphino ) Methane, 1,
2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, triethylphosphine, tributylphosphine, triphenylphosphine, triphenylphosphite, triphenylphosphine Phosphorus-containing organic compounds such as phenylphosphine oxide and triphenylphosphate can be exemplified. Among these, a phosphorus-containing organic compound is preferable, and 1,2-bis (diphenylphosphino) ethane is particularly preferably used.

Examples of the transition metal complex in which an organic ligand is coordinated to a transition metal compound in advance include, for example, 1,2-bis (diphenylphosphino) ethanecobalt (II) chloride (φ ₂ PCH ₂ CH) ₂ Pφ ₂ ) CoCl ₂ (in the formula, φ represents a phenyl group).

Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; alkylaluminum dihydrides such as isobutylaluminum dihydride; Dialkylaluminum chloride such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, alkylaluminum sesquichloride such as ethylaluminum sesquichloride, alkylaluminum dichloride such as ethylaluminum dichloride, dimethylaluminum bromide, odor Diethylaluminum bromide, dipropylaluminum bromide Dialkyl aluminum bromide such as diisobutyl aluminum bromide, alkyl aluminum sesquibromide such as ethyl aluminum sesquibromide, alkyl aluminum dibromide such as ethyl aluminum dibromide, dimethyl aluminum iodide, diethyl aluminum iodide, dipropyl iodide Aluminum, dialkylaluminum iodide such as diisobutylaluminum iodide, alkylaluminum sesquiiodide such as ethylaluminum sesquiiodide, alkylaluminum diiodide such as ethylaluminum diiodide, dimethylaluminum methoxide, diethylaluminum ethoxide and the like Examples thereof include dialkyl aluminum alkoxides.

In the present invention, among these, a trialkylaluminum such as triethylaluminum and a dialkylaluminum chloride such as diethylaluminum chloride are particularly preferably used. These organoaluminum compounds can be used as they are, but can also be used as a toluene solution or a hexane solution. These organoaluminum compounds may be used alone or in combination of two or more.

In the method of the present invention, the amount of the transition metal catalyst used is usually 0.001 to 10 mol%, preferably 0.01 to 10 mol%, based on the conjugated diene compound.
It is used so as to be in a range of 1 mol%. The coordination compound is usually used in a molar amount of 20 times or less, preferably 0.1 to 10 times the molar amount of the transition metal compound. On the other hand, the amount of the organoaluminum compound is usually 1 to 200 times, preferably 3 to
It is used in a range of 100 moles.

When using a transition metal complex prepared in advance,
The transition metal complex is 0.001 based on the conjugated diene compound.
-10 mol%, preferably 0.01-1 mol%.

The catalyst used in the present invention can be preferably obtained by reacting a transition metal compound with an organoaluminum compound. Such a catalyst may be prepared by reacting a transition metal compound and an organoaluminum compound in situ in a reaction system containing ethylene and a conjugated diene. May be reacted, and the resulting reaction product may be used as a catalyst to supply a reaction system containing ethylene and a conjugated diene to carry out the reaction.

In the method of the present invention, the reaction between ethylene and the conjugated diene compound varies depending on the type of the conjugated diene compound, but is usually carried out in the presence of a transition metal catalyst comprising a transition metal compound and an organoaluminum compound. ~ 2
00C, preferably at a temperature in the range of 50-150C,
Ethylene pressure 0.5-100 kg / cm ² , preferably 2-7
It is performed under a pressure of 0 kg / cm ² . The reaction time is not particularly limited, but is usually in the range of 0.5 to 3 hours. However, the reaction atmosphere may be an atmosphere of ethylene alone or an atmosphere containing an inert gas such as nitrogen or argon together with ethylene. In the reaction between ethylene and the conjugated diene compound, the reaction solvent does not need to be particularly used, but may be used. In this case, as the reaction solvent, for example, hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, undecane, tridecane, toluene, and xylene can be preferably used. However, it is not limited to these.

According to the method of the present invention, after reacting ethylene and a conjugated diene compound in the presence of a transition metal catalyst as described above, the resulting reaction mixture is treated with water and an oxidizing agent. This completely deactivates the transition metal catalyst contained in the reaction mixture.

Here, according to the present invention, any of the treatment of the reaction mixture with water and the treatment with the oxidizing agent may be carried out by first adding the reaction mixture to the reaction mixture.
In addition, water and an oxidizing agent may be simultaneously added to the reaction mixture, and the reaction may be performed simultaneously. However, if an oxidizing agent is added to the reaction mixture first to perform the oxidation treatment, the oxidizing agent is consumed for the oxidation of the organoaluminum compound contained in the reaction mixture.To prevent this, water is first added to the reaction mixture. It is preferable to add and perform water treatment, and then add an oxidizing agent to perform oxidation treatment.

In the method of the present invention, the amount of water to be added to the reaction mixture is usually in the range of 0.1 to 5 times, preferably 0.2 to 1 time by weight of the reaction mixture. When adding this water, water may be added alone, but it is preferable to add an acid or an alkali at the same time in order to dissolve the aluminum hydroxide generated by hydrolysis of the organic aluminum compound in the aqueous phase. . Here, the acid or alkali may be usually added in the range of 0.1 to 100 mol per 1 mol of the organic aluminum compound.

Further, in order to dissolve a transition metal hydroxide or the like generated by partial hydrolysis of the transition metal compound in the aqueous layer, a so-called chelate coordinating compound such as ethylenediaminetetraacetic acid (EDTA) is simultaneously added. Is preferred.
The chelate coordinating compound is usually preferably added in an amount of at least equimolar to the transition metal compound in the reaction mixture. In particular, according to the present invention, it is most preferred to add this chelate coordinating compound to the reaction mixture together with the acid or alkali described above.

After completion of the reaction, water, preferably an acid or alkali and a chelate coordinating compound are added to the reaction mixture, and the reaction mixture is treated with water (washing treatment). In order to increase the contact efficiency with water, it is preferable to stir the reaction mixture under heating, if necessary. Such stirring is generally performed at a temperature in the range of 0 to 90 ° C, preferably 10 to 50 ° C. The stirring time is not particularly limited, but is usually 0.1 to 0.1.
The range is one hour.

Next, the oxidizing agent used in the present invention includes oxidizing gases such as air, oxygen, ozone and nitrogen oxide, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, m-chloroperbenzoic acid and the like. Inorganic nitrogen compounds such as peroxides, nitrates and nitrites; metal oxide acids such as chromic acid and permanganic acid; N such as pyridine-N-oxide;
-Oxides, sulfoxides such as dimethyl sulfoxide, and the like. Of these, air,
Oxygen or hydrogen peroxide is preferably used.

The oxidizing agent is usually used in an amount of 1 to 20 moles, preferably 1 to 5 moles, based on the total amount of the transition metal compound and the coordination compound. By using the oxidizing agent in such a range, the transition metal catalyst can be effectively deactivated, and the inconvenience such as conversion of the desired branched polyene compound into peroxide is small.

The above-mentioned oxidizing agent can be used as it is. When the oxidizing agent is an oxidizing gas, it may be used after being diluted with an inert gas such as nitrogen or argon. When it is a solid, it may be used after being diluted with an appropriate solvent such as water, toluene, and hexane.

After adding the oxidizing agent to the reaction mixture, the reaction mixture is usually stirred. This stirring is also usually performed at 0 to 9
It is carried out at a temperature of 0 ° C, preferably in the range of 10 to 50 ° C. The stirring time is not particularly limited, but is usually in the range of 0.1 to 10 hours.

Thus, according to the method of the present invention,
After reacting ethylene and a conjugated diene compound in the presence of a transition metal catalyst composed of a transition metal compound and an organoaluminum, the resulting reaction mixture is treated with water and an oxidizing agent to obtain a transition mixture contained in the reaction mixture. By deactivating the metal catalyst, the desired product, a branched polyene compound as a target product, is suppressed from isomerization to an internal olefin compound by ordinary distillation and purification from the reaction mixture, thereby obtaining a high yield. Can be obtained.

In particular, according to the present invention, when the reaction mixture is treated with water and then oxidized after the completion of the reaction, specifically, the reaction mixture contains water, preferably an acid or alkali, together with a chelate coordinating compound. After adding an aqueous solution, stirring and washing with water, the aqueous layer is removed, and thus the obtained oil phase may be oxidized with an oxidizing agent. By distilling the finally obtained oil phase in this manner, the desired branched polyene compound does not undergo isomerization to the internal olefin compound, and thus the desired branched polyene compound can be obtained at a high yield. Rate can be obtained.

However, in the present invention, the separation of the desired branched polyene compound from the obtained reaction mixture by distillation after the completion of the reaction means that the desired branched polyene compound is separated from the reaction mixture. Means that the intended branched polyene compound is separated from the reaction mixture by a separation operation including distillation. Therefore, in the present invention, separating the target branched polyene compound from the obtained reaction mixture by distillation after completion of the reaction means that the target branched polyene compound itself is distilled from the reaction mixture as a fraction. In addition to the case where the reaction solvent is removed from the reaction mixture,
Including the case where the intended branched polyene compound is separated from the reaction mixture, and further including the case of performing the plurality of distillation operations to separate the intended branched polyene compound from the reaction mixture. .

According to the present invention, the following various branched polyene compounds can be obtained by appropriately selecting the conjugated diene compound used as a raw material.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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In particular, according to the present invention, ethylene and 7-methyl-3-methylene-1,6-octadiene (β
-Myrcene) to give 4-ethylidene-8-methyl-1,7-nonadiene, and ethylene and 7,11-dimethyl-3-methylene-1,6,10 -Dodecatriene (β-farnesene)
To give 4-ethylidene-8,12-
Dimethyl-1,7,11-tridecatriene can be obtained.

The branched polyene compound obtainable by the method of the present invention is not only capable of high-speed vulcanization by copolymerizing it with an α-olefin such as ethylene or propylene, but also has high weather resistance, An ethylenically unsaturated copolymer having excellent heat resistance and ozone resistance can be obtained.

[0087]

According to the present invention, after reacting ethylene and the conjugated diene compound in the presence of a transition metal catalyst comprising a transition metal compound and an organoaluminum compound, the obtained reaction mixture is mixed with water. Since it is treated with an oxidizing agent to completely deactivate the transition metal catalyst, the desired branched chain polyene compound is then separated from the reaction mixture by distillation and purification to remove the branched chain polyene compound. Conversion to an internal olefin compound that does not participate in polymerization by isomerization can be suppressed, and thus the desired branched polyene compound can be obtained in high yield. The branched polyene compound thus obtained is excellent in weather resistance, heat resistance and ozone resistance by copolymerizing it with an α-olefin such as ethylene and propylene, and has a high vulcanization rate. The unsaturated unsaturated copolymer can be obtained.

[0088]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, the yield of the target product is represented by (p) where p is the number of moles of the target product and c ₀ is the charged mole number of the raw material conjugated diene used in the reaction.
/ C ₀ ) × 100 (%). The conversion rate of the conjugated diene as a raw material is [(c ₀ −c) / c ₀ ] × 100 (%), where c is the number of moles of the conjugated diene after the reaction.
I asked for it.

Example 1 (Synthesis of 4-ethylidene-8-methyl-1,7-nonadiene) A 1500 ml stainless steel (S
2.86 g of 2-bis (diphenylphosphino) ethanecobalt (II) chloride was placed in an autoclave made by US316).
(5.42 mmol), 70 g of anhydrous toluene, and 593 g (4.02 mol) of 7-methyl-3-methylene-1,6-octadiene (β-myrcene) were charged and stirred at room temperature for 1 hour. Next, 70.5 mL (64.2 mmol) of a toluene solution of triethylaluminum (0.91 mol / L) was added, and the autoclave was sealed.

Thereafter, an ethylene cylinder was directly connected to the autoclave, ethylene was introduced, and the inside of the autoclave was filled with 5 g of ethylene.
It was pressurized to kg / cm ² and heated to 80 ° C. The ethylene pressure is increased to 4 to 4 while intermittently adding the consumed ethylene.
The reaction was carried out at 80 ° C. for 4 hours while maintaining the pressure at 5 kg / cm ² .

After completion of the reaction, the autoclave was cooled and then opened, and a part of the obtained reaction mixture was collected and analyzed by gas chromatography to determine the product and its yield. As a result, the conversion of β-myrcene was 99%,
The yield of the desired product, 4-ethylidene-8-methyl-1,7-nonadiene, was 461 g (70% yield). Further, the yield of the reaction by-product 5,9-dimethyl-1,4,8-decatriene was 119 g (18% yield).

Next, 200 g of the above reaction mixture was charged into a glass separable flask with a stirring blade having a capacity of 1000 mL under a nitrogen atmosphere, followed by containing 5% sodium hydroxide and 2% disodium ethylenediaminetetraacetate. 67 g of an aqueous solution was added, and the mixture was stirred at room temperature for 20 minutes, and then allowed to stand for 20 minutes. After extracting the aqueous layer, 67 g of water was added to the oil phase, and the mixture was further stirred at room temperature for 20 minutes.
The mixture was allowed to stand for minutes, and the aqueous layer was extracted (water treatment of the reaction mixture). Thereafter, the oil phase was stirred for 30 minutes while flowing air (oxidizing agent) at a rate of 200 m / min through the gas phase of the separable flask (air oxidation of the oil phase).

160 g of the oil phase thus treated (containing 79 g of 4-ethylidene-8-methyl-1,7-nonadiene) was transferred to a 300 mL flask, heated to 140 ° C., and heated at 140 ° C. for 5 hours. did. After the heating was completed, a part of the oil phase was collected and analyzed by gas chromatography.
The reaction products from ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene were investigated. As a result, the conversions of 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene were all 0%, and conversion to internal olefin compounds not involved in polymerization was carried out. Was not observed.

Example 2 In a nitrogen atmosphere, 200 g of the reaction mixture obtained in Example 1 was charged into a separable flask made of glass with a stirring blade having a capacity of 1000 mL, and subsequently, 5% sodium hydroxide and 2% ethylenediamine tetrahydrate were added. 67 g of an aqueous solution containing disodium acetate was added, and the mixture was stirred at room temperature for 20 minutes, and then allowed to stand for 20 minutes. After extracting the aqueous layer, 67 g of water was added to the oil phase, further stirred at room temperature for 20 minutes, and allowed to stand for 20 minutes to extract the aqueous layer. Thereafter, 63 g of a 0.1% aqueous hydrogen peroxide solution was added to the oil phase, and the mixture was stirred at room temperature for 20 minutes.
After standing for 0 minutes, the aqueous layer was extracted.

The oil phase 160 g (4
79 g of ethylidene-8-methyl-1,7-nonadiene
Including. ) Was transferred to a 300 mL flask and 140
Heat to 140 ° C and 5 hours at 140 ° C. After heating,
A part of the oil phase is sampled and analyzed by gas chromatography,
4-ethylidene-8-methyl-1,7-nonadiene and 5.9
The reaction products from -dimethyl-1,4,8-decatriene were investigated. As a result, 4-ethylidene-8-methyl-1,7
The conversions of -nonadiene and 5,9-dimethyl-1,4,8-decatriene were all 0%, and no isomerization to an internal olefin compound not involved in the polymerization was observed.

Comparative Example 1 In Example 1, after the reaction of ethylene with 7-methyl-3-methylene-1,6-octadiene (β-myrcene) was completed, the obtained reaction mixture was not subjected to an air oxidation treatment. Except for the above, the same treatment was carried out as in Example 1 to give 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,
The reaction product from 4,8-decatriene was investigated. As a result, 34% of 4-ethylidene-8-methyl-1,7-nonadiene was isomerized to 4-ethylidene-8-methyl-2,7-nonadiene, and 5,9-dimethyl-1,4 , 8-
It was confirmed that 93% of the decatriene was isomerized to 5,9-dimethyl-2,4,8-decatriene.

Comparative Example 2 The procedure of Example 1 was repeated, except that the reaction mixture was not washed with water and the oil phase was not subjected to air oxidation, but was treated in the same manner as in 4-ethylidene-8-methyl-1,4 The reaction product from 7-nonadiene and 5,9-dimethyl-1,4,8-decatriene was investigated. As a result, 5% of 4-ethylidene-8-methyl-1,7-nonadiene was isomerized to 4-ethylidene-8-methyl-2,7-nonadiene, and
It was confirmed that 40% of -dimethyl-1,4,8-decatriene was isomerized to 5,9-dimethyl-2,4,8-decatriene.

Claims (9)

[Claims] (1) Ethylene and general formula (I) (Wherein f represents an integer of 1 to 5, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or a general formula (II) (In the formula, n represents an integer of 1 to 5, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, provided that R ⁴ , R ⁵ and R ⁶ Are not hydrogen atoms at the same time.). However,
R ¹ , R ² and R ³ are not simultaneously hydrogen atoms. Is reacted with a conjugated diene compound represented by the formula (III) in the presence of a transition metal catalyst. (Wherein, f, R ¹ , R ² and R ³ are the same as described above). In the method for producing a branched polyene compound represented by the formula: A method for producing a branched polyene compound, comprising treating the mixture with water and an oxidizing agent to deactivate the transition metal catalyst, and then separating the branched polyene compound from the reaction mixture by distillation. . 2. An ethylene compound represented by the general formula (I ′): (In the formula, f represents an integer of 1 to 5, n represents an integer of 1 to 5, and R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a carbon number of 1 to 5. Wherein R ⁴ , R ⁵ and R ⁶ are not hydrogen atoms at the same time) with a conjugated diene compound represented by the formula (III) ') (Wherein, f, n, R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are the same as described above). In the method for producing a branched polyene compound represented by the formula: Treating the reaction mixture containing the branched polyene compound with water and an oxidizing agent,
A method for producing a branched polyene compound, comprising deactivating the transition metal catalyst and then separating the branched polyene compound from the reaction mixture by distillation. 3. The method for producing a branched polyene compound according to claim 1, wherein the conjugated diene compound is 7-methyl-3-methylene-1,6-octadiene. 4. The method according to claim 1, wherein the conjugated diene compound is 7,11-dimethyl-3-.
The method for producing a branched polyene compound according to claim 2, wherein the compound is methylene-1,6,10-dodecatriene. 5. The method according to claim 1, wherein the transition metal catalyst is iron, cobalt, nickel,
The method for producing a branched polyene compound according to claim 1 or 2, which is a catalyst obtained by reacting a compound of a transition metal selected from rhodium or palladium with an organoaluminum compound. 6. The transition metal compound according to claim 1, wherein the transition metal compound is a complex of a transition metal selected from iron, cobalt, nickel, rhodium and palladium having 1,2-bis (diphenylphosphino) ethane as a ligand. 3. The method for producing a branched polyene compound according to item 2. 7. The method for producing a branched polyene compound according to claim 1, wherein the oxidizing agent is oxygen. 8. The method according to claim 1, wherein the oxidizing agent is hydrogen peroxide.
3. The method for producing a branched polyene compound according to item 1. 9. The method for producing a branched polyene compound according to claim 1, wherein after the reaction between ethylene and the conjugated diene is completed, the obtained reaction mixture is treated with water and then treated with an oxidizing agent. Method.