JPH11222446A - Branched chain-like polyene compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound capable of forming an ethylenic unsaturated copolymer excellent in weatherability, heat resistance and ozone resistance and having fast curing rate. SOLUTION: This compound is represented by formula I [R<1> and R<2> are each H or methyl; R<3> to R<7> are each H or a 1-3C alkyl; (n) is 1-5], e.g. 4- vinyl-2,6-dimethyl-2,6-octadiene. The compound of formula I is obtained by reacting a conjugated diene compound of formula II (e.g. a compound of formula III or formula IV) with ethylene, preferably at 50-150 deg.C, under ethylene pressure of 2-20 kg,/cm<2> for 0.5-30 hr, in the presence of a catalyst comprising a transition metal compound [e.g. cobalt chloride (II) or iron chloride (110] and an organoaluminum compound (e.g. trimethylaluminum or dimethylaluminum chloride) as necessary in a solvent (e.g. hexane or heptane). The transition metal compound is used in an amount of preferably 0.01-1 mol.% based on the conjugated diene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel branched polyene compound and a method for producing the same.

[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, when copolymerized with an α-olefin such as ethylene, an ethylenically unsaturated copolymer having excellent weather resistance, heat resistance and ozone resistance and a high vulcanization rate can be formed. If such a polyene compound appears, its industrial value will be extremely large.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has excellent weather resistance, heat resistance, and ozone resistance and a high vulcanization rate. It is an object of the present invention to provide a novel branched polyene compound capable of forming a copolymer and a method for producing the same.

[0009]

The branched polyene compound according to the present invention is a novel polyene compound and is represented by the following general formula [I].

[0010]

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Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a carbon atom ~
And n is an integer of 1 to 5. However, when n is 2 or more, R ³ and R ⁴ may be different from each other. ). In the present invention, it is preferable that R ³ and R ⁴ are all hydrogen atoms. In the present invention, n is preferably 1. The method for producing a branched polyene compound according to the present invention as described above is characterized by reacting a conjugated diene compound represented by the following general formula [II] with ethylene.

[0012]

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(In the formula, R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a carbon atom. ~
And n is an integer of 1 to 5. However, when n is 2 or more, R ³ and R ⁴ may be different from each other. ). In the present invention, the above reaction is desirably performed in the presence of a catalyst comprising a transition metal compound and an organoaluminum compound.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the branched polyene compound according to the present invention and a method for producing the same will be described in detail.

Branched Polyene Compound The branched polyene compound according to the present invention is a novel polyene compound and is represented by the following general formula [I].

[0016]

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In the formula, R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a carbon atom. 3
And n is an integer of 1 to 5. However, when n is 2 or more, R ³ and R ⁴ may be different from each other. 1-carbon as above
Specific examples of the alkyl group 3 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
In the present invention, it is preferable that R ³ and R ⁴ are all hydrogen atoms. In the present invention, n is preferably 1. In particular, R ³ and R ⁴ are all hydrogen atoms, and n
Is more preferably 1.

Specific examples of the branched polyene compound represented by the formula [I] include the following compounds.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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Embedded image The structure of the branched polyene compound [I] as described above can be determined by mass spectrometry, infrared absorption spectrum, ¹ H-NMR spectrum, and the like. The branched polyene compound [I] according to the present invention usually has a stereoisomer structure (trans form, cis form).

When the branched polyene compound [I] according to the present invention as described above is copolymerized with an α-olefin such as ethylene or propylene, an ethylenically unsaturated copolymer capable of high-speed vulcanization can be obtained. Can be. Moreover, this ethylenically unsaturated copolymer is excellent in weather resistance, heat resistance and ozone resistance.

The branched polyene compound [I] used in producing the ethylenically unsaturated copolymer may be a mixture of a trans form and a cis form, and may be a trans form alone or a cis form alone. You may.

Process for Producing Branched Polyene Compound The branched polyene compound [I] according to the present invention has the following formula [II]
Can be produced by reacting a compound having a conjugated diene structure (also referred to as a conjugated diene compound [II]) with ethylene.

[0031]

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In the formula, R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a C 1 -C 1 group. 3
And n is an integer of 1 to 5. However, when n is 2 or more, R ³ and R ⁴ may be different from each other. 1-carbon as above
Specific examples of the alkyl group 3 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
Specific examples of the conjugated diene compound represented by the formula [II] include, for example,

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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And the like. The reaction between the conjugated diene compound [II] and ethylene as described above can be represented by the following formula.

[0042]

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According to the above reaction, the branched polyene compound [I] is usually obtained as a mixture of a trans form and a cis form. Depending on the structure of the branched polyene compound [I], the trans form and the cis form can be separated by distillation.

The reaction between the conjugated diene compound [II] and ethylene as described above varies depending on the conjugated diene compound [II], but is usually 30 to 200 ° C., preferably 50 to 150 ° C.
At an ethylene pressure of 0.5 to 100 kg / cm ² ,
It is preferably carried out under a pressure of ^{2 to} 70 kg / cm ² . The reaction time is not particularly limited, but is usually 0.5 to 0.5.
The range is 30 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 above reaction, the reaction solvent need not 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.

The reaction between the conjugated diene compound [II] and ethylene is usually carried out in the presence of a catalyst. Especially this reaction,
When the reaction is performed in the presence of a catalyst comprising a transition metal compound and an organoaluminum, a branched polyene compound [I] can be efficiently obtained.

Specific examples of such transition metal compounds include iron groups such as iron and ruthenium, cobalt, rhodium, and the like.
A transition metal chloride, bromide, iodide, carbonate, sulfate, nitrate, phosphate, acetate, or a transition metal selected from a cobalt group such as iridium, nickel, and a nickel group such as palladium,
Acetyl acetonate and the like can be mentioned. Of these, cobalt (II) chloride or iron (II) chloride is preferred, and cobalt (II) chloride is particularly preferred.

Such a transition metal compound can be used as it is for preparing a catalyst. However, according to the present invention, for the preparation of the catalyst, the transition metal compound is
It is advantageous to use it as a transition metal complex to 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.

Examples of the compound which can serve as a ligand include oxygen-containing compounds such as dimethyl ether, diethyl ether, dipropyl ether, tetrahydrofuran, and acetylacetone, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, and cyclohexyl. Amine, dicyclohexylamine, aniline, diphenylamine, pyridine, picoline, 2,2′-bipyridine, 1,10-phenanthroline and other nitrogen-containing compounds, triethylphosphine, tripropylphosphine, tributylphosphine, triphenylphosphine, bis (diphenylphosphino ) Methane, 1,2-bis (diphenylphosphino) ethane, 1,3
And phosphorus-containing compounds such as -bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, triphenylphosphite, triphenylphosphine oxide, and triphenylphosphate. Among these, a phosphorus-containing compound is preferable, and 1,2-bis (diphenylphosphino) ethane is particularly preferable.

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
(Ph ₂ PCH ₂ CH ₂ PPh ₂ ) CoCl _{2 and the} like.

As the organic aluminum compound, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum ethoxide and the like can be used. Of these, triethylaluminum is preferably used. Organic aluminum compounds
It may be used as it is, or may be used as a toluene solution or a hexane solution.

In the reaction between the conjugated diene compound [II] and ethylene, the transition metal compound is usually used in an amount of 0.001 to 10 mol%, preferably 0.01 to 10 mol%, based on the conjugated diene compound [II]. It is used so as to be in a range of 1 mol%.
In addition, the coordination compound is usually
It is used in a molar amount of 20 times or less, preferably 0.1 to 10 times by mole.

On the other hand, the organoaluminum compound is used in an amount of 1 to 200 times, preferably 3
It is used in the range of 100 to 100 moles.

After completion of the reaction between the conjugated diene compound [II] and ethylene, the solvent, by-products, and the like are removed from the reaction mixture by a conventional method, for example, distillation to obtain a branched polyene compound [I]. can do. When a catalyst is used in the above reaction, it is preferable to perform a demineralization treatment such as washing the reaction mixture with water.

[0055]

According to the present invention, a novel branched polyene compound and a method for producing the same are provided. When this branched polyene compound is copolymerized with an α-olefin, an ethylenically unsaturated copolymer having excellent weather resistance, heat resistance and ozone resistance and a high vulcanization rate can be formed. Further, according to the present invention, the branched polyene compound can be produced with high yield.

[0056]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples. In Examples, the conversion rate of the conjugated diene compound as a raw material is defined as c ₀ , where the charged mole number of the raw material conjugated diene used in the reaction is c ₀ and the mole number of the conjugated diene after the reaction is c.
It was determined by [(c ₀ -c) / c ₀ ] × 100 (%). The yield of the target product was determined by (p / c ₀ ) × 100 (%), where p is the number of moles of the target product.

[0057]

Embodiment 1

[0058]

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In a nitrogen atmosphere, a 1,2-bis (diphenylphosphino) ethanecobalt (II) chloride 62 was placed in a 50 ml stainless steel (SUS316) autoclave.
3 mg (1.179 mmol) and 7.56 g (55.5 mmol) of 2,6-dimethyl-1,3,6-octatriene were charged and stirred at room temperature for 30 minutes. Next, 12.4 ml (11.5 mmol) of a toluene solution of triethylaluminum (0.95 mol / l) was added, and the mixture was sealed.

Thereafter, ethylene was introduced into the autoclave by directly connecting an ethylene cylinder to the autoclave.
Pressurized to kg / cm ² and heated to 80 ° C. The ethylene pressure was increased to 9 to 10 while intermittently adding the consumed ethylene.
The reaction was carried out at 80 ° C. for 3 hours while maintaining the pressure at kg / cm ² . After the completion of the reaction, the autoclave was cooled and then opened, and the obtained reaction mixture was poured into 50 ml of water to separate an organic layer and an aqueous phase. The separated organic layer was analyzed by gas chromatography after removing the solid content by filtration.

The yield of the desired product, 4-vinyl-2,6-dimethyl-2,6-octadiene, was 96% (the conversion of 2,6-dimethyl-1,3,6-octatriene was 100%).
%)Met.

The above 4-vinyl-2,6-dimethyl-
The organic layer containing 2,6-octadiene was subjected to precise vacuum distillation using a 30-stage distillation column.

As a result, the desired product, 4-vinyl-2,
7.5 g of 6-dimethyl-2,6-octadiene were obtained. 4-vinyl-2,6-dimethyl- obtained above
The analysis results of 2,6-octadiene are shown below.

(1) Boiling point: 75 ° C./20 mmHg (2) Mass spectrum: m / z 164 (M ⁺ molecular ion peak), 149, 135, 121, 108, 95;
77, 67 (3) ¹ H-NMR spectrum (solvent: CDCl ₃ ) The absorption peak is shown below. ppm (δ) 1.54 to 1.74 (12H, multiplet) 2.1 (2H, doublet) 3.1 (1H, multiplet) 4.86 to 5.05 (3H, multiplet) 5.26 (1H, multiplet) multiplet) 5.74 (1H, multiplet)

[0065]

Example 2 In a nitrogen atmosphere, a 1,2-bis (diphenylphosphino) ethaneiron (II) chloride (77.2 m) was placed in a 50 ml stainless steel (SUS316) autoclave.
g (0.147 mmol), 10 ml of toluene and 0.47 g of 2,6-dimethyl-1,3,6-octatriene
(3.47 mmol) and stirred at room temperature for 30 minutes. Next, a toluene solution of triethylaluminum (0.
95 mol / liter) 1.55 ml (1.44 mmol)
And sealed.

Thereafter, an ethylene cylinder was directly connected to the autoclave, and ethylene was introduced thereinto.
Pressurized to kg / cm ² and heated to 80 ° C. The ethylene pressure was increased to 9 to 10 while intermittently adding the consumed ethylene.
The reaction was carried out at 80 ° C. for 2 hours while maintaining the pressure at kg / cm ² . After the completion of the reaction, the autoclave was cooled and then opened, and the obtained reaction mixture was poured into 50 ml of water to separate an organic layer and an aqueous phase. The separated organic layer was analyzed by gas chromatography after removing the solid content by filtration.

4-vinyl-2,6-dimethyl-2,6-
Octadiene yield was 56% (2,6-dimethyl-1,1).
The conversion of 3,6-octatriene was 79%).

[0068]

EXAMPLE 3 Instead of using 1,2-bis (diphenylphosphino) ethaneiron (II) chloride in Example 2, 19.1 mg (0.147 mmol) of anhydrous cobalt (II) chloride and triphenyl Phosphite 0.077ml
(0.293 mmol), except that it was added separately.

4-vinyl-2,6-dimethyl-2,6-
Octadiene yield was 65% (2,6-dimethyl-1,1).
The conversion of 3,6-octatriene was 92%).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 236/22 C08F 236/22

Claims (5)

[Claims] 1. A branched polyene compound represented by the following general formula [I]: (In the formula, R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a C 1 -C 3 An alkyl group, and n is an integer of 1 to 5. However, when n is 2 or more, R ³ and R ⁴ may be different from each other.) 2. The branched polyene compound according to claim 1, wherein in the formula [I], R ³ and R ⁴ are all hydrogen atoms. 3. The branched polyene compound according to claim 1, wherein n = 1 in the formula [I]. 4. The method for producing a branched polyene compound according to claim 1, wherein the conjugated diene compound represented by the following general formula [II] is reacted with ethylene. Formula 2 (In the formula, R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a C 1 -C 3 An alkyl group, and n is an integer of 1 to 5. However, when n is 2 or more, R ³ and R ⁴ may be different from each other.) 5. The method for producing a branched polyene compound according to claim 3, wherein the reaction is carried out in the presence of a catalyst comprising a transition metal compound and an organoaluminum compound.