JPH08127547A - Chain polyene compound and its production - Google Patents

Abstract

PURPOSE: To obtain the subject new compound excellent in weather resistance, heat resistance and ozone resistance and useful as a component for forming unsaturated 2-olefin copolymers large in vulcanization rates. CONSTITUTION: A compound of formula I (R<1> is H, a1-3C alkyl; R<2> , R<3> are each a 1-3C alkyl), e.g. 3,4,8-trimethyl-1,4,7-nonatriene. The compound of formula I is obtained by reacting a conjugated triene compound of formula II with ethylene at 50-200 deg.C at an ethylene pressure of 1-100kg/cm<2> for 0.5-30hrs. The catalyst is preferably used in the form of a metal complex [e.g. [1,2-bis(diphenylphosphinoethane)] cobalt (II) chloride] produced by coordinating organic ligands to a transition metal compound (e.g. anhydrous cobalt chloride). The complex is preferably preliminarily brought into contact with an organic aluminum compound (e.g. triethyl aluminum) and subsequently used as the catalyst.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Polyene compounds are compounds having two or more carbon-carbon double bonds in one molecule, and many have been known in the past. For example 1,3-butadiene,
1,3-pentadiene, 1,4-hexadiene, ethylidene-2-
Polyene compounds such as norbornene and dicyclopentadiene are generally widely known.

An α-olefin / polyene copolymer obtained by copolymerizing such a polyene compound and an α-olefin such as ethylene or propylene is a vulcanizable polymer because it has an unsaturated bond. , Excellent in weather resistance, heat resistance and ozone resistance, as a rubber product (vulcanized rubber) such as automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering building materials, rubberized cloth, polypropylene, polystyrene, etc. It is widely used as a material for plastic blending.

Among the α-olefin / polyene copolymers having unsaturated bonds (hereinafter referred to as unsaturated α-olefin copolymers), ethylene / propylene / 5-ethylidene-2-norbornene copolymer The coalescence has a higher vulcanization rate than other unsaturated α-olefin-based copolymers and is particularly widely used.

However, the unsaturated α-olefin copolymer is the above-mentioned ethylene / propylene / 5-ethylidene.
-2-Norbornene copolymer has a slower vulcanization speed than other rubbers such as natural rubber, styrene / butadiene rubber, isoprene rubber, butadiene rubber, nitrile rubber, and high speed vulcanization. However, there is a problem in that the co-vulcanizability with diene rubber and the like is poor.

Further, since the unsaturated α-olefin copolymers as described above have a slow vulcanization rate, the energy consumption during vulcanization is shortened by shortening the vulcanization time or lowering the vulcanization temperature. It was difficult to reduce the amount, and it was difficult to produce a vulcanized rubber from an unsaturated α-olefin copolymer with high productivity.

Therefore, if it is copolymerized with an α-olefin such as ethylene, it forms an unsaturated α-olefin copolymer which is excellent in weather resistance, heat resistance and ozone resistance and has a high vulcanization rate. If such a polyene compound appears, its industrial value will be extremely great.

[0008]

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

[0009]

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

[0010]

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(In the formula, R ¹ represents a hydrogen atom or a carbon number of 1 to 1.
3 is an alkyl group, and R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms. ). The method for producing a chain polyene compound according to the present invention as described above is characterized by reacting a conjugated triene compound represented by the following general formula [II] with ethylene.

[0012]

[Chemical 4]

(In the formula, R ¹ is a hydrogen atom or a carbon number of 1 to
3 is an alkyl group, and R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms. ). In the present invention, the above reaction is preferably carried out in the presence of a catalyst composed of a transition metal compound and an organoaluminum compound.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The chain polyene compound and the method for producing the same according to the present invention will be specifically described below.

Chain Polyene Compound The chain 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 is a hydrogen atom or has 1 to 3 carbon atoms.
R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms. As the alkyl group having 1 to 3 carbon atoms as described above, specifically, a methyl group,
Examples thereof include ethyl group, n-propyl group and isopropyl group.

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

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

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[0022]

[Chemical 9]

[0023]

[Chemical 10]

The structure of the chain polyene compound [I] as described above has a mass spectrum, an infrared absorption spectrum and ¹ H-
It can be determined by NMR spectrum or the like.
The chain polyene compound [I] according to the present invention usually has a stereoisomeric structure (trans isomer, cis isomer).

When the chain polyene compound [I] according to the present invention as described above is copolymerized with an α-olefin such as ethylene or propylene, a rapid vulcanizable unsaturated α-olefin copolymer is obtained. Obtainable. Moreover, this unsaturated α-olefin-based copolymer has weather resistance, heat resistance,
It also has excellent ozone resistance.

The chain polyene compound [I] used for producing the unsaturated α-olefin copolymer is
It may be a mixture of trans isomer and cis isomer, and may be trans isomer alone or cis isomer alone.

Method for producing chain polyene compound The chain polyene compound [I] according to the present invention has the following formula [I]
It can be produced by reacting a compound having a conjugated triene structure represented by I] (also referred to as a conjugated triene compound [II]) with ethylene.

[0028]

[Chemical 11]

Specific examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Specific examples of the conjugated triene compound represented by the formula [II] include:

[0030]

[Chemical 12]

[0031]

[Chemical 13]

[0032]

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[0033]

[Chemical 15]

[0034]

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

[0036]

[Chemical 17]

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

Although the reaction between the conjugated triene compound [II] and ethylene as described above varies depending on the conjugated triene compound [II], it is usually 50 to 200 ° C., preferably 70 to 15 ° C.
At a temperature of 0 ° C., ethylene pressure 1 to 100 kg / cm ^2, preferably under a pressure of 3~70kg / cm ^2, it is carried out from 0.5 to 30 hours.

This reaction may be carried out in an atmosphere of an inert gas such as nitrogen or argon. The reaction can be performed without using a solvent. Can also.

The ethylene reaction with the conjugated triene compound [II] is usually carried out in the presence of a catalyst. Especially this reaction
When carried out in the presence of a catalyst composed of a transition metal compound and an organoaluminum compound, the chain polyene compound [I] can be efficiently obtained.

Specific examples of such a transition metal compound include chlorides of transition metals selected from the iron group such as iron and ruthenium, the cobalt group such as cobalt, rhodium and iridium, and the nickel group such as nickel and palladium. Examples thereof include bromide, acetylacetonate salt, 1,1,1,5,5,5-hexafluoroacetylacetonate salt, and dipivaloylmethane salt.

Of these, cobalt, iron, nickel,
Chlorides of rhodium and palladium are preferable, and chlorides of cobalt compounds are particularly preferable. Such a transition metal compound (for example, a transition metal chloride) can be used in the reaction as it is, but it is preferably used as a transition metal complex in which an organic ligand is coordinated with the transition metal compound. That is, together with this transition metal compound, an organic compound (coordination compound) that can serve as a ligand of the transition metal is allowed to coexist in the reaction system, or a transition metal complex is previously formed from the transition metal compound and the coordination compound as described above. Is preferably used.

Examples of the compound which can be such a ligand include bis (diphenylphosphino) methane,
1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, triethylphosphine, tributylphosphine, triphenylphosphine, cyclooctadiene, Examples include cyclooctatetraene.

Further, as a complex in which an organic ligand is coordinated to a transition metal compound in advance, [1,2-bis (diphenylphosphino) ethane] cobalt (II) chloride, [1,2-bis (diphenylphosphine) Fino) ethane] nickel (II) chloride,
Bis (triphenylphosphine) nickel (II) chloride and the like are preferably used.

As the organic aluminum compound, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum ethoxide, etc. can be used. Of these, triethylaluminum is preferably used. The organoaluminum compound is
It may be used as it is, or may be used as a toluene solution or a hexane solution.

In the reaction of the conjugated triene compound [II] with ethylene, the transition metal compound is preferably 0.001 to 10 relative to the conjugated triene compound [II].
It is used in an amount of mol%, particularly preferably in an amount of 0.01 to 1 mol%. Further, the coordination compound is preferably used in an amount of 0 to 20 times, and particularly preferably 0.1 to 5 times the amount of the transition metal compound.

The organoaluminum compound is preferably used in an amount of 1 to 200 mol times, and particularly preferably 3 to 100 mol times, relative to the transition metal compound.

In the present invention, the transition metal compound (or transition metal complex) as described above and the organoaluminum compound are preferably contacted with each other in advance and then used as a catalyst.

[0049]

INDUSTRIAL APPLICABILITY According to the present invention, a novel chain polyene compound and a method for producing the same are provided. The novel chain polyene compound, when copolymerized with an α-olefin, has weather resistance, heat resistance and resistance. It is possible to form an unsaturated α-olefin copolymer having excellent ozone properties and a high vulcanization rate.

[0050]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0051]

Embodiment 1

[0052]

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300 m with stirring blade under argon atmosphere
l In a stainless steel (SUS316) autoclave,
43 mg (0.33 mmol) anhydrous cobalt (II) chloride,
1,2-bis (diphenylphosphino) ethane 1.00g
(1.893 mmol) and 2,6-dimethyl-2,4,6-octatriene (100 g, 734 mmol) were added to give 25
The mixture was stirred at ° C for 2 hours. Then, at 25 ° C., a triethylaluminum / hexane solution having a concentration of 1 mol / liter 30
ml (30 mmol of triethylaluminum) was added and stirred for 2 hours.

Next, an ethylene cylinder was directly connected to the autoclave, ethylene was introduced, and the inside of the autoclave was cooled to 3
The pressure was increased to 5 kg / cm ² . Then heat to 100 ° C,
Add ethylene consumed 5 times intermittently for a total of 5
The reaction was carried out over time.

The autoclave was cooled and then opened, and the resulting reaction mixture was poured into 100 ml of water to separate an organic layer and an aqueous layer. The separated organic layer was subjected to an evaporator to remove low-boiling substances, and then 20 stages of precision vacuum distillation was performed.

84 g of the desired product, 3,4,8-trimethyl-1,4,7-nonatriene, was obtained (yield 70%, conversion rate of 2,6-dimethyl-2,4,6-octatriene). 93%). The analysis results of the 3,4,8-trimethyl-1,4,7-nonatriene obtained above are shown below.

(1) Boiling point: 80 ° C./9 mmHg (2) GC-MS (gas chromatography-mass spectrometry): m / z 164 (M⁺Molecular ion peak), 149, 1
21, 93 79, 67 (Gas chromatography measurement conditions: column: J & W Scientific Co., capillary column DB-1701 0.25 mm × 30
m Vaporization temperature: 250 ° C. Column temperature: After holding at 60 ° C. for 5 minutes, up to 200 ° C. 10
(Increases temperature in ° C / min) (3) Infrared absorption spectrum (neat) Absorption peak: 3080 cm^-1, 2975cm^-1, 292
5 cm^-1, 2875cm^-1, 1820 cm^-1, 1640
cm^-1, 1450cm^-1, 1380cm^-1, 1280c
m^-11,105 cm^-11020 cm^-1, 1000 cm
^-1, 905cm ^-1, 830 cm^-1 (Four) ¹1 H-NMR spectrum (solvent: CDCl₃) The absorption peak is shown below.

Ppm (δ) (proton number, peak) 1.12 (3H, doublet, J = 7 Hz) 1.60 (3H, singlet) 1.66 (3H, singlet) 1.72 (3H, singlet) 2 .74 (2H, triplet, J = 7Hz) 4.9 to 5.3 (4H, multiplet) 5.8 (1H, multiplet)

[0059]

Example 2 In Example 1, cobalt chloride and 1,2-
Instead of using a catalyst prepared by adding bis (diphenylphosphino) ethane separately to the flask, a complex previously prepared and isolated from cobalt chloride and 1,2-bis (diphenylphosphino) ethane [ 1,2-Bis (diphenylphosphino) ethane] cobalt (II) chloride 174m
The reaction was performed in the same manner as in Example 1 except that g (0.33 mmol) was used.

The yield of 3,4,8-trimethyl-1,4,7-nonatriene was 65% (conversion rate of 2,6-dimethyl-2,4,6-octatriene was 85%).

[0061]

Example 3 In Example 1, cobalt chloride and 1,2-
Instead of using a catalyst prepared by adding bis (diphenylphosphino) ethane separately to the flask, a complex previously prepared and isolated from nickel chloride and 1,2-bis (diphenylphosphino) ethane [ 1,2-Bis (diphenylphosphino) ethane] nickel (II) chloride 179m
The reaction was performed in the same manner as in Example 1 except that g (0.33 mmol) was used as a catalyst.

The yield of 3,4,8-trimethyl-1,4,7-nonatriene was 48% (conversion rate of 2,6-dimethyl-2,4,6-octatriene was 60%).

[0063]

Example 4 In Example 1, cobalt chloride and 1,2-
Instead of using the catalyst prepared by adding bis (diphenylphosphino) ethane separately to the flask, iron (II
The reaction was performed in the same manner as in Example 1 except that 117 mg (0.33 mmol) of I) acetylacetonate salt was used as a catalyst.

The yield of 3,4,8-trimethyl-1,4,7-nonatriene was 43% (conversion rate of 2,6-dimethyl-2,4,6-octatriene was 54%).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nori Kihara Aki 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industries, Ltd. (72) Inventor Toshihiro Aone Chiyoda-ku, Tokyo 3-25 Kasumigaseki Mitsui Petrochemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A chain polyene compound represented by the following general formula [I]: (In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms.). 2. A method for producing a chain polyene compound according to claim 1, characterized in that a conjugated triene compound represented by the following general formula [II] is reacted with ethylene: (In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms.). 3. The method for producing a chain polyene compound according to claim 2, wherein the reaction is carried out in the presence of a catalyst composed of a transition metal compound and an organoaluminum compound.