JPH08133993A - Production of norbornene compound having chain polyene group - Google Patents

Abstract

PURPOSE: To obtain the subject compound, excellent in weather and heat resistances, etc., and capable of providing an unsaturated α-olefin-polyene copolymer having a high vulcanization rate by reacting a vinylnorbornene compound with a conjugated diene compound in the presence of a catalyst. CONSTITUTION: A vinylnorbornene compound of formula I (R<1> and R<2> are each H or a 1-5C alkyl) (preferably 5-vinylnorbornene, etc.) is reacted with a conjugated diene compound of formula II (R<3> and R<4> are each H or a 1-5C alkyl; R<5> is H or a 1-4C alkyl, with the proviso that R<3> and R<4> are not simultaneously H) (e.g. isoprene) in the presence of a catalyst to afford the objective compound of formula III. Furthermore, a catalyst comprising a transition metallic complex in which an organic ligand is coordinated with Co chloride and triethylaluminum is preferred as the catalyst. 9146/28}1,2-Bis(diphenylphosphino)ethane]cobalt (II) chloride, etc., are preferred as the transition metallic complex. The reaction is preferably carried out at 70-150 deg.C under 10-70kg/cm<2> ethylene pressure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a norbornene compound having a chain polyene group.

[0002]

BACKGROUND OF THE INVENTION A polyene compound is a compound having two or more carbon-carbon double bonds in one molecule, and many polyene compounds have hitherto been known. For example, as polyene compounds, 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, ethylidene-2-norbornene, dicyclopentadiene and the like are 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. ,Weatherability,
It has excellent heat resistance and ozone resistance, and is used as a rubber product (vulcanized rubber) such as automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering building materials, rubberized cloth, and plastics such as polypropylene and polystyrene. Widely used as a blending material.

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

However, even if the unsaturated α-olefin / polyene copolymer is the above-mentioned ethylene / propylene / 5-ethylidene-2-norbornene copolymer, other rubbers such as natural rubber and styrene / butadiene rubber are used. As compared with diene rubbers such as isoprene rubber, butadiene rubber and nitrile rubber, the vulcanization rate is slower and there is a problem that covulcanizability with diene rubbers capable of high speed vulcanization is poor.

Further, the unsaturated α-olefin / polyene copolymer as described above has a slow vulcanization rate, so that it is consumed at the time of vulcanization by shortening the vulcanization time or lowering the vulcanization temperature. It was difficult to reduce the amount of energy, and it was difficult to produce a vulcanized rubber from an unsaturated α-olefin / polyene copolymer with high productivity.

Therefore, if it is copolymerized with an α-olefin such as ethylene, it forms an unsaturated α-olefin / polyene copolymer having excellent weather resistance, heat resistance, ozone resistance and fast vulcanization rate. If a method for producing a polyene compound capable of obtaining such a polyene compound appears, its industrial value will be extremely great.

[0008]

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

[0009]

SUMMARY OF THE INVENTION A method for producing a norbornene compound having a chain polyene group according to the present invention comprises a vinyl norbornene compound represented by the following general formula [I]:

[0010]

[Chemical 4]

(Wherein R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), a conjugated diene compound represented by the following general formula [II];

[0012]

Embedded image

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R ³ and R ⁴ are not hydrogen atoms at the same time. ) And in the presence of a catalyst, the following [II
[1] is characterized by producing a norbornene compound having a chain polyene group.

[0014]

[Chemical 6]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Group, provided that R ³ and R ⁴ are not hydrogen atoms at the same time.)

[0016]

DETAILED DESCRIPTION OF THE INVENTION In the method for producing a norbornene compound having a chain polyene group according to the present invention, a vinyl norbornene compound represented by the formula [I] and a conjugated diene compound represented by the formula [II] are used as a catalyst. In the presence of
A norbornene compound having a chain polyene group represented by the following [III] is produced.

[0017]

[Chemical 7]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a group. provided that R ³ and R ⁴ are never hydrogen atom simultaneously.) later the detail norbornene compound represented by the formula [III], the norbornene having a chain polyene group according to the present invention the following The method for producing the compound will be specifically described.

The vinyl norbornene compound used in the present invention is represented by the following formula [I].

[0020]

Embedded image

(In the formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) , Methyl group, ethyl group, n-propyl group, i-
Propyl group, n-butyl group, i-butyl group, sec-butyl group,
Examples thereof include t-butyl group, n-pentyl group and i-pentyl group.

Specific examples of the vinyl norbornene compound represented by the formula [I] include the following compounds.

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

Embedded image

[0029]

[Chemical 15]

[0030]

Embedded image

Of these,

[0032]

[Chemical 17]

And the like are preferably used. The conjugated diene compound used in the present invention is represented by the following general formula [II].

[0034]

Embedded image

In the formula, R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 3
⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
However, R ³ and R ⁴ are not hydrogen atoms at the same time.

Specific examples of the alkyl group having 1 to 5 carbon atoms include the same groups as the alkyl group in the formula [I]. As the alkyl group having 1 to 4 carbon atoms, Among these examples, groups excluding an alkyl group having 5 carbon atoms can be mentioned.

Specific examples of the conjugated diene compound represented by the formula [II] include CH ₂ ═CH—C (CH ₃ ) ═CH ₂ CH ₂ ═CH—C (CH ₃ ) ═CH ( _{CH 3), CH 2 = CH} -C (CH 3) = CH (C 2 H 5), CH 2 = CH-C (CH 3) = CH (n- or _{i-C 3 H 7),} CH 2 = _{CH-C (CH 3) =} CH (n-, i-, sec- or t-
_{C 4 H 9), CH 2} = CH-C (C 2 H 5) = CH 2, CH 2 = CH-C (C 2 H 5) = CH (CH 3), CH 2 = CH-C (C 2 _{H 5) = CH (C 2} H 5), CH 2 = CH-C (C 2 H 5) = CH (n- or _{i-C 3 H 7),} CH 2 = CH-C (C 2 H 5) = CH (n-, i-, sec- or t-
_{C 4 H 9), CH 2} = CH-C (n- or _{i-C 3 H 7) =} CH 2, CH 2 = CH-C (n- or _{i-C 3 H 7) =} CH (CH 3) _{, CH 2 = CH-C (} n- or _{i-C 3 H 7) =} CH (C 2 H 5), CH 2 = CH-C (n- or _{i-C 3 H 7) =} CH (n- or i-
_{C 3 H 7), CH 2} = CH-C (n- or _{i-C 3 H 7) =} CH (n-, i-, se
c- or _{t-C 4 H 9),} CH 2 = CH-C (n-, i-, sec- or _{t-C 4 H 9) =} C
_{H 2, CH 2 = CH-} C (n-, i-, sec- or _{t-C 4 H 9) =} CH
_{(CH 3), CH 2 =} CH-C (n-, i-, sec- or _{t-C 4 H 9) =} CH
_{(C 2 H 5), CH} 2 = CH-C (n-, i-, sec- or _{t-C 4 H 9) =} CH
(n- or _{i-C 3 H 7),} CH 2 = CH-C (n-, i-, sec- or _{t-C 4 H 9) =} CH
_{(i-C 3 H 7)} , CH 2 = CH-C (n-, i-, sec- or _{t-C 4 H 9) =} CH
(n-, i-, sec- or _{t-C 4 H 9),} CH 2 = CH-C (n- or _{i-C 5 H 11) =} CHH 2, CH 2 = CH-C (n- or i _{-C 5 H 11) = CH (} CH 3), CH 2 = CH-C (n- or _{i-C 5 H 11) =} CH (C 2 H 5), CH 2 = CH-C (n- or i -C ₅ H ₁₁ ) = CH (n- or i
_{-C 3 H 7), CH 2} = CH-C (n- or _{i-C 5 H 11) =} CH (n-, i-, s
ec- or _{t-C 4 H 9),} CH 2 = C (CH 3) -CH = CH 2, CH 2 = C (CH 3) -CH = CH (CH 3) CH 2 = C (CH 3) - _{CH = CH (C 2 H 5} ) CH 2 = C (CH 3) -CH = CH (n- or _{i-C 3 H 7),} CH 2 = C (CH 3) -CH = CH (n-, i -, Sec- or t-
_{C 4 H 9), CH 2} = C (C 2 H 5) -CH = CH 2, CH 2 = C (C 2 H 5) -CH = CH (CH 3) CH 2 = C (C 2 H 5) _{-CH = CH (C 2 H 5} ) CH 2 = C (C 2 H 5) -CH = CH (n- or _{i-C 3 H 7),} CH 2 = C (C 2 H 5) -CH = CH (n-, i-, sec- or t-
_{C 4 H 9), CH 2} = C (n- or _{i-C 3 H 7) -CH} = CH 2, CH 2 = C (n- or _{i-C 3 H 7) -CH} = CH (CH 3) CH ₂ = C (n- or _{i-C 3 H 7) -CH} = CH (C 2 H 5) CH 2 = C (n- or _{i-C 3 H 7) -CH} = CH (n- or i-
_{C 3 H 7), CH 2} = C (n- or _{i-C 3 H 7) -CH} = CH (n-, i-, se
c- or _{t-C 4 H 9),} CH 2 = C (n-, i-, sec- or _{t-C 4 H 9) -CH} = C
_{H 2, CH 2 = C (} n-, i-, sec- or _{t-C 4 H 9) -CH} = CH
_{(CH 3) CH 2 = C} (n-, i-, sec- or _{t-C 4 H 9) -CH} = CH
_{(C 2 H 5) CH 2} = C (n-, i-, sec- or _{t-C 4 H 9) -CH} = CH
(n- or _{i-C 3 H 7),} CH 2 = C (n-, i-, sec- or _{t-C 4 H 9) -CH} = CH
(n-, i-, sec- or _{t-C 4 H 9),} CH 2 = C (n- or _{i-C 5 H 11) -CH} = CH 2, CH 2 = C (n- or i-C _{5 H 11) -CH = CH (} CH 3) CH 2 = C (n- or _{i-C 5 H 11) -CH} = CH (C 2 H 5) CH 2 = C (n- or i-C ₅ H ₁₁ ) -CH = CH (n- or i
_{-C 3 H 7), CH 2} = C (n- or _{i-C 5 H 11) -CH} = CH (n-, i-, s
ec- or _{t-C 4 H 9),} CH 2 = C (CH 3) -C (CH 3) = CH 2, CH 2 = C (CH 3) -C (CH 3) = CH (CH 3), _{CH 2 = C (CH 3)} -C (CH 3) = CH (C 2 H 5), CH 2 = C (CH 3) -C (CH 3) = CH (n- or i-C
_{3 H 7), CH 2 =} C (CH 3) -C (CH 3) = CH (n-, i-, sec- or _{t-C 4 H 9),} CH 2 = C (CH 3) -C ( _{C 2 H 5) = CH 2} , CH 2 = C (CH 3) -C (C 2 H 5) = CH (CH 3), CH 2 = C (CH 3) -C (C 2 H 5) = CH _{(C 2 H 5), CH} 2 = C (CH 3) -C (C 2 H 5) = CH (n- or i-C ₃ H
_{7), CH 2 = C (} CH 3) -C (C 2 H 5) = CH (n-, i-, sec- or t-C ₄ H _9), and the like.

The reaction of the vinyl norbornene compound [I] and the conjugated diene compound [II] as described above can be represented by the following formula.

[0039]

[Chemical 19]

When the vinyl norbornene compound [I] is reacted with the conjugated diene compound [II], usually, the vinyl norbornene compound [I] is added in an amount of 0.1 to 4 with respect to 1 mol of the conjugated diene compound [II]. It is used in a molar amount, preferably 0.2 to 3 mol.

The reaction between the vinyl norbornene compound [I] and the conjugated diene compound [II] varies depending on the kind of these compounds, but is usually 50 to 200 ° C., preferably 70 to 1
It is carried out at a temperature of 50 ° C. under an ethylene pressure of 1 to 100 kg / cm ^{2 and} preferably 10 to 70 kg / cm ² for 0.5 to 30 hours.

The reaction between the vinyl norbornene compound [I] and the conjugated diene compound [II] as described above is carried out in the presence of a catalyst. Specifically, for example, when the reaction is carried out in the presence of a catalyst composed of a transition metal compound and an organoaluminum compound, the norbornene compound [I] having a chain polyene group 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, dimethyl aluminum chloride, triethyl aluminum, diethyl aluminum chloride, diethyl aluminum ethoxide, ethyl aluminum dichloride, triisobutyl aluminum, 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 above reaction, the transition metal compound is preferably 0.1 to the conjugated diene compound [II].
An amount of 001 to 10 mol%, particularly preferably 0.01 to
Used in an amount of 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, of the transition metal compound.

In the present invention, it is preferable to use, as a catalyst, the one in which the above transition metal compound (or transition metal complex) and the organoaluminum compound are brought into contact in advance. This reaction may be carried out under an atmosphere of an inert gas such as nitrogen or argon. Further, a radical polymerization inhibitor such as hydroquinone can be added to the reaction system.

The above reaction can be carried out without using a solvent, but in the presence of a reaction-inert hydrocarbon solvent such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, toluene and xylene. You may go to

According to the above reaction, the norbornene compound [III] having a conjugated diene group is usually obtained as a mixture of an endo form and an exo form. Depending on the structure of the norbornene compound [III] having a conjugated diene group, the endo body and the exo body can be separated by distillation. It may also be obtained as a stereoisomeric mixture of trans and cis isomers.

Norbornene Compound Having Conjugated Diene Group The norbornene compound having a conjugated diene group obtained in the present invention is a compound represented by the general formula [III].

[0054]

Embedded image

In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Is. However, R ³ and R ⁴ are not hydrogen atoms at the same time.

Alkyl groups R ¹ , R ² , R ³ and R ^{4 in the} formula
And R ⁵ are the same as those shown in the formulas [I] and [II]. The norbornene compound having a conjugated diene group obtained in the present invention usually has a stereoisomeric structure, and as this stereoisomeric structure, an endo isomer and an exo isomer based on the arrangement of the conjugated diene group bonded to the norbornene skeleton, And trans- and cis-forms based on the substituent attached to the double bond carbon of the conjugated diene group.

The norbornene compound having a conjugated diene group obtained in the present invention has the following stereoisomeric structural formula [I
V], and may be a stereoisomeric mixture of the structure represented by the formula [III] and the structure represented by the formula [IV].

[0058]

[Chemical 21]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above, R ^{5 ′} is an alkyl group having 1 to 5 carbon atoms, and R ³ is a group represented by formula [III]. is one less carbon atoms than R ^3, and as R ^{5 'are} norbornene compound having a conjugated diene group represented by the number of carbon atoms than R ⁵ is one more.) such expressions [III] (or [IV]) Specifically, the following compounds may be mentioned.

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23]

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

The structure of the norbornene compound having a conjugated diene group in the side chain as described above can be determined by mass spectrometry, infrared absorption spectrum, ¹ H-NMR spectrum and the like.

The norbornene compound having a conjugated diene group obtained in the present invention is converted into an α-form of ethylene, propylene or the like.
When copolymerized with an olefin, an unsaturated α-olefin / polyene copolymer capable of rapid vulcanization can be obtained. Moreover, this unsaturated α-olefin / polyene copolymer is also excellent in weather resistance, heat resistance and ozone resistance.

The norbornene compound having a conjugated diene group used in the production of the α-olefin / polyene copolymer may be a mixture of the above various stereoisomeric structures, and may also be an endo isomer, an exo isomer or a trans isomer. Alternatively, the cis form may be used alone.

[0067]

According to the present invention, there is provided a method for producing a novel norbornene compound having a conjugated diene group. A norbornene compound having this novel conjugated diene group,
By copolymerizing with an α-olefin such as ethylene, an unsaturated α-olefin / polyene copolymer having excellent weather resistance, heat resistance and ozone resistance and having a high vulcanization rate can be obtained.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0069]

Example 5- (5-methyl-1,4-hexadienyl) -2-norbornene (1)
And 5- (4-methyl-1,4-hexadienyl) -2-norbornene
(2) Mixture synthesis

[0070]

[Chemical formula 26]

300 m with a stirring blade in an argon atmosphere
Into a stainless steel (SUS316) autoclave, 1.5 g (2.84 mmol) of [1,2 bis (diphenylphosphino) ethane] cobalt (II) chloride and 50.0 g (416 mmol) of vinylnorbornene were placed, The mixture was stirred at 25 ° C for 0.5 hours. Then, 29 ml (29 mmol) of a hexane solution of triethylaluminum having a concentration of 1 mol / l was added under an argon atmosphere, and the mixture was stirred for 2 hours. Then, pressurize with nitrogen to 20kg /
After the temperature was adjusted to cm ² and the temperature was raised to 105 ° C., isoprene was pressure-fed at a flow rate of 0.6 ml / min using a metering pump to feed a total of 57.0 g (837 mmol) into the autoclave. 1 more after the feed is over
The reaction was carried out at 05 ° C for 4 hours.

After the completion of the reaction, the autoclave was cooled and then opened, and the obtained reaction mixture was poured into 100 ml of water for liquid separation. The organic layer was separated, low-boiling substances were removed by an evaporator, and then 80-stage precision vacuum distillation was performed.

As a result, the desired product 5- (5-methyl-1,4-
Hexadienyl) -2-norbornene and 5- (4-methyl-1,
17 g of 4-hexadienyl) -2-norbornene mixture was obtained (yield 15%, vinylnorbornene conversion 35
%).

The thus-obtained 5- (5-methyl-1,4-
Hexadienyl) -2-norbornene and 5- (4-methyl-1,
The analysis results of the 4-hexadienyl) -2-norbornene mixture are shown below.

(1) Boiling point: 95 to 97 ° C./9 mmHg (2) GC-MS (gas chromatography-mass spectrometry):
m / z 188 (M ⁺ ), 119, 93, 69 (Gas chromatography measurement condition: 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
(3) Infrared absorption spectrum (neat, absorption peak c)
m ^-1 ) 3060, 2975, 2930, 2875, 1640,
1575, 1450, 1380, 1340, 1280,
1260, 1230, 1040, 1100, 1020,
990, 960, 890, 840, 820, 770, 7
20 (4) ¹ H-NMR spectrum (solvent: CDCl ₃ ) ppm (δ) (proton number, peak) 1.0 to 2.0 (6H, multiplet) 1.64 (3H, singlet) 2.5 to 3 .0 (3H, multiplet) 4.5 to 4.8 (2H, multiplet) 5.3 (1H, multiplet) 5.9 (1H, multiplet) 6.1 (1H, multiplet)

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 9, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

The reaction between the vinyl norbornene compound [I] and the conjugated diene compound [II] as described above is carried out in the presence of a catalyst. Specifically, for example, when the reaction is performed in the presence of a catalyst composed of a transition metal compound and an organoaluminum compound, a norbornene compound [ III ] having a chain polyene group can be efficiently obtained.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

In the present invention, it is preferable to use, as a catalyst, the one in which the above transition metal compound (or transition metal complex) and the organoaluminum compound are brought into contact in advance. This reaction may be carried out under an atmosphere of an inert gas such as nitrogen or argon.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

According to the above reaction, the norbornene compound [III] having a chain polyene group is usually obtained as a mixture of an endo form and an exo form. Depending on the structure of the norbornene compound [III] having a chain polyene group , the endo body and the exo body can be separated by distillation.
It may also be obtained as a stereoisomeric mixture of trans and cis isomers.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

Norbornene Compound Having Chain Polyene Group
The norbornene compound having a chain polyene group obtained in the present invention is a compound represented by the general formula [III].

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

Alkyl groups R ¹ , R ² , R ³ and R ^{4 in the} formula
And R ⁵ are the same as those shown in the formulas [I] and [II]. The norbornene compound having a chain polyene group obtained in the present invention usually has a stereoisomeric structure, and as this stereoisomeric structure, an endo isomer and an exo isomer based on the arrangement of a conjugated diene group bonded to the norbornene skeleton are provided. , And trans- and cis-forms based on the substituent bonded to the double bond carbon of the chain polyene group .

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

The norbornene compound having a chain polyene group obtained in the present invention may be represented by the following stereoisomeric structural formula [IV], and is represented by the formula [III] and the formula [IV]. It may be a stereoisomeric mixture with the structure shown.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

[0058]

[Chemical 21]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above, R ^{5 ′} is an alkyl group having 1 to 5 carbon atoms, and R ³ is a group represented by formula [III]. The carbon number of R ³ is 1 less than that of R ³ , and the carbon number of R ^{5 ′} is 1 more than that of R ^5. ) Such a chain represented by the formula [III] (or [IV])
Specific examples of the norbornene compound having a polyene group include the following compounds.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

The structure of the norbornene compound having a chain polyene group as a side chain as described above can be determined by mass spectrometry, infrared absorption spectrum, ¹ H-NMR spectrum and the like.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction content]

The norbornene compound having a chain polyene group obtained in the present invention is converted into ethylene, propylene or the like by α
-When copolymerized with an olefin, an unsaturated α-olefin / polyene copolymer capable of rapid vulcanization can be obtained. Moreover, this unsaturated α-olefin / polyene copolymer is also excellent in weather resistance, heat resistance and ozone resistance.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction content]

The norbornene compound having a chain polyene group used for producing the α-olefin / polyene copolymer may be a mixture of the above various stereoisomeric structures, and may be an endo isomer, an exo isomer or a trans isomer. The body or cis body may be used alone.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

[0067]

According to the present invention, there is provided a method for producing a novel norbornene compound having a chain polyene group .
When this norbornene compound having a novel chain polyene group is copolymerized with an α-olefin such as ethylene,
It is possible to obtain an unsaturated α-olefin / polyene copolymer having excellent weather resistance, heat resistance and ozone resistance, and having a high vulcanization rate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nori Kihara Akira 6-1, 1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (1)

[Claims] Claims: A vinyl norbornene compound represented by the following general formula [I]: (wherein R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and the following general formula [II] A conjugated diene compound represented by: (Wherein, R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However R ³
And R ⁴ are not hydrogen atoms at the same time. ) Are reacted with each other in the presence of a catalyst to produce a norbornene compound having a chain polyene group represented by the following [III]; (In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
However, R ³ and R ⁴ are not hydrogen atoms at the same time. )