JPH0873382A - Norbornene compound having chain polyene group and its production - Google Patents

Abstract

PURPOSE: To obtain a new compound capable of providing an unsaturated α- olefin-polyene copolymer, excellent in weather, heat and ozone resistances and having a high vulcanization rate by copolymerization thereof with an α-olefin. CONSTITUTION: This compound is expressed by formula I [(n) is 1-5; R<1> to R<5> are each H or a 1-5C alkyl, with the proviso that R<3> to R<5> are not simultaneously H], e.g. 5-(1,5-dimethyl-1,4-hexadienyl)-2-norbornene. The compound is obtained by reacting cyclopentadine with a chain polyene compound having a conjugated diene of formula II such as 3,7-dimethyl-1,3,6-octatriene, preferably at 100-200 deg.C temperature under 5-70kg/cm<2> pressure usually for 0.5-30hr. Furthermore, the cyclopentadiene is used in an amount of 0.5-3 pts.wt. based on 1 pt.wt. compound of formula II.

Description

Detailed Description of the Invention

[0001]

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

[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 polyene compound that can be used appears, its industrial value is extremely large.

[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 novel norbornene compound having a chain polyene group capable of forming a polyene copolymer and a method for producing the same.

[0009]

SUMMARY OF THE INVENTION The norbornene compound having a chain polyene group according to the present invention is represented by the following general formula [I].

[0010]

Embedded image

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

The method for producing a norbornene compound having a chain polyene group according to the present invention comprises cyclopentadiene and
It is characterized by reacting with a chain polyene compound having a conjugated diene represented by the following general formula [II].

H ₂ C = CH-CR ¹ = CR ^2- (CH ₂ ) _n -CR ³ = CR ⁴ R ⁵ [II] (In the formula, n is an integer of 1 to 5, and R ¹ and R ² , R ³ ,
R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R ³ , R ⁴ and R ⁵ are not hydrogen atoms at the same time. ).

[0014]

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

Norbornene compounds having a chain polyene group
The norbornene compound having a chain polyene group according to the present invention is a novel compound and is represented by the following general formula [I].

[0016]

[Chemical 3]

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

Specific examples of the alkyl group having 1 to 5 carbon atoms as described above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-
Examples thereof include a butyl group, a t-butyl group, an n-pentyl group and an isopentyl group.

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

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

Embedded image

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

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.

The norbornene compound having a chain polyene group according to the present invention usually has a stereoisomeric structure. As this stereoisomeric structure, an endo body based on the arrangement of the chain polyene group bonded to the norbornene skeleton is used. And exo-forms, as well as trans-forms and cis-forms based on a substituent bonded to a double bond carbon of a chain polyene group.

When the norbornene compound having a chain polyene group 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 / polyene copolymer is obtained. You can get coalesced. Moreover, this unsaturated α-olefin / polyene copolymer is also excellent in weather resistance, heat resistance and ozone resistance.

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

Norbornene Compound Having Chain Polyene Group
Manufacturing method of thing The norbornene compound having a chain polyene group according to the present invention is a chain polyene compound having a cyclopentadiene and a conjugated diene represented by the following general formula [II] (hereinafter also referred to as chain polyene compound [II] ) And are reacted.

H ₂ C = CH-CR ¹ = CR ^2- (CH ₂ ) _n -CR ³ = CR ⁴ R ⁵ [II] In the formula, n is an integer of 1 to 5 and R ¹ , R ² , R ³ , R
⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R ³ , R ⁴ and R
⁵ cannot be a hydrogen atom at the same time.

Specific examples of the alkyl group having 1 to 5 carbon atoms as described above include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec-
Examples thereof include a butyl group, a t-butyl group, an n-pentyl group and an isopentyl group.

[0035] Examples of the chain polyene compound represented by the formula [II], specifically for _{example, CH 2 = CH-CH =} CH-CH 2 -CH = CH (CH 3) CH 2 = CH-CH _{= CH-CH 2 -CH = C} (CH 3) 2 CH 2 = CH-CH = CH-CH 2 -C (CH 3) = CH (C
_{H 3) CH 2 = CH-} CH = CH-CH 2 -C (CH 3) = C (CH
_{3) 2 CH 2 = CH-} CH = CH-CH 2 -C (C 2 H 5) = C (C 2
_{H 5) 2 CH 2 = CH} -CH = C (CH 3) -CH 2 -CH = C (C
_{H 3) 2 CH 2 = CH} -CH = C (CH 3) -CH 2 -C (CH 3) = C
_{(C 2 H 5) 2 CH} 2 = CH-CH = C (C 2 H 5) -CH 2 -CH = C (n-
_{C 4 H 9) 2 CH 2} = CH-CH = C (n-C 3 H 7) -CH 2 -CH = CH
_{(CH 3) CH 2 = CH} -CH = C (i-C 3 H 7) -CH 2 -CH = C
_{(CH 3) 2 CH 2 =} CH-C (CH 3) = CH-CH 2 -CH = CH (C
_{H 3) CH 2 = CH-} C (CH 3) = CH-CH 2 -CH = CH (C
_{2 H 5) CH 2 = CH} -C (CH 3) = CH-CH 2 -CH = CH (t-
_{C 4 H 9) CH 2 =} CH-C (CH 3) = CH-CH 2 -CH = CH (n-
_{C 5 H 11) CH 2 =} CH-C (CH 3) = CH-CH 2 -CH = C (CH
₃ ) ₂ CH ₂ = CH-C (CH ₃ ) = CH-CH ₂ -CH = C (CH
_{3) (C 2 H 5)} CH 2 = CH-C (CH 3) = CH-CH 2 -CH = C (C 2
_{H 5) 2 CH 2 = CH} -C (CH 3) = CH-CH 2 -CH = C (n-C
_{3 H 7) 2 CH 2 =} CH-C (CH 3) = CH-CH 2 -CH = C (i-C
_{3 H 7) 2 CH 2 =} CH-C (CH 3) = CH-CH 2 -CH = C (n-C
_{4 H 9) 2 CH 2 =} CH-C (CH 3) = CH-CH 2 -CH = C (i-C
_{4 H 9) 2 CH 2 =} CH-C (CH 3) = CH-CH 2 -CH = C (t-C
_{4 H 9) 2 CH 2 =} CH-C (CH 3) = CH-CH 2 -C (CH 3) = C
_{H (n-C 3 H 7} ) CH 2 = CH-C (CH 3) = CH-CH 2 -C (CH 3) = C
_{H (n-C 4 H 9} ) CH 2 = CH-C (CH 3) = CH-CH 2 -C (CH 3) = C
_{H (i-C 4 H 9} ) CH 2 = CH-C (CH 3) = CH-CH 2 -C (CH 3) = C
_{H (t-C 4 H 9} ) CH 2 = CH-C (n-C 3 H 7) = CH-CH 2 -CH = CH
_{(CH 3) CH 2 = CH} -C (C 2 H 5) = CH-CH 2 -CH = C (C
_{H 3) 2 CH 2 = CH} -C (n-C 4 H 9) = CH-CH 2 -CH = C
_{(CH 3) 2 CH 2 =} CH-C (CH 3) = C (CH 3) -CH 2 -CH = C
_{H (CH 3) CH 2 =} CH-C (CH 3) = C (CH 3) -CH 2 -CH = C
_{(C 2 H 5) 2 CH} 2 = CH-C (CH 3) = C (CH 3) -CH 2 -C (C
_{H 3) = C (CH 3} ) 2 CH 2 = CH-C (CH 3) = C (C 2 H 5) -CH 2 -C (CH
_{3) = C (CH 3)} 2 CH 2 = CH-C (C 2 H 5) = C (C 2 H 5) -CH 2 -C (C 2 H
₅ ) = C (C ₂ H ₅ ) _{2 and the} like.

The reaction between the above chain polyene compound [II] and cyclopentadiene can be represented by the following formula.

[0037]

[Chemical 12]

When the cyclopentadiene and the chain polyene compound [II] containing a conjugated diene are reacted with each other, usually 0.2 to 4 cyclopentadiene is added to 1 part by weight of the chain polyene compound [II]. Parts by weight, preferably 0.5-
Used in an amount of 3 parts by weight.

The reaction between cyclopentadiene and the chain polyene compound [II] varies depending on the chain polyene compound [II], but is usually 50 to 250 ° C., preferably 100 to 2
1 to 100 kg / cm ² at a temperature of 00 ° C, preferably 5 to 7
It is carried out under a pressure of 0 kg / cm ² for 0.5 to 30 hours.

This reaction may be carried out in 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 an inert hydrocarbon solvent such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, toluene and xylene. You may do it.

According to the above reaction, the norbornene compound [I] 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 [I] having a chain polyene group, the endo body and the exo body can be separated by distillation.

[0043]

INDUSTRIAL APPLICABILITY According to the present invention, a novel norbornene compound having a chain polyene group and a method for producing the same are provided, and the novel norbornene compound having a chain polyene group is mixed with an α-olefin such as ethylene. When polymerized, 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.

[0045]

Example 5- (1,5-dimethyl-1,4-hexadienyl) -2-norbornene
Synthesis

[0046]

[Chemical 13]

3,7-Dimethyl-1,3,6-octatriene 8
1.6 g (0.585 mol) and cyclopentadiene
77.5 g (1.172 mol) was put into a 300 ml stainless steel autoclave and pressurized with nitrogen (40 kg / c).
m ² ), stirred at 200 ° C. for 3 hours, cooled to room temperature, and opened the autoclave.

After removing the low-boiling substance of the obtained reaction mixture under reduced pressure, 20-stage precision vacuum distillation was carried out. 42.6 g of the target product, 5- (1,5-dimethyl-1,4-hexadienyl) -2-norbornene, was obtained. The yield was 36%.

The analysis results of 5- (1,5-dimethyl-1,4-hexadienyl) -2-norbornene obtained above are shown below. (1) Boiling point: 109-110 ° C / 2 mmHg (2) GC-MS (gas chromatography-mass spectrometry):
m / z 202 (M ⁺ molecular ion peak), 133, 1
05, 91 (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 40 ° C for 5 minutes, 5 ° C up to 200 ° C
(3) Infrared absorption spectrum (neat) Absorption peaks: 3040 cm ^-1 , 2970 cm ^-1 , 292
^{5cm -1, 1670cm -1, 1650cm -1} , 1625
^{cm -1, 1450cm -1, 1380cm -1} , 1360c
m ^-1 , 1260 cm ^-1 , 1160 cm ^-1 , 1110 cm
^-1 , 995 cm ^-1 , 965 cm ^-1 , 945 cm ^-1 , 91
^{0cm -1, 830cm -1, 810cm -1} , 790c
m ^-1 , 740 cm ^-1 , 700 cm ^-1 (4) ¹ H-NMR spectrum (solvent: CDCl ₃ ) ppm (δ) (proton number, peak) 1.64 (3H, singlet), 1.72 (6H, singlet), 1.6-3.0 (9H, multiplet) 5.1-5.8 (4H, multiplet)

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

Claims (2)

[Claims] 1. A norbornene compound having a chain polyene group represented by the following general formula [I]; (In the formula, n is an integer of 1 to 5, and R ¹ , R ² , R ³ ,
R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R ³ , R ⁴ and R ⁵ are not hydrogen atoms at the same time. ). 2. Cyclopentadiene and the following general formula [II]
The method for producing a norbornene compound having a chain polyene group according to claim 1, which comprises reacting the chain polyene compound having a conjugated diene represented by the formula; H ₂ C = CH-CR ¹ = CR ^{2- _{(CH 2) n -CR 3 =}} CR 4 R 5 ... [II] ( wherein, n is an integer from 1 to ^{5, R 1, R 2, R} 3,
R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, R ³ , R ⁴ and R ⁵ are not hydrogen atoms at the same time. ).