JP2000026329A - Tetracyclododecene composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tetracyclododecene(TCD) composition by controlling the contamination of reaction byproducts within a specific range so as to afford the corresponding polymer through addition polymerization of the composition in high reactivity without gelling due to crosslinking reaction. SOLUTION: This composition intended for addition polymerization using a Ziegler-type catalyst comprises (B) tetracyclododecene(TCD) of the formula containing (A) 100-5,000 ppm of cyclopentadiene trimer. The composition with the content of the component A limited as mentioned above is obtained by reaction under heating between norbornene, cyclopentadiene and/or dicyclopentadiene, and ethylene pref. in the molar ratios of the cyclopentadiene and/or dicyclopentadiene/norbornene and the ethylene/norbornene at 0.1-0.6 (in terms of cyclopentadiene) and 0.05-0.3, respectively. Addition polymerization of the composition in the presence of a Ziegler-type catalyst affords the corresponding polymer without gelling.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tetracyclododecene composition for addition polymerization with a Ziegler-type catalyst,
Specifically, the content of the trimer of cyclopentadiene is 10
The present invention relates to a composition comprising 0 to 5,000 ppm of tetracyclododecene.

[0002]

2. Description of the Related Art In recent years, it has been found that cyclic olefins represented by tetracyclododecene are very useful as raw materials for resins having excellent optical properties, heat resistance and oil absorption. These cyclic olefins are subjected to polymerization using an organometallic complex catalyst.One of them is homopolymerization or copolymerization with a lower α-olefin using a Ziegler catalyst containing a metallocene catalyst at the olefin site of the cyclic olefin. There is a way to do it. This polymerization is a simple addition polymerization of an olefin, and usually does not involve cleavage of an olefinic carbon-carbon double bond or a ring-opening reaction. Therefore, the resulting polymer hardly has a carbon-carbon unsaturated bond, and even if it does, it has only one carbon-carbon double bond at the molecular terminal.

The following is known as a method for producing tetracyclododecene. Japanese Patent Publication No. 1-60011 discloses a method for heating an α-olefin, cyclopentadiene and / or dicyclopentadiene, and norbornene to produce a mixture containing norbornene and tetracyclododecene, in which norbornene is recycled. It is disclosed. JP-A-7-17308
No. 5 discloses a compound having a structure corresponding to a trimer of cyclopentadiene represented by the following formula [II] of 50 to 5,000.
A tetracyclododecene derivative composition containing 0 ppm is disclosed. This publication discloses that the obtained tetracyclododecene derivative composition is used as a monomer for metathesis ring-opening polymerization. In addition, there is no specific disclosure about the manufacturing method of the composition.

[0004]

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[0005]

(A) Norbornene,
The product obtained by the Diels-Alder type thermal addition reaction of (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene is cyclopentadiene other than the target tetracyclododecene and norbornene as an intermediate product. In some cases. Since the trimer of cyclopentadiene has a boiling point close to that of the target product, tetracyclododecene, it is easily mixed into tetracyclododecene when tetracyclododecene is obtained by distillation. The trimer of cyclopentadiene has the following formula [II
A diolefin compound having a norbornene-type olefin structure and a cyclopentene-type olefin structure represented by formula (I), and a diolefin compound having two sets of norbornene-type olefin structures represented by the formula (II) is there. Any of these diolefin compounds may cause a crosslinking reaction during homopolymerization at the olefin site of the cyclic olefin or copolymerization with a lower α-olefin in addition polymerization, which may cause gelation.

[0006]

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[0007] Accordingly, an object of the present invention is to provide a tetracyclo which does not cause a gelation due to a crosslinking reaction during homopolymerization at the olefin site of a cyclic olefin or copolymerization with a lower α-olefin in addition polymerization. It is to provide a dodecene composition.

[0008]

According to the first aspect of the present invention, the content of the trimer of cyclopentadiene is 100 to 5,000 p.
The present invention relates to a composition for addition polymerization using a Ziegler-type catalyst, which is composed of tetracyclododecene represented by the following formula [I], which is represented by the following formula [I]:

[0009]

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A second aspect of the present invention is the first aspect of the present invention, wherein
The present invention relates to a tetracyclododecene composition having a content of a trimer of cyclopentadiene represented by the following formula [II] of 100 to 3,000 ppm.

[0011]

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A third aspect of the present invention is the first or second aspect of the present invention.
Wherein (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene and (c)
The present invention relates to a tetracyclododecene composition produced by mixing and heating and reacting ethylene. A fourth aspect of the present invention is the third aspect of the present invention, wherein the molar ratio of (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene is such that the norbornene is 1.0, and the cyclopentadiene and // the cyclopentadiene conversion amount of dicyclopentadiene is 0.1 to 0.6,
It relates to a tetracyclododecene composition in which ethylene is 0.05 to 0.3. A fifth aspect of the present invention is the fourth aspect of the present invention, wherein the cyclopentadiene of cyclopentadiene and / or dicyclopentadiene with respect to the total weight of (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene is used. It relates to a tetracyclododecene composition having a reduced weight ratio of 0.06 to 0.30. A sixth aspect of the present invention relates to the third aspect of the present invention, which relates to a tetracyclododecene composition obtained by using a hydrocarbon solvent inert to the reaction (d) during the reaction. A seventh aspect of the present invention is the sixth aspect of the present invention, wherein a total of (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene, (c) ethylene and (d) a hydrocarbon solvent inert to the reaction. The ratio of the weight of cyclopentadiene and / or dicyclopentadiene in terms of cyclopentadiene to the weight is 0.05 to 0.25.
And a tetracyclododecene composition. The eighth aspect of the present invention relates to the tetracyclododecene composition according to the sixth aspect of the present invention, wherein the hydrocarbon solvent inert to the reaction (d) is a branched aliphatic hydrocarbon or an alicyclic hydrocarbon. According to a ninth aspect of the present invention, in any one of the third to eighth aspects of the present invention, a tetracyclodone having a reaction temperature of 130 to 350 ° C, a pressure of normal pressure to 20 MPa, and a residence time of 0.1 to 4 hours. It relates to a decene composition.

Hereinafter, the present invention will be described more specifically. Tetracyclododecene is represented by the formula (I),
The present invention is a composition for addition polymerization with a Ziegler-type catalyst, comprising tetracyclododecene containing a specific amount of a trimer of cyclopentadiene. Preferred is a tetracyclododecene composition containing a specific amount of the cyclopentadiene trimer having the structure represented by the formula [II]. The tetracyclododecene composition of the present invention comprises (a)
Norbornene, (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene are subjected to a Diels-Alder reaction type thermal addition reaction, and the resulting reaction mixture is distilled to obtain the tetracyclodone represented by the above formula [I]. It can be manufactured by obtaining decene.

The reaction mixture obtained here contains, in addition to the desired tetracyclododecene, unreacted ethylene, norbornene which is an intermediate product, and the compound represented by the formula [II] as a part of isomers. Cyclopentadiene 3
It contains a monomer and the like. Of these, the trimer of cyclopentadiene has a boiling point close to that of tetracyclododecene for any of its isomers, and thus is easily mixed into tetracyclododecene during distillation and purification. Specific examples of the trimer of cyclopentadiene include a diolefin compound having a norbornene-type olefin structure represented by the above formula [III] and a cyclopentene-type olefin structure, and a norbornene represented by the above formula [II]. And diolefin compounds having two sets of olefin structures. The presence of these diolefin compounds is not preferred because, in addition polymerization with a Ziegler-type catalyst, gelation tends to occur during homopolymerization of the cyclic olefin at the olefin site or copolymerization with a lower α-olefin.

Therefore, the tetracyclododecene composition of the present invention can be used to prepare a cyclopentadiene trimer in an amount of from 100 to 5,000.
It is contained in an amount of 0 ppm, preferably 100 to 4,000 ppm, more preferably 100 to 3,000 ppm. Among the cyclopentadiene trimers, the above formula [II]
The content of the structure represented by is 100 to 3,000p
pm, preferably in the range of 100 to 2,500 ppm, more preferably 100 to 2,000 ppm. When the amount of the cyclopentadiene trimer exceeds the upper limit of the above range, crosslinking during the homopolymerization of the cyclic olefin at the olefin site or the copolymerization with the lower α-olefin in the addition polymerization using a Ziegler-type catalyst. This is not preferable because a reaction may be caused, the polydispersed structure may be remarkable, and gelation may occur. Also, cyclopentadiene 3
It is not economically preferable to make the content of the monomer less than the above lower limit, since this results in a burden on distillation purification and an increase in the number of distillation columns and the amount of reflux.

The ethylene which can be used in the production of the composition of the present invention includes naphtha, natural gas or polymerization grade ethylene obtained by steam cracking a gas fraction obtained from petroleum refining, and ethane of ethane. Ethylene obtained by dehydrogenation or dehydration of ethanol can be used, but it is preferable to use polymerization grade.

Cyclopentadiene is commercially available in the form of a dimer, ie, dicyclopentadiene, which can be easily obtained by thermal decomposition. When performing a Diels-Alder reaction for cyclododecene synthesis, dicyclopentadiene can also be used as a raw material. Dicyclopentadiene (DCPD)
Is preferably 90% or more. If the impurities in DCPD are large, it is not preferable because heavy by-products such as cyclopentadiene trimer also increase in the obtained tetracyclododecene composition.

Norbornene is prepared by using ethylene and cyclopentadiene and / or dicyclopentadiene as raw materials at a reaction temperature of 100 to 400 ° C., and a reaction pressure of normal pressure to 30.
It can be synthesized under the conditions of MPa. Therefore, it is also possible to use norbornene separately synthesized by such a method. However, norbornene is a compound that is difficult to obtain industrially. Therefore, when producing the tetracyclododecene composition of the present invention, (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene coexist. Since cyclopentadiene and / or dicyclopentadiene are supplied, norbornene is simultaneously synthesized in the presence of ethylene. Therefore, if norbornene co-produced is recovered and reused, tetracyclododecene can be synthesized without apparently supplying new norbornene.

In the present invention, (a) norbornene,
When the reaction is carried out by supplying (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene to the reactor, the molar ratio between the above components is such that the norbornene is 1.0, and the cyclopentadiene and / or Cyclopentadiene is in the range of 0.1 to 0.6, preferably 0.1 to 0.5, more preferably 0.1 to 0.4 in terms of cyclopentadiene, and ethylene is 0.05 to 0.5.
3, preferably 0.05 to 0.25, more preferably 0.2.
It is in the range of 0.5 to 0.2. When the amount of norbornene is too large, the yield of heavy components in the reaction solution is relatively small,
If the amount of norbornene is too small, it is not advisable because the amount of circulating norbornene increases.
A large amount of heavy components of the trimer of cyclopentadiene is produced as a by-product, and a large burden is imposed on distillation purification of tetracyclododecene, which is not preferable.

Further, the ratio of the weight of cyclopentadiene and / or dicyclopentadiene in terms of cyclopentadiene to the total weight of (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene is set at 0.1. It is important to carry out the reaction while controlling the amount in the range of from 0.6 to 0.3, preferably from 0.1 to 0.25, more preferably from 0.1 to 0.2.
When the weight ratio of cyclopentadiene and / or dicyclopentadiene is higher than the upper limit, a considerably large amount of trimer of cyclopentadiene or the like is by-produced with respect to the generated tetracyclododecene, and the effective utilization rate of the raw material is reduced. descend.
On the other hand, when the weight ratio of cyclopentadiene and / or dicyclopentadiene is lower than the lower limit, the production amount of tetracyclododecene decreases. By limiting the supply amount of (di) cyclopentadiene to the total amount of the raw materials within this range, the raw materials are efficiently consumed, and as a result, by-products of cyclopentadiene trimer can be suppressed, and high purity A tetracyclododecene composition can be obtained.

[0021] The reaction temperature can be selected from the range of 130 to 350 ° C. In particular, when dicyclopentadiene is used as a raw material, the reaction temperature is 150 ° C. in order to decompose dicyclopentadiene and convert it to cyclopentadiene.
The temperature is preferably in the range of -350 ° C, more preferably in the range of 150-300 ° C. The residence time for continuously reacting the raw material mixture is 0.1 to 4 hours, preferably 0.1 to 3.5 hours, more preferably 0.1 to 3 hours. If the residence time is less than 0.1 hour, the amount of unreacted substances increases, which is not appropriate. The reaction pressure is from normal pressure to 20 MPa, preferably from 1.0 to 20 MPa.
Range. The reaction can be arbitrarily performed within the range of the reaction conditions. Preferably, the ethylene is liquid in the reaction system. Conditions for the presence of liquid ethylene in the reaction system include (a) norbornene, (b) dicyclopentadiene and / or cyclopentadiene and (c)
For example, the molar ratio of norbornene / dicyclopentadiene / ethylene is 8 /
When the temperature is 1/1 and the temperature is 180 ° C., a pressure of about 2.5 MPa or more is required. If the ethylene content is higher than this, a higher pressure is required at a higher temperature, and 260 ° C.
In this case, about 3.9 MPa or more is required.

The operation of the reaction and the purification by distillation in the present invention can be achieved by either a batch system or a continuous flow system, but it is preferable to select a continuous flow system industrially.

When synthesizing tetracyclododecene from (a) norbornene, (b) dicyclopentadiene and / or cyclopentadiene and (c) ethylene as raw materials, cyclopentadiene and / or dicyclopentadiene are supplied with a booster or a pump. And introduced into the reactor. Norbornene, which is another raw material, may be previously mixed with cyclopentadiene and / or dicyclopentadiene, or may be supplied separately.

As the reactor, any type such as a complete mixing type and a piston flow type can be used. As the piston flow type reactor, “Static Mixer” manufactured by Noritake Co., Ltd., “Sluzer Mixer” manufactured by Sumitomo Heavy Industries, Ltd., “Skeya Mixer” manufactured by Sakura Seisakusho Co., Ltd., and the like are commercially available. In either case of the complete mixing type or the piston flow type, it is desirable that the raw materials are uniformly mixed, and both types can be used alone or in combination. The reaction can be carried out in one or more stages. In the case of multiple stages, the reactors of the complete mixing type and the piston flow type can be used alone or in combination, or both can be used in series or in parallel.

The reaction mixture extracted from the reactor is led to a purification step, and a tetracyclododecene composition is obtained through purification. Distillation is preferably used for purification. Batch distillation or continuous distillation may be used, but continuous distillation is industrially preferable. Since tetracyclododecene may be thermally decomposed at high temperatures, it is preferable that tetracyclododecene is not decomposed in the distillation column.

In the production of the composition of the present invention, an antioxidant, a polymerization inhibitor and the like can be appropriately added to the reaction system. For example, hydroquinone, 2,6-di-tert
Preferred are phenolic compounds such as -butylphenol, 2,6-di-tert-butyl-p-cresol and 4-methoxyphenol, and hydroxylamine compounds such as N, N-dimethylhydroxylamine and N, N-diethylhydroxylamine. Is added to The addition amount is usually 10 to 10,000 based on the total amount of the reaction raw materials supplied into the reactor.
00 ppm, preferably in the range of 50-5,000 ppm. It can be similarly added to the tetracyclododecene composition as a product.

The tetracyclododecene composition of the present invention produced as described above is used for addition polymerization using a Ziegler type catalyst. Examples of the addition polymerization using a Ziegler-type catalyst include homopolymerization of tetracyclododecene at an olefin site (olefinic carbon-carbon double bond site) or copolymerization with another olefin, for example, a lower α-olefin. Ziegler-type catalysts are most broadly defined as transition metal compounds having a metal-carbon bond into which olefin units can be repeatedly inserted. Usually, the catalyst consists of a combination of two components, one of which is a transition metal salt, often a halide, or a complex thereof, and one of which is typically a transition metal salt capable of forming an active metal-carbon bond. Metal alkyl compounds (also considered activators). These include so-called metallocene catalysts. The type of polymerization using the Ziegler-type catalyst is addition polymerization. The addition polymerization is a simple addition reaction of an unsaturated compound such as an olefin as described above, and usually does not involve cleavage of an olefinic carbon-carbon double bond or ring-opening reaction. Therefore, the obtained polymer also has almost no carbon-carbon unsaturated bond, and even if it has one, there is only one carbon-carbon double bond at the molecular terminal.

The Ziegler catalyst in a narrow sense includes titanium,
Compounds such as vanadium have been used. For example, as described in JP-A-9-176396, JP-A-62-252406, JP-A-62-252407, etc. An α-olefin such as ethylene and tetracyclododecene can be copolymerized by a method using a catalyst formed from a soluble vanadium compound and an organoaluminum compound.

The Ziegler type catalyst in a broad sense includes a so-called metallocene type catalyst, which uses a Group IV bent metallocene such as Zr, Hf, Ti or the like. It is an aluminum compound. A more specific example of the use of a metallocene catalyst is disclosed in
5612, JP-A-2-173112, JP-A-4-06807, JP-A-64-000106
And Japanese Patent Application Laid-Open No. 61-221206. For example, (a) of the periodic table of Zr, Hf, Ti, etc.
There is a method using a catalyst comprising a compound component comprising a transition metal of the IVB, VB or VIB group and (b) an organoaluminum oxy compound component. The transition metal compound component (a) is
At least two cycloalkadienyl groups or a substituted product thereof, or a compound in which the cycloalkadienyl group or the substituted product is bonded via a hydrocarbon group, a silylene group, or a substituted silylene group, is a polydentate ligand. Complex compounds as ligands. (b) The organic aluminum oxy compound component is a compound represented by the following formula [IV] or the following formula [V]. R in the formula is an independent hydrocarbon group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, and the like, m is 2 or more,
It preferably represents an integer of 2 to 100.

[0030]

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When polymerizing tetracyclododecene in the present invention, it is possible to copolymerize with another kind of olefinic compound, for example, ethylene, propylene or the like. For example, as disclosed in Japanese Patent Publication No. Hei 7-103223, the balance of various physical properties can be adjusted by changing the copolymerization ratio.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples.

<Example 1> A norbornene / dicyclopentadiene / ethylene molar ratio of 8/1/1 was supplied to a reactor. The purity of the first raw material norbornene is 99.
7%. The purity of continuously supplied dicyclopentadiene and ethylene was 94.7% and 99.9%, respectively.
%Met. The ratio of dicyclopentadiene to the total reaction raw material solution introduced into the reactor was 12.9% by weight. The pressure in the reactor was maintained at 5 MPa, the residence time was 0.25 hours, and the reaction temperature was 230 ° C.

By distilling the reaction mixture withdrawn from the reactor, a tetracyclododecene fraction having a purity of 99.6% was obtained. 3 in the obtained tetracyclododecene fraction
The content of the monomer was 1,000 ppm, and the content of the tetracyclododecene trimer having the structure represented by the formula [II] was 150 ppm. In addition, stable continuous operation was possible without any change over time in the reaction, distillation, and the like. The conversion of dicyclopentadiene was 9
The conversion of ethylene was 2%, and the conversion of ethylene was 72%. Purity 99.
The yield of 6% tetracyclododecene was 76% (based on dicyclopentadiene).

In a 2 liter eggplant-shaped flask equipped with stirring blades, 1,000 ml of toluene dried under a nitrogen atmosphere was added.
ml was introduced. The flask further contained 1 mmol of dichloroethoxyoxovanadium and the content of the previously synthesized cyclopentadiene trimer was 1,000 ppm,
Among them, cyclopentadiene 3 represented by the above formula [II]
10 g of a tetracyclododecene composition having a monomer content of 150 ppm was added. While stirring this solution, a mixed gas of ethylene and nitrogen (molar ratio: ethylene / nitrogen =
1: 5) was bubbled through the solution at a flow rate of 200 l / h. Further, 10 mmol of ethyl aluminum sesquichloride was added dropwise thereto to start polymerization, and polymerization was carried out at 5 ° C. for 20 minutes. The polymerization was stopped by adding 30 ml of methanol, and the reaction mixture was poured into 2 liters of methanol to precipitate a copolymer. The copolymer is dried under vacuum and
A 1 mm-thick press sheet was prepared at 40 ° C. A homogeneous transparent sheet was obtained, and no gel was observed.

Comparative Example 1 In Example 1, the molar ratio of norbornene / dicyclopentadiene / ethylene was changed to 8 /
The same operation was performed instead of 4/1. At this time, the ratio of dicyclopentadiene to the total reaction raw material solution introduced into the reactor was 36.7% by weight. The purity of the obtained tetracyclododecene composition is 98.5%, and the content of the cyclopentadiene trimer is 8,500 ppm, of which the cyclopentadiene trimer represented by the formula [II] is contained. Was 3,500 ppm. Except for using the above tetracyclododecene composition, copolymerization with ethylene was carried out in the same manner as in Example 1 to produce a press sheet. The presence of gel was confirmed in the sheet. The gel was cut out and heated to 300 ° C. on a hot plate, but did not melt.

[0036]

According to the tetracyclododecene composition of the present invention, the content of the trimer of cyclopentadiene is within a specific range. Therefore, in the addition polymerization reaction, the Ziegler catalyst containing a metallocene catalyst is used (co). Good reactivity during polymerization, and low gelation in the polymer.
The tetracyclododecene composition of the present invention can be easily industrially produced by using a specific range of synthesis conditions, and can be easily purified using ordinary distillation.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yasuo Matsumura 463-1-205 Kamiiida, Izumi-ku, Yokohama-shi, Kanagawa F-term (reference) 4H006 AA01 AA02 AB46 AC28 BB11 BC10 BC31 BC35

Claims (9)

[Claims] 1. A composition for addition polymerization with a Ziegler-type catalyst, comprising tetracyclododecene represented by the following formula [I], wherein the content of a trimer of cyclopentadiene is 100 to 5,000 ppm. Embedded image 2. The tetracyclododecene composition according to claim 1, wherein the content of the trimer of cyclopentadiene represented by the following formula [II] is from 100 to 3,000 ppm. Embedded image 3. The tetracyclododecene composition according to claim 1, wherein (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene are mixed and produced by heating and reaction. object. 4. The molar ratio of (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene, wherein the molar ratio of norbornene to 1.0 is cyclopentadiene and / or cyclopentadiene of dicyclopentadiene. The conversion amount is 0.1 to 0.6,
The tetracyclododecene composition according to claim 3, wherein the ethylene is 0.05 to 0.3. 5. The ratio of the weight of cyclopentadiene and / or dicyclopentadiene in terms of cyclopentadiene to the total weight of (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene and (c) ethylene is 0.1. The tetracyclododecene composition according to claim 4, wherein the ratio is from 0.6 to 0.30. 6. The tetracyclododecene composition according to claim 3, wherein a hydrocarbon solvent inert to the reaction (d) is used in the reaction. 7. The (a) norbornene, (b) cyclopentadiene and / or dicyclopentadiene,
The ratio of the weight of cyclopentadiene and / or dicyclopentadiene in terms of cyclopentadiene to the total weight of (c) ethylene and the hydrocarbon solvent inert to the reaction (d) is 0.05 to 0.25. The tetracyclododecene composition according to the above. 8. The tetracyclododecene composition according to claim 6, wherein the hydrocarbon solvent inert to the reaction (d) is a branched aliphatic hydrocarbon or an alicyclic hydrocarbon. 9. The temperature in the reaction is 130 to 350.
° C, pressure is normal pressure ~ 20MPa and residence time is 0.1 ~
The tetracyclododecene composition according to any one of claims 3 to 8, which is for 4 hours.