JP2000026330A - 1,4-METHANO-1,4,4a,9a-TETRAHYDROFLUORENE COMPOSITION - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition affording the corresponding polymer with no substantial decline in e.g. optical properties due to gelling during its polymerization process by controlling the content of a specific cyclopentadiene trimer. SOLUTION: This composition of 1,4-methano-1,4,4a,9a-tetrahydrofluorene of formula III contains 100-5,000 ppm of cyclopentadiene trimers of formula I and/or formula II, wherein the content of the trimer of formula II in this composition is pref. 100-3,000 ppm. The composition is obtained by reaction between cyclopentadiene and/or dicyclopentadiene and indene under heating in the molar ratio the indene/cyclopentadiene and/or dicyclopentadiene pref. at 2-1,000 (based on the cyclopentadiene). Polymerization of the composition affords the corresponding polymer with excellent optical performance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to 1,4-methano-
The 1,4,4a, 9a-tetrahydrofluorene composition, specifically, 1,4-methano-1,4,4a, 9 containing a specific structure among trimers of cyclopentadiene
The present invention relates to an a-tetrahydrofluorene composition.

[0002]

2. Description of the Related Art In recent years, cyclic olefins represented by 1,4-methano-1,4,4a, 9a-tetrahydrofluorene have been used as a raw material for resins having excellent optical properties, heat resistance and oil absorption properties. It is known to be useful.
This cyclic olefin is subjected to polymerization using an organometallic complex catalyst, and the polymerization method can be roughly classified into two. One is metathesis ring-opening polymerization, and the other is homopolymerization of these cyclic olefins at the olefin site or copolymerization with lower α-olefins using a Ziegler catalyst, a metallocene catalyst or the like. 1,4-Methano-1,4,4a, 9a-tetrahydrofluorene was prepared from indene and an addition reaction product of cyclopentadiene, and the resulting 1,4-methano-1,4,
A method using 4a, 9a-tetrahydrofluorene as a polymer polymerization raw material has been proposed. For example, as a polymerization example, JP-A-5-97719 discloses that 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is copolymerized with an olefin such as ethylene in the presence of a vanadium catalyst or a metallocene catalyst. To produce optically superior resins. Also, Japanese Patent Application Laid-Open No. 7-536
No. 80 discloses 1,4-methano-1,1a, 4,4a, 9.
It is described that a resin having excellent optical properties can be obtained by subjecting a-tetrahydrofluorene to ring-opening polymerization followed by hydrogenation or cyclization.

In general, in the Diels-Alder reaction between indene and cyclopentadiene, 1,4-methano-1,4,
In addition to 4a, 9a-tetrahydrofluorene, a trimer of cyclopentadiene is by-produced. 1,4-methano-1,
4,4a, 9a-tetrahydrofluorene has a small difference in boiling point from the trimer of cyclopentadiene, so that industrial separation such as distillation is difficult, and as a result, the trimer is often contained as an impurity. And these impurities are
It is a cause of gelation in the above polymerization reaction,
As a result, it was found that the optical properties of the obtained polymer were reduced.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide 1,4-methano-1,4,4a, 9a which, when used for polymerization or the like, does not substantially reduce optical properties and the like due to gelation. −
An object of the present invention is to provide a tetrahydrofluorene composition.

[0005]

According to a first aspect of the present invention, the content of a trimer of cyclopentadiene represented by the following formula [II] or [III] is 100 to 5,000 ppm:
1,4-methano-1,4,4a, 9 represented by the following formula [I]
It relates to a composition of a-tetrahydrofluorene.

[0006]

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A second aspect of the present invention is the first aspect of the present invention,
The content of the cyclopentadiene trimer represented by the formula [III] is from 100 to 3,000 ppm,
The present invention relates to a 4-methano-1,4,4a, 9a-tetrahydrofluorene composition. A third aspect of the present invention is the first or second aspect of the present invention, wherein 1,4-methano-1,4,4a obtained by mixing cyclopentadiene and / or dicyclopentadiene and indene and heating and reacting the mixture. , 9a
A tetrahydrofluorene composition. A fourth aspect of the present invention is the third aspect of the present invention, wherein the molar ratio of cyclopentadiene and / or dicyclopentadiene to indene is set such that the amount of cyclopentadiene and / or dicyclopentadiene is 1 in terms of cyclopentadiene, and 1,4-methano-1,4,4a which is 1,000
9a-tetrahydrofluorene composition. According to a fifth aspect of the present invention, in the third aspect of the present invention, when cyclopentadiene and / or dicyclopentadiene and indene are mixed and heated / reacted, the mixture is produced by using a hydrocarbon solvent inert to the reaction. 1,4-methano-1,4,4a,
9a-tetrahydrofluorene composition. According to a sixth aspect of the present invention, in the fifth aspect of the present invention, the ratio of the weight in terms of dicyclopentadiene to the total weight of cyclopentadiene and / or dicyclopentadiene, and indene, and the hydrocarbon solvent inert to the reaction is: 0.0
1,4-methano-1,4,4a, 9a- which is 2 to 0.20
The present invention relates to a tetrahydrofluorene composition. Hereinafter, the present invention will be described specifically.

In the present invention, the 1,4-formula represented by the formula [I]
The methano-1,4,4a, 9a-tetrahydrofluorene composition can be synthesized by performing a Diels-Alder reaction type thermal addition reaction of cyclopentadiene and / or dicyclopentadiene and indene. The resulting reaction mixture contains, in addition to the desired 1,4-methano-1,4,4a, 9a-tetrahydrofluorene,
It includes unreacted cyclopentadiene, dicyclopentadiene, indene, and a trimer of cyclopentadiene comprising a compound represented by the formula [II] or [III]. Since the boiling point of these trimers of cyclopentadiene is close to 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4
It is easy to mix in 4,4a, 9a-tetrahydrofluorene. The structure of the cyclopentadiene trimer includes a diolefin compound having a norbornene-type olefin structure represented by the formula [II] and a cyclopentene-type olefin structure, and a norbornene-type olefin structure represented by the formula [III]. It is a diolefin compound having two sets. These diolefins, not only in metathesis ring-opening polymerization, but also in homopolymerization or copolymerization with a lower α-olefin at the olefin site of a cyclic olefin using a Ziegler catalyst or the like, lower the optical properties of the obtained polymer. It has been found.

Therefore, the total content of the diolefin in the composition of the present invention of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene represented by the above formula [I] is 100 to 5, 000 ppm, preferably 100-4,000
It is in the range of 0 ppm, more preferably 100 to 3,000 ppm. The content of the cyclopentadiene trimer represented by the formula [III] is 100 to 3,000 ppm,
It is preferably in the range of 100 to 2,500 ppm, more preferably 100 to 2,000 ppm. When the cyclopentadiene trimer is contained in excess of the upper limit of these ranges, not only metathesis ring-opening polymerization but also homopolymerization at the olefin site of the cyclic olefin or copolymerization with a lower α-olefin. Also causes a crosslinking reaction,
The resulting polymer has a pronounced polydisperse structure and is highly likely to gel. Further, to be less than the lower limit of the above range, the burden on distillation purification, the number of distillation column stages,
This results in an increase in the amount of reflux and the like, which is not economically preferable.

As described above, the 1,4-methano-1,4,4a, 9a-tetrahydrofluorene composition represented by the formula [I] in the present invention comprises cyclopentadiene and / or dicyclopentadiene; It can be synthesized by performing a Diels-Alder reaction type thermal addition reaction of indene. Here, when using cyclopentadiene, one obtained by previously subjecting dicyclopentadiene to thermal decomposition distillation is used. Dicyclopentadiene can be supplied as it is, and thermally decomposed into cyclopentadiene in the reaction system before use. As such a dicyclopentadiene, a commercially available dicyclopentadiene can be used, and its purity is desirably 90% or more. The impurities of dicyclopentadiene mainly consist of tetrahydromethylindene and adducts of C _{5 to} C ₆ chain or cyclic diolefins with cyclopentadiene. When the amount of these impurities is large, cyclopentadiene trimer and It is preferable to use a high-purity raw material because the amount of heavy by-products increases.

The indene which can be used in the present invention preferably has a purity of 30% or more, more preferably 60% or more, further preferably 90% or more. Benzonitrile, benzoindene, dialkylbenzene and the like may be contained as impurities.

Cyclopentadiene and dicyclopentadiene are introduced into the reaction system using a pressure booster and a pump, but they may be mixed in advance with indene as another raw material, or these raw materials may be supplied separately. You may. However, in the case of separate supply, two raw material tanks and two pumps are required, so that it is preferable to mix them in advance.

The supply ratio of indene to cyclopentadiene is such that the molar ratio of indene / cyclopentadiene is 2 to 1,
000, preferably 2 to 100, more preferably 2 to 20. Note that dicyclopentadiene is converted to the number of moles as cyclopentadiene. When the amount of indene is larger than the upper limit of this range, unreacted indene increases, which is not preferable. Conversely, if the amount of cyclopentadiene or dicyclopentadiene is larger than the lower limit of this range, a large amount of trimer or more of cyclopentadiene represented by the formula [II] or [III] is generated, and Effective utilization rate of raw materials decreases.

In producing the composition of the present invention, a solvent may be used. The purpose is to reduce the concentration of each component and to reduce heavy components as by-products. As the solvent, specifically, a hydrocarbon having 6 to 13 carbon atoms is suitable, and among these, normal hexane, isohexane, normal heptane, isoheptane, normal octane, isooctane, normal nonene, isononene, normal decane, normal Undecane, normal dodecane, normal tridecane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, diethylbenzene, triethylbenzene, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane and the like are preferably used. You may mix and use these 2 or more types.

When a solvent is used, dicyclopentadiene, indene, 1,4-methano-1,4,4a, 9a
-Tetrahydrofluorene having a boiling point difference of 5 ° C or more from each boiling point is preferable. Also, when using such a solvent, before feeding to the reaction system, indene,
Alternatively, it is preferable to mix indene with cyclopentadiene and dicyclopentadiene.

Using these as raw materials, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is synthesized using a solvent as required. The manufacturing method is not particularly limited, and any method can be adopted. The operation of the reaction 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. As for the reactor, either a complete mixing type or a piston flow type can be used. Commercially available products include "Noritake Co., Ltd. Static Mixer" and Sumitomo Heavy Industries, Ltd.
"Sleather mixer" manufactured by Sakura Seisakusho Co., Ltd. and the like. The reaction can be carried out in one or two or more stages, and a complete mixing type or piston flow type reactor can be used in combination in series or in parallel.

[0017] The reaction temperature is 100 to 350 ° C. In particular, when dicyclopentadiene is used as a raw material, the reaction temperature is preferably 100 ° C. or higher, more preferably 150 ° C. or higher. In any case, when the temperature exceeds 350 ° C., a large amount of heavy components represented by the formulas [II] and [III] is generated. When cyclopentadiene is used as a raw material, the reaction temperature is preferably from 100 to 350 ° C. The reaction conditions in the case of a batch reactor are a reaction time of 0.01 to 100 hours, preferably 0.05 to 5 hours.
r, more preferably 0.1 to 3 hr. The reaction pressure is from normal pressure to 10,000 kPa. The reaction conditions for the continuous reactor is a space velocity 0.01～100H ^-1, preferably 0.05～50H ^-1, more preferably 0.
¹ to 10 h ^-1 . When the space velocity exceeds 100 h ⁻¹ , unreacted substances increase, which is inappropriate. The reaction pressure is from normal pressure to 10,000 kPa.

The reaction mixture withdrawn from the reactor is introduced into a purification step. As a purification method, distillation separation is preferable,
Batch type or continuous type may be used. Industrially, continuous distillation is preferred. In the case of a batch type, the remaining cyclopentadiene, solvent (if used), dicyclopentadiene,
In addition, there are a method of separating indene into each component and a method of simultaneously separating 3 to 4 components. In order to increase the separation efficiency, the distillation column can be filled with various packing materials or refluxed. The theoretical plate number is 1 to 100 plates in each distillation column, preferably 2 to 50 plates, and more preferably 3 to 30 plates. The reflux ratio is determined depending on the state of separation of the distillation column, and is suitably 1 to 50.

In batch distillation, residual cyclopentadiene is first separated from the reaction mixture withdrawn from the reactor. The distillation conditions were 0.01 to 1.0 pressure.
It can be arbitrarily selected from a range of 00 kPa and a temperature of 0 to 200 ° C. The solvent (if used), residual dicyclopentadiene, and indene are then separated. Distillation conditions include a temperature of 30 to 150 ° C. and a pressure of 10 kP.
a The following are appropriate. Further, the distillation conditions of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene as the target component are a temperature of 50 to 200 ° C. and a pressure of 1 kPa or less. A heavy substance that is a reaction by-product is obtained from the bottom. Next, as a method of simultaneously separating two or three components, the remaining three components of cyclopentadiene, dicyclopentadiene and indene are simultaneously separated. Distillation conditions, temperature 30 ~
A temperature of 150 ° C. and a pressure of 10 kPa or less are suitable.
The distillation conditions of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene are as follows: temperature: 50 to 200 ° C .;
Pa or less.

In the case of continuous distillation, the process preferably includes at least two distillation columns. When two distillation columns are used, cyclopentadiene, a solvent (if used), residual dicyclopentadiene, and indene are collected from the top of the first column, and the mixture at the bottom of the column is sent to the second column. From the top of the two towers, 1,4-methano-1,
This gives 4,4a, 9a-tetrahydrofluorene. Heavy matter is obtained from the bottom of the tower. In this case, the distillation conditions in the first column are as follows: when dicyclopentadiene and indene remain, the temperature is 30 to 150 ° C., and the pressure is 10 kPa.
The following is appropriate, and if there is no residual, pressure 1-1
00 kPa and temperature 20-140 ° C. The conditions for the second column are a temperature of 50 to 200 ° C. and a pressure of 1 kPa or less. When cyclopentadine and indene do not exist, cyclopentadiene and a solvent (if used) under the conditions of a pressure of 1 to 100 kPa and a temperature of 20 to 140 ° C.
Is collected, but when there is an impurity contained in dicyclopentadiene, a temperature of 30 to 150 ° C. and a pressure of 10 k are used.
It is preferable to add an operation of removing under the conditions below Pa. Thereby, the purity of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene can be kept high.

When there are three distillation columns, the first column mainly separates cyclopentadiene from the top of the column. Distillation conditions can be arbitrarily selected from a range of a pressure of 0.1 to 1 MPa and a temperature of 0 to 100 ° C. The mixture obtained from the bottom is sent to a second column, at the top of which a solvent (if used) and optionally residual dicyclopentadie and indene are simultaneously recovered. When dicyclopentadiene and indene remain, the temperature is suitably 30 to 150 ° C. and the pressure is 10 kPa or less. When not remaining, the pressure is 1 to 100 kPa and the temperature is 20 to 140 ° C.
It is. The mixture obtained from the bottom of the second column is sent to the third column, and from the top of the third column, at a temperature of 50 to 200 ° C. and a pressure of 1 kPa or less, 1,4-methano-1,4,4a. ,
9a-Tetrahydrofluorene is separated and purified. When no dicyclopentadiene remains, the distillation conditions are 1-1.
The solvent (when used) is recovered at 00 kPa and a temperature of 20 to 140 ° C. If there is an impurity contained in dicyclopentadiene, an operation of removing the solvent at a temperature of 30 to 150 ° C and a pressure of 10 kPa or less is performed. It is preferable to add them. Thus, 1,4-methano-1,4,4a,
The purity of 9a-tetrahydrofluorene can be kept high.

When four distillation columns are used, in the first column,
Cyclopentadiene is separated from the top. Distillation conditions can be arbitrarily selected from a range of a pressure of 0.1 to 1 MPa and a temperature of 0 to 100 ° C. The mixture obtained from the bottom is led to the second column, and from the top, the solvent (if used)
Collect. The distillation conditions are a pressure of 1 to 100 kPa and a temperature of 20 to 140 ° C. The mixture obtained from the bottom of this column is led to the third column, and a mixture containing dicyclopentadiene and indene as main components is separated from the top of the column. Suitable distillation conditions are a temperature of 30 to 150 ° C. and a pressure of 10 kPa or less. The mixture obtained from the bottom of the third column is the fourth
Guided to the tower, at a temperature of 50 to 200 ° C and a pressure of 1 kPa
In the following, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is separated, and a heavy substance as a reaction by-product is obtained from the bottom of the column.

Another method using four distillation columns is as follows.
Cyclopentadiene is separated from the top of the first column. Distillation conditions can be arbitrarily selected from the range of a pressure of 0.11 MPa and a temperature of 0 to 100 ° C. The mixture obtained from the bottom of this column is led to the second column, and the solvent (if used), dicyclopentadiene and indene are simultaneously recovered from the top of the column. Distillation conditions are pressure 10 kPa or less and temperature 3
0-150 ° C. The mixture obtained from the top is led to the third column, the solvent (if used) is separated from the top,
Dicyclopentadiene and indene are separated from the bottom. Suitable distillation conditions for the third column are a pressure of 1 to 100 kPa and a temperature of 20 to 140 ° C. The mixture obtained from the bottom of the second column is led to the fourth column, where the temperature is 50 to 20.
At 0 ° C. and a pressure of 1 kPa or less, 1,4-methano-1,4,
4a, 9a-Tetrahydrofluorene is separated from the top of the column, and a heavy substance as a reaction by-product is obtained from the bottom of the column.

In both the batch type and the continuous type,
Since 1,4-methano-1,4,4a, 9a-tetrahydrofluorene decomposes at a high temperature, it is important to carry out distillation while keeping the maximum temperature at 200 ° C. or lower. Further, when a solvent is used, the boiling point differs depending on the type of the solvent, so that the distillation conditions also differ. Each distillation column can be filled with various packing materials or refluxed to increase the separation efficiency. The theoretical plate number is 1 to 100 plates in each distillation column, preferably 2 to 50 plates, and more preferably 3 to 30 plates. The reflux ratio is determined based on the state of separation of each distillation column.
0 is appropriate. The unreacted cyclopentadiene, dicyclopentadiene and indene separated in the distillation step, and the separated solvent are preferably reused.

The 1,4-methano-1,4,4a, 9a-tetrahydrofluorene produced by the above method is a mixture of isomers of an endo-form and an exo-form.
The molar ratio of the exo form is in the range of 80/20 to 60/40.

In the reaction used in the present invention, an antioxidant, a polymerization inhibitor and the like can be appropriately added to the reaction raw materials. For example, hydroquinone, 2,6-di-tert-
Phenol 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 are preferred. Is added. 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. 1,4-methano-1,4, of the present invention as a product
Similarly, it can be appropriately added to the 4a, 9a-tetrahydrofluorene composition.

According to the present invention produced as described above,
The 4-methano-1,4,4a, 9a-tetrahydrofluorene composition can be subjected to metathesis polymerization or Ziegler-catalyzed polymerization by a conventionally known method.
Metathesis polymerization is described in, for example, JP-A-9-183832, JP-A-8-151435, and JP-A-5-04.
No. 3663, JP-A-1-172422, JP-A-1-172421, JP-A-1-168725, JP-A-1-168724, JP-A-60-0
The method can be performed by a method disclosed in, for example, Japanese Patent No. 26024. Specifically, a method using a catalyst comprising (a) a transition metal compound catalyst component and (b) a metal compound promoter component.

(A) Transition metal compound The catalyst component is a compound of a transition metal belonging to Group IVB, VB, VIB, VIIB or VIII of the periodic table, and is a halide, oxyhalide, alkoxyhalide, Examples of the complex include alkoxides, carboxylate salts, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, derivatives thereof, and complexes thereof with complexing agents such as phosphine compounds. (b) As the metal compound promoter component, Periodic Tables IA and II
A, IIB, IIIA or IVA group metal compound having at least one metal element-carbon bond or metal element-hydrogen bond, for example, Al, Sn, Li, N
Organic compounds such as a, Mg, Zn, Cd, and B are exemplified.
Further, in order to enhance the metathesis polymerization activity, (a), (b)
In addition to both components, aliphatic tertiary amines, aromatic tertiary amines, molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acid chlorides, esters, ketones,
Nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other Lewis acids can be added.

On the other hand, homopolymerization at the olefin site of tetracyclododecene or copolymerization with a lower α-olefin can be carried out using a Ziegler catalyst containing a metallocene catalyst. When a metallocene catalyst is used, for example, Japanese Patent Application Laid-Open Nos.
173112, JP-A-4-063807,
JP-A-64-000106, JP-A-61-221
No. 206, etc. Specifically, there is a method using (c) a catalyst component composed of a transition metal compound component consisting of the IVB, VB or VIB group of the periodic table and (d) an organoaluminum oxy compound component.

The transition metal compound component (c) is a component of the periodic table.
A compound of a transition metal belonging to the group IVB, VB or VIB, wherein at least two cycloalkadienyl groups or a substituted product thereof, or a cycloalkadienyl group or a substituted product thereof is a hydrocarbon group, a silylene group or a substituted product; A compound having a polydentate compound bound via a silylene group as a ligand is exemplified. (d) The organic aluminum oxy compound component has the following formula (I
V] and a compound represented by the following formula [V]. R in the formula is a hydrocarbon group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, and the like, and m represents an integer of 2 or more.

[0031]

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As the Ziegler catalyst, 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. By a method using a catalyst formed from a soluble vanadium compound and an organoaluminum compound, a copolymer of an α-olefin such as ethylene and a cyclic olefin can be synthesized.

When the composition of the present invention is polymerized, the occurrence of gelation is small in any of the above polymerizations, and the possibility that the optical performance of the obtained polymer is reduced is low. When performing ring-opening polymerization, the obtained polymer may contain an unsaturated bond. Therefore, when heat deterioration resistance or light resistance is low, part or all of the unsaturated bond may be improved to improve this. Can be hydrogenated. In the hydrogenation reaction, a precious metal such as nickel, palladium, or platinum dispersed and supported on an inorganic carrier is used. A homogeneous hydrogenation catalyst can also be used. The hydrogenation conditions are a pressure of 0.1 to 20 MPa and a temperature of 0 to 200 ° C.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples. The percentages described below are percentages by weight unless otherwise specified.

<Example 1> Indene (purity 94.2%),
Dicyclopentadiene (purity 94.7%) and methylcyclohexane are mixed at a weight ratio of 44/6/50, and 50 ml is mixed.
Continuously introduced into the autoclave and increased the pressure to 5,000k
A method of continuously extracting the reaction product while maintaining the pressure at Pa was used. The reaction temperature was 230 ° C. and the space velocity was 4 h ⁻¹
For 5 hours. The reaction product is 0.07 kPa
Purification was performed under the conditions of a reflux ratio of 10 to obtain 72 g of a fraction at 88 to 92 ° C. As a result of analysis by gas chromatography, the purity of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene was 99.6%. In this fraction, 2,600 ppm of the compound of the formula [II] and the compound of the formula [I
1,200 ppm of the compound of the formula [II].

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 was further charged with dichloroethoxyoxovanadium (1 mmol), 2,600 ppm of the compound of the formula [II] and 1,200 ppm of the compound of the formula [III]. 4a, 9
a-Tetrahydrofluorene (10 g) was added. While stirring the 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 liter / h. Ethyl aluminum sesquichloride (10 mmol) was further added dropwise to initiate polymerization, and polymerization was performed 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 was vacuum dried to produce a 1 mm thick press sheet at 240 ° C. A homogeneous transparent sheet was obtained, and no gel was observed.

Comparative Example 1 Indene, dicyclopentadiene and normal hexane were mixed at a weight ratio of 32/18/50.
An experiment was performed in the same manner as in Example 1 except that the raw materials mixed in Example 1 were used. Further, the reaction product was rectified under the conditions of 0.07 kPa and a reflux ratio of 10, and a fraction 11 at 88 to 92 ° C.
8 g were obtained. As a result of analysis by gas chromatography, the purity of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene was 96.2%. In this fraction, 27,100 ppm of the compound of the formula [II] and the compound of the formula [II
10,100 ppm of the compound [I]. A press sheet was prepared in the same manner as in Example 1 except that the 1,4-methano-1,4,4a, 9a-tetrahydrofluorene composition obtained above was used. 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.

Example 2 Formula [I] synthesized in Example 1
1,4-methano-1,4,4a, 9 containing 2,600 ppm of the compound of the formula [I] and 1,200 ppm of the compound of the formula [III]
a-tetrahydrofluorene composition (20 g), norbornene (2.5 g), dicyclopentadiene (2.5 g)
And toluene (200 ml) were sufficiently dried 500
ml autoclave. Triethylaluminum (3 mmol) was added thereto, and titanium tetrachloride (0.7 mmol) and triethylamine (7 mmol) were further added.
Was added and ring opening polymerization was performed at 30 ° C. for 6 hours. The reaction product was poured into a mixture of acetone and isopropyl alcohol to precipitate the polymer, the obtained polymer was dissolved in toluene again, and the reprecipitation operation was repeated twice, followed by drying under reduced pressure to obtain a polymer (21 g). Was. 0.5% palladium carbon (0.4%) was placed in a 200 ml autoclave.
g) and toluene (100 ml) were introduced, and a ring-opened polymer (4 g) was further added. Hydrogenation was performed at 20 ° C. and a hydrogen pressure of 5 MPa for 1 hour. After the reaction,
The catalyst was filtered and reprecipitated using methanol. The obtained copolymer was vacuum-dried to prepare a 1 mm-thick press sheet at 350 ° C. A homogeneous transparent sheet was obtained, and no gel was observed.

<Comparative Example 2> The formula [I
1,4-methano-1,4,4 containing 27,100 ppm of the compound of the formula [I] and 10,100 ppm of the compound of the formula [III]
Polymerization and hydrogenation were carried out in the same manner as in Example 2 except for using the a, 9a-tetrahydrofluorene composition to obtain a polymer. A gel sheet was found in the press sheet produced using this.

[0039]

The 1,4-methano-1,4,4a, 9 of the present invention
When the a-tetrahydrofluorene composition is used as a raw material for polymerization, substantial generation of gel can be prevented, and a polymer having excellent optical performance can be obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yasuo Matsumura 463-1-205 Kamiiida, Izumi-ku, Yokohama-shi, Kanagawa F-term (reference) 4H006 AA01 AA03 AB46 AC28 AD11 BA90 BA94 BB12 BC10 BC11 BC37 BJ30

Claims (6)

[Claims] 1. A cyclopentadiene trimer represented by the following formula [II] or [III] having a content of 100 to 5,
A composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene represented by the following formula [I], which is 000 ppm. Embedded image Embedded image Embedded image 2. The composition according to claim 1, wherein the content of the trimer of cyclopentadiene represented by the formula [III] is 100 to 3,000 ppm among the trimers of cyclopentadiene. 3. The composition according to claim 1, wherein cyclopentadiene and / or dicyclopentadiene and indene are mixed, and the mixture is produced by heating and reacting. 4. The molar ratio of the cyclopentadiene and / or dicyclopentadiene to indene is such that the indene is 2 to 1, with the cyclopentadiene and / or dicyclopentadiene being in terms of cyclopentadiene in terms of 1.
4. The composition of claim 3, wherein the composition is 000. 5. Mixing the cyclopentadiene and / or dicyclopentadiene and indene and heating the mixture.
The composition according to claim 3, wherein the composition is produced by using a hydrocarbon solvent inert to the reaction. 6. A ratio of the weight of cyclopentadiene and / or dicyclopentadiene, indene, and the hydrocarbon solvent inert to the reaction in terms of dicyclopentadiene to the total weight of from 0.02 to 0.20. Item 6. The composition according to Item 5.