JP2000026331A - PRODUCTION OF 1,4-METHANO-1,4,4a,9a-TETRAHYDROFLUORENE COMPOSITION - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition with controlled content of specific cyclopentadiene timer(s) by reaction between cyclopentadiene and/or dicyclopentadiene and a specified amount of indene followed by recovering a specific fraction. SOLUTION: This composition of 1,4-methano-1,4,4a,9a-tetrahydrofluorene of formula III which contains 100-5,000 ppm of cyclopentadiene trimer(s) of formula I and/or formula II is obtained by reaction under heating between (A) cyclopentadiene and/or dicyclopentadiene and (B) indene at 2-50 molar times based on the cyclopentadiene to form a reaction mixture, which, in turn, is rectified to recover a fraction consisting mainly of the components with their boiling points within the range of 250 to 300 deg.C in terms of normal pressures, wherein the content of the trimer of formula II in the composition is pref. 100-3,000 ppm. In the above reaction, a hydrocarbon-based solvent inert to the reaction is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to 1,4-methano-
The present invention relates to a method for producing a 1,4,4a, 9a-tetrahydrofluorene composition. More specifically, the present invention relates to a method for producing a 1,4-methano-1,4,4a, 9a-tetrahydrofluorene composition containing a trimer of cyclopentadiene.

[0002]

2. Description of the Related Art In recent years, cyclic olefins represented by 1,4-methano-1,4,4a, 9a-tetrahydrofluorene are very useful as raw materials for resins having excellent optical properties, heat resistance and oil absorption properties in recent years. It is known that This cyclic olefin is polymerized 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 using a Ziegler catalyst or metallocene catalyst, or copolymerization with a lower α-olefin. 1,4-methano-1,4,4a, 9
a-Tetrahydrofluorene has been conventionally synthesized as an addition reaction product of indene and cyclopentadiene, and the obtained 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is used as a polymer raw material as described above. The method used has been proposed. For example, JP-A-5-97
In the '719 publication, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene and ethylene are copolymerized with an olefin such as ethylene in the presence of a vanadium catalyst or a metallocene catalyst to produce an optically superior resin. . Japanese Patent Application Laid-Open No. 7-53680 discloses 1,4-methano-1,1.
Ring-opening polymerization of a, 4,4a, 9a-tetrahydrofluorene, followed by hydrogenation or cyclization produces an optically superior resin.

In general, in the Diels-Alder reaction between indene and cyclopentadiene, 1,4-methano-1,4,4a,
In addition to 9a-tetrahydrofluorene, trimers of cyclopentadiene and the like are by-produced. 1,4-methano-1,4,4
a, 9a-Tetrahydrofluorene had almost no difference in boiling point from the cyclopentadiene trimer, and the cyclopentadiene trimer became a cross-linking component in the above polymerization reaction, causing gelation and deteriorating optical properties.

[0004]

An object of the present invention is to provide a resin obtained by metathesis ring-opening polymerization, homopolymerization of a cyclic olefin at an olefin site, or copolymerization with a lower α-olefin. An object of the present invention is to provide a method for producing a 1,4-methano-1,4,4a, 9a-tetrahydrofluorene composition which does not substantially decrease.

[0005]

SUMMARY OF THE INVENTION The first aspect of the present invention is to heat-react cyclopentadiene and / or dicyclopentadiene with 2 to 50 times mol of indene based on cyclopentadiene to rectify the obtained reaction mixture. Recovering a fraction mainly composed of components contained in the range of 250 to 300 ° C. in terms of normal pressure, the following formulas (II) and (II)
1,4-methano-1,4,4a, 9a-tetrahydrofluorene represented by the following formula [I] having a total content of trimers of cyclopentadiene represented by the formula [I] of 100 to 5,000 ppm: And a method for producing the composition of the present invention.

[0006]

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A second aspect of the present invention is the first aspect of the present invention,
Among the trimers of cyclopentadiene, the content of the trimer of cyclopentadiene represented by the formula [III] is from 100 to
The present invention relates to a method for producing a 1,4-methano-1,4,4a, 9a-tetrahydrofluorene composition represented by the formula [I] at 3,000 ppm. The third aspect of the present invention is the first aspect of the present invention.
Wherein, when cyclopentadiene and / or dicyclopentadiene and indene are mixed and heated / reacted, a hydrocarbon solvent inert to the reaction is used, so that 1,4 represented by the formula [I] is used. -Methano-1,4,4
The present invention relates to a method for producing a composition of a, 9a-tetrahydrofluorene. A fourth aspect of the present invention is the third aspect of the present invention, wherein 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. 1, which is represented by the formula [I] which is .02 to 0.20,
The present invention relates to a method for producing a composition of 4-methano-1,4,4a, 9a-tetrahydrofluorene. A fifth aspect of the present invention is the third aspect of the present invention, wherein the temperature in the reaction is 100 to 350.
° C, pressure from normal pressure to 10 MPa and residence time 0.01
1,4-methanol represented by the formula [I]
The present invention relates to a method for producing a composition of 1,4,4a, 9a-tetrahydrofluorene. A sixth aspect of the present invention is the third aspect of the present invention, wherein the unreacted cyclopentadiene or dicyclopentadiene, indene, and a hydrocarbon solvent inert to the reaction are recycled and reused by the formula [I]. The present invention relates to a method for producing the composition of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene represented. Hereinafter, the present invention will be described specifically.

In the present invention, the 1,4-formula represented by the formula [I]
The composition of methano-1,4,4a, 9a-tetrahydrofluorene is synthesized by performing a Diels-Alder reaction type thermal addition reaction of cyclopentadiene and / or dicyclopentadiene and indene.
When cyclopentadiene is used, dicyclopentadiene which has been subjected to pyrolysis distillation in advance is used. Dicyclopentadiene readily thermally decomposes to form cyclopentadiene. Therefore, if dicyclopentadiene is thermally decomposed in the reaction system, dicyclopentadiene can also be used as a reaction raw material. As the dicyclopentadiene that can be used, a commercially available dicyclopentadiene is desirably used, and its purity is desirably 90% or more. In addition to dicyclopentadiene impurities mainly Tetrahydromethylphthalic indene, many chain or cyclic diene compound and an adduct of cyclopentadiene C ₅ -C _9,
When these amounts are large, heavy by-products increase.

The indene that can be used in the present invention preferably has a purity of 30% or more, more preferably 60% or more, and still more preferably 9% or more.
0% or more. Benzonitrile, benzoindene, dialkylbenzene and the like may be contained as impurities.

[0010] Cyclopentadiene and dicyclopentadiene are supplied to the reaction system by means of a pressurizer and a pump, but they may be mixed in advance with the other raw material, indene, or supplied separately. However, if they are separately supplied, two raw material tanks and two pumps are required, so it is preferable to mix them in advance.

The mixing ratio is indene / cyclopentadiene (dicyclopentadiene is converted to cyclopentadiene) = 2 to 1,000, preferably 2 in molar ratio.
-100, more preferably 2-20. When the amount of indene is large, the yield of the heavy component in the reaction is relatively small, but it is not advisable because unreacted inden increases. If the amount of cyclopentadiene or dicyclopentadiene is large, a large amount of heavy components represented by compound 2 or 3 is generated, and the effective utilization rate of the raw material is reduced.

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

When a solvent is used, those having a boiling point difference of 5 ° C. or more from each of dicyclopentadiene, indene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene are preferable, and When such a solvent is used, it is preferable to mix indene or indene with cyclopentadiene and dicyclopentadiene in advance.

The synthesis of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is carried out using these as raw materials and, if necessary, using a solvent, but the production method such as the reaction type is not particularly limited. . The operation of the reaction and distillation purification in the present invention can be achieved in any of a batch system and a continuous flow system, but it is preferable to select a continuous flow system industrially. As for the reactor, either a complete mixing type reactor or a piston flow type reactor can be used. As a commercially available product, "Static Mixer" manufactured by Noritake Company, Ltd., Sumitomo Heavy Industries, Ltd.
"Sluzer Mixer" manufactured by Sakura Seisakusho Co., Ltd. and "Skeya Mixer" manufactured by Sakura Seisakusho Co., Ltd. The reaction can be carried out in one or more stages, and a complete mixing type reactor and a piston flow type reactor can be used in combination in parallel or in series.

[0015] 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, and more preferably the reaction temperature is 150 ° C. or higher. If the reaction temperature is higher than 350 ° C., a large amount of heavy components represented by the formulas [II] and [III] will be produced. When cyclopentadiene is used as a raw material, the reaction temperature is 100 to 350 ° C.
Is preferred. The reaction conditions in the batch-type reactor are a reaction time of 0.01 to 100 h, preferably 0.05 to 5 h, and more preferably 0.1 to 3 h. The reaction pressure is from normal pressure to 10,000 kPa. The reaction conditions in the continuous reactor is a space velocity 0.01～100H ^-1, preferably 0.05～50H ^-1, more preferably 0.
¹ to 10 h ^-1 . If 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 led to a purification step. Purification generally includes methods such as chromatographic separation, crystal separation, and distillation separation. However, distillation separation is preferable, and batch distillation or continuous distillation may be used. In the case of batch distillation, there are a method of separating the remaining cyclopentadiene, the solvent (if used), dicyclopentadiene, and indene components, and a method of simultaneously separating three to four components. In order to increase the separation efficiency, the distillation column can be filled with various packing materials or refluxed. The number of theoretical plates is 1 to 100 plates in each distillation column, preferably 2 to 5 plates.
0 stages, more preferably 3 to 30 stages. The reflux ratio is determined based on the separation state of the distillation column.
Is appropriate.

First, as a method for separating each component, residual cyclopentadiene is separated, and the distillation conditions are set to a pressure of 0.0.
It is arbitrarily selected at 1 to 1000 kPa and at a temperature of 20 to 200 ° C. Next, the solvent (if used), residual dicyclopentadiene and indene are separated. Distillation conditions are temperature 30-1
It is appropriate that the temperature is 50 ° C. and the pressure is 10 kPa or less. Further, distillation conditions of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, which is a target component, are separated at 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. Appropriate distillation conditions are a temperature of 30 to 150 ° C. and a pressure of 10 kPa or less. The distillation conditions of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene are as follows: temperature 50 to 200 ° C., pressure 1 k
Separate below Pa.

In the case of continuous distillation, it is preferable that the process includes at least two or more distillation columns. When there are two distillation columns, the first column is the first column, and cyclopentadiene, a solvent (if used), residual dicyclopentadiene, and indene are recovered from the top, and the mixture at the bottom is sent to the second column.
At the top of the second tower, the target product, 1,4-methano-1,4,4a, 9
a-Tetrahydrofluorene is obtained. If a solvent is used, it must also be recovered. Heavy matter is obtained from the bottom of the tower. In this case, the distillation conditions in the first column are set to a temperature of 30 to 15 when dicyclopentadiene and indene remain.
0 ° C., the pressure is suitably 10 kPa or less, and when there is no residual, the distillation conditions are 1 to 100 kPa and the temperature is 20 to 1 kPa.
40 ° C. In the second column, the temperature is 50 to 200 ° C and the pressure is 1
kPa or less. When dicyclopentadiene and indene do not remain, distillation conditions are 1 to 100 kPa, cyclopentadiene at a temperature of 20 to 140 ° C., and when used, the solvent is recovered, but when there is an impurity contained in dicyclopentadiene, , Temperature 30-150 ° C, pressure 1
It is preferable to add an operation of removing under the condition of 0 kPa or less. By doing so, 1,4-methano-1,4,
The purity of 4a, 9a-tetrahydrofluorene can be kept high.

When there are three distillation columns, the first column is used to mainly separate cyclopentadiene from the top of the column. Distillation conditions are arbitrarily selected at 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 the second column, and at the top of the second column, the solvent (if used) and possibly the remaining dicyclopentadiene and indene are simultaneously recovered.
When dicyclopentadiene and indene remain,
A temperature of 30 to 150 ° C. and a pressure of 10 kPa or less are appropriate.
a, The temperature is 20 to 140 ° C. The mixture obtained from the bottom of the second column is sent to the third column, and a temperature of 5
1,4-Methano-1,4,4a, 9a-tetrahydrofluorene is separated and purified under the conditions of 0 to 200 ° C. and a pressure of 1 kPa or less. When dicyclopentadiene does not remain,
The solvent (when used) is recovered at a distillation condition of 1 to 100 kPa and a temperature of 20 to 140 ° C. However, when there is an impurity contained in dicyclopentadiene, the temperature is 30 to 15 ° C.
It is preferable to add an operation of removing at 0 ° C. and a pressure of 10 kPa or less. By doing so, 1,4-
The purity of methano-1,4,4a, 9a-tetrahydrofluorene can be kept high.

When four distillation columns are used, cyclopentadiene is separated from the top of the first column. Distillation conditions are arbitrarily selected at a pressure of 0.1 to 1 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) is simultaneously recovered from the top of the column. Distillation conditions are 1-100 kPa, temperature 20-140.
° C. The mixture obtained from the bottom of this column is led to the third column, where a mixture mainly composed of dicyclopentadiene and indene is separated. Appropriate 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 led to the fourth column, where the temperature is 50 to 200 ° C.
1,4-methano-1,4,4a, 9a-
Tetrahydrofluorene is separated, and a heavy product 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 are arbitrarily selected at a pressure of 0.1 to 1 MPa and a temperature of 0 to 100 ° C. The mixture obtained from the bottom of the column is led to the second column, and the solvent (if used), dicyclopentadiene, and indene are simultaneously recovered from the top of the column. The distillation conditions are 10 kPa or less, and the temperature is 30 to 150 ° C.
The mixture obtained from the top of this column is led to a third column, the solvent (if used) is separated from the top, and 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, and is heated at a temperature of 50 to 200 ° C. and a pressure of 1 kPa or lower to 1,4-.
Methano-1,4,4a, 9a-tetrahydrofluorene is separated from the top of the column, and a heavy product as a reaction by-product is obtained from the bottom of the column.

1,4
-Since methano-1,4,4a, 9a-tetrahydrofluorene decomposes at high temperature, it is important to keep the maximum temperature at 200 ° C. or lower and carry out distillation. Further, when a solvent is used, the boiling point differs depending on each solvent, so that the distillation conditions are different from those of the distillation column. Each distillation column can be filled with various packing materials or refluxed to increase the separation efficiency. Regarding the number of theoretical plates, 1 to 10
0 stages, preferably 2 to 50 stages, more preferably 3 stages.
~ 30 stages. The reflux ratio is determined based on the separation state of each distillation column, but is preferably 1 to 50. By adopting the production method described above, the formula (II) or (II
1,4-methano-1,4,4a, 9a-tetrahydrofluorene having a reduced content of the cyclopentadiene trimer represented by I] is obtained.

Here, the trimer of cyclopentadiene is composed of 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 olefin structures and reduces the optical properties of the resin obtained not only during metathesis ring-opening polymerization, but also during homopolymerization at the olefin site of the cyclic olefin or copolymerization with a lower α-olefin. May be caused. By adopting the manufacturing method of the present invention as described above,
The total content of the cyclopentadiene trimer represented by the formula [II] or [III] is 5,000 ppm or less, preferably 4,000 ppm or less, more preferably 3,000 ppm or less.
It can be in the range of ppm or less. Formula (III)
The content of is 3,0 by adopting the production method of the present invention.
00 ppm or less, preferably 2,500 ppm or less,
More preferably, it can be 2,000 ppm or less. By setting the content of the compound of the formula [II] or the formula [III] to the above range, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene represented by the obtained compound 1 can be metathesized. In addition to ring-opening polymerization, even when this material is used during homopolymerization at the olefin site of a cyclic olefin or copolymerization with a lower α-olefin, gelation is less likely to occur, and substantial optical properties of the resin are obtained. Less decrease. The total amount of the compounds of the formulas [II] and [III] is 1
When the content is less than 00 ppm, it can be more preferably used as a monomer for polymerization, but a load is required when performing distillation purification, and the number of distillation columns, the amount of reflux is increased, and the production is economically preferable. Absent.

Unreacted cyclopentadiene separated by distillation, solvent (if used), dicyclopentadiene,
Indene is preferably recycled and economically inexpensive to produce. 1,4-methano-1,
4,4a, 9a-tetrahydrofluorene is an endo-form,
It is a mixture of exo isomers, and the molar ratio between the endo and exo isomers is 80/20 to 60/40.

In this reaction, an antioxidant and a polymerization inhibitor can be added. For example, hydroquinone,
2,6-di-tert-butylphenol, 2,6-di-tert-
Phenol compounds such as butyl-p-cresol and 4-methoxyphenol, and hydroxylamine compounds such as N, N-dimethylhydroxylamine and N, N-diethylhydroxylamine are preferably added. The added amount is usually 10 to 10,000 ppm, preferably 50 to 10,000 ppm based on the total amount of the reaction raw materials supplied into the reactor.
It is in the range of 5,000 ppm.

According to the present invention,
4-Methano-1,4,4a, 9a-tetrahydrofluorene can be polymerized by the above-mentioned known method.
When performing metathesis polymerization, for example, Japanese Patent Application Laid-Open
183832, JP-A-8-151435,
JP-A-5-043663, JP-A-1-17242
No. 2, JP-A-1-172421, JP-A-1-172
JP-A-168725, JP-A-1-168724,
It can be carried out by a method as disclosed in JP-A-60-026024. Specifically, a method using a catalyst comprising (a) a transition metal compound catalyst component and (b) a metal compound promoter component is used.

(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 a halide, oxyhalide, alkoxyhalide, Complexes of alkoxides, carboxylate salts, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, derivatives thereof, and complexing agents with complexing agents such as phosphine compounds are exemplified. (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, Na, M
Organic compounds such as g, Zn, Cd, and B are exemplified. Further, in order to increase the metathesis polymerization activity, in addition to both components (a) and (b), aliphatic tertiary amine, aromatic tertiary amine, molecular oxygen, alcohol, ether, peroxide, carboxylic acid Acid, acid anhydride, acid chloride, ester, ketone,
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, JP-A-3-04612, JP-A-2-173
112, JP-A-4-063807, JP-A-64-000106, JP-A-61-221206
The method can be carried out by a method disclosed in Japanese Patent Application Laid-Open Publication No. H10-15095.
Specifically, a method using a catalyst comprising (c) 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 are a polydentate compound, or the cycloalkadienyl group or the substituted product is a hydrocarbon group. Alternatively, a compound in which a polydentate compound bonded through a silylene group or a substituted silylene group is used as a ligand may be used. (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.

[0030]

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As the Ziegler catalyst, titanium and vanadium compounds are used as the catalyst, and are described in, for example, JP-A-9-176396, JP-A-62-252406, and JP-A-62-252407. of,
By a method using a catalyst formed from a vanadium compound and an organoaluminum compound soluble in a hydrocarbon solvent, a copolymer of an α-olefin such as ethylene and a cyclic olefin is synthesized.

When the ring-opening polymerization is carried out, the resulting polymer may contain olefins, so that part or all of the olefins can be hydrogenated to improve heat deterioration resistance and light resistance. . In the hydrogenation reaction, a precious metal such as nickel, palladium, or platinum supported and dispersed on an inorganic carrier is used. A homogeneous hydrogenation catalyst can also be used. Hydrogen pressure is 0.1-20M
Pa, temperature is 0-200 ° C.

[0033]

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 that the composition of a, 9a-tetrahydrofluorene was used, to obtain a polymer. A gel sheet was found in the press sheet produced using this.

[0038]

The 1,4 obtained by the production method of the present invention.
-Methano-1,4,4a, 9a-tetrahydrofluorene has a low content of trimers of cyclopentadiene, and as a result, the resulting 1,4-methano-1,4,4a, 9a-tetrahydrofluorene When the polymerization is carried out using the resin, it is possible to substantially prevent the generation of a gel in the resin, and the optical properties of the resin are hardly reduced.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasuo Matsumura 463-1-205 Kamiiida, Izumi-ku, Yokohama-shi, Kanagawa F-term (reference) 4H006 AA02 AB46 AC28 AD11 AD40 AD41 BA90 BA94 BB11 BB49 BC11 BC18 BC31 BJ30

Claims (6)

[Claims] 1. A cyclopentadiene and / or dicyclopentadiene and 2 to 5 based on cyclopentadiene.
A reaction reaction mixture obtained by heating and reacting 0 times mole of indene, rectifying the obtained reaction mixture, and recovering a fraction mainly composed of components contained in the range of 250 to 300 ° C. in terms of normal pressure, the following formula [ II] and the total content of the cyclopentadiene trimer represented by the formula [III] is from 100 to 5,000 ppm.
1,4-methano-1,4, represented by the following formula [I]:
A method for producing a composition of 4a, 9a-tetrahydrofluorene. Embedded image Embedded image Embedded image 2. The method 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. Production method. 3. The production method according to claim 1, wherein, when cyclopentadiene and / or dicyclopentadiene and indene are mixed and heated and reacted, a hydrocarbon solvent inert to the reaction is used. . 4. The ratio of the weight in terms of dicyclopentadiene to the total weight of cyclopentadiene and / or dicyclopentadiene, indene and a hydrocarbon solvent inert to the reaction is 0.02 to 0.20. Item 4. The production method according to Item 3. 5. The temperature in the reaction is 100 to 350.
° C, pressure from normal pressure to 10 MPa and residence time 0.01
The method according to claim 3, wherein the time is from 100 hours to 100 hours. 6. The method according to claim 3, wherein unreacted cyclopentadiene or dicyclopentadiene, indene, and a hydrocarbon solvent inert to the reaction are recycled and reused.
The production method described in 1.