JP2000026332A - COMPOSITION FOR POLYMERIZING 2-ETHYL-1,4,5,8-DIMETHANO-1,2,3,4,4 a,5,8,8a-OCTAHYDRONAPHTHALENE - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of substantially preventing gel formation when used as a material for polymerizing itself by controlling the content of specific cyclopentadiene trimer(s). SOLUTION: The composition intended or polymerizing 2-ethyl-1,2,3,4,4a,5,8,8a- octahydronaphthalene of formula III contains 100-5,000 ppm of cyclopentadiene trimer(s) of formula I and/or formula II, wherein the content of the trimer of formula II in the composition is pref. 100-3,000 ppm. The composition is obtained by reaction between cyclopentadiene and/or dicyclopentadiene, 5-ethyl-2- norbornene of formula IV, and butene-1 under heating. Thereby, a composition suitable for a wide range of polymerization can be afforded, promising polymers with excellent optical properties, high transparency, high heat resistance, and oil absorptivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to 2-ethyl-1,4,
The present invention relates to a composition for polymerization of 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

[0002]

2. Description of the Related Art Cycloolefin (co) polymers have attracted attention as polymers having excellent optical properties, high transparency, heat resistance, and oil absorption, and cyclic olefins represented by tetracyclododecenes are used as raw materials. Useful.
These cyclic olefins are generally subjected to polymerization using an organometallic complex catalyst, but homopolymerization of the cyclic olefin at the olefin site using a Ziegler catalyst or a metallocene catalyst, or copolymerization with a lower α-olefin, and carbene There are two main types of polymerization, metathesis polymerization using complex complexes.

[0003] As a method for producing tetracyclododecenes, for example, Japanese Patent Publication No. 1-60011 is known, in which an α-olefin, cyclopentadiene (or dicyclopentadiene) and norbornene are heated. It is disclosed that in a method for producing a mixture containing norbornene and tetracyclododecenes, norbornene is recycled. However, the tetracyclododecenes obtained may contain a small amount of isomers and other compounds due to the production method itself and other reasons. Certain of these compounds may inhibit certain polymerizations of tetracyclododecenes. For example, JP-A-7-173085 discloses a tetracyclododecene composition containing a specific diolefin compound in which two norbornene rings each have an unsaturated double bond. It has been proposed that the content of the above specific diolefin compound should be in the range of 50 to 5,000 ppm because it causes gelation during metathesis polymerization of tetracyclododecenes. Incidentally, the composition described in the above publication,
Specifically, it relates to a monomer for ring-opening polymerization of metathesis, and does not mention homopolymerization at an olefin site using a Ziegler catalyst including a metallocene catalyst or copolymerization with a lower α-olefin. Further, only the above specific diolefin compound is mentioned.

[0004]

Accordingly, an object of the present invention is to examine various polymerizations of specific tetracyclododecenes and to find a polymerization composition suitable for a wide range of polymerizations.

[0005]

That is, the first aspect of the present invention is as follows.
Has a total content of cyclopentadiene trimer represented by the following formula [II] or [III] of 100 to 5,000 p
pm, 2-ethyl-1, represented by the following formula [IV]:
4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-
The present invention relates to a composition for polymerization of octahydronaphthalene.

[0006]

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A second aspect of the present invention is the first aspect of the present invention,
2-ethyl-1,4,5,8-dimethano-1, represented by the formula [IV], wherein the content of the cyclopentadiene trimer represented by the formula [III] is 100 to 3,000 ppm. Two,
The present invention relates to a composition for polymerization of 3,4,4a, 5,8,8a-octahydronaphthalene. A third aspect of the present invention is the method according to the first or second aspect of the present invention, wherein cyclopentadiene and / or dicyclopentadiene are combined with 5-cyclopentadiene represented by the formula [I].
It relates to a composition obtained by heating and mixing ethyl-2-norbornene. The fourth aspect of the present invention is the first aspect of the present invention.
Or in the second, cyclopentadiene and / or dicyclopentadiene and 5 represented by the above formula [I]
-Ethyl-2-norbornene and a composition obtained by heating and mixing butene-1.

Hereinafter, the present invention will be described in detail. One of the reaction raw materials of the present invention is cyclopentadiene. Dicyclopentadiene decomposes under heating to form cyclopentadiene. Therefore, when the reaction temperature is such that dicyclopentadiene is decomposed, dicyclopentadiene can be used as the reaction raw material of the present invention instead of cyclopentadiene. In addition, a mixture of cyclopentadiene and dicyclopentadiene can be appropriately used as a raw material. Cyclopentadiene and / or dicyclopentadiene;
Using 5-ethyl-2-norbornene represented by the formula [I] as a raw material, a reaction temperature of 100 to 350 ° C. and a reaction pressure of 0.1 to 2 are used.
By reacting under the condition of 0 MPa, 2-ethyl-1,4,5,8-dimetano-1,2,3,
4,4a, 5,8,8a-Octahydronaphthalene is formed.

Here, 5-ethyl- represented by the formula [I]
2-Norbornene is obtained by using 1-butene and cyclopentadiene or dicyclopentadiene as raw materials, and using 2-ethyl-1,4,5,8-dimethano-1,2,2 represented by the formula [IV].
The 3,4,4a, 5,8,8a-octahydronaphthalene is produced under the above production conditions. Therefore, by mixing 1-butene when heating and mixing dicyclopentadiene and / or cyclopentadiene, and 5-ethyl-2-norbornene, 2-ethyl-1,4, 5,8-dimethano-1,2,3,4,
4a, 5,8,8a-Octahydronaphthalene is synthesized, and 5-ethyl-2-norbornene is also produced. Therefore, if the generated 5-ethyl-2-norbornene is separated and recovered, and is recycled and reused, it is apparently unnecessary to newly supply 5-ethyl-2-norbornene, depending on the reaction conditions. When reacting cyclopentadiene and / or dicyclopentadiene with 5-ethyl-2-norbornene represented by the formula [I] as a raw material,
When dicyclopentadiene and / or cyclopentadiene and 5-ethyl-2-norbornene are mixed by heating when 1-butene is present, in each case, the compound is represented by the formulas [II] and [III]. 2-ethyl- represented by the formula [IV] containing a cyclopentadiene trimer
1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a
-An octahydronaphthalene composition is obtained.

The total content of the cyclopentadiene trimers represented by the formulas [II] and [III] is from 100 to 3,000.
It is 0 ppm. Compositions of less than 100 ppm are difficult to produce even after raw material purification, rectification, etc.
A composition exceeding m is not preferable for use in polymerization by a Ziegler catalyst such as metallocene in addition to metathesis polymerization, even when copolymerized with another monomer such as an α-olefin. Preferably,
A composition having a content of the cyclopentadiene trimer represented by the formula [III] of 100 to 2,000 ppm is used.
The compounds of the formulas [II] and [III] have 15 carbon atoms, and the compound of the formula [IV], which is the object of the present application, has 14 carbon atoms.
Therefore, separation by distillation is not impossible, but very difficult. It is difficult to achieve the range of less than 100 ppm by distillation at least from the viewpoint of economy such as distillation efficiency.

The cyclopentadiene trimer is a diolefin compound having a norbornene-type olefin structure represented by the formula [II] and a cyclopentene-type olefin structure, or a norbornene-type olefin represented by the formula [III] It is a diolefin compound having two sets of structures. As a ratio containing these, 100 to 5,000 ppm as a total of the two diolefin compounds,
Preferably, it is in the range of 100 to 3,000 ppm.
When the cyclopentadiene trimer is contained beyond such a range, not only metathesis ring-opening polymerization but also homopolymerization of cyclic olefin at olefin site by Ziegler catalyst such as metallocene catalyst or lower α
-A cross-linking reaction is likely to occur during copolymerization with an olefin, and the polydispersed structure becomes remarkable and gelation occurs. On the other hand, if it is less than the above range, the cost for separation and purification increases, which is not economically preferable. A preferred trimer of cyclopentadiene is a composition containing a diolefin compound having a norbornene-type olefin structure and a cyclopentene-type olefin structure represented by the formula [III]. The content of the compound of the formula [III] is 100 to 3,000.
0 ppm, preferably 100 to 2,000 ppm
It is.

When the dicyclopentadiene and / or cyclopentadiene and 5-ethyl-2-norbornene are mixed by heating, the composition of the present invention is produced by the coexistence of 1-butene. The supplied dicyclopentadiene preferably has a purity of 90% or more. Other impurities mainly Tetrahydromethylphthalic indene dicyclopentadiene, an adduct of linear or cyclic diolefins with cyclopentadiene C _5, becomes large by-products of heavy and amount of these heavy impurities often . When cyclopentadiene is used, dicyclopentadiene which has been subjected to pyrolysis distillation in advance is used.

The 1-butene used as a reaction raw material includes those produced from a petroleum refining plant or various cracking processes using butane, naphtha or light oil as raw materials, those produced by the disproportionation reaction of propylene, and those of ethylene. 1-butene produced by any kind of production method, such as that produced by a quantification reaction, can be used.

The cyclopentadiene and / or dicyclopentadiene is transported to the reaction system by using any method, but in the case of continuous production, a pressure booster and / or a pump can be used. 5-ethyl-2
-May be mixed with norbornene in advance and supplied to the reaction system, or may be supplied separately. However, since two raw material tanks and two pumps are required for separate supply, it is preferable to mix them in advance.

The supply ratio of each component in the present invention is not particularly limited, and is optional. In the presence of butene-1, 5-ethyl-2-norbornene is recovered and circulated while 2-ethyl-1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8.
The following reaction conditions are recommended for synthesizing a-octahydronaphthalene. That is, the cyclopentadiene and / or dicyclopentadiene is based on the number of moles of dicyclopentadiene (for example, 2 moles of dicyclopentadiene in a mixture of 2 moles of cyclopentadiene and 1 mole of dicyclopentadiene).
-The mixing ratio with butene is 0.1 to 10 in molar ratio,
It is preferably from 0.2 to 8, more preferably from 0.5 to 5. If the amount of 1-butene is less than the above range, the amount of heavy matter generated increases. On the other hand, when the amount is large, the heavy component decreases, but the effective yield of the raw material decreases.

The mixing ratio with 5-ethyl-2-norbornene is from 1 to 20 in molar ratio, preferably from 2 to 1
0, more preferably 3 to 8. When the amount of 5-ethyl-2-norbornene is large, the yield of heavy components represented by the formulas [II] and [III] tends to be relatively small. Conversely, when the amount is small, the amount of heavy substances represented by the formulas [II] and [III] tends to increase.

In producing the composition of the present invention, a solvent may be used. Any of paraffinic, naphthenic and aromatic solvents can be used. For example, carbon number 6 ~
About 13 hydrocarbons are preferred. Among them, generally, isohexane, heptane, isoheptane, normal octane, isooctane, dimethylcyclohexane, ethylcyclohexane, tetrahydronaphthalene, decahydronaphthalene, toluene, xylene, ethylbenzene, trimethylbenzene and the like are preferably used. In addition, by using a solvent, 2-ethyl-1,4,5,
The yield of 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene is also improved.

Using these as raw materials and optionally using a solvent, 2-ethyl-1,4,5,8-dimethano-1,2,
Synthesis of 3,4,4a, 5,8,8a-octahydronaphthalene is performed. The reaction type may be a batch type or a continuous type. In the case of a batch type, a completely mixed type reactor is used. In the case of a continuous system, the reactor may be either a completely mixed type or a piston flow type. Commercial products of the piston flow type reactor include "Static Mixer" manufactured by Noritake Co., Ltd., "Sluzer Mixer" manufactured by Sumitomo Heavy Industries, Ltd., and "Skeya Mixer" manufactured by Sakura Seisakusho Co., Ltd. The reaction can be performed in one or more stages. When the reaction is performed in multiple stages, a completely mixed type or piston flow type reactor can be used in series or in parallel.

Among the reaction conditions in the continuous and batch reactors, the reaction pressure is 0.1 to 50 MPa, preferably 0.5 to 40 MPa, more preferably 1 to 10 MPa.
MPa. The reaction temperature is 0 to 350 ° C, preferably 100 to 330 ° C, more preferably 200 to 300 ° C.
° C. In particular, when dicyclopentadiene is used as a raw material, decomposition to cyclopentadiene does not occur unless the reaction temperature is 100 ° C. or higher. When the reaction temperature is high, a large amount of heavy components represented by the formulas [II] and [III] tend to be formed.

In the continuous system, the space velocity is 0.001 to 10
0 h ^-1 , preferably 0.1 to 50 h ^-1 , more preferably ¹ to 10 h ^-1 . When the space velocity exceeds 100 h ⁻¹ , unreacted substances increase, which is inappropriate.

The reaction mixture withdrawn from the reactor is led to a distillation step where the recycled 5-ethyl-2-norbornene, solvent (if used), and 2-ethyl-
1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a
Octahydronaphthalene is separated and purified. Distillation is preferably used for purification, and the distillation may be a batch type or a continuous type.

In the case of batch distillation, the reaction mixture may contain unreacted 1-butene and cyclopentadiene, and these are first separated. The distillation conditions are pressure 0.
It is arbitrarily selected from the range of 1 to 1 MPa and the temperature of 0 to 100 ° C. Next, 5-ethyl-2-norbornene and, especially when a solvent is used, the solvent are simultaneously recovered, but the distillation conditions are 10 to 100 kPa and the temperature is 35 to 140 ° C.
It is. The mixture of the recovered 5-ethyl-2-norbornene and the solvent is adjusted as necessary and reused as a raw material. Subsequently, the remaining dicyclopentadiene is recovered, but at a temperature of 40 to 170 ° C. and a pressure of 1 to 100 k.
Pa is appropriate. If no dicyclopentadiene remains, there is no need to perform this distillation. However, when there is an impurity derived from dicyclopentadiene, it is preferable to add an operation for removing the impurities under the above conditions. Thereby 2
-Ethyl-1,4,5,8-dimethano-1,2,3,4,4
The purity of a, 5,8,8a-octahydronaphthalene can be kept high. Subsequent 2-ethyl-1,4,5,
The distillation conditions for 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene are a temperature of 40 to 160 ° C and a pressure of 0.01 to 30 kPa.

In the case of continuous distillation, it is preferred 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 1-butene, cyclopentadiene, 5-ethyl-2-norbornene, a solvent (if used), and residual dicyclopentadiene are recovered from the top of the column, and the bottom is collected. The mixture was sent to the second column, and the desired product, 2-ethyl-1,4,5,8-dimethano-1,2,2, was added at the top of the second column.
3,4,4a, 5,8,8a-Octahydronaphthalene is obtained. Heavy matter is obtained from the bottom of the tower. In this case, the distillation conditions in the first column are suitably in the range of temperature of 20 to 173 ° C. and pressure of 1 to 100 kPa when dicyclopentadiene remains, and in the range of 1 to 100 kPa when dicyclopentadiene does not remain.
The kPa and the temperature range from 35 to 140 ° C. In the second column, the temperature is 40 to 160 ° C. and the pressure is 0.01 to 30 kPa.
It is. When dicyclopentadiene does not remain,
Distillation conditions are 1-100 kPa and temperature 30-140 ° C
With 1-butene, cyclopentadiene, 5-ethyl-2-
Norbornene and solvent (if used) are recovered. When there is an impurity contained in dicyclopentadiene,
It is preferable to add an operation of removing at a temperature of 20 to 173 ° C. and a pressure of 1 to 100 kPa. Thereby 2-ethyl-1,4,5,8-dimethano-1,2,3,4,
The purity of 4a, 5,8,8a-octahydronaphthalene can be kept high. However, the recovered dicyclopentadiene has an increased content of impurities such as tetrahydromethylindene, which has a very high decomposition temperature.
When mixed with -ethyl-2-norbornene, it is accumulated due to the recycle use of norbornene, and more by-products are generated. If the reaction is carried out at a high temperature to promote the decomposition, a large amount of by-products will be generated. Therefore, the process with two distillation columns requires no dicyclopentadiene in the reaction product or only a very small amount. Applied if not present.

In the case where there are three distillation columns, the first column separates 1-butene and cyclopentadiene mainly from the top of the column.
The distillation conditions are a pressure of 0.1 to 1 MPa and a temperature of 0 to 100.
It is arbitrarily selected from the range of ° C. The mixture obtained from the bottom of the column is sent to the second column, and 5-ethyl-2-
The norbornene and solvent (if used) and, optionally, residual dicyclopentadiene are recovered simultaneously. If dicyclopentadiene remains, the temperature is 20-173.
C. and a pressure of 1 to 100 kPa are appropriate, and distillation conditions are 1 to 100 kPa and a temperature of 35
~ 140 ° C. The mixture obtained from the bottom of the second column is sent to the third column, and the temperature is 40 to 160 ° C. from the top of the third column.
And a pressure of 0.01 to 30 kPa.
1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a
-Separation and purification of octahydronaphthalene. When no dicyclopentadiene remains, the distillation conditions are 1 to 100.
5-ethyl-2-norbornene and a solvent (if used) are recovered at kPa and a temperature of 20 to 140 ° C., but when there are impurities contained in dicyclopentadiene, a temperature of 50 to 100 ° C. and a pressure of 20 kPa It is preferable to add a removal operation under the following conditions. Thereby 2-ethyl-1,4,5,8-dimethano-1,2,3,
The purity of 4,4a, 5,8,8a-octahydronaphthalene can be kept high.

When four distillation columns are used, 1-butene and cyclopentadiene are separated from the top of the first column. Distillation conditions are pressure 0.1 to 1 MPa and temperature 0 to 100 ° C.
Arbitrarily selected from the range. The mixture obtained from the bottom of this column is led to the second column, and 5-ethyl-2-norbornene and a solvent (if used) are simultaneously recovered from the top of the column. Distillation conditions are 1-100 kPa and temperature 35-140 ° C. The mixture obtained from the bottom of this column is led to the third column, where a mixture containing dicyclopentadiene as a main component is separated. Distillation conditions are temperature 40-173 ° C and pressure 1-10.
0 kPa is appropriate. However, the recovered dicyclopentadiene has an increased content of impurities such as tetrahydromethylindene, which has a very high decomposition temperature, and when these are mixed into 5-ethyl-2-norbornene, they accumulate by circulating use of norbornene, Also, more by-products are generated. Further, if the reaction is carried out at a high temperature to promote the decomposition, a large amount of by-products will be generated.
Mixing into -ethyl-2-norbornene is preferably suppressed as much as possible because accumulation of dicyclopentadiene occurs. The mixture obtained from the bottom of the third column is led to the fourth column, where the temperature is 40 to 160 ° C. and the pressure is 0.01 to 30 kPa.
With 2-ethyl-1,4,5,8-dimethano-1,2,3,4,
4a, 5,8,8a-Octahydronaphthalene 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.
1-butene and cyclopentadiene are separated from the top of the first column. Distillation conditions are pressure 0.1 to 1 MPa and temperature 0.
-100 ° C. The mixture obtained from the bottom of this column is led to the second column at the bottom, and 5-min.
Ethyl-2-norbornene and dicyclopentadiene are separated and recovered. The distillation conditions are a pressure of 1 to 100 kPa and a temperature of 20 to 173 ° C. The mixture obtained from the top of this column is led to a third column, where 5-ethyl-2-norbornene is separated from the top and dicyclopentadiene is separated from the bottom. Suitable distillation conditions for the third column are a pressure of 1 to 100 kPa and a temperature of 35 to 140 ° C. However, the recovered dicyclopentadiene has an increased content of impurities such as tetrahydromethylindene, which has a very high decomposition temperature,
When these are mixed into 5-ethyl-2-norbornene,
Recycling of norbornene accumulates and produces more by-products. Further, if the reaction is performed at a high temperature to promote the decomposition, a large amount of by-products will be generated. Therefore, it is preferable to minimize the incorporation into 5-ethyl-2-norbornene. The mixture obtained from the bottom of the second column is led to the fourth column, and is subjected to 2-ethyl-1,4,5,8-dimethano-1,2,2 at a temperature of 40 to 160 ° C. and a pressure of 0.01 to 30 kPa. 3,4,4a, 5,8,8a-Octahydronaphthalene 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.

In both the batch type and the continuous type,
The resulting 2-ethyl-1,4,5,8-dimetano-1,2,2
It is necessary to distill under conditions such that 3,4,4a, 5,8,8a-octahydronaphthalene does not decompose. 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 separation state of each distillation column, but is preferably 1 to 50.

The thus recovered 5-ethyl-2-norbornene or a mixture of 5-ethyl-2-norbornene and a solvent is returned to a raw material tank and used for circulation.
5-Ethyl-2-norbornene and / or solvent lost in the exhaust gas by distillation can be appropriately replenished from the raw material tank, and norbornene increased by the reaction is appropriately extracted to keep the concentration at a constant value. Can be.
In this reaction, an antioxidant, a polymerization inhibitor and the like can be added.

The 2-ethyl-produced as described above
1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a
The octahydronaphthalene compound can be subjected to polymerization by a known method. When performing metathesis polymerization, for example, JP-A-9-183832, JP-A-8-151435, JP-A-5-43663, JP-A-1-172422, JP-A-1-172.
No. 421, JP-A-1-168725, JP-A-1-168724, and JP-A-60-26024. Specifically, (a) a transition metal compound catalyst component, and (b)
This is a method using a catalyst comprising 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 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-3-45612 and JP-A-2-
173112, JP-A-4-63807, JP-A-64-106, JP-A-61-221206, and the like. Specifically, a method using a catalyst comprising (c) a transition metal compound component consisting of a group IVB, VB or VIB of the periodic table and (d) an organoaluminum oxy compound component.

The transition metal compound component of (c) is represented by the following formula:
A compound of a transition metal belonging to the group IVB, VB or VIB, wherein a polydentate compound of at least two cycloalkadienyl groups or a substituted product thereof is used as a ligand, or a cycloalkadienyl group or a substituted product thereof. Compounds in which a polydentate compound whose body is bonded through a hydrocarbon group, a silylene group, or a substituted silylene group are used as a ligand. (d) The organic aluminum oxy compound component has the following formula (V)
And a compound represented by the following formula [VI]. R in the formula
Is a hydrocarbon group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group or the like, and m represents an integer of 2 or more.

[0033]

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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. Copolymerization with other cyclic olefins such as norbornene and dicyclopentadiene is also possible. In addition, 2-ethyl-1,4,
When polymerizing 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, it is possible to copolymerize with another type of olefinic compound, for example, As disclosed in Japanese Patent Publication No. 7-103223, various physical property balances can be adjusted by changing the copolymerization ratio.

When ring-opening polymerization is carried out, the resulting polymer may contain an unsaturated double bond. Therefore, when heat deterioration resistance and light resistance are low, a part of the olefin is used to improve the deterioration. Alternatively, all 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 pressure of the hydrogenation reaction is 0.1-20 MPa, and the temperature is 0-20.
It is in the range of 0 ° C.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to embodiments.

<Example 1> A tube type reactor having an inner diameter of 5 mm was used, and only a portion having an inner volume of 25 ml (127 cm) was used.
It was immersed in an oil bath whose temperature was adjusted to 250 ° C. 5-Ethyl-2-norbornene (3400 g) and dicyclopentadiene (460 g) were mixed and fed to a tube reactor using a pump so that the space velocity was 4 h ^-1 .
Before entering the heating zone, 1-butene was added continuously so that the molar ratio with dicyclopentadiene was 1: 1.
The pressure in the reaction system was maintained at 5 MPa using a pressure regulating valve. The mixture was continuously operated for 10 hours to obtain a reaction mixture, and rectification was performed to give 2-ethyl-1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydro. 108 g of naphthalene were obtained. In this fraction, 3,650 ppm of the compound of the formula [II] and 1,25 ppm of the compound of the formula [III] were added.
0 ppm was contained.

<Polymerization Example 1> To a 2-liter eggplant-shaped flask equipped with a stirring blade, 1,000 ml of toluene dried under a nitrogen atmosphere was introduced. The flask further contains dichloroethoxyoxovanadium (1 mmol), 3,650 ppm of the compound of the formula [II] and 1,250 ppm of the compound of the formula [III], and the 2-ethyl-1,4,5 obtained in Example 1 was used. , 8-Dimethano-1,2,3,4,4a, 5,8,
8a-Octahydronaphthalene (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 thereto to start the reaction, 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 was vacuum dried to produce a 1 mm thick press sheet at 240 ° C. A homogeneous transparent sheet is obtained,
No gel was observed.

Comparative Example 1 2-ethyl-1,4,5,8-
The procedure of Example 1 was repeated, except that the synthesis reaction of dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene was carried out at 380 ° C., and 2-ethyl-1,4,5, There were obtained 92 g of 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. In this fraction, 5,300 ppm of the compound of the formula [II] and 3,5 ppm of the compound of the formula [III] were added.
00 ppm was contained.

<Polymerization Example 2> Formula [II] obtained in Comparative Example 1
5,300 ppm of the compound of formula (III)
Polymerization Example 1 was repeated in the same manner as in Polymerization Example 1 except that 2-ethyl-1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene containing 500 ppm was used. Copolymerization was performed 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.

<Polymerization Example 3> Formula [II] synthesized in Example 1
3,650 ppm of the compound of formula [III]
2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (20 g) containing 250 ppm, norbornene (2.5 g), dicyclopentadiene (2.5 g) and toluene (200 ml)
Was introduced into a well-dried 500 ml autoclave. Here is triethylaluminum (3 mmol)
Was added, and titanium tetrachloride (0.7 mmol) and triethylamine (7 mmol) were further 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 again in toluene, and the reprecipitation operation was repeated twice, followed by drying under reduced pressure to obtain polymer 21.
g was obtained. In a 200 ml autoclave, 0.5% palladium carbon (0.4 g) and toluene (100 m
l) was 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 completion of 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.

<Polymerization Example 4> Formula [II] synthesized in Comparative Example 1
5,300 ppm of the compound of formula (III)
Polymerization was performed in the same manner as in Polymerization Example 3 except that 2-ethyl-1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene containing 500 ppm was used. And hydrogenation to obtain a polymer. A gel sheet was found in the press sheet produced using this.

[0042]

The composition of 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene of the present invention has the formula [II] And since the content of the cyclopentadiene trimer represented by the formula [III] is limited to a specific range, when used as a polymerization raw material,
The generation of gel can be substantially prevented.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Yasuo Matsumura 463-1-205 Kamiiida, Izumi-ku, Yokohama-shi, Kanagawa F-term (reference) 4H006 AA03 AA05 AB46 AC28 BC10

Claims (4)

[Claims] A total content of cyclopentadiene trimers represented by the following formulas [II] and [III] is from 100 to 100:
2-5,000 represented by the following formula [IV], which is 5,000 ppm
Ethyl-1,4,5,8-dimethano-1,2,3,4,4a,
A composition for polymerization of 5,8,8a-octahydronaphthalene. Embedded image Embedded image Embedded image Embedded image 2. The 2-ethyl-1,4,5,5,2-cyclopentadiene represented by the formula [IV], wherein the content of the cyclopentadiene trimer represented by the formula [III] is 100 to 3,000 ppm. 8
-A composition for polymerization of dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. 3. The composition according to claim 1, which is obtained by heating and mixing cyclopentadiene and / or dicyclopentadiene with 5-ethyl-2-norbornene represented by the formula [I]. . 4. The method according to claim 1, which is obtained by heating and mixing cyclopentadiene and / or dicyclopentadiene, 5-ethyl-2-norbornene represented by the formula [I], and butene-1. A composition according to claim 1.