JPH10287592A - Crude tetracyclododecene mixture and its production, production of purified tetracyclododecene and apparatus for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crude tetracyclododecene mixture capable of providing high purity tetracyclododecene having <=1.0 wt.% cyclopentadiene trimer content in good productivity, provide a method for producing such crude tetracyclododecene mixture, obtain high purity tetracyclododecene from such crude tetracyclododecene mixture and provide a production apparatus therefor. SOLUTION: A mixture in which a molar ratio of norbornene to cyclopentadiene is >=3.4 is reacted by retaining the mixture at 170 deg.C to 205 deg.C for 1-10 hr to provide the objective crude tetracyclododecene mixture. Further, the crude tetracyclododecene mixture is purified by distillation to efficiently produce the objective high-purity tetracyclododecene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a crude tetracyclododecene mixture, a method for producing the same, and a method for producing a purified tetracyclododecene. More specifically, a method for producing purified tetracyclododecene, which has a low content of cyclopentadiene trimer and is suitable as a raw material for thermoplastic polymers and the like, and a raw material for thermosetting polymers and the like and a raw material for purified tetracyclododecene The present invention relates to a suitable crude tetrachlordodecene mixture and a method for producing the same.

[0002]

2. Description of the Related Art Tetracyclododecene or its alkyl derivative is useful as a raw material for paints and thermosetting or thermoplastic resins. Recently, a cyclic olefin polymer resin, which is particularly transparent and has excellent heat resistance, is disclosed in JP-A-51-80400 and JP-A-60-2.
6024, JP-A-1-168725, JP-A-1-190726, JP-A-3-14882, JP-A-3-122137, JP-A-4-638
07, JP-A-2-227424, JP-A-2-227424
No. 2,276,842 and the like, and ZEONEX (trade name, manufactured by Zeon Corporation), APEL, APO (trade name, manufactured by Mitsui Petrochemical Industry Co., Ltd.) are widely used as molding materials for injection molding and the like. The main raw materials of these cyclic olefin polymer resins are cyclic olefins and cyclic dienes, and in particular, tetracyclododecene, which is one of olefins having many ring structures, has a particularly high heat resistance by using this as a raw material. Since a cyclic olefin polymer resin is obtained, it is used as a suitable monomer raw material.

[0003] Tetracyclododecenes (hereinafter referred to as TCDs) are, in principle, produced by the reaction shown in Chemical Formula 1.

Embedded image From a crude TCD mixture obtained by a Diels-Alder addition reaction of norbornenes (hereinafter, referred to as NB) and cyclopentadiene (hereinafter, referred to as CPD), components having a lower boiling point than TCD such as NB and CPD and the same amount as unnecessary TCD or Although high-boiling by-product components are produced by separation by distillation and purification, industrially, ethylene is further added to a mixture of NB and CPD and reacted under high pressure to form NB from ethylene and CPD in the system. Is generally performed by a one-step method of synthesizing TCD while generating as a reaction intermediate. The production method is described in Japanese Patent Application Laid-Open No. 57-15413.
No. 3, JP-A-3-128333 and the like.

Such by-products include cyclopentadiene trimers (hereinafter referred to as 3C), tetramers (hereinafter referred to as 4C), and pentamers (hereinafter referred to as 4C), which are Diels-Alder addition products of CPDs. 5C), and a compound such as a compound obtained by further adding CPD to TCD. It is known that these components include a component that inhibits or causes a runaway of the polymerization reaction. For example, as shown in Chemical Formula 2 and Chemical Formula 3 in 3C,

Embedded image

Embedded image There are two types of isomers, symmetric and asymmetric, and both exist at a fixed ratio of about 15 to 85.
Is a compound having a norbornene ring structure having polymerization activity in a molecule.
Since it owns, it acts as a cross-linking reaction component during the polymerization reaction, and when polymerizing TCD containing a large amount of symmetric 3C to synthesize a thermoplastic resin, polymer molecules in the course of the polymerization reaction are cross-linked, There is known a problem that the reaction cannot be controlled or a gel component is generated to deteriorate the quality of the polymer.

[0005] As a method of manufacturing a TCD, many methods mainly using a one-step method have been disclosed.

JP-A-57-154133 discloses a method for producing tetracyclododecenes by a one-step method by reacting a mixture of an olefin and cyclopentadiene under specific conditions. Since the method is a one-step method, the product is a mixture of cyclopentadienes containing a large amount of norbornenes, and when olefins (C3 = propylene in the publication) and CPD are directly mixed and reacted thermally, Cyclododecenes (MTD =
The yield of methyltetracyclododecene) is poor, and is 1/10 or less of norbornenes (the same MNB = methylnorbornene). In order to compensate for this, norbornenes are additionally supplemented separately (the same CPD / MNB = 1/1 molar ratio), and the reaction is carried out in the presence of propylene (2 to 5 times the molar ratio of the same CPD or MNB). 3C (the same Tr) relative to 100 parts by weight of the tetracyclododecenes (the same MTD) in the product
im) is as high as 10 parts by weight or more (2.1: 18 at the same molar ratio = 13.3: 100 by weight).
In this publication, a part of CPD reacts with olefins to form norbornenes, which are added to additional norbornenes and react with CPD. However, the charging ratio of norbornenes to CPD is molar. No technique using a norbornene in excess of 1/1 in ratio is disclosed. The reaction temperature is as high as 204 to 315 ° C. when no additional norbornenes are used, and 231 to 317 ° C. when additional norbornenes are used.

[0007] JP-A-3-128333, JP-A-6-128333
JP-A-72909 discloses that T
A method for producing CDs is disclosed.
This technique aims to improve the efficiency of the distillation step by adding a high-boiling component to the technique disclosed in JP-A-154133, and does not improve the amount of 3C produced.

A method for producing tetracyclododecenes from norbornenes and CPD (hereinafter referred to as a two-step method) is disclosed in, for example, JP-A-47-31970, which discloses that ethylidene norbornene and CPD are used. Manufactures ethylidenetetracyclododecene from
The charged molar ratio of ethylidene norbornene to PD is 1
２2, and the ratio of 3C in the product is not described. However, when this method was repeated by the inventors, it was found that ethylidenetetracyclododecene 10
3C to 0 parts by weight was 10 parts by weight or more.

As described above, a crude TCD mixture synthesized by a conventionally known method has a high 3C content, and usually contains at least 15 parts by weight, and at least 10 parts by weight, based on 100 parts by weight of TCD. It was inconvenient. In addition, reducing the amount of 3C generated in the purification step increases the loss of the step or decreases the production efficiency. Low-boiling components such as unreacted NB (boiling point 96 ° C) and CPD (boiling point 42 ° C) have sufficiently lower boiling points than TCD (boiling point 205 ° C), which is the target substance, and should be easily separated by distillation. Can be. 4C, 5C etc. and T
High-boiling components such as compounds in which CPD is further added to CD have a sufficiently high boiling point, and thus can be easily separated. However, for 3C, both symmetric and asymmetric types have T
This is because the boiling points are relatively close to each other as compared with CD and are about 40 ° C., so that it is somewhat difficult to separate the TCD from the TCD to increase the purity when removing 3C as an impurity. Certainly, by increasing the number of theoretical plates of the distillation equipment and performing precise distillation, it is possible to separate the fraction if the boiling point difference is such a degree, but if the equipment becomes large or the same equipment, In order to increase the number of theoretical plates, the residence time is prolonged, that is, the feed rate, which is the productivity, must be reduced, or the yield becomes poor.
For example, from a crude TCD mixture containing about 15 parts by weight of 3C to 100 parts by weight of TCD, 1C or less of 3C
When it is intended to obtain a purified TCD with a content of less than 6 parts by weight or less than a crude TCD mixture containing only 3C, if the feed rate is less than half, or if the same feed rate is used, an extra high boiling point component is obtained. Must be removed, resulting in a disadvantage that the yield is reduced by several tens%. Therefore, a highly pure TCD mixture could not be obtained with high productivity from a crude TCD mixture synthesized by a conventionally known method.

On the other hand, the present inventors have studied and found that TC
When the content of 3C in D is 1 part by weight or less based on 100 parts by weight of TCD, the polymerization reaction is easily controlled, and a thermoplastic polymer having excellent quality can be obtained. It has been found that TCD is suitable as a raw material for a thermoplastic polymer. It has been found that such high-purity TCD is suitable for both addition-type polymerization and ring-opening polymerization.

As described above, high purity TCD having a 3C content of 1 part by weight or less with respect to 100 parts by weight of TCD is useful, but is obtained from crude TCD with good productivity.
No CD mixtures or methods for synthesizing such crude TCD mixtures were known.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a TC
Provided is a crude TCD mixture that can obtain a high-purity TCD having a 3C content of 1 part by weight or less based on 100 parts by weight of D with high productivity, a method of synthesizing such a crude TCD mixture, and a method of synthesizing such a crude TCD mixture. TCD of purity
To provide a method for obtaining

[0013]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies and found that a crude TCD mixture having a specific composition can be used to prepare TCD10.
High purity TC with 3C content of 1 part by weight or less based on 0 part by weight
D can be obtained with high productivity, and by conducting a synthesis reaction under specific conditions, crude TCD having such a specific composition can be obtained.
The inventors have found that a mixture can be obtained and that a high-purity TCD can be obtained from such a specific crude TCD mixture with high productivity, and the present invention has been completed.

Thus, according to the present invention, a mixture having a molar ratio of NB to CPD of 3.4 or more is treated at a temperature of 170
There is provided a method for producing a crude TCD mixture, wherein the reaction is carried out by maintaining the temperature in a range of from 0 ° C to 205 ° C for 1 to 10 hours.

According to the present invention, according to the above-described manufacturing method,
A crude TCD mixture comprising TCD and NB,
A crude TCD mixture is provided, wherein the ratio of NB to TCD is 2.4 or more in molar ratio, and the content of 3C is 6 parts by weight or less based on 100 parts by weight of TCD.

Further, according to the present invention, the above crude TCD
A method for producing a purified TCD having a 3C content of 1 part by weight or less and a norbornene content of 0.5 part by weight or less based on 100 parts by weight of the TCD is provided by distilling the mixture.

Further, according to the present invention, the reactor comprises a reservoir tank for norbornene, a reservoir tank for cyclopentadiene, a reactor, and at least one purification column, which can be maintained at a temperature of 50 ° C. or higher. In the reactor, norbornene and cyclopentadiene are supplied via piping, and the reactor is equipped with a stirrer for the contents and a heat source capable of controlling the temperature to an arbitrary temperature in the range of 170 to 205 ° C. A refining tower is connected to the reactor via a pipe, and an unreacted norbornene-based fraction is collected at the top of at least one of the refining towers to recover norbornene. An apparatus for producing purified tetracyclododecene, characterized by being provided with a pipe capable of maintaining the temperature at 50 ° C. or higher for supplying to a reservoir tank. It is provided.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each item constituting the present invention will be described in detail.

The method for producing a crude TCD mixture of the present application comprises reacting a specific ratio of NB and TCD under specific reaction conditions.

(Raw Materials) As the NB used in the present invention, a NB synthesized by a Diels-Alder addition reaction of ethylene and CPD may be used without purification or a NB having a higher purity by purification such as distillation. Good. In addition, it is generally available as a reagent from Aldrich or the like, and industrially, NB manufactured by Atochem of France is also available.

The purity of NB is 80% by weight or more, preferably 90% by weight or more, as measured by gas chromatography. Examples of the impurities include methylnorbornene, methylcyclohexene, and CPD. For the purpose of the present invention, the content of 3C is usually 4 parts by weight or less, preferably 2 parts by weight or less, particularly preferably 1 part by weight, based on 100 parts by weight of NB.
Use parts by weight or less. If an NB having a higher 3C content is used, the 3C content in the crude TCD mixture after the TCD synthesis reaction increases, which is not preferable.

The CPD used in the present invention is obtained by extracting a C5 fraction obtained by distilling crude oil, and is available as dicyclopentadiene from Zeon Corporation. Normally, dicyclopentadiene CPD is a mixture of CPD dimer dicyclopentadiene and CPD, and dicyclopentadiene is easily decomposed into CPD by heating. Thus, as in the Diels-Alder addition reaction of the present invention, When the reaction is carried out at a temperature higher than room temperature, dicyclopentadiene is also decomposed and reacted as cyclopentadiene. In the present invention, a mixture of CPD and dicyclopentadiene is referred to as CPD, and the number of moles thereof is CPD. Shall be converted to the amount of

The purity of CPD is at least 80% by weight, preferably at least 90% by weight, as measured by the same method as for NB. Examples of the impurities include 5-isopropenylnorbornene, 5-vinylnorbornene, methyltetrahydroindene, methylcyclopentadiene dimer, methylbicyclononadiene, and 3C. From the viewpoint of the present invention, the content of 3C is the most important. Yes, usually 4 parts by weight or less, preferably 2 parts by weight or less, particularly preferably 1 part by weight or less, based on 100 parts by weight of TCD. When an NB having a higher 3C content is used, the 3C content in the crude TCD mixture after the TCD synthesis reaction increases,
Not preferred.

Further, since these NBs and CPDs themselves are monomers that cause a polymerization reaction, etc., during storage,
Purity tends to decrease due to polymerization reaction and the like, and for the purpose of preventing this, 2,6-di-t-butylphenol, 2,6-
Di-tert-butyl-4-methylphenol, 4-methoxyphenol, 2,2'-dihydroxy-3,3'-di-
t-butyl-5,5'-dimethoxy-diphenylmethane, tetrakis [methylene-3- (3 ', 5'-di-t
-Butyl-4-hydroxylphenyl) propionate], quinone-based polymerization inhibitors such as t-butylcatechol, hydroquinone, resorcinol, pyrogallol, N, N-dimethylhydroxylamine, N, N-diethylhydroxyl It is preferable to add a hydroxylamine-based polymerization inhibitor such as an amine.

Further, these polymerization inhibitors remain without being removed even during the Diels-Alder addition reaction, and the TCD synthesis reaction proceeds, which has the effect of reducing by-products of oligomer components such as 4C and 5C. Is preferred.

The amount of the polymerization inhibitor to be added is not particularly limited, but is usually from 10 to 10,000 ppm, preferably from 50 to 5,000 in terms of the weight of NB and CPD.
ppm. When the amount of addition is in this range, the obtained crude TCD mixture has a low 3C content, a good TCD yield, and optimal conditions. These polymerization inhibitors may be used alone or in combination of two or more.

(Reaction conditions) The mixing ratio of CPD and NB used in the Diels-Alder addition reaction
Is 3.4 or more, preferably 3.8 or more.
As the molar ratio of NB to CPD decreases, the selectivity of TCD as a product decreases, and at the same time, the selectivity of 3C formation increases.
No CD mixture is obtained.

The reaction temperature is from 170 ° C. to 205 ° C., preferably from 190 ° C. to 200 ° C. Reaction temperature 170 ° C
When the temperature is lower, the reaction of decomposing dicyclopentadiene contained in CPD into cyclopentadiene does not sufficiently proceed, and particularly at 150 ° C. or lower, the decomposition reaction hardly proceeds. Therefore, the amount of cyclopentadiene used for TCD generation becomes extremely small, and the progress of the TCD generation reaction is hindered. When the reaction temperature is higher than 205 ° C., the rate of progress of the Diels-Alder reaction increases, but the selectivity of TCD to 3C decreases, and the crude T
It is not preferable because a CD mixture cannot be obtained.

The reaction time is 1 to 10 hours, preferably 2 hours.
8 hours. If the reaction time is shorter than 1 hour, the reaction yield decreases, and if it is longer than 10 hours, the content of 3C increases, which is not preferable. The reaction time as referred to herein is a time maintained at the above-mentioned reaction temperature, and the time required for raising and lowering the temperature is not particularly limited, and can be appropriately determined according to the capacity of the apparatus used for the reaction.

The reaction apparatus is not particularly limited as long as it can perform the above reaction conditions, and a known apparatus can be used. FIG. 1 shows a schematic diagram of a typical apparatus that is usually used. (Crude TCD Mixture) A crude TCD mixture obtained by the production method of the present invention is provided, but the ratio of each component is in a specific range. The ratio of NB to TCD is 2.4 or more in molar ratio, and the content of 3C to 100 parts by weight of TCD is 6 weight or less. When the crude TCD mixture has such a composition ratio, by purifying the mixture, a high-purity TCD having a 3C content of 1.0% or less can be produced with high productivity.

The ratio of NB to TCD is 2.
It is 4 or more, particularly preferably 2.8 or more. When the ratio in the mixture is in this range, the viscosity of the liquid as a whole of the crude TCD mixture shows appropriate fluidity, and distillation with good productivity becomes possible. Although there is no particular upper limit, it is usually 7 or less, preferably 4.5 or less, particularly preferably 4.0 or less. If the amount is too large, the ratio of TCD in the crude TCD is reduced, so that the amount of the crude TCD mixture for purifying and obtaining a certain amount of TCD is increased and the productivity is reduced. It is not preferable in terms of becoming. From the above, the molar ratio is usually 2.4 or more, preferably 2.4 to 7, particularly preferably 2.4 to 4.5, and most preferably 2.8 to 4. Good productivity.

The content of 3C in the crude TCD mixture is
6 parts by weight or less, preferably 5 parts by weight, per 100 parts by weight of CD
It is at most 3 parts by weight, particularly preferably at most 3 parts by weight. In such a range, a high-purity TCD having a 3C content in the TCD of 1 part by weight or less can be produced with high productivity.

The crude TCD mixture contains, as other components, low-boiling components such as CPD and methyltetrahydroindene, and high-boiling components such as 4C, 5C, compounds obtained by adding CPD to TCD, and cyclopentadiene. May be. Since these components can be easily separated from TCD by distillation, the amount to be contained is not particularly limited, but CPD is usually 10 parts by weight or less, preferably 5 parts by weight or less based on 100 parts by weight of TCD. Sometimes the productivity of the distillation process is good. The amount of other low boiling components is usually 2 parts by weight or less, preferably 1 part by weight or less. The amount of the high boiling component is usually 10 parts by weight or less, preferably 5 parts by weight or less, and when it is within this range, the productivity of the distillation step is good.

(Production Apparatus) Since the crude TCD of the present invention has a low content of 3C, which is a polymerization inhibitory component, it can be directly used for the polymerization reaction. However, depending on the required purity of the TCD, the crude TCD is subjected to distillation. Low boiling components and high boiling components can be separated and purified. FIG. 1 shows a schematic diagram of a manufacturing rent suitable for the present invention. Hereinafter, the manufacturing process and the apparatus will be described with reference to the schematic diagram shown in FIG.

The materials of the reservoir tank, the reactor, the piping, the stirrer, the purification tower, the liquid pump and the like are not particularly limited.
Materials generally usable for chemical plants, such as iron and stainless steel, or those obtained by subjecting their liquid contact surfaces to anticorrosion treatment such as glass lining and Teflon lining can be used. In addition, since the raw materials and products in the reactor, piping, and purification tower become high temperature and are susceptible to oxidative deterioration in the presence of oxygen, the gas layer that comes into contact with these raw materials and products contains nitrogen gas. It is preferable and often necessary to replace the gas with an inert gas such as that described above, and to have a structure in which oxygen such as in the atmosphere is not mixed during the operation of the apparatus. The reservoir tank 1 for norbornene and the pipe 7 connecting it to the first purification tower must control the temperature of the norbornene or the mixture thereof to at least 47 ° C. or higher, preferably 50 ° C. or higher. In this case, the pipes are clogged and the recovery rate of norbornene is reduced, and the productivity is reduced. There is no particular upper limit to the temperature at which the temperature is kept, but if the temperature is raised more than necessary, the thermal efficiency deteriorates.
0 ° C. or less is sufficient.

The crude TCD mixture obtained by the reaction is
NB and C are supplied to the first purification column, and unreacted NB and C
By recovering the mixture of PD, 3C,
TCDs containing high-boiling components such as 4C, 5C and compounds obtained by adding CPD to TCD (hereinafter referred to as first-stage purified TCD) are obtained. The first-stage purified TCD has a 3C content of 6 parts by weight or less, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, based on 100 parts by weight of TCD.
Not more than parts by weight. In addition, this first-stage purified TCD is:
Since it does not contain a low boiling point component, it can be used as a raw material monomer of a thermosetting cyclic olefin polymer resin by mixing with, for example, dicyclopentadiene as necessary.

Further, the first-stage purified TCD is supplied to a second purification column, high boiling components are recovered from the bottom of the purification column, and the desired purified TCD can be obtained from the top of the column.
A feature of the present invention is that, due to the low 3C content of the crude TCD mixture, and thus the low 3C content in the first stage purified TCD, etc., the TCD (as pure) The recovery is high, the loss due to the generation of by-products is small, and the production efficiency is very high. As shown in Chemical Formula 1, NB and CPD react stoichiometrically at a molar ratio of 1: 1. However, since CPD is more reactive than NB, the reaction is performed at the charge ratio and temperature according to the present invention. Was found to be the most efficient. In the present invention, an excessive amount of NB is charged in excess of the stoichiometric ratio, but NB remaining as a result of the reaction is efficiently recovered in the first purification column, and can be returned to the reaction system again. Almost no loss. In addition, since the recovered NB contains a small amount of impurities such as CPD, the purity of NB in the NB reservoir tank may be reduced. Therefore, the raw material charging ratio may be manually or automatically determined based on the analysis result. It is also good to fine-tune and control within the desired range.

In some cases, depending on the structure of the purification tower, or when the 3C in the obtained crude TCD mixture is sufficiently small, for example, 1 part by weight or less, it may be possible to perform only one step. The operating conditions of the first and second purification columns are not particularly limited, but preferred conditions are shown below.

The distillation conditions for the first purification column are as follows:
20 to 180 ° C, preferably 140 to 160 ° C. If the temperature is higher than 180 ° C., a decomposition reaction or side reaction of TCD occurs, and the yield decreases. If the temperature is lower than 120 ° C., it takes a long time to separate low-boiling components, which undesirably lowers productivity. The bottom pressure is 150 to 210 Torr,
Preferably it is 170 to 190 Torr. 150T
If it is lower than orr, the resolution will be poor and the overall yield will decrease. On the other hand, if the pressure is higher than 210 Torr, it takes time to separate low-boiling components, and the productivity is lowered, which is not preferable.
The top temperature is 40 to 60 ° C., preferably 45 to 55 ° C.
° C.

The distillation conditions when the second purification column is used are such that the temperature at the bottom of the column is 110 to 170 ° C., preferably 130 to 150 ° C. If the temperature is higher than 180 ° C., TCD is decomposed and the yield decreases. If the temperature is lower than 110 ° C., it takes time to separate low-boiling components, which is not preferable because the productivity is lowered. The bottom pressure is 0.5 to 50 Torr,
Preferably it is 10 to 30 Torr. 50 Torr
If the temperature is higher, it takes time to separate low-boiling components, which lowers the productivity and increases the temperature at the bottom of the column, so that the decomposition reaction and side reaction of TCD are likely to occur, which is not preferable. The top temperature is 70 to 130 ° C., preferably 90 to 11 ° C.
0 ° C.

When low-boiling components and high-boiling components are separated from the crude TCD mixture obtained by the present invention by distillation, unreacted NB has a high melting point of 47 ° C., so that if water is used as a refrigerant, water in the condenser will Blocking the line by coagulation to a degree interrupts the distillation process, which is undesirable. N
In order to prevent coagulation of B, warm water of 40 to 60 ° C. may be flowed, or a solvent or the like may be added as an antifreezing agent. Preferred among solvents and the like are those which have an antifreezing effect on NB, do not cause a chemical reaction with NB, can be mixed without phase separation, and have a boiling point of 5%.
What is 0-170 degreeC, Preferably it is 60-150 degreeC is preferable. If the boiling point is too high, separation from TCD becomes difficult, and precision distillation is required, which is not preferable. On the other hand, if the boiling point is too low, it is not distilled out as a mixture with NB, and the purpose of addition is not achieved. The solvent is not limited as long as it satisfies the above conditions, and examples thereof include aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane and methylcyclohexane. Alicyclic hydrocarbons such as, styrene dichloride, dichloroethane, dichloroethylene,
Halogenated hydrocarbons such as tetrachloroethane and chlorobenzene; Among them, aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as n-hexane and n-heptane are preferable, and aliphatic hydrocarbons such as n-hexane and n-heptane are particularly preferable, and particularly n
-Hexane can be used effectively, and the same effect can be obtained with a small amount of 0.6 times or less as compared with the case of toluene. This is not limited to the purification of the TCD of the present invention, but is
This is a purification method applicable to the purification of a reactive compound having a boiling point of 50 ° C.

The solvent for such purification may be added to the reaction system before the reaction, or may be added to the mixture after the reaction and before the purification by distillation. The amount of the solvent to be added is 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the NB. If the amount is too small, the effect of addition cannot be obtained. If the amount is too large, it takes time to separate TCD, energy loss is large, and it is uneconomical.

(Purified TCD) According to the production method of the present invention,
High-purity purified TCD having a 3C content of 1 part by weight or less based on 100 parts by weight of TCD can be efficiently produced. The present inventors have found that the content of 3C in high-purity TCD needs to be 1 part by weight or less based on 100 parts by weight of TCD when used as a raw material for a polymerization reaction. The amount of 3C in the purified TCD must be 1 part by weight or less, preferably 0.5 part by weight or less, more preferably 0.2 part by weight or less. The content of norbornene is usually 0.5 parts by weight or less, preferably 0.2 parts by weight or less, particularly preferably 0.1 parts by weight or less. When it is in this range, the polymerization reaction using purified TCD as a raw material is easily controlled, and a high-quality thermoplastic polymer with less generation of a gel component can be obtained.

[0044]

EXAMPLES Examples will be shown below, but the present invention is not limited to the examples. As a raw material, CPD is dicyclopentadiene (purity 94%, 3C
Content is a total amount of dicyclopentadiene and CPD of 10
0.1 parts by weight or less with respect to 0 parts by weight), NB is manufactured by Atochem, France (purity 99.5%, 3C content is N
0.1 parts by weight or less with respect to 100 parts by weight of B). (Example 1) In a pressure-resistant reactor equipped with a stirrer, a mixed liquid having a charged molar ratio of NB and CPD of 4 was charged in a nitrogen atmosphere. For the actual reaction, the reactor shown in FIG. 1 was used, and the reservoir tank for NB was kept at 55 ° C. In order to measure the quality of the crude TCD, an experiment was conducted by collecting the entire amount without sending the solution to the first purification tower. After keeping the reaction temperature at 200 ° C. for 4 hours, the mixture was cooled to obtain a crude TCD mixture. Table 1 shows the result of analyzing the composition of the obtained crude TCD mixture by gas chromatography. At this time, the content of 3C was 5.1 parts by weight based on 100 parts by weight of TCD.

(Examples 2 to 5) The reaction was carried out under the same conditions as in Example 1 except that the charged molar ratio of NB and CPD, the reaction time and the reaction temperature were appropriately changed. The obtained composition TCD
Table 1 shows the composition of the mixture.

(Example 6) Under the same conditions as in Example 1, the product after the reaction was sent to the purification tower without being extracted in front of the purification tower and operated. The resulting crude TCD mixture was withdrawn from the reactor at a rate of the total weight of the charged mixture × 0.2 / hour and sent to the first purification column (theoretical plate number: 7). The operating conditions of the refining tower are as follows: tower bottom temperature 145 ° C., tower bottom pressure 180 Torr
r, the temperature at the top of the column was 50 ° C., the pressure at the top of the column was 180 Torr, and the reflux ratio was 1.5. The cooling water temperature of the condenser is 4
5 ° C. Purified TCD was extracted from the bottom of the purification tower at a rate of the total weight of the charged mixture × 0.06 / hour and fed to the second purification tower (theoretical number of plates: 9). The operating conditions of the second purification tower were as follows: tower bottom temperature 160 ° C., tower bottom pressure 18 Torr,
Top temperature: 98 ° C, top pressure: 12 Torr, reflux ratio: 1
. Performed at 0. At this time, purification T
The CD was extracted at a rate of the total weight of the charged mixture × 0.05 / hour. The 3C content of the obtained purified TCD was TCD
It was 0.15 parts by weight with respect to 100 parts by weight, and the content of NB was 0.05 parts by weight or less. Obtained purified TC
Table 2 shows the composition of D.

(Example 7) Crude TC obtained in Example 1
To the NB contained in the D mixture, 20% toluene was added, and the operating conditions of the first purification column were changed to a bottom temperature of 144 ° C,
Distillation was performed under the same conditions as in Example 6 except that the pressure at the bottom of the column was 152 Torr, the temperature at the top of the column was 50 ° C., the pressure at the top of the column was 148 Torr, and the reflux ratio was 1.5. . At this time, the obtained purified TCD
And the content of 3C were almost the same as the results of Example 6. Table 2 shows the composition of the obtained high-purity TCD.

Example 8 Crude TC obtained in Example 1
Distillation was performed under the same conditions as in Example 7, except that 10% of n-hexane was added to NB contained in the D mixture. At this time, the purity of the obtained purified TCD and the content of 3C were almost the same as the results of Example 6. Table 2 shows the composition of the obtained high-purity TCD.

(Comparative Example 1) A crude TCD mixture was synthesized by a method considered to have been conventionally performed. That is, in the same reactor as in Example 1, a mixed liquid of NB and CPD with a charged molar ratio of 1 was charged, kept at a reaction temperature of 250 ° C. for 6 hours, and then cooled to obtain a crude TCD mixture. Table 1 shows the result of analyzing the composition of the obtained mixture. The content of 3C was very high.

(Comparative Examples 2 to 6) The reaction was carried out under the same conditions as in Example 1 except that the charged molar ratio of NB and CPD, the reaction time and the reaction temperature were appropriately changed. The obtained composition TCD
Table 1 shows the composition of the mixture. In each case, the content of 3C was large or the yield was low.

Comparative Example 7 Crude TC obtained in Comparative Example 2
Distillation was performed under the same conditions as in Example 6 except that the D mixture was used. The recovery of TCD from the crude TCD was 95%. At this time, the content of 3C was 1.2 parts by weight based on 100 parts by weight of TCD. Table 1 shows the composition of the purified TCD analyzed by gas chromatography.

(Comparative Example 8) In Comparative Example 7, 3
Since the C content was large, the feed rate was lowered. Using the crude TCD mixture obtained in Comparative Example 2, the same procedure as in Example 6 was carried out, but in order to make the content of 3C in the purified TCD 0.6 parts by weight with respect to 100 parts by weight of TCD. The reflux ratio was set to 3.0, and the rate of withdrawal from the top of the second purification tower had to be reduced to a rate of the total weight of the charged mixture × 0.07 / hour. The yield of the obtained purified TCD was 95%. Table 1 shows the composition of the obtained purified TCD.

(Comparative Example 9) In the method of Comparative Example 8, since the production efficiency was reduced, the amount of withdrawal from the bottom of the purification tower was increased and the TC
Distillation was performed under the same conditions as in Example 6, except that the amount of D withdrawn was a rate of the total weight of the charged mixture × 0.15 / hour.
The recovery of TCD from the obtained crude TCD was 70%. Table 1 shows the composition of the obtained purified TCD. At this time, the content of 3C in the purified TCD was 0.7 parts by weight based on 100 parts by weight of TCD. Although the withdrawal speed could be increased, the yield was greatly reduced.

(Synthesis Example 1 of Resin) 10 parts by weight of the purified TCD obtained in Example 6, 150 parts by weight of cyclohexane, 0.40 part by weight of 1-hexene as a molecular weight regulator, 0.22 part by weight of tetrabutyltin, dibutyl ether 0.4
The mixture was placed in a polymerization reactor in which 2 parts by weight and 0.52 parts by weight of tungsten hexachloride were replaced with nitrogen, and stirred at 60 ° C. for 5 minutes. Thereafter, 90 parts by weight of the purified TCD and 0.7 part of tungsten hexachloride were immediately placed in the polymerization reactor while stirring.
7 parts by weight were continuously added at a constant speed for 30 minutes, and further stirred for 30 minutes after the completion of the dropwise addition.

When the molecular weight of the obtained polymer was measured as a polyisoprene conversion value by gel permeation chromatography (GPC) using cyclohexane as a solvent, the number average molecular weight (Mn) was 19,200 and the polymerization molecular weight ( Mw) is 39,100 and the molecular weight distribution (Mw /
Mn) was 2.04. No gel was generated during and after the polymerization reaction, and the polymerizability was good. The reaction solution was treated with acetone / isopropyl alcohol (1 /
The mixture was poured into 1) to coagulate the polymer, and the precipitate was separated by filtration and dried to obtain 97 parts by weight of the polymer. The yield was 97%.

(Synthesis Example 2 of Resin)
Using CD, polymerization was carried out under the same conditions as in Resin Synthesis Example 1. First, generation of a gel was observed when 10 parts by weight of TCD was stirred at 60 ° C. with a solvent, a catalyst and the like, and generation of a large amount of insolubilized gel was confirmed at the end of the reaction. The molecular weight could not be measured because it was insoluble in organic solvents such as cyclohexane.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

According to the present invention, there is provided a crude TCD mixture which can be applied to various uses and is suitable as an intermediate material for obtaining high-purity TCD with high productivity, and a production method for obtaining the same. Further, according to the present invention, high-purity TCD can be produced with high productivity from such a crude TCD mixture. The high-purity TCD obtained by the production method of the present invention is particularly suitable as a monomer component for addition polymerization or ring-opening polymerization, easily controls the polymerization reaction, and generates less polymer gel in the produced polymer. It has the feature of. The polymer produced in this way can be a highly heat-resistant, transparent molding material, and can be used as a plastic lens, an optical information recording medium substrate, an optical device such as an information display device, a medical container, a syringe, It is suitable for various molding materials including medical device applications such as test devices.

[0060]

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a commonly used distillation apparatus.

[Explanation of symbols]

 1: Reservoir tank of norbornene 2: Reservoir tank of cyclopentadiene 3: Preheater 4: Reactor 5: First purification column 6: Second purification column 7: Piping for recovery of norbornene

Claims (4)

[Claims] 1. A mixture having a molar ratio of norbornene to cyclopentadiene of 3.4 or more is heated to a temperature of 170 ° C.
A method for producing a crude mixture of tetracyclododecene, wherein the reaction is carried out by maintaining the temperature in the range from 1 to 205 ° C for 1 to 10 hours. 2. A crude tetracyclododecene mixture comprising tetracyclododecene and norbornene,
The molar ratio of norbornene to tetracyclododecene is 2.4 or more;
2. The crude tetracyclododecene mixture obtained by the production method according to claim 1, wherein the content of the cyclopentadiene trimer relative to 0 parts by weight is 6 parts by weight or less. 3. The crude tetracyclododecene mixture according to claim 2 is distilled to obtain a cyclopentadiene trimer content of 1 part by weight or less and norbornene content of 100 parts by weight of tetracyclododecene. A method for producing a purified tetracyclododecene having an amount of 0.5 part by weight or less. 4. A tank for norbornene having a structure capable of keeping the temperature at 50 ° C. or higher, a reservoir tank for cyclopentadiene, a reactor, and at least one purification column. Pentadiene is supplied through a pipe, and the reactor is equipped with a stirrer for the content and a temperature of 170 to 2.
A heat source capable of controlling the temperature to an arbitrary temperature in the range of 05 ° C. is provided, and a purification tower is connected to the reactor via a pipe, and the purification tower is not provided at the top of at least one of the purification towers. Producing a purified tetracyclododecene characterized by being provided with a pipe capable of keeping the temperature at 50 ° C. or higher for recovering a fraction containing norbornene as a main component and supplying the fraction to a reservoir tank for norbornene; apparatus.