JP3259498B2 - Norbornene derivative compositions for metathesis ring-opening polymerization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a norbornene derivative composition for metathesis ring-opening polymerization.

[0002]

2. Description of the Related Art In recent years, it has been known that a norbornene derivative represented by the following general formula (3) is very useful as a raw material for a transparent resin having excellent optical properties and heat resistance. .

[0003]

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[0004] (wherein, R ¹ to R ¹² are each hydrogen atom, an halogen atom and monovalent organic radicals, which may be the same or different from each .R ⁹ and R
¹⁰ or R ¹¹ and R ¹² may be combined to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² are bonded to each other to form a cyclic structure It may be. m is an integer of 0 to 2. )

The norbornene derivative is obtained by subjecting a cyclopentadiene and / or dicyclopentadiene to a dienophile compound as a reaction raw material to a Diels-Alder type heat addition reaction, followed by purification by distillation or the like. It is. This norbornene derivative is
It is used as a raw material monomer for ring-opening polymerization using a metathesis catalyst (hereinafter, referred to as “metathesis ring-opening polymerization”).

[0006]

The above norbornene derivative is usually introduced and stored in a container such as a tank sealed with an inert gas such as nitrogen gas. However, usually, since a small amount of oxygen is also contained in the inert gas for sealing, when the storage period is long, a part of the norbornene derivative is oxidized, yellowing of the hue occurs, and good transparency is obtained. However, there is a problem that a polymer cannot be produced, and a polymerization conversion rate in a metathesis ring-opening polymerization reaction is reduced.

The present invention solves the above problems and has excellent storage stability. Therefore, even after long-term storage, there is no change in hue, and the metathesis ring-opening polymerization reaction has a sufficiently high polymerization conversion. An object of the present invention is to provide a norbornene derivative composition capable of performing the following.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present invention has shown that storage stability is greatly improved by adding a specific antioxidant to a norbornene derivative. The norbornene derivative composition has been completed by being found to polymerize at a sufficiently high polymerization conversion rate when used as a raw material for metathesis ring-opening polymerization even after long-term storage. is there.

The norbornene derivative composition for metathesis ring-opening polymerization of the present invention has a content of 10 to 10,000 ppm with a norbornene derivative represented by the following general formula (1).
And a phenolic compound represented by the following general formula (2) .

[0010]

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[0011]

[0012]

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[0013] (wherein, X, Y is the number of hydrogen atoms or carbon 1
Z is a hydrogen atom, and has 1 to 10 carbon atoms.
A hydrocarbon group having 10 or an organic group having 1 to 20 carbon atoms (excluding a hydrocarbon group having 1 to 10 carbon atoms). )

Hereinafter, the present invention will be described specifically.
Metathesis ring-opening polymerization of norbornene derivative composition of the present invention comprises a norbornene derivative represented by the above general formula (1), the one content is 10~10,000ppm
It comprises a phenolic compound represented by the general formula (2) .

<Norbornene Derivative> The norbornene derivative, which is the main component of the norbornene derivative composition of the present invention, is a compound having a structure represented by the above general formula (1) , ie, 8-methyl-8-carboxymethyl.
Letetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene.

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

<Synthesis of Norbornene Derivative> The above-mentioned norbornene derivative is obtained by using Diels using cyclopentadiene and / or dicyclopentadiene and a dienophile compound selected according to the kind of the intended norbornene derivative as reaction raw materials. -It can be synthesized by performing an alder-type heat addition reaction. The reaction temperature is preferably in the range of 80 to 250 ° C,
The temperature is more preferably 130 to 220 ° C. Also this
Under the reaction system of the synthesis, with cyclopentadiene and / or dicyclopentadiene and dienophile compound which is a reaction raw material, an intermediate product in the reaction of the synthesis
By supplying the bicycloheptene derivative represented by the general formula (4) , a tetracyclododecene derivative can be obtained with a high reaction selectivity.

[0028]

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[0029]

Further, in the above reaction, N, N-
Diethylhydroxylamine, tetrakis [methylene-
By adding a polymerization inhibitor such as [3- (3'.5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, the reaction selectivity of the target norbornene derivative can be improved.

<Purification of Norbornene Derivative> In addition to the intended norbornene derivative, unreacted cyclopentadiene and / or dicyclopentadiene, dienophile compound, intermediate product in the reaction are obtained in addition to the intended norbornene derivative. Product, and further contains a heavy component having a molecular weight larger than that of the norbornene derivative.
A highly pure norbornene derivative can be obtained. As a method of the purification treatment, a method of performing the distillation treatment a plurality of times by changing conditions such as the temperature in the distillation column is usually employed, whereby a high-purity norbornene derivative can be obtained. The distillation treatment is preferably performed under reduced pressure so that the temperature in the distillation column is 200 ° C. or lower, preferably 180 ° C. or lower. When the temperature inside the distillation column is high, the synthesized norbornene derivative may be decomposed.

<Specific antioxidant> The norbornene derivative obtained as described above
A phenolic compound having a structure represented by the general formula (2) (hereinafter, referred to as “specific antioxidant”) is contained. In the general formula (2) , X and Y each represent a hydrogen atom or a hydrocarbon group represented by an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; A hydrogen atom, a hydrocarbon group represented by an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; or a carbon group such as an alkoxy group such as a methoxy group and an ethoxy group and an alkyl ester group. Other organic groups represented by Formulas 1 to 20. the above
Specific examples of the phenolic compound represented by the general formula (2) include 2,6-di-t-butylphenol, and 2,6-di-t-butylphenol.
Examples thereof include di-t-butyl-4-methylphenol, 4-methoxyphenol, and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.

The specific antioxidant content is 10 to 1
0.00000 ppm, preferably from 20 to 1,000 ppm.
It is contained in the ratio of ppm. If it is less than 10 ppm, the storage stability over a long period of time will be insufficient.
If it exceeds 000 ppm, not only is it economically disadvantageous, but also the polymerization conversion rate in the metathesis ring-opening polymerization reaction may undesirably decrease, which is not preferable.

<Metathesis Ring-Opening Polymerization> Metathesis ring-opening polymerization is carried out using the above-described norbornene derivative as a raw material monomer to produce a polymer. This metathesis ring-opening polymerization is usually carried out in the presence of a solvent such as toluene or xylene as a catalyst by using (a) W such as WCl ₆ , MoCl ₅ or ReOCl ₃ ,
At least one selected from the compounds of Mo and Re, (b) n-C 4 H 9 Li, (C 2 H 5) 3 Al,
(C ₂ H ₅ ) ₂ AlCl, LiH and the like are used as a mixture of at least one selected from compounds of Group IA elements and Group IIIA elements of the Periodic Table of Deming. In this metathesis ring-opening polymerization, further, alcohols, aldehydes, etc. can be suitably used as additives, and the amount of α-olefins, etc., coexisting in the reaction system as a molecular weight regulator is adjusted. Thereby, the molecular weight of the target polymer can be controlled.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.

EXAMPLES [Synthesis Example] In a reactor equipped with a stirrer having an inner volume of 50 liter and maintained at a temperature of 180 ° C. and a pressure of 3.5 kg / cm ² · G, methyl methacrylate and dicyclopentadiene were added using a metering pump. And 5-methyl-5-carboxymethyl-bicyclo [2.2.1] -2-heptene, which is a bicycloheptene derivative represented by the general formula (4) , and their molar ratio is 1: 1.2: 2.4 was supplied.

[0036]

The feed rate of these three to the reactor was 4 kg / hour so that the residence time in the reactor was 8 hours. Further, as polymerization inhibitors, N, N-diethylhydroxylamine and tetrakis [methylene-3-
(3′.5′-Di-tert-butyl-4-hydroxyphenyl) propionate] methane was dissolved in methyl methacrylate and added continuously. Each addition amount was an amount corresponding to a ratio of 300 ppm to the total supply amount of the above three. The reaction solution obtained in the reactor was withdrawn from the reactor at a rate of 4 kg per hour, and the reaction solution was subjected to a pressure of 3 kg / h.
The mixture was continuously supplied to a flash tank maintained at 0 torr and a temperature of 105 ° C. to recover a part of unreacted methyl methacrylate, dicyclopentadiene and bicycloheptene derivatives present in the reaction solution. Thereafter, the bottom liquid from the flash tank was continuously fed to a distillation column having a diameter of 3 inches packed with a filler “Sulzer packing BX (manufactured by Sumitomo Heavy Industries, Ltd.)” (the same applies hereinafter) at a height of 221 cm. And distilled under the conditions of a top pressure of 5 torr, a reflux ratio of 1 and a bottom temperature of 145 ° C., and unreacted methyl methacrylate not recovered in the flash tank;
It is recovered dicyclopentadiene and the bicycloheptene derivatives from the top, of 67% by weight represented by the general formula (1) 8-methyl-8-carboxymethyl tetracyclo [4.4.0.1 ^{2, 5.} A ^bottoms containing [ ^17,10 ] -3-dodecene was recovered from the bottom of the column.

[0038]

The unreacted methyl methacrylate, dicyclopentadiene and bicycloheptene derivatives recovered as described above were all circulated to the reactor and used again. On the other hand, the bottom liquid was continuously supplied to a distillation column having a distillation column diameter of 3 inches and a packing material packed at a height of 119 cm, and distillation was performed at a top pressure of 2 torr, a reflux ratio of 1, and a bottom temperature of 160 ° C. The high boiling point component was removed from the bottom of the column, and 86% by weight of 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 .
The distillate containing the ^1,7,10 ] -3-dodecene was recovered, and the distillate was further subjected to a column diameter of 3 inches and a packing material of 340 cm.
To a distillation column packed at a height of
Distillation was carried out at torr, a reflux ratio of 10, and a bottom temperature of 150 ° C., and a tricyclopentadiene fraction was recovered from the top of the column, and 8-methyl-8-carboxymethyl having a purity of 99.7% by weight was obtained from the vapor phase at the bottom of the column. Tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene was obtained, condensed and introduced into a vessel under a nitrogen blanket.

Example 1 8-methyl-2-methylbenzene having a purity of 99.7% by weight obtained in the above synthesis example.
Ru-8-carboxymethyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-Part of dodecene under nitrogen seal
To a flask equipped with a stirrer, and
Methoxyphenol is converted to the 8-methyl-8-carboxy
Cimethyltetracyclo [4.4.0.1 ^2,5. 1^7,10]
-3- The amount corresponding to 100 ppm relative to dodecene
And then homogenize by stirring to obtain a raw material A for polymerization.
Was.

Example 2 8-methyl-8-carboxymethyltetracyclo [4.4.0.9% by weight obtained in the above synthesis example and having a purity of 99.7% by weight.
^12.5 . 1 ^7,10 ] -3-Dodecene was transferred to a flask equipped with a stirrer under a nitrogen blanket,
6-di-t-butyl-4-methylphenol is converted to 8
-Methyl-8-carboxymethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-100 against dodecene
The raw material for polymerization B was obtained by adding an amount corresponding to the ratio of ppm and stirring to homogenize.

Comparative Example 1 8-methyl-8-carboxymethyltetracyclo [4.4.0.% Having a purity of 99.7% by weight and obtained in the above synthesis example.
^12.5 . A portion of [ ^17,10 ] -3-dodecene was transferred to a flask equipped with a stirrer under a nitrogen seal, and a raw material C for polymerization was obtained without adding an antioxidant.

Comparative Example 2 8-methyl-8-carboxymethyltetracyclo [4.4.0.
^12.5 . A portion of the ^1,7,10 ] -3-dodecene was transferred to a flask equipped with a stirrer under a nitrogen seal, and hydroquinone as an antioxidant was added to the 8-methyl-8-carboxymethyltetracyclo [4.4.0]. .1 ^2,5 . 1 ^7,10 ] -3-Dodecene was added in an amount corresponding to 100 ppm, and the mixture was stirred to homogenize, thereby obtaining a raw material D for polymerization.

Comparative Example 3 8-methyl-8-carboxymethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-Dodecene was transferred to a flask equipped with a stirrer under a blanket of nitrogen, and 4-dodecene was used as an antioxidant.
Methoxyphenol is converted to the 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-Dodecene was added in an amount corresponding to a ratio of 12,000 ppm, and the mixture was stirred to be homogenized.
I got

With respect to the raw materials for polymerization obtained in Examples 1 and 2 and Comparative Examples 1 to 3, the hue was evaluated and the polymerization conversion in the metathesis ring-opening polymerization reaction was measured. Hereinafter, a specific description will be given.

<Test> Evaluation of Hue The raw material A for polymerization obtained in Example 1 was evaluated by visually observing the hue. Table 1 shows the results. -Metathesis ring-opening polymerization 80 g of the raw material for polymerization A, 240 g of toluene containing 5 ppm of water, and 1- being a molecular weight regulator
5.8 g of hexene and 1.4 g of a toluene solution of diethylaluminum chloride having a concentration of 0.96 mol / l.
Was charged into a flask equipped with a stirrer sealed with nitrogen, heated to 80 ° C., and charged with 1.4 g of a toluene solution of tungsten hexachloride having a concentration of 0.05 mol / l for 3 hours for metathesis ring-opening polymerization. Was done. -Measurement of polymerization conversion The gas chromatography analysis was performed on the polymerization reaction solution obtained by the above-mentioned metathesis ring-opening polymerization, and 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 in the metathesis ring-opening polymerization reaction was performed. ^2,5 . The polymerization conversion of ^1,7,10 ] -3-dodecene was measured. Table 1 shows the results.

<Test> Storage of Polymerization Raw Material The polymerization raw material A obtained in Example 1 was stored in a constant temperature room at 50 ° C. for 30 days. -Hue evaluation About this raw material A for polymerization, hue evaluation was performed like the test. Table 1 shows the results. -Metathesis ring-opening polymerization Using this raw material A for polymerization, metathesis ring-opening polymerization was carried out in the same manner as in the test. -Measurement of polymerization conversion The polymerization reaction solution obtained by the metathesis ring-opening polymerization was analyzed in the same manner as in the test, and the polymerization conversion was measured. Table 1 shows the results.

<Test to Test> Each of the raw materials for polymerization B to E was stored in the same manner as in the test.
Thereafter, the hue was evaluated, and the metathesis ring-opening polymerization and the polymerization conversion were measured. Table 1 shows the results.

[0049]

[Table 1]

As is clear from the above results, the norbornene derivative compositions of the present invention according to Examples 1 and 2 containing a specific antioxidant at a specific ratio are 30%.
No change in hue was observed before and after storage for a period of days, and when the norbornene derivative composition was used as a raw material for metathesis ring-opening polymerization after storage for 30 days, the polymerization conversion in the metathesis ring-opening polymerization reaction was also observed. Rate 9
It is sufficiently high at about 8.0%, and does not cause a decrease in polymerization conversion unlike the case where another antioxidant is used.

[0051]

The norbornene derivative composition for metathesis ring-opening polymerization of the present invention contains a specific antioxidant in a specific ratio, and thus has excellent storage stability. Even after the elapse of the period, the polymerization conversion in the metathesis ring-opening polymerization reaction is sufficiently high, so that long-term storage is possible. Therefore, it can be suitably used as a raw material for a transparent resin having excellent optical properties.

Continuation of front page (56) References JP-A-1-149738 (JP, A) JP-A-5-262822 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61 / 06-61/08 C08L 65/00

Claims (1)

(57) [Claims] 1. A composition comprising a norbornene derivative represented by the following general formula (1) and a phenolic compound represented by the following general formula (2) having a content of 10 to 10,000 ppm. Norbornene derivative composition for metathesis ring-opening polymerization. Embedded image Embedded image (In the formula , X and Y are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Z is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an organic group having 1 to 20 carbon atoms (1 carbon atom) Excluding hydrocarbon groups of 10 to 10.)