JPH07173085A - Tetracyclododecene derivative composition - Google Patents

Abstract

PURPOSE:To obtain a tetracyclododecene derivative composition containing a specific norbornene ring compound and useful for metathesis ring-opening polymerizations. CONSTITUTION:This tetracyclododecene derivative composition comprises a compound of formula II (R<9> and R<10>, R<11> and R<12> can integrally form divalent monovalent hydrocarbon groups, respectively; R<9> and R<10>, R<11> and R<12> can together form rings, respectively) containing a compound of formula I (R<1>-R<12> each is H, a 1-10C hydrocarbon, a halogen, a monovalent organic group; (n) is 1, 2) in an amount of 50-5000ppm. The compound of formula I is e.g. pentacyclo[9,2,1<1.4>,1<7.10>,0<5.13>, 0<6.11>]-2,8-pentadecadiene, and the compound of formula II is e.g. 8-methyltetracyclo[4,4,0,1<2>,<5>,1<7>,<10>]-3-dodecene. The compound of formula II is useful as a raw material for transparent resins having good optical characteristics and heat resistance, can industrially easily be produced, and is good in the reactivity of metathesis ring-opening polymerization.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a tetracyclododecene derivative composition for metathesis ring-opening polymerization containing a specific norbornene ring compound.

[0002]

2. Description of the Related Art In recent years, it has been known that the tetracyclododecene derivative having a norbol ring represented by the above chemical formula 2 is very useful as a raw material for a transparent resin having excellent optical characteristics and heat resistance. . The derivative can be obtained by carrying out a Diels-Alder type thermal addition reaction using cyclopentadiene and / or dicyclopentadiene and a dienophile compound as raw materials, and then performing purification such as distillation.

[0003]

The products produced by the Diels-Alder type thermal addition reaction include cyclohexadecene derivatives represented by the following chemical formula 3 which is an intermediate product, and cyclohexadecene derivatives, which are intermediate products. It contains trimers, tetramers, etc. of pentadienes. The trimer and tetramer of cyclopentadiene have a boiling point close to that of the target tetracyclododecene derivative, and are easily mixed when the tetracyclododecene derivative is obtained by distillation purification. In particular, among the trimers and tetramers, the diolefin compound containing two sets of olefins having a double bond in the norbornene ring represented by the above chemical formula 1 causes a cross-linking reaction during the metathesis ring-opening polymerization to cause gelation. It has been a problem to cause.

[0004]

[Chemical 3]

(In Chemical Formula 3, R ^{5 to} R ¹² are the same as those in Chemical Formula 2, respectively.)

The present invention has conducted extensive studies on the above problems, and as a result, controlling the ratio of the chemical formula 1 contained in the tetracyclododecene derivative within a specific range substantially adversely affects the metathesis ring-opening polymerization. The present invention has been completed by discovering that it is not possible and that it can be manufactured by an industrially possible method.

[0007]

The present invention provides a norbornene ring compound represented by the following chemical formula 4 in an amount of 50 to 5,000 pp.
The present invention provides a tetracyclododecene derivative composition represented by the following chemical formula 5 for metathesis ring-opening polymerization containing m.

[0008]

[Chemical 4]

[0009]

[Chemical 5]

(In the chemical formulas 4 and 5, R ^{1 to} R ¹² are each a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom or a monovalent organic group, and are the same or different. R ⁹ and R ¹⁰ or R ¹¹ and R ¹² may combine to form a divalent monovalent hydrogen group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. May be formed, and n is 1 or 2.).
Hereinafter, the present invention will be specifically described.

<Specific Tetracyclododecene Derivative> In the present invention, the tetracyclododecene derivative is represented by the following chemical formula 5.
A compound having a structure represented by the following formula, wherein R ^{1 to} R ¹²
Is a hydrogen atom, or a hydrocarbon group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group or the like, halogen atom such as chlorine or bromine, or methoxy group, ethoxy group, carboxymethyl group, carboxyethyl group It is either a monovalent organic group such as a group and may be the same or different. Further, R ⁹ and R ¹⁰ or R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group, and may be bonded to a carbon atom forming a norbornene ring by an unsaturated bond. Examples of the divalent hydrocarbon group integrally formed include alkylidene groups such as ethylidene group and propylidene group. Further, R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. The ring thus formed is
It may be a monocycle, a condensed polycycle, a polycycle having a bridge, or a ring having an unsaturated bond. Specific examples of such a ring include those shown in Chemical formula 6 below, and these rings may have a substituent such as a methyl group.

[0012]

[Chemical 6]

In the above Chemical Formula 6, the atoms with A and B respectively represent the carbon atoms to which R ^{9 to} R ¹² are bonded in the above Chemical Formula 5.

Among the compounds represented by the above chemical formula 5, preferred specific examples include, for example, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Ethyl tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
3-dodecene, 8-propyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8-butylpropyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-vinyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 5-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
7-Methyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8,8-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-Dimethyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 5,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
2,10-Dimethyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-dodecene, 11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 2,7,9-trimethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidene-9-methyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] -3-dodecene, 8-ethylidene-9-ethyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-Dodecene, 8-n-propylidenetetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] 4,10
Pentadecadiene, 9,11,12-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-9-propyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

Furthermore, 8-methyl-8-carboxymethyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-
Dodecene, 8-methyl-8-carboxyethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-Methyl-8-carboxyn-propyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Methyl-8-carboxy n-butyl tetracyclo [4.
4.0.1 ^2,5 . 1 ^{7, 10]} -3-dodecene, 8-methyl-8-carboxy sec- butyl tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxycyclohexyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxytetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8-methyl-8-carboxy t-butyl tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxyisopropyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene and the like can be mentioned.

<Specific Diolefin Compound> In the present invention, the specific diolefin compound contained in the tetracyclododecene derivative in a specific range is a compound represented by the above chemical formula 4, wherein R ^{1 to} R ⁸ Is a hydrogen atom, or a hydrocarbon group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group or the like, halogen atom such as chlorine or bromine, or methoxy group, ethoxy group, carboxymethyl group, carboxyethyl group It is either a monovalent organic group such as a group and may be the same or different. Among the formula 4 compound represented by, as specific examples thereof, pentacyclo [9.2.1 ^1,4.
1 ^7,10 . 0 ^5,13 . 0 ^6,11] -2,8-penta-octadecadienoic, heptacyclo [9.6.1 ^{1, 11.} 1 ^5,8 .
1 ^13,16 . 0 ^2,10 . 0 ^4,9 . 0 ^12,17 ] -6,14-heptadecadiene and the like.

<Tetracyclododecene derivative synthesis reaction>
In the present invention, the compound represented by the chemical formula 5 is a cyclopentadiene compound and / or a dicyclopentadiene compound, and a dienophile compound selected according to the type of a target tetracyclododecene derivative (hereinafter, these are collectively referred to as Then, it is synthesized by performing a Diels-Alder reaction type thermal addition reaction with a "raw material". The reaction temperature during the heat addition reaction is preferably in the range of 80 to 250 ° C, more preferably 130 to 220 ° C. At the time of this thermal addition reaction, by supplying the bicycloheptene derivative represented by the above chemical formula 6 which is an intermediate product of the tetracyclododecene derivative together with the above raw material, the tetracyclododecene derivative can be obtained with high selectivity. it can.

<Purification of Tetracyclododecene Derivative> The reaction solution obtained by the above synthesis reaction is the unreacted (di) cyclopentadiene, dienophile compound, and bicycloheptene which is an intermediate product in addition to the target tetracyclododecene derivative. A derivative, and a trimer of cyclopentadiene containing the compound represented by the above chemical formula 4 as a part of isomers,
It contains a tetramer and is purified to obtain a highly pure tetracyclododecene derivative. The trimer and tetramer of cyclopentadiene have a boiling point close to that of the tetracyclododecene derivative, and particularly contain two sets of olefins having a double bond in the norbornene ring represented by the above chemical formula 4, which is a part of the isomer. The diolefin compound to be used has an adverse effect on the metathesis ring-opening polymerization, so that the content thereof needs to be controlled during purification. Although the purification method varies depending on the type of the tetracyclododecene derivative, it is usually a combination of distillation. As the distillation conditions, the temperature in the distillation column is 200 ° C. or lower, preferably 180 ° C., because it easily decomposes at high temperatures.
It is preferable to perform the treatment under reduced pressure so that the temperature becomes not higher than ° C. The ratio of the diolefin compound represented by the above chemical formula 1 to be controlled and contained in the purification is 50 to 5,000 pp.
m, more preferably 100 to 2,000 ppm
Is. If it is 50 ppm or less, a load is applied during the purification by distillation, and the number of stages of the distillation column and the amount of reflux are large, which is not economically preferable, and if it is 5,000 ppm or more, as described above, crosslinking is carried out during the metathesis ring-opening polymerization. A reaction occurs, the polydisperse structure becomes remarkable, and gelation occurs. The purified tetracyclododecene derivative was treated with 2,6-di-t-butylphenol, until it was subjected to metathesis ring-opening polymerization.
2,6-di-t-butyl-4-methylphenol, 4-
It is preferable to store the product under a nitrogen blanket by containing an antioxidant such as methoxyphenol.

<Metathesis Ring-Opening Polymerization Reaction> In the metathesis ring-opening polymerization reaction using a tetracyclododecene derivative as a raw material, (a) WCl ₆ , MoCl ₅ , ReOCl ₃ or the like is usually used as a catalyst in the presence of a solvent such as toluene or xylene. At least 1 selected from compounds of W, Mo and Re of
And _{species, (b) n-C 4} H 9 Li, (C 2 H 5) 3 Al,
A mixture of at least one combination selected from compounds of Group IA and Group IIIA elements of the Deming Periodic Table such as (C ₂ H ₅ ) ₂ AlCl and LiH is used. Further, alcohols, aldehydes and the like can be preferably used as additives. Also, as a molecular weight regulator, α
-Molecular weight can be controlled by allowing olefins and the like to coexist in the reaction rate and controlling the amount thereof.

[0020]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to these. Example 1 <Production of Specific Tetracyclododecene Derivative>
8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-The following procedure was performed to obtain dodecene. Temperature 1
Internal volume 5 kept at 80 ° C and pressure of 3.5 kg / cm ² · G
In a 0 liter reactor equipped with a stirrer, methylmethacrylate, dicyclopentadiene, and 5-methyl-5-carboxymethyl-bicyclo [2.2.1]-represented by the structural formula (2) shown below are represented. 2-Heptene was fed in a molar ratio of 1: 1.2: 2.4. The amount of the reaction raw material and the bicycloheptene derivative supplied to the reactor was 4 kg / hour so that the residence time in the reactor was 8 hours.
And 4 kg / h of the reaction liquid was withdrawn from the reactor, and this reaction liquid was continuously supplied to a flash tank kept at 30 torr and 105 ° C. to recover unreacted methyl methacrylate, dicyclopentadiene and a part of the above bicycloheptene derivative. . After this, the tower diameter was 3 inches and the packing material "Sulzer Packing BX" (manufactured by Sumitomo Heavy Industries, Ltd.) was 221.
The NO. The bottom liquid from the flash tank was continuously supplied to one distillation column, and the column top pressure was 5
The unreacted methyl methacrylate, dicyclopentadiene and the above bicycloheptene derivative which were not recovered in the flash tank were recovered from the top of the column by distillation at a torr, a reflux ratio of 1, and a bottom temperature of 145 ° C., and 67 wt. % 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
The bottoms containing 3-dodecene were removed. All of the unreacted methyl methacrylate, dicyclopentadiene and the above bicycloheptene derivative recovered as described above were circulated to the reactor and subjected to the reaction again.

The bottom solution was NO. 3 with a column diameter of 3 inches and a filler (same as above) filled to a height of 119 cm.
It is continuously fed to two distillation columns, distillation is performed at a column top pressure of 2 torr, a reflux ratio of 1, and a column bottom temperature of 160 ° C. to remove heavy boiling point components from the column bottom, and 86% by weight of 8% from the column top.
Methyl-8-carboxymethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] -3-dodecene was removed distillate containing, packed more column diameter 3 inches to該留exudates filler (the same) to a height of 340 cm NO. Three
It is continuously fed to a distillation column, distillation is performed at a column top pressure of 2 torr, a reflux ratio of 10, and a column bottom temperature of 150 ° C., and a trimer fraction of cyclopentadiene is taken out from the column top, and a purity is obtained from a vapor phase at the column bottom. 99.7% by weight of 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene was taken out, condensed and introduced into a container under a nitrogen seal. The resulting 8-methyl-8-carboxymethyl tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10] -3-pentacyclo represented by the following Chemical Formula 9 structural formula in dodecene (3) [9.2.1 ^1,4. 1 ^7,10 .
0 ^5,13 . 0 ^6,11 ] -2,8-Pentadecadiene, and heptacyclo [9.6.11 ^1,11 . 1 ^5,8 . 1 ^13,16 . 0 ^2,10 .
0 ^4,9 . The proportion of 0 ^12,17 ] -6,14-heptadecadiene was 20% from the analysis by gas chromatography.
It was 0 ppm and 150 ppm, and was 350 ppm in total. The obtained tetracyclododecene derivative is
The mixture was transferred to a stirrer flask under a nitrogen blanket, and 4-methoxy-phenol as an antioxidant was added in an amount of 100 ppm corresponding to the tetracyclododecene, and the mixture was homogenized and stored.

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

<Reactivity Experiment of Metathesis Ring-Opening Polymerization> 8-Methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 80 g of ^1,7,10 ] -3-dodecene and 240 parts of toluene having a water content of 5 ppm or less.
g, 5.8 g of 1-hexene, which is a molecular weight regulator, and 1.4 g of a toluene solution of diethylaluminum chloride having a concentration of 0.96 mol / liter, which is a catalyst for metathesis polymerization, were charged in a nitrogen-stirred flask equipped with a stirrer. After heating to 80 ° C., 1.4 g of a toluene solution having a concentration of 0.05 mol / liter, which is the other catalyst for the metathesis polymerization, was charged and the polymerization reaction was carried out for 3 hours. The conversion rate of the monomer (tetracyclododecene derivative) in this polymerization reaction was 98.0% according to the gas chromatography analysis of the obtained polymerization reaction liquid, and it was a transparent solution without gel.

Comparative Example 1 In Example 1, NO. The operating conditions of the three distillation columns were changed to a reflux ratio of 1.0 (1/10 of Example 1) and a column bottom temperature of 148 ° C. to carry out distillation, and the vapor phase at the column bottom had a purity of 96.5% by weight. Methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene was obtained. In the obtained tetracyclododecene derivative,
The proportions of the compounds represented by the structural formula (3) and the structural formula (4) of the above Chemical Formula 10 are 5,100 ppm and 10%, respectively.
It was 0 ppm, and the total was 5,200 ppm. The obtained tetracyclododecene derivative was added with 4-methoxyphenol as an antioxidant and stored under a nitrogen blanket as in Example 1. 8-stored in the above
Methyl-8-carboxymethyltetracyclo [4.4.
0.1 ^2,5 . A reactivity experiment of metathesis ring-opening polymerization was carried out in the same manner as in Example 1 using ^1,7,10 ] -3-dodecene. The conversion rate of the monomer (tetracyclododecene derivative) in this polymerization reaction was 98.5%, but part of the solution was an agar-like gel.

[0028]

INDUSTRIAL APPLICABILITY According to the method of the present invention, a composition in which a specific tetracyclododecene derivative contains a specific diolefin compound in a specific range is easy to produce industrially and metathesis-opening is easy. The reactivity of ring polymerization is also good.

Claims (1)

[Claims] 1. A tetracyclododecene derivative composition represented by the following chemical formula 2 for metathesis ring-opening polymerization containing 50 to 5,000 ppm of the norbornene ring compound represented by the following chemical formula 1. [Chemical 1] [Chemical 2] (In Chemical Formula 1 and Chemical Formula 2, R ^{1 to} R ¹² are each a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom or a monovalent organic group, and they may be the same or different. R ⁹ and R ¹⁰ or R ¹¹ and R ¹² may combine to form a divalent monovalent hydrogen group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. Also, n is 1 or 2.)