JP2006169215A - Vinyl ether derivative and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an unknown transparent and heat-resistant resin material that can be expected to be used for heat-resistant plastic film for liquid crystal displays, for optical purpose such as optical components and the like. <P>SOLUTION: The vinyl ether derivative represented by general formula (1) (wherein X and Y are each independently methylene, oxygen atom, sulfur atom or tellurium atom; n is 0 or a positive integer) is produced by reaction between a vinyl ether represented by general formula (2) (wherein Y is methylene, O atom, S atom or Te atom) and a cyclodiene represented by general formula (3)(wherein X is methylene, O atom, S atom or Te atom). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides a novel transparent heat-resistant resin raw material expected to be used for optical applications such as a heat-resistant plastic film for liquid crystal displays and optical parts, and a method for producing the same.

  So far, as a transparent heat-resistant resin used for optical applications, a cyclic olefin resin has been known. Reference)), addition polymers of ethylene and norbornene compounds, or ethylene and cyclodecene compounds (see Patent Document 5), addition polymers of norbornene compounds (see Patent Documents 6 to 9), and alkoxysilyl groups. Examples include addition polymers of norbornene compounds (see Patent Document 10). The heat resistance of these resins was determined by the glass transition point and was generally 165 ° C. or lower. On the other hand, the required heat resistance of optical resins has been increasing year by year, and a resin exceeding the heat resistance of these resins has been desired.

  Further, tricyclodecane vinyl ether compounds and polymers thereof are known. For example, although a homopolymer polymerization technique is described (see Non-Patent Document 1), tricyclodecane vinyl ether and cyclopentadiene are described. There are no reports on the double bond-containing cycloaliphatic ethers obtained by addition of and polymers thereof.

Japanese Patent No. 3050196 JP 60-26024 A Japanese Patent Laid-Open No. 1-132625 Japanese Patent Laid-Open No. 5-214079 JP 61-292601 A JP-A-4-63807 JP-A-8-198919 JP-A-9-508649 Japanese Patent Laid-Open No. 11-505880 JP-A-7-196736 “Journal of Polymer Science” (USA), 2004, 42, 3649.

  The present invention has been made based on such a demand, and provides a raw material for a transparent resin used for a heat-resistant optical film having a high glass transition point. This vinyl ether derivative is useful as a raw material for heat-resistant amorphous resin, and can provide an amorphous heat-resistant resin that can be used for optical applications.

  As a result of intensive studies to solve such problems, the present inventor has found that a vinyl ether derivative having a specific structure is effective as a target transparent resin material having heat resistance, and has led to the present invention.

That is, the present invention provides the following general formula (1)

（ここで、Ｘ及びＹはそれぞれ独立にメチレン基、酸素原子、硫黄原子又はテルル原子を表わし、ｎは０または正の整数を表わす。）
で表わされるビニルエーテル誘導体、及び
下記の一般式（２）

(Here, X and Y each independently represent a methylene group, oxygen atom, sulfur atom or tellurium atom, and n represents 0 or a positive integer.)
And a vinyl ether derivative represented by the following general formula (2)

（ここで、Ｙはメチレン基、酸素原子、硫黄原子又はテルル原子を表わす。）
で表わされるビニルエーテル化合物、
及び下記の一般式（３）

(Y represents a methylene group, an oxygen atom, a sulfur atom or a tellurium atom.)
Vinyl ether compounds represented by
And the following general formula (3)

（ここで、Ｘはメチレン基、酸素原子、硫黄原子又はテルル原子を表わす。）
で表わされるシクロジエン類を反応させることを特徴とする一般式（１）で表されるビニルエーテル誘導体の製造方法に関する。

(Here, X represents a methylene group, an oxygen atom, a sulfur atom or a tellurium atom.)
And a method for producing a vinyl ether derivative represented by the general formula (1).

  Hereinafter, the present invention will be described in detail.

  The vinyl ether derivative of the present invention is produced by a Diels-Alder reaction of a vinyl ether compound represented by the general formula (2) and a cyclodiene represented by the general formula (3). As the vinyl ether compound, tricyclodecane vinyl ether or the like can be used. As the cyclodienes, aliphatic cyclic dienes to which vinyl ether can be added by Diels-Alder reaction, such as cyclopentadiene and dicyclopentadiene, are used. In the above addition reaction, a target product in which n is 0 in the general formula (1) is generated by the addition reaction between vinyl ethers and cyclic dienes. In addition to this reaction, an addition reaction between cyclic dienes also occurs. Accordingly, the addition reaction further proceeds between the produced cyclic dienes and vinyl ethers, and the target product in which n is defined as 1 in the general formula (1) is also produced. By such a side reaction, a target product in which n is defined as 0 or a positive integer in the general formula (1) is obtained as a mixed composition having different n, and the vinyl ether derivative of the present invention has essentially different n. Contains several ingredients. The target component can be separated from this mixture by distillation or the like, but it is not economically advantageous to take out essentially only one component. Usually, n of 2% to 40% of the main component is present. A plurality of different components may be included.

  The charged molar ratio of cyclodiene to vinyl ether compound in this reaction is preferably 15 to 0.6, and more preferably 10 to 1.5. If this ratio is 15 or more, the yield of the product is low and there is a problem in economical efficiency.

  This reaction is preferably carried out without a solvent, but there is no limitation to adding an inert solvent to the reaction, and alkanes such as pentane, octane and nonane, and cycloalkanes such as cyclohexane, cycloheptane and cyclooctane. In addition to aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated alkanes, halogenated aromatic hydrocarbons, carboxylic acid esters, cyclic ethers, linear dialkyl ethers, and the like are exemplified.

  The reaction temperature is usually 50 to 300 ° C, preferably 100 to 250 ° C, more preferably 180 to 240 ° C. The reaction method is not limited at all, and either batch or continuous reaction can be used, but continuous reaction is preferable from the viewpoint of economy.

Specific compound names of the vinyl ether derivative of the present invention include bicyclo [2,2,1 ^1,4 ] -heptenyl tricyclo [3,2,1,0 0 ^1,7 ] -decanyl ether, bicyclo [2,2, 1 ^1,4 ] -heptenyl 1,7-epoxytricyclo [3,2,1,0 ^1,7 ] -decanyl ether, bicyclo [2,2,1 ^1,4 ] -heptenyl 1,7-thioepoxytri cyclo [3,2,1,0 ^1,7] - decanyl ether, 1,4-epoxy-bicyclo ^{[2,2,1 1,4]} - heptenyl tricyclo [3,2,1,0 ^1,7] - decanyl ether, 1,4-epoxy-bicyclo ^{[2,2,1 1,4]} - heptenyl 1,7 epoxytricyclo [3,2,1,0 ^1,7] - decanyl ether, 1,4-epoxy-bicyclo [ 2,2,1 ^1,4] - heptenyl 1,7 thio epoxytricyclo [3,2,1,0 ^1,7] - decanyl ether, 1,4-thio epoxy bicyclo ^{[2,2,1 1,4]} - heptenyl tricyclo [3,2,1,0 ^1,7] - decanyl ether, 1,4-thio epoxy bicyclo ^{[2,2,1 1,4]} - heptenyl 1,7 epoxytricyclo [3,2,1,0 ^1,7] - decanyl ether, 1,4-thio epoxy bicyclo ^{[2,2,1 1,4]} - heptenyl 1,7 thio epoxytricyclo [3,2,1,0 ^1,7] - decanyl ether Further, compounds having a structure in which the oxygen atom or sulfur atom of these compounds is substituted with a tellurium atom can also be used.

The vinyl ether derivatives of the present invention include cyclobutene, cyclopentene, cyclooctene, tricyclo [3.2.1.0 ^1,7 ] -8-decene, tricyclo [3.2.1.0 ^1,7 ] -decane-2, It can be copolymerized with cycloolefin such as 7-diene. The charging ratio of these compounds in the copolymerization is determined by the glass transition point of the polymer to be produced and is not particularly limited. However, the monomer to be copolymerized is used in a range not exceeding 50 mol% with respect to the main raw material monomer, preferably It is 30 mol% or less, More preferably, it is 20 mol% or less.

  The vinyl ether derivative of the present invention can be converted into a polymer by a metathesis ring-opening polymerization method, and known metathesis polymerization catalysts can be used. That is, at least one metal compound (I) selected from ruthenium, palladium, rhodium, iridium, platinum, tungsten, molybdenum, and a rhenium compound, and a metal compound (II) of Groups 1 to 4 in the periodic table can be used. .

Examples of tungsten, molybdenum, and rhenium compounds include halides, oxyhalides, alkoxy halides, carboxylates, acetylacetonate coordination products, oxide acetylacetonate coordination products, acetonitrile coordination products, and hydride complexes. However, halides and oxyhalides are particularly preferred because of their high polymerization activity. WCl ₆ , WOCl ₄ , MoCl ₅ , MoOCl ₃ , ReCl ₃ , WCl ₂ (OC ₆ H ₅ ) ₄ , MoO ₂ (acac) ₂ , W (OCOR) ₅ , and WCl ₆ and MoCl ₅ are particularly preferable.

  Examples of the periodic table 1-4 metal compounds include n-butyllithium, diethyl zinc, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum hydride, trimethylgallium, trimethyltin, and n-butyltin. In particular, tetramethyltin and tetraphenyltin are preferable. The ratio of the metal compounds (I) and (II) is used in the range of 1/1 to 1/30, preferably 1/2 to 1/20 as the molar ratio of metal atoms. Alcohols, aldehydes, ketones, and amines may be added as activity improvers.

  As the polymer molecular weight regulator, α-olefins such as ethylene, 1-hexene and 1-heptene are preferably used. Two or more molecular weight regulators can be used in combination. The amount of the molecular weight regulator used is 0.001 to 0.5 mol, preferably 0.002 to 0.4 mol, per mol of charged monomer, but may be appropriately changed depending on the polymerization temperature, the type of polymerization catalyst and the amount thereof. preferable.

  The polymer is preferably hydrogenated in order to improve stability and heat resistance. For hydrogenation, a conventional hydrogenation catalyst of an olefinic compound can be used. In addition to a supported catalyst in which palladium, platinum, nickel, rhodium, ruthenium, etc. are supported on carbon, silica, alumina, titania, a uniform catalyst is used. Catalysts can also be used, nickel naphthenate, nickel acetylacetonate, cobalt octenoate, titanocene dichloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) Examples include ruthenium and dichlorocarbonyltris (triphenylphosphine) ruthenium. Moreover, alkylaluminums such as triethylaluminum and alkyllithiums such as n-butyllithium can be used as a cocatalyst for these catalysts.

  The form of the catalyst used is not particularly limited, and can be used without any problem in the form of powder or particles. The amount of the hydrogenation catalyst used is preferably 0.5 to 2 ppm by weight with respect to the ring-opened polymer. The hydrogenation rate is usually 60%, preferably 90%, more preferably 98%. If the hydrogenation rate is 60% or less, there may be a problem in the thermal stability of the obtained hydrogenated product. Therefore, it is preferable to increase the hydrogenation rate as much as possible. When the hydrogenation rate exceeds 90%, the thermal stability is excellent, and when the hydrogenation rate reaches 98%, thermal stability equivalent to 100% complete hydrogenation product is exhibited.

  Hydrogen can be added by adding hydrogen to the polymer solution and reacting at normal pressure to 300 atm, preferably 3 to 200 atm. As temperature in this case, 0-200 degreeC, More preferably, 20-180 degreeC is used.

  The hydrogenation solvent is not particularly limited, and any solvent may be used as long as it is not hydrogenated under the above hydrogenation reaction conditions. From the viewpoint of economy and workability, it is preferably the same as the polymer solvent. It is preferable to use one.

  According to the present invention, it is possible to provide a raw material of a heat-resistant optical resin that can be used as a molded body such as a sheet or a film in optical applications such as liquid crystal display.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, a present Example does not restrict | limit this invention at all.

  The raw materials used in the examples and the availability are as follows.

Dicyclopentadiene: Wako Pure Chemicals Reagent grade 1 Tricyclodecane vinyl ether: TCD-VE made by Maruzen Petrochemical
Hydroquinone: Wako Pure Chemicals Reagent grade Example 1
A 300 ml glass distillation apparatus was charged with 100 ml of dicyclopentadiene, heated to 220 ° C. with a mantle heater, and the fraction having a boiling point of 39.5 ° C. of cyclopentadiene produced by thermal decomposition was cooled in a dry ice methanol bath. It separated by the technique of liquefying in the receiver.

Next, 16.26 g (0.247 mol) of cyclopentadiene, 76 g (0.37 mol) of tricyclodecane vinyl ether, and a catalytic amount of hydroquinone were charged into a 300 ml stainless steel autoclave and purged with nitrogen. The mixture was heated and reacted for 5 hours in the heated state. Thereafter, the reactor was cooled, and the content of tricyclodecane vinyl ether having a boiling point of 71 ° C. was separated from the contents under reduced pressure of 10 mmHg. Further, under this reduced pressure, tricyclodecane vinyl ether added with cyclopentadiene having a boiling point of 112 ° C. A derivative (tricyclodecanyl-tricyclodecenyl ether) (hereinafter referred to as a monomer) having, as a main component, bicyclo [2,2,1 ^1,4 ] -heptenyl tricyclo [3,2,0,1 ^{1, The} component containing 95% of ⁷ ] -decanyl ether was isolated. The structure of this compound is confirmed by using the component ratio by gas chromatograph, mass analysis by GC mass spectrum, and the strength ratio of double bond part, methine and methylene part hydrogen by ¹ H-NMR. did. Yield was 8 grams.

Example 2
32.52 g (0.494 mol) of cyclopentadiene obtained in the same manner as in Example 1, 152 g (0.78 mol) of tricyclodecane vinyl ether, and a catalytic amount of hydroquinone were charged into a 1 liter stainless steel autoclave. After purging with nitrogen, it was heated to 220 ° C. and reacted for 5 hours in the heated state. Thereafter, the reactor was cooled, and the content of tricyclodecane vinyl ether having a boiling point of 71 ° C. was separated from the contents under reduced pressure of 10 mmHg. Further, under this reduced pressure, tricyclodecane vinyl ether added with cyclopentadiene having a boiling point of 112 ° C. Derivative (tricyclodecanyl-tricyclodecenyl ether) having bicyclo [2,2,1 ^1,4 ] -heptenyl tricyclo [3,2,0,1 ^1,7 ] -decanyl ether as a main component The component containing 95% was isolated. The structure of this compound is confirmed by using the component ratio by gas chromatograph, mass analysis by GC mass spectrum, and the strength ratio of double bond part, methine and methylene part hydrogen by ¹ H-NMR. did. Yield was 20 grams.

Reference example 1
A 300 ml reactor purged with nitrogen was charged with 100 ml of cyclohexane, 8 grams of the monomer obtained in Example 1, 2 ml of a chlorobenzene solution of tungsten hexachloride at a concentration of 0.1 mol / l as a catalyst, and a concentration of 0.1 ml of diethylaluminum chloride. 0.2 ml of a mol / l chlorobenzene solution was charged, and the mixture was reacted at 60 ° C. under a nitrogen stream at a stirring speed of 100 rpm for 5 hours. The obtained reaction solution was poured into methanol to isolate the polymer. After washing several times with methanol, vacuum drying was performed at 40 ° C. for a whole day and night to obtain 7.9 g of a polymer. The weight average molecular weight of the obtained polymer in terms of polystyrene was 120,000 by GPC measurement.

  7 grams of the polymer obtained, 30 grams of toluene and 0.1 mg of ruthenium hydride triphenylphosphine complex were charged into a 100 cc stainless steel autoclave and stirred to obtain a uniform polymer solution. Subsequently, a hydrogenation reaction was performed with stirring for 4 hours at a hydrogen gas pressure of 10 MPa and a temperature of 160 ° C. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was poured into a large amount of hydrochloric acid-methanol solution to isolate the polymer. The obtained polymer was dried under reduced pressure overnight at 50 ° C. to obtain 7 g of a polymer. The polymer had a weight average molecular weight of 150,000 and a glass transition point of 171 ° C. The hydrogen conversion rate was 99.5%.

Reference example 2
In a 500 ml reactor purged with nitrogen, 180 ml of cyclohexane, 20 grams of the monomer obtained in Example 1, 4 ml of a chlorobenzene solution with a concentration of 0.1 mol / l tungsten hexachloride as a catalyst, and a concentration of 0.1 ml of diethylaluminum chloride. 0.4 ml of a mol / l chlorobenzene solution was charged, and the mixture was reacted at 60 ° C. under a nitrogen stream at a stirring speed of 100 rpm for 5 hours. The polymer solution thus obtained was charged with 0.2 mg of a ruthenium hydride triphenylphosphine complex, and further hydrogen gas was injected, and a hydrogenation reaction was performed at a pressure of 10 MPa and a temperature of 160 ° C. with stirring for 5 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was poured into a large amount of hydrochloric acid-methanol solution to isolate the polymer. The obtained polymer was dried under reduced pressure overnight at 50 ° C. to obtain 14 g of a polymer. This polymer had a weight average molecular weight of 120,000 and a glass transition point of 171 ° C. The hydrogen conversion rate was 99.4%.

Claims (2)

The following general formula (1)

(Here, X and Y each independently represent a methylene group, oxygen atom, sulfur atom or tellurium atom, and n represents 0 or a positive integer.)
Vinyl ether derivatives represented by The following general formula (2)

(Y represents a methylene group, an oxygen atom, a sulfur atom or a tellurium atom.)
Vinyl ether compounds represented by
And the following general formula (3)

(Here, X represents a methylene group, an oxygen atom, a sulfur atom or a tellurium atom.)
2. The method for producing a vinyl ether derivative according to claim 1, wherein the cyclodiene represented by the formula is reacted.