JP2563267B2 - Polycyclic alkyl (meth) acrylate and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has extremely small light scattering properties and excellent transparency,
Moreover, it has excellent physical and scientific properties such as heat resistance, thermal stability, chemical resistance, solvent resistance, and dielectric properties, and also has excellent mechanical properties such as rigidity. Therefore, especially optical fiber and optical memory. Disclosed is a novel polycyclic alkyl (meth) acrylate monomer used for producing a novel (meth) acrylate polymer useful for applications such as a disk, and a method for producing the same. The expression polycyclic alkyl (meth) acrylate described below shall refer to both alkyl acrylates and alkyl methacrylates as is customary in the art.

[Conventional technology]

Conventionally, a (meth) acrylate polymer has been proposed as an optical material such as an optical fiber and an optical memory disk, and is actually used for this purpose. However, conventionally known (meth) acrylate polymers such as polymethylmethacrylate are not sufficient in properties such as heat resistance, heat stability, chemical resistance, and solvent resistance, and these properties are excellent. The material was requested. In order to improve the properties of this (meth) acrylate-based polymer, a polycyclic alicyclic alcohol is used as the alcohol component of the (meth) acrylate monomer, that is, a polycyclic alicyclic alkyl (meth) acrylate. It has been proposed to homopolymerize or copolymerize. As prior art documents proposed so far, JP-A-58-221808, JP-A-59-136704, JP-A-59-162503, JP-A-59-172603, JP-A-59-172603, 59-176703, JP-A-59-200202, JP-A-59-214802, JP-A-60-124605, and JP-A-60-144313. Discloses various polycyclic alicyclic alkyl (meth) acrylates. All of the polymers or copolymers of polycyclic alicyclic alkyl (meth) acrylates disclosed in these prior art documents are compared with conventionally used (meth) acrylate-based polymers. Although the heat resistance and heat stability are improved, further improvement of these properties is required.

[Problems to be solved by the invention]

The present inventors have recognized that the (meth) acrylate-based polymer in the use of optical materials such as optical fibers, optical memory disks, optical cards, and plastic lenses is in the above situation, and has low light scattering property and transparency. Research and development of a (meth) acrylate-based polymer that excels in various properties such as heat resistance, chemical resistance, solvent resistance, dielectric properties, and water absorption resistance, and is also excellent in mechanical properties such as rigidity. I went. As a result, we have the following general formula: (In the formula, n is an integer of 1 to 4, ^one of X ¹ and X ² is an acryloyloxy group or a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group such as C.
_{1 to 6} alkyl groups, wherein R ¹ to R ¹² are hydrogen atoms or alkyl groups, for example, C _{1 to 6} alkyl groups). It has been found to have. Therefore, the present invention provides a novel polycyclic alkyl (meth) acrylate for synthesizing the above-mentioned polymer. The present invention also provides a method for producing the novel polycyclic alkyl (meth) acrylate.

[Means for Solving Problems and Effect of the Present Invention]

The present invention has the general formula (In the formula, n is an integer of 1 to 4, ^one of X ¹ and X ² is an acryloyloxy group or a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group, R ¹
Or R ¹² is a hydrogen atom or an alkyl group), and an acrylic ester or methacrylic ester selected from the group consisting of polycyclic alkyl acrylates and polycyclic alkyl methacrylates represented by is there.

The compound represented by the above general formula [I] has the following general formula (In the formula, n is an integer of 1 to 4, and R ¹ to R ¹² are hydrogen atoms or alkyl groups.) Formic acid is added to the unsaturated bond of the polycyclic olefin, and the polycyclic olefin After the formic acid ester is formed, the formic acid ester is hydrolyzed to give the following general formula [II]. (In the formula, one of ▲ X ¹ ₀ ▼ and ▲ X ² ₀ ▼ is a hydroxyl group, the other is a hydrogen atom or an alkyl group, and n
And R ¹ to R ¹² are all as described above), and acrylic acid or methacrylic acid, or ester-forming property of acrylic acid or methacrylic acid is further added to the polycyclic alcohol. It can be obtained by reacting a derivative such as an acrylic acid halide or a methacrylic acid halide.

The polycyclic olefin represented by the general formula [III], which is a starting material used for producing the general formula [II], is a cyclopentadiene or an alkyl-substituted compound having an alkyl group as a substituent on a ring carbon atom thereof. Cyclopentadiene and a derivative of norbornene or a derivative of norbornene having a substituent on the ring carbon atom thereof or having the carbon atoms at the 2-position and 3-position of the norbornene nucleus bonded by an alkylene group having 3 or 4 carbon atoms. It is obtained by reacting by a reaction.

 This reaction is represented by the following equation.

The reaction of polycyclic olefin represented by the general formula [III] with formic acid is usually 1 to 10 times, preferably 2 to 6 times the mixture of formic acid with respect to the polycyclic olefin, usually 50 to 200 ° C.,
It is preferably carried out at 70 to 150 ° C., particularly preferably under the condition that formic acid is refluxed. According to this reaction, the general formula [II
Formic acid is added to the double bond of the compound represented by the formula [I] to form the corresponding formic acid ester of polycyclic alcohol. The formic acid ester of the polycyclic alcohol is reacted in a water / ethanol mixed solvent with a caustic alkali such as caustic soda at a temperature from room temperature to 100 ° C. to give a compound represented by the general formula [I
A polycyclic alcohol represented by I] is obtained. In that case, the proportion of caustic used is usually 0.7 to 2, preferably 1.0 to 2, in terms of the molar ratio of the polycyclic alcohol to the formate ester.
It is in the range of 1.5.

Then, the thus-obtained compound represented by the general formula [II] is reacted with acrylic acid, methacrylic acid or an ester-forming derivative thereof to give the desired compound represented by the general formula [I]. You can get it.

When this esterification reaction is carried out by the direct esterification reaction of the polycyclic alcohol represented by the general formula [II] and (meth) acrylic acid, it is preferable to carry out under the following reaction conditions: 60 ℃ ~ 150 ℃ using a catalyst
Is carried out while removing the water generated in. Specific examples of the acidic catalyst include sulfuric acid, p-toluenesulfonic acid, sulfonic acid type ion exchange resin, hydrochloric acid and the like.

The esterification reaction can also be carried out using an ester-forming derivative of (meth) acrylic acid, and specific examples of the ester-forming derivative include acrylic acid chloride and methacrylic acid chloride. This reaction is carried out at atmospheric pressure and -10 ° C to 30 ° C for several hours. At this time, an alkali such as triethylamine or sodium hydroxide may be added as a receptor for the hydrochloric acid generated. This reaction provides the polycyclic alkyl acrylate or polycyclic methacrylate of the present invention.

Furthermore, the compound represented by the above general formula [I] has the following general formula (In the formula, n is an integer of 1 to 4 and R ¹ to R ¹² are hydrogen atoms or alkyl groups) and are obtained by addition reaction with a polycyclic olefin, acrylic acid or methacrylic acid.

The reaction of the compound represented by the general formula [III] with acrylic acid or methacrylic acid is carried out at 60 ° C. to 150 ° C. for several hours at normal pressure or under pressure using an acidic catalyst.

Specific examples of the acidic catalyst include sulfuric acid, boron trifluoride perfluoroacetic acid, polyphosphoric acid, activated clay, and acidic ion exchange resin. Also by this method, the polycyclic alkyl acrylate or polycyclic methacrylate of the present invention can be obtained.

Specific examples of the compounds of the present invention obtained by these methods are shown in Table 1.

Next, the method of the present invention will be described with reference to examples.

Example 1 Tetracyclo [4,4,0,1 ^2,5 , 1 ^7,10 ] dodecene (TD) 50 g, acrylic acid 90 g, concentrated sulfuric acid 6.1 g, hydroquinone was placed in a 500 ml glass reactor equipped with a stirrer. Put 0.5g, 8
Stirring was continued for 2 hours at a temperature of 0 ° C. At this time, the reaction rate of TD was 84%. The reaction solution was diluted with ether and washed with water, diluted alkaline water and water, then the ether was distilled off, a small amount of N, N'-di-β-naphthyl-p-phenylenediamine was added, and the mixture was distilled under reduced pressure. The product obtained is 99.5% pure.
The acrylic acid TD ester of IR, NMR and refractive index are shown in Table 2.

Example 2 The TD of Example 1 was prepared using 8-methyl-tetracyclo [4,4,0,1
^2,5, to obtain a 1 ^7,10] dodecene in the same manner as in Example 1 in place of (MTD) 99.2% acrylic acid MTD ester mixture. The data of IR, NMR, refractive index and boiling point are shown in Table 2.

Example 3 TD50g in a 500 ml glass reactor equipped with stirrer,
Methacrylic acid 100g, Amberlyst 15 (Organo Co., ion exchange resin) 1g, Hydroquinone 0.5g
The reaction was continued at 80 ° C for 5 hours. The conversion rate of TD at this time is 9
It was 9.1%. The reaction solution was passed and the solid catalyst was removed, and purification was carried out in the same manner as in Example 1 to obtain methacrylic acid TD ester having a purity of 99.6%. The data of IR, NMR, refractive index and boiling point are shown in Table 2.

Example 4 Methacrylic acid having a purity of 99.3% was used in the same manner as in Example 3 except that TD of Example 3 was replaced with MTD and Amberlyst 15 was replaced with activated clay.
An MTD ester mixture was obtained. The data of IR, NMR, refractive index and boiling point are shown in Table 2.

Example 5 50 ml of formic acid was added to a 500 ml glass reactor equipped with a stirrer.
Then, TD50g was added dropwise at 70 ° C over 30 minutes.
Then, the reaction was continued under reflux of formic acid for 4 hours. Then, after removing the formic acid by distillation under normal pressure, 200 ml of potassium hydroxide solution (KOH / water / ethanol = 1/1/3) was added and saponification was carried out at 50 ° C. for 2 hours.
By the fact that vacuum distillation after washing the reaction solution connexion purity 99.2% of 2-hydroxy-tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] was obtained dodecene the (TD-OH).

10 g of TD-OH obtained above and 50 ml of toluene were charged into a 300 ml flask equipped with a stirrer, and a 40 vol% toluene solution of acrylic acid chloride was added dropwise at 0 ° C. over 15 minutes in 15 ml. After the dropping, the temperature was raised until the acrylic chloride was refluxed over 1 hour, and the reaction was continued for 5 hours. The obtained reaction solution was washed with water, toluene was distilled off, and the residue was purified by distillation to obtain a TD ester of acrylic acid having a purity of 97.2% (TD-OH conversion 90%). The product was confirmed in the same manner as in Example 1.

[Production of polymer]

Reference Examples 1 to 4 99 parts by weight of the polycyclic alkyl (meth) acrylate produced in Examples 1 to 4, 0.05 part of n-octyl mercaptan,
A monomer mixture consisting of 0.05 parts of 2,2'-azobisisobutyronitrile was mixed in the absence of oxygen and polymerized at 80 ° C for 24 hours. 220m for measuring physical properties, 1m by hot press
Press-formed sheets with m and 2 mm thickness were prepared. This polymer was evaluated by the following methods, and the results are shown in Table 3.

(1) Intrinsic viscosity [η] Measured in toluene solution at 30 ° C (2) Glass transition temperature (Tg) Measured with TMA (manufactured by Dupon) (3) Softening point Measured with TMA (manufactured by Dupon) (4) Crystallization Degree Measured by X-ray diffraction method (5) Refractive index (n ^D ) Measured by Atsube refractometer (6) Transparency Measured according to ASTM D 1003-52 (7) Stiffness (FM) Measured according to ASTM D 790 Then measure

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Claims (3)

(57) [Claims] 1. The following general formula (In the formula, n is an integer of 1 to 4, ^one of X ¹ and X ² is an acryloyloxy group or a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group, R ¹
To R ¹² are hydrogen atoms or alkyl groups) an acrylic ester or methacrylic ester selected from the group consisting of polycyclic alkyl acrylates and polycyclic alkyl methacrylates. 2. Acrylic acid, methacrylic acid or their ester-forming derivatives and the following general formula (In the formula, n is an integer from 1 to 4, ^{one of} ▲ X ¹ ₀ ▼ and ▲ X ² ₀ ▼ is a hydroxyl group, the other is a hydrogen atom or an alkyl group, and R ¹ to R ¹² are hydrogen. Which is an atom or an alkyl group) with a polycyclic alcohol represented by any of (In the formula, n and R ¹ to R ¹² have the meanings as described above, ^one of X ¹ and X ² is an acryloyloxy group or a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group. A) A process for producing an acrylic acid ester or a methacrylic acid ester selected from the group consisting of polycyclic alkyl acrylates and polycyclic alkyl methacrylates. 3. Acrylic acid or methacrylic acid and the following general formula (Wherein, n is an integer of 1 to 4 and R ¹ to R ¹² are hydrogen atoms or alkyl groups) and a polycyclic olefin represented by formula (In the formula, n and R ¹ to R ¹² have the meanings as described above, ^one of X ¹ and X ² is an acryloyloxy group or a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group. A) A process for producing an acrylic acid ester or a methacrylic acid ester selected from the group consisting of polycyclic alkyl acrylates and polycyclic alkyl methacrylates.