JPS638355A - Polycyclic alkyl (meth)acrylate and production thereof - Google Patents

Abstract

NEW MATERIAL:A (meth)acrylic ester shown by formula I (n is 1-4; one of X<1> and X<2> is acryloyloxy, methacryloyloxy and the other is H or alkyl; R<1>-R<10> are H or alkyl). EXAMPLE:Tetracyclo[4,4,0,1<2>,<5>,1<7>,<10>]dodecyl-3-acrylate. USE:A monomer for producing (meth)acrylate polymer useful for optical fiber, optical memory disc, etc., having small light scattering, improved heat resistance, heat stability, chemical resistance, dielectric characteristics, etc., and improved properties such as rigidity, etc. PREPARATION:(Meth)acrylic acid is reacted with a compound shown by formula II (one of X<1>0 and X<2>0 is hydroxyl and the other is H, etc.) under an ester forming condition to give a compound shown by formula I.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention has extremely low light scattering, excellent transparency, and has excellent heat resistance, thermal stability, chemical resistance, solvent resistance, dielectric properties, etc. This cleaning method is used to produce novel (meth)acrylate polymers that have excellent physical and chemical properties as well as mechanical properties such as rigidity, and are therefore particularly useful for applications such as optical fibers and optical memory disks. The present invention provides a novel polycyclic alkyl (meth)acrylate monomer that can be used and a method for producing the same. The expression polycyclic alkyl (meth)acrylates described below is intended to refer to both alkyl acrylates and alkyl methacrylates as conventionally used in the art.

[Conventional technology]

BACKGROUND ART (Meth)acrylate polymers have been proposed as optical materials for optical fibers, optical memory disks, and the like, and are actually used for this purpose.

However, conventionally known (meth)acrylate polymers such as polymethyl tacrylate do not have sufficient properties such as heat resistance, heat stability, chemical resistance, and solvent resistance. Excellent materials were required.

Then, the properties of this (meth)acrylate polymer were changed@
Therefore, it has been proposed to use a polycyclic alicyclic alcohol as the alcohol component of the K (meth)acrylate monomer, that is, to homopolymerize or copolymerize a polycyclic alicyclic alkyl (meth)acrylate. ing. As a prior art document proposed so far, Japanese Patent Application Laid-Open No. 58-221808
Publication No. 136704/1983, % Publication No. 1983
-162503, JP 59-172603, JP 59-176705, IFI JP 59-176705
-200202, JP 59-214802, JP 60-124605, JP 60-1
44313, in which various polycyclic alicyclic alkyl (meth)acrylates are disclosed. All of the polycyclic alicyclic alkyl (meth)acrylate polymers or copolymers disclosed in these prior art documents have been conventionally used (
Although it has improved heat resistance and heat stability compared to meth)acrylate polymers, further improvements in these properties are required.

[Problem that the invention seeks to solve]

The present inventors have recognized that (meth)acrylate polymers used in optical materials such as optical fibers, optical memory disks, optical cards, and plastic lenses are in the above situation, and have achieved low light scattering and transparency. Research and development of (meth)azilylate polymers that have excellent properties such as heat resistance, chemical resistance, solvent resistance, dielectric properties, and thermal water absorption properties, as well as mechanical properties such as rigidity. As a result, the present inventors obtained the following general formula (where n is an integer of 1 to 4,
Either one of Xl and Xl is an acryloyloxy group or a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group, for example, an alkyl group of 01 to 6, and R1 to R1 (1 is a hydrogen atom or an alkyl group,
It has been found that polymers of polycyclic alkyl (meth)acrylates represented by, for example, C1-6 alkyl groups, have this desirable property. Therefore, the present invention provides novel polycyclic alkyl (meth)acrylates for synthesizing the above-mentioned polymers. The present invention also provides a method for producing this novel polycyclic alkyl (meth)acrylate.

[Means for solving the problems and effects of the present invention.

[Effects] As described above, the present invention is based on the following general formula (where n is an integer of 1 to 4, one of Xl and x2 is an acryloyloxy group or a methacryloyloxy group, and the other is a hydrogen atom or an alkyl Base J
, R1 to R10 are hydrogen atoms or alkyl groups. It is something to do.

The compound represented by the above general formula symbol is a polycyclic olefin compound represented by the corresponding general formula (wherein, n is an integer of 1 to 4, and R1 to R+2 represent a hydrogen atom or an alkyl group). After adding formic acid to the saturated bond to form a formic acid ester of the polycyclic olefin, the @acid ester is hydrolyzed to form the following general formula (in which either one of xo and is a hydroxyl group, the other is a hydrogen atom or an alkyl group, and n and R
1 to B10 are as described above) A polycyclic alcohol represented by , for example, by reacting acrylic acid halide, methacrylic acid halide, etc.

The polycyclic olefin represented by the general formula of the starting material used to produce this general formula is cyclo-ntadiene or an alkyl-substituted cyclopentadiene having an alkyl group as a substituent on the ring carbon atom. and norbornene or a norbornene derivative having a substituent on its ring carbon atom or in which the carbon atoms at the 2- and 3-positions of the norbornene nucleus are bonded with an alkylene group having 3 or 4 carbon atoms by a Diels-Alder reaction. You can get it.

This reaction is expressed by the following formula.

The reaction with formic acid is usually 1 to 10 times, preferably 2 to 6 times, the amount of the polycyclic olefin.
The reaction is carried out at a temperature of 00°C, preferably from 70 to 150°C, particularly preferably under conditions where formic acid is refluxed. Through this reaction, formic acid is added to the double bond of the compound represented by the general formula to produce a corresponding formic acid ester of a polycyclic alcohol. By reacting the formic acid ester of the polycyclic alcohol with a caustic alkali such as caustic soda in a mixed solvent of water and ethanol at a temperature of room temperature to 100°C, the polycyclic alcohol shown by the general formula can be obtained. . The proportion of caustic alkali to be used in this case is usually Q, 7 to 2, preferably 1 in molar ratio to the acid ester of the polycyclic alcohol.
．． It is in the range of 0 to 1.5.

Then, by reacting the compound represented by the general formula (2) obtained by the above reaction with acrylic acid, methacrylic acid, or an ester-forming derivative thereof, the desired compound represented by the general formula can be obtained.

When this esterification reaction is carried out by a direct esterification reaction between the polycyclic alcohol represented by the general formula (2) and (meth)acrylic acid, it is preferable to carry out the reaction under the following reaction conditions, that is, using an acidic catalyst at normal pressure. This is carried out after removing the water produced at temperatures between 150°C and 150°C. Specific examples of acidic catalysts include sulfuric acid, p-toluenesulfonic acid, sulfonic acid type ion exchange resins, and acidic acid.

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 1, methacrylic acid chloride, and the like. This reaction is carried out at normal pressure and from -10°C to 60°C over several hours.

An alkali such as triethylamine or sodium hydroxide may be added as a receptor for the hydrochloric acid produced at this time. This reaction yields the polycyclic alkyl acrylate or polycyclic methacrylate of the present invention.

Furthermore, the compound represented by the above general formula symbol is represented by the corresponding following general formula (wherein n is an integer of 1 to 4 and R1... and R12 is a hydrogen atom or an alkyl group). It can be obtained by addition reaction with polycyclic olefins, acrylic acid or methacrylic acid.

The reaction between the compound represented by the general formula and acrylic acid or methacrylic acid is carried out at 60° C. to 150° C. over several hours using an acidic catalyst under normal pressure or increased pressure.

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

Specific examples of the compounds of the present invention provided by these traditions are shown in Table 1.

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

Example 1 Tetracyclo (4 + 4 + 0, 12 + 5, 17,
+ 0) Dodecene ('rD) 50r, acrylic acid 90
? SL sulfuric acid 6.11F.

Hydroquinone α5? was added, and stirring was continued for 2 hours at a temperature of 80°C. At this time, the TD reaction rate was 84%.

The reaction solution was diluted with ether, washed with water, diluted alkaline water, and then water. The ether was distilled off, and a small amount of N,N'-di-
β-naphthyl-p-phenyl diamine was added and distilled under reduced pressure.

The product obtained was 995% pure acrylic acid TD ester. The mechanical strength, NMR, and refractive index are shown in Table 2.

Example 2 TD of Example 1 was converted to 8-methyl-tetracyclo(4,4,
0,12+s, 17+10] Instead of dodecene (MTD), acrylic acid MT with a purity of 992% was pressed in the same manner as in Example 1.
A D ester mixture was obtained. IR, NMR, refractive index, and boiling point data are shown in Table 2.

Example 3 A TD5 was placed in a 500-capacity glass reactor equipped with an agitator.
0? , methacrylic acid 1002, Amberlyst 15 (manufactured by Organo Co., Ltd., ion exchange resin) 12, hydroquinone C1,5? was added and the reaction was continued at 80°C for 5 hours.

The conversion rate of TD at this time was 99.1%. The reaction solution was filtered to remove the solid catalyst, and purified in the same manner as in Example 1 to obtain methacrylic acid TD ester with a purity of 996%. Engineering R1N
The data of MR, refractive index, and boiling point are shown in Table 2.

Example 4 TD in Example 6 was changed to MTD, Amberlyst 15 was changed to activated clay, the uM was the same as in Fruiting Example 3, and a methacrylic acid MTD ester mixture with a purity of 99.6% was obtained. l, NM
Data on R, refractive index, and boiling point are shown in Table 2.

Olefin Boiling Point Example 5 A 500rnt capacity glass reactor equipped with a stirrer was charged with formic acid 50-, and TD50P was added dropwise over 60 minutes at 70°C. Thereafter, the reaction was continued for 4 hours under reflux of formic acid. After that, under normal pressure @ after distilling off the acid, potassium hydroxide solution (
KOH/water/ethanol=1/i/3) 200- was added and saponified at 50°C for 2 hours. The reaction solution was washed with water and subjected to forced distillation to obtain 2-hydroxytetracycloC4,4,0,12.5.17.1] dodecene (TD-OH) with a purity of 992%.

The TD-OH (10 fl) obtained above was charged into a 300 flask equipped with a stirrer, and a 40 vol% toluene solution of acrylic acid chloride was added at 15 mA at 0°C.
It was added dropwise over 30 minutes. After dropping, the temperature was raised over 1 hour until the acrylic acid chloride refluxed, and the reaction was continued for 5 hours. The resulting reaction solution was washed with water, toluene was distilled off, and purified by distillation to obtain acrylic acid TD ester with a purity of 97.2% (TD-OH conversion rate of 90%). The product was evaluated as N in the same manner as in Example 1.

[Production of polymer]

Reference Examples 1 to 4 A monomer consisting of 99 parts by weight of the polycyclic alkyl (meth)acrylate produced in Examples 1 to 4, 05 parts of n-octylmercapmene α, and 5 parts of 2.2'-azobisisobutyronitrile CLO. The polymer mixture was mixed in the absence of oxygen, and heated at 80°C.
Polymerization occurred in 24 hours. 220℃, h to measure physical properties
Press-molded sheets of 1 and 2 rpan thickness were prepared on the day of pre-preparation. This polymer was evaluated by the following method, and the results are shown in Table 3.

(1) Intrinsic viscosity [η] Measured in toluene solution at 30℃ (
21 Glass transition temperature (Tg) TMA (measured by Dupon Co., Ltd. (3) Softening point TMA (manufactured by Dupon Co.)
(4) Crystallinity Measured by X-ray diffraction method (9 refractive index (n”)) Measured by Atsube refractometer (6
) Transparency Measured in accordance with ABTM D 1003-52 (Forceability (FM) Measured in accordance with ASTM D 790 -

Claims (1)

[Claims] 1) The following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, n is an integer from 1 to 4, and either 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^1
An acrylic ester or methacrylic ester selected from the group consisting of polycyclic alkyl acrylates and polycyclic alkyl methacrylates represented by ^0 is a hydrogen atom or an alkyl group. 2) Acrylic acid, methacrylic acid or their ester-forming derivatives, and the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, n is an integer from 1 to 4, X^1_0) and X^2
One of _0 is a hydroxyl group, the other is a hydrogen atom or an alkyl group, and R^1 to R^1^
0 is a hydrogen atom or an alkyl group) or its ester-forming derivative under ester-forming conditions, the following general formula ▲ mathematical formula, chemical formula , tables, etc.▼[I] (In the formula, n and R^1 to R^1^0 have the above meanings, and either X^1 or X^2 is an acryloyloxy group or a methacryloyloxy group, and the other is a hydrogen atom or an alkyl group. 3) Acrylic acid or methacrylic acid and the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] (In the formula, n is an integer from 1 to 4 and R^1 to R^1^
2 is a hydrogen atom or an alkyl group) is reacted with a polycyclic olefin represented by 2 under ester-forming conditions. There are the following general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [I] (Formula In the formula, n and R^1 to R^1^0 have the meanings as described above, and either 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 method for producing an acrylic ester or methacrylic ester selected from the group consisting of polycyclic alkyl acrylate and polycyclic alkyl methacrylate.