JPH05140231A - Polycyclic acrylate compound having aromatic group - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful for obtaining a polymer excellent in transparency, heat resistance, chemical resistance, rigidity, etc., and useful for an optical use by selecting a specified compound. CONSTITUTION:The objective compound is one represented by formula I wherein (p) and (q) are each 0, 1 or greater; (m) and (n) are each 0-2; R<1> to R<19> are each H, halogen, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or alkoxy; the carbon atom to which R<9> and R<10> are bonded and the carbon atom to which R<13> or R<11> is bonded may be combined with each other directly or through 1-3C alkylene; R<15> and R<12> or R<15> and R<19> may be combined with each other to form a monocyclic or polycyclic aromatic ring when n=m=0; one of X1 and X2 is a group of formula II (wherein R is H or CH3) and the other is H or alkyl.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycyclic acrylate compound having an aromatic group and a method for producing the same, and more particularly to a novel compound useful as an optical material such as an optical fiber, an optical memory disk and a plastic lens. The present invention relates to a polycyclic acrylate compound having a novel aromatic group capable of forming an acrylate polymer or a methacrylate polymer (hereinafter, acrylate and methacrylate may be abbreviated to (meth) acrylate) and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Conventionally, (meth) acrylate polymers such as PMMA (polymethylmethacrylate) are excellent in transparency and weather resistance and have little birefringence, so that they are particularly suitable for optical fibers, optical memory disks and the like. Widely used as a material.

Such conventionally used (meth) acrylate polymers have transparency, heat resistance, and
In reality, further improvement in thermal stability, chemical resistance, solvent resistance and the like is desired.

In order to meet such a demand, Japanese Patent Laid-Open No. 221808/58 and Japanese Patent Laid-Open No. 13670/1984 are available.
4, JP-A-59-162503, and JP-A-5-162503.
9-172603, JP-A-59-176703, JP-A-59-200202, JP-A-59-
No. 214802, JP-A-60-124605 and JP-A-60-144313 disclose (meth) acrylate copolymers obtained by homopolymerization or copolymerization of polycyclic alicyclic alkyl (meth) acrylates. Coalescing is proposed. In the polycyclic alicyclic alkyl (meth) acrylate polymers or copolymers disclosed in these publications, heat resistance and thermal stability are higher than those of conventionally used (meth) acrylate polymers. Has been improved.

However, as described above, the demands on the (meth) acrylate polymer have become stricter, and the heat resistance and the heat stability have been further improved, and further, the chemical resistance, the solvent resistance, and the induction property. It is desired to develop a (meth) acrylate polymer which is excellent in properties and the like and which is imparted with mechanical properties such as excellent rigidity. Therefore, a monomer for providing such a polymer is desired. Appearance is desired.

The present inventors have conducted research in view of the above-mentioned conventional techniques, and as a result, have shown that the radical-polymerizable polycyclic ring having an aromatic group represented by the general formula [I] ( By finding a (meth) acrylate compound and polymerizing the polycyclic (meth) acrylate compound having an aromatic group, it is possible to obtain a polycyclic (meth) acrylate polymer having excellent properties. He found out and completed the invention.

[0007]

It is an object of the present invention to have a very small light scattering property, excellent transparency, heat resistance, thermal stability, chemical resistance, solvent resistance, induction characteristics, and mechanical properties such as rigidity. Used to produce novel (meth) acrylate polymers that are also particularly useful in optical applications,
It is an object of the present invention to provide a polycyclic (meth) acrylate having a novel aromatic group and a method for producing the same.

[0008]

SUMMARY OF THE INVENTION A polycyclic acrylate compound having an aromatic group according to the present invention is represented by the following general formula [I];

[0009]

[Chemical 9]

(In the formula [I], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, Represents an atom or group selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, wherein the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded, or The carbon atom to which R ¹¹ is bonded may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R 11
¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and X ¹ and X
^{One of 2} is an acryloyloxy group or a methacryloyloxy group represented by the following formula [X],
The other is a hydrogen atom or an alkyl group. );

[0011]

[Chemical 10]

(Wherein R is a hydrogen atom or a methyl group). The polycyclic acrylate compound [I] having an aromatic group according to the present invention includes acrylic acid, methacrylic acid or their ester-forming derivatives, and a polycyclic alcohol represented by the following general formula [II] or It can be produced by reacting with the ester-forming derivative.

[0013]

[Chemical 11]

(In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, Represents an atom or group selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, wherein the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded, or The carbon atom to which R ¹¹ is bonded may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R 11
¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and Y ¹ and Y
^{One of 2} is a hydroxyl group and the other is a hydrogen atom or an alkyl group. ).

The polycyclic acrylate compound [I] having an aromatic group as described above is obtained by reacting acrylic acid or methacrylic acid with a polycyclic olefin represented by the following general formula [III]. Can be manufactured by.

[0016]

[Chemical 12]

(In the formula [III], p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2
And R ^{1 to} R ¹⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ⁹ and R ¹⁰ are The bonded carbon atom and the carbon atom bonded to R ¹³ or the carbon atom bonded to R ¹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, When n = m = 0, R
¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ).

[0018]

DETAILED DESCRIPTION OF THE INVENTION The polycyclic acrylate compound having an aromatic group according to the present invention will be specifically described below.

The polycyclic acrylate compound having an aromatic group according to the present invention is represented by the following general formula [I].

[0020]

[Chemical 13]

However, in the above general formula [I], p and q are 0 or integers of 1 or more, m and n are 0,
1 or 2. R ^{1 to} R ¹⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ⁹ and R ¹⁰ are bonded to each other. The carbon atom bonded to R ¹³ and the carbon atom bonded to R ¹³ or the carbon atom bonded to R ¹¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms.

When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. One of X ¹ and X ² is an acryloyloxy group or a methacryloyloxy group represented by the following formula, and the other is a hydrogen atom or an alkyl group.

[0023]

[Chemical 14]

In the present invention, as the polycyclic acrylate compound having an aromatic group represented by the above formula [I], the following compounds can be specifically exemplified. 5 (or 6) -phenyl-bicyclo [2.2.1] heptyl-2-acrylate,

[0025]

[Chemical 15]

5 (or 6) -methyl-5 (or 6) -phenyl-
Bicyclo [2.2.1] heptyl-2-acrylate (shown below is a structure having a phenyl group and a methyl group bonded to the 5-position),

[0027]

[Chemical 16]

5 (or 6) -benzyl-bicyclo [2.2.1]
Heptyl-2-acrylate,

[0029]

[Chemical 17]

5 (or 6)-(2-phenylethyl) -bicyclo [2.2.1] heptyl-2-acrylate,

[0031]

[Chemical 18]

5 (or 6) -tolyl-bicyclo [2.2.1] heptyl-2-acrylate,

[0033]

[Chemical 19]

5 (or 6)-(ethylphenyl) -bicyclo [2.2.1] heptyl-2-acrylate,

[0035]

[Chemical 20]

5 (or 6)-(isopropylphenyl) -bicyclo [2.2.1] heptyl-2-acrylate,

[0037]

[Chemical 21]

8,9-benzo-tricyclo [4.3.0.1 ^2,5 ] -decyl-3 (or 4) -acrylate,

[0039]

[Chemical formula 22]

8,9-benzo-tricyclo [4.3.0.1 ^2,5 ] -undecyl-3-acrylate,

[0041]

[Chemical formula 23]

Cyclopentadiene-acenaphthylene adduct acrylated compound,

[0043]

[Chemical formula 24]

5 (or 6)-(α-naphthyl) -bicyclo [2.
2.1] heptyl-2-acrylate,

[0045]

[Chemical 25]

5 (or 6)-(anthracenyl) -bicyclo [2.2.1] heptyl-2-acrylate,

[0047]

[Chemical formula 26]

8 (or 9) -phenyl-tetracyclo [4.4.
0.1 ^2,5 .1 ^7,10 ] dodecyl-3-acrylate,

[0049]

[Chemical 27]

[0050] 11 (or 12) - phenyl - hexacyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-4-acrylate,

[0051]

[Chemical 28]

5 (or 6) -phenyl-bicyclo [2.2.1]
Heptyl-2-methacrylate,

[0053]

[Chemical 29]

5 (or 6) -methyl 5 (or 6) -phenyl
-Bicyclo [2.2.1] heptyl-2-methacrylate (shown below is a structure in which a phenyl group and a methyl group are bonded to the 5-position),

[0055]

[Chemical 30]

5 (or 6) -benzyl-bicyclo [2.2.1]
Heptyl-2-methacrylate,

[0057]

[Chemical 31]

5 (or 6)-(2-phenylethyl) -bicyclo [2.2.1] heptyl-2-methacrylate,

[0059]

[Chemical 32]

5 (or 6) -tolyl-bicyclo [2.2.1] heptyl-2-methacrylate,

[0061]

[Chemical 33]

5 (or 6)-(ethylphenyl) -bicyclo [2.2.1] heptyl-2-methacrylate,

[0063]

[Chemical 34]

5 (or 6)-(isopropylphenyl) -bicyclo [2.2.1] heptyl-2-methacrylate,

[0065]

[Chemical 35]

8,9-benzo-tricyclo [4.3.0.1 ^2,5 ] -decyl-3 (or 4) -methacrylate,

[0067]

[Chemical 36]

8,9-benzo-tricyclo [4.3.0.1 ^2,5 ] -undecyl-3-methacrylate,

[0069]

[Chemical 37]

A compound obtained by methacrylate-forming a cyclopentadiene-acenaphthylene adduct,

[0071]

[Chemical 38]

5 (or 6)-(α-naphthyl) -bicyclo [2.
2.1] heptyl-2-methacrylate,

[0073]

[Chemical Formula 39]

5 (or 6)-(anthracenyl) -bicyclo [2.2.1] heptyl-2-methacrylate,

[0075]

[Chemical 40]

8 (or 9) -phenyl-tetracyclo [4.4.
0.1 ^2,5 .1 ^7,10 ] dodecyl-3-methacrylate,

[0077]

[Chemical 41]

[0078] 11 (or 12) - phenyl - hexacyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-4-methacrylate,

[0079]

[Chemical 42]

Having an aromatic group represented by the above general formula [I]
The polycyclic acrylate compound is
Identification by analytical methods and NMR (nuclear magnetic resonance)
You can For example, in the formula [I], p, q, m
And n are 0 and R¹~ R ¹⁹And X²Each is water
Elementary atom, X¹Is a methacryloyloxy group
5-phenyl-bicyclo [2.2.1] heptyl-2-methac
Regarding the relation, the IR spectrum shows 172
5 cm^-1And 1635 cm^-1Methacryloyl
Peaks derived from the C═O bond and C═C bond of the
700 cm^-1A peak derived from the phenyl group
Be done. Moreover, in the NMR spectrum, it is 7.1-7.3 ppm.
Peak derived from phenyl group is 4.7-5.1ppm
The peak derived from the norbornene ring is 5.5 to 6.5.
A peak derived from methacrylic acid ester was observed at ppm.
Be done.

The polycyclic acrylate compound having an aromatic group represented by the above general formula [I] according to the present invention is a novel compound. When such a polycyclic acrylate compound having an aromatic group represented by the general formula [I] is homopolymerized or copolymerized, it is excellent in transparency and heat resistance, heat stability, chemical resistance, and solvent resistance. It is possible to obtain a novel (meth) acrylate polymer which is excellent in properties and induction properties, and particularly excellent in mechanical properties such as rigidity, and which is particularly useful for optical applications.

Next, a method for producing a polycyclic acrylate compound having an aromatic group represented by the above general formula [I] will be described. The first method for producing a polycyclic acrylate compound represented by the general formula [I] according to the present invention corresponds to acrylic acid, methacrylic acid or their ester-forming derivatives, and the polycyclic acrylate compound. A polycyclic alcohol having a structure represented by the following general formula [II] or an ester-forming derivative thereof is reacted.

[0083]

[Chemical 43]

[II] In the above formula [II], p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom,
Represents an atom or group selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, R ⁹
And the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are bonded directly or via an alkylene group having 1 to 3 carbon atoms. May be. Also, when n = m = 0, R ¹⁵ and R ¹²
Alternatively, R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. One of Y ¹ and Y ² is a hydroxyl group, and the other is a hydrogen atom or an alkyl group.

The polycyclic alcohol represented by the general formula [II] or the ester-forming derivative thereof has the following general formula [III] having a structure corresponding to the alcohol compound represented by the general formula [II]. ] The formic acid can be produced by adding the formic acid to the unsaturated bond of the polycyclic olefin represented by the formula] to form the formic acid ester of the polycyclic olefin, and then hydrolyzing the formic acid ester.

[0086]

[Chemical 44]

In the above formula [III], p and q are 0.
Alternatively, it is an integer of 1 or more, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom,
A carbon atom to which R ⁹ and R ¹⁰ are bonded, which represents an atom or a group selected from the group consisting of a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group,
The carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. When n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. The method for preparing such a cyclic olefin will be described in detail later.

The reaction between the polycyclic olefin represented by the general formula [III] and formic acid is usually 1 to 10 times, preferably 2 to 10 times, the molar ratio of the polycyclic olefin and the polycyclic olefin. A mixture with 6 times the amount of formic acid, usually 50-200 ℃,
It is preferably carried out at 70 to 150 ° C., particularly preferably under the condition that formic acid is refluxed. In this reaction, the general formula [II
Formic acid is added to the double bond site of the cyclic olefin represented by [I] to form a formic acid ester of polycyclic olefin. Next, the formic acid ester of the polycyclic olefin is treated with water.
The polycyclic alcohol represented by the general formula [II] can be obtained by hydrolyzing in a mixed solvent of ethanol using a caustic soda or the like at room temperature to 100 ° C. At this time, it is desirable to use caustic in a molar ratio of usually 0.7 to 2, preferably 1.0 to 1.5 with respect to the formate ester of the polycyclic olefin.

Then, the polycyclic alcohol represented by the above general formula [II] is reacted with (i) acrylic acid or methacrylic acid, or (ii) an ester-forming derivative of acrylic acid or methacrylic acid. Then, an ester is formed to obtain a polycyclic acrylate compound represented by the general formula [I].

This esterification reaction is carried out under the following conditions. When the polycyclic alcohol represented by the general formula [II] and (i) (meth) acrylic acid are directly esterified, the alcohol and (meth) acrylic acid are added in the presence of an acidic catalyst, It is preferable to carry out the esterification reaction under the conditions of normal pressure and 60 ° C. to 150 ° C. while removing the produced water. As the acidic catalyst, specifically, sulfuric acid,
p-toluenesulfonic acid, sulfonic acid type ion exchange resin,
Examples thereof include hydrochloric acid.

When an esterification reaction is carried out using a polycyclic alcohol [II] and (ii) an ester-forming derivative of (meth) acrylic acid, ester formation of the alcohol and (meth) acrylic acid is carried out. And a sex derivative at atmospheric pressure,
It is preferable to carry out the esterification reaction at -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 generated hydrochloric acid. Specific examples of the ester-forming derivative of (meth) acrylic acid include acrylic acid halides such as acrylic acid chloride and methacrylic acid chloride, and methacrylic acid halides.

In the present invention, the polycyclic acrylate compound represented by the above general formula [I] can be further produced by the following second production method. That is, it can be obtained by addition-reacting acrylic acid or methacrylic acid with a polycyclic olefin represented by the above general formula [III] having a structure corresponding to the desired polycyclic acrylate compound.

The polycyclic olefin represented by the above general formula [III] is an aromatic olefin (or a norbornene ring carbon atom having a reactive double bond site) with a cyclopentadiene compound as described below. It can be prepared by a Diels-Alder reaction with a norbornene derivative having an aromatic group.

This reaction is specifically represented by the following formula.
In the polycyclic olefin represented by the above general formula [III], when p is 0, it is represented by the following formula.

[0095]

[Chemical 45]

In the polycyclic olefin represented by the above general formula [III], when p is 1 or more, it is represented by the following formula.

[0097]

[Chemical 46]

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 atmospheric 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 resins. The polycyclic acrylate or methacrylate having an aromatic group represented by the general formula [I] according to the present invention can be obtained by the first or second production method as described above.

[0100]

The polycyclic acrylate compound having an aromatic group represented by the general formula [I] according to the present invention is a novel compound, and the polycyclic acrylate compound is homopolymerized or copolymerized. By doing so, it has excellent physical and chemical properties such as transparency, heat resistance, thermal stability, chemical resistance, solvent resistance, and induction properties, and moreover, it has excellent mechanical properties such as rigidity (meta). Acrylate-based polymers can be formed.

[0101]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0102]

Example 1 (5 (or 6) -phenyl-bicyclo [2.2.1] heptyl-2-
Synthesis of acrylate) 5-phenyl-bicyclo [2.2.1] hept-2-ene (PBH) 5 was added to a 500 ml glass reactor equipped with a stirrer.
0 g, acrylic acid 90 g, concentrated sulfuric acid 6.1 g, and hydroquinone 0.5 g were added, and stirring was continued at a temperature of 80 ° C. for 2 hours. At this time, the reaction rate of PBH was 86%. The reaction solution was diluted with ether, 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 resulting product was a 99.3% pure acrylic acid PBH ester. The IR spectrum, NMR spectrum and MS spectrum are shown in Table 1. The NMR chart is shown in FIG.

[0103]

Example 2 (8,9-Benzo-tricyclo [4.3.0 ^1,6 .1 ^2,5 ] -decyl-3
Synthesis of (or 4) -acrylate The PBH of Example 1 was prepared from 8,9-benzo-tricyclo [4.3.0 ^1,6 .
1 ^2,5 ] -3-decene (BTCD) was used in the same manner as in Example 1 to obtain an acrylic acid MTD ester mixture having a purity of 98.9%. The IR spectrum, NMR spectrum, and MS spectrum data are shown in Table 1.

[0104]

Example 3 (5 (or 6) -phenyl-bicyclo [2.2.1] heptyl-
Synthesis of 2-methacrylate) PBH was added to a 500 ml glass reactor equipped with a stirrer.
50 g, methacrylic acid 100 g, Amberlyst 15
(Organo Co., Ltd., ion exchange resin) 1 g and hydroquinone 0.5 g were added, and the reaction was continued at 80 ° C. for 5 hours. At this time, the conversion rate of PBH was 98.6%. The reaction solution was filtered, the solid catalyst was removed, and the purification was carried out in the same manner as in Example 1 to obtain a methacrylic acid PBH ester having a purity of 99.1%. The IR spectrum, NMR spectrum, and MS spectrum data are shown in Table 1.

[0105]

Example 4 (8,9-Benzo-tricyclo [4.3.0 ^1,6 .1 ^2,5 ] -decyl-3
(Or 4) -Methacrylate Synthesis In the same manner as in Example 3, except that PBH in Example 3 was changed to BTCD and Amberlyst 15 was changed to activated clay, a methacrylic acid BTCD ester mixture having a purity of 98.8% was obtained. The IR spectrum, NMR spectrum, and MS spectrum data are shown in Table 1. The NMR chart is shown in FIG.

[0106]

Example 5 (5 (or 6) -phenyl-bicyclo [2.2.1] heptyl-2-
Synthesis of acrylate) 5 ml of formic acid was added to a 500 ml glass reactor equipped with a stirrer.
0 ml was charged and 50 g of PBH was added dropwise at 70 ° C. over 30 minutes. Then, the reaction was continued under reflux of formic acid for 4 hours. After distilling off formic acid 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. The reaction solution was washed with water and distilled under reduced pressure to obtain 2 (or 3) with a purity of 99.1%.
-Hydroxy-5-phenyl-bicyclo [2.2.1] heptane (PBH-OH) was obtained.

10 g of PBH-OH obtained above and 50 ml of toluene were charged into a 300 ml flask equipped with a stirrer,
At 0 ° C., 15 ml of a 40 vol% toluene solution of acrylic acid chloride was added dropwise over 30 minutes. The temperature was raised until the acrylic acid chloride was refluxed over 1 hour after the dropping, 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 an acrylic acid PBH ester having a purity of 97.4% (PBH-OH conversion rate 91.
%). The product was confirmed in the same manner as in Example 1. [Production of polymer]

[0108]

[Reference Examples 1 to 4] 99 parts by weight of the polycyclic alkyl (meth) acrylate prepared in Examples 1 to 4, 0.05 part of n-octyl mercaptan, and 2,2'-azobisisobutyronitrile 0.05. The monomer mixture consisting of 10 parts was mixed in the absence of oxygen and polymerized at 80 ° C. for 24 hours. In order to measure the physical properties, press-formed sheets having a thickness of 1 mm and 2 mm were prepared by hot pressing at 220 ° C. This polymer was evaluated by the following methods, and the results are shown in Table 2. (1) Intrinsic viscosity [η] Measured at 30 ° C in toluene solution (2) Glass transition point (Tg) Measured at TMA (manufactured by Dupon) (3) Softening point Measured at TMA (manufactured by Dupon) (4) Crystallization Degree X-ray diffractometry (5) Refractive index (n ^D ) Measured by Atsube refractometer (6) Transparency Measured according to ASTM D 1003-52 (7) Stiffness (FM) According to ASTM D 790 Measurement

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

[Chemical 47]

[Brief description of drawings]

FIG. 1 5 (or 6) -phenyl-synthesized in Example 1
Bicyclo [2.2.1] heptyl-2-acrylate ¹ H-N
It is an MR spectrum.

[Figure 2] synthesized in Example 4 8,9-Benzo - tricyclo [4.3.0 ^1,6 .1 ^2,5] - decyl-3 (or 4) - a ¹ H-NMR spectrum of the acrylate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihisa Toda 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A polycyclic acrylate compound having an aromatic group represented by the general formula [I]; [I] (In the formula [I], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ¹ to
R ¹⁹ independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon atom to which R ⁹ and R ¹⁰ are bonded. And the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n = m = When 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and ^one of X ¹ and X ² is represented by the following formula: It is an acryloyloxy group or a methacryloyloxy group represented by [X], and the other is a hydrogen atom or an alkyl group. ); (In the formula, R is a hydrogen atom or a methyl group.). 2. Acrylic acid, methacrylic acid or an ester-forming derivative thereof is reacted with a polycyclic alcohol represented by the following general formula [II] or an ester-forming derivative thereof to give a compound represented by the following general formula [I ] A method for producing a polycyclic acrylate compound having an aromatic group represented by: [II] (In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ¹ to
R ¹⁹ independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon atom to which R ⁹ and R ¹⁰ are bonded. And the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n = m = When 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and ^one of Y ¹ and Y ² is a hydroxyl group. And the other is a hydrogen atom or an alkyl group. ), [Chemical 4] [I] (In the formula [I], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ¹ to
R ¹⁹ independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon atom to which R ⁹ and R ¹⁰ are bonded. And the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n = m = When 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and ^one of X ¹ and X ² is represented by the following formula: It is an acryloyloxy group or a methacryloyloxy group represented by [X], and the other is a hydrogen atom or an alkyl group. ); (In the formula, R is a hydrogen atom or a methyl group.). 3. A polycyclic acrylate having an aromatic group represented by the following general formula [I] by reacting acrylic acid or methacrylic acid with a polycyclic olefin represented by the following general formula [III]. Method for producing a compound of the formula; (In the formula [III], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ¹
To R ¹⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon to which R ⁹ and R ¹⁰ are bonded. The atom and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n = m. When = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ), [Chemical 7] [I] (In the formula [I], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ¹ to
R ¹⁹ independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and the carbon atom to which R ⁹ and R ¹⁰ are bonded. And the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and n = m = When 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and ^one of X ¹ and X ² is represented by the following formula: It is an acryloyloxy group or a methacryloyloxy group represented by [X], and the other is a hydrogen atom or an alkyl group. ); (In the formula, R is a hydrogen atom or a methyl group.).