JPH0761980B2 - Adamantyl mono (meth) acrylate derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel adamantyl mono (meth) acrylate derivative. For example, by using this derivative as a polymerization component, heat resistance and optical properties can be improved. An excellent polymer can be obtained.

[Prior Art] Certain adamantane unsaturated ester derivatives are already known, and for example, JP-A-60-100537 discloses diallyl adamantanedicarboxylic acid represented by the following general formula.

[Wherein R and R'are hydrogen or a methyl group, and A is (CH ₂ )
_n (n is an integer of 0 to 4)] The polymer containing diallyl adamantanedicarboxylate as a main monomer component has not only excellent heat resistance but also high hardness and excellent impact resistance. In addition, since it has many features such as a large optical refractive index, it is expected to be effectively used as various optical materials such as heat-resistant plastic materials and eyeglass lenses.

That is, for example, when attention is focused on the use as a plastic lens, a plastic lens made of an acrylic resin, a polycarbonate resin, an allyl diglycol carbonate resin, a polystyrene resin, or the like, which has been generally used, has poor heat resistance as compared with a glass lens. And, although it has a drawback that the light refractive index is small, the plastic lens containing the above-mentioned diallyl adamantanedicarboxylate as a main monomer component has not only excellent heat resistance as compared with conventional plastic lenses. However, since it has a high level of light transmittance and a large light refractive index, great expectations are placed on improving the performance of plastic lenses.

[Object of the Invention] However, the adamantane unsaturated ester derivative is a relatively new polymerizable monomer, and its manufacturing method has not been established, either, improving reactivity as a polymerizable monomer or improving physical properties as a polymer. It will be a large part of future research including the above.

The present inventors have long been conducting research with a focus on improving the performance of various plastic materials and developing new applications, but the object of the present invention is to focus particularly on the above-mentioned characteristics of the adamantane-based polymer, It is intended to provide a novel adamantane-based monomer which gives a polymer having physical and optical properties which are not inferior or superior to those of diallyl adamantane dicarboxylate.

DISCLOSURE OF THE INVENTION The adamantyl mono (meth) acrylate derivative according to the present invention has a reactive double bond 1 represented by the following general formula [I].
It is characterized in that it is composed of an adamantane derivative having an individual number.

[Wherein R ¹ is hydrogen or a lower alkyl group, R ^{2 to} R ⁴ are the same or different and each represents hydrogen, a lower alkyl group, halogen or a hydroxyl group, and at least one is a halogen or a hydroxyl group. The above-mentioned adamantane derivative of the formula [I] has a polymerized unit represented by the following formula [II] in the molecule by polymerizing it as a polymerization component or a copolymerization component, and has heat resistance, light transmittance, and photorefractive index. It gives an adamantane-based polymer having excellent rate and impact resistance.

[Wherein R ¹ is hydrogen or a lower alkyl group, R ^{2 to} R ⁴ are the same or different and each represents hydrogen, a lower alkyl group, halogen or a hydroxyl group, and at least one is a halogen or a hydroxyl group. ] In the above formulas [I] and [II], as lower alkyl,
Examples include methyl, ethyl, propyl, butyl, etc.
The most common is methyl. Also as halogen
Br, Cl, F and I are mentioned, but Br and Cl are most preferred.

Adamantyl mono (meta) represented by the above general formula [I]
Typical examples of the acrylate derivative are as follows.

The adamantyl mono (meth) acrylate derivatives as shown in the above (A) to (T) are produced, for example, by using adamantane or a lower alkyl-substituted adamantane as a starting material and undergoing the reactions as shown in the following (1) to (3). can do. As the lower alkyl-substituted adamantane, methyl-substituted adamantane will be representatively described below.

(1) Bromination of adamantane or methyl-substituted adamantane The monobromination reaction can be easily carried out, for example, by reacting anhydrous bromine with adamantane (or its methyl-substituted product) in a nitrogen atmosphere by heating, and di-, tri-, tetra-brom The chemical reaction can be effectively promoted by heating and reacting anhydrous bromine and adamantane (or a methyl-substituted product thereof) in the presence of a Lewis acid catalyst such as aluminum bromide or boron bromide. After completion of the reaction, excess bromine is distilled off, followed by extraction with carbon tetrachloride or the like and recrystallization with methanol or the like to obtain a highly pure brominated product.

(2) Hydroxylation of brominated form Brominated adamantane (or its methyl-substituted form) is reacted with concentrated sulfuric acid in the presence of silver sulfate, or hydrolyzed with hydrochloric acid to obtain adamantane under hydroxyl (or its methyl derivative). Substitute)

Since the hydroxylated product usually precipitates in the reaction system as a solid, it can be obtained as a high-purity product by filtering off after the reaction and recrystallizing with n-hexane or the like.

(3) Mono (meth) acrylic esterification of hydroxylated product The hydroxylated product is dissolved in a solvent such as toluene and heated to react with acrylic acid or methacrylic acid in the presence of a catalyst such as p-toluenesulfonic acid. The mono (meth) acrylated product can be obtained by terminating the reaction when the amount is reached. After completion of the reaction, the product is neutralized with an alkali, then the insoluble matter and the solvent are removed, and recrystallized using n-hexane or the like to obtain a highly pure hydroxyadamantyl mono (meth) acrylate (target product).

Further, when hydroxyadamantyl mono (meth) acrylate is reacted with phosphorus tribromide, the hydroxyl group is replaced with bromine, and bromoadamantyl mono (meth) acrylate (target compound) can be derived.

The adamantyl mono (meth) acrylate derivative of the present invention can be produced, for example, by the method described above, but the production method itself is not limited in the present invention. It is of course possible to apply and manufacture it, and all of them are included in the technical scope of the present invention as long as they satisfy the constituent requirements of the general formula [I].

The acryl group or methacryl group in the adamantyl mono (meth) acrylate derivative thus obtained has radical polymerization activity, and -OH and halogen introduced into the adamantane nucleus are the same as usual hydroxyl group and halogen group. Since it has reaction activity, it can be effectively used as a raw material for various organic syntheses, but the most practical one is the use as a polymerizable monomer that utilizes the polymerization activity of an acrylic group or a methacrylic group. is there. That is, this adamantyl mono (meth) acrylate derivative is a radical polymerization initiator such as acetophenones such as 2,2-diethoxyacetophenone, peroxides such as benzyl peroxide, and azo compounds such as azobisisobutyronitrile. It polymerizes easily in the presence of an agent, gives a polymer having excellent physical properties such as excellent heat resistance and impact resistance, high light transmittance, high refractive index, and small polymerization shrinkage and hardness. Incidentally, it is of course possible to accelerate the polymerization reaction by heat or light, and when the polymer is used as an optical material such as a plastic lens, a colorless and highly transparent material is adopted by adopting a photopolymerization method. Easy to obtain.

Further, this adamantyl mono (meth) acrylate derivative may be homopolymerized, or by copolymerizing two or more of the derivatives, or by copolymerizing with a copolymerizable monomer other than the derivative. A copolymer having further improved physical properties can be obtained depending on the purpose. The type of such a copolymerizable monomer is not particularly limited, but as a preferable copolymerizable monomer when the obtained copolymer is to be used as an optical material, acrylic acid, methacrylic acid and a polymerizable derivative thereof, Non-limiting examples are aromatic or aliphatic vinyl compounds such as styrene, vinylcyclohexene and vinylnaphthalene, and monofunctional or polyfunctional monomers such as alkylallyl ethers.

The method of polymerization or copolymerization is not particularly limited, and for example, bulk polymerization, emulsion polymerization, solution polymerization, ultraviolet polymerization, radiation polymerization or the like can be appropriately selected and adopted.

Adamantyl mono (meta) represented by the general formula [I]
An acrylate derivative homopolymer or copolymer has a very high melting point as compared with conventional optical plastic materials, is colorless and transparent, has a high surface hardness, and has a large optical refractive index. As it has, various lenses for glasses, contact lenses, camera lenses, etc., prisms, photosensitive materials for recording, optical fiber materials such as optical fibers, light transmission / reflection of video disks, compact disks, etc. It is extremely useful as a material for an optical member utilizing. In particular, the polymer obtained from a derivative in which a halogen has been introduced into the adamantane nucleus as a main raw material has particularly excellent optical properties (especially optical transparency and optical refractive index) and is extremely suitable as an optical material. Can be said. The heat resistance of this polymer is of course dependent on the degree of polymerization, etc., but it has a higher melting point and surface hardness than general vinyl polymers and acrylic polymers, and this melting point and hardness is a small amount of multifunctional copolymerizability. It can be further enhanced by copolymerizing the monomers. Therefore, application development as a heat resistant plastic material or a heat resistant film forming material is expected.

[Example] Example 1 (Production of 3-bromoadamantyl methacrylate) (1-1) Bromination of adamantane 2400 g (15 mol) of anhydrous bromine in 2 glass Kolben equipped with a stirrer, nitrogen inlet tube, reflux condenser and dropping funnel
220 g of adamantane with stirring and after nitrogen replacement
(1.6 mol) was added over 3 hours, and the reaction was further carried out at the reflux temperature of bromine (64 ° C) for 7 hours. After completion of the reaction, excess bromine was distilled off under reduced pressure, 200 ml of carbon tetrachloride was added, the remaining bromine was decomposed with sodium sulfite, and the organic layer was removed to obtain a crude product. The crude product was recrystallized from methanol to give 317 g of white powdery 1-bromoadamantane (melting point).
119 ° C, yield 92.1%) was obtained.

(1-2) Hydroxylation of 1-bromoadamantane 1-Brom adamantane 215 g (1 mol), 0.67 N-hydrochloric acid 4
00 ml and 450 ml of N, N'-dimethylformamide were placed in a glass Kolben 2 and stirred at the reflux temperature (105 ° C) for 1 hour. After completion of the reaction, the solid formed was collected by filtration and recrystallized from n-hexane to give 145 g of white needle-shaped 1-hydroxyadamantane [melting point: 280 ° C. (in sealed tube), yield: 95.4
%]was gotten.

(1-3) Dihydroxylation of 1-hydroxyadamantane 50 g (0.329 mol) of 1-hydroxyadamantane was placed in a glass Kolben (1), poured into 324 ml of 70% sulfuric acid and stirred at 95 ° C. for 4 hours for reaction. After completion of the reaction, the reaction product was poured into ice water and then extracted with ether. The aqueous layer was neutralized with an aqueous sodium hydroxide solution, extracted with n-butanol, the solvent was distilled off from the extract under reduced pressure, and recrystallized with n-hexane to give powdery 1,3-dihydroxyadamantane 19.5. g (yield 42.8%) was obtained. On the other hand, when the solvent is removed under reduced pressure from the ether extraction layer, adamantane
A mixture of 16 g, 1-hydroxyadamantane 8.8 g and 2-hydroxyadamantane 5.5 g was obtained.

(1-4) Production of monomethacrylate of dihydroxyadamantane In 500 ml of glass Kolben equipped with a water separator, 200 ml of toluene, 20 g (119 mmol) of 1,3-dihydroxyadamantane, 1.13 g (5.95 mmol) of p-toluenesulfonic acid, 210 mg (1.70 mmol) of p-methoxyphenol.
Then, 10.6 g (123.2 mmol) of methacrylic acid is added little by little while stirring. After completion of dropping, the mixture is heated and stirred at the toluene reflux temperature (105 to 110 ° C) to proceed the esterification reaction,
The reaction was terminated when the amount of water collected by the water separator reached the theoretical amount of dehydration (about 13 hours).

The reaction product was neutralized with a 10% aqueous sodium hydroxide solution, and the resulting precipitate was filtered off, and toluene was removed under reduced pressure. The resulting crude product was recrystallized from n-hexane to give white powdery 3-hydroxyadamantyl methacrylate 24.5
g (target product, yield 87.2%, melting point 89 ° C.) was obtained.

The ¹³ C-NMR spectrum of the product is shown in FIG. ¹³ C-NMR (CDCl ₃ , TMS standard): δ18.3 (CH, q), 31.2
(D), 34.8 (t), 39.9 (t), 43.9 (t), 49.1
(T), 70.1 (s) , 81.2 (s), 124.4 (-C = CH 2, t),
137.6 (-C = CH ₂ , s), 166.2 (C = 0, s) Further, the IR spectrum is as shown in FIG. 2, the peak derived from the hydroxyl group is at 3280 cm ^-1 , and the C of the ester group is at 0. The peak derived from 1715 cm ^-1 and the peak derived from C = C appear clearly at 1640 cm ^-1 , respectively.

(1-5) Conversion to bromine derivative In a 300 ml glass Kolben, put 23.6 g (100 mmol) of 3-hydroxyadamantyl methacrylate and 100 ml of dehydrated methylene chloride, and under a nitrogen stream, 13.5 g of phosphorus tribromide.
(49.9 mmol) was added dropwise, and the mixture was stirred at 0 ° C for 1 hr. The reaction solution was passed through a column packed with silica gel using methylene chloride as a developing agent to remove the phosphate, and the solvent was distilled off from the organic layer.
8.7 g (9 as 3-bromoadamantyl methacrylate
6.0 mmol) was obtained. As a result of gel permeation chromatography analysis, ¹ H-NMR and ¹³ C-NMR spectrum analysis, and IR spectrum analysis, this viscous liquid was confirmed to be 3-bromoadamantyl methacrylate. ¹ H-NMR and ¹³ C-NMR spectra are shown in FIGS. ¹ H-NMR (CDCl ₃ , TMS standard): δ1.7 (3H: CH ₃ ), 1.9-1.9
5 (2H), 2.2 (2H ), 2.4 (8H), 2.75 (2H, Br-CH 2 -0
~), 5.5-5.6 (1H), 6.0 (1H) ¹³ C-NMR (CDCl ₃ , TMS standard): δ 18.1 (CH ₃ , q) 32.9
(D), 34.0 (t), 39.2 (t), 47.6 (t), 52.1
(T), 62.2 (s) , 80.7 (s), 124.5 (-C = CH 2, t),
_{137.1 (-C = CH 2, s} ), 165.6 (C = 0, s) The IR spectrum is as shown in FIG. 5, 1720 cm ^-1
The peak derived from C = 0 of the ester group is 1640 cm
^The peaks derived from C = C are confirmed at ^-1 .

Example 2 (Production of 3,5-dibromoadamantyl methacrylate) (2-1) Tribromination of adamantane 800g (5mol) of anhydrous bromine in 1 glass Kolben,
20 g (75 mmol) of anhydrous aluminum bromide and 68 g (0.5 mol) of adamantane were added, and the mixture was reacted at the reflux temperature of bromine (65 ° C.) for 4 hours while stirring. After completion of the reaction, excess bromine was distilled off under reduced pressure, and 200 ml of carbon tetrachloride was added to the residue. Further, the residual bromine was decomposed with sodium sulfite (ice water), the organic layer was removed to obtain a crude product, which was recrystallized with methanol to give 136 g of white powdery 1,3,5-tribromoadamantane ( 364.6 mmol) (yield 72.9%, melting point 127.5)
C) was obtained.

(2-2) Hydroxylation of tribrom adamantane 50 g (134 mmol) of 1,3,5-tribromoadamantane, 100 ml of concentrated sulfuric acid, 30 ml of water and 83 g (266 mmol) of silver sulfate were put into a glass Kolben 1 and stirred at reflux temperature (95%).
The reaction was carried out for 5 hours. After completion of the reaction, the mixture was cooled, the precipitated silver bromide was filtered off, and then neutralized with 20% sodium hydroxide,
Evaporated to dryness. Soxhlet extraction of the residue with ethanol and removal of the solvent under reduced pressure gave 1,3,5-
10.5 g (57 mmol) of trihydroxyadamantane (yield 42.5%) was obtained.

(2-3) Production of trihydroxyadamantane monomethacrylate When 1,3,5-trihydroxyadamantane (10.0 g: 54.3 mmol) was used as a raw material and was monoesterified with methacrylic acid in the same manner as in (1-3) of Example 1, white powder was obtained.
3,5-dihydroxyadamantyl methacrylate 11.0 g
(Yield 80.4%) was obtained. In addition, the product identification is described in (1)
It was performed by IR spectrum and NMR spectrum analysis as in -3).

(2-4) Conversion to bromine derivative 3,5-dihydroxyadamantyl methacrylate (10.0
When g: 39.7 mmol was used as a raw material and monoesterification was performed with methacrylic acid in the same manner as in (1-4) of Example 1, 1,3,
14.1 g of 5-dibromoadamanryl methacrylate (yield 9
4.0%) was obtained. The target product was identified by gel permeation chromatographic analysis, ¹ H-NM, as in (1-4) above.
It was performed by R and ¹³ C-NMR and IR spectral analysis.

Example 3 (Production of 3,5,7-tribromoadamantyl methacrylate) (3-1) Bromination of tribromoadamantane 1,3,5-tribromoadamantane 6 obtained in the above (2-1)
g (16.1 mmol), 26 g (162.5 mmol) of anhydrous bromine and 4.3 g (16.1 mmol) of anhydrous aluminum bromide were sealed in a 50 ml glass tube, heated to 150 ° C. in an oil bath and reacted for 3 hours. After completion of the reaction, the mixture was cooled, 50 ml of carbon tetrachloride and 50 ml of water were added to the reaction product, sodium sulphite was further added to decompose excess bromine, and the solvent was removed from the organic layer under reduced pressure. When the obtained crude product was recrystallized from methanol, white powdery 1,3,5,7-tetrabromoadamantane 5.2 g was obtained.
(Yield 71.7%, melting point 244.5 ° C.) was obtained.

(3-2) Hydroxylation of tetrabrom adamantane Using 1,3,5,7-tetraadamantane (9.0 g: 19.9 mmol) as a starting material, hydroxylation was carried out in the same manner as in (2-2) of Example 2 to give 1,3,5 as a white powder. 1.8 g (yield 45.2%) of 7,7-tetrahydroxyadamantane was obtained.

(3-3) Production of monomethacrylate Using 2.0 g (10 mmol) of 1,3,5,7-tetrahydroxyadamantane as a raw material, monoesterification with methacrylic acid was performed according to the method described in (1-4) of Example 1,
2.2 g (yield 82.1%) of 3,5,7-trihydroxyadamantyl methacrylate in the form of white powder was obtained.

This compound was identified by IR and NMR as in (1-4) above.
It was done by spectral analysis.

(3-4) Conversion to bromine derivative 3,5,7-Trihydroxyadamantyl methacrylate 2.0
Using g (7.5 mmol) as a raw material, (1-
When the bromine conversion of the hydroxyl group was carried out according to 5), 3.1 g of 3,5,7-tribromoadamantyl methacrylate (yield 90.4
%)was gotten. The product was identified by IR and NMR spectrum analysis according to the above (1-5).

Example 4 (Production of 3,5-dimethyl-7-bromoadamantyl methacrylate) (4-1) Dibromination of dimethyladamantane 264 g (1.65 mol) of anhydrous bromine in 1 glass Kolben,
After adding 11.7 g (47 mmol) of boron bromide and 120 mg (0.45 mmol) of anhydrous aluminum bromide, 20 g (122 mmol) of 1,3-dimethyladamantane was added dropwise over 3 hours with stirring under a nitrogen atmosphere. Further, the reaction was carried out at the reflux temperature of bromine (65 ° C.) for 2 hours.

After completion of the reaction, treatment and purification were carried out according to the method shown in (1-1) of Example 1 to obtain 32.6 g (yield 83.1%) of 1,3-dimethyl-5,7-dibromoadamantane. .

(4-2) Hydroxylation of dimethyldibrom adamantane 1,3-Dimethyl-5,7-dibromoadamantane 10.0 g (31
(3 mmol) as a starting material, and hydroxylation is performed according to (2-2) of Example 2 to give 1,3-dimethyl-
3.26 g of 5,7-dihydroxyadamantane (yield 53.5%) was obtained.

(4-3) Production of monomethacrylate 3.0 g of 1,3-dimethyl-5,7-dihydroxyadamantane
(15.3 mmol was used as a starting material, and (1-4) of Example 1 was used.
The monoesterification with methacrylic acid is performed according to
3.25 g of 3,5-dimethyl-7-hydroxyadamantyl methacrylate was obtained (yield 80.5%). The compound was identified by IR and NMR spectral analyses.

(4-4) Conversion to bromine derivative When 3.0 g (11.4 mmol) of 3,5-dimethyl-7-hydroxyadamantyl methacrylate was used as a starting material and bromine substitution of the hydroxyl group was carried out in the same manner as in (1-5) of Example 1, 3,5-dimethyl-7 was obtained. -3.4 g (91.5% yield) of bromadamantyl methacrylate was obtained. Identification of this compound was carried out by IR and NMR spectral analysis as described above.

Example 5 (Production of 3-chloroadamantyl methacrylate) 3-hydroxyadamantyl methacrylate 11.8 g (50
(3.5 mmol) as a starting material, 3.5 g (16.8 mmol) of phosphorus pentachloride was added under a nitrogen stream in 50 ml of dehydrated carbon tetrachloride, and the mixture was stirred and reacted under reflux for 30 minutes. When treated in the same manner as in (1-5) of Example 1, 9.3 g (36.5 mmol) of 3-chloroadamantyl methacrylate [yield 73.0%] was obtained.
The product was identified by IR and NMR spectrum analysis.

Example 6 (Production of 3,5-dichloroadamantyl methacrylate) 3,5-dihydroxyadamantyl methacrylate 10.0 g
Using (39.7 mmol) as a starting material and adding 7.0 g (33.6 mmol) of phosphorus pentachloride in the same manner as in Example 5, the reaction was carried out to give 7.7 g (2 g of 3,5-dichloroadamantyl methacrylate).
6.6 mmol) [yield 67.0%] was obtained. The target product was identified by NMR and IR spectrum analysis as described above.

Example 7 (Production of 3,5,7-trichloroadamantyl methacrylate) 3,5,7-Trihydroxyadamantyl methacrylate 2.0
Using g (7.5 mmol) as a starting material, 2 g (9.6 mmol) of phosphorus pentachloride was added and reacted in the same manner as in Example 5 above.
3,5,7-Trichloroadamantyl methacrylate 1.2g
(3.7 mmol) [yield 49.3%] was obtained. The target product was identified by NMR and IR spectrum analysis as described above.

Application Example 1 The 3-bromoadamantyl methacrylate obtained in Example 1 is combined with two glass plates and a gasket with a monomer prepared by dissolving 0.1% by weight of 2,2-diethoxyacetophenone as a photopolymerization initiator. It was poured into a mold and irradiated with ultraviolet rays for 5 to 10 minutes using a high pressure mercury lamp to be photocured to obtain a colorless transparent polymer (A).

The physical properties and optical properties of this polymer are as shown in Table 1 below.

Application Example 2 To a mixed monomer of 30 parts by weight of 3-hydroxyadamantyl methacrylate and 70 parts by weight of adamantyl methacrylate.
Dissolve 0.1% by weight of 2,2-diethoxyacetophenone,
Thereafter, photopolymerization was carried out in the same manner as in Application Example 1 to obtain a colorless and transparent copolymer (B).

The physical properties and optical characteristics of this copolymer (B) were as shown in Table 1 below.

Application Example 3 In the same manner as in Application Example 1, a monomer obtained by dissolving 0.1% by weight of 2,2-diethoxyacetophenone as a photopolymerization initiator in the 3-chloroadamantyl methacrylate obtained in Example 5 was subjected to photocuring by ultraviolet light in the same manner as in Application Example 1. Polymer (C) was obtained.
The physical properties and optical properties of this polymer are as shown in Table 1 below.

Application Example 4 3-Bromadamantyl methacrylate obtained in Example 1
0.1% by weight to 70 parts by weight and 30 parts by weight of neopentyl glycol dimethacrylate as a copolymerization component mixed monomer
2,2-diethoxyacetophenone was dissolved and photopolymerization was carried out in the same manner as in Application Example 1 to obtain a colorless and transparent copolymer (E).

The refractive index (▲ n ^D ₂₀ ▼) of this polymer (E) was 1.5563, the dispersion rate was 50.7%, and the surface hardness was 4H.

Comparative Example 1 Adamantyl methacrylate was added as a photopolymerization initiator in an amount of 0.
The monomer in which 1% by weight of 2,2-diethoxyacetophenone was dissolved was subjected to photocuring with ultraviolet rays in the same manner as in Application Example 1 to obtain a polymer (D). The physical properties and optical properties of this polymer are as shown in Table 1 below.

The test methods for the evaluation items shown in Table 1 were as follows.

Refractive index: Measured with an Abbe refractometer using methylene iodide as the contact liquid.

Dispersion rate: Measured with an Abbe refractometer using methylene iodide as the contact liquid.

Light transmittance: ASTM-D-1003-61 Surface hardness: JIS-K-5400 Pencil hardness Softening point: Differential heat was measured using a thermal analyzer.

Water absorption rate: ASTM-D570 (100 ℃ -2hr) For reference, the physical properties and optical properties of diethylene glycol bisallyl carbonate (trade name: CR-39, manufactured by PPG Co., USA), which is the most widely used for eyeglass lenses at present, are listed below. It is also shown in Table 1.

[Effects of the Invention] The present invention is configured as described above, and the effects thereof are summarized as follows.

(1) The adamantyl mono (meth) acrylate derivative of the present invention has excellent reaction activity (particularly polymerization activity) and can be widely used as a polymerizable monomer, and also used for various other organic syntheses. be able to.

(2) The polymers and copolymers obtained by using the adamantyl mono (meth) acrylate derivative of the present invention as a monomer component are superior in heat resistance and surface hardness to conventional plastic materials, and are also impact resistant. Since it is also good, it can be widely used for various molded products, cast products, surface protection materials (coating materials), etc. as heat resistant, imperial plastic materials. Further, since the polymer of the present invention can be provided with arbitrary physical properties by changing the copolymerization composition ratio depending on the type of copolymerizable monomer to be combined, its applicable range is further expanded. For example, by using a fibrous filler such as carbon fiber or glass fiber or an inorganic filler such as silica, alumina or calcium carbonate in the polymer or copolymer of the present invention, strength, heat resistance and dimensional stability can be improved. It can also be applied as an excellent material.

(3) In particular, the polymers and copolymers containing the derivative of the present invention as polymerized units have very excellent optical properties in terms of light transmittance, refractive index, etc., and therefore, for eyeglasses, contact lenses, Lenses for camera lenses, prisms, recording photosensitive materials, optical fiber materials such as optical fibers,
It has a great practical value as an optical material for discs such as video discs and compact discs.

[Brief description of drawings]

1, 3 and 4 are NMR spectra of the adamantyl mono (meth) acrylate derivative obtained in the examples, and FIGS. 2 and 5 are IR spectra of the derivative.

Claims (1)

[Claims] 1. An adamantyl mono (meth) acrylate derivative represented by the following general formula. [Wherein R ¹ is hydrogen or a lower alkyl group, R ^{2 to} R ⁴ are the same or different and represent hydrogen, a lower alkyl group, halogen or a hydroxyl group, and at least one is a halogen or a hydroxyl group. ]