JPH0159260B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel diallyl adamantane dicarboxylate. Conventionally, diallyl phthalate, diallyl isophthalate, diethylene glycol bisallyl carbonate, and the like have been known as esterified products of unsaturated alcohols and carboxyl group-containing compounds, and all of them produce crosslinked polymers through polymerization. Diallyl phthalate and diallyl isophthalate are used as raw materials for diallyl phthalate resin, but although they have various advantages due to their aromatic nuclei, they also have disadvantages. That is, among the strength characteristics,
In particular, poor impact resistance, shrinkage during polymerization, ease of occurrence of birefringence among optical properties, high dispersion, etc. are mentioned. On the other hand, diethylene glycol bisallyl carbonate is used as a lens for eyeglasses under the name CR-39, but it has drawbacks such as a lower refractive index than conventional lens glasses and low heat resistance. The object of the present invention is to produce a crosslinked polymer having the following formula (1), which does not have the above disadvantages, by homopolymerization or copolymerization with other monomers. (R is hydrogen or a methyl group, R' is hydrogen or a methyl group, and A is an integer of (CH ₂ )n:n=0 to 4.) be. The above-mentioned compound of the present invention can be obtained by various routes, and can be produced, for example, by the following method. (1) A method in which a dicarboxylic acid ester of adamantane or dimethyladamantane is reacted with allyl alcohol in the presence of a conventional transesterification catalyst. (2) A method in which a dicarboxylic acid such as adamantane or dimethyladamantane is reacted with allyl alcohol without a catalyst or in the presence of a conventional esterification catalyst. (3) A method in which a metal salt of a dicarboxylic acid such as adamantane or dimethyladamantane is reacted with an allyl halide in the presence of a conventional tertiary amine catalyst. (4) A method in which dicarboxylic acid such as adamantane or dimethyladamantane is reacted with sodium carbonate and allyl halide using a tertiary amine or quaternary ammonium salt as a catalyst. In addition to adamantane, the adamantanes used in the above production method include dimethyladamantane. The following description of the invention will be exemplified by adamantane for simplicity. The adamantane dicarboxylic acid used in the present invention may be produced using any known method, and the method is not particularly limited. Examples of methods for carboxylating adamantane include the following. (1) Adamantane in the presence of a boron tribromide catalyst,
Bromination with bromine to give the corresponding dibrome compound.
A method in which the dibrome compound is reacted with formic acid in concentrated sulfuric acid to obtain the corresponding dicarboxylic acid. (2) Adamantane is oxidized with chromium trioxide in acetic acid to give the corresponding diol compound.
A method in which a diol compound is reacted with formic acid in concentrated sulfuric acid to obtain the corresponding dicarboxylic acid. (3) A method for obtaining the corresponding dicarboxylic acid by heating a dibrome compound with vinylidene chloride in sulfuric acid. (4) A method of obtaining the corresponding dicarboxylic acid (or diester) by reacting a dibrome compound and a diol compound with carbon monoxide in concentrated sulfuric acid and treating with water (or alcohol) after the reaction. Note that carboxylic acid salts can be obtained by saponifying carboxylic acids and esters. The compound represented by the above general formula (1) as a monomer of the present invention is, for example, Dicarboaryloxyadamantane (adamantane-dicarboxylic acid diallyl ester) Dicarboallyloxydimethyladamantane (dimethyladamantane-dicarboxylic acid diallyl ester) (Adamantane-diacetic acid diallyl ester) (Dimethyladamantane-diacetic acid diallyl ester) and the like. The reaction product of adamantane dicarboxylic acid and allyl alcohol or allyl halide obtained in the above reaction can be purified by vacuum distillation, as the case may be. The compound obtained in the present invention is a bifunctional compound and is useful as a third monomer for modifying unsaturated polyesters and the like. In addition, the polymer obtained by polymerizing this compound as a monomer component has small shrinkage during curing and does not easily cause birefringence, and has a high surface hardness, excellent impact resistance, low dispersion, and high refractive index. It is a cross-linked heat-resistant transparent resin with excellent insulation properties. Therefore,
Extremely effective as optical and electrical materials. EXAMPLES The present invention will be explained in further detail by way of Examples below. Example 1 (Production method of diallyl ester of adamantane dicarboxylic acid) a. Dibromination of adamantane; Bromination of adamantane can be carried out according to a known method using bromine in the presence of a Lewis acid. i.e. 134 g (1.0 mol) of adamantane
1600 g of non-hydrobromine in the presence of 62.8 g (0.25 mol) of boron tribromide and 0.05 g of aluminum bromide
The mixture was reacted for 2 hours at the bromine reflux temperature (65°C). After the reaction, excess bromine was distilled off under reduced pressure to obtain a carbon tetrachloride solution. In order to further remove remaining bromine,
Washing was performed using sodium thiosulfate solution and water. After that, carbon tetrachloride was distilled off to obtain a crude product,
This was recrystallized using methanol to obtain 235 g (yield: 80%). The melting point of the obtained compound is 108℃
As a result of elemental analysis, the bromine content is 54.2% (the theoretical bromine content of dibromoadamantane is 54.7%).
%), it was confirmed that it was the desired product. b Conversion of the above dibromoadamantane to dicarboxylic acid; 100 g of dibromoadamantane in 3.0 sulfuric acid
(0.34 mol) and 83 g (0.27 mol) of silver sulfate at 20°C.
Formic anhydride was added as follows (cooled in an ice bath).
After the reaction was carried out for 6.5 hours and the precipitated silver bromide was filtered off, the reaction mixture was diluted with 6 parts of ice water, and concentrated hydrochloric acid was added thereto to adjust the pH to 2 or less. Then, a crude product was precipitated, which was filtered and then recrystallized using methanol to obtain 53.3 g (yield: 70%) of adamantane dicarboxylic acid. The melting point of this compound is 270℃, and the elemental analysis value is C:
64.4%, H: 7.3%, O: 28.1% (theoretical values of adamantane-dicarboxylic acid are C: 64.3%, H:
7.1%, O: 28.6%), which was confirmed to be the desired product. c Diallyl esterification of the above adamantane-dicarboxylic acid; P-toluenesulfonic acid in 100 ml of toluene
1.52g (0.008mol), P-methoxyphenol 0.4
22.4 g (0.10 mol) of adamantane dicarboxylic acid and allyl alcohol in the presence of g (0.003 mol)
17.4 g (0.30 mol) were reacted at toluene reflux temperature (91-96° C.) using an apparatus equipped with a water separator. The reaction was terminated when the amount of water produced and distilled off reached almost the theoretical amount (16.5 hours). After the reaction, the precipitate in the reaction mixture was removed, washed with water (200 ml x 3 times), and then toluene was distilled off.
The obtained oil was treated with activated carbon and then distilled under reduced pressure to obtain 24.8 g (yield: 81%) of a fraction with a boiling point of 162° C./0.18 mmHg. The iodine value of this compound was 162 (theoretical value for diallyl ester of adamantane dicarboxylic acid 167). When the ¹ H-NMR spectrum of the product was examined, as shown in Figure 1, the methylene proton peak of the -COOC ₂ CH=CH ₂ group was at 4.5 ppm, and -
COOCH ₂ CH=CH The peaks of protons bonded to the olefin moiety of ₂ groups are 5.0-5.4ppm (4H), 5.5-
Appeared at 6.1ppm (2H). As shown in Figure 2, the IR spectrum has a peak derived from C=O at 1725 cm ^-1 and a peak derived from C=C at 1645 cm -1.
^-1 was recognized. From the above results, it was confirmed that the product was a diallyl ester of adamantane dicarboxylic acid. Example 2 (Method for producing diallyl ester of dimethyladamantane-dicarboxylic acid) a. Dibromination of dimethyladamantane; Dibromination of dimethyladamantane was performed in the same manner as the dibromination of adamantane in Example 1, and 256 g (yield 78%) A dibrominated product of dimethyladamantane was obtained. As a result of GPC analysis, the obtained compound was found to be a single product, and as a result of Br analysis, the Br content was 49.8% (the theoretical Br content of dimethyldibromoadamantane is 49.6).
%), it was confirmed that it was the desired product. b Carboxylation of the above dimethyldibromoadamantane: Dimethyldibromoadamantane was carboxylated in the same manner as the carboxylation in Example 1 to obtain 72.6 g (yield: 82%) of the target product. As a result of GPC analysis, the obtained compound was found to be a single product with an acid value of 442 (theoretical acid value of dicarboxylic acid dimethyladamantane: 447), and was confirmed to be the target compound. c Diallyl esterification of the above dimethyladamantane-dicarboxylic acid; Dimethyladamantane-dicarboxylic acid was esterified with allyl alcohol using the same recipe as in Example 1. Next, perform vacuum distillation, boiling point 165℃/0.12mm
28.3 g (yield: 85%) of Hg fraction was obtained. As a result of GPC analysis, this compound was found to be a single product, and its iodine value was 149. (Theoretical iodine value of dimethyladamantane-dicarboxylic acid diallyl ester: 153). From ^{the 1H} -NMR and IR spectra of the product, the product is dimethyladamantane-
It was confirmed that it was dicarboxylic acid diallyl ester. Example 3 From the dibromoadamantane obtained in Example 1, the corresponding diacetic acid was prepared by heating with vinylidene chloride in H ₂ SO ₄ according to a known method (Chem. Ber. Vol. 101, p. 564). The obtained adamantane-diacetic acid was esterified with allyl alcohol in the same manner as in Example 1. Next, perform vacuum distillation to obtain a fraction with a boiling point of 176℃/0.14mmHg.
13.6g was obtained. As a result of GPC analysis, this compound was found to be a single product with an iodine value of 147 (theoretical iodine value of adamantane-diacetic acid diallyl ester).
152). From the ¹ H-NMR and IR spectra of the product, it was confirmed that the product was adamantane-diacetic acid diallyl ester shown by the following formula. Test Example A monomer solution in which 4% by weight of benzoyl peroxide was dissolved in the monomers obtained in Examples 1, 2, and 3,
It was injected into a mold made up of two glass plates and a gasket, and heated at 80°C for 3 hours under _N2 gas and at 100°C for 2 hours.
After being heated and cured for 2 hours at 120℃,
The mold was released to obtain casting plates (A), (B), and (C). Obtained casting plate (A)
For (C), the refractive index, dispersion rate, light transmittance, birefringence, surface hardness, water absorption, heat distortion temperature, and polymerization shrinkage rate were measured. The results obtained are shown in Table-1.

【table】

[Table] Comparative example 4% by weight of benzoyl peroxide in the following compound
In addition, after heating to 60℃ to make it into a molten state, 2
It was poured into a mold fitted with a glass plate and a gasket and heated to 80°C under _N2 gas. Compound: Ten minutes after the start of heating, a gap began to form between the glass mold surface and the polymerizing resin. Also, 30
After a few minutes, the resin cracked and broke. As can be seen from the comparison between the test example and comparative example above,
Although the compound of the present invention requires a long time to heat cure,
Since molding shrinkage progresses gradually, it is easy to manufacture plate-shaped molded products. In addition, in test examples using the compound of the present invention, the compound of the present invention was molded using a gasket while absorbing molding shrinkage. Therefore, not only the desired molded product can be obtained reliably, but also an optically uniform molded product with low birefringence, which is one of the causes of residual strain in the molded product. On the other hand, with the compounds of the above comparative examples, it is not easy to produce molded products.

[Brief explanation of drawings]

Figure 1 shows ¹ H of adamantane dicarboxylic acid diallyl ester obtained in Example 1 of the present invention.
-NMR spectrum chart, Figure 2 shows its IR spectrum chart.

Claims (1)

[Claims] 1 General formula (1) (R is hydrogen or a methyl group, R' is hydrogen or a methyl group, A is (CH ₂ ) n: n = 0 to 4
diallyl adamantane dicarboxylate, which is an integer of