JPH05170702A - New bisphenol derivative and its production - Google Patents

Abstract

PURPOSE:To provide a new bisphenol derivative slowly polymerizing by (meth) allyl polymerization to facilitate the control of cast polymerization and giving a polymer having low strain, high transparency and refractive index and low dispersion and useful as an optical resin. CONSTITUTION:The compound of formula I [R is H or methyl; A is 1-2C alkylene; B is single bond, O, S, CR<1>R<2>, group of formula II SO2 or SO (R<1> and R<2> are H, methyl, ethyl, phenyl or diphenyl; R<3> is 3-12C alkylene, cycloalkylene or diphenylene); X is methyl or halogen other than F; (1) and (m) are 0-4], e.g. 4,4'-bis(allyloxycarbonylmethoxy)diphenyl ether. The compound can be produced by reacting a bisphenol derivative of formula III with an ester derivative of formula IV (Y is halogen other than F) (e.g. allyl chloroacetate) in the presence of a base.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel bisphenol derivative and a method for producing the same, and more particularly to a bisphenol derivative useful as a monomer for plastic lenses, for example.

[0002]

2. Description of the Related Art Conventionally, inorganic glass products have been widely used as lenses for vision correction or for optical equipment, but in recent years, plastic lenses have been gradually increasing in demand. There is. The plastic lens is superior to the inorganic glass in terms of its lightness, safety (impact resistance), workability, and economical efficiency, but it is a general-purpose product, diethylene glycol bisallyl carbonate.
(CR-39) has a low refractive index of n _D = 1.50, the edge thickness (edge thickness) becomes thicker when used as a lens for myopia correction, and the central thickness becomes thicker when used as a lens for hyperopia correction, Not only is it inferior in fashionability, but it also has the drawback that the original characteristics of lightness cannot be utilized. In order to solve the problem of low refractive index which is the only demerit of CR-39, polycarbonate and polystyrene type high refractive index resin (n _D = about 1.60) have been proposed. Moldability is poor, strain is likely to occur, and it is optically unstable, and polystyrene is apt to cause birefringence, and has a weather resistance problem.

Recently, a large number of monomers for high refractive index lenses have been proposed, which are composed of a compound having a bisphenol skeleton as one component, and most of them have been disclosed, for example, in Japanese Examined Patent Publication No. 58-1752.
Like (7), the main component is (meth) acrylate.
The (meth) acrylate has a drawback that the polymerization and the cross-linking reaction proceed rapidly as compared with the allyl compound, and it is difficult to control the cast polymerization.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that (meta)
The inventors have found that a bisphenol derivative having an allyl ester residue is suitable as a raw material for a high refractive index resin, and completed the present invention. That is, the present invention has the following general formula [I]

[0005]

[Chemical 9]

(Wherein R represents a hydrogen atom or a methyl group, A represents a linear or branched alkylene group having 1 to 2 carbon atoms, and B represents

[0007]

[Chemical 10]

A bifunctional group represented by the following formulas, wherein R ¹ , R
² each represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group or a diphenyl group, which may be the same or different, and R ³ is an alkylene group having 3 to 12 carbon atoms, a cycloalkylene group, or a diphenylene group. Indicates. X is a methyl group or a halogen atom excluding fluorine, and l and m each represent an integer of 0 to 4. ) Related to the bisphenol derivative (hereinafter referred to as compound [I]) and a method for producing the same.

The compound [I] will be described in more detail. Examples of the alkylene group represented by A in the formula include methylene, ethylene and methylmethylene. When A is an alkylene group having 3 or more carbon atoms, the decrease in the refractive index of the compound [I] is gradually increased, which is not preferable. Also, in the formula, B is

[0010]

[Chemical 11]

A bifunctional group represented by the following formulas, wherein R ¹ , R
² each represents a hydrogen atom, a methyl group, an ethyl group, a phenyl group or a diphenyl group, which may be the same or different, and R ³ is an alkylene group having 3 to 12 carbon atoms, a cycloalkylene group, or a diphenylene group. Indicates. A specific example of B in this case is shown in Chemical formula 12.

[0012]

[Chemical 12]

In the formula, R represents a hydrogen atom or a methyl group, and therefore the compound [I] represents an allyl ester or a methallyl ester. Further, in the formula, X represents a methyl group or a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom) excluding a fluorine atom, and the numbers 1 and m thereof represent an integer of 0 to 4,
More preferably, it is 0-2. Specific examples of the compound [I] are shown in Chemical formulas 13 to 14.

[0014]

[Chemical 13]

(In the formula, A represents an allyl group or a methallyl group. The same applies hereinafter.)

[0016]

[Chemical 14]

There are the following four methods for producing the above compound [I]. The first production method is the following general formula [II]

[0018]

[Chemical 15]

(In the formula, B, X, l and m are the same as above.) A bisphenol derivative (hereinafter, compound
[II]) and the following general formula [III]

[0020]

[Chemical 16]

(Wherein A and R are the same as above, Y is a halogen atom excluding a fluorine atom), and the ester derivative (hereinafter referred to as compound [III]) is reacted in the presence of a base. Is. Specific examples of the compound [III] include allyl chloroacetate, allyl bromoacetate, methallyl chloroacetate, methallyl bromoacetate, allyl 2-chloropropionate, allyl 2-bromopropionate, methallyl 2-chloropropionate, 2-bromo. Methallyl propionate, allyl 3-chloropropionate, allyl 3-bromopropionate, methallyl 3-chloropropionate, 3-
Examples include methallyl bromopropionate and the like. This reaction is carried out using 2 to 4 mol, more preferably 2 to 2.8 mol, of compound [III], relative to 1 mol of compound [II]. Since an acid is produced as a by-product in this reaction, it is necessary to remove the acid using a base as an acid acceptor. Examples of the base include potassium carbonate, sodium carbonate, calcium carbonate and other alkali metal and alkaline earth metal carbonates, potassium hydrogen carbonate,
Alkali metal hydrogen carbonate such as sodium hydrogen carbonate,

Alkali metal hydrides such as potassium hydroxide and sodium hydroxide, alkaline earth metal oxides such as barium oxide, alkali metal or alkaline earth metal hydrides such as sodium hydride and calcium hydride, sodium amide Alkali metal amides such as, and organic amines such as pyridine, lutidine, trimethylamine, and triethylamine are preferable. It is preferable to use 1 to 10 mol of these bases for 1 mol of the compound [III]. Solvents for this reaction include water, methanol, ethanol,
Lower alcohols such as propanol, isopropanol, butanol, isobutanol and t-butanol, ketones such as acetone and methyl ethyl ketone, ethers, tetrahydrofuran (hereinafter referred to as THF), ethers such as ethylene glycol dimethyl ether, benzene,
Hydrocarbons such as toluene and hexane, halogenated hydrocarbons such as chloroform and dichloromethane, amides such as dimethylformamide (hereinafter referred to as DMF), dimethylacetamide (hereinafter referred to as DMA), dimethyl sulfoxide (hereinafter referred to as dimethyl sulfoxide) , DMSO) and the like, and may be a single solvent or a mixture of two or more solvents. The amount of solvent used is 1 mol of the compound,
The amount is preferably 100 ml to 100 l, the reaction proceeds sufficiently even under normal pressure, and a device such as pressurization is not particularly required. The reaction temperature depends on the solvent, but is preferably 30 ° C or higher and the atmospheric pressure boiling point or lower of the solvent used. In this reaction, the used compound [I] [II]
It usually finishes in 0.5 to 48 hours depending on the conditions. Compound
The second production method of [I] is the following general formula [IV]

[0023]

[Chemical 17]

(Wherein A, B, X, l and m are the same as above), a dicarboxylic acid derivative (hereinafter referred to as compound [IV]) is dehydrated and condensed with allyl alcohol or methallyl alcohol. It is a method to let. In this reaction, allyl alcohol or methallyl alcohol is used as compound [IV] 1
It is preferable to use it in a range of 2 to 10 mol, preferably 2 to 2.8 mol, based on mol, to remove water by-produced in the presence of an acid catalyst. As the acid catalyst, mineral acids such as hydrochloric acid and sulfuric acid, and organic sulfones such as benzenesulfonic acid and toluenesulfonic acid are preferable, and the amount thereof is 0.01 to 0.5 mol with respect to 1 mol of the compound [IV]. Is preferred. In this reaction, it is desirable to use a water separator such as a Dean-Stark apparatus or a Soxhlet extractor filled with molecular sieves in order to remove by-product water.

As the solvent for this reaction, those having an azeotropic composition with water are preferable, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as chloroform and methylene chloride. The amount used is preferably 100 ml to 10 l per 1 mol of the compound [IV]. This reaction is carried out under normal pressure, and the reaction temperature is preferably carried out at the normal pressure boiling point of the solvent used. It is usual to return the solvent to the reaction system after removing water from the azeotropic mixture with water. Although the reaction time of this reaction depends on the compound [IV], it is usually 1 to 12
It's time. The third production method of the compound [I] is as follows.
[V]

[0026]

[Chemical 18]

(Wherein A, B, X, l, m, and Y are the same as above), the acid halide derivative (hereinafter referred to as compound [V]) is reacted with allyl alcohol or methallyl alcohol. It is a method to let. The production method of compound [V] is not particularly limited, and compound [V] obtained by any method can be used. Compounds that are generally the corresponding carboxylic acids [I
A known method obtained by reacting V] with a halogenating agent such as thionyl chloride is suitable. The compound [V], whether purified or not, can be similarly used in this reaction.
The amount of allyl alcohol or methacrylic alcohol used in this reaction is not particularly limited, but is usually the compound [V]
2-4 mol is preferable to 1 mol.

In this reaction, acid (HY) is produced as a by-product,
It is preferable to use an acid acceptor, and 2 to 20 mol, preferably 2 to 4 mol of an acid acceptor is used with respect to 1 mol of the compound [V]. Examples of the acid acceptor include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, or alkaline earth metal carbonates. Examples thereof include salts, alkaline earth metal oxides such as calcium oxide, and organic amines such as pyridine, triethylamine and dimethylaniline. As the solvent used in this reaction, ethers such as diethyl ether and THF,
Aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloromethane, and esters such as ethyl acetate are preferable.
[V] 1 mol is preferably 100 ml to 10 l. This reaction is carried out under normal pressure, and the reaction temperature is not particularly limited, but is usually −20 to 100 ° C., preferably 0 to 60 ° C. A reaction time of 0.1 to 12 hours is generally sufficient. The fourth production method of the compound [I] is represented by the following general formula [VI]

[0029]

[Chemical 19]

(Wherein A, B, X, l and m are the same as defined above, and M is a lithium, sodium or potassium atom) and a carboxylic acid salt derivative (hereinafter referred to as compound [V
I]) is represented by the general formula [VII]

[0031]

[Chemical 20]

(In the formula, R and Y are the same as above.) The reaction is carried out with an allyl halide or methallyl halide (hereinafter referred to as compound [VII]). Compound [V
The method for producing I] is not particularly limited, but a known method generally obtained by reacting compound [IV], which is a corresponding carboxylic acid, with a corresponding base (for example, MOH) is common. Further, the compound [VI] does not require any particular purification. Compound [VII]
Specific examples include allyl chloride, allyl bromide, methallyl chloride, and methallyl bromide. The amount used is not particularly limited, but preferably 2 to 2 per 1 mol of compound [VI].
It is 0 mol. As the solvent for this reaction, ketones such as acetone and ethylmethylketone, esters such as ethyl acetate or compound [VII] are preferable, and compound [VI] is also preferable.
Usually, 100 ml to 10 l is used per 1 mol. In this reaction, organic amines such as trimethylamine, triethylamine, tripropylamine, aniline and pyridine, and benzyltrimethylammonium chloride
The reaction rate may be improved by using a catalytic amount of a secondary ammonium salt or an iodide such as sodium iodide. The amount of the catalyst used is usually 0.01 to 1 mol with respect to 1 mol of the compound [VI].
0.5 mol is preferred. This reaction is carried out at normal pressure or under increased pressure and is usually carried out at 1-10 atm, preferably 1-6 atm. On the other hand, the reaction temperature is not particularly limited, but is usually 20 to 20.
It is 0 ° C, preferably 40 to 140 ° C. This reaction is usually 1
~ 24 hours to finish.

The method for isolating and purifying the desired compound [I] from the reaction system of each production method of the above compound [I] is not particularly specified, and known methods such as distillation, recrystallization, solvent extraction and column chromatography are used. Can be adopted.

The compound [I] can be polymerized alone in the presence of a radical polymerization initiator, or can be copolymerized with another radically polymerizable unsaturated monomer. Other radically polymerizable unsaturated monomers include allyl carbonates (for example, ethylene glycol bis allyl carbonate, diethylene glycol bis allyl carbonate, triethylene glycol bis allyl carbonate,
Tetraethylene glycol bis allyl carbonate, glycerin tris allyl carbonate, trimethylol propane tris allyl carbonate), methallyl carbonates (eg ethylene glycol bis methallyl carbonate, diethylene glycol bis methallyl carbonate, triethylene glycol bis methallyl carbonate, tetraethylene glycol) Bismethallyl carbonate, glycerin trismethallyl carbonate, trimethylolpropane trismethallyl carbonate), allyl esters (eg diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, triallyl cyanurate, triallyl isocyanurate, Diallyl maleate, diallyl fumarate, allyl benzoate, pt-butyl Allyl benzoate, allyl cinnamate, allyl phenoxyacetate, allyl 2,4-dibromophenoxyacetate, allyl 2,4,6-tribromophenoxyacetate, methallyl esters (eg dimethallyl phthalate, dimethallyl isophthalate, dimethallyl terephthalate) ， Trimethallyl trimellitate ，

Trimethallyl cyanurate, trimethallyl isocyanurate, dimethallyl maleate, dimethallyl fumarate, methallyl benzoate, methallyl p-t-butylbenzoate, methallyl cinnamate, methallyl phenoxyacetate, 4,
6-dibromophenoxy methallyl acetate, 2,4,6-tribromophenoxy methallyl acetate), allyl ethers
(For example, allyl phenyl ether, o-phenyl phenyl allyl ether, 2,4-dibromophenyl allyl ether, 2,4,6-tribromophenyl allyl ether), methallyl ethers (for example, methallyl phenyl ether, o-phenyl phenyl methallyl). Ruther, 2,
4-dibromophenylmethallyl ether, 2,4,6-
Tribromophenylmethallyl ether), maleic acid esters (eg, dibenzyl maleate, dimethyl maleate, diethyl maleate, di-n-propyl maleate, di-n-butyl maleate), fumaric acid esters
(For example, dibenzyl fumarate, dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, di-n-fumarate
-Butyl), acrylates (eg benzyl acrylate, phenyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, allyl acrylate), methacrylic acid esters (eg methacrylic acid) Benzyl acid,
Phenyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, benzyl methacrylate, allyl methacrylate), vinyl compounds (eg, styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-
Bromostyrene, m-bromostyrene, p-bromostyrene, α-methylstyrene, divinylbenzene, vinyl benzoate, vinyl acetate) and the like.

When at least one compound of the compound [I] is copolymerized with at least one compound selected from the above radically polymerizable unsaturated monomers, the use ratio thereof is not particularly limited, but is preferably It is desirable to use the compound [I] in an amount of 15% by weight or more. This is because if it is less than 15%, the characteristics of the compound [I] for increasing the refractive index cannot be utilized. Radical polymerization used when homopolymerizing compound [I] and when copolymerizing at least one compound of compound [I] with at least one compound selected from the above radically polymerizable unsaturated monomers The type of the initiator is not limited to one, but representative ones are diisopropyl peroxydicarbonate (IPP), di-sec-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and the like. Peroxydicarbonates, benzoyl peroxide (BPO), decanoyl peroxide, lauroyl peroxide, acetyl peroxide and other diacyl peroxides, tert-butylperoxyisobutyrate, tert-butylperoxy-2-
Examples thereof include alkyl oxyperesters such as ethyl hexanate and tert-butyl peroxypivalate, and azo compounds such as azobisisobutyronitrile. The proportion of these radical polymerization initiators used is
(Mixture) 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight. If it is less than 0.01 parts by weight, the curing will not be sufficient, and if it is more than 10 parts by weight, it will be excessively cured, which may cause cracks and decrease in impact resistance, which is not preferable.

[0037]

EXAMPLES The present invention will be described in more detail below with reference to examples and application examples, but the present invention is not limited thereto. The methods for measuring various physical properties of the compound [I] obtained in the present invention are as follows. (1) ¹ H-NMR spectrum It was measured using JEOL Ltd. GSX-270J type (270 MHz) and using tetramethylsilane as an internal standard in deuterated chloroform. (2) Refractive index The refractive index at 30 ° C. was measured using an Appe's refractometer. When the compound [I] was solid at room temperature, it was dissolved in a liquid having a known refractive index and its refractive index was determined by extrapolation.

Example 1 10.1 g of 4,4'-dihydroxydiphenyl ether was placed in a 1 liter three-necked flask equipped with a thermometer, a stirrer and a reflux tube.
(0.05 mol), allyl chloroacetate 14.8 g
(0.11 mol), powdered potassium carbonate 138 g (1 m
Ol) and 400 ml of acetone were charged, and the mixture was reacted for 4 hours under reflux with stirring. The reaction mixture was cooled to room temperature and the precipitate was filtered off. Subsequently, the solvent and excess allyl chloroacetate were distilled off under reduced pressure to remove 4,4'-bis
(Aryloxycarbonylmethoxy) diphenyl ether (18.3 g) was obtained as a colorless transparent oil. Yield is 91.9
%Met. The refractive index of this product was n _D 1.546. The measurement result of ¹ H-NMR is as follows, which is consistent with the following structure. δ (ppm) 4.61 (4H,
s), 4.70 (4H, d), 5.27 (2H, d),
5.33 (2H, d), 5.82-5.99 (2H,
m), 6.88 (8H, d)

[0039]

[Chemical 21]

The elemental analysis values (values in parentheses are calculated values) are C: 66.38% (66.32%) and H:
It was 5.61% (5.57%), which was in good agreement with the calculated value. Examples 2-5 By the method similar to Example 1, the compound described in Table 1 was synthesize | combined. Table 1 shows the results of elemental analysis and the refractive index thereof. Example 6 50 equipped with stirrer and Dean Stark moisture separator
2,2-bis (3,5-dibromo-4-carboxymethoxyphenyl) propane 33.
0 g (0.05 mol), allyl alcohol 12.8 g
(0.2 mol), rose toluenesulfonic acid 2 g (0.
(01 mol) and 200 ml of toluene were charged and dehydration condensation was performed under reflux. After 5 hours, heating and stirring were stopped when the amount of water produced was 1.8 ml, and the reaction mixture was cooled to room temperature. The reaction solution was washed with an aqueous sodium carbonate solution (10%) and then with water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure to give the desired 2,2-bis (4-allyloxycarbonylmethoxy-).
Colorless crystals of 32.5 g of 3,5-dibromophenyl) propane were obtained. The yield was 88%. The melting point of this product is m.p. p. 103.0 to 105.0 ° C. (recrystallized from ethanol), and the refractive index determined by extrapolation is n _D 1.5.
It was 798. The measurement result of ¹ H-NMR is as follows, which is consistent with the following structure. δ (ppm) 1.60
(6H, s), 4.65 (4H, s), 4.76 (4
H, d), 5.28 (2H, d), 5.38 (2H,
d), 5.92-6.02 (2H, m), 7.30 (4
H, s)

[0041]

[Chemical formula 22]

Further, elemental analysis values (values in parentheses are calculated values) are C: 40.61% (40.57%), H:
3.25% (3.27%), Br: 43.20% (4
3.19%), which was in good agreement with the calculated value.

Examples 7 to 12 By the same method as in Example 6, the compound described in the first item was synthesized. Table 1 shows the results of elemental analysis and the refractive index thereof.

Example 13 In a 300 ml three-necked flask equipped with a stirrer and a reflux tube, α, α-bis (4-carboxymethoxy-3,5-dibromophenyl) ethylbenzene 36 g (0.05 mo)
l), thionyl chloride 14.3 gr (0.12 mol),
After charging 100 ml of benzene and reacting under reflux for 3 hours, benzene and excess thionyl chloride were distilled off under reduced pressure to obtain an acid halide. The obtained acid chloride was dissolved in 100 ml of toluene without purification. Allyl alcohol 6.4 g (0.11 mol) and triethylamine 1 were placed in a 500 ml three-necked flask equipped with a dropping funnel and a stirrer.
2.2 g (0.12 mol) and 200 ml of toluene were charged, the toluene solution of the above acid chloride was dropped from a dropping funnel, and the mixture was reacted at room temperature for 6 hours. The reaction solution was washed with an aqueous sodium carbonate solution (10%) and then with water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 29.66 g of desired α, α-bis (4-allyloxycarbonylmethoxy-3,5-dibromophenyl) ethylbenzene as colorless crystals. Obtained. Yield 74
%Met. The melting point of this product is m.p. p. 110-117 ° C
(Recrystallized from ethanol), and the refractive index determined by extrapolation was n _D 1.5819. ¹ H-NMR
The measurement result of was as follows, and it was in agreement with the following structure.
δ (ppm) 2.09 (3H, s), 4.67 (4
H, s), 4.76 (4H, d), 5.28 (2H,
d), 5.38 (2H, d), 5.92-6.03 (2
H, m), 7.12-6.99 (2H, m), 7.18.
(4H, s), 7.35-7.27 (3H, m)

[0045]

[Chemical formula 23]

The elemental analysis values (() are calculated values.) C: 44.88% (44.92%), H:
3.25% (3.27%), Br: 39.88% (3
9.85%), which was in good agreement with the calculated value. Examples 14 to 16 By the method similar to that in Example 13, the compounds shown in Table 1 were synthesized. Table 1 shows the results of elemental analysis and the refractive index thereof.

Example 17 4,4'-bis (carboxymethoxy) diphenyl 1 was placed in a 100 ml three-necked flask equipped with a stirrer and a reflux tube.
5.1 g (0.05 mol), sodium hydroxide 4 g
(0.10 mol) and 20 ml of water were charged and stirred,
It was heated to 60 ° C. and reacted for 1 hour to completely dissolve it. Water was distilled off under reduced pressure to obtain sodium carboxylic acid salt. This product and allyl chloride 30.6 g (0.4 mol),
Triethylamine (1 g, 0.01 mol) was charged into a pressure reactor, and reacted at 110 ° C. for 6 hours while stirring. The reactor pressure was 6-4 atm. After cooling, 200 ml of toluene and 300 ml of water were added to the reaction liquid to separate it. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure to give the desired 4,4′-bis (allyloxycarbonylmethoxy) diphenyl (18.7 g) as colorless crystals. The yield was 98%. The melting point of this product is m.p.
p. The temperature was 84.5 to 86.0 ° C (recrystallized from ethanol), and the refractive index determined by extrapolation was n _D 1.5736. The measurement result of ¹ H-NMR is as follows, which is consistent with the following structure. δ (ppm) 4.68 (4H,
s), 4.71 (4H, d), 5.27 (2H, d),
5.34 (2H, d), 5.86-5.98 (2H,
m), 6.96 (4H, d), 7.46 (4H, d)

[0048]

[Chemical formula 24]

The elemental analysis values (() are calculated values.) C: 69.16% (69.10%), H:
It was 5.84% (5.80%), which was in good agreement with the calculated value. Examples 18 to 21 By the same method as in Example 17, compounds 25 to 27 and Table 1
The compound described in 1. was synthesized. Table 1 shows the results of elemental analysis and the refractive index thereof.

[0050]

[Chemical 25]

[0051]

[Chemical formula 26]

[0052]

[Chemical 27]

[0053]

[Table 1]

(Application Examples 1 to 10) The bisphenol derivative of the present invention shown above was prepared as a monomer or a mixture of monomers at the ratio (weight basis) shown in Table 2, and 100 parts by weight of radical polymerization was performed. 4 parts by weight of diisopropyl peroxydicarbonate (IPP) as an initiator was added, and this was injected into a casting mold composed of two glass plates and a silicone rubber gasket to carry out polymerization. Polymerization was carried out by using a hot-air circulation furnace at 40 ° C. for 5 hours, then gradually increasing the temperature from 40 ° C. to 80 ° C. over 11 hours, holding at 80 ° C. for 2 hours, and then gradually cooling to 60 ° C. It was Table 2 shows the physical properties of the obtained polymer.

The measuring methods of various physical properties of the obtained polymer are as follows. (1) Refractive index n _D and Abbe number [nu _D thickness 4 mm, length 20 mm, refractive index n _D of the test piece width of 10 mm, an Abbe refractometer Abbe number [nu _D used was measured at room temperature. As the contact liquid, α-bromonaphthalene was used. (2) Transmittance The transmittance of a test piece having a thickness of 4 mm, a length of 30 mm and a width of 30 mm was measured with a luminous transmittance photometer. (Comparative Example) Diethylene glycol bisallyl carbonate (CR-39) was used as a monomer and polymerized in the same manner as in the application example. Table 2 also shows the physical properties of the obtained polymer.

[0056]

[Table 2]

[0057]

INDUSTRIAL APPLICABILITY The compound [I] of the present invention can be polymerized by itself or can be made into a polymer by copolymerizing with various polymerizable compounds. The compound [I] is slowly polymerized by (meth) allyl polymerization, and it is easy to control the cast polymerization, and the obtained polymer has little distortion,
It is useful as a monomer that gives an optical resin with high transparency, high refractive index and low dispersion. The polymers and copolymers obtained by polymerizing the compound [I] are most suitable as optical lenses such as spectacle lenses and lenses for optical devices.
It can be suitably used for optical resins such as optical disk substrates, optical fibers and optical waveguides.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 67/31 317/22 7419-4H 323/20 7419-4H G02B 1/04 7132-2K // C08F 18/16 MLL 6904-4J 18/20

Claims (8)

[Claims] 1. A bisphenol derivative represented by the following general formula [I]. [Chemical 1] (In the formula, R represents a hydrogen atom or a methyl group, and A represents a linear or branched alkylene group having 1 to 2 carbon atoms.
Is Wherein R ¹ and R ² are each a hydrogen atom, a methyl group, an ethyl group, a phenyl group or a diphenyl group, and they may be the same or different, and R ³
Represents an alkylene group having 3 to 12 carbon atoms, a cycloalkylene group or a diphenylene group. X is a halogen atom excluding a methyl group or a fluorine atom, and l and m each represent an integer of 0 to 4. ) 2. The bisphenol derivative according to claim 1, wherein R in the general formula [I] is H. 3. The bisphenol derivative according to claim 1 or _2, wherein A in the general formula [I] is —CH ₂ —. 4. The bisphenol derivative according to claim 1, 2 or 3, wherein X in the general formula [I] is a bromine atom. 5. The following general formula [II]: (B, X, l and m are the same as those described above.) And a bisphenol derivative represented by the following general formula [III] (Wherein R and A are the same as those described above. Y represents a halogen atom excluding fluorine) and the ester derivative is reacted in the presence of a base. Item 4. A method for producing the bisphenol derivative according to any one of items 4. 6. A compound represented by the following general formula [IV]: (Wherein A, B, X, l, and m are the same as those described above), the dicarboxylic acid derivative is dehydrated and condensed with allyl alcohol or methallyl alcohol. A method for producing the bisphenol derivative according to any one of items 4. 7. The following general formula [V]: (In the formula, A, B, X, l, m and Y are the same as the above.)
The method for producing a bisphenol derivative according to any one of claims 1 to 4, characterized in that the acid halide derivative represented by (5) is reacted with allyl alcohol or methallyl alcohol. 8. A compound represented by the following general formula [VI]: (In the formula, A, B, X, l, and m are the same as the above. M
Represents a lithium, sodium or potassium atom. ), A carboxylate derivative represented by the general formula [VII] The bisphenol derivative according to any one of claims 1 to 4, wherein the bisphenol derivative is reacted with an allyl halide or methallyl halide represented by the formula (wherein R and Y are the same as those described above). Manufacturing method.