JPH05271257A - Phosphorous-containing compound - Google Patents

Abstract

PURPOSE:To obtain a new compound suitable as a resin raw material having a high refractive index usable as an optical material such as lens. CONSTITUTION:A compound of formula I (A1 and A1' are alkylene or thioalkylene; R1 and R1' are H or methyl; R2 is alkyl, aryl, aralkyl, alkoxy, etc.; X is 0 or S). The compound is obtained by reacting a compound of formula II (X6 is halogen) and a compound of formula III or a compound of formula IV and a compound of formula V with a phosphorus halide of formula VI (Z is halogen) in a solvent (e.g. hexane) at -50 to 50 deg.C. The compound of formula I is useful as monomer for a resin having a high refractive index, a low specific gravity, excellent transparency, weather resistance, etc., and the resin having a high refractive index obtained by copolymerizing the monomer is useful as organic glass and is most suitable as optical lenses such as lenses for eye-glasses, lenses of optical devices, etc.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polymerizable monomer,
In particular, the present invention relates to a novel phosphorus-containing compound which is useful as a monomer of a raw material of an optical material and is also useful in paints, inks, adhesives, etc.

[0002]

2. Description of the Related Art At present, a widely used optical material is a resin obtained by casting polymerization of diethylene glycol bisallyl carbonate. However, this resin has a refractive index (n _D ) of 1.50, which is smaller than that of an inorganic lens, and it is necessary to increase the center thickness, edge thickness, and curvature of the lens in order to obtain optical characteristics equivalent to those of an inorganic lens. However, it is unavoidable that the overall thickness becomes thick. Therefore, introduction of a halogen atom other than fluorine, an aromatic ring, and a sulfur atom into the molecular structure of the resin, that is, the molecular structure of the monomer has been studied as a means for increasing the refractive index of the resin (Japanese Patent Laid-Open Publication No. Sho 6-62).
1-86701, 63-45081, and 63-130614).

[0003]

The resin obtained from the above-mentioned monomers has a considerably higher refractive index than conventional lens materials. However, it is not a material that is well balanced in terms of optical characteristics such as specific gravity, transparency, and weather resistance, and is not always satisfactory as a lens material.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a thioacrylate or thiomethacrylate compound having a phosphorus atom is a novel polymerizable monomer capable of achieving the above object. After finding out that there is something, the present invention has been proposed.

That is, the present invention provides the following formula (1)

[0006]

[Chemical 3]

[0007] [where, A ₁ and A ₁ 'are each the same or a different _{- (R 4 -X 1) m} -, - (R 4 -X 1) m -R 5 - or - (R ₄ -X _{1) m -R 5 -X 2 -} ( where, X ₁ and X ₂
Are each an oxygen atom or a sulfur atom, and R ₄ and R ₅ are the same or different alkylene groups, phenylene groups, toluene-α-diyl groups or xylene- groups, respectively.
It is an α, α′-diyl group, and m is an integer of 0 or more. And R ₁ and R ₁ ′ are each a hydrogen atom or a methyl group, and R ₂ is an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aralkylthio group, or

[0008]

[Chemical 4]

{However, A ₂ is-(R ₇ -X ₃ ) _n -,-(R
₇ -X _{3) n} -R ₈ - or _{- (R 7 -X 3) n} -R 8 -X 4 - ( where, X ₃ and X ₄ are each oxygen atom or a sulfur atom, R ₇ and R ₈ is the same or different alkylene group, phenylene group, toluene-α-diyl group or xylene-α, α'-diyl group, respectively, and n is an integer of 0 or more.), And R ₆ is It is a hydrogen atom or a methyl group, and X ₅ is an oxygen atom or a sulfur atom. } And X is an oxygen atom or a sulfur atom. ] The phosphorus-containing compound shown by these.

The alkylene group represented by R ₄ , R ₅ , R ₇ and R ₈ in the general formula (1) is not particularly limited, but the refractive index decreases as the number of carbon atoms increases, so that the number of carbon atoms increases. Two
It is preferable to select in the range of 6 to 6, particularly in the range of 2 to 4.

Further, in the general formula (1), R ₄ , R ₅ ,
R ₇ and R ₈ may be a phenylene group, a toluene-α-diyl group (-CH ₂ -Ph-), and a xylene-α, α'-diyl group (-CH ₂ -Ph-CH _2- ). Good.
(However, in the above formula, Ph is a phenylene group.) X, X ₁ , X ₂ , X ₃ , X ₄ and X _{5 in the} general formula (1).
Is an oxygen atom or a sulfur atom, but a sulfur atom is preferable in order to obtain a resin having a high refractive index.

Further, m and n in the general formula (1) are 0.
The above integers may be used, but if m and n become too large, the heat resistance of the obtained resin will be impaired, so a range of 0 to 5, particularly 0 to 2 is preferable. is there. In addition, when m and n are 0,-(R _4-
X _{1) m} - and _{- (R 7 -X 3) n} - represents a bond.

Further, the alkyl group represented by R ₂ in the general formula (1) is not particularly limited, but in general, a linear or branched one having 1 to 4 carbon atoms is preferable. .. Typical examples of the alkyl groups that are generally and preferably used include methyl group, ethyl group, n-propyl group, is
Examples thereof include o-propyl group, n-butyl group and t-butyl group.

The aryl group represented by R ₂ is not particularly limited in the number of carbon atoms, but is a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a tolyl group, a xylyl group or the like having 6 to 10 carbon atoms. 14 aryl groups are preferred. The aralkyl group represented by R ₂ is not particularly limited in carbon number, but an aralkyl group having 7 to 10 carbon atoms such as a benzyl group, a phenethyl group, a phenylpropyl group and a phenylbutyl group is preferable.

Further, the alkoxy group represented by R ₂ in the general formula (1) is not particularly limited, but is generally a group containing a linear or branched alkyl group having 1 to 4 carbon atoms. It is suitable. Specific examples of the alkoxy group which are generally and preferably used include methoxy group, ethoxy group, n-propoxy group, t-butoxy group and the like.

The alkylthio group represented by R ₂ in the general formula (1) is not particularly limited, but a group containing a linear or branched alkyl group having 1 to 4 carbon atoms is generally preferred. Is. Typical examples of the alkylthio group which are generally and preferably used include methylthio group, ethylthio group,
Examples thereof include n-propylthio group and t-butylthio group.

In the general formula (1), the arylthio group represented by R ₂ is not particularly limited in the number of carbon atoms, but is a phenylthio group, a naphthylthio group, a phenanthrylthio group, an anthrylthio group, An arylthio group having 6 to 14 carbon atoms such as a tolylthio group or a xylylthio group is preferable.

In the general formula (1), the aralkylthio group represented by R ₂ is not particularly limited in the number of carbon atoms, but is a benzylthio group, a phenethylthio group,
Aralkylthio groups having 7 to 10 carbon atoms such as phenylpropylthio group and phenylbutylthio group are preferable.

The structure of the compound represented by the general formula (1) of the present invention can be confirmed by the following means.

(A) By measuring the infrared absorption spectrum (IR), C--H around 3150-2800 cm ^-1
Absorption based on bond, strong absorption of carbonyl group based on thioester group around 1660 to 1690 cm ^-1 , 1700
A strong absorption of a carbonyl group based on an ester group near ˜1750 cm ⁻¹ and an absorption based on a terminal unsaturated hydrocarbon group near 1650 to 1600 cm ⁻¹ can be observed.

(B) ¹ H-nuclear magnetic resonance spectrum ( ¹ H
By measuring -NMR), the bonding mode of hydrogen atoms present in the compound of the present invention represented by the general formula (1) can be known.

(C) By elemental analysis, the weight% of carbon, hydrogen, sulfur, and phosphorus can be obtained, and the weight% of oxygen can be calculated by subtracting the sum of the weight% of the recognized elements from 100. Therefore, the composition formula of the compound can be determined.

The phosphorus-containing compound represented by the general formula (1) is
Although it may be obtained by any method, the following two methods can be mentioned as typical production methods.

(A) General formulas (2) and (3)

[0025]

[Chemical 5]

[0026]

[Chemical 6]

And / or general formulas (4) and (5)

[0028]

[Chemical 7]

[0029]

[Chemical 8]

(However, A ₁ and A ₁ ′ are the same or different-(R ₄ -X ₁ ) _m -,-(R ₄ -X ₁ ) _m -R _{5-, respectively.}
Or _{- (R 4 -X 1) m} -R 5 -X 2 - ( where, X ₁ and X ₂
Are each an oxygen atom or a sulfur atom, and R ₄
And R ₅ are the same or different alkylene groups,
It is a phenylene group, a toluene-α-diyl group or a xylene-α, α'-diyl group, and m is an integer of 0 or more. ), R ₁ and R ₁ ′ are each a hydrogen atom or a methyl group, and X ₆ is a halogen atom. }
And a compound represented by the following formula (6)

[0031]

[Chemical 9]

[Wherein R ₂ is an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aralkylthio group, or

[0033]

[Chemical 10]

{However, A ₂ is-(R ₇ -X ₃ ) _n -,-(R
₇ -X _{3) n} -R ₈ - or _{- (R 7 -X 3) n} -R 8 -X 4 - ( where, X ₃ and X ₄ are each oxygen atom or a sulfur atom, R ₇ and R ₈ is the same or different alkylene group, phenylene group, toluene-α-diyl group or xylene-α, α'-diyl group, respectively, and n is an integer of 0 or more.), And R ₆ is It is a hydrogen atom or a methyl group, and X ₅ is an oxygen atom or a sulfur atom. }, Z is a halogen atom, and X is an oxygen atom or a sulfur atom. ] The method of reacting with the phosphorus halide compound shown by these.

B) General formulas (7) and (8)

[0036]

[Chemical 11]

[0037]

[Chemical 12]

(However, A ₁ and A ₁ ′ are the same or different types of-(R ₄ -X ₁ ) _m -,-(R ₄ -X ₁ ) _m -R _5-
Or _{- (R 4 -X 1) m} -R 5 -X 2 - ( where, X ₁ and X ₂
Are each an oxygen atom or a sulfur atom, and R ₄
And R ₅ are the same or different alkylene groups,
It is a phenylene group, a toluene-α-diyl group or a xylene-α, α'-diyl group, and m is an integer of 0 or more. ), R ₁ and R ₁ ′ are each a hydrogen atom or a methyl group, and M is a hydrogen atom or an alkali metal. } The method of making the compound shown by these and the phosphorus halide compound shown by the said General formula (6) react.

Specific examples of the reaction for obtaining the compound represented by the general formula (1) are shown below.

The method represented by A), that is, the general formula (2)
And a compound represented by the general formula (3), or a method of reacting the compound represented by the general formula (4) and the general formula (5) with the compound represented by the general formula (6), halogen is used in the reaction system. It is a reaction involving the formation of magnesium halide and / or lithium halide, and it is generally preferable to use an organic solvent. Examples of those suitably used as the solvent include aliphatic or aromatic hydrocarbons such as hexane, heptane, petroleum ether, benzene and toluene;
Ethers such as diethyl ether, tetrahydrofuran, dioxane and the like can be mentioned.

The charged molar ratio of each compound in the above reaction may be appropriately determined according to need. Usually, the compounds represented by the general formula (2) and the general formula (3) or the general formula (4) and It is general that the compound represented by the general formula (6) is reacted with the compound represented by the general formula (5) in a stoichiometric amount, that is, in an equimolar amount.

The temperature in the above reaction varies depending on the type of raw material and the type of solvent, but is generally preferably -50 to 50 ° C. The reaction time also varies depending on the type of raw material, but it is usually sufficient to select from the range of 5 minutes to 24 hours, preferably 30 minutes to 12 hours. In addition, it is preferable to perform stirring during the reaction.

The method represented by B), that is, the general formula (7)
And the method of reacting the compound represented by the general formula (8) with the compound represented by the general formula (6) is a reaction for dehydrohalogenating or dehalogenating an alkali metal from the reaction system, particularly in the case of the former case. In order to remove the generated hydrogen halide from the reaction system, it is preferable to allow a base to coexist in the reaction system as a hydrogen halide scavenger. The base as the hydrogen halide scavenger is not particularly limited, and known bases can be used. Examples of generally suitably used bases include trialkylamines such as trimethylamine and triethylamine, pyridine, tetramethylurea and the like.

Alkali metal compounds such as alkali carbonate, alkali hydroxide and alkali hydride are allowed to exist in the reaction system and reacted with the compounds represented by the general formulas (7) and (8) to give an alcoholate or It is preferred to produce the thiolate and carry out the above reaction.

The charged molar ratio of each compound in the above reaction may be appropriately determined according to need. Usually, the general formula (6) is added to the compounds represented by the general formulas (7) and (8). It is general to react the compound represented by the formula (1) in a stoichiometric amount, that is, in an equimolar amount.

In the reaction, it is generally preferable to use an organic solvent. Examples of those preferably used as the solvent include aliphatic or aromatic hydrocarbons such as hexane, heptane, petroleum ether, benzene, toluene, chloroform, methylene chloride and ethylene chloride, or halogenated hydrocarbons; Ethers such as diethyl ether, tetrahydrofuran, dioxane; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile; dialkylamides such as N, N-dimethylformamide; dimethyl sulfoxide and the like.

The temperature in the above reaction varies depending on the type of raw material and the type of solvent, but generally 0 ° C. to the reflux temperature of the solvent are preferable. The reaction time also varies depending on the type of raw material, but is usually 5 minutes to 40 hours, preferably 30 minutes to 24 hours.
It is sufficient to choose from a time range. Further, it is preferable to carry out stirring during the reaction.

The method of isolating and purifying the desired product, that is, the compound represented by the general formula (1) from the reaction system is not particularly limited, and a known method can be employed.

The compound represented by the general formula (1) of the present invention gives a resin having a high refractive index, a small specific gravity and an excellent transparency. When an optical material, particularly a lens material, is obtained using the phosphorus-containing compound of the present invention, when the compound represented by the general formula (1) is monofunctional, radically copolymerizable polyfunctional unsaturated monomer is used. It is preferred to copolymerize with the body. Examples of the polyfunctional unsaturated monomer are as follows. still,
Acrylate and methacrylate are collectively referred to as (meth) acrylate. Examples include di (meth) acrylates such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and thioglycol di (meth) acrylate; divinylbenzene, 2,5-divinylpyridine and the like.

Further, from the viewpoint of obtaining a polymer having a high refractive index, it is preferable to use a polyfunctional unsaturated monomer whose homopolymer has a refractive index of 1.55 or more. Specific examples of such a polyfunctional unsaturated monomer include bisphenol A, bisphenol S, 2,2 ', 6,6'-tetrachlorobisphenol A, 2,2', 6,6'-tetra Chlorobisphenol S, 2,2 ', 6,6'-tetrabromobisphenol A or bisβ-methallyl carbonate, diacrylate or dimethacrylate of bisphenols such as 2,2', 6,6'-tetrabromobisphenol S Bisβ-such as tetrachlorophthalic acid bishydroxyethyl ester, tetrachloroisophthalic acid bishydroxyethyl ester, tetrachloroterephthalic acid bishydroxyethyl ester, tetrabromophthalic acid bishydroxyethyl ester or tetrabromoterephthalic acid bishydroxyethyl ester Metallic Luka Carbonate, diacrylate or dimethacrylate;
Examples include divinylbenzene and 2,5-divinylpyridine.

On the other hand, it is possible to use a monofunctional unsaturated monomer capable of radical copolymerization together with the above-mentioned polyfunctional unsaturated monomer. The monofunctional unsaturated monomer has a refractive index of 1.5 as a homopolymer from the viewpoint of obtaining a polymer having a high refractive index.
It is preferable to use 5 or more monomers.

Specifically, it is as follows. Phenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate,
Trichlorophenyl (meth) acrylate, monobromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, pentabromophenyl (meth) acrylate,
Monochlorophenoxyethyl (meth) acrylate, dichlorophenoxyethyl (meth) acrylate, trichlorophenoxyethyl (meth) acrylate, monobromophenoxyethyl (meth) acrylate, dibromophenoxyethyl (meth) acrylate, tribromophenoxyethyl (meth) acrylate, Pentabromophenoxyethyl (meth) acrylate, phenylthio (meth) acrylate, benzylthio (meth) acrylate, benzylthioethylthio (meth) acrylate, styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, iodostyrene, methylstyrene, Methoxystyrene, 2-vinylthiophene, vinylnaphthalene, N-vinylcarbazole, benzyl (meth) acrylate Ethyl vinyl benzene. These monomers can be used alone or in combination of two or more.

When obtaining an optical material, especially a lens material, in the present invention, the composition ratio of the monomers is such that the ratio of the compound represented by the general formula (1) to all the monomers is 10 to 10.
It is preferably used in an amount of 0% by weight, particularly 40 to 100% by weight. On the other hand, the amount of the polyfunctional unsaturated monomer capable of radical copolymerization is 0 to 9 as a proportion of the total monomers.
A range of 0% by weight, particularly 0 to 60% by weight is preferable. Further, the amount of the monofunctional unsaturated monomer capable of radical copolymerization is preferably 0 to 90% by weight, more preferably 0 to 60% by weight, based on the total monomers.

The polymerization method for obtaining a high refractive index resin using the above-mentioned monomer composition is not particularly limited, and a known cast polymerization method can be adopted. The polymerization can be initiated by using radical polymerization initiators such as various peroxides and azo compounds, irradiation with ultraviolet rays, α rays, β rays, γ rays or the like, or a combination of both. To illustrate a typical polymerization method,
The above-mentioned monomer composition containing a radical polymerization initiator may be injected between molds held by an elastomer gasket or a spacer, cured in an air oven, and then taken out.

The radical polymerization initiator is not particularly limited and known ones can be used. Typical examples thereof include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide and lauroyl peroxide. , Diacetyl peroxides such as acetyl peroxide; peroxyesters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate and t-butylperoxybenzoate; Percarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; azo compounds such as azobisisobutyronitrile. The amount of the radical polymerization initiator used varies depending on the polymerization conditions, the type of the initiator, and the composition of the above-mentioned monomer composition and cannot be unconditionally limited, but generally, relative to 100 parts by weight of the monomer composition. 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight.

Among the polymerization conditions, the temperature particularly affects the properties of the obtained high refractive index resin. This temperature condition is affected by the kind and amount of the initiator and the kind of the monomer composition, and therefore cannot be unconditionally limited, but generally the polymerization is started at a relatively low temperature, and the temperature is slowly raised. It is preferable to carry out a so-called taper type two-stage polymerization in which curing is performed at a high temperature at the end of the polymerization. Since the polymerization time also depends on various factors like the temperature, it is preferable to determine the optimum time in advance according to these conditions, but generally, the conditions are selected so that the polymerization is completed in 2 to 40 hours. Is preferred.

Needless to say, various stabilizers and additives such as a release agent, an ultraviolet absorber, an antioxidant, an anti-coloring agent, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance, etc., may be added as necessary during the polymerization. Can be selected and used.

Further, the high refractive index resin obtained by the above method may be subjected to the following treatments depending on its use. That is, dyeing using a dye such as a disperse dye, a silane coupling agent or silicon, zirconia, antimony,
Hard coating treatment with a hard coating agent containing sol of oxide such as aluminum as a main component or a hard coating agent containing organic polymer as a main component, SiO ₂ , Ti
It is also possible to perform processing such as antireflection treatment and antistatic treatment by vapor deposition of a thin film of a metal oxide such as O ₂ or ZrO ₂ or coating of a thin film of an organic polymer, and secondary treatment.

[0059]

The phosphorus-containing compound of the present invention is useful as a monomer that gives a resin having a high refractive index, a small specific gravity, and excellent transparency, weather resistance and the like. Therefore, the high refractive index resin obtained by homopolymerization of the phosphorus-containing compound of the present invention or copolymerization of the compound with an unsaturated monomer is useful as an organic glass, for example, spectacle lenses, optical equipment lenses, etc. It is most suitable as an optical lens and can be suitably used for applications such as prisms, optical disk substrates, and optical fibers.

[0060]

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

Various properties of the phosphorus-containing compound and the high refractive index resin obtained in the examples were measured by the following test methods.

(1) IR spectrum A DIGLAB FIS-7 manufactured by BIO-RAD, a Fourier transform infrared spectrophotometer was used to measure by the liquid film method or the KBr method.

(2) ¹ H-NMR spectrum PMX-60SI type (60 MHz) manufactured by JEOL Ltd.
Was used to dilute the sample in CDCl ₃ and tetramethylsilane was measured as an internal standard.

(3) Refractive Index The refractive index at 20 ° C. was measured using an Abbe refractometer manufactured by Atago Co., Ltd. Bromonaphthalene or methylene iodide was used as the contact liquid.

The refractive index of the phosphorus-containing compound was determined by extrapolation by dissolving it in a liquid unsaturated monomer when the compound was solid at room temperature.

(4) Appearance It was measured visually.

(5) Weather resistance A sample and polystyrene for comparison were placed in a long life xenon fade meter (FAC-25AX-HC type) manufactured by Suga Test Instruments Co., Ltd., and exposed to xenon light for 100 hours, and then polystyrene. A sample having a lower degree of coloring was evaluated as ◯, an equivalent sample was evaluated as Δ, and a higher sample was evaluated as x.

The unsaturated monomers used in the following examples are represented by the following symbols. However, the value in [] is the refractive index of the homopolymer.

St: Styrene [1.590] ClSt: Chlorostyrene (a mixture of o and m isomers)
[1.610] DVB: Divinylbenzene [1.615] Example 1 A thermometer, a dropping funnel and a mechanical stirrer were attached.
10.0 g of thiophosphonyl chloride in a 500 ml three-necked flask
(0.059 mol) and pyridine 15.4 g (0.195 mol) in methylene chloride 2
It was dissolved in 00 ml and cooled at 0 ° C. While stirring, 2-
9.6 g (0.059 mol) of mercaptoethylthiomethacrylate was gradually added dropwise. Then, 16.9 g (0.13 mol) of 2-hydroxyethyl methacrylate was added dropwise. At this time, the reaction temperature was kept at 0 to 5 ° C., and after completion of dropping, the mixture was further stirred at 20 ° C. for 2 hours. Then, the reaction mixture was poured into water, the organic layer was washed with dilute hydrochloric acid and a dilute aqueous solution of sodium carbonate, and then washed with water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give a colorless transparent viscous material 2
8.0 g (yield 87%) was obtained.

The IR chart of this product is shown in FIG.
Absorption based on C-H bond in the 3150-2800cm ^-1, 1716 and respectively methacryloyl groups and thio in 1661Cm ^{-1-methacryloyl-derived} group strong absorption of groups, 1634C
Absorption based on CH ₂ ═CH group was observed in m ⁻¹ .

A chart of ¹ H-NMR (in CDCl ₃ solvent, tetramethylsilane standard, ppm) of this product is shown in FIG. At δ2.0 ppm, the nine peaks derived from methyl hydrogen of the thiomethacryloyl group are singlet,
And 6.0 ppm at 6 peaks derived from methylene hydrogen of thiomethacryloyl group as doublet, δ2.7-3.4 ppm,
Also, 12 peaks derived from hydrogen of S-methylene and O-methylene were observed as multiple lines at δ 4.1-4.4 ppm.

Further, elemental analysis values (values in parentheses are calculated values) are C: 43.99% (44.80%), H: 5.53% (5.64%),
S: 20.15% (19.94%) and P: 6.34% (6.42%), which were in good agreement with the calculated values. Also, when the refractive index was measured, n _D =
It was 1.534.

From the above, it was found that the obtained compound has the following structural formula.

[0074]

[Chemical 13]

Example 2 The phosphorus-containing compounds shown in Table 1 were synthesized in the same manner as described in detail in Example 1 using various raw materials. The properties of the obtained phosphorus-containing compound are shown in Table 1.
The elemental analysis results and the refractive index are also shown.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

[0085]

[Table 10]

[0086]

[Table 11]

[0087]

[Table 12]

[0088]

[Table 13]

[0089]

[Table 14]

Example 42 100 parts by weight of a mixture of 60 parts by weight of the phosphorus-containing compound synthesized in Example 1 and 40 parts by weight of styrene as an unsaturated monomer was added to t-butylperoxy-2 as a radical polymerization initiator. Add 1 part by weight of ethylene hexanate and mix well. This mixed solution was poured into a mold composed of a gasket composed of a glass plate and an ethylene-vinyl acetate copolymer, and cast polymerization was carried out. Polymerization using an air furnace 3
The temperature was gradually raised from 0 ° C. to 90 ° C. over 18 hours, and was maintained at 90 ° C. for 2 hours. After completion of the polymerization, the mold was taken out of the air furnace, allowed to cool, and the polymer was removed from the glass of the mold.

The obtained polymer was colorless and transparent, had a refractive index n _D = 1.587, a specific gravity of 1.18, and had a light resistance of ◯.

Example 43 Example 43 was carried out in the same manner as in Example 42 except that the composition containing the phosphorus-containing compound shown in Table 2 and a monomer copolymerizable therewith was used. The physical properties of the obtained polymer were measured and are also shown in Table 2.
It was shown to.

[0093]

[Table 15]

[0094]

[Table 16]

[0095]

[Table 17]

[Brief description of drawings]

1 is an infrared absorption spectrum chart of the phosphorus-containing compound of the present invention obtained in Example 1. FIG.

FIG. 2 is a ¹ H-nuclear magnetic resonance spectrum chart of the phosphorus-containing compound of the present invention obtained in Example 1.

Claims (1)

[Claims] 1. The following formula: [However, A ₁ and A ₁ ′ are the same or different
_{(R 4 -X 1) m -} , - (R 4 -X 1) m -R 5 - or - (R ₄ -
X ₁ ) _m —R ₅ —X ₂ — (wherein X ₁ and X ₂ are each an oxygen atom or a sulfur atom, and R ₄ and R ₅ are the same or different alkylene groups, phenylene groups,
It is a toluene-α-diyl group or a xylene-α, α'-diyl group, and m is an integer of 0 or more. And R ₁ and R ₁ ′ are each a hydrogen atom or a methyl group, and R ₂ is an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aralkylthio group, or 2] {However, A _{2 is, - (R 7 -X 3)} n -, - (R 7 -X 3) n -R
₈ - or _{- (R 7 -X 3) n} -R 8 -X 4 - ( where, X ₃ and X ₄ are each oxygen atom or a sulfur atom, R
₇ and R ₈ are the same or different alkylene groups, phenylene groups, toluene-α-diyl groups or xylene-α, α'-diyl groups, respectively, and n is an integer of 0 or more. ), R ₆ is a hydrogen atom or a methyl group, and X ₅ is an oxygen atom or a sulfur atom. } And X is an oxygen atom or a sulfur atom. ] The phosphorus-containing compound shown by these.