JP2001294592A - Metal-containing episulfide compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metal-containing episulfide compound useful as a raw material for an optical material having a high refractive index and a high Abbe's number and to provide a method for efficiently producing the same. SOLUTION: This metal-containing episulfide compound is represented by general formula (1) (M is Si, Ge, Sn or Ti; (x) is an integer of 1-4; (y) is 1 or 2). The method for producing a metal sulfide compound of general formula (1-a) comprises reacting a metal tetrahalide of the general formula MZ4 (M is as shown above; Z is a halogen atom) with 2:3-epithiomercaptopropane. The method for producing a metal-containing episulfide compound of general formula (1) ((x) is an integer of 1-3; (y) is 1 or 2) comprises reacting a chloromethylated substance or a vinyl substitution product of the metal tetrahalide with 2:3- epithiomercaptopropane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel metal-containing episulfide compound and a method for producing the same, and more particularly, to a metal-containing episulfide compound useful as a raw material for an optical material having a high refractive index and a high Abbe number, and its efficiency. It relates to a method of manufacturing well.

[0002]

2. Description of the Related Art Plastics have been widely used in various optical applications such as lenses in recent years, since plastics are lighter in weight, harder to break and easier to dye than glass. Poly (diethylene glycol bisallyl carbonate) (CR-39) and poly (methyl methacrylate) are generally used as optical plastic materials. However, since these plastic materials have a refractive index of 1.50 or less, for example, when a lens is made of such a plastic material, the lens becomes thicker as the power of the lens increases, and the advantage of a plastic lens having an advantage of light weight is superior. Sex is impaired. In particular, a concave lens having high strength is not preferable because the periphery of the lens becomes thick and birefringence and chromatic aberration occur. Furthermore, in eyeglass applications, thick lenses are
Aesthetics tend to be poor. In order to obtain a thin lens, it is effective to increase the refractive index of the material forming the lens. In general, the Abbe number of glass and plastic decreases as the refractive index increases, and as a result, their chromatic aberration increases. Therefore, a plastic material having both a high refractive index and an Abbe number is desired. Examples of the plastic material having such performance include (1) a polyurethane obtained by polyaddition of a polyol having bromine in the molecule and a polyisocyanate (JP-A-58-164615).
Japanese Patent Application Laid-Open No. 4-58), (2) Polythiourethane obtained by polyaddition of polythiol and polyisocyanate
No. 489, Japanese Patent Publication No. 5-148340). In particular, as a polythiol used as a raw material of the polythiourethane of (2), a branched chain having an increased sulfur atom content (Polythiol JP-A-2-270859, JP-A-5-70859)
No. 148340) and polythiols having a dithiane structure introduced to increase the number of sulfur atoms (JP-B-6-5323, JP-A-7-118390). further,
(3) An alkyl sulfide polymer having episulfide as a polymerization functional group has been proposed (JP-A-9-72580).
JP, JP-A-9-110979).

However, the polyurethane of the above (1) is
Although the refractive index is slightly improved, it has disadvantages such as low Abbe number, poor light resistance, high specific gravity, and impaired lightness. Among the polythiourethanes of (2), the polythiourethane obtained by using a polythiol as a raw material and using a polythiol having a high sulfur content has a refractive index increased to, for example, about 1.60 to 1.68. But,
There is a problem that the Abbe number is lower than that of an optical inorganic glass having the same refractive index, and the Abbe number must be further increased. On the other hand, the alkyl sulfide polymer of (3) has, for example, an Abbe number of 36 and a refractive index of 1.70, and the lens obtained by using this polymer is significantly thinned, and Although it is lighter, a plastic material having higher refractive index and Abbe number at the same time is desired.

[0004]

Under such circumstances, the present invention can provide an optical material having both a high refractive index and a high Abbe number and having excellent heat resistance, weather resistance, transparency and the like. An object of the present invention is to provide a novel compound and a method for efficiently producing the compound.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a metal containing a metal atom such as silicon, germanium, tin or titanium to which an episulfide derivative is bonded. The present inventors have found that an episulfide compound is a novel compound, which can be adapted to the above-mentioned purpose, and that this compound can be efficiently obtained by a specific method, and based on this finding, completed the present invention. . That is, the present invention provides (1) the general formula
(1)

[0006]

Embedded image

(Wherein, M represents silicon, germanium, tin or titanium, x represents an integer of 1 to 4, and y represents 1
Or 2 is indicated. A) a metal-containing episulfide compound represented by the general formula MZ ₄ (where M is the same as described above;
Z represents a halogen atom), and reacting 2: 3-epithiomercaptopropane with a metal tetrahalide represented by the general formula (1-a):

[0008]

Embedded image

(Wherein M is the same as described above), and (3) a chloromethylated or vinyl-substituted metal tetrahalide and a 2: 3 -General formula (1) characterized by reacting epithiomercaptopropane

[0010]

Embedded image

(Where M is the same as above, and x is 1 to
3 represents an integer, and y represents 1 or 2. A) a method for producing a metal-containing episulfide compound represented by the formula:

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The metal-containing sulfide compound of the present invention has the general formula (1)

[0013]

Embedded image

(Wherein, M represents silicon, germanium, tin or titanium, x represents an integer of 1-4, and y represents 1
Or 2 is indicated. ). As is clear from the above general formula (1), four identical or different two types of episulfide derivatives are bonded to metal atoms selected from silicon, germanium, tin and titanium. It is characterized by doing. The refractive index of a substance increases with increasing refractive index (atomic refraction) and decreasing molecular volume of constituent elements. This atomic refraction increases with the atomic number. Therefore, compared to episulfide compounds whose skeleton is composed of carbon, silicon, germanium,
The refractive index of the metal-containing episulfide compound of the present invention into which a metal atom such as tin or titanium has been introduced is significantly increased, and the refractive index of a polymer obtained using this compound as a raw material is also increased. Since the metal-containing episulfide compound of the present invention is tetrafunctional, and the functional groups are composed of as few elements as possible, a decrease in molecular volume is caused by an increase in crosslink density, and as a result, the metal-containing episulfide compound of the present invention is reduced. The refractive index of the polymer obtained using the episulfide compound,
To increase. Therefore, in order to maintain the high crosslinking density and increase the refractive index without lowering the Abbe number, the number of methylene chains represented by y in the general formula (1) must be 1 or 2. One of these substituents is represented by the general formula (1)
= 4) or two types (x = 1 to x in the general formula (1))
3) By bonding, the optical, thermal, and mechanical properties of the polymer obtained using the metal-containing episulfide compound of the present invention can be adjusted.

As the metal-containing episulfide compound represented by the general formula (1), specifically, tetrakis (2: 3-
Epithiopropylthio) silane, tetrakis (2: 3-epithiopropylthio) germane, tetrakis (2: 3-epithiopropylthio) tin, tetrakis (2: 3-epithiopropylthio) titanium, tris (2: 3-epithiopropylthio) -2-thia-4: 5-epithiopentylsilane, tris (2: 3-epithiopropylthio) -2-thia-4: 5-epithiopentylgermane, tris (2: 3-Epithiopropylthio) -2-thia-4: 5-epithiopentyltin, tris (2: 3-epithiopropylthio) -2
-Thia-4: 5 -epithiopentyl titanium, tris (2: 3
-Epithiopropylthio) -3-thia-5: 6-epithiohexylsilane, tris (2: 3-epithiopropylthio) -3-thia-5: 6-epithiohexylgermane, tris (2: 3 -Epithiopropylthio) -3-thia-5: 6
-Epithiohexyltin, tris (2: 3-epithiopropylthio) -3-thia-5: 6-epithiohexyltitanium, tris (2-thia-4: 5-epithiopentyl) -2:
3-epithiopropylthiogermane and the like.
The metal-containing episulfide compound represented by the general formula (1) can be efficiently produced by the following method of the present invention depending on its structure. (1) In the general formula (1), the compound of x = 4 is represented by a reaction formula

[0016]

Embedded image

Accordingly, 2: 3-epithiomercaptopropane and a tetrahalide of a metal corresponding to M in the general formula (1) are dissolved in a solvent such as tetrahydrofuran, dimethylsulfoxide or dimethylformamide in the presence of a base. It is obtained by reacting with. Tetrachloride is preferred as the tetrahalide. The reaction temperature is from 20 ° C to -30 ° C, and pyridine, triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene and the like are preferably used as a base. Note that 2: 3-epithiomercaptopropane used as one of the raw materials can be obtained by a known method, for example, the method described in “Journal of Chemical Society (J. Chem. So
c.)), page 2665 (1960). (2) In the general formula (1), the compound of x = 1 to 3 and y = 1 is represented by the reaction formula

[0018]

Embedded image

[0019] That is, a metal tetrachloride corresponding to M in the general formula (1) is dissolved in diazomethane and a solvent such as dichloromethane or ethyl ether for 10 to 3 times.
The reaction is carried out at 0 ° C. to form a chloromethylated product of the corresponding metal. Ethyl ether was distilled off and the isolated product was treated with a base and thiolate previously formed with 2: 3-epithiomercaptopropane and dichloromethane, methanol, ethanol, ethyl ether, tetrahydrofuran, dimethyl sulfoxide, dimethyl The reaction is carried out in formamide or a mixed solvent thereof. As this base, sodium methoxide, sodium ethoxide, sodium hydride, normal butyllithium and the like are used, and the added amount is equivalent to a chlorine atom directly bonded to the metal. (3) In the general formula (1), the compound of x = 1 to 3 and y = 2 is obtained by the reaction formula

[0020]

Embedded image

[0021] In other words, the general formula (1) tetrahalide of the metal corresponding to M in, i.e. tetrahalide metal represented by the general formula MZ _4, obtained preferably by reacting the tetrachloride with vinyl magnesium bromide and 0 to 30 ° C. The obtained vinyl-substituted product was mixed with 2: 3-epithiomercaptopropane firstly in the presence of a base in dichloromethane,
The reaction is carried out in tetrahydrofuran, ethyl ether, dimethyl sulfoxide, dimethyl formamide or a mixed solvent thereof at 10 ° C to -30 ° C, and then at 40 to 80 ° C in the presence of a radical generator. As the base, pyridine, triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene and the like are preferable, and as the radical generator, benzoyl peroxide, azobisdimethylbutyronitrile, azobisdimethylvaleronitrile and the like are preferable. Used. The amount of the base added is equivalent to the chlorine atom directly bonded to the metal, and that of the radical generator is 0.01 to 0.0001 equivalent to the vinyl group. In the reaction of this vinyl-substituted product with 2: 3-epithiomercaptopropane, instead of heating in the presence of a radical generator, the intensity at 350 nm with a high-pressure mercury lamp is 0.0 to 10%.
The same compound can be obtained by irradiating ultraviolet rays of 0 mW / cm ² in tetrahydrofuran or normal hexane, or without solvent.

Next, an optical material obtained by using the metal-containing episulfide compound of the present invention will be described. The metal-containing episulfide compound represented by the general formula (1) is an essential component, and may be used alone or in combination of two or more. Furthermore, the metal-containing episulfide compound may be polymerized with another episulfide compound, an epoxy compound and a compound selected from homopolymerizable vinyl monomers as an optional component for appropriately improving the properties and the like of the obtained polymer. Good. Examples of the other episulfide compounds suitably used above include bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, and 1,3-bis (β-epithiothio). Propylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4-bis ( β-epithiopropylthio) butane, 1,3-bis (β-epithiopropylthio) butane, 1- (β-epithiopropylthio)-
3- (β-epithiopropylthiomethyl) butane, 1,
5-bis (β-epithiopropylthio) pentane, 1-
(Β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) hexane, 1- (β-epithiopropylthio) -5 (Β-epithiopropylthiomethyl)
Hexane, 1- (β-epithiopropylthio) -2-
[(2-β-epithiopropylthioethyl) thio] ethane, 1- (β-epithiopropylthio) -2-[[2-
(2-β-epithiopropylthioethyl) thioethyl]
A chain organic compound such as [thio] ethane, etc., and tetrakis (β-epithiopropylthiomethyl) methane,
1,1-tris (β-epithiopropylthiomethyl) propane, 1,5-bis (β-epithiopropylthio)-
2- (β-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio)-
2,4-bis (β-epithiopropylthiomethyl) -3
-Thiapentane, 1- (β-epithiopropylthio)-
2,2-bis (β-epithiopropylthiomethyl) -4
-Thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (β-epithiopropylthio) -4 -(Β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane , 1,8-
Bis (β-epithiopropylthio) -4,4-bis (β
-Epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio)-
2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,5-bis (β-epithiopropylthiomethyl ) -3,6-dithiaoctane, 1,9
-Bis (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) -5-[(2-β-epithiopropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10- Bis (β-epithiopropylthio)-
5,6-bis [(2-β-epithiopropylthioethyl) thio] -3,6,9-trithiadecane, 1,11-
Bis (β-epithiopropylthio) -4,8-bis (β
-Epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6 , 9-Trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-[(2-β
-Epithiopropylthioethyl) thiomethyl] -3,
Branched such as 6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane Organic compounds and compounds in which at least one hydrogen of the episulfide group of these compounds is substituted with a methyl group, and the like, further include 1,3 and 1,4-bis (β
-Epithiopropylthio) cyclohexane, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [ 4- (β
-Epithiopropylthio) cyclohexyl] propane,
Bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-
Cycloaliphatic organic compounds such as (epithiopropylthioethylthiomethyl) -1,4-dithiane; compounds in which at least one hydrogen of the episulfide group of these compounds is substituted with a methyl group; 4-bis (β-epithiopropylthio) benzene, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, , 2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4-
(Β-epithiopropylthio) phenyl] sulfone,
Aromatic organic compounds such as 4,4′-bis (β-epithiopropylthio) biphenyl and compounds in which at least one hydrogen of the episulfide group of these compounds is substituted with a methyl group, etc. Alternatively, two or more kinds may be used in combination. These are preferably used in an amount of 0.01 to 50 mol% based on the total amount of the metal-containing episulfide compound represented by the general formula (1).

Examples of the epoxy compounds suitably used include polyquinones such as hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, bisphenol sulfide, halogenated bisphenol A, and novolak resin. Phenolic epoxy compound produced by condensation of phenol compound and epihalohydrin; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane Remethacrylate, pentaerythritol, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A-ethylene oxide adduct, bisphenol A-propylene oxide addition Epoxy compounds produced by condensation of a polyhydric alcohol compound such as a product with epihalohydrin; adipic acid, sebacic acid, dodecanedicarboxylic acid,
Dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hetonic acid, nadic acid, maleic acid,
Succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalenedicarboxylic acid, a glycidyl ester-based epoxy compound produced by condensation of a polycarboxylic acid compound such as diphenyldicarboxylic acid and epihalohydrin; ethylenediamine; 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, , 7-diaminoheptane, 1,8-diaminooctane, bis- (3-
Aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, 1,2-,
1,3- or 1,4-bisaminocyclohexane,
1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diamino Diphenylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, m- or p-phenylenediamine, 2,
4- or 2,6-tolylenediamine, m- or p-
Xylylenediamine, 1,5- or 2,6-naphthalenediamine, 4,4′-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 2,2-
Primary diamines such as (4,4'-diaminodiphenyl) propane, N, N'-dimethylethylenediamine, N,
N'-dimethyl-1,2-diaminopropane, N, N '
-Dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,2-diaminobutane, N, N'-dimethyl-1,3-diaminobutane, N, N'-dimethyl-1,
4-diaminobutane, N, N'-dimethyl-1,5-diaminopentane, N, N'-dimethyl-1,6-diaminohexane, N, N'-dimethyl-1,7-diaminoheptane, N, N '-Diethylethylenediamine, N,
N'-diethyl-1,2-diaminopropane, N, N '
-Diethyl-1,3-diaminopropane, N, N'-diethyl-1,2-diaminobutane, N, N'-diethyl-1,3-diaminobutane, N, N'-diethyl-1,
4-diaminobutane, N, N'-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine,
2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) -methane,
1,2-di- (4-piperidyl) -ethane, 1,3-di- (4-piperidyl) -propane, 1,4-di- (4-
Amine-based epoxy compounds produced by condensation of a secondary diamine such as piperidyl) -butane and epihalohydrin;
3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexanedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, Alicyclic epoxy compounds such as bis (3,4-epoxycyclohexyl) adipate; epoxy compounds produced by epoxidation of unsaturated compounds such as cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene and vinylcyclohexene epoxide; And urethane-based epoxy compounds produced from phenol compounds and diisocyanates and glycidol. These may be used alone or in combination of two or more. These are preferably used in an amount of 0.01 to 5 mol% based on the total amount of the metal-containing episulfide compound represented by the general formula (1).

Examples of the suitable homopolymerizable vinyl monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol. Ethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate,
1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polypropylene glycol diacrylate,
Polypropylene glycol dimethacrylate, 2,2-
Bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2 -Screw [4
-(Methacryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (acryloxy-polyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, hexaacrylate of bis (2,2,2-trimethylolethyl) ether, hexamethacrylate of bis (2,2,2-trimethylolethyl) ether, etc. Having an ester structure of acrylic acid or methacrylic acid with a monohydric or higher alcohol and allylation of allyl sulfide, diallyl phthalate, diethylene glycol bisallyl carbonate, etc. Products; vinyl compounds such as acrolein, acrylonitrile and vinyl sulfide; styrene, α-methylstyrene, methylvinylbenzene, ethylvinylbenzene, α-chlorostyrene, chlorovinylbenzene, vinylbenzyl chloride, paradivinylbenzene, metadivinylbenzene, etc. Examples thereof include aromatic vinyl compounds, and these may be used alone or in combination of two or more. The amount of these used is 0.
It is preferably from 01 to 20 mol%.

The above-mentioned polymerizable composition may, if desired, improve the weather resistance as long as the object of the present invention is not impaired.
Additives such as an ultraviolet absorber, an antioxidant, a coloring inhibitor, and a fluorescent dye may be appropriately added. Further, a catalyst for improving the polymerization reaction may be appropriately used, and examples thereof include amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and mineral acids. , Lewis acids, organic acids, silicic acids, and boric acid tetrafluoride are effective. The optical material obtained by using the metal-containing episulfide compound of the present invention can be produced, for example, according to the following method. First,
A uniform composition containing the polymerizable compound and various additives used as needed is prepared. Next, the composition is poured into a mold in which a glass or metal mold and a resin gasket are combined using a known casting polymerization method, and is cured by heating. At this time, in order to facilitate removal of the resin after molding, the mold may be subjected to a releasing treatment in advance, or a releasing agent may be mixed with the composition. The polymerization temperature varies depending on the compound used, but is generally -20 to 150 ° C, and the polymerization time is about 0.5 to 72 hours. The polymer released after the polymerization can be easily dyed in water or an organic solvent using a usual disperse dye. At this time, in order to further facilitate dyeing, a carrier may be added to the dye dispersion, or heating may be performed. The use of the optical material thus obtained is not particularly limited, but it is particularly preferably used as an optical product such as a plastic lens.

[0026]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the physical properties of the metal-containing episulfide compound obtained in the examples, and the physical properties of the polymers obtained in the application examples and the comparative application examples were measured according to the methods described below. Refractive index <Physical Properties of the metal-containing episulfide compounds> (n _d), Abbe number (ν _d): a Kalnew Co. precision refractometer KPR-200 was measured at 25 ° C. using. 1) Refractive index <Properties of polymer> (n _d), Abbe number ([nu _d): was measured in the same manner as described above. 2) Appearance: Observed with the naked eye. 3) Weather resistance: The plastic lens was set on a weather meter equipped with a sunshine carbon arc lamp, and after 200 hours, the plastic lens was taken out and the hue was compared with the plastic lens before the test. The evaluation criteria were no change (○), slight yellowing (△),
Yellowing (x). 4) Heat resistance: 0.5mmφ using Rigaku TMA device
TMA measurement was performed with a load of 98 mN (10 gf) using the above pin, and the evaluation was made based on the peak temperature of the chart obtained at a temperature increase of 10 ° C./min. 5) Optical distortion: Visual observation was performed by the Schlieren method. Those without distortion were evaluated as ○, and those with distortion were evaluated as x.

Example 1 Tetrakis (2: 3-epithiopropylthio) germane
(E1) (M = Ge, x = 4 in the general formula (1))
Preparation Example 2: To a solution of 3- epithiopropylmercaptan (10.04 g) in tetrahydrofuran (94.5 mL) was added dry pyridine (10.47 g) at -30 ° C, and the mixture was stirred for 5 minutes.
At that temperature, a solution of germanium tetrachloride (5.07 g) in tetrahydrofuran (47.2 mL) was added dropwise over 2 hours.
The mixture was stirred at -20 ° C for 4 hours. 2N-
Hydrochloric acid (30 mL) was added, and the product was treated with benzene (50 m
L), and the organic layer was washed with 2N-hydrochloric acid (30 mL) and water, and dried over magnesium sulfate.
The residue obtained by distilling off benzene from this extract was purified by silica gel column chromatography using a mixed solvent of benzene and normal hexane (mixing volume ratio = 7/3) as a mobile phase to obtain tetrakis (2: 3- Epithiopropylthio) germane (7.06 g, yield = 60.6%)
I got This compound has a refractive index of 1.691 and an Abbe number of 2
8.3. The analysis results for determining the structure of this compound are shown below. ¹ H-NMR (solvent: CDCl ₃ , internal standard: TM
S); δ2.33 (dd, 1H), δ2.60 (dt, 1H), δ2.84 (d
d, 1H), δ 3.23 to 3.14 (m, 1H), δ 3.31 (dd, 1H). IR (liquid film); 2987, 1439, 1423, 1239, 1088, 1045,
684, 660, 617 cm ^-1 .

Example 2 Tetrakis (2: 3-epithiopropylthio) tin (E
2) (Production example of (M = Sn, x = 4 in the general formula (1)) 2: Dry pyridine (1) was added to a solution of 3-epithiopropylmercaptan (10.04 g) in dichloromethane (94.5 mL).
0.47 g) at −30 ° C., and the mixture was stirred for 5 minutes. At that temperature, 1.0 M tin tetrachloride in dichloromethane (23.
6 mL) was added dropwise over 2 hours, and the mixture was stirred at -20 ° C for 4 hours. 2N-hydrochloric acid (30 mL) was added to the reaction mixture, and the product was extracted twice with benzene (50 mL). The organic layer was washed with 2N-hydrochloric acid (30 mL) and water, and dried over magnesium sulfate. The residue obtained by distilling off benzene from this extract was purified by silica gel column chromatography using n-hexane as a mobile phase to obtain tetrakis (2: 3-epithiopropylthio) tin (9.09 g, yield = 71.4%). This compound had a refractive index of 1.706 and an Abbe number of 29.2. The analysis results for determining the structure of this compound are shown below. ¹ H-NMR (solvent: CDCl ₃ , internal standard: TM
S); δ2.31 (dd, 1H), δ2.58 (dt, 1H), δ2.81 (d
d, 1H),? 3.22 to 3.13 (m, 1H),? 3.29 (dd, 1H). IR (liquid film); 2978, 1428, 1418, 1245, 1080, 1039,
688, 611 cm ^-1 .

Example 3 Tris (4: 5-epithio-2-thiapentyl) -2: 3-
Epithiopropylthiotitanium (E3) (in general formula (1)
Preparation example of M = Ti, x = 1, y = 1) 1.0 M-dichloromethane solution of titanium tetrachloride (25.0 m
To L), a solution of diazomethane in ether (150 mL) generated from 1-methyl-3-nitro-1-nitrosoguanidine (15.76 g) was added at 0 ° C., and the mixture was stirred at that temperature for 30 minutes. To this reaction mixture, thiolate prepared from 2: 3-epithiopropylmercaptan (10.62 g) and sodium ethoxide (6.80 g) was added dropwise at −10 ° C. in tetrahydrofuran (100 mL) over 1 hour. Thereafter, the mixture was stirred at 0 ° C. for 12 hours. 2N-hydrochloric acid (60 mL) was added to the reaction mixture, and the product was extracted twice with chloroform (70 mL). The organic phase was washed with water and dried over magnesium sulfate. The residue obtained by evaporating the solvent from this extract was purified by silica gel column chromatography using a mixed solvent of normal hexane and ethyl acetate (mixed volume ratio = 4/1) as a mobile phase to obtain a tris (4: 5 -Epithio-2-thiapentyl)-
2: 3-Epithiopropylthiotitanium (7.18 g, yield =
56.2 g) were obtained. This compound had a refractive index of 1.677 and an Abbe number of 34.8. The analysis results for determining the structure of this compound are shown below. ¹ H-NMR (solvent: CDCl ₃ , internal standard: TM
S); δ2.38 (dd, 2H), δ2.47 (s, 3H), δ2.64 (dt,
2H), δ2.92 (dd, 2H), δ3.41 to 3.33 (m, 2H), δ
3.51 (dd, 2H). IR (liquid film); 2966, 1440, 1435, 1219, 1120, 1085,
653, 608 cm ^-1 .

Example 4 Tris (2: 3-epithiopropylthio) -5: 6-epithi
O-3-Thiahexylsilane (E4) (in the general formula (1)
Preparation Example of M = Si, x = 3, y = 2) Silicon tetrachloride (4.25 g) in tetrahydrofuran (25.0)
1.0M-vinylmagnesium bromide in tetrahydrofuran solution (25.0 mL) was added dropwise to the solution at 10 ° C over 2 hours. After the reaction mixture was stirred at that temperature for 2 hours, it was cooled to -15 ° C, dry pyridine (8.31 g) was added thereto, and the mixture was stirred for 5 minutes and then mixed with 2: 3-epithiopropylmercaptan (10.62 g). ) In tetrahydrofuran (50 mL) was added dropwise over 1 hour. After stirring the reaction mixture for 4 hours at 0 ° C., azobisdimethylvaleronitrile (6.3 mg) was added thereto and the mixture was refluxed for 6 hours. 2N-hydrochloric acid (60 mL) was added to the reaction mixture cooled to room temperature, and the product was treated with benzene (70 mL).
, And the organic phase was washed with water and dried over magnesium sulfate. The residue obtained by distilling off the solvent from this extract is
Purification was performed using silica gel column chromatography using a mixed solvent of normal hexane and ethyl acetate (mixed volume ratio = 9/1) as a mobile phase to obtain tris (2: 3-
(Epithiopropylthio) -5: 6-epithio-3-thiahexylsilane (5.76 g, yield = 48.3%) was obtained. This compound had a refractive index of 1.634 and an Abbe number of 32.6. The analysis results for determining the structure of this compound are shown below. ¹ H-NMR (solvent: CDCl ₃ , internal standard: TM
S); δ 0.99 (h, 1H), δ 2.28 (dd, 2H), δ 2.38 (s,
3H), δ2.51 (h, 1H), δ2.59 (dt, 2H), δ2.84 (d
d, 2H), δ 3.22 to 3.31 (m, 2H), δ 3.42 (dd, 2H). IR (liquid film); 2930, 1411, 1392, 1241, 1209, 1110,
1060, 620, 614 cm ^-1 .

Application Example 1 Production of Optical Material Consisting of Polymer 0.05 mol of tetrakis (2: 3-epithiopropylthio) germane (E1) obtained in Example 1 and tetra (normal butyl) as a polymerization catalyst A mixture of 2 × 10 ⁻⁵ mol of phosphonium bromide (CT1) was uniformly stirred, poured into two glass molds for lens molding, and was heated at 50 ° C. for 10 hours, then at 60 ° C. for 5 hours, and further at 120 ° C. Heat polymerization was performed for 3 hours to obtain a lens-shaped polymer. Table 1 shows the physical properties of the obtained polymer. From Table 1, the polymer obtained in this Application Example 1 was colorless and transparent refractive index (n _d) is 1.75
7, which was as high as 7 (abbe number) (v _d ) as high as 29.0 (low dispersion), excellent in weather resistance and heat resistance (117 ° C.), and free of optical distortion. Therefore, the obtained polymer was suitable as an optical material. Application Examples 2 to 5 Production of Optical Material Consisting of Polymer The metal-containing episulfide compound of the present invention (component C1),
Other episulfide compounds, epoxy compounds and / or vinyl monomers (C2 component), and polymerization catalysts were used as shown in Table 1, and the same operation as in Application Example 1 was performed except that the polymerization conditions were appropriately changed. Thus, a lens-shaped polymer was obtained. Table 1 shows the physical properties of these polymers.
From Table 1, the polymer obtained in this Application Example 2 to 5 is also colorless and transparent refractive index (n _d) is very high as from 1.712 to 1.764, an Abbe number ([nu _d) also 28. High (low dispersion) of 8 to 36.3, weather resistance and heat resistance (111 to 138 ° C)
And no optical distortion.

Application Comparative Example 1 As shown in Table 1, 0.1 mol of pentaerythritol tetrakis (mercaptopropionate) (CE5), 0.2 mol of m-xylylene diisocyanate (CE6) and 1.1 mol of dibutyltin dichloride (CT5). The mixture of 0 × 10 ^-4 mol was uniformly stirred, poured into two glass molds for lens molding, heated at 50 ° C. for 10 hours, then heated at 60 ° C. for 5 hours, and further heated at 120 ° C. for 3 hours to form a lens. A polymer having a shape was obtained. Table 1 shows properties of the obtained polymer. Table 1
From this, the polymer of Application Comparative Example 1 was colorless and transparent, and no optical distortion was observed. However, n _d / v _d was 1.59 / 36, the refractive index was low, and the heat resistance was poor at 86 ° C. Application Comparative Examples 2 and 3 The same operation as in Application Comparative Example 1 was performed except that the raw material compositions shown in Table 1 were used, and a lens-shaped polymer was obtained.
Table 1 shows the physical properties of these polymers. As shown in Table 1, the polymer of Comparative Example 2 has a low n _d / v _d of 1.67 / 28, and has relatively good heat resistance (94 ° C.), but is inferior in weather resistance and colored. Was observed, and optical distortion was observed.
The polymer of Application Comparative Example 3 had a relatively high Abbe number (ν _d ) of 36, was excellent in weather resistance, was colorless and transparent, and no optical distortion was observed, but was heat resistant (90 ° C.). Is inferior,
The refractive index (n _d ) was not very high at 1.70, and the polymer was brittle.

[0033]

[Table 1]

(Abbreviations in Table 1) EI: Tetrakis (2: 3-epithiopropylthio) germane E2: Tetrakis (2: 3-epithiopropylthio) tin E3: Tris (4: 5-epithio-2-thiapentyl) )
-2: 3-Epithiopropylthiotitanium E4: Tris (2: 3-epithiopropylthio) -5: 6
-Epithio-3-thiahexylsilane E5: Tris (2: 3-epithiopropylthio) -4: 5
-Epithio-2-thiapentylgermane CE1: 2: 3-Epithiopropyl sulfide CE2: 2,2-bis (4- (2-glycidyloxy)
Ethoxyphenyl) propane CE3: Cyclohexene oxide CE4: Bis (2-acryloxyethyl) -1,4-xylylcarbamate CE5: Pentaerythritol tetrakis (mercaptopropionate) CE6: m-Xylylenediisocyanate CE7: 1,3, 5-trimercaptobenzene CE8: 2: 3-epithiopropylsulfide CT1: tetra (normalbutyl) phosphonium bromide CT2: triethylamine CT3: 2,4,6-tridimethylaminophenol CT4: boron trifluoride-pyridine complex CT5: dibutyltin dichloride

[0035]

The metal-containing episulfide compound of the present invention is a novel compound in which four reactive substituents having a terminal episulfide group are bonded to metal atoms such as silicon, germanium, tin and titanium, and It is suitably used as a raw material for. Further, the optical material obtained by using the metal-containing episulfide compound of the present invention has a high refractive index, a high Abbe number, and has excellent heat resistance, weather resistance, and transparency. It is suitable as a material for producing optical products such as a recording medium substrate used for an optical fiber, an optical disk, a magnetic disk, and the like, a coloring filter, an infrared absorption filter, and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H049 VN01 VN02 VN03 VN05 VP01 VQ61 VR21 VR22 VR23 VR61 VR62 VR63 VR64 VS09 VT51 VU20 VW02

Claims (6)

[Claims] (1) General formula (1) (In the formula, M represents silicon, germanium, tin or titanium, x represents an integer of 1 to 4, and y represents 1 or 2.) A metal-containing episulfide compound represented by the following formula: 2. The metal-containing episulfide compound is tetrakis (2: 3-epithiopropylthio) germane, tetrakis (2: 3-epithiopropylthio) tin, tris (4: 5-epithio-2-thiapentyl)-. The metal-containing episulfide compound according to claim 1, which is 2: 3-epithiopropylthiotitanium or tris (2: 3-epithiopropylthio) -5: 6-epithio-3-thiahexylsilane. 3. The general formula MZ ₄ (where M is the same as above,
Z represents a halogen atom), and reacting 2: 3-epithiomercaptopropane with a metal tetrahalide represented by the general formula (1-a): (In the formula, M is the same as described above.) A method for producing a metal-containing episulfide compound represented by the formula: 4. The metal tetrahalide is metal tetrachloride,
When the metal-containing episulfide compound is tetrakis (2: 3-
Epithiopropylthio) germane or tetrakis (2:
4. The method according to claim 3, wherein the compound is 3-epithiopropylthio) tin. 5. A reaction of 2: 3-epithiomercaptopropane with a chloromethylated or vinyl-substituted metal tetrahalide represented by the general formula MZ ₄ (M and Z are as defined above). General formula (1) characterized by the following: (In the formula, M is the same as above, x represents an integer of 1 to 3, and y represents 1 or 2.) A method for producing a metal-containing episulfide compound represented by the formula: 6. The metal tetrahalide is metal tetrachloride,
The metal-containing episulfide compound is tris (4: 5-epithio-2-thiapentyl) -2: 3-epithiopropylthiotitanium or tris (2: 3-epithiopropylthio)
The production method according to claim 6, wherein -5: 6-epithio-3-thiahexylsilane is used.