JP6476088B2 - Method for producing episulfide compound - Google Patents

Description

  The present invention relates to a method for producing an episulfide compound by reacting an epoxy compound with a sulfur-containing compound.

  The epoxy resin is cured with various curing agents to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, epoxy resins are used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials. Conventionally, bisphenol A-type epoxy resins and the like are known as the most commonly used epoxy resins in the industry, but such epoxy resins sometimes have insufficient heat resistance depending on applications. Furthermore, epoxy resins are also used for optical materials and the like. However, recent optical materials require high optical properties, and thus require a high refractive index. Therefore, in order to satisfy such requirements, attempts have been made to introduce a 9,9-bisphenylfluorene skeleton into a resin raw material and to use an episulfide compound instead of an epoxy compound.

  JP-A-2001-181276 (Patent Document 1) discloses an episulfide compound represented by the following formula.

(In the formula, X represents an oxygen atom or a sulfur atom, and at least one is a sulfur atom. R _{1 to} R ₈ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and Or different.)

  This document describes, as a method for producing the episulfide compound, a method in which a glycidyl ether compound having a fluorene skeleton is reacted with a thio compound. Moreover, in the manufacturing method of the said episulfide compound, it is described that it is preferable to add acids, such as nitric acid, a sulfuric acid, hydrochloric acid, phosphoric acid, an acetic acid, propionic acid, as a reaction accelerator, and the sulfuric acid is used in the Example.

  However, episulfide compounds cannot be reacted at high temperatures because they are easily gelled by heating, but it is difficult to produce episulfide compounds in high yields at low temperatures and in a short time by the production method of this document.

  In addition, as a fluorene skeleton-containing episulfide compound capable of achieving both excellent handling properties, high heat resistance, a high refractive index, and the like, JP2013-124339A (Patent Document 2) is represented by the following formula (1a). Episulfide compounds are disclosed.

(In the formula, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, R ² is an alkylene group, R ³ is a substituent, k is an integer of 0 to 4, m is an integer of 1 or more, and n is It is an integer greater than or equal to 0).

  This document describes a method for reacting an epoxy compound having a fluorene skeleton with a sulfur-containing compound as a method for producing the episulfide compound. This document describes that the reaction may be carried out in various solvents. In the examples, an epoxy compound having a fluorene skeleton and thiourea are reacted in tetrahydrofuran and methanol.

  Furthermore, Phosphorus, Sulfur and Silicon and the Related Elements (2011), 186 (9), 1902-1909 (Non-Patent Document 1) discloses a method of modifying an epoxy resin into an episulfide resin using molecular sieves. ing.

  However, even with the methods described in Patent Document 2 and Non-Patent Document 1, it is difficult to produce an episulfide compound in a high yield at a low temperature and in a short time.

JP 2001-181276 A (Claim 1, paragraphs [0013] and [0015], Examples) JP 2013-124339 A (Claim 1, paragraphs [0072] [0075], Examples)

Phosphorus, Sulfur and Silicon and the Related Elements (2011), 186 (9), 1902-1909

  Accordingly, an object of the present invention is to provide a method for efficiently producing an episulfide compound.

  Another object of the present invention is to provide a method for producing an episulfide compound in a high yield at a low temperature and in a short time.

  Still another object of the present invention is to provide a method for producing an episulfide compound that is excellent in handling properties and has both high strength, high heat resistance, and high refractive index.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an episulfide compound can be obtained efficiently by reacting an epoxy compound with a sulfur-containing compound in the presence of a reaction aid containing a crown ether. The present invention has been completed.

  That is, the production method of the present invention is a method for producing an episulfide compound by reacting an epoxy compound with a sulfur-containing compound in the presence of a reaction aid containing a crown ether. The reaction aid may further contain a porous adsorbent (particularly molecular sieves). The weight ratio of the crown ether and the porous adsorbent is about 1/50 to 1/5000 of crown ether / porous adsorbent. The crown ether may have an 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) skeleton. The weight ratio of the crown ether to the epoxy compound is about crown ether / epoxy compound = 1/100 to 1/10000. The epoxy compound may be an epoxy compound having a fluorene skeleton. This epoxy compound having a fluorene skeleton contains an epoxy compound represented by the following formula (A), and the obtained episulfide compound may contain an episulfide compound represented by the following formula (1).

(In the formula, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, R ² is an alkylene group, R ³ is a substituent, k is an integer of 0 to 4, m is an integer of 0 or more, and p is An integer of 1 or more, and n is an integer of 0 or more).

  In the formulas (A) and (1), p may be 1 or 2. The sulfur-containing compound may be a thiourea. The method of the present invention may be reacted in the presence of a solvent containing an aromatic hydrocarbon. In the method of the present invention, the reaction temperature may be 60 ° C. or less.

  In the present invention, since an epoxy compound and a sulfur-containing compound are reacted in the presence of a reaction aid containing a crown ether, an episulfide compound can be produced efficiently. In particular, an episulfide compound can be produced in a high yield at a low temperature and in a short time. Can be manufactured. Furthermore, when an epoxy compound having a fluorene skeleton is used as the epoxy compound, an episulfide compound that is excellent in handling properties and has high strength, high heat resistance, high refractive index and the like can be produced.

FIG. 1 is an IR spectrum chart of the episulfide compound obtained in Example 4.

[Method for producing episulfide compound]
In the present invention, an episulfide compound is produced by reacting an epoxy compound with a sulfur-containing compound in the presence of a reaction aid containing a crown ether.

(Epoxy compound)
The epoxy compound is not particularly limited as long as it has an epoxy group, and is a general-purpose epoxy resin such as a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, an alicyclic epoxy resin, a glycidyl amine type epoxy resin, etc. However, an epoxy compound having a fluorene skeleton is preferable because an episulfide compound having excellent handling properties and high strength, high heat resistance, and high refractive index can be obtained. Furthermore, the epoxy compound having a fluorene skeleton may contain at least an epoxy compound represented by the following formula (A).

(In the formula, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, R ² is an alkylene group, R ³ is a substituent, k is an integer of 0 to 4, m is an integer of 0 or more, and p is An integer of 1 or more, and n is an integer of 0 or more).

In the formula (A), examples of the aromatic hydrocarbon ring represented by the ring Z include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, an indene ring, a naphthalene, C _8-20 condensed bicyclic hydrocarbon rings such as rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic hydrocarbon rings (eg, anthracene ring, phenanthrene ring, etc.) Bi- to tetracyclic hydrocarbon rings, etc.]. Preferred aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring and the like, and a benzene ring or a naphthalene ring (particularly a benzene ring) is particularly preferable. The two rings Z substituted at the 9-position of fluorene may be the same or different rings, and may usually be the same ring.

  In addition, the substitution position of the ring Z substituted at the 9th position of fluorene is not particularly limited. For example, the naphthyl group substituted at the 9th position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, or the like. Particularly preferred is a 2-naphthyl group.

Examples of the substituent represented by the group R ¹ include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydrocarbon group [eg, an alkyl group, an aryl group (C _6-6 such as a phenyl group). ₁₀ aryl group), etc.] non-reactive substituent (particularly non epoxy substituent) can be mentioned, such as, in particular, a halogen atom, it is often a cyano group or an alkyl group (particularly an alkyl group). Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when the group R ¹ is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

Examples of the alkylene group represented by the group R ² include C _2-6 alkylene groups such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, tetramethylene group, preferably C _2-4 alkylene group. More preferably, a _C2-3 alkylene group, especially an ethylene group is used. When m is 2 or more, the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group.

The number (number of added moles) m of the oxyalkylene group (OR ² ) can be selected from the range of, for example, about 0 to 25 (for example, 0 to 20) according to the use and desired performance, and is usually 0 to 18 (for example, 0 to 15), preferably 0 to 12 (for example, 0 to 10), more preferably 0 to 8 (for example, 0 to 7). In particular, it is preferably an integer of 1 or more from the viewpoint that both handleability, high strength, high heat resistance, and high refractive index can be achieved. For example, it can be selected from a range of about 1 to 25 (for example, 1 to 20), Usually, it may be 1 to 15, preferably 1 to 10, more preferably 1 to 8 (for example, 1 to 5), particularly about 1 to 3 (for example, 1 to 2).

  The total of m may be, for example, 0 to 30 (for example, 0 to 25), preferably 0 to 20 (for example, 0 to 18), more preferably 0 to 16 (for example, 0 to 14), and particularly 0. It may be about ~ 8. In particular, the total of m is, for example, 2 to 30 (for example, 2 to 20), preferably 2 to 15 (for example, 2 to 10), since handling properties, high strength, high heat resistance, and a high refractive index can be compatible. ), More preferably 2 to 6 (for example, 2 to 4). Note that m may be the same or different.

  The compound represented by the formula (A) may be an aggregate of compounds having the same value of m, or an aggregate of compounds having different values of m. In the latter case, the value of m and the sum of m are average values (arithmetic average or arithmetic average).

  In the formula (A), the substitution number p may be the same or different and may be an integer of 1 or more, and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. . In addition, the substitution number p may be the same or different in each ring Z, and is usually the same in many cases.

Examples of the substituent R ³ substituted on the ring Z include an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, preferably a C _1-8 alkyl group). More preferably a C _1-6 alkyl group), a cycloalkyl group (C _5-8 cycloalkyl group such as a cyclohexyl group, preferably a C _5-6 cycloalkyl group etc.), an aryl group (for example, a phenyl group). , C _6-14 aryl groups such as tolyl group and xylyl group, preferably C _6-10 aryl group, more preferably C _6-8 aryl group, etc., aralkyl groups (C _6-10 such as benzyl group, phenethyl group, etc.) Hydrocarbon groups such as aryl-C _1-4 alkyl groups; alkoxy groups (C _1-8 alkoxy groups such as methoxy groups, preferably C _1-6 A group such as a alkoxy group), a cycloalkoxy group (such as a C _5-10 cycloalkyloxy group), and an aryloxy group (such as a C _6-10 aryloxy group) —OR ⁴ [wherein R ⁴ represents a hydrocarbon group ( The above-exemplified hydrocarbon groups, etc.]; groups such as alkylthio groups (C _1-8 alkylthio groups such as methylthio groups, preferably C _1-6 alkylthio groups) and the like —SR ⁴ (wherein R ⁴ represents An acyl group (C _1-6 acyl group such as acetyl group); alkoxycarbonyl group (C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine) Hydroxyl group; nitro group; cyano group; substituted amino group (for example, dialkylamino group such as dimethylamino group), etc. Non epoxy substituents.

Of these, the group R ³ is preferably a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, and the like. Particularly preferred groups R ³ are hydrocarbon groups [eg alkyl groups (eg C _1-4 alkyl groups)], alkoxy groups (C _1-4 alkoxy groups etc.), halogen atoms (fluorine atoms, chlorine atoms, bromines). Atoms, iodine atoms, etc.).

In addition, in the same ring Z, when the group R ³ is plural (two or more), the groups R ³ may be different from each other or the same. In the two rings Z, the groups R ³ may be the same or different. The preferred substitution number n may be 0 to 8, preferably 0 to 6 (for example, 1 to 5), more preferably 0 to 4, particularly 0 to 2 (for example, 0 to 1). In the two rings Z, the number of substitutions n may be the same or different from each other.

  The position of substitution of the epoxy group (or the epoxy group-containing group) with respect to the ring Z is not particularly limited as long as it is substituted at an appropriate position of the ring Z. For example, when p is 1 and ring Z is a benzene ring, the epoxy group-containing group may be substituted at the 3-position or 4-position, particularly 4-position. When p is 2 and ring Z is a benzene ring, the epoxy group-containing group may be substituted at the 3-position and 5-position. In addition, when p is 1 and the ring Z is a condensed polycyclic aromatic hydrocarbon ring, in particular, a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of fluorene (for example, naphthalene And the combination of the epoxy group-containing group of the naphthalene ring and the substitution position of fluorene is typically 1,5-position or 2,6-position. There are many cases.

Typical examples of the epoxy compound represented by the formula (A) include 9,9-bis (glycidyloxyphenyl) fluorene [eg, 9,9-bis (4-glycidyloxyphenyl) fluorene], 9, 9-bis (glycidyloxynaphthyl) fluorene [eg, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9,9-bis (5-glycidyloxy-1-naphthyl) fluorene] In (A), a compound wherein m is 0 and p is 1; 9,9-bis [di or tri (glycidyloxy) phenyl] fluorene {eg, 9,9-bis [3,5-di (glycidyl) In the formula (A) such as oxy) phenyl] fluorene}, m is 0, and p is 2 or more (for example, 2 to 4, preferably 2 to 3, more preferably 2) a compound which is 9,9-bis (glycidyloxyalkoxyphenyl) fluorene {for example, 9,9-bis [(glycidyloxy) such as 9,9-bis [4- (2-glycidyloxyethoxy) phenyl] fluorene C _2-4 alkoxy) phenyl] fluorene}, 9,9-bis (glycidyloxyalkoxynaphthyl) fluorene {eg, 9,9-bis [6- (2-glycidyloxyethoxy) -2-naphthyl] fluorene, 9,9-bis [(glycidyloxy C _2-4 alkoxy) naphthyl] fluorene}, 9,9-bis (glycidyloxypoly) such as 9-bis [5- (2-glycidyloxyethoxy) -1-naphthyl] fluorene Alkoxyphenyl) fluorene {eg, 9,9-bis [4- (2-glycidyloxyate) Carboxymethyl) 9,9-bis such ethoxyphenyl) fluorene [(glycidyloxy poly _{C 2-4} alkoxy) phenyl] fluorene}, 9,9-bis (glycidyloxy polyalkoxy naphthyl) fluorene {e.g., 9,9-bis {6- [2- (2-glycidyloxy) ethoxy] -2-naphthyl} 9,9-bis fluorene [(glycidyloxy poly _{C 2-4} alkoxy) naphthyl] the expression, such as fluorene} (a ) In which m is 1 or more (eg 1 to 4, preferably 1 to 3, more preferably 1 to 2, especially 1) and p is 1; 9,9-bis [di or tri (glycidyloxy) Alkoxy) phenyl] fluorene {eg, 9,9-bis [3,5-di (2-glycidyloxyethoxy) phenyl] fluorene Which of 9,9-bis in [3,5-di (glycidyloxy _{C 2-4} alkoxy) phenyl] Formula of fluorene} (A), m is 1 or more (e.g. 1 to 4, preferably 1 to 3, More preferably, it is 1 to 2, particularly 1), and a compound in which p is 2 or more (for example, 2 to 4, preferably 2 to 3, more preferably 2) is included.

  A commercially available product may be used as the epoxy compound represented by the formula (A). In particular, an epoxy compound represented by the formula (A) and p is 1 is represented by a conventional method (for example, represented by the following formula: For example, a method of reacting a compound to be reacted with an epihalohydrin such as epichlorohydrin).

(In the formula, Z, R ¹ , R ² , R ³ , k, m, and n are the same as above).

  In addition, the compound represented by Formula (A) can also be manufactured with reference to Unexamined-Japanese-Patent No. 2009-155256 etc.

  In addition, when manufacturing as mentioned above, in addition to the epoxy compound represented by formula (A) and p is 1, a multimer of epoxy compounds represented by formula (A) and p is 1 (Epoxy compound represented by the following formula (B)) or a monofunctional epoxy compound (epoxy compound represented by the following formula (C)) may be produced.

(In the formula, q represents an integer of 1 or more, and Z, R ¹ , R ² , R ³ , k, m, and n are the same as above).

  In the formula (B), q may be, for example, 1 to 10, preferably 1 to 4, more preferably 1 to 3, particularly 1 to 2. Usually, the epoxy compound represented by Formula (B) contains at least the compound in which q is 1 in Formula (B). The ratio of the compound in which q is 1 in the formula (B) to the whole compound represented by the formula (B) is, for example, 40 mol% or more (for example, 45 to 100 mol%), preferably 50 mol%. It may be more (for example, 55 to 99 mol%), more preferably 60 mol% or more (for example, 65 to 97 mol%), particularly 70 mol% or more (for example, 75 to 95 mol%).

  The proportion of the compound represented by the formula (B) is 50 mol% or less (for example, 1 to 45 mol%), preferably 40 mol% or less of the whole epoxy compound represented by the formula (A) to (C) ( For example, it may be 2 to 35 mol%), more preferably 30 mol% or less (for example, 3 to 25 mol%).

  The proportion of the compound represented by the formula (C) is 30 mol% or less (for example, 0.5 to 25 mol%), preferably 25 mol% of the whole epoxy compound represented by the formula (A) to (C). It may be the following (for example, 1 to 22 mol%), more preferably 20 mol% or less (for example, 2 to 18 mol%).

  Moreover, the ratio of the total amount of the compound represented by Formula (B) and the compound represented by Formula (C) is 50 mol% or less of the whole epoxy compound represented by Formula (A)-(C) (for example, 1 to 45 mol%), preferably 40 mol% or less (for example, 3 to 35 mol%), more preferably 30 mol% or less (for example, 5 to 25 mol%), and usually 3 to 20 mol%. % (For example, 5 to 15 mol%) may be sufficient.

  The ratio (molar ratio) between the epoxy compound represented by the formula (B) and the epoxy compound represented by the formula (C) is, for example, the former / the latter = 99/1 to 1/99 (for example, 97 / 3 to 10/90), preferably 95/5 to 15/85 (for example, 93/7 to 20/80), more preferably about 90/10 to 30/70 (for example, 85/15 to 40/60). It may be.

  Further, when the obtained episulfide compound is used as a curable resin, the formula is compared with the epoxy compounds represented by the formulas (B) and (C) from the viewpoint of improving the crosslinking density and improving the strength of the cured product. It is preferable to contain an epoxy compound represented by (A) and p = 1 as a main component. The proportion of the epoxy compound represented by the formula (A) and p is 1 is 50 mol% or more (for example, 50 to 100 mol%) with respect to the entire epoxy compound represented by the formula (A) to (C). ), For example, 60 mol% or more (for example, 65 to 99 mol%), preferably 70 mol% or more (for example, 75 to 98 mol%), more preferably 80 mol% or more (especially 85 to 99 mol%). 97 mol%), and usually about 80 to 95 mol% (for example, 85 to 93 mol%). If the proportion of the epoxy compound (A) is too small, the strength and refractive index of the cured product may be reduced.

  In this invention, the ratio of the epoxy compound represented by Formula (A)-(C) can be calculated | required by measuring the purity (area ratio, area%) by a high performance liquid chromatography (HPLC).

  In the epoxy compound represented by the formula (A) and p is 1, the ratio of the epoxy compound represented by the formula (B) and the epoxy compound represented by the formula (C) is the production condition of the epoxy compound. It can be easily adjusted by such as. In addition, an epoxy compound represented by formula (B) and an epoxy compound represented by formula (C) are separately prepared and mixed with an epoxy compound represented by formula (A) and p is 1, and an epoxy composition A product can also be prepared.

  And the epoxy compound represented by Formula (A) and p is 1, the multimer epoxy compound represented by the said Formula (B), and the monofunctional epoxy compound represented by Formula (C) are included. Episulfiding the epoxy composition gives the corresponding episulfide composition.

(Sulfur-containing compounds)
The sulfur-containing compound is not particularly limited as long as it contains a sulfur atom and can be episulfided (thioepoxidized), but for example, thioureas (thiourea; ethylenethiourea, propylenethiourea, thiobarbituric acid, dithiourazole, And cyclic thiourea such as thiohydantoin and dithiohydantoin), thiocyanic acid or a salt thereof, triphenylphosphine sulfide, 3-methylbenzothiazole-2-thione and the like. These sulfur-containing compounds can be used alone or in combination of two or more. Of these sulfur-containing compounds, thioureas (particularly thiourea) are preferred.

  The proportion of the sulfur-containing compound can be selected according to the proportion of the epoxy group, and is, for example, 2 mol or more (for example, 2.1 to 30 mol), preferably 1 mol with respect to 1 mol of the epoxy compound (or the composition of the epoxy compound). May be about 2.5 to 20 mol, more preferably about 3 to 15 mol (for example, 3 to 10 mol). If the ratio of the sulfur-containing compound is too small, the yield may decrease.

(Crown ether)
In the present invention, the reaction between the epoxy compound and the sulfur-containing compound can be promoted by reacting in the presence of a reaction aid containing a crown ether, and a high yield episulfide compound can be obtained in a short time even at low temperatures. Is obtained.

  The crown ether may be a macrocyclic compound having a heteroatom such as oxygen, nitrogen and sulfur, and may be an ether containing an oxygen atom and a nitrogen atom as a heteroatom such as diaza crown ether. From the viewpoint of improving the reaction efficiency, a crown ether containing an oxygen atom as a hetero atom is preferred.

  Such a crown ether has at least an oxacycloalkane skeleton, and the number of members of the oxacycloalkane skeleton (oxacycloalkane ring) is, for example, 10 to 50 membered ring, preferably 12 to 40 membered ring, The number may preferably be about 14 to 30 members (especially 16 to 20 members). The number of oxygen atoms contained in the oxacycloalkane skeleton is, for example, about 2 to 20, preferably about 3 to 15, and more preferably about 4 to 10 (particularly 5 to 8).

Further, the crown ether may be condensed with an oxacycloalkane skeleton by a benzene ring or a naphthalene ring, and may have a substituent. Examples of the substituent include an alkyl group such as a methyl group (eg, a C _1-4 alkyl group such as a methyl group), an alkenyl group (eg, a C _2-6 alkenyl group such as a vinyl group), and a cycloalkyl group. (For example, C _5-12 cycloalkyl group such as cyclohexyl group), aryl group (phenyl group, naphthyl group, etc.) and the like.

  Examples of the crown ether include crown ethers having a 12-crown-4 (12-crown 4-ether or 12-crown-O-4) skeleton (for example, 12-crown-4, benzo-12-crown-4). , Cyclohexyl-12-crown-4, etc.), crown ethers having a 14-crown-4 skeleton (for example, 14-crown-4, dibenzo-14-crown-4 etc.), crown ethers having a 15-crown-5 skeleton (For example, 15-crown-5, benzo-15-crown-5, 1,2-decalyl-15-crown-5, 1,2-naphth-15-crown-5, 1,2-vinylbenzo-15-crown -5), crown ethers having a 16-crown-5 skeleton (for example, 16-crown-5, 3, 4, 5- Phthalyl-16-crown-5, etc.), crown ethers having an 18-crown-6 skeleton (for example, 18-crown-6, benzo-18-crown-6, dibenzo-18-crown-6, tribenzo-18-crown) -6, 1,2-methylbenzo-18-crown-6, 1,2-t-butyl-18-crown-6, etc.), crown ethers having a 20-crown-7 skeleton (for example, 20-crown-7, 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7 and the like) and crown ethers having a 22-crown-6 skeleton (for example, 22-crown-6, dibenzo-22-crown-6) Etc.), crown ethers having a 24-crown-6 skeleton (for example, 24-crown-6, dibenzo-24-crown-8, etc.), 2 -Crown ether having a crown-8 skeleton (for example, 24-crown-8, dicyclohexyl-24-crown-8, etc.), Crown ether having a 30-crown-10 skeleton (for example, 30-crown-10, dibenzo-30) -Crown-10 etc.) etc. are mentioned.

  These crown ethers can be used alone or in combination of two or more. Of these crown ethers, crown ethers having an 18-crown-6 skeleton (particularly 18-crown-6) are preferred.

  The weight ratio of the crown ether to the epoxy compound is as follows: crown ether / epoxy compound = 1/100 to 1/10000, preferably 1/300 to 1/5000, more preferably 1/500 to 1/3000 (particularly 1/1000). About 1/2000). If the proportion of crown ether is too small, the reaction efficiency may be reduced.

(Other reaction aids)
In the present invention, in order to further improve the reaction efficiency, a porous adsorbent may be used as a reaction aid in addition to the crown ether.

  The porous adsorbent is preferably a conventional porous adsorbent or an inorganic porous adsorbent, and examples thereof include activated carbon, zeolite, molecular sieves, amorphous silica, silica gel, bentonite, activated alumina, and activated clay. These porous adsorbents can be used alone or in combination of two or more. Of these porous adsorbents, molecular sieves (or molecular sieves) are preferable from the viewpoint of a large effect of improving the reaction efficiency.

The molecular sieves, zeolite molecular sieves have been widely, typically the general _{formula: M 2 / n O · Al} 2 O 3 · xSiO 2 · yH 2 O ( wherein, M is a metal of an alkali metal or alkaline earth metal Cations, n is 1 to 2, x is an integer of 2 to 10, and y is an integer of 2 to 7).

  Examples of the metal cation represented by M in the formula include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as barium, magnesium and calcium. Of these, alkali metals such as sodium are preferred.

  The molecular sieves may be any type such as 3A type, 4A type, 5A type, and 13X type. The type of zeolite may be any of LTA type, FER type, MWW type, MFI type, MOR type, LTL type, FAU type, BEA type, etc., but LTA type, FAU type and the like are preferable.

  The average pore diameter of the porous adsorbent (particularly molecular sieves) is, for example, about 1 to 50 mm, preferably 2 to 30 mm, and more preferably about 3 to 20 mm (particularly 4 to 15 mm). If the pore diameter is too large, the reaction efficiency may decrease, and if it is too small, the reaction efficiency may decrease.

  The shape of the porous adsorbent (particularly molecular sieves) is, for example, spherical (true or nearly spherical), ellipsoidal, polygonal (polygonal, tetrahedral, rectangular, etc.), plate, rod, or fiber. And indefinite shape. These shapes may be the same shape or a combination of different shapes.

  The average diameter of the porous adsorbent (particularly molecular sieves) (average value of the major axis and the minor axis of the anisotropic shape) is, for example, 0.1 to 30 mm, preferably 0.5 to 20 mm, and more preferably 1 to 10 mm ( Particularly, it is about 2 to 5 mm).

  The weight ratio of the crown ether and the porous adsorbent (particularly molecular sieves) is as follows: crown ether / epoxy compound = 1/50 to 1/5000, preferably 1/100 to 1/3000, more preferably 1/300 to 1 / 2000 (particularly 1/400 to 1/1000). If the ratio of the porous adsorbent is too small, there is no effect of improving the reaction efficiency, and if it is too large, the reaction efficiency may be lowered.

  The reaction aid may further contain a conventional reaction accelerator. Examples of the reaction accelerator include inorganic acids (eg, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, etc.), organic acids (carboxylic acids such as acetic acid, propionic acid, etc.), and the like. The ratio of the reaction accelerator is 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, and more preferably about 5 to 30 parts by weight with respect to 100 parts by weight of the epoxy compound.

(solvent)
The method of the present invention may be performed in the presence of a solvent. Solvents include alcohols (alkyl alcohols such as methanol, ethanol, propanol and isopropanol, glycols such as ethylene glycol and propylene glycol), hydrocarbons (aliphatic hydrocarbons such as hexane, alicyclic rings such as cyclohexane, etc.) Formula hydrocarbons, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.), ethers (chain ethers such as dimethyl ether, diethyl ether, dioxane, tetrahydrofuran, etc.) Cyclic ethers), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), ketones (acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), cellosolves, carbitols, propiol Glycol monoalkyl ethers, glycol ether esters (ethylene glycol monomethyl ether acetate etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide etc.), sulfoxides (dimethyl sulfoxide etc.), nitriles ( Organic solvents such as acetonitrile and benzonitrile). The solvent can be used alone or as a mixed solvent.

Among these solvents, a solvent containing a hydrocarbon is preferable, and a solvent containing an aromatic hydrocarbon such as toluene is particularly preferable. Further, the solvent containing aromatic hydrocarbon is preferably a combination of aromatic hydrocarbon and alcohol (especially _C1-4 alkyl alcohol such as methanol), and the volume ratio of both is aromatic hydrocarbon / alcohol. = 10/1 to 1/10, preferably 5/1 to 1/5, more preferably 2/1 to 1/2 (especially 1.5 / 1 to 1 / 1.5).

  The weight ratio of the solvent and the epoxy resin is solvent / epoxy compound = 2/1 to 1000/1, preferably 5/1 to 500/1, more preferably 10/1 to 100/1 (particularly 20/1 to 50). / 1) grade.

(Reaction conditions)
In the method of the present invention, the reaction temperature may be, for example, 60 ° C. or less, for example, 0 to 60 ° C., preferably 10 to 55 ° C. (for example, 20 to 50 ° C.), more preferably 25 to 45 ° C. It may be about (especially 30-40 degreeC). If the reaction temperature is too high, the resulting episulfide compound may be gelled. In the present invention, an episulfide compound can be obtained in high yield even at such a low temperature.

  In the method of the present invention, an episulfide compound can be obtained in a short time even at a low temperature as described above. The reaction time may be, for example, about 30 minutes to 50 hours, preferably about 1 to 30 hours, more preferably about 3 to 20 hours (particularly 5 to 15 hours).

  The reaction may be performed while refluxing or may be performed while removing by-products. Further, the reaction may be performed with stirring, may be performed in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed under normal pressure, increased pressure, or reduced pressure.

  The produced compound (episulfide compound or episulfide composition represented by the formula (1) described later) is separated by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography and the like. Alternatively, it may be separated and purified by a separation means combining these.

[Episulfide compounds]
An episulfide compound is obtained by the above reaction. For example, when an epoxy compound represented by the formula (A) is used as the epoxy compound, an episulfide compound represented by the following formula (1) is obtained.

(In the formula, Z, R ¹ , R ² , R ³ , k, m, p, and n are the same as above).

  A representative episulfide compound (1) includes a compound represented by the following formula (1A) (a compound in which ring Z is a benzene ring and p is 1 in formula (1)), and is represented by the following formula (1B). A compound represented by formula (1) wherein ring Z is a naphthalene ring and p is 1, a compound represented by formula (1C) below (wherein ring Z is a benzene ring, p Is a compound of which is 2.

(In the formula, n1 represents an integer of 0 to 4, n2 to n4 each represents an integer of 0 to 3, and R ¹ , R ² , R ³ , k, and m are the same as above).

  Representative episulfide compounds (1) include 9,9-bis [(2,3-epithiopropoxy) (poly) alkoxyphenyl] fluorenes (or compounds represented by the formula (1A)), 9,9 -Bis [(2,3-epithiopropoxy) (poly) alkoxynaphthyl] fluorenes (such as a compound represented by the formula (1B)), 9,9-bis {di [(2,3-epithiopropoxy) (Poly) alkoxy] phenyl} fluorenes (such as a compound represented by the formula (1C)).

As 9,9-bis [(2,3-epithiopropoxy) (poly) alkoxyphenyl] fluorenes, for example, 9,9-bis {4- [2- (2,3-epithiopropoxy) ethoxy] 9,9-bis [2- (2,3-epi) such as phenyl} fluorene (or 9,9-bis {4- [2- (2,3-thioepoxypropoxy) ethoxy] phenyl} fluorene, the same applies hereinafter) _{thiopropoxy) C 2-4} alkoxyphenyl] fluorene; 9,9-bis {4- [2- (2,3-epithiopropyl propoxy) ethoxy] -3-methylphenyl} fluorene, 9,9-bis {4- [2- (2,3-epithiopropyl propoxy) ethoxy] -3,5-dimethylphenyl} fluorene 9,9-bis [2- (2,3-epithiopropyl _{propoxy) C 2-4} alkoxy - Al 9,9-bis [2- (2,3-epithio) such as 9,9-bis {4- [2- (2,3-epithiopropoxy) ethoxy] -3-phenylphenyl} fluorene (9) Propoxy) 9,9-bis [(2,3-epithiopropoxy) alkoxyphenyl] fluorenes represented by C _2-4 alkoxy-arylphenyl] fluorene and the like (a compound in which m is 1 in formula (1A)) ), A compound corresponding to these compounds, and a compound in which the sum of two m exceeds 2 in formula (1A) is included.

Examples of 9,9-bis [(2,3-epithiopropoxy) (poly) alkoxynaphthyl] fluorenes include 9,9-bis {6- [2- (2,3-epithiopropoxy) ethoxy]. 9,9-bis [2- (2,3-), such as 2-naphthyl} fluorene, 9,9-bis {5- [2- (2,3-epithiopropoxy) ethoxy] -1-naphthyl} fluorene Epithiopropoxy) 9,9-bis [(2,3-epithiopropoxy) alkoxynaphthyl] fluorenes represented by C _2-4 alkoxynaphthyl] fluorene and the like (compounds wherein m is 1 in formula (1B)) ), A compound corresponding to these compounds, and a compound in which the sum of two m exceeds 2 in formula (1B) is included.

Examples of 9,9-bis {di [(2,3-epithiopropoxy) (poly) alkoxy] phenyl} fluorenes include 9,9-bis {3,5-di [2- (2,3- 9,9-bis such epithiopropyl propoxy) ethoxy] phenyl} fluorene {3,5-di [2- (2,3-epithiopropyl _{propoxy) C 2-4} alkoxy] phenyl} 9 typified fluorene, 9-bis {3,5-di [2- (2,3-epithiopropoxy) alkoxy] phenyl} fluorene (a compound in which m is 1 in formula (1C)), corresponding to these compounds, 1C) includes compounds in which the sum of four m exceeds 4.

  As described above, the epoxy compound (A) represented by the formula (A) and p is 1 usually contains a small amount of the epoxy compound represented by the formulas (B) and (C). Therefore, a composition containing an episulfide compound corresponding to the epoxy compounds represented by the formulas (B) and (C) can also be easily prepared.

  In the present invention, such an episulfide compound can be obtained in high yield under low temperature and short time conditions. The conversion rate from the epoxy compound to the episulfide compound may be, for example, 80% or more, for example, 85 to 100%, preferably 86 to 99.99%, more preferably 87 to 99.9% (especially 88%). ~ 99.5%), and by combining crown ether and molecular sieves, a high yield of 90% or more, preferably 95-99.99%, more preferably 98-99.9% realizable.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  Various characteristics were measured and evaluated by the following methods.

[GPC (gel permeation chromatography)]
Using a high-speed GPC device (“HLC-8320GPC” manufactured by Tosoh Corporation), the sample was dissolved in tetrahydrofuran and measured at a flow rate of 1.0 mL / min, an injection amount of 100 μL, and a temperature of 40 ° C.

(HPLC (High Performance Liquid Chromatography))
Using high performance liquid chromatography (“L-2000” manufactured by Hitachi High-Technologies Corporation), the sample was diluted 2000 times (acetonitrile), temperature 30 ° C., wavelength 254 nm, flow rate 0.5 mL / min, water / Acetonitrile (weight ratio) = 30/70 was measured for 30 minutes, and then water / acetonitrile (weight ratio) = 0/100 was measured for 30 minutes.

(Refractive index)
Using a multi-wavelength Abbe refractometer “DR-M2 / 1550” (manufactured by Atago Co., Ltd.), measurement was performed at a light source wavelength of 589 nm and a measurement temperature of 25 ° C.

(IR spectrum)
A Fourier transform infrared device (“Spectrum 100” manufactured by PERKIN ELMER) was used as a measurement device, and measurement was performed under the conditions of measurement range: 5000 to 400 cm ⁻¹ , integration count: 4 times, and resolution: 4 cm ⁻¹ .

Example 1
42 g (0.096 mol) of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) was added to chloromethyloxirane (special grade, Kishida Chemical Co., Ltd.). The product was dissolved in 88 g (0.96 mol), and 2.0 g of benzyltriethylammonium chloride (special grade, manufactured by Kanto Chemical Co., Inc.) was further added, followed by stirring at 60 ° C. for 1 hour. Next, under reduced pressure (650 mmHg), 30 g of a 40% aqueous sodium hydroxide solution was added dropwise at 45 ° C. over 1.5 hours. Meanwhile, the water produced was removed from the system by azeotropy with chloromethyloxirane, and the distilled chloromethyloxirane was returned to the system. After completion of the dropwise addition, the reaction was continued for another 3 hours. Then, the salt produced | generated by filtration was removed, and also after washing with water, chloromethyl oxirane was distilled off and the viscous liquid was obtained. The obtained viscous liquid was analyzed by HPLC and GPC. As a result, 9,9-bis [4- (2-glycidyloxyethoxy) phenyl] fluorene [or 9,9-bis (4-hydroxyethoxyphenyl) fluorene diene was analyzed. It was confirmed that it was an epoxy compound (epoxy resin) mainly containing glycidyl ether and BPF-2EOG].

  10 g of the obtained viscous liquid (BPF-2EOG) and 200 ml of toluene were added and stirred at room temperature until the viscous liquid was dissolved. A solution prepared by dissolving 5.52 g of thiourea in 200 ml of methanol was further added to the obtained solution. In the resulting solution, molecular sieves (manufactured by Wako Pure Chemical Industries, Ltd., average pore diameter of 4 mm, pellet diameter of 1/8 inch = about 3.2 mmφ, pellet length of about 2 to 6 mm) 3.6 g was further added. To the obtained solution, 7.3 mg of 18-crown 6-ether was further added and stirred while heating at 35 ° C. for 10 hours. And the obtained solution was suction-filtered, In order to remove the solvent in a filtrate, it concentrated to 16.7g with the evaporator. In order to remove thiourea dissolved in toluene, 120 ml of distilled water was added and washed with water. Finally, toluene was removed with an evaporator to obtain the desired product.

  As a result of analyzing the obtained target product by HPLC, GPC, FT-IR and NMR, an episulfide compound of 9,9-bis [4- (2-glycidyloxyethoxy) phenyl] fluorene (a compound represented by the following formula) ) Was mainly included. The purity (conversion rate) was determined by the area ratio by HPLC.

(Example 2)
The target product was obtained in the same manner as in Example 1 except that no molecular sieve was added.

(Example 3)
The target product was obtained in the same manner as in Example 1 except that no molecular sieves were added and the addition amount of 18-crown 6-ether was changed to 14.7 g.

(Comparative Example 1)
The target product was obtained in the same manner as in Example 1 except that 18-crown 6-ether was not added.

(Comparative Example 2)
The target product was obtained in the same manner as in Example 1 except that molecular sieves and 18-crown 6-ether were not added and the reaction was carried out at 25 ° C. for 15 hours.

  Table 1 shows the conversion rates of the objects obtained by the methods of Examples 1 to 3 and Comparative Examples 1 and 2.

  As is apparent from the results in Table 1, the target product was obtained at a high conversion rate in the method of the example. In particular, in Example 1, the target product was obtained at a very high conversion rate.

Example 4
The target product was obtained in the same manner as in Example 1 except that 9,9-bis [3,5-di (2-hydroxyethoxy) phenyl] fluorene (BREF) was used instead of BPEF.

  A chart of the IR spectrum of the obtained target product is shown in FIG. As a result of analysis by IR spectrum, it was confirmed that an episulfide compound of 9-bis [3,5-di (2-glycidyloxyethoxy) phenyl] fluorene (compound represented by the following formula) was mainly contained.

  A molded product obtained using the episulfide compound obtained by the method of the present invention has excellent properties such as a high refractive index and high heat resistance. In particular, a compound having a fluorene skeleton is excellent in dispersibility of additives such as pigments.

  Such episulfide compounds (or molded products) are useful as insulating materials between electronic component layers, solder resists for printed circuit boards, resist materials such as coverlays, color filters, inks (printing inks, etc.), Sealant (semiconductor sealant, etc.), paint, coating agent, adhesive, adhesive, underfill, antistatic agent, filler, conductive member or conductive material, laminated material, thermal material (thermal paper material, etc.) , Carbon materials, insulating materials, foams, pressure sensitive materials, fuel cell membranes, optical materials (transparent materials) [for example, lenses (reflow lenses, pickup lenses, micro lenses, etc.), polarizing films, antireflection films, touch panels Film, flexible substrate film, display film, optical fiber, optical waveguide, hologram] That the material (electric and electronic materials, optical materials) useful as.

Claims (11)

A method for producing an episulfide compound by reacting an epoxy compound with a sulfur-containing compound in the presence of a reaction aid containing a crown ether , wherein the sulfur-containing compound contains thiourea or cyclic thiourea .   The method of claim 1, wherein the reaction aid further comprises a porous adsorbent.   The method according to claim 2, wherein the porous adsorbent is molecular sieves.   The method according to claim 2 or 3, wherein the weight ratio of the crown ether to the porous adsorbent is crown ether / porous adsorbent = 1/50 to 1/5000.   The method according to claim 1, wherein the crown ether has an 18-crown-6 skeleton.   The method according to claim 1, wherein the weight ratio of the crown ether to the epoxy compound is crown ether / epoxy compound = 1/100 to 1/10000.   The method according to any one of claims 1 to 6, wherein the epoxy compound is an epoxy compound having a fluorene skeleton. The method according to claim 7, wherein the epoxy compound having a fluorene skeleton contains an epoxy compound represented by the following formula (A), and the obtained episulfide compound comprises an episulfide compound represented by the following formula (1).
(In the formula, ring Z is an aromatic hydrocarbon ring, R ¹ is a substituent, R ² is an alkylene group, R ³ is a substituent, k is an integer of 0 to 4, m is an integer of 0 or more, and p is An integer of 1 or more and n is an integer of 0 or more)   The method according to claim 8, wherein p is 1 or 2 in formulas (A) and (1). The method according to any one of claims 1 to 9 , wherein the reaction is carried out in the presence of a solvent containing an aromatic hydrocarbon. The method according to any one of claims 1 to 10 , wherein the reaction temperature is 60 ° C or lower.