JP2006233039A - Sulfur atom-containing cyclic compound, method for producing the same and cross-linkable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new sulfur atom-containing cyclic compound containing sulfur atoms at a high density and resultantly useful as an optical material, to provide a method for producing the compound and to provide a cross-linkable composition. <P>SOLUTION: The sulfur atom-containing cyclic compound is characterized in that the compound is represented by general formula (1) [wherein, R<SP>1</SP>is a group represented by a CH<SB>2</SB>=CHCOO-R<SP>2</SP>- or a CH<SB>2</SB>=CCH<SB>3</SB>COO-R<SP>2</SP>- (wherein, R<SP>2</SP>represents a methylene group or a 2-10C alkylene group); m is an integer of ≥1; and n is an integer of ≥1]. The method for producing the sulfur atom-containing cyclic compound is characterized as follows. A specific cyclic thioester is reacted with a specified sulfide compound to thereby provide the sulfur atom-containing cyclic compound. The cross-linkable composition is characterized as comprising the sulfur atom-containing cyclic compound represented by general formula (1) and a photoradical polymerization initiator. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a sulfur atom-containing cyclic compound, a method for producing the same, and a crosslinkable composition.

In general, a substance having translucency is useful as a material for various optical members. At present, inorganic glass or organic polymer is used as the material of the optical member. In particular, a light-transmitting substance having a high refractive index is useful as a material for lenses, optical filters, and the like. In addition, when a substance having a certain optical property has a film forming ability, it is useful as a coating material for forming a coating layer on the surface of a substrate and as a film forming material, and has a higher refractive index. In some cases, an antireflection film can be formed by combining this with a film having a low refractive index to form a laminated film.
Furthermore, even when the substance does not have a film-forming ability, a film can be formed by combining it with an appropriate binder. Therefore, by utilizing the optical characteristics of the substance, for example, a high refractive index It can be used to form a rate layer.
Conventionally, organic compounds containing sulfur atoms have been known as substances having a high refractive index. Examples of such sulfur atom-containing compounds include, for example, Patent Document 1, 4,4′-thiobisbenzenethiol and phenylene dicarboxylic acid. A cyclic thioaryl ester obtained by reaction with an acid halide is disclosed, and Patent Document 2 discloses a cyclic arylthiocarbonate obtained by reaction of an aromatic dithiol and an aromatic compound having a bifunctional haloformyloxy group. Patent Document 3 discloses a sulfur atom-containing polymer obtained by heat polymerization of the above cyclic thioaryl ester, and Patent Documents 4 and 5 disclose heat polymerization of a specific cyclic thiocarbonate compound. A sulfur atom-containing polymer obtained in this manner is disclosed.

JP-A-11-322742 JP 2000-239386 A Japanese Patent Laid-Open No. 2001-261834 JP 2001-316470 A JP 2001-316471 A

The present invention has been obtained as a result of various studies on a sulfur atom-containing cyclic compound having a relatively large molecular weight against the background described above.
An object of the present invention is to provide a novel sulfur atom-containing cyclic compound, a process for producing the same, and a crosslinkable composition which contain sulfur atoms at a high density and are therefore useful as optical materials.

  The sulfur atom-containing cyclic compound of the present invention is represented by the following general formula (1).

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). And m is an integer of 1 or more, and n is an integer of 1 or more. ]

  The method for producing a sulfur atom-containing cyclic compound of the present invention comprises the above-described sulfur atom-containing reaction by reacting a cyclic thioester represented by the following formula (i) with a sulfide compound represented by the following general formula (2). A cyclic compound is obtained.

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). It is a group represented. ]

  The crosslinkable composition of the present invention comprises a sulfur atom-containing cyclic compound represented by the general formula (1) and a photo radical polymerization initiator.

  The sulfur atom-containing cyclic compound of the present invention is represented by the following general formula (3).

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). R ³ is represented by R ⁴ —O—CH ₂ — (wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). And p is an integer of 1 or more, q is an integer of 1 or more, and r is an integer of 1 or more. ]

  The method for producing a sulfur atom-containing cyclic compound of the present invention is represented by the cyclic thioester represented by the above formula (i), the sulfide compound represented by the above general formula (2), and the following general formula (4). The above sulfur atom-containing cyclic compound is obtained by reacting with a sulfide compound.

[Wherein R ³ is a group represented by R ⁴ —O—CH ₂ — (wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). . ]

  The crosslinkable composition of the present invention comprises a sulfur atom-containing cyclic compound represented by the general formula (3) and a photo radical polymerization initiator.

  The crosslinkable composition of the present invention preferably contains a reaction diluent composed of a monofunctional (meth) acrylate compound.

  The sulfur atom-containing cyclic compound of the present invention is a novel sulfur atom-containing cyclic compound that contains sulfur atoms at a high density and has a (meth) acryloyl moiety, and is useful as an optical material.

  According to the method for producing a sulfur atom cyclic compound of the present invention, the above sulfur atom-containing cyclic compound can be obtained.

  Since the crosslinkable composition of the present invention contains the above-mentioned sulfur atom-containing cyclic compound, it is useful as an optical material, and the sulfur atom-containing cyclic compound is a functional site (meta). Since it has an acryloyl moiety, a crosslinked body is formed by the action of light, and the crosslinked body has the excellent characteristics possessed by the sulfur atom-containing cyclic compound, and more excellent optical characteristics. can get.

Embodiments of the present invention will be described below.
The sulfur atom-containing cyclic compound according to the present invention has a structure represented by the above general formula (1) (hereinafter also referred to as “first cyclic compound”), or is represented by the above general formula (3). (Hereinafter referred to as “second cyclic compound”).

[First cyclic compound]
The first cyclic compound according to the present invention is represented by the general formula (1).

In the general formula (1), R ¹ is a composite group of a (meth) methacryloyl group represented by CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — and a —R ² — group. It is. Here, R ² is a methylene group or an alkylene group having 2 to 10 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a heptylene group, and an octylene group. It is done.

M is an integer of 1 or more, preferably 1-1000.
N is an integer of 1 or more, preferably 1-1000.

  The first cyclic compound has a polystyrene-equivalent number average molecular weight Mn (hereinafter referred to as “number average molecular weight Mn”) measured by size exclusion chromatography (SEC), for example, from 500 to 300,000, and the same molecular weight distribution Mw / Mn is 1.1-30.

  As shown in the following reaction formula (1), such a first cyclic compound includes a cyclic thioester represented by the above formula (i) (hereinafter also referred to as “specific cyclic thioester”) and the above. Specifically, the sulfide compound represented by the general formula (2) (hereinafter referred to as “first sulfide compound”) is usually subjected to an addition reaction by heating in the presence of a catalyst. The thioester moiety in the thioester is cleaved, and the C—C bond in the sulfide group of one or more first sulfide compounds is inserted (insertion reaction), and further, the thioester moiety in the resulting compound Is produced by cleavage and recombination (exchange reaction).

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). And m is an integer of 1 or more, and n is an integer of 1 or more. ]

The specific cyclic thioester can be prepared, for example, by reacting a sulfone compound represented by the following formula (ii) with 4,4′-bisbenzenethiol.
Here, the sulfone compound represented by the following formula (ii) synthesizes 2,2-bis (4-bromomethylphenyl) sulfone by reacting, for example, p-tolylsulfone and N-bromosuccinimide. 2,2-bis (4-bromomethylphenyl) sulfone and ethyl-2-hydroxybenzoate were reacted to synthesize 2,2-bis (chlorocarbonylphenoxymethylphenyl) sulfone. , 2-bis (chlorocarbonylphenoxymethylphenyl) sulfone and thionyl chloride can be prepared.

  Specific examples of the first sulfide compound used for producing the first cyclic compound include thiranyl methacrylate (TMA) and thiranyl acrylate (TA).

The reaction represented by the reaction formula (1) is performed by using a catalyst such as a quaternary onium salt in an appropriate solvent.
Here, as the solvent, it is preferable to use a polar solvent capable of dissolving a specific cyclic thioester, and specific examples thereof include N-methylpyrrolidone, dichlorobenzene, etc. Among these, they have high polarity. In this respect, N-methylpyrrolidone is preferable.
When a solvent with low polarity is used, the thioester moiety in a specific cyclic thioester may be difficult to cleave.
Moreover, it is preferable that the density | concentration of the specific cyclic thioester in a solvent is 0.05 mol / L or more, More preferably, it is 0.1-1 mol / L. When this concentration is too small, the reaction of the specific cyclic thioester does not proceed sufficiently, and the obtained first cyclic compound tends to have a low molecular weight.

Specific examples of the quaternary onium salt used as the catalyst include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, cetyltrimethylammonium bromide, tetra Examples include propylammonium bromide and benzyltriethylammonium chloride. Further, these quaternary salts are used in combination with salts such as 18-crown-6-ether, potassium chloride, potassium bromide, potassium iodide, cesium chloride, potassium phenoxide, sodium phenoxide, potassium benzoate and the like. You can also.
The use ratio of the catalyst is, for example, 5 to 100 mol% with respect to the reaction raw material.

  Moreover, it is preferable that reaction temperature is less than 90 degreeC, More preferably, it is 50-70 degreeC. If the reaction temperature is too high, a radical polymerization reaction may occur at the (meth) acryloyl site in the reaction product.

The ratio between the specific cyclic thioester and the first sulfide compound is required to be 2 mol or more of the first sulfide compound with respect to 1 mol of the specific cyclic thioester. It is suitably selected depending on the kind of the cyclic compound.
For example, by using 2 mol of the first sulfide compound with respect to 1 mol of the specific cyclic thioester, a compound in which n in the general formula (1) is 1 can be obtained, and for example, with respect to 1 mol of the specific cyclic thioester By using 10 mol or more of the first sulfide compound, a compound having a high molecular weight in which n in the general formula (1) is 5 or more can be obtained.
Moreover, it is preferable that the ratio of a 1st sulfide compound is less than 30 mol with respect to 1 mol of specific cyclic | annular thioesters. When the ratio of the first sulfide compound is excessive, an unnecessary part may be generated in the product.

  Such a first cyclic compound is a stable compound containing 6 or more sulfur atoms in the main chain of one repeating unit and has a (meth) acryloyl moiety. In addition, it has a high refractive index because it has a high density of sulfur atoms and has a functional part consisting of a (meth) acryloyl part.

[Second cyclic compound]
The second cyclic compound according to the present invention is represented by the general formula (3).

R ¹ in this general formula (3) is the same as R ¹ in the general formula (1) described above.

R ³ is a group represented by R ⁴ —O—CH ₂ —.
Here, R ⁴ is an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group. Specific examples thereof include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, and an isopropoxymethyl group. , N-butoxymethyl group, isobutoxymethyl group, n-pentoxymethyl group, isopentoxymethyl group, n-hexoxymethyl group, isohexoxymethyl group, substituted or unsubstituted phenoxymethyl group, etc. .

Moreover, although p is an integer greater than or equal to 1, Preferably it is 1-1000.
Q is an integer of 1 or more, preferably 1-1000.
R is an integer of 1 or more, preferably 1-1000.

  The second cyclic compound has a polystyrene-equivalent number average molecular weight Mn measured by size exclusion chromatography (SEC) of, for example, 500 to 300,000, and a molecular weight distribution Mw / Mn of 1.1 to 30.

  Such a second cyclic compound includes a specific thioester represented by the above formula (i) and a first sulfide represented by the general formula (2) as shown in the following reaction formula (2). A compound and a sulfide compound represented by the above general formula (4) (hereinafter also referred to as “second sulfide compound”) are usually subjected to an addition reaction by heating in the presence of a catalyst. Is inserted by interrupting the C—C bond in each sulfide group of one first sulfide compound and one or more second sulfide compounds, with the thioester moiety in a specific cyclic thioester cleaved. (Insertion reaction), and further, the thioester moiety in the compound obtained thereby is obtained by cleavage and recombination (exchange reaction).

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). R ³ is represented by R ⁴ —O—CH ₂ — (wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). And p is an integer of 1 or more, q is an integer of 1 or more, and r is an integer of 1 or more. ]

  Specific examples of the first sulfide compound used for producing the second cyclic compound include thiranyl methacrylate (TMA) and thiranyl acrylate (TA).

Specific examples of the second sulfide compound used for producing the second cyclic compound include phenoxypropylene sulfide in which R ⁴ is a phenyl group, and n-butoxypropylene in which R ⁴ is an n-butoxymethyl group. And sulfides.

The reaction represented by the reaction formula (2) is performed by using a catalyst such as a quaternary onium salt in an appropriate solvent.
Here, as the solvent, it is preferable to use a polar solvent capable of dissolving a specific cyclic thioester, and specific examples thereof include N-methylpyrrolidone and dichlorobenzene. Among these, high polarity N-methylpyrrolidone is preferable in that it has
When a solvent with low polarity is used, the thioester moiety in a specific cyclic thioester may be difficult to cleave.
Moreover, it is preferable that the density | concentration of the specific cyclic thioester in a solvent is 0.05 mol / L or more, More preferably, it is 0.1-1 mol / L. When this concentration is too small, the reaction of the specific cyclic thioester does not proceed sufficiently, and the obtained second cyclic compound tends to have a low molecular weight.

Specific examples of the quaternary onium salt used as a catalyst include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, cetyltrimethylammonium bromide , Tetrapropylammonium bromide, benzyltriethylammonium chloride and the like. Further, these quaternary salts are used in combination with salts such as 18-crown-6-ether, potassium chloride, potassium bromide, potassium iodide, cesium chloride, potassium phenoxide, sodium phenoxide, potassium benzoate and the like. You can also.
The use ratio of the catalyst is, for example, 5 to 100 mol% with respect to the reaction raw material.

  Moreover, it is preferable that reaction temperature is less than 90 degreeC, More preferably, it is 50-70 degreeC. If the reaction temperature is too high, a radical polymerization reaction may occur at the (meth) acryloyl site in the reaction product.

The ratio of the specific cyclic thioester, the first sulfide compound, and the second sulfide compound is such that the ratio of the first sulfide compound is 2 mol or more with respect to 1 mol of the specific cyclic thioester, The ratio of the sulfide compound of 2 is required to be 2 mol or more with respect to 1 mol of the specific cyclic thioester, and more specifically, it is appropriately selected depending on the kind of the second cyclic compound of interest.
For example, by using 2 mol of the first sulfide compound and 2 mol of the second sulfide compound with respect to 1 mol of the specific cyclic thioester, a compound in which p and q in the general formula (3) are 1 can be obtained. For example, by using 10 mol or more of the first sulfide compound and 10 mol or more of the second sulfide compound with respect to 1 mol of the specific cyclic thioester, p and q in the general formula (3) are compounds having a high molecular weight of 5 or more. Can be obtained.

  Such a second cyclic compound is a stable compound containing 8 or more sulfur atoms in the main chain of one repeating unit and has a (meth) acryloyl moiety. In addition, it has a high refractive index because it has a high density of sulfur atoms and has a functional part consisting of a (meth) acryloyl part.

The first cyclic compound and the second cyclic compound according to the present invention (hereinafter collectively referred to as “specific cyclic compound”) are combined with a crosslinkable composition by combining with a radical photopolymerization initiator. Is done.
The crosslinkable composition containing the specific cyclic compound and photoradical polymerization initiator according to the present invention (hereinafter also referred to as “specific crosslinkable composition”) is cross-linked by radicals generated by the action of light. The obtained crosslinked product has excellent characteristics possessed by the specific cyclic compound constituting the specific crosslinkable composition and is formed by forming a crosslinked structure. Optical characteristics (specifically, a high refractive index) will be obtained.

  In a specific crosslinkable composition, it is preferable that the content rate of a specific cyclic compound is 5-99.9 mass% with respect to the whole composition.

As the radical photopolymerization initiator, a known radical photopolymerization initiator can be used, and examples thereof include a compound represented by the following formula (iii).
The content ratio of the radical photopolymerization initiator is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass with respect to the entire composition.

Further, the specific crosslinkable composition may contain an arbitrary additive such as a sensitizer.
As a sensitizer, 2-ethylanthraquinone etc. can be used, for example, and it is preferable that the content rate of a sensitizer is 0.1-20 mass% with respect to the whole composition.

Further, the specific crosslinkable composition containing the second cyclic compound as the specific cyclic compound contains a reaction diluent made of a monofunctional (meth) acrylate compound such as 2-hydroxyethyl methacrylate, for example. Is preferred. By containing the reaction diluent, a high crosslinking rate can be obtained.
It is preferable that the content rate of a reaction diluent is 3-95 mass% with respect to the whole composition.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

(Preparation of specific cyclic thioester)
(1) Preparation of 2,2-bis (4-bromomethylphenyl) sulfone:
7.39 g (30 mmol) of p-tolylsulfone, 11.8 g (66 mmol) of N-bromosuccinimide, and 0.36 g (1.5 mmol) of benzoyl peroxide were added to 65 mL of chloroform and reacted for 48 hours under reflux. After completion of the reaction, the resultant was washed twice with 100 mL of a 0.1 mol / L iron sulfate aqueous solution and twice with distilled water, the organic phase was extracted, dried with anhydrous magnesium sulfate, and then anhydrous magnesium sulfate was filtered. Separately, chloroform was distilled off under reduced pressure to obtain a yellowish white solid. This was recrystallized from methanol to obtain 5.98 g of white needle crystals with a yield of 46%.
From the results of IR analysis and ¹ H-NMR analysis, the resulting product was obtained as a compound represented by the following formula (a) [2,2-bis (4-bromomethylphenyl) sulfone (hereinafter referred to as “Bis-BMPS”). )]]. The melting point of the product was 136.6 to 137.0 ° C.

The results of IR analysis and ¹ H-NMR analysis of the obtained product are shown below.
○ IR (KRS film) (cm ^-1 ):
3019 (νC-H aromatic),
2960 (νC-H aliphatic),
1595, 1490 (νC = C aromatic),
1306 (νO = S = O),
557 (νC-Br)
○ ¹ H NMR (500 MHz, CDCl ₃ , TMS) δ (ppm):
4.49 (s, 1.0 H, H ^c ),
7.36 (d, 4.0H, H ^b ),
7.41 (d, 4.0H ^a)

(2) Preparation of 2,2-bis (2-carboxyphenoxymethylphenyl) sulfone:
In a 50 mL eggplant flask, 2.66 g (16 mmol) of ethyl-2-hydroxybenzoate, 1.09 g (16 mmol) of an 85% aqueous potassium hydroxide solution as a base in terms of —OH equivalent, and tetrabutylammonium bromide (hereinafter, “ It was also referred to as “TBAB”.) 0.26 g (5 mol%) was added, and 5 mL of N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”) was further added, followed by stirring at room temperature for 3 hours. Thereafter, 3.23 g (8 mmol) of Bis-BMPS was added and stirred at room temperature for 3 hours, and then an excess of an aqueous potassium hydroxide solution and tetrahydrofuran (hereinafter also referred to as “THF”) were added, followed by stirring at 70 ° C. for 3 hours. And reacted. After completion of the reaction, distilled water and chloroform were added and washed twice, and hydrochloric acid was added to the aqueous phase and acidified to obtain 3.8 g of a yellowish white solid with a yield of 92%.
From the results of IR analysis, ¹ H-NMR analysis and ¹³ C-NMR analysis, the obtained product was obtained by the compound [2,2-bis ( 2-carboxyphenoxymethylphenyl) sulfone (hereinafter referred to as “Bis-CPMS”)]. The melting point of the product was 178.1 to 178.7 ° C.

The results of IR analysis, ¹ H-NMR analysis and ¹³ C-NMR analysis of the obtained product are shown below.
○ IR (KRS film) (cm ^-1 ):
3100-2100 (ν-OH carboxylate),
3019 (νC-H aromatic),
2938 (νC-H aliphtic),
1696 (νC = O carboxylic acid),
1600, 1578 (νC = C aromatic),
1244 (νC-O-C ether)
○ ¹ H NMR (500 MHz, DMSO-d ₆ , TMS) δ (ppm):
5.31 (s, 4.0H, H ^c ),
6.99 (dd, 2H.H ^f ),
7.07 (d, 2H, H ^d ),
^{7.43 (dd, 2H, H e} ),
^{7.56 (d, 2H, H g} ),
7.71 (d, 4H, H ^b ),
^{7.98 (d, 4H, H a} )
○ ¹³ C NMR (125 MHz, DMSO-d ₆ , TMS) δ (ppm):
68.7 (C ^a ),
113.9, 120.7, 121.7, 127.6, 127.9, 131.0, 133.1, 140.3, 143.4, 156.8 (aromatic C),
167.2 (C ^b )

(3) Preparation of 2,2-bis (chlorocarbonylphenoxymethylphenyl) sulfone:
In a 100 mL eggplant flask, 3.11 g (6 mmol) of Bis-CPMS, 3.00 g (24 mmol) of thionyl chloride and 1 drop of dimethylformamide were stirred for 2 hours at 60 ° C., and then heated to reflux at 80 ° C. The reaction was stirred for 6 hours below. After the reaction was completed, thionyl chloride was distilled off under reduced pressure to obtain a yellowish white solid. This was recrystallized using n-hexane to obtain 2.3 g of white crystals in a yield of 70%.
From the results of IR analysis, ¹ H-NMR analysis and ¹³ C-NMR analysis, the obtained product was a sulfone compound represented by the following formula (c-1) or the following formula (c-2) [2,2-bis (Chlorocarbonylphenoxymethylphenyl) sulfone (hereinafter also referred to as “Bis-CCPMS”)]. Moreover, melting | fusing point of the product was 102.4-103.1 degreeC.

The results of IR analysis, ¹ H-NMR analysis and ¹³ C-NMR analysis of the obtained product are shown below.
○ IR (KRS film) (cm ^-1 ):
3019 (νC-H aromatic),
2938 (νC-H aliphtic),
1632 (νC = O benzoyl chloride),
1600, 1578 (νC = C aromatic),
1244 (νC-O-C ether)
○ ¹ H NMR (500 MHz, CDCl ₃ , TMS) δ (ppm):
^{5.31 (s, 4.0H, H a} ),
6.98-7.52 (m, 16.0H, aromatic H)
○ ¹³ C NMR (125 MHz, CDCl ₃ , TMS) δ (ppm):
68.7 (C ^a ),
113.9, 120.7, 121.8, 127.4, 127.6, 130.9, 133.1, 140.3, 143.4, 156.8 (aromatic C),
161.2 (C ^b )

(4) Preparation of cyclic thioester:
0.92 g (1.6 mmol) of Bis-CCPMS was placed in an Erlenmeyer flask, and 11 mL of chloroform was added as a solvent for dissolution. On the other hand, 0.41 g (1.6 mmol) of 4,4′-thiobisbenzenethiol (hereinafter referred to as “TBBT”) was placed in another Erlenmeyer flask, and 11 mL of chloroform as a solvent was added and dissolved. Next, the two solutions were dropped into a chloroform solution (300 mL) in which 0.31 g (3.0 mmol) of triethylamine was dissolved at a rate of 10 mL / h at room temperature, and then further stirred for 1 hour to be reacted. After completion of the reaction, washing was performed twice with a 0.1 mol / L aqueous citric acid solution, twice with an aqueous sodium carbonate solution, and further twice with distilled water. Subsequently, after drying using anhydrous magnesium sulfate, anhydrous magnesium sulfate was filtered off, and chloroform was distilled off under reduced pressure to obtain 1.03 g of a yellowish white solid with a yield of 89%.
The resulting product was washed twice with THF and recrystallized using chloroform to obtain 0.35 g of a white solid with a yield of 32%.
From the results of IR analysis, ¹ H-NMR analysis, ¹³ C-NMR analysis, mass spectrometry and elemental analysis, the obtained product (white solid) is represented by the following formulas (d-1) and (d-2). It was identified as a specific cyclic thioester (hereinafter also referred to as “cyclic thioester (1)”). The melting point of the product was 149.7 to 150.3 ° C.

The results of IR analysis, ¹ H-NMR analysis, ¹³ C-NMR analysis, mass spectrometry and elemental analysis of the obtained product are shown below.
○ IR (KRS film) (cm ^-1 ):
3019 (νC-H aromatic),
3016 (νC-H aliphatic),
1681 (νC = O thioester),
1595, 1576 (νC = C aromatic),
1258 (νC—O—C ether),
756 (C-S-C sulfide)
○ ¹ H NMR (500 MHz, CDCl ₃ , TMS) δ (ppm):
5.40 (s, 4.0H, H ^c ),
^{7.26 (dd, 2.0H, H f} ),
7.47 (d, 2.0H, H ^d ),
7.59 (d, 4.0H, H ^h ),
7.65 (d, 4.0H, H ⁱ ),
^{7.73 (dd, 2.0H, H e} ),
7.87 (d, 4.0H, H ^b ),
^{7.94 (d, 2.0H, H g} ),
^{8.15 (d, 4.0H, H a} )
○ ¹³ C NMR (125 MHz, CDCl ₃ , TMS) δ (ppm):
68.9 (C ^a ),
114.6, 121.8, 127.6, 128.1, 128.2, 128.5, 129.9, 132.6, 135.1, 136.6, 136.9, 137.9, 141. 6, 156.3 (aromatic C),
188.8 (C ^b )
○ Mass spectrometry (MALDI-TOF MS):
Actual value (m / z) 754.93 [M + Na]
Calculated value (m / z) 755.92 [M + Na]
(Matrix: α-Cyano-4-hydroxycinnamic acid)
-Elemental analysis (MALDI-TOF MS):
Actual value (%) C: 65.37, H: 3.64
Calculated value (%) C: 65.55, H: 3.85

(Preparation of linear thioester)
TBBT (3.8 g, 15 mmol) and triethylamine (3.0 g, 30 mmol) as a base were added to chloroform (100 mL) and stirred under a nitrogen atmosphere. Thereafter, 5.1 g (30 mmol) of o-anisole chloride was dropped over 30 minutes, and the mixture was stirred for 1 hour to be reacted. After the reaction is completed, the organic phase is extracted by washing twice with 0.1 mol / L citric acid aqueous solution, twice with sodium hydrogen carbonate aqueous solution and twice with distilled water, and dried using anhydrous magnesium sulfate. Then, anhydrous magnesium sulfate was filtered off, and chloroform was distilled off under reduced pressure to obtain 7.4 g of a yellowish white solid with a yield of 95%. This was recrystallized using a mixed solvent of chloroform and n-hexane to obtain 5.1 g of a product with a yield of 71%.
From the results of IR analysis, ¹ H-NMR analysis and ¹³ C-NMR analysis, the resulting product was obtained from the compound represented by the following formula (e-1) or the following formula (e-2) (hereinafter referred to as “linear thioester”). (1) ")). The melting point of the product was 141.9 to 142.6 ° C.

The results of IR analysis, ¹ H-NMR analysis and ¹³ C-NMR analysis of the obtained product are shown below.
○ IR (KRS film) (cm ^-1 ):
3072 (νC-H aromatic),
3010 (νC-H aliphatic),
1697 (νC = O thioester),
1595, 1577 (νC = C aromatic),
1284 (νC—O—C ether),
758 (C-S-C sulfide)
○ ¹ H NMR (500 MHz, CDCl ₃ , TMS) δ (ppm):
^{3.95 (s, 6.0H, H a} ),
7.01 (d, 2.0H, H ^b ),
7.02 (dd, 2.0 H, H ^d ),
7.41 (d, 4.0H, J = 2.8 Hz, H ^f ),
7.46 (d, 4.0H, J = 2.8 Hz, H ^g ),
7.50 (dd, 2.0H, H ^c ),
^{7.85 (d, 4.0H, H e} )
○ ¹³ C NMR (125 MHz, CDCl ₃ , TMS) δ (ppm):
56.77 (C ^a ),
113.04, 121.50, 127.02, 128.81, 130.89, 132.26, 135.09, 136.56, 137.84, 159.09, (aromatic C), 161.2 (C ^b )

<Example 1 (Synthesis of first cyclic compound)>
In a dry pack with a humidity of 10% or less, 0.027 g (0.10 mmol) of tetra-n-butylammonium chloride (hereinafter also referred to as “TBAC”) is added to the ampule tube as a catalyst, and a rotor is further added. A vacuum drying treatment was performed by stirring at 40 ° C. for 5 hours. Next, 0.016 g (0.10 mmol) of thiranyl methacrylate (hereinafter also referred to as “TMA”), 0.037 g (0.05 mmol) of cyclic thioester (1) and 1.0 mL of NMP, and a polymerization inhibitor were added to the ampule tube. After adding a small amount of hydroquinone and attaching a two-way cock, the ampoule tube was taken out from the dry pack. Next, the sample in the ampule tube was frozen and degassed using liquid nitrogen, and then thawed at room temperature, and the inside of the ampule tube was replaced with high-purity dry nitrogen. This operation was repeated three times, and after further freezing and degassing for 30 minutes, the ampule tube was sealed. Next, the sample in the ampoule tube was thawed at room temperature, and the reaction was performed under the conditions of a reaction temperature of 70 ° C. and a reaction time of 96 hours. After the reaction is completed, the reaction solution is poured into methanol, methanol-insoluble matter is recovered and dissolved in chloroform, reprecipitation purification is performed using methanol as a poor solvent, and vacuum drying is performed at room temperature for 24 hours. A white solid 0.048 g was obtained at a rate of 91%.
When the obtained product was subjected to SEC analysis, IR analysis, and ¹ H-NMR analysis, it was also referred to as a first cyclic compound (hereinafter referred to as “cyclic compound (1-1)”) represented by the following formula (f). It was confirmed that the number average molecular weight Mn was 2.0 × 10 ³ and the molecular weight distribution Mw / Mn was 2.8. Moreover, the insertion reaction rate of TMA with respect to cyclic thioester (1) was 99% or more.

The results of ¹ H-NMR analysis of the obtained product are shown below, and the IR spectrum is shown in FIG.
In FIG. 1, the IR spectrum of the obtained product is shown as (b), and the IR spectrum of the cyclic thioester (1) is shown as (a).
○ ¹ H NMR (500 MHz, CDCl ₃ , TMS) δ (ppm):
^{1.92 (s, 6.0H, H e} ),
3.08-3.34 (m, 4.0H, H ^d ),
^{4.37-4.46 (m, 4.0H, H c} ),
4.44 (s, 2.0H, H ^b ),
^{5.22 (s, 4.0H, H a} ),
5.57 (s, 2.0H, H ^f ),
6.11 (s, 2.0H, H ^{f ′} ),
6.93-7.98 (m, 24.0H, aromatic H)

<Examples 2 to 6 (synthesis of first cyclic compound)>
The same operation as in Example 1 except that the amount of the solvent used was changed and the concentration of the cyclic thioester (1) in the solvent (hereinafter also referred to as “raw material concentration”) and the reaction time were in accordance with Table 1 below. Went.
When each of the obtained products was subjected to SEC analysis, IR analysis, and ¹ H-NMR analysis, each product was confirmed to be a first cyclic compound having the same structure as the cyclic compound (1-1). It was done.
Table 1 below shows the yield, the TMA insertion reaction rate, and the number average molecular weight Mn and the molecular weight distribution Mw / Mn in the obtained first cyclic compound.

The following is understood from the results of Examples 1 to 6.
(1) When the reaction time is long, the TMA insertion reaction rate increases.
(2) When the raw material concentration is low (specifically, when the raw material concentration condition is 0.025 mol / L), it is difficult to allow the reaction to proceed quantitatively.

<Example 7 (Synthesis of first cyclic compound)>
By performing the same operation as in Example 1 except that the amount of TMA used was changed to 0.160 g (1.00 mmol), 0.17 g of a product was obtained in a yield of 90%.
When the obtained product was subjected to SEC analysis, IR analysis, and ¹ H-NMR analysis, it was also referred to as a first cyclic compound (hereinafter, “cyclic compound (1-7)”) represented by the following formula (g). It was confirmed that the number average molecular weight Mn was 6.6 × 10 ³ and the molecular weight distribution Mw / Mn was 10.8. Moreover, the insertion reaction rate of TMA with respect to cyclic thioester (1) was 99% or more.

The results of IR analysis and ¹ H-NMR analysis of the obtained product are shown below.
○ IR (KRS film) (cm ^-1 ):
3024 (νC-H aromatic),
2925 (νC-H aliphatic),
1720 (νC═O ester),
1669 (νC = O S-Alkyl thioester),
1637 (νC = C vinyl),
1597, 1577 (νC = C aromatic),
1294 (νC—O—C ether),
758 (C-S-C sulfide)
○ ¹ H NMR (500 MHz, CDCl ₃ , TMS) δ (ppm):
^{1.92 (s, 60.0H, H e} ),
^{3.08-3.34 (m, 40.0H, H d} ),
^{4.37-4.46 (m, 40.0H, H c} ),
4.44 (s, 20.0 H, H ^b ),
^{5.22 (s, 4.0H, H a} ),
^{5.57 (s, 20.0H, H f} ),
6.11 (s, 20.0 H, H ^{f ′} ),
6.93-7.98 (m, 24.0H, aromatic H)

<Example 8 (Synthesis of first cyclic compound)>
A product was obtained in a yield of 93% by performing the same operation as in Example 1 except that the amount of TMA used was changed to 0.080 g (0.5 mmol).
When the obtained product was subjected to SEC analysis, IR analysis and ¹ H-NMR analysis, R ¹ was CH ₂ ═CCH ₃ COO—CH ₂ — in the general formula (1) and n was 5. A first cyclic compound (hereinafter also referred to as “cyclic compound (1-8)”) having a number average molecular weight Mn of 3.3 × 10 ³ and a molecular weight distribution Mw / Mn of 8.3. It was confirmed. Moreover, the insertion reaction rate of TMA with respect to cyclic thioester (1) was 99% or more.

<Reference Example 1>
Except that the amount of TMA used was changed to 0.240 g (1.5 mmol), the same operation as in Example 1 was performed, and an unnecessary part was confirmed in the product.

From the results of Example 1, Example 7, Example 8, and Reference Example 1, the following is understood.
(1) When the molar ratio of TMA to a specific cyclic thioester is 2 to 20, the reaction proceeds quantitatively with respect to the amount of TMA used.
(2) When the molar ratio of TMA to a specific cyclic thioester is as large as 30 or more, an insoluble part is generated in the product.

When the glass transition temperature Tg of each of the first cyclic compounds obtained in Example 1, Example 7 and Example 8 was measured by DSC analysis, the cyclic compound according to Example 1 (1-1 ) Was 75.6 ° C., but a clear glass transition temperature was confirmed in the cyclic compound (1-7) according to Example 7 and the cyclic compound (1-8) according to Example 8. I couldn't.
In addition, for each of the first cyclic compounds obtained in Example 1, Example 7 and Example 8, a cyclic compound solution composed of the first cyclic compound was prepared by using THF as a cast solvent. The compound liquid was applied onto a silicon wafer by spin coating, and the coating film was dried under reduced pressure at room temperature for 24 hours to obtain a film made of the first cyclic compound. The refractive index of light having a wavelength of 632.8 nm of this film (N _D ) was measured with an ellipsometer. The results are shown in Table 2.
In Table 2, the film made of the cyclic compound (1-1) is “film (1-A)”, the film made of the cyclic compound (1-8) is “film (1-B)”, and the cyclic compound (1 -7) The manufactured film was referred to as “film (1-C)”. In Table 2, “Raw material usage ratio” means the molar ratio of the usage amount of the raw material used for the reaction to obtain the first cyclic compound as the film material, “TMA usage amount: cyclic thioester. "Amount used (1)".

  From the results in Table 2, it is understood that the refractive index tends to increase as the sulfur atom content ratio increases.

<Example 9 to Example 11 (synthesis of crosslinkable composition)>
Using each of the first cyclic compounds obtained in Example 1, Example 7 and Example 8 as a base material, 0.200 g (60% by mass) of the first cyclic compound and the above as a radical photopolymerization initiator A small amount (specifically 2 mL) of a system in which 0.009 g (3% by mass) of the compound represented by the formula (iii) and 0.003 g (1% by mass) of 2-ethylanthraquinone as a sensitizer were mixed. A specific crosslinkable composition liquid was prepared by adding THF, the obtained crosslinkable composition liquid was applied onto a substrate made of potassium bromide, and the coating film was dried to prepare a film. .
Each of the obtained films was irradiated with light having a wavelength of 254 nm under the condition of 9 mW / cm ² for 20 minutes using a high-pressure mercury lamp with a power consumption of 250 W as a light source, and this was caused by νC = C of the methacryloyl group in the IR spectrum. The crosslinking rate was confirmed by measuring the conversion of 1637 cm ⁻¹ . The final conversion rate of the film according to Example 9 (the film made of the crosslinkable composition liquid containing the cyclic compound (1-1)) was 8%, and the film according to Example 10 (cyclic compound (1- The final conversion rate of the film made of the crosslinkable composition liquid containing 8) is 24%, and the film according to Example 11 (the film made of the crosslinkable composition liquid containing the cyclic compound (1-7)) The final conversion of was 32%. The measurement results are shown in FIG.
In FIG. 2, the curve (A) shows the measured value of the film made of the crosslinkable composition liquid containing the cyclic compound (1-1), and the curve (B) shows the crosslinkability containing the cyclic compound (1-8). The measured value of the film made of the composition liquid is shown, and the curve (c) shows the measured value of the film made of the crosslinkable composition liquid containing the cyclic compound (1-7).

From the results of Examples 9 to 11, the following is understood.
(1) As the first cyclic compound constituting the specific crosslinkable composition has a larger value of n in the general formula (1), the crosslinking rate tends to increase.
(2) The final crosslinking rate tends to increase as the value of n in the general formula (1) of the first cyclic compound constituting the specific crosslinkable composition increases.

<Example 12 (synthesis of second cyclic compound)>
In a dry pack with a humidity of 10% or less, 0.027 g (0.10 mmol) of TBAC as a catalyst was placed in an ampoule tube, and a rotor was further added thereto, followed by stirring at 40 ° C. for 5 hours for vacuum drying. Next, TMA 0.016 g (0.10 mmol), cyclic thioester (1) 0.037 g (0.05 mmol), phenoxypropylene sulfide (hereinafter also referred to as “PPS”) 0.40 g (2.5 mmol) NMP 1.0 mL (0.05 mol / L) and a small amount of hydroquinone as a polymerization inhibitor were added and a two-way cock was attached. Then, the ampoule tube was taken out of the dry pack. Next, the sample in the ampule tube was frozen and degassed using liquid nitrogen, and then thawed at room temperature, and the inside of the ampule tube was replaced with high-purity dry nitrogen. This operation was repeated three times, and after further freezing and degassing for 30 minutes, the ampule tube was sealed. Next, the sample in the ampoule tube was thawed at room temperature, and the reaction was performed under the conditions of a reaction temperature of 70 ° C. and a reaction time of 96 hours. After the reaction is completed, the reaction solution is poured into methanol, methanol insoluble matter is recovered and dissolved in chloroform, reprecipitation purification is performed using methanol as a poor solvent, and a colorless transparent viscous solid is obtained by drying under reduced pressure. The product was further dried under reduced pressure at room temperature for 24 hours to obtain 0.43 g of the product with a yield of 94%.
When the obtained product was subjected to SEC analysis, IR analysis and ¹ H-NMR analysis, it was also referred to as a second cyclic compound (hereinafter referred to as “cyclic compound (2-1)”) represented by the following formula (h). ) And the number average molecular weight Mn was 14.2 × 10 ³ and the molecular weight distribution Mw / Mn was 9.0. Moreover, the insertion reaction rate of TMA and PPS with respect to cyclic thioester (1) was 99% or less.

The results of IR analysis and ¹ H-NMR analysis of the obtained compound are shown below, and the ¹ H-NMR spectrum is shown in FIG.
○ IR (KRS film) (cm ^-1 ):
3039 (νC-H aromatic),
2925 (νC-H aliphatic),
1716 (νC═O ester),
1669 (νC = O S-Alkyl thioester),
1637 (νC = C vinyl),
1598, 1587 (νC = C aromatic),
1230 (νC—O—C ether),
754 (C-S-C sulfide)
○ ¹ H NMR (500 MHz, CDCl ₃ , TMS) δ (ppm):
^{1.90 (s, 6.0H, H e} ),
^{3.00-3.15 (m, 150.0H, H b} , H d),
^{4.06-4.12 (m, 100.0H, H g} ),
4.34 (s, 2.0H, H ^{b ′} ),
4.43 (d, 4.0H, H ^c ),
^{5.13 (s, 4.0H, H a} ),
^{5.48 (s, 2.0H, H f} ),
6.07 (s, 2.0H, H ^{f ′} ),
6.70-7.85 (m, 274.0H, aromatic H)

<Examples 13 to 16 (synthesis of second cyclic compound)>
The same operation as in Example 12 was performed except that the amount of PPS used was changed according to Table 3 below.
Each of the obtained products was subjected to SEC analysis, IR analysis, and ¹ H-NMR analysis. As a result, the product according to Example 13 was obtained in the general formula (3) where R ¹ was CH ₂ ═CCH ₃ COO. A _second cyclic compound (hereinafter also referred to as “cyclic compound (2-2)”) in which —CH ₂ —, q is 1, R ⁴ is a methylene group, and p is 5. The product according to Example 14 has the formula (3) in which R ¹ is CH ₂ ═CCH ₃ COO—CH ₂ —, q is 1, R ⁴ is a methylene group, and p is 10. 2 and the product according to Example 15 is the product of General Formula (3) in which R ¹ is CH ₂ ═CCH ₃ COO—CH ₂ —. a is q is 1, the second cyclic compound exhibiting p is 15 R ⁴ is a methylene group . Hereinafter referred to as "cyclic compound (2-4)"), and the product according to Example 16 R ¹ in the general formula (3) is _{CH 2 = CCH 3 COO-CH} 2 - is a a and q 1 and R ⁴ is a methylene group and p is 20, it was confirmed that it is a second cyclic compound (hereinafter also referred to as “cyclic compound (2-5)”).
Table 3 below shows the yield, the insertion reaction rate of TMA and PPS, and the number average molecular weight Mn and the molecular weight distribution Mw / Mn in the obtained second cyclic compound.

  From the results of Examples 12 to 16, it is understood that the reaction proceeds quantitatively with respect to the amount of PPS used.

Here, the glass transition temperature of each of the second cyclic compounds obtained in Examples 12 to 16 was measured by DSC analysis. A result is shown in Table 4, and the graph which shows the relationship between the molar ratio of PPS with respect to cyclic | annular thioester (1) and glass transition temperature which was used for reaction in order to obtain a 2nd cyclic compound is shown in FIG.
In Table 4, the measurement results of the glass transition temperature of the first cyclic compound (cyclic compound (1-1)) according to Example 1 are shown together. In Table 4, “Raw material usage ratio” means the molar ratio of the raw material used for the reaction to obtain the second cyclic compound, “TMA usage: PPS usage: cyclic thioester ( 1) “Use amount”.

  From the results of Table 4 and FIG. 4, it is understood that the glass transition temperature tends to decrease as the amount of PPS used increases.

Further, for each of the second cyclic compounds obtained in Examples 12 to 16, a cyclic compound solution made of the second cyclic compound was prepared by using THF as a cast solvent, and this cyclic compound solution was used as silicon. A film made of a second cyclic compound is obtained by applying the coating film on a wafer by a spin coating method and drying under reduced pressure at room temperature for 24 hours, and the refractive index (n _D ) of light having a wavelength of 632.8 nm. Was measured with an ellipsometer. The results are shown in Table 5, and a graph showing the relationship between the molar ratio of PPS to the cyclic thioester (1) subjected to the reaction to obtain the second cyclic compound as the film material and the refractive index is shown in FIG. .
In Table 5, the film made of the cyclic compound (2-2) is “film (2-A)”, the film made of the cyclic compound (2-3) is “film (2-B)”, and the cyclic compound (2 -4) The film made of the cyclic compound (2-1) is referred to as "film (2-C)", the film made of the cyclic compound (2-5) is referred to as "film (2-D)", Film (2-E) ". In Table 5, “Raw material usage ratio” means the molar ratio of the raw material used for the reaction to obtain the second cyclic compound as the film material, “TMA usage: PPS usage. "Amount: amount of cyclic thioester (1) used".

And the following is understood from the results of Table 5 and FIG.
(1) When the molar ratio of PPS to a specific cyclic thioester is less than 30, the refractive index tends to increase as the sulfur atom content ratio increases.
(2) When the molar ratio of PPS to the specific cyclic thioester is 30 or more, the refractive index becomes substantially constant as the sulfur atom content ratio increases.

<Example 17 and Example 18 (synthesis of crosslinkable composition)>
Using each of the second cyclic compounds obtained in Example 12 and Example 14 as a base material, 0.200 g (60% by mass) of the second cyclic compound and the above formula (iii) as a radical photopolymerization initiator A small amount (specifically 2 mL) of THF is added to a system in which 0.009 g (3% by mass) of a compound represented by formula and 0.003 g (1% by mass) of 2-ethylanthraquinone as a sensitizer are mixed. By preparing a specific crosslinkable composition liquid, applying the obtained crosslinkable composition liquid on a substrate made of potassium bromide, and drying the coating film, a film was produced. This film, together with measuring the thickness, refractive index of light having a wavelength of 632.8nm the (n _D) was measured by an ellipsometer.
Next, each of the obtained films was irradiated with light having a wavelength of 254 nm for 20 minutes under a condition of 9 mW / cm ² using a high-pressure mercury lamp with a power consumption of 250 W as a light source, and νC = C of the methacryloyl group in the IR spectrum The resulting conversion of 1637 cm ⁻¹ was measured. The final conversion rate of the film according to Example 17 (film made of the crosslinkable composition liquid containing the cyclic compound (2-1)) was 24%, and the film according to Example 18 (cyclic compound (2-3)) The final conversion rate of the film made of the crosslinkable composition liquid containing was 24%. The measurement results are shown in FIG.
In FIG. 6, the curve (I) shows the measured value of the film made of the crosslinkable composition liquid containing the cyclic compound (2-1), and the curve (B) shows the crosslinkability containing the cyclic compound (2-3). The measured value of the film made of the composition liquid is shown, and the measured value of the film made of the crosslinkable composition liquid containing the cyclic compound (1-1) measured in Example 9 is shown together as a curve (c). It was.

  Moreover, when the thickness and refractive index of the film after light irradiation for 20 minutes were confirmed, the film which consists of a crosslinkable composition liquid containing a cyclic compound (2-1) has a refractive index compared with before light irradiation processing. Is 102.7% larger, the thickness is 92.9% thinner, and the film made of the crosslinkable composition liquid containing the cyclic compound (2-3) has a refractive index as compared with that before the light irradiation treatment. Was 103.5% larger and the thickness was 89.4% thinner.

<Example 19 and Example 20 (synthesis of crosslinkable composition)>
Using each of the second cyclic compounds obtained in Example 12 and Example 14 as a base material, 0.200 g (60% by mass) of the second cyclic compound and the above formula (iii) as a radical photopolymerization initiator 0.009 g (3% by mass) of a compound represented by the formula, 0.003 g (1% by mass) of 2-ethylanthraquinone as a sensitizer, and 0.130 g (20% by mass) of 2-hydroxymethyl methacrylate as a reaction diluent. A specific crosslinkable composition liquid is prepared by adding a small amount (specifically, 2 mL) of THF to the mixed system, and the obtained crosslinkable composition liquid is applied onto a potassium bromide substrate. And the film was produced by carrying out the drying process of the coating film.
Each of the obtained films was irradiated with light having a wavelength of 254 nm under the condition of 9 mW / cm ² for 20 minutes using a high-pressure mercury lamp with a power consumption of 250 W as a light source, and this was caused by νC = C of the methacryloyl group in the IR spectrum. The crosslinking rate was confirmed by measuring the conversion of 1637 cm ⁻¹ . The results are shown in FIG.
In FIG. 7, the curve (A) shows the measured value of the film according to Example 19 (the film made of the crosslinkable composition liquid containing the cyclic compound (2-1)), and the curve (B) shows the value in Example 20. The measured value of the film (film which consists of a crosslinkable composition liquid containing a cyclic compound (2-3)) is shown.

The following is understood from the results of Examples 17 to 20.
(1) The second cyclic compound constituting the specific crosslinkable composition tends to have a higher crosslinking rate as the value of q in the general formula (3) becomes larger.
(2) As the second cyclic compound constituting the specific crosslinkable composition has a larger q value in the general formula (3), the final crosslinking rate tends to increase.
(3) A film made of a crosslinkable composition having a characteristic tends to have a higher refractive index when subjected to light irradiation treatment.
(4) A film made of a characteristic crosslinkable composition tends to be thinned by light irradiation treatment.
(5) A higher crosslinking rate can be obtained by using a reaction diluent.

  Hereinafter, Experimental Examples 1 to 3 performed to determine the reaction temperature in the reaction system for obtaining a specific cyclic compound are shown.

<Experimental example 1>
In a dry pack with a humidity of 10% or less, 0.027 g (0.10 mmol) of TBAC as a catalyst was placed in an ampoule tube, and a rotor was further added thereto, followed by stirring at 40 ° C. for 5 hours for vacuum drying. Next, 0.016 g (0.10 mmol) of TMA, 0.024 g (0.05 mmol) of linear thioester (1) and 0.5 mL (0.10 mol / L) of NMP were added to the ampule tube, and a small amount of hydroquinone was added as a polymerization inhibitor. After attaching the two-way cock, the ampoule tube was taken out from the dry pack. Next, the sample in the ampule tube was frozen and degassed using liquid nitrogen, and then thawed at room temperature, and the inside of the ampule tube was replaced with high-purity dry nitrogen. This operation was repeated three times, and after further freezing and degassing for 30 minutes, the ampule tube was sealed. Next, the sample in the ampoule tube was thawed at room temperature, and the reaction was performed under the conditions of a reaction temperature of 70 ° C. and a reaction time of 24 hours. After the reaction is completed, the reaction solution is poured into methanol, methanol-insoluble matter is recovered and dissolved in chloroform, reprecipitation purification is performed using methanol as a poor solvent, and vacuum drying is performed at room temperature for 24 hours. A white solid 0.39 g was obtained at a rate of 96%.
When the obtained product was subjected to SEC analysis, IR analysis and ¹ H-NMR analysis, it was a compound represented by the following formula (A) (hereinafter also referred to as “linear compound (1) for comparison”). The number average molecular weight Mn was 3.1 × 10 ³ and the molecular weight distribution Mw / Mn was 1.5. The TMA insertion reaction rate with respect to the linear thioester (1) was 99%.

The results of ¹ H-NMR analysis of the obtained product are shown below, and the IR spectrum is shown in FIG.
In FIG. 8, while showing the IR spectrum figure of the obtained product as (b), the IR spectrum figure of linear thioester (1) was shown as (a).
○ ¹ H NMR (500 MHz, CDCl ₃ , TMS) δ (ppm):
^{1.93 (s, 6.0H, H e} ),
^{3.38-3.27 (m, 4.0H, H c} ),
^{3.91 (s, 6.0H, H a} ),
4.41-4.08 (m, 4.0H, H ^d ),
4.59 (s, 2.0H, H ^b ),
5.58 (s, 2.0H, H ^f ),
6.10 (s, 2.0H, H ^{f ′} ),
7.75-6.96 (m, 16.0H, aromatic H)

<Experimental Examples 2-3>
The same operation as in Experimental Example 1 was performed except that the reaction time was in accordance with Table 6 below.
Each of the obtained products was subjected to SEC analysis, IR analysis, and ¹ H-NMR analysis. As a result, it was confirmed that each was a linear compound having the same structure as the comparative linear compound (1). It was.
Table 6 below shows the yield, the TMA insertion reaction rate, and the number average molecular weight Mn and the molecular weight distribution Mw / Mn in the obtained linear compound.

From the results of the above Experimental Examples 1 to 3, it is understood that a radical polymerization reaction occurs in the methacryloyl moiety at a reaction temperature of 90 ° C. or higher.
Therefore, in said Example 1- Example 8 and Example 12- Example 16, it was decided to react on conditions with reaction temperature less than 90 degreeC.

  Since the sulfur atom-containing cyclic compound and the crosslinkable composition according to the present invention contain sulfur atoms at a high density and have a (meth) acryloyl moiety, thereby having a high refractive index. It is useful as a material for various optical components.

1 is an IR spectrum diagram of the product obtained in Example 1. FIG. It is a graph which shows the relationship between the light irradiation time which concerns on Example 9-Example 11, and a conversion rate. ¹ is a ¹ H-NMR spectrum diagram of the product obtained in Example 12. FIG. It is a graph which shows the relationship between the molar ratio of PPS with respect to cyclic | annular thioester (1) which concerns on the product obtained in Example 12-Example 16, and glass transition temperature. It is a graph which shows the relationship between the PPS molar ratio with respect to cyclic | annular thioester (1) which concerns on the film which consists of a product obtained in Example 12- Example 16, and a refractive index. It is a graph which shows the relationship between the light irradiation time which concerns on Example 17 and Example 18, and a conversion rate. It is a graph which shows the relationship between the light irradiation time which concerns on Example 19 and Example 20, and a conversion rate. 2 is an IR spectrum diagram of the product obtained in Experimental Example 1. FIG.

Claims (7)

A sulfur atom-containing cyclic compound represented by the following general formula (1):

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). And m is an integer of 1 or more, and n is an integer of 1 or more. ] The sulfur atom-containing cyclic compound according to claim 1 is obtained by reacting a cyclic thioester represented by the following formula (i) with a sulfide compound represented by the following general formula (2). A method for producing a sulfur atom-containing cyclic compound.

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). It is a group represented. ] A crosslinkable composition comprising a sulfur atom-containing cyclic compound represented by the following general formula (1) and a photoradical polymerization initiator.

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). And m is an integer of 1 or more, and n is an integer of 1 or more. ] A sulfur atom-containing cyclic compound represented by the following general formula (3):

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). R ³ is represented by R ⁴ —O—CH ₂ — (wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). And p is an integer of 1 or more, q is an integer of 1 or more, and r is an integer of 1 or more. ] By reacting a cyclic thioester represented by the following formula (i), a sulfide compound represented by the following general formula (2), and a sulfide compound represented by the following general formula (4), A method for producing a sulfur atom-containing cyclic compound, comprising obtaining the sulfur atom-containing cyclic compound described above.

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). It is a group represented. ]

[Wherein R ³ is a group represented by R ⁴ —O—CH ₂ — (wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). . ] A crosslinkable composition comprising a sulfur atom-containing cyclic compound represented by the following general formula (3) and a radical photopolymerization initiator.

[Wherein R ¹ is CH ₂ ═CHCOO—R ² — or CH ₂ ═CCH ₃ COO—R ² — (wherein R ² represents a methylene group or an alkylene group having 2 to 10 carbon atoms). R ³ is represented by R ⁴ —O—CH ₂ — (wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group). And p is an integer of 1 or more, q is an integer of 1 or more, and r is an integer of 1 or more. ]   The crosslinkable composition according to claim 6, further comprising a reaction diluent made of a monofunctional (meth) acrylate compound.

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