JP5145642B2 - Sulfur-containing cyclic olefin resin and process for producing the same - Google Patents

Description

  The present invention has high transparency and a high refractive index, and various plastic lenses such as condenser lenses, prism sheets, transparent coating materials such as antireflection films and optical fiber coating materials, and optical films such as optical films. The present invention relates to a novel sulfur-containing cyclic olefin resin expected to be applied to materials and a method for producing the same.

  In recent years, cyclic olefin resins have attracted attention as transparent heat-resistant resins used for optical materials (see, for example, Non-Patent Document 1). For example, cyclic olefin resins obtained by metathesis polymerization of hydrogenated tetracyclodecene compounds and norbornene compounds. (For example, refer to Patent Documents 1 to 4.), addition polymer of ethylene and norbornene compound, or ethylene and cyclodecene compound (for example, refer to Patent Document 5), addition polymer of norbornene compound (for example, Patent Documents 6 to 9) Etc.) have been proposed.

  The polymer of the norbornene compound has excellent characteristics as a transparent material for optical use, which is excellent in transparency, heat resistance and moldability and has a high Abbe number.

  On the other hand, in recent years, a material having a high refractive index has been demanded due to the trend of reducing the weight and size of portable devices. However, the polymer of the norbornene compound has a problem that the refractive index is low.

  As a method for achieving a high refractive index of transparent heat-resistant resin, a method of introducing an aromatic ring or a sulfur atom into a molecular structure is known. As a material having an aromatic ring introduced, a material having a fluorene skeleton introduced therein Is proposed (for example, see Patent Document 10 or Non-Patent Document 2), and a thiourethane resin into which a sulfur atom is introduced has been proposed (for example, see Patent Document 11).

Japanese Patent No. 3050196 Japanese Patent Laid-Open No. 60-026024 Japanese Patent Laid-Open No. 01-132625 Japanese Patent No. 3087421 JP 61-292601 A Japanese Patent Laid-Open No. 04-063807 Japanese Patent No. 3534127 JP 09-508649 A Japanese Patent Laid-Open No. 11-505880 Japanese Patent Laid-Open No. 11-060706 Japanese Patent Publication No. 06-005323 Polyfile, September issue, p. 36-43 (2004) NIKKEI ELECTRONICS p. 79-85 (2004. 9.13)

  However, the material introduced with the fluorene skeleton proposed in Patent Document 10 or Non-Patent Document 2 has a problem that the refractive index is as high as 1.6 or more but the Abbe number is low. The thiourethane resin introduced with sulfur atoms proposed in Patent Document 11 has a high refractive index of 1.6 or more and an Abbe number of 40 or more, but has a low heat resistance of about 100 ° C. It had a problem.

  Accordingly, the present invention provides a novel sulfur-containing cyclic olefin resin that solves the above-described problems, has good heat resistance, and is useful as a resin for optical applications with high transparency and high refractive index, and a method for producing the same. To do.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin having a specific structure has good heat resistance and is useful as a resin for optical applications having high transparency and high refractive index. The headline and the present invention have been completed.

  That is, this invention relates to the sulfur-containing cyclic olefin resin which consists of a unit represented by following General formula (1), and is the weight average molecular weight 1000-1 million, and its manufacturing method.

（１）
（ここで、Ｒ_１〜Ｒ_６は、それぞれ独立して水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアラルキル基、炭素数１〜２０の芳香族基、シアノ基、炭素数１〜１０のアルコキシ基、複素環化合物であり、さらにＲ_３〜Ｒ_６は、ハロゲン基であってもよく、Ｒ_３とＲ_４、Ｒ_５とＲ_６とが、炭素、酸素、硫黄、窒素を含有する環を形成していてもよく、Ｒ_７、Ｒ_７’、Ｒ_８及びＲ_８’は、それぞれ独立して水素原子、メチル基であり、・・・は単結合または二重結合を表し、ｌ，ｍはそれぞれ０または１を表す。）
そして、特に下記の一般式（２）で表わされる単位よりなり、重量平均分子量１０００〜１００００００であることを特徴とする含硫黄環状オレフィン樹脂、

(1)
(Here, R _{1 to} R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. It is an alkoxy group of formulas 1 to 10, a heterocyclic compound, and R _{3 to} R ₆ may be a halogen group, and R ₃ and R ₄ , R ₅ and R ₆ are carbon, oxygen, sulfur, A ring containing nitrogen may be formed, and R ₇ , R _{7 ′} , R ₈ and R _{8 ′} are each independently a hydrogen atom or a methyl group,. Where l and m each represents 0 or 1)
And especially the sulfur-containing cyclic olefin resin which consists of a unit represented by following General formula (2), and is the weight average molecular weight 1000-1 million,

（２）
（ここで、Ｒ_９およびＲ_１０は、それぞれ独立して水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアラルキル基、炭素数１〜２０の芳香族基、シアノ基、炭素数１〜１０のアルコキシ基、複素環化合物であり、・・・は単結合または二重結合を表し、ｎは０または１である。）
又は、下記の一般式（３）で表わされる単位よりなり、重量平均分子量１０００〜１００００００であることを特徴とする含硫黄環状オレフィン樹脂、その製造方法に関するものである。

(2)
(Here, R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. An alkoxy group of formula 1 to 10, a heterocyclic compound,... Represents a single bond or a double bond, and n is 0 or 1.
Alternatively, the present invention relates to a sulfur-containing cyclic olefin resin comprising a unit represented by the following general formula (3) and having a weight average molecular weight of 1,000 to 1,000,000, and a method for producing the same.

（３）
（ここで、Ｒ_１１〜Ｒ_１４は、それぞれ独立して水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアラルキル基、炭素数１〜２０の芳香族基、シアノ基、炭素数１〜１０のアルコキシ基、複素環化合物、ハロゲン基を表し、Ｒ_１１とＲ_１２、Ｒ_１３とＲ_１４とは、炭素、酸素、硫黄、窒素を含有する環を形成していてもよく、・・・は単結合または二重結合を表し、ｐは０または１である。）
以下に、本発明を詳細に説明する。

(3)
(Here, R _{11 to} R ₁₄ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. C 1 -C 10 alkoxy group, a heterocyclic compound, a halogen _group, and _{R 11} and _{R 12, R 13} and _{R 14,} may carbon, oxygen, sulfur, to form a ring containing nitrogen, Represents a single bond or a double bond, and p is 0 or 1.)
The present invention is described in detail below.

  The sulfur-containing cyclic olefin resin of the present invention comprises units represented by the above general formula (1), and has a weight average molecular weight of 1,000 to 1,000,000. In addition, the weight average molecular weight here can be measured by gel permeation chromatography.

Here, R _{1 to} R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or a carbon number. 1 to 10 alkoxy groups and heterocyclic compounds, and R _{3 to} R ₆ may be halogen groups, and R ₃ and R ₄ , R ₅ and R ₆ are carbon, oxygen, sulfur, nitrogen In which R ₇ , R _{7 ′} , R ₈ and R _{8 ′} are each independently a hydrogen atom or a methyl group,... Represent a single bond or a double bond. L and m are 0 or 1 respectively. R _{1 to} R ₆ include, for example, hydrogen atom; alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, octyl group, dodecyl group; aralkyl group such as benzyl group; phenyl group, tolyl Group, aromatic group such as naphthyl group; alkoxy group such as methoxy group and ethoxy group; heterocyclic compound group such as thienyl group and pyridyl group; and cyano group. Furthermore, as R _{3 to} R ₆ , Mention may be made of halogen groups such as fluorine, chlorine, bromine and iodine. When R ₁ to R ₆ is other than these, the resulting resin becomes inferior in heat resistance and transparency. Moreover, when a weight average molecular weight is less than 1000, it will become very brittle. On the other hand, when the weight average molecular weight exceeds 1,000,000, the viscosity at the time of melting or dissolution becomes very high, so that the handleability is poor.

As the sulfur-containing cyclic olefin resin of the present invention, in particular, R _{3 to} R ₈ , R _{7 ′} and R _{8 ′ in the} unit represented by the general formula (1) are hydrogen atoms and m is 1 It is preferably a sulfur-containing cyclic olefin resin comprising a unit represented by the formula (2).

Here, R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or a carbon number. 1 to 10 alkoxy groups and heterocyclic compounds, and n is 0 or 1. R ₉ and R ₁₀ include, for example, hydrogen atom; alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, octyl group, dodecyl group; aralkyl group such as benzyl group; phenyl group, tolyl Groups, aromatic groups such as naphthyl groups; alkoxy groups such as methoxy groups and ethoxy groups; heterocyclic compound groups such as thienyl groups and pyridyl groups; and cyano groups. And it is especially preferable that it is a sulfur-containing cyclic olefin resin which consists of a unit whose R < ₉ > and R < ₁₀ > in a unit shown by the said General formula (2) are a hydrogen atom, and n is 0.

Further, as the sulfur-containing cyclic olefin resin of the present invention, R ₇ , R _{7 ′} , R ₈ and R _{8 ′ in the} unit represented by the general formula (1) are hydrogen atoms, and m is 0. A sulfur-containing cyclic olefin resin composed of a unit represented by the formula (3) is preferred.

Here, R _{11 to} R ₁₄ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or a carbon number. Represents an alkoxy group of 1 to 10, a heterocyclic compound, or a halogen group, and R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ may form a ring containing carbon, oxygen, sulfur, or nitrogen; Is 0 or 1. R _{11 to} R ₁₄ include, for example, a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, and a dodecyl group; an aralkyl group such as a benzyl group; a phenyl group, and tolyl Groups, aromatic groups such as naphthyl groups; alkoxy groups such as methoxy groups and ethoxy groups; heterocyclic compound groups such as thienyl groups and pyridyl groups; cyano groups; halogen groups such as fluorine, chlorine, bromine and iodine. . Then, particularly preferably sulfur-containing cyclic olefin resins both are composed of units hydrogen atom, p is 0 R ₁₁ to R ₁₄ in the units of formula (3).

  As the method for producing the sulfur-containing cyclic olefin resin of the present invention, any production method may be used as long as the sulfur-containing cyclic olefin resin can be produced. For example, the sulfur-containing cyclic olefin resin represented by the following general formula (4) may be used. It can be produced by metathesis polymerization of a sulfur cyclic compound. Further, hydrogenation may be performed after the metathesis polymerization.

（４）
（ここで、Ｒ_１５〜Ｒ_２０は、それぞれ独立して水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアラルキル基、炭素数１〜２０の芳香族基、シアノ基、炭素数１〜１０のアルコキシ基、複素環化合物であり、さらにＲ_１７〜Ｒ_２０は、ハロゲン基であってもよく、Ｒ_１７とＲ_１８、Ｒ_１９とＲ_２０とが、炭素、酸素、硫黄、窒素を含有する環を形成していてもよく、Ｒ_２１及びＲ_２２は、それぞれ独立して水素原子、メチル基であり、ｑは１又は２であり、ｒは０または１を表す。）
そして、Ｒ_１５〜Ｒ_２０としては、例えば水素原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、オクチル基、ドデシル基等のアルキル基；ベンジル基等のアラルキル基；フェニル基、トリル基、ナフチル基等の芳香族基；メトキシ基、エトキシ基等のアルコキシ基；チエニル基、ピリジル基等の複素環化合物基；シアノ基を挙げることができ、さらに、Ｒ_１７〜Ｒ_２０としては、フッ素、塩素、臭素、ヨウ素のハロゲン基を挙げることができる。

(4)
(Here, R _{15 to} R ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. C 1 -C 10 alkoxy group, a heterocyclic compound, further _R 17 _{to R 20} may be a halogen _group, and the _{R 17} and _{R 18, R 19} and _{R 20,} the carbon, oxygen, sulfur, A ring containing nitrogen may be formed, and R ₂₁ and R ₂₂ are each independently a hydrogen atom or a methyl group, q is 1 or 2, and r represents 0 or 1.)
R _{15 to} R ₂₀ include, for example, a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, and a dodecyl group; an aralkyl group such as a benzyl group; a phenyl group, and tolyl Groups, aromatic groups such as naphthyl groups; alkoxy groups such as methoxy groups and ethoxy groups; heterocyclic compound groups such as thienyl groups and pyridyl groups; and cyano groups. Furthermore, as R _{17 to} R ₂₀ , Mention may be made of halogen groups such as fluorine, chlorine, bromine and iodine.

Further, when the sulfur-containing cyclic polyolefin resin represented by the general formula (2) is produced, R _{17 to} R ₂₂ of the sulfur-containing cyclic compound represented by the general formula (4) are hydrogen atoms, and r is 1. The corresponding sulfur-containing cyclic compound represented by the following general formula (5) is preferably subjected to metathesis polymerization. Further, hydrogenation may be performed after the metathesis polymerization.

（５）
（式中、Ｒ_２３およびＲ_２４は、それぞれ独立して水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアラルキル基、炭素数１〜２０の芳香族基、シアノ基、炭素数１〜１０のアルコキシ基、複素環化合物であり、ｓは１または２である。）
そして、Ｒ_２３、Ｒ_２４としては、例えば水素原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、オクチル基、ドデシル基等の炭化水素基；ベンジル基等のアラルキル基；フェニル基、トリル基、ナフチル基等の芳香族基；シアノ基；メトキシ基、エトキシ基等のアルコキシ基；チエニル基、ピリジル基等の複素環化合物基を挙げることができる。

(5)
(In the formula, R ₂₃ and R ₂₄ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. (It is an alkoxy group of formula 1 to 10 or a heterocyclic compound, and s is 1 or 2.)
R ₂₃ and R ₂₄ include, for example, a hydrogen atom; a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, and a dodecyl group; an aralkyl group such as a benzyl group; a phenyl group; An aromatic group such as a tolyl group and a naphthyl group; a cyano group; an alkoxy group such as a methoxy group and an ethoxy group; and a heterocyclic compound group such as a thienyl group and a pyridyl group.

The general formula (5) sulfur-containing cyclic compound represented by, for example, 1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2-methyl-1,3 dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2-ethyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2-propyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2-isopropyl-1,3-dithio tricyclo - [5,4,0,1 ^{6 ,} 9] -7-dodecene, 2-butyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2-octyl-1,3-dithio tricyclo - [ 5,4,0,1 ^6,9] -7-dodecene, 2-dodecyl-1,3-dithio tricyclo - [5,4,0,1 ^{6 9]} -7-dodecene, 2-phenyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2,2-dimethyl-1,3-dithio tricycloalkyl - ^[5,4,0,1 6,9] -7-dodecene, 2,2-diethyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2, 2-dipropyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2,2-dibutyl-1,3-dithio tricyclo - [5,4,0, 1 ^6,9] -7-dodecene, 2,2-diphenyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2-methyl-2-ethyl -1 , 3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2-methyl-2-propyl-1,3-dithio Rishikuro - ^[5,4,0,1 6,9] -7-dodecene, 2-methyl-2-butyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7 dodecene, 2-methyl-2-phenyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2-ethyl-2-propyl-1,3-dithio tricycloalkyl - ^[5,4,0,1 6,9] -7-dodecene, 2-ethyl-2-butyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene , 2-ethyl-2-phenyl-1,3-dithio tricyclo - ^[5,4,0,1 6,9] -7-dodecene, 2-propyl-2-phenyl-1,3-dithio tricycloalkyl - ^[5,4,0,1 6,9] -7-dodecene, and the like can be given.

When the sulfur-containing cyclic olefin resin represented by the general formula (3) is produced, R ₂₁ and R ₂₂ of the sulfur-containing cyclic compound represented by the general formula (4) are hydrogen atoms, and r is 0. It is preferable to metathesis polymerize a sulfur-containing cyclic compound represented by the following general formula (6). Further, hydrogenation may be performed after the metathesis polymerization.

（６）
（ここで、Ｒ_２５〜Ｒ_２８は、それぞれ独立して水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアラルキル基、炭素数１〜２０の芳香族基、シアノ基、炭素数１〜１０のアルコキシ基、複素環化合物、ハロゲン基を表し、Ｒ_２５とＲ_２６、Ｒ_２７とＲ_２８とは、炭素、酸素、硫黄、窒素を含有する環を形成していてもよく、ｔは１または２である。）
そして、Ｒ_２５〜Ｒ_２８としては、例えば水素原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、オクチル基、ドデシル基等のアルキル基；ベンジル基等のアラルキル基；フェニル基、トリル基、ナフチル基等の芳香族基；シアノ基；メトキシ基、エトキシ基等のアルコキシ基；チエニル基、ピリジル基等の複素環化合物基；フッ素、塩素、臭素、ヨウ素のハロゲン基を挙げることができる。

(6)
(Here, R _{25 to} R ₂₈ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. Represents an alkoxy group of formulas 1 to 10, a heterocyclic compound, and a halogen group, and R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ may form a ring containing carbon, oxygen, sulfur, and nitrogen, t is 1 or 2.)
R _{25 to} R ₂₈ include, for example, a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an octyl group, and a dodecyl group; an aralkyl group such as a benzyl group; a phenyl group, and tolyl And aromatic groups such as naphthyl groups; cyano groups; alkoxy groups such as methoxy groups and ethoxy groups; heterocyclic compound groups such as thienyl groups and pyridyl groups; and halogen groups such as fluorine, chlorine, bromine and iodine. .

  Examples of the sulfur-containing cyclic compound represented by the general formula (6) include 2-thia-1,2-dihydroxydicyclopentadiene, 2-thia-1,3-dimethyl-1,2-dihydroxydicyclopentadiene, 2 -Thia-1,3-diethyl-1,2-dihydroxydicyclopentadiene, 2-thia-1,3-dipropyl-1,2-dihydroxydicyclopentadiene, 2-thia-1,3-dibutyl-1,2 -Dihydroxydicyclopentadiene, 2-thia-1,3-dioctyl-1,2-dihydroxydicyclopentadiene, 2-thia-1,3-didodecyl-1,2-dihydroxydicyclopentadiene, 2-thia-1, 3-dimethoxy-1,2-dihydroxydicyclopentadiene, 2-thia-1,3-diethoxy-1,2-dihydroxydicyclopen Diene, 2-thia-1,3-dicyano-1,2-dihydroxydicyclopentadiene, 2-thia-1,3-di (2-thienyl) -1,2-dihydroxydicyclopentadiene, 2-thia-1 , 3-Di (2-pyridinyl) -1,2-dihydroxydicyclopentadiene, 2-thia-1,3-di (4-pyridinyl) -1,2-dihydroxydicyclopentadiene, 2-thia-1,3 -Dichloro-1,2-dihydroxydicyclopentadiene, 2-thia-1,3-dibromo-1,2-dihydroxydicyclopentadiene, 2-thia-1,3-diiodo-1,2-dihydroxydicyclopentadiene, etc. Can be mentioned.

  As the metathesis polymerization catalyst for the metathesis polymerization of the sulfur-containing cyclic compounds represented by the general formulas (4), (5) and (6), known ones can be used, for example, ruthenium compounds, palladium compounds, rhodium compounds. A polymerization catalyst comprising at least one metal compound (I) selected from iridium compounds, platinum compounds, tungsten compounds, molybdenum compounds and rhenium compounds, and metal compounds (II) belonging to groups 1, 2, 3, and 4 of the periodic table Can be mentioned.

  Examples of the metal compound (I), ruthenium compound, palladium compound, rhodium compound, iridium compound, platinum compound, tungsten compound, molybdenum compound, rhenium compound, halide, oxyhalide, alkoxy halide, carboxylate, acetyl Examples thereof include acetonate coordination products, oxide acetylacetonate coordination products, acetonitrile coordination products, hydride complexes, and carbene complexes. In particular, metathesis polymerization catalysts represented by the following general formulas (7) and (8) Is preferably used.

（７）

(7)

（８）
また、ハロゲン化物、オキシハロゲン化物は重合活性が高く好適であり、具体的にはＷＣｌ_６，ＷＯＣｌ_４，ＭｏＣｌ_５，ＭｏＯＣｌ_３，ＲｅＣｌ_３，ＷＣｌ_２（ＯＣ_６Ｈ_５）_４、ＭｏＯ_２（ａｃａｃ）_２，Ｗ（ＯＣＯＲ）_５等を例示できる。

(8)
In addition, halides and oxyhalides are preferable because of their high polymerization activity. Specifically, WCl ₆ , WOCl ₄ , MoCl ₅ , MoOCl ₃ , ReCl ₃ , WCl ₂ (OC ₆ H ₅ ) ₄ , MoO ₂ (acac ) ₂ , W (OCOR) _{5 and the} like.

  Examples of the metal compound of Group 1, 2, 3, and 4 of the periodic table as the metal compound (II) include n-butyl lithium, diethyl zinc, triethyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum hydride, trimethyl. Examples include gallium, trimethyltin, and n-butyltin, and tetramethyltin and tetraphenyltin are particularly preferable.

  When the metal compound (I) is a carbene complex, the metal compound (I) alone is sufficiently active as a metathesis polymerization catalyst. The ratio when the metal compound (I) and the metal compound (II) are combined to form a metathesis polymerization catalyst is as follows: metal compound (I) / metal compound (II) (molar ratio of metal atoms) = 1/1 to 1/30 In particular, it is preferable to use in the range of 1/2 to 1/20. Alcohols, aldehydes, ketones, and amines may be added as activity improvers.

  In the metathesis polymerization, a solvent may be used. Examples of the solvent include alkanes such as pentane, octane and nonane; cycloalkanes such as cyclohexane, cycloheptane and cyclooctane; aromatics such as benzene, toluene and xylene. Halogenated alkanes such as methylene chloride, dichloroethane and chloroform; Halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Carboxylic acid esters; Cyclic ethers such as tetrahydrofuran; Linear dialkyl ethers and the like .

  In the metathesis polymerization, a molecular weight regulator can also be used. As the molecular weight regulator, an acyclic olefin compound is generally used, for example, an α-olefin such as ethylene, 1-hexene, 1-heptene, etc. Vinyl sulfide compounds such as vinyl-phenyl sulfide, vinyl ethers such as vinyl-ethyl ether; monoolefins such as stilbene, 1,4-dichloro-2-butene, 1,4-diacetoxy-2-butene, and 2-butene A compound can be preferably used. Two or more molecular weight regulators can be used in combination. The used amount of the molecular weight regulator is preferably charged monomer / molecular weight regulator (molar ratio) = 1 / 0.001 to 0.5, particularly preferably 1 / 0.002 to 0.4.

  The polymerization temperature in the metathesis polymerization is preferably −30 ° C. to 150 ° C., and the polymerization time is preferably several minutes to 10 hours.

In addition, when producing the sulfur-containing cyclic olefin resin of the present invention, the sulfur-containing cyclic compound represented by the above general formulas (4), (5), and (6) may be used together without departing from the object of the present invention. A polymerizable copolymerizable monomer may be copolymerized. Examples of the copolymerizable monomer include cyclobutene, cyclopentene, cyclooctene, 1,5-cyclooctadiene, 1,5,9- cyclododecatriene, bicyclo [2,2,1] -2-heptene, tricyclo ^[5,2,1,0 2,6] -3-decene, tricyclo ^[5,2,1,0 2,6] -8 - decene, tricyclo ^[6,2,1,0 1,8] -9-undecene, tricyclo ^[6,2,1,0 1,8] -4-undecene, tetracyclo [4,4,0,1 ^{2, 5, 1} 7,10] -3-dodecene, pentacyclo 6,5,1,1 ^{3,6, 0 2,7, 0} 9,13] -4-pentadecene, pentacyclo ^{[6,5,1,1 3,6,} 0 ^{2,7, 0 9,13]} - 11-pentadecene, pentacyclo ^{[6,5,1,1 3,6,} 0 ^{2,7, 0} 9,14] -4-hexadecene, pentacyclo ^{[6,5,1,1 3,6, 0 2,7,} 0 ^9,13] - pentadeca-4,11-diene and the like, cycloolefins are preferably used among them.

  The polymer obtained immediately after metathesis polymerization has a double bond in the polymer structure. This double bond can be converted to a single bond by hydrogenation. For the hydrogenation, a normal hydrogenation catalyst for olefinic compounds can be used. As the hydrogenation catalyst, for example, palladium, platinum, nickel, rhodium, ruthenium and the like are supported on carbon, silica, alumina, and titania. Supported catalyst: nickel naphthenate, nickel acetylacetonate, cobalt octenoate, titanocene dichloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium And homogeneous catalysts such as dichlorocarbonyltris (triphenylphosphine) ruthenium, etc. Further, as promoters of these catalysts, for example, alkylaluminums such as triethylaluminum; Or it may be used in combination alkyllithium such as um.

  The form of the hydrogenation catalyst is not particularly limited, and can be used without any problem in the form of powder or particles. The amount of the hydrogenation catalyst used is preferably 0.01 to 50% by weight with respect to the polymer.

  As conditions for hydrogenation, the reaction pressure is preferably from normal pressure to 300 atm, and particularly preferably from 3 to 200 atm. Moreover, as reaction temperature, 0-200 degreeC is preferable, and it is especially preferable that it is 20-180 degreeC.

  The solvent for hydrogenation is not particularly limited, and from the viewpoint of economy and workability, it is preferable to use the same solvent as the polymerization solvent for metathesis polymerization.

  As another hydrogenation method, hydrogenation can be easily performed by using a reducing agent such as p-toluenesulfonyl hydrazide. In this case, the reducing agent is preferably used in a molar ratio of 1 to 50 times with respect to the double bond in the polymer.

  The hydrogenation rate is usually 60% or more, preferably 90% or more, more preferably 98% or more.

  As hydrogenation conditions in the case of using a reducing agent, the reaction temperature is preferably 0 to 200 ° C, and particularly preferably 20 to 180 ° C.

  Further, the solvent at that time is not particularly limited, and from the viewpoint of economy and workability, it is preferable to use the same solvent as the polymerization solvent for metathesis polymerization.

  The sulfur-containing cyclic compound represented by the general formulas (4), (5) and (6), which are the raw materials of the sulfur-containing cyclic olefin resin of the present invention, may be produced by any method, for example, the general formula ( The sulfur-containing cyclic compound represented by 5) can be produced by reacting a compound represented by the following general formula (9) with ketones, aldehydes, acetals or dihalides.

（９）
（ここで、Ｙは水素原子、Ｎａ、Ｋ、Ｒｂ、Ｃｓを表し、ｕは１または２を表す。）
一般式（９）で表される化合物の製造方法としては如何なる製造方法を用いてもよい。例えば一般式（９）のうちＹが水素原子のものは、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１０９，６８２５〜６８３６(１９８７)に記載の方法が挙げられる。

(9)
(Here, Y represents a hydrogen atom, Na, K, Rb, or Cs, and u represents 1 or 2.)
As a method for producing the compound represented by the general formula (9), any production method may be used. For example, in the general formula (9), Y is a hydrogen atom. Am. Chem. Soc. 109, 6825 to 6836 (1987).

  In the above-described method, 2,3-bis (hydroxymethyl) -5-norbornene and toluenesulfonyl chloride are reacted to form ditosylate. Next, after reacting this ditosylate with potassium thiocyanate to convert the tosyl group into a thiocyano group, reduction with lithium aluminum hydride was carried out to synthesize a compound of general formula (9) where Y is a hydrogen atom. ing.

  The ratio of 2,3-bis (hydroxymethyl) -5-norbornene and toluenesulfonyl chloride used is 2 mol or more of toluenesulfonyl chloride with respect to 1 mol of 2,3-bis (hydroxymethyl) -5-norbornene, preferably Is 2 mol to 3 mol. The tosylation reaction is carried out in a solvent, and examples of the solvent include pyridine, triethylamine, and dimethylaniline. These solvents may be used in combination of two or more, and may be used in combination with hydrocarbon solvents such as toluene and xylene. The reaction temperature may generally be -78 ° C to 150 ° C, and particularly preferably -20 ° C to 100 ° C. The reaction time may be from several minutes to 96 hours, and particularly preferably from 1 hour to 72 hours.

  The resulting ditosylate is potassium thiocyanate, which converts the tosyl group to a thiocyano group.

  The ratio of ditosylate to potassium thiocyanate is 2 moles or more, preferably 2 to 4 moles of potassium thiocyanate per mole of ditosylate. This reaction is carried out in a solvent, and examples of the solvent include dimethylacetamide, dimethylformamide, dimethylsulfoxide, sulfolane, and N-methylpyrrolidone. Moreover, these solvents may be used in combination of two or more, and alcohols such as methanol and ethanol and water may be used in combination. The reaction temperature may generally be -78 ° C to 200 ° C, and particularly preferably -20 ° C to 150 ° C. The reaction time may be from several minutes to 72 hours, and particularly preferably from 1 hour to 48 hours.

  When the obtained dithiocyano compound is reduced with lithium aluminum hydride, it becomes dithiol. The ratio of the dithiocyano compound to lithium aluminum hydride is 1 mol to 10 mol of lithium aluminum hydride with respect to 1 mol of dithiocyano compound, and 2 to 4 mol is particularly preferable. The reaction is carried out in a solvent, and examples of the solvent include dimethoxyethane, diethyl ether, tetrahydrofuran, and dioxane. These solvents may be used in combination of two or more. The reaction temperature may generally be -78 ° C to 200 ° C, and is particularly preferably -78 ° C to 100 ° C. The reaction time may be from several minutes to 72 hours, and particularly preferably from 1 hour to 48 hours.

  The sulfur-containing cyclic compound represented by the general formula (5) is obtained by reacting the compound represented by the general formula (9) with a compound selected from the group consisting of aldehydes, ketones and acetals. Can be obtained by cyclization reaction in a solvent in the presence of. Examples of the aldehydes include formaldehyde, acetaldehyde, propyl aldehyde, benzaldehyde, naphthyl aldehyde, octyl aldehyde, dodecyl aldehyde, α-formyl toluene, 2-thiophene carbaldehyde, 3-thiophene carbaldehyde, and 2-pyridine carbaldehyde. And 4-pyridinecarbaldehyde. Examples of the ketones include acetone, ethyl methyl ketone, acetophenone, benzophenone, fluorenone, 2-acetylthiophene, 2-acetylpyridine, 4-acetylpyridine, and the acetal. Examples include dimethoxymethane, 1,1-dimethoxyethane, 2,2-dimethoxypropane, α-dimethoxyethylbenzene, 9,9-dimethoxyfluorine. And the like.

  Examples of the solvent used in the cyclization reaction include hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether and dioxane; methanol, ethanol, ethylene glycol and the like. Alcohols; water; halogenated hydrocarbons such as dichloromethane and chloroform, and the like. These solvents may be used alone or in combination of two or more. Examples of the acid catalyst include proton acids such as hydrogen chloride, hydrogen bromide, and sulfuric acid; Lewis acids such as boron trifluoride and aluminum chloride; complexes of ethers, alcohols, and carboxylic acids of the Lewis acid. . Moreover, as reaction temperature, the range of -78 degreeC-200 degreeC is preferable, and it is especially preferable that it is the range of -20 degreeC-150 degreeC. The reaction time is preferably from several minutes to 100 hours, particularly preferably from 1 to 48 hours.

  Among the compounds represented by the general formula (9), those in which Y is Na, K, Rb, and Cs are obtained by neutralizing those in which Y is a hydrogen atom with an alkali metal compound, and then dihalides. Can be reacted to produce a sulfur-containing cyclic compound represented by the general formula (5).

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate. Is mentioned.

  The neutralization reaction is performed in a solvent that does not participate in the reaction. Examples of the solvent include hydrocarbon solvents such as n-hexane, benzene, and toluene; ethers such as diethyl ether; dimethylformamide, dimethylacetamide, and N-methyl. Examples include aprotic polar solvents such as 2-pyrrolidone, dimethyl sulfoxide, and sulfolane; and alcohols such as methanol and ethanol. As reaction temperature, -78 degreeC-150 degreeC is preferable, and it is preferable to set it as 50 degrees C or less especially in the initial stage of reaction. The reaction time is preferably in the range of 10 minutes to 10 hours.

  The sulfur-containing cyclic compound represented by the general formula (5) can be obtained by cyclizing the compound represented by the general formula (9) and a dihalide. Examples of the dihalogen compound include dichloromethane, 1,1-dichloroethane, 1,1-dichloropropane, 2,2-dichloropropane, α, α-dichlorotoluene, dichloroacetonitrile, 1,1-dichloro-3,3-dimethyl. Butane, α, α-dichloroethylbenzene, 2-dichloromethylthiophene, 2-dichloromethylpyridine, 4-dichloromethylpyridine, dibromomethane, 1,1-dibromoethane, 1,1-dibromopropane, 2,2-dibromopropane , Α, α-dibromotoluene, dibromoacetonitrile, 1,1-dibromo-3,3-dimethylbutane, α, α-dibromoethylbenzene, 9,9-dibromofluorene, 2-dibromomethylthiophene, 2-dibromomethylpyridine, Examples include 4-dibromomethylpyridine Can.

  The cyclization reaction can be performed in a solvent. Examples of the solvent include hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether and dioxane. Alcohols such as methanol, ethanol and ethylene glycol; water and the like. The reaction temperature is preferably in the range of −78 ° C. to 200 ° C., particularly preferably in the range of −20 ° C. to 150 ° C. The reaction time is preferably from a few minutes to 100 hours, particularly preferably from 1 to 20 hours.

  The sulfur-containing cyclic compound represented by the general formula (6) can be synthesized by, for example, a Diels-Alder reaction of cyclopentadiene or dicyclopentadiene and a 2,5-dihydrothiophene derivative. The Diels-Alder reaction can be carried out by mixing cyclopentadiene and a 2,5-dihydrothiophene derivative in a solvent or without a solvent and heating. Examples of the solvent include hydrocarbon solvents such as n-hexane, benzene, and toluene. And since cyclopentadiene and dicyclopentadiene are liquid and act as a solvent, it is preferable to react without a solvent in consideration of economical efficiency.

  Here, 2,5-dihydrothiophene derivative / cyclopentadiene or dicyclopentadiene (molar ratio) = 1 / 0.01 to 5 is preferable, and 1 / 0.1 to 2 is particularly preferable. In carrying out the Diels-Alder reaction, a catalyst may be used in the absence of a catalyst or to promote the reaction. When a catalyst is used, a 1,2-dihydrothiophene derivative / catalyst (molar ratio) = 1 / 0.001-1 is preferable. As the catalyst, for example, Lewis acids such as aluminum chloride, aluminum bromide, tin tetrachloride, titanium tetrachloride, zinc chloride and boron fluoride are preferable. Moreover, as reaction temperature, the range of -10-300 degreeC is preferable, and it is especially preferable that it is 20-230 degreeC. The reaction time is preferably several minutes to 100 hours, particularly preferably 30 minutes to 50 hours, and more preferably 1 to 20 hours.

In addition, among the sulfur-containing cyclic compounds represented by the general formula (6), as a synthesis of a compound in which t is 1 and R _{25 to} R ₂₈ are hydrogen atoms, J. et al. Org. Chem. , 30, 2560 to 2564 (1965).

In the above method, 2,3-bis (hydroxymethyl) -5-norbornene and methanesulfonyl chloride are reacted to form dimesylate. Next, sodium sulfide is reacted with this dimesylate to synthesize a compound in which t is 1 and R _{25 to} R ₂₈ correspond to hydrogen atoms among the sulfur-containing cyclic compounds represented by the general formula (6).

  The ratio of 2,3-bis (hydroxymethyl) -5-norbornene to methanesulfonyl chloride is 2 mol or more of methanesulfonyl chloride with respect to 1 mol of 2,3-bis (hydroxymethyl) -5-norbornene, preferably 2 mol to 3 mol. The mesylation reaction is performed in a solvent, and examples of the solvent include pyridine, triethylamine, and dimethylaniline. These solvents may be used in combination of two or more, and may be used in combination with hydrocarbon solvents such as toluene and xylene. The reaction temperature may generally be -78 ° C to 150 ° C, and particularly preferably -20 ° C to 100 ° C. The reaction time may be from several minutes to 96 hours, and particularly preferably from 1 hour to 72 hours.

The obtained dimesylate is reacted with sodium sulfide to synthesize a compound in which t is 1 and R _{25 to} R ₂₈ are hydrogen atoms among the sulfur-containing cyclic compounds represented by the general formula (6).

  The ratio of dimesylate and sodium sulfide is 1 mol or more, preferably 2 to 4 mol of sodium sulfide with respect to 1 mol of dimesylate. This reaction is performed in a solvent, and examples of the solvent include methanol, ethanol, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, sulfolane, and N-methylpyrrolidone. These solvents may be used in combination of two or more, and may be used in combination. The reaction temperature may generally be -78 ° C to 200 ° C, and particularly preferably -20 ° C to 150 ° C. The reaction time may be from several minutes to 72 hours, and particularly preferably from 1 hour to 48 hours.

  The sulfur-containing cyclic olefin resin of the present invention has high transparency, and is used as a transparent coating material such as an antireflection film or an optical fiber coating material, an optical material such as an optical film, various films, sheets, lenses, substrates, etc. Among them, since it has a high refractive index, it can be used as a plastic lens represented by a condenser lens, a prism sheet, or the like.

  The sulfur-containing cyclic olefin resin of the present invention has high transparency and a high refractive index, and is useful as a raw material for various plastic lenses and prism sheets.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, a present Example does not restrict | limit this invention at all.

~ Measurement of weight average molecular weight ~
Using gel permeation chromatography (GPC) (trade name HLC8020GPC, manufactured by Tosoh Corporation), it was measured as a standard polystyrene conversion value from an elution curve measured at 40 ° C. using chloroform as a solvent.

~ Measurement of infrared absorption spectrum (IR) ~
The IR spectrum was measured by the KBr method using an infrared absorption measuring apparatus (trade name Infrared Spectrophotometer 270-30, manufactured by Hitachi, Ltd.).

~ Measurement of NMR spectrum ~
Using a nuclear magnetic resonance spectrum measuring apparatus (trade name GSX270WB, manufactured by JEOL Ltd.), measurement was performed using deuterated chloroform as a heavy solvent.

~ Measurement of GC-MS ~
Using a gas chromatography-mass spectrometer (trade name: mass spectrometer 5971 series, manufactured by Hewlett Packard), a capillary column (product name: DB-1 manufactured by GL Science) having an outer diameter of 0.25 mm and a length of 30 m is used as the column. And measured.

~ Light transmittance ~
The measurement was performed according to JIS K7105.

-Refractive index (nd)-
Using an Abbe refractometer (trade name: DR-M2 manufactured by Atago Co., Ltd.), measurement was performed by d-line.

Refractive index of ~ sulfur-containing cyclic compound _(n D) -
Using a liquid refractometer (trade name: RX-5000α (digital refractometer), manufactured by Atago Co., Ltd.), the measurement was performed as a toluene solution.

Synthesis example 1
<Synthesis of 5-norbornene-2,3-dicarboxylic acid isopropyl ester>
A 200 ml autoclave was charged with 27.1 g (0.2 mol) of dicyclopentadiene and 80.4 g (0.4 mol) of diisopropyl fumarate, and the system was sufficiently substituted with nitrogen, followed by reaction at 170 ° C. for 5 hours. The reaction solution was distilled under a reduced pressure of 0.4 kPa to obtain 88 g of a fraction at 124 to 126 ° C. This fraction was confirmed to be 5-norbornene-2,3-dicarboxylic acid isopropyl ester from ¹ H-NMR spectrum and GC-MS. Yield 83%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 (12H), 1.4 to 1.6 (2H), 2.6 (1H), 3.1 to 3.4 (3H), 5.0 (2H), 6.1-6.3 (2H)
EI-MS: 266 (M)
<Synthesis of 5-norbornene-2,3-dimethanol>
A glass 1000 ml four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube was charged with 25.8 g (0.68 mol) of lithium aluminum hydride, and the inside of the system was sufficiently replaced with nitrogen. While cooling in an ice-water bath, 450 ml of tetrahydrofuran (hereinafter referred to as THF) was slowly added. To this, a mixed solution of 37.8 g (0.14 mol) of 5-norbornene-2,3-dicarboxylic acid isopropyl ester and 50 ml of THF was added dropwise so that the temperature of the reaction system did not exceed 10 ° C. After completion of the dropwise addition, the reaction was performed at the reflux temperature of THF for 5 hours. After completion of the reaction, the reaction system was cooled again to 5 ° C. in an ice water bath, and 150 g of 3% NaOH aqueous solution was added dropwise over about 1 hour. Stirring was continued for about 30 minutes, and the precipitate was suction filtered.

The solvent was removed with an evaporator, and dried with a vacuum dryer at room temperature for 5 hours to obtain 20.4 g of a pale orange viscous liquid. This viscous liquid was 5-norbornene-2,3-dimethanol from ¹ H-NMR spectrum and GC-MS. Yield 98%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.3 (1H), 1.6 to 2.0 (2H), 2.5 to 3.1 (5H), 3.4 to 3.8 (4H), 6.0-6.2 (2H)
EI-MS: 154 (M)
<Synthesis of 5-norbornene-2,3-dimethanol-di-p-toluenesulfonate>
A glass 500 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube was charged with 20.3 g (0.13 mol) of 5-norbornene-2,3-dimethanol and 90 ml of pyridine, ice water The reaction system was cooled to 5 ° C. with a bath. To this solution, 59.4 g (0.31 mol) of p-toluenesulfonic acid chloride was added over 20 minutes. When stirring was continued for about 20 minutes, the reaction system solidified, and the whole reactor was placed in a refrigerator adjusted to 4 ° C. for 72 hours.

The reaction was added to 300 ml of 6% aqueous HCl and stirred at room temperature for 2 hours. The produced white slurry solution was subjected to suction filtration, and the obtained white solid was washed twice with 200 ml of methanol and dried in a vacuum dryer at 50 ° C. for 2 hours to obtain 53.2 g of a white solid. This solid was 5-norbornene-2,3-dimethanol-di-p-toluenesulfonate from ¹ H-NMR spectrum. Yield 87%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 (1H), 1.3 to 1.4 (2H), 1.9 (1H), 2.4 (6H), 2.6 ( 1H), 2.8 (1H), 3.5-4.0 (4H), 5.8 (1H), 6.1 (1H), 7.3 (4H), 7.7 (4H)
<Synthesis of 5-norbornene-2,3-dimethylthiocyanate>
In a glass 1000 ml four-necked flask equipped with a stirrer, a condenser tube, a thermometer, and a nitrogen inlet tube, 147 g of potassium thiocyanate (0.62 mol), dimethylformamide (hereinafter referred to as DMF) 236 ml, 5-norbornene- After charging 53 g (0.11 mol) of 2,3-dimethanol-di-p-toluenesulfonate and sufficiently substituting the inside of the system with nitrogen, the temperature of the reaction system was raised and the reaction was carried out at 70-80 ° C. for 20 hours. did. The reaction solution was allowed to cool, 200 ml of pure water was added, and the mixture was extracted twice with 200 ml of diethyl ether. Diethyl ether was removed from the diethyl ether layer by an evaporator to obtain 23.5 g of a yellow viscous liquid. This viscous liquid was 5-norbornene-2,3-dimethylthiocyanate from ¹ H-NMR spectrum and GC-MS. Yield 88%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.3 to 1.5 (3H), 2.2 (1H), 2.7 to 3.2 (6H), 6.1 (1H), 6.3 (1H)
EI-MS: 236 (M)
<1,3 dithio tricyclo - [5,4,0,1 ^6,9] -7 Synthesis of dodecene>
After charging 16.4 g (0.43 mol) of lithium aluminum hydride into a glass 1000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introducing tube, and sufficiently replacing the system with nitrogen, ice water While cooling in a bath, 400 ml of THF was slowly added. Here, a mixed solution of 23 g (0.1 mol) of 5-norbornene-2,3-dimethylthiocyanate and 100 ml of THF was dropped over about 1 hour. After completion of the dropwise addition, the reaction was performed at room temperature for 2 hours. After completion of the reaction, the reaction system was cooled again to 5 ° C. in an ice water bath, and 25 ml of 5% aqueous sulfuric acid solution was added dropwise. Stirring was continued for about 1 hour, and the precipitate was suction filtered. When the obtained filtrate was analyzed by GC-MS, the starting 5-norbornene-2,3-dimethylthiocyanate was not observed, and the formation of 5-norbornene-2,3-dimercaptomethyl was observed. EI-MS: 186.

The filtrate was concentrated to 50 g with an evaporator, and 400 ml of methanol was added thereto. To this methanol solution was added a solution obtained by dissolving 22 g (0.33 mol) of 85% potassium hydroxide in 350 ml of methanol, and the mixture was stirred at room temperature for 30 minutes. Next, a mixed solution of 18.7 g (0.11 mol) of dibromomethane and 100 ml of methanol was dropped over about 30 minutes, and the mixture was stirred at room temperature for 13 hours. In the reaction solution, the precipitated salt was filtered and methanol was removed by an evaporator. After adding 100 ml of chloroform to the obtained slurry and filtering the solid content again, the filtrate was concentrated with an evaporator to obtain 16.8 g of a viscous liquid. The obtained viscous solution was distilled under a reduced pressure of 0.3 kPa to obtain 7.6 g of a distillate in the range of 111 to 114 ° C. This ^fraction, 1 H-NMR spectrum and GC-MS from 1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7 In dodecene (formula (5) _{R 23} and R ₂₄ is a hydrogen atom and s is 1.).

270 MHz ¹ H-NMR measurement results; δ (CDCl ₃ ): 1.6 (3H), 2.2 (2H), 2.6 (2H), 2.8 (2H), 3.0 (1H), 6.1 (1H), 6.3 (1H)
EI-MS: 198 (M)
Refractive index (n _D ): 1.597
Synthesis example 2
<Synthesis of bis-1,4-dichloro-2-butene bisisothiuronium salt>
A glass 1000 ml four-necked flask equipped with a stirrer, a condenser tube, a thermometer, and a nitrogen inlet tube was charged with 120 g (1.58 mol) of thiourea and 310 ml of 95% ethanol. After sufficiently replacing the reaction system with nitrogen, the temperature was raised to 40 ° C., and a mixture of 90 g (0.72 mol) of cis-1,4-dichloro-2-butene and 20 ml of 95% ethanol was added dropwise over about 30 minutes. (At this time, an exotherm occurs.) After completion of the dropwise addition, the reaction system was heated to the ethanol reflux temperature and reacted for 1 hour. After completion of the reaction, the mixture was allowed to cool to room temperature and the solid content was filtered. This solid content was washed twice with 250 ml of ethanol and dried in a vacuum dryer at room temperature for 8 hours to obtain 182 g of a white solid. This white solid was a bisisothiuronium salt of cis-1,4-dichloro-2-butene based on ¹ H-NMR spectrum and FT-IR spectrum. Yield 90%.

Measurement result of 270 MHz ¹ H-NMR; δ (D ₂ O): 4.0 (4H), 5.9 (2H)
Measurement result of FT-IR (KBr method): 3000 to 3500 cm ⁻¹ (NH)
<Synthesis of 4,7-dihydro-1,3-dithiepine>
A glass 5000 ml four-necked flask equipped with a stirrer, a condenser tube, a thermometer, and a nitrogen inlet tube was charged with 182 g (0.66 mol) of bisisothiuronium salt of cis-1,4-dichloro-2-butene and 1900 ml of methanol. The reaction system was cooled to 4 ° C. To this slurry solution, 218 g (3.31 mol) of 85% potassium hydroxide was added over 1 hour, and reacted at 2-4 ° C. for 16 hours. To the obtained reaction solution, a mixed solution of 143 g (0.82 mol) of dibromomethane and 650 ml of methanol was added dropwise over 6 hours so that the reaction temperature did not exceed 5 ° C. The reaction solution was slowly returned to room temperature overnight and continued to stir for 60 hours.

The obtained reaction solution was filtered to remove solids, and then the methanol was removed by an evaporator, followed by drying at room temperature for 1 hour in a vacuum dryer to obtain 50.1 g of a pale yellow solid. This pale yellow solid was 4,7-dihydro-1,3-dithiepine from ¹ H-NMR spectrum and GC-MS. Yield 58%.

270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 3.45 (4H), 4.02 (2H), 6.00 (2H)
EI-MS: 132 (M)
<1,3 dithio tricyclo - [5,4,0,1 ^6,9] -7 Synthesis of dodecene>
A 200 ml autoclave was charged with 12.2 g (0.09 mol) of dicyclopentadiene and 49.1 g (0.37 mol) of 4,7-dihydro-1,3-dithiepine, and the inside of the system was sufficiently replaced with nitrogen, followed by stirring. The heating and stirring were continued at 170 ° C. for 5 hours. After completion of the reaction, the temperature was lowered to 25 ° C., and the reaction solution was taken out from the autoclave. The reaction solution was a brown solution. The obtained brown solution was distilled under a reduced pressure of 0.3 kPa, thereby obtaining 23.5 g of a distillate having a range of 111 to 114 ° C. This fraction solidified at room temperature. Under 5,4,0,1 ^6,9] -7-dodecene _{(R 23} and _{R 24} in the general formula (5) is a hydrogen atom - ¹ H-NMR spectrum and GC-MS from 1,3-dithio tricycloalkyl , Compound in which s is 1.). This compound is an isomer of the compound obtained in Synthesis Example 1.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 (2H), 2.5 to 3.0 (8H), 4.0 (2H), 5.8 to 6.2 (2H)
EI-MS: 198 (M)
Refractive index (n _D ): 1.610
Synthesis example 3
<Synthesis of bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboxylic acid>
A 2-liter titanium autoclave was charged with 212 g (1.6 mol) of dicyclopentadiene, 371 g (3.2 mol) of maleic acid, and 500 g of toluene, and the system was sufficiently substituted with nitrogen, followed by reaction at 170 ° C. for 5 hours. did. Toluene was removed from the resulting reaction solution with an evaporator to obtain white crystals. The white crystals were washed with a small amount of hexane to obtain 540 g of bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboxylic acid.

^{From 1} H-NMR spectrum, it was confirmed to be bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboxylic acid.
<Synthesis of bicyclo- [2,2,1] -hept-5-ene-2,3-bishydroxymethyl>
A solution prepared by dissolving 18 g (0.475 mol) of lithium aluminum hydride in 450 ml of THF was added to a glass one-liter four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube. To this solution, a solution of 18.2 g (0.1 mol) of bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboxylic acid synthesized previously and 110 ml of THF was added dropwise, and the addition was completed. Thereafter, the mixture was reacted for 5 hours under reflux conditions. After completion of the reaction, the reaction solution was cooled to 0 ° C., 78 g of a 1 mol / liter sodium hydroxide aqueous solution was added, and the mixture was stirred for 2 hours. After filtering the solution, the THF phase was separated and concentrated by an evaporator to obtain 14.6 g of a liquid.

^{From 1} H-NMR spectrum, it was confirmed that it was bicyclo- [2,2,1] -hept-5-ene-2,3-bishydroxymethyl.
<Tosylation of bicyclo- [2,2,1] -hept-5-ene-2,3-bishydroxylmethyl>
14.6 g of bicyclo- [2,2,1] -hept-5-ene-2,3-bishydroxymethyl in a glass 300 ml four-necked flask equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet tube (0.095 mol) and 70 ml of dry pyridine were added and cooled to 0 ° C. To this, 45.5 g (0.24 mol) of toluenesulfonyl chloride was slowly added and reacted at this temperature for 3 days. The reaction solution was poured into 300 ml of 1 mol / liter hydrochloric acid. The deposited precipitate was filtered off and washed several times with pure water. Extraction was performed 3 times with 200 ml of ether, and the solvent was concentrated to obtain 43 g of a white solid.

^{From 1} H-NMR spectrum, it was confirmed that it was bicyclo- [2,2,1] -hept-5-ene-2,3-bistosylmethyl.
<Synthesis of bicyclo- [2,2,1] -hept-5-ene-2,3-bismercaptomethyl>
A solution prepared by dissolving 22.6 g (0.28 mol) of potassium thiocyanate in 200 ml of dimethyl sulfoxide was added to a glass 500 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube. A solution prepared by dissolving 43 g (0.093 mol) of bicyclo- [2,2,1] -hept-5-ene-2,3-bistosylmethyl in 200 ml of dimethyl sulfoxide was added dropwise to this solution, and the resulting solution was kept at 70 ° C. for 48 hours. Reacted. The reaction solution was poured into 1000 ml of cold water and extracted three times with 200 ml of dichloromethane.

  The dichloromethane phase was concentrated with an evaporator. The obtained crude product was diluted with 200 ml of THF and added dropwise to a solution of 18 g (0.474 mol) of lithium aluminum hydride dissolved in 500 ml of THF. After reacting under reflux for 2 hours, the mixture was cooled to 0 ° C., 80 g of 1 mol / liter aqueous sodium hydroxide solution was added, and the mixture was stirred for 2 hours. After filtering the solution, the THF phase was separated and concentrated with an evaporator, and the resulting compositional organism was distilled under reduced pressure at a pressure of 1 torr to recover 10.8 g of a colorless and transparent liquid fraction at 57 to 61 ° C.

^{From 1} H-NMR spectrum, it was confirmed that it was bicyclo- [2,2,1] -hept-5-ene-2,3-bismercaptomethyl.
<Cyclization reaction>
Bicyclo- [2,2,1] -hept-5-ene-2,3-bismercapto obtained in a glass 300 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube 10.8 g (0.058 mol) of methyl, 0.052 g (0.53 mmol) of 98% sulfuric acid and 40 g of dioxane were weighed, and 5.4 g (0.054 mol) of 30% aqueous formaldehyde solution was added to the mixed solution. The solution was added dropwise at 25 ° C. over 30 minutes. After further reaction at 70 ° C. for 5 hours, the reaction product was discharged into 100 g of water and extracted with methylene chloride. The organic phase (methylene chloride solution) was washed with water until the aqueous layer became neutral, and liquid separation was repeated. Then, the organic phase was taken out. Methylene chloride was removed under reduced pressure on a rotary evaporator to give a yellow liquid. The obtained liquid was distilled under a reduced pressure of 0.4 kPa to obtain 8 g of a colorless and transparent fraction at 120 ° C. to 123 ° C.

^{GC-MS, 1} from H-NMR spectrum, the obtained liquid 1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7-dodecene in (formula (5) _{R 23} And R ₂₄ is a hydrogen atom and s is 1.).

In addition, the refractive index (n _D ) of this liquid at 25 ° C. was 1.61.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 (2H), 2.5 to 3.0 (8H), 4.0 (2H), 5.8 to 6.2 (2H)
EI-MS: 198 (M)
Synthesis example 4
A glass 500 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introducing tube was charged with 200 ml of methanol and 22 g of 85% potassium hydroxide to prepare a solution. This solution was cooled to 0 ° C., and 9.3 g (0.05 mol) of bicyclo- [2,2,1] -hept-5-ene-2,3-bismercaptomethyl synthesized by the same method as in Synthesis Example 3. Was slowly added dropwise and stirring was continued for 1 hour. Next, a solution obtained by diluting 12.5 g (0.05 mol) of α, α-dibromotoluene in 50 ml of methanol was added over about 30 minutes. The reaction solution was returned to room temperature and reacted overnight.

  The precipitate was filtered off, and the solution was concentrated with an evaporator, ether and water were added, and the resulting liquid was washed several times. The ether layer was concentrated with an evaporator, and the resulting liquid was distilled under a reduced pressure of 0.1 kPa to obtain 11 g of a colorless and transparent fraction at 115 ° C to 120 ° C.

From ^{GC-MS, 1} H-NMR spectrum, the obtained liquid, 2-phenyl-1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7-dodecene (formula (5 ) In which R ₂₃ is a phenyl group, R ₂₄ is a hydrogen atom, and s is 1. In addition, the refractive index (n _D ) of this liquid at 25 ° C. was 1.65.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 (2H), 2.5 to 3.0 (8H), 4.0 (1H), 6.0 to 6.4 (2H), 7.0-7.1 (5H)
EI-MS: 274 (M)
Synthesis example 5
18 ml of boron trifluoride diethyl ether complex, 36 ml of glacial acetic acid and 60 ml of chloroform were placed in a glass-made 500 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube and a dropping funnel. When the mixture was heated under stirring and gently refluxed, bicyclo- [2,2,1] -hept-5-ene-2,3-bismercaptomethyl synthesized in the same manner as in Synthesis Example 3 was added to this solution. A solution obtained by diluting 27.9 g (0.15 mol) and 2,2-dimethoxypropane 17.2 g (0.165 mol) with 230 ml of chloroform was added dropwise over 4 hours. After reacting for 1 hour as it was, the mixture was cooled to room temperature, and the reaction solution was washed with 50 ml of water 4 times, 150 ml of 10% aqueous sodium hydroxide solution twice, and 50 ml of water twice.

  Chloroform was removed with an evaporator, and the resulting liquid was distilled under a reduced pressure of 0.1 kPa to obtain 23 g of a colorless and transparent fraction at 103 ° C to 110 ° C.

^{GC-MS, 1} from H-NMR spectrum, the obtained liquid 2,2-dimethyl-1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7-dodecene (formula ( 5), it was confirmed that R ₂₃ and R ₂₄ are methyl groups and s is 1. The refractive index (n _D ) of this liquid at 25 ° C. was 1.60.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 (2H), 1.8 (6H), 2.5 to 3.0 (8H), 6.0 to 6.4 (2H),
EI-MS: 226 (M)
Synthesis Example 6
Bicyclo- [2,2,1] -hept-5 synthesized in the same manner as in Synthesis Example 3 in a glass 300 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube En-2,3-bismercaptomethyl (5 g, 0.027 mol), 98% sulfuric acid (0.026 g, 0.27 mmol) and dioxane (20 g) were weighed, and 2-thiophenecarbaldehyde (3 g, 0.027 mol) was weighed into the mixed solution. ) Was added dropwise to 10 g of dioxane at 25 ° C. over 30 minutes. After further reaction at 70 ° C. for 5 hours, the reaction product was discharged into 50 g of water and extracted with methylene chloride. The organic layer (methylene chloride solution) was washed with water until the aqueous layer became neutral, and liquid separation was repeated. Then, the organic layer was taken out. Methylene chloride was removed under reduced pressure on a rotary evaporator to give a yellow liquid.

  The obtained liquid was distilled under a reduced pressure of 0.1 kPa to obtain 4.5 g of a colorless and transparent fraction at 120 ° C. to 123 ° C.

From ^{GC-MS, 1} H-NMR spectrum, the obtained liquid, 2- (2-thienyl) -1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7-dodecene ( In General Formula (5), it was confirmed that R ₂₃ is a thienyl group, R ₂₄ is a hydrogen atom, and s is 1. In addition, the refractive index (n _D ) of this liquid at 25 ° C. was 1.65.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 (2H), 2.5 to 3.0 (8H), 4.0 (1H), 5.8 to 6.2 (5H)
EI-MS: 280 (M)
Synthesis example 7
<Synthesis of 7-methyl-5-norbornene-2,3-dicarboxylic acid isopropyl ester>
A 200 ml autoclave was charged with 32.0 g (0.4 mol) of 1-methylcyclopentadiene and 80.4 g (0.4 mol) of diisopropyl fumarate, and the system was sufficiently replaced with nitrogen, followed by reaction at 170 ° C. for 5 hours. . The reaction solution was distilled under a reduced pressure of 0.4 kPa to obtain 94 g of a fraction at 124 to 126 ° C. From this ¹ H-NMR spectrum and GC-MS, this fraction was confirmed to be 7-methyl-5-norbornene-2,3-dicarboxylic acid isopropyl ester. Yield 84%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 (14H), 1.4 to 1.6 (2H), 2.6 (1H), 3.1 to 3.4 (3H), 5.0 (2H), 6.1-6.3 (2H)
EI-MS: 280 (M)
<Synthesis of 7-methyl-5-norbornene-2,3-dimethanol>
A glass 1000 ml four-necked flask equipped with a stirrer, cooling tube, thermometer, and nitrogen inlet tube was charged with 25.8 g (0.68 mol) of lithium aluminum hydride, and the system was sufficiently replaced with nitrogen. While cooling in a bath, 450 ml of THF was slowly added. Here, a mixed solution of 39.2 g (0.14 mol) of 7-methyl-5-norbornene-2,3-dicarboxylic acid isopropyl ester and 50 ml of THF was added dropwise so that the temperature of the reaction system did not exceed 10 ° C. After completion of the dropwise addition, the reaction was performed at the reflux temperature of THF for 5 hours. After completion of the reaction, the reaction system was cooled again to 5 ° C. in an ice water bath, and 150 g of 3% NaOH aqueous solution was added dropwise over about 1 hour. Stirring was continued for about 30 minutes, and the precipitate was suction filtered.

The solvent was removed with an evaporator and dried in a vacuum dryer at room temperature for 5 hours to obtain 23.1 g of a pale orange viscous liquid. This viscous liquid was 7-methyl-5-norbornene-2,3-dimethanol from ¹ H-NMR spectrum and GC-MS. Yield 98%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.3 (4H), 1.6 to 2.0 (1H), 2.5 to 3.1 (5H), 3.4 to 3.8 (4H), 6.0-6.2 (2H)
EI-MS: 168 (M)
<Synthesis of 7-methyl-5-norbornene-2,3-dimethanol-di-p-toluenesulfonate>
A glass 500 ml four-necked flask equipped with a stirrer, a condenser tube, a thermometer, and a nitrogen inlet tube was charged with 21.8 g (0.13 mol) of 7-methyl-5-norbornene-2,3-dimethanol and 90 ml of pyridine. And the inside of the reaction system was cooled to 5 ° C. with an ice-water bath. To this solution, 59.4 g (0.31 mol) of p-toluenesulfonic acid chloride was added over 20 minutes. When stirring was continued for about 20 minutes, the reaction system solidified, and the whole reactor was placed in a refrigerator adjusted to 4 ° C. for 72 hours.

The reaction was added to 300 ml of 6% aqueous HCl and stirred at room temperature for 2 hours. The produced white slurry solution was subjected to suction filtration, and the obtained white solid was washed twice with 200 ml of methanol and dried in a vacuum dryer at 50 ° C. for 2 hours to obtain 53.8 g of a white solid. This solid was 7-methyl-5-norbornene-2,3-dimethanol-di-p-toluenesulfonate from ¹ H-NMR spectrum. Yield 87%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 (4H), 1.3 to 1.4 (1H), 1.9 (1H), 2.4 (6H), 2.6 ( 1H), 2.8 (1H), 3.5-4.0 (4H), 5.8 (1H), 6.1 (1H), 7.3 (4H), 7.7 (4H)
<Synthesis of 7-methyl-5-norbornene-2,3-dimethylthiocyanate>
In a glass 1000 ml four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube, 147 g (0.62 mol) of potassium thiocyanate, 236 ml of DMF, 7-methyl-5-norbornene-2,3-di After charging 53 g (0.11 mol) of methanol-di-p-toluenesulfonate and sufficiently substituting the inside of the system with nitrogen, the temperature of the reaction system was raised and reacted at 70 to 80 ° C. for 20 hours. The reaction solution was allowed to cool, 200 ml of pure water was added, and the mixture was extracted twice with 200 ml of diethyl ether. Diethyl ether was removed from the diethyl ether layer by an evaporator to obtain 23.8 g of a yellow viscous liquid. This viscous liquid was 7-methyl-5-norbornene-2,3-dimethylthiocyanate from ¹ H-NMR spectrum and GC-MS. Yield 87%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.3 to 1.5 (3H), 2.2 (1H), 2.7 to 3.2 (6H), 6.1 (1H), 6.3 (1H)
EI-MS: 250 (M)
<12-methyl-1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7 Synthesis of dodecene>
After charging 16.4 g (0.43 mol) of lithium aluminum hydride into a glass 1000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introducing tube, and sufficiently replacing the system with nitrogen, While cooling with an ice-water bath, 400 ml of THF was slowly added. To this, a mixed solution of 7-methyl-5-norbornene-2,3-dimethylthiocyanate 23 g (0.09 mol) and THF 100 ml was dropped over about 1 hour. After completion of the dropwise addition, the reaction was performed at room temperature for 2 hours. After completion of the reaction, the reaction system was cooled again to 5 ° C. in an ice water bath, and 25 ml of 5% aqueous sulfuric acid solution was added dropwise. Stirring was continued for about 1 hour, and the precipitate was suction filtered. When the obtained filtrate was analyzed by GC-MS, the starting material 7-methyl-5-norbornene-2,3-dimethylthiocyanate was not observed, and the formation of 7-methyl-5-norbornene-2,3-dimercaptomethyl was observed. Admitted. EI-MS: 200.

The filtrate was concentrated to 50 g with an evaporator, and 400 ml of methanol was added thereto. To this methanol solution was added a solution obtained by dissolving 22 g (0.33 mol) of 85% potassium hydroxide in 350 ml of methanol, and the mixture was stirred at room temperature for 30 minutes. Next, a mixed solution of 18.7 g (0.11 mol) of dibromomethane and 100 ml of methanol was dropped over about 30 minutes, and the mixture was stirred at room temperature for 13 hours. In the reaction solution, the precipitated salt was filtered and methanol was removed by an evaporator. After adding 100 ml of chloroform to the obtained slurry and filtering the solid content again, the filtrate was concentrated with an evaporator to obtain 17.0 g of a viscous liquid. The obtained viscous solution was distilled under a reduced pressure of 0.3 kPa to obtain 7.8 g of a distillate in the range of 115 to 119 ° C. This ^fraction, 1 H-NMR from spectrum and GC-MS 12-methyl-1,3-dithio tricyclo - In [5,4,0,1 ^6,9] -7-dodecene (formula (4) R _{15 to} R ₂₁ are hydrogen atoms, R ₂₂ is a methyl group, and q is 1.

270 MHz ¹ H-NMR measurement results; δ (CDCl ₃ ): 1.6 (5H), 2.2 (2H), 2.6 (2H), 2.8 (2H), 3.0 (1H), 6.1 (1H), 6.3 (1H)
EI-MS: 212 (M)
Refractive index (n _D ): 1.590
Synthesis Example 8
<Synthesis of 5-norbornene-2,3-dimethanol-dimethanesulfonate>
In the same manner as in Synthesis Example 1, 31 g of 5-norbornene-2,3-dimethanol was obtained.

  A glass 500 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introducing tube was charged with 140 ml of pyridine, and the system was sufficiently replaced with nitrogen, and then cooled in an ice water bath. The temperature was lowered to 3 ° C. In this, 50.3 g (0.44 mol) of methanesulfonic acid chloride was dripped over about 1 hour. After stirring this solution for 1 hour, a mixed liquid of 30 g (0.2 mol) of 5-norbornene-2,3-dimethanol and 125 ml of pyridine was slowly added over 5 hours so that the temperature inside the system did not exceed 5 ° C. . The reaction system became a brown slurry and reacted for 15 hours.

  The reaction solution was slowly added to 4% aqueous HCl ice solution, and the precipitated brown solid was suction filtered. The obtained brown solid was washed twice with 500 ml of pure water and then dried at 50 ° C. for 8 hours in a vacuum dryer to obtain 54.5 g of a light brown solid.

^{From 1} H-NMR spectrum, it was confirmed to be 5-norbornene-2,3-dimethanol-dimethanesulfonate. Yield 90%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 to 1.4 (2H), 2.7 (2H), 3.0 (8H), 3.9 to 4.1 (4H), 6.1 (2H)
<Synthesis of 2-thia-1,2-dihydrodicyclopentadiene>
A glass 500 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube was charged with 25 g (0.08 mol) of 5-norbornene-2,3-dimethanol-dimethanesulfonate and 250 ml of methanol, After sufficiently substituting the inside of the system with nitrogen, 5-norbornene-2,3-dimethanol-dimethanesulfonate was dissolved under heating and reflux. To this solution, an aqueous solution in which 62 g (0.26 mol) of sodium sulfide nonahydrate was dissolved in 150 ml of pure water was dropped over about 4 hours. After completion of the dropwise addition, the reaction was continued for 2 hours. The reaction solution was extracted twice with 100 ml of diethyl ether after cooling. The diethyl ether layer was washed once with 100 ml of 10% NaOH aqueous solution, and after liquid separation, diethyl ether was removed by a rotary evaporator to obtain 10.6 g of a black liquid. This liquid was distilled under a reduced pressure of 0.1 kPa to obtain 3.8 g of a 59-60 ° C. fraction. ¹ H-NMR spectrum and GC-MS confirm that it is 2-thia-1,2-dihydrodicyclopentadiene (a compound in which R _{25 to} R ₂₈ are hydrogen atoms and t is 1 in the general formula (6)) did. Yield 31%.

270 MHz ¹ H-NMR measurement results; δ (CDCl ₃ ): 1.62-1.80 (2H), 2.26-2.42 (2H), 2.60-2.82 (2H), 3. 08-3.28 (2H), 6.11 (2H)
EI-MS: 152 (M)
Refractive index (n _D ): 1.557
Synthesis Example 9
<Synthesis of 5-norbornene-2,3-dimethanol>
A 200 ml autoclave was charged with 26.4 g (0.2 mol) of dicyclopentadiene and 70.4 g (0.8 mol) of cis-1,4-dihydroxy-2-butene, and the system was sufficiently replaced with nitrogen, followed by stirring. While raising the temperature to 170 ° C., heating and stirring were continued for 6 hours. After completion of the reaction, the temperature was lowered to 25 ° C., and the reaction solution was taken out from the autoclave. The reaction solution was a brown solution. The resulting brown solution was distilled under a reduced pressure of 0.3 kPa to obtain 36.3 g of a distillate having a temperature in the range of 120 to 122 ° C. This fraction was confirmed to be 5-norbornene-2,3-dimethanol from ¹ H-NMR spectrum and GC-MS. Yield 59%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.4 (2H), 2.4 to 2.8 (4H), 3.2 to 4.3 (6H), 6.0 (2H)
EI-MS: 154 (M)
<Synthesis of 5-norbornene-2,3-dimethanol-dimethanesulfonate>
A glass 500 ml four-necked flask equipped with a stirrer, cooling tube, thermometer, and nitrogen inlet tube was charged with 140 ml of pyridine, and the system was sufficiently replaced with nitrogen. Was lowered to 3 ° C. In this, 50.3 g (0.44 mol) of methanesulfonic acid chloride was dripped over about 1 hour. After stirring this solution for 1 hour, a mixed liquid of 30 g (0.2 mol) of 5-norbornene-2,3-dimethanol and 125 ml of pyridine was slowly added over 5 hours so that the temperature inside the system did not exceed 5 ° C. . The reaction system became a brown slurry and reacted for 15 hours.

  The reaction solution was slowly added to 4% aqueous HCl ice solution, and the precipitated brown solid was suction filtered. The obtained brown solid was washed twice with 500 ml of pure water and then dried at 50 ° C. for 8 hours in a vacuum dryer to obtain 54.5 g of a light brown solid.

^{From 1} H-NMR spectrum, it was confirmed to be 5-norbornene-2,3-dimethanol-dimethanesulfonate. Yield 90%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.2 to 1.4 (2H), 2.7 (2H), 3.0 (8H), 3.9 to 4.1 (4H), 6.1 (2H)
<Synthesis of 2-thia-1,2-dihydrodicyclopentadiene>
A glass 500 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube was charged with 25 g (0.08 mol) of 5-norbornene-2,3-dimethanol-dimethanesulfonate and 250 ml of methanol, After sufficiently substituting the inside of the system with nitrogen, 5-norbornene-2,3-dimethanol-dimethanesulfonate was dissolved under heating and reflux. To this solution, an aqueous solution in which 62 g (0.26 mol) of sodium sulfide nonahydrate was dissolved in 150 ml of pure water was dropped over about 4 hours. After completion of the dropwise addition, the reaction was continued for 2 hours. The reaction solution was extracted twice with 100 ml of diethyl ether after cooling. The diethyl ether layer was washed once with 100 ml of 10% NaOH aqueous solution, and after liquid separation, diethyl ether was removed by a rotary evaporator to obtain 10.6 g of a black liquid. This liquid was distilled under a reduced pressure of 0.1 kPa to obtain 3.8 g of a 59-60 ° C. fraction. ¹ H-NMR spectrum and GC-MS confirm that it is 2-thia-1,2-dihydrodicyclopentadiene (a compound in which R _{25 to} R ₂₈ are hydrogen atoms and t is 1 in the general formula (6)) did. This compound is an isomer of the compound obtained in Synthesis Example 8. Yield 31%.

Measurement results by 270 MHz ¹ H-NMR δ (CDCl ₃ ): 1.8 (2H), 2.4 (2H), 2.7 (4H), 3.2 (2H), 6.2 (2H)
EI-MS: 152 (M)
Refractive index (n _D ): 1.555
Synthesis Example 10
In a 200 ml autoclave, 43 g (0.5 mol) of 2,5-dihydrothiophene and 33 g (0.5 mol) of cyclopentadiene were added and reacted at 170 ° C. for 5 hours.

  The obtained reaction liquid was distilled under reduced pressure to obtain 15 g of a fraction at 116 to 120 ° C./2.4 kPa.

This fraction was determined to be 2-thia-1,2-dihydrodicyclopentadiene (a compound in which R _{25 to} R ₂₈ are a hydrogen atom and t is 1 in the general formula (6)) by NMR and GC-MS. confirmed.

Synthesis Example 11
In a 200 ml autoclave, 57 g (0.5 mol) of 2,5-dimethyl-2,5-dihydrothiophene and 33 g (0.5 mol) of cyclopentadiene were added and reacted at 170 ° C. for 5 hours.

  The obtained reaction liquid was distilled under reduced pressure to obtain 18 g of a fraction of 101 to 105 ° C./0.4 kPa.

This fraction was analyzed by NMR and GC-MS using 2-thia-1,3-dimethyl-1,2-dihydrodicyclopentadiene (in the general formula (6), R ₂₅ and R ₂₆ are methyl groups, R ₂₇ and R ₂₈ Is a hydrogen atom, and t is 1.

Synthesis Example 12
In a 200 ml autoclave, 119 g (0.5 mol) of 2,5-diphenyl-2,5-dihydrothiophene and 33 g (0.5 mol) of cyclopentadiene were placed and reacted at 170 ° C. for 5 hours.

  The obtained reaction liquid was distilled under reduced pressure to obtain 28 g of a fraction of 135 to 140 ° C./0.1 kPa.

This fraction was analyzed by NMR and GC-MS using 2-thia-1,3-diphenyl-1,2-dihydrodicyclopentadiene (in the general formula (6), R ₂₅ and R ₂₆ are phenyl groups, R ₂₇ and R ₂₈ Is a hydrogen atom, and t is 1.

Synthesis Example 13
In a 200 ml autoclave, 71 g (0.5 mol) of 2,2,5,5-tetramethyl-thiophene and 33 g (0.5 mol) of cyclopentadiene were added and reacted at 170 ° C. for 5 hours.

  The obtained reaction liquid was distilled under reduced pressure to obtain 23 g of a fraction of 115 to 120 ° C./0.1 kPa.

This fraction was determined by NMR and GC-MS to be 2-thia-1,1,3,3-tetramethyl-dicyclopentadiene (in the general formula (6), R _{25 to} R ₂₈ are methyl groups and t is 1). Compound).

Synthesis Example 14
In a 200 ml autoclave, 30 g (0.2 mol) of 2-thia-1,2-dihydrodicyclopentadiene obtained by the same method as in Synthesis Example 10 and 13 g (0.2 mol) of cyclopentadiene were placed, and 170 ° C. for 5 hours. Reaction was performed.

  The obtained reaction liquid was distilled under reduced pressure to obtain 10 g of a fraction of 115 to 120 ° C./0.2 kPa.

This fraction by NMR and GC-MS, 1-thio represented by the following general formula (10) - pentacyclo ^{[6,5,1 4,11, 1 6,9, 0} 5,10, ^{0 3, 12} ] -7-pentadecene (a compound in which R _{25 to} R ₂₈ are hydrogen and t is 2 in the general formula (6)).

（１０）
実施例１
磁気回転子が入った１００ｍｌシュレンク管を減圧下にヒートガンで乾燥し、十分窒素で置換した。ここに、上記の一般式（７）で示されるルテニウム錯体８５ｍｇ（０．１ｍｍｏｌ）を入れた。このシュレンク管に乾燥クロロホルム４５ｍｌとフェニルビニルスルフィド２３ｍｇ（０．１７ｍｍｏｌ）をシリンジで秤入れ、メタセシス重合触媒溶液を調製した。次に、合成例１で得られた１，３−ジチオトリシクロ−[５，４，０，１^６，９]−７−ドデセン５．０ｇ（２５ｍｍｏｌ）を仕込み、６０℃に調整したオイルバスに浸け、４時間重合を行なった。

(10)
Example 1
A 100 ml Schlenk tube containing a magnetic rotor was dried with a heat gun under reduced pressure, and sufficiently substituted with nitrogen. Here, 85 mg (0.1 mmol) of the ruthenium complex represented by the general formula (7) was added. To this Schlenk tube, 45 ml of dry chloroform and 23 mg (0.17 mmol) of phenyl vinyl sulfide were weighed with a syringe to prepare a metathesis polymerization catalyst solution. Then, obtained in Synthesis Example 1 1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7-dodecene 5.0g were charged (25 mmol), the oil bath was adjusted to 60 ° C. And was polymerized for 4 hours.

  The polymerization solution was poured into 150 ml of acetone containing 0.1% of 2,6-di-t-butyl-4-hydroxytoluene to precipitate the polymer. After filtering the solvent, the recovered polymer was dried in a vacuum dryer at room temperature for 8 hours to obtain 2.6 g of polymer.

The resulting ^polymer from the 1 H-NMR spectrum analysis, 1,3-dithio tricycloalkyl - was confirmed to be [5,4,0,1 ^6,9] -7-opening metathesis polymer of dodecene .

Measurement result of 270 MHz ¹ H-NMR; δ (CDCl ₃ ): 1.2 to 3.1 (10H), 3.9 (2H), 5.3 (2H)
The weight average molecular weight (Mw) of this polymer was 13000, and the 10% thermal weight loss temperature was 370 ° C.

  This polymer was dissolved in chloroform and cast on a polyethylene terephthalate film (hereinafter referred to as PET film) to form a film having a thickness of 100 μm. This film had a refractive index (nd) of 1.657 and an Abbe number of 20. The total light transmittance was 88%.

Example 2
A 300 ml four-necked flask containing a magnetic rotor was dried with a heat gun under reduced pressure and replaced with nitrogen. Here, in the obtained 1,3-dithio tricycloalkyl Example 1 - [5,4,0,1 ^6,9] -7-dodecene ring-opening metathesis polymer 3.5g and 1,1,2-trichloroethane 120 ml was charged and dissolved with stirring at room temperature. To this solution, 16.5 g (88.8 mmol) of p-toluenesulfonyl hydrazide and 11.3 g (88.8 mmol) of N, N′-dimethylcyclohexylamine were added and reacted at 110 ° C. for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and poured into 300 ml of methanol to precipitate a polymer. The precipitated polymer was filtered and then dissolved in 100 ml of chloroform, and the insoluble matter was filtered off. The filtrate was poured into 300 ml of methanol to precipitate the polymer again. After filtration, the recovered polymer was dried in a vacuum dryer at 100 ° C. for 5 hours to obtain 2.7 g of polymer. The resulting ^polymer from the 1 H-NMR spectrum analysis, 1,3-dithio tricycloalkyl - was [5,4,0,1 ^6,9] -7-hydride ring-opening metathesis polymer of dodecene .

270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 1.4 to 3.6 (10H), 5.2 to 5.6 (2H)
The weight average molecular weight (Mw) of this polymer was 13000. This polymer was pressed at 220 ° C. to form a film having a thickness of 100 μm. This film had a refractive index (nd) of 1.623 and an Abbe number of 45. The total light transmittance was 88%.

Example 3
A 100 ml Schlenk tube containing a magnetic rotor was dried with a heat gun under reduced pressure and sufficiently substituted with nitrogen. Here, 85 mg (0.1 mmol) of the ruthenium complex represented by the general formula (7) was added. To this Schlenk tube, 45 ml of dry chloroform was weighed with a syringe to prepare a metathesis polymerization catalyst solution. Then, obtained in Synthesis Example 2 1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7 were charged dodecene the (endo isomer) 5.0g (25mmol), 60 ℃ Soaking was carried out for 4 hours in an oil bath.

  The polymerization solution was poured into 150 ml of acetone containing 0.1% of 2,6-di-t-butyl-4-hydroxytoluene to precipitate the polymer. After filtering the solvent, the recovered polymer was dried in a vacuum dryer at room temperature for 8 hours to obtain 1.5 g of polymer.

The resulting ^polymer from the 1 H-NMR spectrum analysis, 1,3-dithio tricycloalkyl - was confirmed to be [5,4,0,1 ^6,9] -7-opening metathesis polymer of dodecene .

Measurement result of 270 MHz ¹ H-NMR; δ (CDCl ₃ ): 1.2 to 3.1 (10H), 3.9 (2H), 5.3 (2H)
The weight average molecular weight (Mw) of this polymer was 7000, and the 10% thermal weight loss temperature was 370 ° C.

  This polymer was dissolved in chloroform and cast on a PET film to prepare a film having a thickness of 100 μm. The refractive index (nd) of this film was 1.647 and the Abbe number was 22. The total light transmittance was 88%.

Example 4
A 200 ml four-necked flask containing a magnetic rotor was dried with a heat gun under reduced pressure and replaced with nitrogen. Here, in the obtained 1,3-dithio tricycloalkyl Example 3 - [5,4,0,1 ^6,9] -7-dodecene ring-opening metathesis polymer 1.5g and 1,1,2-trichloroethane 50 ml was charged and dissolved with stirring at room temperature. To this solution, 7.1 g (38.2 mmol) of p-toluenesulfonyl hydrazide and 4.9 g (38.2 mmol) of N, N′-dimethylcyclohexylamine were added and reacted at 110 ° C. for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and poured into 150 ml of methanol to precipitate a polymer. The precipitated polymer was filtered and then dissolved in 50 ml of chloroform, and the insoluble matter was filtered off. The filtrate was poured into 150 ml of methanol to precipitate the polymer again. After filtration, the recovered polymer was dried at 100 ° C. for 5 hours in a vacuum dryer to obtain 1.2 g of polymer. The resulting ^polymer from the 1 H-NMR spectrum analysis, 1,3-dithio tricycloalkyl - was [5,4,0,1 ^6,9] -7-hydride ring-opening metathesis polymer of dodecene .

270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 1.4 to 3.6 (10H), 5.2 to 5.6 (2H)
The weight average molecular weight (Mw) of this polymer was 7000. This polymer was pressed at 220 ° C. to form a film having a thickness of 100 μm. The film had a light transmittance of 89%, a refractive index (nd) of 1.601, and an Abbe number of 43.

Example 5
In a nitrogen-purged reactor 1000 ml, a dry methylene chloride 500 ml, 1,3-dithio tricycloalkyl obtained by Synthesis Example 3 - [5,4,0,1 ^6,9] -7-dodecene 8 g (0. 04 mol), 0.1 g of ethyl vinyl ether was added, a solution of 13.6 mg of Cl ₂ (PCy ₃ ) ₂ Ru═CHPh complex dissolved in 1 ml of methylene chloride was added as a metathesis polymerization catalyst, and the mixture was polymerized under reflux for 1 hour. The polymerization solution was added to 300 ml of hydrochloric acid-methanol solution to recover the polymer. The obtained polymer was washed several times with methanol and then dried under reduced pressure at 40 ° C. for a whole day and night to obtain 7.9 g of a sulfur-containing cyclic olefin resin. It was confirmed from the NMR spectrum that the sulfur-containing cyclic olefin resin has a double bond.

  7 g of the obtained sulfur-containing cyclic olefin resin, 50 g of cyclohexane, and 1 g of 5% palladium-supported activated carbon were charged into a 200 ml stainless steel autoclave, and a hydrogenation reaction was performed with stirring at a hydrogen gas pressure of 1 MPa and a temperature of 100 ° C. for 4 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was filtered to remove the catalyst. The polymer solution was poured into a large amount of hydrochloric acid-methanol solution to separate the polymer. The obtained polymer was dried at 50 ° C. under reduced pressure overnight to obtain 7 g of a sulfur-containing cyclic olefin resin subjected to hydrogenation treatment. The sulfur-containing cyclic olefin resin after the hydrogenation treatment had a polystyrene-equivalent weight average molecular weight of 80000 and a glass transition temperature of 111 ° C. Further, no double bond was detected from the NMR spectrum.

  The obtained sulfur-containing cyclic olefin resin after the hydrogenation treatment was dissolved in tetrahydrofuran, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 89%, a refractive index (nd) of 1.601, and an Abbe number of 43.

Example 6
The reactor purged with nitrogen 1000 ml, a dry methylene chloride 500 ml, Synthesis Example was obtained by 4 2-phenyl-1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7-dodecene 11 g (0.04 mol) and 0.1 g of ethyl vinyl ether were added, and a solution of 13.6 mg of Cl ₂ (PCy ₃ ) ₂ Ru═CHPh complex dissolved in 1 ml of methylene chloride was added as a metathesis polymerization catalyst. Polymerized for hours. The polymerization solution was added to 300 ml of hydrochloric acid-methanol solution to recover the polymer. The obtained polymer was washed several times with methanol, and then dried under reduced pressure at 40 ° C. overnight to obtain 10.8 g of a sulfur-containing cyclic olefin resin. It was confirmed from the NMR spectrum that the sulfur-containing cyclic olefin resin has a double bond.

  10 g of the obtained sulfur-containing cyclic olefin resin, 50 g of cyclohexane, and 1 g of 5% palladium-supported activated carbon were charged into a 200 ml stainless steel autoclave, and a hydrogenation reaction was performed with stirring at a hydrogen gas pressure of 1 MPa and a temperature of 100 ° C. for 4 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was filtered to remove the catalyst. The polymer solution was poured into a large amount of hydrochloric acid-methanol solution to separate the polymer. The obtained polymer was dried under reduced pressure at 50 ° C. for a whole day and night to obtain a sulfur-containing cyclic olefin resin subjected to 10 g of hydrogenation treatment. The sulfur-containing cyclic olefin resin after the hydrogenation treatment had a polystyrene-equivalent weight average molecular weight of 70000 and a glass transition temperature of 157 ° C. Further, no double bond was detected from the NMR spectrum.

  The obtained sulfur-containing cyclic olefin resin after the hydrogenation treatment was dissolved in tetrahydrofuran, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 88%, a refractive index (nd) of 1.62, and an Abbe number of 40.

Example 7
The reactor purged with nitrogen 1000 ml, a dry methylene chloride 500 ml, obtained by Synthesis Example 5 2,2-dimethyl-1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7 -9 g (0.04 mol) of dodecene and 0.1 g of ethyl vinyl ether were added, and a solution of 13.6 mg of Cl ₂ (PCy ₃ ) ₂ Ru = CHPh complex dissolved in 1 ml of methylene chloride was added as a metathesis polymerization catalyst. For 1 hour. The polymerization solution was added to 300 ml of hydrochloric acid-methanol solution to recover the polymer. The obtained polymer was washed several times with methanol and then dried under reduced pressure at 40 ° C. for a whole day and night to obtain 8.3 g of a sulfur-containing cyclic olefin resin. It was confirmed from the NMR spectrum that the sulfur-containing cyclic olefin resin has a double bond.

  8 g of the obtained sulfur-containing cyclic olefin resin, 50 g of cyclohexane, and 1 g of 5% palladium-supported activated carbon were charged into a 200 ml stainless steel autoclave, and a hydrogenation reaction was performed with stirring at a hydrogen gas pressure of 1 MPa and a temperature of 100 ° C. for 4 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was filtered to remove the catalyst. The polymer solution was poured into a large amount of hydrochloric acid-methanol solution to separate the polymer. The obtained polymer was dried under reduced pressure at 50 ° C. for a whole day and night to obtain 8 g of a sulfur-containing cyclic olefin resin subjected to hydrogenation treatment. The sulfur-containing cyclic olefin resin after the hydrogenation treatment had a weight average molecular weight of 80000 and a glass transition temperature of 136 ° C. Further, no double bond was detected from the NMR spectrum.

  The obtained sulfur-containing cyclic olefin resin after the hydrogenation treatment was dissolved in tetrahydrofuran, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 89%, a refractive index (nd) of 1.60, and an Abbe number of 45.

Example 8
In a nitrogen-purged reactor 1000 ml, a dry methylene chloride 500 ml, resulting 2- (2-thienyl) obtained by Synthesis Example 6 1,3-dithio tricyclo - [5,4,0,1 ^6,9] 11.2 g (0.04 mol) of -7-dodecene and 0.1 g of ethyl vinyl ether were added, and a solution of 13.6 mg of Cl ₂ (PCy ₃ ) ₂ Ru = CHPh complex dissolved in 1 ml of methylene chloride was added as a metathesis polymerization catalyst. And polymerized for 1 hour under reflux. The polymerization solution was added to 300 ml of hydrochloric acid-methanol solution to recover the polymer. The obtained polymer was washed several times with methanol, and then dried under reduced pressure at 40 ° C. overnight to obtain 11 g of a sulfur-containing cyclic olefin resin. It was confirmed from the NMR spectrum that the sulfur-containing cyclic olefin resin has a double bond.

  11 g of the obtained sulfur-containing cyclic olefin resin, 50 g of cyclohexane, and 1 g of 5% palladium-supported activated carbon were charged into a 200 ml stainless steel autoclave, and a hydrogenation reaction was performed with stirring at a hydrogen gas pressure of 1 MPa and a temperature of 100 ° C. for 4 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was filtered to remove the catalyst. The polymer solution was poured into a large amount of hydrochloric acid-methanol solution to separate the polymer. The obtained polymer was dried under reduced pressure at 50 ° C. for a whole day and night to obtain 8 g of a sulfur-containing cyclic olefin resin subjected to hydrogenation treatment. The sulfur-containing cyclic olefin resin after the hydrogenation treatment had a polystyrene-equivalent weight average molecular weight of 80000 and a glass transition temperature of 156 ° C. Further, no double bond was detected from the NMR spectrum.

  The obtained sulfur-containing cyclic olefin resin after the hydrogenation treatment was dissolved in tetrahydrofuran, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 88%, a refractive index (nd) of 1.65, and an Abbe number of 38.

Example 9
A 100 ml Schlenk tube containing a magnetic rotor was dried with a heat gun under reduced pressure, and sufficiently substituted with nitrogen. Here, 76 mg (0.1 mmol) of the molybdenum complex represented by the above general formula (8) was added. To this Schlenk tube, 45 ml of dry chloroform and 23 mg (0.17 mmol) of phenyl vinyl sulfide were weighed with a syringe to prepare a metathesis polymerization catalyst solution. Then, obtained in Synthesis Example 1 1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7-dodecene 5.0g were charged (25 mmol), the oil bath was adjusted to 60 ° C. And was polymerized for 4 hours.

  The polymerization solution was poured into 150 ml of acetone containing 0.1% of 2,6-di-t-butyl-4-hydroxytoluene to precipitate the polymer. After filtering the solvent, the recovered polymer was dried in a vacuum dryer at room temperature for 8 hours to obtain 2.6 g of polymer.

The resulting ^polymer from the 1 H-NMR spectrum analysis, 1,3-dithio tricycloalkyl - was confirmed to be [5,4,0,1 ^6,9] -7-opening metathesis polymer of dodecene .

Measurement result of 270 MHz ¹ H-NMR; δ (CDCl ₃ ): 1.2 to 3.1 (10H), 3.9 (2H), 5.3 (2H)
The weight average molecular weight (Mw) of this polymer was 23000, and the 10% thermogravimetric temperature reduction temperature was 370 ° C.

  This polymer was dissolved in chloroform and cast on a PET film to prepare a film having a thickness of 100 μm. This film had a refractive index (nd) of 1.657 and an Abbe number of 20. The total light transmittance was 88%.

Example 10
A 100 ml Schlenk tube containing a magnetic rotor was dried with a heat gun under reduced pressure, and sufficiently substituted with nitrogen. Here, 85 mg (0.1 mmol) of the ruthenium complex represented by the general formula (7) was added. To this Schlenk tube, 45 ml of dry chloroform and 23 mg (0.17 mmol) of phenyl vinyl sulfide were weighed with a syringe to prepare a metathesis polymerization catalyst solution. Then, the resulting 12-methyl-1,3-dithio tricycloalkyl in Synthesis Example 7 - [5,4,0,1 ^6,9] -7-dodecene was charged 5.3g of (25 mmol), in 60 ° C. It was immersed in the adjusted oil bath and polymerized for 4 hours.

  The polymerization solution was poured into 150 ml of acetone containing 0.1% of 2,6-di-t-butyl-4-hydroxytoluene to precipitate the polymer. After filtering the solvent, the recovered polymer was dried in a vacuum dryer at room temperature for 8 hours to obtain 2.7 g of polymer.

The resulting ^polymer from the 1 H-NMR spectrum analysis, 12-methyl-1,3-dithio tricycloalkyl - is [5,4,0,1 ^6,9] -7-dodecene ring-opening metathesis polymer of It was confirmed.

Measurement result of 270 MHz ¹ H-NMR; δ (CDCl ₃ ): 1.2 to 3.1 (12H), 3.9 (2H), 5.3 (2H)
The weight average molecular weight (Mw) of this polymer was 14000, and the 10% thermal weight loss temperature was 380 ° C.

  This polymer was dissolved in chloroform and cast on a PET film to prepare a film having a thickness of 100 μm. This film had a refractive index (nd) of 1.463 and an Abbe number of 25. The total light transmittance was 88%.

Example 11
The 50 ml Schlenk tube containing the magnetic rotor was dried with a heat gun under reduced pressure, and fully substituted with nitrogen. Here, 13.2 mg (15.5 μmol) of the ruthenium complex represented by the general formula (7) was weighed. To this Schlenk tube, 10 ml of dry chloroform and 140.3 mg (1.03 mmol) of phenyl vinyl sulfide were weighed with a syringe to prepare a metathesis polymerization catalyst solution.

  Meanwhile, a 500 ml four-necked flask containing a magnetic rotor was dried with a heat gun under reduced pressure and replaced with nitrogen. Into this, 23.6 g (155.3 mmol) of 2-thia-1,2-dihydrodicyclopentadiene obtained in Synthesis Example 8 and 140 ml of dry chloroform were charged in a nitrogen stream, and a cooling tube was attached. Immerse in an adjusted oil bath. After stirring for 30 minutes, the entire amount of the prepared metathesis polymerization catalyst solution was added, and polymerization was performed at 60 ° C. for 4 hours. The polymerization solution was poured into 300 ml of acetone containing 0.1% of 2,6-di-t-butyl-4-hydroxytoluene to precipitate the polymer. After filtration, the recovered polymer was dried in a vacuum dryer at room temperature for 8 hours to obtain 20.6 g of polymer.

The obtained polymer was confirmed to be a ring-opening metathesis polymer of 2-thia-1,2-dihydrodicyclopentadiene by ¹ H-NMR spectrum analysis.

270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 1.4 to 3.6 (10H), 5.2 to 5.6 (2H)
The weight average molecular weight (Mw) of this polymer was 72000.

  This polymer was dissolved in chloroform and cast on a PET film to prepare a film having a thickness of 100 μm. This film had a refractive index (nd) of 1.590 and an Abbe number of 41. The total light transmittance was 89%.

Example 12
A 300 ml four-necked flask containing a magnetic rotor was dried with a heat gun under reduced pressure and replaced with nitrogen. Here, 2.7 g of a ring-opening metathesis polymer of 2-thia-1,2-dihydrodicyclopentadiene obtained in Example 11 and 120 ml of o-dichlorobenzene were charged and stirred and dissolved at room temperature. To this solution, 16.5 g (88.8 mmol) of p-toluenesulfonyl hydrazide and 11.3 g (88.8 mmol) of N, N′-dimethylcyclohexylamine were added and reacted at 110 ° C. for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and poured into 300 ml of methanol to precipitate a polymer. The precipitated polymer was filtered and then dissolved in 100 ml of chloroform, and the insoluble matter was filtered off. The filtrate was poured into 300 ml of methanol to precipitate the polymer again. After filtration, the recovered polymer was dried in a vacuum dryer at 100 ° C. for 5 hours to obtain 2.7 g of polymer. The obtained polymer was a hydride of 2-thia-1,2-dihydrodicyclopentadiene ring-opening metathesis polymer from ¹ H-NMR spectrum analysis.

270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 1.4 to 3.6 (10H), 5.2 to 5.6 (2H)
The weight average molecular weight (Mw) of this polymer was 72000.

  This polymer was pressed at 220 ° C. to form a film having a thickness of 100 μm. This film had a refractive index (nd) of 1.583 and an Abbe number of 46. The total light transmittance was 89%.

Example 13
A 100 ml Schlenk tube containing a magnetic rotor was dried with a heat gun under reduced pressure and thoroughly replaced with nitrogen. Here, 21 mg (25 μmol) of the ruthenium complex represented by the above general formula (7) was added. To this Schlenk tube, 46 ml of dry chloroform and 34 mg (0.25 mmol) of phenyl vinyl sulfide were weighed with a syringe to prepare a metathesis polymerization catalyst solution. Next, 3.8 g (25 mmol) of 2-thia-1,2-dihydrodicyclopentadiene (isomer) obtained in Synthesis Example 9 was charged, immersed in an oil bath adjusted to 60 ° C., and polymerized for 5 hours. It was.

  The polymerization solution was poured into 150 ml of acetone containing 0.1% of 2,6-di-t-butyl-4-hydroxytoluene to precipitate the polymer. After filtration, the recovered polymer was dried in a vacuum dryer at room temperature for 8 hours to obtain 1.1 g of polymer.

The obtained polymer was confirmed to be a ring-opening metathesis polymer of 2-thia-1,2-dihydrodicyclopentadiene by ¹ H-NMR spectrum analysis.

270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 1.4 to 3.6 (10H), 5.2 to 5.6 (2H)
The weight average molecular weight (Mw) of this polymer was 18000.

  This polymer was dissolved in chloroform and cast on a PET film to prepare a film having a thickness of 100 μm. This film had a refractive index (nd) of 1.585 and an Abbe number of 42. The total light transmittance was 89%.

Example 14
A 200 ml four-necked flask containing a magnetic rotor was dried with a heat gun under reduced pressure and replaced with nitrogen. Here, 1.0 g of a ring-opening metathesis polymer of 2-thia-1,2-dihydrodicyclopentadiene obtained in Example 13 and 45 ml of o-dichlorobenzene were charged and stirred and dissolved at room temperature. To this solution, 6.1 g (32.9 mmol) of p-toluenesulfonyl hydrazide and 4.2 g (32.9 mmol) of N, N′-dimethylcyclohexylamine were added and reacted at 110 ° C. for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and poured into 150 ml of methanol to precipitate a polymer. The precipitated polymer was filtered and then dissolved in 50 ml of chloroform, and the insoluble matter was filtered off. The filtrate was poured into 150 ml of methanol to precipitate the polymer again. After filtration, the recovered polymer was dried in a vacuum dryer at 100 ° C. for 5 hours to obtain 0.9 g of polymer. The obtained polymer was a hydride of 2-thia-1,2-dihydrodicyclopentadiene ring-opening metathesis polymer from ¹ H-NMR spectrum analysis.

270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 1.4 to 3.6 (10H), 5.2 to 5.6 (2H)
The weight average molecular weight (Mw) of this polymer was 18000.

  This polymer was pressed at 220 ° C. to form a film having a thickness of 100 μm. The film had a light transmittance of 90%, a refractive index (nd) of 1.57, and an Abbe number of 45.

Example 15
In a 1000 ml reactor purged with nitrogen, 500 ml of dehydrated methylene chloride, 6 g (0.04 mol) of 2-thia-1,2-dihydrodicyclopentadiene obtained in Synthesis Example 10, and 0.1 g of ethyl vinyl ether were added. As a metathesis polymerization catalyst, a solution prepared by dissolving 13.6 mg of Cl ₂ (PCy ₃ ) ₂ Ru═CHPh complex in 1 ml of methylene chloride was added, and polymerization was performed under reflux for 1 hour. The polymerization solution was added to 300 ml of hydrochloric acid-methanol solution to precipitate a polymer. The obtained polymer was washed several times with methanol, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain 5.9 g of polymer. . From NMR, it was confirmed to be a sulfur-containing cyclic olefin resin having a double bond.

  5.9 g of the sulfur-containing cyclic olefin resin, 50 g of cyclohexane, and 1 g of 5% palladium-supported activated carbon were charged into a 200 ml stainless steel autoclave and subjected to a hydrogenation reaction with stirring at a hydrogen gas pressure of 1 MPa and a temperature of 100 ° C. for 4 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was filtered to remove the catalyst. The polymer solution was poured into a large amount of hydrochloric acid-methanol solution to separate the polymer. The obtained polymer was dried under reduced pressure overnight at 50 ° C. to obtain 5.9 g of a hydrogenated sulfur-containing cyclic olefin resin. The polymer had a weight average molecular weight in terms of polystyrene of 80000 and a glass transition temperature of 110 ° C. Also, no double bond was detected from NMR.

  The obtained hydrogenated sulfur-containing cyclic olefin resin was dissolved in tetrahydrofuran, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 90%, a refractive index (nd) of 1.57, and an Abbe number of 45.

Example 16
To a 1000 ml reactor purged with nitrogen, 500 ml of dehydrated methylene chloride, 7.2 g (0.04 mol) of 2-thia-1,3-dimethyl-1,2-dihydrodicyclopentadiene obtained in Synthesis Example 11; 0.1 g of ethyl vinyl ether was added, a solution of 13.6 mg of Cl ₂ (PCy ₃ ) ₂ Ru═CHPh complex dissolved in 1 ml of methylene chloride was added as a metathesis polymerization catalyst, and polymerization was performed under reflux for 1 hour. The polymerization solution was added to 300 ml of hydrochloric acid-methanol solution to precipitate a polymer. The obtained polymer was washed several times with methanol, and then dried under reduced pressure at 40 ° C. overnight to obtain 7 g of polymer. From NMR, it was confirmed to be a sulfur-containing cyclic olefin resin having a double bond.

  7 g of the sulfur-containing cyclic olefin resin, 50 g of cyclohexane, and 1 g of 5% palladium-supported activated carbon were charged into a 200 ml stainless steel autoclave, and a hydrogenation reaction was performed with stirring at a hydrogen gas pressure of 1 MPa and a temperature of 100 ° C. for 4 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was filtered to remove the catalyst. The polymer solution was poured into a large amount of hydrochloric acid-methanol solution to separate the polymer. The obtained polymer was dried under reduced pressure overnight at 50 ° C. to obtain 7 g of a hydrogenated sulfur-containing cyclic olefin resin. The weight average molecular weight of this polymer in terms of polystyrene was 80000, and the glass transition temperature was 115 ° C. Also, no double bond was detected from NMR.

  The obtained hydrogenated sulfur-containing cyclic olefin resin was dissolved in tetrahydrofuran, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 90%, a refractive index (nd) of 1.57, and an Abbe number of 45.

Example 17
In a 1000 ml reactor purged with nitrogen, 500 ml of dehydrated methylene chloride, 12.1 g (0.04 mol) of 2-thia-1,3-diphenyl-1,2-dihydrodicyclopentadiene obtained in Synthesis Example 12; 0.1 g of ethyl vinyl ether was added, a solution of 13.6 mg of Cl ₂ (PCy ₃ ) ₂ Ru═CHPh complex dissolved in 1 ml of methylene chloride was added as a metathesis polymerization catalyst, and polymerization was performed under reflux for 1 hour. The polymerization solution was added to 300 ml of hydrochloric acid-methanol solution to precipitate a polymer. The obtained polymer was washed several times with methanol and then dried under reduced pressure at 40 ° C. for a whole day and night to obtain 11.8 g of polymer. From NMR, it was confirmed to be a sulfur-containing cyclic olefin resin having a double bond.

  11.8 g of the sulfur-containing cyclic olefin resin, 50 g of cyclohexane, and 1 g of 5% palladium-supported activated carbon were charged into a 200 ml stainless steel autoclave, and a hydrogenation reaction was performed with stirring at a hydrogen gas pressure of 1 MPa and a temperature of 100 ° C. for 4 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was filtered to remove the catalyst. The polymer solution was poured into a large amount of hydrochloric acid-methanol solution to separate the polymer. The obtained polymer was dried under reduced pressure overnight at 50 ° C. to obtain 11.8 g of a hydrogenated sulfur-containing cyclic olefin resin. The weight average molecular weight of this polymer in terms of polystyrene was 70000, and the glass transition temperature was 110 ° C. Also, no double bond was detected from NMR.

  The obtained hydrogenated sulfur-containing cyclic olefin resin was dissolved in tetrahydrofuran, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 88%, a refractive index (nd) of 1.65, and an Abbe number of 38.

Example 18
In a 1000 ml reactor purged with nitrogen, 500 ml of dehydrated methylene chloride and 8.9 g (0.04 mol) of 2-thia-1,1,3,3-tetramethyl-dicyclopentadiene obtained in Synthesis Example 13 were obtained. 0.1 g of ethyl vinyl ether was added, a solution of 13.6 mg of Cl ₂ (PCy ₃ ) ₂ Ru═CHPh complex dissolved in 1 ml of methylene chloride was added as a metathesis polymerization catalyst, and polymerization was performed under reflux for 1 hour. The polymerization solution was added to 300 ml of hydrochloric acid-methanol solution to precipitate a polymer. The obtained polymer was washed several times with methanol and then dried under reduced pressure at 40 ° C. overnight to obtain 8.5 g of a polymer. From NMR, it was confirmed to be a sulfur-containing cyclic olefin resin having a double bond.

  8.5 g of the sulfur-containing cyclic olefin resin, 50 g of cyclohexane, and 1 g of 5% palladium-supported activated carbon were charged into a 200 ml stainless steel autoclave and subjected to a hydrogenation reaction with stirring at a hydrogen gas pressure of 1 MPa and a temperature of 100 ° C. for 4 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was filtered to remove the catalyst. The polymer solution was poured into a large amount of hydrochloric acid-methanol solution to separate the polymer. The obtained polymer was dried under reduced pressure overnight at 50 ° C. to obtain 8.5 g of a hydrogenated sulfur-containing cyclic olefin resin. The weight average molecular weight of this polymer in terms of polystyrene was 80000, and the glass transition temperature was 120 ° C. Also, no double bond was detected from NMR.

  The obtained hydrogenated sulfur-containing cyclic olefin resin was dissolved in tetrahydrofuran, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 90%, a refractive index (nd) of 1.57, and an Abbe number of 45.

Example 19
In a nitrogen-purged reactor 1000 ml, a dry methylene chloride 500 ml, obtained by Synthesis Example 14 1-thio - pentacyclo ^{[6,5,1 4,11, 1 6,9, 0} 5,10, ^{0 3, 12} ] -7-pentadecene (8.7 g, 0.04 mol) and ethyl vinyl ether (0.1 g) were added.

To this solution, a solution of 13.6 mg of Cl ₂ (PCy ₃ ) ₂ Ru═CHPh complex dissolved in 1 ml of methylene chloride as a metathesis polymerization catalyst was added and polymerized for 1 hour under reflux. The polymerization solution was added to 300 ml of hydrochloric acid-methanol solution to recover the polymer. The obtained polymer was washed several times with methanol and then dried under reduced pressure at 40 ° C. overnight to obtain 8.5 g of a polymer. From NMR, it was confirmed to be a sulfur-containing cyclic olefin resin having a double bond.

  8.5 g of a sulfur-containing cyclic olefin resin, 50 g of cyclohexane, and 1 g of 5% palladium-supported activated carbon were charged into a 200 ml stainless steel autoclave and subjected to a hydrogenation reaction with stirring at a hydrogen gas pressure of 1 MPa and a temperature of 100 ° C. for 4 hours. After cooling the reaction solution, excess hydrogen was released, and after depressurization, the reaction solution was filtered to remove the catalyst. The polymer solution was poured into a large amount of hydrochloric acid-methanol solution to separate the polymer. The obtained polymer was dried under reduced pressure overnight at 50 ° C. to obtain 8.5 g of a hydrogenated sulfur-containing cyclic olefin resin. The weight average molecular weight of this polymer in terms of polystyrene was 80000, and the glass transition temperature was 125 ° C. Also, no double bond was detected from NMR.

  The obtained hydrogenated sulfur-containing cyclic olefin resin was dissolved in tetrahydrofuran, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 90%, a refractive index (nd) of 1.56, and an Abbe number of 47.

Example 20
The 50 ml Schlenk tube containing the magnetic rotor was dried with a heat gun under reduced pressure, and fully replaced with nitrogen. Here, 7.6 mg (10 μmol) of the molybdenum complex represented by the general formula (8) was weighed. To this Schlenk tube, 4.6 ml of dry chloroform and 3.4 mg (25 μmol) of phenyl vinyl sulfide were weighed with a syringe to prepare a metathesis polymerization catalyst solution. Next, 0.38 g (2.5 mmol) of 2-thia-1,2-dihydrodicyclopentadiene obtained in Synthesis Example 8 was charged, immersed in an oil bath adjusted to 60 ° C., and polymerized at room temperature for 30 minutes. .

  The polymerization solution was poured into 150 ml of acetone containing 0.1% of 2,6-di-t-butyl-4-hydroxytoluene to precipitate the polymer. After filtration, the collected polymer was dried in a vacuum dryer at room temperature for 8 hours to obtain 0.37 g of polymer.

The obtained polymer was confirmed to be a ring-opening metathesis polymer of 2-thia-1,2-dihydrodicyclopentadiene by ¹ H-NMR spectrum analysis.
270 MHz ¹ H-NMR measurement result; δ (CDCl ₃ ): 1.4 to 3.6 (10H), 5.2 to 5.6 (2H)
The weight average molecular weight (Mw) of this polymer was 100,000.

  This polymer was dissolved in chloroform and cast on a PET film to prepare a film having a thickness of 100 μm. This film had a refractive index (nd) of 1.590 and an Abbe number of 41. The total light transmittance was 89%.

Comparative Example 1
1,3-dithio tricyclo - [5,4,0,1 ^6,9] -7 instead of dodecene 5.0g except for using dicyclopentadiene 20.5 g, in the same manner as in Example 1 By polymerization, 20.3 g of a ring-opening metathesis polymer of dicyclopentadiene was obtained. The weight average molecular weight in terms of polystyrene of this ring-opening metathesis polymer of dicyclopentadiene was 90000.

Then, 1,3-dithio tricyclo - the 5,4,0,1 ^6,9] -7-dodecene ring-opening metathesis polymer 20g of dicyclopentadiene instead of ring-opening metathesis polymer 3.5g of Except for the use, hydrogenation was carried out in the same manner as in Example 2 to obtain a hydride of a ring-opening metathesis polymer of dicyclopentadiene. The hydride had a weight average molecular weight of 90000 and a glass transition temperature of 95 ° C.

  The obtained polymer was dissolved in chloroform, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 90%, a refractive index (nd) of 1.531, and an Abbe number of 58.

Comparative Example 2
Commercially available polystyrene (weight average molecular weight 190000, glass transition temperature 87 ° C.) was dissolved in chloroform, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 88%, a refractive index (nd) of 1.591, and an Abbe number of 31.

Comparative Example 3
A commercially available polycarbonate (weight average molecular weight 190000, glass transition temperature 147 ° C.) was dissolved in methylene chloride, and a film having a thickness of 100 μm was prepared by a casting method.

  The film had a light transmittance of 89%, a refractive index (nd) of 1.584, and an Abbe number of 31.

Comparative Example 4
A commercially available acrylonitrile-styrene copolymer (weight average molecular weight: 130,000, glass transition temperature: 106 ° C., acrylonitrile content: 29 wt%) was dissolved in methylene chloride, and a film having a thickness of 100 μm was prepared by a casting method.

The film had a light transmittance of 90%, a refractive index (nd) of 1.564, and an Abbe number of 35.

Claims (14)

A sulfur-containing cyclic olefin resin comprising units represented by the following general formula (1) and having a weight average molecular weight of 1,000 to 1,000,000.

(1)
(Here, R _{1 to} R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. It is an alkoxy group of formulas 1 to 10, a heterocyclic compound, and R _{3 to} R ₆ may be a halogen group, and R ₃ and R ₄ , R ₅ and R ₆ are carbon, oxygen, sulfur, A ring containing nitrogen may be formed, and R ₇ , R _{7 ′} , R ₈ and R _{8 ′} are each independently a hydrogen atom or a methyl group,. Where l and m each represents 0 or 1) The sulfur-containing cyclic olefin resin according to claim 1, comprising a unit represented by the following general formula (2) and having a weight average molecular weight of 1,000 to 1,000,000.

(2)
(Here, R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. An alkoxy group of formula 1 to 10, a heterocyclic compound,... Represents a single bond or a double bond, and n is 0 or 1. The sulfur-containing cyclic olefin resin according to claim 1, comprising a unit represented by the following general formula (3) and having a weight average molecular weight of 1,000 to 1,000,000.

(3)
(Here, R _{11 to} R ₁₄ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. C 1 -C 10 alkoxy group, a heterocyclic compound, a halogen _group, and _{R 11} and _{R 12, R 13} and _{R 14,} may carbon, oxygen, sulfur, to form a ring containing nitrogen, Represents a single bond or a double bond, and p is 0 or 1.) 3. The sulfur-containing cyclic group according to claim 2, wherein in the general formula (2), R ₉ and R ₁₀ are each a hydrogen atom and n is a unit having a weight average molecular weight of 1,000 to 1,000,000. Olefin resin. In said general formula (3), all of R < ₁₁ > -R < ₁₄ > consists of a unit which is a hydrogen atom, p is 0, and is the weight average molecular weights 1000-1 million, It is characterized by the above-mentioned. Sulfur-containing cyclic olefin resin. The method for producing a sulfur-containing cyclic olefin resin according to claim 1, wherein the sulfur-containing cyclic compound represented by the following general formula (4) is subjected to metathesis polymerization.

(4)
(Here, R _{15 to} R ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. C 1 -C 10 alkoxy group, a heterocyclic compound, further _R 17 _{to R 20} may be a halogen _group, and the _{R 17} and _{R 18, R 19} and _{R 20,} the carbon, oxygen, sulfur, A ring containing nitrogen may be formed, and R ₂₁ and R ₂₂ are each independently a hydrogen atom or a methyl group, q is 1 or 2, and r represents 0 or 1.) The method for producing a sulfur-containing cyclic olefin resin according to claim 1, wherein hydrogenation is performed after metathesis polymerization of the sulfur-containing cyclic compound represented by the general formula (4). The method for producing a sulfur-containing cyclic olefin resin according to claim 2, wherein the sulfur-containing cyclic compound represented by the following general formula (5) is subjected to metathesis polymerization.

(5)
(In the formula, R ₂₃ and R ₂₄ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. (It is an alkoxy group of formula 1 to 10 or a heterocyclic compound, and s is 1 or 2.) The method for producing a sulfur-containing cyclic olefin resin according to claim 2, wherein hydrogenation is performed after metathesis polymerization of the sulfur-containing cyclic compound represented by the general formula (5). The method for producing a sulfur-containing cyclic olefin resin according to claim 3, wherein the sulfur-containing cyclic compound represented by the following general formula (6) is subjected to metathesis polymerization.

(6)
(Here, R _{25 to} R ₂₈ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, an aromatic group having 1 to 20 carbon atoms, a cyano group, or carbon. Represents an alkoxy group of formulas 1 to 10, a heterocyclic compound, and a halogen group, and R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ may form a ring containing carbon, oxygen, sulfur, and nitrogen, t is 1 or 2.) The method for producing a sulfur-containing cyclic olefin resin according to claim 3, wherein the sulfur-containing cyclic compound represented by the general formula (6) is subjected to hydrogenation after metathesis polymerization. An optical material comprising the sulfur-containing cyclic olefin resin according to any one of claims 1 to 5. A lens comprising the sulfur-containing cyclic olefin resin according to any one of claims 1 to 5. A condensing lens comprising the sulfur-containing cyclic olefin resin according to any one of claims 1 to 5.