CN101228206B - Sulfur-containing cycloolefin resin and process for producing the same - Google Patents

Abstract

A sulfur-containing cycloolefin resin of 1000 to 1,000,000 weight average molecular weight comprised of any of units of the general formula (1): wherein each of R<SUB>1</SUB> to R<SUB>6</SUB> independently is a hydrogen atom, a C<SUB>1</SUB>-C<SUB>20</SUB> alkyl, a C<SUB>1</SUB>-C<SUB>20</SUB> aralkyl, a C<SUB>1</SUB>-C<SUB>20</SUB> aromatic group, cyano, a C<SUB>1</SUB>-C<SUB>10</SUB> alkoxy or a heterocyclic compound, provided that each of R<SUB>3</SUB> to R<SUB>6</SUB> may be a halogen, and provided that R<SUB>3</SUB> and R<SUB>4</SUB>, or R<SUB>5</SUB> and R<SUB>6</SUB>, may form a ring containing carbon, oxygen, sulfur and nitrogen; each of R<SUB>7</SUB> and R<SUB>8</SUB> independently is a hydrogen atom or methyl; is a single bond or double bond; and each of l and m is 0 or 1.

Description

Sulfur-containing cycloolefin resin and manufacture method thereof

Technical field

The present invention relates to novel sulfurized cyclic olefin resin, can be used as novel sulfurized ring compound, its manufacture method of its raw material, described sulfur-containing cycloolefin resin has high transparent and high refractive index, and being expected to be applied to the condensing lens is in the optical materials such as transparent coated material, blooming such as various plastic lenss, prismatic lens, antireflection film and fibre coating material of representative.

Background technology

As the transparency and heat-proof resin that can in optical material, use, cyclic olefin resins receive publicity in recent years (for example with reference to non-patent literature 1), for example, proposition is with Fourth Ring decene compounds, the cyclic olefin resins (for example with reference to patent documentation 1～4) that norbornylene compounds metathesis polymerization (metathesis polymerization, メ タ セ シ ス overlaps) and hydrogenation obtain, the addition polymer of ethene and norbornylene compounds or ethene and cyclodecene compounds (for example with reference to patent documentation 5), the addition polymer of norbornylene compounds (for example with reference to patent documentation 6～9) etc.

And the polymkeric substance of this norbornene compound has excellent feature as the transparency, thermotolerance, the transparent material that is used for optical applications that has excellent formability, have high Abbe constant.

On the other hand, in recent years along with the lightweight of portable machine, the trend of miniaturization, the material of seeking to have high refractive index.But there is the low problem of specific refractory power in the polymkeric substance of this norbornene compound.

And, as the method that realizes transparency and heat-proof resin high refractive indexization, the known method that in molecular structure, imports aromatic nucleus or sulphur atom, as the material that has imported aromatic nucleus, the material that proposition has imported fluorene skeleton (for example, with reference to patent documentation 10 or non-patent literature 2), in addition, propose to have imported the thiourethane resinoid (for example with reference to patent documentation 11) of sulphur atom.

Patent documentation 1: No. 3050196 communique of Japanese Patent

Patent documentation 2: the spy opens clear 60-026024 communique

Patent documentation 3: the spy opens flat 01-132625 communique

Patent documentation 4: No. 3087421 communique of Japanese Patent

Patent documentation 5: the spy opens clear 61-292601 communique

Patent documentation 6: the spy opens flat 04-063807 communique

Patent documentation 7: No. 3534127 communique of Japanese Patent

Patent documentation 8: the spy opens flat 09-508649 communique

Patent documentation 9: the spy opens flat 11-505880 communique

Patent documentation 10: the spy opens flat 11-060706 communique

Patent documentation 11: special fair 06-005323 communique

Non-patent literature 1:Polyfile (Port リ Off ア イ Le), September number, p.36～43 (2004)

Non-patent literature 2:NIKKEI ELECTRONICS is (2004.9.13) p.79～85

Summary of the invention

The problem that invention will solve

But, the importing that in patent documentation 10 or non-patent literature 2, proposes in the material of fluorene skeleton, specific refractory power is up to 1.6, but has the low problem of Abbe constant.In addition, the importing that in patent documentation 11, proposes the thiourethane resinoid of sulphur atom be specific refractory power up to more than 1.6, Abbe constant is also up to the resin more than 40, still, exists thermotolerance to be low to moderate problem about 100 ℃.

Therefore, the present invention is for addressing the above problem, provide a kind of thermotolerance good, can be used as the novel sulfurized cyclic olefin resin of the optical applications resin of high transparent, high refractive index, the novel sulfurized ring compound that can be used as its raw material, its manufacture method.

What the inventor etc. deeply discussed in order to address the above problem found that to have the resin of ad hoc structure, and thermotolerance is good, can be used as the optical applications resin of high transparent, high refractive index, so that finished the present invention.

That is, the present invention relates to comprise the unit of following general formula (1) expression, and weight-average molecular weight is 1,000～1,000,000 sulfur-containing cycloolefin resin and manufacture method thereof.

(wherein, R ₁～R ₆Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₃～R ₆Optional is halogen group, R ₃And R ₄, R ₅And R ₆Optional formation contains the ring of carbon, oxygen, sulphur or nitrogen; R ₇, R ₇' and R ₈, R ₈' represent hydrogen atom, methyl respectively independently; Expression singly-bound or two key; L, m represent 0 or 1 separately).

And, especially, relate to the unit that comprises following general formula (2) expression, and weight-average molecular weight is 1,000～1,000,000 sulfur-containing cycloolefin resin,

(wherein, R ₉And R ₁₀Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently; Expression singly-bound or two key; N is 0 or 1);

Perhaps, comprise the unit of following general formula (3) expression, and weight-average molecular weight is 1,000～1,000,000 sulfur-containing cycloolefin resin, its manufacture method,

(wherein, R ₁₁～R ₁₄Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, heterogeneous ring compound, the halogen group of representing hydrogen atom, carbonatoms 1～20 respectively independently, R ₁₁And R ₁₂, R ₁₃And R ₁₄Optional formation contains the ring of carbon, oxygen, sulphur or nitrogen ... expression singly-bound or two key, p is 0 or 1.)

The invention effect

Sulfur-containing cycloolefin resin of the present invention has high transparent and high refractive index, can be used as the raw material of various plastic lenss or prismatic lens etc.

Embodiment

Below describe the present invention in detail.

Sulfur-containing cycloolefin resin of the present invention comprises the unit of above-mentioned general formula (1) expression, and weight-average molecular weight is 1,000～1, and 000,000.In addition, so-called here weight-average molecular weight can be passed through gel permeation chromatography.

Wherein, R ₁～R ₆Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₃～R ₆Optional is halogen group, R ₃And R ₄, R ₅And R ₆Optional formation contains the ring of carbon, oxygen, sulphur or nitrogen, R ₇, R ₇', R ₈, R ₈' represent hydrogen atom, methyl respectively independently; Expression singly-bound or two key, l, m represent 0 or 1 respectively.And, as R ₁～R ₆, for example, can enumerate hydrogen atom; Alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, octyl group, dodecyl; Aralkyl such as benzyl; Aromatic series bases such as phenyl, tolyl, naphthyl; Alkoxyl group such as methoxyl group, oxyethyl group; Heterogeneous ring compound bases such as thienyl (thienyl), pyridyl; Cyano group etc.In addition, as R ₃～R ₆Can enumerate halogen groups such as fluorine, chlorine, bromine, iodine.And, R ₁～R ₆When being the group beyond these groups, the thermotolerance of the resin that obtains, transparent poor.In addition, weight-average molecular weight was less than 1,000 o'clock, and becoming is highly brittle.On the other hand, weight-average molecular weight is greater than 1,000,000 o'clock, during fusion or the viscosity during dissolving become very high, the property handled variation.

Then, sulfur-containing cycloolefin resin of the present invention especially preferably comprises the unit of above-mentioned general formula (2) expression, and the unit of above-mentioned general formula (2) expression is equivalent to the R in the unit of above-mentioned general formula (1) expression ₃～R ₈, R _{7 '}And R _{8 '}Be hydrogen atom, m is 1 unit.

Wherein, R ₉And R ₁₀Represent alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of hydrogen atom, carbonatoms 1～20 respectively independently, n is 0 or 1.And, R ₉And R ₁₀, for example can enumerate hydrogen atom; Alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, octyl group, dodecyl; Aralkyl such as benzyl; Aromatic series bases such as phenyl, tolyl, naphthyl; Alkoxyl group such as methoxyl group, oxyethyl group; Heterogeneous ring compound such as thienyl, pyridyl base; Cyano group etc.And, especially preferably comprise the R in the unit of above-mentioned general formula (2) expression ₉And R ₁₀Be hydrogen atom, n is 0 unitary sulfur-containing cycloolefin resin.

In addition, sulfur-containing cycloolefin resin of the present invention especially preferably comprises the unitary sulfur-containing cycloolefin resin of above-mentioned general formula (3) expression, and the unit of above-mentioned general formula (3) expression is equivalent to the R in the unit of above-mentioned general formula (1) expression ₇, R _{7 '}, R ₈, R _{8 '}Be that hydrogen atom, m are 0 unit.

Wherein, R ₁₁～R ₁₄Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, heterogeneous ring compound, the halogen group of representing hydrogen atom, carbonatoms 1～20 respectively independently, R ₁₁And R ₁₂, R ₁₃And R ₁₄Optional formation contains the ring of carbon, oxygen, sulphur, nitrogen, and p is 0 or 1.And, as R ₁₁～R ₁₄, for example can enumerate hydrogen atom; Alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, octyl group, dodecyl; Aralkyl such as benzyl; Aromatic series bases such as phenyl, tolyl, naphthyl; Alkoxyl group such as methoxyl group, oxyethyl group; Heterogeneous ring compound such as thienyl, pyridyl base; Cyano group; Halogen groups such as fluorine, chlorine, bromine, iodine.And, particularly preferably be the R in the unit that comprises above-mentioned general formula (3) expression ₁₁～R ₁₄All be that hydrogen atom and p are 0 unitary sulfur-containing cycloolefin resins.

Manufacture method as sulfur-containing cycloolefin resin of the present invention, as long as can make this sulfur-containing cycloolefin resin, can use manufacture method arbitrarily, for example, can carry out metathesis polymerization by the sulphur-containing cyclic olefin(e) compound that makes following general formula (4) expression and make.In addition, also can be at the metathesis polymerization back end hydrogenation.

(wherein, R ₁₅～R ₂₀Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently, R ₁₇～R ₂₀Optional is halogen group, R ₁₇And R ₁₈, R ₁₉And R ₂₀Optional formation contains the ring of carbon, oxygen, sulphur, nitrogen, R ₂₁And R ₂₂Represent hydrogen atom, methyl respectively independently, q is 1 or 2, and r represents 0 or 1).

And, as R ₁₅～R ₂₀, for example, can enumerate hydrogen atom; Alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, octyl group, dodecyl; Aralkyl such as benzyl; Aromatic series bases such as phenyl, tolyl, naphthyl; Alkoxyl group such as methoxyl group, oxyethyl group; Heterogeneous ring compound such as thienyl, pyridyl base; Cyano group is as R ₁₇～R ₂₀, can enumerate halogen groups such as fluorine, chlorine, bromine, iodine.

Have again, when manufacturing contains the sulfur-containing cycloolefin resin of above-mentioned general formula (2) expression, preferably make the novel sulfurized ring compound of following general formula (5) expression carry out metathesis polymerization, the novel sulfurized ring compound of general formula (5) expression is equivalent to the R of the sulphur-containing cyclic compound of general formula (4) expression ₁₇～R ₂₀Be that hydrogen atom and r are 1 compound.In addition, also can be at the metathesis polymerization back end hydrogenation.In addition, the sulphur-containing cyclic compound of following general formula (5) expression is to have the novel cpd of sulfur-bearing ring structure as constitutional features.

(in the formula, R ₂₃And R ₂₄Represent alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of hydrogen atom, carbonatoms 1～20 respectively independently, s is 1 or 2).

And, as R ₂₃, R ₂₄, for example can enumerate hydrogen atom; Alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, octyl group, dodecyl; Aralkyl such as benzyl; Aromatic series bases such as phenyl, tolyl, naphthyl; Cyano group; Alkoxyl group such as methoxyl group, oxyethyl group; Heterogeneous ring compound such as thienyl, pyridyl base.

The sulphur-containing cyclic compound of general formula (5) expression for example can enumerate 1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-methyl isophthalic acid, 3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-ethyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-propyl group-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-sec.-propyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-butyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-octyl group-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-dodecyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-phenyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2,2-dimethyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2,2-diethyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2,2-dipropyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2,2-dibutyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2,2-phenylbenzene-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-methyl-2-ethyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-methyl-2-propyl group-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-methyl-2-butyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-methyl-2-phenyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-ethyl-2-propyl group-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-ethyl-2-butyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-ethyl-2-phenyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene, 2-propyl group-2-phenyl-1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene etc.

In addition, when making the sulfur-containing cycloolefin resin of representing with above-mentioned general formula (3), preferably make the sulphur-containing cyclic compound of following general formula (6) expression carry out metathesis polymerization, the sulphur-containing cyclic compound of general formula (6) expression is equivalent to the R of the sulphur-containing cyclic compound of general formula (4) expression ₂₁And R ₂₂Be that hydrogen atom and r are 0 compounds.In addition, also can be at the metathesis polymerization back end hydrogenation.

(wherein, R ₂₅～R ₂₈Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, heterogeneous ring compound, the halogen group of representing hydrogen atom, carbonatoms 1～20 respectively independently, R ₂₅And R ₂₆, R ₂₇And R ₂₈Optional formation contains the ring of carbon, oxygen, sulphur, nitrogen, and t is 1 or 2).

And, R ₂₅～R ₂₈, for example can enumerate hydrogen atom; Alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, octyl group, dodecyl; Aralkyl such as benzyl; Aromatic series bases such as phenyl, tolyl, naphthyl; Cyano group; Alkoxyl group such as methoxyl group, oxyethyl group; Heterogeneous ring compound such as thienyl, pyridyl base, halogen groups such as fluorine, chlorine, bromine, iodine.

Sulphur-containing cyclic compound with general formula (6) expression, for example can enumerate 2-thia (チ ア)-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-dimethyl-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-diethyl-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-dipropyl-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-dibutyl-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-dioctyl-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-dilauryl-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-dimethoxy-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-diethoxy-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-dicyano-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-two (2-thienyl)-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-two (2-pyridyl)-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-two (4-pyridyl)-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-two chloro-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-two bromo-1,2-dihydroxyl Dicyclopentadiene (DCPD), 2-thia-1,3-two iodo-1,2-dihydroxyl Dicyclopentadiene (DCPD) etc.

Metathesis polymerization catalyzer during the sulphur-containing cyclic compound of metathesis polymerization general formula (4), (5), (6) expression, can use known catalyzer, for example, can enumerate the polymerizing catalyst of the metallic compound (II) that comprises metallic compound (I) and periodictable 1,2,3,4 families, described metallic compound (I) is selected from least a kind in ruthenium compound, palladium compound, rhodium compound, iridic compound, platinic compound, tungsten compound, molybdenum mixture, the rhenium compound.

As metallic compound (I), be ruthenium compound, palladium compound, rhodium compound, iridic compound, platinic compound, tungsten compound, molybdenum mixture, rhenium compound, for example, the methyl ethyl diketone coordination compound, acetonitrile coordination compound, hydride coordination compound, Cabbeen coordination compound of halogenide, oxyhalogenation thing, alkoxy halide, carboxylate salt, methyl ethyl diketone coordination compound, oxide compound etc. can be enumerated, the metathesis polymerization catalyzer of following general formula (10), (11) expression can be especially preferably used.

In addition, the polymerization activity height of halogenide, oxyhalogenation thing, thus preferred, particularly can illustration WCl ₆, WOCl ₄, MoCl ₅, MoOCl ₃, ReCl ₃, WCl ₂(OC ₆H ₅) ₄, MoO ₂(acac) ₂, W (OCOR) ₅Deng.

In addition, as metallic compound (II) is the metallic compound of periodictable 1,2,3,4 families, for example, can the illustration n-Butyl Lithium, zinc ethyl, triethyl aluminum, diethyl aluminum muriate, ethyl aluminum dichloride, diethyl aluminum halogenide, trimethyl-gallium, tin tetramethide, tin tetraphenyl etc., preferred especially tin tetramethide, tin tetraphenyl.

When metallic compound (I) is the Cabbeen coordination compound,, also can demonstrate sufficient activity even use as the metathesis polymerization catalyzer separately.Ratio when using metallic compound (I) and metallic compound (II) simultaneously as the metathesis polymerization catalyzer, preferable alloy compound (I)/metallic compound (II) (mol ratio of atoms metal)=1/1～1/30, the scope particularly preferably in 1/2～1/20 is used.In addition, as active rising agent, also can add alcohols, aldehydes, ketone, amine.

When metathesis polymerization, also solvent can be used,, for example paraffinics such as pentane, octane, nonane can be enumerated as this solvent; Naphthenic such as hexanaphthene, suberane, cyclooctane; Benzene,toluene,xylenes etc. are aromatic hydrocarbon based; Haloalkane hydro carbons such as methylene dichloride, ethylene dichloride, chloroform; Halogenated aromatic such as chlorobenzene, dichlorobenzene hydrocarbon; Carboxylicesters; Cyclic ethers such as tetrahydrofuran (THF); Chain dialkyl ether etc.

Also can use molecular weight regulator when metathesis polymerization, this molecular weight regulator can use the non-ring olefin compound usually, for example, can compatibly use alhpa olefin classes such as ethene, 1-hexene, 1-heptene; Vinyl ethers such as vinyl sulfide compound, EVE such as ethenylphenyl thioether; Stilbene, 1,4-two chloro-2-butylene, 1, monoolefine compounds such as 4-diacetoxy-2-butylene, 2-butylene.In addition, two or more kinds may be used for molecular weight regulator.The consumption of molecular weight regulator, the preferred monomer/molecular weight regulator (mol ratio)=1/0.001～0.5 that adds, preferred especially 1/0.002～0.4.

Polymerization temperature during metathesis polymerization preferably-30～150 ℃, polymerization time preferably several minutes～10 hours.

In addition, when making sulfur-containing cycloolefin resin of the present invention, only otherwise break away from purpose of the present invention, can also copolymerization can with the co-polymerized monomer of the sulphur-containing cyclic compound copolymerization of above-mentioned general formula (4), (5), (6) expression, as this co-polymerized monomer, for example can enumerate cyclobutene, cyclopentenes, cyclooctene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, dicyclo [2,2,1]-the 2-heptene, three the ring [5,2,1,0 ^2,6]-3-decene, three rings [5,2,1,0 ^2,6]-8-decene, three rings [6,2,1,0 ^1,8]-9-undecylene, three rings [6,2,1,0 ^1,8]-4-undecylene, Fourth Ring [4,4,0,1 ^2,5, 1 ^7,10]-3-dodecylene, five rings [6,5,1 ^3,6, 0 ^2,7, 0 ^9,13]-4-15 carbenes, five rings [6,5,1,1 ^3,6, 0 ^2,7, 0 ^9,13]-11-15 carbenes, five rings [6,5,1,1 ^3,6, 0 ^2,70 ^9,13]-4-cetene, five rings [6,5,1,1 ^3,6, 0 ^2,70 ^9,13]-15 carbon-4,11-diene etc. wherein, can compatibly use the cyclenes hydro carbons.

The polymkeric substance that has just obtained behind the metathesis polymerization contains two keys at polymer architecture.This pair key can be transformed to singly-bound by hydrogenation.Hydrogenation can use the hydrogenation catalyst of common alkenes compounds, and this hydrogenation catalyst for example can be set forth in carbon, silicon-dioxide, aluminum oxide, titanium dioxide and upload the attached catalyzer that carries that attached palladium, platinum, nickel, rhodium, ruthenium etc. obtain; Nickel naphthenate, nickel acetylacetonate, the octylenic acid cobalt, cyclopentadienyl titanium dichloride (チ タ ノ セ Application ジ Network ロ リ De), the acetic acid rhodium, chlorine three (triphenylphosphine) closes rhodium, dichloro three (triphenylphosphine) closes ruthenium, chlorine hydrogen carbonyl three (triphenylphosphine) closes ruthenium (Network ロ ロ ヒ De ロ カ Le ボ ニ Le ト リ ス (ト リ Off エ ニ Le ホ ス Off イ Application) Le テ ニ ウ system, chlorohydrocarbonyltris (trisphenylphosphine)-ruthenium), two chloroformyl three (triphenylphosphines) close ruthenium (ジ Network ロ ロ カ Le ボ ニ Le ト リ ス (ト リ Off エ ニ Le ホ ス Off イ Application) Le テ ニ ウ system, dichlorocarbonyltris even catalyzer such as (trisphenylphosphine)-ruthenium) etc., promotor as these catalyzer, for example, can and with aluminum alkyls classes such as triethyl aluminums; Lithium alkylide classes such as n-Butyl Lithium.

The form of this hydrogenation catalyst is not particularly limited, and no matter is pulverulence or granular can the use no problemly.The consumption of hydrogenation catalyst can be being that weight ratio 0.01～50% is compatibly used with respect to polymkeric substance.

As hydroconversion condition, preferred reaction pressure is normal pressure～300 normal atmosphere, particularly preferably in the reaction down of 3～200 normal atmosphere.In addition, preferred 0～200 ℃ of temperature of reaction, preferred especially 20～180 ℃.

Solvent during hydrogenation is not particularly limited, from the viewpoint of economy, operation, and the same solvent of polymer solvent when preferred use and metathesis polymerization.

In addition, as other method for hydrogenation, can use reductive agents such as p-toluene sulfonyl hydrazide to carry out hydrogenation easily.The reductive agent consumption of this moment can be 1 times～50 times with mol ratio with respect to the two keys in the polymkeric substance compatibly to be used.

In addition, hydrogenation ratio is normally more than 60%, and is preferred more than 90%, is more preferably more than 98%.

Hydroconversion condition when using reductive agent, preferred 0～200 ℃ of temperature of reaction, preferred especially 20～180 ℃.

In addition, the solvent of this moment is not particularly limited, from the viewpoint of economy, operation, and the same solvent of polymer solvent when preferred use and metathesis polymerization.

Sulphur-containing cyclic compound as the general formula (4) of sulfur-containing cycloolefin resin raw material of the present invention, (5), (6) expression, can be with any means manufacturing, for example, the novel sulfurized ring compound of general formula (5) expression, for example can enumerate following method: a) in the presence of acid catalyst, react the method for making by following general formula (7) compound of representing and the compound that is selected from ketone, aldehydes and acetals; B) method of making by the compound and the dihalide reaction of following general formula (8) expression; C) compound by following general formula (9) expression and cyclopentadiene or Dicyclopentadiene (DCPD) carry out the method that Diels-Alder reaction is made.

(in the formula, u is 1 or 2.)

(in the formula, Y is Na, K, Rb, Cs, and v is 1 or 2.)

(in the formula, R ₂₉And R ₃₀Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently).

Below, specifically illustrate an embodiment of the novel sulfurized ring compound preferable production process of general formula (5) expression.

A) method: under acid catalyst, the compound by above-mentioned general formula (7) expression and be selected from compound by ketone, aldehydes and acetals and react and make novel sulfurized ring compound.

As the manufacture method of the compound of general formula (7) expression, can use manufacture method arbitrarily, for example, can be set forth in J.Am.Chem.Soc., the methods of record in 109,6825～6836 (1987).

In the aforesaid method, make 2,3-two (methylol)-5-norbornylene and toluene sulfonyl chloride reaction obtain xylene sulfonate (ditosylate, ジ ト シ レ one ト).Then, make the reaction of xylene sulfonate and potassium sulfocyanate, tosyl group is transformed to thiocyanogen after, be the compound of general formula (7) expression with the lithium aluminium hydride reduction.

2 of use, the ratio of 3-two (methylol)-5-norbornylene and toluene sulfonyl chloride, relative 1 mole 2,3-two (methylol)-5-norbornylene, toluene sulfonyl chloride are more than 2 moles, preferably 2～3 moles.Tosylation is reflected in the solvent to be carried out, and the solvent of use can the illustration pyridine, triethylamine, xylidine.In addition, two or more kinds may be used for these solvents, also can and use varsols such as toluene, dimethylbenzene.Temperature of reaction normally-78～150 ℃, preferred-20～100 ℃ especially.Reaction times can be several minutes～96 hours, especially preferably 1 hour～72 hours.

The xylene sulfonate that obtains is transformed to thiocyanogen by potassium sulfocyanate with tosyl group.

The ratio of xylene sulfonate and potassium sulfocyanate, relative 1 mole of xylene sulfonate, potassium sulfocyanate is more than 2 moles, preferred 2～4 moles.This reaction solution carries out in solvent, and the solvent of use can the illustration N,N-DIMETHYLACETAMIDE, dimethyl formamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, N-Methyl pyrrolidone.In addition, two or more kinds may be used for these solvents, also can and with alcohols or water such as methyl alcohol or ethanol.Temperature of reaction generally can be-78～200 ℃, preferred-20～150 ℃ especially.Reaction times can be several minutes～72 hours, especially preferably 1 hour～48 hours.

The two sulphur cyanogen bodies that obtain by lithium aluminium hydride reduction, become two mercaptan.The ratio of two sulphur cyanogen bodies and lithium aluminum hydride is that relative 1 mole of two sulphur cyanogen body uses 1 mole～10 moles lithium aluminum hydrides, especially preferably uses 2～4 moles.Be reflected in the solvent and carry out, the solvent of use can the illustration glycol dimethyl ether, diethoxyethane, Anaesthetie Ether, tetrahydrofuran (THF), two

Alkane.In addition, two or more kinds may be used for these solvents.Temperature of reaction generally can be-78～200 ℃, preferred-78～100 ℃ especially.Reaction times can be several minutes～72 hours, preferred especially 1 hour～48 hours.

And, novel sulfurized ring compound with general formula (5) expression can obtain by the following method, in the presence of acid catalyst, in solvent, make the compound of general formula (7) expression that obtains and the compound that is selected from by aldehydes, ketone and acetal compound carry out cyclization.Here; this aldehydes can be enumerated formaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, naphthaldehyde, octanal, dodecyl aldehyde, α-formyl radical toluene, 2 thiophene carboxaldehyde, 3-thiophenecarboxaldehyde, 2-pyridylaldehyde, 4-pyridylaldehyde etc.; this ketone; for example can enumerate acetone, methylethylketone, methyl phenyl ketone, benzophenone, Fluorenone, 2-acetyl thiophene, 2-acetopyridine, 4-acetylpyridine etc.; this acetals; for example; can enumerate Methylal(dimethoxymethane), 1; 1-glycol dimethyl ether, 2; 2-Propanal dimethyl acetal, alpha, alpha-dimethyl oxygen base ethylbenzene, 9,9-dimethoxy fluorenes etc.

The solvent that uses when this cyclization for example, can be enumerated hydro carbons such as hexane or hexanaphthene; Arene such as benzene or toluene; Anaesthetie Ether or two

Ethers such as alkane; Alcohols such as methyl alcohol, ethanol, ethylene glycol; Water; Halons such as methylene dichloride or chloroform etc., this solvent can be separately or and with more than 2 kinds.As acid catalyst, for example, can enumerate protonic acids such as hydrogenchloride, hydrogen bromide, sulfuric acid; Lewis acid such as boron trifluoride or aluminum chloride; The coordination compound of this lewis acidic ether, alcohol, carboxylic acid etc. etc.In addition, temperature of reaction preferably-78～200 ℃, preferred-20～150 ℃ especially.Preferably several minutes～100 hours reaction times, preferred especially 1 hour～48 hours.

B) method: novel sulfurized ring compound is made in compound and dihalide reaction by above-mentioned general formula (8) expression.

With the compound of general formula (8) expression, for example by in the alkali metal compound and the compound represented of general formula (7) obtain.

Alkali metal compound for example can be enumerated sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, sodium hydride, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate, sodium bicarbonate, saleratus.

Neutralization reaction is carried out in the solvent that does not participate in reacting, as solvent, and for example can the illustration normal hexane, varsol such as benzene or toluene; Ethers such as Anaesthetie Ether; Non-proton property polar solvents such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), tetramethylene sulfone, alcohols such as methyl alcohol, ethanol.Temperature of reaction preferably-78～150 ℃, and is particularly, preferred below 50 ℃ in initial reaction stage.The scope that reaction times is preferred 10 minutes～10 hours.

The novel sulfurized ring compound of general formula (5) expression can be by making general formula (8) expression compound and dihalide carry out cyclization and obtain.For example, this dihalide can be enumerated methylene dichloride, 1, the 1-ethylene dichloride, 1, propylidene chloride 1,2, the 2-propylene dichloride, α, α-toluene dichloride, two chloromethyl cyanides, 1,1-two chloro-3, the 3-dimethylbutane, α, α-styrenedichloridea, 2-dichloromethyl thiophene, 2-dichloromethyl pyridine, 4-dichloromethyl pyridine, methylene bromide, 1, the 1-ethylene dibromide, 1, the 1-dibromopropane, 2, the 2-dibromopropane, α, α-dibromomethylbenzene, dibromo-acetonitrile, 1,1-two bromo-3,3-dimethylbutane, α, α-dibromo ethylbenzene, 9,9-dibromo fluorenes, 2-two bromomethyl thiophenes, 2-two bromo methyl cycloheptapyridines, 4-two bromo methyl cycloheptapyridines etc.

This cyclization can carry out in solvent, as this solvent, for example, can enumerate hydro carbons such as hexane or hexanaphthene; Arene such as benzene or toluene; Anaesthetie Ether or two

Ethers such as alkane; Alcohols such as methyl alcohol, ethanol, ethylene glycol; Water etc.Temperature of reaction preferably-78～200 ℃, preferred-20～150 ℃ scope especially.Preferably several minutes～100 hours reaction times, preferred especially 1 hour～20 hours.

C) method: make the compound of above-mentioned general formula (9) expression and cyclopentadiene or Dicyclopentadiene (DCPD) carry out Diels-Alder reaction and make novel sulfurized ring compound.

The compound of above-mentioned general formula (9) expression can obtain with manufacture method arbitrarily, for example, can be set forth in Organic Preparations and Procedures International, 10, the method for 133～136 (1978) middle records.

In this reaction, by suitable-1,4-two chloro-2-butylene and thiocarbamide synthesize two isothiuronium salts (diisothiuronium, ジ イ ソ チ ウ ロ ニ ウ system), decompose this salt with potassium hydroxide aqueous solution, after making it to produce an alkali metal salt of two mercaptan,, obtain the compound of general formula (9) expression with the dihalide reaction.

Suitable-1,4-two chloro-2-butylene and being reflected in the organic solvent of thiocarbamide are carried out.At this moment, preferably suitable-1,4-two chloro-2-butylene/thiocarbamides (mol ratio)=1/1～4, preferred especially 1/1.9～2.1.In addition, as the organic solvent in when reaction, for example can illustration methyl alcohol, alcohols such as ethanol, propyl alcohol, butanols, ethylene glycol, triglycol; Non-proton property polar solvent such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, methyl-sulphoxide, tetramethylene sulfone etc., special particular methanol, ethanol, suitable relatively-1, the total amount of 4-two chloro-2-butylene and thiocarbamide, preferred 50～500 weight % of the consumption of this organic solvent, preferred especially 100～300 weight %.Preferred 0～150 ℃ of temperature of reaction, especially preferably 50～130 ℃.In preferred 10 minutes～24 hours of reaction times, carried out in preferred 30 minutes～12 hours.In addition, suitable-1, the reaction of 4-two chloro-2-butylene and thiocarbamide can be under catalyst-free/carry out in the presence of the acid catalyst, as acid catalyst, for example, protonic acids such as preferably sulfuric acid, hydrochloric acid, Hydrogen bromide, acetic acid.

In addition, be cooled to-78～80 ℃, preferably be cooled to-20～50 ℃, can reclaim two isothiuronium saltss by the reaction solution that will obtain.

This two isothiuronium salts decomposes in alkaline aqueous solution or amine, can synthesize 1, the metal-salt of 4-dimercapto-2-butylene two mercaptan or this two mercaptan.Basic cpd, for example can enumerate sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate, sodium bicarbonate etc., as amine, for example can enumerate ammonia, methylamine, Trimethylamine 99, triethylamine, morpholine, diazabicylo [2,2,2]-octane etc., wherein, especially preferably decompose by the alkaline aqueous solution that uses sodium hydroxide, potassium hydroxide.

In addition, these two isothiuronium saltss/basic cpd or amine (mol ratio) are preferably=1/2～1 5, preferred especially 1/4～10.Preferred 0～150 ℃ of the temperature of reaction of this moment, preferred especially 50～130 ℃.

Then, by make this 1, the reaction of an alkali metal salt of 4-dimercapto-2-butylene and dihalide can obtain the compound with general formula (9) expression.This dihalide, for example, can enumerate methylene dichloride, 1, the 1-ethylene dichloride, 1, propylidene chloride 1,2, the 2-propylene dichloride, α, α-toluene dichloride, two chloromethyl cyanides, 1,1-two chloro-3, the 3-dimethylbutane, α, α-styrenedichloridea, 2-dichloromethyl thiophene, 2-dichloromethyl pyridine, 4-dichloromethyl pyridine, methylene bromide, 1, the 1-ethylene dibromide, 1, the 1-dibromopropane, 2, the 2-dibromopropane, α, α-dibromomethylbenzene, dibromo-acetonitrile, 1,1-two bromo-3, the 3-dimethylbutane, α, α-dibromo ethyl benzene, 9,9-dibromo fluorenes, 2-two bromomethyl thiophenes, 2-two bromo methyl cycloheptapyridines, 4-two bromo methyl cycloheptapyridines etc. are as this organic solvent, for example, can enumerate methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, alcohols such as triglycol; Non-proton property polar solvents such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), tetramethylene sulfone.

At this moment, preferred 1, an alkali metal salt/dihalide of 4-dimercapto-2-butylene (mol ratio)=1/0.1～2, preferred especially 1/0.9～1.1.In addition, relative 1, an alkali metal salt of 4-dimercapto-2-butylene and the total amount of dihalide, preferred 100～2000 weight % of the consumption of organic solvent, preferred especially 200～1000 weight %.Preferred-78～150 ℃ of temperature of reaction, preferred-20～130 ℃ especially.

In addition, decompose two isothiuronium saltss, or with in the acid and 1, an alkali metal salt of 4-dimercapto-2-butylene just can obtain 1,4-dimercapto-2-butylene with amine.In organic solvent, use acid catalyst make this 1,4-sulfydryl-2-butylene and the compound that is selected from by aldehydes, ketone, acetals react, and just can synthesize the compound that above-mentioned general formula (9) is represented.

This aldehydes; for example can enumerate formaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, naphthyl aldehyde, octanal, dodecyl aldehyde, α-formyl radical toluene, 2 thiophene carboxaldehyde, 3-thiophenecarboxaldehyde, 2-pyridylaldehyde, 4-pyridylaldehyde etc.; this ketone; for example can enumerate acetone, methylethylketone, methyl phenyl ketone, benzophenone, Fluorenone, 2-acetyl thiophene, 2-acetopyridine, 4-acetylpyridine etc.; this acetals; for example; can enumerate Methylal(dimethoxymethane), 1; 1-glycol dimethyl ether, 2; 2-Propanal dimethyl acetal, alpha, alpha-dimethyl oxygen base ethylbenzene, 9,9-dimethoxy fluorenes etc.

The solvent that uses when this cyclization for example, can be enumerated hydro carbons such as hexane or hexanaphthene; Arene such as benzene or toluene; Anaesthetie Ether or two

Ethers such as alkane; Alcohols such as methyl alcohol, ethanol, ethylene glycol; Water; Halons such as methylene dichloride or chloroform etc., this solvent can be separately or and with more than 2 kinds.As acid catalyst, for example can enumerate protonic acids such as hydrogenchloride, hydrogen bromide, sulfuric acid; Lewis acid such as boron trifluoride or aluminum chloride; The coordination compound of this lewis acidic ether, alcohol, carboxylic acid etc. etc.In addition, preferably-78～200 ℃ scope of temperature of reaction, special scope preferably-20～150 ℃.Preferably several minutes～100 hours reaction times, especially preferably 1～48 hour.

With the novel sulfurized ring compound of general formula (5) expression, can make by the compound of above-mentioned general formula (9) expression and the Diels-Alder reaction of cyclopentadiene or Dicyclopentadiene (DCPD).This Diels-Alder reaction can be by in solvent or under the solvent-free situation, and the compound of the above-mentioned general formula of Hybrid Heating (9) expression and cyclopentadiene or Dicyclopentadiene (DCPD) are implemented.As solvent, for example can enumerate varsols such as normal hexane, benzene or toluene.In addition, because cyclopentadiene or Dicyclopentadiene (DCPD) play a role as solvent, so, if consider economy, then preferably in solvent-free reaction down.

Here, the compound/cyclopentadiene or the Dicyclopentadiene (DCPD) (mol ratio)=1/0.01～5 of preferred formula (9) expression, preferred especially 1/0.1～2.0.In addition, when implementing Diels-Alder reaction, under catalyst-free or in order to promote reaction also can use catalyzer, when using catalyzer, the compound/catalyzer (mol ratio)=1/0.001～1 of preferred formula (9) expression.As this catalyzer, for example, Lewis acids such as preferred aluminum chloride, aluminum bromide, tin tetrachloride, titanium tetrachloride, zinc chloride, boron fluoride.In addition, the scope that temperature of reaction is preferred-10～300 ℃, especially preferably 20～230 ℃.Preferably several minutes～100 hours reaction times, preferred especially 30 minutes～50 hours, be more preferably 1 hour～20 hours.

In addition, the sulphur-containing cyclic compound of above-mentioned general formula (6) expression can be by for example making cyclopentadiene or Dicyclopentadiene (DCPD) and 2, and 5-dihydro-thiophene derivative carries out Diels-Alder reaction and synthesizes.This Diels-Alder reaction by in solvent or solvent-free down, Hybrid Heating cyclopentadiene and 2,5-dihydro-thiophene derivative is implemented.As solvent, for example can enumerate varsols such as normal hexane, benzene or toluene etc.Then,, can be used as solvent because cyclopentadiene or Dicyclopentadiene (DCPD) are liquid, so, if consider economy, preferably in solvent-free reaction down.

Here, preferred 2,5-dihydro-thiophene derivative/cyclopentadiene or Dicyclopentadiene (DCPD) (mol ratio)=1/0.01～5, preferred especially 1/0.1～2.In addition, preferred 2 when using catalyzer under catalyst-free or in order to promote reaction also can use catalyzer when implementing Diels-Alder reaction, 5-dihydro-thiophene derivative/catalyzer (mol ratio)=1/0.001～1.As this catalyzer, Lewis acids such as for example preferred aluminum chloride, aluminum bromide, tin tetrachloride, titanium tetrachloride, zinc chloride, boron fluoride.In addition, the scope that temperature of reaction is preferred-10～300 ℃, especially preferably 20～230 ℃.In preferably several minutes～100 hours reaction times, preferred especially 30 minutes～50 hours, be more preferably 1～20 hour.

In addition, as being equivalent in the sulphur-containing cyclic compound of general formula (6) expression, t is 1, R ₂₅～R ₂₈Be the synthetic method of the compound of hydrogen atom, can be set forth in J.Org.Chem., the method for 30,2560～2564 (1965) middle records.

Aforesaid method makes 2, and 3-two (methylol)-5-norbornylene and toluene sulfonyl chloride reaction obtain xylene sulfonate.Then, make the reaction of sodium sulphite and this xylene sulfonate, synthetic be equivalent in the sulphur-containing cyclic compound of general formula (6) expression that t is 1, R ₂₅～R ₂₈It is the compound of hydrogen atom.

2, the ratio of 3-two (methylol)-5-norbornylene and toluene sulfonyl chloride, with respect to 1 mole 2,3-two (methylol)-5-norbornylene, toluene sulfonyl chloride be more than 2 moles, preferably 2～3 moles.Methylsulfonylization is reflected in the solvent carries out, and as solvent, can enumerate pyridine, triethylamine, xylidine.In addition, two or more kinds may be used for these solvents, also can be used in combination varsols such as toluene, dimethylbenzene.Temperature of reaction generally be-78～150 ℃, especially preferably-20～100 ℃.Reaction times can be several minutes～96 hours, especially preferably 1 hour～72 hours.

Make the reaction of the xylene sulfonate that obtains and sodium sulphite, can synthesize and be equivalent in the sulphur-containing cyclic compound of general formula (6) expression, t is 1 and R ₂₅～R ₂₈It is the compound of hydrogen atom.

The ratio of xylene sulfonate and sodium sulphite, with respect to 1 mole of xylene sulfonate, sodium sulphite is more than 1 mole, preferably 2～4 moles.This is reflected in the solvent and carries out, and solvent can illustration methyl alcohol, ethanol, N,N-DIMETHYLACETAMIDE, dimethyl formyl, dimethyl sulfoxide (DMSO), tetramethylene sulfone, N-Methyl pyrrolidone.In addition, two or more kinds may be used for these solvents, also can be used in combination water.Temperature of reaction generally be-78～200 ℃, especially preferably-20～150 ℃.Reaction times can be several minutes～72 hours, especially preferably 1～48 hour.

Sulfur-containing cycloolefin resin of the present invention has high transparent, can be as uses such as optical material, various film, sheet, lens, substrate such as the transparent coated material of antireflection film or fiber optics coated material etc., bloomings, wherein, because have high refractive index, so can be used as with the condensing lens is the use such as plastic lens, prismatic lens of representative.

Embodiment

Below, by embodiment the present invention is described, but present embodiment does not limit the present invention at all.

The mensuration of～weight-average molecular weight～

Using gel permeation chromatography (GPC) (production of eastern Cao (TOSOH ， East ソ one) Co., Ltd., trade(brand)name HL C8020GPC), is solvent with the chloroform, is measured as the polystyrene standard scaled value by the elution curve 40 ℃ of mensuration.

The mensuration of～infrared absorption spectrum (IR)～

Use infrared absorption determinator (Hitachi produces, trade(brand)name InfraredSpectrophotometer 270-30), measure IR spectrum with the KBr method.

～NMR spectrographic mensuration～

Use nuclear magnetic resonance spectrometry device (NEC production, trade(brand)name GSX270WB), in the deuterate solvent, use deuterochloroform to measure.

The mensuration of～GC-MS～

(Hewlett-Packard (Hewlett-packard) produces to use Gas Chromatography-mass Spectrometer (GCMS), trade(brand)name: mass spectrograph 5971 series), post uses capillary column (capillary column, キ ヤ ピ ラ リ one カ ラ system) (GL Siences (サ イ エ Application ス) production, the trade(brand)name: DB-1) measure of external diameter 0.25mm, long 30cm.

～light penetration～

Measure according to JIS K7105.

～specific refractory power (nd)～

(ATAGO (ア タ go) produces, trade(brand)name: DR-M2), measure by the d line to use Abbe refractomecer.

Specific refractory power (the n of～sulphur-containing cyclic compound _D)～

(ATAGO produces, trade(brand)name: RX-5000 α (digital refractometer)), measure with toluene solution to use the liquid refractivity instrument.

[synthesis example 1]

＜5-norbornylene-2,3-dicarboxylic acid diisopropyl ester synthetic 〉

In the 200ml autoclave, add 27.1g (0.2mol) Dicyclopentadiene (DCPD), 80.4g (0.4mol) fumaric acid diisopropyl ester, fully replace system inside with nitrogen after, with 170 ℃ the reaction 5 hours.Distillation reaction liquid under 0.4kPa decompression obtains 124～126 ℃ of cuts of 88g.By ¹H-NMR spectrum and GC-MS confirm that this cut is a 5-norbornylene-2,3-dicarboxylic acid isopropyl ester.Yield 83%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.2 (12H), 1.4～1.6 (2H), 2.6 (1H), 3.1～3.4 (3H), 5.0 (2H), 6.1～6.3 (2H),

EI-MS：266(M)

＜5-norbornylene-2,3-dimethanol synthetic 〉

In the 1000ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, add 25.8g (0.68mol) lithium aluminum hydride, after fully replacing system inside with nitrogen, cool off with ice-water bath on the limit, and the limit adds 450ml tetrahydrofuran (THF) (being designated as THF later on) at leisure.Therein, drip the 5-norbornylene-2 of 37.8g (0.14mol), the mixed solution of 3-dicarboxylic acid diisopropyl ester and 50mlTHF also makes the reactive system temperature not be higher than 10 ℃.After drip finishing, with the reflux temperature reaction of THF 5 hours.Reaction was cooled to 5 ℃ with ice-water bath with reactive system after finishing again, dripped the 3%NaOH aqueous solution of 150g through about 1 hour.Continued stir about 30 minutes, the suction filtration throw out.

Remove with vaporizer and to desolvate, drying at room temperature 5 hours, obtain the greenish orange look viscous liquid of 20.4g with Vacuumdrier.By ¹H-NMR spectrum and GC-MS confirm that this viscous liquid is a 5-norbornylene-2, the 3-dimethanol.Yield 98%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.3 (1H), 1.6～2.0 (2H), 2.5～3.1 (5H), 3.4～3.8 (4H), 6.0～6.2 (2H)

EI-MS：154(M)

＜5-norbornylene-2,3-dimethanol-two-p-toluenesulfonic esters synthetic 〉

Add the 5-norbornylene-2 of 20.3g (0.13mol) in the 500ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, 3-dimethanol, 90ml pyridine be cooled to 5 ℃ with ice-water bath with reactive system inside.In this solution to add 59.4g (0.31mol) Tosyl chloride in 20 minutes.If continued stir about 20 minutes, reactive system just solidifies, so placed 72 hours in being adjusted into 4 ℃ refrigerator together with reactor.

Reactant is joined in the 300ml 6%HCl aqueous solution stirring at room 2 hours.The white pasty state solution that suction filtration generates, the white solid that obtains is with 200ml methanol cleaning 2 times, with 50 ℃ of dryings 2 hours, obtains the 53.2g white solid in Vacuumdrier.By ¹H-NMR spectrum confirms that this solid is a 5-norbornylene-2,3-dimethanol-two-p-toluenesulfonic esters.Yield 87%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.2 (1H), 1.3～1.4 (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)

＜5-norbornylene-2,3-dimethyl sulphide cyanate synthetic 〉

In the 1000ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, add 147g (0.62mol) potassium sulfocyanate, 236ml dimethyl formamide (being designated as DMF later on), 53g (0.11mol) 5-norbornylene-2,3-dimethanol-two-p-toluenesulfonic esters, after in the abundant exchange system of nitrogen, reactive system is heated up, and reaction is 20 hours between 70～80 ℃.Reaction solution put cold after, add the 200ml pure water, with 200ml Anaesthetie Ether extraction 2 times.At the Anaesthetie Ether layer, remove Anaesthetie Ether with vaporizer after, obtain the 23.5g yellow viscous liquid.By ¹H-NMR spectrum and GC-MS confirm that this viscous liquid is a 5-norbornylene-2,3-dimethyl sulphide cyanate.Yield 88%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.3～1.5 (3H), 2.2 (1H), 2.7～3.2 (6H), 6.1 (1H), 6.3 (1H)

EI-MS：236(M)

＜1,3-two sulphur three rings [5,4,0,1 ^6,9Synthesizing of]-7-dodecylene 〉

Add 16.4g (0.43mol) lithium aluminum hydride in the 1000ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, after in the abundant exchange system of nitrogen, the limit adds 400mlTHF at leisure with ice-water bath cooling limit.Therein, to drip the 5-norbornylene-2 of 23g (0.1mol), the mixed solution of 3-dimethyl sulphide cyanate and 100mlTHF in about 1 hour.After dripping end, room temperature reaction 2 hours.Reaction is cooled to 5 ℃ with ice-water bath with reactive system after finishing again, drips 25ml 5% aqueous sulfuric acid.Continued stir about 1 hour, the suction filtration throw out.GC-MS analyzes the filtrate that obtains, and can not confirm raw material 5-norbornylene-2,3-dimethyl sulphide cyanate, can confirm to generate 5-norbornylene-2,3-diformazan mercaptan (5-norbornene-2,3-dimercaptomethyl, 5-ノ ボ Le ネ Application-2,3-ジ メ Le カ プ ト メ チ Le).EI-MS：186。

With vaporizer filtrate is concentrated to 50g, adds 400ml methyl alcohol therein.In this methanol solution, be added in the liquid that dissolved 22g (0.33mol) 85% potassium hydroxide in the 350ml methyl alcohol and obtained stirring at room 30 minutes.Then, to drip the mixed solution of 18.7g (0.11mol) methylene bromide and 100ml methyl alcohol, stirring at room 13 hours in about 30 minutes.The salt that filtering reacting liquid is separated out is removed methyl alcohol with vaporizer.In the slurry that obtains, add the 100ml chloroform, refilter solid part after, with the vaporizer concentrated filtrate, obtain the 16.8g viscous liquid.Under the 0.3KPa decompression, distill the viscous soln that obtains, obtain 111～114 ℃ of scope cuts of 7.6g.By ¹H-NMR spectrum and GC-MS confirm that this cut is 1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene (in general formula (5), R ₂₃And R ₂₄Be hydrogen atom, s is 1 compound).

270MHz ¹The measurement result of H-NMR, δ (CDCl ₃): 1.63 (3H), 2.2 (2H), 2.6 (2H), 2.8 (2H), 3.0 (1H), 6.1 (1H), 6.3 (1H)

EI-MS：198(M)

Specific refractory power (n _D): 1.597

[synthesis example 2]

＜suitable-1, two isothiuronium saltss of 4-two chloro-2-butylene are synthetic 〉

In the 1000ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, add 120g (1.58mol) thiocarbamide, 310ml 95% ethanol.Behind the abundant exchange system of nitrogen inside, be warmed up to 40 ℃, suitable-1 to drip 90g (0.72mol) in about 30 minutes, 4-two chloro-2-butylene and 20ml95% alcoholic acid mixed solution (causing heating this moment).After dripping end, reactive system is warmed up to the alcoholic acid reflux temperature, reacted 1 hour.Reaction is put and is as cold as room temperature after finishing, and crosses the filter solid composition.This solid composition is cleaned 2 times with 250ml ethanol, and in Vacuumdrier, drying is 8 hours under the room temperature, obtains the 182g white solid.By ¹H-NMR spectrum and FT-IR spectrum confirm that this white solid is suitable-1, two isothiuronium saltss of 4-two chloro-2-butylene.Yield 90%.

270MHz ¹The measurement result of H-NMR: δ (D ₂O): 4.0 (4H), 5.9 (2H)

The measurement result of FT-IR (KBr method): 3000～3500cm ^-1(NH)

＜4,7-dihydro-1,3-dithia

( 4,7-dihydro-1,3-dithiepin) synthetic

It is suitable-1 to add 182g (0.66mol) in the 5000ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, and two isothiuronium saltss and the 1900ml methyl alcohol of 4-two chloro-2-butylene are cooled to 4 ℃ with the temperature of reactive system.In this paste solution, to add 85% potassium hydroxide of 218g (3.31mol) in 1 hour, directly 2～4 ℃ of reactions 16 hours.In the reaction solution that obtains, dripped the mixed solution of 143g (0.82mol) methylene bromide and 650ml methyl alcohol through 6 hours.Reaction solution slowly returns to room temperature through a night, former state continues to stir 60 hours.

The reaction solution that obtains is removed methyl alcohol with vaporizer behind the solids removed by filtration composition, with Vacuumdrier drying at room temperature 1 hour, obtain the 50.1g faint yellow solid.By ¹H-NMR spectrum and GC-MS confirm that this faint yellow solid is 4,7-dihydro-1,3-dithia Yield 58%.

270MHz ¹The measurement result of H-NMR: δ (CDCl ₃): 3.45 (4H), 4.02 (2H), 6.00 (2H) EI-MS:132 (M)

＜1,3-two sulphur three rings [5,4,0,1 ^6,9Synthesizing of]-7-dodecylene 〉

In the 200ml autoclave, add 12.2g (0.09mol) Dicyclopentadiene (DCPD), 49.1g (0.37mol) 4,7-dihydro-1,3-dithia

, behind the abundant exchange system of the employing nitrogen inside, continued heated and stirred 5 hours with 170 ℃ while stirring.After reaction finished, temperature dropped to 25 ℃, takes out reaction solution from autoclave.Reaction solution is dark brown solution.Under the 0.3KPa decompression, distill the dark brown solution that obtains, obtain 111～114 ℃ of scope cuts of 23.5g.This cut at room temperature solidifies.By ¹H-NMR spectrum and GC-MS are confirmed to be 1,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene (in general formula (5), R ₂₃And R ₂₄Be hydrogen atom, s is 1 compound).This compound is the isomer of the compound that obtains in synthesis example 1.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.2 (2H), 2.5～3.0 (8H), 4.0 (2H), 5.8～6.2 (2H)

EI-MS：198(M)

Specific refractory power (n _D): 1.610

[synthesis example 3]

＜7-methyl-5-norbornylene-2,3-dicarboxylic acid diisopropyl ester synthetic 〉

In the 200ml autoclave, add 32.0g (0.4mol) 1-methyl cyclopentadiene, 80.4g (0.4mol) fumaric acid diisopropyl ester, behind the abundant exchange system of nitrogen inside, with 170 ℃ of reactions 5 hours.Distillation reaction liquid under 0.4KPa decompression obtains 124～126 ℃ of cuts of 94g.By ¹H-NMR spectrum and GC-MS confirm that this cut is 7-methyl-5-norbornylene-2,3-dicarboxylic acid isopropyl ester.Yield 84%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.2 (14H), 1.4～1.6 (2H), 2.6 (1H), 3.1～3.4 (3H), 5.0 (2H), 6.1～6.3 (2H)

EI-MS：280(M)

＜7-methyl-5-norbornylene-2,3-dimethanol synthetic 〉

Add 25.8g (0.68mol) lithium aluminum hydride in the 1000ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, behind the abundant exchange system of the nitrogen inside, the limit adds 450mlTHF at leisure with ice-water bath cooling limit.To wherein dripping 39.2g (0.14mol) 7-methyl-5-norbornylene-2, the mixed solution of 3-dicarboxylic acid diisopropyl ester and 50mlTHF.After drip finishing, with the reflux temperature reaction of THF 5 hours.Reaction is cooled to 5 ℃ with ice-water bath with reactive system after finishing, to drip the 3%NaOH aqueous solution of 150g in about 1 hour.Continued stir about 30 minutes, the suction filtration throw out.

Remove with vaporizer and to desolvate,, obtain the greenish orange look viscous liquid of 23.1g with Vacuumdrier at room temperature dry 5 hours.By ¹H-NMR spectrum and GC-MS confirm that this viscous liquid is 7-methyl-5-norbornylene-2, the 3-dimethanol.Yield 98%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.3 (4H), 1.6～2.0 (1H), 2.5～3.1 (5H), 3.4～3.8 (4H), 6.0～6.2 (2H)

EI-MS：168(M)

＜7-methyl-5-norbornylene-2,3-dimethanol-two p-toluenesulfonic esters synthetic 〉

Add 21.8g (0.13mol) 7-methyl-5-norbornylene-2 in the 500ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, 3-dimethanol, 90ml pyridine are cooled to 5 ℃ with ice-water bath with reactive system inside.In this solution, added 59.4g (0.31mol) Tosyl chloride through 20 minutes.If continued stir about 20 minutes, reactive system can solidify, so placed 72 hours in being adjusted into 4 ℃ refrigerator together with reactor.

Reactant adds the 300ml 6%HCl aqueous solution, stirring at room 2 hours.The white pasty state solution that suction filtration generates, the white solid that obtains is with 200ml methanol cleaning 2 times, with 50 ℃ of dryings 2 hours, obtains the 53.8g white solid in Vacuumdrier.By ¹H-NMR spectrum confirms that this solid is a 5-norbornylene-2,3-dimethanol-two-p-toluenesulfonic esters.Yield 87%.

By 270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.2 (4H), 1.3～1.4 (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)

＜7-methyl-5-norbornylene-2,3-dimethyl sulphide cyanate synthetic 〉

In the 1000ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, add 147g (0.62mol) potassium sulfocyanate, 236mlDMF, 53g (0.11mol) 7-methyl-5-norbornylene-2,3-dimethanol-two p-toluenesulfonic esters, behind the abundant exchange system of nitrogen inside, reactive system is heated up, and reaction is 20 hours between 70～80 ℃.Reaction solution put cold after, add the 200ml pure water, extract 2 times with the 200ml Anaesthetie Ether.The Anaesthetie Ether layer is removed Anaesthetie Ether with vaporizer, obtains the 23.8g yellow viscous liquid.By ¹H-NMR spectrum and GC-MS confirm that this viscous liquid is 7-methyl-5-norbornylene-2,3-dimethyl sulphide cyanate.Yield 87%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.3～1.5 (3H), 2.2 (1H), 2.7～3.2 (6H), 6.1 (1H), 6.3 (1H)

EI-MS：250(M)

＜12-methyl isophthalic acid, 3-two sulphur three rings [5,4,0,1 ^6,9Synthesizing of]-7-dodecylene 〉

Add 16.4g (0.43mol) lithium aluminum hydride in the 1000ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, behind the abundant exchange system of the nitrogen inside, the limit adds 400mlTHF at leisure with ice-water bath cooling limit.Through about 1 hour to wherein dripping 23g (0.09mol) 7-methyl-5-norbornylene-2, the mixed solution of 3-dimethyl sulphide cyanate and 100mlTHF.After dripping end, room temperature reaction 2 hours.Reaction is cooled to 5 ℃ with ice-water bath with reactive system after finishing again, drips 25ml 5% aqueous sulfuric acid.Continued stir about 1 hour, the suction filtration throw out.GC-MS analyzes the filtrate obtain, can not confirm the 7-methyl-5-norbornylene-2 of raw material, 3-dimethyl sulphide cyanate, can confirm to have generated 7-methyl-5-norbornylene-2,3-dimercapto methyl esters.EI-MS：200。

With vaporizer filtrate is concentrated to 50g, adds 400ml methyl alcohol therein.In this methanol solution, be added in and dissolved the liquid that 22g (0.33mol) 85% potassium hydroxide obtains, stirring at room 30 minutes in the 350ml methyl alcohol.Then, to drip the mixed solution of 18.7g (0.11mol) methylene bromide and 100ml methyl alcohol, stirring at room 13 hours through 30 minutes.For reaction solution, filter out the salt of separating out, remove methyl alcohol with vaporizer.In the paste that obtains, add the 100ml chloroform, refilter solid part after, with the vaporizer concentrated filtrate, obtain the 17.0g viscous liquid.Under the 0.3KPa decompression, distill the viscous soln that obtains, obtain the cut of 7.8g115～119 ℃ scope.By ¹H-NMR spectrum and GC-MS confirm that this cut is the 12-methyl isophthalic acid, 3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene (in general formula (4), R ₁₅～R ₂₁Be hydrogen atom, R ₂₂Be that methyl, q are 1 compounds).

270MHz ¹The measurement result of H-NMR, 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)

Specific refractory power (n _D): 1.590

[synthesis example 4]

＜5-norbornylene-2,3-dimethanol-two methanesulfonates synthetic 〉

By the method same, obtain the 5-norbornylene-2 of 31g, the 3-dimethanol with synthesis example 1.

In the 500ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, add the 140ml pyridine, behind the abundant exchange system of the nitrogen inside,, the temperature of internal system is dropped to 3 ℃ with the ice-water bath cooling.Therein, with about 1 hour Dropwise 5 0.3g (0.44mol) methylsulfonyl chloride.Stir this solution after 1 hour, slowly added 30g (0.2mol) 5-norbornylene-2 through 5 hours, the mixed solution of 3-dimethanol and 125ml pyridine, and make the interior temperature of system be no more than 5 ℃.Reactive system becomes the brown pasty state, and reaction is 15 hours under this state.

In 4%HCl frozen water solution, slowly add reaction solution, the dark brown solid that suction filtration is separated out.After the dark brown solid that obtains is cleaned 2 times with the 500ml pure water, in Vacuumdrier,, obtain the shallow dark brown solid of 54.5g with 50 ℃ of dryings 8 hours.

¹H-NMR spectrum is confirmed to be 5-norbornylene-2,3-dimethanol-two methanesulfonates.Yield 90%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.2～1.4 (2H), 2.7 (2H), 3.0 (8H), 3.9～4.1 (4H), 6.1 (2H)

＜2-thia-1,2-dihydro Dicyclopentadiene (DCPD) synthetic 〉

In the 500ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, add 25g (0.08mol) 5-norbornylene-2,3-dimethanol-two methanesulfonates, 250ml methyl alcohol, behind the abundant exchange system of nitrogen inside, under reflux, dissolving 5-norbornylene-2,3-dimethanol-two methanesulfonates.In this solution, in the 150ml pure water, dissolved the aqueous solution that 62g (0.26mol) sodium sulphite 9 hydrates obtain with dropping in about 4 hours.After dripping end, direct reaction 2 hours.Reaction solution extracts 2 times with the 100ml Anaesthetie Ether after cooling.The Anaesthetie Ether layer is cleaned 1 time with the 10%NaOH aqueous solution of 100ml, behind the separatory, removes Anaesthetie Ether with rotatory evaporator, obtains the 10.6g black liquor.Under the 0.1kPa decompression, distill this liquid, obtain 59～60 ℃ of cuts of 3.8g. ¹H-NMR spectrum and GC-MS are confirmed to be 2-thia (thia)-1,2-dihydro Dicyclopentadiene (DCPD) (R in general formula (6) ₂₅～R ₂₈Be hydrogen atom, t is 1 compound).Yield 31%.

270MHz ¹H-NMR measurement result: 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)

Specific refractory power (n _D): 1.557

[synthesis example 5]

＜5-norbornylene-2,3-dimethanol synthetic 〉

It is suitable-1 to add 26.4g (0.2mol) Dicyclopentadiene (DCPD), 70.4g (0.8mol) in the 200ml autoclave, 4-dihydroxyl-2-butylene, and behind the abundant exchange system of nitrogen inside, warming while stirring to 170 ℃ continued heated and stirred 6 hours.Reaction drops to 25 ℃ with temperature after finishing, and takes out reaction solution from autoclave.Reaction solution is dark brown solution.The dark brown solution that distillation obtains under the 0.3kPa decompression obtains 120～122 ℃ of scope cuts of 36.3g.By ¹H-NMR spectrum and GC-MS confirm that this cut is a 5-norbornylene-2, the 3-dimethanol.Yield 59%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.4 (2H), 2.4～2.8 (4H), 3.2～4.3 (6H), 6.0 (2H)

EI-MS：154(M)

＜5-norbornylene-2,3-dimethanol-two methanesulfonates synthetic 〉

In the 500ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, add the 140ml pyridine, behind the abundant exchange system of the nitrogen inside,, the internal system temperature is dropped to 3 ℃ with the ice-water bath cooling.Therein, with about 1 hour Dropwise 5 0.3g (0.44mol) methylsulfonyl chloride.Stir this solution after 1 hour, slowly added 30g (0.2mol) 5-norbornylene-2 through 5 hours, the mixed solution of 3-dimethanol and 125ml pyridine, and make that temperature is not higher than 5 ℃ in the system.Reactive system becomes the brown pasty state, and reaction is 15 hours under this state.

In 4%HCl frozen water solution, slowly add reaction solution, the dark brown solid that suction filtration is separated out.After the dark brown solid that obtains is cleaned 2 times with the 500ml pure water, in Vacuumdrier,, obtain the shallow dark brown solid of 54.5g with 50 ℃ of dryings 8 hours.

¹H-NMR spectrum is confirmed to be 5-norbornylene-2,3-dimethanol-two methanesulfonates.Yield 90%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.2～1.4 (2H), 2.7 (2H), 3.0 (8H), 3.9～4.1 (4H), 6.1 (2H)

＜2-thia-1,2-dihydro Dicyclopentadiene (DCPD) synthetic 〉

In the 500ml four-hole glass flask that stirrer, cooling tube, thermometer, nitrogen ingress pipe have been installed, add 25g (0.08mol) 5-norbornylene-2,3-dimethanol-two methanesulfonates, 250ml methyl alcohol, behind the abundant exchange system of nitrogen inside, under reflux, dissolving 5-norbornylene-2,3-dimethanol-two methanesulfonates.In this solution, in the 150ml pure water, dissolved the aqueous solution that 62g (0.26mol) sodium sulphite 9 hydrates obtain with dropping in about 4 hours.After dripping end, direct reaction 2 hours.Reaction solution is after cooling, with 100ml Anaesthetie Ether extraction 2 times.The Anaesthetie Ether layer is cleaned 1 time with the 10%NaOH aqueous solution of 100ml, behind the separatory, removes Anaesthetie Ether with rotatory evaporator, obtains the 10.6g black liquor.Under the 0.1KPa decompression, distill this liquid, obtain 59～60 ℃ of cuts of 3.8g. ¹H-NMR spectrum and GC-MS are confirmed to be 2-thia-1, and 2-dihydro Dicyclopentadiene (DCPD) (in general formula (6), R ₂₅～R ₂₈Be hydrogen atom, t is 1 compound).This compound is the isomer of the compound that obtains in synthesis example 4.Yield 31%.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.8 (2H), 2.4 (2H), 2.7 (4H), 3.2 (2H), 6.2 (2H)

EI-MS：152(M)

Specific refractory power (n _D): 1.555

Embodiment 1

Under reduced pressure, fully replace with nitrogen with packed into the 100ml Shi Lunke pipe (Schlenk flask, シ ユ レ Application Network pipe) of magnet rotor of fan heater (heat gun, ヒ one ト ガ Application) drying.The ruthenium complex that adds above-mentioned general formula (10) expression of 85mg (0.1mmol) therein.With dry chloroform of syringe weighing 45ml in this Shi Lunke pipe and 23mg (0.17mmol) phenyl vinyl sulfide, preparation metathesis polymerization catalyst solution.Then, add that 5.0g (25mmol) obtains in synthesis example 11,3-two sulphur three rings-[5,4,0,1 ^6,9]-7-dodecylene immerses in the oil bath that is adjusted into 60 ℃, carries out polymerization in 4 hours.

Polymer fluid flow into 150ml contain 0.1% 2, the acetone of 6-di-t-butyl-4-hydroxytoluene is separated out polymkeric substance.After the filter solvents, the polymkeric substance of recovery drying at room temperature 8 hours in Vacuumdrier obtains the 2.6g polymkeric substance.

¹H-NMR spectrum confirms that the polymkeric substance that obtains is 1,3-two sulphur three rings-[5,4,0,1 ^6,9The Romp polymer of]-7-dodecylene.

270MHz ¹H-NMR δ (CDCl ₃) measurement result: 1.2～3.1 (10H), 3.9 (2H), 5.3 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 13,000, and it is 370 ℃ that 10% thermogravimetric amount reduces temperature.

This polymkeric substance of dissolving in chloroform, curtain coating is made the film of thick 100 μ m on polyethylene terephthalate film (below be designated as the PET film).Specific refractory power (the n of this film _d) be 1.657, Abbe constant is 20.In addition, total light penetration be 88%,

Embodiment 2

The 300ml four-hole boiling flask of magnet rotor under reduced pressure is housed with the fan heater drying, and with nitrogen replacement.Add therein that 3.5g obtains in embodiment 11,3-two sulphur three rings-[5,4,0,1 ^6,9The Romp polymer of]-7-dodecylene and the vinyl trichloride of 120ml, the stirring at room dissolving.In this solution, add 16.5g (88.8mmol) p-toluene sulfonyl hydrazide and 11.3g (88.8mmol) N, N ,-dimethylcyclohexylamine was 110 ℃ of reactions 4 hours.After reaction finished, the reaction solution cool to room temperature was put in the 300ml methyl alcohol, and polymkeric substance is separated out.In 100 ℃ of chloroforms, dissolve behind the polymer filtration of separating out, filter not solvent components.Filtrate is put in the 300ml methyl alcohol, and polymkeric substance is separated out.After the filtration, the polymkeric substance of recovery with 100 ℃ of dryings 5 hours, obtains the 2.7g polymkeric substance in Vacuumdrier.By ¹The H-NMR spectroscopic analysis confirms that the polymkeric substance that obtains is 1,3-two sulphur three rings-[5,4,0,1 ^6,9The hydrogenation thing of]-7-dodecylene Romp polymer.

270MHz ¹H-NMR measurement result: δ (CDCl ₃): 1.4～3.6 (10H), 5.2～5.6 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 13,000.At 220 ℃ of these polymkeric substance of compacting, make the film of thick 100 μ m.Specific refractory power (the n of this film _d) be 1.623, Abbe constant is 45.In addition, total light penetration is 88%.

Embodiment 3

Under reduced pressure, fully replace with nitrogen with packed into the 100ml Shi Lunke pipe of magnet rotor of fan heater drying.The ruthenium complex that adds above-mentioned general formula (10) expression of 85mg (0.1mmol) therein.With the dry chloroform of syringe weighing 45ml in this Shi Lunke pipe, preparation metathesis polymerization catalyst solution.Then, add that 5.0g (25mmol) obtains in synthesis example 21,3-two sulphur three rings [5,4,0,1 ^6.9]-7-dodecylene (endo isomer) immerses in the oil bath that is adjusted into 60 ℃, carries out polymerization in 4 hours.

Polymer fluid flow into 150ml contain 0.1% 2, the acetone of 6-di-t-butyl-4-hydroxytoluene is separated out polymkeric substance.After the filter solvents, the polymkeric substance of recovery drying at room temperature 8 hours in Vacuumdrier obtains the 1.5g polymkeric substance.

¹The H-NMR spectroscopic analysis confirms that the polymkeric substance that obtains is 1,3-two sulphur three rings [5,4,0,1 ^6,9The Romp polymer of]-7-dodecylene.

270MHz ¹The measurement result of H-NMR: δ (CDCl ₃): 1.2～3.1 (10H), 3.9 (2H), 5.3 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 7,000, and it is 370 ℃ that 10% thermogravimetric amount reduces temperature.

This polymkeric substance of dissolving in chloroform, curtain coating is made the film of thick 100 μ m on the PET film.Specific refractory power (the n of this film _d) be 1.647, Abbe constant is 22.In addition, total light penetration be 88%,

Embodiment 4

Under reduced pressure with packed into the 200ml four-hole boiling flask of magnet rotor of fan heater drying, with nitrogen replacement.Add therein that 1.5mg obtains in embodiment 31,3-two sulphur three rings [5,4,0,1 ^6,9The Romp polymer of]-7-dodecylene and the vinyl trichloride of 50ml, stirring and dissolving under the room temperature.Add 7.1g (38.2mmol) p-toluene sulfonyl hydrazide and 4.9g (38.2mmol) N in this solution, N '-dimethylcyclohexylamine was 110 ℃ of reactions 4 hours.After reaction finishes, the reaction solution cool to room temperature, the reaction solution cool to room temperature is put in the 150ml methyl alcohol, and polymkeric substance is separated out.Behind the polymer filtration of separating out, in the 50ml chloroform, dissolve, filter not solvent components.Filtrate is put in the 150ml methyl alcohol, and polymkeric substance is separated out.After the filtration, the polymkeric substance of recovery with 100 ℃ of dryings 5 hours, obtains the 1.2g polymkeric substance in Vacuumdrier. ¹The H-NMR spectroscopic analysis confirms that the polymkeric substance that obtains is 1,3-two sulphur three rings [5,4,0,1 ^6,9The hydrogenation thing of]-7-dodecylene Romp polymer.

270MHz ¹H-NMR measurement result: δ (CDCl ₃): 1.4～3.6 (10H), 5.2～5.6 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 7,000.Suppress this polymkeric substance down at 220 ℃, make the film of thick 100 μ m.The light penetration of this film is 89%, specific refractory power (n _d) be 1.601, Abbe constant is 43.

Embodiment 5

Under reduced pressure, fully replace with nitrogen with packed into the 100ml Shi Lunke pipe of magnet rotor of fan heater drying.The molybdenum complex that adds above-mentioned general formula (11) expression of 76mg (0.1mmol) therein.With dry chloroform of syringe weighing 45ml in this Shi Lunke pipe and 23mg (0.17mmol) phenyl vinyl sulfide, preparation metathesis polymerization catalyst solution.Then, add that 5.0g (25mmol) obtains in synthesis example 11,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene immerses in the oil bath that is adjusted into 60 ℃, carries out polymerization in 4 hours.

Polymer fluid flow into 150ml contain 0.1% 2, in the acetone of 6-di-t-butyl-4-hydroxytoluene, polymkeric substance is separated out.After the filter solvents, the polymkeric substance of recovery drying at room temperature 8 hours in Vacuumdrier obtains the 2.6g polymkeric substance.

¹H-NMR spectrum confirms that the polymkeric substance that obtains is 1,3-two sulphur three rings-[5,4,0,1 ^6,9The Romp polymer of]-7-dodecylene.

270MHz ¹The measurement result of H-NMR: δ (CDCl ₃): 1.2～3.1 (10H), 3.9 (2H), 5.3 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 23,000, and it is 370 ℃ that 10% thermogravimetric amount reduces temperature.

This polymkeric substance of dissolving in chloroform, curtain coating on the PET film is made the film of thick 100 μ m.Specific refractory power (the n of this film _d) be 1.657, Abbe constant is 20.In addition, total light penetration is 88%.

Embodiment 6

Under reduced pressure, fully replace with nitrogen with packed into the 100ml Shi Lunke pipe of magnet rotor of fan heater drying.The ruthenium complex that adds above-mentioned general formula (10) expression of 85mg (0.1mmol) therein.With dry chloroform of syringe weighing 45ml in this Shi Lunke pipe and 23mg (0.17mmol) phenyl vinyl sulfide, preparation metathesis polymerization catalyst solution.Then, add the 12-methyl isophthalic acid that 5.3g (25mmol) obtains in synthesis example 3,3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene immerses in the oil bath that is adjusted into 60 ℃, carries out polymerization in 4 hours.

Polymer fluid flow into 150ml contain 0.1% 2, in the acetone of 6-di-t-butyl-4-hydroxytoluene, polymkeric substance is separated out.After the filter solvents, the polymkeric substance of recovery drying at room temperature 8 hours in Vacuumdrier obtains the 2.7g polymkeric substance.

¹H-NMR spectrum confirms that the polymkeric substance that obtains is the 12-methyl isophthalic acid, 3-two sulphur three rings-[5,4,0,1 ^6,9The Romp polymer of]-7-dodecylene.

270MHz ¹H-NMR measurement result: δ (CDCl ₃): 1.2～3.1 (12H), 3.9 (2H), 5.3 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 14,000, and it is 380 ℃ that 10% thermogravimetric amount reduces temperature.

This polymkeric substance of dissolving in chloroform, curtain coating on the PET film is made the film of thick 100 μ m.Specific refractory power (the n of this film _d) be 1.643, Abbe constant is 25.In addition, all light penetration is 88%.

Embodiment 7

Under reduced pressure, fully replace with nitrogen with packed into the 50ml Shi Lunke pipe of magnet rotor of fan heater drying.The ruthenium complex that adds above-mentioned general formula (10) expression of 13.2mg (15.5 μ mol) therein.With dry chloroform of syringe weighing 10ml in this Shi Lunke pipe and 140.3mg (1.03mmol) phenyl vinyl sulfide, preparation metathesis polymerization catalyst solution.

On the other hand, under reduced pressure with packed into the 500ml four-hole boiling flask of magnet rotor of fan heater drying, with nitrogen replacement.Add the 2-thia-1 that 23.6g (155.3mmol) obtains in synthesis example 4 therein, 2-dihydro Dicyclopentadiene (DCPD) immerses in the oil bath that is adjusted into 60 ℃.After carrying out stirring in 30 minutes, add all metathesis polymerization catalyst solutions for preparing of amount, carry out polymerization in 4 hours.Polymer fluid flow into 300ml contain 0.1% 2, in the acetone of 6-di-t-butyl-4-hydroxytoluene, polymkeric substance is separated out.After the filtration, the polymkeric substance of recovery drying at room temperature 8 hours in Vacuumdrier obtains the 20.6g polymkeric substance.

¹The H-NMR spectroscopic analysis confirms that the polymkeric substance that obtains is a 2-thia-1, the Romp polymer of 2-dihydro Dicyclopentadiene (DCPD).

270MHz ¹H-NMR measurement result: δ (CDCl ₃): 1.4～3.6 (10H), 5.2～5.6 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 72,000.

This polymkeric substance of dissolving in chloroform, curtain coating on the PET film is made the film of thick 100 μ m.Specific refractory power (the n of this film _d) be 1.590, Abbe constant is 41.In addition, total light penetration is 89%.

Embodiment 8

Under reduced pressure with packed into the 300ml four-hole boiling flask of magnet rotor of fan heater drying, with nitrogen replacement.Add the 2-thia-1 that 2.7g obtains therein in embodiment 7, the Romp polymer of 2-dihydro Dicyclopentadiene (DCPD) and 120ml orthodichlorobenzene, stirring at room dissolving.Add 16.5g (88.8mmol) p-toluene sulfonyl hydrazide and 11.3g (88.8mmol) N in this solution, N '-dimethylcyclohexylamine carries out reaction in 4 hours under 110 ℃.After reaction finished, the reaction solution cool to room temperature was put in the 300ml methyl alcohol, and polymkeric substance is separated out.Behind the polymer filtration of separating out, in the 100ml chloroform, dissolve, filter insoluble composition.Filtrate is put in the 300ml methyl alcohol again, and polymkeric substance is separated out.After the filtration, the polymkeric substance of recovery in 100 ℃ times dry 8 hours, obtains the 2.7g polymkeric substance in Vacuumdrier. ¹The H-NMR spectroscopic analysis confirms that the polymkeric substance that obtains is a 2-thia-1, the hydride of 2-dihydro Dicyclopentadiene (DCPD) Romp polymer.

270MHz ¹H-NMR δ measurement result: (CDCl ₃): the weight-average molecular weight (Mw) of 1.4～3.6 (10H), 5.2～5.6 (2H) this polymkeric substance is 72,000.

With 220 ℃ of these polymkeric substance of pressure, make the film of thick 100 μ m.Specific refractory power (the n of this film _d) be 1.583, Abbe constant is 46.In addition, total light penetration is 89%.

Embodiment 9

Under reduced pressure, fully replace with nitrogen with packed into the 100ml Shi Lunke pipe of magnet rotor of fan heater drying.The ruthenium complex that adds above-mentioned general formula (10) expression of 21mg (25 μ mol) therein.With dry chloroform of syringe weighing 46ml in this Shi Lunke pipe and 34mg (0.25mmol) phenyl vinyl sulfide, preparation metathesis polymerization catalyst solution.Then, add the 2-thia-1 that 3.8g (25mmol) obtains in synthesis example 5,2-dihydro Dicyclopentadiene (DCPD) (isomer) immerses in the oil bath that is adjusted into 60 ℃, carries out polymerization in 5 hours.

Polymer fluid flow into 150ml contain 0.1% 2, in the acetone of 6-di-t-butyl-4-hydroxytoluene, polymkeric substance is separated out.After the filtration, the polymkeric substance of recovery drying at room temperature 8 hours in Vacuumdrier obtains the 1.1g polymkeric substance.

¹The H-NMR spectroscopic analysis confirms that the polymkeric substance that obtains is a 2-thia-1, the Romp polymer of 2-dihydro Dicyclopentadiene (DCPD).

270MHz ¹H-NMR measurement result: δ (CDCl ₃): 1.4～3.6 (10H), 5.2～5.6 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 18,000.

This polymkeric substance of dissolving in chloroform, curtain coating on the PET film is made the film of thick 100 μ m.Specific refractory power (the n of this film _d) be 1.590, Abbe constant is 41.In addition, total light penetration is 89%.

Embodiment 10

Under reduced pressure with packed into the 200ml four-hole boiling flask of magnet rotor of fan heater drying, with nitrogen replacement.Add the 2-thia-1 that 1.0g obtains therein in embodiment 9, the Romp polymer of 2-dihydro Dicyclopentadiene (DCPD) and 45ml orthodichlorobenzene, stirring at room dissolving.Add 6.1g (32.9mmol) p-toluene sulfonyl hydrazide and 4.2g (32.9mmol) N in this solution, N '-dimethylcyclohexylamine was 110 ℃ of reactions 4 hours.After reaction finished, the reaction solution cool to room temperature was put in the 150ml methyl alcohol, and polymkeric substance is separated out.Behind the polymer filtration of separating out, in the 50ml chloroform, dissolve, filter insoluble composition.Filtrate is put in the 150ml methyl alcohol again, and polymkeric substance is separated out.After the filtration, the polymkeric substance of recovery in 100 ℃ of dryings 5 hours, obtains the 0.9g polymkeric substance in Vacuumdrier. ¹The H-NMR spectroscopic analysis confirms that the polymkeric substance that obtains is a 2-thia-1, the hydride of 2-dihydro Dicyclopentadiene (DCPD) Romp polymer.

270MHz ¹The H-NMR measurement result, δ (CDCl ₃): 1.4～3.6 (10H), 5.2～5.6 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 18,000.

Suppress this polymkeric substance down at 220 ℃, make the film of thick 100 μ m.The light penetration of this film is 90%, specific refractory power (n _d) be 1.57, Abbe constant is 45.

Embodiment 11

Under reduced pressure, fully replace with nitrogen with packed into the 50ml Shi Lunke pipe of magnet rotor of fan heater drying.The molybdenum complex that adds above-mentioned general formula (11) expression of 7.6mg (10 μ mol) therein.With dry chloroform of syringe weighing 4.6ml in this Shi Lunke pipe and 3.4mg (25 μ mol) phenyl vinyl sulfide, preparation metathesis polymerization catalyst solution.Then, add the 2-thia-1 that 0.38g (2.5mmol) obtains in synthesis example 4,2-dihydro Dicyclopentadiene (DCPD) immerses in the oil bath that is adjusted into 60 ℃ polymerized at room temperature 30 minutes.

Polymer fluid flow into 150ml contain 0.1% 2, in the acetone of 6-di-t-butyl-4-hydroxytoluene, polymkeric substance is separated out.After the filtration, the polymkeric substance of recovery drying at room temperature 8 hours in Vacuumdrier obtains the 0.37g polymkeric substance.

¹The H-NMR spectroscopic analysis confirms that the polymkeric substance that obtains is a 2-thia-1, the Romp polymer of 2-dihydro Dicyclopentadiene (DCPD).

270MHz ¹The H-NMR measurement result, δ (CDCl ₃): 1.4～3.6 (10H), 5.2～5.6 (2H)

The weight-average molecular weight of this polymkeric substance (Mw) is 100,000.

This polymkeric substance of dissolving in chloroform, curtain coating on the PET film is made the film of thick 100 μ m.Specific refractory power (the n of this film _d) be 1.590, Abbe constant is 41.In addition, total light penetration be 89%,

[comparative example 1]

Replace 1 of 5.0g beyond using the 20.5g Dicyclopentadiene (DCPD), 3-two sulphur three rings [5,4,0,1 ^6,9]-7-dodecylene adopts the method polymerization identical with embodiment 1, obtains the Romp polymer of 20.3g Dicyclopentadiene (DCPD).The polystyrene conversion weight-average molecular weight of the Romp polymer of this Dicyclopentadiene (DCPD) is 90,000.

In addition, use the Romp polymer of this Dicyclopentadiene (DCPD) of 20g to replace 1 of 3.5g, 3-two sulphur three rings [5,4,0,1 ^6,9Beyond the Romp polymer of]-7-dodecylene, carry out hydrogenation, obtain the hydrogenation thing of Dicyclopentadiene (DCPD) Romp polymer by method similarly to Example 2.The weight-average molecular weight of this hydrogenation thing is 90,000, and second-order transition temperature is 95 ℃.

In chloroform, dissolve the polymer poly compound that obtains, make the film of thick 100 μ m by curtain coating.

The light penetration of this film is 90%, specific refractory power (n _d) be 1.531, Abbe constant is 58.

[comparative example 2]

In chloroform, dissolve commercially available polystyrene (weight-average molecular weight is 190,000, and second-order transition temperature is 87 ℃), make the film of thick 100 μ m by curtain coating.

The light penetration of this film is 88%, specific refractory power (n _d) be 1.591, Abbe constant is 31.

[comparative example 3]

In methylene dichloride, dissolve commercially available polycarbonate (weight-average molecular weight is 190,000, and second-order transition temperature is 147 ℃), make the film of thick 100 μ m by curtain coating.

The light penetration of this film is 89%, specific refractory power (n _d) be 1.584, Abbe constant is 31.

[comparative example 4]

The commercially available acrylonitritrile-styrene resin of dissolving in methylene dichloride (weight-average molecular weight is 130,000, second-order transition temperature be that 106 ℃, acrylonitrile content are 29wt%) is made the film of thick 100 μ m by curtain coating.

The light penetration of this film is 90%, specific refractory power (n _d) be 1.564, Abbe constant is 35.

Understand the present invention in detail with reference to specific embodiment, but carry out various changes or correction not breaking away from the spirit and scope of the present invention, this it will be apparent to those skilled in the art that.

Japanese patent application (the special 2005-162287 of hope) of filing an application in the Japanese patent application (the special 2005-150640 of hope) of filing an application in the Japanese patent application that the application filed an application based on May 24th, 2005 (the special 2005-150639 of hope), on May 24th, 2005, on June 2nd, 2005 and the Japanese patent application (the special 2006-071438 of hope) of filing an application on March 15th, 2006, its content here is used as with reference to writing.

Industrial applicibility

Sulfur-containing cycloolefin resin of the present invention has high transparent and high index of refraction, can be used as the raw material such as various plastic lens or prismatic lens. Therefore, industrial value of the present invention is remarkable.

Claims (10)

1. sulfur-containing cycloolefin resin, it comprises the unit of following general formula (1) expression, and the weight-average molecular weight of this resin is 1,000～1,000,000;

In the formula: R ₁～R ₆Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₃～R ₆Optional is halogen group, R ₃And R ₄, R ₅And R ₆Optional formation contains the ring of carbon, oxygen, sulphur or nitrogen; R ₇, R ₇', R ₈, R ₈' _'Represent hydrogen atom, methyl respectively independently; Expression singly-bound or two key; L represents 0 or 1, and m represents 0.

2. according to the described sulfur-containing cycloolefin resin of claim 1, it comprises the unit of following general formula (2) expression, and the weight-average molecular weight of this resin is 1,000～1, and 000,000, the unit of described general formula (2) expression is R in the above-mentioned general formula (1) ₇, R ₈, R ₇' _'And R ₈' _'Be hydrogen atom, m is 0 unit;

In the formula, R ₁₁～R ₁₄Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, heterogeneous ring compound, the halogen group of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₁₁And R ₁₂, R ₁₃And R ₁₄Optional formation contains the ring of carbon, oxygen, sulphur or nitrogen; Expression singly-bound or two key; P is 0 or 1.

3. according to the described sulfur-containing cycloolefin resin of claim 1, it comprises R in the described general formula (1) ₃～R ₆, R ₇' _'And R ₈' _'Be hydrogen atom, m, l are 0 unit, and the weight-average molecular weight of this resin is 1000～1,000,000.

4. the manufacture method of a sulfur-containing cycloolefin resin, it is used for making the unit that comprises following general formula (1) expression, and weight-average molecular weight is 1,000～1,000,000 sulfur-containing cycloolefin resin, this method comprises, makes the sulphur-containing cyclic compound of following general formula (3) expression carry out metathesis polymerization;

In the formula, R ₁～R ₆Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₃～R ₆Optional is halogen group, R ₃And R ₄, R ₅And R ₆Optional formation contains the ring of carbon, oxygen, sulphur or nitrogen; R ₇, R ₇' _', R ₈, R ₈' _'Represent hydrogen atom, methyl respectively independently; Expression singly-bound or two key; L represents 0 or 1, and m represents 0;

In the formula, R ₁₅～R ₂₀Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₁₇～R ₂₀Optional is halogen group, R ₁₇And R ₁₈, R ₁₉And R ₂₀Optional formation contains the ring of carbon, oxygen, sulphur or nitrogen; R ₂₁And R ₂₂Represent hydrogen atom, methyl respectively independently; Q is 1 or 2, and r represents 0.

5. according to the manufacture method of the described sulfur-containing cycloolefin resin of claim 4, wherein, after carrying out metathesis polymerization, the sulphur-containing cyclic compound that makes described general formula (3) expression carries out hydrogenation.

6. according to the manufacture method of the described sulfur-containing cycloolefin resin of claim 4, wherein, make R in the described general formula (3) ₂₁And R ₂₂Be hydrogen atom, r is that the sulphur-containing cyclic compound of 0 the following general formula of usefulness (4) expression carries out metathesis polymerization.

In the formula, R ₂₅～R ₂₈Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, heterogeneous ring compound, the halogen group of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₂₅And R ₂₆, R ₂₇And R ₂₈Optional formation contains the ring of carbon, oxygen, sulphur, nitrogen; T is 1 or 2.

7. according to the manufacture method of the described sulfur-containing cycloolefin resin of claim 6, wherein, behind the sulphur-containing cyclic compound metathesis polymerization that makes described general formula (4) expression, carry out hydrogenation.

8. optical material, it comprises sulfur-containing cycloolefin resin, and described sulfur-containing cycloolefin resin comprises the unit of following general formula (1) expression, and the weight-average molecular weight of this resin is 1,000～1,000,000;

In the formula, R ₁～R ₆Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₃～R ₆Optional is halogen group, R ₃And R ₄, R ₅And R ₆Optional formation contains the ring of carbon, oxygen, sulphur, nitrogen; R ₇, R ₇' _'And R ₈, R ₈' _'Represent hydrogen atom, methyl respectively independently; Expression singly-bound or two key; L represents 0 or 1, and m represents 0.

9. lens, it comprises sulfur-containing cycloolefin resin, and described sulfur-containing cycloolefin resin comprises the unit of following general formula (1) expression, and the weight-average molecular weight of this resin is 1,000～1,000,000;

In the formula, R ₁～R ₆Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₃～R ₆Optional is halogen group, R ₃And R ₄, R ₅And R ₆Optional formation contains the ring of carbon, oxygen, sulphur, nitrogen; R ₇, R ₇' _'And R ₈, R ₈' _'Represent hydrogen atom, methyl respectively independently; Expression singly-bound or two key; L represents 0 or 1, and m represents 0.

10. condensing lens, it comprises sulfur-containing cycloolefin resin, and described sulfur-containing cycloolefin resin comprises the unit of following general formula (1) expression, and the weight-average molecular weight of this resin is 1,000～1,000,000;

In the formula, R ₁～R ₆Alkyl, the aralkyl of carbonatoms 1～20, the aromatic series base of carbonatoms 1～20, cyano group, the alkoxyl group of carbonatoms 1～10, the heterogeneous ring compound of representing hydrogen atom, carbonatoms 1～20 respectively independently; R ₃～R ₆Optional is halogen group, R ₃And R ₄, R ₅And R ₆Optional formation contains the ring of carbon, oxygen, sulphur, nitrogen; R ₇, R ₇' _', R ₈, R ₈' _'Represent hydrogen atom, methyl respectively independently; Expression singly-bound or two key; L represents 0 or 1, and m represents 0.