JP3705993B2 - Metal-containing episulfide compound and method for producing the same - Google Patents
Metal-containing episulfide compound and method for producing the same Download PDFInfo
- Publication number
- JP3705993B2 JP3705993B2 JP2000112530A JP2000112530A JP3705993B2 JP 3705993 B2 JP3705993 B2 JP 3705993B2 JP 2000112530 A JP2000112530 A JP 2000112530A JP 2000112530 A JP2000112530 A JP 2000112530A JP 3705993 B2 JP3705993 B2 JP 3705993B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- epithiopropylthio
- bis
- general formula
- episulfide compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 episulfide compound Chemical class 0.000 title claims description 60
- 229910052751 metal Inorganic materials 0.000 title claims description 52
- 239000002184 metal Substances 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000007983 Tris buffer Substances 0.000 claims description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000010936 titanium Chemical group 0.000 claims description 10
- 229910052719 titanium Chemical group 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000078 germane Inorganic materials 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 37
- 229920000642 polymer Polymers 0.000 description 27
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- 230000003287 optical effect Effects 0.000 description 23
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- 230000000704 physical effect Effects 0.000 description 9
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
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- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 4
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
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- 238000010898 silica gel chromatography Methods 0.000 description 4
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- DXNAKHSYGOEAGV-UHFFFAOYSA-N 2-methyl-3-(3-methylthiiran-2-yl)sulfanylthiirane Chemical compound CC1SC1SC1C(C)S1 DXNAKHSYGOEAGV-UHFFFAOYSA-N 0.000 description 2
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Description
【0001】
【発明の属する技術分野】
本発明は、新規な金属含有エピスルフィド化合物及びその製造方法に関し、さらに詳しくは、屈折率及びアッベ数の高い光学材料の原料として有用な金属含有エピスルフィド化合物、及びそれを効率よく製造する方法に関するものである。
【0002】
【従来の技術】
プラスチックはガラスに比較して軽量で割れにくく染色が容易であるため、近年、レンズ等の各種光学用途に多用されている。そして、光学用プラスチック材料としては、ポリ( ジエチレングリコールビスアリルカーボネート)(CR−39)やポリ( メチルメタクリレート) が、一般的に用いられている。しかしながら、これらのプラスチック材料は1.50以下の屈折率を有するため、これらのプラスチック材料で例えばレンズを構成した場合、レンズの度数が強くなるほどレンズが厚くなり、軽量を長所とするプラスチックレンズの優位性が損なわれてしまう。特に強度の凹レンズは、レンズ周辺が肉厚となり、複屈折や色収差が生じることから好ましくない。さらに眼鏡用途において肉厚のレンズは、審美性を悪くする傾向にある。肉薄のレンズを得るためには、レンズを構成する材料の屈折率を高めることが効果的である。一般的にガラスやプラスチックは、屈折率の増加に伴いアッベ数が減少し、その結果、それらの色収差は増加する。従って、高い屈折率とアッベ数を兼ね備えたプラスチック材料が望まれている。
このような性能を有するプラスチック材料としては、例えば(1) 分子内に臭素を有するポリオールとポリイソシアネートとの重付加により得られるポリウレタン(特開昭58−164615号公報)、(2) ポリチオールとポリイソシアネートとの重付加により得られるポリチオウレタン(特公平4 −58489 号公報、特公平5 −148340号公報)が提案されている。そして、特に(2) のポリチオウレタンの原料となるポリチオールとして、イオウ原子の含有率を高めた分岐鎖(ポリチオール特開平2 −270859号公報、特開平5 −148340号公報)や、イオウ原子を高めるためジチアン構造を導入したポリチオール(特公平6 −5323号公報、特開平7 −118390号公報)が提案されている。さらに、(3) エピサルファイドを重合官能基としたアルキルサルファイドの重合体が提案されている(特開平9 −72580 号公報、特開平9 −110979号公報)。
【0003】
しかしながら上記(1) のポリウレタンは、屈折率がわずかに改良されているものの、アッベ数が低く、かつ耐光性に劣る上、比重が高く、軽量性が損なわれるなどの欠点を有している。また(2) のポリチオウレタンのうち、原料のポリチオールして高イオウ含有率のポリチオールを用いて得られたポリチオウレタンは、屈折率が例えば1.60〜1.68程度に高められているが、同等の屈折率を有する光学用無機ガラスに比べてアッベ数が低く、さらにアッベ数を高めなければならないという課題を有している。一方、(3) のアルキルサルファイド重合体は、一例としてアッベ数が36において、屈折率が1.70に高められており、この重合体を用いて得られたレンズは、著しく肉薄化され、かつ軽量化されているが、屈折率とアッベ数を同時に、さらに高めたプラスチック材料が望まれている。
【0004】
【発明が解決しようとする課題】
本発明は、このような事情のもとで、屈折率とアッベ数が共に高く、かつ耐熱性、耐候性、透明性などに優れる光学材料を与えることのできる新規な化合物及びこのものを効率よく製造する方法を提供することを目的とするものである。
【0005】
【課題を解決するための手段】
本発明者は、上記目的を達成するために鋭意研究を重ねた結果、シリコン、ゲルマニウム、スズ、チタンなどの金属原子にエピスルフィドの誘導体が結合してなる金属含有エピスルフィド化合物が新規な化合物であり、上記の目的に適合しうること、そして、このものは、特定の方法により、効率よく得られることを見出し、この知見に基づいて本発明を完成するに至った。
すなわち、本発明は、(1)一般式 (1)
【0006】
【化4】
【0007】
(式中、Mはケイ素、ゲルマニウム、スズまたはチタンを示し、xは1〜4の整数を示し、yは1または2を示す。)
で表される金属含有エピスルフィド化合物、
(2)一般式MZ4 (Mは上記と同じであり、Zはハロゲン原子を示す)で表される四ハロゲン化金属と2:3 −エピチオメルカプトプロパンを反応させることを特徴とする、一般式(1−a)
【0008】
【化5】
【0009】
(式中、Mは上記と同じである。)
で表される金属含有エピスルフィド化合物の製造方法、および
(3)上記四ハロゲン化金属のクロロメチル化体またはビニル置換体と2:3 −エピチオメルカプトプロパンを反応させることを特徴とする一般式(1)
【0010】
【化6】
【0011】
(式中、Mは上記と同じであり、xは1〜3の整数を示し、yは1または2を示す。)
で表される金属含有エピスルフィド化合物の製造方法、を提供するものである。
【0012】
【発明の実施の形態】
本発明の金属含有スルフィド化合物は、一般式 (1)
【0013】
【化7】
【0014】
(式中、Mはケイ素、ゲルマニウム、スズまたはチタンを示し、xは1〜4の整数を示し、yは1または2を示す。)
で表される新規化合物であり、上記一般式(1) から明らかなように、ケイ素、ゲルマニウム、スズおよびチタンから選ばれる金属原子に4つとも同一の、あるいは異なる二種のエピスルフィド誘導体が結合していることを特徴とするものである。
ある物質の屈折率は、構成元素の屈折率(原子屈折)の増加および分子容の減少と共に増加する。この原子屈折は原子番号と共に増加する。従って、骨格が炭素で構成されたエピスルフィド化合物に比べると、ケイ素、ゲルマニウム、スズ、チタンなどの金属原子を導入した本発明の金属含有エピスルフィド化合物の屈折率は著しく高まり、この化合物を原料として得られた重合体の屈折率も増加することとなる。
本発明の金属含有エピスルフィド化合物は4官能性であり、その官能基間はできるだけ少ない元素で構成されているため、架橋密度の増加により分子容の減少が引き起こされ、その結果、本発明の金属含有エピスルフィド化合物を用いて得られた重合体の屈折率は、増加する。従って、高架橋密度を維持しアッベ数を低下させることなく屈折率を高めるために、一般式(1) においてyで示されるメチレン鎖数は1または2でなければならない。これら置換基を一種(一般式(1) においてx=4 )、もしくは二種(一般式(1) においてx=1〜3)結合させることで、本発明の金属含有エピスルフィド化合物を用いて得られる重合体の光学特性、熱的特性および機械特性を調整することができる。
【0015】
上記一般式(1) で表される金属含有エピスルフィド化合物として具体的には、テトラキス(2:3 −エピチオプロピルチオ)シラン、テトラキス(2:3 −エピチオプロピルチオ)ゲルマン、テトラキス(2:3 −エピチオプロピルチオ)スズ、テトラキス(2:3 −エピチオプロピルチオ)チタン、トリス(2:3 −エピチオプロピルチオ)−2 −チア−4:5 −エピチオペンチルシラン、トリス(2:3 −エピチオプロピルチオ)−2 −チア−4:5 −エピチオペンチルゲルマン、トリス(2:3 −エピチオプロピルチオ)−2 −チア−4:5 −エピチオペンチルスズ、トリス(2:3 −エピチオプロピルチオ)−2 −チア−4:5 −エピチオペンチルチタン、トリス(2:3 −エピチオプロピルチオ)−3 −チア−5:6 −エピチオヘキシルシラン、トリス(2:3 −エピチオプロピルチオ)−3 −チア−5:6 −エピチオヘキシルゲルマン、トリス(2:3 −エピチオプロピルチオ)−3 −チア−5:6 −エピチオヘキシルスズ、トリス(2:3 −エピチオプロピルチオ)−3 −チア−5:6 −エピチオヘキシルチタン、トリス(2 −チア−4:5 −エピチオペンチル)−2:3 −エピチオプロピルチオゲルマンなどが挙げられる。
この一般式(1) で表される金属含有エピスルフィド化合物は、その構造によって、以下に示す本発明の方法により、効率よく製造することができる。
(1)一般式(1) において、x=4 の化合物は、反応式
【0016】
【化8】
【0017】
に従い、2:3 −エピチオメルカプトプロパンと一般式(1) におけるMに相当する金属の四ハロゲン化物を塩基の存在下、テトラヒドロフラン、ジメチルスフォキサイド、ジメチルフォルムアミドなどの溶媒中で反応させることで得られる。四ハロゲン化物としては四塩化物が好ましい。反応温度は20℃〜−30℃であり、塩基としてピリジン、トリエチルアミン、1,8 −ジアザビシクロ[5,4,0] −7−ウンデセン等が好ましく用いられる。なお、原料の一つとして用いられる2:3 −エピチオメルカプトプロパンは、公知の方法、例えば「ジャーナル・オブ・ケミカル・ソサエティ(J. Chem. Soc. )」第2665ページ(1960年)に記載の方法に従って調製することができる。
(2)一般式(1) において、x=1〜3、y=1の化合物は、反応式
【0018】
【化9】
【0019】
に従い得られる。すなわち、一般式(1) におけるMに相当する金属の四塩化物をジアゾメタンとジクロロメタンやエチルエーテルなどの溶媒中、10〜30℃にて反応させ相当する金属のクロロメチル化体を生成させる。エチルエーテルを溜去し単離されたこの生成物を、あらかじめ塩基と2:3 −エピチオメルカプトプロパンで生成させたチオレートとジクロロメタン、メタノール、エタノール、エチルエーテル、テトラヒドロフラン、ジメチルスフォキサイド、ジメチルフォルムアミドやそれらの混合溶媒中で反応させる。この塩基としては、ナトリウムメトキサイド、ナトリウムエトキサイド、水素化ナトリウム、ノルマルブチルリチウムなどが用いられ、その添加量は金属に直接結合した塩素原子と当量である。
(3)一般式(1) においてx=1〜3、y=2の化合物は、反応式
【0020】
【化10】
【0021】
に従い得られる。すなわち、一般式(1) におけるMに相当する金属の四ハロゲン化物、すなわち一般式MZ4 で表される四ハロゲン化金属、好ましくは四塩化物をビニルマグネシウムブロマイドと0〜30℃で反応させ得られたビニル置換体を2:3 −エピチオメルカプトプロパンと、まず、塩基存在下、ジクロロメタン、テトラヒドロフラン、エチルエーテル、ジメチルスフォキサイド、ジメチルフォルムアミドやそれらの混合溶媒中、10℃〜−30℃で反応させ、次いで、ラジカル発生剤の存在下、40〜80℃で反応させる。この塩基としてピリジン、トリエチルアミン、1,8 −ジアザビシクロ[5,4,0] −7−ウンデセン等が、またラジカル発生剤として過酸化ベンゾイル、アゾビスジメチルブチロニトリル、アゾビスジメチルバレロニトリルなどが好ましく用いられる。この塩基の添加量は金属に直接結合した塩素原子と当量であり、また、ラジカル発生剤のそれはビニル基に対して0.01〜0.0001当量である。このビニル置換体と2:3 −エピチオメルカプトプロパンの反応において、ラジカル発生剤の存在下で加熱する代わりに、高圧水銀灯で350nmにおける強度が0.0〜100mW/cm2 の紫外線をテトラヒドロフランやノルマルヘキサン中、もしくは無溶媒にて照射することでも同じ化合物が得られる。
【0022】
次に、本発明の金属含有エピスルフィド化合物を用いて得られる光学材料について説明する。一般式(1) で表される金属含有エピスルフィド化合物は必須成分であり、一種用いてもよいし、二種以上を組み合わせて用いてもよい。さらに、この金属含有エピスルフィド化合物と、得られる重合体の物性などを適宜改良するための任意成分として、他のエピスルフィド化合物、エポキシ化合物および単独重合可能なビニルモノマーから選ばれる化合物とを重合させてもよい。
上記の適宜用いられる他のエピスルフィド化合物の例としては、ビス(β−エピチオプロピルチオ)メタン、1,2−ビス(β−エピチオプロピルチオ)エタン、1,3−ビス(β−エピチオプロピルチオ)プロパン、1,2−ビス(β−エピチオプロピルチオ)プロパン、1−(β−エピチオプロピルチオ)−2−(β−エピチオプロピルチオメチル)プロパン、1,4−ビス(β−エピチオプロピルチオ)ブタン、1,3−ビス(β−エピチオプロピルチオ)ブタン、1−(β−エピチオプロピルチオ)−3−(β−エピチオプロピルチオメチル)ブタン、1,5−ビス(β−エピチオプロピルチオ)ペンタン、1−(β−エピチオプロピルチオ)−4−(β−エピチオプロピルチオメチル)ペンタン、1,6−ビス(β−エピチオプロピルチオ)ヘキサン、1−(β−エピチオプロピルチオ)−5−(β−エピチオプロピルチオメチル)ヘキサン、1−(β−エピチオプロピルチオ)−2−〔(2−β−エピチオプロピルチオエチル)チオ〕エタン、1−(β−エピチオプロピルチオ)−2−[〔2−(2−β−エピチオプロピルチオエチル)チオエチル〕チオ]エタン等の鎖状有機化合物等を、また、テトラキス(β−エピチオプロピルチオメチル)メタン、1,1,1−トリス(β−エピチオプロピルチオメチル)プロパン、1,5−ビス(β−エピチオプロピルチオ)−2−(β−エピチオプロピルチオメチル)−3−チアペンタン、1,5−ビス(β−エピチオプロピルチオ)−2,4−ビス(β−エピチオプロピルチオメチル)−3−チアペンタン、1−(β−エピチオプロピルチオ)−2,2−ビス(β−エピチオプロピルチオメチル)−4−チアヘキサン、1,5,6−トリス(β−エピチオプロピルチオ)−4−(β−エピチオプロピルチオメチル)−3−チアヘキサン、1,8−ビス(β−エピチオプロピルチオ)−4−(β−エピチオプロピルチオメチル)−3,6−ジチアオクタン、1,8−ビス(β−エピチオプロピルチオ)−4,5ビス(β−エピチオプロピルチオメチル)−3,6−ジチアオクタン、1,8−ビス(β−エピチオプロピルチオ)−4,4−ビス(β−エピチオプロピルチオメチル)−3,6−ジチアオクタン、1,8−ビス(β−エピチオプロピルチオ)−2,4,5−トリス(β−エピチオプロピルチオメチル)−3,6−ジチアオクタン、1,8−ビス(β−エピチオプロピルチオ)−2,5−ビス(β−エピチオプロピルチオメチル)−3,6−ジチアオクタン、1,9−ビス(β−エピチオプロピルチオ)−5−(β−エピチオプロピルチオメチル)−5−〔(2−β−エピチオプロピルチオエチル)チオメチル〕−3,7−ジチアノナン、1,10−ビス(β−エピチオプロピルチオ)−5,6−ビス〔(2−β−エピチオプロピルチオエチル)チオ〕−3,6,9−トリチアデカン、1,11−ビス(β−エピチオプロピルチオ)−4,8−ビス(β−エピチオプロピルチオメチル)−3,6,9−トリチアウンデカン、1,11−ビス(β−エピチオプロピルチオ)−5,7−ビス(β−エピチオプロピルチオメチル)−3,6,9−トリチアウンデカン、1,11−ビス(β−エピチオプロピルチオ)−5,7−〔(2−β−エピチオプロピルチオエチル)チオメチル〕−3,6,9−トリチアウンデカン、1,11−ビス(β−エピチオプロピルチオ)−4,7−ビス(β−エピチオプロピルチオメチル)−3,6,9−トリチアウンデカン等の分岐状有機化合物およびこれらの化合物のエピスルフィド基の水素の少なくとも1個がメチル基で置換された化合物等が、さらには1,3および1,4−ビス(β−エピチオプロピルチオ)シクロヘキサン、1,3および1,4−ビス(β−エピチオプロピルチオメチル)シクロヘキサン、ビス〔4−(β−エピチオプロピルチオ)シクロヘキシル〕メタン、2,2−ビス〔4−(β−エピチオプロピルチオ)シクロヘキシル〕プロパン、ビス〔4−(β−エピチオプロピルチオ)シクロヘキシル〕スルフィド、2,5−ビス(β−エピチオプロピルチオメチル)−1,4−ジチアン、2,5−ビス(β−エピチオプロピルチオエチルチオメチル)−1,4−ジチアン等の環状脂肪族有機化合物およびこれらの化合物のエピスルフィド基の水素の少なくとも1個がメチル基で置換された化合物、および1,3および1,4−ビス(β−エピチオプロピルチオ)ベンゼン、1,3および1,4−ビス(β−エピチオプロピルチオメチル)ベンゼン、ビス〔4−(β−エピチオプロピルチオ)フェニル〕メタン、2,2−ビス〔4−(β−エピチオプロピルチオ)フェニル〕プロパン、ビス〔4−(β−エピチオプロピルチオ)フェニル〕スルフィド、ビス〔4−(β−エピチオプロピルチオ)フェニル〕スルフォン、4,4' −ビス(β−エピチオプロピルチオ)ビフェニル等の芳香族有機化合物およびこれらの化合物のエピスルフィド基の水素の少なくとも1個がメチル基で置換された化合物等が挙げられ、これらは単独もしくは二種以上を組み合わせて用いてもよい。これらの使用量は、一般式(1) で表される金属含有エピスルフィド化合物の総量に対して0.01〜50モル%が好ましい。
【0023】
上記の適宜用いられるエポキシ化合物の例としては、ヒドロキノン、カテコール、レゾルシン、ビスフェノールA、ビスフェノールF、ビスフェノールスルフォン、ビスフェノールエーテル、ビスフェノールスルフィド、ビスフェノールスルフィド、ハロゲン化ビスフェノールA、ノボラック樹脂等の多価フェノール化合物とエピハロヒドリンの縮合により製造されるフェノール系エポキシ化合物;エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、1、3−プロパンジオール、1、4−ブタンジオール、1、6−ヘキサンジオール、ネオペンチルグリコール、グリセリン、トリメチロールプロパントリメタクリレート、ペンタエリスリトール、1、3−および1、4−シクロヘキサンジオール、1、3−および1、4−シクロヘキサンジメタノール、水添ビスフェノールA、ビスフェノルA・エチレンオキサイド付加物、ビスフェノルA・プロピレンオキサイド付加物等の多価アルコール化合物とエピハロヒドリンの縮合により製造されるアルコール系エポキシ化合物;アジピン酸、セバチン酸、ドデカンジカルボン酸、ダイマー酸、フタル酸、イソ、テレフタル酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、ヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、ヘット酸、ナジック酸、マレイン酸、コハク酸、フマール酸、トリメリット酸、ベンゼンテトラカルボン酸、ベンゾフェノンテトラカルボン酸、ナフタリンジカルボン酸、ジフェニルジカルボン酸等の多価カルボン酸化合物とエピハロヒドリンの縮合により製造されるグリシジルエステル系エポキシ化合物;エチレンジアミン、1,2−ジアミノプロパン、1,3−ジアミノプロパン、1,2−ジアミノブタン、1,3−ジアミノブタン、1,4−ジアミノブタン、1,5−ジアミノペンタン、1,6−ジアミノヘキサン、1,7−ジアミノヘプタン、1,8−ジアミノオクタン、ビス−(3−アミノプロピル)エーテル、1,2−ビス−(3−アミノプロポキシ)エタン、1,3−ビス−(3−アミノプロポキシ)−2,2' −ジメチルプロパン、1,2−、1,3−または1,4−ビスアミノシクロヘキサン、1,3−または1,4−ビスアミノメチルシクロヘキサン、1,3−または1,4−ビスアミノエチルシクロヘキサン、1,3−または1,4−ビスアミノプロピルシクロヘキサン、水添4,4' −ジアミノジフェニルメタン、イソホロンジアミン、1,4−ビスアミノプロピルピペラジン、m−またはp−フェニレンジアミン、2,4−または2,6−トリレンジアミン、m−またはp−キシリレンジアミン、1,5−または2,6−ナフタレンジアミン、4,4' −ジアミノジフェニルメタン、4,4' −ジアミノジフェニルエーテル、2,2−(4,4' −ジアミノジフェニル)プロパン等の一級ジアミン、N,N' −ジメチルエチレンジアミン、N,N' −ジメチル−1,2−ジアミノプロパン、N,N' −ジメチル−1,3−ジアミノプロパン、N,N' −ジメチル−1,2−ジアミノブタン、N,N' −ジメチル−1,3−ジアミノブタン、N,N' −ジメチル−1,4−ジアミノブタン、N,N' −ジメチル−1,5−ジアミノペンタン、N,N' −ジメチル−1,6−ジアミノヘキサン、N,N' −ジメチル−1,7−ジアミノヘプタン、N,N' −ジエチルエチレンジアミン、N,N' −ジエチル−1,2−ジアミノプロパン、N,N' −ジエチル−1,3−ジアミノプロパン、N,N' −ジエチル−1,2−ジアミノブタン、N,N' −ジエチル−1,3−ジアミノブタン、N,N' −ジエチル−1,4−ジアミノブタン、N,N' −ジエチル−1,6−ジアミノヘキサン、ピペラジン、2−メチルピペラジン、2,5−または2,6−ジメチルピペラジン、ホモピペラジン、1,1−ジ−(4−ピペリジル)−メタン、1,2−ジ−(4−ピペリジル)−エタン、1,3−ジ−(4−ピペリジル)−プロパン、1,4−ジ−(4−ピペリジル)−ブタン等のニ級ジアミンとエピハロヒドリンの縮合により製造されるアミン系エポキシ化合物;3、4−エポキシシクロヘキシル−3、4−エポキシシクロヘキサンカルボキシレート、ビニルシクリヘキサンジオキサイド、2−(3、4−エポキシシクロヘキシル)−5、5−スピロ−3、4−エポキシシクロヘキサン−メタ−ジオキサン、ビス(3、4−エポキシシクロヘキシル)アジペート等の脂環式エポキシ化合物;シクロペンタジエンエポキシド、エポキシ化大豆油、エポキシ化ポリブタジエン、ビニルシクロヘキセンエポキシド等の不飽和化合物のエポキシ化により製造されるエポキシ化合物;上述の多価アルコール、フェノール化合物とジイソシアネートおよびグリシドール等から製造されるウレタン系エポキシ化合物等が挙げられ、これらは単独もしくは二種以上を組み合わせて用いてもよい。これらの使用量は、一般式(1) で表される金属含有エピスルフィド化合物の総量に対して0.01〜5モル%が好ましい。
【0024】
上記の適宜用いられる単独重合可能なビニルモノマーの例としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、ポリエチレングリコールジアクリレート、ポリエチレングリコールジメタクリレート、1,3−ブチレングリコールジアクリレート、1,3−ブチレングリコールジメタクリレート、1,6−ヘキサンジオールジアクリレート、1,6−ヘキサンジオールジメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、ポリプロピレングリコールジアクリレート、ポリプロピレングリコールジメタクリレート、2,2−ビス〔4−(アクリロキシエトキシ)フェニル〕プロパン、2,2−ビス〔4−(メタクリロキシエトキシ)フェニル〕プロパン、2,2−ビス〔4−(アクリロキシ・ジエトキシ)フェニル〕プロパン、2,2−ビス〔4−(メタクリロキシ・ジエトキシ)フェニル〕プロパン、2,2−ビス〔4−(アクリロキシ・ポリエトキシ)フェニル〕プロパン、2,2−ビス〔4−(メタクリロキシ・ポリエトキシ)フェニル〕プロパン、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ビス(2,2,2−トリメチロールエチル)エーテルのヘキサアクリレート、ビス(2,2,2−トリメチロールエチル)エーテルのヘキサメタクリレート等の1価以上のアルコールとアクリル酸、メタクリル酸のエステル構造を有する化合物;アリルスルフィド、ジアリルフタレート、ジエチレングリコールビスアリルカーボネート等のアリル化合物;アクロレイン、アクリロニトリル、ビニルスルフィド等のビニル化合物;スチレン、α−メチルスチレン、メチルビニルベンゼン、エチルビニルベンゼン、α−クロロスチレン、クロロビニルベンゼン、ビニルベンジルクロライド、パラジビニルベンゼン、メタジビニルベンゼン等の芳香族ビニル化合物等が挙げられ、これらは単独もしくは二種以上を組み合わせて用いてもよい。これらの使用量は一般式(1) で表される金属含有エピスルフィド化合物の総量に対して0.01〜20モル%が好ましい。
【0025】
上記の重合性組成物には、本発明の目的が損なわれない範囲で、所望により、耐候性改良のため、紫外線吸収剤、酸化防止剤、着色防止剤、蛍光染料などの添加剤を適宜加えてもよい。また、重合反応向上のための触媒を適宜使用してもよく、例えばアミン類、フォスフィン類、第4級アンモニウム塩類、第4級ホスホニウム塩類、第3級スルホニウム塩類、第2級ヨードニウム塩類、鉱酸類、ルイス酸類、有機酸類、ケイ酸類、四フッ化ホウ酸等が効果的である。
本発明の金属含有エピスルフィド化合物を用いて得られる光学材料は、例えば以下に示す方法に従って製造することができる。
まず、上記重合性化合物、および必要に応じて用いられる各種添加剤を含む均一な組成物を調製する。次いで、この組成物を公知の注型重合法を用いて、ガラス製または金属製のモールドと樹脂性のガスケットを組み合わせた型の中に注入し、加熱して硬化させる。この際、成形後の樹脂の取り出しを容易にするためにあらかじめモールドを離型処理したり、この組成物に離型剤を混合してもよい。重合温度は、使用する化合物により異なるが、一般には−20〜150℃で、重合時間は0.5〜72時間程度である。重合後離型された重合体は通常の分散染料を用い、水もしくは有機溶媒中で容易に染色できる。この際さらに染色を容易にするために、染料分散液にキャリアーを加えてもよく、また加熱してもよい。このようにして得られた光学材料の用途は特に限定されるものではないが、プラスチックレンズ等の光学製品として特に好ましく用いられる。
【0026】
【実施例】
次に、本発明を実施例により、さらに具体的に説明するが、本発明は、これらの例によってなんら限定されるものではない。なお、実施例で得られた金属含有エピスルフィド化合物の物性、および応用例、比較応用例で得られた重合体の物性は、以下に示す方法に従って測定した。
<金属含有エピスルフィド化合物の物性>
屈折率(nd ) 、アッベ数(νd ):カルニュー社製精密屈折率計KPR−200を用いて25℃にて測定した。
<重合体の物性>
1) 屈折率(nd ) 、アッベ数(νd ): 上記と同様にして測定した。
2) 外 観: 肉眼により観察した。
3) 耐候性: サンシャインカーボンアークランプを装備したウエザーメーターにプラスチックレンズをセットし、200時間経過したところでプラスチックレンズを取り出し、試験前のプラスチックレンズと色相を比較した。評価基準は変化なし (○) 、わずかに黄変 (△) 、黄変 (×) とした。
4) 耐熱性: リガク社製TMA装置により0.5mmφのピンを用いて98mN(10gf)の荷重でTMA測定を行ない、10℃/minの昇温で得られたチャートのピーク温度により評価した。
5) 光学歪: シュリーレン法による目視観察を行なった。歪の無いものを○、歪のあるものを×と評価した。
【0027】
実施例1
テトラキス( 2:3 −エピチオプロピルチオ)ゲルマン(E1) ( 一般式 (1) においてM=Ge、x=4)の製造例
2:3 −エピチオプロピルメルカプタン(10.04g)のテトラヒドロフラン (94.5mL)溶液に乾燥ピリジン(10.47g)を−30℃にて加え5分間攪拌した後、その温度で四塩化ゲルマニウム(5.07g)のテトラヒドロフラン (47.2mL)溶液を2時間かけて滴下し、−20℃にて4時間攪拌した。この反応混合物に2N−塩酸(30mL)を加え、生成物をベンゼン(50mL)で二回抽出し、有機層を2N−塩酸(30mL)および水で洗浄した後、硫酸マグネシウムで乾燥させた。この抽出物からベンゼンを溜去した残渣を、ベンゼンとノルマルヘキサン(混合体積比率=7/3)の混合溶媒を移動相としたシリカゲルカラムクロマトグラフィーを用いて精製することによりテトラキス(2:3 −エピチオプロピルチオ)ゲルマン(7.06g、収率=60.6%)を得た。
この化合物の屈折率は1.691、アッベ数は28.3あった。以下にこの化合物の構造決定のための分析結果を示す。
1H−NMR(溶媒:CDCl3 、内部標準物質:TMS);δ2.33 (dd, 1H) 、δ2.60 (dt, 1H) 、δ2.84 (dd, 1H) 、δ3.23〜3.14 (m, 1H)、δ3.31 (dd, 1H) 。
IR(液膜);2987、1439、1423、1239、1088、1045、684 、660 、617 cm-1。
【0028】
実施例2
テトラキス( 2:3 −エピチオプロピルチオ)スズ(E2) ( 一般式 (1) においてM=Sn、x=4)の製造例
2:3 −エピチオプロピルメルカプタン(10.04g)のジクロロメタン (94.5mL)溶液に乾燥ピリジン(10.47g)を−30℃にて加え5分間攪拌した後、その温度で1.0M−四塩化スズのジクロロメタン溶液 (23.6mL)を2時間かけて滴下し、−20℃にて4時間攪拌した。この反応混合物に2N−塩酸(30mL)を加え、生成物をベンゼン(50mL)で二回抽出し、有機層を2N−塩酸(30mL)および水で洗浄した後、硫酸マグネシウムで乾燥させた。この抽出物からベンゼンを溜去した残渣を、ノルマルヘキサンを移動相としたシリカゲルカラムクロマトグラフィーを用いて精製することによりテトラキス(2:3 −エピチオプロピルチオ)スズ(9.09g、収率=71.4%)を得た。
この化合物の屈折率は1.706、アッベ数は29.2であった。以下にこの化合物の構造決定のための分析結果を示す。
1H−NMR(溶媒:CDCl3 、内部標準物質:TMS);δ2.31 (dd, 1H) 、δ2.58 (dt, 1H) 、δ2.81 (dd, 1H) 、δ3.22〜3.13 (m, 1H)、δ3.29 (dd, 1H) 。
IR(液膜);2978、1428、1418、1245、1080、1039、688 、611 cm-1。
【0029】
実施例3
トリス( 4:5 −エピチオ− 2 −チアペンチル)− 2:3 −エピチオプロピルチオチタン(E3) ( 一般式 (1) においてM=Ti、x=1、y=1)の製造例
1.0M−四塩化チタンのジクロロメタン溶液(25.0mL)に1 −メチル−3 −ニトロ−1 −ニトロソグアニジン(15.76g)から発生させたジアゾメタンのエーテル(150mL)溶液を0℃にて加え、30分間その温度で攪拌した。この反応混合物に、テトラヒドロフラン(100mL)中で−10℃にて2:3 −エピチオプロピルメルカプタン(10.62g)とナトリウムエトキサイド(6.80g)から調製したチオレートを1時間かけて滴下し、その後0℃にて12時間攪拌した。この反応混合物に2N−塩酸(60mL)を加え、生成物をクロロホルム(70mL)で二回抽出し、有機相を水洗した後、硫酸マグネシウムで乾燥させた。この抽出物から溶媒を溜去した残渣を、ノルマルヘキサンと酢酸エチルの混合溶媒(混合体積比率=4/1)を移動相としたシリカゲルカラムクロマトグラフィーを用いて精製することによりトリス(4:5 −エピチオ−2 −チアペンチル)−2:3 −エピチオプロピルチオチタン(7.18g、収率=56.2g)を得た。
この化合物の屈折率は1.677、アッベ数は34.8であった。以下にこの化合物の構造決定のための分析結果を示す。
1H−NMR(溶媒:CDCl3 、内部標準物質:TMS);δ2.38 (dd, 2H) 、δ2.47 (s, 3H)、δ2.64 (dt, 2H) 、δ2.92 (dd, 2H) 、δ3.41〜3.33 (m, 2H)、δ3.51 (dd, 2H) 。
IR(液膜);2966、1440、1435、1219、1120、1085、653 、608 cm-1。
【0030】
実施例4
トリス( 2:3 −エピチオプロピルチオ)− 5:6 −エピチオ− 3 −チアヘキシルシラン(E4) ( 一般式 (1) においてM=Si、x=3、y=2)の製造例
四塩化ケイ素(4.25g)のテトラヒドフラン(25.0mL)溶液に1.0M−ビニルマグネシウムブロマイドのテトラヒドフラン溶液(25.0mL)を10℃にて2時間かけて滴下した。この反応混合物をその温度で2時間攪拌したのち、−15℃に冷却し、そこへ乾燥ピリジン(8.31g)を加え、5分攪拌した後、2:3 −エピチオプロピルメルカプタン(10.62g)のテトラヒドロフラン(50mL) 溶液を1時間かけて滴下した。この反応混合物を4時間、0℃にて攪拌した後、そこへアゾビスジメチルバレロニトリル(6.3mg)を加え、6時間還流した。室温まで冷却したこの反応混合物に2N−塩酸(60mL)を加え、生成物をベンゼン(70mL)で二回抽出し、有機相を水洗した後、硫酸マグネシウムで乾燥させた。この抽出物から溶媒を溜去した残渣を、ノルマルヘキサンと酢酸エチルの混合溶媒(混合体積比率=9/1)を移動相としたシリカゲルカラムクロマトグラフィーを用いて精製することによりトリス(2:3 −エピチオプロピルチオ)−5:6 −エピチオ−3 −チアヘキシルシラン(5.76g、収率=48.3%) を得た。
この化合物の屈折率は1.634、アッベ数は32.6であった。以下にこの化合物の構造決定のための分析結果を示す。
1H−NMR(溶媒:CDCl3 、内部標準物質:TMS);δ0.99 (h, 1H)、δ2.28 (dd, 2H) 、δ2.38 (s, 3H)、δ2.51 (h, 1H)、δ2.59 (dt, 2H) 、δ2.84 (dd, 2H) 、δ3.22〜3.31 (m, 2H)、δ3.42 (dd, 2H) 。
IR(液膜);2930、1411、1392、1241、1209、1110、1060、620 、614 cm-1。
【0031】
応用例1
重合体からなる光学材料の製造
実施例1で得られたテトラキス(2:3 −エピチオプロピルチオ)ゲルマン(E1)0.05モルと重合触媒であるテトラ(ノルマルブチル)フォスフォニウムブロマイド(CT1)2×10-5モルの混合物を均一に攪拌し、二枚のレンズ成形用ガラス型に注入し、50℃で10時間、その後60℃で5時間、さらに120℃で3時間加熱重合させてレンズ形状の重合体を得た。得られた重合体の諸物性を表1に示す。表1から、本応用例1で得られた重合体は無色透明であり、屈折率(nd ) は1.757と非常に高く、アッベ数(νd )も29.0と高い(低分散)ものであり、耐候性、耐熱性(117℃)に優れ、光学歪みのないものであった。従って、得られた重合体は光学材料として好適であった。
応用例2〜5
重合体からなる光学材料の製造
本発明の金属含有エピスルフィド化合物(C1成分)、それ以外のエピスルフィド化合物、エポキシ化合物および/またはビニルモノマー(C2成分)、および重合触媒を表1に示すように使用して、重合条件を適宜変更した以外は、応用例1と同様の操作を行い、レンズ形状の重合体を得た。これらの重合体の諸物性を表1に示す。表1から、本応用例2〜5で得られた重合体も無色透明であり、屈折率(nd ) は1.712〜1.764と非常に高く、アッベ数(νd )も28.8〜36.3と高い(低分散)ものであり、耐候性、耐熱性(111〜138℃)に優れ、光学歪みのないものであった。
【0032】
応用比較例1
表1に示すようにペンタエリスリトールテトラキス(メルカプトプロピオネート)(CE5)0.1モル、m −キシリレンジイソシアネート(CE6)0.2モルおよびジブチルスズジクロライド(CT5)1.0×10-4モルの混合物を均一に撹拌し、二枚のレンズ成形用ガラス型に注入し、50℃で10時間、その後60℃で5時間、さらに120℃で3時間加熱重合させてレンズ形状の重合体を得た。得られた重合体の諸物性を表1 に示す。表1から、本応用比較例1の重合体は無色透明で光学歪も観察されなかったが、nd /νd が1.59/36と屈折率が低く、耐熱性も86℃と劣っていた。
応用比較例2、3
表1に示した原料組成物を使用した以外は、応用比較例1と同様の操作を行ない、レンズ形状の重合体を得た。これらの重合体の諸物性を表1に示す。表1から、本応用比較例2の重合体はnd /νd が1.67/28といずれも低く、耐熱性(94℃)は比較的良好であるが、耐候性に劣り、かつ着色が見られ、光学歪が観察された。また、本応用比較例3の重合体は、アッベ数(νd )が36と比較的高く、耐候性に優れており、無色透明で光学歪は観察されなかったが、耐熱性(90℃)が劣り、屈折率(nd ) が1.70とそれほど高くなく、また、重合体は脆弱であった。
【0033】
【表1】
【0034】
(表1における略号)
EI: テトラキス(2:3 −エピチオプロピルチオ)ゲルマン
E2: テトラキス(2:3 −エピチオプロピルチオ)スズ
E3: トリス(4:5 −エピチオ−2 −チアペンチル)−2:3 −エピチオプロピルチオチタン
E4: トリス(2:3 −エピチオプロピルチオ)−5:6 −エピチオ−3 −チアヘキシルシラン
E5: トリス(2:3 −エピチオプロピルチオ)−4:5 −エピチオ−2 −チアペンチルゲルマン
CE1: 2:3 −エピチオプロピルスルフィド
CE2: 2,2 −ビス(4 −(2 −グリシジルオキシ)エトキシフェニル)プロパン
CE3: シクロヘキセンオキサイド
CE4: ビス(2 −アクリロキシエチル)−1,4 −キシリルカルバメート
CE5: ペンタエリスリトールテトラキス( メルカプトプロピオネート)
CE6: m −キシリレンジイソシアネート
CE7: 1,3,5 −トリメルカプトベンゼン
CE8: 2 :3 −エピチオプロピルサルファイド
CT1: テトラ(ノルマルブチル)フォスフォニウムブロマイド
CT2: トリエチルアミン
CT3: 2,4,6 −トリジメチルアミノフェノール
CT4: 三弗化ホウ素−ピリジン錯体
CT5: ジブチルスズジクロライド
【0035】
【発明の効果】
本発明の金属含有エピスルフィド化合物は、ケイ素、ゲルマニウム、スズ、チタンなどの金属原子に末端エピスルフィド基含有の反応性置換基が4個結合している新規化合物であって、光学材料の原料として好適に用いられる。また、本発明の金属含有エピスルフィド化合物を用いて得られる光学材料は、屈折率、アッベ数が高く、耐熱性、耐候性、透明性に優れているので眼鏡レンズ、カメラレンズ等のレンズ、プリズム、光ファイバー、光ディスク、磁気ディスク等に用いられる記録媒体基板、着色フィルター、赤外線吸収フィルター等の光学製品を作製する材料として好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel metal-containing episulfide compound and a method for producing the same, and more particularly to a metal-containing episulfide compound useful as a raw material for optical materials having a high refractive index and high Abbe number, and a method for efficiently producing the same. is there.
[0002]
[Prior art]
In recent years, plastics are widely used in various optical applications such as lenses because they are lighter than glass and are difficult to break and can be easily dyed. As the optical plastic material, poly (diethylene glycol bisallyl carbonate) (CR-39) or poly (methyl methacrylate) is generally used. However, since these plastic materials have a refractive index of 1.50 or less, when a lens is made of these plastic materials, for example, the lens becomes thicker as the power of the lens increases, and the advantage of the plastic lens that has the advantage of light weight. Sexuality will be impaired. In particular, a strong concave lens is not preferable because the periphery of the lens becomes thick and birefringence and chromatic aberration occur. In addition, thick lenses in eyeglass applications tend to degrade aesthetics. In order to obtain a thin lens, it is effective to increase the refractive index of the material constituting the lens. In general, in glass and plastic, the Abbe number decreases as the refractive index increases, and as a result, their chromatic aberration increases. Therefore, a plastic material having a high refractive index and Abbe number is desired.
Examples of plastic materials having such performance include (1) polyurethane obtained by polyaddition of a polyol having bromine in the molecule and polyisocyanate (Japanese Patent Laid-Open No. 58-164615), and (2) polythiol and polyisocyanate. Polythiourethanes obtained by polyaddition with isocyanate (Japanese Patent Publication No. 4-58489, Japanese Patent Publication No. 5-148340) have been proposed. In particular, as a polythiol used as a raw material for the polythiourethane (2), a branched chain having an increased content of sulfur atoms (polythiol JP-A-2-270859, JP-A-5-148340), sulfur atoms In order to enhance this, polythiols (Japanese Patent Publication No. 6-5323 and Japanese Patent Application Laid-Open No. 7-118390) in which a dithian structure is introduced have been proposed. Further, (3) alkylsulfide polymers having episulfide as a polymerization functional group have been proposed (Japanese Patent Laid-Open Nos. 9-72580 and 9-110979).
[0003]
However, although the polyurethane of the above (1) has a slightly improved refractive index, it has disadvantages such as a low Abbe number and inferior light resistance, a high specific gravity, and a reduction in lightness. In addition, among the polythiourethanes of (2), the polythiourethane obtained by using a polythiol as a raw material polythiol having a high sulfur content has a refractive index increased to about 1.60 to 1.68, for example. However, the Abbe number is lower than that of the optical inorganic glass having the same refractive index, and the Abbe number has to be increased. On the other hand, the alkyl sulfide polymer (3) has, for example, an Abbe number of 36 and a refractive index increased to 1.70, and a lens obtained using this polymer is remarkably thinned, and Although it has been reduced in weight, a plastic material having a refractive index and an Abbe number that are further increased is desired.
[0004]
[Problems to be solved by the invention]
Under such circumstances, the present invention is a novel compound capable of providing an optical material having both a high refractive index and an Abbe number and excellent in heat resistance, weather resistance, transparency, and the like, and this compound efficiently. The object is to provide a method of manufacturing.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventor is a novel compound containing a metal-containing episulfide compound in which an episulfide derivative is bonded to a metal atom such as silicon, germanium, tin, or titanium, It has been found that the above object can be met and that it can be efficiently obtained by a specific method, and the present invention has been completed based on this finding.
That is, the present invention provides (1) the general formula (1)
[0006]
[Formula 4]
[0007]
(In the formula, M represents silicon, germanium, tin or titanium, x represents an integer of 1 to 4, and y represents 1 or 2.)
A metal-containing episulfide compound represented by:
(2) General formula MZFour(M is the same as described above, Z represents a halogen atom) and a metal tetrahalide represented by 2: 3-epithiomercaptopropane is reacted,
[0008]
[Chemical formula 5]
[0009]
(Wherein M is the same as above)
And a method for producing a metal-containing episulfide compound represented by:
(3) A general formula (1), characterized by reacting a chloromethylated or vinyl-substituted metal tetrahalide with a 2: 3-epithiomercaptopropane
[0010]
[Chemical 6]
[0011]
(In the formula, M is the same as described above, x represents an integer of 1 to 3, and y represents 1 or 2.)
The manufacturing method of the metal containing episulfide compound represented by these is provided.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The metal-containing sulfide compound of the present invention has the general formula (1)
[0013]
[Chemical 7]
[0014]
(In the formula, M represents silicon, germanium, tin or titanium, x represents an integer of 1 to 4, and y represents 1 or 2.)
As is clear from the above general formula (1), the same or different two types of episulfide derivatives are bonded to a metal atom selected from silicon, germanium, tin and titanium. It is characterized by that.
The refractive index of a substance increases as the refractive index (atomic refraction) of the constituent elements increases and the molecular volume decreases. This atomic refraction increases with the atomic number. Accordingly, the refractive index of the metal-containing episulfide compound of the present invention in which metal atoms such as silicon, germanium, tin, and titanium are introduced is remarkably higher than that of an episulfide compound having a skeleton composed of carbon. The refractive index of the polymer will also increase.
Since the metal-containing episulfide compound of the present invention is tetrafunctional and is composed of as few elements as possible between the functional groups, a decrease in molecular volume is caused by an increase in crosslink density. The refractive index of the polymer obtained using the episulfide compound increases. Accordingly, in order to maintain the high crosslink density and increase the refractive index without decreasing the Abbe number, the number of methylene chains represented by y in the general formula (1) must be 1 or 2. By combining these substituents with one kind (x = 4 in the general formula (1)) or two kinds (x = 1 to 3 in the general formula (1)), the metal-containing episulfide compound of the present invention can be used. The optical properties, thermal properties and mechanical properties of the polymer can be adjusted.
[0015]
Specific examples of the metal-containing episulfide compound represented by the general formula (1) include tetrakis (2: 3-epithiopropylthio) silane, tetrakis (2: 3-epithiopropylthio) germane, tetrakis (2: 3-epithiopropylthio) tin, tetrakis (2: 3-epithiopropylthio) titanium, tris (2: 3-epithiopropylthio) -2-thia-4: 5-epithiopentylsilane, tris (2 : 3-epithiopropylthio) -2-thia-4: 5-epithiopentylgermane, tris (2: 3-epithiopropylthio) -2-thia-4: 5-epithiopentyltin, tris (2 : 3 -epithiopropylthio) -2 -thia-4: 5 -epithiopentyltitanium, tris (2: 3-epithiopropylthio) -3-thia-5: 6 -epithiohexylsilane, tris (2 : 3-Epithiopropylthio) -3 -Thia-5: 6 -epithiohexylgermane, tris (2: 3-epithiopropylthio) -3 -thia-5: 6 -epithiohexyltin, tris (2: 3-epithiopropylthio) -3 -Thia-5: 6-epithiohexyl titanium, tris (2-thia-4: 5-epithiopentyl) -2: 3-epithiopropylthiogermane and the like.
The metal-containing episulfide compound represented by the general formula (1) can be efficiently produced by the method of the present invention shown below depending on its structure.
(1) In general formula (1), the compound of x = 4 is the reaction formula
[0016]
[Chemical 8]
[0017]
According to the above, 2: 3-epithiomercaptopropane is reacted with a metal tetrahalide corresponding to M in the general formula (1) in a solvent such as tetrahydrofuran, dimethyl sfoxide and dimethylformamide in the presence of a base. Can be obtained. As the tetrahalide, tetrachloride is preferred. The reaction temperature is 20 ° C. to −30 ° C., and pyridine, triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene and the like are preferably used as the base. The 2: 3-epithiomercaptopropane used as one of the raw materials is described in a known method, for example, “J. Chem. Soc.”, Page 2665 (1960). It can be prepared according to the method.
(2) In general formula (1), the compound of x = 1-3 and y = 1 is reaction formula.
[0018]
[Chemical 9]
[0019]
According to That is, a metal tetrachloride corresponding to M in the general formula (1) is reacted with diazomethane in a solvent such as dichloromethane or ethyl ether at 10 to 30 ° C. to produce a corresponding metal chloromethylated product. This product, which was isolated by distilling off the ethyl ether, was converted into a thiolate previously prepared with a base and 2: 3-epithiomercaptopropane and dichloromethane, methanol, ethanol, ethyl ether, tetrahydrofuran, dimethyl sfoxide, dimethyl The reaction is carried out in formamide or a mixed solvent thereof. As this base, sodium methoxide, sodium ethoxide, sodium hydride, normal butyllithium and the like are used, and the addition amount is equivalent to the chlorine atom directly bonded to the metal.
(3) In the general formula (1), the compound of x = 1 to 3 and y = 2 is a reaction formula
[0020]
[Chemical Formula 10]
[0021]
According to That is, the metal tetrahalide corresponding to M in the general formula (1), that is, the general formula MZFourA vinyl-substituted product obtained by reacting a metal tetrahalide represented by the following formula, preferably tetrachloride with vinylmagnesium bromide at 0 to 30 ° C., is converted into 2: 3-epithiomercaptopropane and dichloromethane in the presence of a base. , Tetrahydrofuran, ethyl ether, dimethyl sulfoxide, dimethylformamide or a mixed solvent thereof at 10 ° C. to −30 ° C., followed by reaction at 40-80 ° C. in the presence of a radical generator. Pyridine, triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene and the like are preferable as the base, and benzoyl peroxide, azobisdimethylbutyronitrile, azobisdimethylvaleronitrile and the like are preferable as the radical generator. Used. The amount of the base added is equivalent to the chlorine atom directly bonded to the metal, and that of the radical generator is 0.01 to 0.0001 equivalent to the vinyl group. In the reaction of this vinyl-substituted product with 2: 3-epithiomercaptopropane, instead of heating in the presence of a radical generator, the intensity at 350 nm with a high-pressure mercury lamp is 0.0 to 100 mW / cm.2The same compound can also be obtained by irradiating with UV light in tetrahydrofuran or normal hexane or without solvent.
[0022]
Next, an optical material obtained using the metal-containing episulfide compound of the present invention will be described. The metal-containing episulfide compound represented by the general formula (1) is an essential component and may be used alone or in combination of two or more. Furthermore, this metal-containing episulfide compound and a compound selected from other episulfide compounds, epoxy compounds and homopolymerizable vinyl monomers can be polymerized as optional components for improving the physical properties of the resulting polymer as appropriate. Good.
Examples of other episulfide compounds used as appropriate include bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithio). Propylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4-bis ( β-epithiopropylthio) butane, 1,3-bis (β-epithiopropylthio) butane, 1- (β-epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1, 5-bis (β-epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) Hexane, 1- (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- (β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) )]] Ethane, chain organic compounds such as 1- (β-epithiopropylthio) -2-[[2- (2-β-epithiopropylthioethyl) thioethyl] thio] ethane, tetrakis (Β-epithiopropylthiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,5-bis (β-epithiopropylthio) -2- (β-epithio) Propylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1- (β-epithiopropyl) Thio -2,2-bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3- Thiahexane, 1,8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4, 5bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6 Dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithio) Propylthio) -2,5 -Bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) -5-[(2- β-epithiopropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylthio) -5,6-bis [(2-β-epithiopropylthioethyl) thio] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1, 11-bis (β-epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-[(2-β-D Thiopropylthioethyl) thiomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6 Branched organic compounds such as 1,9-trithiaundecane and compounds in which at least one hydrogen of the episulfide group of these compounds is substituted with a methyl group, and the like, and 1,3 and 1,4-bis (β- Epithiopropylthio) cyclohexane, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4 -(Β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis ( Cyclic aliphatic organic compounds such as β-epithiopropylthiomethyl) -1,4-dithiane and 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane and episulfides of these compounds Compounds in which at least one of the hydrogens of the group is replaced by a methyl group, and 1,3 and 1,4-bis (β-epithiopropylthio) benzene, 1,3 and 1,4-bis (β-epithio) Propylthiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epi Thiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfone, 4,4′-bis (β-epithiopropylthio) biphenyl, etc. Aromatic organic compound and at least one hydrogen of the episulfide group of these compounds include compounds substituted with a methyl group, and these may be used singly or in combination of two or more. The amount of these used is preferably 0.01 to 50 mol% with respect to the total amount of the metal-containing episulfide compound represented by the general formula (1).
[0023]
Examples of the epoxy compound used as appropriate include polyhydric phenol compounds such as hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, bisphenol sulfide, halogenated bisphenol A, and novolac resin. Phenolic epoxy compounds produced by condensation of epihalohydrins; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane trimethacrylate , Pentaerythritol, 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide addition Alcohol-based epoxy compounds produced by condensation of polyhydric alcohol compounds such as products and epihalohydrins; adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, Hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, het acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, Glycidyl ester epoxy compounds produced by condensation of polycarboxylic acid compounds such as phthaline dicarboxylic acid and diphenyl dicarboxylic acid and epihalohydrin; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diamino Butane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, bis- (3-amino Propyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, 1,2-, 1,3- or 1 , 4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, m- or p- Phenylenediamine, 2,4- or 2,6-tolylenediamine, m- or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'- Primary diamines such as diaminodiphenyl ether, 2,2- (4,4′-diaminodiphenyl) propane, N, N′-dimethylethylenediamine, N, N′-dimethyl-1,2-diaminopropane, N, N′-dimethyl -1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl 1,3-diaminobutane, N, N′-dimethyl-1,4-diaminobutane, N, N′-dimethyl-1,5-diaminopentane, N, N′-dimethyl-1,6-diaminohexane N, N′-dimethyl-1,7-diaminoheptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1,3-diaminopropane N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N′-diethyl- 1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) -methane, 1,2-di- ( 4-piperi And amine-based epoxy compounds produced by condensation of secondary diamines such as 1,3-di- (4-piperidyl) -propane, 1,4-di- (4-piperidyl) -butane and epihalohydrin; 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexanedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, Cycloaliphatic epoxy compounds such as bis (3,4-epoxycyclohexyl) adipate; epoxy compounds produced by epoxidation of unsaturated compounds such as cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, vinylcyclohexene epoxide; Polyhydric alcohol, phenolization Examples thereof include urethane-based epoxy compounds produced from a compound, diisocyanate, glycidol and the like, and these may be used alone or in combination of two or more. The amount of these used is preferably 0.01 to 5 mol% with respect to the total amount of the metal-containing episulfide compound represented by the general formula (1).
[0024]
Examples of the above-mentioned suitably homopolymerizable vinyl monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate. Acrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexane Diol dimethacrylate, neopentyl glycol diacrylate, neopentyl Cold dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2, 2-bis [4- (acryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (acryloxy-polyethoxy) phenyl] propane, 2, , 2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate Ester structures of monohydric or higher alcohols such as hexaacrylate of bis (2,2,2-trimethylolethyl) ether, hexamethacrylate of bis (2,2,2-trimethylolethyl) ether, acrylic acid and methacrylic acid Compounds having allyl; allyl compounds such as allyl sulfide, diallyl phthalate, diethylene glycol bisallyl carbonate; vinyl compounds such as acrolein, acrylonitrile, vinyl sulfide; styrene, α-methyl styrene, methyl vinyl benzene, ethyl vinyl benzene, α-chloro styrene, Aromatic vinyl compounds such as chlorovinylbenzene, vinylbenzyl chloride, paradivinylbenzene, metadivinylbenzene and the like may be mentioned, and these may be used alone or in combination of two or more. The amount of these used is preferably 0.01 to 20 mol% based on the total amount of the metal-containing episulfide compound represented by the general formula (1).
[0025]
To the above-mentioned polymerizable composition, additives such as ultraviolet absorbers, antioxidants, anti-coloring agents and fluorescent dyes are appropriately added for improving the weather resistance as long as the purpose of the present invention is not impaired. May be. Further, a catalyst for improving the polymerization reaction may be used as appropriate, for example, amines, phosphine, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, mineral acids. Lewis acids, organic acids, silicic acids, tetrafluoroboric acid and the like are effective.
The optical material obtained using the metal-containing episulfide compound of the present invention can be produced, for example, according to the following method.
First, a uniform composition containing the polymerizable compound and various additives used as necessary is prepared. Next, this composition is poured into a mold in which a glass or metal mold and a resinous gasket are combined using a known casting polymerization method, and is cured by heating. At this time, in order to make it easy to take out the resin after molding, the mold may be released in advance, or a release agent may be mixed with the composition. The polymerization temperature varies depending on the compound used, but is generally -20 to 150 ° C., and the polymerization time is about 0.5 to 72 hours. The polymer released after the polymerization can be easily dyed in water or an organic solvent using an ordinary disperse dye. At this time, in order to further facilitate dyeing, a carrier may be added to the dye dispersion, or it may be heated. The use of the optical material thus obtained is not particularly limited, but is particularly preferably used as an optical product such as a plastic lens.
[0026]
【Example】
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In addition, the physical property of the metal containing episulfide compound obtained by the Example, and the physical property of the polymer obtained by the application example and the comparative application example were measured in accordance with the method shown below.
<Physical properties of metal-containing episulfide compounds>
Refractive index (nd), Abbe number (νd): Measured at 25 ° C. using a precision refractometer KPR-200 manufactured by Kalnew.
<Physical properties of polymer>
1) Refractive index (nd), Abbe number (νd): Measured in the same manner as above.
2) Appearance: Observed with the naked eye.
3) Weather resistance: A plastic lens was set in a weather meter equipped with a sunshine carbon arc lamp, and after 200 hours, the plastic lens was taken out, and the hue was compared with the plastic lens before the test. The evaluation criteria were no change (○), slightly yellow (△), and yellow (×).
4) Heat resistance: TMA measurement was performed with a load of 98 mN (10 gf) using a 0.5 mmφ pin by a TMA apparatus manufactured by Rigaku Corporation, and evaluation was made based on the peak temperature of the chart obtained at a temperature rise of 10 ° C./min.
5) Optical distortion: Visual observation was performed by the Schlieren method. Those having no distortion were evaluated as ◯, and those having distortion were evaluated as ×.
[0027]
Example 1
Tetrakis ( 2: 3 -Epithiopropylthio) germane (E1) ( General formula (1) M = Ge, x = 4)
2: 3-Epithiopropyl mercaptan (10.04 g) in tetrahydrofuran (94.5 mL) was added dry pyridine (10.47 g) at −30 ° C. and stirred for 5 minutes, and at that temperature germanium tetrachloride (5 0.07 g) in tetrahydrofuran (47.2 mL) was added dropwise over 2 hours, and the mixture was stirred at −20 ° C. for 4 hours. 2N-hydrochloric acid (30 mL) was added to the reaction mixture, the product was extracted twice with benzene (50 mL), and the organic layer was washed with 2N-hydrochloric acid (30 mL) and water, and then dried over magnesium sulfate. The residue obtained by distilling benzene from this extract was purified by silica gel column chromatography using a mixed solvent of benzene and normal hexane (mixed volume ratio = 7/3) as a mobile phase to produce tetrakis (2: 3- Epithiopropylthio) germane (7.06 g, yield = 60.6%) was obtained.
This compound had a refractive index of 1.691 and an Abbe number of 28.3. The analysis results for determining the structure of this compound are shown below.
1H-NMR (solvent: CDClThree, Internal standard: TMS); δ2.33 (dd, 1H), δ2.60 (dt, 1H), δ2.84 (dd, 1H), δ3.23-3.14 (m, 1H), δ3.31 ( dd, 1H).
IR (liquid film); 2987, 1439, 1423, 1239, 1088, 1045, 684, 660, 617 cm-1.
[0028]
Example 2
Tetrakis ( 2: 3 -Epithiopropylthio) tin (E2) ( General formula (1) M = Sn, x = 4)
2: 3-Epithiopropyl mercaptan (10.04 g) in dichloromethane (94.5 mL) was added dry pyridine (10.47 g) at −30 ° C. and stirred for 5 minutes. A solution of tin chloride in dichloromethane (23.6 mL) was added dropwise over 2 hours, and the mixture was stirred at −20 ° C. for 4 hours. 2N-hydrochloric acid (30 mL) was added to the reaction mixture, the product was extracted twice with benzene (50 mL), and the organic layer was washed with 2N-hydrochloric acid (30 mL) and water, and then dried over magnesium sulfate. The residue obtained by distilling benzene from this extract was purified by silica gel column chromatography using normal hexane as a mobile phase to obtain tetrakis (2: 3-epithiopropylthio) tin (9.09 g, yield = 71.4%).
This compound had a refractive index of 1.706 and an Abbe number of 29.2. The analysis results for determining the structure of this compound are shown below.
1H-NMR (solvent: CDClThree, Internal standard: TMS); δ2.31 (dd, 1H), δ2.58 (dt, 1H), δ2.81 (dd, 1H), δ3.22 to 3.13 (m, 1H), δ3.29 ( dd, 1H).
IR (liquid film); 2978, 1428, 1418, 1245, 1080, 1039, 688, 611 cm-1.
[0029]
Example 3
Tris ( 4: 5 -Epithio- 2 -Thiapentyl)- 2: 3 -Epithiopropylthiotitanium (E3) ( General formula (1) M = Ti, x = 1, y = 1)
A solution of diazomethane in ether (150 mL) generated from 1-methyl-3-nitro-1-nitrosoguanidine (15.76 g) was added at 0 ° C. to 1.0 M titanium tetrachloride in dichloromethane (25.0 mL). And stirred at that temperature for 30 minutes. To this reaction mixture, a thiolate prepared from 2: 3-epithiopropyl mercaptan (10.62 g) and sodium ethoxide (6.80 g) in tetrahydrofuran (100 mL) at −10 ° C. was added dropwise over 1 hour. Thereafter, the mixture was stirred at 0 ° C. for 12 hours. 2N-hydrochloric acid (60 mL) was added to the reaction mixture, and the product was extracted twice with chloroform (70 mL). The organic phase was washed with water and then dried over magnesium sulfate. The residue obtained by distilling off the solvent from this extract was purified by silica gel column chromatography using a mixed solvent of normal hexane and ethyl acetate (mixing volume ratio = 4/1) as a mobile phase to obtain Tris (4: 5 -Epithio-2-thiapentyl) -2: 3-epithiopropylthiotitanium (7.18 g, yield = 56.2 g) was obtained.
This compound had a refractive index of 1.677 and an Abbe number of 34.8. The analysis results for determining the structure of this compound are shown below.
1H-NMR (solvent: CDClThree, Internal standard substance: TMS); δ2.38 (dd, 2H), δ2.47 (s, 3H), δ2.64 (dt, 2H), δ2.92 (dd, 2H), δ3.41 to 3.33 ( m, 2H), δ3.51 (dd, 2H).
IR (liquid film): 2966, 1440, 1435, 1219, 1120, 1085, 653, 608 cm-1.
[0030]
Example 4
Tris ( 2: 3 -Epithiopropylthio)- 5: 6 -Epithio- Three -Thiahexylsilane (E4) ( General formula (1) M = Si, x = 3, y = 2)
To a solution of silicon tetrachloride (4.25 g) in tetrahydrane (25.0 mL), 1.0 M-vinylmagnesium bromide in tetrahydrfuran (25.0 mL) was added dropwise at 10 ° C. over 2 hours. The reaction mixture was stirred at that temperature for 2 hours, cooled to −15 ° C., dried pyridine (8.31 g) was added thereto, stirred for 5 minutes, and then 2: 3-epithiopropyl mercaptan (10.62 g). ) In tetrahydrofuran (50 mL) was added dropwise over 1 hour. The reaction mixture was stirred for 4 hours at 0 ° C., azobisdimethylvaleronitrile (6.3 mg) was added thereto, and the mixture was refluxed for 6 hours. To this reaction mixture cooled to room temperature, 2N-hydrochloric acid (60 mL) was added, the product was extracted twice with benzene (70 mL), the organic phase was washed with water and then dried over magnesium sulfate. The residue obtained by distilling off the solvent from this extract was purified by silica gel column chromatography using a mixed solvent of normal hexane and ethyl acetate (mixing volume ratio = 9/1) as a mobile phase to obtain Tris (2: 3 -Epithiopropylthio) -5: 6-epithio-3-thiahexylsilane (5.76 g, yield = 48.3%) was obtained.
This compound had a refractive index of 1.634 and an Abbe number of 32.6. The analysis results for determining the structure of this compound are shown below.
1H-NMR (solvent: CDClThree, Internal standard: TMS); δ0.99 (h, 1H), δ2.28 (dd, 2H), δ2.38 (s, 3H), δ2.51 (h, 1H), δ2.59 (dt, 2H), δ2.84 (dd, 2H), δ3.22 to 3.31 (m, 2H), δ3.42 (dd, 2H).
IR (liquid film); 2930, 1411, 1392, 1241, 1209, 1110, 1060, 620, 614 cm-1.
[0031]
Application example 1
Production of optical materials made of polymers
0.05 mol of tetrakis (2: 3-epithiopropylthio) germane (E1) obtained in Example 1 and tetra (normal butyl) phosphonium bromide (CT1) 2 × 10 which is a polymerization catalyst-FiveThe molar mixture is stirred uniformly, poured into two lens molding glass molds, and heated and polymerized at 50 ° C. for 10 hours, then at 60 ° C. for 5 hours, and further at 120 ° C. for 3 hours to obtain a lens-shaped polymer. Obtained. Table 1 shows various physical properties of the polymer thus obtained. From Table 1, the polymer obtained in this application example 1 is colorless and transparent, and has a refractive index (nd) Is very high at 1.757, and the Abbe number (νd) Was as high as 29.0 (low dispersion), had excellent weather resistance and heat resistance (117 ° C.), and had no optical distortion. Therefore, the obtained polymer was suitable as an optical material.
Application examples 2-5
Production of optical materials made of polymers
The metal-containing episulfide compound (C1 component) of the present invention, other episulfide compound, epoxy compound and / or vinyl monomer (C2 component), and polymerization catalyst were used as shown in Table 1, and the polymerization conditions were appropriately changed. Except for the above, the same operation as in Application Example 1 was performed to obtain a lens-shaped polymer. Table 1 shows the physical properties of these polymers. From Table 1, the polymers obtained in Application Examples 2 to 5 are also colorless and transparent, and have a refractive index (nd) Is very high at 1.712 to 1.764, and the Abbe number (νd) Was as high as 28.8 to 36.3 (low dispersion), excellent in weather resistance and heat resistance (111 to 138 ° C.), and free from optical distortion.
[0032]
Application comparison example 1
As shown in Table 1, pentaerythritol tetrakis (mercaptopropionate) (CE5) 0.1 mol, m-xylylene diisocyanate (CE6) 0.2 mol and dibutyltin dichloride (CT5) 1.0 × 10-FourThe molar mixture is stirred uniformly, poured into two lens-molding glass molds, heated and polymerized at 50 ° C. for 10 hours, then at 60 ° C. for 5 hours, and further at 120 ° C. for 3 hours to form a lens-shaped polymer. Obtained. Table 1 shows the physical properties of the polymer obtained. From Table 1, the polymer of this application comparative example 1 was colorless and transparent and no optical distortion was observed.d/ ΝdHowever, the refractive index was as low as 1.59 / 36 and the heat resistance was inferior at 86 ° C.
Application Comparative Examples 2 and 3
Except for using the raw material composition shown in Table 1, the same operation as in Application Comparative Example 1 was performed to obtain a lens-shaped polymer. Table 1 shows the physical properties of these polymers. From Table 1, the polymer of this application comparative example 2 is nd/ ΝdHowever, the heat resistance (94 ° C.) was relatively good, but the weather resistance was inferior, coloring was observed, and optical distortion was observed. In addition, the polymer of this comparative application example 3 has an Abbe number (νd) Is relatively high at 36, excellent in weather resistance, colorless and transparent, and no optical distortion was observed, but heat resistance (90 ° C.) was poor, and refractive index (nd) Was not as high as 1.70 and the polymer was fragile.
[0033]
[Table 1]
[0034]
(Abbreviations in Table 1)
EI: Tetrakis (2: 3-epithiopropylthio) germane
E2: Tetrakis (2: 3-epithiopropylthio) tin
E3: Tris (4: 5-epithio-2-thiapentyl) -2: 3-epithiopropylthiotitanium
E4: Tris (2: 3-epithiopropylthio) -5: 6-epithio-3-thiahexylsilane
E5: Tris (2: 3-epithiopropylthio) -4: 5-epithio-2-thiapentylgermane
CE1: 2: 3-Epithiopropyl sulfide
CE2: 2,2-bis (4- (2-glycidyloxy) ethoxyphenyl) propane
CE3: Cyclohexene oxide
CE4: Bis (2-acryloxyethyl) -1,4-xylylcarbamate
CE5: Pentaerythritol tetrakis (mercaptopropionate)
CE6: m-xylylene diisocyanate
CE7: 1,3,5-trimercaptobenzene
CE8: 2: 3-Epithiopropyl sulfide
CT1: Tetra (normal butyl) phosphonium bromide
CT2: Triethylamine
CT3: 2,4,6-tridimethylaminophenol
CT4: Boron trifluoride-pyridine complex
CT5: Dibutyltin dichloride
[0035]
【The invention's effect】
The metal-containing episulfide compound of the present invention is a novel compound in which four reactive substituents containing a terminal episulfide group are bonded to a metal atom such as silicon, germanium, tin, or titanium, and is suitable as a raw material for optical materials. Used. In addition, the optical material obtained using the metal-containing episulfide compound of the present invention has a high refractive index and high Abbe number, and is excellent in heat resistance, weather resistance, and transparency. It is suitable as a material for producing optical products such as recording medium substrates, colored filters, infrared absorption filters and the like used for optical fibers, optical disks, magnetic disks and the like.
Claims (6)
で表される金属含有エピスルフィド化合物。General formula (1)
A metal-containing episulfide compound represented by:
で表される金属含有エピスルフィド化合物の製造方法。A general formula (1), characterized in that a metal tetrahalide represented by the general formula MZ 4 (M is the same as above, Z represents a halogen atom) and 2: 3-epithiomercaptopropane are reacted. −a)
The manufacturing method of the metal containing episulfide compound represented by these.
で表される金属含有エピスルフィド化合物の製造方法。Characterized by reacting a chloromethylated or vinyl-substituted metal tetrahalide represented by the general formula MZ 4 (M and Z are the same as above) with 2: 3-epithiomercaptopropane. General formula (1)
The manufacturing method of the metal containing episulfide compound represented by these.
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JP2006169190A (en) * | 2004-12-17 | 2006-06-29 | Mitsui Chemicals Inc | Polymerizable compound and its application |
WO2013015174A1 (en) * | 2011-07-22 | 2013-01-31 | 旭化成ケミカルズ株式会社 | Composition and polymer |
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JP2010037304A (en) * | 2008-08-07 | 2010-02-18 | Mitsubishi Gas Chemical Co Inc | New metal-containing compound |
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