JP3899758B2 - Method for producing sulfur-containing acrylic compound - Google Patents
Method for producing sulfur-containing acrylic compound Download PDFInfo
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- JP3899758B2 JP3899758B2 JP36612299A JP36612299A JP3899758B2 JP 3899758 B2 JP3899758 B2 JP 3899758B2 JP 36612299 A JP36612299 A JP 36612299A JP 36612299 A JP36612299 A JP 36612299A JP 3899758 B2 JP3899758 B2 JP 3899758B2
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- sulfur
- containing acrylic
- acrylic compound
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- -1 acrylic compound Chemical class 0.000 title claims description 65
- 229910052717 sulfur Inorganic materials 0.000 title claims description 49
- 239000011593 sulfur Substances 0.000 title claims description 49
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000002904 solvent Substances 0.000 claims description 25
- 230000003287 optical effect Effects 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000003463 sulfur Chemical class 0.000 claims 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、硫黄含有アクリル化合物の製造方法に関する。詳しくは、粗硫黄含有アクリル化合物を非溶媒の存在下で結晶化させて高純度の硫黄含有アクリル化合物を製造する方法に関する。
本発明により得られる高純度の硫黄含有アクリル化合物を原料として用いることにより、光学用として高屈折の、しかも製造ロット間における屈折率の変動の少ない樹脂を製造することができる。
【０００２】
【従来の技術】
硫黄含有アクリル化合物の重合体が高屈折率を有する成形体となることは従来から知られており、該化合物及びその製造方法については、いろいろと提案がなされている（特開昭６０−２６０１０号、同６１−７２７４８号、同６２−１９５３５７号各公報等）。
これらの硫黄含有アクリル化合物を眼鏡レンズとして利用すれば、従来より利用されているジエチレングリコールビスアリルカーボネートより肉厚が薄くなるという利点があり、現在利用されつつある。
【０００３】
一方、最近の光学機器は非球面レンズ等のより高度な成型加工を必要とする光学部品を組み込むことが多くなっており、ガラスでは成型加工が難しいため注型成型の出来る高屈折率プラスチックレンズが注目を浴びている。これらの光学機器に硫黄含有アクリル化合物を利用すれば、その高屈折率な特性からコンパクト化等が可能となるため、検討されているが、光学機器は精密な設計によりレンズ形状が決定されており、製造ロット間によるレンズの屈折率の変動は設計そのものに影響する大きな問題となっている。
【０００４】
【発明が解決しようとする課題】
しかしながら、硫黄含有アクリル化合物は、蒸留精製のできない、当該業界で言ういわゆる「ボトム製品」であり、従来方法で製造された硫黄含有アクリル化合物については、製造ロット毎に組成が微妙に変動する。従って、これを原料として製造された樹脂についても、製造ロット間において屈折率が変動するという問題がある。
本発明は、従来技術の問題点を克服し、高純度で、且つ原料として用いた場合、高屈折率で、且つ製造ロット間の屈折率の変動の少ない樹脂が得られるところの、硫黄含有アクリル化合物の製造方法を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明者らは、かかる事情に鑑み鋭意検討した結果、粗硫黄含有アクリル化合物を非溶媒の存在下で結晶化させることにより、高純度の硫黄含有アクリル化合物を分離、取得することができ、これを原料として用いることにより、製造ロット間における屈折率の変動の少ない樹脂が得られることを見い出し、本発明を完成するに至った。
即ち、本発明の要旨は、下記一般式（１）で示される光学樹脂用硫黄含有アクリル化合物の製造方法であって、その粗硫黄含有アクリル化合物を、該硫黄含有アクリル化合物１００重量部に対して５０〜５００重量部の非溶媒の存在下、常温〜−２０℃の温度で結晶化させ、得られたスラリーから非溶媒を分離し、得られたケーキに重合禁止剤を、該硫黄含有アクリル化合物１００重量部に対して０．０１〜０．５重量部加え、減圧下で非溶媒を除去して高純度の硫黄含有アクリル化合物を分離、取得することを特徴とする光学樹脂用硫黄含有アクリル化合物の製造方法、にある。
【化３】
【０００６】
【発明の実施の形態】
以下、本発明を詳細に説明する。
（結晶化・分離工程）
本発明の方法は、粗硫黄含有アクリル化合物を非溶媒の存在下で結晶化させ、高純度の硫黄含有アクリル化合物を分離、取得することを特徴とする。
本発明の対象となる硫黄含有アクリル化合物については、特に限定されるものではないが、例えば式（１）の化合物が好ましい。
【０００７】
【化４】
（式中、Ｒ1 は水素原子又はメチル基を表し、Ｒ2 は炭素数１〜１２の二価の炭化水素基を表し、Ｘは塩素原子又は臭素原子を表し、Ｙは−ＳＯ2 −、−Ｓ−又は−ＣＯ−を表し、ｍ及びｎは１〜３の整数を表し、且つｐ及びｑは０〜４の整数を表す）
【０００９】
式（１）において、Ｒ2 は炭素数１〜１２、好ましくは１〜４の、二価の炭化水素基であり、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、例えばメチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、等が挙げられる。これらの中、エチレン基、プロピレン基が好ましい。
【００１０】
そして、このような式（１）の化合物の具体例としては、例えば、４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホン、４，４′−ビス（β−アクリロイルオキシエチルチオ）ジフェニルスルホン、４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルケトン、４，４′−ビス（β−アクリロイルオキシエチルチオ）ジフェニルケトン、２，４−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルケトン、２，４−ビス（β−アクリロイルオキシエチルチオ）ジフェニルケトン、４，４′−ビス（β−メタクリロイルオキシエチルチオ）３，３′，５，５′−テトラブロムジフェニルケトン等を挙げることができる。
【００１１】
本発明で用いられる非溶媒としては、硫黄含有アクリル化合物を溶解しないものであれば特に限定されるものではないが、その具体例としては、例えばメタノール、エタノール等のアルコール類、ヘプタン、シクロヘキサン等の脂肪族炭化水素類が挙げられる。これらの中、メタノール、ヘプタンが好ましい。
なお、これらは単独で用いてもよく、二種以上混合して用いてもよい。
【００１２】
非溶媒の使用量は、硫黄含有アクリル化合物１００重量部に対して、５０〜５００重量部、好ましくは１００〜３００重量部である。
また、硫黄含有アクリル化合物が均一溶解しない範囲であれば、アセトン、メチルエチルケトン等のケトン類や、ベンゼン、トルエン等の芳香族炭化水素類の硫黄含有アクリル化合物の溶媒との混合物でも良い。混合物中の用いることのできる硫黄含有アクリル化合物の溶媒の量は、全量中１〜５０重量％、好ましくは、１〜３０重量％であり、溶媒量が多いと結晶化を阻害する。
【００１３】
粗硫黄含有アクリル化合物については、通常液状であり、非溶媒と混合すると、液／液に分離する。仮に該化合物が結晶化している場合には、結晶を予め加熱、融解させてから非溶媒を加えることが好ましい。
結晶化については、この液／液分離相を常温又は常温〜−２０℃に冷却し、必要に応じて少量の硫黄含有アクリル化合物の結晶を種として加えて行われる。
【００１４】
また、この結晶化については、静置状態で行ってもよいが、緩やかな攪拌下で行うとスラリー状の結晶が得られ、分離操作がしやすくなり、好ましい。
そして、この結晶化操作により、高純度の硫黄含有アクリル化合物が結晶化し、粗硫黄含有アクリル化合物中に含まれていた不純物等は非溶媒に移行するので、高純度の硫黄含有アクリル化合物を結晶として分離、取得することができる。
【００１５】
得られたスラリーについては、濾過又は遠心分離により非溶媒と分け、得られたケーキについては、所望により、新しい非溶媒で洗浄し、次いでこのケーキにハイドロキノンモノメチルエーテル等の公知の重合禁止剤を硫黄含有アクリル化合物１００重量部に対して、通常０．０１〜０．５重量部加えた後、減圧下に乾燥して非溶媒を除去することにより、目的とする高純度で色相も良好な硫黄含有アクリル化合物が得られる。
かくして得られた高純度の硫黄含有アクリル化合物は、加熱すると液状になるので注型成型には便利であり、また、これを原料として得られた樹脂は屈折率の安定した成型体を与える。
【００１６】
（反応・後処理工程）
本発明に用いられる硫黄含有アクリル化合物が式（１）の化合物である場合、式（１）の化合物の製造方法については特に限定されるものではないが、例えば式（２）のポリオールと（メタ）アクリル酸ハライド、（メタ）アクリル酸又は（メタ）アクリル酸エステルのようなアシル化剤とを反応させることにより製造するのが好ましい。これらの中、アシル化剤が安価であり、且つ目的生成物の純度を低下させない方法として、式（２）のポリオールと（メタ）アクリル酸メチルとのエステル交換法により製造するのが好ましく、以下、このエステル交換反応及びその後処理について説明する。
この場合、原料ポリオールとしては、式（２）の硫黄含有ポリオールが用いられる。
【００１７】
【化５】
（式中、Ｒ2 、Ｘ、Ｙ、ｍ、ｎ、ｐ及びｑについては、式（１）と同義である）式（２）において、Ｒ2 は前記と同様炭素数１〜１２、好ましくは１〜４の、二価の炭化水素基であり、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、例えばメチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、等が挙げられる。これらの中、メチレン基、エチレン基が好ましい。
【００１９】
そして、このようなポリオール化合物の具体例としては、例えば、４，４′−ビス（２−ヒドロキシエチルチオ）ジフェニルスルホン、４，４′−ビス（２−ヒドロキシエチルチオ）ジフェニルケトン、２，４−ビス（２−ヒドロキシエチルチオ）ジフェニルケトン、４，４′−ビス（２−ヒドロキシエチルチオ）３，３′，５，５′−テトラブロムジフェニルケトン等が挙げられる。
これらの中、４，４′−ビス（２−ヒドロキシエチルチオ）ジフェニルスルホン、４，４′−ビス（２−ヒドロキシエチルチオ）ジフェニルケトンが好ましい。
【００２０】
なお、これらのポリオールは、例えばＮ．Ｋｈａｒａｓｃｈ、ＯｒｇａｎｉｃＳｕｌｆｕｒ Ｃｏｍｐｏｕｎｄｓ、第１巻、第９７〜１１１頁、又は 米国特許第３，８２４，２９３号明細書に記載の合成法に準拠して合成することができる。
（メタ）アクリル酸メチルについては、市販のものをそのまま使用することができる。なお、（メタ）アクリル酸メチルは、硫黄含有ポリオール１モルに対して、通常２〜２０モル、好ましくは３〜１０モル用いられる。
【００２１】
エステル交換触媒については、特に限定されず、通常用いられているものを使用できるが、好ましい触媒として、例えばテトラブチルチタネート、テトライソプロピルチタネート、テトラ（２−エチルヘキシル）チタネート、カリウムブトキシド等の金属アルコキシド類を挙げることができる。
その使用量は、硫黄含有ポリオール１モルに対して、通常０．０１〜０．１モルである。
重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル等の公知の重合禁止剤が用いられる。その使用量は、硫黄含有ポリオール１００重量部に対して、０．０１〜１０重量部、好ましくは０．１〜５重量部である。
【００２２】
本エステル交換反応については、無溶媒で行うこともできるが、ベンゼン、トルエン、キシレン等の芳香族炭化水素、トリクロロエチレン、テトラクロロエチレン等のハロゲン化炭化水素等の溶媒を用いるのが好ましい。溶媒の使用量は、硫黄含有ポリオール１００重量部に対して、通常１０〜５００重量部、好ましくは１００〜２００重量部である。
【００２３】
エステル交換反応については、例えば反応器に硫黄含有ポリオール、（メタ）アクリル酸メチル、溶媒、エステル交換触媒、重合禁止剤を仕込み、好ましくは攪拌下で、好ましくは窒素等の不活性ガス雰囲気下で、加熱下に生成するメタノールを系外に除去しながら行われる。反応温度は、通常６０〜１３０℃、好ましくは８０〜１２０℃、反応圧力は、通常常圧で、反応時間は、通常５〜３０時間、好ましくは１０〜２０時間である。
【００２４】
エステル交換反応終了後、反応溶液から過剰の（メタ）アクリル酸メチルを除去した後、反応溶液を５％塩酸水溶液のような酸水溶液で洗浄し、次いで５％苛性ソーダ水溶液のようなアルカリ水溶液で洗浄した後、中性になる迄水洗する。その後、前記の方法により溶媒を減圧留去して、結晶化処理すべき粗硫黄含有アクリル化合物を得る。
【００２５】
【実施例】
以下に実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を越えない限り、これらの実施例に限定されるものではない。
【００２６】
実施例１
（反応・後処理工程）
攪拌器、温度計、冷却管及び分離器を備え付けた１リットルの四ツ口フラスコに、４，４′−ビス（２−ヒドロキシエチルチオ）ジフェニルスルホン１００重量部、メタクリル酸メチル２７０重量部、ハイドロキノンモノメチルエーテル０．１３５重量部及びトルエン２００重量部を仕込み、攪拌しながら８０℃まで昇温したところへ、テトラブチルチタネート２．８重量部を加えた。その後更に昇温し、１００〜１２０℃で２０時間、メタノールを留去させながら反応を行った。メタノールの留去は毎分４ｃｃの空気を反応系内に吹き込みながら行った。反応後、過剰のメタクリル酸メチルを除去し、その後、反応溶液を室温まで冷却した。この溶液にトルエン１００重量部を加え、５％塩酸水溶液、続いて５％水酸化ナトリウム水溶液で洗浄し、更に中性になるまで水洗した。この溶液にハイドロキノンモノメチルエーテル０．１３５重量部を加え、減圧下でトルエンを留去し、１３０重量部の４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホンを得た。
【００２７】
（結晶化・分離工程）
前工程で得られた４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホンに、３００重量部のメタノールを加えたところ、液／液に分離していた。これを攪拌しながら０℃に冷却し、２時間攪拌を続けたところ、スラリー状態になった。このスラリーを素早く濾過し、冷メタノールで洗浄した。得られたケーキに０．０９５重量部のハイドロキノンモノメチルエーテルを加え、減圧下でメタノールを除去することにより、４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホン９５重量部を得た。得られた４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホンは、無色であり、高速液体クロマトグラフによる純度は、９９．８％、アッベの屈折計で測定した２５℃の屈折率ｎＤは、１．６０９４であった。
【００２８】
実施例２
反応・後処理工程において、トルエン留去を、トルエンが５重量部残存した状態で停止した以外は、実施例１と同様に反応・後処理を行い、同様に結晶化・分離を行った。得られた９３重量部の４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホンは、無色であり、高速液体クロマトグラフによる純度は、９９．８％であった。アッベの屈折計で測定した２５℃の屈折率ｎＤは、１．６０９４であった。
【００２９】
実施例３
反応・後処理工程において、トルエン留去を、トルエンが１０重量部残存した状態で停止し、結晶化・分離工程において、メタノールの代わりにヘプタンを用い、結晶化を室温で行った以外は、実施例１と同様に行った。得られた９６重量部の４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホンは、無色であり、高速液体クロマトグラフによる純度は、９９．８％であった。アッベの屈折計で測定した２５℃の屈折率ｎＤは１．６０９５であった。
【００３０】
比較例１〜３
結晶化・分離工程を行わない以外は、実施例１と同様に反応・後処理工程を行った。３度繰り返し行ったところ、得られた４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホンは表１の通りであった。
【００３１】
【表１】
参考例１
実施例１〜３及び、比較例１〜３で得られた４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホンを以下に示す方法で硬化成型し、アッベの屈折計で硬化物の屈折率を測定した。
４，４′−ビス（β−メタクリロイルオキシエチルチオ）ジフェニルスルホン１００重量部に、光開始剤として、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキシド（ＢＡＳＦ社製「ルシリンＴＰＯ」）０．０５重量部、ベンゾフェノン０．０５重量部を均一に混合攪拌した後、脱泡して組成物を得た。この組成物をスペーサーとして厚さ０．４ｍｍのシリコン板を用いた光学研磨ガラスの型に注入し、ガラス面上にある出力８０Ｗ／ｃｍのメタルハライドランプにてガラス型面に４０Ｊ／ｃｍ2 のエネルギーになるよう照射後、ガラス型を離型し、厚さ約０．４ｍｍの光硬化樹脂を得た。
得られた値を表２に示す。
【００３３】
【表２】
【発明の効果】
本発明の方法によれば、製造ロット間の屈折率の変動の少ないイオウ含有アクリル化合物を製造することが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a sulfur-containing acrylic compound. Specifically, the present invention relates to a method for producing a high-purity sulfur-containing acrylic compound by crystallizing a crude sulfur-containing acrylic compound in the presence of a non-solvent.
By using the high-purity sulfur-containing acrylic compound obtained by the present invention as a raw material, it is possible to produce a resin having a high refractive index and a small refractive index variation between production lots for optical use.
[0002]
[Prior art]
It has been heretofore known that a polymer of a sulfur-containing acrylic compound becomes a molded article having a high refractive index, and various proposals have been made regarding the compound and its production method (Japanese Patent Laid-Open No. 60-26010). 61-72748, 62-195357, etc.).
When these sulfur-containing acrylic compounds are used as spectacle lenses, there is an advantage that the wall thickness is thinner than that of diethylene glycol bisallyl carbonate which has been conventionally used, and it is currently being used.
[0003]
On the other hand, recent optical instruments are often incorporating optical components that require more sophisticated molding processes such as aspherical lenses. Since glass is difficult to mold, high refractive index plastic lenses that can be cast are produced. Has attracted attention. The use of sulfur-containing acrylic compounds in these optical instruments is being studied because it can be made compact due to its high refractive index characteristics, but the lens shape of optical instruments is determined by precise design. The variation in the refractive index of the lens between production lots is a big problem affecting the design itself.
[0004]
[Problems to be solved by the invention]
However, the sulfur-containing acrylic compound is a so-called “bottom product” in the industry that cannot be purified by distillation, and the composition of the sulfur-containing acrylic compound produced by the conventional method slightly varies from production lot to production lot. Therefore, the resin manufactured using this as a raw material also has a problem that the refractive index varies between production lots.
The present invention overcomes the problems of the prior art, and when used as a raw material with high purity, a resin having a high refractive index and a small variation in refractive index between production lots can be obtained. It aims at providing the manufacturing method of a compound.
[0005]
[Means for Solving the Problems]
As a result of intensive studies in view of such circumstances, the present inventors can separate and obtain a high-purity sulfur-containing acrylic compound by crystallizing the crude sulfur-containing acrylic compound in the presence of a non-solvent. As a raw material, it was found that a resin having a small variation in refractive index between production lots was obtained, and the present invention was completed.
That is, the gist of the present invention is a method for producing a sulfur-containing acrylic compound for optical resins represented by the following general formula (1), wherein the crude sulfur-containing acrylic compound is added to 100 parts by weight of the sulfur-containing acrylic compound . In the presence of 50 to 500 parts by weight of a non-solvent, crystallization is performed at a temperature of from room temperature to -20 ° C., the non-solvent is separated from the resulting slurry, and the polymerization inhibitor is added to the obtained cake, the sulfur-containing acrylic compound in addition 0.01 to 0.5 parts by weight per 100 parts by weight, separation of high-purity sulfur-containing acrylic compound to remove the non-solvent under reduced pressure, the optical resin for a sulfur-containing acrylic compound and acquires In the manufacturing method.
[Chemical Formula 3]
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
(Crystallization / separation process)
The method of the present invention is characterized in that a crude sulfur-containing acrylic compound is crystallized in the presence of a non-solvent, and a high-purity sulfur-containing acrylic compound is separated and obtained.
Although it does not specifically limit about the sulfur containing acrylic compound used as the object of this invention, For example, the compound of Formula (1) is preferable.
[0007]
[Formula 4]
(Wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, X represents a chlorine atom or a bromine atom, Y represents —SO 2 —, -S- or -CO- is represented, m and n represent an integer of 1 to 3, and p and q represent an integer of 0 to 4)
[0009]
In the formula (1), R 2 is a divalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, which may be linear, branched or cyclic, and specific examples thereof include: For example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, etc. are mentioned. Among these, an ethylene group and a propylene group are preferable.
[0010]
Specific examples of such a compound of formula (1) include, for example, 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone, 4,4′-bis (β-acryloyloxyethylthio). Diphenyl sulfone, 4,4′-bis (β-methacryloyloxyethylthio) diphenyl ketone, 4,4′-bis (β-acryloyloxyethylthio) diphenyl ketone, 2,4-bis (β-methacryloyloxyethylthio) Diphenyl ketone, 2,4-bis (β-acryloyloxyethylthio) diphenyl ketone, 4,4′-bis (β-methacryloyloxyethylthio) 3,3 ′, 5,5′-tetrabromodiphenyl ketone, etc. be able to.
[0011]
The non-solvent used in the present invention is not particularly limited as long as it does not dissolve the sulfur-containing acrylic compound. Specific examples thereof include alcohols such as methanol and ethanol, heptane, cyclohexane and the like. Aliphatic hydrocarbons are exemplified. Of these, methanol and heptane are preferred.
In addition, these may be used independently and may be used in mixture of 2 or more types.
[0012]
The usage-amount of a non-solvent is 50-500 weight part with respect to 100 weight part of sulfur containing acrylic compounds, Preferably it is 100-300 weight part.
Moreover, as long as the sulfur-containing acrylic compound does not dissolve uniformly, a mixture of ketones such as acetone and methyl ethyl ketone and a solvent of sulfur-containing acrylic compounds of aromatic hydrocarbons such as benzene and toluene may be used. The amount of the sulfur-containing acrylic compound solvent that can be used in the mixture is 1 to 50% by weight, preferably 1 to 30% by weight, based on the total amount. If the amount of the solvent is large, crystallization is inhibited.
[0013]
The crude sulfur-containing acrylic compound is usually in a liquid state and is separated into a liquid / liquid when mixed with a non-solvent. If the compound is crystallized, it is preferable to add a non-solvent after heating and melting the crystals in advance.
For crystallization, this liquid / liquid separation phase is cooled to room temperature or from room temperature to −20 ° C., and a small amount of sulfur-containing acrylic compound crystals are added as seeds as necessary.
[0014]
Further, this crystallization may be performed in a stationary state. However, it is preferable to perform the crystallization under gentle stirring because a slurry-like crystal is obtained and the separation operation is facilitated.
And by this crystallization operation, a high purity sulfur-containing acrylic compound is crystallized, and impurities contained in the crude sulfur-containing acrylic compound are transferred to a non-solvent. Can be separated and acquired.
[0015]
The obtained slurry is separated from the non-solvent by filtration or centrifugation, and the obtained cake is washed with a new non-solvent, if desired, and then a known polymerization inhibitor such as hydroquinone monomethyl ether is added to the cake with sulfur. After adding 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the acrylic compound contained, it is dried under reduced pressure to remove the non-solvent, thereby containing the desired high purity and good hue. An acrylic compound is obtained.
The high-purity sulfur-containing acrylic compound thus obtained is liquid when heated, and is convenient for cast molding, and the resin obtained using this as a raw material gives a molded article having a stable refractive index.
[0016]
(Reaction and post-treatment process)
When the sulfur-containing acrylic compound used in the present invention is a compound of the formula (1), the production method of the compound of the formula (1) is not particularly limited, but for example, a polyol of the formula (2) and (meta It is preferably produced by reacting with an acylating agent such as acrylic acid halide, (meth) acrylic acid or (meth) acrylic acid ester. Among these, the acylating agent is inexpensive and is preferably produced by a transesterification method between the polyol of formula (2) and methyl (meth) acrylate as a method that does not reduce the purity of the target product. The transesterification reaction and the subsequent treatment will be described.
In this case, a sulfur-containing polyol of the formula (2) is used as the raw material polyol.
[0017]
[Chemical formula 5]
(Wherein R 2 , X, Y, m, n, p and q have the same meanings as those in formula (1)) In formula (2), R 2 has 1 to 12 carbon atoms as described above, preferably 1-4, which is a divalent hydrocarbon group, which may be linear, branched or cyclic, and specific examples thereof include, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, Etc. Among these, a methylene group and an ethylene group are preferable.
[0019]
Specific examples of such a polyol compound include, for example, 4,4′-bis (2-hydroxyethylthio) diphenyl sulfone, 4,4′-bis (2-hydroxyethylthio) diphenyl ketone, 2,4 -Bis (2-hydroxyethylthio) diphenyl ketone, 4,4'-bis (2-hydroxyethylthio) 3,3 ', 5,5'-tetrabromodiphenyl ketone and the like.
Among these, 4,4′-bis (2-hydroxyethylthio) diphenyl sulfone and 4,4′-bis (2-hydroxyethylthio) diphenyl ketone are preferable.
[0020]
These polyols are exemplified by N.I. It can be synthesized according to the synthesis method described in Kharasch, OrganicSulfur Compounds, Volume 1, pages 97-111, or US Pat. No. 3,824,293.
About methyl (meth) acrylate, a commercially available thing can be used as it is. The methyl (meth) acrylate is usually used in an amount of 2 to 20 mol, preferably 3 to 10 mol, per 1 mol of the sulfur-containing polyol.
[0021]
Although it does not specifically limit about a transesterification catalyst, Although what is used normally can be used, For example, as a preferable catalyst, metal alkoxides, such as tetrabutyl titanate, tetraisopropyl titanate, tetra (2-ethylhexyl) titanate, potassium butoxide, etc. Can be mentioned.
The usage-amount is 0.01-0.1 mol normally with respect to 1 mol of sulfur containing polyols.
As the polymerization inhibitor, known polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether are used. The usage-amount is 0.01-10 weight part with respect to 100 weight part of sulfur containing polyols, Preferably it is 0.1-5 weight part.
[0022]
Although this transesterification reaction can be carried out without a solvent, it is preferable to use a solvent such as an aromatic hydrocarbon such as benzene, toluene or xylene, or a halogenated hydrocarbon such as trichloroethylene or tetrachloroethylene. The usage-amount of a solvent is 10-500 weight part normally with respect to 100 weight part of sulfur containing polyols, Preferably it is 100-200 weight part.
[0023]
For the transesterification reaction, for example, a reactor is charged with a sulfur-containing polyol, methyl (meth) acrylate, a solvent, a transesterification catalyst, and a polymerization inhibitor, preferably under stirring, preferably under an inert gas atmosphere such as nitrogen. , While removing methanol produced under heating out of the system. The reaction temperature is usually 60 to 130 ° C., preferably 80 to 120 ° C., the reaction pressure is usually atmospheric pressure, and the reaction time is usually 5 to 30 hours, preferably 10 to 20 hours.
[0024]
After the transesterification reaction, excess methyl (meth) acrylate is removed from the reaction solution, and then the reaction solution is washed with an acid aqueous solution such as a 5% aqueous hydrochloric acid solution, and then washed with an alkaline aqueous solution such as a 5% aqueous sodium hydroxide solution. Then wash with water until neutral. Thereafter, the solvent is distilled off under reduced pressure by the above method to obtain a crude sulfur-containing acrylic compound to be crystallized.
[0025]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples unless it exceeds the gist.
[0026]
Example 1
(Reaction and post-treatment process)
In a 1 liter four-necked flask equipped with a stirrer, thermometer, condenser and separator, 100 parts by weight of 4,4′-bis (2-hydroxyethylthio) diphenylsulfone, 270 parts by weight of methyl methacrylate, hydroquinone 0.135 parts by weight of monomethyl ether and 200 parts by weight of toluene were charged, and 2.8 parts by weight of tetrabutyl titanate was added to the mixture where the temperature was raised to 80 ° C. with stirring. Thereafter, the temperature was further raised, and the reaction was carried out while distilling off methanol at 100 to 120 ° C. for 20 hours. The methanol was distilled off while blowing 4 cc of air per minute into the reaction system. After the reaction, excess methyl methacrylate was removed, and then the reaction solution was cooled to room temperature. To this solution, 100 parts by weight of toluene was added, washed with a 5% aqueous hydrochloric acid solution, followed by a 5% aqueous sodium hydroxide solution, and further washed with water until neutrality. To this solution was added 0.135 parts by weight of hydroquinone monomethyl ether, and toluene was distilled off under reduced pressure to obtain 130 parts by weight of 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone.
[0027]
(Crystallization / separation process)
When 300 parts by weight of methanol was added to 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone obtained in the previous step, it was separated into a liquid / liquid. This was cooled to 0 ° C. with stirring, and stirring was continued for 2 hours, resulting in a slurry state. The slurry was quickly filtered and washed with cold methanol. 0.095 parts by weight of hydroquinone monomethyl ether was added to the obtained cake, and methanol was removed under reduced pressure to obtain 95 parts by weight of 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone. The obtained 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone was colorless and had a purity of 99.8% as determined by high performance liquid chromatography, and a refractive index of 25 ° C. measured with an Abbe refractometer. The nD was 1.6094.
[0028]
Example 2
In the reaction / post-treatment step, toluene / evaporation was stopped in a state where 5 parts by weight of toluene remained, and the reaction / post-treatment was performed in the same manner as in Example 1, and crystallization / separation was performed in the same manner. The obtained 93 parts by weight of 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone was colorless and its purity by high performance liquid chromatography was 99.8%. The refractive index nD at 25 ° C. measured with an Abbe refractometer was 1.6094.
[0029]
Example 3
In the reaction / post-treatment step, toluene distillation was stopped with 10 parts by weight of toluene remaining, and in the crystallization / separation step, heptane was used instead of methanol, and crystallization was performed at room temperature. Performed as in Example 1. The obtained 96 parts by weight of 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone was colorless and its purity by high performance liquid chromatography was 99.8%. The refractive index nD at 25 ° C. measured with an Abbe refractometer was 1.6095.
[0030]
Comparative Examples 1-3
The reaction and post-treatment steps were performed in the same manner as in Example 1 except that the crystallization / separation step was not performed. When repeated 3 times, the obtained 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone was as shown in Table 1.
[0031]
[Table 1]
Reference example 1
The 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was cured and molded by the method shown below, and the cured product was measured with an Abbe refractometer. The refractive index was measured.
2,4,6-Trimethylbenzoyldiphenylphosphine oxide (“BAC company“ Lucirin TPO ”) 0.05 as a photoinitiator was added to 100 parts by weight of 4,4′-bis (β-methacryloyloxyethylthio) diphenylsulfone. Part by weight and 0.05 part by weight of benzophenone were uniformly mixed and stirred, and then defoamed to obtain a composition. This composition was poured into an optical polishing glass mold using a silicon plate having a thickness of 0.4 mm as a spacer, and an energy of 40 J / cm 2 was applied to the glass mold surface with a metal halide lamp having an output of 80 W / cm on the glass surface. After the irradiation, the glass mold was released to obtain a photo-curing resin having a thickness of about 0.4 mm.
The obtained values are shown in Table 2.
[0033]
[Table 2]
【The invention's effect】
According to the method of the present invention, it is possible to produce a sulfur-containing acrylic compound with little variation in refractive index between production lots.
Claims (2)
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| Application Number | Priority Date | Filing Date | Title |
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| JP36612299A JP3899758B2 (en) | 1999-12-24 | 1999-12-24 | Method for producing sulfur-containing acrylic compound |
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| JP36612299A JP3899758B2 (en) | 1999-12-24 | 1999-12-24 | Method for producing sulfur-containing acrylic compound |
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| JP2001181258A JP2001181258A (en) | 2001-07-03 |
| JP3899758B2 true JP3899758B2 (en) | 2007-03-28 |
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| JP36612299A Expired - Fee Related JP3899758B2 (en) | 1999-12-24 | 1999-12-24 | Method for producing sulfur-containing acrylic compound |
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