JP2004307737A - Method for producing sulfonic acid group-containing organic polymer siloxane - Google Patents
Method for producing sulfonic acid group-containing organic polymer siloxane Download PDFInfo
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- JP2004307737A JP2004307737A JP2003106167A JP2003106167A JP2004307737A JP 2004307737 A JP2004307737 A JP 2004307737A JP 2003106167 A JP2003106167 A JP 2003106167A JP 2003106167 A JP2003106167 A JP 2003106167A JP 2004307737 A JP2004307737 A JP 2004307737A
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- acid group
- sulfonic acid
- organic polymer
- containing organic
- polymer siloxane
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 125000000542 sulfonic acid group Chemical group 0.000 title abstract description 29
- 229920000620 organic polymer Polymers 0.000 title abstract description 17
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 150000003377 silicon compounds Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 abstract description 22
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 abstract description 16
- 150000003961 organosilicon compounds Chemical class 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000011973 solid acid Substances 0.000 description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000005054 phenyltrichlorosilane Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000012070 reactive reagent Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- -1 siloxanes Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、イオン交換体及び固体酸触媒として有用なスルホン酸基含有有機高分子シロキサンの製造方法に関する。
【０００２】
【従来の技術】
スルホン酸基を有する強酸性イオン交換体は、例えば、水及び水溶液の脱塩、化学合成における固体酸触媒等として広く利用されている。ほとんどの場合使用されるカチオン交換体はポリスチレン骨格を有し、フェニルスルホン酸基を有する一般的に陽イオン交換樹脂と呼ばれるものである。陽イオン交換樹脂は耐熱性が低く、一般的に１００〜１３０℃が使用の上限とされている。また、著しい膨潤性による破壊、機械的強度の脆さ等の不利な点を有している。
【０００３】
これに対し、無機ポリマー系イオン交換体の例として、有機高分子シロキサンが挙げられる。有機高分子シロキサンについては特開昭５９−２０３２５号、特開昭６１−２７２２３７号公報にスルホン酸基が有機スペーサー基によってシリカマトリックスに結合しているスルホン酸基含有有機高分子シロキサンが開示されている。上記スルホン酸基含有有機高分子シロキサンは多硫化物ポリマーの酸化処理及び固体有機高分子シロキサンのスルホン化処理等によるもので、スルホン化工程が固体との反応である為、スルホン化の反応効率が悪く、また溶媒によってはスルホン化中に有機高分子シロキサンが溶出するため、製造法としては問題が多かった。また、特開平６−２０７０２１号公報にはスルホン酸基含有シロキサン水溶液を合成し、他のアルコキシシランとの加水分解、脱水縮合によりスルホン酸基含有有機高分子シロキサンを製造する方法が開示されている。しかしながら本方法ではスルホン酸基を有するシロキサン水溶液は明らかにポリマーであり、スルホン酸基濃度の高いポリマーが単に固定化されているため、耐水性に問題があることは明白である。
【０００４】
これに対し、特開平１１−２０９４７２号公報にはスルホン酸基含有アルコキシシランを用いたスルホン酸基含有有機高分子シロキサン製造法が開示されている。この方法ではアルコキシシラン分子同士を均一に混合し、同時に加水分解、共縮合しているので、スルホン酸基が均一に分散していると考えられ、耐水性が飛躍的に向上することが記述されている。スルホン酸基含有アルコキシシランの合成法としては、フェニル基含有有機珪素化合物をスルホン化剤と接触させることで合成している。フェニル基のスルホン化剤としては、一般的に硫酸、発煙硫酸、クロロ硫酸、三酸化硫黄等が知られているが、高分子シロキサンマトリックスを形成しうる有機珪素化合物は加水分解性を有しているため、非水性のクロロ硫酸、三酸化硫黄等が用いられる。実施例中には塩化メチレン溶媒中でフェニルトリクロロシランに１当量の三酸化硫黄の塩化メチレン溶液を滴下し、常温で数時間攪拌することによりスルホン化を行う方法が記載されている。フェニルスルホン酸基を有する有機珪素化合物は単離が困難である為、そのままテトラエトキシシラン等のシリカマトリックスを形成しうる母剤と混合し、加水分解、重縮合により有機高分子シロキサンを得ている。その固体酸量を測定することで、フェニルスルホン酸基の量を定量し、スルホン化の収率を算出することができる。
【０００５】
しかしながら、前記特許では、仕込みのフェニル基の量に対し、４０〜４５％と低い収率でしかスルホン酸量を得ることができないという問題を有していた。スルホン化を高収率化するためには、スルホン化の反応温度の高温化、スルホン化剤量の過剰な添加により、反応効率を増大させる方法が当然考えられるが、Ｊ．Ｏｒｇ．Ｃｈｅｍ．，２０，４５５（１９５５年）に記載されているように、スルホン化反応では過剰なスルホン化剤は逆にスルホンの副生等、スルホン酸の収率上好ましくない事が良く知られており、またスルホン化剤は通常、有機物の分解に用いられるような反応性の激しい試薬なので、実際にスルホン化剤を過剰に用いたりすることは試みられてはいなかった。
【０００６】
【本発明が解決しようとする課題】
本発明は、フェニルスルホン酸基を有する有機珪素化合物を用いたスルホン酸基含有高分子シロキサンの製造において、フェニル基含有有機珪素化合物をスルホン化する際の反応温度を制御し、三酸化硫黄量を過剰に用いることにより、スルホン化収率の高いフェニルスルホン酸基含有有機高分子シロキサンを得ることを特徴としている。
【０００７】
【課題を解決するための手段】
本発明者らは、かかる問題を解決するため鋭意研究を行い、フェニル基含有有機珪素化合物を、「フェニル基含有有機珪素化合物のモル量」：「三酸化硫黄のモル量」＝１：２〜３となる過剰量の三酸化硫黄と接触させることにより、スルホン化収率の高いフェニルスルホン酸基含有有機高分子シロキサンが得られることを見出し、本発明を完成するに至ったものである。
【０００８】
【発明の実施の形態】
本発明におけるフェニルスルホン酸基を有する有機珪素化合物の製造は特開平１１−２０９４７２に記載されているようにフェニル基含有有機珪素化合物を無溶媒、もしくは不活性溶媒の存在下で三酸化硫黄と接触させることにより得ることができる。スルホン化の反応温度は３０〜９０℃が好ましく、特に３０〜４５℃が好ましい。
フェニル基含有有機珪素化合物とは、一般式
【０００９】
【化２】
【００１０】
ここで本発明におけるフェニルスルホン酸基を有する有機珪素化合物合成法について具体的に説明する。溶媒存在下でフェニル基含有有機珪素化合物［１］に対し過剰量の三酸化硫黄を加える。スルホン化は発熱反応であるが、反応温度を好ましくは３０〜９０℃、特に好ましくは３０〜４５℃に制御し、数時間攪拌することで、フェニルスルホン酸基含有有機珪素化合物を得ることができる。次いで、ハロゲン基に対して過剰量のアルコールを加え、発生する塩化水素を除きながらアルコキシ化を行い、フェニルスルホン酸基を有するアルコキシシラン化合物を含有するアルコール溶液を得る。この溶液をシリカマトリックスを形成しうるテトラアルコキシシランと任意の割合で混合し、ゾル−ゲル調製によりフェニルスルホン酸基含有有機高分子シロキサンを調製する。ゾル−ゲル調製とは高分子シロキサンマトリックスを形成しうるスルホン酸基含有アルコキシシラン化合物と、シリカマトリックスを形成しうるテトラアルコキシシラン化合物を混合し、同時に加水分解することにより得られる混合ゾルの脱水縮合によるゲル化により、高分子シロキサンマトリックスを形成したスルホン酸基含有有機高分子シロキサンを製造する調製法である。
【００１１】
ここにおいて本発明における混合ゲル化について述べる。本発明における混合ゲル化は通常の異種アルコキシシランの混合ゾル−ゲル反応により充分達成される。実施し易い混合ゲル化方法として具体的に例示すれば、触媒の酸成分となる上記したスルホン酸基を有するアルコキシシラン化合物を目的とする量を仕込み、テトラエトキシシラン等、テトラアルコキシシラン化合物とを混合し、必要であるならばエタノール等の溶媒を用いて均一な混合溶液とする。これにアルコキシ基の加水分解に必要な量の水を加えた後、攪拌しながら、通常、温度１０〜２００℃、好ましくは、３０〜１００℃で、１時間〜３週間、酸性条件下で反応させる。得られた高粘度の液体は一般にシリカゾルと呼ばれるものである。上記したゾルに対してアルコキシ基の加水分解に必要な量の水に対して過剰の水とアンモニア水等を加え、塩基性条件下で、通常、温度１０〜２００℃、好ましくは、３０〜１００℃で、１時間〜３週間の条件でゲル化させる。またこの時必要であるならば加熱攪拌し、長時間熟成させることもできる。
【００１２】
これらゲル化を実施するに際して、ゾルに対して不活性であるアルコール、または脂肪族飽和炭化水素（ヘキサン、ヘプタン等）等の媒体に希釈させてゲル化させることも可能である。得られたゲルは濾過または溶媒を留去する等により単離できる。このゲルはスルホン酸がアンモニウム塩型であるため、イオン交換体及び固体酸触媒として用いるためには塩酸等による酸処理により酸型にもどす必要がある。この有機高分子シロキサンは陽イオン交換樹脂の酸量測定等で一般的に用いられる処方、すなはち予想される酸量に対して過剰の塩化ナトリウム水溶液でイオン交換し、遊離した塩酸を定量する事でそのスルホン酸量を求めることが可能である。
【００１３】
【実施例】
以下、本発明を実施例、および比較例により具体的に説明する。しかしながら、この実施例は単なる例示であって、本発明はこれらに限定されるものではない。また、実施例において、得られたスルホン化の収率をスルホン化収率（仕込みのフェニルトリクロロシランに対し、調製した有機高分子シロキサンのフェニルスルホン酸基の量）で表した。
【００１４】
【実施例１】
滴下ロートを取り付けた２口の３００ｍｌの丸底フラスコに塩化メチレンを１００ｍｌ入れ、これにフェニルトリクロロシラン３９．１ｇ（０．１９ｍｏｌ）を加え、氷冷した。これに三酸化硫黄３７．３ｇ（０．４７ｍｏｌ）の塩化メチレン溶液２０ｍｌを、１時間かけて滴下した。滴下後、還流下、４５℃で２時間反応を行った。さらに還流下、エタノール４６．０ｇを、窒素気流下で塩化水素を除きながら１時間かけて滴下した後、塩化メチレンを留去した。さらに、これにエタノール４６．０ｇを滴下し、２時間還流し、フェニルスルホン酸基含有エトキシシランのエタノール溶液１４６．０ｇを得た。このエタノール溶液２２．０ｇを冷却管及び攪拌棒を取り付けた３口の５００ｍｌの丸底フラスコにテトラエトキシシラン８３．２ｇ（０．４０ｍｏｌ）、エタノール１００ｍｌを加え混合する。これに水１４．４ｇを３０分間で滴下した。次いでオイルバス中で加熱し、６０℃で３時間攪拌した。放冷後、水７２．０ｇを混合し、２８％アンモニア水１０ｍｌを加えたところ、反応液は固化した。室温で４時間放置し、減圧下溶媒を留去した。得られた固体を５００ｍｌのビーカーに入れ、２Ｎ塩酸２００ｍｌを加え、攪拌機を用いて３０分間攪拌し、濾別した。この酸処理の操作を再度繰り返した後、漏斗上で純水３００ｍｌで洗浄する操作を２回繰り返した。固体を減圧乾燥器に入れ、１０ｍｍＨｇの減圧下、１００℃で６時間乾燥させ、スルホン酸基含有有機高分子シロキサンを３０．０ｇ得た。この有機高分子シロキサンの固体酸量を上記した処方により、測定した結果、０．６５ｍｍｏｌ／ｇであった。従って、得られたスルホン酸の量は１９．５ｍｍｏｌとなり、原料のトリクロロフェニルシランに対するスルホン化の収率は７０％とスルホン化剤を過剰に用い、スルホン化の反応温度を４５℃とすることで、高い収率が得られた。
【００１５】
【実施例２】
滴下ロートを取り付けた２口の３００ｍｌの丸底フラスコに１，２−ジクロロエタンを１００ｍｌ入れ、これにフェニルトリクロロシラン４３．０ｇ（０．２０ｍｏｌ）を加え、氷冷した。これに三酸化硫黄４１．０ｇ（０．５１ｍｏｌ）の１，２−ジクロロエタン溶液２０ｍｌを、１時間かけて滴下した。滴下後、還流下、８５℃で２時間反応を行った。更に還流下、エタノール５１．０ｇを窒素気流下、塩化水素を除きながら１時間かけて滴下し、ついで１，２−ジクロロエタンを留去した。さらに、エタノール５１．０ｇを滴下し、２時間還流し、スルホン酸基含有エトキシシランのエタノール溶液１５８．０ｇを得た。このエタノール溶液１９．３ｇを冷却管及び攪拌棒を取り付けた３口の５００ｍｌの丸底フラスコにテトラエトキシシラン８７．７ｇ（０．４２ｍｏｌ）、エタノール１００ｍｌを加え混合する。これに水１５．１ｇを３０分間で滴下した。次いでオイルバス中で過熱し、６０℃で３時間攪拌した。放冷後、水７６．０ｇを混合し、２８％アンモニア水１０ｍｌを加えたところ、反応液は固化した。室温で４時間放置し、減圧下溶媒を留去した。得られた固体を５００ｍｌのビーカーに入れ、２Ｎ塩酸２００ｍｌを加え、攪拌機を用いて３０分間攪拌し、濾別した。この酸処理の操作を再度繰り返した後、漏斗上で純水３００ｍｌで洗浄する操作を２回繰り返した。固体を減圧乾燥器に入れ、１０ｍｍＨｇの減圧下、１００℃で６時間乾燥させ、スルホン酸基含有有機高分子シロキサンを３１．０ｇ得た。この有機高分子シロキサンの固体酸量を上記した処方により、測定した結果、０．４８ｍｍｏｌ／ｇであった。従って、得られたスルホン酸の量は１５．０ｍｍｏｌとなり、原料のトリクロロフェニルシランに対するスルホン化の収率は６０％であった。
【００１６】
【比較例１】
特開平１１−２０９４７２号公報実施例１に記載の方法に従い、スルホン酸基含有エトキシシランのエタノール溶液の合成を行った。 滴下ロートを取り付けた２口の５００ｍｌの丸底フラスコにトリクロロフェニルシラン１２４．０ｇ（０．５９ｍｏｌ）、塩化メチレンを２００ｍｌ入れ、氷冷する。これに三酸化硫黄４６．８ｇ（０．５９ｍｏｌ）を塩化メチレン１００ｍｌに溶解させた溶液を３０分かけて滴下した。室温で５時間攪拌した後、オイルバスを用いて加熱し、塩化メチレンを留去した。さらにエタノール１６１．５ｇを滴下し、次いで窒素をバブリングし、発生する塩化水素を取り除きながら、５０時間還流した。これを放冷し、スルホン酸基含有エトキシシランのエタノール溶液２３６．０ｇを得た。このエタノール溶液１５．６ｇを冷却管及び攪拌棒を取り付けた３口の５００ｍｌの丸底フラスコにテトラエトキシシラン８７．０ｇ（０．４２ｍｏｌ）、エタノール１００ｍｌを加え混合する。これに水１５．０ｇを３０分間で滴下した。次いでオイルバス中で過熱し、６０℃で３時間攪拌した。放冷後、水７６．０ｇを混合し、２８％アンモニア水１０ｍｌを加えたところ、反応液は固化した。室温で４時間放置し、減圧下溶媒を留去した。得られた固体を５００ｍｌのビーカーに入れ、２Ｎ塩酸２００ｍｌを加え、攪拌機を用いて３０分間攪拌し、濾別した。この酸処理の操作を再度繰り返した後、漏斗上で純水３００ｍｌで洗浄する操作を２回繰り返した。固体を減圧乾燥器に入れ、１０ｍｍＨｇの減圧下、１００℃で６時間乾燥させ、スルホン酸基含有有機高分子シロキサンを３０．５ｇ得た。この有機高分子シロキサンの固体酸量を上記した処方により、測定した結果、０．５２ｍｍｏｌ／ｇであった。従って、得られたスルホン酸の量は１５．６ｍｍｏｌとなり、原料のトリクロロフェニルシランに対するスルホン化の収率は４０％であった。
【００１７】
【比較例２】
滴下ロートを取り付けた２口の３００ｍｌの丸底フラスコに１，２−ジクロロエタンを１００ｍｌ入れ、これにフェニルトリクロロシラン４３．０ｇ（０．２０ｍｏｌ）を加え、氷冷した。これに三酸化硫黄１６．０ｇ（０．２０ｍｏｌ）の１，２−ジクロロエタン溶液２０ｍｌを、１時間かけて滴下した。滴下後、還流下、８５℃で２時間反応を行った。さらにエタノール５１．０ｇを窒素気流下、塩化水素を除きながら１時間かけて滴下し、ついで１，２−ジクロロエタンを留去した。さらに、エタノール５１．０ｇを滴下し、２時間還流し、スルホン酸基含有エトキシシランのエタノール溶液１３３．０ｇを得た。このエタノール溶液１９．５ｇを冷却管及び攪拌棒を取り付けた３口の５００ｍｌの丸底フラスコにテトラエトキシシラン８７．７ｇ（０．４２ｍｏｌ）、エタノール１００ｍｌを加え混合する。これに水１５．１ｇを３０分間で滴下した。次いでオイルバス中で過熱し、６０℃で３時間攪拌した。放冷後、水７６．０ｇを混合し、２８％アンモニア水１０ｍｌを加えたところ、反応液は固化した。室温で４時間放置し、減圧下溶媒を留去した。得られた固体を５００ｍｌのビーカーに入れ、２Ｎ塩酸２００ｍｌを加え、攪拌機を用いて３０分間攪拌し、濾別した。この酸処理の操作を再度繰り返した後、漏斗上で純水３００ｍｌで洗浄する操作を２回繰り返した。固体を減圧乾燥器に入れ、１０ｍｍＨｇの減圧下、１００℃で６時間乾燥させ、スルホン酸基含有有機高分子シロキサンを３０．０ｇ得た。この有機高分子シロキサンの固体酸量を上記した処方により、測定した結果、０．５０ｍｍｏｌ／ｇであった。従って、得られたスルホン酸の量は１５．０ｍｍｏｌとなり、原料のトリクロロフェニルシランに対するスルホン化の収率は５０％であった。
【００１８】
【発明の効果】
本発明の方法により、高いスルホン化収率でフェニルスルホン酸基を有する有機高分子シロキサンを得ることができ、工業的に極めて有利にスルホン酸基含有有機高分子シロキサンの製造を行うことができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a sulfonic acid group-containing organic high molecular siloxane useful as an ion exchanger and a solid acid catalyst.
[0002]
[Prior art]
Strongly acidic ion exchangers having a sulfonic acid group are widely used, for example, as desalination of water and aqueous solutions, solid acid catalysts in chemical synthesis, and the like. The cation exchangers used in most cases have a polystyrene skeleton and have phenylsulfonic acid groups, commonly referred to as cation exchange resins. Cation exchange resins have low heat resistance, and the upper limit of use is generally 100 to 130 ° C. In addition, it has disadvantages such as breakage due to remarkable swelling property and brittleness of mechanical strength.
[0003]
On the other hand, examples of the inorganic polymer-based ion exchanger include an organic polymer siloxane. JP-A-59-20325 and JP-A-61-272237 disclose sulfonic acid group-containing organic high molecular siloxanes in which sulfonic acid groups are bonded to a silica matrix by an organic spacer group. I have. The sulfonic acid group-containing organic high molecular siloxane is obtained by oxidizing a polysulfide polymer and sulfonating a solid organic high molecular siloxane. Since the sulfonation step is a reaction with a solid, the sulfonation reaction efficiency is low. However, the organic polymer siloxane is eluted during sulfonation depending on the solvent, so that there are many problems in the production method. JP-A-6-207022 discloses a method of synthesizing an aqueous solution of a sulfonic acid group-containing siloxane and hydrolyzing it with another alkoxysilane to produce a sulfonic acid group-containing organic polymer siloxane. . However, in this method, the siloxane aqueous solution having a sulfonic acid group is obviously a polymer, and it is clear that there is a problem in water resistance because the polymer having a high sulfonic acid group concentration is simply immobilized.
[0004]
On the other hand, JP-A-11-209472 discloses a method for producing a sulfonic acid group-containing organic polymer siloxane using a sulfonic acid group-containing alkoxysilane. In this method, the alkoxysilane molecules are uniformly mixed and simultaneously hydrolyzed and co-condensed, so the sulfonic acid groups are considered to be uniformly dispersed, and the water resistance is dramatically improved. ing. As a method for synthesizing a sulfonic acid group-containing alkoxysilane, a phenyl group-containing organosilicon compound is contacted with a sulfonating agent. As sulfonating agents for phenyl groups, sulfuric acid, fuming sulfuric acid, chlorosulfuric acid, sulfur trioxide and the like are generally known, but organosilicon compounds capable of forming a polymeric siloxane matrix have hydrolytic properties. Therefore, non-aqueous chlorosulfuric acid, sulfur trioxide and the like are used. The examples describe a method in which a solution of 1 equivalent of sulfur trioxide in methylene chloride is added dropwise to phenyltrichlorosilane in a methylene chloride solvent, and the mixture is stirred at room temperature for several hours to perform sulfonation. Since it is difficult to isolate an organosilicon compound having a phenylsulfonic acid group, it is mixed with a parent agent capable of forming a silica matrix such as tetraethoxysilane, and an organic polymer siloxane is obtained by hydrolysis and polycondensation. . By measuring the amount of the solid acid, the amount of the phenylsulfonic acid group can be quantified, and the sulfonation yield can be calculated.
[0005]
However, the patent has a problem that the amount of sulfonic acid can be obtained only in a low yield of 40 to 45% with respect to the amount of phenyl group charged. In order to increase the yield of sulfonation, a method of increasing the reaction efficiency by increasing the reaction temperature of sulfonation and excessively adding the amount of the sulfonating agent is naturally considered. Org. Chem. , 20, 455 (1955), it is well known that excess sulfonating agent is not preferable in the yield of sulfonic acid, such as by-product of sulfone, in the sulfonation reaction. Further, since the sulfonating agent is generally a highly reactive reagent used for decomposing organic substances, no attempt has been made to actually use the sulfonating agent in excess.
[0006]
[Problems to be solved by the present invention]
The present invention provides a method for producing a sulfonic acid group-containing polymer siloxane using an organic silicon compound having a phenylsulfonic acid group, by controlling the reaction temperature when sulfonating the phenyl group-containing organic silicon compound to reduce the amount of sulfur trioxide. By using it in excess, a phenylsulfonic acid group-containing organic polymer siloxane having a high sulfonation yield is obtained.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve such a problem, and determined that the phenyl group-containing organosilicon compound was converted into “molar amount of phenyl group-containing organic silicon compound”: “molar amount of sulfur trioxide” = 1: 2 to 2 The present inventors have found that a phenylsulfonic acid group-containing organic high molecular siloxane having a high sulfonation yield can be obtained by contacting with an excessive amount of sulfur trioxide, which is 3, and the present invention has been completed.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The production of an organosilicon compound having a phenylsulfonic acid group in the present invention is carried out by contacting a phenyl group-containing organosilicon compound with sulfur trioxide in the absence of a solvent or in the presence of an inert solvent as described in JP-A-11-209472. Can be obtained. The reaction temperature of the sulfonation is preferably from 30 to 90 ° C, particularly preferably from 30 to 45 ° C.
The phenyl group-containing organosilicon compound has the general formula:
Embedded image
[0010]
Here, the method for synthesizing an organosilicon compound having a phenylsulfonic acid group in the present invention will be specifically described. An excess amount of sulfur trioxide is added to the phenyl group-containing organosilicon compound [1] in the presence of a solvent. Sulfonation is an exothermic reaction, but the reaction temperature is preferably controlled at 30 to 90 ° C., particularly preferably 30 to 45 ° C., and the mixture is stirred for several hours to obtain a phenylsulfonic acid group-containing organosilicon compound. . Next, an excess amount of alcohol is added to the halogen group, and alkoxylation is performed while removing generated hydrogen chloride, to obtain an alcohol solution containing an alkoxysilane compound having a phenylsulfonic acid group. This solution is mixed with a tetraalkoxysilane capable of forming a silica matrix at an arbitrary ratio, and a phenylsulfonic acid group-containing organic high molecular siloxane is prepared by sol-gel preparation. Sol-gel preparation is a dehydration condensation of a mixed sol obtained by mixing a sulfonic acid group-containing alkoxysilane compound capable of forming a polymer siloxane matrix and a tetraalkoxysilane compound capable of forming a silica matrix and simultaneously hydrolyzing the mixture. This is a preparation method for producing a sulfonic acid group-containing organic high molecular siloxane in which a high molecular siloxane matrix is formed by gelation by the method.
[0011]
Here, the mixed gelation in the present invention will be described. The mixed gelation in the present invention is sufficiently achieved by a general mixed sol-gel reaction of different alkoxysilanes. As a specific example of a mixed gelation method which is easy to carry out, a desired amount of the above-mentioned alkoxysilane compound having a sulfonic acid group as an acid component of the catalyst is charged, and a tetraalkoxysilane compound such as tetraethoxysilane is added. Mix, and if necessary, make a uniform mixed solution using a solvent such as ethanol. After adding an amount of water necessary for hydrolysis of the alkoxy group thereto, the mixture is reacted under acidic conditions at a temperature of usually 10 to 200 ° C., preferably 30 to 100 ° C. for 1 hour to 3 weeks with stirring. Let it. The obtained high-viscosity liquid is generally called silica sol. Excess water and aqueous ammonia are added to the above sol with respect to the amount of water necessary for hydrolysis of the alkoxy group, and under basic conditions, the temperature is usually 10 to 200 ° C, preferably 30 to 100 ° C. Gel at 1 ° C for 1 hour to 3 weeks. In this case, if necessary, the mixture may be heated and stirred to ripen it for a long time.
[0012]
In carrying out the gelation, the gelation may be carried out by diluting in a medium such as an alcohol or an aliphatic saturated hydrocarbon (hexane, heptane, etc.) which is inert to the sol. The obtained gel can be isolated by filtration or distilling off the solvent. Since the sulfonic acid in this gel is an ammonium salt type, it must be returned to the acid form by an acid treatment with hydrochloric acid or the like in order to use it as an ion exchanger and a solid acid catalyst. This organic high molecular siloxane is a formula generally used for measuring the acid content of cation exchange resin, that is, the amount of hydrochloric acid released is determined by ion-exchange with an excess sodium chloride aqueous solution with respect to the expected acid content. It is possible to obtain the amount of the sulfonic acid.
[0013]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, this embodiment is merely an example, and the present invention is not limited thereto. In the examples, the obtained sulfonation yield was represented by the sulfonation yield (the amount of phenylsulfonic acid groups of the prepared organic polymer siloxane with respect to the charged phenyltrichlorosilane).
[0014]
Embodiment 1
100 ml of methylene chloride was placed in a 300 ml round bottom flask equipped with a dropping funnel and 39.1 g (0.19 mol) of phenyltrichlorosilane was added thereto, followed by cooling with ice. 20 ml of a methylene chloride solution containing 37.3 g (0.47 mol) of sulfur trioxide was added dropwise thereto over 1 hour. After the addition, the reaction was carried out at 45 ° C. for 2 hours under reflux. Under reflux, 46.0 g of ethanol was added dropwise over 1 hour while removing hydrogen chloride under a nitrogen stream, and then methylene chloride was distilled off. Further, 46.0 g of ethanol was added dropwise thereto and refluxed for 2 hours to obtain 146.0 g of an ethanol solution of ethoxysilane containing a phenylsulfonic acid group. Into a three-necked 500 ml round bottom flask equipped with a cooling tube and a stirring rod, 83.2 g (0.40 mol) of tetraethoxysilane and 100 ml of ethanol were added and mixed with 22.0 g of the ethanol solution. To this was added 14.4 g of water dropwise over 30 minutes. Then, the mixture was heated in an oil bath and stirred at 60 ° C. for 3 hours. After cooling, 72.0 g of water was mixed and 10 ml of 28% aqueous ammonia was added, and the reaction solution was solidified. After leaving at room temperature for 4 hours, the solvent was distilled off under reduced pressure. The obtained solid was placed in a 500 ml beaker, 200 ml of 2N hydrochloric acid was added, the mixture was stirred for 30 minutes using a stirrer, and filtered. After repeating the operation of the acid treatment, the operation of washing with 300 ml of pure water on the funnel was repeated twice. The solid was placed in a vacuum dryer and dried at 100 ° C. for 6 hours under a reduced pressure of 10 mmHg to obtain 30.0 g of a sulfonic acid group-containing organic high molecular siloxane. As a result of measuring the solid acid amount of this organic polymer siloxane by the above-mentioned recipe, it was 0.65 mmol / g. Accordingly, the amount of the obtained sulfonic acid was 19.5 mmol, the sulfonation yield relative to the raw material trichlorophenylsilane was 70%, and the sulfonating agent was used in excess and the sulfonation reaction temperature was set to 45 ° C. , High yields were obtained.
[0015]
Embodiment 2
100 ml of 1,2-dichloroethane was put into a two-necked 300 ml round bottom flask equipped with a dropping funnel, and 43.0 g (0.20 mol) of phenyltrichlorosilane was added thereto, followed by cooling with ice. To this, 20 ml of a solution of 41.0 g (0.51 mol) of sulfur trioxide in 1,2-dichloroethane was added dropwise over 1 hour. After the addition, the reaction was carried out at 85 ° C. for 2 hours under reflux. Further, under reflux, 51.0 g of ethanol was added dropwise over 1 hour while removing hydrogen chloride under a nitrogen stream, and then 1,2-dichloroethane was distilled off. Further, 51.0 g of ethanol was added dropwise, and the mixture was refluxed for 2 hours to obtain 158.0 g of an ethanol solution of sulfonic acid group-containing ethoxysilane. Into a three-necked 500 ml round bottom flask equipped with a cooling tube and a stirring rod, 87.3 g (0.42 mol) of tetraethoxysilane and 100 ml of ethanol are mixed with 19.3 g of the ethanol solution. To this, 15.1 g of water was added dropwise over 30 minutes. Then, the mixture was heated in an oil bath and stirred at 60 ° C. for 3 hours. After cooling, 76.0 g of water was mixed, and 10 ml of 28% aqueous ammonia was added, whereby the reaction solution was solidified. After leaving at room temperature for 4 hours, the solvent was distilled off under reduced pressure. The obtained solid was placed in a 500 ml beaker, 200 ml of 2N hydrochloric acid was added, the mixture was stirred for 30 minutes using a stirrer, and filtered. After repeating the operation of the acid treatment, the operation of washing with 300 ml of pure water on the funnel was repeated twice. The solid was placed in a vacuum drier and dried at 100 ° C. for 6 hours under a reduced pressure of 10 mmHg to obtain 31.0 g of a sulfonic acid group-containing organic high molecular siloxane. As a result of measuring the amount of solid acid of this organic polymer siloxane by the above-mentioned recipe, it was 0.48 mmol / g. Therefore, the amount of the obtained sulfonic acid was 15.0 mmol, and the yield of sulfonation based on the starting material trichlorophenylsilane was 60%.
[0016]
[Comparative Example 1]
According to the method described in Example 1 of JP-A-11-209472, an ethanol solution of sulfonic acid group-containing ethoxysilane was synthesized. 124.0 g (0.59 mol) of trichlorophenylsilane and 200 ml of methylene chloride are placed in a two-necked 500 ml round bottom flask equipped with a dropping funnel, and cooled with ice. To this, a solution in which 46.8 g (0.59 mol) of sulfur trioxide was dissolved in 100 ml of methylene chloride was added dropwise over 30 minutes. After stirring at room temperature for 5 hours, the mixture was heated using an oil bath to distill off methylene chloride. Further, 161.5 g of ethanol was added dropwise, and the mixture was refluxed for 50 hours while bubbling nitrogen to remove generated hydrogen chloride. This was allowed to cool, and 236.0 g of an ethanol solution of sulfonic acid group-containing ethoxysilane was obtained. Into a three-necked 500 ml round bottom flask equipped with a condenser and a stirring rod, 15.6 g of this ethanol solution was mixed with 87.0 g (0.42 mol) of tetraethoxysilane and 100 ml of ethanol and mixed. To this, 15.0 g of water was added dropwise over 30 minutes. Then, the mixture was heated in an oil bath and stirred at 60 ° C. for 3 hours. After cooling, 76.0 g of water was mixed, and 10 ml of 28% aqueous ammonia was added, whereby the reaction solution was solidified. After leaving at room temperature for 4 hours, the solvent was distilled off under reduced pressure. The obtained solid was placed in a 500 ml beaker, 200 ml of 2N hydrochloric acid was added, the mixture was stirred for 30 minutes using a stirrer, and filtered. After repeating the operation of the acid treatment, the operation of washing with 300 ml of pure water on the funnel was repeated twice. The solid was placed in a vacuum dryer and dried at 100 ° C. for 6 hours under a reduced pressure of 10 mmHg to obtain 30.5 g of a sulfonic acid group-containing organic polymer siloxane. As a result of measuring the solid acid amount of this organic polymer siloxane by the above-mentioned recipe, it was 0.52 mmol / g. Therefore, the amount of the obtained sulfonic acid was 15.6 mmol, and the yield of sulfonation based on the raw material trichlorophenylsilane was 40%.
[0017]
[Comparative Example 2]
100 ml of 1,2-dichloroethane was put into a two-necked 300 ml round bottom flask equipped with a dropping funnel, and 43.0 g (0.20 mol) of phenyltrichlorosilane was added thereto, followed by cooling with ice. To this, 20 ml of a solution of 16.0 g (0.20 mol) of sulfur trioxide in 1,2-dichloroethane was added dropwise over 1 hour. After the addition, the reaction was carried out at 85 ° C. for 2 hours under reflux. Further, 51.0 g of ethanol was added dropwise over 1 hour while removing hydrogen chloride under a nitrogen stream, and then 1,2-dichloroethane was distilled off. Further, 51.0 g of ethanol was added dropwise and refluxed for 2 hours to obtain 133.0 g of an ethanol solution of sulfonic acid group-containing ethoxysilane. To a three-necked 500 ml round-bottomed flask equipped with a cooling tube and a stirring rod, 19.7 g of this ethanol solution was mixed with 87.7 g (0.42 mol) of tetraethoxysilane and 100 ml of ethanol, and mixed. To this, 15.1 g of water was added dropwise over 30 minutes. Then, the mixture was heated in an oil bath and stirred at 60 ° C. for 3 hours. After cooling, 76.0 g of water was mixed, and 10 ml of 28% aqueous ammonia was added, whereby the reaction solution was solidified. After leaving at room temperature for 4 hours, the solvent was distilled off under reduced pressure. The obtained solid was placed in a 500 ml beaker, 200 ml of 2N hydrochloric acid was added, the mixture was stirred for 30 minutes using a stirrer, and filtered. After repeating this acid treatment operation, the operation of washing with 300 ml of pure water on the funnel was repeated twice. The solid was placed in a vacuum dryer and dried at 100 ° C. for 6 hours under a reduced pressure of 10 mmHg to obtain 30.0 g of a sulfonic acid group-containing organic high molecular siloxane. As a result of measuring the solid acid amount of this organic polymer siloxane by the above-mentioned recipe, it was 0.50 mmol / g. Therefore, the amount of the obtained sulfonic acid was 15.0 mmol, and the yield of sulfonation based on the raw material trichlorophenylsilane was 50%.
[0018]
【The invention's effect】
According to the method of the present invention, an organic high molecular siloxane having a phenylsulfonic acid group can be obtained with a high sulfonation yield, and the production of an organic high molecular siloxane containing a sulfonic acid group can be extremely advantageously performed industrially.
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| JP2003106167A JP2004307737A (en) | 2003-04-10 | 2003-04-10 | Method for producing sulfonic acid group-containing organic polymer siloxane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007224299A (en) * | 2006-02-21 | 2007-09-06 | Samsung Sdi Co Ltd | Polysiloxane compound, its preparation process, polymer electrolyte membrane, membrane electrode assembly and fuel cell |
| EP2283064A1 (en) * | 2008-05-23 | 2011-02-16 | University Of Ontario Institute Of Technology | Sulfonated poly 2-(phenyl ethyl) siloxane polymer electrolyte membranes |
-
2003
- 2003-04-10 JP JP2003106167A patent/JP2004307737A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007224299A (en) * | 2006-02-21 | 2007-09-06 | Samsung Sdi Co Ltd | Polysiloxane compound, its preparation process, polymer electrolyte membrane, membrane electrode assembly and fuel cell |
| US7833665B2 (en) | 2006-02-21 | 2010-11-16 | Samsung Sdi Co., Ltd. | Polysiloxane compound containing sulfonic acid groups, method of preparing the same and fuel cell including the same |
| EP2283064A1 (en) * | 2008-05-23 | 2011-02-16 | University Of Ontario Institute Of Technology | Sulfonated poly 2-(phenyl ethyl) siloxane polymer electrolyte membranes |
| EP2283064A4 (en) * | 2008-05-23 | 2012-02-01 | Univ Ontario Inst Of Technology | Sulfonated poly 2-(phenyl ethyl) siloxane polymer electrolyte membranes |
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