JP3849837B2 - Synthesis method of dimethyltin dichloride - Google Patents
Synthesis method of dimethyltin dichloride Download PDFInfo
- Publication number
- JP3849837B2 JP3849837B2 JP35257499A JP35257499A JP3849837B2 JP 3849837 B2 JP3849837 B2 JP 3849837B2 JP 35257499 A JP35257499 A JP 35257499A JP 35257499 A JP35257499 A JP 35257499A JP 3849837 B2 JP3849837 B2 JP 3849837B2
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- JP
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- Prior art keywords
- dimethyltin dichloride
- catalyst
- iodine
- tin
- synthesis method
- 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.)
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- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 title claims description 33
- 238000001308 synthesis method Methods 0.000 title claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229940050176 methyl chloride Drugs 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 15
- 239000011630 iodine Substances 0.000 description 15
- 229910052740 iodine Inorganic materials 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 150000002903 organophosphorus compounds Chemical class 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052794 bromium Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ORICWOYODJGJMY-UHFFFAOYSA-N dibutyl(phenyl)phosphane Chemical compound CCCCP(CCCC)C1=CC=CC=C1 ORICWOYODJGJMY-UHFFFAOYSA-N 0.000 description 1
- -1 dimethyloctadecyl- Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 1
- QRPRIOOKPZSVFN-UHFFFAOYSA-M methyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 QRPRIOOKPZSVFN-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- OTRDBBWACSONSO-UHFFFAOYSA-M tetra(propan-2-yl)phosphanium bromide Chemical compound [Br-].C(C)(C)[P+](C(C)C)(C(C)C)C(C)C OTRDBBWACSONSO-UHFFFAOYSA-M 0.000 description 1
- WPAXXEKCJAHNDT-UHFFFAOYSA-M tetra(propan-2-yl)phosphanium;chloride Chemical compound [Cl-].CC(C)[P+](C(C)C)(C(C)C)C(C)C WPAXXEKCJAHNDT-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 1
- FBOJNMRAZJRCNS-UHFFFAOYSA-M tetraethylphosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC FBOJNMRAZJRCNS-UHFFFAOYSA-M 0.000 description 1
- ZTXFOCMYRCGSMU-UHFFFAOYSA-M tetramethylphosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C ZTXFOCMYRCGSMU-UHFFFAOYSA-M 0.000 description 1
- NJFUXFRJVIXVSG-UHFFFAOYSA-M tetramethylphosphanium;chloride Chemical compound [Cl-].C[P+](C)(C)C NJFUXFRJVIXVSG-UHFFFAOYSA-M 0.000 description 1
- BWXDLFXRIPTPKN-UHFFFAOYSA-N tetraoctadecylphosphanium Chemical compound CCCCCCCCCCCCCCCCCC[P+](CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC BWXDLFXRIPTPKN-UHFFFAOYSA-N 0.000 description 1
- DLBWLSUBWVYALN-UHFFFAOYSA-M tetraoctadecylphosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[P+](CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC DLBWLSUBWVYALN-UHFFFAOYSA-M 0.000 description 1
- QVBRLOSUBRKEJW-UHFFFAOYSA-M tetraoctylphosphanium;bromide Chemical compound [Br-].CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QVBRLOSUBRKEJW-UHFFFAOYSA-M 0.000 description 1
- AXTXARBFPWQUQA-UHFFFAOYSA-M tetraoctylphosphanium;chloride Chemical compound [Cl-].CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC AXTXARBFPWQUQA-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は太陽電池を構成する透明導電膜ＳｎＯ2の原料として使用することができる高純度の二塩化ジメチルスズの合成方法に関するものである。
【０００２】
【従来の技術】
二塩化ジメチルスズを合成する方法において、金属スズと塩化メチルとを原料とし、触媒を用いて合成する方法が多数開発されている。実用的な収率を得るための方法としては、触媒としてヨウ素含有化合物を用いる方法が提案されている（米国特許３５１９６６５号、及び英国特許１０５３９９６号）。しかし、一般的にこのようなヨウ素含有化合物は高価であるので、コストを下げるために使用済みの触媒を回収・再生する等の方法もなされているが、この作業自体が時間もコストもかかるので、結果として、大きなコストダウンにはなっていない。
また、ヨウ素化合物を触媒として用いて合成された二塩化ジメチルスズの粗結晶の純度は５０〜９９％であるので、精製する必要がある。精製後に得られる製品中には、副生成物はもちろん、触媒も残留していないことが望ましい。これは、如何なる触媒を使って他の化合物を合成する場合でも当然要求される特性であるが、ヨウ素化合物を触媒として用いた場合、精製工程を経てもヨウ素分が残留し易い。特に、よく用いられている蒸留法で精製を行う場合に多く残留し易い。これは、ヨウ素が持つ昇華性が原因の一つであり、製品を蒸留する時にヨウ素も同時に昇華してしまうためである。そうすると、日数が経つにつれて残留ヨウ素分によって製品である二塩化ジメチルスズが着色してくるという問題が生じる。着色した二塩化ジメチルスズは、透明性導電膜ＳｎＯ2の原料としては用いることは難しい。
【０００３】
【発明が解決しようとする課題】
本発明は上記した問題点を解決することにあり、経済的で、しかも高純度で着色の心配のない二塩化ジメチルスズの合成方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明者等は触媒としてヨウ素含有化合物を用いずに二塩化ジメチルスズを合成する方法を鋭意検討した結果、有機リン化合物を触媒として用いることにより二塩化ジメチルスズが得られることを見いだし、本発明を成すに至った。
【０００５】
すなわち本発明は、触媒の存在下で金属スズと塩化メチルとを反応させる二塩化ジメチルスズの合成方法であって、前記触媒は下記の一般式（Ｉ）で示される有機リン化合物であることを特徴とする二塩化ジメチルスズの合成方法である。
【０００６】
【化２】
【０００７】
また、前記有機リン化合物は、スズ１グラム原子当たり０．００１〜０．０５モル添加することが好ましい。
【０００８】
さらにまた、前記反応は、反応温度１００〜３００℃、反応圧力は１〜１０ＭＰａで行われることが好ましい。
【０００９】
【発明の実施の形態】
本発明では、二塩化ジメチルスズの合成時に、触媒として下記の一般式（Ｉ）で示される有機リン化合物を用いる。
【００１０】
【化３】
【００１１】
有機リン化合物の具体的な例としては、トリメチルホスフィン、トリイソプロピル−、トリブチル−、トリｓ−ブチル−、トリオクチル−、ジブチルドデシル−、ジメチルオクタデシル−、トリフェニル−、ジブチルフェニルホスフィン、テトラメチルホスホニウムクロライド、テトラメチルホスホニウムブロマイド、テトラエチルホスホニウムクロライド、テトラエチルホスホニウムブロマイド、テトライソプロピルホスホニウムクロライド、テトライソプロピルホスホニウムブロマイド、テトラブチルホスホニウムクロライド、テトラブチルホスホニウムブロマイド、テトラオクチルホスホニウムクロライド、テトラオクチルホスホニウムブロマイド、テトラオクタデシルホスホニウムクロライド、テトラオクタデシルホスホニウムブロマイド、テトラフェニルホスホニウムクロライド、テトラフェニルホスホニウムブロマイド、メチルトリフェニルホスホニウムクロライド、メチルトリフェニルホスホニウムブロマイド等がある。好ましい化合物としてはトリフェニルホスフィン等が挙げられる。
【００１２】
これら有機リン化合物は、ヨウ素のような昇華性を有していないので、二塩化ジメチルスズ合成後の精製時に蒸留法を用いても、製品である二塩化ジメチルスズ中に残留しにくいので、高純度のものが得られる。
【００１３】
有機リン化合物の添加量は、スズ１グラム原子当り０．００１〜０．０５モル用いるのが好ましく、さらに好ましくは０．０１〜０．０３モルである。０．０５モルより多く用いると、二塩化ジメチルスズ中にリン成分が多く残留し易くなるので好ましくない。また、０．００１モル未満の極低濃度においてはスズの転化率が低下し、未反応の原料が残って二塩化ジメチルスズの収率が減少するので好ましくない。
【００１４】
また、反応媒体としては、有機エーテル又はこれらと芳香族炭化水素溶媒、もしくは脂肪族炭化水素溶媒との混合物を用いることができる。具体的な例としては、有機エーテルとしてはジエチルエーテル、ジブチルエーテル、テトラヒドロフラン等、芳香族炭化水素溶媒としてはベンゼン、トルエン、キシレン等、脂肪族炭化水素溶媒としてはヘキサン、ヘプタン、オクタン等が挙げられる。これらのうち、好ましくはエーテル化合物であり、さらに好ましくはテトラヒドロフランである。使用する溶媒の量は、金属スズに対して重量比で０．０１〜１０倍であればよく、反応容器等に応じてこの範囲内の取り扱いやすい量に設定することができる。
【００１５】
塩化メチルの添加量は、スズ１グラム原子当たり２．０〜４．０モルの範囲が好ましく、特に好ましくは２．４〜２．８モルである。この範囲で使用することにより（ＣＨ3）nＳｎＣｌ4-n（ｎ＝０，１，３，４）で示される副生成物の生成を抑制することができる。
【００１６】
反応温度は１００〜３００℃が好ましく、さらに好ましくは１５０〜２５０℃である。反応温度が１００℃未満では反応が進みにくく、また、３００℃をこえると副生成物が生成し易くなるので好ましくない。圧力は１〜１０ＭＰａが好ましく、さらに好ましくは２〜４．５ＭＰａである。圧力が１ＭＰａ未満では反応が進みにくく、また、１０ＭＰａをこえると、副生成物が生成するため好ましくない。
【００１７】
金属スズの形状は、生成する二塩化ジメチルスズの特性に影響を与えるものではないので、任意の形状のものを用いることができるが、好ましくは表面積の大きな金属スズである。このような金属スズを用いれば反応を早く終了させることができ、工程時間を短縮することができる。
【００１８】
【実施例】
実施例で本発明の二塩化ジメチルスズの合成方法について詳述するが、以下に示す実施例は本発明を具現化させる一例を示すものであり、本発明を拘束するものではない。
【００１９】
（実施例１）
内容量２０Ｌの耐圧反応容器にスズ微細片１６００g、トリフェニルホスフィン３５．４g（スズ１グラム原子当り０．０１モル）、塩化メチル１９００ｇ及びテトラヒドロフラン７２０ｍＬを入れ、圧力３．７ＭＰａ、温度１６５℃で８時間加熱しながら撹拌して、二塩化ジメチルスズを得た。得られた二塩化ジメチルスズ２９４６．５ｇをキシレン８．９Ｌに溶解し、加熱しながら１．０時間還流させた後、溶液が冷えないうちに濾過した。室温まで冷却して結晶を析出させた後、この結晶を濾過、乾燥して本発明の二塩化ジメチルスズ２７９９．２g（精製収率９４．５％）を得た。得られた二塩化ジメチルスズのリンの分析値は６．５ｐｐｍであった。なお、分析は、ＩＣＰを用いて測定した。
【００２０】
（実施例２）
内容量２０Ｌの耐圧反応容器にスズ微細片１６００g、トリフェニルホスフィン３．５g（スズ１グラム原子当り０．００１モル）、塩化メチル１９５８ｇ及びテトラヒドロフラン７４２ｍＬを入れ、圧力３．８ＭＰａ、温度１７０℃で８時間加熱しながら撹拌して、二塩化ジメチルスズを得た。得られた二塩化ジメチルスズ２７２４ｇをキシレン８．３Ｌに溶解し、加熱しながら１．０時間還流させた後、溶液が冷えないうちに濾過した。室温まで冷却して結晶を析出させた後、この結晶を濾過、乾燥して本発明の二塩化ジメチルスズ２５９０g（精製収率８７．５％）を得た。得られた二塩化ジメチルスズのリンの分析値は２．４ｐｐｍであった。
【００２１】
（比較例１）
内容量２０Ｌの耐圧反応容器にスズ微細片１６００g、ヨウ素含有触媒としてヨウ化ブチル１３５g、マグネシウム３．２g、塩化メチル１６３５g及びテトラヒドロフラン７５０ｍＬを入れ、圧力３．３５ＭＰａ、温度１７０℃で７時間加熱しながら撹拌して、二塩化ジメチルスズを得た。得られた二塩化ジメチルスズ３．６ｋｇ、をキシレン８．２Ｌに溶解し、加熱しながら０．５時間還流させた後、溶液が冷えないうちに濾過した。室温まで冷却して結晶を析出させた後、この結晶を濾過、乾燥して二塩化ジメチルスズ２５８０ｇ（精製収率８７．４％）を得た。得られた二塩化ジメチルスズについて、デンプン水溶液によるヨウ素の有無テストを行った結果、デンプン水溶液が青紫色に変色た。また、ヨウ素の分析値は２０ｐｐｍであった。なお、二塩化ジメチルスズ中に含まれるヨウ素分の定性には１ｗｔ％デンプン水溶液を用いた。具体的には、二塩化ジメチルスズ３ｇを水３ｍＬに溶解させ、１ｗｔ％デンプン水溶液を０．２ｍＬ添加して色の変化を見た。無色ならヨウ素は存在せず（検出限界０．０１ｐｐｍ）、青紫色になればヨウ素分が含まれている。又、ヨウ素の定量には、１ｗｔ％デンプン水溶液を指示薬としてチオ硫酸ナトリウム水溶液による滴定で行った。
【００２２】
【発明の効果】
以上説明したように、本発明の二塩化ジメチルスズの合成方法では、触媒として有機リン化合物を使用する。そのため、従来のようなヨウ素含有化合物を触媒に用いた場合に比べて、有機リン化合物自体が安価である上に、触媒の回収等の余計な工程も必要なくなって工程が短縮されるので、さらにコストが安価になる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for synthesizing high-purity dimethyltin chloride that can be used as a raw material for a transparent conductive film SnO 2 constituting a solar cell.
[0002]
[Prior art]
In the method of synthesizing dimethyltin dichloride, many methods have been developed using metal tin and methyl chloride as raw materials and using a catalyst. As a method for obtaining a practical yield, a method using an iodine-containing compound as a catalyst has been proposed (US Pat. No. 3,519,665 and British Patent 1053996). However, since such iodine-containing compounds are generally expensive, there are methods such as collecting and regenerating used catalysts in order to reduce costs. However, this work itself takes time and costs. As a result, the cost is not greatly reduced.
Moreover, since the purity of the crude crystals of dimethyltin dichloride synthesized using an iodine compound as a catalyst is 50 to 99%, it needs to be purified. In the product obtained after purification, it is desirable that not only by-products but also catalyst remain. This is a characteristic that is naturally required when other compounds are synthesized using any catalyst. However, when an iodine compound is used as a catalyst, iodine content tends to remain even after a purification step. In particular, a large amount tends to remain when purification is performed by a commonly used distillation method. This is because the sublimation property of iodine is one of the causes, and iodine is also sublimated simultaneously when the product is distilled. If it does so, the problem that dimethyltin dichloride which is a product will color with a residual iodine content as days pass will arise. The colored dimethyltin dichloride is difficult to use as a raw material for the transparent conductive film SnO 2 .
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for synthesizing dimethyltin dichloride which is economical and has high purity and is free from worry about coloring.
[0004]
[Means for Solving the Problems]
As a result of intensive studies on a method for synthesizing dimethyltin dichloride without using an iodine-containing compound as a catalyst, the present inventors have found that dimethyltin dichloride can be obtained by using an organophosphorus compound as a catalyst. It came to.
[0005]
That is, the present invention is a method for synthesizing dimethyltin dichloride in which metal tin and methyl chloride are reacted in the presence of a catalyst, wherein the catalyst is an organophosphorus compound represented by the following general formula (I): And dimethyltin dichloride synthesis method.
[0006]
[Chemical 2]
[0007]
The organophosphorus compound is preferably added in an amount of 0.001 to 0.05 mol per gram atom of tin.
[0008]
Furthermore, the reaction is preferably performed at a reaction temperature of 100 to 300 ° C. and a reaction pressure of 1 to 10 MPa.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, an organophosphorus compound represented by the following general formula (I) is used as a catalyst during the synthesis of dimethyltin dichloride.
[0010]
[Chemical 3]
[0011]
Specific examples of the organic phosphorus compound include trimethylphosphine, triisopropyl-, tributyl-, tris-butyl-, trioctyl-, dibutyldodecyl-, dimethyloctadecyl-, triphenyl-, dibutylphenylphosphine, tetramethylphosphonium chloride. , Tetramethylphosphonium bromide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetraisopropylphosphonium chloride, tetraisopropylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetraoctylphosphonium chloride, tetraoctylphosphonium bromide, tetraoctadecylphosphonium chloride, tetra Octadecylphosphonium bromide Id, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, methyltriphenylphosphonium chloride, and the like methyltriphenylphosphonium bromide. Preferred examples of the compound include triphenylphosphine.
[0012]
Since these organophosphorus compounds do not have sublimation properties like iodine, even if a distillation method is used during purification after synthesis of dimethyltin dichloride, it is difficult to remain in the product dimethyltin dichloride. Things are obtained.
[0013]
The amount of the organophosphorus compound added is preferably 0.001 to 0.05 mol, more preferably 0.01 to 0.03 mol, per gram atom of tin. If it is used in an amount of more than 0.05 mol, a large amount of phosphorus component tends to remain in dimethyltin dichloride, which is not preferable. Further, an extremely low concentration of less than 0.001 mol is not preferable because the conversion rate of tin is lowered, and unreacted raw materials remain to reduce the yield of dimethyltin dichloride.
[0014]
Moreover, as a reaction medium, organic ether or a mixture of these with an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent can be used. Specific examples include diethyl ether, dibutyl ether, tetrahydrofuran, etc. as organic ethers, benzene, toluene, xylene, etc. as aromatic hydrocarbon solvents, and hexane, heptane, octane, etc. as aliphatic hydrocarbon solvents. . Of these, ether compounds are preferable, and tetrahydrofuran is more preferable. The amount of the solvent to be used may be 0.01 to 10 times by weight with respect to the metal tin, and can be set to an easy-to-handle amount within this range depending on the reaction vessel and the like.
[0015]
The amount of methyl chloride added is preferably in the range of 2.0 to 4.0 moles per gram atom of tin, particularly preferably 2.4 to 2.8 moles. The formation of by-products represented by Using in this range (CH 3) n SnCl 4- n (n = 0,1,3,4) can be suppressed.
[0016]
The reaction temperature is preferably 100 to 300 ° C, more preferably 150 to 250 ° C. If the reaction temperature is less than 100 ° C., the reaction is difficult to proceed, and if it exceeds 300 ° C., a by-product tends to be generated, which is not preferable. The pressure is preferably 1 to 10 MPa, more preferably 2 to 4.5 MPa. If the pressure is less than 1 MPa, the reaction hardly proceeds, and if it exceeds 10 MPa, a by-product is generated, which is not preferable.
[0017]
The shape of metallic tin does not affect the properties of the dimethyltin dichloride produced, so that any shape can be used, but metallic tin with a large surface area is preferred. If such metal tin is used, the reaction can be completed quickly, and the process time can be shortened.
[0018]
【Example】
The synthesis method of dimethyltin dichloride of the present invention will be described in detail in the examples. However, the examples shown below are merely examples for embodying the present invention and do not restrict the present invention.
[0019]
Example 1
A pressure-resistant reaction vessel with an internal volume of 20 L is charged with 1600 g of fine tin pieces, 35.4 g of triphenylphosphine (0.01 mol per gram atom of tin), 1900 g of methyl chloride, and 720 mL of tetrahydrofuran, and 8 at a pressure of 3.7 MPa and a temperature of 165 ° C. Stirring with heating for hours, dimethyltin dichloride was obtained. 2946.5 g of the obtained dimethyltin dichloride was dissolved in 8.9 L of xylene, refluxed for 1.0 hour while heating, and then filtered before the solution was cooled. After cooling to room temperature to precipitate crystals, the crystals were filtered and dried to obtain 2799.2 g (purification yield 94.5%) of dimethyltin dichloride of the present invention. The analytical value of phosphorus of the obtained dimethyltin dichloride was 6.5 ppm. The analysis was performed using ICP.
[0020]
(Example 2)
A pressure-resistant reaction vessel having an internal capacity of 20 L is charged with 1600 g of fine tin pieces, 3.5 g of triphenylphosphine (0.001 mol per gram atom of tin), 1958 g of methyl chloride, and 742 mL of tetrahydrofuran, and at a pressure of 3.8 MPa and a temperature of 170 ° C. Stirring with heating for hours, dimethyltin dichloride was obtained. 2724 g of the obtained dimethyltin chloride was dissolved in 8.3 L of xylene and refluxed for 1.0 hour while heating, and then filtered before the solution was cooled. After cooling to room temperature to precipitate crystals, the crystals were filtered and dried to obtain 2590 g of dimethyltin dichloride of the present invention (purification yield: 87.5%). The analytical value of phosphorus of the obtained dimethyltin dichloride was 2.4 ppm.
[0021]
(Comparative Example 1)
A pressure-resistant reaction vessel having an internal volume of 20 L is charged with 1600 g of fine tin pieces, 135 g of butyl iodide, 3.2 g of magnesium, 1635 g of methyl chloride and 750 mL of tetrahydrofuran as an iodine-containing catalyst, and heated for 7 hours at a pressure of 3.35 MPa and a temperature of 170 ° C. Upon stirring, dimethyltin dichloride was obtained. The obtained dimethyltin dichloride (3.6 kg) was dissolved in xylene (8.2 L), refluxed for 0.5 hours with heating, and then filtered before the solution was cooled. After cooling to room temperature to precipitate crystals, the crystals were filtered and dried to obtain 2580 g of dimethyltin dichloride (purified yield: 87.4%). The obtained dimethyltin dichloride was tested for the presence or absence of iodine using an aqueous starch solution, and as a result, the aqueous starch solution turned blue-purple. The analytical value of iodine was 20 ppm. In addition, 1 wt% starch aqueous solution was used for the qualification of the iodine content contained in dimethyltin dichloride. Specifically, 3 g of dimethyltin dichloride was dissolved in 3 mL of water, and 0.2 mL of 1 wt% starch aqueous solution was added to observe the color change. If it is colorless, iodine does not exist (detection limit 0.01 ppm), and if it turns blue-purple, iodine is contained. The iodine was quantified by titration with an aqueous sodium thiosulfate solution using a 1 wt% starch aqueous solution as an indicator.
[0022]
【The invention's effect】
As explained above, in the method for synthesizing dimethyltin dichloride of the present invention, an organic phosphorus compound is used as a catalyst. Therefore, compared to the conventional case where an iodine-containing compound is used as a catalyst, the organophosphorus compound itself is cheaper, and an additional step such as recovery of the catalyst is not necessary, so the process is shortened. Cost is low.
Claims (1)
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