JP2006290674A - Method for reacting silicon hydride halide - Google Patents
Method for reacting silicon hydride halide Download PDFInfo
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- JP2006290674A JP2006290674A JP2005113194A JP2005113194A JP2006290674A JP 2006290674 A JP2006290674 A JP 2006290674A JP 2005113194 A JP2005113194 A JP 2005113194A JP 2005113194 A JP2005113194 A JP 2005113194A JP 2006290674 A JP2006290674 A JP 2006290674A
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910052990 silicon hydride Inorganic materials 0.000 title claims abstract description 30
- -1 silicon hydride halide Chemical class 0.000 title claims abstract description 19
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 25
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 15
- 239000005052 trichlorosilane Substances 0.000 claims description 15
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000005046 Chlorosilane Substances 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 230000003442 weekly effect Effects 0.000 abstract 1
- 238000007323 disproportionation reaction Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
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- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、水素化ハロゲン化珪素の反応方法に関する。例えば、トリクロロシラン等を触媒の存在下に反応させることにより、ジクロロシランを製造する方法に関する。 The present invention relates to a method for reacting a silicon hydride halide. For example, the present invention relates to a method for producing dichlorosilane by reacting trichlorosilane or the like in the presence of a catalyst.
水素化ハロゲン化珪素は、一般的に水素化ハロゲン化珪素を不均化して目的とするシラン化合物を含む混合物を得、次いでこれを蒸留等の方法により必要とする成分を精製して製造される。 A silicon hydride is generally produced by disproportionating a silicon hydride to obtain a mixture containing a desired silane compound, and then purifying necessary components by a method such as distillation. .
水素化ハロゲン化珪素の反応方法としては、不均化反応方法が挙げられ、特許文献１〜３記載の方法が挙げられる。例えば、水素化ハロゲン化珪素は弱塩基性陰イオン交換樹脂と接触すると、塩素原子と水素原子をやり取りする不均化反応を起こすため、これを利用してトリクロロシランからジクロロシランを、ジクロロシランからモノシランを製造する。 Examples of the reaction method of silicon hydride include a disproportionation reaction method, and the methods described in Patent Documents 1 to 3 can be mentioned. For example, when a silicon hydride halide comes into contact with a weakly basic anion exchange resin, it causes a disproportionation reaction in which chlorine atoms and hydrogen atoms are exchanged, and this is used to convert dichlorosilane from trichlorosilane to dichlorosilane. Monosilane is produced.
特許文献１〜３には、水素化ハロゲン化珪素をロームアンドハース社製の弱塩基性陰イオン交換樹脂（商品名：アンバーリストＡ−２１）と接触させることにより、不均化反応方法を達成することが記載されている。アンバーリストＡ−２１は、芳香族環に式（II）で表される官能基を結合し、比表面積２０〜３０ｍ２／ｇを有する、スチレン単位を有する架橋共重合体からなる弱塩基性陰イオン交換樹脂である。
式（II）−ＣＨ２Ｎ（ＣＨ３）２
Formula (II) -CH 2 N (CH 3) 2
本発明者らは、比表面積が小さい弱塩基性陰イオン交換樹脂を触媒として使用した場合、目的とする水素化ハロゲン化珪素の収量が多くなることを見出した。 The present inventors have found that when a weakly basic anion exchange resin having a small specific surface area is used as a catalyst, the yield of the target silicon hydride halide increases.
本発明は、（１）芳香族環に式（Ｉ）で表される官能基を結合してなり、かつ、比表面積が１５ｍ２／ｇ以上２０ｍ２／ｇ未満である、スチレン単位を有する架橋共重合体からなる弱塩基性陰イオン交換樹脂を水素化ハロゲン化珪素と接触させる水素化ハロゲン化珪素の反応方法、
式（Ｉ）−ＣＨ２ＮＲ１Ｒ２（Ｒ１、Ｒ２は、水素、アルキル基又はヒドロキシアルキル基）
（２）式（Ｉ）のＲ１、Ｒ２がメチル基である（１）記載の水素化ハロゲン化珪素の反応方法、（３）弱塩基性陰イオン交換樹脂の細孔容積が０．５〜１．０ｍｌ／ｇである（１）又は（２）記載の水素化ハロゲン化珪素の反応方法、（４）芳香族環に式（Ｉ）で表される官能基を結合してなり、かつ、比表面積が１５ｍ２／ｇ以上２０ｍ２／ｇ未満である、スチレン単位を有する架橋共重合体からなる弱塩基性陰イオン交換樹脂をトリクロロシランと接触させることによるジクロロシランの製造方法、
式（Ｉ）−ＣＨ２ＮＲ１Ｒ２（Ｒ１、Ｒ２は、水素、アルキル基又はヒドロキシアルキル基）
（５）芳香族環に式（Ｉ）で表される官能基を結合してなり、かつ、比表面積１５〜２５ｍ２／ｇである、スチレン単位を有する架橋共重合体からなる弱塩基性陰イオン交換樹脂をトリクロロシランと接触させることにより製造してなるジクロロシランである。
The present invention is (1) a bridge having a styrene unit, which is formed by bonding a functional group represented by the formula (I) to an aromatic ring and having a specific surface area of 15 m 2 / g or more and less than 20 m 2 / g. A method of reacting silicon hydride, wherein a weakly basic anion exchange resin comprising a copolymer is brought into contact with the silicon hydride.
Formula (I) -CH 2 NR 1 R 2 (R 1, R 2 is hydrogen, alkyl or hydroxyalkyl group)
(2) The reaction method of silicon hydride according to (1), wherein R 1 and R 2 in formula (I) are methyl groups, (3) the pore volume of the weakly basic anion exchange resin is 0.5 The reaction method of silicon hydride according to (1) or (2), which is ˜1.0 ml / g, (4) a functional group represented by formula (I) bonded to an aromatic ring, and A method for producing dichlorosilane by bringing a weak basic anion exchange resin comprising a crosslinked copolymer having a styrene unit into contact with trichlorosilane, having a specific surface area of 15 m 2 / g or more and less than 20 m 2 / g,
Formula (I) -CH 2 NR 1 R 2 (R 1, R 2 is hydrogen, alkyl or hydroxyalkyl group)
(5) A weakly basic anion comprising a crosslinked copolymer having a styrene unit and having a functional group represented by the formula (I) bonded to an aromatic ring and having a specific surface area of 15 to 25 m 2 / g. It is a dichlorosilane produced by bringing an ion exchange resin into contact with trichlorosilane.
本発明によれば、従来の方法に比べ、水素化ハロゲン化珪素の収量を向上させることができる。 According to the present invention, the yield of silicon hydride halide can be improved as compared with the conventional method.
水素化ハロゲン化珪素は、珪素に結合した水素原子及びハロゲン原子を各々少なくとも一つ有するシラン化合物である。例えば、テトラクロルシラン、トリクロルシラン、ジクロルシラン、クロルシラン、メチルトリクロロシラン、フェニルトリクロロシラン、メチルジクロロシラン、ジメチルジクロロシラン及びトリメチルクロロシラン等が挙げられる。 The silicon hydride is a silane compound having at least one hydrogen atom and halogen atom bonded to silicon. Examples thereof include tetrachlorosilane, trichlorosilane, dichlorosilane, chlorosilane, methyltrichlorosilane, phenyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane.
これらの中では、トリクロロシラン、ジクロロシラン及びモノクロロシランから選ばれる化合物の１種以上が好ましく、トリクロロシランがより好ましい。トリクロロシランを使用した場合、ジクロロシランの収量を多くできる。 Among these, one or more compounds selected from trichlorosilane, dichlorosilane, and monochlorosilane are preferable, and trichlorosilane is more preferable. When trichlorosilane is used, the yield of dichlorosilane can be increased.
水素化ハロゲン化珪素の反応方法としては不均化反応方法が挙げられる。不均化反応とは、例えば、以下式（１）〜（３）の反応をいう。
２ＳｉＨＣｌ3 ⇔ ＳｉＣｌ4 ＋ＳｉＨ2 Ｃｌ2 （１）
２ＳｉＨ2 Ｃｌ2 ⇔ ＳｉＨＣｌ3 ＋ＳｉＨ3 Ｃｌ （２）
２ＳｉＨ3 Ｃｌ ⇔ ＳｉＨ2 Ｃｌ2 ＋ＳｉＨ4 （３）
Examples of the reaction method of silicon hydride include a disproportionation reaction method. A disproportionation reaction means reaction of Formula (1)-(3) below, for example.
2SiHCl 3 ＳｉSiCl 4 + SiH 2 Cl 2 (1)
2SiH 2 Cl 2 ＳｉSiHCl 3 + SiH 3 Cl (2)
2SiH 3 Cl Ｓｉ SiH 2 Cl 2 + SiH 4 (3)
モノシランやメチルシランのような、珪素原子に結合したハロゲン原子を有さない水素化珪素、及び、四塩化珪素やメチルトリクロロシランのような、珪素原子に結合した水素原子を有さないハロゲン化珪素も、上記の不均化反応式のように関与する。
本発明では、原料として、水素化ハロゲン化珪素以外に、ハロゲン化珪素、水素化珪素を含んでいても良い。
Silicon hydrides that do not have halogen atoms bonded to silicon atoms, such as monosilane and methylsilane, and silicon halides that do not have hydrogen atoms bonded to silicon atoms, such as silicon tetrachloride and methyltrichlorosilane Are involved as in the disproportionation reaction equation above.
In the present invention, as a raw material, silicon halide and silicon hydride may be contained in addition to the hydrogenated silicon halide.
本発明の弱塩基性陰イオン交換樹脂は、芳香族環に式（Ｉ）で表される官能基を結合してなり、かつ、比表面積が１５ｍ２／ｇ以上２０ｍ２／ｇ未満である、スチレン単位を有する架橋共重合体からなる弱塩基性陰イオン交換樹脂である。例えば、このような弱塩基性陰イオン交換樹脂としては、三菱化学社製のダイヤイオンＷＡ−３０が挙げられる。
式（Ｉ）−ＣＨ２ＮＲ１Ｒ２（Ｒ１、Ｒ２は、水素、アルキル基又はヒドロキシアルキル基）
The weakly basic anion exchange resin of the present invention is formed by bonding a functional group represented by the formula (I) to an aromatic ring, and has a specific surface area of 15 m 2 / g or more and less than 20 m 2 / g. It is a weakly basic anion exchange resin comprising a crosslinked copolymer having a styrene unit. For example, as such a weakly basic anion exchange resin, Diaion WA-30 manufactured by Mitsubishi Chemical Corporation may be mentioned.
Formula (I) -CH 2 NR 1 R 2 (R 1, R 2 is hydrogen, alkyl or hydroxyalkyl group)
比表面積は、収量を多くできる点で、１５ｍ２／ｇ以上２０ｍ２／ｇ未満が好ましく、１７〜１９ｍ２／ｇがより好ましい。
細孔容積は、収量を多くできる点で、０．５〜１．０ｍｌ／ｇが好ましく、０．６〜０．７ｍｌ／ｇがより好ましい。
弱塩基性陰イオン交換樹脂は、収量を多くできる点で、ポーラス型が好ましい。ポーラス型の中では、収量を多くできる点で、ハイポーラス型がより好ましい。
The specific surface area, in that it can increase the yield, 15 m 2 / g or more 20m is preferably less than 2 / g, 17~19m 2 / g is more preferable.
The pore volume is preferably 0.5 to 1.0 ml / g, more preferably 0.6 to 0.7 ml / g, in that the yield can be increased.
The weakly basic anion exchange resin is preferably a porous type in that the yield can be increased. Among the porous types, the high porous type is more preferable in that the yield can be increased.
式（Ｉ）のＲ１、Ｒ２は、収量を多くできる点で、水素、アルキル基又はヒドロキシアルキル基が好ましく、メチル基がより好ましい。 R 1 and R 2 in formula (I) are preferably hydrogen, an alkyl group, or a hydroxyalkyl group, and more preferably a methyl group, in that the yield can be increased.
弱塩基性陰イオン交換樹脂は、３次元網目構造の高分子基体にイオン交換基を結合したものであって、原料モノマー（スチレン等）と２官能以上の架橋剤（ジビニルベンゼン等）の共重合体からなる。弱塩基性陰イオン交換樹脂は、イオン交換基が弱塩基性である陰イオン交換樹脂で、例えば、１級アミン、２級アミン、３級アミンをイオン交換基とする（非特許文献１）。
弱塩基性陰イオン交換樹脂の製造方法は、例えば、非特許文献１に記載されている。
スチレンとジビニルベンゼンの共重合体ビーズを、ＡｌＣｌ３、ＳｎＣｌ４、ＺｎＣｌ２等のルイス酸を触媒として、クロロメチルエーテルでクロロメチル化する。クロロメチル化したビーズを、１級アミン、２級アミン、３級アミンでアミノ化し、弱塩基性陰イオン交換樹脂を得る。
A method for producing a weakly basic anion exchange resin is described in Non-Patent Document 1, for example.
Copolymer beads of styrene and divinylbenzene are chloromethylated with chloromethyl ether using a Lewis acid such as AlCl 3 , SnCl 4 , ZnCl 2 or the like as a catalyst. The chloromethylated beads are aminated with a primary amine, secondary amine, and tertiary amine to obtain a weakly basic anion exchange resin.
弱塩基性陰イオン交換樹脂は、通常入手できる弱塩基性陰イオン交換樹脂が用いられるが、必要があれば、上記製造方法に従い、製造してもよい。 As the weakly basic anion exchange resin, a commonly available weakly basic anion exchange resin is used, but if necessary, it may be produced according to the above production method.
水素化ハロゲン化珪素の反応方法としては不均化反応方法が挙げられるが、不均化反応方法の実施形態は、連続式、バッチ式どちらでもかまわないが、工業的には連続式が好ましい。不均化反応の反応容器としては、例えば、充填塔が用いられる。 Examples of the reaction method of silicon hydride include a disproportionation reaction method, and the embodiment of the disproportionation reaction method may be either a continuous type or a batch type, but a continuous type is preferred industrially. As a reaction vessel for the disproportionation reaction, for example, a packed tower is used.
反応温度は、高いほうがより短い接触時間で平衡に達することができるが、低沸点成分の蒸気圧が上昇し、圧力が上昇し、触媒の耐熱性の問題も発生する場合があるため、２０〜１００℃が好ましく、４０〜７０℃がより好ましい。 A higher reaction temperature can reach equilibrium with a shorter contact time, but the vapor pressure of low-boiling components increases, the pressure increases, and the problem of heat resistance of the catalyst may also occur. 100 degreeC is preferable and 40-70 degreeC is more preferable.
水素化ハロゲン化珪素の反応方法としては不均化反応方法が挙げられるが、不均化反応方法は、原料の水素化ハロゲン化珪素を、触媒と接触することにより実施される。接触方法は特に制限されないが、例えば、通常の固体−液体反応に適した方法が採用できる。 Examples of the reaction method of the silicon hydride halide include a disproportionation reaction method. The disproportionation reaction method is carried out by bringing the raw material silicon hydride halide into contact with a catalyst. The contacting method is not particularly limited, and for example, a method suitable for a normal solid-liquid reaction can be adopted.
接触時間は、反応系が平衡組成に到達する程度か、それよりも短く設定することが望ましい。例えば、接触時間が長過ぎる場合、本発明の効果が薄れ、性能が劣る触媒と同等になる場合がある。同時に、単位体積当たりや単位時間当たりの収量が低下し、経済性に劣る場合がある。接触時間は、５〜６０分が好ましく、１０〜３０分がより好ましい。 It is desirable to set the contact time so that the reaction system reaches an equilibrium composition or shorter. For example, if the contact time is too long, the effect of the present invention may be reduced, and the catalyst may be equivalent to a catalyst with poor performance. At the same time, the yield per unit volume or unit time may be reduced, and the economy may be inferior. The contact time is preferably 5 to 60 minutes, and more preferably 10 to 30 minutes.
水素化ハロゲン化珪素の反応方法としては不均化反応方法が挙げられるが、不均化反応方法によれば、原料の水素化ハロゲン化珪素は、不均化反応により数種類の混合物となる。この混合物を、蒸留等の一般的な精製法にて不必要な成分を除くとよい。 As a reaction method of silicon hydride, there is a disproportionation reaction method. According to the disproportionation reaction method, the raw material silicon hydride becomes a mixture of several kinds by the disproportionation reaction. In this mixture, unnecessary components may be removed by a general purification method such as distillation.
本発明では、原料の水素化ハロゲン化珪素として、特にトリクロロシランが好ましい。トリクロロシランの含有量が９０％以上の水素化ハロゲン化珪素を使用し、トリクロロシランよりも高次に水素化されたジクロロシラン等を取得するのが特に好ましい。 In the present invention, trichlorosilane is particularly preferable as the raw material silicon hydride. It is particularly preferable to use silicon hydride having a trichlorosilane content of 90% or more and to obtain dichlorosilane or the like hydrogenated in a higher order than trichlorosilane.
本発明によれば、従来の方法に比べ、より短い接触時間でシラン化合物の製造を行うことができる。即ち、本発明の触媒を使用すれば、単位時間当たりや単位体積当たりの収量を向上させることができる。例えば、より短い接触時間で目的物を製造できる。 According to the present invention, it is possible to produce a silane compound with a shorter contact time than in the conventional method. That is, if the catalyst of the present invention is used, the yield per unit time or unit volume can be improved. For example, the object can be produced with a shorter contact time.
本発明を具体例により説明するが、本発明はこれらの例によって限定されるものではない。 The present invention will be described with reference to specific examples, but the present invention is not limited to these examples.
用いた触媒（弱塩基性陰イオン交換樹脂）を表１に示した。
（測定方法）
比表面積：乾燥状態の樹脂をＢＥＴの測定器を用い、窒素ガス吸収量から求めた値を比表面積とした。
細孔容積：水銀圧入式ポロシメーターで測定した値を細孔容積とした。
The catalyst (weakly basic anion exchange resin) used is shown in Table 1.
(Measuring method)
Specific surface area: A value obtained from the nitrogen gas absorption amount of the dried resin using a BET measuring device was taken as the specific surface area.
Pore volume: The value measured with a mercury intrusion porosimeter was defined as the pore volume.
実施例１
内径５０ｍｍ、高さ１０００ｍｍのステンレス製反応管に、表１の弱塩基性陰イオン交換樹脂（三菱化学株式会社製、ダイヤイオンＷＡ−３０）を約２．４Ｌ充填し、各反応温度に設定し、トリクロロシランを連続的に２Ｌ／ｈrの供給速度で流通させた。反応圧力は０．５５ＭＰａで実施した。反応が安定した段階で、供給速度を変更し、各接触時間ごとに反応液をサンプリングし、反応物の各組成をガスクロマトグラフィーで測定した。
結果を表２、表３に示した。
（測定方法）
接触時間：触媒容積をＶ［Ｌ］、単位時間当たりのトリクロロシラン供給速度をｖ［Ｌ／ｈr］とした時に、Ｖ／ｖで表された値を接触時間とした。
Example 1
A stainless steel reaction tube with an inner diameter of 50 mm and a height of 1000 mm is filled with about 2.4 L of the weakly basic anion exchange resin (Mitsubishi Chemical Corporation, Diaion WA-30) shown in Table 1 and set to each reaction temperature. Trichlorosilane was continuously circulated at a supply rate of 2 L / hr. The reaction pressure was 0.55 MPa. When the reaction was stable, the supply rate was changed, the reaction solution was sampled at each contact time, and each composition of the reaction product was measured by gas chromatography.
The results are shown in Tables 2 and 3.
(Measuring method)
Contact time: When the catalyst volume is V [L] and the trichlorosilane supply rate per unit time is v [L / hr], the value represented by V / v is the contact time.
比較例１
弱塩基性陰イオン交換樹脂をロームアンドハース社製、アンバーリストＡ−２１に変更したこと以外は、実施例１と同じ条件で試験した。結果を表４、表５に示した。
Comparative Example 1
The test was conducted under the same conditions as in Example 1 except that the weakly basic anion exchange resin was changed to Amberlyst A-21 manufactured by Rohm and Haas. The results are shown in Tables 4 and 5.
Claims (5)
式（Ｉ）−ＣＨ２ＮＲ１Ｒ２（Ｒ１、Ｒ２は、水素、アルキル基又はヒドロキシアルキル基） A weak base comprising a crosslinked copolymer having a styrene unit, wherein the functional group represented by the formula (I) is bonded to an aromatic ring, and the specific surface area is 15 m 2 / g or more and less than 20 m 2 / g. The reaction method of the silicon hydride halide which makes a property anion exchange resin contact with a silicon hydride halide.
Formula (I) -CH 2 NR 1 R 2 (R 1, R 2 is hydrogen, alkyl or hydroxyalkyl group)
式（Ｉ）−ＣＨ２ＮＲ１Ｒ２（Ｒ１、Ｒ２は、水素、アルキル基又はヒドロキシアルキル基） A weak base comprising a crosslinked copolymer having a styrene unit, wherein the functional group represented by the formula (I) is bonded to an aromatic ring, and the specific surface area is 15 m 2 / g or more and less than 20 m 2 / g. A process for producing dichlorosilane by bringing a cationic anion exchange resin into contact with trichlorosilane.
Formula (I) -CH 2 NR 1 R 2 (R 1, R 2 is hydrogen, alkyl or hydroxyalkyl group)
式（Ｉ）−ＣＨ２ＮＲ１Ｒ２（Ｒ１、Ｒ２は、水素、アルキル基又はヒドロキシアルキル基） A weakly basic anion exchange resin comprising a cross-linked copolymer having a styrene unit, wherein the functional group represented by the formula (I) is bonded to an aromatic ring and has a specific surface area of 15 to 25 m 2 / g. A dichlorosilane produced by bringing a chlorosilane into contact with trichlorosilane.
Formula (I) -CH 2 NR 1 R 2 (R 1, R 2 is hydrogen, alkyl or hydroxyalkyl group)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017507880A (en) * | 2014-01-24 | 2017-03-23 | ハンワ ケミカル コーポレイション | Waste gas purification method and purification apparatus |
| CN115023407A (en) * | 2020-11-05 | 2022-09-06 | 瓦克化学股份公司 | Process for removing impurities from chlorosilane mixtures |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017507880A (en) * | 2014-01-24 | 2017-03-23 | ハンワ ケミカル コーポレイション | Waste gas purification method and purification apparatus |
| US10016724B2 (en) | 2014-01-24 | 2018-07-10 | Hanwha Chemical Corporation | Purification method and purification apparatus for off-gas |
| CN115023407A (en) * | 2020-11-05 | 2022-09-06 | 瓦克化学股份公司 | Process for removing impurities from chlorosilane mixtures |
| CN115023407B (en) * | 2020-11-05 | 2024-05-24 | 瓦克化学股份公司 | Method for removing impurities from chlorosilane mixtures |
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