JP5373508B2 - Production method of diborane - Google Patents
Production method of diborane Download PDFInfo
- Publication number
- JP5373508B2 JP5373508B2 JP2009197316A JP2009197316A JP5373508B2 JP 5373508 B2 JP5373508 B2 JP 5373508B2 JP 2009197316 A JP2009197316 A JP 2009197316A JP 2009197316 A JP2009197316 A JP 2009197316A JP 5373508 B2 JP5373508 B2 JP 5373508B2
- Authority
- JP
- Japan
- Prior art keywords
- diborane
- boron
- reaction
- sodium borohydride
- vol
- 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.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 19
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 14
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 12
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical group ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910015900 BF3 Inorganic materials 0.000 claims description 6
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 abstract description 23
- 229910000085 borane Inorganic materials 0.000 abstract description 12
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract description 2
- 239000003380 propellant Substances 0.000 abstract description 2
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 abstract 1
- 150000001638 boron Chemical class 0.000 abstract 1
- 239000005368 silicate glass Substances 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005380 borophosphosilicate glass Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
Description
本発明は、半導体製造や太陽電池製造におけるドーパントやＢＰＳＧ絶縁膜形成材料およびロケット推進薬等として有用なジボランの製造方法に関する。 The present invention relates to a method for producing diborane useful as a dopant, a BPSG insulating film forming material, a rocket propellant or the like in semiconductor production or solar cell production.
ジボランの製造方法としては、三塩化ホウ素や三フッ化ホウ素の還元による方法が知られ、ソジウムボロハイドライドと三塩化ホウ素からジボランを得る方法が、提案されている（特許文献１、特許文献２）。しかしながら、ジボラン分子（Ｂ２Ｈ６）は、重合しやすく、高次ボラン（例えば、Ｂ４Ｈ１０、Ｂ５Ｈ９、Ｂ５Ｈ１１等）を生成する性質を有することから、ジボランの製造において、高次ボランが生成して純度が低下する場合がある。特に、半導体製造用の材料に適したホウ素源として、超高純度のジボランが求められる場合には、ジボランの製造後、引き続き、精製する必要があるが、蒸留精製に要する負荷が大きくなることや収率が低下するなどの不具合がある。そこで、高次ボラン含有量が低く、純度の高いジボランが得られる製造方法の開発が望まれている。 As a method for producing diborane, a method by reduction of boron trichloride or boron trifluoride is known, and methods for obtaining diborane from sodium borohydride and boron trichloride have been proposed (Patent Documents 1 and 2). ). However, since diborane molecules (B 2 H 6 ) are easily polymerized and have the property of producing higher-order boranes (eg, B 4 H 10 , B 5 H 9 , B 5 H 11, etc.), production of diborane In this case, higher-order borane may be generated to lower the purity. In particular, when ultra-high-purity diborane is required as a boron source suitable for semiconductor manufacturing materials, it is necessary to continue purification after the production of diborane. There are problems such as a decrease in yield. Therefore, development of a production method that can obtain diborane having a low high-order borane content and high purity is desired.
本発明は、簡便で安価な方法により、高次ボラン含量が低く、純度の高いジボランを収率よく製造する方法を提供することを目的とする。 An object of the present invention is to provide a method for producing diborane having a low high-order borane content and high purity in a high yield by a simple and inexpensive method.
本発明は、ソジウムボロハイドライドと、三ハロゲン化ホウ素とを、溶媒の存在下、水素濃度が０．０１〜５０ｖｏｌ％である不活性ガスの雰囲気で反応させる、ジボランの製造方法に関する。 The present invention relates to a method for producing diborane, in which sodium borohydride and boron trihalide are reacted in an inert gas atmosphere having a hydrogen concentration of 0.01 to 50 vol% in the presence of a solvent.
本発明にかかるソジウムボロハイドライドと、三ハロゲン化ホウ素とからジボランを得る反応は、ソジウムボロハイドライド１モルに対して、三ハロゲン化ホウ素０．１２〜０．１６モルを反応温度−１０〜４０℃で、反応させる第１の反応工程と、三ハロゲン化ホウ素０．１７〜０．２１モルを反応温度２０〜６０℃で、反応させる第２の反応工程とからなることが好ましい。 In the reaction for obtaining diborane from the sodium borohydride and boron trihalide according to the present invention, 0.12 to 0.16 mol of boron trihalide is added at a reaction temperature of -10 to 0.1 mol per 1 mol of sodium borohydride. It preferably comprises a first reaction step for reacting at 40 ° C. and a second reaction step for reacting 0.17 to 0.21 mol of boron trihalide at a reaction temperature of 20 to 60 ° C.
前記第１の反応工程における反応温度は、−１０〜４０℃であり、０〜４０℃であることが好適である。反応時間としては、例えば、１〜２時間とするのが好ましい。 The reaction temperature in the first reaction step is −10 to 40 ° C., and preferably 0 to 40 ° C. As reaction time, it is preferable to set it as 1-2 hours, for example.
前記第２の反応工程における反応温度は、２０〜６０℃であり、３０〜５０℃であることが好適である。反応時間としては、例えば、１〜６時間とするのが好ましい。 The reaction temperature in the second reaction step is 20 to 60 ° C, and preferably 30 to 50 ° C. The reaction time is preferably 1 to 6 hours, for example.
前記三ハロゲン化ホウ素は、例えば、三塩化ホウ素、三フッ化ホウ素および三臭化ホウ素等が挙げられる。これらの中でも、三塩化ホウ素および三フッ化ホウ素である場合が好ましい。 Examples of the boron trihalide include boron trichloride, boron trifluoride, and boron tribromide. Of these, boron trichloride and boron trifluoride are preferred.
本発明にかかる第１の反応工程および第２の反応工程は、三ハロゲン化ホウ素が三塩化ホウ素である場合、それぞれ、下式（１）、（２）の反応式で表されるものと考えられる。 When the boron trihalide is boron trichloride, the first reaction step and the second reaction step according to the present invention are considered to be represented by the following reaction formulas (1) and (2), respectively. It is done.
７ＮａＢＨ４＋ＢＣｌ３→４ＮａＢ２Ｈ７＋３ＮａＣｌ （１）
６ＮａＢ２Ｈ７＋２ＢＣｌ３→７Ｂ２Ｈ６＋６ＮａＣｌ （２）
即ち、式（１）で表される第１の発熱反応と式（２）で表される第２の吸熱反応により、２工程に分けて反応を行えば、目的とするジボランを収率よく、高純度で得られるので好適である。
7NaBH 4 + BCl 3 → 4NaB 2 H 7 + 3NaCl (1)
6NaB 2 H 7 + 2BCl 3 → 7B 2 H 6 + 6NaCl (2)
That is, if the reaction is carried out in two steps by the first exothermic reaction represented by the formula (1) and the second endothermic reaction represented by the formula (2), the target diborane is obtained in a high yield, It is suitable because it is obtained with high purity.
本発明にかかるソジウムボロハイドライドと、三ハロゲン化ホウ素との反応に用いられる溶媒としては、例えば、ジグライムおよびトリグライム等のエチレングリコールジメチルエーテル化合物が挙げられる。これらの中でも、ジグライムおよびトリグライムが好ましく用いられる。 Examples of the solvent used in the reaction of the sodium borohydride according to the present invention with boron trihalide include ethylene glycol dimethyl ether compounds such as diglyme and triglyme. Among these, diglyme and triglyme are preferably used.
前記溶媒の使用量としては、例えば、ソジウムボロハイドライド１ｋｇに対して、８〜３０Ｌであることが好ましく、１０〜１８Ｌであることがより好ましい。 As the usage-amount of the said solvent, it is preferable that it is 8-30L with respect to 1 kg of sodium borohydride, for example, and it is more preferable that it is 10-18L.
前記溶媒の使用量が、ソジウムボロハイドライド１ｋｇに対して、８Ｌ未満の場合、ソジウムボロハイドライドが、十分に溶解せず、反応しにくくなるおそれがあり、３０Ｌを超える場合、容積効率が低く経済的でない。 When the amount of the solvent used is less than 8 L with respect to 1 kg of sodium borohydride, the sodium borohydride may not be sufficiently dissolved and may become difficult to react. When it exceeds 30 L, volume efficiency is low. Not economical.
前記不活性ガスとしては、例えば、窒素、ヘリウムおよびアルゴン等が挙げられる。これらの中でも、窒素およびヘリウムが好ましく、窒素がより好ましく用いられる。 Examples of the inert gas include nitrogen, helium, and argon. Among these, nitrogen and helium are preferable, and nitrogen is more preferably used.
本発明にかかる水素ガスと前記不活性ガスとの混合ガス中における水素ガスの濃度は、０．０１〜５０ｖｏｌ％であり、１〜３０ｖｏｌ％であることが好ましい。混合ガス中の水素濃度が、０．０１ｖｏｌ％未満である場合、高次ジボランの生成が抑制されにくく、５０ｖｏｌ％を超える場合、使用量に見合う効果がなく経済的でない。 The density | concentration of the hydrogen gas in the mixed gas of the hydrogen gas concerning this invention and the said inert gas is 0.01-50 vol%, and it is preferable that it is 1-30 vol%. When the hydrogen concentration in the mixed gas is less than 0.01 vol%, the formation of higher-order diborane is difficult to suppress, and when it exceeds 50 vol%, there is no effect commensurate with the amount used and it is not economical.
次に、本発明の実施態様について、具体的に説明する。 Next, embodiments of the present invention will be specifically described.
ガス吹込み管，撹拌器および還流冷却器を備えたステンレス製の反応容器に、所定量の溶媒およびソジウムボロハイドライドを仕込み、所定濃度の水素含有不活性ガスを冷却下（例えば、３０℃以下）に液相に吹き込んで反応系内を置換する。次に、所定濃度の水素含有不活性ガスを用いて加圧状態（例えば、０．０３ＭＰａＧ）とし、所定の反応温度に保って、第１反応を行なう。この場合、未溶解のソジウムボロハイドライドが、懸濁状態を示す場合もあるが、そのまま、三ハロゲン化ホウ素の吹き込みを始め、所定量を添加して停止する。第１の反応工程は１〜２時間で完結するのがよい。時間が長くなるとメタン生成等の副反応等が起こって、収率や純度を向上する上で好ましくない。 A stainless steel reaction vessel equipped with a gas blowing tube, a stirrer, and a reflux condenser is charged with a predetermined amount of solvent and sodium borohydride, and a predetermined concentration of hydrogen-containing inert gas is cooled (for example, 30 ° C. or less) B) into the liquid phase to replace the reaction system. Next, a pressurized state (for example, 0.03 MPaG) is set using a hydrogen-containing inert gas having a predetermined concentration, and the first reaction is performed while maintaining a predetermined reaction temperature. In this case, undissolved sodium borohydride may show a suspended state, but as it is, blowing of boron trihalide is started, and a predetermined amount is added and stopped. The first reaction step is preferably completed in 1 to 2 hours. If the time is long, side reactions such as methane formation occur, which is not preferable for improving yield and purity.
第１反応において、少量のメタンや塩化メチル等のガスが発生するため、次の第２の反応工程に先立って、所定濃度の水素含有不活性ガスを用いて反応系内から排出させる。 In the first reaction, a small amount of gas such as methane or methyl chloride is generated. Therefore, prior to the next second reaction step, a hydrogen-containing inert gas having a predetermined concentration is used to discharge from the reaction system.
所定濃度の水素含有不活性ガスによって、前述の副生ガスを含むガス成分をパージ後、引き続き、所定濃度の水素含有不活性ガスを用いて加圧状態（例えば、０．０４ＭＰａＧ）とし、所定の反応温度まで上げ、所定量の三ハロゲン化ホウ素を吹き込んで第２の反応工程を行なう。 After purging the gas component containing the by-product gas with a hydrogen-containing inert gas having a predetermined concentration, the hydrogen-containing inert gas having a predetermined concentration is subsequently used to be pressurized (for example, 0.04 MPaG). The temperature is raised to the reaction temperature, and a predetermined amount of boron trihalide is blown into the second reaction step.
第２の反応工程の三ハロゲン化ホウ素の吹き込みにともなって、反応液中にジボランが生成する。かくして得られたジボランは、水素含有不活性ガスとともに、例えば、液体窒素を用いて約−１９６℃に冷却されたコールドトラップに導き、ジボランを凝縮、固化させることにより単離することができる。 As the boron trihalide is blown in the second reaction step, diborane is generated in the reaction solution. The diborane thus obtained can be isolated by condensing and solidifying the diborane together with a hydrogen-containing inert gas, for example, in a cold trap cooled to about −196 ° C. using liquid nitrogen.
このようにして得られたジボランは、従来法で得られたものと比べて、高次ボラン含有量は低く、高い純度を有し、その結果、後述する蒸留精製における負荷を低減し、収率を高めることができる。 The diborane obtained in this way has a lower high-order borane content and higher purity than those obtained by the conventional method. Can be increased.
本発明にかかる製造方法によって得られたジボランは、例えば、次のような方法で精製するとよい。 For example, diborane obtained by the production method according to the present invention may be purified by the following method.
即ち、上記のようにして得られたジボランをリボイラーでガス化し、次いで均一な細孔を持つ吸着剤を充填した充填塔で、ジボランと沸点が近接するＣＯ２やＣ２Ｈ６等の不純物を吸着除去するとともに、還流液と向流接触させた後、塔上部に付設したコンデンサーで凝縮し、還流させることで精製することができる。 That is, the diborane obtained as described above is gasified with a reboiler, and then impurities such as CO 2 and C 2 H 6 having a boiling point close to that of diborane are packed in a packed tower packed with an adsorbent having uniform pores. It can be purified by adsorbing and removing, condensing with refluxing liquid, condensing with a condenser attached to the upper part of the tower, and refluxing.
前記吸着剤としては、シリカゲル、ゼオライトモレキュラーシーブおよび活性アルミナ等が挙げられるが、ジボランの品質に影響を及ぼさないものがよく、ゼオライトモレキュラーシーブが好適に用いられる。 Examples of the adsorbent include silica gel, zeolite molecular sieve, activated alumina, and the like, but those that do not affect the quality of diborane are good, and zeolite molecular sieve is preferably used.
蒸留の圧力は０．０１〜１．５ＭＰａＧであることが好ましい。０．０１ＭＰａＧ未満の場合、外気の漏れこみ等、安全上の問題を生じるおそれがあり、１．５ＭＰａＧを超える場合、装置の安全設計にコストがかかり経済的ではない。 The distillation pressure is preferably 0.01 to 1.5 MPaG. If it is less than 0.01 MPaG, there is a risk of causing safety problems such as leakage of outside air. If it exceeds 1.5 MPaG, the safety design of the apparatus is costly and not economical.
また、蒸留温度は、前記圧力に対応して定まり、−９０〜−２０℃であることが好ましい。 The distillation temperature is determined according to the pressure and is preferably -90 to -20 ° C.
本発明により、簡便で安価な方法により、高次ボラン含量が低く、純度の高いジボランを収率よく製造することができる。例えば、半導体用途などで要求される超高純度ジボランを工業的に効率よく製造することができる。 According to the present invention, diborane having a low high-order borane content and high purity can be produced with high yield by a simple and inexpensive method. For example, ultra-high purity diborane required for semiconductor applications can be industrially efficiently produced.
以下に本発明を実施例により具体的に説明するが、本発明はこれら実施例のみに何ら限定されるものでない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
実施例１
反応器出口に−５０℃に冷却した還流冷却器を備え、その後に約−７８℃に冷却した第１コールドトラップおよび約−１９６℃に冷却した第２コールドトラップを備えた内容積１０ＬのＳＵＳ３０４製電磁撹拌式の反応器を用意した。
Example 1
Made of SUS304 with an internal volume of 10 L equipped with a reflux condenser cooled to −50 ° C. at the outlet of the reactor, followed by a first cold trap cooled to about −78 ° C. and a second cold trap cooled to about −196 ° C. An electromagnetic stirring type reactor was prepared.
前記反応器に、トリグライム６Ｌを仕込み、さらに粉末状のソジウムボロハイドライド５００ｇ（１３．２モル）を加え、１ｖｏｌ％水素含有窒素ガスを、１０Ｌ／分で吹き込みながら、内容液を２５℃にした。 The reactor was charged with 6 L of triglyme, 500 g (13.2 mol) of powdered sodium borohydride was added, and the content liquid was brought to 25 ° C. while blowing 1 vol% hydrogen-containing nitrogen gas at 10 L / min. .
次に、前記反応器の内容液中に、ガス状の三塩化ホウ素２２１．０ｇ（１．８９モル）を、流量計を用いて、１時間かけて吹き込み、第１の反応工程を行った。反応は発熱反応であり、少量のメタン含むガスが発生した。 Next, 221.0 g (1.89 mol) of gaseous boron trichloride was blown into the content liquid of the reactor over a period of 1 hour using a flow meter to perform the first reaction step. The reaction was exothermic and a small amount of methane-containing gas was generated.
次に、反応系内を１ｖｏｌ％水素含有窒素ガスで置換した後、昇温して反応液温を４０℃とし、三塩化ホウ素２９４．６g（２．５１モル）を１．５時間かけて吹き込み第２反応を行った。 Next, after replacing the inside of the reaction system with nitrogen gas containing 1 vol% hydrogen, the temperature was raised to 40 ° C., and 294.6 g (2.51 mol) of boron trichloride was blown in over 1.5 hours. A second reaction was performed.
全量の三塩化ホウ素を吹き込んだ後も、さらに４０℃にて３時間、１ｖｏｌ％水素含有窒素ガスの吹き込みを継続し、生成するジボランの発生を完結させた。前記第２コールドトラップに捕集されたジボランのソジウムボロハイドライドに対する収率、純度および高次ボラン含量を表１に示す。 After blowing all the amount of boron trichloride, blowing of nitrogen gas containing 1 vol% hydrogen was further continued at 40 ° C. for 3 hours to complete generation of diborane to be generated. Table 1 shows the yield, purity, and high-order borane content of diborane collected in the second cold trap with respect to sodium borohydride.
得られたジボランを気化させた後、内径３１ｍｍφ、有効長さ１０００ｍｍのＳＵＳ３１６管に、吸着剤としてゼオライト モレキュラーシーブ（東ソー株式会社製ゼオラム４Ａ（平均細孔径４Å））を充填したカラムを用い、吸着低温蒸留精製を行った。 After vaporizing the obtained diborane, a SUS316 tube having an inner diameter of 31 mmφ and an effective length of 1000 mm was adsorbed using a column packed with zeolite molecular sieve (Zeoram 4A (average pore diameter 4 mm) manufactured by Tosoh Corporation) as an adsorbent. Low temperature distillation purification was performed.
ゼオラム４Ａは予め１．６ｍｍφ×５〜７ｍｍの押出円柱品を、４００℃でヘリウム気流中で、４時間焼成したものを７００ｍｌ充填した。原料ガスを導入する前に、全系を１ｖｏｌ％水素含有窒素ガスで置換し、無酸素状態にした。その後、リボイラーのジャケットを液体窒素で冷却しながら、前述で得られたジボランを仕込み、コンデンサーを−８０℃、充填塔を−７６℃に冷却した。リボイラーの温度を徐々に昇温し、ジボランを蒸発させた。昇温方法はリボイラーの冷媒を液体窒素からドライアイスメタノール液に切替え、これにメタノールを添加することにより約−７１℃に温度調節しながら、前記ジボランを蒸発させ、精留を行った。この時の蒸留圧力は０．１５ＭＰａＧに保った。全還流運転を実施した後、コンデンサー頂部に濃縮した低沸点ガスを放出し、精製された液化ジボランを分析し、メタン濃度が１０ｐｐｍ以下になった時点で精製ジボランとして回収した。精製ジボランのソジウムボロハイドライドに対する収率、純度および高次ボラン含量を表１に示す。 ZEOLAM 4A was previously filled with 700 ml of an extruded cylindrical product having a diameter of 1.6 mmφ × 5 to 7 mm, which was fired at 400 ° C. in a helium stream for 4 hours. Before introducing the raw material gas, the entire system was replaced with nitrogen gas containing 1 vol% hydrogen to make it oxygen-free. Then, while cooling the reboiler jacket with liquid nitrogen, the diborane obtained above was charged, and the condenser was cooled to -80 ° C and the packed tower was cooled to -76 ° C. The temperature of the reboiler was gradually raised to evaporate diborane. In the temperature raising method, the reboiler refrigerant was switched from liquid nitrogen to dry ice methanol solution, and methanol was added thereto to adjust the temperature to about -71 ° C, while evaporating the diborane to perform rectification. The distillation pressure at this time was kept at 0.15 MPaG. After carrying out the total reflux operation, the concentrated low boiling point gas was discharged to the top of the condenser, and the purified liquefied diborane was analyzed, and recovered as purified diborane when the methane concentration became 10 ppm or less. Table 1 shows the yield, purity, and high-order borane content of purified diborane relative to sodium borohydride.
実施例２
実施例１において、１ｖｏｌ％水素含有窒素ガスに代えて、２０ｖｏｌ％水素含有窒素ガスを用いた以外は、実施例１と同様にして、ジポランを製造した。また、実施例１において、全系を１ｖｏｌ％水素含有窒素ガスで置換する代わりに、２０ｖｏｌ％水素含有窒素ガスを用いた以外は、実施例１と同様にして、前記ジボランを精製し、精製ジボランを得た。得られたジボランおよび精製ジボランのソジウムボロハイドライドに対する収率、純度および高次ボラン含量を表１に示す。
Example 2
In Example 1, dipolane was produced in the same manner as in Example 1 except that 20 vol% hydrogen-containing nitrogen gas was used instead of 1 vol% hydrogen-containing nitrogen gas. In Example 1, the diborane was purified in the same manner as in Example 1 except that 20 vol% hydrogen-containing nitrogen gas was used instead of replacing the entire system with 1 vol% hydrogen-containing nitrogen gas. Got. Table 1 shows the yield, purity, and high-order borane content of the obtained diborane and purified diborane with respect to sodium borohydride.
実施例３
実施例１において、トリグライム６Ｌに代えて、ジグライム６Ｌを、第１の反応工程における三塩化ホウ素２２１．０ｇ（１．８９モル）に代えて、三フッ化ホウ素１２８．１ｇ（１．８９モル）を、第２の反応工程における三塩化ホウ素２９４．６g（２．５１モル）に代えて、三フッ化ホウ素１７０．２ｇ（２．５１モル）を、それぞれ用いた以外は、実施例１と同様にして、ジボランを製造した。また、実施例１と同様にして、前記ジボランを精製し、精製ジボランを得た。得られたジボランおよび精製ジボランのソジウムボロハイドライドに対する収率、純度および高次ボラン含量を表１に示す。
Example 3
In Example 1, instead of triglyme 6L, diglyme 6L was replaced with 221.0 g (1.89 mol) of boron trichloride in the first reaction step, and 128.1 g (1.89 mol) of boron trifluoride. Was replaced with 294.6 g (2.51 mol) of boron trichloride in the second reaction step, except that 170.2 g (2.51 mol) of boron trifluoride was used. Thus, diborane was produced. Further, in the same manner as in Example 1, the diborane was purified to obtain purified diborane. Table 1 shows the yield, purity, and high-order borane content of the obtained diborane and purified diborane with respect to sodium borohydride.
比較例１
実施例１において、１ｖｏｌ％水素含有窒素ガスに代えて、窒素ガス単独を用いた以外は、実施例１と同様にして、ジボランを製造した。また、実施例１において、全系を１ｖｏｌ％水素含有窒素ガスで置換する代わりに、窒素ガス単独を用いた以外は、実施例１と同様にして、前記ジボランを精製し、精製ジボランを得た。得られたジボランおよび精製ジボランのソジウムボロハイドライドに対する収率、純度および高次ボラン含量を表１に示す。
Comparative Example 1
In Example 1, diborane was produced in the same manner as in Example 1 except that nitrogen gas alone was used instead of 1 vol% hydrogen-containing nitrogen gas. In Example 1, the diborane was purified in the same manner as in Example 1 except that nitrogen gas alone was used instead of replacing the entire system with 1 vol% hydrogen-containing nitrogen gas to obtain purified diborane. . Table 1 shows the yield, purity, and high-order borane content of the obtained diborane and purified diborane with respect to sodium borohydride.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009197316A JP5373508B2 (en) | 2009-08-27 | 2009-08-27 | Production method of diborane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009197316A JP5373508B2 (en) | 2009-08-27 | 2009-08-27 | Production method of diborane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011046569A JP2011046569A (en) | 2011-03-10 |
| JP5373508B2 true JP5373508B2 (en) | 2013-12-18 |
Family
ID=43833312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009197316A Active JP5373508B2 (en) | 2009-08-27 | 2009-08-27 | Production method of diborane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5373508B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9570271B2 (en) * | 2014-03-03 | 2017-02-14 | Praxair Technology, Inc. | Boron-containing dopant compositions, systems and methods of use thereof for improving ion beam current and performance during boron ion implantation |
| EP3188214A1 (en) * | 2015-12-29 | 2017-07-05 | Praxair Technology, Inc. | Boron-containing dopant compositions, systems and methods of use thereof for improving ion beam current and performance during boron ion implantation |
| KR102193572B1 (en) * | 2019-01-15 | 2020-12-22 | 대성산업가스 주식회사 | Method for generating high purity diborane using BF3 simultaneous reaction process and apparatus for the same |
| CN111892020A (en) * | 2020-08-14 | 2020-11-06 | 河南科技大学 | Synthesis method and device of high-purity electronic-grade diborane |
| CN116437057B (en) * | 2023-06-13 | 2023-09-19 | 博纯材料股份有限公司 | System optimization method and system for diborane production monitoring system |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60221301A (en) * | 1984-04-13 | 1985-11-06 | Mitsui Toatsu Chem Inc | Novel manufacture of germanium hydride |
| JP2759685B2 (en) * | 1989-09-05 | 1998-05-28 | 住友精化株式会社 | Diborane manufacturing method |
| CN1309619A (en) * | 1998-04-09 | 2001-08-22 | Uhp材料有限公司 | Preparation and purification of diborane |
| JP2002193604A (en) * | 2000-12-22 | 2002-07-10 | Toyota Central Res & Dev Lab Inc | Method for manufacturing metal borohydride |
| JP4373933B2 (en) * | 2005-01-31 | 2009-11-25 | 独立行政法人科学技術振興機構 | (1S, 2S)-or (1R, 2R) -cis-1-arylphosphorane-2-carboxylic acid / borane complex and method for producing the same |
-
2009
- 2009-08-27 JP JP2009197316A patent/JP5373508B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011046569A (en) | 2011-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5373508B2 (en) | Production method of diborane | |
| JP6175439B2 (en) | Apparatus and method for the production of trisilylamine by concentrated phase | |
| JP5756180B2 (en) | Method and system for producing high purity hydrogen chloride | |
| KR101159674B1 (en) | Process for purification of monosilane | |
| JP4867474B2 (en) | Method for producing perfluoroalkyne compound | |
| JP2013545704A5 (en) | ||
| CN110606490A (en) | Synthesis and purification method of high-purity silicon tetrafluoride | |
| JP2003183021A (en) | Method and apparatus for continuously purifying ammonia gas | |
| CN103910600A (en) | Method for preparing ultrapure fluoromethane | |
| KR101203490B1 (en) | A production method and production system for high purity hydrogen chloride | |
| JP2018093233A (en) | Dry etching method | |
| Wang et al. | Thiazole functionalized covalent triazine frameworks for C 2 H 6/C 2 H 4 separation with remarkable ethane uptake | |
| KR20130039249A (en) | A production method and production system for high purity hydrogen chloride | |
| KR101363571B1 (en) | Method for generating high quality GeH₄and Apparatus for generating high quality GeH₄ | |
| JP4765630B2 (en) | Method and apparatus for producing carbonyl fluoride | |
| JP5495642B2 (en) | Method for purifying carbonyl difluoride | |
| JP6941035B2 (en) | Acetic acid (2,2,2-trifluoroethyl) and its production method | |
| JP2021014410A (en) | Production method of vinyl compound | |
| JP4904032B2 (en) | Process for producing purified borazine compound | |
| JP5373259B2 (en) | Method for producing N-alkylborazine | |
| JP4498152B2 (en) | Method for purifying trimethylsilane | |
| KR101609011B1 (en) | Process for producing high-purity chlorine | |
| JP5215600B2 (en) | Method for producing N-alkylborazine | |
| JP5213408B2 (en) | Method for handling alkali borohydride and method for producing borazine compound | |
| CN115925734A (en) | Preparation method of dimethyl diethoxysilane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120615 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20120615 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130906 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130910 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130919 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5373508 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |