JPS6145632B2 - - Google Patents
Info
- Publication number
- JPS6145632B2 JPS6145632B2 JP53074981A JP7498178A JPS6145632B2 JP S6145632 B2 JPS6145632 B2 JP S6145632B2 JP 53074981 A JP53074981 A JP 53074981A JP 7498178 A JP7498178 A JP 7498178A JP S6145632 B2 JPS6145632 B2 JP S6145632B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- triethoxysilane
- reaction
- solvent
- produced
- 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.)
- Expired
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 125000005654 1,2-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([*:2])C([H])([*:1])C1([H])[H] 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- -1 benzene hydrocarbons Chemical class 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- WJECKFZULSWXPN-UHFFFAOYSA-N 1,2-didodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1CCCCCCCCCCCC WJECKFZULSWXPN-UHFFFAOYSA-N 0.000 description 1
- AXHVNJGQOJFMHT-UHFFFAOYSA-N 1-tert-butyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C(C)(C)C AXHVNJGQOJFMHT-UHFFFAOYSA-N 0.000 description 1
- GQRWGIWRQMNZNT-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadecane Chemical compound O1CCOCCOCCOCCOC2CCCCC21 GQRWGIWRQMNZNT-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- JKCQOMAQPUYHPL-UHFFFAOYSA-N dibenzo-21-crown-7 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 JKCQOMAQPUYHPL-UHFFFAOYSA-N 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- VXNSQGRKHCZUSU-UHFFFAOYSA-N octylbenzene Chemical compound [CH2]CCCCCCCC1=CC=CC=C1 VXNSQGRKHCZUSU-UHFFFAOYSA-N 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 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
【発明の詳細な説明】
本発明はアルコキシシランの製造法に関する。
詳しくは、銅触媒の存在下に、珪素と脂肪族アル
コールとを反応させて、一般式(RO)nSiH4-n
(ただし、Rはアルキル基、mは1〜4の整数を
表わす。以下同じ。)で示されるアルコキシシラ
ン、とくに、トリエトキシシランを製造する方法
の改良に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing alkoxysilanes.
Specifically, silicon and aliphatic alcohol are reacted in the presence of a copper catalyst to form the general formula (RO) n SiH 4-n
(However, R represents an alkyl group and m represents an integer of 1 to 4. The same applies hereinafter.) The present invention relates to an improvement in a method for producing alkoxysilane, particularly triethoxysilane.
従来、アルコキシシランの製法としては、一般
式ClnSiH4-nで示されるクロルシランと脂肪族ア
ルコールとを反応させる方法、および珪素金属と
脂肪族アルコールとを反応させる方法が知られて
いる。 Conventionally, known methods for producing alkoxysilane include a method in which chlorosilane represented by the general formula Cl n SiH 4-n is reacted with an aliphatic alcohol, and a method in which a silicon metal is reacted with an aliphatic alcohol.
第1の方法では、下記(1)式に示すように、反応
物中に塩酸が副生する。塩酸は、反応物中からの
回収が困難で、反応装置などの機器を腐食させる
ばかりでなく、生成したアルコキシシランを一部
分解するので、アルコキシシランの収率を低下さ
せる。 In the first method, as shown in the following formula (1), hydrochloric acid is produced as a by-product in the reaction product. Hydrochloric acid is difficult to recover from the reactants, not only corrodes equipment such as reaction equipment, but also partially decomposes the alkoxysilane produced, reducing the yield of alkoxysilane.
ClnSiH4-n+mROH→(RO)nSiH4-n+mHCl
……(1)
第2の方法では、反応は、銅触媒の存在下気相
系または液相系で行なわれ、下記(2)式に示すよう
に、種々のアルコキシシランおよび水素が生成す
る。Cl n SiH 4-n +mROH→(RO) n SiH 4-n +mHCl
...(1) In the second method, the reaction is carried out in a gas phase system or a liquid phase system in the presence of a copper catalyst, and various alkoxysilanes and hydrogen are produced as shown in the following formula (2).
Si+ROH→(RO)SiH3+(RO)2SiH2
+(RO)3SiH+(RO)4Si+H2 ………(2)
気相系で上記反応を行なわせると、テトラアル
コキシシラン(RO)4Siの生成が優先し、より有
用なトリアルコキシシラン(RO)3SiHの生成率
は低い。Si + ROH → (RO) SiH 3 + (RO) 2 SiH 2 + (RO) 3 SiH + (RO) 4 Si + H 2 ………(2) When the above reaction is performed in a gas phase system, tetraalkoxysilane (RO) 4 The production of Si takes priority, and the production rate of the more useful trialkoxysilane (RO) 3 SiH is low.
一方、液相系で上記反応を行なわせると、トリ
アルコキシシランが比較的高い選択率で生成する
が、珪素の反応率および反応速度等の点で工業的
製法としては、必ずしも満足し得るものではな
い。 On the other hand, when the above reaction is carried out in a liquid phase system, trialkoxysilane is produced with a relatively high selectivity, but it is not necessarily satisfactory as an industrial production method in terms of silicon reaction rate and reaction rate. do not have.
そこで、本発明者らは、銅触媒を用いて溶媒中
で珪素とエチルアルコールとから、トリエトキシ
シランを製造する方法について研究した結果、溶
媒中に適量の特定の環状ポリエーテルを存在させ
て反応を行なわせると、高収率、かつ、高反応速
度でトリエトキシシランを製造し得ることを見出
し、本発明に到達した。 Therefore, the present inventors conducted research on a method for producing triethoxysilane from silicon and ethyl alcohol in a solvent using a copper catalyst. It has been discovered that triethoxysilane can be produced in high yield and at a high reaction rate by carrying out this process, and the present invention has been achieved.
すなわち、本発明の目的は、高収率、かつ、高
反応速度でアルコキシシラン、とくにトリエトキ
シシランを製造することであり、この目的は、銅
触媒を用いて、珪素とエチルアルコールとを溶媒
中で反応させてアルコキシシランを製造する方法
において、溶媒中に、下記一般式(イ)で示される環
状ポリエーテルを存在させることによつて達成さ
れる。 That is, an object of the present invention is to produce alkoxysilane, particularly triethoxysilane, in high yield and at a high reaction rate. In the method for producing an alkoxysilane by the reaction, this is achieved by causing a cyclic polyether represented by the following general formula (A) to be present in the solvent.
(ただし、Rはメチレン基、エチレン基、プロピ
レン基、1・2−シクロヘキシレン基、1・2−
フエニレン基、および2・3−ナフタレン基から
なる群から選ばれる1種の2価炭化水素基を表わ
し、複数のRは互いに異つていてもよい。nは3
以上の整数である。)
次に、本発明を詳細に説明する。 (However, R is a methylene group, an ethylene group, a propylene group, a 1,2-cyclohexylene group, a 1,2-
It represents one type of divalent hydrocarbon group selected from the group consisting of a phenylene group and a 2,3-naphthalene group, and the plurality of R's may be different from each other. n is 3
is an integer greater than or equal to ) Next, the present invention will be explained in detail.
本発明方法において、原料である珪素として
は、通常、純度が80〜99%の珪素金属を、200μ
以下、好ましくは100μ以下の平均粒度に粉末化
したものが用いられる。 In the method of the present invention, the raw material silicon is usually silicon metal with a purity of 80 to 99%.
Hereinafter, powdered powder with an average particle size of preferably 100 μm or less is used.
アルコールの使用量は、珪素金属1モルに対し
て0.1〜50倍モルの範囲から選ばれる。 The amount of alcohol to be used is selected from the range of 0.1 to 50 times the mole of silicon metal.
銅触媒としては、金属銅または銅化合物が用い
られる。銅化合物としては、ハロゲン化物、カル
ボン酸塩、キレート化合物、酸化物など種種のも
のを用いることができ、具体的には、例えば、塩
化第1銅、塩化第2銅、シユウ化第1銅、シユウ
化第2銅、ヨウ化第1銅、ヨウ化第2銅、ギ酸
銅、銅アセチルアセトナート、酢酸第1銅、酢酸
第2銅、酸化第1銅などが挙げられる。銅触媒の
使用量は珪素金属1モルに対して0.0001〜0.5倍
モルの範囲から選ばれる。 Metallic copper or a copper compound is used as the copper catalyst. Various types of copper compounds can be used, such as halides, carboxylates, chelate compounds, and oxides. Specifically, for example, cuprous chloride, cupric chloride, cuprous oxalide, Examples include cupric oxalide, cuprous iodide, cupric iodide, copper formate, copper acetylacetonate, cuprous acetate, cupric acetate, cuprous oxide, and the like. The amount of copper catalyst to be used is selected from the range of 0.0001 to 0.5 times the mole of silicon metal.
溶媒としては、種々の炭化水素化合物を用いる
ことができ、例えば、オクタン、ノナン、デカ
ン、ドデカン、テトラデカン、ヘキサデカン、オ
クタデカン、エイコサン等のパラフイン系炭化水
素、エチルベンゼン、トリメチルベンゼン、シメ
ン、ジエチルベンゼン、ブチルベンゼン、t−ブ
チルトルエン、オクチルベンゼン、ドデシルベン
ゼン、ジドデシルベンゼン等のベンゼン系炭化水
素が好適に用いられる。これらの溶媒の使用量は
珪素金属1グラムに対して1ml〜10の範囲から
選ばれる。 Various hydrocarbon compounds can be used as the solvent, such as paraffinic hydrocarbons such as octane, nonane, decane, dodecane, tetradecane, hexadecane, octadecane, and eicosane, ethylbenzene, trimethylbenzene, cymene, diethylbenzene, and butylbenzene. , t-butyltoluene, octylbenzene, dodecylbenzene, didodecylbenzene, and other benzene hydrocarbons are preferably used. The amount of these solvents to be used is selected from the range of 1 ml to 10 ml per gram of silicon metal.
本発明方法では、溶媒中に下記一般式(イ)で示さ
れる環状ポリエーテルを含有させることが必要で
ある。 In the method of the present invention, it is necessary to contain a cyclic polyether represented by the following general formula (A) in the solvent.
ただし、Rはメチレン基、エチレン基、プロピ
レン基、1・2−シクロヘキシレン基、1・2−
フエニレン基および2・3−ナフタレン基からな
る群から選ばれる1種の2価炭化水素基を表わ
し、複数のRは互いに異なつていてもよい。そし
てnは3以上、好ましくは4〜10の整数である。
上記一般式(イ)で示される環状ポリエーテルとして
は、具体的には、例えば、ベンゾ−15−クラウン
−5、シクロヘキシル−15−クラウン−5、β−
ナフト−15−クラウン−5、ジベンゾ−18−クラ
ウン−6、ジシクロヘキシル−18−クラウン−
6、β−ナフト−18−クラウン−6、ジベンゾ−
21−クラウン−7、ジベンゾ−24−クラウン−8
等が挙げられる。 However, R is a methylene group, an ethylene group, a propylene group, a 1,2-cyclohexylene group, a 1,2-
It represents one kind of divalent hydrocarbon group selected from the group consisting of a phenylene group and a 2,3-naphthalene group, and the plurality of R's may be different from each other. And n is an integer of 3 or more, preferably 4 to 10.
Specifically, the cyclic polyether represented by the above general formula (A) includes, for example, benzo-15-crown-5, cyclohexyl-15-crown-5, β-
naphtho-15-crown-5, dibenzo-18-crown-6, dicyclohexyl-18-crown-
6, β-naphtho-18-crown-6, dibenzo-
21-crown-7, dibenzo-24-crown-8
etc.
溶媒中にこれらの環状ポリエーテルの1種また
は2種以上を含有させることにより、トリエトキ
シシランの収率および反応速度を著しく向上させ
ることができる。 By containing one or more of these cyclic polyethers in the solvent, the yield and reaction rate of triethoxysilane can be significantly improved.
溶媒中に含有させる環状ポリエーテルの量は、
銅触媒の使用量に対応して決定され、通常、0.01
〜10倍モルの範囲から選ばれる。 The amount of cyclic polyether contained in the solvent is
Determined according to the amount of copper catalyst used, typically 0.01
Selected from the range of ~10 times the mole.
反応温度は100〜300℃、好ましくは150〜250℃
である。 Reaction temperature is 100-300℃, preferably 150-250℃
It is.
以上、説明したように、本発明によれば、珪素
とエチルアルコールとから、高収率、かつ、高反
応速度でトリエトキシシランを製造することがで
きる。 As described above, according to the present invention, triethoxysilane can be produced from silicon and ethyl alcohol in a high yield and at a high reaction rate.
次に、本発明を実施例により、具体的に説明す
るが、本発明はその要旨を超えない限り以下の実
施例に限定されるものではない。 Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
なお、以下の実施例において、トリエトキシシ
ランの生成速度および選択率は下記によつて定義
される。 In addition, in the following examples, the production rate and selectivity of triethoxysilane are defined as follows.
(1) 生成速度は、珪素にアルコールを添加し始め
てから一定時間経過した時点の前1時間におけ
るトリエトキシシランの生成量を、溶媒量で除
すことにより算出する。(1) The production rate is calculated by dividing the amount of triethoxysilane produced in one hour before the elapse of a certain period of time from the start of adding alcohol to silicon by the amount of solvent.
(2) 選択率(%)
反応物中のトリエトキシシランのモル数/反応混合物中のトリエトキシシランおよびテトラアルコキシシラ
ンの総モル数×100
実施例 1
アルコール導入管、撹拌器および生成物留出管
を有する100c.c.反応容器にケイ素金属粉末(純度
98%)10.0g、塩化第一銅0.25gジベンゾ−18−
クラウン−6 0.2gおよびドデシルベンゼン20
c.c.を仕込んだ。(2) Selectivity (%) Number of moles of triethoxysilane in the reactant/Total number of moles of triethoxysilane and tetraalkoxysilane in the reaction mixture x 100 Example 1 Alcohol inlet tube, stirrer, and product distillation Silicon metal powder (purity
98%) 10.0g, cuprous chloride 0.25g dibenzo-18-
Crown-6 0.2g and dodecylbenzene 20
I installed cc.
留出管出口には冷却管を付し、留出してくる生
成アルコキシシランおよび未反応アルコールを捕
集できるようにした。 A cooling tube was attached to the outlet of the distillation tube to collect the alkoxysilane produced and unreacted alcohol distilled out.
次に、反応容器を加温し、浴温度が220℃に達
したところで導入管よりエタノールの導入を開始
した。導入速度は反応中7.5c.c./時で一定にし
た。導入開始後、1.5時間経過した時点のトリエ
トキシシランの収量は2.1gで生成速度は0.10Kg/
・hrであつた。 Next, the reaction vessel was heated, and when the bath temperature reached 220°C, introduction of ethanol was started from the introduction tube. The introduction rate was kept constant at 7.5 cc/hour during the reaction. The yield of triethoxysilane 1.5 hours after the start of introduction was 2.1g, and the production rate was 0.10Kg/
・It was hot in hr.
またこの時の選択率は96%であつた。その後、
新たに珪素金属を補給することなしに、エタノー
ルの導入を続けて反応を行なつたところ、5時間
経過後のトリエトキシシランの収量は8.2gで、
生成速度は0.08Kg/・hrであつた。 The selection rate at this time was 96%. after that,
When the reaction was carried out by continuing to introduce ethanol without replenishing silicon metal, the yield of triethoxysilane after 5 hours was 8.2 g.
The production rate was 0.08Kg/hr.
比較例 1
ジベンゾ−18−クラウン−6の添加を省略した
以外は実施例1と全く同じ条件で反応を行つたと
ころ、エタノール導入開始後2時間でトリエトキ
シシラン、テトラエトキシシランの生成は痕跡量
しか認められず、ほとんどのエタノールが回収さ
れた。Comparative Example 1 A reaction was carried out under exactly the same conditions as in Example 1 except that the addition of dibenzo-18-crown-6 was omitted, and only trace amounts of triethoxysilane and tetraethoxysilane were produced within 2 hours after the start of ethanol introduction. Most of the ethanol was recovered.
さらに5時間経過した時点でも同様であつた。 The same thing was true even after 5 hours had elapsed.
Claims (1)
を溶媒中で反応させてエトキシシランを製造する
方法において、溶媒中に、下記一般式(イ)で示され
る環状ポリエーテルを存在させることを特徴とす
るトリエトキシシランの製造法。 (ただし、Rはメチレン基、エチレン基、プロピ
レン基、1・2−シクロヘキシレン基、1・2−
フエニレン基および2・3−ナフタレン基からな
る群から選ばれる1種の2価炭化水素基を表わ
し、複数のRは互いに異なつていてもよい。nは
3以上の整数である。)[Claims] 1. In a method for producing ethoxysilane by reacting silicon and ethyl alcohol in a solvent using a copper catalyst, a cyclic polyether represented by the following general formula (a) is added to the solvent. A method for producing triethoxysilane, characterized in that it is produced in the presence of triethoxysilane. (However, R is a methylene group, an ethylene group, a propylene group, a 1,2-cyclohexylene group, a 1,2-
It represents one kind of divalent hydrocarbon group selected from the group consisting of a phenylene group and a 2,3-naphthalene group, and the plurality of R's may be different from each other. n is an integer of 3 or more. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7498178A JPS552641A (en) | 1978-06-21 | 1978-06-21 | Preparation of alkoxysilane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7498178A JPS552641A (en) | 1978-06-21 | 1978-06-21 | Preparation of alkoxysilane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS552641A JPS552641A (en) | 1980-01-10 |
JPS6145632B2 true JPS6145632B2 (en) | 1986-10-08 |
Family
ID=13562963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7498178A Granted JPS552641A (en) | 1978-06-21 | 1978-06-21 | Preparation of alkoxysilane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS552641A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6365309A (en) * | 1986-09-08 | 1988-03-23 | Toyota Autom Loom Works Ltd | Warning method for life of clutch plate |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS611693A (en) * | 1984-06-12 | 1986-01-07 | Shin Etsu Chem Co Ltd | Preparation of alkoxysilane |
US4727173A (en) * | 1987-03-31 | 1988-02-23 | Union Carbide Corporation | Process for producing trialkoxysilanes from the reaction of silicon metal and alcohol |
US4761492A (en) * | 1987-09-28 | 1988-08-02 | Union Carbide Corporation | Process for recovering trimethoxysilane from a trimethoxysilane and methanol mixture |
US4762939A (en) * | 1987-09-30 | 1988-08-09 | Union Carbide Corporation | Process for trialkoxysilane/tetraalkoxysilane mixtures from silicon metal and alcohol |
US5783720A (en) | 1996-10-10 | 1998-07-21 | Osi Specialties, Inc. | Surface-active additives in the direct synthesis of trialkoxysilanes |
US7339068B2 (en) | 2001-01-31 | 2008-03-04 | Momentive Performance Materials Inc. | Nanosized copper catalyst precursors for the direct synthesis of trialkoxysilanes |
US7858818B2 (en) | 2001-01-31 | 2010-12-28 | Momentive Performance Materials Inc. | Nanosized copper catalyst precursors for the direct synthesis of trialkoxysilanes |
US7652164B2 (en) | 2005-09-13 | 2010-01-26 | Momentive Performance Materials Inc. | Process for the direct synthesis of trialkoxysilane |
JP5527520B2 (en) | 2006-12-01 | 2014-06-18 | プロチミー インターナショナル,エルエルシー | Preparation process of alkoxysilane |
-
1978
- 1978-06-21 JP JP7498178A patent/JPS552641A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6365309A (en) * | 1986-09-08 | 1988-03-23 | Toyota Autom Loom Works Ltd | Warning method for life of clutch plate |
Also Published As
Publication number | Publication date |
---|---|
JPS552641A (en) | 1980-01-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5527520B2 (en) | Preparation process of alkoxysilane | |
JP2562833B2 (en) | Method for producing trialkoxysilane-tetraalkoxysilane mixture | |
KR950007594B1 (en) | Trimethoxysilane preparation via the methanol-silicon reaction with recyle | |
JPH0717656B2 (en) | An improved process for the production of trialkoxysilanes by the reaction of silicon metal with alcohols. | |
US10150785B2 (en) | Method for producing dialkylaminosilane | |
JP2848908B2 (en) | Production method of alkoxysilanes | |
JPH0458478B2 (en) | ||
JPS6145632B2 (en) | ||
US11028108B2 (en) | Method for producing dialkylaminosilane | |
EP0280517B1 (en) | Process for the production of trialkoxysilanes | |
JP5450884B2 (en) | Siloxacyclene | |
JPS633869B2 (en) | ||
EP0405560A2 (en) | Preparation of tertiary-hydrocarbylsilyl compounds | |
JPS6341919B2 (en) | ||
US2414058A (en) | Method of making lead alkyls | |
KR100371312B1 (en) | Preparation of alkyl(amino) dialkoxysilanes | |
JP2563305B2 (en) | Method for producing trialkoxysilane | |
JP2002138093A (en) | Method for producing trialkoxy silane using copper fluoride salt as catalyst | |
JP2584772B2 (en) | Method for producing trialkoxysilane | |
JP2584775B2 (en) | Separation and purification method of trialkoxysilane | |
JPS633870B2 (en) | ||
JPH085899B2 (en) | Method for producing alkoxysilane | |
JPH10168084A (en) | Production of alkoxysilane | |
JPS6121478B2 (en) | ||
JPS6145634B2 (en) |