JPS6236519B2 - - Google Patents
Info
- Publication number
- JPS6236519B2 JPS6236519B2 JP55021600A JP2160080A JPS6236519B2 JP S6236519 B2 JPS6236519 B2 JP S6236519B2 JP 55021600 A JP55021600 A JP 55021600A JP 2160080 A JP2160080 A JP 2160080A JP S6236519 B2 JPS6236519 B2 JP S6236519B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- alcohol
- silicon
- crown
- ester
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 150000003983 crown ethers Chemical class 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- -1 silicate ester Chemical class 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- QMLGNDFKJAFKGZ-UHFFFAOYSA-N dicyclohexano-24-crown-8 Chemical compound O1CCOCCOCCOC2CCCCC2OCCOCCOCCOC2CCCCC21 QMLGNDFKJAFKGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002633 crown compound Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-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
- 238000006266 etherification reaction Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension 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】
本発明はオルトケイ酸テトラアルキルエステル
の製造法に関し、殊に、多価アルコールとクラウ
ンエーテルの共存下に、ケイ素と低級アルコール
をアルカリ触媒の存在下に反応させてオルトケイ
酸テトラアルキルエステルを製造する方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing orthosilicic acid tetraalkyl ester, and in particular to a method for producing orthosilicic acid tetraalkyl ester by reacting silicon and a lower alcohol in the presence of an alkali catalyst in the coexistence of a polyhydric alcohol and a crown ether. The present invention relates to a method for producing a tetraalkyl ester.
オルトケイ酸アルキルエステルSi（OR）4〔た
だし、Ｒはアルキル基〕は有機ケイ素化合物とし
て種々の用途を有しており、就中、エチルシリケ
ートSi（OC2H5）4は無機質強防食性塗料、耐熱塗
料、耐熱コーテイング剤、耐熱接着剤、精密鋳造
や窯業製品の耐熱バインダーなどに用いられる有
用な物質である。 Orthosilicate alkyl ester Si (OR) 4 [where R is an alkyl group] has various uses as an organosilicon compound, and in particular, ethyl silicate Si (OC 2 H 5 ) 4 is used as an inorganic strong anticorrosion paint. It is a useful substance used in heat-resistant paints, heat-resistant coatings, heat-resistant adhesives, and heat-resistant binders for precision casting and ceramic products.
オルトケイ酸テトラアルキルエステルは工業的
には四塩化ケイ素と対応するアルコールとの反応
により製造されているが、この方法では副生する
塩化水素とアルコールから、および原料の四塩化
ケイ素により促進されるアルコールのエーテル化
反応により水が生成し、この水が原料及び生成物
の加水分解反応を生起させ、ケイ酸エステルのポ
リマーが副生する等の欠点を有している。 Orthosilicate tetraalkyl esters are industrially produced by the reaction of silicon tetrachloride with the corresponding alcohol, but in this method, the alcohol is produced from the by-product hydrogen chloride and alcohol, and the alcohol promoted by the raw material silicon tetrachloride. Water is produced by the etherification reaction, and this water causes a hydrolysis reaction of the raw materials and products, resulting in the production of a silicate ester polymer as a by-product.
原料として四塩化ケイ素を使用せず、金属ケイ
素とアルコールからオルトケイ酸テトラアルキル
エステルを製造する方法についても従来より種々
提案されており、触媒としてアルカリ金属のアル
コキサイドが効果的であることが知られている。
しかし、ケイ素とアルコールを触媒としてアルカ
リ金属アルコキサイドの存在下に反応させる方法
は実質的にメタノールからメチレート触媒にてメ
チルシリケート〔Si（OCH3）4〕を製造する方法に
限られ、エチルシリケート他炭素数の多いもので
は反応速度が著しく低く、工業的製法としては全
く考慮の対象とはなり得ない。 Various methods have been proposed to produce orthosilicate tetraalkyl esters from metallic silicon and alcohol without using silicon tetrachloride as a raw material, and it is known that alkali metal alkoxides are effective as catalysts. There is.
However, the method of reacting silicon and alcohol in the presence of an alkali metal alkoxide as a catalyst is essentially limited to the production of methyl silicate [Si(OCH 3 ) 4 ] from methanol with a methylate catalyst, If the number is large, the reaction rate is extremely low and it cannot be considered as an industrial production method at all.
本発明はケイ素と低級アルコールをアルカリ触
媒の存在下に反応させてオルトケイ酸テトラアル
キルエステルを製造する方法、殊に、メチルシリ
ケートのみならず、工業的に種々の有用な用途を
有するエチルシリケート等をも実用上有利に製造
し得る方法に関し、該反応を少量の多価アルコー
ル及びクラウンエーテルの共存下に行うことを特
徴とする方法を提供せんとするものである。 The present invention relates to a method for producing orthosilicate tetraalkyl esters by reacting silicon and lower alcohols in the presence of an alkali catalyst, and in particular, to produce not only methyl silicate but also ethyl silicate, which has various industrially useful uses. The object of the present invention is to provide a method that can be produced with practical advantage, and is characterized in that the reaction is carried out in the coexistence of a small amount of a polyhydric alcohol and a crown ether.
以下、本発明の方法について更に詳しく説明す
る。 The method of the present invention will be explained in more detail below.
本反応において原料として使用するケイ素は単
体ケイ素でも鉄分等を含有するケイ化鉄、ケイ素
−鉄合金等であつても良い。ただ、反応を効率良
く行うためには少くともケイ素分を80％以上、好
ましくは90％以上含有するものであることが望ま
しい。また、粒度の影響は比較的大きく、反応速
度の向上のためには接触面積の大きな微粉状のも
のを用いることが望ましい。他の原料である低級
アルコールとしては炭素数１〜４を有するアルコ
ール、のいずれでも用いることができ、それぞれ
反応するメチルエステル、エチルエステル、プロ
ピルエステル、ブチルエステルを製造することが
できる。 The silicon used as a raw material in this reaction may be simple silicon, iron silicide containing iron, silicon-iron alloy, or the like. However, in order to carry out the reaction efficiently, it is desirable that the silicon content be at least 80% or more, preferably 90% or more. Further, the influence of particle size is relatively large, and in order to improve the reaction rate, it is desirable to use a fine powder with a large contact area. As the lower alcohol, which is another raw material, any alcohol having 1 to 4 carbon atoms can be used, and methyl ester, ethyl ester, propyl ester, and butyl ester can be produced by reacting with each alcohol.
アルカリ触媒はリチウム、ナトリウム、カリウ
ム、ルビジウムなどのアルカリ金属の酸化物、水
酸化物、アルコキサイドなど一般的なものが用い
られ、就中、アルコキサイドが最も好ましい。
尚、触媒としてアルカリ金属アルコキサイドを用
いる場合、アルコキシ基は通常原料アルコール
（及び生成物アルキルエステル）と同じものが用
いられ、例えば、エチルアルコールよりエチルシ
リケートを製造する場合の触媒としては、エトキ
サイドが用いられるが、必ずしも限定はされな
い。必要に応じて、後述の多価アルコールとのア
ルコキサイドとして用いても良い。また、これら
は別途調製されたものでも或いは同一の反応器に
て予めアルカリ金属とアルコールとの反応により
調製し、そのままケイ素との反応に供しても良
い。 Common alkali catalysts such as oxides, hydroxides, and alkoxides of alkali metals such as lithium, sodium, potassium, and rubidium are used, and among them, alkoxides are most preferred.
In addition, when an alkali metal alkoxide is used as a catalyst, the alkoxy group is usually the same as that of the raw material alcohol (and the product alkyl ester). For example, when producing ethyl silicate from ethyl alcohol, ethoxide is used as a catalyst. However, it is not necessarily limited. If necessary, it may be used as an alkoxide with a polyhydric alcohol described below. Further, these may be prepared separately or may be prepared in advance by reacting an alkali metal and alcohol in the same reactor and then directly subjected to the reaction with silicon.
反応促進剤として使用する価アルコールとして
は、例えば、エチレングリコール、プロピレング
リリコール、ブチレングリコール、ペンチルグリ
コールなどのグリコール類やグリセリン、ペンタ
エリスリトール等が代表的なものとして掲げられ
る。これら多価アルコールは通常はそのまま用い
られるが、必要に応じて上記の如くアルカリ金属
のアルコキサイド（グリコキサイド）として反応
液に加えることもできる。 Typical examples of the alcohol used as a reaction promoter include glycols such as ethylene glycol, propylene glycol, butylene glycol, and pentyl glycol, glycerin, and pentaerythritol. These polyhydric alcohols are usually used as they are, but if necessary, they can also be added to the reaction solution as alkali metal alkoxides (glycosides) as described above.
反応促進剤として使用するもう一つの成分であ
るクラウン化合物は、電子供与性のドナー原子を
環構造中に持ち、カチオンを環の空孔内に取り込
む機能を持つ大環状化合物であつて、代表的なも
のとしては環状ポリエーテルであるクラウンエー
テルが挙げられる。更に具体的には15−クラウン
−５・18−クラウン−６、ジベンゾ−18−クラウ
ン−６、ジシクロヘキシル−18−クラウン６−、
ジベンゾ−24−クラウン−８、ジシクロヘキシル
−24−クラウン−８等のクラウンエーテルが挙げ
られる。 Crown compounds, which are another component used as reaction accelerators, are macrocyclic compounds that have an electron-donating donor atom in their ring structure and have the function of incorporating cations into the ring vacancies. Examples include crown ether, which is a cyclic polyether. More specifically, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown 6-,
Examples include crown ethers such as dibenzo-24-crown-8 and dicyclohexyl-24-crown-8.
本発明の反応は液相条件下に行われるが、その
ための特別な溶媒は必要ではない。しかし、必要
に応じて、適当な溶媒を用いることを阻げない。
反応当初使用すべき原料の量比については、必ず
しも厳密な制限はないが、一般にケイ素１モルに
対し、アルコールを0.01〜100モル、好ましくは
１〜10モルの範囲で行うことが適当である。アル
カリ触媒及び多価アルコール、クラウンエーテル
の量（濃度）についても特に厳密な制限はない
が、少な過ぎるときは所期の効果が得られず、目
的とするアルキルエステルが得られないことは勿
論であり、１方、多量に用いた場合、その量に比
例して得られる効果には自ら制限があり、必ずし
も期待する効果が得られるわけではなく、場合に
よつては過剰使用による種々の弊害を招くことに
もなるため、通常は、ケイ素１モルに対し、アル
カリ触媒は0.001〜0.1モル、好ましくは0.01〜
0.05モル、多価アルコールは0.001〜1.0モル、好
ましくは0.01〜0.5モル及びクラウンエーテルは
0.0001〜0.1モル、好ましくは0.001〜0.05モル程
度の範囲で用いることが適当と言える。反応温度
は100℃以上を要し、これ以下の温度では実質的
に充分な反応速度は得られない。通常は140℃〜
300℃、好ましくは150〜200℃にて行われる。圧
力は反応荷を液相に保つに必要な圧力は最低限必
要とされるが、特にそれ以上の積極的な加圧は不
要である。 Although the reaction of the present invention is carried out under liquid phase conditions, no special solvent is required for this purpose. However, this does not prevent the use of a suitable solvent if necessary.
Although there are no strict limitations on the ratio of raw materials to be used at the beginning of the reaction, it is generally appropriate to use alcohol in a range of 0.01 to 100 moles, preferably 1 to 10 moles, per mole of silicon. There is no particular strict limit on the amount (concentration) of the alkali catalyst, polyhydric alcohol, and crown ether, but if it is too small, the desired effect will not be obtained, and it goes without saying that the desired alkyl ester will not be obtained. On the other hand, when used in large amounts, there is a limit to the effect that can be obtained in proportion to the amount, and the desired effect may not necessarily be obtained, and in some cases, there may be various adverse effects due to excessive use. Therefore, the amount of alkaline catalyst is usually 0.001 to 0.1 mol, preferably 0.01 to 0.1 mol, per 1 mol of silicon.
0.05 mol, polyhydric alcohol 0.001-1.0 mol, preferably 0.01-0.5 mol and crown ether
It can be said that it is appropriate to use it in a range of about 0.0001 to 0.1 mol, preferably about 0.001 to 0.05 mol. The reaction temperature is required to be 100°C or higher, and a substantially sufficient reaction rate cannot be obtained at a temperature lower than this. Usually 140℃～
It is carried out at 300°C, preferably 150-200°C. The minimum pressure necessary to keep the reactant in the liquid phase is required, but no more aggressive pressure is required.
反応は回分式、連続式いずれの方法でも実施す
ることができる。連続式反応においてケイ素を供
給する方法としては、微粉状にして別個に供給す
る方法或いは原料アルコール又は生成物のオルト
ケイ酸エステルの懸濁液として反応系に添加され
る。また、場合によつては、予め化学量論的に大
過剰のケイ素を反応器に保持し、触媒及び反応促
進剤を溶解したアルコール溶液を流通せしめる方
法も可能である。 The reaction can be carried out either batchwise or continuously. In a continuous reaction, silicon can be supplied by separately supplying it in the form of fine powder, or by adding it to the reaction system as a suspension of raw material alcohol or product orthosilicate ester. In some cases, it is also possible to maintain a large stoichiometric excess of silicon in a reactor in advance, and to flow an alcohol solution in which a catalyst and a reaction accelerator are dissolved.
以下、本発明の方法について代表的な例を示
し、更に具体的に説明するが、これらは本発明の
方法についての理解を容易にするための条件を絞
つた単なる例示であり、従つて、本発明はこれら
のみに限定されないことは勿論のこと、これらに
よつて何ら制限されないことは言うまでもない。 Hereinafter, typical examples of the method of the present invention will be shown and explained in more detail, but these are merely examples with narrowed down conditions to facilitate understanding of the method of the present invention, and therefore, the method of the present invention will be explained in more detail. It goes without saying that the invention is not limited to these only, and is not limited in any way by these.
実施例 １（比較例）
300c.c.のオートクレーブにエチルアルコール100
ml、粉末状金属ケイ素25ｇ、ナトリウムエチラー
ト１ｇ、エチレングリコール７mlを充填し反応器
内を窒素で置換し、155〜180℃で３時間反応をお
こなつた。Example 1 (comparative example) Ethyl alcohol 100% in a 300c.c. autoclave
ml, 25 g of powdered silicon metal, 1 g of sodium ethylate, and 7 ml of ethylene glycol, the inside of the reactor was purged with nitrogen, and the reaction was carried out at 155 to 180° C. for 3 hours.
反応中水素の発生が認められオルトケイ酸エチ
ルエステルが８ｇ生成した。 During the reaction, generation of hydrogen was observed, and 8 g of orthosilicate ethyl ester was produced.
実施例 ２
クラウンエーテル、18−クラウン−６ １ｇを
加えた以外は実施例１と同様に反応をおこなつ
た。Example 2 The reaction was carried out in the same manner as in Example 1, except that 1 g of crown ether, 18-crown-6, was added.
反応中水素の発生が認められ、オルトケイ酸エ
チルエエステルが21.8ｇ生成した。 During the reaction, generation of hydrogen was observed, and 21.8 g of orthosilicate ethyl ester was produced.
実施例 ３（比較例）
エチルアルコール100ml、ケイ素20ｇ、エチレ
ングリコール７ml、水酸化カリウム0.8ｇをオー
トクレーブに充填し、155〜186℃８時間応した。Example 3 (Comparative Example) 100 ml of ethyl alcohol, 20 g of silicon, 7 ml of ethylene glycol, and 0.8 g of potassium hydroxide were charged into an autoclave and heated at 155-186°C for 8 hours.
反応中水素が発生し、オルトケイ酸エチルエス
テルが31.4ｇ生成した。 During the reaction, hydrogen was generated and 31.4 g of orthosilicate ethyl ester was produced.
実施例 ４
クラウンエーテル、18−クラウン−６ １ｇを
加えた以外は実施例３と同様に反応をおこなつ
た。反応中水素の発生が認められオルトケイ酸エ
チエステルが53.1ｇ生成した。Example 4 The reaction was carried out in the same manner as in Example 3, except that 1 g of crown ether, 18-crown-6, was added. During the reaction, generation of hydrogen was observed, and 53.1 g of orthosilicate ethyl ester was produced.
実施例 ５
クラウンエーテル、ジシクロヘキシル−18−ク
ラウン−６ 0.8ｇを加えた以外は実施例３と同
様の反応おこなつた。Example 5 The same reaction as in Example 3 was carried out except that 0.8 g of crown ether, dicyclohexyl-18-crown-6, was added.
反応中水素の発生が認められオルトケイ酸エチ
ルエステルが39.5ｇ生成した。 During the reaction, generation of hydrogen was observed, and 39.5 g of orthosilicate ethyl ester was produced.
実施例 ６
300c.c.オートクレーブにエチルアルコール100
ml、粉末状金属ケイ素40ｇ、水酸化カリウム0.8
ｇ、エチレングリコール７ml、クラウンエーテル
18−クラウン−６ 0.7ｇを充填し反応器内を
窒素で置換し155〜183℃で４、５時間反応をおこ
なつた。Example 6 100% ethyl alcohol in a 300c.c. autoclave
ml, powdered silicon metal 40g, potassium hydroxide 0.8
g, ethylene glycol 7ml, crown ether
0.7 g of 18-crown-6 was charged, the inside of the reactor was purged with nitrogen, and the reaction was carried out at 155 to 183°C for 4 to 5 hours.
反応中水素の発生が認められオルトケイ酸エチ
ルエステルが72.6ｇ生成した。 During the reaction, generation of hydrogen was observed, and 72.6 g of orthosilicate ethyl ester was produced.
実施例 ７
クラウンエーテル、ジシクロヘキシル−24−ク
ラウン−８ 1.2ｇを加えた以外は実施例３と同
様の反応を５時間おこなつた。Example 7 The same reaction as in Example 3 was carried out for 5 hours, except that 1.2 g of crown ether, dicyclohexyl-24-crown-8, was added.
反応中水素の発生が認められオルトケイ酸エチ
ルエステルが35.5ｇ生成した。 During the reaction, generation of hydrogen was observed, and 35.5 g of orthosilicate ethyl ester was produced.
実施例 ８（比較例）
エチレングリコールを加えない以外は実施例４
と同様の反応をおこなつた。反応中の水素発生速
度は実施例４に比較して１／10以下であつた。Example 8 (comparative example) Example 4 except that ethylene glycol is not added
I made a similar reaction. The hydrogen generation rate during the reaction was 1/10 or less compared to Example 4.
Claims (1)
在下に反応させてオルトケイ酸テトラアルキルエ
ステルを製造する方法に於いて、該反応を多価ア
ルコールとクラウンエーテルの共存下に行うこと
を特徴とする方法。1. A method for producing an orthosilicate tetraalkyl ester by reacting silicon and a lower alcohol in the presence of an alkali catalyst, characterized in that the reaction is carried out in the coexistence of a polyhydric alcohol and a crown ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2160080A JPS56118088A (en) | 1980-02-25 | 1980-02-25 | Preparation of orthosilicic acid tetraalkyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2160080A JPS56118088A (en) | 1980-02-25 | 1980-02-25 | Preparation of orthosilicic acid tetraalkyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56118088A JPS56118088A (en) | 1981-09-16 |
| JPS6236519B2 true JPS6236519B2 (en) | 1987-08-07 |
Family
ID=12059524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2160080A Granted JPS56118088A (en) | 1980-02-25 | 1980-02-25 | Preparation of orthosilicic acid tetraalkyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56118088A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62120390A (en) * | 1985-11-20 | 1987-06-01 | Chisso Corp | Production of tetraalkoxysilane |
-
1980
- 1980-02-25 JP JP2160080A patent/JPS56118088A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56118088A (en) | 1981-09-16 |
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