JP3091993B2 - Method for producing mercaptopropylsilane compound - Google Patents
Method for producing mercaptopropylsilane compoundInfo
- Publication number
- JP3091993B2 JP3091993B2 JP07097119A JP9711995A JP3091993B2 JP 3091993 B2 JP3091993 B2 JP 3091993B2 JP 07097119 A JP07097119 A JP 07097119A JP 9711995 A JP9711995 A JP 9711995A JP 3091993 B2 JP3091993 B2 JP 3091993B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- mercaptopropylsilane
- acid
- alkali metal
- producing
- 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 - Fee Related
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、メトキシ基またはエト
キシ基のアルコキシル基を有するメルカプトプロピルシ
ラン化合物の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a mercaptopropylsilane compound having a methoxy or ethoxy alkoxyl group.
【０００２】[0002]
【従来の技術】メルカプトプロピルシラン化合物は、カ
ップリング剤、樹脂改質剤、無機物質の表面処理剤また
はシリコーン樹脂の原料として知られている。2. Description of the Related Art Mercaptopropylsilane compounds are known as coupling agents, resin modifiers, surface treatment agents for inorganic substances, or raw materials for silicone resins.
【０００３】メルカプトプロピルシラン化合物の製造方
法として、英国特許第１１０２２５１号明細書にハロゲ
ノプロピルシラン化合物とアルカリ金属水硫化物とをア
ルコール溶媒中で反応させる方法が記載されている。As a method for producing a mercaptopropylsilane compound, British Patent No. 1102251 discloses a method in which a halogenopropylsilane compound is reacted with an alkali metal hydrosulfide in an alcohol solvent.
【０００４】この方法において、アルカリ金属水硫化物
の量がハロゲノプロピルシラン化合物と同量程度である
と、反応時間が非常に長いだけでなく、原料のハロゲノ
プロピルシラン化合物が、目的物のメルカプトプロピル
シラン化合物と沸点が近いために反応後も残存してしま
い、その分離のために収率が著しく低下してしまう。こ
のためアルカリ金属水硫化物は、ハロゲノプロピルシラ
ン化合物に対して過剰量使用することが望ましい。In this method, when the amount of the alkali metal hydrosulfide is about the same as that of the halogenopropylsilane compound, not only the reaction time is extremely long, but also the halogenopropylsilane compound as the raw material is converted into the mercaptopropyl compound as the target. Since the boiling point of the silane compound is close to that of the silane compound, it remains even after the reaction, and the yield is significantly reduced due to the separation. For this reason, it is desirable to use an excess amount of the alkali metal hydrosulfide with respect to the halogenopropylsilane compound.
【０００５】しかしながら、アルカリ金属水硫化物をハ
ロゲノプロピルシラン化合物に対して過剰量使用する
と、反応終了後に蒸留単離する際に、反応に使用されな
かったアルカリ金属水硫化物が熱不均化反応をおこして
硫化水素が発生し、それが生成したメルカプトプロピル
シラン化合物に混入して強い不快臭を発生したり、過剰
量のアルカリ金属水硫化物によるアルカリ性が原因とな
って、生成したメルカプトプロピルシラン化合物が脱ア
ルコール閉環縮合反応を起こして純度の高いメルカプト
プロピルシラン化合物が得られないことがあった。[0005] However, if the alkali metal hydrosulfide is used in an excess amount relative to the halogenopropylsilane compound, the alkali metal hydrosulfide not used in the reaction may be subjected to a thermal disproportionation reaction upon distillation and isolation after completion of the reaction. Hydrogen sulfide is generated, which is mixed with the generated mercaptopropylsilane compound to generate a strong unpleasant odor, or the mercaptopropylsilane generated due to the alkalinity due to an excessive amount of alkali metal hydrosulfide. In some cases, the compound undergoes a dealcoholization ring-closing condensation reaction, so that a highly pure mercaptopropylsilane compound cannot be obtained.
【０００６】[0006]
【発明が解決しようとする課題】このため、ハロゲノプ
ロピルシラン化合物とアルカリ金属水硫化物とをアルコ
ール溶媒中で短時間で完全に反応させることができ、生
成したメルカプトプロピルシラン化合物を蒸留単離する
時に不快臭を発生することがなく、高収率で高純度なメ
ルカプトプロピルシラン化合物の製造方法が望まれてい
た。Therefore, the halogenopropylsilane compound and the alkali metal hydrosulfide can be completely reacted in an alcohol solvent in a short time, and the produced mercaptopropylsilane compound is isolated by distillation. There has been a demand for a method for producing a mercaptopropylsilane compound with high yield and high purity, which does not sometimes generate an unpleasant odor.
【０００７】本発明は前記の課題を解決するためなされ
たもので、ハロゲノプロピルシラン化合物とアルカリ金
属水硫化物とをアルコール溶媒中で短時間で完全に反応
させることができ、生成したメルカプトプロピルシラン
化合物を蒸留単離する時に硫化水素が発生、混入して不
快臭を発生することがなく、生成したメルカプトプロピ
ルシラン化合物が閉環縮合物を副生することがなく、高
収率で高純度なメルカプトプロピルシラン化合物の製造
方法を提供することを目的とする。The present invention has been made to solve the above-mentioned problems, and can completely react a halogenopropylsilane compound with an alkali metal hydrosulfide in an alcohol solvent in a short time. Hydrogen sulfide is not generated and mixed when separating and isolating the compound by distillation, and does not generate an unpleasant odor. An object of the present invention is to provide a method for producing a propylsilane compound.
【０００８】[0008]
【課題を解決するための手段】前記の目的を達成するた
めになされた本発明のメルカプトプロピルシラン化合物
の製造方法は、アルカリ金属水硫化物のアルコール溶液
に、下記式〔I〕 Ｘ−(ＣＨ2)3−Ｓｉ(ＣＨ3)n(ＯＲ)3-n 〔I〕 で表されるハロゲノプロピルシラン化合物を加えて反応
させた後、酸を加えて濾過し、濾液を蒸留単離して下記
式〔II〕 ＨＳ−(ＣＨ2)3−Ｓｉ(ＣＨ3)n(ＯＲ)3-n 〔II〕 （〔I〕、〔II〕式中のＸは塩素原子または臭素原子、
Ｒはメチル基またはエチル基、ｎは０〜２の整数）で表
される３−メルカプトプロピルトリメトキシシラン、３
−メルカプトプロピルトリエトキシシラン、３−メルカ
プトプロピルメチルジメトキシシラン、３−メルカプト
プロピルメチルジエトキシシラン、３−メルカプトプロ
ピルジメチルメトキシシラン、または３−メルカプトプ
ロピルジメチルエトキシシランのメルカプトプロピルシ
ラン化合物を得る方法である。In order to achieve the above-mentioned object, a method for producing a mercaptopropylsilane compound according to the present invention comprises the steps of preparing a solution of an alkali metal hydrosulfide in an alcohol solution of the following formula [I] X- (CH 2 ) 3- Si (CH 3 ) n (OR) 3-n A halogenopropylsilane compound represented by [I] is added and reacted, an acid is added, and the mixture is filtered. [II] HS- (CH 2 ) 3 —Si (CH 3 ) n (OR) 3-n [II] (X in the formulas [I] and [II] is a chlorine atom or a bromine atom,
R is a methyl group or an ethyl group, n is an integer of 0 to 2) 3-mercaptopropyltrimethoxysilane, 3
-A method for obtaining a mercaptopropylsilane compound of mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyldimethylmethoxysilane, or 3-mercaptopropyldimethylethoxysilane. .
【０００９】前記酸は水溶液でない酸、例えば蟻酸、酢
酸、プロピオン酸、シュウ酸、マロン酸、コハク酸等の
有機酸、または塩化水素、臭化水素、ヨウ化水素、リン
酸、ほう酸等の無機酸であれば何でも良く、中でも価
格、扱い易さの面から酢酸または塩化水素が好ましい。
塩酸等の水溶液の酸を使用すると、生成したメルカプト
プロピルシラン化合物が加水分解縮合物を副生してしま
う。The above-mentioned acid is an acid which is not an aqueous solution, for example, an organic acid such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid and succinic acid, or an inorganic acid such as hydrogen chloride, hydrogen bromide, hydrogen iodide, phosphoric acid and boric acid. Any acid may be used, and among them, acetic acid or hydrogen chloride is preferred from the viewpoint of cost and ease of handling.
When an acid in an aqueous solution such as hydrochloric acid is used, the generated mercaptopropylsilane compound produces a hydrolysis condensate as a by-product.
【００１０】前記アルカリ金属水硫化物は、水硫化リチ
ウム、水硫化ナトリウムまたは水硫化カリウムが挙げら
れる。[0010] Examples of the alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide and potassium hydrosulfide.
【００１１】前記ハロゲノプロピルシラン化合物は、具
体的には３−クロロプロピルトリメトキシシラン、３−
クロロプロピルトリエトキシシラン、３−クロロプロピ
ルメチルジメトキシシラン、３−クロロプロピルメチル
ジエトキシシラン、３−クロロプロピルジメチルメトキ
シシラン、３−クロロプトプロピルジメチルエトキシシ
ラン、３−ブロモプロピルトリメトキシシラン、３−ブ
ロモプロピルトリエトキシシラン、３−ブロモプロピル
メチルジメトキシシラン、３−ブロモプロピルメチルジ
エトキシシラン、３−ブロモプロピルジメチルメトキシ
シラン、または３−ブロモプロピルジメチルエトキシシ
ランである。The above-mentioned halogenopropylsilane compound is specifically 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane,
Chloropropyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloropropylpropyldimethylethoxysilane, 3-bromopropyltrimethoxysilane, 3- Bromopropyltriethoxysilane, 3-bromopropylmethyldimethoxysilane, 3-bromopropylmethyldiethoxysilane, 3-bromopropyldimethylmethoxysilane, or 3-bromopropyldimethylethoxysilane.
【００１２】使用する酸の量は、アルカリ金属水硫化物
と同量程度が好ましいが、同量以下または同量以上でも
無添加の場合に比較して良好な結果が得られる。The amount of the acid used is preferably about the same as that of the alkali metal hydrosulfide, but a good result can be obtained even when the amount is less than or equal to that of the case where no additive is used.
【００１３】[0013]
【発明の効果】本発明の方法でメルカプトプロピルシラ
ン化合物を製造すると、ハロゲノプロピルシラン化合物
とアルカリ金属水硫化物とをアルコール溶媒中で短時間
で完全に反応させることができ、生成したメルカプトプ
ロピルシラン化合物を蒸留単離する時に硫化水素が発
生、混入して不快臭を発生することがなく、生成したメ
ルカプトプロピルシラン化合物が閉環縮合物を副生する
ことがなく、高収率で高純度なメルカプトプロピルシラ
ン化合物を得ることができる。When the mercaptopropylsilane compound is produced by the method of the present invention, the halogenopropylsilane compound and the alkali metal hydrosulfide can be completely reacted in an alcohol solvent in a short time, and the resulting mercaptopropylsilane Hydrogen sulfide is not generated and mixed to generate unpleasant odor when the compound is isolated by distillation, and the generated mercaptopropylsilane compound does not produce by-products as ring-closing condensate. A propylsilane compound can be obtained.
【００１４】[0014]
【実施例】以下、本発明の実施例を詳細に説明する。Embodiments of the present invention will be described below in detail.
【００１５】実施例１ ナトリウムメトキシドの濃度２８重量％メタノール溶液
３４７．２ｇ（ナトリウムメトキシド：１．８ｍｏｌ）
を２リットルのオートクレーブに仕込み、密閉して室温
下で硫化水素６３．１ｇ（１．８５ｍｏｌ）を吹き込み
水硫化ナトリウムのメタノール溶液を得た。この溶液に
密閉したオートクレーブ中７０℃下で、３−クロロプロ
ピルトリメトキシシラン２９８．１ｇ（１．５０ｍｏ
ｌ）を２時間かけて加えた後、７０℃下で４時間静置し
て反応を完結させた。Example 1 347.2 g of a 28% by weight methanol solution of sodium methoxide (sodium methoxide: 1.8 mol)
Was charged in a 2 liter autoclave, sealed and blown with 63.1 g (1.85 mol) of hydrogen sulfide at room temperature to obtain a methanol solution of sodium hydrosulfide. 298.1 g of 3-chloropropyltrimethoxysilane (1.50 mol) was added to this solution in an autoclave sealed at 70 ° C.
After 1) was added over 2 hours, the mixture was allowed to stand at 70 ° C. for 4 hours to complete the reaction.
【００１６】この反応液に、室温下で酢酸１８．０ｇ
（０．３ｍｏｌ）を加えた後、濾過して塩を除去し、濾
液を減圧下で蒸留して８１〜８２℃／６ｍｍＨｇの留分
を分取することにより、３−メルカプトプロピルトリメ
トキシシラン２３８．４ｇ（収率８１％）を得た。得ら
れた３−メルカプトプロピルトリメトキシシランの純度
をガスクロマトグラフィーで調べたところ９９％であっ
た。また硫化水素臭は全くなかった。18.0 g of acetic acid was added to the reaction solution at room temperature.
After adding (0.3 mol), the mixture was filtered to remove salts, the filtrate was distilled under reduced pressure, and a fraction of 81 to 82 ° C./6 mmHg was collected to give 3-mercaptopropyltrimethoxysilane 238. 0.4 g (yield 81%) was obtained. The purity of the obtained 3-mercaptopropyltrimethoxysilane was determined by gas chromatography and found to be 99%. There was no smell of hydrogen sulfide.
【００１７】比較例１ 酢酸を加えないことを除き実施例１と同様にして３−メ
ルカプトプロピルトリメトキシシラン２２７．５ｇ（収
率７７．２％）を得た。得られた３−メルカプトプロピ
ルトリメトキシシランの純度をガスクロマトグラフィー
で調べたところ脱メタノール閉環縮合化合物が４．６％
含まれていた。また強い硫化水素臭を発していた。Comparative Example 1 227.5 g (yield: 77.2%) of 3-mercaptopropyltrimethoxysilane was obtained in the same manner as in Example 1 except that acetic acid was not added. When the purity of the obtained 3-mercaptopropyltrimethoxysilane was examined by gas chromatography, 4.6% of the demethanol ring-closing condensed compound was obtained.
Was included. It also had a strong hydrogen sulfide odor.
【００１８】実施例２ ナトリウムメトキシドの濃度２８重量％メタノール溶液
４０５．０ｇ（ナトリウムメトキシド：２．１ｍｏｌ）
を２リットルのオートクレーブに仕込み、密閉して室温
下で硫化水素７３．０ｇ（２．１４ｍｏｌ）を吹き込み
水硫化ナトリウムのメタノール溶液を得た。この溶液に
密閉したオートクレーブ中７０℃下で、３−クロロプロ
ピルトリメトキシシラン２９８．１ｇ（１．５０ｍｏ
ｌ）を２時間かけて加えた後、１００℃下で２時間静置
して反応を完結させた。Example 2 405.0 g of a 28% by weight methanol solution of sodium methoxide (sodium methoxide: 2.1 mol)
Was charged into a 2 liter autoclave, sealed and blown with 73.0 g (2.14 mol) of hydrogen sulfide at room temperature to obtain a methanol solution of sodium hydrosulfide. 298.1 g of 3-chloropropyltrimethoxysilane (1.50 mol) was added to this solution in an autoclave sealed at 70 ° C.
After 1) was added over 2 hours, the mixture was allowed to stand at 100 ° C. for 2 hours to complete the reaction.
【００１９】この反応液に、室温下で塩化水素３．６ｇ
（０．１ｍｏｌ）を加えた後、濾過して塩を除去し、濾
液を減圧下で蒸留して８１〜８２℃／６ｍｍＨｇの留分
を分取することにより、３−メルカプトプロピルトリメ
トキシシラン３２８．１ｇ（収率８４％）を得た。得ら
れた３−メルカプトプロピルトリメトキシシランの純度
をガスクロマトグラフィーで調べたところ９９％であっ
た。また硫化水素臭は全くなかった。3.6 g of hydrogen chloride was added to the reaction solution at room temperature.
(0.1 mol) was added, followed by filtration to remove salts. The filtrate was distilled under reduced pressure to collect a fraction at 81 to 82 ° C / 6 mmHg, thereby obtaining 3-mercaptopropyltrimethoxysilane 328. .1 g (84% yield). The purity of the obtained 3-mercaptopropyltrimethoxysilane was determined by gas chromatography and found to be 99%. There was no smell of hydrogen sulfide.
【００２０】実施例３ ３−クロロプロピルトリメトキシシラン２９８．１ｇ
（１．５０ｍｏｌ）の代わりに３−クロロプロピルメチ
ルジメトキシシラン２７４．１ｇ（１．５０ｍｏｌ）を
使用し、８１〜８２℃／１５ｍｍＨｇの留分を分取した
ことを除き実施例１と同様にして３−メルカプトプロピ
ルメチルジメトキシシラン２１３．７ｇ（収率７９％）
を得た。得られた３−メルカプトプロピルメチルジメト
キシシランの純度をガスクロマトグラフィーで調べたと
ころ９９％であった。また硫化水素臭は全くなかった。Example 3 298.1 g of 3-chloropropyltrimethoxysilane
In the same manner as in Example 1 except that 274.1 g (1.50 mol) of 3-chloropropylmethyldimethoxysilane was used instead of (1.50 mol) and a fraction at 81 to 82 ° C./15 mmHg was fractionated. 213.7 g of 3-mercaptopropylmethyldimethoxysilane (79% yield)
I got The purity of the obtained 3-mercaptopropylmethyldimethoxysilane was determined by gas chromatography and found to be 99%. There was no smell of hydrogen sulfide.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 遠藤 幹夫 新潟県中頸城郡頸城村大字西福島28番地 の１ 信越化学工業株式会社合成技術研 究所内 (72)発明者 山本 昭 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社シリコーン電子 材料技術研究所内 (72)発明者 工藤 宗夫 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社シリコーン電子 材料技術研究所内 (56)参考文献 特開 平４−217689（ＪＰ，Ａ) 特開 昭59−80689（ＪＰ，Ａ) 特開 平３−255064（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07F 7/18 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mikio Endo 28-1, Nishifukushima, Oku-ku, Nikushiro-mura, Nakakibijo-gun, Niigata Prefecture Within Synthetic Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Akira Yamamoto Matsui, Usui-gun, Gunma Prefecture Hitomi Tamachi 1-10, Shin-Etsu Chemical Co., Ltd. Silicone Electronics Materials Research Laboratory (72) Inventor Muneo Kudo 1-10, Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronics Materials Research Laboratory (56 References JP-A-4-217689 (JP, A) JP-A-59-80689 (JP, A) JP-A-3-255064 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB Name) C07F 7/18
Claims (2)
に、下記式〔I〕 Ｘ−(ＣＨ2)3−Ｓｉ(ＣＨ3)n(ＯＲ)3-n 〔I〕 で表されるハロゲノプロピルシラン化合物を加えて反応
させた後、酸を加えて濾過し、濾液を蒸留単離すること
を特徴とする下記式〔II〕 ＨＳ−(ＣＨ2)3−Ｓｉ(ＣＨ3)n(ＯＲ)3-n 〔II〕 （〔I〕、〔II〕式中のＸは塩素原子または臭素原子、
Ｒはメチル基またはエチル基、ｎは０〜２の整数）で表
されるメルカプトプロピルシラン化合物の製造方法。1. A halogenopropylsilane represented by the following formula [I] X- (CH 2 ) 3 -Si (CH 3 ) n (OR) 3-n [I] in an alcohol solution of an alkali metal hydrosulfide. After adding the compound and reacting, an acid is added and the mixture is filtered, and the filtrate is distilled and isolated. The following formula [II] HS- (CH 2 ) 3 -Si (CH 3 ) n (OR) 3 -n [II] (X in the formulas (I) and [II] represents a chlorine atom or a bromine atom,
R represents a methyl group or an ethyl group, and n represents an integer of 0 to 2).
ウム、水硫化ナトリウムまたは水硫化カリウム、前記酸
が酢酸または塩化水素であることを特徴とする請求項１
に記載のメルカプトプロピルシラン化合物の製造方法。2. The method according to claim 1, wherein said alkali metal hydrosulfide is lithium, sodium or potassium hydrosulfide, and said acid is acetic acid or hydrogen chloride.
3. The method for producing a mercaptopropylsilane compound described in 1. above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07097119A JP3091993B2 (en) | 1995-04-21 | 1995-04-21 | Method for producing mercaptopropylsilane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07097119A JP3091993B2 (en) | 1995-04-21 | 1995-04-21 | Method for producing mercaptopropylsilane compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08291184A JPH08291184A (en) | 1996-11-05 |
| JP3091993B2 true JP3091993B2 (en) | 2000-09-25 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07097119A Expired - Fee Related JP3091993B2 (en) | 1995-04-21 | 1995-04-21 | Method for producing mercaptopropylsilane compound |
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| Country | Link |
|---|---|
| JP (1) | JP3091993B2 (en) |
Cited By (1)
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|---|---|---|---|---|
| KR102473427B1 (en) | 2020-11-09 | 2022-12-05 | 고진희 | Wall mounting apparatus for shelves |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4574034B2 (en) * | 2001-02-27 | 2010-11-04 | 日本曹達株式会社 | Method for producing silicon compound having mercapto group |
| JP4574875B2 (en) * | 2001-02-27 | 2010-11-04 | 日本曹達株式会社 | A solvent recovery and regeneration method for producing a silicon compound having a hydrolyzable group. |
| JP4574876B2 (en) * | 2001-02-27 | 2010-11-04 | 日本曹達株式会社 | Method for producing silicon compound having mercapto group |
| DE102004030737A1 (en) | 2004-06-25 | 2006-01-12 | Degussa Ag | Method and device for extracting substances from silane-modified fillers |
| DE102005020535B3 (en) | 2005-05-03 | 2006-06-08 | Degussa Ag | Preparation of mercapto organyl(alkoxysilane) comprises reaction of bis(alkoxysilylorganyl)polysulfide with hydrogen in the presence of an alcohol and a doped metal catalyst (containing e.g. (iron) compound and a doping component) |
| DE102005038791A1 (en) | 2005-08-17 | 2007-02-22 | Degussa Ag | New organosilicon compounds based on triethanolamine, useful as components of rubber mixtures for making e.g. tires, tubes and cable coatings |
| DE102005060122A1 (en) * | 2005-12-16 | 2007-06-21 | Degussa Gmbh | Process for the preparation of (mercaptoorganyl) alkyl polyether silanes |
| DE102006027235A1 (en) | 2006-06-09 | 2008-01-17 | Evonik Degussa Gmbh | rubber compounds |
| JP2013108024A (en) * | 2011-11-24 | 2013-06-06 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing and electronic component device |
| DE102014209221A1 (en) * | 2014-05-15 | 2015-11-19 | Evonik Degussa Gmbh | Process for the preparation of urea-containing mercaptosilanes |
-
1995
- 1995-04-21 JP JP07097119A patent/JP3091993B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102473427B1 (en) | 2020-11-09 | 2022-12-05 | 고진희 | Wall mounting apparatus for shelves |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08291184A (en) | 1996-11-05 |
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