JPH1017578A - Production of 3-aminopropylalkoxysilane compound - Google Patents
Production of 3-aminopropylalkoxysilane compoundInfo
- Publication number
- JPH1017578A JPH1017578A JP8190010A JP19001096A JPH1017578A JP H1017578 A JPH1017578 A JP H1017578A JP 8190010 A JP8190010 A JP 8190010A JP 19001096 A JP19001096 A JP 19001096A JP H1017578 A JPH1017578 A JP H1017578A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- allylamine
- aminopropylalkoxysilane
- trimethylsilyl
- bis
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- CVNCFZIIZGNVFD-UHFFFAOYSA-N n,n-bis(trimethylsilyl)prop-2-en-1-amine Chemical compound C[Si](C)(C)N([Si](C)(C)C)CC=C CVNCFZIIZGNVFD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229920002545 silicone oil Polymers 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 12
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 125000003277 amino group Chemical group 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- -1 2-cyanoethylchlorosilane compound Chemical class 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BNYFUBOZYDQIDU-UHFFFAOYSA-N 3-[diethoxy(ethyl)silyl]propan-1-amine Chemical compound CCO[Si](CC)(OCC)CCCN BNYFUBOZYDQIDU-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- MCDMXLBJUUYSNX-UHFFFAOYSA-N 4-[diethoxy(methyl)silyl]oxypentan-1-amine Chemical compound CCO[Si](C)(OCC)OC(C)CCCN MCDMXLBJUUYSNX-UHFFFAOYSA-N 0.000 description 1
- JJXWHZXRUMIBNO-UHFFFAOYSA-N 4-[dimethoxy(methyl)silyl]oxybutan-1-amine Chemical compound CO[Si](C)(OC)OCCCCN JJXWHZXRUMIBNO-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シランカップリン
グ剤、アミノ変性シリコーンオイルの製造原料等として
有用な３−アミノプロピルアルコキシシラン化合物を工
業的に有利に製造することができる新規な製造方法に関
する。TECHNICAL FIELD The present invention relates to a novel production method capable of industrially advantageously producing a 3-aminopropylalkoxysilane compound useful as a silane coupling agent, a raw material for producing an amino-modified silicone oil, and the like. .
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】３−ア
ミノプロピルアルコキシシラン化合物は、有機材料と無
機材料の界面の接着性を改善し、ＦＲＰ、積層板、レジ
ンコンクリート、樹脂封止剤、人工大理石、プラスチッ
クマグネット等の複合材料の機械的強度、耐水性、耐熱
性を改良するために使用されるシランカップリング剤の
中でも非常に多く使用されている化合物である。また、
アミノ基の吸着能力を生かして繊維処理剤、つや出し
剤、塗料添加剤及び樹脂改質用オイル等の用途で広く使
用されているアミノ変性シリコーンオイルの製造原料と
しても多用されている非常に有用な化合物である。2. Description of the Related Art A 3-aminopropylalkoxysilane compound improves the adhesiveness of an interface between an organic material and an inorganic material, and is used for FRP, laminate, resin concrete, resin sealant, It is a compound that is very widely used among silane coupling agents used to improve the mechanical strength, water resistance, and heat resistance of composite materials such as marble and plastic magnets. Also,
Utilizing the amino group adsorption capacity, it is very useful as a raw material for producing amino-modified silicone oil widely used in applications such as fiber treatment agents, polishing agents, paint additives, and resin modifying oils. Compound.
【０００３】３−アミノプロピルアルコキシシラン化合
物の最も簡単な製造方法としては、遊離のアミノ基を有
するアリルアミンとハイドロジェンアルコキシシラン化
合物とを白金触媒の存在下に反応させる方法が知られて
いる（例えば特開昭６０−８１１８９号公報）。[0003] As the simplest method for producing a 3-aminopropylalkoxysilane compound, a method is known in which an allylamine having a free amino group is reacted with a hydrogenalkoxysilane compound in the presence of a platinum catalyst (for example, a method known in the art). JP-A-60-81189).
【０００４】しかしながら、この方法では、アリルアミ
ン由来の遊離のアミノ基の触媒毒性により、反応を実用
的な時間内で行うには非常に多くの触媒を使用するか、
あるいは加圧下で行う必要があるため、コスト高である
上、目的化合物の異性体であるが性能の落ちる２−アミ
ノ−１−メチルエチルアルコキシシラン化合物が１０％
以上も副生するという問題点もあった。However, in this method, due to the catalytic toxicity of the free amino group derived from allylamine, it is necessary to use a very large number of catalysts to carry out the reaction within a practical time.
Alternatively, since it is necessary to perform the reaction under pressure, the cost is high, and 10% of the 2-amino-1-methylethylalkoxysilane compound, which is an isomer of the target compound but has low performance, is used.
There was also the problem of by-products.
【０００５】上記のような異性体副生を抑える方法とし
ては、ロジウム触媒を使用する方法が報告されている
（特開平２−７９１号公報参照）が、ロジウムは非常に
高価な触媒であり、またこの場合も遊離のアミノ基の触
媒毒性のためか、多量の触媒が必要であり、工業的製造
においてはコスト的に問題があった。A method using a rhodium catalyst has been reported as a method for suppressing such isomer by-products (see JP-A-2-791), but rhodium is a very expensive catalyst. Also in this case, a large amount of catalyst is required, probably because of the catalytic toxicity of the free amino group, and there is a problem in terms of cost in industrial production.
【０００６】そこで、現状では一般的にアクリロニトリ
ルにハイドロジェンクロロシランを付加して、２−シア
ノエチルクロロシラン化合物とした後、アルコールと反
応させて２−シアノエチルアルコキシシラン化合物に変
換し、更に水素添加により３−アミノプロピルアルコキ
シシラン化合物を得るという方法により製造されている
〔シリコーンハンドブック（日刊工業新聞社）、４８
（１９９０）記載〕。しかし、この方法は工程が長い
上、重合性のアクリロニトリルを使用しなければならな
いなど問題点も多く、より工業的に有利な製造方法の開
発が望まれる。Therefore, under the present circumstances, hydrogen chlorosilane is generally added to acrylonitrile to form a 2-cyanoethylchlorosilane compound, which is then reacted with an alcohol to convert it to a 2-cyanoethylalkoxysilane compound, and further hydrogenated to add 3-cyanoethylalkoxysilane compound. It is manufactured by a method of obtaining an aminopropylalkoxysilane compound [Silicone Handbook (Nikkan Kogyo Shimbun), 48
(1990)]. However, this method has many problems such as a long process and the necessity of using polymerizable acrylonitrile, and development of a more industrially advantageous production method is desired.
【０００７】本発明は、上記事情に鑑みなされたもの
で、より安価かつ簡便に、しかも異性体を生成させるこ
となく高収率で３−アミノプロピルアルコキシシラン化
合物を製造することができる３−アミノプロピルアルコ
キシシラン化合物の製造方法を提供することを目的とす
る。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a 3-aminopropylalkoxysilane compound which can be produced at a lower cost, easily and in a high yield without producing an isomer. An object of the present invention is to provide a method for producing a propylalkoxysilane compound.
【０００８】[0008]
【課題を解決するための手段及び発明の実施の形態】本
発明者は上記目的を達成するため鋭意検討を重ねた結
果、遊離のアミノ基を持たないＮ，Ｎ−ビス（トリメチ
ルシリル）アリルアミンとハイドロジェンアルコキシシ
ラン化合物とを白金触媒下反応させた場合、触媒毒性と
なる遊離のアミノ基が生成しないため、わずかな触媒量
でも反応は容易に進行し、しかも異性体は全く生成しな
いことを見出し、更に検討を進めた結果、Ｎ，Ｎ−ビス
（トリメチルシリル）アリルアミンに下記一般式（１） ＨＳｉ（ＣＨ3）n（ＯＲ）3-n （１） （但し、式中Ｒはメチル基又はエチル基、ｎは０又は１
である。）で示されるハイドロジェンアルコキシシラン
化合物とを白金触媒の存在下に反応させた後、下記一般
式（２） ＲＯＨ （２） （但し、式中Ｒはメチル基又はエチル基である。）で示
されるアルコールと反応させることにより、安価かつ簡
便に、しかも異性体が生成することなく、高収率で下記
一般式（３） Ｈ2ＮＣＨ2ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）n（ＯＲ）3-n （３） （但し、式中Ｒはメチル基又はエチル基、ｎは０又は１
である。）で示される３−アミノプロピルアルコキシシ
ラン化合物を得ることができることを知見し、本発明を
なすに至った。Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, have found that N, N-bis (trimethylsilyl) allylamine having no free amino group and hydro When reacting with a genalkoxysilane compound in the presence of a platinum catalyst, a free amino group that becomes catalytically toxic is not generated, so that the reaction easily proceeds even with a small amount of catalyst, and furthermore, it has been found that isomers are not generated at all, As a result of further study, N, N-bis (trimethylsilyl) allylamine was converted to the following general formula (1) HSi (CH 3 ) n (OR) 3-n (1) (where R represents a methyl group or an ethyl group) , N is 0 or 1
It is. ) Is reacted with a hydrogen alkoxysilane compound represented by the formula (1) in the presence of a platinum catalyst, and then represented by the following general formula (2) ROH (2) (wherein R is a methyl group or an ethyl group). By reacting with the alcohol to be obtained, the following general formula (3) H 2 NCH 2 CH 2 CH 2 Si (CH 3 ) n (OR) 3 can be obtained inexpensively and simply, and without producing isomers, in high yield. -n (3) (where R is a methyl or ethyl group, and n is 0 or 1)
It is. The present inventors have found that a 3-aminopropylalkoxysilane compound represented by the formula (1) can be obtained, and have accomplished the present invention.
【０００９】従って、本発明は、Ｎ，Ｎ−ビス（トリメ
チルシリル）アリルアミンと上記一般式（１）で示され
るハイドロジェンアルコキシシラン化合物とを白金触媒
の存在下に反応させた後、上記一般式（２）で示される
アルコールと反応させることを特徴とする上記一般式
（３）で示される３−アミノプロピルアルコキシシラン
化合物の製造方法を提供する。Accordingly, the present invention provides a method for reacting N, N-bis (trimethylsilyl) allylamine with a hydrogenalkoxysilane compound represented by the general formula (1) in the presence of a platinum catalyst, A method for producing a 3-aminopropylalkoxysilane compound represented by the above general formula (3), characterized by reacting the compound with the alcohol represented by the formula (2).
【００１０】以下、本発明につき更に詳細に説明する
と、本発明の３−アミノプロピルアルコキシシラン化合
物の製造方法では、まず基質としてのＮ，Ｎ−ビス（ト
リメチルシリル）アリルアミンと下記一般式（１） ＨＳｉ（ＣＨ3）n（ＯＲ）3-n （１） （但し、式中Ｒはメチル基又はエチル基、ｎは０又は１
である。）で示されるハイドロジェンアルコキシシラン
化合物とを使用し、これら化合物を白金触媒の存在下で
反応させる第一反応を行う。Now, the present invention will be described in further detail. In the method for producing a 3-aminopropylalkoxysilane compound of the present invention, first, N, N-bis (trimethylsilyl) allylamine as a substrate and the following general formula (1) (CH 3 ) n (OR) 3-n (1) (where R is a methyl group or an ethyl group, and n is 0 or 1)
It is. The first reaction of reacting these compounds in the presence of a platinum catalyst is performed using the hydrogen alkoxysilane compound represented by the formula (1).
【００１１】ここで、Ｎ，Ｎ−ビス（トリメチルシリ
ル）アリルアミンは、アリルアミンとトリメチルクロロ
シランをトリエチルアミンとルイス酸触媒の存在下に反
応させる公知の方法（Ｐｈｏｓｐｈｏｒｕｓ，Ｓｕｌｆ
ｕｒ，ａｎｄ Ｓｉｌｉｃｏｎｅ ６８，２５（１９９
２）等）で容易に得ることができる。Here, N, N-bis (trimethylsilyl) allylamine is prepared by a known method (Phosphorus, Sulfur) in which allylamine and trimethylchlorosilane are reacted with triethylamine in the presence of a Lewis acid catalyst.
ur, and Silicone 68, 25 (199
2) etc.).
【００１２】上記式（１）のハイドロジェンアルコキシ
シラン化合物としては、具体的にメチルジメトキシシラ
ン、メチルジエトキシシラン、トリメトキシシラン、ト
リエトキシシランが例示される。Specific examples of the hydrogen alkoxysilane compound of the above formula (1) include methyldimethoxysilane, methyldiethoxysilane, trimethoxysilane, and triethoxysilane.
【００１３】Ｎ，Ｎ−ビス（トリメチルシリル）アリル
アミンと上記式（１）のハイドロジェンアルコキシシラ
ン化合物との使用量は、Ｎ，Ｎ−ビス（トリメチルシリ
ル）アリルアミン１モルに対して上記式（１）のハイド
ロジェンアルコキシシラン化合物を０．５〜３モル、特
に１〜１．５モルの割合で使用することが好ましい。The amount of the N, N-bis (trimethylsilyl) allylamine and the hydrogen alkoxysilane compound of the above formula (1) used is based on the above formula (1) per mole of N, N-bis (trimethylsilyl) allylamine. It is preferable to use the hydrogen alkoxysilane compound in a ratio of 0.5 to 3 mol, particularly 1 to 1.5 mol.
【００１４】また、上記反応で使用される白金触媒とし
ては、例えば白金金属、塩化白金酸等の白金化合物や、
〔ＰｔＣｌ2（ＰＰｈ3）2〕，〔ＰｄＣｌ2（ＰＰ
ｈ3）2〕，〔ＲｈＣｌ（ＰＰｈ3）3〕（Ｐｈはフェニル
基である。）のような錯体などが挙げられる。The platinum catalyst used in the above reaction includes, for example, platinum metal, platinum compounds such as chloroplatinic acid, and the like.
[PtCl 2 (PPh 3 ) 2 ], [PdCl 2 (PP
h 3) 2], [RhCl (PPh 3) 3] (Ph is like complexes such as a phenyl group.).
【００１５】上記白金触媒の使用量は、基質であるＮ，
Ｎ−ビス（トリメチルシリル）アリルアミンが遊離のア
ミノ基を持たないため、通常のオレフィンとのヒドロシ
リル化において使用される使用量である０．１〜５００
ｐｐｍ、特に１０〜２００ｐｐｍの範囲とすることが好
ましい。The amount of the platinum catalyst used is determined by the amount of the substrate N,
Since N-bis (trimethylsilyl) allylamine does not have a free amino group, it is used in an amount of 0.1 to 500 which is usually used in hydrosilylation with an olefin.
ppm, particularly preferably in the range of 10 to 200 ppm.
【００１６】上記反応は、Ｎ，Ｎ−ビス（トリメチルシ
リル）アリルアミンを上記式（１）のハイドロジェンア
ルコキシシラン化合物へ加える方法でも、また、その逆
の方法でもよい。なお、Ｎ，Ｎ−ビス（トリメチルシリ
ル）アリルアミンと上記式（１）のハイドロジェンアル
コキシシラン化合物との反応温度は適宜調整できるが、
０〜２００℃、特に５０〜１２０℃で行われることが好
ましい。The above reaction may be carried out by adding N, N-bis (trimethylsilyl) allylamine to the hydrogenalkoxysilane compound of the above formula (1) or vice versa. The reaction temperature between N, N-bis (trimethylsilyl) allylamine and the hydrogen alkoxysilane compound of the above formula (1) can be appropriately adjusted,
It is preferably carried out at 0 to 200 ° C, especially 50 to 120 ° C.
【００１７】次に、本発明では、上記第一反応を行った
後、反応液に下記一般式（２） ＲＯＨ （２） （但し、式中Ｒはメチル基又はエチル基である。）で示
されるアルコールを反応させる第二反応を行う。アルコ
ールとしては、メタノール又はエタノールを使用する。Next, in the present invention, after performing the first reaction, the reaction solution is represented by the following general formula (2) ROH (2) (wherein R is a methyl group or an ethyl group). A second reaction is performed to react the alcohol to be produced. As the alcohol, methanol or ethanol is used.
【００１８】上記式（２）のアルコールの使用量は、
Ｎ，Ｎ−ビス（トリメチルシリル）アリルアミン１モル
に対して２〜１００モル、特に５〜２０モルが好まし
い。The amount of the alcohol of the above formula (2) is
It is preferably from 2 to 100 mol, particularly preferably from 5 to 20 mol, per mol of N, N-bis (trimethylsilyl) allylamine.
【００１９】なお、このアルコールとの第二反応におい
ては、触媒は必要ないが、より反応時間を短縮させるた
めにアンモニウム塩等の塩類やｐ−トルエンスルホン酸
等の酸を触媒として添加してもよい。なお、これら触媒
の添加量は、触媒量とすることができる。In the second reaction with the alcohol, a catalyst is not required, but a salt such as an ammonium salt or an acid such as p-toluenesulfonic acid may be added as a catalyst to further shorten the reaction time. Good. In addition, the addition amount of these catalysts can be a catalyst amount.
【００２０】上記第二反応の反応条件は、０〜２００
℃、特に還流下で１〜２０時間である。The reaction conditions for the second reaction are from 0 to 200
C., especially under reflux for 1 to 20 hours.
【００２１】本発明において、上記第一、第二反応は、
本質的に無溶媒で行うことが可能であるが、場合によっ
てはトルエン、キシレン、ヘキサン、デカン、テトラヒ
ドロフラン等の非プロトン性溶媒を使用することも可能
である。なお、溶媒の使用量は、通常量とすることがで
きる。In the present invention, the first and second reactions are performed as follows:
The reaction can be carried out essentially without a solvent, but in some cases, an aprotic solvent such as toluene, xylene, hexane, decane, or tetrahydrofuran can be used. The amount of the solvent used can be a usual amount.
【００２２】上記した本発明に係る反応により得られる
化合物は、下記一般式（３） Ｈ2ＮＣＨ2ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）n（ＯＲ）3-n （３） （但し、式中Ｒ，ｎは上記と同様である。）で示される
３−アミノプロピルアルコキシシラン化合物である。The compound obtained by the above-mentioned reaction according to the present invention is represented by the following general formula (3): H 2 NCH 2 CH 2 CH 2 Si (CH 3 ) n (OR) 3-n (3) R and n are the same as described above.)
【００２３】上記式（３）の３−アミノプロピルアルコ
キシシラン化合物として具体的には、３−アミノプロピ
ルメチルジメトキシシラン、３−アミノプロピルメチル
ジエトキシシラン、３−アミノプロピルメチルトリメト
キシシラン、３−アミノプロピルメチルトリエトキシシ
ラン等が例示される。Specific examples of the 3-aminopropylalkoxysilane compound of the above formula (3) include 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyltrimethoxysilane, Aminopropylmethyltriethoxysilane and the like are exemplified.
【００２４】[0024]
【発明の効果】本発明の製造方法によれば、シランカッ
プリング剤、アミノ変性シリコーンオイル等の製造原料
等として有用な上記式（３）の３−アミノプロピルアル
コキシシラン化合物を安価かつ簡便に、しかも異性体が
副生することなく高収率で製造することができる。According to the production method of the present invention, a 3-aminopropylalkoxysilane compound of the above formula (3), which is useful as a raw material for producing a silane coupling agent, an amino-modified silicone oil or the like, can be produced inexpensively and simply. In addition, it can be produced in high yield without isomer by-product.
【００２５】[0025]
【実施例】以下、合成例及び実施例を示して本発明を具
体的に説明するが、本発明は下記実施例に制限されるも
のではない。EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.
【００２６】〔合成例〕撹拌機、還流冷却器、温度計及
び滴下ロートを備えた２リットルのガラスフラスコ中に
トリメチルクロロシラン３２５．９ｇ（３．０ｍｏ
ｌ）、ジクロロメタン６００ｍｌ及び触媒として四塩化
チタン５．７ｇ（３０ｍｍｏｌ）を仕込み、そこに滴下
ロートよりアリルアミン８５．７ｇ（１．５ｍｏｌ）及
びトリエチルアミン３３３．９ｇ（３．３ｍｏｌ）を内
温を５０〜６０℃に保ちながら３時間で滴下し、そのま
ま６時間熟成した。この反応液へ水酸化ナトリウム水を
加えて生成したトリエチルアミン塩酸塩を溶解した後、
有機層を分離し、減圧蒸留により９０〜９１℃／４０ｍ
ｍＨｇの留分を分取することにより、Ｎ，Ｎ−ビス（ト
リメチルシリル）アリルアミン２５９．８ｇが得られ
た。[Synthesis Example] In a 2 liter glass flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 325.9 g (3.0 mol) of trimethylchlorosilane was added.
l), 600 ml of dichloromethane and 5.7 g (30 mmol) of titanium tetrachloride as a catalyst, and 85.7 g (1.5 mol) of allylamine and 333.9 g (3.3 mol) of triethylamine from the dropping funnel at an internal temperature of 50 to The solution was added dropwise over 3 hours while maintaining the temperature at 60 ° C., followed by aging for 6 hours. After dissolving triethylamine hydrochloride generated by adding aqueous sodium hydroxide to the reaction solution,
Separate the organic layer and distill under reduced pressure to 90-91 ° C / 40m
By fractionating the mHg fraction, 259.8 g of N, N-bis (trimethylsilyl) allylamine was obtained.
【００２７】〔実施例１〕撹拌機、還流冷却器、温度計
及び滴下ロートを備えた１リットルのガラスフラスコ中
に上記合成例で得られたＮ，Ｎ−ビス（トリメチルシリ
ル）アリルアミン２０１．５ｇ（１．０ｍｏｌ）及びＨ
2ＰｔＣｌ6・６Ｈ2Ｏの４％イソプロピルアルコール溶
液０．９８ｇを仕込み、そこに滴下ロートよりメチルジ
メトキシシラン１０６．２ｇ（１．０ｍｏｌ）を７０〜
８０℃にて３時間かけて滴下し、そのまま６時間熟成し
た後、この反応液へメタノール３２０．４ｇを加え、４
時間還流し、反応させた。得られた反応液をガスクロマ
トグラフィーにより分析した結果、３−アミノプロピル
メチルジメトキシシランの生成が確認され、その異性体
の生成は確認されなかった。この反応液から減圧蒸留に
より９９〜１００℃／３９ｍｍＨｇの留分を分取するこ
とにより、３−アミノプロピルメチルジメトキシシラン
１４２．２ｇを得た（収率８７％）。Example 1 In a 1-liter glass flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 201.5 g of the N, N-bis (trimethylsilyl) allylamine obtained in the above Synthesis Example ( 1.0 mol) and H
G of 4% isopropyl alcohol solution 0.98g of 2 PtCl 6 · 6H 2 O, 70~ methyldimethoxysilane 106.2 g (1.0 mol) from there to the dropping funnel
The mixture was added dropwise at 80 ° C. over 3 hours, aged for 6 hours, and 320.4 g of methanol was added to the reaction solution.
The mixture was refluxed for an hour and reacted. As a result of analyzing the obtained reaction solution by gas chromatography, formation of 3-aminopropylmethyldimethoxysilane was confirmed, and formation of its isomer was not confirmed. A fraction of 99 to 100 ° C./39 mmHg was fractionated from the reaction solution by distillation under reduced pressure to obtain 142.2 g of 3-aminopropylmethyldimethoxysilane (87% yield).
【００２８】〔実施例２〕メチルジメトキシシラン１０
６．２ｇ（１．０ｍｏｌ）をトリメトキシシラン１２
２．２ｇ（１．０ｍｏｌ）に変更した以外は、実施例１
と同様にして反応を行った。得られた反応液をガスクロ
マトグラフィーにより分析した結果、３−アミノプロピ
ルトリメトキシシランの生成が確認され、その異性体の
生成は確認されなかった。この反応液から減圧蒸留によ
り８０〜８１℃／８ｍｍＨｇの留分を分取することによ
り、３−アミノプロピルメチルジメトキシシラン１５
０．３ｇを得た（収率８４％）。Example 2 Methyldimethoxysilane 10
6.2 g (1.0 mol) of trimethoxysilane 12
Example 1 except that the amount was changed to 2.2 g (1.0 mol).
The reaction was carried out in the same manner as in. As a result of analyzing the obtained reaction solution by gas chromatography, formation of 3-aminopropyltrimethoxysilane was confirmed, and formation of its isomer was not confirmed. A fraction of 80 to 81 ° C./8 mmHg was fractionated from the reaction solution by distillation under reduced pressure to obtain 3-aminopropylmethyldimethoxysilane 15
0.3 g was obtained (yield 84%).
【００２９】〔実施例３〕撹拌機、還流冷却器、温度計
及び滴下ロートを備えた１リットルのガラスフラスコ中
に上記合成例で得られたＮ，Ｎ−ビス（トリメチルシリ
ル）アリルアミン２０１．５ｇ（１．０ｍｏｌ）及びＨ
2ＰｔＣｌ6・６Ｈ2Ｏの４％イソプロピルアルコール溶
液０．９８ｇを仕込み、そこに滴下ロートよりメチルジ
エトキシシラン１３４．３ｇ（１．０ｍｏｌ）を７０〜
８０℃にて３時間かけて滴下し、そのまま６時間熟成し
た後、この反応液へエタノール４６０．７ｇを加え、４
時間還流し、反応させた。得られた反応液をガスクロマ
トグラフィーにより分析した結果、３−アミノプロピル
エチルジエトキシシランの生成が確認され、その異性体
の生成は確認されなかった。この反応液から減圧蒸留に
より８５〜８６℃／８ｍｍＨｇの留分を分取することに
より、３−アミノプロピルメチルジエトキシシラン１６
８．４ｇを得た（収率８８％）。Example 3 In a 1-liter glass flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 201.5 g of N, N-bis (trimethylsilyl) allylamine obtained in the above Synthesis Example ( 1.0 mol) and H
G of 4% isopropyl alcohol solution 0.98g of 2 PtCl 6 · 6H 2 O, 70~ methyl diethoxy silane 134.3 g (1.0 mol) from there to the dropping funnel
The mixture was added dropwise at 80 ° C. over 3 hours, aged for 6 hours, and 460.7 g of ethanol was added to the reaction mixture.
The mixture was refluxed for an hour and reacted. As a result of analyzing the obtained reaction solution by gas chromatography, formation of 3-aminopropylethyldiethoxysilane was confirmed, and formation of its isomer was not confirmed. A fraction of 85 to 86 ° C./8 mmHg was fractionated from the reaction solution by distillation under reduced pressure to obtain 3-aminopropylmethyldiethoxysilane 16
8.4 g were obtained (88% yield).
【００３０】〔実施例４〕メチルジエトキシシラン１３
４．３ｇ（１．０ｍｏｌ）をトリエトキシシラン１６
４．３ｇ（１．０ｍｏｌ）に変更した以外は、実施例３
と同様にして反応を行った。得られた反応液をガスクロ
マトグラフィーにより分析した結果、３−アミノプロピ
ルトリエトキシシランの生成が確認され、その異性体の
生成は確認されなかった。この反応液から減圧蒸留によ
り６７〜６８℃／３ｍｍＨｇの留分を分取することによ
り、３−アミノプロピルメチルジエトキシシラン１８
７．７ｇを得た（収率８５％）。Example 4 Methyldiethoxysilane 13
4.3 g (1.0 mol) of triethoxysilane 16
Example 3 except that the amount was changed to 4.3 g (1.0 mol).
The reaction was carried out in the same manner as in. As a result of analyzing the obtained reaction solution by gas chromatography, formation of 3-aminopropyltriethoxysilane was confirmed, and formation of its isomer was not confirmed. By distilling a fraction of 67-68 ° C./3 mmHg from the reaction solution by distillation under reduced pressure, 3-aminopropylmethyldiethoxysilane 18 was obtained.
7.7 g was obtained (85% yield).
Claims (1)
ルアミンと下記一般式（１） ＨＳｉ（ＣＨ3）n（ＯＲ）3-n （１） （但し、式中Ｒはメチル基又はエチル基、ｎは０又は１
である。）で示されるハイドロジェンアルコキシシラン
化合物とを白金触媒の存在下に反応させた後、下記一般
式（２） ＲＯＨ （２） （但し、式中Ｒはメチル基又はエチル基である。）で示
されるアルコールと反応させることを特徴とする下記一
般式（３） Ｈ2ＮＣＨ2ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）n（ＯＲ）3-n （３） （但し、式中Ｒはメチル基又はエチル基、ｎは０又は１
である。）で示される３−アミノプロピルアルコキシシ
ラン化合物の製造方法。1. N, N-bis (trimethylsilyl) allylamine and the following general formula (1) HSi (CH 3 ) n (OR) 3-n (1) (where R is a methyl or ethyl group, n Is 0 or 1
It is. ) Is reacted in the presence of a platinum catalyst in the presence of a platinum catalyst, and then represented by the following general formula (2) ROH (2) (wherein R is a methyl group or an ethyl group). (3) H 2 NCH 2 CH 2 CH 2 Si (CH 3 ) n (OR) 3-n (3) wherein R is a methyl group or ethyl Group, n is 0 or 1
It is. A method for producing a 3-aminopropylalkoxysilane compound represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19001096A JP3419207B2 (en) | 1996-07-01 | 1996-07-01 | Method for producing 3-aminopropylalkoxysilane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19001096A JP3419207B2 (en) | 1996-07-01 | 1996-07-01 | Method for producing 3-aminopropylalkoxysilane compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1017578A true JPH1017578A (en) | 1998-01-20 |
| JP3419207B2 JP3419207B2 (en) | 2003-06-23 |
Family
ID=16250881
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19001096A Expired - Fee Related JP3419207B2 (en) | 1996-07-01 | 1996-07-01 | Method for producing 3-aminopropylalkoxysilane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3419207B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007055950A (en) * | 2005-08-25 | 2007-03-08 | Shin Etsu Chem Co Ltd | Bisorganoxysilane compound having amino group protected with silyl group and method for producing the same |
| CN107556478A (en) * | 2016-07-01 | 2018-01-09 | 信越化学工业株式会社 | Siloxanes and its manufacture method containing aminoalkyl |
| EP3315503A2 (en) | 2016-10-28 | 2018-05-02 | Shin-Etsu Chemical Co., Ltd. | Method for producing silane compound including bis(silyl)amino group |
| EP4144789A1 (en) | 2021-09-02 | 2023-03-08 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane composition |
-
1996
- 1996-07-01 JP JP19001096A patent/JP3419207B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007055950A (en) * | 2005-08-25 | 2007-03-08 | Shin Etsu Chem Co Ltd | Bisorganoxysilane compound having amino group protected with silyl group and method for producing the same |
| JP4662042B2 (en) * | 2005-08-25 | 2011-03-30 | 信越化学工業株式会社 | Bisorganoxysilane compound having amino group protected by silyl group and method for producing the same |
| CN107556478A (en) * | 2016-07-01 | 2018-01-09 | 信越化学工业株式会社 | Siloxanes and its manufacture method containing aminoalkyl |
| JP2018002874A (en) * | 2016-07-01 | 2018-01-11 | 信越化学工業株式会社 | Aminoalkyl group-containing siloxane, an aminoalkyl group-and polyoxyalkylene group-containing siloxane, and method for producing them |
| US10421839B2 (en) | 2016-07-01 | 2019-09-24 | Shin-Etsu Chemical Co., Ltd. | Aminoalkyl group-containing siloxane and a method for preparing the same |
| EP3315503A2 (en) | 2016-10-28 | 2018-05-02 | Shin-Etsu Chemical Co., Ltd. | Method for producing silane compound including bis(silyl)amino group |
| EP4144789A1 (en) | 2021-09-02 | 2023-03-08 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane composition |
| KR20230034160A (en) | 2021-09-02 | 2023-03-09 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Organopolysiloxane Composition |
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| Publication number | Publication date |
|---|---|
| JP3419207B2 (en) | 2003-06-23 |
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