JPS63275591A - Production of diaminopropylidisiloxane - Google Patents
Production of diaminopropylidisiloxaneInfo
- Publication number
- JPS63275591A JPS63275591A JP62108175A JP10817587A JPS63275591A JP S63275591 A JPS63275591 A JP S63275591A JP 62108175 A JP62108175 A JP 62108175A JP 10817587 A JP10817587 A JP 10817587A JP S63275591 A JPS63275591 A JP S63275591A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- disiloxane
- expressed
- mixture
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 8
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- KPGXUDMQIXCONY-UHFFFAOYSA-N 3-silyloxysilylpropane-1,1-diamine Chemical compound NC(N)CC[SiH2]O[SiH3] KPGXUDMQIXCONY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000002262 Schiff base Substances 0.000 abstract description 9
- 150000004753 Schiff bases Chemical class 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 229920001296 polysiloxane Polymers 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- GXFNRLVWKGAVGK-UHFFFAOYSA-N 1-phenyl-n-prop-2-enylmethanimine Chemical compound C=CCN=CC1=CC=CC=C1 GXFNRLVWKGAVGK-UHFFFAOYSA-N 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- DMMPEDIYXNEVTK-UHFFFAOYSA-N N[SiH](N)O[SiH3] Chemical compound N[SiH](N)O[SiH3] DMMPEDIYXNEVTK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- -1 amine hydrochloride Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- JWMKUKRBNODZFA-UHFFFAOYSA-N 1-ethoxy-2-methylbenzene Chemical compound CCOC1=CC=CC=C1C JWMKUKRBNODZFA-UHFFFAOYSA-N 0.000 description 1
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-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
- FTZRIMQWFYCRRB-UHFFFAOYSA-N 3-(3-aminopropylsilyloxysilyl)propan-1-amine Chemical compound NCCC[SiH2]O[SiH2]CCCN FTZRIMQWFYCRRB-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Abstract
Description
【発明の詳細な説明】
〔従来の技術〕
ＩＣ、トランジスター等の電子部品の製造に用いられる
プラスチックモールデイングコンパウンドとしては、一
般に、エポキシ樹脂が用いられている。ＩＣの集積度が
高くなるにつれ、このエポキシ樹脂にも可とう性が強く
要求されるため、分子内にソフトセグメントを組み入れ
るなどしてエポキシ樹脂に可とう性を付与する試みがな
されている。オルガノシロキサンは、分子容積が大きく
、シロキサン結合の結合距離が長く、しかも分子回転の
自由度が大きいなどの特徴を有しているので、このよう
なソフトセグメントとして大いに期待されている。この
オルガノシロキサン構造を前記ソフトセグメン１−とし
てエポキシ樹脂に導入するのに有用な化合物として、１
，３−ジ（Ｔ−アミノプロピル）テトラメチルジシロキ
サンが挙げられる。DETAILED DESCRIPTION OF THE INVENTION [Prior Art] Epoxy resin is generally used as a plastic molding compound used in the manufacture of electronic components such as ICs and transistors. As the degree of integration of ICs increases, flexibility is strongly required for this epoxy resin, so attempts have been made to impart flexibility to the epoxy resin by incorporating soft segments into the molecule. Organosiloxane has the characteristics of a large molecular volume, a long siloxane bond distance, and a large degree of freedom in molecular rotation, and is therefore highly expected to be used as such a soft segment. Compounds useful for introducing this organosiloxane structure into the epoxy resin as the soft segment 1-
, 3-di(T-aminopropyl)tetramethyldisiloxane.
従来、１，３−ジ（γ−アミノプロピル）テトラメチル
ジシロキサンの製造方法としては、ベンジリデンアリル
アミンと触媒量の白金との混合物を１７０℃〜１８０℃
に加熱した後、１．１．３．３−テトラメチルジシロキ
サンを滴下して反応させ、式：％式％
で表わされるビス（ベンジリデンイミノプロピル）テト
ラメチルジシロキサンを合成し、次に該化合物を塩酸で
加水分解してアミン塩酸塩とし、さらに水酸化ナトリウ
ムで中和して遊離のアミンを得るという方法が発表され
ている。Conventionally, as a method for producing 1,3-di(γ-aminopropyl)tetramethyldisiloxane, a mixture of benzylideneallylamine and a catalytic amount of platinum is heated at 170°C to 180°C.
After heating to , 1.1.3.3-tetramethyldisiloxane is added dropwise and reacted to synthesize bis(benzylideneiminopropyl)tetramethyldisiloxane represented by the formula: % formula %, and then the compound A method has been published in which the amine is hydrolyzed with hydrochloric acid to produce the amine hydrochloride, which is further neutralized with sodium hydroxide to obtain the free amine.
（Ｄｉｅ Ｍａｃｒｏｓ＋ｏｌｅｋｕｌａｒｅ Ｃｈｅ
ｍｉｅ、 ５７．１５０（１９６２））。(Die Macros+olekulare Che
mie, 57.150 (1962)).
しかし、上記の方法は、本発明者が試みたところ、ベン
ジリデンアリルアミンと白金との混合物を１７０〜１８
０℃に加熱すると重合反応が起き、５時間後には、生成
物のほとんどがポリマー化してしまい、数％の収率でし
か目的の化合物を得ることができないという問題を有す
るものであった。However, when the present inventor tried the above method, the mixture of benzylideneallylamine and platinum was
When heated to 0° C., a polymerization reaction occurs, and after 5 hours, most of the product is polymerized, resulting in the problem that the desired compound can only be obtained with a yield of a few percent.
そこで、本発明の目的は、前記の中間体であるビス（ベ
ンジリデンイミノプロピル）テトラメチルジシロキサン
を高収率で合成でき、よって１，３−ジ（アミノプロピ
ル）ジシロキサンを高収率で得ることのできる製造方法
を提供することにある。Therefore, an object of the present invention is to be able to synthesize the above-mentioned intermediate bis(benzylideneiminopropyl)tetramethyldisiloxane in a high yield, thereby obtaining 1,3-di(aminopropyl)disiloxane in a high yield. The objective is to provide a manufacturing method that can
本発明は、前記問題点を解決するものとして、一般式（
Ｉ）：
〔式中、Ｒ１は同一でも異なってもよく、メチル、エチ
ル、プロピル等のアルキル基、フェニル、トリル等のア
ルキル基又はベンジル等のアラルキル基である〕
で表わされるジアミノプロピルジシロキサン製法であっ
て、
一般式（■）：
〔式中、Ｒ１は前記のとおり〕
で表わされジシロキサン、白金系触媒及び非極性溶媒を
含む混合物を９０〜１５０℃に保ちながら、
一般式（■）：
〔式中、Ｒχは一価炭化水素基であり、Ｒ３は水素原子
又は−価炭化水素である〕
で表わされるシッフ塩基を滴下させて、一般式（■）
：
〔式中、Ｒ１、Ｒ冨およびＲ３は前記のとおり〕で表わ
される有機ケイ素化合物を合成し、次に、該有機ケイ素
化合物を酸性下で加水分解後反応混合物を中和する、
ことからなるジアミノプロピルジシロキサンの製法を提
供するものである。The present invention solves the above-mentioned problems by the general formula (
I): [In the formula, R1 may be the same or different and is an alkyl group such as methyl, ethyl, propyl, an alkyl group such as phenyl, tolyl, or an aralkyl group such as benzyl.] The mixture represented by the general formula (■): [wherein R1 is as described above] and containing disiloxane, a platinum-based catalyst, and a nonpolar solvent is maintained at 90 to 150°C, and the general formula (■ ): [In the formula, Rχ is a monovalent hydrocarbon group, and R3 is a hydrogen atom or a -valent hydrocarbon] A Schiff base represented by the following is added dropwise to form the general formula (■).
: Synthesizing an organosilicon compound represented by the formula [wherein R1, R-value, and R3 are as described above], then hydrolyzing the organosilicon compound under acidic conditions, and then neutralizing the reaction mixture. A method for producing diaminopropyldisiloxane is provided.
本発明の方法に原料として用いられる一般式（ｎ）のジ
シロキサンは公知の方法により容易に製造し得るもので
ある。The disiloxane of general formula (n) used as a raw material in the method of the present invention can be easily produced by a known method.
また、一般式（Ｉ［［）のシッフ塩基において、Ｒ２又
はＲ３が表し得る一価炭化水素基としては、メチル、エ
チル、プロピル等のアルキル基、シクロヘキシル、メチ
ルシクロヘキシル、シクロヘプチル等のシクロアルキル
基、フェニル、トリル等のアリール基等が挙げられ、好
ましくは、メチル基、エチル基、フェニル基等である。In addition, in the Schiff base of general formula (I [ , phenyl, tolyl, and other aryl groups, and preferably methyl, ethyl, phenyl, and the like.
かかる一般式（Ｉ［Ｉ）のシッフ塩基の代表的な例とし
ては、
Ｃｈｉｓ ＣＨ＝ ＮＣＨｚＣＨ” ＣＨｚ。A typical example of such a Schiff base of general formula (I[I) is: Chis CH= NCHzCH'' CHz.
（ＣＨ３） ｚｃ ＝ ＮＣＨｚＣＨ＝ ＣＨｚ。(CH3) zc = NCHzCH = CHz.
などが挙げられ、中でも安定性が良好である点から
ＣａＨｓ −ＣＩ ＝ ＮＣＨｘＣＨ＝ Ｃｕｔが好ま
しい、この一般式（ＩＩＩ）のシッフ塩基は、一般式（
ＩＩ）のジシロキサンに対しほぼ当量で使用し反応させ
ることが好ましい。Among them, CaHs -CI=NCHxCH=Cut is preferable from the viewpoint of good stability.The Schiff base of the general formula (III) has the general formula (
It is preferable to use and react in an approximately equivalent amount to the disiloxane II).
本発明の方法に用いられる白金系触媒としては、例えば
、塩化白金酸、塩化白金酸−アルコール溶液、白金黒、
白金−オレフインコンプレックス等公知のものを使用す
ることができ、一般式（ｎ）のジシロキサン１００重量
部当り、通常０．０００１〜ｏ、ｏｏｓ重量部程度用い
ればよい。Examples of the platinum-based catalyst used in the method of the present invention include chloroplatinic acid, chloroplatinic acid-alcohol solution, platinum black,
Known platinum-olefin complexes and the like can be used, and usually about 0.0001 to 0.00 parts by weight may be used per 100 parts by weight of the disiloxane of general formula (n).
本発明の方法に用いられる非極性溶媒としては、例えば
、キシレン、メトキシトルエン、エトキシトルエン、エ
チルトルエン、ｔ−ブチルトルエン等が挙げられるが、
通常はジシロキサンの５ｉ−Ｈのシッフ塩基への付加反
応が円滑に進行し価格が安いキシレンが用いられる。Examples of the non-polar solvent used in the method of the present invention include xylene, methoxytoluene, ethoxytoluene, ethyltoluene, t-butyltoluene, etc.
Usually, xylene is used because the addition reaction of 5i-H of disiloxane to the Schiff base proceeds smoothly and is inexpensive.
一般式（ＩＩ）のジシロキサンと一般式（ＩＩＩ）のシ
ッフ塩基との反応は、９０〜１５０℃の温度で行なう必
要があり、好ましくは１００〜１２０℃である０反応塩
度が９０℃未満では前記の付加反応が極端に遅くなり、
１５０℃を超えると生成物のポリマー化が進行し目的と
するジアミノアルキルジシロキサンの収率が低下する。The reaction between the disiloxane of general formula (II) and the Schiff base of general formula (III) must be carried out at a temperature of 90 to 150°C, preferably 100 to 120°C, with a zero reaction salinity of less than 90°C. In this case, the above addition reaction becomes extremely slow,
If the temperature exceeds 150°C, polymerization of the product will proceed and the yield of the desired diaminoalkyldisiloxane will decrease.
この反応を行なう際の圧力は特に限定されないが、通常
、常圧下で十分であり、その場合反応混合物の沸点が９
０〜１５０℃となるように溶媒の種類及び使用量を選択
し、還流下で反応させることが望ましい。The pressure at which this reaction is carried out is not particularly limited, but normal pressure is usually sufficient, in which case the boiling point of the reaction mixture is 9.
It is desirable to select the type and amount of solvent to be used so that the temperature is 0 to 150°C, and to conduct the reaction under reflux.
このような実施態様に適する溶媒としても、前記の例示
の非極性溶媒を挙げることができる。Suitable solvents for such embodiments include the above-mentioned non-polar solvents.
本発明の方法では、まず、一般式（ｎ）のジシロキサン
、非極性溶媒及び白金系触媒を反応容器に入れ、所要の
反応温度に加熱し、保ちながら、一般式（ＩＩＩ）のシ
ッフ塩基を滴下することにより行なうことができる。In the method of the present invention, first, a disiloxane of general formula (n), a nonpolar solvent, and a platinum-based catalyst are placed in a reaction vessel, and while heating and maintaining the required reaction temperature, a Schiff base of general formula (III) is added. This can be done by dripping.
次に、上記の反応により得られた前記一般式（ＩＶ）の
有機ケイ素化合物を酸性下で加水分解後中和する。この
酸性下の加水分解は、例えば、前記の反応で得られた反
応混合物に酸水溶液を添加すればよく、使用される酸と
しては、例えば、塩酸等が挙げられる。このとき使用す
る酸の量は、一般式（ＩＶ）の有機ケイ素化合物に対し
当量以上であることが必要で、この酸による加水分解で
、ジアミノプロピルジシロキサン酸付加塩が生成する。Next, the organosilicon compound of the general formula (IV) obtained by the above reaction is hydrolyzed under acidic conditions and then neutralized. This hydrolysis under acidic conditions may be carried out, for example, by adding an acid aqueous solution to the reaction mixture obtained in the above reaction, and examples of the acid used include hydrochloric acid. The amount of acid used at this time needs to be at least equivalent to the organosilicon compound of general formula (IV), and diaminopropyldisiloxanoic acid addition salt is produced by hydrolysis with this acid.
次に、核酸付加塩を含む溶液を、例えば水酸化ナトリウ
ム、水酸化カリウム、水酸化カルシウム、炭酸ナトリウ
ム等で中和することにより、目的とするジアミノプロピ
ルジシロキサンが遊離の状態で得られる。Next, the target diaminopropyldisiloxane is obtained in a free state by neutralizing the solution containing the nucleic acid addition salt with, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, or the like.
次に、本発明を実施例により具体的に説明する。 Next, the present invention will be specifically explained using examples.
実施例１
温度針、攪拌装置、還流装置を備えた２１の反応フラス
コに、Ｌｌ、３．３−テトラメチルジシロキサン３００
ｇ、キシレン６００ｇを入れ、さらに、塩化白金酸の
イソプロパツール溶液（白金分２ｗｔχ）を０．６ｇ加
え１００℃に加熱した。次に、ベンジリデンアリルアミ
ン６９０ｇを２時間かけて滴下して反応させ、滴下終了
後さらに１５０℃で３時間反応させた０反応終了後室温
まで冷却し、１７％塩酸を１１００ｇ加えて加水分解し
た。二層に分離し、水層に等量のトルエンを加えて洗浄
し、さらに水層にＮａＯＨ１９０ｇ、水５５０ｇを加え
た。Example 1 300 Ll, 3,3-tetramethyldisiloxane was placed in a 21 reaction flask equipped with a temperature needle, a stirrer, and a reflux device.
g and 600 g of xylene were added, and further, 0.6 g of an isopropanol solution of chloroplatinic acid (platinum content: 2 wt.chi.) was added and heated to 100.degree. Next, 690 g of benzylideneallylamine was added dropwise over 2 hours to react, and after completion of the dropwise addition, the reaction was further carried out at 150° C. for 3 hours. After the completion of the reaction, the mixture was cooled to room temperature, and 1100 g of 17% hydrochloric acid was added for hydrolysis. The mixture was separated into two layers, and the aqueous layer was washed with an equal amount of toluene, and 190 g of NaOH and 550 g of water were added to the aqueous layer.
さらにトルエン１０００ｇを加えて有機層を抽出し、Ｎ
ａｚＳＯｎで乾燥後蒸留すると、沸点１２０〜１２５℃
／ ７ ｍＨｇの無色透明な液体が３９０ｇ得られた。Furthermore, 1000 g of toluene was added to extract the organic layer, and N
When distilled after drying with azSOn, the boiling point is 120-125℃
390 g of a colorless and transparent liquid of 7 mHg was obtained.
収率は７０．４％であった。The yield was 70.4%.
得られた化合物は下記の分析結果がら式％式％）
で表わされる１、３−ジ（γ−アミノプロピル）テトラ
メチルジシロキサンであることが確認された。The obtained compound was confirmed to be 1,3-di(γ-aminopropyl)tetramethyldisiloxane represented by the formula % from the following analysis results.
・ＮＭＲスペクトル：図１に示す。-NMR spectrum: shown in Figure 1.
・ＩＲスペクトル：図２に示す。-IR spectrum: shown in Figure 2.
・元素分析値
理論値（％） 実測値（％）
Ｃ： ４８．３３ ４８．５２Ｈ： １１
．３６ １１．４２Ｓｉ ： ２２．６１
２２．５９比較例１
温度計、攪拌装置、還流装置を備えた２Ｎの反応フラス
コに、ベンジリデンアリルアミン６９０ｇ、塩化白金酸
のイソプロパツール溶液（白金分２ｗｔ％）０．６ｇを
仕込み１７０〜１８０℃に加熱し、１．１．３．３−テ
トラメチルジシロキサンを２時間かけて滴下して反応さ
せ、滴下終了後さらに１７０〜１８０℃で３時間反応さ
せた。この反応の終了後、１７％塩酸による加水分解以
降の操作は実施例１と同様にして行なった。目的とする
１、３−ジ（γ−アミノプロピル）テトラメチルジシロ
キサンが５０ｇ得られ、収率９％であった。・Elemental analysis value Theoretical value (%) Actual value (%) C: 48.33 48.52H: 11
．． 36 11.42Si: 22.61
22.59 Comparative Example 1 A 2N reaction flask equipped with a thermometer, a stirring device, and a reflux device was charged with 690 g of benzylideneallylamine and 0.6 g of an isopropanol solution of chloroplatinic acid (platinum content: 2 wt%) at 170 to 180°C. 1.1.3.3-Tetramethyldisiloxane was added dropwise over 2 hours to react, and after the dropwise addition was completed, the reaction was further carried out at 170 to 180°C for 3 hours. After completion of this reaction, the operations after hydrolysis with 17% hydrochloric acid were carried out in the same manner as in Example 1. 50 g of the desired 1,3-di(γ-aminopropyl)tetramethyldisiloxane was obtained, with a yield of 9%.
比較例２
１．１．３．３−テトラメチルジシロキサンの仕込みの
際にキシレン６００ｇを使用しない以外は、実施例１と
全く同様の操作を繰返したが、１，３−ジ（γ−アミノ
プロピル）テトラメチルジシロキサンは得られなかった
。Comparative Example 2 The same operation as in Example 1 was repeated except that 600 g of xylene was not used when charging 1.1.3.3-tetramethyldisiloxane, but 1,3-di(γ-amino Propyl)tetramethyldisiloxane was not obtained.
比較例３
ベンジリデンアリルアミンを滴下する際の加熱温度１０
０℃を６０℃に変え、滴下終了後の反応温度も６０℃と
した以外は、実施例１と全（同様の操作を繰返したが、
１，３−ジ（γ−アミノプロピル）テトラメチルジシロ
キサンは得られなかった。Comparative Example 3 Heating temperature when dropping benzylideneallylamine 10
The same procedure as in Example 1 was repeated except that 0°C was changed to 60°C and the reaction temperature after the dropwise addition was also 60°C.
1,3-di(γ-aminopropyl)tetramethyldisiloxane was not obtained.
本発明の方法により、７０〜８０％の高収率でジアミノ
ジシロキサンを得ることができる。また、このジアミノ
ジシロキサンは、ポリイミド樹脂、エポキシ樹脂の改質
に用いられるアミノ変性シリコーンの基本原料として有
用である。By the method of the invention, diaminodisiloxane can be obtained with a high yield of 70-80%. Furthermore, this diaminodisiloxane is useful as a basic raw material for amino-modified silicones used for modifying polyimide resins and epoxy resins.
第１図は、実施例１で得られた１、３−ジ（γ−アミノ
プロピル）テトラメチルジシロキサンのＮＭＲスペクト
ルを示す。
第２図は、実施例１で得られた１、３−ジ（γ−アミノ
プロビル）テトラメチルジシロキサンのＩＲスペクトル
を示す。FIG. 1 shows the NMR spectrum of 1,3-di(γ-aminopropyl)tetramethyldisiloxane obtained in Example 1. FIG. 2 shows the IR spectrum of 1,3-di(γ-aminoprobyl)tetramethyldisiloxane obtained in Example 1.
Claims (1)
、アリール基又はアラルキル基である。〕で表されるジ
アミノプロピルジシロキサンの製法であって、 一般式（II）： ▲数式、化学式、表等があります▼（II） 〔式中、Ｒ＾１は前記のとおり〕 で表されるジシロキサン、白金系触媒及び非極性溶媒を
含む混合物を９０〜１５０℃に保ちながら、一般式（I
II）： ▲数式、化学式、表等があります▼（III） 〔式中、Ｒ＾２は一価炭化水素基であり、Ｒ＾３は水素
原子又は一価炭化水素基である〕 で表されるシッフ塩基を滴下させて、 一般式（IV）： ▲数式、化学式、表等があります▼（IV） 〔式中、Ｒ＾１、Ｒ＾２及びＲ＾３は前記のとおり〕で
表わされる有機ケイ素化合物を合成し、 次に、該有機ケイ素化合物を酸性下で加水分解後反応混
合物を中和する、 ことからなるジアミノプロピルジシロキサンの製法。[Claims] General formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 may be the same or different, and is an alkyl group, an aryl group, or an aralkyl group. . ] General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R^1 is as above] While maintaining a mixture containing disiloxane, a platinum-based catalyst, and a nonpolar solvent at 90 to 150°C, the general formula (I
II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, R^2 is a monovalent hydrocarbon group, and R^3 is a hydrogen atom or a monovalent hydrocarbon group] General formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) [In the formula, R^1, R^2 and R^3 are as above] A method for producing diaminopropyldisiloxane, which comprises synthesizing an organosilicon compound, then hydrolyzing the organosilicon compound under acidic conditions, and then neutralizing the reaction mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62108175A JPH0755953B2 (en) | 1987-05-01 | 1987-05-01 | Manufacturing method of diaminopropyldisiloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62108175A JPH0755953B2 (en) | 1987-05-01 | 1987-05-01 | Manufacturing method of diaminopropyldisiloxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63275591A true JPS63275591A (en) | 1988-11-14 |
| JPH0755953B2 JPH0755953B2 (en) | 1995-06-14 |
Family
ID=14477889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62108175A Expired - Fee Related JPH0755953B2 (en) | 1987-05-01 | 1987-05-01 | Manufacturing method of diaminopropyldisiloxane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0755953B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010108785A1 (en) | 2009-03-23 | 2010-09-30 | Wacker Chemie Ag | Process for the synthesis of 1,3-bis(aminoalkyl)disiloxanes |
| CN113698575A (en) * | 2021-09-02 | 2021-11-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
-
1987
- 1987-05-01 JP JP62108175A patent/JPH0755953B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010108785A1 (en) | 2009-03-23 | 2010-09-30 | Wacker Chemie Ag | Process for the synthesis of 1,3-bis(aminoalkyl)disiloxanes |
| DE102009001758A1 (en) | 2009-03-23 | 2010-09-30 | Wacker Chemie Ag | Process for the synthesis of 1,3-bis (aminoalkyl) disiloxanes |
| JP2012521381A (en) * | 2009-03-23 | 2012-09-13 | ワッカー ケミー アクチエンゲゼルシャフト | Method for synthesizing 1,3-bis (aminoalkyl) disiloxane |
| CN113698575A (en) * | 2021-09-02 | 2021-11-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0755953B2 (en) | 1995-06-14 |
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