JPH04103587A - Production of siloxane compound having diaminoalkyl group - Google Patents
Production of siloxane compound having diaminoalkyl groupInfo
- Publication number
- JPH04103587A JPH04103587A JP22075890A JP22075890A JPH04103587A JP H04103587 A JPH04103587 A JP H04103587A JP 22075890 A JP22075890 A JP 22075890A JP 22075890 A JP22075890 A JP 22075890A JP H04103587 A JPH04103587 A JP H04103587A
- Authority
- JP
- Japan
- Prior art keywords
- group
- siloxane compound
- compound
- reaction
- formula
- 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
- -1 siloxane compound Chemical class 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 5
- 125000005543 phthalimide group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 229920003002 synthetic resin Polymers 0.000 abstract description 6
- 239000000057 synthetic resin Substances 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- KGLPWQKSKUVKMJ-UHFFFAOYSA-N 2,3-dihydrophthalazine-1,4-dione Chemical compound C1=CC=C2C(=O)NNC(=O)C2=C1 KGLPWQKSKUVKMJ-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- PRCGMIFKQRXNBS-UHFFFAOYSA-N 2-methylidenepropane-1,3-diamine Chemical compound NCC(=C)CN PRCGMIFKQRXNBS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- YXJUYBFONHLFSE-UHFFFAOYSA-N NCCC(N)=C Chemical compound NCCC(N)=C YXJUYBFONHLFSE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は合成樹脂の特性改質に用いる有機ケイ素化合物
の製造方法に関し、更に詳しくはポリイミド、ポリアミ
ド、ポリウレタンなどのアミノ基の反応性を応用した合
成樹脂の界面特性の改質に有用とされる、ジアミノアル
キル基を有するシロキサン化合物の新規な製造方法に関
するものである。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a method for producing an organosilicon compound used for modifying the properties of synthetic resins, and more specifically, it relates to a method for producing an organosilicon compound used for modifying the properties of synthetic resins, and more specifically, it relates to a method for producing an organosilicon compound used for modifying the properties of synthetic resins. The present invention relates to a novel method for producing a siloxane compound having a diaminoalkyl group, which is useful for modifying the interfacial properties of synthetic resins.
本発明者等は先に、上記の如き合成樹脂の界面特性の改
質に有用である新規なジアミノアルキル基を有するシロ
キサン化合物を見出し、特許出願した（特願平１−８７
２９６号）。そして該明細書において、斯かる化合物は
例えば１，３ジアミノ−２−メチレンプロペン等と片末
端ハドロジエン変性ジオルガノシキロサンとを付加反応
させる方法により合成できる旨を明らかにした。The present inventors previously discovered a novel siloxane compound having a diaminoalkyl group that is useful for modifying the interfacial properties of synthetic resins as described above, and filed a patent application (Japanese Patent Application No. 1-87
No. 296). In the specification, it has been clarified that such a compound can be synthesized, for example, by an addition reaction between 1,3 diamino-2-methylenepropene or the like and a diorganosykilosane modified with a one-terminal hadrodiene.
ところが、更に研究を進めた結果、斯かる合成方法には
やや問題点があることが判明した。However, as a result of further research, it was found that there were some problems with this synthesis method.
即ち、この方法は、付加反応の際、好ましくない異性体
の生成や脱水素反応の併発があるという欠点がある。ま
た、反応原料である１、３−ジアミノ−メチレンプロパ
ンは水溶性や吸湿性が非常に高く、高収率で安定に製造
することが難しいという欠点もある。That is, this method has the disadvantage that undesirable isomers are produced and dehydrogenation reactions occur simultaneously during the addition reaction. In addition, 1,3-diamino-methylenepropane, which is a reaction raw material, has very high water solubility and hygroscopicity, and has the disadvantage that it is difficult to stably produce it at a high yield.
かくして、高純度のジアミノアルキル基を有するシロキ
サン化合物を工業的に高収率で得ることは、これまで困
難であった。Thus, it has hitherto been difficult to industrially obtain a highly purified siloxane compound having a diaminoalkyl group in a high yield.
本発明の目的は、従来方法のこのような問題点を解消し
、入手の容易な原料を使用して、高純度のジアミノアル
キル基を有するシロキサン化合物を高収率で得る製造方
法を提供することである。An object of the present invention is to provide a manufacturing method for obtaining a highly purified siloxane compound having a diaminoalkyl group at a high yield by using easily available raw materials and solving the problems of the conventional methods. It is.
本発明者らは、このような目的を達成すべく鋭意検討し
た結果、フタルイミド基を有するシロキサン化合物とヒ
ドラジン１水和物を反応させることにより、ジアミノア
ルキル基を有するシロキサン化合物が高純度、高収率で
得られることを見出し、この知見に基づいて本発明をな
すに到った。As a result of intensive studies to achieve such an objective, the present inventors have found that by reacting a siloxane compound having a phthalimide group with hydrazine monohydrate, a siloxane compound having a diaminoalkyl group can be produced with high purity and high yield. The present invention was completed based on this finding.
即ち、本発明は、−船人（Ｉｔ）
（式中、Ｒは互いに同−又は相異なるアルキル基、アリ
ール基又はパーフルオロアルキル基を示し、ｎは０〜１
，０００の整数を示す）で表されるフタルイミド基を有
するシロキサン化合物とヒドラジンｌ水和物とを反応さ
せることを特徴とする一般式（Ｉ）
Ｒ
（式中、Ｒ及びｎは前記と同じである）で表されるジア
ミノアルキル基を有するシロキサン化合物の製造方法で
ある。That is, the present invention provides -Shipen (It) (wherein R represents an alkyl group, an aryl group, or a perfluoroalkyl group that is the same or different from each other, and n is 0 to 1.
,000) is reacted with a siloxane compound having a phthalimide group and hydrazine hydrate. This is a method for producing a siloxane compound having a diaminoalkyl group represented by
本発明の方法を化学反応式で表すと次式（１）のように
なる。The method of the present invention can be expressed as a chemical reaction formula as shown in the following formula (1).
（ＩＩ）
（式中、Ｒ及びわは前記と同じである）反応式（１）は
、フタルイミド基がヒドラジンにより分解されて、ジア
ミノアルキル基に変換され、副生物としてフタルヒドラ
ジドが生成することを示している。(II) (In the formula, R and I are the same as above) Reaction formula (1) shows that the phthalimide group is decomposed by hydrazine and converted to a diaminoalkyl group, producing phthalhydrazide as a by-product. It shows.
反応式（１）において、反応試剤として使用されるヒド
ラジン１永和物は市販されており、容易に入手できるも
のである。In Reaction Formula (1), hydrazine monohydrate used as a reaction reagent is commercially available and can be easily obtained.
反応式（１）において、反応原料として使用されるフタ
ルイミド基を有するシロキサン化合物（ＩＩ）は、本発
明者の提案した先願明細書（特願平２−１８４２５９号
）に記載された方法によって合成することが可能である
。化合物（ｎ）において、Ｒは互いに同−又は相異なる
アルキル基、アリール基又はパーフルオロアルキル基で
ある。In reaction formula (1), the phthalimide group-containing siloxane compound (II) used as a reaction raw material is synthesized by the method described in the specification of the earlier application (Japanese Patent Application No. 184259/1999) proposed by the present inventor. It is possible to do so. In compound (n), R is the same or different alkyl group, aryl group or perfluoroalkyl group.
例えばアルキル基としてはメチル基、エチル基、プロピ
ル基、ブチル基、ペンチル基、ヘキシル基、ドデシル基
など、アリール基としてはフェニル基、トリル基など、
またパーフルオロアルキル基としては３．３．３−トリ
フルオロプロピル基、ヘプタデカフルオロデシル基など
が例示される。これらの中で、原料の入手及び合成の容
易なことから炭素数１〜４のアルキル基、とりわけメチ
ル基が好ましい。ｎは０〜１，０００ 、好ましくは１
〜２００の整数である。ｎが１，０００を超えるものは
制御よく合成することが困難である。このような化合物
（ｎ）の具体例としては、次のような化合物が挙げられ
る。For example, alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, dodecyl, etc.; aryl groups include phenyl, tolyl, etc.
Examples of the perfluoroalkyl group include a 3.3.3-trifluoropropyl group and a heptadecafluorodecyl group. Among these, an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, is preferred because of easy availability of raw materials and easy synthesis. n is 0 to 1,000, preferably 1
~200 integer. When n exceeds 1,000, it is difficult to synthesize with good control. Specific examples of such compound (n) include the following compounds.
ＩＩ ＣＨ３ＣＨ３反応式（１
）において、化合物（Ｉｆ）とヒドラジン１水和物との
使用割合は特に限定されないが、化学量論的使用量が経
済上好ましい。II CH3CH3 reaction formula (1
), the usage ratio of compound (If) and hydrazine monohydrate is not particularly limited, but stoichiometric usage is economically preferable.
又、反応式（１）において、有機溶媒は必須ではないが
、反応を円滑に進めるために有機溶剤を使用することが
好ましい。所望により使用する場合はメタノール、エタ
ノールなどのアルコール類；アセトンなどのケトン類；
ヘキサン、ヘプタンなどの脂肪族炭化水素；シクロヘキ
サンなどの脂環式炭化水素；エチルエーテルなどのエー
テル類；トルエン、キシレンなどの芳香族炭化水素：及
び１．２−ジクロロエタンなどのハロゲン化炭化水素類
などが好ましく、これらの中でも反応の制御性、円滑性
、反応後の目的化合物Ｎ）と副生じたフタルヒドラジド
との液固分離が容易であることからエタノールの使用が
望ましい。有機溶媒の使用量は特に限定されないが、化
合物（ｎ）に対して１０重量％以上、２０００重量％未
満の範囲とすることが好ましい。Further, in reaction formula (1), although an organic solvent is not essential, it is preferable to use an organic solvent in order to proceed with the reaction smoothly. Alcohols such as methanol and ethanol, if desired; ketones such as acetone;
Aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; ethers such as ethyl ether; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as 1,2-dichloroethane. Among these, it is desirable to use ethanol because of the controllability and smoothness of the reaction and the ease of liquid-solid separation between the target compound N) and the by-produced phthalhydrazide after the reaction. The amount of the organic solvent used is not particularly limited, but is preferably in the range of 10% by weight or more and less than 2000% by weight based on compound (n).
また、本反応は、化合物（Ｉ［）及び有機溶媒を反応容
器に仕込み、所定の温度で、ヒドラジン１永和物を滴下
反応させる方法によって行うことが、反応制御上好まし
い。反応温度は−２０〜９０°Ｃ１好ましくは０〜７０
°Ｃの温度範囲である。In addition, from the viewpoint of reaction control, this reaction is preferably carried out by charging compound (I[) and an organic solvent into a reaction vessel, and reacting dropwise hydrazine monohydrate at a predetermined temperature. The reaction temperature is -20 to 90°C, preferably 0 to 70°C.
The temperature range is °C.
反応時の圧力は特に限定されないが、通常は常圧で行わ
れる。反応時間は反応条件によるが、通常は０．５〜２
４時間で充分である。The pressure during the reaction is not particularly limited, but it is usually carried out at normal pressure. The reaction time depends on the reaction conditions, but is usually 0.5 to 2
4 hours is sufficient.
かくして得られた反応混合物からの化合物（１）の単離
及び精製は、有機合成化学の分野で通常用いられている
手法によって行うことができる。例えば反応後、フタル
ヒドラジドの沈澱を濾過分離し、その濾液から低沸点成
分を蒸留除去することによって、ジアミノアルキル基を
有するシロキサン化合物（１）が得られる。Isolation and purification of compound (1) from the reaction mixture thus obtained can be performed by techniques commonly used in the field of synthetic organic chemistry. For example, after the reaction, the phthalhydrazide precipitate is separated by filtration, and low-boiling components are distilled off from the filtrate to obtain the siloxane compound (1) having a diaminoalkyl group.
本発明の方法に従うと、入手の容易な原料を用いて、高
純度のジアミノアルキル基を有するシロキサン化合物（
Ｉ）を高収率で得ることができるので、工業的製造方法
として好適である。According to the method of the present invention, a highly purified siloxane compound having a diaminoalkyl group (
Since I) can be obtained in high yield, it is suitable as an industrial production method.
本発明の方法で得られたジアミノアルキル基を有するシ
ロキサン化合物（Ｉ）は有機材料の変性用反応性オリゴ
マー原料として使用するとき有利であり、また分子設計
的にも極めて信軌性のある材料が得られる。即ち、有機
モノマーあるいはそれらのポリマーと本発明の方法で得
られたジアミノアルキル基を有するシロキサン化合物Ｎ
）とを反応させて変性すると、従来の有機材料に密着性
、接着性、耐熱性、耐候性、撥水性、耐摩耗性、気体透
過性などのシリコーン特有の優れた性質を付与すること
ができる。The siloxane compound (I) having a diaminoalkyl group obtained by the method of the present invention is advantageous when used as a reactive oligomer raw material for modifying organic materials, and is also a material with extremely high reliability in terms of molecular design. can get. That is, an organic monomer or a polymer thereof and a siloxane compound N having a diaminoalkyl group obtained by the method of the present invention.
) can give conventional organic materials the excellent properties unique to silicone, such as adhesion, adhesion, heat resistance, weather resistance, water repellency, abrasion resistance, and gas permeability. .
以下において、実施例を挙げ、本発明を更に詳しく説明
する。なお、本発明の範囲は以下の実施例のみに限定さ
れるものではない。EXAMPLES Below, the present invention will be explained in more detail with reference to Examples. Note that the scope of the present invention is not limited only to the following examples.
実施例１
撹拌機、温度計、滴下漏斗、還流冷却器及びオイルバス
を備えた内容積５００ ｍ７のフラスコに、フタルイミ
ド基を有するシロキサン化合物として
４９．４ｇ （０，１０モル）及びエタノール７５ｇ
を仕込み、２０℃で撹拌を開始した。Example 1 In a flask with an internal volume of 500 m7 equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser and an oil bath, 49.4 g (0.10 mol) of a siloxane compound having a phthalimide group and 75 g of ethanol are added.
was charged, and stirring was started at 20°C.
これに、ヒドラジン１水和物１０．１ｇ （０，２０
モル）を、液温２０〜３０°Ｃに保ちながら、１０分か
けて滴下した。滴下終了後、液温２５℃で２時間撹拌し
、更に液温５５°Ｃで１時間加熱撹拌した。To this, 10.1 g of hydrazine monohydrate (0,20
mol) was added dropwise over 10 minutes while maintaining the liquid temperature at 20 to 30°C. After the dropwise addition was completed, the mixture was stirred for 2 hours at a liquid temperature of 25°C, and further heated and stirred for 1 hour at a liquid temperature of 55°C.
反応容器より試料を取り出して、液体クロマトグラフィ
ー分析を行い、反応原料である前記のフタルイミド基を
有するシロキサン化合物のピークが消失していることを
確認した。A sample was taken out from the reaction vessel and analyzed by liquid chromatography, and it was confirmed that the peak of the phthalimide group-containing siloxane compound, which was a reaction raw material, had disappeared.
反応混合物を冷却した後、吸引濾過によりフタルヒドラ
ジドの沈澱を分離し、その濾液から減圧蒸留で沸点９２
〜９３°Ｃ／４Ｔｏｒｒの留分を分取した結果、無色透
明液状の１−（２−アミノメチル−３−アミノプロピル
）−１，１，３，３，３−ペンタメチルジシロキサン２
１．１ｇを得た。これは、前記のフタルイミド基を有す
るシロキサン化合物に対して９０％の収率であった。After cooling the reaction mixture, the precipitate of phthalhydrazide was separated by suction filtration, and the phthalhydrazide precipitate was distilled from the filtrate under reduced pressure.
As a result of fractionating the fraction at ~93°C/4 Torr, a colorless transparent liquid 1-(2-aminomethyl-3-aminopropyl)-1,1,3,3,3-pentamethyldisiloxane 2 was obtained.
1.1 g was obtained. This was a 90% yield based on the phthalimide group-containing siloxane compound described above.
こうして得られた１−（２−アミノメチル−３−アミノ
プロピル）−１，１，３，３，３−ペンタメチルジシロ
キサンのガスクロマトグラフィー分析、赤外吸収スペク
トル分析、′Ｈ核磁気共鳴吸収分析及び質量スペクトル
分析の結果は下記の通りであり、次式の分子構造である
ことを確認した。尚、第１図、第２図に該化合物の’Ｈ
核磁気共鳴吸収スペクトル、赤外吸収スペクトルのチャ
ートを示す。Gas chromatography analysis, infrared absorption spectrum analysis, 'H nuclear magnetic resonance absorption of the 1-(2-aminomethyl-3-aminopropyl)-1,1,3,3,3-pentamethyldisiloxane thus obtained. The results of the analysis and mass spectrometry analysis are as follows, and it was confirmed that the molecular structure was as shown below. In addition, 'H' of the compound is shown in Figures 1 and 2.
Charts of nuclear magnetic resonance absorption spectra and infrared absorption spectra are shown.
ＣＨ３ＣＨ２
ガスクロマトグラフィー分析： ９８．０％赤外吸収ス
ペクトル分析（液膜法）：
波数（ｃｍ−’） 帰属
３３６０ Ｎ−Ｆｌ
３２７０ Ｎ−Ｈ
１２５０Ｓｔ ＣＨ３
１１００〜１０００ Ｓｉ ＯＳｉ＋Ｈ核磁気共
鳴吸収スペクトル分析（９０ＭＨｚＣＤＣ１３中）：
位置 化学シフトδ（ｐｐｍ）
ａ １．５〜１．６
ｂ ２．６〜２．７
ｃ １．４〜１．７
ｄ Ｏ３４〜０．６
ｅＯｏｌ
ｆＯ８１
・質量スペクトル分析（ｍ／ｅ） ： ２３４（Ｍ”）
比較例１
撹拌機、温度計、滴下漏斗、還流冷却器及びオイルバス
を備えた内容積１００−のフラスコに、１．３−ジアミ
ノ−２−メチレンプロパン１７．２ｇ（０，２０モル）
及び白金原子として０．００５ｇを含む１．３，５．７
−チトラビニルーＬ３，５．７−チトラメチルシクロテ
トラシロキサンをリガンドとする白金錯体を仕込み、撹
拌を開始し、液温７０°Ｃに加熱した。CH3CH2 Gas chromatography analysis: 98.0% infrared absorption spectroscopy (liquid film method): Wave number (cm-') Attribution 3360 N-Fl 3270 N-H 1250St CH3 1100-1000 Si OSi+H nuclear magnetic resonance absorption spectroscopy ( (in 90 MHz CDC13): Position Chemical shift δ (ppm) a 1.5-1.6 b 2.6-2.7 c 1.4-1.7 d O34-0.6 eOol fO81 ・Mass spectrum analysis (m/ e): 234 (M”)
Comparative Example 1 17.2 g (0.20 mol) of 1,3-diamino-2-methylenepropane was placed in a 100-volume flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser, and oil bath.
and 1.3,5.7 containing 0.005g as platinum atoms
A platinum complex having -Titravinyl-L3,5.7-titramethylcyclotetrasiloxane as a ligand was charged, stirring was started, and the solution was heated to a temperature of 70°C.
これに、滴下漏斗より、１．１．３，３．３−ペンタメ
チルジシロキサン２９．６ｇ （０，２０モル）を液温
７０〜９０℃に保持しながら、１５分かけて滴下した。To this, 29.6 g (0.20 mol) of 1.1.3,3.3-pentamethyldisiloxane was added dropwise over 15 minutes from a dropping funnel while maintaining the liquid temperature at 70 to 90°C.
滴下終了後、ガスクロマトグラフィー分析により、１．
１，３，３．３−ペンタメチルジシロキサンのピークが
消失するまで、液温７０〜１００”Ｃで８時間加熱撹拌
した。After completion of the dropwise addition, gas chromatography analysis revealed that 1.
The mixture was heated and stirred at a liquid temperature of 70 to 100''C for 8 hours until the peak of 1,3,3.3-pentamethyldisiloxane disappeared.
放冷後、実施例１と同様に減圧蒸留することにより、１
−（２−アミノメチル−３−アミノプロピル）−１，１
，３，３，３−ペンタメチルジシロキサン３２．７ｇを
得た。ガスクロマトグラフィー分析の結果、このものの
純度は８９．０％であり、不純物として目的物質の異性
体や目的物質と１゜１．３．３．３−ペンタメチルジシ
ロキサンとの脱水素生成物が含まれていることを確認し
た。また、１．３−ジアミノ−２−メチレンプロパンに
対する収率は７０％であることを確認した。After cooling, vacuum distillation was performed in the same manner as in Example 1 to obtain 1.
-(2-aminomethyl-3-aminopropyl)-1,1
, 32.7 g of 3,3,3-pentamethyldisiloxane were obtained. As a result of gas chromatography analysis, the purity of this product was 89.0%, and impurities include isomers of the target substance and dehydrogenation products of the target substance and 1°1.3.3.3-pentamethyldisiloxane. Confirmed that it is included. Further, it was confirmed that the yield based on 1,3-diamino-2-methylenepropane was 70%.
第１図は、実施例１で得られた１−（２−アミノメチル
−３−アミノプロピル） −１，１，３，３゜３−ペン
タメチルジシロキサンの１Ｈ核磁気共鳴吸収スペクトル
を示すチャートである。
第２図は、実施例１で得られたニー（２−アミノメチル
−３−アミノプロピル） −１，１，３，３゜３−ペン
タメチルジシロキサンの赤外吸収スペクトルを示すチャ
ートである。
出願人代理人 古 谷 馨
（外３名）FIG. 1 is a chart showing the 1H nuclear magnetic resonance absorption spectrum of 1-(2-aminomethyl-3-aminopropyl)-1,1,3,3°3-pentamethyldisiloxane obtained in Example 1. It is. FIG. 2 is a chart showing an infrared absorption spectrum of ni(2-aminomethyl-3-aminopropyl)-1,1,3,3°3-pentamethyldisiloxane obtained in Example 1. Applicant's agent: Kaoru Furuya (3 others)
Claims (1)
ール基又はパーフルオロアルキル基を示し、ｎは０〜１
，０００の整数を示す）で表されるフタルイミド基を有
するシロキサン化合物とヒドラジン１水和物とを反応さ
せることを特徴とする 一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ及びｎは前記と同じである）で表されるジア
ミノアルキル基を有するシロキサン化合物の製造方法。[Claims] 1 General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R represents an alkyl group, an aryl group, or a perfluoroalkyl group that is the same or different from each other, and n is 0-1
General formula (I) characterized by reacting a siloxane compound having a phthalimide group (representing an integer of ,000) with hydrazine monohydrate ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) A method for producing a siloxane compound having a diaminoalkyl group represented by the formula (wherein R and n are the same as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22075890A JP2862977B2 (en) | 1990-08-21 | 1990-08-21 | Method for producing siloxane compound having diaminoalkyl group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22075890A JP2862977B2 (en) | 1990-08-21 | 1990-08-21 | Method for producing siloxane compound having diaminoalkyl group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04103587A true JPH04103587A (en) | 1992-04-06 |
| JP2862977B2 JP2862977B2 (en) | 1999-03-03 |
Family
ID=16756086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22075890A Expired - Lifetime JP2862977B2 (en) | 1990-08-21 | 1990-08-21 | Method for producing siloxane compound having diaminoalkyl group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2862977B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108362791B (en) * | 2018-01-30 | 2020-07-28 | 中国农业科学院茶叶研究所 | Method for detecting phthalimide in tea |
-
1990
- 1990-08-21 JP JP22075890A patent/JP2862977B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2862977B2 (en) | 1999-03-03 |
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