JPH0255439B2 - - Google Patents
Info
- Publication number
- JPH0255439B2 JPH0255439B2 JP60204781A JP20478185A JPH0255439B2 JP H0255439 B2 JPH0255439 B2 JP H0255439B2 JP 60204781 A JP60204781 A JP 60204781A JP 20478185 A JP20478185 A JP 20478185A JP H0255439 B2 JPH0255439 B2 JP H0255439B2
- Authority
- JP
- Japan
- Prior art keywords
- siloxane oligomer
- formula
- represented
- sich
- nmr
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- DOGMJCPBZJUYGB-UHFFFAOYSA-N 3-trichlorosilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](Cl)(Cl)Cl DOGMJCPBZJUYGB-UHFFFAOYSA-N 0.000 description 1
- GIWOHOUNSAJDGH-UHFFFAOYSA-N 3-tris[[dimethyl(3,3,3-trifluoropropyl)silyl]oxy]silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)CCC(F)(F)F)(O[Si](C)(C)CCC(F)(F)F)O[Si](C)(C)CCC(F)(F)F GIWOHOUNSAJDGH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229960004676 antithrombotic agent Drugs 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 trifluoropropylmethylsiloxane Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
（産業上の利用分野）
本発明は文献未載の新規なシロキサンオリゴマ
ー、とくには機能的高分子の中間体またはシリコ
ーン変成高分子用として有用されるシロキサンオ
リゴマーに関するものある。
（発明の構成）
本発明は一般式
（こゝにＹは水素原子、ClCH2、
(Industrial Application Field) The present invention relates to a novel siloxane oligomer that has not been described in any literature, particularly to a siloxane oligomer that is useful as an intermediate for functional polymers or for silicone-modified polymers. (Structure of the invention) The present invention is based on the general formula (Here, Y is a hydrogen atom, ClCH 2 ,
【式】で示される基から選択さ
れる原子または基）で示される文献未載の新規な
シロキサンオリゴマーに関するものである。
上記した式(1)におけるＹは水素原子、
ClCH2、The present invention relates to a novel siloxane oligomer represented by an atom or group selected from the groups represented by the following formula and not yet described in the literature. Y in the above formula (1) is a hydrogen atom, ClCH 2 ,
【式】で示される基
から選択される原子または基であり、したがつて
これにはつぎの３種のものが例示される。
このシロキサンオリゴマーは例えば
（こゝにＸはハロゲン原子）で示される有機け
い素ハロマグネシウム塩に一般式
Ｙ−Si−Z3 …(3)
（こゝにＹは前記に同じ、Ｚはハロゲン原子ま
たは低級アルコキシ基）で示されるハロシランま
たはアルコキシシランを反応させると、この反応
が次式
によつて進行するので、反応終了後これらを水中
に注ぎ有機層を蒸溜すれば目的とするシロキサン
オリゴマーを高純度、高収率で得ることができる
が、この反応は０℃〜還流温度の範囲、好ましく
は30〜80℃で行わせればよい。
なお、上記した一般式(2)で示される有機けい素
ハロマグネシウム塩は常法で製造した
RMgX（Ｒは一価炭化水素基）で示されるグリ
ニヤール試薬に式
で示されるオルガノシロキサンを滴下し50〜120
℃で反応させることによつて得ることができる。
また、この有機けい素ハロマグネシウム塩に添加
される上記した一般式(3)で示されるオルガノシラ
ンとしては HSiCl3、HSi（OCH3）3、
ClCH2SiCl3、
などが例示される。
本発明のシロキサンオリゴマーは種々の用途に
使用されるが、これは特にはガス透過性が撥水性
の機能を有する機能高分子化合物、シリコー変性
高分子化合物となるので、コンタクトレンズ、包
帯、抗血栓性材料などのような医療用高分子物質
として有用とされるほか、透湿性防水布などの分
野にも有用とされる。
つぎに本発明の実施例をあげる。
実施例 １
反応器中に金属マグネシウム24.3ｇ（１モル）
とテトラハイドロフラン300mlを仕込んだのち、
これにメチルクロライドを吹き込んでメチルマグ
ネシウムクロライドのテトラハイドロフラン溶液
を作り、これに還流下でトリフルオロプロピルメ
チルシロキサントリマー
It is an atom or group selected from the groups represented by the formula, and the following three types are exemplified. This siloxane oligomer is for example (Here, X is a halogen atom) Organosilicon halomagnesium salt represented by the general formula Y-Si-Z 3 ...(3) (Here, Y is the same as above, Z is a halogen atom or a lower alkoxy group) When a halosilane or alkoxysilane represented by is reacted, the reaction is expressed by the following formula: After the reaction is complete, the desired siloxane oligomer can be obtained with high purity and high yield by pouring them into water and distilling the organic layer. , preferably at 30 to 80°C. The organosilicon halomagnesium salt represented by the general formula (2) above is prepared by adding the formula to a Grignard reagent represented by RMgX (R is a monovalent hydrocarbon group) prepared by a conventional method. Drop the organosiloxane shown in 50 to 120
It can be obtained by reacting at ℃.
In addition, the organosilane represented by the above general formula (3) added to this organosilicon halomagnesium salt includes HSiCl 3 , HSi(OCH 3 ) 3 ,
ClCH2SiCl3 , Examples include. The siloxane oligomer of the present invention can be used for various purposes, and in particular, it can be used as a functional polymer compound with gas permeability and water repellency, or as a silicone-modified polymer compound, so it can be used in contact lenses, bandages, antithrombotic agents, etc. It is said to be useful as a medical polymer substance such as a flexible material, and is also useful in fields such as moisture-permeable waterproof fabric. Next, examples of the present invention will be given. Example 1 24.3 g (1 mol) of metallic magnesium in the reactor
After adding 300ml of tetrahydrofuran,
Methyl chloride is bubbled into this to create a tetrahydrofuran solution of methylmagnesium chloride, and trifluoropropylmethylsiloxane trimer is added to this under reflux.
【式】156ｇをテトラハイ
ドロフラン200mlにとかして液を２時間で滴下し
て反応させ、さらに２時間還流させてから、この
反応液にトリクロロシラン（HSiCl3）45ｇ（0.33
モル）を還流温度で滴下して反応させたのち、こ
れを水１中に注ぎ込み、分離した有機層を減圧
蒸溜したところ、４mmHg、125℃の留分（GC純
度99.2％）のものが146ｇ得られた。
このものは屈折率n25 Dが1.3700であり、これに
ついてIR、NMRおよび元素分析を行つたとこ
ろ、これらについて
IR ：第１図
NMR：δ0.17ppm −SiCH3 18H
δ0.77ppm −SiCH2 6H
δ2.0ppm −CH2CF3 6H
δ5.25ppm −SiH 1H
元素分析：
Ｃ％ Ｈ％ Si％
計算値 33.19 5.76 20.70
実測値 33.16 5.76 20.74
が得られたので、これは次式
で示されるシロキサンオリゴマーであることが確
認された。
実施例 ２
実施例１におけるトリクロロシラン45ｇの代り
にクロロメチルトリクロロシラン（ClCH2SiCl3）
61ｇを使用したほかは実施例１と同様に処理した
ところ、４mmHg、139℃の留分（GC純度96％）
のものが156ｇ得られた。
このものは屈折率n25 Dが1.3850であり、そのIR、
NMRおよび元素分析結果が
IR：第２図
NMR：δ0.17ppm −SiCH3 18H
δ0.77ppm −SiCH2 6H
δ2.0ppm −CH2CF3 6H
δ2.55ppm −SiCH2Cl 2H
元素分析：
Ｃ％ Ｈ％ Si％
計算値 32.56 5.46 19.00
実測値 32.59 5.47 18.96
であることから、これは次式
で示されるクロロメチルトレス（トリフルオロジ
メチルシロキシ）シランであることが確認され
た。
実施例 ３
実施例１におけるトリクロロシラン45ｇの代り
に３−メタクリロキシプロピルトリクロロシラン
86ｇを使用したほかは実施例１と同様に処理した
ところ、１mmHg、156℃の留分（GC純度96％）
のものが161ｇ得られた。
このものは屈折率n25 Dが1.4005であり、このIR、
NMRおよび元素分析結果が
IF：第３図
NMR：δ0.17ppm −SICH3 18H
δ0.77ppm −SiCH2 6H
δ2.0ppm
−CH2CF3
−CH2−
−Ｃ−CH3 12H
δ4.04ppm −COOCH2− 2H
δ5.45ppm 1H
δ6.99ppm −CH2＝Ｃ− 1H
元素分析：
Ｃ％ Ｈ％ Si％
計算値 39.50 6.18 16.80
実測値 39.44 6.18 16.82
であることから、これは次式
で示される３−メタクリロキシプロピルトリス
（トリフルオロプロピルジメチルシロキシ）シラ
ンであることが確認された。[Formula] 156 g was dissolved in 200 ml of tetrahydrofuran, the solution was added dropwise over 2 hours to react, and after refluxing for another 2 hours, 45 g (0.33
mol) was added dropwise at reflux temperature to react, and then poured into 1 volume of water, and the separated organic layer was distilled under reduced pressure to obtain 146 g of a fraction (GC purity 99.2%) at 4 mmHg and 125°C. It was done. This material has a refractive index n 25 D of 1.3700, and when IR, NMR and elemental analysis were performed on it, IR: Figure 1 NMR: δ0.17ppm -SiCH 3 18H δ0.77ppm -SiCH 2 6H δ2 .0ppm −CH 2 CF 3 6H δ5.25ppm −SiH 1H Elemental analysis: C% H% Si% Calculated value 33.19 5.76 20.70 Actual value 33.16 5.76 20.74 was obtained, so this is calculated by the following formula It was confirmed that it was a siloxane oligomer shown by Example 2 Chloromethyltrichlorosilane (ClCH 2 SiCl 3 ) was used instead of 45 g of trichlorosilane in Example 1.
When treated in the same manner as in Example 1 except that 61 g was used, a fraction of 4 mmHg and 139°C (GC purity 96%) was obtained.
156g of this product was obtained. This one has a refractive index n 25 D of 1.3850, and its IR,
NMR and elemental analysis results are IR: Figure 2 NMR: δ0.17ppm -SiCH 3 18H δ0.77ppm -SiCH 2 6H δ2.0ppm -CH 2 CF 3 6H δ2.55ppm -SiCH 2 Cl 2H Elemental analysis: C% H %Si% Calculated value 32.56 5.46 19.00 Actual value 32.59 5.47 18.96 Therefore, this is calculated using the following formula. It was confirmed that it was chloromethyltres(trifluorodimethylsiloxy)silane shown by Example 3 3-methacryloxypropyltrichlorosilane instead of 45 g of trichlorosilane in Example 1 When treated in the same manner as in Example 1 except that 86 g was used, a fraction of 1 mmHg and 156°C (GC purity 96%) was obtained.
161g of this product was obtained. This one has a refractive index n 25 D of 1.4005, and this IR,
NMR and elemental analysis results are IF: Figure 3 NMR: δ0.17ppm -SICH 3 18H δ0.77ppm -SiCH 2 6H δ2.0ppm -CH 2 CF 3 -CH 2 - -C-CH 3 12H δ4.04ppm -COOCH 2 − 2H δ5.45ppm 1H δ6.99ppm −CH 2 =C− 1H Elemental analysis: C% H% Si% Calculated value 39.50 6.18 16.80 Actual value 39.44 6.18 16.82 Therefore, this is the following formula It was confirmed that it was 3-methacryloxypropyltris(trifluoropropyldimethylsiloxy)silane shown by
図はいずれも本発明のシロキサンオリゴマーの
赤外線吸収スペクトル（IR）を示したものであ
り、第１図〜第３図はそれぞれ実施例１〜３で得
られたシロキサンオリゴマーのIRを図示したも
のである。
Each figure shows the infrared absorption spectrum (IR) of the siloxane oligomer of the present invention, and Figures 1 to 3 illustrate the IR of the siloxane oligomer obtained in Examples 1 to 3, respectively. be.
Claims (1)
【式】で示される基から選択さ れる原子または基）で示されるシロキサンオリゴ
マー。[Claims] 1. General formula (Here, Y is a hydrogen atom, ClCH 2 ,
A siloxane oligomer represented by an atom or group selected from the group represented by the formula:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60204781A JPS6263596A (en) | 1985-09-17 | 1985-09-17 | Siloxane oligomer |
| US06/905,576 US4727172A (en) | 1985-09-12 | 1986-09-09 | Method for the preparation of an organosiloxane oligomer and a novel organosiloxane oligomer thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60204781A JPS6263596A (en) | 1985-09-17 | 1985-09-17 | Siloxane oligomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6263596A JPS6263596A (en) | 1987-03-20 |
| JPH0255439B2 true JPH0255439B2 (en) | 1990-11-27 |
Family
ID=16496238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60204781A Granted JPS6263596A (en) | 1985-09-12 | 1985-09-17 | Siloxane oligomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6263596A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2655683B2 (en) * | 1988-06-30 | 1997-09-24 | チッソ株式会社 | Polyorganosiloxane |
| JP3772933B2 (en) * | 1996-03-22 | 2006-05-10 | 株式会社村田製作所 | Method for producing magnetic garnet single crystal containing trivalent cerium |
| AU2002238890B2 (en) | 2001-03-14 | 2006-06-22 | Showa Denko K.K. | Layered heat exchanger, layered evaporator for motor vehicle air conditioners and refrigeration system |
| WO2015142560A1 (en) * | 2014-03-17 | 2015-09-24 | Dow Corning Corporation | Fluorinated compound, curable composition comprising same, and cured product |
-
1985
- 1985-09-17 JP JP60204781A patent/JPS6263596A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6263596A (en) | 1987-03-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |