JP2605340B2 - Fluorine-containing silane compound and method for producing the same - Google Patents
Fluorine-containing silane compound and method for producing the sameInfo
- Publication number
- JP2605340B2 JP2605340B2 JP63101463A JP10146388A JP2605340B2 JP 2605340 B2 JP2605340 B2 JP 2605340B2 JP 63101463 A JP63101463 A JP 63101463A JP 10146388 A JP10146388 A JP 10146388A JP 2605340 B2 JP2605340 B2 JP 2605340B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- general formula
- propyl
- chlorine
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 silane compound Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910000077 silane Inorganic materials 0.000 title description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title description 3
- 229910052731 fluorine Inorganic materials 0.000 title description 3
- 239000011737 fluorine Substances 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- RRRXPPIDPYTNJG-UHFFFAOYSA-N perfluorooctanesulfonamide Chemical compound NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RRRXPPIDPYTNJG-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000011147 inorganic material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 2
- YEAMHXDZHZNOQE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-n-propyloctane-1-sulfonamide Chemical compound CCCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YEAMHXDZHZNOQE-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BHFJBHMTEDLICO-UHFFFAOYSA-N Perfluorooctylsulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O BHFJBHMTEDLICO-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- HUEPADWXXGLLSW-UHFFFAOYSA-N n-prop-2-enylpropan-1-amine Chemical compound CCCNCC=C HUEPADWXXGLLSW-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical group Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 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
Landscapes
- Surface Treatment Of Glass (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、新規な化合物Ｎ−プロピル−Ｎ−（３−シ
リルプロピル）ペルフルオロオクチルスルホンアミド
と、その製造方法に関する。本発明の化合物は、文献未
記載の新規物質であり、シラン化合物として使用でき
る。Description: TECHNICAL FIELD The present invention relates to a novel compound N-propyl-N- (3-silylpropyl) perfluorooctylsulfonamide and a method for producing the same. The compound of the present invention is a novel substance not described in any literature, and can be used as a silane compound.
［従来の技術と本発明の解決課題］ 近年、樹脂および無機質材料表面の撥水、撥油性、非
粘着性の向上が要求されており、此れ等の材料の表面特
性を改善する処理剤として、従来、或る種のシランカッ
プリング剤が知られている。ところが、従来のシランカ
ップリング剤は、撥水、撥油、非粘着性が充分でない欠
点があった。[Related Art and Problems to be Solved by the Present Invention] In recent years, it has been required to improve the water repellency, oil repellency, and non-adhesiveness of the surfaces of resins and inorganic materials, and as a treatment agent for improving the surface properties of these materials. Conventionally, certain silane coupling agents are known. However, the conventional silane coupling agent has a drawback that water repellency, oil repellency and non-adhesion are not sufficient.
一方、従来の表面処理剤であるシランカップリング剤
の他にペルフルオロアルキル基を有するシラン化合物が
知られており、離型剤としての利用も検討されている
（特公昭60−90851参照）。このペルフルオロアルキル
基を有するシラン化合物は、従来の表面処理剤の欠点が
比較的少ないが、基質との接着性、熱的、化学的安定性
が充分ではなく、化合物によっては合成時のヒドロシリ
ル化反応において原料の分解が生じ、収率が低いという
欠点があった。On the other hand, a silane compound having a perfluoroalkyl group is known in addition to a silane coupling agent which is a conventional surface treatment agent, and its use as a release agent is also being studied (see Japanese Patent Publication No. 60-90851). This silane compound having a perfluoroalkyl group has relatively few disadvantages of the conventional surface treating agent, but has insufficient adhesion to a substrate, thermal and chemical stability, and depending on the compound, a hydrosilylation reaction during synthesis may occur. In this case, the raw material was decomposed and the yield was low.
本発明は上記課題を解決を試み、分子中に長鎖のペル
フルオロアルキル基と、スルホンアミド結合を有するシ
ラン化合物は、樹脂や各種無機材料の表面処理材として
優れた効果を達成することを見出した。The present invention has attempted to solve the above problems, and has found that a silane compound having a long-chain perfluoroalkyl group and a sulfonamide bond in the molecule achieves an excellent effect as a surface treatment material for resins and various inorganic materials. .
［発明の構成］ 本発明は、一般式Ｉ （式中、Ａは塩素、臭素、メトキシ基またはエトキシ
基） で表されるＮ−プロピル−Ｎ−（３−シリルプロピル）
ペルフルオロオクチルスルホンアミドを提供する。[Constitution of the Invention] The present invention relates to a compound of the general formula I (Wherein A is chlorine, bromine, methoxy or ethoxy) N-propyl-N- (3-silylpropyl)
A perfluorooctylsulfonamide is provided.
また、本発明は、上記一般式Ｉで示される化合物の製
法であって、構造式II で示されるＮ−アリル−Ｎ−プロピルペルフルオロオク
チルスルホンアミドを一般式III HSiX3 （III） （式中Ｘは塩素または臭素）で表わされるトリハロゲ
ノシランと付加触媒の存在のもとに反応させ、必要なら
ばその生成物をさらにメタノールまたはエタノールと反
応させることとからなる製法を提供する。The present invention also relates to a process for producing a compound represented by the above general formula I, Is reacted with a trihalogenosilane represented by the general formula III HSiX 3 (III) (wherein X is chlorine or bromine) in the presence of an addition catalyst, and N-allyl-N-propylperfluorooctylsulfonamide represented by the following formula: If necessary, further reacting the product with methanol or ethanol.
また本発明は前記の製法であって付加触媒が塩化白金
酸、アゾビスイソブチロニトリル、過酸化ジベンゾイ
ル、オクタカルボニルのコバルト錯体、白金錯体、ロジ
ウム錯体のいずれかである製法を提供する。好ましい付
加触媒は塩化白金酸である。The present invention also provides the above-mentioned production method, wherein the addition catalyst is any one of chloroplatinic acid, azobisisobutyronitrile, dibenzoyl peroxide, a cobalt complex of octacarbonyl, a platinum complex, and a rhodium complex. A preferred addition catalyst is chloroplatinic acid.
また本発明は前記の方法であって、付加生成物とメタ
ノールまたはエタノールと反応を、乾燥気体の吹込み法
かまたは大気圧以下の減圧で実施する製法を提供する。The present invention also provides a process as described above, wherein the reaction of the addition product with methanol or ethanol is carried out by blowing dry gas or under reduced pressure below atmospheric pressure.
また本発明は前記の化合物からなる無機質材料のため
の撥水、撥油、非粘着性向上剤を提供する。The present invention also provides a water-repellent, oil-repellent, and non-tackiness improver for an inorganic material comprising the above compound.
本発明化合物の撥水、撥油性、非粘着性はこのペルフ
ルオロアルキル基によって発揮されるもので、トリハロ
ゲノシリル基、およびトリアルコキシシリル基がそのま
ま無機質材料表面の水酸基と反応し、あるいは予め水と
反応してトリヒドロキシシリル基となった後に無機質材
料表面に存在する水酸基との間で脱水縮合、または水素
結合等を起して結合する。The water-repellent, oil-repellent and non-adhesive properties of the compound of the present invention are exhibited by this perfluoroalkyl group, and the trihalogenosilyl group and trialkoxysilyl group react with the hydroxyl groups on the surface of the inorganic material as they are, or After reacting to form a trihydroxysilyl group, dehydration condensation with a hydroxyl group present on the surface of the inorganic material, or hydrogen bond or the like is caused to occur.
また、スルホンアミド結合は、カルボン酸エステル、
カルボン酸アミド型化合物に比較して熱的、化学的安定
性、およびその合成時におけるヒドロシリル化反応の高
収率をさらには、ペルフルオロアルキル基の配向をもた
らし、撥水、撥油性、非粘着性をより高める効果をもた
らす。Further, the sulfonamide bond is a carboxylic acid ester,
Thermal and chemical stability compared to carboxylic acid amide type compounds, and high yield of hydrosilylation reaction during its synthesis, and furthermore, orientation of perfluoroalkyl group, water repellency, oil repellency, non-stickiness Brings more effect.
さらに、窒素原子を結合しているプロピル基は、溶媒
との相溶性を高める。Further, the propyl group linking the nitrogen atom enhances the compatibility with the solvent.
以上の効果があいまって、一般式Ｉで示される本発明
の化合物は、炭化水素系有機溶媒に任意割合で溶解可能
という高い溶解性と、高い撥水・撥油性とを備えてい
る。In combination with the above effects, the compound of the present invention represented by the general formula I has high solubility, which can be dissolved in a hydrocarbon organic solvent at an arbitrary ratio, and high water / oil repellency.
本発明化合物（一般式Ｉ）の製造方法において、一般
式IIで表わされる化合物は、電解フッ素化法により製造
されるペルフルオロオクチルスルホニルフルオリドに、
Ｎ−プロピルアリルアミンを反応させるかまたは、Ｎ−
プロピルアミンを反応させてＮ−プロピルペルフルオロ
オクチルスルホンアミドを合成した後に、ハロゲン化ア
リルをアルカリの存在下で反応させることによって容易
に合成される。In the method for producing the compound of the present invention (general formula I), the compound represented by the general formula II is converted into perfluorooctylsulfonyl fluoride produced by an electrolytic fluorination method,
Reacting N-propylallylamine or N-
It is easily synthesized by reacting propylamine to synthesize N-propylperfluorooctylsulfonamide and then reacting allyl halide in the presence of an alkali.
一般式IIIで表わされる化合物は、一般式IIで表わさ
れる化合物に対し、１モル当量以上、好ましくは1.3〜
1.5モル当量用いる。一般式IIで表わされる化合物と、
一般式IIIで表わされる化合物の反応は、30℃〜150℃、
好ましくは40℃〜80℃の温度範囲で加熱撹拌することに
よって行なわれる。The compound represented by the general formula III is at least 1 molar equivalent, preferably 1.3 to
Use 1.5 molar equivalents. A compound represented by the general formula II;
The reaction of the compound represented by the general formula III is performed at 30 ° C. to 150 ° C.,
It is preferably carried out by heating and stirring in a temperature range of 40 ° C to 80 ° C.
触媒の使用量は、通常一般式IIで表わされる化合物に
対して１×10-5〜１×10-2重量パーセントでよく、好ま
しくは１×10-4〜５×10-4重量パーセントでよい。The amount of the catalyst used may be generally 1 × 10 −5 to 1 × 10 −2 weight percent, preferably 1 × 10 −4 to 5 × 10 −4 weight percent, based on the compound represented by the general formula II. .
また、一般式Ｉで表わされＡが塩素または臭素である
化合物と、メタノール、エタノールとの反応は、10℃〜
60℃、好ましくは30℃〜40℃の温度範囲で、乾燥気体の
吹込み法かまたは大気圧以下40mmHgまでの減圧下で撹拌
することによって容易に行なわれる。The reaction of a compound represented by the general formula I, wherein A is chlorine or bromine, with methanol or ethanol is carried out at a temperature of 10 ° C.
It is easily carried out at a temperature of 60 ° C., preferably 30 ° C. to 40 ° C., by blowing dry gas or by stirring under reduced pressure of 40 mmHg or less below atmospheric pressure.
乾燥気体は、一般式Ｉで表わされＡが塩素または臭素
である化合物と、メタノール、エタノールと反応しない
ものであり、具体的には、乾燥したN2,He,Ar等があげら
れる。The dry gas is a compound represented by the general formula I wherein A is chlorine or bromine and does not react with methanol or ethanol, and specific examples thereof include dried N 2 , He, Ar and the like.
ここで、乾燥気体の吹込み法は、反応で生ずるハロゲ
ン化水素を除去する効果をもたらし、また大気圧以下で
の減圧もまた同様の効果を持つ。Here, the method of injecting a dry gas has an effect of removing hydrogen halide generated by the reaction, and reducing the pressure below the atmospheric pressure has the same effect.
本発明化合物を基質表面に適用するには、水または有
機溶媒に溶解した溶液とすることが好ましい。In order to apply the compound of the present invention to the substrate surface, it is preferable to use a solution dissolved in water or an organic solvent.
表面上への塗布方法は特に限定されないが、無水また
はアミンまたは酸の水溶液を少量添加した塩素系、フッ
素系炭化水素、あるいはアセトン、テトラヒドロフラ
ン、ヘキサン、各種アルコール等の溶媒に溶解し、吹付
け法、浸漬法など既知の塗布方法により行なわれる。The method of coating on the surface is not particularly limited, but is dissolved in a solvent such as chlorine-based, fluorine-based hydrocarbon, or acetone, tetrahydrofuran, hexane, or various alcohols to which a small amount of an anhydrous or amine or acid aqueous solution is added, and sprayed. This is performed by a known coating method such as a dipping method.
塗布後は、通常は自然乾燥で溶媒を蒸発させて乾燥塗
膜とするが、無水の溶媒を用いた場合は必要に応じて、
アミン、または酸の水溶液による加熱処理を行って基質
表面と強固に接着するように処理される。After application, the solvent is usually evaporated by natural drying to form a dry coating film, but if an anhydrous solvent is used, if necessary,
Heat treatment with an aqueous solution of an amine or an acid is performed so as to firmly adhere to the substrate surface.
［実施例および比較例］ 実施例１ 磁気撹拌装置、温度計、還流器を備えた500ml三ツ口
フラスコに、Ｎ−ｎ−プロピル−Ｎ−ペルフルオロオク
チルスルホンアミド（新秋田化成株式会社製、商品名EF
−111）108.1g（0.200mol）、水酸化カリウム（85％）1
5.4g（0.233mol）、アセトン200mlを入れ、室温でアリ
ルブロミド30.71g（0.254mol）を10分間かけて滴下し、
その後４時間撹拌した。反応混合物を濾過した後、濾液
を100ml程度まで濃縮し、５％塩化アンモニウム水溶液
に注ぎ、有機層を分離、減圧蒸留によってＮ−アリル−
Ｎ−ｎ−プロピルペルフルオロオクチルスルホンアミド
を得た。[Examples and Comparative Examples] Example 1 Nn-propyl-N-perfluorooctylsulfonamide (manufactured by Shin-Akita Chemical Co., Ltd., trade name EF) was placed in a 500 ml three-necked flask equipped with a magnetic stirrer, a thermometer, and a reflux condenser.
−111) 108.1 g (0.200 mol), potassium hydroxide (85%) 1
5.4 g (0.233 mol) and 200 ml of acetone were added, and 30.71 g (0.254 mol) of allyl bromide was added dropwise at room temperature over 10 minutes.
Thereafter, the mixture was stirred for 4 hours. After the reaction mixture was filtered, the filtrate was concentrated to about 100 ml, poured into a 5% aqueous ammonium chloride solution, the organic layer was separated, and N-allyl-
N-n-propylperfluorooctylsulfonamide was obtained.
続いて、磁気撹拌装置、温度計、還流器を備えた100m
l三ツ口フラスコに上記Ｎ−アリル−Ｎ−ｎ−プロピル
ペルフルオロオクチルスルホンアミド96.9g（0.167mo
l）、塩化白金酸六水和物5mg（9.67×10-3mmol）を入
れ、50℃でトリクロロシラン25.3ml（0.250mol）を30分
で滴下した。Subsequently, 100m equipped with a magnetic stirrer, thermometer and reflux
l In a three-necked flask, 96.9 g (0.167 mole) of the above N-allyl-NN-propylperfluorooctylsulfonamide
l), 5 mg (9.67 × 10 −3 mmol) of chloroplatinic acid hexahydrate was added, and 25.3 ml (0.250 mol) of trichlorosilane was added dropwise at 50 ° C. in 30 minutes.
滴下終了後２時間撹拌した後、減圧蒸留によりＮ−ｎ
−プロピル−Ｎ−（３−（トリクロロシリル）プロピ
ル）ペルフルオロオクチルスルホンアミド110.3g（0.15
4mol）を得た。収率92.3％、沸点153℃/2.0mmHg。After stirring for 2 hours after the completion of the dropwise addition, N-n was distilled off under reduced pressure.
-Propyl-N- (3- (trichlorosilyl) propyl) perfluorooctylsulfonamide 110.3 g (0.15
4 mol). Yield 92.3%, boiling point 153 ° C / 2.0mmHg.
下記のNMR分析、DI−MS分析、IR分析の結果より生成
物が であることを確認した。なお、NMR分析、DI−MS分析、I
R分析の測定条件等は次の通りである。From the results of the following NMR analysis, DI-MS analysis and IR analysis, Was confirmed. In addition, NMR analysis, DI-MS analysis, I
The measurement conditions and the like for the R analysis are as follows.
1HNMR（測定条件、溶媒:F−113、内部標準ベンゼン）
δ1.30（t,3H,H−ａ）、δ1.6〜2.5（m,6H,H−b,d,
e）、δ3.5〜4.0（m,4H,H−c,f） DI−MS（測定条件：イオン化電圧:70eV）（m/e、相対
強度、）、554（60.5％、M+−+CH2CH2SiCl3）133（15.0
％、+SiCl3）69（100％、+CF3） IR（neat,cm-1）3350,2950,1390,1260〜1130 実施例２ 機械撹拌装置、トラップおよびアスピレータを接続し
た還流器、温度計を備えた300ml4ツ口フラスコにＮ−
［３−（トリクロロシリル）プロピル］−Ｎ−ｎ−プロ
ピルペルフルオロオクチルスルホンアミド48.1g（0.067
1mol）を入れ、減圧下15〜20℃でメタノール50mlを２時
間で滴下した。滴下終了後、減圧蒸留により、Ｎ−ｎ−
プロピル−Ｎ−［３−（トリメトキシシリル）プロピ
ル］ペルフルオロオクチルスルホンアミド40.1g（0.057
mol）を得た。収率85.0％、沸点134℃/0.25mmHgであっ
た。 1 HNMR (measurement conditions, solvent: F-113, internal standard benzene)
δ 1.30 (t, 3H, Ha), δ 1.6 to 2.5 (m, 6H, H-b, d,
e), δ3.5~4.0 (m, 4H , H-c, f) DI-MS ( Measurement conditions: Ionization voltage: 70eV) (m / e, relative intensity,), 554 (60.5%, M + - + CH 2 CH 2 SiCl 3 ) 133 (15.0
%, + SiCl 3 ) 69 (100%, + CF 3 ) IR (neat, cm −1 ) 3350, 2950, 1390, 1260 to 1130 Example 2 Refluxer, thermometer connected with mechanical stirring device, trap and aspirator Into a 300 ml four-necked flask equipped with
[3- (Trichlorosilyl) propyl] -Nn-propylperfluorooctylsulfonamide 48.1 g (0.067
1 mol), and 50 ml of methanol was added dropwise at 15 to 20 ° C under reduced pressure over 2 hours. After completion of the dropping, Nn-
Propyl-N- [3- (trimethoxysilyl) propyl] perfluorooctylsulfonamide 40.1 g (0.057
mol). The yield was 85.0% and the boiling point was 134 ° C./0.25 mmHg.
下記のNMR分析、DI−MS分析、IR分析の結果より、生
成物が であることを確認した。なお、NMR分析、DI−MS分析、I
R分析の測定条件等は次の通りである。From the results of the following NMR analysis, DI-MS analysis, and IR analysis, Was confirmed. In addition, NMR analysis, DI-MS analysis, I
The measurement conditions and the like for the R analysis are as follows.
1HNMR（測定条件、溶媒:F−113、内部標準ベンゼン）
δ0.9（t,2H,H−ｅ）、δ1.25（t,3H,H−ｃ）、δ1.6〜
2.5（m,6H,H−b,f）、δ3.5〜4.0（m,4H,H−c,g）、δ
3.8（s,9H,H−ｄ） DI−MS（測定条件：イオン化電圧:70eV）（m/e、相対
強度、）、672（22.6％、M+−+OCH3） 554（1.8％、M+−+CH2CH2Si（OCH3）３）、121（100
％、+Si（OCH3）３）、69（23％、+CF3） IR（neat,cm-1）3350,2950,1390,1260〜11301090 実施例３ 磁気撹拌装置、トラップを接続した還流器、温度計、
窒素吹込み中を備えた300ml4ツ口フラスコに、Ｎ−［３
−（トリクロロシリル）プロピル］−Ｎ−ｎ−プロピル
ペルフルオロオクチルスルホンアミド50.2g（0.070mo
l）を入れ、フラスコ底部から10〜15℃で乾燥N2を激し
く吹込みながら、メタノール50mlを５時間で滴下した。 1 HNMR (measurement conditions, solvent: F-113, internal standard benzene)
δ 0.9 (t, 2H, He), δ 1.25 (t, 3H, Hc), δ 1.6 to
2.5 (m, 6H, H-b, f), δ 3.5 to 4.0 (m, 4H, H-c, g), δ
3.8 (s, 9H, Hd) DI-MS (measurement condition: ionization voltage: 70 eV) (m / e, relative intensity), 672 (22.6%, M + − + OCH 3 ) 554 (1.8%, M + − + CH 2 CH 2 Si (OCH 3 ) 3 ), 121 (100
%, + Si (OCH 3 ) 3 ), 69 (23%, + CF 3 ) IR (neat, cm −1 ) 3350, 2950, 1390, 1260 to 11301090 Example 3 Refluxer with magnetic stirrer and trap connected ,thermometer,
N- [3] was added to a 300 ml four-necked flask equipped with nitrogen blowing.
-(Trichlorosilyl) propyl] -Nn-propylperfluorooctylsulfonamide 50.2 g (0.070mo
l) was added thereto, and 50 ml of methanol was added dropwise over 5 hours while vigorously blowing dry N 2 at 10 to 15 ° C. from the bottom of the flask.
滴下終了後、そのままの状態で５時間撹拌した後に、
減圧蒸留により、Ｎ−ｎ−プロピル−Ｎ−［３−（トリ
メトキシシリル）プロピル］ペルフルオロオクチルスル
ホンアミド38.2g（0.054mol）を得た。収率は77％であ
った。After completion of the dropwise addition, the mixture was stirred for 5 hours in that state.
By vacuum distillation, 38.2 g (0.054 mol) of Nn-propyl-N- [3- (trimethoxysilyl) propyl] perfluorooctylsulfonamide was obtained. The yield was 77%.
実施例４ 25mm×75mmの並通板ガラスを エタノール100g、10％希塩酸水溶液0.5g、混合溶液中に
30秒間浸した後、室温で乾燥した。Example 4 25 mm × 75 mm side-by-side plate glass 100 g of ethanol, 0.5 g of 10% dilute hydrochloric acid aqueous solution, in a mixed solution
After soaking for 30 seconds, it was dried at room temperature.
このようにして処理されたガラス板の表面の接触角を
測定すると、水で110゜、流動パラフィンで75゜であっ
た。The contact angle of the surface of the glass plate thus treated was 110 ° for water and 75 ° for liquid paraffin.
比較例１ 本発明の含フッ素シラン化合物の代わりに、CH3Si（O
CH3）３を1.0gを用いた以外は、実施例４と同一の処理
を行った。表面接触角は水で35゜、流動パラフィンで37
゜であった。Comparative Example 1 Instead of the fluorinated silane compound of the present invention, CH 3 Si (O
The same treatment as in Example 4 was performed, except that 1.0 g of CH 3 ) 3 was used. Surface contact angle 35 ° for water, 37 for liquid paraffin
Was ゜.
比較例２ 本発明の含フッ素シラン化合物の代わりに、NH2CH2CH
2NHCH2CH2CH2CH2Si（OCH3）３を1.0g用いた以外は実施
例４と同一の処理を行った。Comparative Example 2 Instead of the fluorine-containing silane compound of the present invention, NH 2 CH 2 CH
The same treatment as in Example 4 was performed except that 1.0 g of 2 NHCH 2 CH 2 CH 2 CH 2 Si (OCH 3 ) 3 was used.
表面接触角は水で27゜、流動パラフィンで34゜であっ
た。The surface contact angle was 27 ° for water and 34 ° for liquid paraffin.
比較例３ 下記一般式で示される、実施例２で製造した本発明の
化合物（一般式ＩでＡがメトキシ基である化合物）に類
似する比較用化合物の有機溶媒に対する溶解性を調べ
た。Comparative Example 3 The solubility of a comparative compound represented by the following general formula similar to the compound of the present invention (the compound of the general formula I in which A is a methoxy group) prepared in Example 2 in organic solvent was examined.
C8F17SO2NRCH2CH2CH2Si（OCH3）３ （式中、ＲはＨまたはエチル基） ＲがＨである化合物はｎ−ヘキサンに不溶であり、Ｒ
がエチル基である化合物はｎ−ヘキサン中の溶解度が約
５％であった。C 8 F 17 SO 2 NRCH 2 CH 2 CH 2 Si (OCH 3 ) 3 (where R is H or an ethyl group) A compound in which R is H is insoluble in n-hexane and R
Is a ethyl group, the solubility in n-hexane was about 5%.
比較例４ 比較例３に示す一般式においてＲがブチル基およびヘ
キシル基である比較用化合物の撥油性を実施例４と同様
に調べた。流動パラフィンとの表面接触角は、Ｒがブチ
ル基である場合で約50゜、Ｒがヘキシル基である場合に
は40゜以下であった。Comparative Example 4 The oil repellency of a comparative compound in which R was a butyl group or a hexyl group in the general formula shown in Comparative Example 3 was examined in the same manner as in Example 4. The surface contact angle with liquid paraffin was about 50 ° when R was a butyl group and 40 ° or less when R was a hexyl group.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｋ 3/18 １０４ Ｃ０９Ｋ 3/18 １０４ // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 金子 みどり 埼玉県大宮市北袋町１―297 三菱金属 株式会社中央研究所内 (56)参考文献 特開 昭61−296063（ＪＰ，Ａ) 特開 昭52−47030（ＪＰ，Ａ) 特開 昭61−174392（ＪＰ，Ａ) 特開 昭60−190727（ＪＰ，Ａ) 特開 昭47−18835（ＪＰ，Ａ) 特公 昭47−22803（ＪＰ，Ｂ１) 米国特許3012006（ＵＳ，Ａ) 米国特許3993443（ＵＳ，Ａ)──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 Identification number Agency reference number FI Technical indication location C09K 3/18 104 C09K 3/18 104 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Midori Kaneko 1-297 Kitabukuro-cho, Omiya City, Saitama Prefecture Mitsubishi Metal Corporation Central Research Laboratory (56) Reference JP-A-61-296063 (JP, A) JP-A-52-47030 (JP, A) JP-A Sho 61-174392 (JP, A) JP-A-60-190727 (JP, A) JP-A-47-18835 (JP, A) JP-B-47-22803 (JP, B1) US Patent 3012006 (US, A) US Patent 3993443 (US, A)
Claims (5)
基） で表されるＮ−プロピル−Ｎ−（３−シリルプロピル）
ペルフルオロオクチルスルホンアミド。1. A compound of the general formula I (Wherein A is chlorine, bromine, methoxy or ethoxy) N-propyl-N- (3-silylpropyl)
Perfluorooctylsulfonamide.
−シリルプロピル）ペルフルオロオクチルスルホンアミ
ド（式中、Ａは塩素または臭素）の製法であって、構造
式II で示されるＮ−アリル−Ｎ−プロピルペルフルオロオク
チルスルホンアミドと、一般式III HSiX3 （III） （式中、Ｘは塩素または臭素）で表されるトリハロゲノ
シランとを付加触媒の存在下で反応させることからなる
製法。2. The N-propyl-N- (3) according to claim 1,
-Silylpropyl) perfluorooctylsulfonamide (where A is chlorine or bromine), comprising a compound of the formula II Reaction of N-allyl-N-propylperfluorooctylsulfonamide represented by the formula with a trihalogenosilane represented by the general formula III HSiX 3 (III) (where X is chlorine or bromine) in the presence of an addition catalyst A production method consisting of letting
−シリルプロピル）ペルフルオロオクチルスルホンアミ
ド（式中、Ａはメトキシ基またはエトキシ基）の製法で
あって、構造式II で示されるＮ−アリル−Ｎ−プロピルペルフルオロオク
チルスルホンアミドと、一般式III HSiX3 （III） （式中、Ｘは塩素または臭素）で表されるトリハロゲノ
シランとを付加触媒の存在下で反応させ、その生成物を
さらにメタノールまたはエタノールと反応させることか
らなる製法。3. The N-propyl-N- (3) according to claim 1,
-Silylpropyl) perfluorooctylsulfonamide (wherein A is a methoxy or ethoxy group), wherein the structural formula II Reaction of N-allyl-N-propylperfluorooctylsulfonamide represented by the formula with a trihalogenosilane represented by the general formula III HSiX 3 (III) (where X is chlorine or bromine) in the presence of an addition catalyst And reacting the product with methanol or ethanol.
物とメタノールまたはエタノールとの反応を、乾燥気体
の吹込み法かまたは大気圧以下の減圧で実施する製法。4. The process according to claim 3, wherein the reaction between the addition product and methanol or ethanol is carried out by blowing dry gas or under reduced pressure below atmospheric pressure.
の撥水、撥油、非粘着性向上剤。5. An agent for improving water repellency, oil repellency and non-adhesion of an inorganic material comprising the compound according to claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63101463A JP2605340B2 (en) | 1988-04-26 | 1988-04-26 | Fluorine-containing silane compound and method for producing the same |
| GB8909086A GB2218097A (en) | 1988-04-26 | 1989-04-21 | Perfluoroalkylsulphonamidoalkyl silanes; surface treatment agents |
| DE3913485A DE3913485A1 (en) | 1988-04-26 | 1989-04-24 | FLUOROUS SILVER COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| FR8905409A FR2630443A1 (en) | 1988-04-26 | 1989-04-24 | NOVEL FLUORINATED SILANES, PROCESSES FOR PREPARING SAME, WATER-REPELLENT AND WATER-REPELLENT AGENT CONTAINING THEM, AND VARIOUS MATERIALS TREATED OR CONTAINING AN INGREDIENT TREATED WITH THEM |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63101463A JP2605340B2 (en) | 1988-04-26 | 1988-04-26 | Fluorine-containing silane compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01275586A JPH01275586A (en) | 1989-11-06 |
| JP2605340B2 true JP2605340B2 (en) | 1997-04-30 |
Family
ID=14301403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63101463A Expired - Fee Related JP2605340B2 (en) | 1988-04-26 | 1988-04-26 | Fluorine-containing silane compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2605340B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10321851A1 (en) * | 2003-05-15 | 2004-12-02 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Use of particles hydrophobized with fluorosilanes for the production of self-cleaning surfaces with lipophobic, oleophobic, lactophobic and hydrophobic properties |
| US7495118B2 (en) * | 2004-12-30 | 2009-02-24 | 3M Innovative Properties Company | Compositions containing C4-swallow tail silanes |
| KR101384457B1 (en) * | 2011-08-04 | 2014-04-14 | 주식회사 엘지화학 | Silane-based compounds and photosensitive resin composition comprising the same |
| JP7175726B2 (en) * | 2018-11-28 | 2022-11-21 | 三菱マテリアル電子化成株式会社 | Silane coupling agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3012006A (en) | 1958-04-24 | 1961-12-05 | Dow Corning | Fluorinated alkyl silanes and their use |
| US3993443A (en) | 1974-06-25 | 1976-11-23 | Minnesota Mining And Manufacturing Company | Noxious vapor suppression using glass microbubbles with a fluorosilane or polyfluorosiloxane film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5247030A (en) * | 1975-10-13 | 1977-04-14 | Dainippon Ink & Chem Inc | Thermosetting resin composition |
| JPS60190727A (en) * | 1984-03-09 | 1985-09-28 | Daikin Ind Ltd | Fluorine-containing organic silane compound, preparation and use thereof |
| JPS61174392A (en) * | 1985-01-28 | 1986-08-06 | Pentel Kk | Corrosion resistant industrial material |
| JPH0627263B2 (en) * | 1985-06-26 | 1994-04-13 | 大日本インキ化学工業株式会社 | Polyphenylene sulfide resin composition |
-
1988
- 1988-04-26 JP JP63101463A patent/JP2605340B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3012006A (en) | 1958-04-24 | 1961-12-05 | Dow Corning | Fluorinated alkyl silanes and their use |
| US3993443A (en) | 1974-06-25 | 1976-11-23 | Minnesota Mining And Manufacturing Company | Noxious vapor suppression using glass microbubbles with a fluorosilane or polyfluorosiloxane film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01275586A (en) | 1989-11-06 |
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