JP2011184304A - Silane coupling agent and method for producing the same - Google Patents
Silane coupling agent and method for producing the same Download PDFInfo
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 13
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- DOQQTKLDEQSKIE-UHFFFAOYSA-N silver;isocyanate Chemical compound [Ag+].[N-]=C=O DOQQTKLDEQSKIE-UHFFFAOYSA-N 0.000 claims description 9
- -1 perfluoroalkyl iodide Chemical compound 0.000 claims description 8
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 claims description 7
- 239000006082 mold release agent Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 150000004756 silanes Chemical class 0.000 claims description 7
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 7
- 230000003373 anti-fouling effect Effects 0.000 abstract description 6
- 239000012298 atmosphere Substances 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000007787 solid Substances 0.000 description 24
- 239000011521 glass Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000001819 mass spectrum Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000003708 ampul Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 235000002597 Solanum melongena Nutrition 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 244000061458 Solanum melongena Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WBYCUETVRCXUPE-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-pentacosafluoro-12-iodododecane 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)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I WBYCUETVRCXUPE-UHFFFAOYSA-N 0.000 description 1
- UDWBMXSQHOHKOI-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-henicosafluoro-10-iododecane 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)C(F)(F)C(F)(F)I UDWBMXSQHOHKOI-UHFFFAOYSA-N 0.000 description 1
- KWXGJTSJUKTDQU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-8-iodooctane 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)I KWXGJTSJUKTDQU-UHFFFAOYSA-N 0.000 description 1
- 0 Cc(cc1)ccc1-c1ccc(*)cc1 Chemical compound Cc(cc1)ccc1-c1ccc(*)cc1 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、新規なシランカップリング剤及びその製造方法に関する。 The present invention relates to a novel silane coupling agent and a method for producing the same.
近年、特にシランカップリング剤を離型剤として用い、母型に形成された微細パターンを再現性・解像性良く被転写部材に転写する技術の研究が盛んに行われている。
転写は、母型の微細パターン上に形成した離型剤層上に被転写部材を覆った後、離型剤層から被転写部材を剥離して行われるが、金属を真空蒸着によって、あるいは樹脂を熱硬化させて被転写部材として離型剤層上に設ける場合、離型剤としては高温耐熱性であることが要求される。しかしながら、従来から知られている離型剤にはこの要求に応えられるものがなかった。
In recent years, research has been actively conducted on techniques for transferring a fine pattern formed on a matrix to a member to be transferred with good reproducibility and resolution, particularly using a silane coupling agent as a release agent.
The transfer is performed by covering the member to be transferred on the release agent layer formed on the fine pattern of the mother mold and then peeling the member to be transferred from the release agent layer. Is provided on the release agent layer as a member to be transferred, the release agent is required to have high temperature heat resistance. However, none of the conventionally known release agents can meet this requirement.
そこで、本発明者等は、先に、特に耐熱性及び離型性の点に優れた下記一般式（Ａ）で表されるビフェニルアルキル基を有するシランカップリング剤を開発した（特許文献１参照）。 Accordingly, the present inventors have previously developed a silane coupling agent having a biphenylalkyl group represented by the following general formula (A), which is particularly excellent in heat resistance and releasability (see Patent Document 1). ).
上記一般式（Ａ）で表されるシランカップリング剤を用いると、上述のような真空蒸着あるいは熱硬化のような高温プロセスによって被転写部材を形成する場合でも、１μｍ未満の高さでアスペクト比が２以上あるような超微細な突起群を含むような母型のパターンを、再現性・解像性良く被転写部材に転写することができる。 When the silane coupling agent represented by the above general formula (A) is used, even when the member to be transferred is formed by a high temperature process such as vacuum vapor deposition or thermosetting as described above, the aspect ratio is less than 1 μm. Can be transferred to the transfer member with good reproducibility and resolution.
ところで、離型剤層を形成する際には、母型表面にシランカップリング剤を含む液を塗布した後に、シランカップリング剤を強固に固定させるように、加熱処理等が行われる。
しかしながら、例えば、微細パターン表面に離型剤としてシランカップリング剤層が形成された母型を金型として繰り返し使用して、パターンが転写された被転写部材を数多く作製していくと、離型剤が徐々に微細パターン表面から剥離してしまうことがある。
そこで、このような問題が発生しないような、母型の基質との結合力が高いシランカップリング剤の出現が期待されている。
By the way, when forming the release agent layer, after applying a liquid containing a silane coupling agent to the surface of the matrix, heat treatment or the like is performed so that the silane coupling agent is firmly fixed.
However, for example, when a mold having a silane coupling agent layer formed as a mold release agent on the surface of a fine pattern is repeatedly used as a mold, a large number of members to which a pattern is transferred are produced. The agent may gradually peel from the surface of the fine pattern.
Therefore, the appearance of a silane coupling agent that has a high binding force with the matrix substrate so that such a problem does not occur is expected.
本発明は、上記事情に鑑みてなされたものであり、その第一の課題は基質との結合力の高いシランカップリング剤を提供することにある。さらに第二の課題は耐熱性、離型性、及び防汚性の良好な、特に３５０℃以上の温度においても、これら化合物による改質表面接触角の低下が見られない等の優れた物性を有するシランカップリング剤を提供することにある。 The present invention has been made in view of the above circumstances, and a first object thereof is to provide a silane coupling agent having a high binding force with a substrate. Further, the second problem is excellent physical properties such as good heat resistance, releasability, and antifouling properties, such as no deterioration of the contact angle of the modified surface due to these compounds even at a temperature of 350 ° C. or higher. It is in providing the silane coupling agent which has.
本発明者等は、特定の一般式で表されるビフェニルアルキル基を有するシランカップリング剤によれば上記課題を解決できることを見出し、本発明を完成させた。より具体的には、本発明は下記のとおりである。 The present inventors have found that the above problems can be solved by a silane coupling agent having a biphenylalkyl group represented by a specific general formula, and have completed the present invention. More specifically, the present invention is as follows.
［１］ 下記一般式（１）で表されるビフェニルアルキル基を有するシランカップリング剤。
［２］ 下記一般式（２）
で表されるペルフルオロアルキルヨージドと極性溶媒中で、銅ブロンズ粉触媒を用いて反応させて、下記一般式（４）
次いで、該４−ペルフルオロアルキル−４’−ブロモビフェニルを、下記式（５）
で表されるアルケニルブロミドと極性溶媒中で、ヨウ化銅触媒を用いて反応させて、下記一般式（６）
次いで、該４−ペルフルオロアルキル−４’−アルケニルビフェニルを、下記式（７）
で表されるトリハロゲン化シランと有機溶媒中で、塩化白金酸触媒を用いて反応させて、下記一般式（８）
で表される（４−ペルフルオロアルキルビフェニル）アルキルトリハロゲン化シランを得る、シランカップリング剤の製造方法。
[2] The following general formula (2)
Is reacted with a perfluoroalkyl iodide represented by the following formula (4) using a copper bronze powder catalyst:
Subsequently, the 4-perfluoroalkyl-4′-bromobiphenyl is represented by the following formula (5):
Is reacted with a copper iodide catalyst in a polar solvent with a alkenyl bromide represented by the following general formula (6):
Subsequently, the 4-perfluoroalkyl-4′-alkenylbiphenyl is represented by the following formula (7):
Is reacted with a trihalogenated silane represented by the formula (8) in an organic solvent using a chloroplatinic acid catalyst.
The manufacturing method of the silane coupling agent which obtains (4-perfluoroalkyl biphenyl) alkyl trihalogenated silane represented by these.
［３］ 下記一般式（８）
で表される（４−ペルフルオロアルキルビフェニル）アルキルトリハロゲン化シランを有機溶媒中で、シアン酸銀と反応させて、下記式（９）
(4-perfluoroalkylbiphenyl) alkyltrihalogenated silane represented by the following formula (9) is reacted with silver cyanate in an organic solvent.
［４］ 下記一般式（１）で表されるシランカップリング剤と溶剤とを含む離型剤。
本発明のシランカップリング剤は、基質との結合力が高く、しかも３５０℃以上の雰囲気に４時間以上曝露しても、これら化合物による改質表面の接触角の低下が見られないというほどの優れた耐熱性、離型性、及び防汚性を有するものであり、格別の効果と有用性を有する。 The silane coupling agent of the present invention has a high binding force to the substrate, and even when exposed to an atmosphere of 350 ° C. or higher for 4 hours or longer, the contact angle of the modified surface due to these compounds is not reduced. It has excellent heat resistance, releasability, and antifouling properties, and has exceptional effects and usefulness.
本発明のシランカップリング剤は下記一般式（１）で表されるものである。 The silane coupling agent of the present invention is represented by the following general formula (1).
上記一般式（１）で表されるシランカップリング剤のうち、Ｘがハロゲン原子であるものは、下記のようにして製造することができる。 Among the silane coupling agents represented by the general formula (1), those in which X is a halogen atom can be produced as follows.
すなわち、下記一般式（２）
で表されるペルフルオロアルキルヨージドと極性溶媒中で、銅ブロンズ粉触媒を用いて反応させて、下記一般式（４）
次いで、該４−ペルフルオロアルキル−４’−ブロモビフェニルを、下記式（５）
で表されるアルケニルブロミドと極性溶媒中で、ヨウ化銅触媒を用いて反応させて、下記一般式（６）
次いで、該４−ペルフルオロアルキル−４’−アルケニルビフェニルを、下記式（７）
で表されるトリハロゲン化シランと有機溶媒中で、塩化白金酸触媒を用いて反応させることにより、下記一般式（８）
で表される本発明の（４−ペルフルオロアルキルビフェニル）アルキルトリハロゲン化シランを得ることができる。
That is, the following general formula (2)
Is reacted with a perfluoroalkyl iodide represented by the following formula (4) using a copper bronze powder catalyst:
Subsequently, the 4-perfluoroalkyl-4′-bromobiphenyl is represented by the following formula (5):
Is reacted with a copper iodide catalyst in a polar solvent with a alkenyl bromide represented by the following general formula (6):
Subsequently, the 4-perfluoroalkyl-4′-alkenylbiphenyl is represented by the following formula (7):
In the organic solvent with a trihalogenated silane represented by the following general formula (8)
The (4-perfluoroalkylbiphenyl) alkyltrihalogenated silane of the present invention represented by
また、上記一般式（１）で表されるシランカップリング剤のうち、Ｘがイソシアナト基であるものは、下記のようにして製造することができる。 Moreover, among the silane coupling agents represented by the general formula (1), those in which X is an isocyanato group can be produced as follows.
すなわち、上記（４−ペルフルオロアルキルビフェニル）アルキルトリハロゲン化シランを有機溶媒中で、シアン酸銀と反応させることにより、下記式（９）
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.
［実施例１］
Ｆ（ＣＦ２）８（Ｃ６Ｈ４）２ＣＨ２ＣＨ２ＣＨ２ＳｉＣｌ３［８Ｆ２Ｐ３Ｓ３Ｃ］の合成
[Example 1]
Synthesis of F (CF 2 ) 8 (C 6 H 4 ) 2 CH 2 CH 2 CH 2 SiCl 3 [8F2P3S3C]
・Ｆ（ＣＦ２）８（Ｃ６Ｈ４）２Ｂｒ［８Ｆ２ＰＢ］の合成
５００ｍｌナス型フラスコを窒素雰囲気に置換し、銅ブロンズ粉６３．６ｇ（１．０ｍｏｌ）、４，４’−ジブロモビフェニル６２．４ｇ（２００ｍｍｏｌ）、ペルフルオロオクチルヨージド１１５ｇ（２１０ｍｍｏｌ）、溶媒としてジメチルスルホキシド（ＤＭＳＯ）３００ｍｌを加え、１４０℃で４０時間加熱撹拌した。溶液を室温まで冷却し、吸引濾過により過剰の銅粉と白色固体（粗製８Ｆ２ＰＢ）とを濾別し、ＤＭＳＯで洗浄した。続いて酢酸エチルを溶媒に用い、銅粉と白色固体の混合物とをソックスレー抽出し、粗製８Ｆ２ＰＢを得た。抽出液を飽和食塩水で洗浄し、さらに抽出液を硫酸マグネシウムで脱水し、酢酸エチルを減圧除去した。残留物を減圧蒸留して、留出物を得た。
得られた留出物についてＭａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）６５１により、８Ｆ２ＰＢであると同定した。ＮＭＲ、ＩＲ、Ｍａｓｓの各スペクトルを図１、図２、図３に示す。
The 500 ml eggplant type flask was replaced with a nitrogen atmosphere, copper bronze powder 63.6 g (1.0 mol), 4,4′-dibromobiphenyl 62.4 g (200 mmol), perfluorooctyl iodide 115 g (210 mmol), dimethyl sulfoxide as a solvent (DMSO) 300 ml was added, and the mixture was heated and stirred at 140 ° C. for 40 hours. The solution was cooled to room temperature, excess copper powder and white solid (crude 8F2PB) were filtered off by suction filtration and washed with DMSO. Subsequently, using ethyl acetate as a solvent, a mixture of copper powder and white solid was subjected to Soxhlet extraction to obtain crude 8F2PB. The extract was washed with saturated brine, and the extract was dehydrated with magnesium sulfate, and ethyl acetate was removed under reduced pressure. The residue was distilled under reduced pressure to obtain a distillate.
As a result of analyzing a Mass spectrum for the obtained distillate, it was identified as 8F2PB by m / z (molecular weight) 651. Each spectrum of NMR, IR, and Mass is shown in FIG. 1, FIG. 2, and FIG.
収量 ６８．０ｇ（１０４ｍｍｏｌ）
収率 ５２％
沸点 １３０−１３５℃／３０Ｐａ
性状 白色固体
Yield 68.0 g (104 mmol)
Yield 52%
Boiling point 130-135 ° C / 30Pa
Property White solid
・Ｆ（ＣＦ２）８（Ｃ６Ｈ４）２ＣＨ２ＣＨ＝ＣＨ２［８Ｆ２ＰＡ］の合成
１Ｌナス型フラスコを窒素置換し、氷冷下に冷却した後、２．７６Ｍ ｎ−ブチルリチウム ヘキサン溶液３２．６ｍｌ（９０．０ｍｍｏｌ）を加え、続いて０．７７Ｍ ｉ−プロピルマグネシウムブロミド／ＴＨＦ溶液５８．４ｍｌ（４５．０ｍｍｏｌ）を加え、氷冷下で１時間撹拌した。その後、７５０ｍｌのジエチルエーテルに溶解させた８Ｆ２ＰＢ １９．５ｇｇ（３０．０ｍｍｏｌ）を滴下し、氷冷下で１時間撹拌した。触媒としてヨウ化銅２．０ｇ（１０．５ｍｍｏｌ）を加えた後、アリルブロミド１８．２ｇ（１５０ｍｍｏｌ）を滴下し、室温で６７時間撹拌後、飽和塩化アンモニウム水溶液を沈殿が生じなくなるまで加え、反応を止めた。反応溶液を酢酸エチルで抽出し、有機層を硫酸マグネシウムで脱水後、溶媒を減圧留去した。得られた黄色固体を減圧蒸留し、さらにヘキサンを展開溶剤としてシリカゲルカラムクトマトグラフィー（ワコーゲルＣ−３００）により精製した。
Ｍａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）６１２により、８Ｆ２ＰＡであると同定した。ＮＭＲ、ＩＲ、Ｍａｓｓの各スペクトルを図４、図５、図６に示す。
The 1 L eggplant-shaped flask was purged with nitrogen and cooled under ice cooling, followed by addition of 32.6 ml (90.0 mmol) of a 2.76 M n-butyllithium hexane solution, followed by a 0.77 M i-propylmagnesium bromide / THF solution. 58.4 ml (45.0 mmol) was added, and the mixture was stirred for 1 hour under ice cooling. Thereafter, 19.5 mg (30.0 mmol) of 8F2PB dissolved in 750 ml of diethyl ether was added dropwise, and the mixture was stirred for 1 hour under ice cooling. After adding 2.0 g (10.5 mmol) of copper iodide as a catalyst, 18.2 g (150 mmol) of allyl bromide was dropped, and after stirring at room temperature for 67 hours, a saturated aqueous solution of ammonium chloride was added until no precipitation occurred. Stopped. The reaction solution was extracted with ethyl acetate, the organic layer was dehydrated with magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained yellow solid was distilled under reduced pressure, and further purified by silica gel column chromatography (Wakogel C-300) using hexane as a developing solvent.
As a result of analyzing the mass spectrum, it was identified as 8F2PA by m / z (molecular weight) 612. Each spectrum of NMR, IR, and Mass is shown in FIG. 4, FIG. 5, and FIG.
収量 １４．７ｇ（２４．０ｍｍｏｌ）
収率 ８０％
沸点 １３０−１３５℃／２０Ｐａ
性状 白色固体
Yield 14.7 g (24.0 mmol)
Boiling point 130-135 ° C / 20Pa
Property White solid
・Ｆ（ＣＦ２）８（Ｃ６Ｈ４）２ＣＨ２ＣＨ２ＣＨ２ＳｉＣｌ３［８Ｆ２Ｐ３Ｓ３Ｃ］の合成
１００ｍｌ肉厚ガラスアンプル管に撹拌子を入れ、ここに８Ｆ２ＰＡ ２．００ｇ（３．２７ｍｍｏｌ）、ＴＨＦ１０ｍｌを採取し、窒素雰囲気に置換し、外部を液体窒素で冷却し、トリクロロシラン１．０ｇ（８．２ｍｍｏｌ）、触媒の０．１Ｍ Ｈ２ＰｔＣｌ６／ＴＨＦ溶液０．１ｍｌ（０．０１ｍｍｏｌ）を採取した。アンプル管内部の試薬類を完全に固化させた後、真空ポンプを用いて４０Ｐａに減圧し、その状態で酸素バーナーにてガラスアンプル管を溶封した。これを室温に戻した後、８０℃で２時間、さらに１００℃で２０時間撹拌した。放冷後開管し、生じた黒色粉末状沈殿（Ｐｔ）を濾別除去した。濾液中からＴＨＦ、トリメクロロシランを減圧留去した。
得られた化合物についてＭａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）７４７により、８Ｆ２Ｐ３Ｓ３Ｃであると同定した。また、ＮＭＲスペクトルをとったところ、実施例３の１０Ｆ２Ｐ３Ｓ３Ｃのものとほぼ同じであった。
A stirrer was placed in a 100 ml thick glass ampule tube, and 2.00 g (3.27 mmol) of 8F2PA and 10 ml of THF were collected therein, and the atmosphere was replaced with a nitrogen atmosphere. The outside was cooled with liquid nitrogen, and 1.0 g of trichlorosilane (8 g 0.2 mmol), 0.1 ml (0.01 mmol) of 0.1 M H 2 PtCl 6 / THF solution of the catalyst was collected. After the reagents in the ampule tube were completely solidified, the pressure was reduced to 40 Pa using a vacuum pump, and in that state, the glass ampule tube was sealed with an oxygen burner. After returning to room temperature, the mixture was stirred at 80 ° C. for 2 hours and further at 100 ° C. for 20 hours. After standing to cool, the tube was opened, and the resulting black powdery precipitate (Pt) was removed by filtration. THF and trimechlorosilane were distilled off from the filtrate under reduced pressure.
As a result of analyzing a mass spectrum for the obtained compound, it was identified as 8F2P3S3C by m / z (molecular weight) 747. Moreover, when the NMR spectrum was taken, it was substantially the same as that of 10F2P3S3C of Example 3.
収量 ２．３２ｇ
収率 ９５％
性状 白色固体
Yield 2.32g
Property White solid
［実施例２］
Ｆ（ＣＦ２）８（Ｃ６Ｈ４）２ＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＮＣＯ）３［８Ｆ２Ｐ３Ｓ３Ｉ］の合成
Synthesis of F (CF 2 ) 8 (C 6 H 4 ) 2 CH 2 CH 2 CH 2 Si (NCO) 3 [8F2P3S3I]
実施例１で得られた８Ｆ２Ｐ３Ｓ３Ｃ ２．０ｇ（２．７ｍｍｏｌ）を１００ｍｌナスフラスコに取り、ＴＨＦ２０ｍｌに溶解し、シアン酸銀２．００ｇ（１３．３ｍｍｏｌ）を加えて沸点で撹拌し、加熱還流操作を５時間行った。室温まで冷却し、生じた塩化銀、未反応のシアン酸銀を濾別除去した。濾液中の揮発成分を減圧除去した。
Ｍａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）７６７により、８Ｆ２Ｐ３Ｓ３Ｉであると同定した。また、ＮＭＲスペクトルをとったところ、実施例４の１０Ｆ２Ｐ３Ｓ３Ｉのものとほぼ同じであった。
Take 8F2P3S3C (2.0 g, 2.7 mmol) obtained in Example 1 in a 100 ml eggplant flask, dissolve in 20 ml of THF, add 2.00 g (13.3 mmol) of silver cyanate, stir at the boiling point, and heat to reflux. For 5 hours. After cooling to room temperature, the resulting silver chloride and unreacted silver cyanate were removed by filtration. Volatile components in the filtrate were removed under reduced pressure.
As a result of analyzing the Mass spectrum, it was identified as 8F2P3S3I by m / z (molecular weight) 767. Moreover, when the NMR spectrum was taken, it was almost the same as that of 10F2P3S3I of Example 4.
収量 １．９７ｇ（２．５ｍｍｏｌ）
収率 ９３％
性状 白色固体
Yield 1.97 g (2.5 mmol)
Yield 93%
Property White solid
［実施例３］
Ｆ（ＣＦ２）１０（Ｃ６Ｈ４）２ＣＨ２ＣＨ２ＣＨ２ＳｉＣｌ３［１０Ｆ２Ｐ３Ｓ３Ｃ］の合成
[Example 3]
Synthesis of F (CF 2 ) 10 (C 6 H 4 ) 2 CH 2 CH 2 CH 2 SiCl 3 [10F2P3S3C]
・Ｆ（ＣＦ２）１０（Ｃ６Ｈ４）２Ｂｒ［１０Ｆ２ＰＢ］の合成
５００ｍｌナス型フラスコを窒素雰囲気に置換し、銅ブロンズ粉６３．６ｇ（１．０ｍｏｌ）、４，４’−ジブロモビフェニル６４．０ｇ（２０５ｍｍｏｌ）、ペルフルオロデシルヨージド１３７ｇ（２１２ｍｍｏｌ）、溶媒としてＤＭＳＯ３５０ｍｌを加えた後、１４０℃で４０時間加熱撹拌した。溶液を室温まで冷却し、吸引濾過により過剰の銅粉と白色固体（粗製１０Ｆ２ＰＢ）とを濾別し、ＤＭＳＯで洗浄した。続いて酢酸エチルを溶媒に用い、銅粉と白色固体との混合物をソックスレー抽出し、粗製１０Ｆ２ＰＢを得た。抽出液を飽和食塩水で洗浄し、さらに抽出液を硫酸マグネシウムで脱水し、酢酸エチルを減圧除去した。残留物を減圧蒸留し、さらにクロロホルム可溶部からクロロホルムを減圧除去し、白色固体として１０Ｆ２ＰＢを得た。
Ｍａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）７５１により、１０Ｆ２ＰＢであると同定した。ＮＭＲ、ＩＲ、Ｍａｓｓの各スペクトルを図７、図８、図９に示す。
The 500 ml eggplant type flask was replaced with a nitrogen atmosphere, and copper bronze powder 63.6 g (1.0 mol), 4,4′-dibromobiphenyl 64.0 g (205 mmol), perfluorodecyl iodide 137 g (212 mmol), DMSO 350 ml as a solvent. After the addition, the mixture was heated and stirred at 140 ° C. for 40 hours. The solution was cooled to room temperature, excess copper powder and white solid (crude 10F2PB) were filtered off by suction filtration and washed with DMSO. Subsequently, using ethyl acetate as a solvent, a mixture of copper powder and white solid was subjected to Soxhlet extraction to obtain crude 10F2PB. The extract was washed with saturated brine, and the extract was dehydrated with magnesium sulfate, and ethyl acetate was removed under reduced pressure. The residue was distilled under reduced pressure, and further, chloroform was removed under reduced pressure from the chloroform soluble portion to obtain 10F2PB as a white solid.
As a result of analyzing the Mass spectrum, it was identified as 10F2PB by m / z (molecular weight) 751. Each spectrum of NMR, IR, and Mass is shown in FIG. 7, FIG. 8, and FIG.
収量 ５９．４ｇ（７９．１ｍｍｏｌ）
収率 ３９％
沸点 １４０−１４５℃／１５Ｐａ
性状 白色固体
Yield 59.4 g (79.1 mmol)
Yield 39%
Boiling point 140-145 ° C / 15Pa
Property White solid
・Ｆ（ＣＦ２）１０（Ｃ６Ｈ４）２ＣＨ２ＣＨ＝ＣＨ２［１０Ｆ２ＰＡ］の合成
１Ｌナス型フラスコを窒素置換し、氷冷下に冷却した後、２．７６Ｍ ｎ−ブチルリチウム ヘキサン溶液３０．６ｍｌ（８４．５ｍｍｏｌ）を加え、続いて０．７７Ｍ ｉ−プロピルマグネシウムブロミド／ＴＨＦ溶液５２．６ｍｌ（４０．５ｍｍｏｌ）を加え、氷冷下で１時間撹拌した。その後、７５０ｍｌのジエチルエーテルに溶解させた１０Ｆ２ＰＢ ２１．０ｇｇ（２７．９ｍｍｏｌ）を滴下し、氷冷下で１時間撹拌した。触媒としてヨウ化銅１．７４ｇ（９．１４ｍｍｏｌ）を加えた後、アリルブロミド２６．９ｇ（２２２ｍｍｏｌ）を滴下し、室温で６７時間撹拌後、飽和塩化アンモニウム水溶液を沈殿が生じなくなるまで加え、反応を止めた。反応溶液を酢酸エチルで抽出し、有機層を硫酸マグネシウムで脱水後、溶媒を減圧留去した。得られた黄色固体を減圧蒸留し、さらにヘキサンを展開溶剤としてシリカゲルカラムクトマトグラフィー（ワコーゲルＣ−３００）により精製した。
Ｍａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）７１２により、１０Ｆ２ＰＡであると同定した。ＮＭＲ、ＩＲ、Ｍａｓｓの各スペクトルを図１０、図１１、図１２に示す。
The 1 L eggplant-shaped flask was purged with nitrogen and cooled under ice cooling, followed by addition of 30.6 ml (84.5 mmol) of a 2.76 M n-butyllithium hexane solution, followed by a 0.77 M i-propylmagnesium bromide / THF solution. 52.6 ml (40.5 mmol) was added, and the mixture was stirred for 1 hour under ice cooling. Thereafter, 21.0 g (27.9 mmol) of 10F2PB dissolved in 750 ml of diethyl ether was added dropwise and stirred for 1 hour under ice cooling. After adding 1.74 g (9.14 mmol) of copper iodide as a catalyst, 26.9 g (222 mmol) of allyl bromide was dropped, and after stirring at room temperature for 67 hours, a saturated aqueous solution of ammonium chloride was added until no precipitation occurred. Stopped. The reaction solution was extracted with ethyl acetate, the organic layer was dehydrated with magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained yellow solid was distilled under reduced pressure, and further purified by silica gel column chromatography (Wakogel C-300) using hexane as a developing solvent.
As a result of analyzing the Mass spectrum, it was identified as 10F2PA by m / z (molecular weight) 712. Each spectrum of NMR, IR, and Mass is shown in FIG. 10, FIG. 11, and FIG.
収量 １６．５ｇ（２３．２ｍｍｏｌ）
収率 ８３％
沸点 １１５−１２０℃／１５Ｐａ
性状 白色固体
Yield 16.5 g (23.2 mmol)
Yield 83%
Boiling point 115-120 ° C / 15Pa
Property White solid
・Ｆ（ＣＦ２）１０（Ｃ６Ｈ４）２ＣＨ２ＣＨ２ＣＨ２ＳｉＣｌ３［１０Ｆ２Ｐ３Ｓ３Ｃ］の合成
１００ｍｌ肉厚ガラスアンプル管に撹拌子を入れ、ここに１０Ｆ２ＰＡ ２．００ｇ（３．０７ｍｍｏｌ）、ＴＨＦ１０ｍｌを採取し、窒素雰囲気に置換し、外部を液体窒素で冷却し、トリクロロシラン１．０ｇ（８．２ｍｍｏｌ）、触媒の０．１Ｍ Ｈ２ＰｔＣｌ６／ＴＨＦ溶液０．１ｍｌ（０．０１ｍｍｏｌ）を採取した。アンプル管内部の試薬類を完全に固化させた後、真空ポンプを用いて４０Ｐａに減圧し、その状態で酸素バーナーにてガラスアンプル管を溶封した。これを室温に戻した後、８０℃で２時間、さらに１００℃で２０時間撹拌した。放冷後開管し、生じた黒色粉末状沈殿（Ｐｔ）を濾別除去した。濾液中からＴＨＦ、トリメクロロシランを減圧留去した。 A stirrer was placed in a 100 ml thick glass ampoule tube, and 2.00 g (3.07 mmol) of 10F2PA and 10 ml of THF were collected therein, replaced with a nitrogen atmosphere, the outside was cooled with liquid nitrogen, and 1.0 g of trichlorosilane (8 g 0.2 mmol), 0.1 ml (0.01 mmol) of 0.1 M H 2 PtCl 6 / THF solution of the catalyst was collected. After the reagents in the ampule tube were completely solidified, the pressure was reduced to 40 Pa using a vacuum pump, and in that state, the glass ampule tube was sealed with an oxygen burner. After returning to room temperature, the mixture was stirred at 80 ° C. for 2 hours and further at 100 ° C. for 20 hours. After standing to cool, the tube was opened, and the resulting black powdery precipitate (Pt) was removed by filtration. THF and trimechlorosilane were distilled off from the filtrate under reduced pressure.
得られた化合物についてＭａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）８４７により、１０Ｆ２Ｐ３Ｓ３Ｃであると同定した。
また、１０Ｆ２Ｐ３Ｓ３ＣのＩＲスペクトルを図１３に示す。１１００〜１２００ｃｍ−１の大きな吸収はＣ−Ｆ伸縮振動を示しているが、２２９０ｃｍ−１付近の吸収ピークがなく、−Ｎ＝Ｃ＝Ｏがないことを示している。
また、１０Ｆ２Ｐ３Ｓ３ＣのＮＭＲスペクトルは、以下の通りであった（Ｈは、下線プロトンの積分比を示す。）。
０．９１１３−０．９３８９ｐｐｍ：多重線 −ＣＨ ２−Ｓｉ ２Ｈ
１．８５８８ｐｐｍ：多重線 −ＣＨ ２−ＣＨ２−Ｓｉ ２Ｈ
２．７１６２ｐｐｍ：多重線 −ＣＨ ２−ＣＨ２−ＣＨ２−Ｓｉ ２Ｈ
７．２９６０−７．７１４７ｐｐｍ：ベンゼン環プロトン ８Ｈ
As a result of analyzing the mass spectrum of the obtained compound, it was identified as 10F2P3S3C by m / z (molecular weight) 847.
FIG. 13 shows the IR spectrum of 10F2P3S3C. Large absorption at 1100 to 1200 cm −1 indicates CF stretching vibration, but there is no absorption peak near 2290 cm −1 , indicating that there is no —N═C═O.
Further, the NMR spectrum of 10F2P3S3C was as follows (H represents the integral ratio of underline protons).
0.9113-0.9389Ppm: multiplet -C H 2 -Si 2H
1.8588Ppm: multiplet -C H 2 -CH 2 -Si 2H
2.7162Ppm: multiplet -C H 2 -CH 2 -CH 2 -Si 2H
7.2960-7.7147 ppm: benzene ring proton 8H
収量 ２．３５ｇ
収率 ９８％
性状 白色固体
Yield 2.35g
Yield 98%
Property White solid
［実施例４］
Ｆ（ＣＦ２）１０（Ｃ６Ｈ４）２ＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＮＣＯ）３［１０Ｆ２Ｐ３Ｓ３Ｉ］の合成
Synthesis of F (CF 2 ) 10 (C 6 H 4 ) 2 CH 2 CH 2 CH 2 Si (NCO) 3 [10F2P3S3I]
実施例３で得られた１０Ｆ２Ｐ３Ｓ３Ｃ ２．３０ｇ（２．７１ｍｍｏｌ）を１００ｍｌナスフラスコに取り、ＴＨＦ２０ｍｌに溶解し、シアン酸銀２．００ｇ（１３．３ｍｍｏｌ）を加えて沸点で撹拌し、加熱還流操作を５時間行った。室温まで冷却し、生じた塩化銀、未反応のシアン酸銀を濾別除去した。濾液中の揮発成分を減圧除去した。
得られた化合物についてＭａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）８６７により、１０Ｆ２Ｐ３Ｓ３Ｉであると同定した。
また、１０Ｆ２Ｐ３Ｓ３ＩのＩＲスペクトルを図１４に示す。１１００〜１２００ｃｍ−１の大きな吸収はＣ−Ｆ伸縮振動を示しており、２２９０ｃｍ−１の吸収ピークが−Ｎ＝Ｃ＝Ｏによる特徴的なピークである。
また、１０Ｆ２Ｐ３Ｓ３ＩのＮＭＲスペクトルは、以下の通りであった（Ｈは、下線プロトンの積分比を示す。）。
０．９１９９ｐｐｍ：多重線 −ＣＨ ２−Ｓｉ ２Ｈ
１．８４３９ｐｐｍ：多重線 −ＣＨ ２−ＣＨ２−Ｓｉ ２Ｈ
２．７１１５ｐｐｍ：多重線 −ＣＨ ２−ＣＨ２−ＣＨ２−Ｓｉ ２Ｈ
７．２９３５−７．６９９１ｐｐｍ：ベンゼン環プロトン ８Ｈ
Take 2.30 g (2.71 mmol) of 10F2P3S3C obtained in Example 3 in a 100 ml eggplant flask, dissolve in 20 ml of THF, add 2.00 g (13.3 mmol) of silver cyanate, and stir at the boiling point. For 5 hours. After cooling to room temperature, the resulting silver chloride and unreacted silver cyanate were removed by filtration. Volatile components in the filtrate were removed under reduced pressure.
As a result of analyzing the mass spectrum of the obtained compound, it was identified as 10F2P3S3I by m / z (molecular weight) 867.
FIG. 14 shows the IR spectrum of 10F2P3S3I. Large absorption at 1100 to 1200 cm −1 indicates CF stretching vibration, and an absorption peak at 2290 cm −1 is a characteristic peak due to —N═C═O.
The NMR spectrum of 10F2P3S3I was as follows (H represents the integral ratio of underline protons).
0.9199 ppm: Multiplex -C H 2 -Si 2H
1.8439Ppm: multiplet -C H 2 -CH 2 -Si 2H
2.7115Ppm: multiplet -C H 2 -CH 2 -CH 2 -Si 2H
7.2935-7.6991 ppm: benzene ring proton 8H
収量 ２．３０ｇ
収率 ９７％
性状 白色固体
Yield 2.30g
Yield 97%
Property White solid
［実施例５］
Ｆ（ＣＦ２）１２（Ｃ６Ｈ４）２ＣＨ２ＣＨ２ＣＨ２ＳｉＣｌ３［１２Ｆ２Ｐ３Ｓ３Ｃ］の合成
[Example 5]
Synthesis of F (CF 2 ) 12 (C 6 H 4 ) 2 CH 2 CH 2 CH 2 SiCl 3 [12F2P3S3C]
・Ｆ（ＣＦ２）１２（Ｃ６Ｈ４）２Ｂｒ［１２Ｆ２ＰＢ］の合成
１００ｍｌナス型フラスコを窒素雰囲気に置換し、銅ブロンズ粉６．４ｇ（０．１ｍｏｌ）、４，４’−ジブロモビフェニル６．３ｇ（２０ｍｍｏｌ）、ペルフルオロドデシルヨージド１５．７ｇ（２１ｍｍｏｌ）、溶媒としてＤＭＳＯ３０ｍｌを加え、１４０℃で４０時間加熱撹拌した。溶液を室温まで冷却し、吸引濾過により過剰の銅粉と白色固体１２Ｆ２ＰＢ（粗製）とを濾別し、ＤＭＳＯで洗浄した。続いて、酢酸エチルを溶媒に用い、銅粉と白色固体との混合物をソックスレー抽出し、粗製１２Ｆ２ＰＢを得た。抽出した溶液を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、酢酸エチルを減圧除去した。残留物を減圧蒸留し、さらにクロロホルム可溶部からクロロホルムを減圧除去し、白色固体として１２Ｆ２ＰＢを得た。
Ｍａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）８５１により、１２Ｆ２ＰＢであると同定した。また、ＮＭＲスペクトルをとったところ、実施例３の１０Ｆ２ＰＢのものとほぼ同じであった。
The 100 ml eggplant type flask was replaced with a nitrogen atmosphere, copper bronze powder 6.4 g (0.1 mol), 4,4′-dibromobiphenyl 6.3 g (20 mmol), perfluorododecyl iodide 15.7 g (21 mmol), as a solvent DMSO (30 ml) was added, and the mixture was stirred with heating at 140 ° C. for 40 hours. The solution was cooled to room temperature, excess copper powder and white solid 12F2PB (crude) were filtered off by suction filtration, and washed with DMSO. Subsequently, using ethyl acetate as a solvent, a mixture of copper powder and white solid was subjected to Soxhlet extraction to obtain crude 12F2PB. The extracted solution was washed with saturated brine, dried over magnesium sulfate, and ethyl acetate was removed under reduced pressure. The residue was distilled under reduced pressure, and further chloroform was removed under reduced pressure from the chloroform soluble part to obtain 12F2PB as a white solid.
As a result of analyzing the mass spectrum, it was identified as 12F2PB by m / z (molecular weight) 851. Moreover, when the NMR spectrum was taken, it was almost the same as that of 10F2PB of Example 3.
収量 ８．５ｇ（１０ｍｍｏｌ）
収率 ５０％
沸点 １４５−１５０℃／１８Ｐａ
性状 白色固体
Yield 8.5 g (10 mmol)
Boiling point: 145-150 ° C / 18Pa
Property White solid
・Ｆ（ＣＦ２）１２（Ｃ６Ｈ４）２ＣＨ２ＣＨ＝ＣＨ２［１２Ｆ２ＰＡ］の合成
１００ｍｌナス型フラスコを窒素置換し、氷冷下に冷却した後、２．７６Ｍ ｎ−ブチルリチウム ヘキサン溶液３．３ｍｌ（９．２ｍｍｏｌ）を加え、続いて０．７７Ｍ ｉ−プロピルマグネシウムブロミド／ＴＨＦ溶液５．８ｍｌ（４．５ｍｍｏｌ）を加え、氷冷下で１時間撹拌した。その後、２０ｍｌのジエチルエーテルに溶解させた１２Ｆ２ＰＢ ２．０ｇ（２．４ｍｍｏｌ）を滴下し、氷冷下で１時間撹拌した。触媒としてヨウ化銅０．２ｇ（１．０ｍｍｏｌ）を加えた後、アリルブロミド１．３ｍｌ（１０．７ｍｍｏｌ）を滴下し、室温で６７時間撹拌後、飽和塩化アンモニウム水溶液を沈殿が生じなくなるまで加え、反応を止めた。反応溶液を酢酸エチルで抽出し、有機層を硫酸マグネシウムで脱水後、溶媒を減圧留去した。得られた黄色固体を減圧蒸留し、さらに展開溶媒にヘキサンを用いたシリカゲルカラムクトマトグラフィー（ワコーゲルＣ−３００）により精製した。
Ｍａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）８１２により、１２Ｆ２ＰＡであると同定した。
The 100 ml eggplant type flask was purged with nitrogen, cooled to ice, and then added with 3.3 ml (9.2 mmol) of a 2.76 M n-butyllithium hexane solution, followed by a 0.77 M i-propylmagnesium bromide / THF solution. 5.8 ml (4.5 mmol) was added, and the mixture was stirred for 1 hour under ice cooling. Thereafter, 2.0 g (2.4 mmol) of 12F2PB dissolved in 20 ml of diethyl ether was added dropwise, and the mixture was stirred for 1 hour under ice cooling. After adding 0.2 g (1.0 mmol) of copper iodide as a catalyst, 1.3 ml (10.7 mmol) of allyl bromide was dropped, and after stirring at room temperature for 67 hours, a saturated aqueous ammonium chloride solution was added until no precipitation occurred. Stopped the reaction. The reaction solution was extracted with ethyl acetate, the organic layer was dehydrated with magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained yellow solid was distilled under reduced pressure, and further purified by silica gel column chromatography (Wakogel C-300) using hexane as a developing solvent.
As a result of analyzing the Mass spectrum, it was identified as 12F2PA by m / z (molecular weight) 812.
収量 １．５ｇ（１．８５ｍｍｏｌ）
収率 ８０％
沸点 １３５−１４０℃／２０Ｐａ
性状 白色固体
Yield 1.5 g (1.85 mmol)
Boiling point 135-140 ° C / 20Pa
Property White solid
・Ｆ（ＣＦ２）１２（Ｃ６Ｈ４）２ＣＨ２ＣＨ２ＣＨ２ＳｉＣｌ３［１２Ｆ２Ｐ３Ｓ３Ｃ］の合成
５０ｍｌ肉厚ガラスアンプル管に撹拌子を入れ、窒素雰囲気に置換し、外部を液体窒素で冷却した状態でＴＨＦ２０ｍｌ、１２Ｆ２ＰＡ １．００ｇ（１．２３ｍｍｏｌ）、トリクロロシラン１．０ｇ（７．４ｍｍｏｌ）、触媒として０．１Ｍ Ｈ２ＰｔＣｌ６／ＴＨＦ溶液０．１ｍｌ（０．０１ｍｍｏｌ）を採取した。アンプル管内部の試薬類を完全に固化させた後、真空ポンプを用いて４０Ｐａに減圧し、その状態で酸素バーナーにてガラスアンプル管を溶封した。これを室温に戻した後、８０℃で２時間、さらに１００℃で２０時間撹拌した。放冷後開管し、内容物から黒色粉末状固体（Ｐｔ）を濾別除去した。濾液中の揮発成分であるＴＨＦ、トリメクロロシランを減圧留去した。
得られた化合物について、Ｍａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）９４７により、１２Ｆ２Ｐ３Ｓ３Ｃであると同定した。また、ＮＭＲスペクトルをとったところ、実施例３の１０Ｆ２Ｐ３Ｓ３Ｃのものとほぼ同じであった。
In a 50 ml thick glass ampoule tube, a stirring bar was placed, and the atmosphere was replaced with a nitrogen atmosphere. With the outside cooled with liquid nitrogen, 20 ml of THF, 1.00 g (1.23 mmol) of 12F2PA, 1.0 g (7.4 mmol) of trichlorosilane, As a catalyst, 0.1 ml (0.01 mmol) of a 0.1 MH 2 PtCl 6 / THF solution was collected. After the reagents in the ampule tube were completely solidified, the pressure was reduced to 40 Pa using a vacuum pump, and in that state, the glass ampule tube was sealed with an oxygen burner. After returning to room temperature, the mixture was stirred at 80 ° C. for 2 hours and further at 100 ° C. for 20 hours. After standing to cool, the tube was opened, and the black powdery solid (Pt) was removed by filtration from the contents. THF and trimechlorosilane which are volatile components in the filtrate were distilled off under reduced pressure.
As a result of analyzing a mass spectrum about the obtained compound, it was identified as 12F2P3S3C by m / z (molecular weight) 947. Moreover, when the NMR spectrum was taken, it was substantially the same as that of 10F2P3S3C of Example 3.
収量 １．０５ｇ
収率 ９０％
性状 白色固体
Yield 1.05g
Property White solid
［実施例６］
Ｆ（ＣＦ２）１２（Ｃ６Ｈ４）２ＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＮＣＯ）３［１２Ｆ２Ｐ３Ｓ３Ｉ］の合成
Synthesis of F (CF 2) 12 (C 6 H 4) 2
実施例５で得られた１２Ｆ２Ｐ３Ｓ３Ｃ １．０５ｇ（１．１ｍｍｏｌ）を１００ｍｌナスフラスコに取り、ＴＨＦ２０ｍｌに溶解し、シアン酸銀１．５ｇ（１０ｍｍｏｌ）を加えて沸点で撹拌し、加熱還流操作を５時間行った。室温まで冷却し、生じた塩化銀、未反応のシアン酸銀を濾別除去した。濾液中の揮発成分を減圧除去した。
得られた化合物についてＭａｓｓスペクトルを分析した結果、ｍ／ｚ（分子量）９６７により、１２Ｆ２Ｐ３Ｓ３Ｉであると同定した。また、ＮＭＲスペクトルをとったところ、実施例４の１０Ｆ２Ｐ３Ｓ３Ｉのものとほぼ同じであった。
Take 1.05 g (1.1 mmol) of 12F2P3S3C obtained in Example 5 in a 100 ml eggplant flask, dissolve in 20 ml of THF, add 1.5 g (10 mmol) of silver cyanate and stir at the boiling point. Went for hours. After cooling to room temperature, the resulting silver chloride and unreacted silver cyanate were removed by filtration. Volatile components in the filtrate were removed under reduced pressure.
As a result of analyzing a mass spectrum for the obtained compound, it was identified as 12F2P3S3I by m / z (molecular weight) 967. Moreover, when the NMR spectrum was taken, it was almost the same as that of 10F2P3S3I of Example 4.
収量 ０．９６ｇ
収率 ９０％
性状 白色固体
Yield 0.96g
Property White solid
［実施例７］
以下に、物性の測定について詳述する。物性の測定は、基質として、ガラスを用いて行った。
（ガラスの洗浄）
スライドガラス（マツナミ製Ｓ−７２１４）を１Ｎ水酸化カリウム水溶液（ｐＨ＞９）に２時間浸した後に取り出し、蒸留水で十分に洗浄した。その後、スライドガラスをデシケーター中で乾燥し、次の表面改質に使用した。
（改質溶液の調製）
実施例４で合成した１０Ｆ２Ｐ３Ｓ３Ｉのシランカップリング剤を用い、ＴＨＦを溶媒とした３％溶液を準備した。
（ガラスの表面改質）
２００ｍｌ広口受器に前記の方法で洗浄済みのスライドガラスを入れ、窒素置換を行った。これに対して、上記の改質溶液を広口受器に加え、改質溶液中にスライドガラスを完全に浸し、７時間加熱還流を行った。冷却後、取り出したガラスをＴＨＦで洗浄し、さらに室温で水に５分間浸漬した後、室温で一昼夜自然乾燥した。
[Example 7]
Below, the measurement of a physical property is explained in full detail. The physical properties were measured using glass as a substrate.
(Washing glass)
A slide glass (manufactured by Matsunami S-7214) was immersed in a 1N aqueous potassium hydroxide solution (pH> 9) for 2 hours and then taken out and washed thoroughly with distilled water. Thereafter, the slide glass was dried in a desiccator and used for the next surface modification.
(Preparation of modified solution)
Using the 10F2P3S3I silane coupling agent synthesized in Example 4, a 3% solution using THF as a solvent was prepared.
(Surface modification of glass)
The glass slide that had been washed by the above method was placed in a 200 ml wide-mouth receiver, and nitrogen substitution was performed. On the other hand, the above-mentioned modified solution was added to the wide-mouth receiver, the slide glass was completely immersed in the modified solution, and heated and refluxed for 7 hours. After cooling, the taken out glass was washed with THF, further immersed in water at room temperature for 5 minutes, and then naturally dried overnight at room temperature.
（改質ガラスの接触角の測定）
シランカップリング剤として用いた１０Ｆ２Ｐ３Ｓ３Ｉの改質ガラスに対する水の接触角を測定した。接触角の測定は、ニック製ＬＳＥ−Ｂ１００Ｌ型接触角測定装置を使用し、０．９μｌの水滴を水平なガラス板上に滴下して接触角を測定する液滴法を用いた。
(Measurement of contact angle of modified glass)
The contact angle of water with respect to the modified glass of 10F2P3S3I used as the silane coupling agent was measured. The contact angle was measured by using a droplet method in which a contact angle was measured by dropping 0.9 μl of water droplets onto a horizontal glass plate using a LSE-B100L contact angle measuring device manufactured by Nick.
（１０Ｆ２Ｐ３Ｓ３Ｉを用いた改質ガラスの耐熱性試験）
上記改質ガラスそのものの接触角は１１５．１度であった。
次に、上記改質ガラスを１３０℃にて３０分間のキュアリングを行ったものの接触角は、１１１．７度であった。
引き続いて、３５０℃で３０分間の熱暴露を行ってから接触角を測定したところ、１０７．４度であり、耐熱性があることが分かった。
さらに続けて、３５０℃で１２０分間の熱暴露を行ってから接触角を測定したところ、９６．７度であった（ここまでで、３５０℃での熱暴露合計時間は２時間３０分である）。
続けて、３５０℃にて６０分間の熱暴露を行ってから接触角を測定したところ、９０．９度であった（ここまでで、３５０℃の熱暴露合計時間は合計３時間３０分である）。
以上の接触角の値の変化状況から、１０Ｆ２Ｐ３Ｓ３Ｉは十分耐熱性があり、また、接触角のデータは満足できる離型性があると言える。
(Heat resistance test of modified glass using 10F2P3S3I)
The contact angle of the modified glass itself was 115.1 degrees.
Next, the modified glass was cured at 130 ° C. for 30 minutes, and the contact angle was 111.7 degrees.
Subsequently, when the contact angle was measured after heat exposure at 350 ° C. for 30 minutes, it was found to be 107.4 degrees and heat resistance.
Further, when the contact angle was measured after 120 minutes of heat exposure at 350 ° C., it was 96.7 degrees (so far, the total heat exposure time at 350 ° C. is 2
Subsequently, when the contact angle was measured after 60 minutes of heat exposure at 350 ° C., it was 90.9 degrees (so far, the total heat exposure time at 350 ° C. is 3
From the above changes in the value of the contact angle, it can be said that 10F2P3S3I has sufficient heat resistance, and that the contact angle data has satisfactory releasability.
以上のデータに示した水との接触角が高いということは、表面自由エネルギーが低いことを示しており、離型性及び防汚性が高いことを示している。
なお、具体的なデータは示さないが、特開２００４−１０７２７４号公報と同様に、本発明のシランカップリング剤は、耐酸性、耐酸化性も高いものである。
The high contact angle with water shown in the above data indicates that the surface free energy is low, indicating that the releasability and antifouling properties are high.
Although specific data is not shown, the silane coupling agent of the present invention has high acid resistance and oxidation resistance as in JP-A-2004-107274.
以上説明したように、本発明のペルフルオロアルキル基及びビフェニルアルキル基を有するシランカップリング剤は、耐熱性、耐久性、離型性、及び防汚性がいずれも高いものである。
また、特に、ＮＣＯ基及びハロゲン基は基質の水酸基との結合性が高いことから、改質表面がモノレーヤー（分子一層）であることも加わって、精密な離型処理が可能な優れた耐熱耐久離型剤として、一般の離型剤としてばかりでなく、ミクロなパターニングを施したＳＯＧのようなシリコン材料、グラシーカーボンのような炭素材料、金属、石英、ニッケル電鋳等に最も適した離型剤となり得る上に、繰り返し転写しても離型剤の剥離を生じない利点を有するものである。
また、近い将来大きな発展が見込まれるナノインプリント用耐熱耐久離型剤として、現段階では最も優れた離型剤となる。
もちろん、耐熱性の高い撥水撥油性表面改質剤として、例えば、電子レンジ内でも使用可能な防汚性のガラス容器等の表面改質剤として使用できる。
また、いずれのシランカップリング剤も、基質や粉体の表面に使用でき、それらの表面を改質できるものである。
さらに、融点が３００℃以上の耐熱性プラスチック、エンジニアリングプラスチックス等に対する離型剤、カップリング剤として格別の効果と有用性を有するものである。
As described above, the silane coupling agent having a perfluoroalkyl group and a biphenylalkyl group of the present invention has high heat resistance, durability, releasability, and antifouling properties.
In particular, since NCO groups and halogen groups have high bonding properties with the hydroxyl groups of the substrate, the modified surface is a monolayer (single molecule), and has excellent heat resistance and durability that enables precise mold release treatment. Not only as a general mold release agent, but also as a mold release agent, it is most suitable for micropatterned silicon materials such as SOG, carbon materials such as glassy carbon, metals, quartz, nickel electroforming, etc. In addition to being a mold agent, it has the advantage that the release agent does not peel off even if it is repeatedly transferred.
Moreover, as a heat-resistant and durable mold release agent for nanoimprint, which is expected to develop greatly in the near future, it is the most excellent mold release agent at this stage.
Of course, it can be used as a water- and oil-repellent surface modifier having high heat resistance, for example, as a surface modifier such as an antifouling glass container that can be used in a microwave oven.
In addition, any silane coupling agent can be used on the surface of a substrate or powder, and the surface can be modified.
Furthermore, it has a special effect and usefulness as a release agent and coupling agent for heat-resistant plastics and engineering plastics having a melting point of 300 ° C. or higher.
Claims (4)
で表されるペルフルオロアルキルヨージドと極性溶媒中で、銅ブロンズ粉触媒を用いて反応させて、下記一般式（４）
次いで、該４−ペルフルオロアルキル−４’−ブロモビフェニルを、下記式（５）
で表されるアルケニルブロミドと極性溶媒中で、ヨウ化銅触媒を用いて反応させて、下記一般式（６）
次いで、該４−ペルフルオロアルキル−４’−アルケニルビフェニルを、下記式（７）
で表されるトリハロゲン化シランと有機溶媒中で、塩化白金酸触媒を用いて反応させて、下記一般式（８）
で表される（４−ペルフルオロアルキルビフェニル）アルキルトリハロゲン化シランを得る、シランカップリング剤の製造方法。 The following general formula (2)
Is reacted with a perfluoroalkyl iodide represented by the following formula (4) using a copper bronze powder catalyst:
Subsequently, the 4-perfluoroalkyl-4′-bromobiphenyl is represented by the following formula (5):
Is reacted with a copper iodide catalyst in a polar solvent with a alkenyl bromide represented by the following general formula (6):
Subsequently, the 4-perfluoroalkyl-4′-alkenylbiphenyl is represented by the following formula (7):
Is reacted with a trihalogenated silane represented by the formula (8) in an organic solvent using a chloroplatinic acid catalyst.
The manufacturing method of the silane coupling agent which obtains (4-perfluoroalkyl biphenyl) alkyl trihalogenated silane represented by these.
で表される（４−ペルフルオロアルキルビフェニル）アルキルトリハロゲン化シランを有機溶媒中で、シアン酸銀と反応させて、下記式（９）
(4-perfluoroalkylbiphenyl) alkyltrihalogenated silane represented by the following formula (9) is reacted with silver cyanate in an organic solvent.
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