JPH1087671A - Silane coupling agent - Google Patents
Silane coupling agentInfo
- Publication number
- JPH1087671A JPH1087671A JP8237424A JP23742496A JPH1087671A JP H1087671 A JPH1087671 A JP H1087671A JP 8237424 A JP8237424 A JP 8237424A JP 23742496 A JP23742496 A JP 23742496A JP H1087671 A JPH1087671 A JP H1087671A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- mmol
- hours
- silane coupling
- 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.)
- Pending
Links
- 239000006087 Silane Coupling Agent Substances 0.000 title abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- -1 silane compound Chemical class 0.000 abstract description 47
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 229910000077 silane Inorganic materials 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011350 dental composite resin Substances 0.000 abstract description 5
- 239000011256 inorganic filler Substances 0.000 abstract description 5
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 2
- 239000000460 chlorine Substances 0.000 abstract 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 238000010992 reflux Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000035484 reaction time Effects 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229910000104 sodium hydride Inorganic materials 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 8
- 229960004624 perflexane Drugs 0.000 description 8
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 8
- 239000012312 sodium hydride Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 239000000805 composite resin Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 244000061458 Solanum melongena Species 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000463 material Substances 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
- 239000003607 modifier Substances 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規なシラン系化
合物に関し、より詳しくは歯科用コンポジットレジンの
シランカップリング剤として好適な化合物に関する。[0001] The present invention relates to a novel silane compound, and more particularly to a compound suitable as a silane coupling agent for a dental composite resin.
【０００２】[0002]
【従来の技術】歯冠修復用材料として、コンポジットレ
ジンが、審美性、操作性、経済性などの理由から広く用
いられている。コンポジットレジンは、無機質フィラー
と有機樹脂からなる複合材料であり、有機樹脂と無機質
フィラーの親和性を高めるため、フィラーはシランカッ
プリング剤により表面改質されたものが用いられてい
る。 一方、口腔内は高湿度で温度変化があるなど過酷
な環境のためにフィラー／有機樹脂間の親和性が低下
し、コンポジットレジンの機械的強度が経時的に低下す
ることが問題点として指摘されている。2. Description of the Related Art As a material for restoring a crown, a composite resin is widely used for reasons such as aesthetics, operability and economy. The composite resin is a composite material comprising an inorganic filler and an organic resin. In order to increase the affinity between the organic resin and the inorganic filler, a filler whose surface is modified by a silane coupling agent is used. On the other hand, it is pointed out as a problem that the affinity between filler / organic resin decreases due to severe environment such as high humidity and temperature change in the oral cavity, and the mechanical strength of composite resin decreases with time. ing.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、歯科用コン
ポジットレジンの耐水性、樹脂と無機質フィラーの接着
強度などを向上するのに好適な化合物を提供することを
目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a compound suitable for improving the water resistance of a dental composite resin, the adhesive strength between a resin and an inorganic filler, and the like.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記課題に
鑑み検討を重ねた結果、オレフィン性重合性基及びパー
フルオロアルキル基を導入した新規シラン系化合物が、
コンポジットレジンの接着強度及び耐水・耐久性を高め
ることを見出した。Means for Solving the Problems As a result of repeated studies in view of the above problems, the present inventor has found that a novel silane compound having an olefinic polymerizable group and a perfluoroalkyl group introduced therein is
It has been found that the adhesive strength, water resistance, and durability of the composite resin are improved.
【０００５】本発明は、一般式（Ｉ）The present invention relates to a compound represented by the general formula (I):
【０００６】[0006]
【化３】 Embedded image
【０００７】〔式中、Ｒ1は水素原子またはメチル基を
示す。Ｒ2は、塩素原子、メトキシ基またはエトキシ基
を示す。Ｒｆは、炭素数４〜１６のパーフルオロアルキ
ル基を示す。〕で表される化合物を提供するものであ
る。[Wherein, R 1 represents a hydrogen atom or a methyl group. R 2 represents a chlorine atom, a methoxy group or an ethoxy group. Rf represents a perfluoroalkyl group having 4 to 16 carbon atoms. ] The compound represented by this is provided.
【０００８】また、本発明は、一般式（II）Further, the present invention provides a compound represented by the general formula (II):
【０００９】[0009]
【化４】 Embedded image
【００１０】〔式中、Ｒ2は、塩素原子またはメトキシ
基を示す。Ｒｆは、炭素数４〜１６のパーフルオロアル
キル基を示す。〕で表される化合物を提供するものであ
る。[Wherein, R 2 represents a chlorine atom or a methoxy group. Rf represents a perfluoroalkyl group having 4 to 16 carbon atoms. ] The compound represented by this is provided.
【００１１】一般式（Ｉ）及び（II）の化合物は、いず
れもシランカップリング剤として有用である。The compounds of the general formulas (I) and (II) are both useful as silane coupling agents.
【００１２】[0012]
【発明の実施の形態】一般式（Ｉ）の化合物において、
Ｒ1は水素原子またはメチル基、好ましくはメチル基を
示す。BEST MODE FOR CARRYING OUT THE INVENTION In the compound of the general formula (I),
R 1 represents a hydrogen atom or a methyl group, preferably a methyl group.
【００１３】Ｒ2は、塩素原子、メトキシ基またはエト
キシ基、好ましくはメトキシ基を示す。R 2 represents a chlorine atom, a methoxy group or an ethoxy group, preferably a methoxy group.
【００１４】Ｒｆは、炭素数４〜１６の直鎖または分岐
を有するパーフルオロアルキル基を示し、好ましくは
（ＣＦ3）2ＣＦ（ＣＦ2）n（ｎ＝２〜６）で表される分
岐を有するパーフルオロアルキル基を示す。Rf represents a linear or branched perfluoroalkyl group having 4 to 16 carbon atoms, preferably a branched group represented by (CF 3 ) 2 CF (CF 2 ) n (n = 2 to 6). A perfluoroalkyl group having the formula:
【００１５】好ましい一般式（Ｉ）の化合物は、Ｒ1＝
水素原子またはメチル基；Ｒ2＝メトキシ基；Ｒｆ＝炭
素数４〜１０のパーフルオロアルキル基の化合物であ
る。Preferred compounds of general formula (I) are those wherein R 1 =
A compound of a hydrogen atom or a methyl group; R 2 = methoxy group; Rf = a perfluoroalkyl group having 4 to 10 carbon atoms.
【００１６】一般式（II）の化合物において、Ｒ2は、
塩素原子、メトキシ基またはエトキシ基、好ましくはメ
トキシ基を示す。In the compound of the general formula (II), R 2 is
It represents a chlorine atom, a methoxy group or an ethoxy group, preferably a methoxy group.
【００１７】Ｒｆは、炭素数４〜１６の直鎖または分岐
を有するパーフルオロアルキル基を示し、好ましくはＦ
（ＣＦ2）n（ｎ＝４〜８）で表される直鎖のパーフルオ
ロアルキル基を示す。Rf represents a linear or branched perfluoroalkyl group having 4 to 16 carbon atoms.
It represents a linear perfluoroalkyl group represented by (CF 2 ) n (n = 4 to 8).
【００１８】好ましい一般式（II）の化合物は、Ｒ2＝
メトキシ基；Ｒｆ＝炭素数４〜１０のパーフルオロアル
キル基の化合物である。Preferred compounds of the general formula (II) are those wherein R 2 =
Methoxy group; Rf = compound of a perfluoroalkyl group having 4 to 10 carbon atoms.
【００１９】一般式（Ｉ）及び（II）の化合物は、例え
ば以下の反応工程式（Ｉ）及び反応工程式（II）に従い
製造できる。The compounds of the general formulas (I) and (II) can be produced, for example, according to the following reaction schemes (I) and (II).
【００２０】＜反応工程式（Ｉ）＞<Reaction process formula (I)>
【００２１】[0021]
【化５】 Embedded image
【００２２】〔式中、Ｒ1、Ｒ2及びＲｆは前記に同
じ。〕Ａ工程 アルコール化合物（１）を溶媒中ＮａＨ及びアリルブロ
ミドと反応させて、エーテル化合物（２）を得る。反応
は、アルコール化合物（１）１モルに対しＮａＨを１〜
１．１モル、アリルブロミドを１モル〜過剰量用い、室
温〜溶媒が還流する温度で２〜７２時間反応させること
により有利に進行する。溶媒としては、ジエチルエーテ
ル、テトラヒドロフラン等のエーテル類を用いることが
できる。Wherein R 1 , R 2 and Rf are the same as above. Step A: The alcohol compound (1) is reacted with NaH and allyl bromide in a solvent to obtain an ether compound (2). In the reaction, 1 mol of NaH is added to 1 mol of the alcohol compound (1).
The reaction proceeds advantageously at room temperature to a temperature at which the solvent is refluxed for 2 to 72 hours using 1.1 mol, 1 mol to excess amount of allyl bromide. Ethers such as diethyl ether and tetrahydrofuran can be used as the solvent.
【００２３】Ｂ工程 エーテル化合物（２）を、触媒の存在下にシラン化合物
（３）と反応させて一般式（Ｉ）のシランカップリング
剤を得る。反応は、エーテル化合物（２）１モルに対
し、シラン化合物（３）を１〜２モル、触媒は触媒量用
いる。触媒としては、Ｈ2ＰｔＣｌ6が用いられる。反応
は、２，５−tert−ブチルヒドロキノンなどのラジカル
重合防止剤を必要量添加して行うのが好ましい。 Step B The ether compound (2) is reacted with the silane compound (3) in the presence of a catalyst to obtain a silane coupling agent of the general formula (I). In the reaction, 1 to 2 mol of the silane compound (3) and 1 to 2 mol of the catalyst are used per 1 mol of the ether compound (2). H 2 PtCl 6 is used as a catalyst. The reaction is preferably performed by adding a required amount of a radical polymerization inhibitor such as 2,5-tert-butylhydroquinone.
【００２４】＜反応工程式（II）＞<Reaction process formula (II)>
【００２５】[0025]
【化６】 Embedded image
【００２６】〔式中、Ｒ2及びＲｆは前記に同じ。〕Ｃ工程 アルコール化合物（４）を溶媒中ＮａＨ及びアリルブロ
ミドと反応させて、エーテル化合物（５）を得る。反応
は、アルコール化合物（４）１モルに対しＮａＨを１〜
１．１過剰量、アリルブロミドを１〜過剰量用い、室温
から溶媒が還流する温度で２〜７２時間反応させること
により有利に進行する。溶媒としては、ジエチルエーテ
ル、テトラヒドロフラン等のエーテル類を用いることが
で きる。 Wherein R 2 and Rf are as defined above. Step C: The alcohol compound (4) is reacted with NaH and allyl bromide in a solvent to obtain an ether compound (5). In the reaction, 1 mol of NaH is used for 1 mol of the alcohol compound (4).
1.1 Advantageously, the reaction proceeds from room temperature to a temperature at which the solvent is refluxed for 2 to 72 hours using an excess amount and an excess amount of allyl bromide. As the solvent, di Echiruete
And ethers such as tetrahydrofuran
Kill at.
【００２７】Ｄ工程 エーテル化合物（５）を、溶媒中触媒の存在下にシラン
化合物（３）と反応させて一般式（II）のシランカップ
リング剤を得る。反応は、エーテル化合物（５）１モル
に対し、シラン化合物（３）を１〜２モル、触媒は触媒
量用いる。触媒としては、例えばＨ2ＰｔＣｌ6が用いら
れる。反応は、２，５−tert−ブチルヒドロキノンなど
のラジカル重合防止剤を必要量添加して行うのが好まし
い。 Step D The ether compound (5) is reacted with the silane compound (3) in a solvent in the presence of a catalyst to obtain a silane coupling agent of the general formula (II). In the reaction, 1 to 2 mol of the silane compound (3) and 1 to 2 mol of the catalyst are used per 1 mol of the ether compound (5). As the catalyst, for example, H 2 PtCl 6 is used. The reaction is preferably performed by adding a required amount of a radical polymerization inhibitor such as 2,5-tert-butylhydroquinone.
【００２８】本発明のシランカップリング剤は、通常の
シランカップリング剤の用途、例えばガラス繊維強化プ
ラスチックス（ＧＦＲＰ）の処理剤、ポリエステルレジ
ンコンクリートの強化剤、有機材料と有機材料、無機材
料または金属の接着させるプライマー、充填剤の表面処
理剤、不飽和結合を有する樹脂の架橋剤等の用途に好適
に使用され、特に歯科用コンポジットレジンの無機質フ
ィラーの樹脂への接着強度及び耐水性を向上させる表面
改質剤として有用である。The silane coupling agent of the present invention may be used for ordinary silane coupling agents, for example, a treatment agent for glass fiber reinforced plastics (GFRP), a reinforcement agent for polyester resin concrete, an organic material and an organic material, an inorganic material or Suitable for applications such as primers for bonding metals, surface treatment agents for fillers, and cross-linking agents for resins having unsaturated bonds, and particularly improves the adhesive strength and water resistance of inorganic fillers of dental composite resins to resins. It is useful as a surface modifier.
【００２９】[0029]
【発明の効果】本発明の化合物は、親水性物質表面の疎
水性化、付着促進、防汚、表面補強などの処理に有用で
ある。特に、歯科用コンポジットレジンのシランカップ
リング剤として用いると、セラミックスに対するレジン
の接着性と耐水耐久性を向上することができる。Industrial Applicability The compound of the present invention is useful for treatments such as making the surface of a hydrophilic substance hydrophobic, promoting adhesion, antifouling, and surface reinforcement. In particular, when used as a silane coupling agent for a dental composite resin, the adhesiveness of the resin to ceramics and the water resistance can be improved.
【００３０】[0030]
【実施例】以下、本発明を参考例、実施例を用いてより
詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to Examples and Examples.
【００３１】参考例１ ３−（ペルフルオロ−３−メチルブチル）−２−アリロ
キシプロピルメタクリレートの製造 還流冷却器、滴下ロートを装備した３００ml二口ナス型
フラスコに、水素化ナトリウム・オイルサスペンジョン
を採り、窒素置換した。置換後、精製ヘキサンにより窒
素下で洗浄する操作を４回繰り返し、ヘキサンを減圧留
去し、青白色粉末の水素化ナトリウム１．５ｇ（６２．
７ｍｍｏｌ）を得た。 Reference Example 1 Production of 3- (perfluoro-3-methylbutyl) -2-allyloxypropyl methacrylate A sodium hydride / oil suspension was placed in a 300 ml two-necked eggplant type flask equipped with a reflux condenser and a dropping funnel. It was replaced with nitrogen. After the replacement, the operation of washing with purified hexane under nitrogen was repeated four times, hexane was distilled off under reduced pressure, and 1.5 g of sodium hydride (62.
7 mmol).
【００３２】３−（ペルフルオロ−３−メチルブチル）
−２−ヒドロキシプロピルメタクリレート２５．８ｇ
（６２．６ｍｍｏｌ）をペルフルオロヘキサン１０mlに
溶解させ、氷冷下でこの溶液を１滴／秒の割合で穏やか
に滴下した。滴下終了後、氷浴から室温に換え、約３時
間撹拌した。ナトリウムアルコキシドに、アリルブロミ
ド８０ml（６６１ｍｍｏｌ）を加え、室温で２時間撹拌
し、その後加熱温度が４８〜５０℃を保つように制御し
て７２時間加熱還流を行った。還流終了後、ヘキサンを
加えヘキサン可溶化物を抽出し、未反応の水素化ナトリ
ウム及び析出した臭化ナトリウムを減圧濾過し、濾液を
十分に水洗し、ペルフルオロヘキサン、過剰のアリルブ
ロミドおよびヘキサンを減圧留去した。残留物を展開溶
媒（ジクロロメタン：ヘキサン＝２：１）に溶解させ、
ワコーゲルＣ−３００を充填したカラムにて副生成物を
除去し、減圧蒸留で目的物を得た。3- (perfluoro-3-methylbutyl)
25.8 g of 2-hydroxypropyl methacrylate
(62.6 mmol) was dissolved in 10 ml of perfluorohexane, and this solution was gently dropped at a rate of 1 drop / sec under ice-cooling. After completion of the dropwise addition, the temperature was changed from an ice bath to room temperature, and the mixture was stirred for about 3 hours. 80 ml (661 mmol) of allyl bromide was added to the sodium alkoxide, and the mixture was stirred at room temperature for 2 hours, and then heated and refluxed for 72 hours while controlling the heating temperature at 48 to 50 ° C. After the reflux was completed, hexane was added to extract a hexane solubilized substance, unreacted sodium hydride and precipitated sodium bromide were filtered under reduced pressure, the filtrate was sufficiently washed with water, and perfluorohexane, excess allyl bromide and hexane were removed under reduced pressure. Distilled off. The residue was dissolved in a developing solvent (dichloromethane: hexane = 2: 1),
By-products were removed with a column packed with Wakogel C-300, and the desired product was obtained by distillation under reduced pressure.
【００３３】収率６５．１％。無色液体。[0033] Yield 65.1%. Colorless liquid.
【００３４】沸点／Ｐａ＝４８〜５０℃／０．０２５1 Ｈ−ＮＭＲ(CDCl3)δ：1.96(s, 3H), 2.34-2.45(m, 2
H), 4.02-4.29(m, 5H),5.19-5.32(m, 2H), 5.61(s, 1
H), 5.85-5.93(m, 1H),6.13(s, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2963, 2869, 1735, 1640, 12
47, 1150 MS(m/e): 452(M+)参考例２ ３−（ペルフルオロ−５−メチルヘキシル）−２−アリ
ロキシプロピルメタクリレートの製造 下記の原料、反応時間、還流時間、還流温度を用いた以
外は参考例１と同様にして標記化合物を得た。収率６
５．１％。無色液体。Boiling point / Pa = 48-50 ° C./0.025 1 H-NMR (CDCl 3 ) δ: 1.96 (s, 3H), 2.34-2.45 (m, 2
H), 4.02-4.29 (m, 5H), 5.19-5.32 (m, 2H), 5.61 (s, 1
H), 5.85-5.93 (m, 1H), 6.13 (s, 1H). IR (KBr) ν (cm -1 ): 2963, 2869, 1735, 1640, 12
47, 1150 MS (m / e): 452 (M + ) Reference Example 2 Production of 3- (perfluoro-5-methylhexyl) -2-allyloxypropyl methacrylate The title compound was obtained in the same manner as in Reference Example 1 except that it was used. Yield 6
5.1%. Colorless liquid.
【００３５】 沸点／Ｐａ＝６３〜６５℃／０．０２５1 Ｈ−ＮＭＲ(CDCl3)δ：1.95(s, 3H), 2.33-2.44(m, 2H), 4.01-4.29(m, 5H), 5.19-5.32(m, 2H), 5.61(s, 1H), 5.84-5.92(m, 1H), 6.13(s, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2963, 2867, 1734, 1640, 1246, 1150 MS(m/e): 552(M+) ・3-(ヘ゜ルフルオロ-5-メチルヘキシル)-2-ヒト゛ロキシフ゜ロヒ゜ルメタクリレート 25.8g (62.6mmol) ・水素化ナトリウム 0.756g (31.5mmol) ・アリルブロミド 100ml (827mmol) ・ペルフルオロヘキサン 10ml アルコキシドの反応時間＝３時間 還流時間＝１００時間 還流温度＝５０℃参考例３ ３−（ペルフルオロ−７−メチルオクチル）−２−アリ
ロキシプロピルメタクリレートの製造 下記の原料、反応時間、還流時間、還流温度を用いた以
外は参考例１と同様にして標記化合物を得た。収率６
５．１％。無色液体。Boiling point / Pa = 63-65 ° C./0.025 1 H-NMR (CDCl 3 ) δ: 1.95 (s, 3H), 2.33-2.44 (m, 2H), 4.01-4.29 (m, 5H), 5.19-5.32 (m, 2H), 5.61 (s, 1H), 5.84-5.92 (m, 1H), 6.13 (s, 1H). IR (KBr) ν (cm -1 ): 2963, 2867, 1734, 1640 , 1246, 1150 MS (m / e): 552 (M + ) ・ 3- (Perfluoro-5-methylhexyl) -2-human peroxyfluoro methacrylate 25.8 g (62.6 mmol) ・ Sodium hydride 0.756 g (31.5 mmol) ・Allyl bromide 100 ml (827 mmol) ・ Perfluorohexane 10 ml Reaction time of alkoxide = 3 hours Reflux time = 100 hours Reflux temperature = 50 ° C. Reference Example 3 Production of 3- (perfluoro-7-methyloctyl) -2-allyloxypropyl methacrylate The title compound was obtained in the same manner as in Reference Example 1 except that the starting material, reaction time, reflux time and reflux temperature were used. Yield 6
5.1%. Colorless liquid.
【００３６】 沸点／Ｐａ＝８０〜８３℃／０．０２５1 Ｈ−ＮＭＲ(CDCl3)δ：1.96(s, 3H), 2.33-2.40(m, 2H), 4.02-4.29(m, 5H), 5.19-5.32(m, 2H), 5.61(s, 1H), 5.86-5.93(m, 1H), 6.14(s, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2963, 2863, 1723, 1640, 1248, 1150 MS(m/e): 652(M+) ・3-(ヘ゜ルフルオロ-7-メチルオクチル)-2-ヒト゛ロキシフ゜ロヒ゜ルメタクリレート 25.1g (41.0mmol) ・水素化ナトリウム 1.0g (31.5mmol) ・アリルブロミド 100ml (827mmol) ・ペルフルオロヘキサン 30ml アルコキシドの反応時間＝６時間 還流時間＝１００時間 還流温度＝６０℃実施例１ ３−〔３−（ペルフルオロ−３−メチルブチル）−１−
メタクリロキシ−２−プロパノキシル〕プロピルトリメ
トキシシランの製造 以下の反応は全て窒素下で行った。還流冷却器、滴下ロ
ートを装備した５０ml二口ナス型フラスコに、３−（ペ
ルフルオロ−３−メチルブチル）−２−アリロキシプロ
ピルメタクリレート4.13g(97.7mmol)、塩化白金（IV）
酸（H2PtCl6；0.1M塩化白金酸メタノール溶液)0.1ml、
ラジカル重合防止剤として2,5-ジ-tert-ブチルヒドロキ
ノン4.0mgを導入した。次に、このフラスコを室温で３
０分撹拌した後、室温でトリメトキシシラン1.5ml(11.8
mmol)を滴下ロートより１時間かけて滴下し、室温で３
時間撹拌した。反応終了後、過剰のトリメトキシシラン
及びメタノールを減圧留去し、反応生成物にヘキサン10
mlを添加し、析出した白金及びゲル（高分子量重合物）
を濾過により除去した。ヘキサンを減圧留去し、減圧蒸
留して目的の標記化合物を得た。収率８５．５％。無色
液体。Boiling point / Pa = 80-83 ° C./0.025 1 H-NMR (CDCl 3 ) δ: 1.96 (s, 3H), 2.33-2.40 (m, 2H), 4.02-4.29 (m, 5H), 5.19-5.32 (m, 2H), 5.61 (s, 1H), 5.86-5.93 (m, 1H), 6.14 (s, 1H). IR (KBr) ν (cm -1 ): 2963, 2863, 1723, 1640 , 1248, 1150 MS (m / e): 652 (M + ) ・ 3- (Perfluoro-7-methyloctyl) -2-human peroxyfluoromethacrylate 25.1 g (41.0 mmol) ・ Sodium hydride 1.0 g (31.5 mmol) ・Allyl bromide 100 ml (827 mmol) ・ Perfluorohexane 30 ml Reaction time of alkoxide = 6 hours Reflux time = 100 hours Reflux temperature = 60 ° C. Example 1 3- [3- (Perfluoro-3-methylbutyl) -1-
Preparation of [methacryloxy-2-propanoxyl] propyltrimethoxysilane The following reactions were all performed under nitrogen. In a 50 ml two-necked eggplant type flask equipped with a reflux condenser and a dropping funnel, 4.13 g (97.7 mmol) of 3- (perfluoro-3-methylbutyl) -2-allyloxypropyl methacrylate, platinum (IV) chloride
0.1 ml of acid (H 2 PtCl 6 ; 0.1M chloroplatinic acid in methanol)
4.0 mg of 2,5-di-tert-butylhydroquinone was introduced as a radical polymerization inhibitor. Next, the flask was placed at room temperature for 3 hours.
After stirring for 0 minutes, 1.5 ml of trimethoxysilane (11.8
mmol) was added dropwise from the dropping funnel over 1 hour.
Stirred for hours. After the completion of the reaction, excess trimethoxysilane and methanol were distilled off under reduced pressure, and hexane 10
Addition of ml, precipitated platinum and gel (high molecular weight polymer)
Was removed by filtration. Hexane was distilled off under reduced pressure and distilled under reduced pressure to obtain the target title compound. 85.5% yield. Colorless liquid.
【００３７】沸点／Ｐａ＝６４〜６８℃／０．０３１1 H-NMR(CDCl3)δ：0.63-0.68(m, 2H), 1.64-1.70(m, 2
H), 1.95(s, 3H),2.34-2.39(m, 2H), 3.42-3.50(m, 2
H), 3.56(s, 9H),3.94-3.97(m, 1H), 4.18-4.28(m, 2
H), 5.61(s, 1H),6.13(s, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2950, 2847, 1735, 1640, 12
49, 1144, 1080実施例２ ３−〔３−（ペルフルオロ−５−メチルヘキシル）−１
−メタクリロキシ−２−プロパノキシル〕プロピルトリ
メトキシシランの製造 下記の原料および反応時間を用いた以外は実施例１と同
様にして標記化合物を得た。収率７２．６％。無色液
体。Boiling point / Pa = 64-68 ° C./0.031 1 H-NMR (CDCl 3 ) δ: 0.63-0.68 (m, 2H), 1.64-1.70 (m, 2
H), 1.95 (s, 3H), 2.34-2.39 (m, 2H), 3.42-3.50 (m, 2
H), 3.56 (s, 9H), 3.94-3.97 (m, 1H), 4.18-4.28 (m, 2
H), 5.61 (s, 1H), 6.13 (s, 1H). IR (KBr) ν (cm -1 ): 2950, 2847, 1735, 1640, 12
49, 1144, 1080 Example 2 3- [3- (Perfluoro-5-methylhexyl) -1
Preparation of -methacryloxy-2-propanoxyl] propyltrimethoxysilane The title compound was obtained in the same manner as in Example 1 except that the following raw materials and reaction time were used. Yield 72.6%. Colorless liquid.
【００３８】 沸点／Ｐａ＝８０〜８２℃／０．０２８1 H-NMR(CDCl3)δ：0.63-0.68(m, 2H), 1.64-1.70(m, 2H), 1.95(s, 3H), 2.34-2.38(m, 2H), 3.42-3.50(m, 2H), 3.56(s, 9H), 3.94-3.97(m, 1H), 4.18-4.27(m, 2H), 5.61(s, 1H), 6.13(s, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2949, 2850, 1735, 1640, 1249, 1144, 1085 ・3-(ヘ゜ルフルオロ-5-メチルヘキシル)-2-アリロキシフ゜ロヒ゜ルメタクリレート 6.04g (10.9mmol) ・トリメトキシシラン 1.7ml (12.3mmol) ・0.1M塩化白金酸メタノール溶液 0.1ml ・2,5-ジ-tert-ブチルヒドロキノン 6.0mg 反応時間＝３時間実施例３ ３−〔３−（ペルフルオロ−７−メチルオクチル）−１
−メタクリロキシ−２−プロパノキシル〕プロピルトリ
メトキシシランの製造 下記の原料および反応時間を用いた以外は実施例１と同
様にして標記化合物を得た。収率８７．２％。無色液
体。Boiling point / Pa = 80-82 ° C./0.028 1 H-NMR (CDCl 3 ) δ: 0.63-0.68 (m, 2H), 1.64-1.70 (m, 2H), 1.95 (s, 3H), 2.34-2.38 (m, 2H), 3.42-3.50 (m, 2H), 3.56 (s, 9H), 3.94-3.97 (m, 1H), 4.18-4.27 (m, 2H), 5.61 (s, 1H), 6.13 (s, 1H). IR (KBr) ν (cm −1 ): 2949, 2850, 1735, 1640, 1249, 1144, 1085 ・ 3- (Hexfluoro-5-methylhexyl) -2-allyloxyfluoromethacrylate 6.04 g (10.9 mmol) ・ Trimethoxysilane 1.7 ml (12.3 mmol) ・ 0.1 M methanol solution of chloroplatinic acid 0.1 ml ・ 2,5-di-tert-butylhydroquinone 6.0 mg Reaction time = 3 hours Example 33- [3 -(Perfluoro-7-methyloctyl) -1
Preparation of -methacryloxy-2-propanoxyl] propyltrimethoxysilane The title compound was obtained in the same manner as in Example 1 except that the following raw materials and reaction time were used. Yield 87.2%. Colorless liquid.
【００３９】 沸点／Ｐａ＝９６〜９９℃／０．０２２1 H-NMR(CDCl3)δ：0.64-0.68(m, 2H), 1.64-1.70(m, 2H), 1.95(s, 3H), 2.33-2.38(m, 2H), 3.42-3.50(m, 2H), 3.56(s, 9H), 3.95-3.97(m, 1H), 4.18-4.27(m, 2H) , 5.61(s, 1H), 6.13(s, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2948, 2846, 1728, 1640, 1250, 1144, 1088 ・3-(ヘ゜ルフルオロ-7-メチルオクチル)-2-アリロキシフ゜ロヒ゜ルメタクリレート 4.05g (6.2mmol) ・トリメトキシシラン 0.95ml (7.5mmol) ・0.1M塩化白金酸メタノール溶液 0.1ml ・2,5-ジ-tert-ブチルヒドロキノン 4.0mg 反応時間＝３時間参考例４ ３−（ペルフルオロブチル）−２−プロペニルアリルエ
ーテルの製造 ３−ペルフルオロブチル−２−プロペン−１−オール３
０．６ｇ（０．１１ｍｏｌ）をペルフルオロヘキサン１
０mlに溶解させ、氷冷下でこの溶液を１滴／秒の割合で
穏やかに滴下した。滴下終了後、氷浴から室温に換え、
約５時間撹拌した。ナトリウムアルコキシドに、アリル
ブロミド１００ml（０．８３ｍｏｌ）を加え、室温で３
時間撹拌し、その後加熱温度が４８〜５０℃を保つよう
に制御して５時間加熱還流を行った。還流終了後、ヘキ
サンを加えヘキサン可溶化物を抽出し、未反応の水素化
ナトリウム及び析出した臭化ナトリウムを減圧濾過し、
濾液を十分に水洗し、ペルフルオロヘキサン、アリルブ
ロミドおよびヘキサンを減圧留去した。残留物の減圧蒸
留により目的とする標記化合物を得た。Boiling point / Pa = 96-99 ° C./0.022 1 H-NMR (CDCl 3 ) δ: 0.64-0.68 (m, 2H), 1.64-1.70 (m, 2H), 1.95 (s, 3H), 2.33-2.38 (m, 2H), 3.42-3.50 (m, 2H), 3.56 (s, 9H), 3.95-3.97 (m, 1H), 4.18-4.27 (m, 2H), 5.61 (s, 1H), 6.13 (s, 1H). IR (KBr) ν (cm -1 ): 2948, 2846, 1728, 1640, 1250, 1144, 1088 ・ 3- (Hethylfluoro-7-methyloctyl) -2-allyloxyfluoromethacrylate 4.05 g (6.2 mmol) Trimethoxysilane 0.95 ml (7.5 mmol) 0.1 M methanol solution of chloroplatinic acid 0.1 ml 2,5-di-tert-butylhydroquinone 4.0 mg Reaction time = 3 hours Reference Example 4 3- (perfluoro Preparation of butyl) -2-propenyl allyl ether 3-perfluorobutyl-2-propen-1-ol 3
0.6 g (0.11 mol) of perfluorohexane 1
The solution was gently dropped at a rate of 1 drop / sec under ice-cooling. After dropping, change from ice bath to room temperature,
Stir for about 5 hours. 100 ml (0.83 mol) of allyl bromide was added to the sodium alkoxide, and the mixture was added at room temperature for 3 hours.
The mixture was stirred for 5 hours, and then heated and refluxed for 5 hours while controlling the heating temperature to be kept at 48 to 50 ° C. After completion of the reflux, hexane was added to extract the hexane solubilized matter, and unreacted sodium hydride and precipitated sodium bromide were filtered under reduced pressure,
The filtrate was sufficiently washed with water, and perfluorohexane, allyl bromide and hexane were distilled off under reduced pressure. The desired title compound was obtained by distillation of the residue under reduced pressure.
【００４０】収率４９．６％。無色液体。[0040] Yield 49.6%. Colorless liquid.
【００４１】沸点／Ｐａ＝５８〜６０℃／１２００1 H-NMR(CDCl3)δ：3.95-3.97(m, 2H), 4.05-4.07(m, 2
H), 5.14-5.25(m, 2H),5.78-5.91(m, 2H), 6.35-6.41
(m, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2859, 1685, 1649, 1221, 11
26 MS(m/e): 316(M+)参考例５ ３−（ペルフルオロヘキシル）−２−プロペニルアリル
エーテルの製造 下記の原料、反応時間、還流時間、還流温度を用いた以
外は参考例４と同様にして標記化合物を得た。収率７
２．６％。無色液体。Boiling point / Pa = 58-60 ° C./1200 1 H-NMR (CDCl 3 ) δ: 3.95-3.97 (m, 2H), 4.05-4.07 (m, 2
H), 5.14-5.25 (m, 2H), 5.78-5.91 (m, 2H), 6.35-6.41
(m, 1H). IR (KBr) ν (cm −1 ): 2859, 1685, 1649, 1221, 11
26 MS (m / e): 316 (M + ) Reference Example 5 Production of 3- (perfluorohexyl) -2-propenyl allyl ether Reference Example 4 except that the following raw materials, reaction time, reflux time and reflux temperature were used. The title compound was obtained in the same manner as described above. Yield 7
2.6%. Colorless liquid.
【００４２】 沸点／Ｐａ＝４９〜５０℃／１５０1 H-NMR(CDCl3)δ：3.95-3.97(m, 2H), 4.05-4.07(m, 2H), 5.14-5.25(m, 2H), 5.77-5.90(m, 2H), 6.34-6.40(m, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2859, 1682, 1649, 1261, 1103 MS(m/e): 416(M+) ・3-ヘ゜ルフルオロヘキシル-2-フ゜ロヘ゜ン-1-オール 30.6g (81.4mmol) ・水素化ナトリウム 2.0g (83.3mmol) ・アリルブロミド 100ml (827mmol) ・ペルフルオロヘキサン 10ml アルコキシドの反応時間＝５時間 還流時間＝１２時間 還流温度＝５０℃参考例６ ３−（ペルフルオロオクチル）−２−プロペニルアリル
エーテルの製造 下記の原料、反応時間、還流時間、還流温度を用いた以
外は参考例４と同様にして標記化合物を得た。収率８
７．２％。無色液体。Boiling point / Pa = 49-50 ° C./150 1 H-NMR (CDCl 3 ) δ: 3.95-3.97 (m, 2H), 4.05-4.07 (m, 2H), 5.14-5.25 (m, 2H), 5.77-5.90 (m, 2H), 6.34-6.40 (m, 1H). IR (KBr) ν (cm -1 ): 2859, 1682, 1649, 1261, 1103 MS (m / e): 416 (M + ) 30.6 g (81.4 mmol) of 3-phenylfluorohexyl-2-fluoropent-1-ol ・ 2.0 g (83.3 mmol) of sodium hydride ・ 100 ml (827 mmol) of allyl bromide ・ 10 ml of perfluorohexane Reaction time of alkoxide = 5 hours Reflux time = 12 hours, reflux temperature = 50 ° C. Reference Example 6 Production of 3- (perfluorooctyl) -2-propenyl allyl ether The title compound was prepared in the same manner as in Reference Example 4 except that the following raw materials, reaction time, reflux time, and reflux temperature were used. I got Yield 8
7.2%. Colorless liquid.
【００４３】 沸点／Ｐａ＝５５〜５７℃／１５1 H-NMR(CDCl3)δ：3.95-3.97(m, 2H), 4.05-4.07(m, 2H), 5.14-5.25(m, 2H), 5.78-5.90(m, 2H), 6.34-6.39(m, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2857, 1682, 1649, 1231, 1111 MS(m/e): 516(M+) ・3-ヘ゜ルフルオロオクチル-2-フ゜ロヘ゜ン-1-オール 30.9g (64.9mmol) ・水素化ナトリウム 1.6g (66.7mmol) ・アリルブロミド 100ml (827mmol) ・ペルフルオロヘキサン 10ml アルコキシドの反応時間＝５時間 還流時間＝２０時間 還流温度＝６０℃実施例４ ３−（ペルフルオロブチル−２−プロペノキシル）プロ
ピルトリメトキシシランの製造 以下の反応は全て窒素下で行った。還流冷却器を装備し
た５０ml二口ナス型フラスコに、３−（ペルフルオロブ
チル−２−プロペニルアリルエーテル9.1g(28.8mmol)、
トリメトキシシラン7.3ml(57.7mmol)、塩化白金（IV）
酸（0.1M塩化白金酸メタノール溶液)0.1ml、ラジカル重
合防止剤として2,5-ジ-tert-ブチルヒドロキノン9.0mg
を導入し、室温で６時間撹拌した。反応終了後、過剰の
トリメトキシシランを減圧留去し、減圧蒸留して目的の
標記化合物を得た。収率５８．６％。無色液体。Boiling point / Pa = 55-57 ° C./15 1 H-NMR (CDCl 3 ) δ: 3.95-3.97 (m, 2H), 4.05-4.07 (m, 2H), 5.14-5.25 (m, 2H), 5.78-5.90 (m, 2H), 6.34-6.39 (m, 1H). IR (KBr) ν (cm -1 ): 2857, 1682, 1649, 1231, 1111 MS (m / e): 516 (M + ) 30.9 g (64.9 mmol) of sodium 3-hydride, 1.6 g (66.7 mmol) of sodium hydride, 100 ml (827 mmol) of allyl bromide, 10 ml of perfluorohexane Reaction time of alkoxide = 5 hours Reflux time = 20 hours, reflux temperature = 60 ° C. Example 4 Preparation of 3- (perfluorobutyl-2-propenoxyl) propyltrimethoxysilane All the following reactions were performed under nitrogen. In a 50 ml two-necked eggplant type flask equipped with a reflux condenser, 9.1 g (28.8 mmol) of 3- (perfluorobutyl-2-propenyl allyl ether) was added.
7.3 ml (57.7 mmol) of trimethoxysilane, platinum (IV) chloride
Acid (0.1 M methanolic chloroplatinic acid solution) 0.1 ml, 2,5-di-tert-butylhydroquinone 9.0 mg as radical polymerization inhibitor
And stirred at room temperature for 6 hours. After the completion of the reaction, excess trimethoxysilane was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain the target title compound. Yield 58.6%. Colorless liquid.
【００４４】沸点／Ｐａ＝６４〜６６℃／１２1 H-NMR(CDCl3)δ：0.64-0.74(m, 2H), 1.66-1.75(m, 2
H),3.43-3.49(t, J=13.5Hz, 2H), 3.56(s, 9H),4.09-4.
12(m, 2H), 5.88-5.96(m, 1H),6.41-6.47(m, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2948, 2844, 1680, 1242, 11
07, 1080実施例５ ３−（ペルフルオロヘキシル−２−プロペノキシル）プ
ロピルトリメトキシシランの製造 下記の原料および反応時間を用いた以外は実施例４と同
様にして標記化合物を得た。収率５３．７％。無色液
体。Boiling point / Pa = 64-66 ° C./12 1 H-NMR (CDCl 3 ) δ: 0.64-0.74 (m, 2H), 1.66-1.75 (m, 2
H), 3.43-3.49 (t, J = 13.5Hz, 2H), 3.56 (s, 9H), 4.09-4.
12 (m, 2H), 5.88-5.96 (m, 1H), 6.41-6.47 (m, 1H). IR (KBr) ν (cm -1 ): 2948, 2844, 1680, 1242, 11
07, 1080 Example 5 Production of 3- (perfluorohexyl-2-propenoxyl) propyltrimethoxysilane The title compound was obtained in the same manner as in Example 4 except that the following raw materials and reaction time were used. Yield 53.7%. Colorless liquid.
【００４５】 沸点／Ｐａ＝７４〜７５℃／１２1 H-NMR(CDCl3)δ：0.63-0.73(m, 2H), 1.65-1.74(m, 2H), 3.42-3.48(t, J=13.5Hz, 2H), 3.56(s, 9H), 4.09-4.12(m, 2H), 5.86-5.96(m, 1H), 6.41-6.47(m, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2949, 2845, 1680, 1252, 1068, 1083 ・3-(ヘ゜ルフルオロヘキシル)-2-フ゜ロヘ゜ニルアリルエーテル 9.9g (23.8mmol) ・トリメトキシシラン 6.0ml (47.1mmol) ・0.1M塩化白金酸メタノール溶液 0.1ml ・2,5-ジ-tert-ブチルヒドロキノン 8.0mg 反応時間＝６時間実施例６ ３−（ペルフルオロオクチル−２−プロペノキシル）プ
ロピルトリメトキシシランの製造 下記の原料および反応時間を用いた以外は実施例４と同
様にして標記化合物を得た。収率５２．４％。無色液
体。Boiling point / Pa = 74-75 ° C./12 1 H-NMR (CDCl 3 ) δ: 0.63-0.73 (m, 2H), 1.65-1.74 (m, 2H), 3.42-3.48 (t, J = 13.5) Hz, 2H), 3.56 (s, 9H), 4.09-4.12 (m, 2H), 5.86-5.96 (m, 1H), 6.41-6.47 (m, 1H). IR (KBr) ν (cm -1 ): 2949, 2845, 1680, 1252, 1068, 1083 ・ 3- (Perfluorohexyl) -2-fluorophenyl allyl ether 9.9 g (23.8 mmol) ・ Trimethoxysilane 6.0 ml (47.1 mmol) ・ 0.1 M methanolic chloroplatinic acid 0.1 ml・ 2,5-di-tert-butylhydroquinone 8.0 mg Reaction time = 6 hours Example 6 Production of 3- (perfluorooctyl-2-propenoxyl) propyltrimethoxysilane Example was performed except that the following raw materials and reaction time were used. The title compound was obtained in the same manner as in Example 4. Yield 52.4%. Colorless liquid.
【００４６】 沸点／Ｐａ＝８４〜８５℃／１０1 H-NMR(CDCl3)δ：0.64-0.75(m, 2H), 1.66-1.74(m, 2H), 3.43-3.49(t, J=13.5Hz, 2H), 3.55(s, 9H), 4.10-4.12(m, 2H), 5.89-5.97(m, 1H), 6.42-6.48(m, 1H). ＩＲ（ＫＢｒ）ν(cm-1)：2945, 2849, 1680, 1248, 1188, 1074 ・3-(ヘ゜ルフルオロオクチル)-2-フ゜ロヘ゜ニルアリルエーテル 9.8g (20.0mmol) ・トリメトキシシラン 5.0ml (39.3mmol) ・0.1M塩化白金酸メタノール溶液 0.1ml ・2,5-ジ-tert-ブチルヒドロキノン 4.0mg 反応時間＝６時間Boiling point / Pa = 84-85 ° C./10 1 H-NMR (CDCl 3 ) δ: 0.64-0.75 (m, 2H), 1.66-1.74 (m, 2H), 3.43-3.49 (t, J = 13.5) Hz, 2H), 3.55 (s, 9H), 4.10-4.12 (m, 2H), 5.89-5.97 (m, 1H), 6.42-6.48 (m, 1H). IR (KBr) ν (cm −1 ): 2945, 2849, 1680, 1248, 1188, 1074 ・ 3- (Perfluorooctyl) -2-fluorophenyl allyl ether 9.8g (20.0mmol) ・ Trimethoxysilane 5.0ml (39.3mmol) ・ 0.1M methanolic chloroplatinic acid 0.1ml 0.1ml・ 2,5-di-tert-butylhydroquinone 4.0mg Reaction time = 6 hours
Claims (2)
塩素原子、メトキシ基またはエトキシ基を示す。Ｒｆ
は、炭素数４〜１６のパーフルオロアルキル基を示
す。〕で表される化合物。1. A compound of the general formula (I) [Wherein, R 1 represents a hydrogen atom or a methyl group. R 2 is
It represents a chlorine atom, a methoxy group or an ethoxy group. Rf
Represents a perfluoroalkyl group having 4 to 16 carbon atoms. ] The compound represented by these.
ｆは、炭素数４〜１６のパーフルオロアルキル基を示
す。〕で表される化合物。2. A compound of the general formula (II) Wherein R 2 represents a chlorine atom or a methoxy group. R
f shows a C4-C16 perfluoroalkyl group. ] The compound represented by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8237424A JPH1087671A (en) | 1996-09-09 | 1996-09-09 | Silane coupling agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8237424A JPH1087671A (en) | 1996-09-09 | 1996-09-09 | Silane coupling agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1087671A true JPH1087671A (en) | 1998-04-07 |
Family
ID=17015158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8237424A Pending JPH1087671A (en) | 1996-09-09 | 1996-09-09 | Silane coupling agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1087671A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011121966A1 (en) * | 2010-03-30 | 2011-10-06 | クラレメディカル株式会社 | One-pack dental adhesive material composition |
| JP2015160816A (en) * | 2014-02-26 | 2015-09-07 | 信越化学工業株式会社 | Polymerizable monomer and monomer for manufacture of ophthalmological device |
| EP2952516A1 (en) * | 2014-06-03 | 2015-12-09 | VOCO GmbH | Polysiloxane compound and dental materials that can be produced from same |
-
1996
- 1996-09-09 JP JP8237424A patent/JPH1087671A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011121966A1 (en) * | 2010-03-30 | 2011-10-06 | クラレメディカル株式会社 | One-pack dental adhesive material composition |
| JP4860788B2 (en) * | 2010-03-30 | 2012-01-25 | クラレメディカル株式会社 | One-part dental adhesive composition |
| US9271901B2 (en) | 2010-03-30 | 2016-03-01 | Kuraray Noritake Dental Inc. | One-part dental adhesive composition |
| JP2015160816A (en) * | 2014-02-26 | 2015-09-07 | 信越化学工業株式会社 | Polymerizable monomer and monomer for manufacture of ophthalmological device |
| EP2952516A1 (en) * | 2014-06-03 | 2015-12-09 | VOCO GmbH | Polysiloxane compound and dental materials that can be produced from same |
| US9532931B2 (en) | 2014-06-03 | 2017-01-03 | Voco Gmbh | Polysiloxane compound and dental materials that can be prepared from it |
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