JP4022712B2 - Fluorine-containing organosilicon compound - Google Patents
Fluorine-containing organosilicon compound Download PDFInfo
- Publication number
- JP4022712B2 JP4022712B2 JP2001122105A JP2001122105A JP4022712B2 JP 4022712 B2 JP4022712 B2 JP 4022712B2 JP 2001122105 A JP2001122105 A JP 2001122105A JP 2001122105 A JP2001122105 A JP 2001122105A JP 4022712 B2 JP4022712 B2 JP 4022712B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- fluorine
- bond
- organosilicon compound
- carbon atoms
- 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
- 229910052731 fluorine Inorganic materials 0.000 title claims description 18
- 239000011737 fluorine Substances 0.000 title claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 17
- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 11
- 125000000962 organic group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- -1 fluorine organosilicon compound Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910018540 Si C Inorganic materials 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 229910010271 silicon carbide Inorganic materials 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000005046 Chlorosilane Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000007818 Grignard reagent Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- PAJFATIYVLZNFC-UHFFFAOYSA-N chloromethyl(dimethyl)silicon Chemical compound C[Si](C)CCl PAJFATIYVLZNFC-UHFFFAOYSA-N 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は、一分子内にパーフルオロアルキレン基又はパーフルオロオキシアルキレン基に隣接するエチレン性不飽和基とヒドロシリル基（ＳｉＨ基）とを有する含フッ素有機ケイ素化合物に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来より、一分子内にパーフルオロアルキレン基又はパーフルオロオキシアルキレン基とエチレン性不飽和基或いはヒドロシリル基（ＳｉＨ基）を有する含フッ素有機ケイ素化合物は種々提案され、幅広い用途に使用されているが、熱硬化性エラストマーなどに添加することにより、架橋点として作用し、架橋密度の調整剤やゴム硬度の向上剤としてより有効な含フッ素有機ケイ素化合物、或いはエラストマー同士の接着を向上させるプライマー化合物やシリカフィラーなどの表面処理剤としてより有用な含フッ素有機ケイ素化合物が望まれている。
【０００３】
【課題を解決するための手段及び発明の実施の形態】
本発明者は、上記要望に応えるために鋭意検討を行った結果、後述する方法によって得られる下記一般式（１）の含フッ素有機ケイ素化合物が熱硬化性エラストマーなどに添加することにより、架橋点として作用し、このため架橋密度の調整剤やゴム硬度の向上剤として有用であり、また、エラストマー同士の接着を向上させるプライマー化合物、シリカフィラーなどの表面処理剤として有用であることを見出し、本発明をなすに至った。
【０００４】
すなわち、本発明は、一分子内にパーフルオロアルキレン基又はパーフルオロオキシアルキレン基若しくはポリパーフルオロオキシアルキレン基に隣接するエチレン性不飽和基と、ヒドロシリル基（ＳｉＨ基）とを有する化合物であって、下記一般式（１）
【化２】
Ｒ1、Ｒ2、Ｒ3は炭素原子数１〜８の非置換又は置換一価炭化水素基、
Ｒｆは二価のパーフルオロアルキレン基又はパーフルオロオキシアルキレン基若しくはポリパーフルオロオキシアルキレン基、
Ｒ4は二価の有機基、
Ｒ5は酸素原子又は二価の有機基、
ａは０〜２の整数を示す。）
で表わされる含フッ素有機ケイ素化合物を提供する。
【０００５】
以下、本発明につき更に詳しく説明する。
本発明の含フッ素有機ケイ素化合物は、上述したように、下記一般式（１）で示されるものである。
【０００６】
【化３】
ここで、Ｒ1、Ｒ2、Ｒ3は炭素原子数１〜８の非置換又は置換一価炭化水素基であり、炭素原子数１〜８の非置換又は置換一価炭化水素基としては、メチル基、エチル基、プロピル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、フェニル基、トリル基などのアリール基、あるいはこれらの基の水素原子が部分的に又は全部がハロゲン原子で置換された基が例示される。
【０００８】
Ｒ4は二価の有機基であり、Ｒ4の二価の有機基としては、結合途中にアミド結合、スルホニルアミド結合、エーテル結合、エステル結合、ウレタン結合から選ばれる結合を含んでいても良い炭素原子数１〜８の非置換又は置換の二価炭化水素基であることが好ましく、炭素原子数１〜８の非置換又は置換二価炭化水素基としては、メチレン基、エチレン基、プロピレン基などのアルキレン基、シクロヘキシレン基などのシクロアルキレン基、フェニレン基などのアリーレン基、あるいはこれらの基の水素原子が部分的に又は全部がハロゲン原子で置換された基が例示される。
【０００９】
また、結合途中にアミド結合、スルホニルアミド結合、エーテル結合、エステル結合、ウレタン結合から選ばれる結合を含むものとしては、それぞれＣＯＮＲ、ＳＯ2ＮＲ、Ｏ、ＣＯＯ、ＯＣＯＮＲ（但し、Ｒは水素原子又はメチル基、エチル基等のアルキル基やフェニル基等のアリール基などの炭素原子数１〜８の一価炭化水素基）として介在又は含有することができ、具体的には下記のものが例示される。
【００１０】
【化４】
【００１１】
Ｒ5は酸素原子（−Ｏ−）又は二価の有機基であり、二価の有機基としては、炭素原子数１〜８の非置換又は置換の二価炭化水素基が好ましく、具体的には、メチレン基、エチレン基、プロピレン基などのアルキレン基、シクロヘキシレン基などのシクロアルキレン基、フェニレン基などのアリーレン基、あるいはこれらの基の水素原子が部分的に又は全部がハロゲン原子で置換された基が例示される。
【００１２】
Ｒｆはパーフルオロアルキレン基又はパーフルオロオキシアルキレン基若しくはポリパーフルオロオキシアルキレン基であり、パーフルオロアルキレン基としては炭素原子数１〜２０のものが、パーフルオロオキシアルキレン基若しくはポリパーフルオロオキシアルキレン基としては炭素原子数２〜１００のものが好ましい。
【００１３】
ここで、パーフルオロアルキレン基は直鎖でも分岐していてもよく、下記のものが例示される。
【００１４】
−Ｃ2Ｆ4−、−Ｃ3Ｆ6−、−Ｃ4Ｆ8−、−Ｃ6Ｆ12−、−Ｃ8Ｆ16−
【００１５】
【化５】
パーフルオロオキシアルキレン基としては、繰り返し単位
（Ｒｆ’−Ｏ）
（式中、Ｒｆ’は炭素原子数１〜６、好ましくは炭素原子数１〜３の直鎖状又は分岐状のパーフルオロアルキレン基である）
を含有するものが挙げられ、例えば下記の単位等が挙げられる。なお、前記パーフルオロオキシアルキレン構造は、これらの繰り返し単位の１種単独で構成されていてもよいし、２種以上の組合せであってもよい。
【００１７】
−ＣＦ2Ｏ−、−ＣＦ2ＣＦ2Ｏ−、−ＣＦ2ＣＦ2ＣＦ2Ｏ−、
−ＣＦ（ＣＦ3）ＣＦ2Ｏ−、−ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−、
−ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−、−Ｃ（ＣＦ3）2Ｏ−
【００１８】
これらの中では特に下記単位が好適である。
−ＣＦ2Ｏ−、−ＣＦ2ＣＦ2Ｏ−、−ＣＦ2ＣＦ2ＣＦ2Ｏ−、
−ＣＦ（ＣＦ3）ＣＦ2Ｏ−
【００１９】
より具体的には、下記のものが例示される。
【化６】
次に、本発明の含フッ素有機ケイ素化合物を例示するが、これらは代表例であり、本発明の有機ケイ素化合物は以下に限定されるものではない。
【００２１】
【化７】
本発明の化合物は、種々な方法で合成可能であるが、例えば以下のような方法で合成できる。
【００２３】
即ち、下記一般式（２）
【化８】
で表わされるクロロシラン化合物を、クロロメチルジメチルシランから誘導されるグリニャール試薬中に滴下反応させ、反応物を２Ｎの塩酸水で洗浄した後、蒸留等で単離することによって下記一般式（１ａ）
【００２４】
【化９】
【００２５】
また、一般式（２）
【化１０】
【００２６】
【化１１】
【００２７】
【発明の効果】
本発明の含フッ素有機ケイ素化合物は、熱硬化性エラストマーなどに添加することにより、架橋点として作用し、このため架橋密度の調整剤、ゴム硬度の向上剤として有用である。また、エラストマー同士の接着を向上させるプライマー化合物、シリカフィラーなどの表面処理剤としても有用である。
【００２８】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
【００２９】
［実施例１］
撹拌棒、温度計、ジムロート、滴下ロートを付した３００ｍｌの四つ口フラスコ内部を乾燥窒素置換してから、マグネシウム粉末４．４７ｇ（０．１８４モル）とテトラヒドロフラン７０ｍｌ、ヨウ素の小片を仕込み、撹拌しながら６０℃に加温し、ヨウ素の褐色が消えるのを確認した後、クロロメチルジメチルシラン１９．０ｇ（０．１７５モル）を約３０分で滴下し、グリニャール試薬を調整した（反応温度５０〜６５℃）。
【００３０】
そこに、下記構造の含フッ素クロロシラン３４．８ｇ（０．０７４３モル）
【化１２】
【００３１】
反応液を２Ｎ塩酸水溶液２００ｍｌ中に投入し、分液により上層を分取し、さらに２００ｍｌの純水で水洗し、上層を分取した。これに硫酸ナトリウム２０ｇを加えて脱水、濾過し、濾液を蒸留して、１２８℃／３ｍｍＨｇの沸点を有する無色透明な留分２６．３ｇを得た。
【００３２】
得られた液体は、粘度（２５℃）＝７．９ｃＳｔ、比重（２５℃）＝１．２０５、屈折率（２５℃）＝１．４０２であった。さらに1Ｈ−ＮＭＲ、ＩＲ、ＧＣ−ＭＳ分析を行った結果、下記構造の化合物であることを確認した。
【００３３】
【化１３】
1 Ｈ−ＮＭＲ（ＴＭＳ標準）
δ＝−０．１９ｐｐｍ，４Ｈ（Ｓｉ−ＣＨ 2−Ｓｉ）
δ＝０．１７ｐｐｍ，１５Ｈ（Ｓｉ−ＣＨ 3）
δ＝０．８４ｐｐｍ，２Ｈ（Ｓｉ−ＣＨ 2−ＣＨ2）
δ＝２．０６ｐｐｍ，２Ｈ（ＣＦ2−ＣＨ 2）
δ＝４．０５ｐｐｍ，２Ｈ（Ｓｉ−Ｈ）
δ＝５．７〜６．２ｐｐｍ，３Ｈ（ＣＨ＝ＣＨ 2）
【００３５】
19 Ｆ−ＮＭＲ（ＣＦＣｌ 3 標準）
ａ：δ＝−１２４ｐｐｍ，４Ｆ
ｂ：δ＝−１２２ｐｐｍ，４Ｆ
ｃ：δ＝−１１６ｐｐｍ，２Ｆ
ｄ：δ＝−１１４ｐｐｍ，２Ｆ
【００３６】
【化１４】
ＩＲ
２１１０ｃｍ-1 ： νSi-H
１１００〜１３００ｃｍ-1 ： νC-F
【００３８】
ＧＣ−ＭＳ
Ｍ+ ＝ ５４３
【００３９】
［実施例２］
撹拌棒、温度計、ジムロート、滴下ロートを付した３００ｍｌの四つ口フラスコに純水７．３２ｇ、濃塩酸１９．６ｇ、テトラメチルジシロキサン４１．０ｇ（０．３０６モル）を仕込み、撹拌しながら内温１０℃以下まで冷却した。
【００４０】
そこに下記構造の含フッ素クロロシラン８３．２ｇ（０．１７０モル）
ＣＨ2＝ＣＨ−Ｃ6Ｆ12−Ｃ2Ｈ4−Ｓｉ−Ｃｌ3
を内温が１５℃以上にならないようにしながら約３０分かけて滴下し、滴下終了後、１５℃以下で１時間半かけて後撹拌し、その後純水６０ｇを投入した。
【００４１】
反応液を分液ロートに移して下層を分取し、これをさらに１００ｇの純水で水洗後、下層を分取した。これに硫酸ナトリウム１０ｇを加えて脱水、濾過し、濾液を蒸留して、１３５℃／２ｍｍＨｇの沸点を有する無色透明な留分５９．８ｇを得た。
【００４２】
得られた液体は、粘度（２５℃）＝４．６ｃＳｔ、比重（２５℃）＝１．１８２、屈折率（２５℃）＝１．３６３であった。さらに1Ｈ−ＮＭＲ、ＩＲ、ＧＣ−ＭＳ分析を行った結果、下記構造の化合物であることを確認した。
【００４３】
【化１５】
1 Ｈ−ＮＭＲ（ＴＭＳ標準）
δ＝０．１８ｐｐｍ，１８Ｈ（Ｓｉ−ＣＨ 3）
δ＝０．８５ｐｐｍ，２Ｈ（Ｓｉ−ＣＨ 2−ＣＨ2）
δ＝２．０５ｐｐｍ，２Ｈ（ＣＦ2−ＣＨ 2）
δ＝４．８１ｐｐｍ，３Ｈ（Ｓｉ−Ｈ）
δ＝５．７〜６．２ｐｐｍ，３Ｈ（ＣＨ＝ＣＨ 2）
【００４５】
19 Ｆ−ＮＭＲ（ＣＦＣｌ 3 標準）
ａ：δ＝−１２４ｐｐｍ，４Ｆ
ｂ：δ＝−１２２ｐｐｍ，４Ｆ
ｃ：δ＝−１１６ｐｐｍ，２Ｆ
ｄ：δ＝−１１４ｐｐｍ，２Ｆ
【００４６】
【化１６】
ＩＲ
２１３０ｃｍ-1 ： νSi-H
１１００〜１３００ｃｍ-1 ： νC-F
【００４８】
ＧＣ−ＭＳ
Ｍ+ ＝ ６０７
【００４９】
［実施例３］
撹拌棒、温度計、ジムロート、滴下ロートを付した３００ｍｌの四つ口フラスコ内部を乾燥窒素置換してから、マグネシウム粉末６．４０ｇ（０．２６モル）とテトラヒドロフラン８６ｍｌ、ヨウ素の小片を仕込み、撹拌しながら６０℃に加温し、ヨウ素の褐色が消えるのを確認した後、クロロメチルジメチルシラン２７．２ｇ（０．２５０モル）を約４０分で滴下し、グリニャール試薬を調整した（反応温度５０〜６５℃）。
【００５０】
そこに、下記構造の含フッ素クロロシラン５０．１ｇ（０．１００モル）
【化１７】
【００５１】
反応液を２Ｎ塩酸水溶液２５０ｍｌ中に投入し、分液により上層を分取し、さらに２５０ｍｌの純水で水洗し、上層を分取した。これに硫酸ナトリウム２４ｇを加えて脱水、濾過し、濾液を蒸留して、１１０℃／３ｍｍＨｇの沸点を有する無色透明な留分３２．３ｇを得た。
【００５２】
得られた液体は、粘度（２５℃）＝６．５ｃＳｔ、比重（２５℃）＝１．２３８、屈折率（２５℃）＝１．３８６であった。さらに1Ｈ−ＮＭＲ、ＩＲ、ＧＣ−ＭＳ分析を行った結果、下記構造の化合物であることを確認した。
【００５３】
【化１８】
1 Ｈ−ＮＭＲ（ＴＭＳ標準）
δ＝−０．１９ｐｐｍ，４Ｈ（Ｓｉ−ＣＨ 2−Ｓｉ）
δ＝０．１８ｐｐｍ，１５Ｈ（Ｓｉ−ＣＨ 3）
δ＝０．８６ｐｐｍ，２Ｈ（Ｓｉ−ＣＨ 2−ＣＨ2）
δ＝２．１８ｐｐｍ，２Ｈ（ＣＦ−ＣＨ 2）
δ＝４．０５ｐｐｍ，２Ｈ（Ｓｉ−Ｈ）
δ＝５．７〜６．２ｐｐｍ，３Ｈ（ＣＨ＝ＣＨ 2）
【００５５】
19 Ｆ−ＮＭＲ（ＣＦＣｌ 3 標準）
ａ：δ＝−１２８ｐｐｍ，２Ｆ
ｂ：δ＝−８５ｐｐｍ，４Ｆ
ｃ：δ＝−８０ｐｐｍ，６Ｆ
【００５６】
【化１９】
ＩＲ
２１１０ｃｍ-1 ： νSi-H
１１００〜１３００ｃｍ-1 ： νC-F
【００５８】
ＧＣ−ＭＳ
Ｍ+ ＝ ５７５[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fluorine-containing organosilicon compound having an ethylenically unsaturated group and a hydrosilyl group (SiH group) adjacent to a perfluoroalkylene group or perfluorooxyalkylene group in one molecule.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, various fluorine-containing organosilicon compounds having a perfluoroalkylene group or perfluorooxyalkylene group and an ethylenically unsaturated group or hydrosilyl group (SiH group) in one molecule have been proposed and used in a wide range of applications. , A fluorine-containing organosilicon compound that acts as a crosslinking point and is more effective as a crosslinking density adjuster and a rubber hardness improver, or a primer compound that improves adhesion between elastomers. A fluorine-containing organosilicon compound that is more useful as a surface treatment agent such as silica filler is desired.
[0003]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to meet the above-mentioned demands, the present inventor has added a fluorine-containing organosilicon compound of the following general formula (1) obtained by the method described later to a thermosetting elastomer and the like, so that a crosslinking point is obtained. It is found that it is useful as a crosslinking density adjuster and rubber hardness improver, and as a surface treatment agent such as a primer compound and silica filler for improving adhesion between elastomers. Invented the invention.
[0004]
That is, the present invention is a compound having an ethylenically unsaturated group adjacent to a perfluoroalkylene group, a perfluorooxyalkylene group or a polyperfluorooxyalkylene group and a hydrosilyl group (SiH group) in one molecule. The following general formula (1)
[Chemical 2]
R 1 , R 2 and R 3 are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms,
Rf is a divalent perfluoroalkylene group , a perfluorooxyalkylene group or a polyperfluorooxyalkylene group ,
R 4 is a divalent organic group,
R 5 represents an oxygen atom or a divalent organic group,
a shows the integer of 0-2. )
The fluorine-containing organosilicon compound represented by these is provided.
[0005]
Hereinafter, the present invention will be described in more detail.
As described above, the fluorine-containing organosilicon compound of the present invention is represented by the following general formula (1).
[0006]
[Chemical 3]
Here, R 1 , R 2 and R 3 are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and examples of an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms are as follows: Alkyl groups such as methyl group, ethyl group, and propyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and tolyl group, or hydrogen atoms of these groups are partially or entirely substituted with halogen atoms Are exemplified.
[0008]
R 4 is a divalent organic group, and the divalent organic group of R 4 may include a bond selected from an amide bond, a sulfonylamide bond, an ether bond, an ester bond, and a urethane bond in the middle of the bond. It is preferably an unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms include a methylene group, an ethylene group, and a propylene group. Examples thereof include alkylene groups such as cycloalkylene groups such as cyclohexylene groups, arylene groups such as phenylene groups, and groups in which hydrogen atoms of these groups are partially or entirely substituted with halogen atoms.
[0009]
Further, those containing a bond selected from an amide bond, a sulfonylamide bond, an ether bond, an ester bond and a urethane bond in the middle of the bond are respectively CONR, SO 2 NR, O, COO, OCONR (where R is a hydrogen atom or A monovalent hydrocarbon group having 1 to 8 carbon atoms, such as an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group). Specific examples thereof include the following. The
[0010]
[Formula 4]
[0011]
R 5 is an oxygen atom (—O—) or a divalent organic group, and the divalent organic group is preferably an unsubstituted or substituted divalent hydrocarbon group having 1 to 8 carbon atoms. Is an alkylene group such as a methylene group, an ethylene group or a propylene group, a cycloalkylene group such as a cyclohexylene group, an arylene group such as a phenylene group, or a hydrogen atom of these groups is partially or entirely substituted with a halogen atom. Are exemplified.
[0012]
Rf is a perfluoroalkylene group, a perfluorooxyalkylene group or a polyperfluorooxyalkylene group , and the perfluoroalkylene group having 1 to 20 carbon atoms is a perfluorooxyalkylene group or a polyperfluorooxyalkylene group. Are preferably those having 2 to 100 carbon atoms.
[0013]
Here, the perfluoroalkylene group may be linear or branched, and the following are exemplified.
[0014]
-C 2 F 4 -, - C 3 F 6 -, - C 4 F 8 -, - C 6 F 12 -, - C 8 F 16 -
[0015]
[Chemical formula 5]
As the perfluorooxyalkylene group, a repeating unit (Rf′-O)
(Wherein Rf ′ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms)
The following units etc. are mentioned, for example. The perfluorooxyalkylene structure may be composed of one of these repeating units or a combination of two or more.
[0017]
-CF 2 O -, - CF 2 CF 2 O -, - CF 2 CF 2 CF 2 O-,
-CF (CF 3) CF 2 O -, - CF 2 CF 2 CF 2 CF 2 O-,
-CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O -, - C (CF 3) 2 O-
[0018]
Of these, the following units are particularly preferred.
-CF 2 O -, - CF 2 CF 2 O -, - CF 2 CF 2 CF 2 O-,
-CF (CF 3 ) CF 2 O-
[0019]
More specifically, the following are exemplified.
[Chemical 6]
Next, although the fluorine-containing organosilicon compound of this invention is illustrated, these are representative examples and the organosilicon compound of this invention is not limited to the following.
[0021]
[Chemical 7]
The compound of the present invention can be synthesized by various methods. For example, it can be synthesized by the following method.
[0023]
That is, the following general formula (2)
[Chemical 8]
A chlorosilane compound represented by the following general formula (1a) is reacted by dropwise addition into a Grignard reagent derived from chloromethyldimethylsilane, and the reaction product is washed with 2N hydrochloric acid and then isolated by distillation or the like.
[0024]
[Chemical 9]
[0025]
In addition, the general formula (2)
Embedded image
[0026]
Embedded image
[0027]
【The invention's effect】
The fluorine-containing organosilicon compound of the present invention acts as a crosslinking point when added to a thermosetting elastomer or the like, and is therefore useful as a crosslinking density adjusting agent and a rubber hardness improving agent. Moreover, it is useful also as surface treating agents, such as a primer compound and a silica filler, which improve adhesion between elastomers.
[0028]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited to the following Example.
[0029]
[Example 1]
The inside of a 300 ml four-necked flask equipped with a stir bar, thermometer, Dim funnel, and dropping funnel was replaced with dry nitrogen, and then 4.47 g (0.184 mol) of magnesium powder, 70 ml of tetrahydrofuran, and a small piece of iodine were charged and stirred. While heating to 60 ° C. and confirming that the brown color of iodine disappeared, 19.0 g (0.175 mol) of chloromethyldimethylsilane was added dropwise in about 30 minutes to prepare a Grignard reagent (reaction temperature 50). ~ 65 ° C).
[0030]
There, 34.8 g (0.0743 mol) of fluorine-containing chlorosilane having the following structure
Embedded image
[0031]
The reaction solution was poured into 200 ml of 2N hydrochloric acid aqueous solution, the upper layer was separated by liquid separation, and further washed with 200 ml of pure water to separate the upper layer. To this was added 20 g of sodium sulfate, followed by dehydration and filtration, and the filtrate was distilled to obtain 26.3 g of a colorless and transparent fraction having a boiling point of 128 ° C./3 mmHg.
[0032]
The obtained liquid had a viscosity (25 ° C.) = 7.9 cSt, a specific gravity (25 ° C.) = 1.205, and a refractive index (25 ° C.) = 1.402. Further, as a result of 1 H-NMR, IR, and GC-MS analysis, it was confirmed that the compound had the following structure.
[0033]
Embedded image
1 H-NMR (TMS standard)
δ = −0.19 ppm, 4H (Si—C H 2 —Si)
δ = 0.17 ppm, 15H (Si—C H 3 )
δ = 0.84 ppm, 2H (Si—C H 2 —CH 2 )
δ = 2.06ppm, 2H (CF 2 -C H 2)
δ = 4.05 ppm, 2H (Si— H )
δ = 5.7-6.2 ppm, 3H (C H = C H 2 )
[0035]
19 F-NMR (CFCl 3 standard)
a: δ = −124 ppm, 4F
b: δ = −122 ppm, 4F
c: δ = −116 ppm, 2F
d: δ = −114 ppm, 2F
[0036]
Embedded image
IR
2110 cm -1 : ν Si-H
1100 to 1300 cm −1 : ν CF
[0038]
GC-MS
M + = 543
[0039]
[Example 2]
A 300 ml four-necked flask equipped with a stir bar, thermometer, Dim funnel, and dropping funnel was charged with 7.32 g of pure water, 19.6 g of concentrated hydrochloric acid, and 41.0 g (0.306 mol) of tetramethyldisiloxane and stirred. The internal temperature was cooled to 10 ° C. or lower.
[0040]
83.2 g (0.170 mol) of fluorine-containing chlorosilane having the following structure
CH 2 = CH-C 6 F 12 -C 2 H 4 -Si-Cl 3
Was added dropwise over about 30 minutes while keeping the internal temperature at 15 ° C. or higher. After completion of the dropwise addition, the mixture was further stirred for 15 hours at 15 ° C. or lower, and then 60 g of pure water was added.
[0041]
The reaction solution was transferred to a separatory funnel, and the lower layer was separated. After further washing with 100 g of pure water, the lower layer was separated. To this was added 10 g of sodium sulfate, followed by dehydration and filtration, and the filtrate was distilled to obtain 59.8 g of a colorless and transparent fraction having a boiling point of 135 ° C./2 mmHg.
[0042]
The obtained liquid had a viscosity (25 ° C.) = 4.6 cSt, a specific gravity (25 ° C.) = 1.182, and a refractive index (25 ° C.) = 1.363. Further, as a result of 1 H-NMR, IR, and GC-MS analysis, it was confirmed that the compound had the following structure.
[0043]
Embedded image
1 H-NMR (TMS standard)
δ = 0.18 ppm, 18H (Si—C H 3 )
δ = 0.85 ppm, 2H (Si—C H 2 —CH 2 )
δ = 2.05ppm, 2H (CF 2 -C H 2)
δ = 4.81 ppm, 3H (Si- H )
δ = 5.7-6.2 ppm, 3H (C H = C H 2 )
[0045]
19 F-NMR (CFCl 3 standard)
a: δ = −124 ppm, 4F
b: δ = −122 ppm, 4F
c: δ = −116 ppm, 2F
d: δ = −114 ppm, 2F
[0046]
Embedded image
IR
2130 cm -1 : ν Si-H
1100 to 1300 cm −1 : ν CF
[0048]
GC-MS
M + = 607
[0049]
[Example 3]
The inside of a 300 ml four-necked flask equipped with a stir bar, thermometer, Jim funnel, and dropping funnel was replaced with dry nitrogen, and then 6.40 g (0.26 mol) of magnesium powder, 86 ml of tetrahydrofuran, and a small piece of iodine were charged and stirred. While heating to 60 ° C. and confirming that the brown color of iodine disappeared, 27.2 g (0.250 mol) of chloromethyldimethylsilane was added dropwise in about 40 minutes to prepare a Grignard reagent (reaction temperature 50). ~ 65 ° C).
[0050]
There, 50.1 g (0.100 mol) of fluorine-containing chlorosilane having the following structure
Embedded image
[0051]
The reaction solution was poured into 250 ml of 2N hydrochloric acid aqueous solution, the upper layer was separated by liquid separation, washed with 250 ml of pure water, and the upper layer was separated. To this was added 24 g of sodium sulfate, followed by dehydration and filtration, and the filtrate was distilled to obtain 32.3 g of a colorless and transparent fraction having a boiling point of 110 ° C./3 mmHg.
[0052]
The obtained liquid had viscosity (25 ° C.) = 6.5 cSt, specific gravity (25 ° C.) = 1.238, and refractive index (25 ° C.) = 1.386. Further, as a result of 1 H-NMR, IR, and GC-MS analysis, it was confirmed that the compound had the following structure.
[0053]
Embedded image
1 H-NMR (TMS standard)
δ = −0.19 ppm, 4H (Si—C H 2 —Si)
δ = 0.18 ppm, 15H (Si—C H 3 )
δ = 0.86 ppm, 2H (Si—C H 2 —CH 2 )
δ = 2.18 ppm, 2H (CF—C H 2 )
δ = 4.05 ppm, 2H (Si— H )
δ = 5.7-6.2 ppm, 3H (C H = C H 2 )
[0055]
19 F-NMR (CFCl 3 standard)
a: δ = −128 ppm, 2F
b: δ = −85 ppm, 4F
c: δ = -80 ppm, 6F
[0056]
Embedded image
IR
2110 cm -1 : ν Si-H
1100 to 1300 cm −1 : ν CF
[0058]
GC-MS
M + = 575
Claims (5)
Ｒ1、Ｒ2、Ｒ3は炭素原子数１〜８の非置換又は置換一価炭化水素基、
Ｒｆは二価のパーフルオロアルキレン基又はパーフルオロオキシアルキレン基若しくはポリパーフルオロオキシアルキレン基、
Ｒ4は二価の有機基、
Ｒ5は酸素原子又は二価の有機基、
ａは０〜２の整数を示す。）
で表わされる含フッ素有機ケイ素化合物。A compound having an ethylenically unsaturated group adjacent to a perfluoroalkylene group, perfluorooxyalkylene group or polyperfluorooxyalkylene group and a hydrosilyl group (SiH group) in one molecule, )
R 1 , R 2 and R 3 are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms,
Rf is a divalent perfluoroalkylene group , a perfluorooxyalkylene group or a polyperfluorooxyalkylene group ,
R 4 is a divalent organic group,
R 5 represents an oxygen atom or a divalent organic group,
a shows the integer of 0-2. )
A fluorine-containing organosilicon compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001122105A JP4022712B2 (en) | 2001-04-20 | 2001-04-20 | Fluorine-containing organosilicon compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001122105A JP4022712B2 (en) | 2001-04-20 | 2001-04-20 | Fluorine-containing organosilicon compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002316993A JP2002316993A (en) | 2002-10-31 |
| JP4022712B2 true JP4022712B2 (en) | 2007-12-19 |
Family
ID=18971868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001122105A Expired - Fee Related JP4022712B2 (en) | 2001-04-20 | 2001-04-20 | Fluorine-containing organosilicon compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4022712B2 (en) |
-
2001
- 2001-04-20 JP JP2001122105A patent/JP4022712B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002316993A (en) | 2002-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5508369A (en) | Organopolysiloxanes having a silanol group and process of making them | |
| JP4013023B2 (en) | Organosilicon compound | |
| JP7310749B2 (en) | Both terminal silanol-modified perfluoropolyether compound and method for producing the same | |
| US5194648A (en) | Fluorinated carboxylic acid derivatives and methods for making | |
| JPH02160031A (en) | Anionic silicone surface active substance and production thereof | |
| JP4022712B2 (en) | Fluorine-containing organosilicon compound | |
| EP1149837B1 (en) | Organosilicon compounds | |
| JPH0559072A (en) | Olefinic and acetylenic azasilacyclopentane and preparation thereof | |
| JP4344936B2 (en) | Method for producing organosilicon compound containing amino groups at both ends | |
| JP3594113B2 (en) | Fluorine-containing amide compound | |
| JP3915883B2 (en) | Organosilicon compound | |
| JPH09100352A (en) | Polysiloxane and its production | |
| US5627251A (en) | Organosilicon compound and process for its production | |
| EP1233020B1 (en) | Fluorinated organosilicon compounds | |
| JP4055397B2 (en) | Fluorine-containing organosilicon compound | |
| JP3233024B2 (en) | Organosilicon compound and method for producing the same | |
| JP2774362B2 (en) | Siloxane compound having di (meth) acryloxyalkyl group | |
| WO2023053885A1 (en) | Method for producing alkoxysilyl alkylaminopropyl-modified polysiloxane compound | |
| JP2632624B2 (en) | Fluorine-containing organosilicon compound | |
| JPH06107671A (en) | Organosilicon compound and its production | |
| JP4055429B2 (en) | Fluorine-containing organosilicon compound | |
| JP2519601B2 (en) | Organic silicon compounds | |
| JPH05247062A (en) | Organic silicon compound | |
| JPH09104757A (en) | Fluorinated polysiloxane and its production | |
| JP2021017427A (en) | Bishaloalkylsiloxane compound and method of producing the same, and method of producing siloxane compound with both terminals functionalized |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070613 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070614 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070808 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070905 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070918 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4022712 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101012 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101012 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131012 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |