JP2864413B2 - Organosilicon compound - Google Patents
Organosilicon compoundInfo
- Publication number
- JP2864413B2 JP2864413B2 JP5117943A JP11794393A JP2864413B2 JP 2864413 B2 JP2864413 B2 JP 2864413B2 JP 5117943 A JP5117943 A JP 5117943A JP 11794393 A JP11794393 A JP 11794393A JP 2864413 B2 JP2864413 B2 JP 2864413B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- represented
- organosilicon compound
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- 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.)
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- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- -1 disiloxane compound Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 239000010702 perfluoropolyether Chemical group 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 8
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、１分子中にケイ素原子
に直結した水素原子（≡ＳｉＨ基）を有すると共に、両
末端にフッ素含有基を有し、このため各種樹脂の架橋剤
として有効に利用することができる新規な有機ケイ素化
合物に関する。BACKGROUND OF THE INVENTION The present invention has a hydrogen atom (@SiH group) directly bonded to a silicon atom in one molecule and a fluorine-containing group at both terminals, so that it is effective as a crosslinking agent for various resins. A novel organosilicon compound that can be used for
【０００２】[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、付加硬化型シリコーン組成物は、各種分野で使用さ
れている。このシリコーン組成物は、下記反応式で示さ
れるヒドロシリル化反応により架橋を起こし、硬化する
ものである。BACKGROUND OF THE INVENTION Conventionally, addition-curable silicone compositions have been used in various fields. This silicone composition undergoes crosslinking by a hydrosilylation reaction represented by the following reaction formula and is cured.
【０００３】[0003]
【化２】 Embedded image
【０００４】この場合、≡ＳｉＨ基を含有するシロキサ
ンは架橋剤として使用されるもので、従来具体的には下
記化合物が使用される。In this case, a siloxane containing a ≡SiH group is used as a crosslinking agent, and specifically, the following compounds are conventionally used.
【０００５】[0005]
【化３】 Embedded image
【０００６】しかしながら、上記のような架橋剤をフッ
素含有率の高い含フッ素シリコーン組成物に配合する
と、両者の相溶性が悪いために硬化性が不十分になると
いう欠点があった。[0006] However, when the above-mentioned crosslinking agent is incorporated into a fluorine-containing silicone composition having a high fluorine content, there is a drawback that the curability is insufficient due to poor compatibility between the two.
【０００７】そこで、近年、架橋剤として下記一般式で
示されるような側鎖にフッ素含有基を有するＳｉＨ基含
有シロキサン化合物を用い、相溶性を改善することが行
われている。Therefore, in recent years, the compatibility has been improved by using a SiH group-containing siloxane compound having a fluorine-containing group in a side chain as shown by the following general formula as a crosslinking agent.
【０００８】[0008]
【化４】 （但し、式中Ｒｆはパーフルオロアルキル基又はパーフ
ルオロポリエーテル基であり、ｉは１以上の整数、ｐは
０以上の整数、ｑは２以上の整数である。）Embedded image (In the formula, Rf is a perfluoroalkyl group or a perfluoropolyether group, i is an integer of 1 or more, p is an integer of 0 or more, and q is an integer of 2 or more.)
【０００９】しかし、上記シロキサン化合物は、側鎖の
フッ素含有基が立体的にＳｉＨ基の反応性に不利に働い
てしまうため、この場合も硬化性が十分とは言い難いも
のであった。[0009] However, the siloxane compound described above is hardly sufficiently curable in this case because the fluorine-containing group in the side chain sterically adversely affects the reactivity of the SiH group.
【００１０】本発明は上記事情に鑑みなされたもので、
各種樹脂、特に含フッ素樹脂との相溶性が良く、付加硬
化型の含フッ素シリコーン組成物、その他脂肪族不飽和
基を有する樹脂組成物の架橋剤として使用した場合、硬
化性に優れ、かつ耐溶剤性、水分透過率に優れた硬化物
を与え得る有機ケイ素化合物を提供することを目的とす
る。The present invention has been made in view of the above circumstances,
It has good compatibility with various resins, especially fluorine-containing resins, and when used as a crosslinking agent for addition-curable fluorine-containing silicone compositions and other resin compositions having an aliphatic unsaturated group, has excellent curability and resistance. An object of the present invention is to provide an organosilicon compound capable of providing a cured product having excellent solvent properties and moisture permeability.
【００１１】[0011]
【課題を解決するための手段及び作用】本発明者は上記
目的を達成するため鋭意検討を重ねた結果、例えば下記
一般式（２）で示されるオルガノハイドロジェンポリシ
ロキサンと下記一般式（３）で示される含フッ素ジシロ
キサン化合物、更に必要により下記一般式（４）で示さ
れるシクロシロキサンとを酸触媒の存在下で平衡化反応
させて式（３）の含フッ素ジシロキサン化合物にＳｉＨ
基を導入することにより、下記一般式（１）で示される
新規な有機ケイ素化合物が得られること、更に、この有
機ケイ素化合物が両末端に含フッ素有機基を有すると共
に、側鎖にケイ素原子に結合した水素原子（ＳｉＨ基）
を有し、ＳｉＨ基がフッ素含有基による立体障害を受け
ることなく脂肪族不飽和基と有利に反応することから各
種樹脂、特に含フッ素シリコーン樹脂との親和性が良
く、各種脂肪族不飽和基を含有する樹脂組成物に架橋剤
として配合した場合、その硬化物の耐溶剤性、水分透過
率の向上に対する寄与が大きく、とりわけ含フッ素シリ
コーン樹脂に対して十分な硬化性を付与し得る架橋剤と
して有用であることを知見し、本発明をなすに至った。The present inventors have made intensive studies to achieve the above object, and as a result, for example, an organohydrogenpolysiloxane represented by the following general formula (2) and a compound represented by the following general formula (3) Is reacted with a cyclosiloxane represented by the following general formula (4), if necessary, in the presence of an acid catalyst to give a fluorine-containing disiloxane compound of the formula (3)
By introducing the group, a novel organosilicon compound represented by the following general formula (1) can be obtained. Further, this organosilicon compound has a fluorine-containing organic group at both terminals and a silicon atom in a side chain. Bonded hydrogen atom (SiH group)
Having a good affinity with various resins, especially fluorine-containing silicone resins, since the SiH group reacts favorably with the aliphatic unsaturated group without being sterically hindered by the fluorine-containing group. When compounded as a cross-linking agent in a resin composition containing, a large contribution to the improvement of the solvent resistance and moisture permeability of the cured product, particularly, a cross-linking agent capable of imparting sufficient curability to a fluorine-containing silicone resin The present invention was found to be useful, and led to the present invention.
【００１２】[0012]
【化５】 （但し、式中Ｒ１及びＲ３はそれぞれ独立に炭素数１〜
６の一価炭化水素基、Ｒ２は間に酸素原子が介在しても
よい炭素数１〜４の低級アルキレン基、Ｒｆはパーフル
オロアルキル基又はパーフルオロポリエーテル基であ
り、ｍは１以上の整数で平均して４〜１００であり、ｎ
は０以上の整数である。）Embedded image (However, in the formula, R 1 and R 3 each independently have 1 to 1 carbon atoms.
6, a monovalent hydrocarbon group, R 2 is a lower alkylene group having 1 to 4 carbon atoms which may have an oxygen atom interposed therebetween, Rf is a perfluoroalkyl group or a perfluoropolyether group, and m is 1 or more. Is an average of 4 to 100, and n
Is an integer of 0 or more. )
【００１３】従って、本発明は、上記式（１）で示され
る有機ケイ素化合物を提供する。Accordingly, the present invention provides an organosilicon compound represented by the above formula (1).
【００１４】以下、本発明につき更に詳細に説明する
と、本発明の有機ケイ素化合物は、下記一般式（１）で
示されるものである。Hereinafter, the present invention will be described in more detail. The organosilicon compound of the present invention is represented by the following general formula (1).
【００１５】[0015]
【化６】 （但し、式中Ｒ１及びＲ３はそれぞれ独立に炭素数１〜
６の一価炭化水素基、Ｒ２は間に酸素原子が介在しても
よい炭素数１〜４の低級アルキレン基、Ｒｆはパーフル
オロアルキル基又はパーフルオロポリエーテル基であ
り、ｍは１以上の整数で平均して４〜１００であり、ｎ
は０以上の整数である。）Embedded image (However, in the formula, R 1 and R 3 each independently have 1 to 1 carbon atoms.
6, a monovalent hydrocarbon group, R 2 is a lower alkylene group having 1 to 4 carbon atoms which may have an oxygen atom interposed therebetween, Rf is a perfluoroalkyl group or a perfluoropolyether group, and m is 1 or more. Is an average of 4 to 100, and n
Is an integer of 0 or more. )
【００１６】ここで、上記式（１）中のＲ１，Ｒ３とし
ては、炭素数１〜６の一価炭化水素基であり、例えばメ
チル基、エチル基等の低級アルキル基、フェニル基など
が挙げられる。Here, R 1 and R 3 in the above formula (1) are monovalent hydrocarbon groups having 1 to 6 carbon atoms, for example, lower alkyl groups such as methyl group and ethyl group, phenyl group and the like. Is mentioned.
【００１７】また、Ｒ２としては、炭素数１〜４の低級
アルキレン基又は間に酸素が介在した低級アルキレン基
であり、具体的には下記式で示される基が例示される。R 2 is a lower alkylene group having 1 to 4 carbon atoms or a lower alkylene group having oxygen interposed therebetween, and specific examples thereof include groups represented by the following formula.
【００１８】[0018]
【化７】 Embedded image
【００１９】更に、上記式（１）においてＲｆはパーフ
ルオロアルキル基又はパーフルオロポリエーテル基であ
り、具体的には下記の基が例示される。Further, in the above formula (1), Rf is a perfluoroalkyl group or a perfluoropolyether group, and specific examples include the following groups.
【００２０】[0020]
【化８】 Embedded image
【００２１】なお、ｍは１以上、好ましくは２以上の整
数であり、平均して４〜１００である。Here, m is an integer of 1 or more, preferably 2 or more, and is 4 to 100 on average.
【００２２】このような式（１）の有機ケイ素化合物と
して具体的には、下記化合物を例示することができる。Specific examples of such an organosilicon compound of the formula (1) include the following compounds.
【００２３】[0023]
【化９】 Embedded image
【００２４】上記式（１）の有機ケイ素化合物は、例え
ば下記一般式（２）で示されるオルガノハイドロジェン
ポリシロキサンと下記一般式（３）で示される含フッ素
ジシロキサン化合物、更に必要により下記一般式（４）
で示されるシクロシロキサンとを酸触媒の存在下で平衡
化反応させることにより合成することができる。The organosilicon compound of the above formula (1) includes, for example, an organohydrogenpolysiloxane represented by the following general formula (2) and a fluorine-containing disiloxane compound represented by the following general formula (3), and if necessary, the following general formula Equation (4)
Can be synthesized by performing an equilibration reaction with the cyclosiloxane represented by the formula (1) in the presence of an acid catalyst.
【００２５】[0025]
【化１０】 （但し、式中Ｒ1、Ｒ2、Ｒｆは前記と同様である。ま
た、ｋは３又は４である。）Embedded image (However, in the formula, R 1 , R 2 , and Rf are the same as described above, and k is 3 or 4.)
【００２６】この場合、式（２）のオルガノハイドロジ
ェンポリシロキサンと式（３）の含フッ素ジシロキサン
化合物、更に式（４）のシクロシロキサンとの混合割合
は、特に限定されるものではない。In this case, the mixing ratio of the organohydrogenpolysiloxane of the formula (2), the fluorinated disiloxane compound of the formula (3) and the cyclosiloxane of the formula (4) is not particularly limited.
【００２７】なお、上記式（１）中のｍは、反応時にお
ける式（２）のオルガノハイドロジェンポリシロキサン
の使用割合を調整することにより目的に応じた適宜な値
にすることができるもので、これにより式（１）の１分
子中のＳｉＨ基の数を変えることができる。M in the above formula (1) can be adjusted to an appropriate value according to the purpose by adjusting the use ratio of the organohydrogenpolysiloxane of the formula (2) in the reaction. Thus, the number of SiH groups in one molecule of the formula (1) can be changed.
【００２８】また、酸触媒としては、例えば硫酸、無水
硫酸、トリフルオロメチルスルホン酸等を使用し得、そ
の添加量は触媒量とすることができる。As the acid catalyst, for example, sulfuric acid, sulfuric anhydride, trifluoromethylsulfonic acid and the like can be used, and the amount of addition can be a catalytic amount.
【００２９】上記平衡反応条件は、別に制限されない
が、２０〜１５０℃で１〜２４時間反応させることが好
ましい。The above equilibrium reaction conditions are not particularly limited, but the reaction is preferably carried out at 20 to 150 ° C. for 1 to 24 hours.
【００３０】本発明の上記式（１）の有機ケイ素化合物
は、単一の化合物としても、あるいは２種類以上の混合
物としても有用なものであるが、特に上記平衡化反応を
行った後、ストリップ等により未反応のジシロキサン、
更には好ましくは式（１）におけるｍ＝１の有機ケイ素
化合物を除去すると、架橋剤としてより好適に使用する
ことができる式（１）の有機ケイ素化合物の混合物を得
ることができる。The organosilicon compound of the above formula (1) of the present invention is useful as a single compound or as a mixture of two or more kinds. Unreacted disiloxane, etc.
Furthermore, preferably, when the organosilicon compound of m = 1 in the formula (1) is removed, a mixture of the organosilicon compound of the formula (1) which can be more suitably used as a crosslinking agent can be obtained.
【００３１】[0031]
【発明の効果】本発明の有機ケイ素化合物は、両末端に
含フッ素有機基を有すると共に、側鎖にケイ素原子に結
合した水素原子（ＳｉＨ基）を有することから、ＳｉＨ
基の脂肪族不飽和基（ビニル基等のアルケニル基など）
に対する反応が含フッ素有機基の立体障害を受けること
なく反応し、付加反応がスムーズに進行し、また各種樹
脂、特に含フッ素シリコーン樹脂との親和性が良く、各
種付加反応硬化型の樹脂組成物に架橋剤として配合した
場合、その硬化物の耐溶剤性、水分透過率の向上に対す
る寄与が大きく、従って含フッ素シリコーン樹脂等に対
して十分な硬化性を付与し得る架橋剤として有効に使用
することができる。The organosilicon compound of the present invention has a fluorinated organic group at both terminals and a hydrogen atom (SiH group) bonded to a silicon atom in a side chain, and thus has an SiH
Aliphatic unsaturated group (alkenyl group such as vinyl group)
Reacts without steric hindrance of the fluorine-containing organic group, the addition reaction proceeds smoothly, and has a good affinity with various resins, especially fluorine-containing silicone resins, and various addition reaction-curable resin compositions When used as a cross-linking agent, it greatly contributes to the improvement of solvent resistance and moisture permeability of the cured product, and is therefore effectively used as a cross-linking agent capable of imparting sufficient curability to fluorine-containing silicone resins and the like. be able to.
【００３２】[0032]
【実施例】以下、実施例及び比較例を示して本発明を具
体的に説明するが、本発明は下記実施例に制限されるも
のではない。なお、各例中の部はいずれも重量部であ
る。EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. All parts in each example are parts by weight.
【００３３】〔実施例１〕下記式（５）で示されるジシ
ロキサン３６．２ｇ（０．０３３モル）、下記式（６）
で示されるシクロシロキサン１５．９ｇ（０．０６６モ
ル）を撹拌装置、冷却管、温度計を備えた１００ｍｌ三
つ口フラスコ内に仕込んで撹拌した。Example 1 36.2 g (0.033 mol) of a disiloxane represented by the following formula (5),
Was charged into a 100 ml three-necked flask equipped with a stirrer, a condenser, and a thermometer and stirred.
【００３４】系内を窒素置換した後、ＣＦ3ＳＯ3Ｈを
０．１５ｇ（０．００１モル）添加し、８０℃にて平衡
化反応を行った。１６時間後に室温まで冷却し、２ｇの
水を加え、１時間撹拌後、水層を分離した。さらに飽和
硫酸ナトリウムにて水洗したところ、下記式（７）で示
される化合物の混合物４５．３ｇが得られた。After the atmosphere in the system was replaced with nitrogen, 0.15 g (0.001 mol) of CF 3 SO 3 H was added, and an equilibration reaction was carried out at 80 ° C. After 16 hours, the mixture was cooled to room temperature, 2 g of water was added, and after stirring for 1 hour, the aqueous layer was separated. Further, when washed with saturated sodium sulfate, 45.3 g of a mixture of compounds represented by the following formula (7) was obtained.
【００３５】[0035]
【化１１】 （但し、式中ｒは０以上の整数であり、その平均値は８
である。）Embedded image (Where r is an integer of 0 or more, and the average value is 8
It is. )
【００３６】次に、上記式（７）の化合物の混合物を１
５０℃、１×１０-4Ｔｏｒｒにてストリップを行ってｒ
＝Ｏ及び１のシロキサン化合物を留去し、ｒが２以上の
シロキサン化合物２０．３ｇを得た。得られた化合物
は、次に示す分析結果から下記式（８）で示される構造
であることが確認された。Next, the mixture of the compound of the above formula (7) is
Strip at 50 ° C and 1 × 10 -4 Torr
The siloxane compound of = 0 and 1 was distilled off to obtain 20.3 g of a siloxane compound having r of 2 or more. The obtained compound was confirmed to have a structure represented by the following formula (8) from the analysis results shown below.
【００３７】[0037]
【化１２】 （但し、ｓは２以上の整数であり、ｓの平均値は１２で
ある。） 元素分析： Ｃ Ｈ Ｓｉ Ｆ 計算値（％） ２３．８６ ３．７８ ２１．７０ ３５．６５ 実測値（％） ２３．５２ ３．８４ ２２．１１ ３５．４７ ＊Ｃ36Ｈ68Ｏ17Ｆ34Ｓｉ14として計算 赤外線吸収スペクトル：波数２１７０ｃｍ-1にＳｉＨ基
に由来する特性吸収が認められた。 Ｓｉ−Ｈ量： 計算値：６．６３×１０-3モル／ｇ 実測値：６．７７×１０-3モル／ｇ1 Ｈ−ＮＭＲスペクトル：（ＴＭＳ基準） δ＝４．６７ｐｐｍ （−ＳｉＨ，ｍ，１２Ｈ） δ＝０．２０ｐｐｍ （−Ｓｉ−ＣＨ3，ｍ、４８
Ｈ） δ＝０．５３〜１．００ｐｐｍ （Ｓｉ−ＣＨ2−
Ｃ，ｍ，４Ｈ） δ＝１．８０〜２．７７ｐｐｍ （ＣＦ−ＣＨ2−
Ｃ，ｍ，４Ｈ）19 Ｆ−ＮＭＲスペクトル：（ＣＦ3ＣＯＯＨ基準） φ＝−３．７９ｐｐｍ （−ＣＦ（ＣＦ3 ）ＣＦ
2−，６Ｆ） φ＝−５．１９ｐｐｍ （ＣＦ3 ＣＦ2ＣＦ2 −，１
０Ｆ） φ＝−７．０９ｐｐｍ （−ＣＦ（ＣＦ3）ＣＦ
2 −，４Ｆ） φ＝−１１．０５ｐｐｍ （−ＣＦ2 ＣＦ2ＣＨ
2−，４Ｆ） φ＝−４３．４３ｐｐｍ （−ＣＦ2ＣＦ2 ＣＨ
2−，４Ｆ） φ＝−５３．１０ｐｐｍ （−ＣＦ3ＣＦ2 ＣＦ
2−，４Ｆ） φ＝−６８．７０ｐｐｍ （−ＣＦ（ＣＦ3）ＣＦ2
−，２Ｆ）Embedded image(However, s is an integer of 2 or more, and the average value of s is 12
is there. ) Elemental analysis: CH Si F calculated (%) 23.86 3.78 21.70 35.65 found (%) 23.52 3.84 22.11 35.47 * C36H68O17F34Si14Infrared absorption spectrum: wave number 2170cm-1SiH group
The characteristic absorption derived from was observed. Si-H amount: Calculated value: 6.63 × 10-3Mol / g found: 6.77 × 10-3Mol / g1 H-NMR spectrum: (TMS standard) δ = 4.67 ppm (-SiH, m, 12H) δ = 0.20 ppm (-Si-CHThree, M, 48
H) δ = 0.53 to 1.00 ppm (Si-CHTwo−
C, m, 4H) δ = 1.80-2.77 ppm (CF-CHTwo−
C, m, 4H)19 F-NMR spectrum: (CFThreeCOOH standard) φ = -3.79 ppm (-CF (CF 3 ) CF
Two−, 6F) φ = −5.19 ppm (CF 3 CFTwoCF 2 −, 1
0F) φ = −7.09 ppm (−CF (CFThree) CF
Two −, 4F) φ = -11.05 ppm (−CF 2 CFTwoCH
Two−, 4F) φ = −43.43 ppm (−CFTwoCF 2 CH
Two−, 4F) φ = −53.10 ppm (−CFThreeCF 2 CF
Two−, 4F) φ = −68.70 ppm (−CF(CFThree) CFTwo
−, 2F)
【００３８】〔実施例２〕実施例１と同様の装置に下記
式（９）で示されるジシロキサン５０．０ｇ（０．０４
９モル）、上記式（６）のシクロシロキサン２３．４ｇ
（０．０９８モル）を仕込んで窒素置換後、ＣＦ3ＳＯ3
Ｈ ０．１５ｇ（０．００１モル）を添加し、実施例１
と同様に反応、後処理を行ったところ、下記式（１０）
で示される化合物の混合物７０．３ｇが得られた。Example 2 In the same apparatus as in Example 1, 50.0 g (0.04 g) of a disiloxane represented by the following formula (9) was used.
9 mol), 23.4 g of the cyclosiloxane of the above formula (6)
(0.098 mol), and after purging with nitrogen, CF 3 SO 3
Example 1 was added by adding 0.15 g (0.001 mol) of H.
When the reaction and post-treatment were carried out in the same manner as described above, the following formula (10) was obtained.
70.3 g of a mixture of the compounds represented by the formula was obtained.
【００３９】[0039]
【化１３】 （但し、式中ｔは０以上の整数であり、ｔの平均値は８
である。）Embedded image (Where t is an integer of 0 or more, and the average value of t is 8
It is. )
【００４０】次に、上記式（１０）の化合物の混合物を
１５０℃）１×１０−２Ｔｏｒｒにてストリップを行っ
て上記式（１０）の化合物中のｔ＝０の化合物を留去し
たところ、ｔが１以上のシロキサン化合物５８．８ｇが
得られた。この化合物は、下記に示す分析結果から下記
式（１１）で示される構造であることが確認された。Next, a mixture of the compound of the above formula (10) was stripped at 150 ° C. at 1 × 10 −2 Torr to distill off the compound of the above formula (10) at t = 0. And 58.8 g of a siloxane compound having a t of 1 or more was obtained. From the analysis results shown below, this compound was confirmed to have a structure represented by the following formula (11).
【００４１】[0041]
【化１４】 （但し、式中ｕは１以上の整数であり、ｕの平均値は１
０である。） 元素分析： Ｃ Ｈ Ｓｉ Ｆ 計算値（％） ２５．２４ ３．１２ ２０．８３ ３９．９３ 実測値（％） ２４．９７ ３．２２ ２０．５４ ４０．１６ ※ Ｃ34Ｈ50Ｏ11Ｆ34Ｓｉ12として計算 赤外線吸収スペクトル：波数２１７０ｃｍ-1にＳｉＨ基
に由来する特性吸収が認められた。 Ｓｉ−Ｈ量： 計算値 ６．６４×１０-3モル／ｇ 実測値 ６．７９×１０-3モル／ｇ1 Ｈ−ＮＭＲスペクトル：（ＴＭＳ基準） δ＝４．５９ｐｐｍ （−Ｓｉ−Ｈ，ｍ，１０Ｈ） δ＝０．１８ｐｐｍ （−Ｓｉ−ＣＨ3，ｍ，４２
Ｈ） δ＝０．５６〜１．０８ｐｐｍ （Ｓｉ−ＣＨ2−
Ｃ，ｍ，４Ｈ） δ＝１．７６〜２．７５ｐｐｍ （ＣＦ−ＣＨ2−
Ｃ，ｍ，４Ｈ）Embedded image (Where u is an integer of 1 or more, and the average value of u is 1
0. ) Elemental analysis: C H Si F Calculated (%) 25.24 3.12 20.83 39.93 Found (%) 24.97 3.22 20.54 40.16 ※ C 34 H 50 O 11 F 34 Si 12 as calculated infrared absorption spectrum: characteristic absorption derived from the SiH group at a wavenumber of 2170 cm -1 was observed. Si-H content: calculated value 6.64 × 10 −3 mol / g measured value 6.79 × 10 −3 mol / g 1 H-NMR spectrum: (based on TMS) δ = 4.59 ppm (—Si—H, m, 10H) δ = 0.18 ppm (—Si—CH 3 , m, 42
H) δ = 0.56~1.08ppm (Si- CH 2 -
C, m, 4H) δ = 1.76~2.75ppm (CF-CH 2 -
C, m, 4H)
【００４２】[0042]
【化１５】 Embedded image
フロントページの続き (72)発明者 佐藤 伸一 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社 シリコーン電 子材料技術研究所内 (72)発明者 木下 博文 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社 シリコーン電 子材料技術研究所内 (72)発明者 荒井 正俊 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社 シリコーン電 子材料技術研究所内 (72)発明者 藤木 弘直 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社 シリコーン電 子材料技術研究所内 (56)参考文献 特開 昭56−167729（ＪＰ，Ａ) 特開 平３−34988（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ) ＷＰＩ（ＤＩＡＬＯＧ)Continued on the front page (72) Inventor Shinichi Sato 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Hirofumi Kinoshita, Daijito Matsuida-cho, Usui-gun, Gunma Prefecture No. 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Masatoshi Arai Matsuida-machi, Usui-gun, Gunma Pref. 1-10 Hitomi Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Hironao Fujiki 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Inside the Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (56) References JP-A-56-167729 (JP, A) JP-A-3-34988 (JP, A) (58) Fields surveyed (Int. Cl. 6 , DB name) CA (STN) REGISTRY (STN) WPI (DIALOG)
Claims (2)
化合物。 【化１】 （但し、式中Ｒ１及びＲ３はそれぞれ独立に炭素数１〜
６の一価炭化水素基、Ｒ２は間に酸素原子が介在しても
よい炭素数１〜４の低級アルキレン基、Ｒｆはパーフル
オロアルキル基又はパーフルオロポリエーテル基であ
り、ｍは１以上の整数で平均して４〜１００であり、ｎ
は０以上の整数である。）1. An organosilicon compound represented by the following general formula (1). Embedded image (However, in the formula, R 1 and R 3 each independently have 1 to 1 carbon atoms.
6, a monovalent hydrocarbon group, R 2 is a lower alkylene group having 1 to 4 carbon atoms which may have an oxygen atom interposed therebetween, Rf is a perfluoroalkyl group or a perfluoropolyether group, and m is 1 or more. Is an average of 4 to 100, and n
Is an integer of 0 or more. )
ロジェンポリシロキサンと、下記一般式（３）で示され
る含フッ素ジシロキサン化合物と、更に必要により下記
一般式（４）で示されるシクロシロキサンとを酸触媒の
存在下で平衡化反応させることにより得られる請求項１
記載の有機ケイ素化合物。 【化１６】 （但し、Ｒ１、Ｒ２、Ｒ３、Ｒｆは上記と同じ意味を示
し、ｋは３又は４である。）2. An organohydrogenpolysiloxane represented by the following formula (2), a fluorine-containing disiloxane compound represented by the following general formula (3), and, if necessary, a cyclosiloxane represented by the following general formula (4): Is obtained by performing an equilibrium reaction between the above and an acid catalyst.
The organosilicon compound according to the above. Embedded image (However, R 1 , R 2 , R 3 , and Rf have the same meaning as described above, and k is 3 or 4.)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5117943A JP2864413B2 (en) | 1993-04-21 | 1993-04-21 | Organosilicon compound |
| US08/230,470 US5412135A (en) | 1993-04-21 | 1994-04-20 | Organic silicon compounds and curable organopolysiloxane compositions |
| DE69409025T DE69409025T2 (en) | 1993-04-21 | 1994-04-21 | Organic silicone compounds and curable organopolysiloxane compositions |
| EP94302860A EP0621316B1 (en) | 1993-04-21 | 1994-04-21 | Organic silicon compounds and curable organopolysiloxane compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5117943A JP2864413B2 (en) | 1993-04-21 | 1993-04-21 | Organosilicon compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06306086A JPH06306086A (en) | 1994-11-01 |
| JP2864413B2 true JP2864413B2 (en) | 1999-03-03 |
Family
ID=14724071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5117943A Expired - Fee Related JP2864413B2 (en) | 1993-04-21 | 1993-04-21 | Organosilicon compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2864413B2 (en) |
-
1993
- 1993-04-21 JP JP5117943A patent/JP2864413B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06306086A (en) | 1994-11-01 |
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